2005 Materials Science Outlook (PDF: 5.55MB)

Transcription

Materials Science Outlook 2005
National Institute for Materials Science
Contents
Introduction • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • iii
PART 1 Prospects of Materials Science-History of Materials Science and Future Trends in Research • • • 3
PART 2 Policies of Materials Research in Japan, USA and EU • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 1 Materials Research Policies of Japan, USA and EU • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 2 Nanotechnology Research Policies of Japan, USA and EU • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
1. Research Policies of Japan, USA and EU • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. Societal Implications of Nanotechnology • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
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PART 3 Public Research Institutes for Materials Research in Respective Countries • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 1 Public Research Institutes for Materials Research in Japan, USA and EU • • • • • • • • • • • • • • • • • • •
1. Japan • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. USA • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
3. Germany • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
4. France • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
5. Spain • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 2 New Nanotechnology Research Institutes in Japan, USA and Europe • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 3 Public Research Institutes in Russia Federation and Poland • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
1. Russian Federation • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. Poland • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
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PART 4 Outlook of Materials Research • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 71
Chapter 1 Nanomaterials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 73
1. Nanotubes • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 73
2. Nanoparticles • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 77
3. Quantum Dots • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 79
4. Nanodevices • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 83
Chapter 2 Superconducting Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 87
1. Oxide Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 87
2. Metallic Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 91
Chapter 3 Magnetic Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 95
Chapter 4 Semiconductor Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 102
Chapter 5 Biomaterials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 106
1. Materials for Artificial Organ and Tissue Engineering • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 106
2. Bioelectronics • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 111
Chapter 6 Ecomaterials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 115
1. Environmental Function Materials (Photocatalytic and Environment Purification Materials) 115
2. System Element Type Ecomaterials - Supporting New Energies and Energy Conservation:
Materials for Hydrogen Energy and Fuel Cells • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 119
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3. Ecomaterials of Lifecycle Design • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 7 High Temperature Materials for Jet Engines and Gas Turbines • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 8 Metals • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
1. Steel - Steel Technology for Strong, Safe Structures • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Steel - Steel Technology for High-Efficiency Energy • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Steel - Steel Technology for Hydrogen Utilization • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Steel - Reliability of Steel Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. Nonferrous Alloys • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
3. Protective Coating for Severe Environments • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 9 Ceramic Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
1. Non-oxides - Carbon • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Non-oxides - Carbides, Nitrides, and Borides • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. Oxides - Alumina, Zirconia, and Magnesia• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Oxides - 3d Transition Metal Oxides • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Oxides - Niobate, Tantalate, and Rare Earth Oxide • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
3. Glass • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 10 Composite Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 11 Polymer Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 12 Analysis and Assessment Technology • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
1. Nanoscale Measurement • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. Extreme Field Measurement • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
3. Electron Transport Modeling in Surface Analysis • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
4. Advancee Transmission Electron Microscope • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
5. Standardization of Assessment Methods • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 13 High Magnetic-Field Generation Technology and Its Applications • • • • • • • • • • • • • • • • • • • • • • • • • • •
1. The Aim of Developing a High Magnetic Field NMR Facility• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. Development of High-Field Whole-Body MRI• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
3. Mass Spectrometry • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 14 Nanosimulation Science • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 15 Technologies New Materials Creation• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
1. Particle-Beam Technologies • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. Applied Technology of Vacuum Process • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 16 Acquisition and Transmission of Materials Information Data and Information • • • • • • • • • •
1. Structural Materials Data Sheets • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. Materials Databases • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Chapter 17 International Standard • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
1. Standard Materials • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
2. International Standardization Research, VAMAS• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
3. Standardization of Nanotechnology and Risk Management • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •
Acknowledgements
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Introduction
Teruo Kishi, President
Four years have passed since NIMS was established as an independent administrative institute. During the first five-year Mid-Term Program from fiscal 2001, we focused on efficient management and
creating a stimulating environment. Consequently, the number of papers, patent applications, and other
research achievements grew dramatically. Going forward, we intend not only to build on those achievements but also to improve the quality of materials science research at NIMS.
NIMS is Japan’s sole independent administrative institute specialized in materials science. From the
second Mid-Term Program from fiscal 2006, we will serve as the hub of all research related to materials
science in Japan, while also forging links with other countries and continuing our own research.
NIMS will centrally compile the latest data on domestic and international research on materials science and make that data available globally. As part of such activities, we published a new book entitled
“Materials Science Outlook”, which identifies and analyzes trends in policies, measures, and research
related to materials science both within and outside Japan.
Materials Science Outlook is intended for policy makers, research institute managers, and materials
science researchers both domestic and overseas. The publication will provide readers with detailed
information to plan policies for their activities.
The 2005 edition is the first edition of Materials Science Outlook. It offers projections from Year
2004 based on past trends in the main fields of materials science research. NIMS also surveyed research
work, policies and organizations engaged in materials science of Japan, the United States, and European
countries.
As a public research organ, NIMS has long been involved in fundamental research and development.
Through Materials Science Outlook, NIMS looks forward to disseminating information about materials
science and promoting research in this fast-moving field both in Japan and abroad.
We look forward to your continued support for NIMS and Materials Science Outlook.
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PART1
Prospects of Materials Science
History of Materials Science
and
Future Trends in Research
01
Prospects of Materials Science
– History of Materials Science and Future Trends in Research –
Teruo Kishi
President, NIMS
1. Classification and transition of materials
Materials can be classified by component: process,
structure, property, and performance. They can also be
classified by dynamic, electronic, photonic, magnetic, and
biotic functions and by applications as is shown in Figure
1. The most common method is first to classify materials
broadly into organic and inorganic materials as shown in
Figure 2, and then into metals, ceramics, semiconductors,
polymers, and composites. Figure 3 shows another method
proposed by Allen et al., where materials are classified by
noncrystal phase, crystal phase, and liquid crystal phase.1)
This structure-based method attaches importance to structural defects such as dislocations.
Figure 4 shows a forecast of the transition of materials
published by Ashby in 1980.2) According to this forecast,
metals will decline in relative importance after peaking at
70 to 80% of all materials in about 1960, and the percentages of polymers, composites, ceramics, and glasses will
increase. It is interesting to note that the figure is horizontally symmetric. In other words, ceramics, composites, and
Applications Public facilities
Aerospace
Automobiles
Electronics
Metals
Ceramics
Polymers
(Semiconductors)
(Composites)
Materials
Components Process
Functions Dynamic
other materials will return to their original percentages
even as natural materials are replaced with artificial ones. It
is also interesting that nonmetallic materials reached a
plateau around 2000, perhaps because ceramics and other
composite materials, whose brittleness makes them unreliable, failed to replace metals as structural materials. If the
problem of brittleness could be solved, the application of
nonmetallic materials may grow.
Figure 5 gives a history of materials, showing the development of metals, nanotechnology, semiconductors, polymers, and composites; the timings of emergence; the supporting techniques of measurement, analysis, and experimentation; the related theories and backgrounds; and actual
products that have resulted. From the figure, we see that the
supporting techniques correspond well to the materials that
emerged, and that theories then appeared accordingly. The
history of each material reveals that measuring and analytical techniques of metal started developing very early, followed in quick succession by their supporting techniques.
Fine ceramics, which appeared after metals, show similar
tendencies to metals, having been supported by unique
Noncrystal phase:
Statistical shortdistance regularity
Non-equilibrium process:
Quick heating, quick cooling,
large deformation, and mixing
Electronic
Photonic
Magnetic
Bio
Nonmetallic
Characteristics
Structural defect
Fig. 1 Components, functions, and application systems of materials.
Inorganic materials
Liquid crystal phase:
Orientation
regularity
Manufacture
Structure
Structure
Property
Performance
Metallic
Crystal phase:
Parallel shortdistance regularity
Fig. 3 Materials classification by structure.1)
Metals
Iron, steel, aluminum, aluminum alloy, copper,
copper alloy, titanium, and titanium alloy
Ceramics
Alumina (Al2O3), silicon carbide (SiC), graphite
(C), diamond (C), and silicon nitride (Si3N4)
Semiconductors
Silicon (Si), germanium (Ge), and gallium
arsenide (GaAs)
Organic materials
Polymers
Polyamide (PA), polycarbonate (PC), polyvinyl
chloride (PVC), and polyethylene (PE)
Composites
Glass fiber reinforced plastics (GFRP) and
carbon fiber reinforced plastics (CFRP)
Reliability issues
Fig. 2 Classification of materials.
Fig. 4 Transition of materials.2)
3
Si, GaAs HfO2
Metals
Nanotechnology
Semiconductors
Polymers
Composites
Fiber reinforced plastics
Carbon nanotube
Hemp Cotton
Earthen ware Copper
Emerged
materials
Vinyl chloride,
Silk
Bronze
Iron
Aluminum
Steel
Microscope
Refining
Measurement, analysis,
and experimentation
Alloying
Reductive reaction Discovery of tin
Related theories
and backgrounds
Hemp and cotton fabrics
Earthenware
Sun-dried bricks
Decorations
Weapons
Refining
nylon, conductive polymer
Titanium
Supersteel
XPS, AES
X-ray diffraction
RBS
TEM
STM
Electrolysis
NMR
SEM
Quantum mechanics Polymer chemistry
Sintering and thermodynamics Dispersion strengthening mechanism
Alchemy Electrochemistry Reductive reaction Grain size refinement
Natural rubber
Ferroconcrete
Voltaic cells
Practical products
LED
Chemical fibers
Transistors, IC, LSI
Duralumin
Aircraft materials
FRP
10,000 B.C.
Fig. 5 Techniques and theories supporting the transition of materials.
Table 1 History of materials science.
measuring techniques and theories, such as sintering and
thermodynamics. More recently, many important polymers
have appeared, as have semiconductor materials which
have progressed rapidly through the linkage of important
theories and analytical techniques. Regarding nanotechnology, it has been the newly developed scanning tunneling
microscope nanotechnology rather than the existing transmission electron microscope that has greatly benefited
materials development. For composites, nondestructive
inspection has been an important technique.
2. History of materials science
Table 1 shows the history of materials science, which
can roughly be divided into three eras. In the era of Curiosity Driven (until 1965), materials science was born from
curiosity about metals, ceramics, polymers, and other materials. In the era of Function Driven (until 1985), functionbased structural materials and various other functional
materials entered practical use. And in the era of System
Driven (until 2000), materials science increasingly found
its way into actual systems. The current era – Nanotechnology and Nanomaterials – merged from Curiosity Driven
and System Driven as shown in Fig. 6. New materials science is expected to emerge thanks to the nanoscale effect of
increasing the surface area, and the quantum effect.
Figure 7 shows the relationship between materials innovation and business cycle.3) The business cycle is about 50
to 60 years. Technical innovations brought by new materials have driven economic development as well as the
Industrial Revolution that produced the steam locomotive
and automobile. In future, materials innovations by nano4
Fig. 6 Future materials science.
materials are expected not only to solve problems related to
the environment and life science, but also to drive economic development.
Mass Transit
Business
Industrial
Revolution
Start of Mass
Consumption Society
World War I
High Economic Growth
and IT Revolution
World War II
Noncrystal phase
Sustained,
Safe Society
Life Science
Crystal phase
Liquid crystal phase
Atomic/Molecular Operations
Non-equilibrium Process
Nanoscale Materials
Nano/microstructures
Nanoscale Effects
New Characteristics
Environment
Iron and
steel
Polymers
Light alloys
Ceramics
Semiconductors
Bonding materials
Nanomaterials
Materials innovation as the prime
mover of economic development
Fig. 7 Relationship between technical innovation and business cycle.3)
Fig. 8 Future materials development (Nanomaterials).
Figure 8 shows two possible routes toward new materials science. On the one route, nanoscale not only reduces
the scale of handling but also yields new characteristics and
functions. On the other route, organic and inorganic materials are handled uniformly in consideration of noncrystal
phase, crystal phase, and liquid crystal phase. Nanomicrostructures are created from non-equilibrium processes
and new characteristics are discovered.
3. Future trends in materials research
In Materials Science Outlook, materials are broadly
classified into the four types shown in Figure 9. First, the
characteristic-seeds materials are: (1) Nanomaterials, (2)
Superconducting materials, (3) Magnetic materials, and (4)
Semiconductor materials. Second, the needs-oriented materials are: (5) Biomaterials, (6) Ecomaterials, and (7) High
temperature materials for jet engines and gas turbines.
Third, the performance-seeking materials are: (8) Metals,
(9) Ceramics, (10) Composite materials, and (11) Polymer
materials. And fourth, the fundamental research areas of
materials are: (12) Analysis and evaluation techniques, (13)
High magnet field generation techniques and applications,
(14) Nano-simulation science, (15) Technologies for creating new materials, (16) Acquisition and transmission of
materials data, and (17) International standards. Research
trends for these items were investigated and analyzed. This
chapter outlines future research trends and Chapter 4
describes the research trends for each item.
3.1 Nanomaterials
Nanomaterials are now attracting great attention and are
widely used. Nanotubes, one of the most attractive groups
of nanomaterials, have to be synthesized with well-controlled methods to obtain semiconducting or metallic nanotubes selectively. For the evaluation of the applicability of
nanotubes to future nanoelectronic devices, further fundamental research is required to understand the functionality
of nanotubes. To create nanoparticles having a controlled
size with a precision of several to tens of nanometers and
also having controlled morphology which is usually related
to the surface structure, we have to develop methods to
control or modify the surface structure of nanoparticles.
Methods to arrange and integrate nanoparticles on a given
substrate are also essential. It is important for the controlled
synthesis of nanoparticles to observe the process of synthesis in situ. Advanced colloid aerosol science and simulation
Characteristic-seeds materials
(1) Nanomaterials
(2) Superconducting materials
(3) Magnetic materials
(4) Semiconductor materials
Performance-seeking materials
(8) Metals
(9) Ceramics
(10) Composites
(11) Polymers
Needs-oriented materials
(5) Biomaterials
(6) Ecomaterials
(7) High temperature materials for
jet engines and gas turbins
R&D materials
(12) Analytical and evaluation techniques
(13) High field generation
techniques and applications
(14) Nano-simulation science
(15) New material creation techniques
(16) Acquisition and launching of materials data
(17) International standards
Fig. 9 Classification of materials in this publication.
technology are also important. Since the quantum dot laser
has almost reached the stage of practical use, studies should
be made regarding its application to nanoelectronic
devices, quantum information processors, spin electronic
devices, and bio-molecular recognition devices. Since further development of semiconductor devices is limited,
much emphasis should be placed on the development of
novel nanoelectronic devices including single-electron
devices and atomic and molecular devices. Researchers
have already been studying the practical application of a
certain atomic device using nanoionic processes. Such
devices will realize high-performance mobile terminals that
are indispensable to the ubiquitous information-oriented
society in the future. These devices may also enable novel
neural networks to be built.
3.2 Superconducting materials
Superconducting materials can be classified into the
oxide type and the metallic type. Compared with metallic
superconducting materials, oxide superconducting materials feature high critical temperature Tc and high upper critical magnetic field Bc 2. Unlike oxide superconducting
materials, however, metallic ones offer excellent resistance
to stress and strain as well as ease of handling. As practical
oxide superconducting materials, bismuth oxides and yttrium oxides are now being studied. Although the bismuthtype Bi2Sr2CaCu2Ox (Bi-2212) and Bi2Sr2Ca2Cu3Oy (Bi2223) wires do not provide adequate characteristics for
practical use yet, they are thought to have good potential
and so ways of improving the characteristics are now being
studied. Meanwhile, for the practical use of yttrium-oxide
superconducting materials, it is necessary to develop a long
wire production technology and to reduce manufacturing
costs.
5
For metallic superconducting materials, the characteristics of Nb3Sn and Nb3Al wires in a high magnetic field
must be improved. R&D is expected to lead to long and
stable wires with low AC losses. MgB2 requires technical
development for improved characteristics, long wires, multifilamentary wires, and stable composite wires. For both
metallic and oxide superconducting materials, wires having
low stimulated radioactivity must also be developed when
considering application to a fusion reactor.
For the development of high-performance superconducting wires, the structure needs to be controlled at the nanolevel. The important research themes for oxide superconducting materials will be the preparation of nano-level
starting materials and the modification of lamellar crystal
and grain structures. Both for oxide and metallic superconducting materials, the introduction of a nano-size artificial
pinning centers dramatically increases the critical current
density Jc, so this should be further studied in future. Also,
in the search for new superconducting materials, syntheses
under ultrahigh pressure, ultrahigh gas pressure and under
other special environments, and application of soft chemistry are interesting fields where progress is expected.
3.3 Magnetic materials
Magnetic materials are key industrial materials that are
widely used in the electric communication, electric power
and automobile industries. Since one automobile uses about
25 to 30 motors, improvement of the performance of the
permanent magnets would lead to a substantial weight
reduction. Hybrid cars or electric vehicles require permanent magnets that can be used at around 200˚C for their
motors. To maintain coercivity at this temperature, current
magnets use dysprosium; however, the natural resources of
dysprosium are limited and the stable supply of dysprosium
may face difficulty in the future. Therefore, a technological
breakthrough to achieve high coercivity without using dysprosium is needed. In addition, the development of thinfilm high-performance permanent magnets is required for
future applications in MEMS and other small portable components.
Although no breakthrough has been made since the
invention of the nanocrystalline soft magnetic materials in
1988, continuous efforts to optimize soft magnetic properties for various specific applications are being made. Due
to the rapid increase of the size of data communication, the
frequency used in portable electro-communication devices
is reaching the GHz range. To solve the electromagnetic
interference (EMI), soft magnetic materials that can be
used for GHz-band communications will be particularly
important. Write heads for high-density magnetic recording
require materials of higher magnetic flux density than can
be achieved with Fe70Co30. To explore the superior properties that cannot be achieved with the conventional material,
searches for new intermetallic compounds with the help of
computational materials science will be necessary. In the
field of permanent magnetic materials, no compound offering better intrinsic properties than those of Nd2Fe14B has
been found in the past 20 years. It will be impossible to
find new materials without the help of computational science. Magnetic recording technology is now shifting from
6
the longitudinal recording method to the perpendicular
recording method. In principle, perpendicular magnetic
recording can attain a much higher recording density than
longitudinal recording. To increase the areal density of
magnetic recording to the range of 1 Tbit/in2, a material
with high magnetocrystalline anisotropy must be adopted
as recording media to overcome thermal instability. However, the coercivity of the media will then become too high
to write using existing write heads. Therefore, soft/hard
nanocomposite media and oblique recording media are now
being investigated as a possible alternative media for the
future high-density recording. When the areal density of
the current perpendicular magnetic recording method
reaches its highest limit, FePt and other high magnetocrystalline materials must be employed as new media. To write
to particulate media composed of high anisotropy materials
such as L10 FePt, the thermal assist recording method is
proposed. A media structure that is appropriate for this
method must be developed by that time, i.e., the twodimensional array of nanoparticles, the suppression of coalescence of the particles during thermal treatment for L10
ordering, and the c-axis orientation of particles.
As the areal density of recording media increases, the
sensitivity of the read head must be increased. Current high
density magnetic recording uses a giant magnetoresistance
(GMR) head for reading, but higher sensitivity is required
for future higher density recording. The structure of the
GMR heads such as spin-valves are becoming complicated
three-dimensional nanostructures, thus detailed structural
characterization of GMR devices is required to understand
the structure–property relationships. Since elaborate 3D
nanostructure analysis is difficult to be executed in industrial laboratories, research collaboration among industry
and academic institutions is becoming essential to obtain a
better understanding of the structure–property relationships
that is required for device designs in industry. For potential
applications to magnetic random memory (MRAM) and
tunneling magnetoresistance (TMR) heads, intensive
researches are being performed in various industrial, governmental and academic laboratories. To achieve TMR
devices, fundamental research on spintoronics devices such
as half-metals is essential.
3.4 Semiconductor materials
To date, Si-based electronic devices have been made
faster and more functional by integration using lithography.
By modifying the materials and structures, this trend will
continue until the gate node width reaches hp 22 nm node
generation (actual gate width: 10 nm). Therefore, highdielectric gate insulating films, metal gates, and low interlayer insulating films will be developed, probably around
the year 2015. In the next 10 years until then, Si devices are
sure to account for more than 90% of semiconductor
devices by using these techniques. For even faster processing, MOSFET using Ge or CNT channels, high-frequency
transistors using GaN, and Si-MOSFET may be packaged
on a single chip to deliver multiple functions. Organic
devices now employed only for some display units could
be applied to flexible and other unique devices. Meanwhile,
compound semiconductors will separate into GaAs-based
materials for quantum dot and various other quantum effect
devices and GaN and related materials for light-emitting
device, lighting apparatuses, THz high-frequency transistors, and other applications.
3.5 Biomaterials
Regarding artificial organ materials and genetic materials for treatment, research should clarify the optimum conditions of spatial nanostructures with the manifestation levels of genes and proteins as indexes, for super-biocompatible materials to avoid foreign-body and immune reactions,
materials to create an environment similar to the extracellular matrix, and materials to induce cell differentiation and
proliferation. To maximize cell functions, cell population
control techniques are needed. Basic material design guidelines and so forth to ensure safe and reliable nanobiotic
materials will also need to be created.
In the field of bioelectronics for diagnosis, high-sensitivity biomolecular measurement using nanofabrication techniques and devices is attracting attention as a future trend.
To meet the growing medical needs of the aging society,
remote medical treatment will become increasingly important. Furthermore, to provide large amounts of useful information quickly, technical development is necessary for a
micro chemical analysis system (µTAS) by semiconductor
nanofabrication, for a lab-on-a-chip, and for a remote medical examination system combined with IT.
3.6 Ecomaterials
The history of ecomaterials started in 1991 when the
term “environmentally conscious materials” was coined,
meaning that the environment and resources should be considered when developing every material. This has now
become a global issue. Ecomaterials are classified into
functional ecomaterials that offer a purification function
and the chemical function of a catalyst or other substance;
system-element ecomaterials necessary for creating an efficient clean energy system; and life-cycle ecomaterials
which are friendly to the environment and can be recycled.
Regarding functional ecomaterials, the applications of
photocatalysts are developing widely. It requires basic
researches indispensable to clarify the photocatalyst reaction mechanism and to improve activity, visibility, and stability. The current task is to develop and implement a new
visible-light responsive photocatalyst. For the selective and
efficient separation, decomposition, and elimination of hazardous chemicals, environmental purification materials
with sophisticated sensing functions need to be developed
by using nanotechnology, self-organization, and template
reaction. However, various issues for these nanomaterials
remain, such as chemical stability in water, soil, and other
terrestrial environments and the desorption of adsorbed
harmful chemical substances. Once these issues have been
solved, the benefits of environmental purification will help
create a safe and comfortable environment.
System-element ecomaterials are indispensable for a
new energy system that adapts to the environment. To
enable the much-vaunted solid polymer fuel cells and to
bring the hydrogen energy system into practical use at an
early stage, and for systematizing the uses of low-tempera-
ture heat sources, we must return to the basics of materials
and proceed with research on enhancing characteristics by
precise analysis and micro-structure control.
Life-cycle ecomaterials reduce environmental loads
throughout the life cycle from mining of resources to disposal and recycling. One good example is lead-free solder,
which is now becoming popular. To make an electronic
package totally free of lead, solder alloys for any adequate
temperatures and their soldering techniques are needed.
Bonding without using a solder alloy, such as conductive
bonding, will become more widespread. In the near future,
industry, government, and academia will need to standardize lead-free related techniques as a national strategy. For
recycling, we should not only proceed with research for
enhancing separation and refinement techniques but also
develop processing techniques that permit the existence of
artificial impurities or that utilize such impurities. To facilitate recycling after use, a recyclable material design may
need to be incorporated in advance.
3.7 High-temperature materials for jet engines and gas turbines
To solve global warming and other such problems by
conserving fossil fuels and reducing CO 2 emissions,
higher-performance jet engines, natural gas combinedcycle gas turbines, and other advanced power systems are
required and so high temperature materials will need to be
improved.
Among Ni-base superalloys which are typical high temperature materials, single-crystal alloys can withstand the
highest temperatures up to 1100˚C. Modern single-crystal
alloys have evolved from the first generation to the second
generation containing about 3 wt% of rhenium (Re), and to
the third generation containing about 5 to 6 wt% of Re.
Fourth-generation alloys with platinum-group metals added
and even fifth-generation Ni-base single-crystal superalloys
are approaching reality for jet engines. Further work will be
carried out to develop next generation single-crystal superalloys.
Much work has been done on alloys based on Nb, Mo,
W, and Ta as potential successors to Ni-base superalloys.
However, they still do not have sufficient oxidation resistance, toughness, and high-temperature strength. Therefore,
these alloys are now used only in vacuum, inert gas, or
other protective atmosphere. Meanwhile, there are growing
expectations for superalloys that have high melting points
and strong oxidation resistance, use high-melting point
platinum-group metals for their bases, and have the same
γ/γ’ structure as Ni-base superalloys. In terms of price, specific weight, and ductility, many issues remain to be
solved. Base metals of γ solid solution mixed from Ni, Co,
Ir, Rh, Pt, and other FCC metals will produce a series of
superalloys having a wide range of characteristics from Ni
base to platinum group, and also offering high cost performance.
3.8 Metals
Since metal research is such a broad area, it is classified
into the fields of steel, nonferrous alloys, and thermal
shield coating and thermal spraying.
7
In the field of iron and steel, techniques for actual use
need to be developed. In East Asia, where temperature and
humidity are high and where earthquakes occur frequently,
for example, steel materials must be resistant to corrosion
and earthquakes. To ensure long-term safety, heat-resistant
steel requires research on the transition of nano-precipitate
during high-temperature use; on the high-temperature,
long-term generation of nano-thick surface protection scale
and its peeling resistance, and also on the brittle fracture
behavior of a welded joint based on fracture mechanics.
Regarding the development of hydrogen fuel cell vehicles,
ways of increasing the storage pressure are now being studied to achieve cruising distances equivalent to those of
gasoline-powered vehicles. Research on materials that are
reliable in hydrogen environments will continue. To ensure
the reliability of materials, it is important to examine the
reliability of structural materials by creating data sheets for
materials development.
In the field of nonferrous alloys, aluminum alloys
require not only technical innovation of material properties
and manufacturing processes but also technical development to maximize the performance of recycled aluminum
alloys. Magnesium alloys will be widely applied to largescale components of automobiles and other parts to reduce
weight. R&D on nanostructural analysis and control for the
optimum dispersion of precipitates will also be sought to
develop new alloys that enable wrought products, like
twin-roll casting, to be produced at low cost. Titanium
alloys will be in high demand for engines of next-generation aircraft and hard bio-tissue substitutes and other biotic
applications, and new alloys will need to be developed.
Regarding porous alloys, we should study high-strength
lightweight materials having excellent shock absorbance
and damping capacity to enhance the collision safety of
vehicles, materials with new functions from in-cell substances different from cell walls, and also hybrid materials
by making good use of cell structures. To extend uses and
to increase the types of useful intermetallic compounds, we
need manufacturing techniques that reduce the cost yet can
improve ductility and toughness and can reduce manufacturing cost. Meanwhile, there are estimated to be thousands
of types of intermetallic compounds whose properties and
functions remain unknown or unused. Extensive fundamental research based on new ideas is needed to use these compounds. For high melting point alloys, the advanced material developments are required to make clear the strengthening mechanism, oxidation resistance, corrosion resistance,
manufacturability, and other conditions at low cost. Extensive researches are under way on shape memory alloys for
growing applications, and a demand for such alloys is
expected to grow for sensors and actuators as multifunctional intelligent materials having high damping capacity
and super-elasticity.
For thermal barrier coating, high heat resistance and
long service life are important. To withstand high heat flux,
researchers have conventionally focused on designing top
coating materials and developing coating processes. For
long service life, however, the first priority is on developing a bond coating material where the under-coating oxide
layer (TGO) grows slowly, is stable, and suppresses struc8
tural changes of the base metal. Thermal spraying is a coating process that can deposit a wide range of materials from
metals to plastics to large areas at high speed. Regarding
this process, the trend for coating by high-velocity and
colder particles will continue in order to refine the sprayed
coating. From materials having nanostructures, films featuring high abrasion resistance and adhesion could be
obtained, and thermal spraying offers tremendous potential
in this field. This is an important technique with many
ways of giving environmental resistance to material surfaces. However, some basic phenomena behind coating formation still remain unclear and await further study.
3.9 Ceramic materials
As a non-oxide ceramic material, carbon is widely used
for structural and electronic applications, and recently its
usage in bio- and environmental fields is also under study.
Superconductivity in diamond and ferromagnetism in
pyrolytic graphite and fullerene have been reported recently as new phenomena. Thus, carbon is still attracting great
attention in many fields. Other representative non-oxide
materials in carbide, nitride, and boride are silicon carbide,
silicon nitride, Sialon, boron nitride, boron carbide, and
metallic boride. These are widely used as engineering
ceramics. Caused by recent discoveries of a new Sialon
phosphor, MgB2 superconductor and boron nitride having
an electron emission characteristic, their optical and electronic functions are also getting researchers’ attention.
Typical examples of oxide fine ceramics are alumina,
zirconia, magnesia, and their composite oxides. These
materials have long been known but the main focus now is
to design and control shapes and arrays or compositions of
intergranular and intragranular structures, grains, pores,
etc., at sizes of 100 nm or smaller. This approach is becoming the mainstream of research. To optimize the combinations of functions, it is becoming crucial to research nanostructure-controlling techniques, experimental and theoretical analyses of nanostructures, and the relationship between
structures and properties.
3d-transition-metal compounds show a great variety of
physical and chemical properties, such as catalytic property, photocatalytic property, ferroelectricity, magnetism, and
superconductivity, etc., and thus they are being widely
studied for applications in environmental, energy-related,
information and communication, and electronic and optical
fields. These compounds will continue to be important and
to be studied intensively. 4d and 5d compounds of niobium
and tantalum oxides are also being studied intensively due
to their ferroelectric functions. In particular, lithium niobate and lithium tantalate single crystals with stoichiometric compositions are attracting great attention for their useful characteristics. Rare earth compounds are used as light
emitting materials for solid-state laser. In this field, translucent ceramics are being studied for application to laser host
systems.
Glass materials are used for various purposes and
recently, higher performances are demanded to meet with
usage in environmental, energy-related, and information
technology fields. One area where research is particularly
intensive is functional glasses called nanoglasses with
highly controlled structures and with new functions. By
using various manufacturing processes, researchers are
seeking highly sophisticated and functionalized glasses.
3.10 Composite materials
In the field of composite materials, we may need techniques for controlling overall performance, ranging from
the conventional handling of materials by parameters such
as reinforcement, matrix, and interface, to the structural
design and control of each material itself and their interfaces. For polymer and ceramic based composite materials
in particular, therefore, we need to study composite materials that offer much greater performance than the conventional characteristics by controlling the matrix and interface
nanostructures and using nano-order differences in the
modulus of elasticity and the coefficient of thermal expansion. In future, new composite effects will be sought by
using nanomaterial techniques, and testing and measuring
techniques will be developed on the basis of recent
progress in general technologies. Meanwhile, the conventional techniques can no longer cope with the expansion
and sophistication of applications of fiber reinforced polymers. In these fields, intensive research is expected to solve
old and new issues such as processing, evaluation of characteristics, and reliability assurance. It is also necessary to
develop not only stand-alone applications of composite
materials but also hybrid applications in conjunction with
other existing materials in order to maximize the characteristics and compensate for the disadvantages of composite
materials.
3.11 Polymer materials
Polymers are basic materials in industry, being widely
used for plastics, rubbers, adhesives, photoresists, separation membranes, gels, and biomaterials. If fibers, styrofoam, and paper are included, polymers can be likened to
the varied complexity of industrial structures found today.
Like metals and ceramics, polymers are produced on
large scales and have a major impact on oil and environmental problems. To reduce environmental loads, halogenfree fire retardants and water-soluble polymer coating compounds containing no volatile organic compounds (VOC)
are being developed. Various research is now in progress
on water treatment using polymer membranes, energy conservation using lightweight polymer composite materials,
fuel cell and other energy-related polymer films, and recyclable carpets. The research has yielded noteworthy new
techniques, such as a non-phosgene polycarbonate process
by using CO2, an auto-extinction epoxy resin, and a recyclable coating system.
Polymers, which are also recognized as important elements of nanotechnology, are indispensable materials in
medicine and biotechnology. Polymers are also important
for solving environmental, safety, energy, and other related
problems in Japan today, and for supporting sustainable
growth.
3.12 Analysis and evaluation techniques
Much of the nano-scale-measurement techniques have
been developed as the target-oriented evaluation methods.
Therefore, they lack generality and cannot be applied to the
measurement of a wide variety of the materials. It is therefore necessary to develop general and universal nano-scalemeasurement instruments and techniques, particularly a
nano-measurement technique that can evaluate large-scale
integrated circuits assembled with atomic-level precision.
A super-parallel large-scale method for the multi-probe
measurement technique can go beyond the framework of
nano-scale-measurement, and provide a nanostructure fabrication and measurement technique of large area with
higher accuracy and spatial resolution. In frontier field
STM measurement, new properties and functions are more
likely to appear at stronger magnetic field, so the competition to develop strong magnetic fields may continue. For
the development of sophisticated measurement techniques,
methods for precision measurement and the creation of
frontier field environments are essential. Since these frontier environments will be powerful tools to know the mechanisms of functions and properties of nanostructures, these
techniques may lead to the discovery of completely new
phenomena of nanofunctions and quantum effects. In surface analysis, it will be important to develop two- and
three-dimensional analysis techniques with short measurement and calculation times to know the precise elemental
distributions and chemical state from the analysis of measured spectra with metrological uncertainty and high spatial
resolution. This analysis requires an accurate physical
quantity database describing interactions between electrons
and materials in solids and also their modeling based on a
precise understanding of electron transportation phenomena in solids. For transmission electron microscopes,
research will be continued to improve the performance of
the stability of the microscope, the coherent electron beams
and correction lens aberration. In-situ property measurement within the transmission electron microscope, including electric and magnetic characteristics as well as morphological, structural, and compositions changes will assist the
research for nanoproperties that depend on the structures
and compositions in nano-scale. For the standardization of
evaluation methods of nanomaterials, guidelines for accurate analysis should be developed, and the purpose of the
measurement should be clarified to ensure the reproducibility and traceability of the analysis results. Standardization
of nano-scale measurements and their publication will
become increasingly important.
3.13 High magnetic fields and their applications
High-field magnets being developed for high-field NMR
include a driven-mode superconducting magnet (1.2 GHz
class) and hybrid magnet (1.5 GHz class). Although compared with a persistent-mode superconducting magnet, the
fields of these magnets are much higher, the field stability
is one order of magnitude lower. Therefore, equipment and
techniques should be developed to enable high-resolution
NMR even under these circumstances.
Another measurement technique using NMR is magnetic
resonance imaging (MRI). The technique has been used for
medical purposes, such as detecting abnormal regions in
organs, but in future it is expected to be used for functional
measurement. Theoretically, the sensitivity of NMR
9
increases in proportion to the 3/2 power of the magnetic
field. For functional measurement, therefore, high-field
MRI is expected to be developed. Compared with the NMR
spectrometer, whole-body MRI requires a space of about
10 times larger in diameter. Research and development is
necessary to use not only NbTi wires but also brittle Nb3Sn
and Nb3Al wires which have higher critical fields under
high electromagnetic force conditions.
Mass analysis has rapidly become important in biological science and nanotechnology. In mass analysis, the performance of the FT-ICR method will be improved remarkably by using a high field of over 10 Tesla. Since the highfield TOF-MS method allows mass analysis and spectroscopy simultaneously, the effects of a high field on
structures and reactivity of mass-selected protein molecules
and nanoclusters can be observed by spectroscopy. This
method will surely advance in the future.
3.14 Nano-simulation science
A number of computational techniques have been developed depending on the size of the target material or the
time scale of phenomena, including first-principles calculations at the electron level, the molecular mechanics method
which handles the collective motions of atoms and molecules, the finite element method and the statistical thermodynamics method for bulk materials, and the phase-field
method for mezzo-scales. In particular, computational science is expected to play essential roles in the research of
nanobiomaterials, in which their innovative functions are
intensively explored by atomic-scale design and control.
This is because computational science will be able to predict a function in a completely controlled environment by
high-accuracy, high-resolution numerical analysis that is
difficult to achieve in experiments, so that the results can
be fed back to experiments. An advanced quantum simulation technique is required to clarify the correlations
between electron states, properties, and functions of
nanobiomaterials. There is an urgent need to develop and
enhance super-large-scale calculations, multifunctional
analysis (multiphysics), strong-correlation modeling, and
multiscale techniques.
3.15 Technologies for creating new materials
Particle beams and the vacuum process offer techniques
for creating new materials. In the particle beam technology,
the fabrication of nanoparticles and nanostructures using
non-equilibrium- and spatially controllable characteristics
of ion implantation will continue, to produce nanoparticles
and nanorods of metals, metal-oxides and other types. To
improve the functionality of these nanomaterials, one- or
two dimensional array structures of nanoparticles, instead
of randomly distributed ones, need to be developed.
Hybridization of beam technology with micro-scale processing or laser irradiation will become more important.
For nanostructure fabrication using electron beam-induced
deposition, it is necessary not only to develop technology
to precisely identify nanostructures created but also to
improve crystallinity and other characteristics of the nanostructures. In the vacuum-process technology, materials for
next-generation devices will expand from semiconductors
10
into nano-sized metals, which are difficult to handle
because of gas adsorption, etc. Ultra-high vacuum processes, which enable us to manipulate nanomaterials at atomic
or molecular levels in an ultra-clean environment, will continue to improve in performance.
3.16 Acquisition and transmission of materials data and
information
To construct a structural materials database on creep, it
is neccessary to acquire the long-term creep properties of
advanced heat-resistant steels and alloys and also to study
the acquisition of creep data for Al alloys, Mg alloys, and
other lightweight nonferrous materials which are in great
demand for reducing automobile weight and therefore
power consumed. Fatigue studies are shifting toward the
clarification of fractures in the ultrahigh-cycle fatigue
regime of 107 cycles or more, especially internal fractures.
In future, giga-cycle fatigue properties under average stress
and the effects of plate thickness and notches on welded
joints will be studied systematically. Future studies will target the high-temperature fatigue properties of Ni-based
superalloys and other test conditions. Regarding corrosion
data, the corrosion properties of various materials including
practical ones will be evaluated in an atmospheric corrosion environment to compile basic data on the phenomena
of atmospheric corrosion. Space use materials strength data
sheets will provide a collection of data on fatigue crack
growth and fractured surfaces, as well as fatigue strength,
for which there is strong demand. Such data sheets will
also consider the acquisition of fatigue data for other
engine materials such as copper alloys and for important
structural materials. To provide universal and high-quality
basic data about materials, data will be gathered under
international cooperation and our knowledge of materials
will be extended through research on data mining.
3.17 International standards
For the nano-area analysis of standard materials, secondary standards featuring field materials metrology and
other practical standards will be established quickly.
According to the Versailles Project on Advanced Materials
and Standards (VAMAS), many countries have incorporated nanomaterials as national measures and have begun to
compete in international standardization. The VAMAS
international standardization activities will surely be of
great importance for countries and industries. The standardization of nanotechnology will progress dramatically in the
next few years. Japan should lead ISO and other international standardization activities to take the initiative in standardizing nanotechnology.
References
1) S. M. Allen and E. L. Thomas, The Structure of Materials, John
Wiley & Sons Inc., (1999).
2) M. F. Ashby, Materials Selection in Mechanical Design, Pergamon
Press Ltd., (1992).
3) White Paper on Science and Technology 2002, Ministry of
Education, Culture, Sports, Science and Technology, Japan [in
Japanese].
PART2
Policies of Materials Research
in
Japan, USA and EU
• Materials Research Policies of Japan, USA and EU
• Nanotechnology Research Policies of Japan, USA and
EU
Chapter 1.
Materials Research Policies of Japan,
USA and EU
Tomoaki Hyodo, Takahiro Fujita, Yoshio Abe
International Affairs Office, NIMS
1. Materials research policies of Japan
Based on the comprehensive strategies planned by the
Council for Science and Technology, the Second Science
and Technology Basic Plan for five years from FY2001
was agreed by the Cabinet in March 2001.1) To resolve the
issues now confronting Japan and to develop good
prospects for the future, this Basic Plan defined Japan to be
“a nation contributing to the world by creation and utilization of scientific knowledge” (creation of wisdom), “a
nation with international competitiveness and ability of
sustainable development” (vitality from wisdom), and “a
nation securing safety and quality of life” (sophisticated
society by wisdom).
The Science and Technology Basic Plan adopted the following as important policies: Strategic Priority Setting in
science and technology (S&T), S&T System Reforms to
Create and Utilize Excellent Results, and Internationalization of S&T Activities.
The policies of Strategic Priority Setting in S&T were to
evaluate S&T fields that contribute most to increasing
intellectual assets, economic effects, and social effects
through creating knowledge; to put priority on the fields of
life sciences, information and telecommunications, envi-
ronmental sciences, and nanotechnology and materials; and
to allocate research and development (R&D) resources
effectively. In addition to the four fields, R&D is being
promoted in the fields of energy, manufacturing technology, infrastructure, and frontier because the four fields are
fundamentals for a nation and Japan should put priority on
them.
The policies of S&T System Reform to Create Excellent
Achievements were to innovate the R&D system first; to
maximize the capabilities of researchers by introducing the
principle of competition widely, by doubling the funds for
competition, by introducing indirect expenses, and by promoting the mobility of human resources; and to innovate
the evaluation system to ensure transparency, fairness, and
appropriate sharing of resources.
The policies of Internationalization of S&T Activities
were to expand voluntary international cooperation activities; to strengthen the ability to distribute information
internationally; and to internationalize the research environment in Japan.
Figure 1 shows the transition of Japan’s S&T budget (8
fields) and Figure 2 shows the percentages by field.2) The
budget in the field of nanotechnology and materials
accounts for about 5% of the total S&T budget.
(100 million
yen)
188
451
242
18
FY2005
1,983 billion yen
(18,031 million
dollars)
206
149
633
97
FY2001
FY2002
Frontier
Naonotechnologies and nanomaterials
FY2003
Social infrastructure
Environment
FY2004
Manufacturing technology
Information and communications
FY2005
Energy
Life science
Fig. 1 Transition of apportioned S&T budgets of 8 fields (except for university budgets).
(billion yen)
Fig. 2 Percentages of FY2005 R&D budgets of 8
fields in 2005 (except for university budgets).
13
Regarding materials R&D, Japan decided to promote: 1)
materials techniques to clarify and control material structures and the shapes of atomic and molecular sizes as the
basis for information & communications and medicine and
to control surfaces and interfaces, 2) energy/environmentrelated materials techniques with high added value to meet
the requirements for energy conservation, recycling, and
resources saving, and 3) materials techniques for creating
safe spaces to live securely.
In June 2002, the Ministry of Education, Culture, Sports,
Science and Technology drew up policies to promote R&D
on nanotechnology and materials. Concerning materials
S&T, the Ministry put priority on the exploitation of environmental conservation materials, energy-efficient materials, safe-space materials, and materials to produce evaluation, processing, and other basic functions, new functions,
and high-level functions.
The Ministry of Agriculture, Forestry and Fisheries is
performing R&D to extend the uses of bio materials by
developing antithrombogenic materials from fibroin (a kind
of silk protein) and materials for artificial bones and ligaments by using bony ingredients from silk.
In order to innovate materials processes, the Ministry of
Economy, Trade and Industry is promoting a project for the
high-level evaluation of next-generation semiconductor
nanomaterials and R&D on synergetic ceramics and metallic glasses.
2. Materials research policies of the USA
Figure 3 shows the percentages of the FY2004 total
research expenses by U.S. department and Figure 4 shows
those of basic research expenses.3) The Department of
Defense (DOD) accounts for over 50% of the total expenses, followed in order by the National Institute of Health
(NIH), National Aeronautics and Space Administration
(NASA), Department of Energy (DOE), and National Science Foundation (NSF). Regarding the basic research
expenses, NSF, DOE, and NASA account for about 10%
each if the 57% of NIH is excluded.
The DOE and NSF are mainly in charge of basic
research related to materials. The R&D expenses of DOE
for science were about 3,200 million dollars in FY2004
(Table 1) of which 559 million dollars was spent on materials research (Table 2 “Basic Energy Sciences: Materials
Sciences). Meanwhile, the NSF spent 251 million dollars of
the basic research expenses on mathematical science (Table
2 “Mathematical and Physical Sciences: Materials
Research”).
In the USA, the DOE and NSF wield great influence
over basic R&D related to materials. The DOE is a main
organ of the Federal Government conducting basic research
in the field of physical science. 4) On September 30, the
DOE announced its strategic plan, which is revised every
three years. The DOE, which is in charge of domestic energy supply and national safety, announced policies for the
next 20 to 25 years in the four fields of national defense,
energy, science, and environment.
The overriding mission of the DOE is to assure the
14
DOD: Department of Defense
NIH: National Institute of Health
NASA: National Aeronautics and Space Administration
DOE: Department of Energy
NSF: National Science Foundation
USDA: United States Department of Agriculture,
Commerce:Department of Commerce
EPA: Environmental Protection Agency
DOT: Department of Transportation
DHS: Department of Homeland Security
Total R&D
expenses
$126.3 billion
(FY2004)
Basic R&D
expenses
$26.5 billion
(FY2004)
Fig. 3 Percentages of total R&D
expenses by department.
Fig. 4 Percentages of basic R&D
expenses by department.
Table 1 R&D expenses of DOE in FY2004.
Field
Energy supply
Science
Fossil energy
Energy consevation
Atomic energy defense
Clean coal technology
Radioactive waste management
Total
Expenses
($ million)
382
3,229
547
379
4,198
– 98
75
8,712
Table 2 FY2004 R&D expenses of DOE in science.
Field of Science
High energy physics
Nuclear physics
Fusion energy sciences
Basic energy sciences
materials sciences
chemical sciences, geo sciences, energy
construction
Advanced scientific computing res.
Biological and environmental res.
Small business, innovative res.
Expenses
($ million)
Inc.
Inc.
Inc.
Total
national, economic, and energy safety for the United States.
To achieve this mission, it promotes science and engineering and ensures a clean environment for the nation’s
nuclear weapon facilities.
To achieve the mission, the DOE adopted a total of
seven long-term general goals in the four fields of national
defense, energy, science, and environment. The general
goal in the field of science corresponds to the fifth goal of
the entire project. The objectives are to supply a world-
class scientific research capacity to enable the DOE to
achieve its mission; to enhance knowledge in leading fields
of physics, biology, medicine, environment, and computational science; and provide global-class research facilities
for science projects by the nation.
To achieve these objectives, the DOE operates huge
national experimental facilities in order to make remarkable progress in the field of energy science, including high
energy physics, atomic physics, plasma science, materials
and chemical science, and biological and environmental
science. In addition, the DOE gathers scientists, engineers,
and technologists having unparalleled biological development skills to support the application of various energyrelated sciences to medicine. The Department invests in
large facilities necessary for basic research and the science
community itself for public benefit.
More specifically, the DOE has eight goals: 1) Advancing high energy physics and nuclear physics, 2) Advancing
the theoretical and experimental understanding of plasma
and fusion science, 3) Advancing energy-related biological
and environmental research, 4) Developing new diagnostic
and therapeutic tools and technology for disease diagnosis
and treatment, 5) Advancing nanoscale sciences built
around foundations in materials, chemistry, engineering,
geo science, and energy biosciences, 6) Significantly
advancing scientific simulation and computation, 7) Providing the Nation’s science community access to worldclass research facilities that advance the physical sciences
and enable the study of complex, interdisciplinary science
questions, and 8) Providing or supporting the Nation’s science community access to world-class, scientific computation and networking facilities.
The DOE strategic plan interim goals with specific limits of execution. Table 3 gives key intermediate objectives
in science. The key intermediate objectives related to the
materials research field are to complete the construction of
a spallation neutron source by the end of 2006, to put five
nanoscience research centers into operation by the end of
2008, and to develop materials having a predictable characteristic for each atom by 2015.
As an independent agency of the U.S. Government, the
NSF was established in 1950.5) The mission of the NSF is
to promote basic research, education, and infrastructure at
universities and research institutions. NSF has few research
organs but mainly grants subsidies for research in all fields
of science and engineering. NSF receives more than 35,000
applications for grants every year and funds about 10,000
of them.
The NSF’s vision is to strengthen the nation’s future
through discovery, learning, and innovation. By investing
in People, Ideas, and Tools (PIT), the NSF strongly promotes science and engineering necessary for securing the
safety, property, and welfare of the nation.
The National Science Foundation Act established in
1950 states in its preamble that the NSF’s missions are to
promote the progress of science, to advance the health,
prosperity, and welfare of the nation, and to secure the
national defense. The NSF Act states the following as its
duties:
• Basic research for fundamental research and engineering
processes
• Programs to strengthen the scientific and engineering
potential of research
• Science and engineering education for all classes in all
fields of science and engineering
• Basic information in science and engineering suitable
for developing national and international policies
The NSF strategic plan (2003 to 2008) announced in
September 2003 defines the long-term strategic goals in
science and engineering by people, ideas, tools, and organizational excellence as follows:6)
• People Goal:
A diverse, competitive, and globally-engaged U.S.
workforce of scientists, engineers, technologists and
well-prepared citizens
• Ideas Goal:
Discovery across the frontier of science and engineering, connected to learning, innovation and service to
society
• Tools Goal:
Table 3 Key intermediate objectives in the science division of DOE.
Timing
End of 2006
Key Interim Goal
Developing a suite of specialized software tools for scientific simulations to utilize terascale computers,
while handling trillions of bytes of data or terabytes (trillion-byte) and high-speed networks
End of 2006
By 2007
End of 2008
End of 2008
Completing the construction of a spallation neutron source
Commencing operation of a large hadron accelerator (LHC), ATLAS, and CMS detector
Commencing operation of five nanoscience research centers
Establishing new basic characteristics for nuclear matter of extremely high temperature and density by using
the Relativistic Heavy Ion Collider (RHIC) at Brookhaven National Laboratory
Completing studies on several next-generation computer architecture to enable the development of a high-end
supercomputer (1,000 times the performance available in 2003)
Starting experiments to determine which of the many unified theories of the fundamental forces could
actually describe nature at the smallest scale
End of 2009
By 2010
By 2013
By 2015
Utilizing research into viewing the makeup of genes in living cells, tissues, and organisms by clinicians
Understanding nanoscale assemblies of materials results in the capability to create materials, atom by atom,
having predictable properties
By 2020
Advancing plasma science and computer modeling to obtain a comprehensive and fully validated plasma
configuration simulation capability
15
MISSION
VISION
To promote the progress of science ; to advance the national
health. prosperity & welfare ; to secure the national defense ; and
for other purposes
STRATEGIC
GOALS
PEOPLE
($1,153M)
IDEAS
($2,696M)
TOOLS
($1,341M)
INVESTMENT
CATEGORIES
Enabling the Nation's future through discovery. learning and innovation
• individuals
• institutions
• Collaborations
• Fundamental S&E
• Centers Programs
• Capability
Enhancement
• Large Facilities
• Infrastructure and
Instrumentation
• Polar Tools & Logistics
• FFRDCs
ORGANIZATIONAL
EXCELLENCE
($291M)
• Human Capital
• Business
Processes
• Technologies and
Tools
Fig. 5 FY2004 requested budgets by strategic goals.
Table 4 Ratios of FY 2004 budgets by accounts and strategic goals.
($ million)
S T R AT E G I C G O A L S
ORGAN.
Account
PEOPLE
IDEAS
TOOLS
EXCELL.
388
765
2,557
139
1,120
19
42
15
0
0
202
0
0
0
1,153
0
0
2,696
0
0
1,341
226
9
291
Research and Related Activities
Education and Human Resources
Major Research Equipment
and Facilities Construction
Salaries & Expenses
Office of the Inspector General
a
Total
a
Numbers may not add to rounding.
Broadly accessible, state-of-the-art S&E facilities,
tools and other infrastructure that enable discovery,
learning and innovation
• Organizational Excellence Goal:
An agile, innovative organization that fulfills its mission through leadership in state-of-the-art business
practices
Figure 5 shows the budget requested by the NSF for
FY2004 by strategic goal.6) The NSF classifies all research
projects into four categories and invests most in Ideas, followed by Tools, People, and Organizational Excellence.
Table 4 classifies the budget requested by the NSF for
FY2004 by accounts and strategic goals. Most of the budget is apportioned to research projects.
In the NSF strategic plan, the NSF selected the following research fields for priority investment:
• Biocomplexity in the Environment (BE)
• Human and Social Dynamics (HSD)
• Information Technology Research (ITR)
• Mathematical Sciences
• Nanoscale Science and Engineering
• Workforce for the 21st Century
To the above priority research fields, the following six
research fields were added for research activities across
fields by the Federal Government:
• Networking and Information Technology
Research & Development (NITRD)
16
•
•
•
•
•
National Nanotechnology Initiative (NNI)
Climate Change Science
Homeland Security and Antiterrorism R&D
Molecular-level Understanding of Life Processes
Education Research
3. Materials research policies of the EU
In 1984, the European Union inaugurated the Framework Programme (FP) to integrate and strengthen individual R&D activities by European countries. The current
Sixth Framework Programme (FP6) will continue until
2006, starting from the preparatory period of 2002.7) The
total budget of FP6 for the four years from 2003 to 2006 is
17.5 billion euros, much greater than the 13.2 billion euros
of FP4 (1994 to 1998) and 15 billion euros of FP5 (1998 to
2002). The research budgets of FP6 are separate from the
government-level ones of each nation.
The overriding aim of FP6 is to create a European
Research Area (ERA) through this program. The concept
of ERA is to integrate national research programs that had
been independent up to FP5 into one EU program and to
create a joint market for research and technological innovation. As the economic unification of European countries
progresses, the EU aims to build a foundation for R&D
through ERA. The construction of ERA is the central sub-
ject of the Lisbon Strategy (March 2000) to make the EU
“the most competitive and dynamic knowledge-driven
economy within 10 years.”
FP6 focuses on the fields of information technology,
biotechnology, nanotechnology, aeronautics and space,
food, energy, and ecosystems. Table 5 lists the research
fields of FP6.
FP6 specified seven fields as priority research fields and
introduced Integrated Projects (IP) and Networks of Excellence (NE) to promote research in those fields.
By mobilizing and integrating research resources scatTable 5 Organization of FP6. 7)
Thematic priorities
• Life sciences, genomics and biotechnology for health
• Information society technologies (IT)
• Nanotechnologies and nanosciences, knowledge-based
multifunctional materials and new production processes
and devices
• Aeronautics and space
• Food quality and safety
• Sustainable development, global change and ecosystems
• Citizens and governance in a knowledge-based society
Specific activities covering a wider field of research
• Supporting policies and anticipating scientific and
technological needs
• Horizontal research activities involving SMEs
• Specific measures in support of international co-operation
Structuring the European Research Area
• Research and innovation
• Human resources and mobility
• Research infrastructures
• Science and society
Strengthening the foundation of the European Research Area
• Support for the coordination of activities
• Support for the coherent development of research and
innovation policies in Europe
Specific program nuclear energy
• Priority thematic areas of research
• Controlled thermonuclear fusion
• Radiation protection
• Other activities in the field of nuclear technologies and
safety
Nuclear Activities of the Joint Research Center
tered across the EU, IP supports purpose-oriented research
to produce new knowledge. Under several basic and
applied themes, three or more countries from the EU and
related countries (Norway, Switzerland, Liechtenstein, and
Israel) are conducting joint research for three to five years.
NE is a concept of networking resources and knowledge
of research across countries in order to boost achievements.
The Joint Programme of Activities (JPA) will realize NE
through information sharing, human resources exchange,
and facilities sharing. With the participation of six or more
research institutions from three or more countries, a large
network of several hundred researchers will be formed. The
research periods range from five to seven years. The standard research funds are 2 million euros/year for 100 participants, 5 million euros/year for 500 participants, and 6 million euros/year for over 1,000 participants.
In the field of materials, Nanotechnologies and
Nanosciences, Knowledge-based Multifunctional Materials, and New Production Processes and Devices were
selected as priority themes. Table 6 lists the research subjects selected for FY2003.
The priority subjects for Nanotechnologies and
Nanosciences are: 1) Long-term interdisciplinary research
into understanding phenomena, mastering processes and
developing research tools, 2) Nano-biotechnologies, 3)
Nanometer-scale engineering techniques to create materials
and components, 4) Development of handling and control
devices and instruments, and 5) Applications in areas such
as health and medical systems, chemistry, energy, optics,
food and the environment.
The priority subjects for Knowledge-based Multifunctional Materials are: 1) Development of fundamental
knowledge, 2) Technologies associated with the production, transformation and processing of knowledge-based
multifunctional materials, and biomaterials, and 3) Engineering support for materials development.
The priority subjects for New Production Processes and
Devices are: 1) Development of new processes and flexible, intelligent manufacturing systems, 2) Systems research
and hazard control, 3) Optimizing the life-cycle of industrial systems, products and services, and 4) Integration of
nanotechnologies, new materials, and new production technologies for improved security and quality of life.
In April 2005, the European Committee announced the
adoption of the Seventh Framework Programme FP7 from
2007 to 2013 (total amount of subsidies: 67 billion euros,
total amount including office and labor expenses: 72.7 billion euros).8) This proposal will be finally settled after
approval by the EU Council and the European Parliament.
FP7, subtitled “Building the Europe of Knowledge”,
consists of four programs: 1) Cooperation (subsidy: 39.3
billion euros), 2) Ideas (10.5 billion euros), People (6.3 billion euros), and 4) Capacities (6.6 billion euros) and nonnuclear actions of the Joint Research Centre (1.6 billion
euros), and European Atomic Energy Community
(EURATOM) (28 billion euros in 2007 to 2011).
Through research cooperation projects and networks for
coordinating the research programs of countries, the cooperation program supports research activities in nine fields:
1) Health, 2) Food, agriculture, and biotechnology, 3)
Information and communication technologies, 4)
Nanosciences, nanotechnologies, materials, and new production technologies, 5) Energy, 6) Environment, 7) Transport, 8) Socio-economic sciences and the humanities, and
9) Security and space.
The goals of the cooperation program for nanosciences,
nanotechnologies, materials, and new production technologies are to improve the competitiveness of European industries and to ensure its transformation from a resource-intensive to a knowledge-based industry by generating breakthrough knowledge for new applications at the crossroads
between different technologies and disciplines. In
Nanosciences and Nanotechnologies, the themes of activities are the creation of new knowledge about interfaces and
size-dependent phenomena, the nanoscale control of material properties for new applications, the integration of technologies at the nanoscale, nano-motors/nanomachines/nano-systems, impact on human safety, and
health and the environment. In Knowledge-based Multi17
Table 6 Materials-related PF6 research subjects in FY2003.7)
Nanotechnologies and nanosciences
• Long-term interdisciplinary research into understanding phenomena, mastering processes and developing research tools
- Expanding knowledge in size-dependent phenomena
- Self-organisation and self-assembling
- Molecular and bio-molecular mechanisms and engines
• Nano-biotechnologies
- Interfaces between biological and non biological systems
• Nano-metre-scale engineering techniques to create materials and components
- Engineering techniques for nanotubes and related systems
• Development of handling and control devices and instruments
- Handling and control instrumentation at the level of single atoms or molecules and/or <10 nm
• Application in areas such as health and medical systems, chemistry, energy, optics, food and the environment
- Roadmaps for nanotechnology
Knowledge-based Multifunctional Materials
• Development of fundamental knowledge
- Understanding materials phenomena
• Technologies associated with the production, transformation and processing of knowledge-based multifunctional
materials, and biomaterials
- Mastering chemistry and creating new processing pathways for multifunctional materials
- Surface and interface science and engineering
• Engineering support for materials development
- New materials by design
- New knowledge-based higher performance materials for macro-scale applications
New Production Processes and Devices
• Development of new processes and flexible, intelligent manufacturing systems
- New production technologies, based on nanotechnology and new materials
- New and user-friendly production equipment and technologies, and their incorporation into the factory of the future
- Creation of “knowledge communities” in production technologies
- Support to the development of new knowledge based added value products and services in traditional less RTD
intensive industries - IP dedicated to SMEs
• Systems research and hazard control
- Radical changes in the “basic materials” industry (excluding steel) for cleaner, safer and more eco-efficient production
- Sustainable waste management and hazard reduction in production, storage and manufacturing
• Optimising the life-cycle of industrial systems, products and services
- Optimisation of “production-use-consumption” interactions
- Increasing the “user awareness”
• Integration of nanotechnologies, new materials, and new production technologies for improved security and quality of life
- Systems, instruments and equipment for better diagnosis and/or surgery, including for remote operations
- Tissue engineering, new biomimetic and bio-hybrid systems
- New generation of sensors, actuators and systems for health, safety and security of people and environment
functional Materials, the themes of activities are the generation of new knowledge on high-performance materials for
new products and processes, knowledge-based materials
having tailored properties, more reliable design and simulation, the integration of nano-molecular-macro levels in the
chemical technology and materials processing industries;
new nano/biotic/hybrid materials, including the design and
control of their processing. In New Production Processes
and Devices, the themes of activities are the creation of
conditions and assets for knowledge-intensive production
including construction, development and validation of new
paradigms responding to emerging industrial needs and
development of generic production assets for adaptive, networked and knowledge-based production; development of
new engineering concepts exploiting the convergence of
technologies (such as nano, bio, information, and cognitive
technologies and their engineering requirements) for the
next generation of high value-added products and services
and adaptation to the changing needs. In Integration of
Technologies for Industrial Applications, the themes of
activities are the integration of new knowledge and technologies on nano, materials and production in sectoral and
cross sectoral applications such as: health, construction,
18
transport, energy, chemistry, the environment, textiles and
clothing, pulp and paper, and mechanical engineering.
The Ideas program will improve the competitive
strength in Europe and strengthen the scientific foundation
of Europe. The Human Resources program will strengthen
activities concerning career development and changes of
European researchers. The Ability program will strengthen
R&D skills to maximize the performance of the European
scientific community and to assist research and innovation
across Europe.
4. Conclusion
Research policies about materials were compared among
Japan, the USA, and the EU.
1) By the Second Science and Technology Basic Plan for
five years from FY2001, Japan is apportioning R&D
resources to put priority on the fields of life science, information and communications, and nanotechnologies and
materials, thus helping to strengthen its intellectual assets,
economic effects, and social effects.
2) In the United States, the Department of Energy (DOE)
and the National Science Foundation (NSF) are making
great contributions to basic R&D on materials. The Department of Energy defined its long-term strategic goals in the
field of science and engineering in a three-year strategic
plan revised in September 2003 and the National Science
Foundation stated its goals in a strategic plan from 2003 to
2008 announced in September 2003 to promote basic R&D
related to materials.
3) The EU is planning the Framework Programme (FP) to
integrate and strengthen R&D activities across European
countries. The priority themes of research selected for the
Sixth Framework Programme (FP6) are Nanotechnologies
and Nanosciences, Knowledge-based Multifunctional
Materials, and New Production Processes and Devices. The
Seventh Framework Programme (FP7) from 2007 to 2013,
adopted by the EU in April 2005, will be finally settled
after being discussed and approved by the EU Council and
the European Parliament.
3)
4)
5)
6)
7)
8)
(February 2005)
http://www8.cao.go.jp/cstp/siryo/haihu43/siryo2-1.pdf
Web page of AAAS:
http://www.aaas.org/spp/rd/
Web page of U.S. Department of Energy
http://www.energy.gov/engine/content.do
Web page of National Science Foundation
http://www.nsf.gov/
National Science Foundation Strategic Plan
FY2003 - 2008 (September, 2003)
http://www.cra.org/Activities/workshops/
broadening.participation/nsf/FY2003-2008plan.pdf
Web page of European Union FP6
http://fp6.cordis.lu/fp6/home.cfm
Web Page of European Union FP7
http://www.cordis.lu/fp7
http://europa.eu.int/comm/research/press/2005/
pr0704-2en.cfm
References
1) Web page of the Council for Science and Technoogy
http://www8.cao.go.jp/cstp/
2) Meeting report for the Council for Science and Technology
19
Chapter 2.
Nanotechnology Research Policies of
Japan, USA and EU
Section 1. Research Policies of Japan, USA and EU
Masahiro Takemura
Nanotechnology Researchers Network Center of Japan
In the FY2001 Budget Message dated January 21, the
then President Clinton positioned nanotechnologies as a
strategic R&D field of the nation and the U.S. National
Nanotechnology Initiative (NNI) was inaugurated. Since
then, nanotechnology R&D has been promoted under
national initiatives in Japan, the USA, Asia, and Europe.
This section outlines the national strategies, policies, and
budgets of Germany, France, and the UK where research
investment in nanotechnologies is especially large.
Table 1 Transition of national budgets for R&D in the fields of
nanotechnologies and materials (Unit: 100 million yen).
FY2001
849
FY2002
911
FY2003
946
FY2004
935
FY2005
971
1. Japan
As mentioned in the previous section, the field of nanotechnologies and nanomaterials was selected as one of the
four priority fields in the Second Science and Technology
Basic Plan.1) In addition, the Council for Science and Technology Policy created the Priority Promotion Strategies by
Fields2) and clarified the current field statuses, priority
areas, and R&D goals and promotion measures. In the field
of nanotechnologies and materials, the following five target
areas were determined and the goals and technical objectives were exemplified in each field.
• Nanodevices and nanomaterials for the next-generation
information and communications systems
• Materials for environment and energy-saving
• Nanobiology for novel medical care technology and biomaterials
• Underlying technologies such as fabrications, analyses,
simulations, etc.
• Novel materials with innovative functions
As the basis of the R&D promotion policies, the following
items were also selected:
• Stimulating competition in R&D and its related areas
• Promoting interdisiplinary research Collaboration
• Constructing mechanisms leading to industries, and
sharing and linking the responsibilities and roles of
industry, academia, and government,
• Securing and training human resources
Table 1 shows the transition of national budgets for
R&D in the field of nanotechnologies and materials. The
actual budgets include additional budgets for nanotechnolo20
gy-related research technology categorized as other fields
such as life science and information.
Figure 1 shows national programs in the field of nanotechnologies. Of the programs, the Nanotechnology Support Project, the Knowledge Cluster Initiative, the Cooperation of Innovative Technology and Advanced Research in
city areas, the 21 Century COE Program, and Nanotechnology Virtual Laboratories (NVL) are geared to promoting
interdisciplinary research and the collaboration among
industry, academia, and government, characteristic to the
policies in this field. These programs are outlined in section
4(2) because they are also related to the creation of new
research institutes. The section below outlines the governmental organization link project and the economy revitalizing research and development project which are related to
early commercialization and industrialization.
1.1 Coordination Programs of R&D Projects
To study specific measures of promoting commercialization and industrialization, the Council for Science and
Technology Policy set up a project team for promoting the
research and development of nanotechnologies and materials in the Specialist Investigation Board for the Priority
Field Promotion Strategy in December 2002.3) The industrial exploitation strategy planned by the team pointed out the
necessity of the Coordination Programs of R&D Projects
where governmental organizations can promote measures
together, extending from R&D to improvement (safety
screening standards, demonstration by model businesses,
Sector
linkage
■Nanomodeling Simulation: MEXT
■Advanced Measurement and Analysis Technology and
Equipment Development Project: MEXT
■Knowledge Cluster Initiative: MEXT
■Cooperation of Innovative Technology
and Advanced Research in City Areas
■Industrial Cluster Project: METI
■21st Century COE Program: MEXT (JSPS)
Nanotechnology
Business Creation
Initiative (NBCI)
Interdisciplinary, intererganitational and international support
- Nanotechnology Support Project
■Nanomaterials Project: METI (NEDO)
■Virtual Laboratory in Nanotechnology Areas: MEXT (JST)
■Coordination Programs of R&D Projects
(Nano-DDS, medical nanodevices, structural
materials, and machining and measurement)
■Economy Revitalizing Research and Development Project
・Ultrahigh Function Research and Development: MIC
・Focus 21 Project: METI
・Incubator Advanced Medical Technology Promotion Research:
MHLW
・Leading Project: MEXT
Personnel
training
Infrastructure
development
Commercial and
industrial R&D
MEXT: Ministry of Education, Culture, Sports, Science and Technology
METI: Ministry of Economy, Trade and Industry
MIC: Ministry of Public Management, Home Affairs, Posts and Telecommunications
MHLW: Ministry of Health, Labour and Welfare
JST: Japan Science and Technology Agency
JSPS: Japan Society for the Promotion of Science
NEDO: New Energy and Industrial Technology Development Organization
NBCI: Nanotechnology Business Creation Initiative
Fig. 1 Representative public programs of Japan in the field of nanotechnologies.
standardization, government procurement to incubate markets, and so forth). More specifically, strategies were
decided on nano-DDS, medical nanodevices, structural
materials, and nano-fabrication/measurement ( structural
materials are innovative ones in the field of materials).
1.2 R&D Projects for Economic Revitalization
In the FY2003 budget request for science and technology, the Council for Science and Technology Policy proposed the R&D Projects for Economic Revitalization to
construct the next-generation industrial foundations that are
expected to become a reality reasonably soon, or in the distant future. As Figure 1 shows, this proposal was actualized
by programs of governmental organizations.
2. USA
The NNI framework from FY2001-2003 consists of the
following five items:4)
• Long-term fundamental nanoscience and engineering
research
• Grand challenges – potential breakthrough –
• Centers and networks of excellence
• Research infrastructure
• Ethical, legal, and societal implications, and workforce
education and training
Fig. 2 Organization of U.S. National Nanotechnology Initiative (NNI).4)
Figure 2 shows the NNI system. Table 2 shows the transition of R&D funds of each governmental organization.4), 5)
After the initiation of the NNI, the amount of funds quickly
increased and reached 991 million dollars in total in
FY2004. In addition to this, state and regional governments
invested about 50% of the amount invested by the NNI,
and enterprises invested about the same amount as that by
the NNI. Table 3 summarizes the comments of Roco of the
National Science Foundation (NSF) concerning the NNI’s
achievements in the first three years.4)
In addition, the 21st Century Nanotechnology Research
and Development Act6) was enacted with the signature of
the president on December 3, 2003. This law materializes
national policies by the National Nanotechnology Program.
The national policies are outlined next.
21
Table 2 Transition of R&D funds by NNI4) Unit: million dollars.
Table 3 Main achievements by NNI in the first three years.4)
Field
Achievements
Research
Support for about 2,500 projects (universities and public institutions: 300, private
companies: 200). Faster development than anticipated (very short lead time until
prototyping)
Education
Education of 7,000 students and teachers in 2003. Nanotechnology-related
courses adopted by all universities of science and engineering. Education for
young people.
Common
infrastructure
Available to 60 or more universities. Establishment of 5 major networks (MCN,
NNIN, OKN, DOE, and NASA). About 40,000 staff.
Industry
Same level of investment in mid-term and long-term R&D as NNI. Participation by
large companies. Started up more than 1,000 companies. The USA holds more
than 5,300 patents (two-thirds of world total) in 2003.
Economic effects
Anticipated to reach one trillion dollars in 2015. Annual growth rate: 25% or more.
Federal-state
linkage
Investment by more than 20 states. More than 22 local networks. (E.g. California
Nanosystems Institute (CNSI))
Academic
associations
Nanotechnology specialist subcommittees as major academic associations. Start
of workshops and education.
Public investment
Activities from the initiation of NNI (workshop held in 2000). Start of the NSF
programs in 2000. Extension of activities and participation by legislative and
judicial organs.
Activities from the initiation of NNI (workshop held in 2000). Start of the NSF
programs in 2000. Extension of activities and participation by legislative and
judicial organs.
The Nanotechnology R&D Act of 2003, the 21st Century of Nanotechnology R&D
Act, and the 5-year National Nanotechnology Program
Social influence
Law
Creation of huge
coalition
Creation of a nanotechnology community
• Developing a fundamental understanding of matter that
enables control and manipulation at the nanoscale.
• Providing grants to individual investigators and interdisciplinary teams of investigators.
• Establishing a network of advanced technology user
22
facilities and centers.
• Establishing, on a merit-reviewed and competitive basis,
interdisciplinary nanotechnology research centers.
• Ensuring the United States global leadership in the
development and application of nanotechnology
• Advancing the United States productivity and industrial
competitiveness through stable, consistent, and coordinated investments in long-term scientific and engineering research in nanotechnology
• Accelerating the deployment and application of nanotechnology research and development in the private
sector, including startup companies
• Encouraging interdisciplinary research, and ensuring
that processes for solicitation and evaluation of proposals under the program encourage interdisciplinary projects and collaboration
• Providing effective education and training for researchers
and professionals skilled in the interdisciplinary perspectives necessary for nanotechnology so that a true
interdisciplinary research culture for nanoscale science,
engineering, and technology can emerge
• Ensuring that ethical, legal, environmental, and other
appropriate social concerns, including the potential use
of nanotechnology in enhancing human intelligence and
in developing artificial intelligence which exceeds
human capacity, are considered during the development
of nanotechnology
Besides, triennial evaluation of the national nanotechnology program by the National Research Council (NRC) of the
National Academy of Sciences
As part of the first triennial review, the NRC shall conduct a one-time study to assess the need for standards,
guidelines, or strategies for ensuring the responsible development of nanotechnology, including, but not limited to:
• Self-replicating nanoscale machines or devices
• The release of such machines in natural environments
• Encryption
• The development of national defensive technologies
• The use of nanotechnology to the enhancement of
human intelligence
• The use of nanotechnology in developing artificial
intelligence
The greatest impact of legislation was that it reconfirmed the R&D budgets and policies more than ever. It
seems appropriate that the national research plans for nanotechnologies are the same as those of the NNI. They are
executed through related governmental agencies or committees and the National Nanotechnology Coordination
Office (NNCO). In a strategic plan announced in December
2004, the NNI set four goals.7)
• Goal 1: Maintain a world-class research and development program aimed at realizing the full potential of
nanotechnology
• Goal 2: Facilitate transfer of new technologies into products for economic growth, jobs, and other public benefit
• Goal 3: Develop educational resources, a skilled work
force, and the supporting infrastructure and tools to
advance nanotechnology
• Goal 4: Support responsible development of nanotechnology
Roco showed the vision for nanotechnology in the next
10 to 20 years, or timeline for beginning of industrial prototyping and commercialization:
• First Generation (Until 2001): Passive nanostructures in
coatings, nanoparticles, and bulk materials (nanostructured metals, polymers, ceramics)
• Second Generation (Until 2005): Active nanostructures
such as semiconductor elements, drug targeting, and
actuators
• Third Generation (Until 2010): 3D nanosystems with
heterogeneous nanocomponents, complex networking,
and new architectures
• Fourth Generation (Until 2020 (?)): Molecular with heterogeneous molecules based on biomimetics and new
designs
Besides, he suggested potential goals that may appear by
2015: Nanoscale visualization and simulation up to three
dimensions, 10 nm or smaller integrated CMOS, new catalysts for the chemical industry, no deaths from cancer, control of nanoparticles in air, soil, or water, and others
Roco also emphasized that the concept of the NBIC:
enhancing human performance by convergence of the four
technological fields of nano, bio, info, and cogno.8)
3. Europe
In May 2004, the European Commission (EC) announced
“Towards a European Strategy for Nanotechnology”9) stating the importance of nanotechnologies, the position of the
EU in the world, and the following subjects for responsible
efforts:
• R&D: Building the momentum – European public
investment in nanotechnology should increase by a factor of 3 by 2010
• Infrastructure: European “Poles of Excellence”
• Investing in human resources
• Industrial innovation: Knowledge to technology
• Integrating the Societal Dimension
• Public health, safety, and environmental and consumer
protection
• A further step: International cooperation
Figure 3 shows the governmental research funds of
European countries in FY2003. The total amount of R&D
funds in Europe is 1,150 million euros (about 15 billion
yen). Of this amount, 350 million euros are from the EC
and the remaining 800 million euros are from the governments of the respective countries. In addition to this
amount, research funds are provided by the local governments and the private sectors. It is interesting to note that
the EC calculates the amount of research funds per citizen
and sets a target amount for the future. According to the EC
data of 2003, Japan ranked first in the amount of research
funds with 6.2 euros/citizen, the USA third with 3.6
euros/citizen, and the EU (25 countries, including new
member countries) 12th with 2.4 euros/citizen. The reason
for tripling the investment by 2010 is said to come from
this data.
Research supported by the EC is now in progress in the
Sixth Framework Program (FP6). FP6 is a five-year program from 2002 until 2006. Hearings for the 7th Framework Program (FP7) from 2007 were started in the fall of
2004.
23
400
350
Publice expenditure (M euro)
300
250
200
150
100
50
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Po
r
Gr
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ce
ain
Ac
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din
Sp
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ar
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Fig. 3 Nanotechnology R&D funds by the EC and European countries (200)9) Unit: million euros.
Table 4 Transition of nanotechnology R&D funds by the German Government10) Unit: million euros.
4. Germany
In Germany, the Federal Ministry of Education and
Research (BMBF: Bundesministerium fur Bildung und
24
Forschung) is the center of nanotechnology R&D policies.
The booklet “Nanotechnology Conquers Markets: German
Innovation Initiative for Nanotechnology” issued by the
Ministry in 2004 describes their strategies.10) Table 4 shows
Table 5 Adoption of nanoscience projects in France (2003).12)
the transition of nanotechnology R&D funds by the Federal
Government of Germany. In the period from 2003 to 2004,
the research funds increased quickly from 8.82 to 123.80
euros. As Table (b) shows, the main fields of investment
are nanomaterials, nano-optics, and nanoelectronics, which
together account for 84% of the total amount. Investments
in nanomaterials include those in nanochemistry and Competence Centers for Nanotechnology (CCN). CCN is introduced in section 4(2). The funds total 293.10 million euros,
including 24.5 million euros from the Federal Ministry of
Economy and Labor (Bundesministerium fur Wirtschaft
und Arbeit, BMWA) and 144.80 million euros to the group
of national institutes. The funding agency of the BMBF is
the German Association of Engineers (VDI: Verein
Deutscher Ingenieure). According to Bachmann of VDI,
the funding ratio of applied research to basic research is
about 5:3 (as of 2003).
In Germany, the regional governments also invest much
in the research and development of nanotechnologies,
amounting to 50% of the funds by the federal government.
To make the automotive, semiconductor, optical, and other
specific local industries more competitive, a network of
research institutes of nanotechnologies is being constructed in each area. From the viewpoint of researchers, they
need to collect 50% of research project funds from regional
governments and the private sector because only 50% is
provided by the BMBF.
5. France
“Programme Nanosciences – Nanotechnologies” announced
by the Ministry of Research (Ministère délégué à la
Recherche) on December 16, 2004 states new efforts being
made by France for nanosciences and nanotechnologies.11)
France announced a three-year subsidy (70 million euros a
year) for the Research Network in Nanosciences and Nanotechnologies (R3N: Reseau National en Nanosciences et
en Nanotechnologies) to be newly established (a total of
210 million euros in the three-year period; 30 million euros
a year until that time). The main purpose is to support the
following three fields:
• Plates-formes scientifiques et nanotechnologiques
(grandes centrals): Platform of nanosciences and nanotechnologies (infra-network)
• Joint research project of basic nanoscience
• R&D project by industry, academia, and the government
R3N is also in charge of the social influences and interna-
tional relations of nanotechnologies. R3N is positioned as
part of the activities of the National Research Agency
(ANR: Agence Nationale de la Recherche). (The budget of
ANR is 350.00 million euros.)
Regarding the platform of nanosciences and nanotechnologies, a new base is added to the conventional facility
network consisting of five public research bases. In France,
the allocations of research fields have long been clearly
separated. Research mainly on basic nanosciences has been
assigned to universities and the National Science Research
Center (CNRS: Central National de la Recherche Scientifique), while mainly applied research has been assigned to
the National Micro and Nano Technology Network
(RMNT: Reseau National de Micro-Nano Technologies)
participated in by 740 industrial, academic, and government organizations. The main purpose of R3N also reflects
this characteristic. The main research bases are introduced
individually in section 4(2).
Some examples of the funding of nanosciences and nanotechnologies are introduced here. Regarding nanosciences
in 2003, 10 million euros were invested in research projects
invited from the public by the Ministry of Research and 2
million euros in education and training, researcher exchange,
information support (Internet), and international programs.12) Table 5 shows the adoption status of submitted
research projects. Of 166 submitted subjects, 54 were
adopted and carried out at 100 laboratories (163 groups).
Regarding nanotechnologies, the RMNT (established in
February 1999), consisting of 740 organizations in the
period from 1999 to 2004, adopted 59 R&D projects from
146 applications. Investment amounts were 50.00 million
euros from public funds and 150.00 million euros from private funds, and manpower spent was 1,069 person-years.13)
The public funds came from the Ministry of Research, the
Ministry of Industry, the Ministry of Defense, and the
National Corporation of Research and Development
Fig. 4 Percentages of France RMNT projects by field.11)
25
(ANVAR) to support small and medium-sized companies.
Figure 4 shows the percentages of projects by field.11)
About 50% of the projects were related to electronics.
6. UK
The nanotechnology R&D policies of the UK are largely
influenced by a report “New Dimension for Manufacturing:
A UK Strategy for Nanotechnology”14) announced in June
2002, by the Department of Trade and Industry (DTI) and
the Office of Science and Technology (OST) of the DTI.
This report was issued by the Advisory Committee Concerning Application of Nanotechnologies headed by John
Taylor, the chairman of the Research Council (RC) and
consisting of 12 members. The report lists the following six
priority fields and also presents specific successes to be
reached in each priority field in five years as “Success in
2006”.
ELECTRONICS AND COMMUNICATIONS
• The UK’s share of products in information and communications technologies begins to increase
• Industrial R&D in this sector increased 10 fold, along
with a similar increase in patent filing
• Annual spending by the Research Councils reaches £80
million: each year 150 PhDs, accompanied by 300 technicians, graduate from training programmes
DRUG DELIVERY
• Double or treble the number of postgraduates work in
drug delivery
• 10 start-up businesses every year
• The first start-ups would approach profitability
INSTRUMENTATION, TOOLING AND METROLOGY
• A national nanotechnology centre will generate SME
start-ups and provide prototyping and small-run manufacturing for 50 new customers a year
• More than five UK companies will use directed selfassembly based on ‘disruptive’ methods compared to
one today
NOVEL MATERIALS
• Seven new products commercialised
• Three product demonstrators at proof-of-concept
SENSORS AND ACTUATORS
• 10 per cent a year growth in the number of UK graduates in nanotechnology
• 100 per cent increase in funding for technology demonstrators
• One field trial of an integrated network of healthcare
sensors in a hospital
• R&D, measured by such numbers as publications, citations and patents, to increase by 50 per cent
• The UK’s share of nanotechnology-based sensor systems grows 10 per cent faster than our main competitors
TISSUE ENGINEERING
• Five to 10 start-up businesses every year
• 10 additional multidisciplinary groups every year
• 2 per cent of a $50 billion market, worth $1 billion to the
UK
• 85 to 90 per cent of UK tissue engineering companies
26
run by UK managers
• New employment of 1500 jobs
• Eight new products commercialised
This report also recommended the following:
• National nanotechnology application strategy and Nanotechnology Application Strategy Board (NASB)
• National Nanotechnology Fabrication Centers (NNFCs)
• Roadmaps – technology and applications
• Awareness, access portals and networking
• Training and education
• International – promotion and inward transfer
Figure 5 shows the nanotechnology R&D system of the
UK Government.15) The Department of Trade and Industry
(DTI) is in charge of industrialization. In the field of basic
sciences, the Engineering and Physical Sciences Research
Council (EPSRC), the Biotechnology and Biological Sciences Research Council (BBSRC), and the Medical
Research Council (MRC) from the seven research councils
of the UK are in charge. Regarding the infrastructures
(buildings and large-scale facilities) of universities and
other institutes of higher education, the Higher Education
Funding Council for England (HEFCE) of the Department
is in charge.
Fig. 5 Nanotechnology R&D system of the UK Government.15)
In July 2003, the DTI made a public commitment to
invest a total of 90 million pounds on the Micro and Nanotechnology Manufacturing Initiative for six years.16) Of
the amount, 50 million pounds will be appropriated for collaborative R&D. In other words, the government will
shoulder 25 to 75% of the expenses to reduce risks of R&D
in specific fields. In the first invitation which ended in July
2004, the DDI adopted 25 projects and decided to invest a
total of 15 million pounds in them. In addition, 40 million
pounds will be appropriated for Capital Projects for the
Micro and Nanotechnology Network (MNT Network).
Under the MNT Network, regional centers are cooperating
to make facility operations efficient. In the Capital Projects,
the appropriation of over 25 million pounds for the following research areas was already determined by the first and
second general invitations (11 projects selected):
• Manufacture and integration of micro and nano devices
• Nano particles and novel materials
• Bionanotechnology
• Characterization and metrology
On February 25, 2005, the third round of invitations was
started. The target research areas are:
• Bionanotechnology
• Microfluidic application centers
• Carbon based electronics
Among RC research, nanotechnologies by EPSRC are
being heavily invested in. The annual amount rose from 10
million to about 13 million pounds from 1996 to 2000 but
started increasing quickly in 2001, reaching about 36 million pounds (more if related fields are included) in 2003.17)
Figure 6 shows the percentages of investment by fields.
Among research supported by RCs, the most noteworthy
ones are Interdisciplinary Research Collaborations (IRCs)
by researchers of different fields, such as physics, electricity, and chemistry. IRCs are introduced in section 4(2).
The Science Research Investment Fund (SRIF) by
HEFCE is now at the third stage. Including fields other
than nanotechnologies, a total of one billion pounds will be
invested in the two years from 2006.
References
1) The Council for Science and Technology: The Second Science and
Technology Basic Plan (March 2001).
2) Specialist Investigation Board for Priority Field Promotion
Strategy, the Council for Science and Technology: Priority
Promotion Strategies by Fields (Draft) (September 2001).
3) The Council for Science and Technology: Promotion of Industrial
Exploitation in the Nanotechnology Field – Promotion by the
governmental organization linkage project – (July 2003).
4) Roco M.C., The National Nanotechnology Initiative: Plans for the
Next Five Years. National Nanotechnology Initiative: From Vision
to Commercialization. April 2004.
5) Tetsuharu Sato (2004), Information on FY2005 Budget Request for
Nanotechnologies in the U.S. Japan Nanonet Bulletin 61.
Nanotechnology Researchers Network Center of Japan.
http://www.nanonet.go.jp/japanese/mailmag/2004/061c.html
6) Congress of the U.S.A. 189, 21st Century Nanotechnology
Research and Development Act.
7) Nanoscale Science, Engineering and Technology Committee
(NSET), The National Nanotechnology Initiative Strategic Plan.
December 2004.
8) Roco M.C., Converging Technologies and Their Societal
Implications. International Symposium on Environmental
Nanotechnology 2004. EPA & MEA, ROC. December 2004: 1-10.
9) European Commission (EC), Towards a European Strategy for
Nanotechnology. Communication from the Commission COM
(2004) 338. May 2004.
10) Bundesministerium fur Bildung und Forschung (BMBF),
Nanotechnology Conquers Market: German Innovation Initiative
for Nanotechnology. 2004.
11) Ministère délégué à la Recherche, Programme Nanosciences –
Nanotechnologies. December 2004.
12) Marzin J., Nanoscience-Nanotechnology Program. October 2004
(slides).
13) Roussille R., The French Research Network in Micro and Nano
Technologies (RMNT). October 2004 (slides).
14) Department of Trade and Industry (DTI), New Dimensions for
Manufacturing: A UK Strategy for Nanotechnology. June 2004.
15) Ryan J., Panel Discussion: International comparison of strategies,
7th International Conference on Nanostructured Materials. June
2004 (slides).
16) Micro and Nanotechnology Manufacturing Initiative, http://mntnet
work.com/
17) Engineering and Physical Sciences Research Council (EPSRC),
Nanotechnology, September 2004.
Fig. 6 Percentages of UK EPSRC invested R&D funds by field.17)
27
02 Nanotechnology Research Policies of Japan, USA and EU
Section 2. Societal Implications of Nanotechnology
Masahiro Takemura
Innovative technologies exert various impacts on society
through industries. However, they may not only bring benefits but also unpredicted effects or even risks. This is also
true for nanotechnologies. So far, no apparent risks have
been pointed out but there have been a considerable number of concerns and warnings. In 1986, for example,
Drexler portrayed a continuously self-reproducing robot in
a book titled “Engines of Creation”1) predicting the emergence of nanotechnologies and named the multipling
nanoparticles Grey Goo. In a book titled “The Big Down:
Atomtech - Technologies Converging at the Nano-scale”,2)
a Canadian NGO “ETC Group” proposed that the Government should call an immediate halt (a moratorium) to the
industrial production of nanomaterials and create a transparent international evaluation system. In the world of novels, Michael Crichton’s near-future SF “Prey”3) depicting
swarms of nanobots self-assembling and attacking humans
became a best-seller in the United States. In Europe and
America, many people involved in nanotechnology policies
think it essential to make best possible predictions without
ignoring these concerns and to continue assessment and
management for maximizing benefits and minimizing risks.
1. Activities of the USA
Regarding the impacts of nanotechnologies on health,
safety, environment, ethics, and society, the United States
selected societal, ethical, and legislative issues as important
subjects at the start of the NNI in 2000 as mentioned
before. More specifically, the most important subjects
regarding the impacts of nanomaterials on health, safety,
and the environment. On the whole, however, these are relatively short-term issues. From a long-term point of view,
problems such as self- replicating, national defensive technologies and the enhancement of human performance are
raised, and were discussed in the first triennial review of
the national nanotechnology program.4)
As one of the reasons for U.S. activities on the societal
implications, the case of Genetically Modified Organisms
(GMO) is often introduced by people involved in nanotechnology in the United States.5), 6) Genetically Modified
Organisms have caused great distrust because suppliers
could not present adequate experimental data refuting the
potential risks that had been pointed out. In the United
States data was then accumulated, and risks unique to
28
Genetically Modified Organisms were finally judged to be
nonexistent. As many people know, however, there is still
little public acceptance of Genetically Modified Organisms
in Japan and Europe, and they hope there is no similar
backlash against nanotechnologies.
The first important activity by the United States was a
workshop called “Societal Implications of Nanoscience and
Nanotechnology”.7) This workshop was held in September
2000, almost at the same as the start of NNI. From industry, government, and academia, natural scientists, social
scientists, and policy-makers gathered and held discussions. and it was followed by various programs. Under
general coordination by the NNCO, each department or
agency is conducting programs on the safety of the products and technologies they are in charge of.8)-12)
• Working environment: Occupational Safety & Health
Administration (OSHA) and National Institute of Occupational Safety & Health (NIOSH)
• Pharmaceuticals: Food & Drug Agency (FDA)
• Foods: FDA and Department of Agriculture (USDA)
• Consumer goods: Consumer Product Safety Commission (CPSC)
• Environment: Environmental Protection Agency (EPA)
• Standardization and measurement: National Institute of
Standard & Technology (NIST)
The NSF, Department of Energy (DOE), and Department of Defense (DOD) are supporting research centers.
Examples of ministry and agency linkage programs are the
National Toxicology Program (NTP) and the Interagency
Working Group on Nanotechnology Environmental &
Health Implications (NEHI). NTP is mainly organized from
the National Institute of Health (NIH), the National Institute of Environmental Health Sciences (NIEHS), the
National Center for Toxicological Research (NCTR) of
FDA, and NIOSH. This program will evaluate carbon nanotubes, quantum dots, titanium dioxide, and fullerene.
NEHI is mainly organized from the EPA, FDA, CPSC,
OSHA, NIOS and USDA, and the program will evaluate
whether it is appropriate to keep or extend existing regulations on the industrialization of nanotechnologies. In 2004,
NNI invested a total of 130 million dollars: over 20 million
dollars each on the environment and on society and education, and over 80 million dollars on health. (Both applications and implications are included for the environment and
health.)
The last examples in the United States are the American
National Standard Institute (ANSI)-Nanotechnology Standard Panel (NSP), inaugurated in September 2004,13) and
the International Council on Nanotechnology (ICON).14)
ICON was inaugurated in October 2004 at the initiative of
the Center for Biological and Environmental Nanotechnology (CBEN) of Rice University supported by NSF, and it
includes NGOs as members as well as industry and academia.
2. Activities of Europe
The following three programs of the EU are related to
environmental, health and safety (EHS) issues of nanotechnology:15)
• NANO-PATHOLOGY Project: Developing diagnostics
methods and equipment, clarifying pathological mechanisms, and verifying pathological importance. For three
years from December 1, 2001 with a fund of about one
million euros. Headed by the Italian Institute for the
Physics of Matter.
• NANODERM Project: Studying the influences of nanomaterials on the skin. For three years from January 1,
2003 with a fund of about 1.10 million euros. Headed by
the University of Leipzig.
• NANOSAFE Project: Assessing risks of nanomaterials
from production processes to consumers. For 15 months
from April 1, 2003 with a fund of about 0.3 million
euros. Headed by NANOGATE Technologies GmbH.
The first stage of NANOSAFE was completed in June
2004 and the second stage is now being prepared. The first
stage is introduced here.16), 17) This project will perform the
following activities related to nanoparticles:
• Assemble available information on the possible hazards
• Evaluate risks to workers, consumers and the environment
• Assess mechanisms of risks to human health
• Formulate codes of good practice to obviate danger as
far as possible
• Recommend guidelines for regulatory measures
For the activities, six working groups were formed: For the
activities, six working groups were formed: WG1 (particle
size and shape, manufacturing and handling procedures),
WG2 (applications, industrial and consumer), WG3 (potential particle release, circumstances and conditions), WG4
(danger to health, reaction mechanism with human organism), WG5 (recommended preventive measures), and WG6
(standards and regulatory recommendations). Regarding
nanoparticles, the working groups discussed the expected
performance of measuring equipment, risk evaluation
items, safety measures for workers, risk evaluation flowcharts, influences on the human body, and regulatory
frameworks and methods. Regarding influences on the
human body, they concluded that the materials may be
absorbed through lungs or intestines but hardly permeate
through the skin, that regions of distribution in the body
depend on the surface properties of nanoparticles, and that
there are no universal nanoparticles or materials that must
be evaluated individually. The achievements in this project
are also summarized in “Industrial Application of Nanomaterials – Chances and Risks, Technology Analysis” (August
2004)18) edited by the German Engineers Association (VDI:
Verein Deutscher Ingenieure).
In addition to the above programs, other investigation
and workshop activities by the EU are summarized in some
reports, such as: “The 4th Nanoforum Report: Benefits,
Risks, Ethical, Legal and Social Aspects of Nanotechnology” (June 2004)19) and “Nanotechnologies: A Preliminary
Risk Analysis on the Basis of a Workshop Organized in
Brussels on 1–2 March 2004” (March 2004).20) The former
is a summary of European discussions at Nanoforum (Nanotechnology network of the EU) as of June 2004. The latter
is a report on a workshop sponsored by the EC and summarizes the discussions and proposals by 17 specialists.
As well as R&D activities, the European countries are
examining social influences. A British report “Nanoscience
and Nanotechnologies: Opportunities and Uncertainties”
(July 2004)21) created a sensation both within and outside
the country. Commissioned by the UK Government, The
Royal Society & Royal Academy of Engineering compiled
this investigation report. Through several workshops, opinions were collected from a total of 221 specialists and 151
institutions such as universities and companies, and awareness surveys were conducted on the general public. In conclusion, the report suggested 21 recommendations22) 23)
regarding industrial uses of nanotechnologies, the possibilities of adverse effects on health, restriction problems,
social and ethical problems, stakeholder and dialogue with
citizens, and responsible R&D.
According to the report, the current industrial uses of
nanotechnologies are still on the stage of improving existing products and the influences on health and the environment are inhalation by workers during the process of manufacturing nanoparticles and nanotubes. Meanwhile, the recommendations propose a risk assessment by a third party,
funding by a research council, handling as harmful substances when there is not enough risk information, risk
assessment throughout the lifecycle, information disclosure, and handling as a restricted new chemical substance.
In the awareness surveys on the general public, 29%
replied that they had heard of nanotechnologies and 19%
replied that they had talked about the definition of nanotechnologies in some way. Of these respondents, 68% felt
that nanotechnologies will enrich their lives in future and
4% felt that their lives will be made worse. Meanwhile, the
recommendations propose open forums about nanotechnologies and comprehensive and quantitative social science
research.
3. International cooperation and its points
International cooperation is indispensable for taking
actions on the societal implications of nanotechnologies
and there is now much international discussion. The main
recent international conferences and their contents are outlined below.
i) International Dialogue on Responsible Research and
Development of Nanotechnology (Alexandria, Virginia
29
State, USA from June 16 to 18, 2004)
Convened by Roco of the NSF, technical policy-makers
gathered from 25 countries, including the representatives
of EC. The attendants presented the nanotechnology policies of their countries and held workshops on four topics:
a) Environment, b) Health and safety, c) Society, economy,
and ethics, and d) Nanotechnologies in developing countries. They also discussed an international framework.9)
ii) The 7th International Conference on Nanostructured
Materials (NANO 2004 in Wiesbaden, Germany from June
20 to 24, 2004)
Under the subject of “Chances and Risks of Nanotechnology,” a panel discussion and lectures were held.24) The
panel discussion was attended by Roco, Tomellini, and
other representatives from the United States and Europe
and also from Green Peace as panelists.25) A report meeting
on the EU program NANOSAFE was held concurrently.
iii) First International Symposium on Occupational Health
Implications of Nanomaterials (October 12 to 14, 2004 in
Buxton, Derbyshire, UK)
This symposium was jointly sponsored by the U.K.
Health & Safety Laboratory (HSL) and the U.S. National
Institute of Occupational Safety & Health (NIOSH), and
marked the world’s first international symposium of nanotechnologies sponsored by a laboratory in charge of occupational safety and health.26) After lectures by technical
policy-makers, toxicologists, and safety & hygiene organizations, four workshops on measurement, management and
restrictions were held by four groups.
At international conferences including this, the risk
assessment and management of nanomaterials attracts most
discussion. As of now, there are no obvious risks or standardized specimens or test methods. Therefore, there is still
not enough systematic data and the risks cannot be judged
yet. Some reports of individual research gave experimental
results indicating toxicity.27) However, it is inappropriate to
judge risks immediately from these results. Systematic and
strategic research will be necessary in future.28)-30)
Judging from the conferences and reports introduced so far,
those concerned generally agree to the following:
• Most discussions start with the definition of nanomaterials. The typical dimension of nanomaterials (diameter of
particle, cross-sectional diameter of fiber, or thickness of
film) is 100 nanometers or less.
• The knowledge held by safety and hygiene specialists
about ultra fine particles should be made full use of.
• It is also important to evaluate whether nanomaterials
are fixed completely in a matrix like bulk materials, peel
like coating, or are free to move.
• Regarding influences on the human body and environment, nanomaterials can roughly be classified into ones
that are taken into the body intentionally for a medical
purpose, such as a drug delivery system (DDS), and
ones taken into the body unintentionally.
• Even when chemical formulas are the same, bulk materials and nanomaterials should be handled differently.
• It is also necessary to distinguish nanoparticles generated and discharged unintentionally, like diesel exhaust
particles, and industrial nanoparticles.
• As Figure 1 shows, priority subjects concerning expo30
3. Maintenance of ecos
ystem and environment
Ecosystem, atmosphere, soil, and waters
Laboratory
in factory
Worker
1. Safety and health
of workers
- Storage
- Transportation
Consumer
2. Safety and health
of consumers
Disposal and recycling
Fig. 1 Priority subjects in the risk assessment and management of
nanomaterials.21)
sure are: 1) Safety and health of workers who have the
highest possibility of being exposed to nanomaterials, 2)
Safety and of consumers who use products and technologies, and 3) Protection of ecosystems and the environment. During the flow from upstream to downstream,
nanomaterials tend to grow in size by cohesion and also
to accumulate and degenerate.
• The framework of risk assessment, management, and
communication about nanomaterials should be based on
the existing one applicable to chemical substances and
foods.
• Figure 2 shows an example of a flowchart far the risk
assessment of nanomaterials. This is to judge “the necessity of assessment and management as nanomaterials”
and not to evaluate the absolute size of a hazard. For a
material soluble in water, the necessity of a new evaluation or management method is small because the conventional evaluation method can be applied. As the
aspect ratio increases, the possibility of penetrating the
lungs like asbestos grows. If a hazard is found, it is necessary to check the toxicity, the influence of size, and
the reaction by dosage.
- Aerosol generation
and discharge
- Human body and
environmental exposure
Toxicity screening
Aspect ratio
Length
- Influences on brain
- Influences on lung
- Influences on unborn child
- Systemic influences
- Oxidation factors
- Environmental hormones
- Sensitization and painkilling
Environmental toxicity
screening
Diameter
Immediately
soluble in water
- Sustainability
(atmosphere and waters)
- Long-distance move
- Biological condensation
- Influences on soil
Yes or Unknown
Necessity: Small
Conventional evaluation
and management
method applicable
Necessity: Medium
Necessity: Large
Fig. 2 Example of flowchart for judging the necessity of new methods
of evaluation of biological and environmental impacts of nanomaterials.16), 20)
• Figure 3 shows a general view of risk management. The
risk is a multiplication of hazard by exposure. Even if
there is a hazard, the risk is small if the possibility of
exposure is low. Communication with the public is necessary at the stages of risk evaluation and management.
Risk management
Risk analysis
Risk evaluation
- Hazard verification
- Hazard characterization
Risk communication
- Exposure evaluation
- Risk characterization
Fig. 3 General view of risk assessment and management.20)
• Regarding the precautionary principle, there are gaps in
the recognition among the EU (excluding the UK), the
UK and the United States. Besides, in terms of the evaluation method, the former generally aims at the establishment of method applicable to all nanomaterials while
the latter aims at the selection of the best method for
each combination of material and application in the
belief that there is no universal evaluation method.31)
References
1) Drexler K.E., Engines of Creation. 1986.
2) ETC Group, The Big Down: Atomtech - Technologies Converging
at the Nano-scale. 2003.
3) Crichton M., Prey. 2002.
4) Roco M.C., Converging Technologies and Their Societal
Implications. International Symposium on Environmental
Nanotechnology 2004. EPA & MEA, ROC. (Dec. 1 to 10, 2004).
5) Yukihide Hirakawa, Biosafety and International Relationship –
Issues and Subjects about Technical Governance. Revision of the
paper read at the 2003 Convention of the Japanese Political Science
Association (Oct. 2003).
6) Masaki Misawa, Risk Analysis of Nanoparticles – Background and
Present Status –, AIST Forum “Nanotechnologies and Society”
(Sep. 2004) (Slides).
7) Roco M.C. & Bainbridge W.S., Societal Implications of
Nanoscience and Nanotechnology (Eds.).
8) Roco M.C., Broader societal issues of nanotechnology. Journal of
Nanoparticle Research 5: 181–189 2003.
9) Meridian Institute, Proceedings of International Dialogue on
Responsible Research and Development of Nanotechnology. (Jun.
2004).
10) Roco M.C., Nanotechnology in U.S. – Research and education and
risk governance. First International Symposium on Occupational
Health Implications of Nanomaterials. Health & Safety Laboratory.
(Oct. 2004) (Slides).
11) Karn B., Nanotechnology and the Environment: What We Have
Learned Since Last Year. International Symposium on
Environmental Nanotechnology 2004. EPA & MEA, ROC. (Dec.
2004) (Slides).
12) Bond P.J., Responsible Development of Nanotechnology.
Conference on nanotechnology “Small size-large impact”. Swiss
Re. (Dec. 2004) (Slides).
13) American National Standards Institute (ANSI), ANSI
Nanotechnology Standards Panel Holds First Meeting.
http://www.ansi.org/news_publications/news_story.aspx?menuid=7
&articleid=783 2004
14) Lafranconi M., Addressing nanotechnology risk in an innovative
and proactive manner. Conference on nanotechnology “Small sizelarge impact”. Swiss Re. (Dec. 2004) (Slides).
15) Dürrenberger F., Höck J. & Höhener K., Overview of completed
and ongoing activities in the field: Safety and Risks of
Nanotechnology, TEMAS AG. 2004.
16) Naß R., Risk Assessment, Toxicological and Health Issues –
Results of the EU Funded Project NANOSAFE. NANO2004
Satellite Workshop The European Project “NANOSAFE”. (Jun.
2004) (Slides).
17) Hoet P., Present knowledge of health effects of nanoparticles and
future implications for workers and consumers. NANO2004
Satellite Workshop - The European Project “NANOSAFE”. (Jun.
2004) (Slides).
18) Verein Deutscher Ingenieure (VDI), Industrial application of
nanomaterials – chances and risks, Technology analysis. 2004.
19) Nanoforum, 4th Nanoforum Report: Benefits, Risks, Ethical, Legal
and Social Aspects of NANOTECHNOLOGY 2004.
20) European Commission (EC), Nanotechnologies: A Preliminary
Risk Analysis on the Basis of a Workshop. (Mar. 2004).
21) Royal Society & Royal Academy of Engineering, Nanoscience and
nanotechnologies: opportunities and uncertainties. (Jul. 2004).
22) Eiichi Ozawa, An investigation report by Royal Society & Royal
Academy of Engineering: Nanoscience and nanotechnologies:
opportunities and uncertainties. Japan Nanonet Bulletin 73.
http://www.nanonet.go.jp/japanese/mailmag/2004/073c.html 2004
23) Welland M., Nanotechnology – Origins and Issues. Conference on
nanotechnology “Small size-large impact”. Swiss Re. (Dec. 2004)
(Slides).
24) DECHEMA, Proceedings of 7th International Conference on
Nanostructured Materials. (Jun. 2004).
25) Masahiro T., 7th International Conference on Nanostructured
Materials (NANO 2004) Part 2: Panel Discussion “Nanotechnology
Policies of Germany and Europe” Japan Nanonet Bulletin 71.
26) Health & Safety Laboratory (HSL), Proceedings of First
International Symposium on Occupational Health Implications of
Nanomaterials. (Oct. 2004).
27) Oberdörster E., Manufactured Nanomaterials (fullerenes, C60)
Induce Oxidative Stress in the Brain of Juvenile Largemouth Bass.
Environmental Health Perspectives 112(10): 1058–1062.
28) Colvin V.L., Environmental Impacts of Engineered Nanomaterials:
A new kind of pollution? Conference on nanotechnology “Small
size-large impact”. Swiss Re. (Dec. 2004) (Slides).
29) Kreyling W.G., Health Implication of Nanoparticles, International
Symposium on Environmental Nanotechnology 2004. EPA &
MEA, ROC. (Dec. 2004): 93–110.
30) Oberdörster G., Nanotoxicology: an Emerging Discipline.
International Symposium on Environmental Nanotechnology 2004.
EPA & MEA, ROC. (Dec. 2004): 71–91.
31) Marburger J., Statement in International Dialogue on Responsible
Research and Development of Nanotechnology. (Jun. 2004).
31
PART3
Public Research Institutes for
Materials Research
in Respective Countries
• Public Research Institutes for Materials Reseach in
Japan, USA and EU
• New Nanotechnology Research Institutes in Japan,
USA and Europe
• Public Research Institutes in Russia Federation and
Poland
Chapter 1.
Public Research Institutes for
Materials Research in Japan, USA
and EU
Section 1. Japan
Tomoaki Hyodo, Yoshio Abe
istry of Education, Culture, Sports, Science and Technology, is conducting a wide range of basic R&D. Two other
independent administrative institutions, RIKEN (under the
jurisdiction of the same ministry) and the National Institute
of Advanced Industrial Science and Technology (AIST,
under the jurisdiction of the Ministry of Economy, Trade
and Industry), are conducting applied research in some
research divisions.
Table 1 compares NIMS and AIST. NIMS conducts
mainly basic research on materials sciences, RIKEN conducts tests and research on technologies, and AIST conducts technical R&D and related activities for the mining
industry.
Figure 1 compares the budgets of the three research
institutes.1)-3) AIST ranks top with about 121 billion yen
(approximately 1,100 million dollars), followd by RIKEN
with 84 billion yen (approximately 764 million dollars) and
then by the NIMS with 23 bilion yen (approximately 209
million dollars).
1. Introduction
In the last decade, 7 public research institutes and
research laboratories of about 40 universities have published papers on materials, excluding laboratories belonging to private companies.
Due to limited space, this report cannot cover all
research institutes engaged in materials research. Therefore, this paper introduces some public research institutes
and university laboratories to compare Japanese research
institutes that are engaged in materials research.
2. Comparison of public research institutions for
materials research
Regarding materials research in Japan, the National
Institute for Materials Science (NIMS), an independent
administrative institution under the jurisdiction of the Min-
Dissemination and
applications
3,032
Redemption
30
Entrusted
research
32
Facility
maintenance
3
Labor
59
Labor
expenses
11,261
Immunity
and
science
3,864
Entrusted
research
8,399
Expenditure
23,100
million yen
Life science
2,547
Leading infrastructure
research
4,018
Strategic
research
promotion
8,424
Total
83,956
million yen
Polygene
2,119
Business
107
Generation and
regeneration
5,214
Genome
science
8,006
Plant science
1,595
(a) National Institute for Materials Science
Facility
maintenance subsidy
3,340
Subsidy for
redemption of facility
maintenance
loan
26,410
Atomic
power
5,859
Expenditure
120,975
million yen
Labor expenses
34,945
Brain
science
9,728
Fusion related research
3,078
Harima Laboratory - Synchrotron radiation
6,813
(b) RIKEN
Direct
research
42,163
Indirect
divisions
14,117
Unit: million yen
(c) National Institute of Advanced Industrial
Science and Technology
Fig. 1 Comparison of expenditures and budgets between National Institute for Materials Science, RIKEN and National Institute of Advanced Industrial
Science and Technology (FY2004).
35
Table 1 Comparison of National Institute for Materials Science, RIKEN, and National Institute of Advanced Industrial Science and Technology.1) ~3)
National Institute for
Materials Science (NIMS)
Rikagaku Kenkyujo (RIKEN)
Established
April 1, 2001
Established by the merging of National
Research Institute for Metals (established
July 1956) and National Institute for
Research in Inorganic Materials
(established April 1966) as an independent
administrative institution.
October 2003
Established as RIKEN Foundation in
1917. Reorganized into the Scientific
Research Institute Ltd. after the world
War2 and inaugurated as the Institute of
Physical and Chemical Research in
October 1958. Established as an
independent administrative institution in
October 2003.
April 1, 2001
Established in January 2001 by the
merging of 8 research institutes previously
under the former Agency of Industrial
Science and Technology at Tsukuba
Center and in 7 other areas. Established as
an independent administrative institution
in April 2001.
Purpose
To raise the level of materials science and
technology by conducting research and
development on associated technologies,
as well as research and intellectual
infrastructure
(Article of the Individual Law)
To raise the level of science and
technology by comprehensive research in
science and technology (excluding only
humanities and social sciences)
(Article 3 of the Individual Law)
To enhance industrial technologies and
disseminate their achievements, and to
contribute to economic and industrial
development and the stable and efficient
supply of mineral resources and energy by
comprehensive research and development
on technologies in the mining industry
Scope of Work
1. Basic research related to material
science and technology, and R&D of
related research and intellectual
infrastructure
2. Encouragement of dissemination and
practical application of the above R&D
results
3. Shared use of institute facilities and
equipment with those engaged in R&D on
science and technology
4. Training and development of
researchers and technicians in materials
5. Work related to 1 to 4 above
1. 1) Testing and research related to
2) Encouragement of dissemination and
practical application of the results of R&D
3) Shared use of institute facilities and
equipment with those engaged in testing
and R&D on science and technology
4) Training and development of
researchers and technicians in science and
technology
5) Work related to the above
2. As well as 1) to 5) above, work
prescribed in Article 8 of the Law for
Promoting the Shared Use of Specific
Synchrotron Radiation Facilities
1. 1) R&D on mining science and
technology and related work
2) Geological survey
3) Setting of measuring standards,
inspection, examination, and R&D on
measuring instruments, and related work
and also training on measurement
4) Technical guidance and dissemination
of achievements related to the work in 3)
5) Work related to the above
2. As well as 1) to 5) above, witnessed
inspection prescribed in Clauses 1 and 2,
Article 148 of the Measurement Law
Supervised By
Ministry of Education, Culture, Sports,
Ministry of Education, Culture, Sports,
Ministry of Economy, Trade and Industry
Personnel
™Full-time staff
• Laboratory staff (non-Japanese)
395 (16)
[Tenured]
[373]
[Fixed-term]
[22]
• Engineering
41
• Office
103
Staff as of April, 2004 539 (16)
™Acceptance of researchers through
various systems (in FY2003)
• Special researchers (postdoctoral)
305
• Special researchers (non-postdoctoral)
13
• NIMS junior researchers
20
• Guest researchers
197
• Visiting researchers
393
™Full-time staff
• Full-time staff (excluding temporary
staff)
685 (as of Apr. 1, 2004)
• Full-time staff (Fixed-term)
1,953 (as of March 31, 2003)
™Full-time staff
• Laboratory staff (non-Japanese)
2,395 (55)
[Tenured]
[2,015]
[Fixed-term]
[380]
• Office staff
719
Staff as of Apri1, 2004
3,114 (55)
™Acceptance of researchers and
technicians from universities and
companies (in FY2003)
• Linked graduate school system
193/year
• Junior associate system
(Students of the second-term doctorate
course)
141/year
• Special fellow system for basic
science
205/year
• Independent chief researcher 5/year
™Acceptance of researchers through the
industry-academia-government linkage
system
• Postdoctoral researchers
800
• From private companies
800
• From universities
1,700
• From overseas
900
(Total number accepted in FY2003)
To promote research and development in the field of
nanotechnologies and nanomaterials, which is one of four
priority fields selected in the Second Science and Technology Basic Plan, NIMS set the following fields as priority
R&D fields in the medium-term program from FY 2001 to
FY2005:
• Nanomaterials
• Environment and energy materials
• Safe materials
• Improvement of research and intellectual infrastructure
Meanwhile, RIKEN is attempting to discover new materials by studying electron states, magnetic statuses, and
nanoproperties at a large synchrotron radiation research
facility (SPring-8: mentioned later). To produce new functional materials, RIKEN is developing ultrahigh precision
techniques to control the properties, structures, and func36
National Institute of Advanced Industrial
Science and Technology (AIST)
tions of materials on the atomic and molecular levels.
RIKEN is also constructing a novel nanosystem using photons and developing infrastructure techniques to observe,
operate, control, and process carbon tubes, fullerene, and
other materials in units of single atoms and molecules.
With nanometer control, nanosystem device creation,
and micro-nanoprocessing technologies, AIST is researching and developing raw composite functional materials and
new carbon materials as the basis of ultrahigh-speed and
large-capacity information processing technologies, as well
as precision-control polymer materials as the foundation
for sustainable development of economic society.
3. University research institutions for materials research
As research institutes belonging to universities, Table 2
gives the Institute for Materials Research, Tohoku University, and a joint-use academic corporation, the Institute for
Molecular Science.4), 5)
Aiming to examine the principles of materials science and
ways of applying them, the Institute for Materials Research,
Tohoku University is conducting R&D to study materials
properties, to design materials, to create structural and functional materials, and to process and evaluate materials.4)
To clarify the structures, functions, and reactions of
molecules and molecular aggregates on the atom and electron levels and to predict and attain new phenomena and
functions, the Institute for Molecular Science is conducting
experimental and theoretical research on the structures and
functions of molecules and molecular aggregates.5)
The budget is about 6.3 billion yen (approximately 57
million dollars in FY2001) for the Institute for Materials
Research, Tohoku University and about 8.1 billion yen
(approximately 74 million dollars in FY2003) for the Institute for Molecular Science.
4. Major research facilities for materials research
Table 2 Profiles of Institute for Materials Research, Tohoku University (IMR) and Institute for Molecular Science (IMS).4), 5)
National University Corporation
Institute for Materials Research, Tohoku University (IMR)
University-shared Academic Corporation
Institute for Molecular Science (IMS)
History
Established in April 1916
Inaugurated as the Second Division of the provisional RIKEN
attached to the Science School of Tohoku Imperial University.
Reinaugurated as Laboratory of Metallic Materials attached to
Tohoku Imperial University in August 1922 and re-inaugurated as a
collaborative research institute attached to Tohoku University in
May 1987.
Established in April 1975.
Integrated with the General Research Organization of Biological
Science in April 1981 and operated together as Okazaki National
Research Institute. Integrated and reorganized with the National
Astronomical Observatory, National Institute for Fusion Science,
Laboratory of Basic Biology, and Laboratory of Physiology.
Reinaugurated as a university-shared academic corporation “Institute
for Molecular Science.”
Purpose
To research principles in materials science and their applications
(Article 2 in the rules of the Institute for Materials Research, Tohoku
University)
[Goals of research]
To find general rules and predict or attain new phenomena and
functions by clarifying the structures, functions, and reactions of
molecules and molecular aggregates on the atom and electron levels
(Extract from mid-term goal)
Activities
The research organization consists of four research divisions and
four attached research institutions. The research divisions conduct
the following:
1. Materials Property Division
Theoretical and experimental research on macroscopic
mechanisms related to the basic properties of materials
2. Materials Design Division
Research on the development and design of new materials by
controlling the basic properties of structural and functional
materials
3. Materials Development Division
Research on the creation of new structural and functional
materials by physical and chemical methods
4. Materials Processing and Characterization Division
Research on processing technologies for new materials and on
the evaluation and analysis of their materials characteristics
(Article 6 of the rules of the Institute for Materials Research, Tohoku
University)
[Actions to achieve goal]
In the field of molecular science, experimental and theoretical
research on the structures, functions, and reactions of molecules and
molecular aggregates are conducted by advanced physiochemical
methods using external fields such as optical X-rays, electron-rays,
and magnetic fields and very low temperature; techniques of
designing and synthesizing molecular materials; theoretical
simulation design; and also synthesis simulation by ultrahigh-speed
computation.
1. Theoretically clarifying universal factors dominating chemical
reactions and molecular properties to create molecular theories for
predicting reactions and designing new properties
2. Expanding fine and high-grade molecular spectroscopy to
establish a technique of evaluating the statuses of molecules and
molecular aggregates. Also proposing practical property
evaluation devices and measuring devices.
3. Developing a new laser as a light source for spectroscopy or
photochemical reactions, and also an extreme ultraviolet source
by synchrotron radiation, and promoting research on the
application of chemical reaction dynamics and creation of new
materials
4. Researching properties to develop molecules, nanoscale molecular
elements, and molecular solids and to establish guidelines for
materials development
5. Proceeding with research by theory and computer simulation to
deepen the fundamental understanding of chemical and physical
phenomena that cannot be clarified by experimentation
(Extract from the mid-term plan)
The attached research institutions are: International Research Center
for Nuclear Materials Science, Advanced Research Center for
Metallic Glasses, High Field Laboratory for Superconducting
Materials, and International Frontier Center for Advanced Materials.
Personnel
™Staff (as of Apr. 1, 2002)
• Professors
133
General staff
89
Part-time staff 80
™Graduates (as of Apr. 1, 2002)
• First-tem course 100 Second-term course 49
Total: 302
™Staff (as of Jan. 1, 2005)
• Chief
1
• Teaching staff 77
• Technical staff 35
Total: 113
Total: 149
™Researchers (as of Apr. 1, 2002)
• Special fellows 33
Budget
Property
Labor
FY2001
¥6,345 mil.
Scholarship grants
Industry-academia research
Scientific research
FY2003
(Settled amount)
¥8,097 mil.
Labor
Property
Facility maintenance
Science and technology
promotion and coordination
37
Table 3 Outline of High Energy Research Accelerator Research Organization.6)
University Research Institute Corporation – High Energy Research Accelerator Research Organization (KEK)
History
• July 1955 The Institute of Nuclear Study established
• April 1971 National Laboratory for High Energy Physics established
• April 1978 Meson Science Facility established as an institution attached to Department of Science, Tokyo University (Reorganized into
Meson Science Laboratory later)
• April 1997 High Energy Accelerator Research Organization established (from National Laboratory for High Energy Physics, and Institute
for Nuclear Research and Meson Science Laboratory, University of Tokyo)
• April 2004 Re-inaugurated as the Inter-University Research Institute Corporation High Accelerator Research Organization
Purpose
To promote research as the basis of comprehensive development for Japan's accelerator science (experimental and theoretical research on
elementary particles and atomic nuclei and on the structures and functions of materials including living organisms, research on enhancing
the performance of the accelerator and on related infrastructure technologies using a high energy accelerator) and to provide domestic and
overseas researchers in related fields with a place for conducting research
Work
The Institute of Particle and Nuclear Studies, Institute of Material Structure Science, Accelerator Laboratory, and Applied Research
Laboratory were established and are now jointly used by universities.
™Institute of Particle and Nuclear Studies
Experimental research on elementary particles and atomic nuclei and their related theoretical research using a high energy accelerator
™Institute of Material Structure Science
Experimental research on the structures and functions of materials and their related theoretical research using a high energy accelerator
™Accelerator Laboratory
Study of high energy accelerators as key facilities for research on elementary particles and atomic nuclei in materials science, and
operation and management of proton accelerators and electron and positron accelerators
™Applied Research Laboratory
Organized from the Radiation Science Center, Computing Research Center, Cryogenics Science Center, and Mechanical Engineering
Center for necessary research and research support with the large accelerator in related fields
Personnel
™Staff (as of April 1, 2004) 692 in total
Chief/manager: 1 Teaching staff: 372 Technical staff: 161 Office staff: 158
™Joint researchers accepted (FY2003) 89,142 person-days in total
™Overseas joint researchers accepted (FY2003) 30,611 person-days in total
Budget
Business (Education and research, general administration)
Facility maintenance
FY2004
¥40,216 mil.
Table 3 outlines the High Energy Research Accelerator
Research Organization (KEK).6) KEK set up and is now
operating the Institute of Particle and Nuclear Studies, the
Institute of Material Structure Science, Accelerator Laboratory, and the Applied Research Laboratory as institutions
shared by universities.
The Japan Synchrotron Radiation Research Institute
Industry-academia research and donations
Redemption of long-term loan
possesses a large-scale synchrotron radiation facility called
SPring-8 (Figure 2).7) SPring-8 was jointly constructed by
the Japan Atomic Energy Research Institute and RIKEN
and put into service in October 1997 for shared use of synchrotron radiation. SPring-8 is now operated by the Japan
Synchrotron Radiation Research Institute (JASRI). JASRI
invites and selects projects wishing to use the facilities and
provides domestic and overseas researchers with synchrotron radiation. The organization also operates and maintains tests and R&D facilities to support usage, the analysis
of atomic arrangements and structures, the analysis of statuses and components, and observation by the imaging
method.
The budget is about 40.3 billion yen (approximately 366
million dollars in FY2004) for the High Energy Research
Accelerator Research Organization and about 10.5 billion
yen (approximately 95 million dollars in FY2004) for
SPring-8 at the Japan Synchrotron Radiation Research
Institute.
5. Conclusion
Fig. 2 SPring-8. (Courtesy of SPring 8)
38
1) The National Institute for Materials Science handles a
wide range of materials research such as nanomaterials.
RIKEN is characterized by searching for new materials by
using the synchrotron radiation facility. AIST is engaged in
such as nanotechnology R&D utilizing nanometer control
and nanodevice system creation technologies and also
micro-nanoprocessing technologies.
2) The Institute for Materials Research, Tohoku University
is conducting R&D to study materials properties, to design
materials, to create structural and functional materials, and
to process and evaluate materials. The Institute for Molecular Science is conducting experimental and theoretical
research on the structures and functions of molecules and
molecular aggregates.
3) The High Energy Research Accelerator Research Organization set up and is now operating the Institute of Particle
and Nuclear Studies, Institute of Material Structure Science, Accelerator Laboratory, and others as shared institutions for materials science. SPring-8 is a shared facility for
the analysis of atomic arrangements and structures.
References
1) Web page of the National Institute for Materials Science
http://www.nims.go.jp/eng/index.html
2) Web page of RIKEN
http://www.riken.jp/engn/index.html
3) Web page of AIST
http://www.aist.go.jp/index_en.html
4) Web page of the Institute for Materials Research, Tohoku
University
http://www.imr.tohoku.ac.jp/Eng/index.html
5) Web page of the Institute for Molecular Science
http://www.ims.ac.jp/index.html
6) Web page of the High Energy Research Accelerator Research
Organization
http://www.kek.jp/intra-e/index.html
7) Web page of SPring-8
http://www.spring8.or.jp/e/
39
01 Public Research Institutes for Materials Science in Japan, USA and EU
Section 2. USA
Tomoaki Hyodo, Oliya V. Owen
1. R&D budgets in the United States
In the United States, basic research on materials is mainly funded by the Department of Energy (DOE) – Basic
Energy Sciences, Materials Science (DOE-BES) and the
National Science Foundation (NSF) – Mathematical and
Physical Sciences, Materials Research (NSF-MPS).1)-3) In
FY2004, the DOE-BES invested 559 million dollars, while
the NSF-MPS invested 251 million dollars on materials
research. The DOE has 14 research institutes. The NSF,
however, is specialized in research funding and has no
research institutes, excluding part of the South Pole Station.
The National Institute of Standards and Technology
(NIST) belongs to the Department of Commerce and conducts research on ceramics, polymers, and other materials
in the Materials Science and Engineering Division and others.4) The research budget is 63 million dollars (requested
in FY2005).
In this report, the NSF is excluded because it operates no
research institutes for materials research.
2. Materials research in DOE-BES
The DOE research and development activities originated
from the Manhattan Project for the atomic bomb. To continue the work of the Manhattan Project after World War
II, the Atomic Energy Commission was established by the
enactment of the Atomic Energy Act in 1946. According to
the Energy Reorganization Act enacted in 1974, the Atomic Energy Commission was abolished and the Nuclear Regulatory Commission and the Energy Research and Development Administration were established. The present DOE
is an administrative organ that was set up in October 1977
as the 12th department of the United States according to the
Department of Energy Organization Act.
The DOE is primarily a national security organization; it
places emphasis on energy development and regulation in
the latter half of the 1970s and on nuclear weapons R&D in
the 1980s. After the Cold War, the DOE focused on the
environmental purification of nuclear weapons compound
facilities, nuclear non-proliferation, property management
of nuclear weapons, energy supply and transportation, and
efficiency enhancement and conservation of energies.
40
The strategic goals of the DOE announced in September
2003 announce a mission of advancing the national, economic, and energy security of the United States to drive
forward the supporting science and engineering. The general goals in the field of science are to provide a world-class
scientific research capability and to ensure that the DOE
achieves its mission of national energy security, oversees
an improvement in knowledge in advanced physics, biology, medicine, environment, and computational science, and
provides world-class research facilities for national scientific projects. The interim goals of materials research,
announced at the same time, are to complete the construction of a spallation neutron source by the end of 2006, to
put nanoscience research centers into operation by the end
of 2008, and to develop materials having characteristics
that can be predicted from each atom based on an understanding of materials nanoscale assembly by 2015.
Table 1 shows the DOE-BES expenses in FY2004.5) Of
the 991 million dollars in total, 559 million dollars are allocated for materials research. Figure 1 shows the breakdown
of the DOE-BES requested budget. Of the requested budget
in FY2006 ($1,105 million), 40% are for the facility operations, 17% for infrastructure, and 14% and 26% respectively for research at universities and public research institutes.
Table 2 shows the DOE-BES expenses in the materials
sciences and engineering fields in 2004. Of the total
expenses, 261 million dollars (47%) are spent on research
and 298 million dollars (53%) on facility operations. Table
3 shows the breakdown of research expenses totaling 261
million dollars. The material research expenses, excluding
those for operating DOE-BES supervised facilities, were
subsidized in many research fields, particularly Neutron
and X-ray Scattering (17.2%), Experimental Condensed
Matter Physics (16.4%), and Materials Chemistry (15.5%).
The priority themes of the DOE-BES are nanoscale science research and hydrogen initiative research. Table 4
shows the transition of budgets on nanoscale science
research and Table 5 shows the budget for hydrogen
research.
Of the total of 200 million dollars for nanoscale scientific research in FY2004, 74 million dollars were spent on
materials science and engineering research and 84 million
dollars on the construction of nanoscale scientific research
centers. The expenses on materials research related to the
Table 1 DOE-BES expenses in FY2004 ($1,000). 5)
Field of Science
• Materials Sciences and Engineering
• Chemical Sciences, Geosciences, and
Energy Biosciences
• Construction
Total
FY2004
558,831
213,778
218,653
991,262
Table 2 Expenses in the materials sciences and
engineering field of DOE-BES in FY2004 ($1,000). 5)
Field of Science
• Materials Sciences and Engineering
Research
• Facilities Operations
Total in the materials sciences and engineering field
FY2004
260,693
298,138
558,831
Fig. 1 Breakdown of research expenses in DOE - BES,
Materials Science (FY2006 requested budget). 5)
Table 3 Breakdown of DOE-BES materials research expenses ($1,000). 5)
Material Research
Neutron and X-ray Scattering
Experimental Condensed Matter Physics
Materials Chemistry
Structure and Composition of Materials
Physical Behavior of Materials
Condensed Matter Theory
Mechanical Behavior and Radiation Effects
Synthesis and Processing Science
Engineering Research
The Center for Nanoscale Materials
Experimental Program to Stimulate Competitive Research (EPSCoR)
Instrumentation for the Spallation Neutron Source
Transmission Electron Aberration Corrected Microscope (TEAM)
Neutron Scattering Instrumentation at the High Flux Isotope Reactor
Linac Coherent Light Source (LCLS)
Nanoscale Science Research Centers
Total of Research Budgets in Materials Science and Engineering Field
FY 2004
44,928
42,631
40,338
22,833
22,148
18,126
13,444
12,710
10,975
10,000
7,673
7,387
3,100
2,000
2,000
400
260,693
%
17.2
16.4
15.5
8.8
8.5
7.0
5.2
4.9
4.2
3.8
2.9
2.8
1.2
0.8
0.8
0.2
100
Table 4 Transition of budgets on nanoscale science research ($1,000). 5)
Expenditure Item in Nanoscale Science
Research
Materials Sciences and Engineering
Chemical Sciences, Geosciences, and Energy Biosciences
Capital Equipment
Argonne, Center for Nanoscale Materials
Nanoscale Science Research Centers
Basic Expenses (All Centers)
Construction Expenses
BNL, Center for Functional Nanomaterials
LBNL, Molecular Foundry
ORNL, Center for Nanophase Materials Sciences
SNL/A and LANL, Center for Integrated Nanotechnologies
Total Budget in BES Nanoscale Science
2004 Estimated
2005 Budget
2006 Requested
73,501
27,833
66,995
28,360
112,632
26,914
10,000
12,000
14,000
2,982
1,996
0
0
34,794
19,882
29,674
198,666
18,317
31,828
17,669
30,650
207,815
36,553
9,606
0
4,626
204,331
Table 5 Transition of budgets by President in hydrogen initiative research ($1,000). 5)
Field of Science
Research
Materials Sciences and Engineering
Chemical Sciences, Geosciences, and Energy Biosciences
Total
2004
Estimated
3,055
4,655
7,710
2005
Budget
14,761
14,422
29,183
2006
Requested
16,600
15,900
32,500
41
hydrogen initiative were 3 million dollars in FY2004 and
the DOE is now requesting a large increase in budget for
the future.
The three institutes in Lawrence Livermore, Sandia, and
Los Alamos are large, with budgets exceeding one billion
dollars, and are mainly engaged in weapons research. Most
DOE research institutes conduct materials research. However, the most active institutes are the Ames Institute,
3. Research institutions for materials research in DOE
Table 6 Classification of DOE laboratories by role.
As Figure 2 shows, the DOE has 14 public research
institutes throughout the United States,6) which are classified by role as shown in Table 6. Table 7 lists the year of
establishment, administration, budget, and number of
researchers in these DOE research institutes.
Classification
Multi-program
Materials
High Energy
Physics
Nuclear Physics
Weapons
Fusion
Energy
Efficiency
Nuclear Energy
Research Institute
Argonne
Brookhaven
Oak Ridge
Lawrence Berkeley
Pacific Northwest
Ames
Fermi,
Stanford: At the Stanford Linear
Accelerator Center, X-ray facilities
were recently added to High
Energy Physics.
Thomas Jefferson,
(Also at Brookhaven)
Lawrence Livermore
Sandia (Albuquerque and
California)
Los Alamos
Princeton
National Renewable Energy
Laboratory
Idaho
Fig. 2 Locations of DOE research institutes. 6)
Table 7 FY2004 budgets of DOE research institutes and the numbers of researchers.
Research Institute
Ames Laboratory
Administration
Budget (FY2004)
Researchers/Total
1947
Iowa State Univ.
$30 million
240/420
1940s
University of Chicago
$500 million
1200/4,000
Stony Brook Univ. –
Battelle
Bechtel – BWX Tech. –
INRA
$436 million
(2003)
Approx. 5,000 /7,000
$800 million
8,000 total
1931
Univ. of California
$500 million
3,800/6843
1952
Univ. of California
$1.6 billion
8,000 total
1943
Univ. of California
$2.2 billion
7,500/10,700
1910
DOE direct control
$926 million
880/1100
National Renewable Energy
Laboratory
1974
Midwest Research
Institute – Battelle –
Bechtel
$230.1 million
(2003)
?
Oak Ridge National Laboratory
(ORNL)
1942
Univ. of Tennessee –
Battelle
$1.0 billion
1,500/3,800 + over
3,000 visiting
researchers
1965
Battelle
$650 million
3,900
1951
Princeton Univ.
$75.5 million
168/427
Sandia National Laboratories (SNL)
1945
Sandia Corp.
(Lockheed Martin)
$2.2 billion
8,600 total
(all locations)
Stanford Linear Accelerator Center
(SLAC)
1960
Stanford Univ.
$184 million
(2000)
1,314 total (FY 2000)
Argonne National Laboratory
(ANL)
Brookhaven National Laboratory
(BNL)
Idaho National Engineering and
Environmental Laboratory (INEL)
Lawrence Berkeley National
Laboratory (LBNL)
Lawrence Livermore National
Laboratory (LLNL)
Los Alamos National Laboratory
(LANL)
National Energy Technology
Laboratory
Pacific Northwest National
Laboratory (PNNL)
Princeton Plasma Physics
Laboratory (PPPL)
42
Established
1946
1949
Table 8 Nanomaterials and nanotechnology research centers of DOE.
Center (Operator)
Center for Functional
Nanomaterials
(Brookhaven Nat’l Lab)
Center for Integrated
Nanotechnologies
(Sandia Nat’l Lab and Los
Alamos Nat’l Lab)
Center for Nanophase
Materials Sciences
(Oak Ridge Nat’l Lab)
Center for Nanoscale
Materials
(Argonne Nat’l Lab)
Molecular Foundry
(La2)rence Berkeley Nat’l Lab)
Field and Purpose
Six Scientific Themes:
1) Strongly Correlated Oxides, 2) Magnetic Nanoassemblies, 3) Nanoscale Catalyst
Materials, 4) Charge Injection and Transport in Nanoscale Materials
5) Nanostructured Organic Films; Structure and Self-assembly
6) Applications of Functional Nanomaterials
Five Scientific Thrusts: (95,000 ft2)
1) Nano-Bio-Micro Interfaces, 2) Nanophotonics and Nanoelectronics
3) Complex Functional Nanomaterials, 4) Nanomechanics
5) Theory and Simulation
Seven Scientific Thrusts: (80,000 ft2)
1) Macromolecular Complex Systems, 2) Functional Nanomaterials
3) Nanoscale Magnetism and Transport, 4) Catalysis and Nano Building Blocks,
5) Nanofabrication, 6) Theory, Modeling, and Simulation
7) Nanoscale Imaging, Characterization, and Manipulation
Eight Primary Research Themes: (24,000 ft2)
1) Bio-Inorganic Interfaces, 2) Complex Oxides, 3) Nanocarbon, 4) Nanomagnetism,
5) Nanophotonics, 6) Theory and Simulation, 7) Nanopatterning, 8) X-ray Nanoprobe
*Six facilities: (94,500 ft2) *Affiliated Foundry Laboratories
1) Inorganic Nanostructures Facility, 2) Organic, Polymer, and Biopolymer
Nanostructures Facility, 3) Nanofabrication Facility, 4) Biological Nanostructures
Facility, 5) Imaging and Manipulation Facility, 6) Theory of Nanostructures Facility
Argonne National Laboratory
Lawrence Berkeley
National Laboratory
Nanoscale materials center
(Advanced photon source: Thirdgeneration synchrotron institute.
High-strength pulse neutron source)
Molecular foundry
(Advanced Light Source:
Second-generation
synchrotron institute)
Brookhaven National Laboratory
Nanofunctional materials center
(Synchrotron orbital radiation
institute. Laser beam
acceleration institute.)
Nanotissue materials
science center
(Spallation neutron
generation institute)
Sandia National Laboratory
Los Alamos National Laboratory
Oak Ridge National Laboratory
Comprehensive nanotechnology
center (Composite Semiconductor
Laboratory, Los Alamos Neutron
Science Center, and High
Magnetic Field Laboratory)
Fig. 3 Locations of DOE nanomaterials and nanotechnology centers.
which is mainly engaged in materials research and the
Argonne, Brookhaven, Oak Ridge, and Lawrence Berkeley
institutes which are multi-program institutes with active
R&D initiatives in many fields. Pacific Northwest, one of
the multi-program research institutes, specializes in chemistry and is involved in relatively little materials research.
The Oak Ridge Institute has a large budget ($1 billion) and
a large personnel (1,500 researchers) whereas the Ames
Institute is comparatively small compared to other DOE
research institutes, with a budget of 300 million dollars and
a staff of 240 researchers.
Apart from the National Energy Technology Laboratory,
all DOE research institutes are operated either by universities or private companies.
According to the mid-term goals set in 2003, the DOE is
constructing five nanotechnology and nanomaterials
research centers. Table 8 lists the fields and the purpose of
research and Figure 3 shows the locations of the research
43
Table 9 Materials research at DOE research institutes.
Research Institute
Ames Laboratory
Argonne Nat'l Lab
Brookhaven Nat'l
Lab
Lawrence Berkeley
Nat'l Lab
Lawrence Livermore
Nat'l Lab
Materials Research
Division
Materials and Engineering
Physics and others
(3 of 10 divisions)
Materials Science and
others(3 of 22 divisions)
others
(4 of 13 divisions)
others
(2 of 18 divisions)
Chemistry and Materials
Science and others
(2 of 11 divisions)
Los Alamos Nat'l
Lab
Technology and others
(2 of 21 divisions)
Oak Ridge Nat'l Lab
Materials Sciences and
others
(3 of 11 divisions)
Pacific Northwest
Nat'l Lab
Energy and others
(2 of 7 divisions)
Sandia Nat'l Lab
Materials and Process
Science and others
(2 of 13 divisions)
Main Materials Research
Experimental and theoretical research on rare earth elements in novel
mechanical, magnetic, and superconducting materials
Research on high-temperature superconductivity, polymeric
superconductors, thin-film magnetism, and surface science
Research problems such as high-temperature superconductivity,
magnetism, structural and phase transformations in solids, and
polymeric conductors
Research on laser spectroscopy, superconductivity, thin films,
femtosecond processes, biopolymers, polymers and composites,
surface science, and theory
Research on metals and alloys, ceramics, materials for lasers,
superplasticity in alloys, and intermetallic metals
Research on electronic materials, the theory of evolving
microstructures, and plasma immersion processes for ion-beam
processing of surfaces for improved hardness, corrosion resistance, and
wear resistance
Basic research which underpins the energy efficiency program in
superconductivity, magnetic materials, pulsed laser ablation, thin films,
lithium battery materials, thermoelectric materials, surfaces, polymers,
structural ceramics, and alloys
Research on stress-corrosion cracking of metals and alloys, hightemperature corrosion fatigue of ceramic materials, and irradiation
effects in ceramic materials
Processing and properties for sol-gel chemistry of ceramic coatings,
the development of nanocrystalline materials, adhesion and wetting of
surfaces of metals, glass, and ceramic materials
centers. At these five research centers, huge research facilities using synchrotron radiation or neutron beams will commence service by the end of 2008.
Table 9 lists the fields of materials research of the DOE
research institutes. Many institutes, including Ames and
Oak Ridge, conduct materials research.
ogy Program promotes innovative technological progress
through joint investments in research by private companies.
Figure 4 shows the FY2005 budgets of NIST. The total
budget is 858 million dollars, of which the NIST research
institute expenses account for the greatest amount with 373
million dollars, followed by the technical service budget in
industry with 244 million dollars. The breakdown is 137
million dollars for the Advanced Technology Program and
4. Main materials research organizations other than
DOE
The National Institute of Standards and Technology
(NIST) is a federal governmental organization, established
under the Department of Commerce in 1901. The mission
of NIST is to develop technologies, measuring methods,
and standards necessary in industry to improve productivity, smoothen trade, and improve the quality of life.4)
NIST achieves its mission through NIST research institutes, Baldrige National Quality Program, Manufacturing
Extension Partnership, and Advanced Technology Program. The NIST research institutes are developing technical infrastructure and conducting standardization R&D in
U. S. heavy industry. The Baldrige National Quality Program gives awards every year to encourage progress by
U.S. manufacturing companies, service companies, educational institutes, and medical institutes. The Manufacturing
Extension Partnership is a nationwide network of local centers that provide small and medium-sized companies with
technologies and business support. The Advanced Technol44
Fig. 4 FY2005 budgets of NIST. 4)
Table 10 Materials research at NIST research institutes. 4)
Materials Science & Engineering Laboratory
–Ceramics Div.
Electronic & Optoelectronic Materials
Characterization Methods
Nanotribology
Data and Standards Technology
Nanomechanical Properties
–Materials Reliability Div.
Microstructure Sensing Group, etc.
–Metallurgy Div.
Electrochemical Processing
Magnetic Materials
Materials Performance
Structure and Characterization
Metallurgical Processing
–Polymers Div.
–NIST Center for Neutron Research (NCNR)
–Center for Theoretical and Computational Materials
Science
Chemical Science & Technology Laboratory (CSTL)
–Biotechnology Div.
DNA Technologies Group
Bioprocess Measurements Group
Structural Biology Group
Cell & Tissue Measurements Group
–Process Measurements Div., etc.
Advanced Technology Program (ATP)
–Chemistry & Life Sciences Office (CLSO)
Chemistry & Materials Group
Life Sciences Group
–Economic Assessment Office
–Information Technology & Electronics Office, etc.
108 million dollars for the Manufacturing Extension Partnership. The total number of staff at NIST is about 3,000.
Table 10 provides materials research information at the
NIST research institutes. NIST is researching ceramics,
metals, and polymers mainly at their Materials Science &
Engineering Laboratory.
Other research institutes, apart from those at the DOE
and NIST are those of the military forces (Navy, Army, and
Air Force) and NASA, as outlined in Table 11.7)-11) These
institutes are involved in the metals and ceramics, and
polymers research for practical uses.
5. Conclusion
1) In the United States, basic research on materials is mainly funded by the Department of Energy – Basic Energy Sciences, Materials Science and the National Science Foundation – Mathematical and Physical Sciences, Materials
Research.
2) The Department of Energy has 14 research institutes.
However, much of the basic research is also being done at
the Ames Institute which is mainly engaged in materials
research and at the Argonne, Brookhaven, Oak Ridge, and
Lawrence Berkeley institutes which are multi-program
institutes.
3) The Department of Energy is constructing five nanotechnology and nanomaterials research centers using synchrotron radiation or neutron beams. These will enter service by the end of 2008.
4) The National Institute of Standards and Technology
under the Department of Commerce has a mission of developing technologies, measuring methods, and standards. The
Materials Science & Engineering Laboratory is leading
research on ceramics, metals, and polymers.
Tables 11 Public research institutes engaged in materials research, other than DOE and NIST. 7) - 11)
Research Institute/
Supervising Government Office
US Naval Research Lab.
Department of the Navy7)
Army Research Laboratory
U.S. Army Research Office8)
Air Force Research Laboratory9)
NASA
Ames Research Center10)
NASA
Glenn Research Center
(Former Lewis Research Center)11)
Established
No. of Researchers
Budget
Materials Research
Related Division
1923
Civilian 2,700
$842 million
(FY2004)
Component Technology,
Nanoscience Institute, etc.
(Total number of research
divisions: Unknown)
R&D across fields to apply new
materials, new technologies, and
marine, space, and aeronautic
technologies to marine purposes
Materials Science
(1 of 12 divisions)
Development of materials having
higher or special performance
Materials and
Manufacturing
(1 of 10 divisions)
Thermal Protection
Materials,
Nanotechnology Branch
divisions: Unknown)
Metals Technologies
Branch
divisions: Unknown)
Development of low-cost military
technologies in space and
aeronautics
1917
Civilian 7,500
Unknown
1997
9,500
$3.8 billion
1939
≥420
$30 million
1941
3,300
Unknown
Outline
Development of new technologies
Space and aeronautic research
45
References
1) Web page of DOE
http://www.energy.gov/engine/content.do
2) Web page of the DOE Basic Energy Science Office
http://www.er.doe.gov/production/bes/BES.html
3) Web page of NSF
http://www.nsf.gov/
4) Web page of NIST
http://www.nist.gov/
5) FY 2006 BES Budget Request (February, 2005)
http://www.er.doe.gov/production/bes/archives/
budget/BES_FY2006budget.pdf
46
6) Web page of DOE (Map of National Labs)
http://www.er.doe.gov/sub/organization/map/
static-map.JPG
7) Web page of the US Naval Research Laboratory
http://www.nrl.navy.mil/
8) Web page of the Army Research Office
http://www.aro.ncren.net/
9) Web page of the Air Force Research Laboratory
http://www.ml.afrl.af.mil/
10) Web page of NASA Ames Research Laboratory
http://www.external.ameslab.gov/
11) Web page of NASA Glenn Research Laboratory
http://www.nasa.gov/centers/glenn/about/index.html
01 Public Research Institutes for Materials Research in Japan, USA and EU
Section 3. Germany
1. Structure of technical institutions in Germany
Figure 1 shows the structure of technical institutes in
Germany. Max-Planck-Gesellschaft zur Förderung der
Bundeskanzler
Federal Prime Minister
Bundeskanzleramt (BK)
Federal Prime Minister’s Office
¨ Bildung und Forschung (BMBF)
Bundesministerium fur
Federal Ministry of Education and Research
Deutche Forchungs-gemeinschaft e.V. (DFG)
German Research Association
¨
Max-Planck-Gesellschaft zur Forderung
der Wissenschaften e. V. (MPG)
Max-Planck Academic Promotion Association
Fraunhofer-Gesellschaft zur Forderung der angewandten Forchung e.V. (FhG)
Fraunhofer Applied Research Promotion Association
Hermann von Heimholtz-Gemeinschaft Deutscher Forschungszentren (HGF)
Helmholtz German Research Center
Wissenschftsgemeinschaft Gottfried Wilhelm Leibniz (WGL)
Union of Gottfried Wilhelm Leibniz Academy
¨ Wirtschaft und Technologie (BMWi)
Bundesministerium fur
Federal Ministry of Economy and Technology
Fig. 1 Structure of technical institutes in Germany.
Wissenschaften e.V. (hereafter, the Max Planck Society),
the Fraunhofer-Gesellschaft zur Forderung der angewandten Forchung e.V. (hereafter, the FraunhoferGesellschaft), and the Hermann von Helmholtz-Gemeinschaft Deutscher Forschungszentren (hereafter, the
Helmholtz Association) belong to the Federal Ministry of
Education and Research. Materials research by public
research institutes is mainly done at the laboratories of the
Max-Planck Society, the laboratories of the FraunhoferGesellschaft, and at the Forschungszentrum Karlsruhe, all
of which belong to the Helmholtz Association. The Federal
Institute for Materials Research and Testing (BAM) conducts materials testing and research and belongs to the Federal Ministry of Economy and Technology.
2. Public research institutes of Germany
Table 1 lists representative public institutes of materials
research in Germany.1) - 4) Established in 1948, the MaxPlanck Society has a total of 78 research institutes, including the Institute of Metals (Max-Planck-Institut für Metallforschung) and the Institute of Iron and Steel (Max-PlanckInstitut für Eisenforschung GmbH). The Max-Planck Society is a comprehensive academic organization covering not
Table 1 Number of researchers and research budgets of German public research institutes.
Name of Institute
Staff
Established
(No. of Researchers)
Budget
Main Research
Ratio of
National and
Federal Grants
Outline
Max Planck
1948
12,300
(4,200)
1,330 mil.
Fundamental
research
About 95%
Subdivided into 78 laboratories by field (polymers,
metals, iron and steel, physics, and history). Five of
them specialize in materials research.
Fraunhofer
1949
12,500
1,000 mil.
Applied
research
About 40%
More than 80 research units, including the 57
Fraunhofer laboratories. Materials research at six
research units, including Manufacturing Engineering
and Applied Materials Research
Karlsruhe
1956
3,800
(1,420)
294 mil.
Fundamental/
Applied
research
About 70%
Invested by the Federal government (9/10) and by
the Baden-Württemberg State (1/10). Materials
research at two laboratories: Nanotechnology and
Materials Research (22 laboratories in total)
Fundamental
testing
About 80%
Serves as a basic research institute and as a test
institute. Mainly engaged in the fabrication of standard
samples and the survey of fractured materials.
BAM
1956
1,640
(About 700)
113 mil.
(FY2003 budget)
47
only science, but also biology (426 divisions), physics (379
divisions), astronomy and astrophysics (105 divisions), history and social science (98 divisions), as well as chemistry
(96 divisions). This Society receives the largest grant of
about 95% from the Federal government of all public
research institutes in Germany and conducts mainly fundamental research. The percentage break down of expenditures from the FY2004 budget of the Association are 40%
for labor, 21% for maintenance, and 13% for projects as
shown in Figure 2.
Figure 3 compares the funds and research themes in the
Max-Planck Society. Since the Fraunhofer-Gesellschaft
mainly conducts applied research, the share of public
investment by the Federal government is no more than
about 40%. Figure 4 shows the transition of income sources
of the Fraunhofer-Gesellschaft over time. Income from
industry has almost doubled in the last decade. Figure 5
shows the number of personnel at the FraunhoferGesellschaft by research field: the Materials and Components field ranks third with about 1,300 staff, after the
Information and Communication Technology field and the
Microelectronics field. Figure 6 shows the breakdown of
Personnel costs
40%
Allocations
7%
8%
Construction expenditure
11%
13%
21%
Other investments
Project funding
Other operating coasts
Fig. 5 Number of personnel at Fraunhofer-Gesellschaft by research field
(2003). 2)
Fig. 2 Expenditure by the Max-Planck Society in FY2004. 1)
Fig. 6 Breakdown of income sources of Fraunhofer-Gesellschaft. 2)
Fig. 3 Comparison of research funds and themes between Max-Planck
Society and Fraunhofer-Gesellschaft. 2)
Table 2 Percentages of research fields
of Forschungszentrum Karlsruhe. 3)
Research Field
Structure of matter
Structure of matter
Earth and Environment
Sustainability and Technology
Atmosphere and Climate
Health
Biomedical Research
Medical Engineering
Energy
Nuclear Fusion
Nuclear Safety Research
Efficient Energy Conversion
Key Technologies
Microsystem Technologies
Nanotechnology
Scientific Computing
Fig. 4 Income sources of Fraunhofer-Gesellschaft. 2)
48
Percentage
10%
25%
15%
25%
25%
income sources of the Fraunhofer-Gesellschaft. The
research expenses are equally split between basic funding,
through contracts with industry, and the federal and local
governments.
The Forschungszentrum Karlsruhe was established in
1956. Grants account for about 40%, of which 90% come
from the federal government and 10% from the BadenWürttemberg State. The Forschungszentrum Karlsruhe is
working hard not only on basic research but also on applied
research, and has about 650 joint projects with industry.
Table 2 shows the percentage break down of research fields
of the Forschungszentrum Karlsruhe. Earth and Environment, Energy, and Key Technologies (including Nanotechnology) account for 25% each.
BAM was reorganized into the present laboratory organization in 1954. Serving as both a basic research institute
and as a testing institute, BAM has produced approximately 450 papers, 900 lectures (including short courses), and
6,000 test reports. The fabrication of standard samples and
survey of accidents such as fractures are important components of their work. In the field of nanotechnologies, BAM
evaluates nanomaterials. The total number of personnel is
1,670, including 1,174 permanent staff (60%).
About 200 research projects are currently in progress at
BAM. As Table 3 shows, they can be classified into five
fields: Technical and public safety, Materials technologies,
Analytical chemistry, Technical and scientific service function, and Environmental compatibility. Technical and public safety accounts for as much as 40% of the total number
of researchers, followed by materials technologies with
20%. Table 4 gives the percentages of researchers by activities: 59% are in research and development, 20% in advice
and information, and 14% in testing, analysis, and
approval.
Table 3 Percentages of BAM researchers by field. 4)
Research Field
Technical and public safety
Materials technologies
Analytical chemistry
Technical and scientific services
Environmental compatibility
Researchers
41%
20%
17%
12%
10%
Table 4 Percentages of researchers at BAM by work. 4)
Activities
Research and development
Advice and information
Testing, analysis, approval
Infrastructure
Researchers
59%
20%
14%
7%
3. Materials research by German public research institutes
Tables 5 to 8 show the materials research divisions of
the Max-Planck Society, the Fraunhofer-Gesellschaft, the
Forschungszentrum Karlsruhe, and BAM.
The Max-Planck Society conducts research on metals,
iron and steel, colloids, biomaterials, nanomaterials, and
polymers at five laboratories. The Fraunhofer-Gesellschaft
conducts materials research at the Materials and Components Institutes and the Nanotechnology Institutes. The
Forschungszentrum Karlsruhe, organized from 11 research
center programs and 22 laboratories, conducts R&D on
nanotechnologies and materials structures. BAM specialTable 5 Materials research by Max-Planck Society. 1)
Max-Planck-Institut für Metallforschung
– Materials synthesis and microstructure design
– Structural materials and thin film systems
– Theory of inhomogeneous condensed matter
– Metastable and low-dimensional materials
– Mechanics and mechanical properties of thin films,
dynamic characteristics of smart materials,
materials failure mechanisms
– Phase transformations; thermodynamics and
kinetics
– Microstructures and interfaces
– Modern magnetic materials: analysis and synthesis
of modern magnetic materials
– Physical understanding of the regulation of adhesive
cell contacts and cell mechanics; consequences for
diseases
Max-Planck-Institut für Eisenforschung GmbH
– Computational materials design
– Interface chemistry and surface engineering
– Materials technology
– Microstructure physics and metal forming
– Metallurgy and process technology
Max-Planck-Institut für Kolloid und
Grenzflächenforschung
– Colloid Dept.
Polymer dispersions
Bioorganic-synthetic hybrid polymers, others
– Theory Dept.
Molecular motors and active systems
Membrane adhesion, polyelectrolytes, others
– Interfaces
(Quasi) Planar interfaces-fluid interfaces
Non-planar interfaces, solid interfaces, others
– Biomaterials
Microscopic fracture and deformation mechanisms of mineralized tissues
Computer modeling of mechanics, growth and
adaptation of biomaterials
Biotemplating
Microscopic fracture and deformation mechanisms of mineralized tissues, others
Max-Planck-Institut für Mikrostrukturphysik
– Experimental Department 1
Correlations of magnetic film properties with
structure and morphology, others
– Experimental Department 2
Quantum structures, ordered porous materials
nanowires, nanoengineering of functional oxides
0D and 1D nanomaterials, others
– Theory Department
Magnetic properties and spin-dependent
scattering in ferromagnets, others
Max Planck Institute for Polymer Research
– Polymer physics
– Material science
– Polymer theory
– Synthetic chemistry, others
49
Table 6 Materials research by Fraunhofer-Gesellschaft. 2)
Materials and Components Institutes (11 units)
– Applied polymer research
– Ceramic technologies and sintered materials
– Manufacturing engineering and applied materials
research
– Mechanics of materials
– Silicate research, others
Nanotechnology Institutes (17 units)
– Ceramic technologies and sintered materials
– Interfacial engineering and biotechnology
– Environmental, safety and energy technology, others
Polymer Surfaces Institutes (7 units)
– Electron and plasma technology, others
Surface technology and photonics (6 units)
– Applied optics and precision engineering
– Electron beam and plasma technology
– Laser technology
– Material and beam technology
– Physical measurement techniques
– Thin films and surface engineering
Table 7 Materials research by Forschungszentrum Karlsruhe. 3)
Research Center Programs (11 programs)
– Nanotechnology
Electron transport in nanoscale systems
Nanostructured materials and low dimensional
systems with new functionalities
– Microsystem technologies
Manufacturing / system integration
materials development, others
– Structure of matter
– Sustainability and technology
– Scientific computing, others
Scientific Institutes (22 laboratories)
– The Institute of Nanotechnology
Molecular electronics
Nanostructured materials
Structure / property correlations in nanoscale
systems
– The Institute for Materials Research
Applied materials physics
Materials and structural mechanics
Materials processing technology
– The Institute for Solid-State Physics
Unconventional superconductivity close to the
transition to magnetic order, others
– The Institute for Synchrotron Radiation
– The Institute for Instrumental Analysis, others
50
Table 8 Materials research by BAM. 4)
Analytical chemistry, reference materials
Chemical safety engineering
Containment systems for dangerous materials
Environmental compatibility of materials
Materials engineering, safety of structures
Performance of polymeric materials
Materials protection, non-destructive testing
Interdisciplinary scientific and technological operations
izes in materials research, testing, and accident surveys.
4. Conclusion
In Germany, materials research is conducted mainly at
the Max-Planck Society, Forschungszentrum Karlsruhe,
and the Fraunhofer-Gesellschaft. The former two organizations specialize in fundamental research, while FraunhoferGesellschaft mainly conducts applied research. Another
influencial organization, BAM, specializes in testing and
safety. Applied research activities tend to be financed by
the private sector.
References
1) Web page of the Max-Planck Society
http://www.mpg.de/
2) Web page of the Fraunhofer-Gesellschaft
http://www.fraunhofer.de/fhg/EN/index.jsp
3) Web page of the Forschungszentrum Karlsruhe
http://www.fzk.de/
4) Web page of the Federal Institute for Materials Research and
Testing (BAM)
http://www.bam.de/
Section 4. France
Tomoaki Hyodo
1. Public materials research institutes of France
The budget of the French Space Development Organization (CNRS: Centre National de la Recherche Scientifique)
accounts for about 25% of the total civil R&D budget,
which amounts to 90,400 million dollars, followed by independent research institutes, the French Space Agency
(CNES) with about 1% and the Atomic Energy Agency
(CEA) with about 10%.1), The research systems of CNRS
and CEA, regularly publish papers on the subject of materials. These institutions` research personnel and budget are
compared in Table 1, not inclusive of CNES. CNRS and
CEA conduct fundamental and applied research respectively.
2. Materials research by CNRS
CNRS was established in 1939 and has been part of the
Ministry of Research (MRT: Ministére de la Rechererche et
de la Technology) since 2000. Figure 1 shows the income
sources of CNRS. The subsidies from the Ministry of Technology and Research account for about 77% and the VAT
compensatory subsidies account for 11%.The CNRS
receives funding from other institutions through research
contracts and royalties of patent rights, which account for
about 12%.
Figure 2 shows the percentage breakdown of expenses
by CNRS. Salaries for research units (62%) account for the
largest share of the organization’s expenses. About 24% of
the expenses are spent on laboratories and research programs, and 14% for support work.
Figure 3 shows the CNRS organization. CNRS is organized into eight research divisions (Engineering Sciences
Table 1 Numbers of researchers and budgets of CNRS and CEA in France. 1), 2)
Research Institute
No. of
Budget
Main Research
Researchers (¥100 mil.)
CNRS (Centre National de la
Recherche Scientifique)
26,000
3,149
Fundamental
CEA (Commissariat à
l'Energie Atomique)
15,024
3,645
Applied
1. Government subsidies: 1,938.753 million euros
2. VAT compensatory subsidies: 278.637 million euros
3. Own funds: 315.389 million euros
Fig. 1 CNRS income sources (2002). 1)
Remarks
8 research divisions subdivided into 1,260 small units and
18 regional offices. Materials research at about 90 units.
Three fields: Energy, IT and health technologies,
and military
1. Activity conducted by the research units:
284.258 million euros
2. Common actions and backup functions, support for
research: 64.244 million euros
3. Collective investment: 108.677 million euros
Fig. 2 Breakdown of CNRS expenses (2002). 1)
51
and other divisions). These research divisions are subdivided into 1,256 smaller units. Table 2 lists the number of
units classified by field. About 90 research units have
matériaux (material), métallurgie (metallurgy), nano,
polymères (polymer), céramiques (ceramics), or molécule
(molecule) in their names. From this, about 7% of the
research units are estimated to be involved in the research
of materials.
References
1) Web page of CNRS: http://www.cnrs.fr/
2) Web page of CEA: http://www.cea.fr/
3. Materials research by CEA
CEA conducts applied R&D in their civil and military
research units.2) Table 3 shows the CEA income data in
2003. The share of subsidies is approximately 60% for civil
research and 98% for military research. Of about 40
research divisions, seven divisions relate to materials
research.
Board of Trustees
National
Committee on
scientific
research
Chairman
Directorate-General
Ethics
Committee
Mission to improve
the role of women
at the CNRS
Mediator
Committee for the
History
of
the
CNRS
Studies and
Programming
Department
Department
in charge of
Relations with
Higher Education
Organizations
International
Relations
Division
Scientific Departments
Nuclear
and Particle
Physics
IN2P3
Chemical
Sciences
Physical
Sciences and
Mathematics
Communication
and Information
Science and
Technology
Enginearing
Sciences
Life
Sciences
Humanities
and Socil
Sciences
Sciences of
the Universe
and INSU
Office
of the
SecretaryGeneral
Industrial
Affairs
Delegation
Principal
Accounting
Agency
Scientific
and Technical
Infomation
Delegation
Detense and
Safety Official
Regional
Offices
Research Units
Secondary
Accoutants
Hygiene and
Security
Service
Fig.3. CNRS organization chart. 1)
Table 2 Numbers of research units by field. 1)
Division
Nuclear and Particle Physics – IN2P3
Physical Sciences and Mathematics
Communication and Information
Engineering Sciences
Chemical Sciences
Sciences of the Universe
Life Sciences
Humanities and Social Sciences
Outside departments and institutes
Total
Units
21
150
83
Table 3 CEA income in FY2003. 2)
Item
Amount
1 mil.
Percentage
%
Civil (Financement Civil)
Subsidies (Subvention)
97
202
105
243
344
11
1,256
For research (Recherche)
486
31.9
For industry (Industrie)
414
27.2
485
31.9
138
9.1
1,523
100.0
1,265
98.0
25
2.0
Total of military
1,290
100.0
Total
2,813
100.0
External funds (Recettes
externes)
Other
Total of civil
Military (Financement Défense)
Subsidies (Subvention)
Other
52
Section 5. Spain
Tomoaki Hyodo
1. Profile of CSIC
CSIC is Spain’s largest public institute for basic
research, supervised by the Ministry of Education and Science (Ministerio de Educación y Ciencia).1) This institute
consists of 120 centers as listed in Table 1. Among the public research institutes of Spain, CSIC specializes in basic
research whereas Centro de Investigaciones Energéticas,
Medioambientales y Tecnológicas (CIEMAT) specializes
in applied research.
CSIC operates according to the basic plan, called
“National Plan for Scientific Research and Technological
Development”, which is enacted every few years. Since
nanotechnology research began quite recently, its activities
are not based on the National Act, but will be included in
Table 1 Number of research centers in each division of CSIC. 1)
Research Division
Humanities and Social Sciences
Biology and Biomedicine
Natural Resources and Environment
Agricultural Sciences
Physics
Material Science and Technology
Food Science and Technology
Chemistry
Other
Total
Centers
18
18
17
12
19
9
5
11
11
120
the next national plan. The National Plan is determined by
12 members of a commission, of whom 6 or 7 are scientists
(university professors or researchers at private enterprises).
The number of personnel at CSIC is 11,115 in total, of
whom 2,063 are permanent staff. The general budget of
CSIC is 110.9 million euros, of which about 11.6 million
euros are spent on materials research.
2. Materials research at CSIC
At CSIC, the nine laboratories listed in Table 2 conduct
materials research. The total number of personnel including
postdoctoral researchers is 1,282. The map of Spain in Figure 1 shows the locations of the laboratories: five for materials research in Madrid and one in each of Barcelona,
Zaragoza, Seville, and San Sebastian.
Table 3 gives the characteristics of the nine laboratories.
Of the five laboratories in Madrid, four (CENIM, ICV,
ICTP, and IETCC) are involved in research of metals,
ceramics, polymers, and structural materials. These laboratories support the economy of Spain through close links
with industry. The laboratories in Barcelona (ICMAB),
Madrid (ICMM), and Seville (ICMS) are more oriented
toward basic research, and those in Barcelona and Seville
are closely linked with universities. Both the laboratories in
Zaragoza (ICMA) and San Sebastian (UFM) also have
close links with universities.
Table 4 lists the numbers of personnel at the nine laboratories. Among the seven laboratories which give the number of personnel on their Web page, ICMS (Seville) has the
Table 2 CSIC laboratories engaged in materials.
i)
ii)
iii)
iv)
v)
vi)
vii)
viii)
ix)
Centro Nacional de Investigaciones Metalúrgicas
Instituto de Cerámica y Vidrio
Instituto de Ciencia de Materiales de Aragón
Instituto de Ciencia de Materiales de Barcelona
Instituto de Ciencia de Materiales de Madrid
Instituto de Ciencia de Materiales de Sevilla
Instituto de Ciencia y Tecnología de Polímeros
Instituto de Ciencias de la Construcción “Eduardo Torroja”
Instituto de Física de Materiales
(CENIM)
(ICV)
(ICMA)
(ICMAB)
(ICMM)
(ICMS)
(ICTP)
(IETCC)
(UFM)
Madrid
Madrid
Zaragoza
Barcelona
Madrid
Sevilla
Madrid
Madrid
San Sebastian
53
3.1 Materials Science Institute of Barcelona (ICMAB)2)
The Materials Science Institute of Barcelona has 194
personnel (including 40 full-time researchers). The total
budget is 7.59 million euros. Of this budget, 58% comes
from subsidies, 13% from the National Plan, 10% from
competitive grants, and 5% from companies.
The research activities of the Barcelona Institute are
evaluated by the International Scientific Committee and
FAME as external organizations. Through an interview
with the director of each CSIC laboratory, the former takes
one week every four years to scrutinize the contents of
research and issues an evaluation report. FAME, initiated
in 2004 and organized from 20 groups in European countries, discusses Interconnection and Integration and spends
5 million euros on Integration with representatives from the
countries at the same table.
The Barcelona Institute established a new organization
called MATGAS. CSIC’s mission is basic research but
MATGAS will focus on applied research (Gases and Materials) in a new building next to the Barcelona Institute.
With 66% investment from a private company, Carburos
Metalicos (60% investment from U.S. Air Products and
San Sebastian
Zaragoza
Barcelona
Madrid
Fig. 1 Locations of CSIC laboratories for materials research. 1)
fewest with 69 and ICMM (Madrid) has the most with 340.
CENIM (Madrid: metal research) and IETCC (Madrid:
steel structure research) have many research assistants that
are not considered technicians. The seven laboratories with
published numbers of personnel feature a high percentage
of students, ranging from 11% to 40% of total staff. Some
researchers that work for CSIC also teach at universities as
professors. This strong linkage produces close ties between
students and CSIC.
Some institutes in CSIC in part are supported by universities, while other CSIC institutes are sponsored by CSIC
alone. Shared sponsorship with universities are more common among CSIC institutes due to closer ties between
CSIC and universities in recent history.
Table 3 Characteristics of CSIC laboratories engaged
in materials research. 1)
Classification Laboratory
CENIM
Close
ICV
links
with
industry ICTP
IETCC
3. Research systems of representative CSIC materials
laboratories
ICMAB
More
basic
ICMM
research
This section details the organizations and budget allocation of the Materials Science Institute of Barcelona
(ICMAB: Instituto de Ciencia de Materiales de Barcelona),
the Materials Science Institute of Madrid (ICMM: Instituto
de Ciencia de Materiales de Madrid), and the Madrid
National Central Institute of Metals (CENIM: Centro
Nacional de Investigaciones Metalúrgicas).
ICMS
ICMA
Other
UFM
City
Characteristics
Madrid
Specialized in metal research
Specialized in ceramics
research
Madrid
Linked with Universitat
Autònoma de Madrid
Specialized in polymer
Madrid
research
Specialized in steel structure
Madrid
research
Linked with Universitat
Barcelona
Autònoma de Barcelona
The most specialized in basic
research among the five
Madrid
laboratories in Madrid
Linked with Universidad de
Seville
Seville
Linked with Universidad de
Zaragoza
Zaragoza
Linked with Universidad del
San
País Vasco and two other
Sebastian
universities
Table 4 Enrollment at nine laboratories engaged in materials research. 1)
Laboratory
i)
ii)
iii)
iv)
v)
vi)
vii)
viii)
ix)
City
Budget
Regular staff
1 mil. (¥100 mil.) Professors Researchers
Madrid
CENIM
8.11
(10.9)
Madrid
ICV
Unknown
Zaragoza
ICMA
3.81
(5.1)
ICMAB Barcelona
7.59
(10.2)
Madrid
ICMM
13.43(*)
(18.1)
Seville
ICMS
Unknown
Madrid
ICTP
2.22(*)
(3.0)
Madrid
IETCC
8.95(*)
(12.1)
UFM
Unknown
San Sebastian
Other
7
44
83
11
10
20
6
30
40
74
9
12
17
35
8
?
95
43
6
29
Total
Contract Postdoctoral/
students/visitors
staff
52
134
Not on web page
33
53
43
67
50
129
23
21
?
9
130
63
Not on web page
Budget: FY2002 data marked * and FY2003 data not, Visit: Includes laboratory-permitted stay.
54
Total
86
272
93
84
161
25
39 ?
40
179
194
340
69
134
233
Chemicals), 22% from CSIC, and 12% from the Materials
Science Institute of Barcelona, the new building was completed within 2004 and research equipment have been
brought in from the beginning of 2005 to prepare for opening in June 2005.
3.2 Materials Science Institute of Madrid (ICMM)3)
The Materials Science Institute of Madrid had the greatest enrollment of 340 among the CSIC laboratories
engaged in materials research, of who about 37% were permanent staff.
Of the FY2002 total budget of this laboratory amounted
to 13.4 million euros, of which 61.2% came from CIS subsidies and 1.7% from companies.
Figure 2 shows the percentages of expense items in the
FY2002 budget of this laboratory. Of the 13.4 million
euros in total, 51.6% was spent on labor and 36.9% was
spent on research project.
Euros
Total : 13,434,154 Euros
Salary
8×106
51.6%
Research
project
6×106
8×106
6×106
38.9%
6
6
4×10
4×10
Ordinary Special
budget budget
2×106
5.0%
e
sd
rio es
a
l
i
Sa alar
S
Pe
4. Conclusion
(1) Of the 120 research centers of CSIC, nine are engaged
in materials research. In particular, the three laboratories of
ICMAB (Barcelona), ICMM (Madrid), and ICMS (Seville)
are specialized in basic research. MATGAS was recently
established with links to the industry entered service in
June 2005. ICMM (Madrid) has a total of 340 staff, which
is greater than those of eight other CSIC research centers
engaged in materials research.
(2) CENIM (metals), ICV (ceramics), ICTP (polymers),
and IETCC (steel structures) in Madrid are research centers
that are involved in research through close links with
industry.
S.
S.
io
ar
les
ion
cia
din
ac
pe
Or et
tig
s
s
o
E
e
st g
nv
es et
ue ud
e I cts
ion dg
up y B
s d roje
cc y Bu
es inar
o
r
A
t
r
P rd
y
ec h P
O
as ina
oy ac
ud ord
Pr ese
Ay xtra
R
E
ly
na
rso
2×106
6.5%
3.3 Madrid National Central Institute of Metals (CENIM)4)
The Madrid National Central Institute of Metals has an
total staff of 272. The total number of professors and
researchers combined is 51. Seven professors and 27
researchers of the 51 are tenured scientists.
The number of projects almost doubled from 68 (1994)
to 130 (2003) in a decade. As Figure 3 shows, however,
CENIM was funded one-third by national institutions
(Spanish Government) and one-third by private companies.
The European Union sponsors about one-sixth of the projects.
The FY2003 budget of this laboratory was 8.1 million
euros, of which about 60% were labor expenses.
Fig. 2 Breakdown of FY2002 budgets of Materials Science Institute of
Madrid. 3)
References
1) CSIC Annual Report 2002.
2) Web page of Instituto de Ciencia de Materiales de Barcelona
(ICMAB)
http://www.icmab.es/org/eng/index.html
3) Web page of Instituto de Ciencia de Materiales de Madrid (ICMM)
http://www.icmm.csic.es/eng/
4) Web page of Centro Nacional de Investigaciones Metalúrgicas
(CENIM)
http://www.cenim.csic.es/
Fig. 3 Percentages of research projects at Materials Science Institute of
Madrid. 3)
55
Chapter 2.
New Nanotechnology Research
Institutes in Japan, USA and Europe
Masahiro Takemura
In Chap.2, section 1, the nanotechnology research policies of Japan, the USA, the EU, Germany, France, and the
UK were outlined. This section introduces nanotechnology
research institutes established by new national programs of
these countries. One of the greatest features of nanotechnology R&D is the convergence of multidisciplinary
research fields in the nanoscale area. To promote such integration, priority is given to building a network consisting of
core infrastructure of research information and its surrounding networks (also called a cluster or consortium).
Such a system is designed to accelerate commercialization
and industrialization by linking industry, academia, and the
government.
1. New nanotechnology research institutes in Japan
In Japan, based on the Second Science and Technology
Basic Plan, new policies were initiated in the field of nanotechnology and materials, one of the four priority fields,
and new technology research bases were established in
Japan. The main ones are as follows.
1.1 Nanotechnology Support Project
To support all the researchers of industriay, academia,
and government in terms of both information and facility,
this project was initiated by the Ministry of Education, Culture, Sports, Science and Technology in FY2002. 1) The
Nanotechnology Researchers Network Center of Japan,
established in the National Institute for Materials Science,
is in charge of information support. This Center disseminate information by website and e-mail newsletters, holds
symposia and seminars, and exchanges researchers with
other countries. For facility support, the following 14
research institutes provide external users with the opportunities to use four kinds of large-scale cutting-edge facilities
free of charge.
i) Ultrahigh-voltage transmission electron microscopes
• National Institute for Materials Science
• Institute for Materials Research, Tohoku University
• Research Center for Ultra-High Voltage Electron
Microscopy, Osaka University
• Research Laboratory for High Voltage Electron
Microscopy, Kyushu University
ii) Nano foundries
56
• National Institute of Advanced Industrial Science and
Technology
• Nanotechnology Research Laboratory, Waseda University
• Quantum Nanoelectronics Research Center, Tokyo Institute of Technology
• Research Center for Nanodevices and Systems, Hiroshima University
• Nanoscience and Nanotechnology Center, Osaka University
iii) Synchrotron radiation
• SPring-8
Japan Synchrotron Radiation Research Institute (JASRI)
Japan Atomic Energy Agency (JAEA)
• SR Center, Ritsumeikan University
iv) Molecular synthesis and analysis
• Institute for Molecular Science, National Institutes of
Natural Sciences
• Institute for Chemical Research, Venture Business Laboratory, and Advanced Research Institute of Nanoscale
Science and Engineering, Kyoto University
• Graduate School of Engineering, Kyushu University
Table 1 lists data on facility-sharing support provided in
FY2003 (2.3 billion yen funded by the Ministry of Education, Culture, Sports, Science and Technology).
Table 1 Nanotechnology Support Project.
Support for facility-sharing in FY2003
( ): FY2002
University
Public
Institute
Company
Total
Ultrahigh-voltage
transmission
electron
97
(81)
23
(20)
35
(30)
155
(131)
106
(66)
49
(16)
102
(34)
257
(116)
93
(92)
16
(13)
30
(10)
139
(115)
157
(94)
39
(11)
57
(38)
253
(143)
453
(333)
127
(60)
224
(112)
804
(505)
microscope
group
Nano foundry
group
Synchrotron
radiation group
Molecular
synthesis and
analysis group
Total
1.2 Knowledge Cluster Initiative
To strengthen global competitiveness while respecting
the independence of local governments, the Ministry of
Education, Culture, Sports, Science and Technology initiated the Knowledge Cluster Initiative in FY2002.2) With universities and public research institutes as the core, this project is organized from related research institutes and R&Dtype enterprises. In the three-year period until FY2004, 18
clusters were selected and R&D has been conducted in
some of the four priority fields. Of the cluster areas, nanotechnology R&D has been conducted in the following
four (core research institutes in parentheses):
• Toyama and Takaoka Area: Toyama Medical-Bio Cluster (Japan Advanced Institute of Science and Technology Hokuriku, Toyama Medical and Pharmaceutical University, Toyama University, Toyama Prefectural University, and Toyama Industrial Technology Center)
• Nagano and Ueda Area: Nagoya/Ueda Smart Device
Cluster (Shinshu University)
• Nagoya Area: Nagoya Nanotechnology Manufacturing
Cluster (Nagoya University and Nagoya University of
Technology)
• Kyoto Area: Kyoto Nanotechnology Cluster (Kyoto
University)
1.3 Cooperation for Innovative Technology and Advanced
Research in City Evolutional Areas (CITY AREA)
To produce new technology seeds, create new businesses, and cultivate local industries based on R&D by using
local characteristics and the wisdom of universities and
other organizations, the Ministry of Education, Culture,
Sports, Science and Technology initiated this project in
FY2002.3) Local voluntary business plans are solicited and
areas for this project are selected. Here, “city areas” are
core cities of prefectures (including ordinance-designated
cities) and their surroundings having R&D potential. They
are substantially areas where universities and other public
research institutes exist and core organs can be used as project entities. The areas can be classified into three types by
project development pattern:
i) Linkage infrastructure establishment type: Mainly subject research and research exchange aiming at establishing
industry-academia-government infrastructure
ii) General type: Mainly joint research for creating new
technical seeds in specific fields (includes some industryacademia-government projects)
iii) Achievement cultivation type: Many industry-academia-government projects done mainly for joint research
and achievement cultivation.
In the three-year period until FY2004, 37 areas were
selected where R&D is being conducted in some of the four
priority fields. Nanotechnology R&D is being done in the
following eight (core research institute in parentheses).
i) Linkage infrastructure establishment type: None
ii) General type
• Iwate Prefecture: Kitakami River Area – “High Function
Manifestation R&D for Triazinethiol Organic Nanothin
Film” (Iwate University)
• Gunma Prefecture: Kiryu and Ota Area – “R&D for
Next-generation Processing” (Gunma University)
• Fukui Prefecture: Fukui Central Area – “Development
of Energy-related Functional Materials Creation Technology by Nanoplating Technology” (Fukui University,
Fukui University of Technology, Fukui National College
of Technology, Industrial Technology Center of Fukui
Prefecture)
• Mie Prefecture: Mie and Ise Bay Area – “Creation of
New Functional Materials for Next-generation Display
and Their Applied Equipment” (Mie University)
• Hyogo Prefecture: Harima Area “Development and
Industrialization of Extremely Thick DLC and Highspeed Nitriding Technologies” (University of Hyogo
and Toyota Technological Institute)
• Wakayama Prefecture: Wakayama City Area “Development of Organic Materials for Next-generation Electronic Devices” (Industrial Technical Center of Wakayama
Prefecture)
iii) Achievement cultivation type
• Osaka Prefecture: Osaka/Izumi Area “Nanostructure
Photonics and Its Applications” (Osaka Prefecture University, Osaka University, and Technology Research
Institute of Osaka Prefecture)
• Kumamoto Prefecture: Kumamoto Area “Development
of Biocompatible Microsensors (Smart Microchips)”
(Kumamoto University)
1.4 21st Century COE Program
To form the world’s highest-level research and education bases for improving research levels and creating
human resources leading the world according to “University Policies of Structural Reform” (June 2001), the Ministry
of Education, Culture, Sports, Science and Technology initiated this program in FY2002.4) The Japan Society for the
Table 2 Research areas of virtual laboratories by nanotechnology field.5)
Strategic Goal
Research Area
Creation of nanodevice
and nanomaterials
systems to overcome
integration and function
limits in information
processing and
communication Creation
of Nanodevice / Material
/ System for
Overcoming Integration
/ Function Limits in Data
Processing and
Communications
Creation of Functional
Materials/ System that
Utilize Nano
Biotechnology for
Realizing a Noninvasive
Medical Treatment
System
Creation of ultrafast, ultralow power,
super-performance nanodevices and
systems
Creation of nanodevices/system
based on new physical phenomena
and functional principles
Nano factory and process monitoring
for advanced information processing
and communication
Creation and application of nanostructural materials for advanced data
processing and communication
Creation of bio-device and biosystems with chemical and biological
molecules for medical use
Creation and application of “soft nanomachine”, the hyperfunctional
molecular machine
Creation of novel nanomaterial/system synthesized by
selforganization for medical use
Creation of Nano Materials/ Creation of nano-structured catalysts
and materials for environmental
System for Realizing
Environmental Conservation conservation
and Advanced Energy
Development of advanced
Recycling to Minimize
nanostructured materials for energy
Stress on the Environment conservation and storage
(Convergence of three Creation of innovative technology by
integration of nanotechnology with information,
fields)
biological, and environmental technologies
57
Promotion of Science set up the 21st Century COE Program to examine and evaluate this program and make
grants to subsidize the formation of program bases.
COE categories under this program do not include the
nanotechnology and materials field. However, about 40
COEs related to this field were selected in the three-year
period until FY2004.
1.5 Nanotechnology Virtual Laboratories
Nanotechnology also serves as the foundation for the
three other priority fields of life science, information, and
the environment, so the Japan Science and Technology
Agency initiated this program in FY2002. As the name
indicates, there are no physical laboratories; this is a new
type of research program to promote academic research. As
Table 2 shows, strategic goals were set respectively in the
three fields and 10 research areas were defined under
them.5) In each area, a research team is integrated from the
research administrator responsible for its operations and
also research groups. Each research group conducts
research as a member of the research institute. For interrelations, these research areas are physically operated and
connected by information exchange, collaboration, joint
symposia, and area meetings spanning the boundaries of
research areas.
2. New nanotechnology research institutes in the USA
To promote discovery and technological innovation, the
NNI has been apportioning budgets to a wide range of special fields (universities and other research organs: 2/3, governmental research organs: 1/4, small enterprises and private divisions: the rest). Research can be roughly classified
into individual research, team research, and center research.
Team research is represented by the Nanoscale Interdisciplinary Research Teams (NIRT) of the NSF. The NSF allocates at least 20% of the NNI investment to research combined from different fields. For center research, centers
with human resources and infrastructures are being set up
in a wide range of fields to cultivate human resources,
industry-academia-government linkage, and international
joint research. The annual amount invested by the NNI is
about 2 million dollars, highlighting the policies.
Table 3 lists the nanotechnology research centers of the
NNI.6) The NSF supports the Nanoscale Science and Engineering Centers (NSECs), the National Nanotechnology
Infrastructure Network (NNIN), and the Network for Computational Nanotechnology (NCN). Most research centers
of the NSF are in universities, and the departments and
research centers have a tightly-knit relationship: a professor
belongs to only one department but may belong to several
centers. (The professor is paid by the department but funded by the centers for research.) There are also centers of
NASA, DOE, and DOD. Regarding the DOE in particular,
the Molecular Foundry of the Lawrence Berkeley National
Laboratory and other infrastructures are actively being
extended.
The Materials Research Science & Engineering Center
(MRSEC, 28 centers) and the Nanobio Technology Center
58
(NBTC, 6 centers) do not belong to the NNI but are supported by the NSF, conducting similar activities to the nanotechnology research centers (only NBTC of Cornell University is positioned as an NNI center). With a mission of
conducting R&D for nanoscale metrology, databases, and
standardization, the U.S. National Institute of Standards
and Technology (NIST) established the Advanced Measurement Laboratory for advanced metrology. This laboratory has the best environment for equipments (temperature,
humidity, and vibration) in the world. In addition, the California Nanosystems Institute (CNSI) was established in
UCLA and UCSB as nanotechnology research centers supported by the state government.
The future trends of the nanotechnology research centers
are described next.
2.1 National Nanotechnology Infrastructure Network
(NNIN)
The NNIN was initiated in January 2004, inheriting the
National Nanofabrication Users Network (NNUN) organized from common facilities of five universities, including
the Nanoscale Science & Technology Facility (CNF) of
Cornell University and the Stanford Nanofabrication Facility (SNF) of Stanford University. The NNIN consists of 13
universities, with fairness in race and area considered.7)-11)
Figure 1 shows the percentages of application fields in
2003 when the institution was still the NNUN (5 universities). The numbers of users are as follows:
• Total number of users: about 2,000
(Including about 700 at CNF and about 600 at SNF)
• Graduates: 1,050 or more
• Postdoctoral or higher researchers: More than 250
• Enterprises: About 350 (including 158 at ventures)
• Other (undergraduates, public institutes, and foreign
countries): More than 250
• Users from 33 states
• External users: About 50%
• Average payment by user: 4000 dollars/year
Other characteristics of users are as follows:
• The average annual rate of increase was about 20% in
the past, and exceeds 50% among corporate users.
• Users are increasing in all fields but the rate of increase
is especially remarkable in materials (especially for
nanoelectronics) and its process and evaluation.
• Since 250 new users are trained at the CNF alone every
year, the NNIN may be a training facility.
Since users at universities account for about 50%, the
NNIN is certainly very advantageous for the member universities.
At the time of the NNUN, NSF support for operations
increased from 2.4 million dollars (1998) to 6 million dollars (2003). In the five years of the NNIN, the amount is
expected to exceed 70 million dollars or 14 million dollars/year on average. Note that grants from the NSF to
these research bases are not used to construct buildings; in
many cases, construction expenses are paid from grants by
the state governments or donations. For example, Duffield
Hall of Cornell University cost 62.5 million dollars to build
and was paid entirely from donations by graduates. This
also applies to NSECs and NCN.
Table 3 Nanotechnology centers and facility networks of U.S. NNI.6)
Not only the NNIN but U.S. universities generally tend
to promote equipment-sharing and reduce maintenance and
management costs mainly because professors try to employ
as many researchers as possible. They prefer equipment
that is very general but not used often to be provided, so
that they can share the equipment and pay only usage
charges. Technicians handling the shared equipment are
paid from the facility charges.
Regarding the service quality, if the NNIN is compared
with the shared facilities of the aforementioned Nanotechnology Support Project of Japan (2.3 billion yen support in
FY2003, support for external users only, 804 cases, and no
user burden), the latter receives a higher amount of support
per case on average, and is provided equipment and equipment contents.
59
Fig. 1 Percentages of U.S. NNUN users by field (2003).11)
2.2 Center for Biological and Environmental Nano-technology (CBEN), Rice university
As an example of NSECs, the Center for Biological and
Environmental Nanotechnology (CBEN) of Rice University, 12) which has recently become conspicuous both in
research and policy, is introduced here. As Table 4 shows,
the CBEN is taking the lead in the United States in research
mainly on the application of nanomaterials to bio and environmental fields but also their safety. The CBEN has a
strong influence on the American National Standard Institute (ANSI) – Nanotechnology Standard Panel (NSP)13)
(inaugurated in September 2004). The annual budget, however, is over 3 million dollars.
2.3 New NSEC in 2005
As the new support areas of the NSF, “Nanoscale Science and Engineering: Program Solicitation for FY 2005”14)
listed the following eight high-risk high-return research and
education areas:
• Biosystems at the Nanoscale
• Nanoscale Structures, Novel Phenomena, and Quantum
Control
• Nanoscale Devices and System Architecture
• Silicon Nanoelectronics and Beyond (SNB)
• Nanoscale Processes in the Environment
• Multi-scale, Multi-phenomena Theory, Modeling and
Simulation at the Nanoscale
• Manufacturing Processes at the Nanoscale
• Societal and Educational Implications of Scientific and
Technological Advances on the Nanoscale
From the above, applications for the following two
NSECs were solicited for FY2005:
• Center on Hierarchical Manufacturing (CHM): Center of
nanoscale manufacturing processes
• Center for Nanotechnology in Society (CNS): Center of
social influences of nanotechnologies
In October 2005, Arizona State University and UCSB
were selected as the CNS. They have been also actively
constructing networks with Europe and Japan holding
international conferences on nanotechnology involving
sociologists, political scientists and ethicists.
3. Nanotechnology research institutes in Germany
In Germany, the Competence Centers for Nanotechnology (CCN) are networks of nanotechnology research centers
of industry, academia and government designated by the
Federal Ministry of Education and Research (BMBF: Bundesministerium fur Bildung und Forschung).15) Each network has its own special fields in nanotechnology research
to play the leading role in the country. Besides, there are
also networks supported by the local governments mainly
aiming at promoting local industries although not introduced here.
3.1 Competence Centers for Nanotechnology (CCN)
Table 5 lists CCNs. There were six networks in the fiveyear period until September 30, 2003, but this number
increased to nine on October 1. Each CCN is a membership
network but has several main institutes. The percentage of
federal funding in the total funds for each CNN used to be
100% under the old system but is now 50%, with the
remaining 50% provided by the local government and others. The federal funds are all provided from VDI, except
for Nanomat. Nanomat is based on the Institute for Nanotechnology (INT) of the Karlsruhe Research Center (FZK:
Forschungzentrum Karlsruhe). Since Nanomat belongs to a
Table 4 Research themes of the Center for Biological and Environmental Nanotechnology (CBEN).12)
Theme of Research (Major)
Theme 1: Fundamental
Bio-Chemistry
(Nanoscience at the
Interface)
Theme 2: Nanomaterials in
Bioengineering
(Nanoparticles that Detect
Treat Disease)
Theme 3: Nanomaterials in
Environment
(Effetive, High-Performance
Water Purification Systems)
60
Theme of Research (Medium)
Activity of Bionanoconjugates
Imaging Biological Charge Distributions
Biomedical Applications of SWNT
SWNT Modeling in Micelles
Fullerene/SWNT Theory
Nanomanufacturing
Nanoshell-based Cancer Therapy
Nanoshell Assisted Tissue Welding
Nanomaterials for Imaging
Nanostuctured Bone Replacements
Anti-fouling Coatings
Cut SWNT for Therapy
Nanostructured Membances and their
Polymer Flow on the Nanoscale
Nanocatalysis for Remediation of Environmental
Pollutants
Sorption of Contaminants onto Engineered
Nanomaterials
Nano-cell Interactions
Environmental Exposure Routes
Main Research
Concatenation of proteins and nanoparticles
Determination of physical nanoscale charge state by electron microscope
Physical fluorescent imaging using single-layer carbon nanotube
Determination of SWCNT micelles dynamic characteristics by surface-active agent
Determination of electrical characteristics of single-layer carbon nanotube
Nanostructure continuous manufacturing in the liquid phase
Cancer treatment by nanoshell (nucleus: silica, shell: gold)
Cell welding by nanoshell
Cancer diagnosis by nanoshell
Bone regeneration by polymer composite nanostructure
Development of ceramic film for water purification
Determination of molecular nanopore transmission behavior
Elimination of environmental contamination factors by
nanocatalyst (titanium oxide)
Elimination of impurities from water by iron oxide
nanoparticles
Toxicity evaluation of industrial nanoparticles
Evaluation of physical exposure to nanomaterials released into the environment
national laboratory, Helmholtz-Gemeinschaft (HGF), however, its funding is provided not through VDI but directly
from the federal government.16), 17)
As an example CCN, this section describes
NanoBioTech, which was established for the first time
under the current system. The name “NanoBioTech” comes
from “Nanotechnology: Functionality by means of chemistry.” The main members are Nano+Bio Center, Kaiserslautern University of Engineering (Technische Universitat
Kaiserslautern – TU Kaiserslautern), NanoBioNet e.V., and
tp21. NanoBioTech is funded by the federal government,
the EU, the Rhinelang-Palatinate State, Saarland State, and
the university. The working funds, except for
NanoBioTech research, total 950,000 euros in three years,
including funds for workshops, meetings, and other events
and network activities. The Nano+Bio Center is the foundation of this network and has a dedicated research building with a clean room in the campus of TU Kaiserslautern.
The laboratory of Ziegler, a director of NanoBioTech, is
conducting pioneering work at TU Kaiserslautern.
NanoBioNet e.V. is a organ of network operations in a narrow sense. tp21 (Your technology partner for the 21st Century) is a group of small and medium-sized enterprises.
structing the Institute for Solid State Research and Metals
Research, and FhG is constructing the Institute for Biomedical Technology. These efforts to build bases are not
limited to the conventional framework; emphasis is placed
on shifting to priority fields, strengthening in-group networks, reforming the organization by introducing and cultivating human resources, and constructing infrastructure.
Regarding FZK, for example, the main area of research
was atomic power but this has been shifted to nanotechnology. In terms of not only R&D but also societal implications, the Institute for Toxicology and Genetics (ITG) of
safety and health, and the Institute for Technology Assessment and Analysis (ITAS) of sociology are moving from
atomic power to nanotechnology and strengthening their
links with INT.
4. France
In the nanotechnology field in France, the facility network “Reseau National en Nanosciences et en Nanotechnologies (R3N)” consisting of CNRS and CEA research
bases and MINATEC led by an R3N member “CEALETI”, are the central bases of national strategies.18)
Table 5 CCN in Germany.15)
Until Sept. 30, 2003 (5 years)
Cease
Continue
Continue
Split
Continue
Split
Oct. 1, 2003 – Sept. 30, 2006
*New establishment or participation (including derivation)
3.2 National research institutes
As mentioned in Chap 2, section 1, there are four large
national research institute groups in Germany: Wissenschaftsgemeinschaft G.W. Leibniz (WGL), HelmholtzGemeinschaft deutscher Forschungszentren (HGF), MaxPlanck-Gesellschaft (MPG), and Fraunhofer-Gesellschaft
(FhG). As recognition of the importance of nanotechnology
R&D is growing, each group is constructing new framework for nanotechnology R&D. For example, WGL is
constructing the Institutes for New Materials (INM), HGF
is constructing the aforementioned FZK INT, MPG is con-
4.1 Reseau National en Nanosciences et en Nanotechnologies (R3N)
R3N was first organized from five research centers: four
from national science research centers “Central National de
la Recherche Scientifique (CNRS)” and one from atomic
power agency “Commissariat a l’energie atomique (CEA)”.
• Laboratoire d’Analyses et d’Architectures des Systemes
(LAAS), Toulouse: Microsystems for bio and IT industries
• Laboratoire de Photonique et de Nanostructures (LPN),
Marcoussis: Photonics and nanostructures19)
• Institut d’Electronique Fondamentale (IEF), Orsay:
Basic electronics
• Institut d’Electronique, de Microelectronique et de Nanotechnologies (IEMN), Lille: Nanoelectronics and
microwaves
• CEA-Leti, Grenoble: Microelectronics
Furthermore, the following research center joined them last
year:
• Franche-Comte Electronique Mechanique Thermique et
Oprique – Sciences et Technologies (FEMTO-ST),
Besancon: Mechanics and optoelectronics
With these five areas (LPN and IEF are both in the suburbs
of Paris) as cores, R3N plans to keep growing by adding
new research centers.
4.2 Laboratoire d’electronique et de technologie de l’information (CEA-LETI) and Micro and Nano-technology
Innovation Center (MINATEC)
The nanotechnology institutes of France in the field of
electronics are in Grenoble. Among them, CEA-LETI is
playing a key role in mediating between basic science and
industrialization, as outlined below:20)
• Staff: 900 regular staffs and 600 tie-up staffs (dispatched
from companies and postdoctoral staff) (CEA: 15,000,
61
Grenoble district: 3,200)
• Annual budget: 160 million euros (1/3 funded by the
government) (CEA: 3,000 million euros, Grenoble District: 250 million euros)
• Achievements: 30 newly established companies and 180
patents/year (about 55% of CEA)
The percentages of R&D activities by CEA-LETI are
60% in the field of silicon electronics, 20% in optoelectronic parts, and 20% in bio, medical, and communications systems. In particular, the field of silicon electronics is led by
a project to develop 300-mm wafer technology called
“Nanotec 300”.
A typical company newly established by CEA-LETI is
SOITEC, a company which specializes in single-crystalline
silicon on insulators (SOI).21) SOITEC was established in
1992, and sales in the first fiscal year amounted to 1.4 million euros. As production capacity was extended, sales
increased quickly from 16.3 million euros in FY1999 to
43.3 million euros in FY2000 and reached 101.4 million
euros in FY2002.
To further strengthen micro-nanotechnology R&D in
Grenoble, MINATEC was established in 2001. 21)
MINATEC consists of CEA-LETI, Institut National Polytechnique de Grenoble (INPG), and local autonomous bodies and private organizations. Currently, MINATEC is constructing a new administration center for education,
research, and industrialization beside CEA-LETI, for a
total cost of 170 million euros (to enter service in February
2006). The new center will occupy a site of 60,000 m2,
with clean rooms of Classes 10 to 1000 totaling 2,645 m2
and laboratory rooms totaling 3473 m2. After completion of
the center, MINATEC will have a workforce of 4,000,
including 1,000 at INPG mainly in charge of education,
1,500 at CEA-LETI mainly in charge of research, and
1,000 at private enterprises mainly in charge of industrialization.
as partners. They have the following three research areas:
• Molecular motors
• Functional membrane proteins
• Nano-electronics & photonics
In addition, the ESPRC has funds for platform grants,
networks, and nanotechnology training outlined below.
i) Platform Grants
Funds for long-term research by universities taking the
lead in five research areas and for global networking
• Nanostructured surfaces: University of Birmingham
• Thin film ferroelectronics for nanotechnology applications: Cranfield University
• Nanocharacterization and nanofabrication of materials:
University of Oxford
• Soft nanotechnology: University of Sheffield
• Rapid prototyping of templated nanomaterials: University of Southampton
ii) Networks
Funds to support networks to encourage communication
between researchers, inter-field fusion, and technical transfer (core research organs in parentheses)
• Ferroelectric materials network (University of Leeds)
• Biomedical applications of micro and nanotechnology
(University of Newcastle-upon-Tyne)
• Molecular machines in nanotechnology (University of
Portsmouth)
iii) Nanotechnology Training
Funds to support the training of graduates in doctoral
courses
• Nanoscale science and technology: University of Leeds
• Microsystems and nanotechnology: Cranfield University
• Nanomaterials: Imperial College London
• Microengineering: Heriot-Watt University
• Life Science Doctorial Training Center in Bio-Nanotechnology (For doctoral course): Bio-Nanotechnology
IRC
5. UK
References
In the United Kingdom, universities are the core of public research bases.
(1)
Nanotechnology research centers supported by Research Councils (RCs)
Interdisciplinary Research Collaborations (IRCs) are
groups of research centers supported by the EPSRC. They
can be divided into Nanotechnology IRC and Bionanotechnology IRC. Nanotechnology IRC is led by the University
of Cambridge, with the University College London and
University of Bristol22)-24) as partners. They have the following four core projects:
• Characterization of nanostructures by Scanning Probe
Microscopy (SPM)
• Nanofabrication
• Computational methods for molecular nanotechnology
• Smart biomaterials
The Bio-nanotechnology IRC is led by the University of
Oxford, with the University of York, the University of
Glasgow, and the National Institute for Medical Research
62
1) Nanotechnology Researchers Network Center of Japan, the
Ministry of Education, Culture, Sports, Science and Technology.
http://www.nanonet.go.jp/
2) The Ministry of Education, Culture, Sports, Science and
Technology, Knowledge Cluster Initiative of FY2004 (April 2004).
3) List of Industry-Academia-Government Linkage Promotion
Projects by the Ministry of Education, Culture, Sports, Science and
Technology in City Areas, 2004.
http://www.mext.go.jp/a_menu/kagaku/chiiki/city_area/index.htm
4) The 21st Century COE Program, the Nanotechnology Researchers
Network Center of Japan, the Ministry of Education, Culture,
Sports, Science and Technology. http://www.nanonet.go.jp/
japanese/info/nanoproject.html?org=2040
5) Nanotechnology Measures in Research Promotion Project for
Strategic Creation by the Japan Science and Technology Agency.
http://www.jst.go.jp/kisoken/nano.html
6) Nanoscale Science, Engineering and Technology Committee
(NSET), the National Nanotechnology Initiative Strategic Plan.
December 2004.
7) Bordogna J., National Nanotechnology Infrastructure Network
(NNIN) Informational Meeting. January 2003.
http://www.nsf.gov/news/speeches/bordogna/03/jb030130nninjsp
8) National Science Foundation (NSF), National Nanotechnology
Infrastructure Network (NNIN), Program Solicitation, NSF 03-519.
2003.
9) Cornell Nanoscale Facility (CNF), Nanometer, Vol. 14. No. 3.
September 2003.
10) Cornell Nanoscale Facility (CNF), Cornell Nanoscale Facility
2003-2004 Research Accomplishments. 2004.
11) Tiwari S., The National Nanotechnology Infrastructure Network
(NNIN). National Nanotechnology Initiative: From Vision to
Commercialization. April 2004.
12) Center for Biological and Environmental Nanotechnology (CBEN).
http://cohesion.rice.edu/centersandinst/cben/
13) American National Standards Institute (ANSI), ANSI
Nanotechnology Standards Panel Holds First Meeting. 2004.
http://www.ansi.org/news_publications/news_story.aspx?menuid=
7&articleid=783
14) National Science Foundation (NSF), Nanoscale Science and
Engineering (NSE), Program Solicitation, NSF 03-043. 2003.
15) Bundesministerium fur Bildung und Forschung (BMBF),
Nanotechnology Conquers Market: German Innovation Initiative
for Nanotechnology. 2004.
16) Masahiro Takemura, Naontechnologies in German Karlsruhe
Research Center (1) Institute of Nanotechnology).
http://www.nanonet.go.jp/japanese/mailmag/2004/055c.html
17) Masahiro Takemura, Naontechnologies in German Karlsruhe
Research Center (2) – NanoMat –. http://www.nanonet.go.jp/
japanese/mailmag/2004/059c.html
18) Ministère délégué à la Recherche, Programme Nanosciences –
Nanotechnologies. December 2004.
19) Marzin J., Laboratory of Photonics and Nanostructures. October
2004 (slides).
20) Holden D., Technological research in micro and nanotechnologies
at CEA-Leti. October 2004 (slides).
21) Soitec, Pamphlet of Soitec. July 2004.
22) Micro and Nanotechnology Innovation Center (MINATEC),
Pamphlet of MINATEC. 2004.
23) Department of Trade and Industry (DTI), New Dimensions for
Manufacturing: A UK Strategy for Nanotechnology. June 2004.
24) Engineering and Physical Sciences Research Council (EPSRC),
Nanotechnology. September 2004.
25) Ryan J., Panel Discussion: International comparison of strategies,
7th International Conference on Nanostructured Materials. June
2004 (slides).
63
Chapter 3.
Public Research Institutes in Russia
Federation and Poland
Section 1. Russian Federation
1. Public research institutes of Russia
The Russian Academy of Science was established by the
Czar Pyotr I of Russian Empire in 1724.1) This is an independent non-profit organization and the outmost authority
on science in Russia. This comprehensive academic organization covers not only science but also Russia’s education,
economy, and culture. The Academy is the center of Russian basic research in natural science and social science. By
area and research, the Academy can be divided into 9 scientific divisions, 3 regional divisions, and 13 regional
research centers, which have more than 30 physical laboratories in total.
The main purpose of the Academy is to promote basic
science and scientific innovation to develop the technology
and economy of the nation. The Acadamy regularly publishes a great variety of academic journals. Table 1 gives
the percentage breakdown of academic journals published
in one year by field; the academic journals in the field of
chemistry and material science account for about 15% of
the total journals published.
Table 1 Percentages of RAS-published academic journals by field.
1. General and Interdisciplinary journals
2. Specialized journals
2.1 Mathematics and physics
2.2 Technical
2.3 Chemistry and Material Science
2.4 Life Sciences
2.5 Earth Sciences
2.6 Humanities
3. Mainstream Science journals
*Number of annual issues
2. Scientific research budgets in Russia
In the Russian Federation, the total scientific budget was
46.0 billion roubles (about 1.6 billion dollars) in FY2004
but is anticipated to increase about 20% to 56.0 billion roubles (about 2.0 billion dollars) in FY2005. While increasing
64
the budget, the government announced a plan to reform and
scale down the initiative of Russia.
In Russia, research funds from outside the country
account for about 20% of scientific expenses. The main
sources of international funds since 1990 have been the
Open Society Institute, the Russian Foundation for Basic
Research, CORDIS, the IEU Science and Technical Funding Program, the International Science and Technology
Center, and the Eurasia Foundation.
3. Public research institutions of Russia engaged in
materials research
Table 2 lists materials research institutes that are part of
the Russian Academy of Science. Tables 3.1 and 3.2 list
the main physical research institutes involved in materials
research. The large number of institutes suggests that the
research activity in Russian in the field of materials and
physics is very broad.
4. Actions for nanotechnologies in Russia
Since the time of the former USSR, research on nanoparticles and nanomaterials has been active in the Russian
Federation, particularly research on metals having nanostructures. In 1976 a paper about nanostructures was published in Russia, and in 1979 a research division for dispersion systems (Ultra-dispersed Systems) was set up in the
Academy of Science.
The Russian Federation is funding nanotechnology
research through the Ministry of Science and Technology,
the Russian Academy of Science, the Ministry of Higher
Education, the Federal National Technology of Russia Program, and the Ministry of Atomic Energy. In particular, the
Ministry of Science and Technology is currently undertaking various nanomaterials research, such as electronic and
optical properties of nanostructures (the Ioffe Institute and
others), solid state physics program, modern problems of
surface science, fullerene and nanotubes, biology, and
advanced materials.
References
1) Web page of each research institute of the Russian Academy of
Science
http://www.pran.ru/eng/, and others
Table 2 Materials-related research institutes of the Russian Academy of Science.
Institute Name,
Location,
Established
Main Fields of Research
Researchers
*
**
D.Sc C.Sc
(Included) (Included)
Tackling the most basic subjects in the physics, chemistry, and
engineering of iron and nonferrous metals
• Physicochemistry and technology of the production of ferrous,
A.A. Baikov
nonferrous and rare metals
Institute of
• Physicochemical principles in the development of new metallic
Metallurgy and
materials
Materials Science
• New production technologies and processes for the treatment of
Moscow
metals and alloys
1938
• Computerized and automated metallurgical processes
• Research methods for studying metals and alloys
Conducting basic research on microelectronics and micro-nanomaterials
characteristics. Concluding science agreements with France, UK, and
Institute of
Germany
Microelectronics
• Spectroscopy of magnetics materials
Technology
• Physics of semiconductor microstructures
Problems and
• X-Ray Acousto-Optics Laboratory, X-ray optics
High Purity Materials
• Local characterization of semiconductor materials
Moscow Region
• Quantum electron kinetics of metallic nanostructures
1984
• Computational Diagnostic Laboratory
• Laboratory of Epitaxial Structures
Research on explosives and rocket propellants in the past and research
Unknown
for thermal explosions in the past
• Center for Macrokinetic Research
Combustion of dispersed systems, Division of Nonlinear Dynamics,
dynamics of microheterogeneous processes, heterogeneous chain
processes, macrokinetics of catalytic processes, X-ray investigation
Institute of
• Center for SHS Research
Structural
(SHS: Self-propagating high-temperature synthesis)
Microkinetics and
Chemical analysis of SHS materials, experimental equipment and
Material Science
standardization, fundamentals of SHS processes, macrokinetics of
Moscow Region
SHS processes, materials
1987
Physical properties investigations, physical stimulation of physicochemical processes, physico-chemical analysis and research,
rheodynamics and plastic deformation of SHS materials, shockdriven processes, SHS melts and cast materials, synthesis of
functional oxide materials
Expanding mesomechanics fused from continuum dynamics and plastic Unknown
Institute of
physics
Strength Physics
Dept. of the Mechanics of Structured Media
and Material
Dept. of the Physics of Strength and Wear-resistance
Science
Dept. of Physical and Technological Problems of Solid Surfaces
Tomsk
Dept. "Republican engineering and technical center for reconditioning
1928
and hardening of parts of machines and mechanisms at ISPMS SB RAS"
One of the oldest Siberian scientific facilities, established as a laboratory
Institute of Solid
of chemistry and metals
State Chemistry and
• Ceramic materials and powders, material science, nanostructures,
Mechanochemistry
inorganic chemistry
Novosibirsk, 1944
• Environment, construction technologies, structural chemistry, solid
state, physical chemistry, photochemistry
Part of researchers doubling as teaching staff at the Moscow State
University
Institute of
Laboratory of Fluid-Magmatic Interactions, Mineral
Experimental
Thermodynamics Laboratory, Laboratory of Ore Deposits Modeling,
Mineralogy
Laboratory of Metamorphism, Laboratory of Lithosphere, Laboratory
Moscow region
of Hydrothermal Systems Thermodynamics, Laboratory of High1969
Temperature Electrochemistry, Laboratory of Mineral Synthesis
Institute of Non-Metallic Materials (Yakutsk, Year of establishment unknown) Details unknown
Institute of Physico-Chemical Ceramic Materials (Moscow, Year of establishment unknown)
Details unknown
* D. Sc: Doctor of Science - Professor-class senior doctorate researcher
** C. Sc: Candidate of Science - Ph.D equivalent doctorate researcher
65
Table 3.1 Main physical research institutes of the Russian Academy of Science engaged in materials research.
Institute Name,
Location,
Established
Ioffe
Physico-Technical
Institute
St. Petersburg
1918
Institute for Physics
of Microstructures
Nizhny Novgorod
1993
P. L. Kapitza
Institute for
Physical Problems
Moscow
1934
A. V. Shubnikov
Institute of
Crystallography
Moscow
1925
Lebedev Physical
Institute
Moscow
1934
(or 1724)
L. D. Landau
Institute for
Theoretical Physics
Moscow
1965
One of Russia’s largest research institutes in physics and engineering
• Centre of Nanoheterostructure Physics
• Division of Solid State Electronics
• Division of Solid State Physics
• Division of Plasma Physics, Atomic Physics and Astrophysics
• Division of Physics of Dielectric and Semiconductors
• Educational Centre
Independent from the Institute of Applied Physics. Closely linked to the
Nizhny Novgorod State University, with 20 or more researchers
teaching at the university
• Semiconductor physics
• Superconductor physics
• Surface physics, interface and multilayer structures
• Heterostructure technology
• Mathematical techniques and computer simulation
• Thin films and technological equipment technology
• Radio engineering
• Microwave spectroscopy
Department of Theoretical Physics headed by Prof. Landau, winner of
the Nobel prize for physics
• Experimental physics
• Theoretical physics
• Applied physics
Specialized in crystallography, based on the three topics of growth,
structure and properties
• Crystal growth
Dept. of High-temperature Crystallization, Dept. of Crystallization
from Smelting, Dept. of Crystallization from a Solution,
Crystallization from High-temperature Solutions
• Crystal structure
Dept. of X-ray Methods in Modern Organic and Inorganic
Materiology, Dept. of Electronic Microscopy, Dept. of X-ray
Structure and Neutronographical Analysis
• Crystal properties
Dept. of Crystallophysics, Dept. of Track Membranes
• The Astrospace Center
• Quantum radiophysics
• Optics
• Theoretical physics
• Solid state physics
• Nuclear physics and astrophysics
• Neutron physical department
• Dept. of Physics of Relativistic Multipartial Systems
• Sector of the theory of the plasma phenomena
• Group FIAN’s “Nonlinear optics and dispersion of light”
Established by five pupils of Prof. Landau. Not only a research institute
but also a unique school of science and known as “Landau School”
• Condensed matter theory
• Quantum field theory
• Nuclear and elementary particle physics
• Computational physics
• Nonlinear dynamics
• Mathematical physics
Researchers
*
**
D. Sc C. Sc
206
261
266
332
208
30
43
61
46
36
121
141
146
182
97
About 100
17
66
Entire institute
About 60
Entire institute
Unknown
180
Unknown
Unknown
85
146
575
80
Unknown
Unknown
Unknown
21
57
32
19
46
6
39
45
92
26
104
Entire institute
66
Table 3.2 Main physical research institutes of the Russian Academy of Science engaged in materials research.
Institute Name,
Location,
Established
Institute of
Spectroscopy
Moscow region
1968
Institute of Solid
State Physics
Moscow region
1963
Institute of
Thermo-physics of
Extreme Conditions
Moscow
1987 or earlier
Details unknown
Researching a wide range of spectroscopy from X-ray to microwave
• Atomic Spectroscopy Department
• Molecular Spectroscopy Department
• Department of Solid State Spectroscopy
• Laser Spectroscopy Department
• Department of Laser-Spectral Instrumentation
• Theoretical Department
• Laboratory of Spectroscopy of Nanostructures
• Laboratory of Experimental Methods of Spectroscopy
*
**
Researchers D. Sc C. Sc
Spectroscopy of defective structures, nonequilibrium electronic
processes, electronic kinetics, quantum transport, quantum crystals,
spectroscopy of surface of metals, superconductivity, theoretical
department, structural research, real structure of crystals, spectroscopy
of molecular structures, spectroscopy of surface of semiconductors,
physics of high pressures, optical durability and diagnostics of crystals,
materiology, reinforced systems, interfaces in metals, crystallization
from high-temperature solutions, controlled growth of crystals, physical
and chemical bases of crystallization, metallurgical chemistry, chemical
bases of complex oxides
203
One of the five large research centers in Russia
• Thermo-physics of extreme conditions
• Physics of pulse influences
• Materiology
• Physics of low temperature plasmas
• Pulse power and geophysics
• Physical gas dynamics
• Experimental thermo-physics
• Department thermo-physical properties of substances
• Chemical thermodynamics
(V.P. Glushko Thermo Center of the Russian Academy of Science)
• Theoretical department (named after L.M. Biberm)
200
≧100
48
146
Entire institute
Unknown
Bereskov Institute
of Catalysis
Novosibirsk
1958
Established as the Siberian branch of RAS. Conducting catalyst and
petrochemical research
• Heterogeneous catalysis
• Homogeneous and coordination catalysis
• Mathematical modeling of catalytic processes
• Nontraditional catalytic processes and technologies
• Physicochemical methods for catalyst investigation
• Catalytic process engineering
• Catalytic methods for environmental protection
• Applied catalysis problem
Nikolaev
Institute of
Inorganic
Chemistry
Novosibirsk
Year of establishment
unknown
• Chemistry of inorganic connections, including coordinate, cluster and
super-molecular connections
• Physical and chemical bases of processes of separation and
purification of substances
• Physico-chemical and technology of functional materials
• Crystal chemistry, electronic structure and thermodynamics of
inorganic substances, and others
≧270
High Energy Physics and Physics of Particles (Protvino, 1963)
Proton accelerator U-70 (70 billion electron-volt) set up in 1967. Details unknown.
40
18
32
27
31
18
11
10
2
40
100
Unknown
67
03 Public Research Institutes in Russia Federation and Poland
Section 2. Poland
Krzysztof Jan Kurzydlowski
Undersecretary of State, Ministry of Education and Science, Poland
Takahiro Fujita
1. Outline
Poland’s science and technology policies are planned by
the Science Council for the Ministry of Education and Science (formerly the State Committee for Scientific Research
– KBN). The Council is a governmental body established
in 2005. It advises the Ministry, among others, on the allocation of research funding responsible for basic research
and the other with projects relevant to industry. The fact
that the Undersecretary of State of the Ministry of Education and Science is Professor Kurzydlowski, an eminent
material scientist, suggests that there is a strong emphasis
on materials research in Poland.
Materials research in Poland is funded by national projects, financial support Networks and Centres of Excellence, and individual projects (Figure 1). In total about 50
research institutions and 4,000 researchers are undertaking
materials research with an emphasis on advanced materials
and nanotechnologies. According to ISI national citations,
dated November 2005, Poland is ranked 22nd among 75
countries in the field of materials science. However, if the
average funding per publication is taken into account,
Poland is in the group of countries which are the most efficient in maintaining an internationally respected position.
2. Materials research institutes
The organizations undertaking materials research in
Poland are universities and institutes of the Polish Academy of Sciences (PAS). They are networked into consortia
involved in national projects, materials networks, and centres of competences (see further text). Most of them are
coordinated by professors from the major universities.
The top two universities of technology are Warsaw University of Technology and the AGH University of Science
and Technology in Krakow.
The Warsaw University of Technology has 32,000 students and consists of 17 faculties. The Faculty of Materials
Science and Engineering (MSE) has 60 academic staff and
415 students engaged in study and research. The MSE Fac68
Fig. 1 Concept of the Polish materials policy.
ulty is the centre of materials research in Poland because
the former Dean, Professor Kurzydlowski, has been serving
on a number of national committees, including the important post of Deputy Vice-Chairman of the Reseach Science
Council in the recent past and currently holds the post of
Undersecretary of State of the Ministry of Education and
Science. He is also Chairman of the Council of Centre of
Advanced Materials and Technologies, CAMAT.
The acronym “AGH” of the AGH University of Science
and Technology translates from Polish as “Academy of
Mining and Metallurgy”. The 15 faculties of the university
cover mining, casting, and other engineering disciplines.
Material faculties include metallurgy, non-ferrous metals,
foundry and ceramics for metals and other materials. AGH
is perhaps the world’s largest materials education and
research institute, with as many as 8,000 students majoring
in materials.
The Polish Academy of Science (PAS) is organized into
seven divisions and has 79 research units. The Institute of
Fundamental Technological Research (Warsaw) and the
Institute of Metallurgy and Materials Science (Krakow) are
actively conducting materials research.
3. National projects
KBN established the national related project “Metallic,
Ceramic and Organic Nanomaterials” in 2000 with the participation of 25 research teams from universities, PAS
Institutes, and industrial research units. Recently, this project has been followed by two new initiatives concerning
nano-metallic components produced by plastic forming and
polymers modified by nano-particles.
Other national projects completed recently covered
intermetallics (ended in 2004) and materials for bio-medical applications (ended in 2005). Newly launched projects
are devoted to (a) functionally graded materials, and (b)
plastic forming of ultra-hard materials.
4. Materials networks
In the past four years, two materials networks were
formed to help increase the Polish contribution to European
Research Area in the Materials Domain of FP6.
The Nanomaterials Network (Figure 2), in which 18 universities, 4 PAS institutes, and 3 industries are participating, covers five fields of nanomaterials, biomaterials, polymers, corrosion and degradation, and characterization of
materials. The network is intended to achieve the critical
mass necessary for further development of the research
groups, to contribute to the wider use of knowledge based
materials in Polish industry and to participate in FP6.
The International Scientific Network for Advanced
Materials and Structures (AMAS-ISN) consists of 36 Polish research institutions and 24 research teams from various
European countries. There are four subject groups in the
network: material microstructure, biomaterials, intelligent
systems, durability and safety.
the Warsaw University of Technology. Under the theme of
nano-crystalline materials, the Nanocenter is researching
magnets, intermetallics, aluminum alloys, and composites
with financial support from the EC and the Polish Government. There are similar centers in Krakow and Wroclaw.
6. Research funds
In the Financial Year 2004, the Polish Government
invested the equivalent of 37 million Zloty in total in the
materials research field: 23 million Zloty for research projects and 14 million Zloty for industrial projects. The
investment ratios are 30% for research projects (engineering area) and 34% for industrial projects. This indicates
that the government is strongly committed to materials
research.
Materials research is also funded by the EU and other
organizations. For example, “Knowledge-Based Multicomponent Materials” proposed by the Institute of Fundamental
Technological Research was adopted as an FP6 Network of
Excellence and received funding equivalent to about 8.1
million Euro in two years.
7. Researchers
The materials research field of Poland is characterized
by a steady increase in the number of young researchers.
Regarding the MSE Faculty of the Warsaw University of
Technology, the number of students in the doctoral course
has increased more than five-fold in the last 12 years (Figure 3). This tendency can be seen throughout Poland.
These facts confirm that the Polish Materials Science
Community has a great potential for collaboration in the
international forum. In recognition of this, the European
Materials Research Society has awarded a series of Fall
Meetings to be held in Warsaw. It is expected that the meetings promote cooperation within the European Research
Area and between researchers from Western, Central and
Eastern Europe.
Fig. 2 Nanomaterials Network in Poland.
5. Centres of Competence
Several Centres of Competences in materials science
have emerged in Poland in recent times, partly in response
to the encouragement by the European Commission. One
of them is the Nanocenter set up at the Faculty of MSE of
Fig. 3 Number of doctoral course students in the Faculty of Materials
Science and Engineering, the Warsaw University of Technology.
69
PART4
Outlook of Materials Research
• Nanomaterials
• Superconducting Materials
• Magnetic Materials
• Semiconductor Materials
• Biomaterials
• Ecomaterials
• High Temperature Materials for Jet Engines and Gas
Turbines
• Metals
• Ceramic Materials
• Composite Materials
• Polymer Materials
• Analysis and Assessment Technology
• High Magnetic-Field Generation Technology and Its
Applications
• Nanosimulation Science
• Technologies New Materials Creation
• Acquisition and Transmission of Materials Information
Data and Information
• International Standard
Chapter 1.
Nanomaterials
Section 1. Nanotubes
Yoshio Bando
Fellow, NIMS
1. Introduction - Global Trend
As a material falls in size to nanoscale, it begins to display a property completely different from that in a bulk
state. Therefore, new nanoscale materials are receiving special attention as nanomaterials that hold the key to nanotechnology development. In particular, nanotubes,
nanowires, and other one-dimensional nanoscale materials
are expected to be applied as new materials for electronics,
environment and energy conservation, and biotics because
they show peculiar forms and structures and excellent characteristics. The representative one-dimensional nanoscale
material is carbon nanotube (CNT). Since its discovery by
Iijima in 1991, carbon nanotube has been actively studied
throughout the world in many fields, such as synthesis,
growth mechanism, structure analysis, properties analysis,
theoretical analysis, and applied development and research.
No other new materials are attracting as much attention as
carbon nanotube among many researchers and engineers in
basic to applied fields, nor causing such fierce development
competition among colleges, public laboratories, and companies throughout the world. With new discoveries made
Table 1 Main compounds of nanotubes.
Compound
Synthesizing Method
C
Arc discharge
BN
MoS2,WS2
NiCl2
Documentation
S. Iijima1)
(1991)
High-temperature heating N. G. Choprra et al.2)
(1995)
of MoOx (WOx) and H2S
Plasma discharge
R. Tenne et al.3)
(1995)
High-temperature heating Y. R. Hacohen et al.4)
of precursor
(1998)
ZnS
CVD with template
J. Q. Hu et al.5)
(2004)
GaN
CVD with template
J. Goldberg et al.6)
(2003)
Si
Two-stage heating,
template
B.K. Teo et al. (2003) 7)
J.Q. Hu et al. (2004) 8)
V2O5
CVD with template
P. M. Ajayan et al.9)
(1995)
TiO2
every day, carbon nanotube technology is progressing very
rapidly.
In addition to carbon, several compounds are known to
form nanotubes. Table 1 lists the main compounds of nanotubes found so far. Among them, molybdenum sulfide
(MoS2), boron nitride (BN), and nickel chloride (NiCl2) are
similar to carbon in that they have atomic arrangements of
nanotube-unique wall structures, such as the zigzag and
armchair types. In contrast, zinc sulfide (ZnS), gallium
nitride (GaN), and silicon (Si) form nanotubes with the sp3
type structure as they do in the bulk state. These compounds form fine tube structures from hollow capillary
crystals. Strictly speaking, these nanotubes should be distinguished from carbon and other nanotubes with nanotubeunique atomic arrangements. However, they are both called
nanotubes.
Among non-carbon nanotubes, BN nanotube is now
being studied most actively, because it has excellent properties not seen in carbon nanotube, such as heat resistance
and chemical stability. Because of these properties, BN
nanotube is expected to be applied as electronics materials,
super heat-resistant light weight materials, and hydrogen
storage materials. Since BN nanotube is difficult to synthesize in a large volume, its properties and functions are still
not clear. Unlike carbon nanotube, the study of BN nanotube has begun. TiO2, V2O5, and other oxide nanotubes
were also recently discovered. Surface decoration and doping with organic and inorganic substances without impairing the innate characteristics of oxides is expected to make
oxide nanotubes applicable to luminescent materials, catalysts, and high-performance magnets. Studies in this field
have also just begun.
Sol-gel process
P. Hoyer et al.
(1996)
10)
2. Trends in and outside Japan
This section introduces recent trends in studies of carbon
nanotube and various other nanotubes, including
nanowires.
2.1 Carbon nanotube
Figure 1 shows the numbers of papers and patents concerning carbon nanotube by year. Since the discovery of
carbon nanotube, both papers and patents have been
73
Number of papers (patents × 10)/year
Paper
Patent
Year
Fig. 1 Numbers of papers and patents on carbon nanotube.
increasing exponentially every year. So far, more than
10,000 papers have been published. The statistical data
indicates active studies of carbon nanotube on a global
scale. Regarding the total number of patents, Japan
accounts for about 53%, the United States for about 13%,
and Europe for about 7%. Japan ranks top in the world with
domestic patents but owns no more than about 10% of
international licenses, far less than the approximately 50%
owned by the United States. The percentage in the field of
patents is about 40% for synthesis and processing, 20% for
electron emission, 9% for composition, 6% for hydrogen
storage, and the rest for others. The trends in the studies on
carbon nanotube can be discussed in terms of 1) synthesis
and processing, 2) structural analysis, functional investigation, and theoretical calculation, and 3) device and other
applied development. This paper describes synthesis and
applied development.
Noteworthy achievements in synthesis and processing
are the volume synthesis of multi-wall nanotubes in 1992,
filling into a carbon nanotube in 1993, the volume synthesis of single-wall nanotubes in 1995, the creation of a peapod (fullerene in a single-wall nanotube) in 1998, and the
unidirectional growths of nanotubes on a Si wiring board in
2000. In addition, large volumes of carbon nanofibers and
nanotubes were synthesized successfully by thermal
decomposition in 1995 and a volume synthesis technology
using a large continuous reactor was developed for multiwall nanotubes in 1999. Now that the volume synthesizing
technology for multi-wall nanotubes is almost established,
researchers are directing their efforts mainly toward the
volume synthesis of single-wall carbon nanotubes and the
development of a chirality control method. Single-wall carbon nanotubes used to be synthesized by the laser oven
method and the arc discharge method. These methods,
however, could synthesize only small volumes of impure
nanotubes but not highly pure single-wall nanotubes.
Because of this disadvantage, many groups are now developing a synthesizing method for highly pure single-wall
nanotubes from the CVD method that uses various metal
particles of several nanometers in diameter as catalysts.
74
Recently, it has been reported that a new synthesizing
method using ethanol instead of hydrocarbons produces
large volumes of single-wall nanotubes at low temperatures
and cost. Thus, the synthesis of single-wall nanotube is also
progressing rapidly.
Since the field emission phenomenon of carbon nanotube was discovered in 1995, mainly Japanese and Korean
companies have been promoting practical applications to
super high-intensity light source tubes and full-color flat
panel displays by utilizing such excellent characteristics as
long service life and high intensity. Active studies are also
in progress to find ways to use nanotubes as hyperfine lines
replacing silicon conductors. Prototype field effect transistors and diodes using nanotubes are being fabricated and
the effectiveness of nanotubes is becoming clear. However,
it is extremely difficult to route wires freely in a complicated electronic circuit. As elemental techniques, researchers
are actively using an electric field to study the growth of
nanotubes in specific places on boards and the orientation
of nanotubes.
2.2 BN nanotube
When carbon nanotube was discovered, researchers
began to search for non-carbon nanotubes and investigate
their functions. BN nanotube was predicted in 1994 and
discovered in 1995. A trace of multi-wall nanotube was
found by plasma arc discharge or laser irradiation. Now the
substitution reaction and CVD with precursor are being
established as synthesizing methods. Single-wall BN nanotube, however, is synthesized in trace quantities because it
is less stable than carbon nanotube. Regarding the properties of BN nanotube, excellent oxidation and hydrogen
storage are now becoming apparent.
2.3 Other nanotubes
V2O5 nanotube is the first oxide nanotube synthesized by
the CVD method with carbon nanotube as a template.
Afterwards, TiO2, SiO2, MoO3, ZrO2, ZnO, WO3, and other
oxide nanotubes were synthesized by the sol-gel process
and other soft chemical techniques or various synthesizing
methods, such as CVD and thermal decomposition. Nanotubes are now synthesized not only from oxides but also
from sulfides, carbides, and nitrides, including WS2, MoS2,
ZnS, PbS, CdS, GaN, AlN, and SiC. Bi, Au, Ni, and other
metallic nanotubes are also synthesized by a method using
a mesoporous alumina template. However, almost all the
properties and functions of these nanotubes are unclear.
Investigations are in progress globally to discover new noncarbon nanotubes having excellent semiconductor and optical characteristics.
2.4 One-dimensional nanoscale materials, such as
nanowire
One-dimensional nanoscale materials other than nanotube are classified by shape into nanowire, nanorod,
nanobelt, and nanocone. Researchers are actively looking
for such new materials and clarifying their functions. All
materials found as nanotubes are synthesized as nanowire
and other capillary crystals of more than 100 types. In particular, wide-gap semiconductor nanowires of ZnO and
Number of papers/year
Year
Fig. 3 Main achievements by recent NIMS studies.
Discovery of carbon nanothermometer.
Fig. 2 Number of papers on nanowire and other one-dimensional
nanoscale materials, excluding nanotube.
SnO2 are also being studied to develop field emission, FET
transistor, and gas sensor applications. Figure 2 shows the
change in the number of papers on nanowire and other onedimensional nanoscale materials. Their total is now almost
equal to the number of papers on carbon nanotube. Recently, especially active research and development in this field
are underway.
(a) Fullerene nanotube
3. Current status and study of NIMS
While effectively utilizing the world’s most advanced
electron microscope technology, the author’s group is tackling the search, creation, and structural analysis of new
nanotubes and nanowires. In particular, the group is taking
the lead in the synthesis and structural analysis of BN nanotube. The group developed a substitution reaction method
with carbon nanotube as a template in 1998, a CVD
method using a precursor in 2001, and laboratory-level volume synthesis of high-purity BN nanotube using a carbonfree synthesizing method in 2002. Unlike carbon nanotube,
BN nanotube was found to prioritize the zigzag type atomic
structure and the existence of cone-shaped BN nanotube
was clarified in 2002. In addition, the hydrogen storage
characteristic of BN nanotube was discovered in 2002.
Meanwhile, new findings by Bando led to a new application field: using carbon nanotube as a temperature sensor
in 2002, which is called a nanothermometer10). This nanothermometer measures the temperature in fine space by using
the volume expansion and contraction phenomena of liquid
gallium enclosed in a carbon nanotube under varying temperature of the outside air. Because of its extremely small
size, the nanothermometer was listed in the Guinness Book
of Records as the world’s smallest thermometer (2004). As
thermometers of non-carbon nanotube, nanothermometers
were also created successfully from MgO, In2O3, SiO2, and
other oxide nanotubes featuring excellent heat resistance
and oxidation resistance.
(b) New nanotube found by NIMS
Fig. 4 Main achievements by recent NIMS studies.
Studies of carbon nanotube include the development of a
technology for fabricating a carbon nanotube by electrophoresis for use as a probe for an atomic force microscope and also a technology for arranging carbon nanotubes in one direction. A new method was also developed
for low-cost production of carbon nanotubes. In this
method, electrodes dipped in alcohol or another liquid are
heated. Unlike the conventional arc discharge, a method
requiring no external carbon supply successfully synthesized carbon nanotubes. In addition, fullerene nanotubes
composed of C60 or C70 fullerene molecules (hollow capillary crystals of hundreds of nanometers in diameter and
75
hundreds of microns in length) were also synthesized.
In studies for new nanotubes, other than carbon and BN
ones, researchers are looking for and creating various inorganic nanotubes and nanowires. The high-temperature
reaction of ZnS and SiO powders produced more than 10
types of nanotubes and nanowires for the first time in the
world and their structures were clarified. They include single-crystal Si-nanotube (having a bulk structure of the sp3
type and about 100 nm in diameter), Si-microtube by SiO
thermal decomposition (several microns in diameter), and
ones from ZnS and AlN.
environment is being set up to clarify its basic electromagnetic, optical, and thermal properties. Through the functional clarification of BN nanotube, basic and fundamental
research will play an even more important part in discussions of whether the hydrogen storage characteristic of BN
nanotube can be improved to a practical level and whether
the conventional insulators can be converted into semiconductors by element doping and used as nanotube elements.
We are also anticipating the discovery of a new nanotube
with better semiconductor and optical characteristics than
carbon nanotube.
4. Outlook
References
Since the discovery of carbon nanotube, many basic
studies have been done almost completely clarifying such
basic characteristics as electrical conductivity, mechanical
strength, thermal conductivity, and field emission. However, there is still no successful synthesizing technology that
controls chirality, the major issue related to carbon nanotube. To achieve the applied development of various nanotubes, it is essential to selectively synthesize and control
nanotubes showing only semiconductor or metal properties.
In the future, the study phase needs to shift from the conventional basic studies toward the industrial sector: applied
and practical studies. It is particularly important to promote
research and development for practical uses in a wide range
of industrial fields, including the fields of electronics and
nanotechnology (flat display panels and nanotube molecular elements), environment and energy (cathodes of lithium
ion batteries and hydrogen gas storage), biotechnology
(DNA biosensors), and composite materials (reinforced
plastics).
Concerning BN nanotube, however, a high-purity synthesizing method is being established by NIMS and an
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76
01 Nanomaterials
Section 2. Nanoparticles
Yoshio Sakka
Fine Particle Processing Group, Materials Engineering Laboratory, NIMS
1. Introduction1)
2. Trends in research
A nanoparticle generally refers to a particle of 100 nm
or smaller in diameter and of cluster size or greater. Systematic research on nanoparticles was initiated by a study
on nanoparticle crystals by Uyeda (Nagoya University),
and the theory of the electronic properties of nanoparticles
was predicted by Kubo (University of Tokyo) from about
1960 to the mid 1970s. Uyeda fabricated nanoparticles by
an inert gas evaporation method, and by observing them
under an electron microscope, discovered new crystalline
structures and morphologies not seen among bulk materials, thus proving the peculiarity of nanoparticles. This
trigged intense research based on the contemporary theory
that Kubo’s effect causes great changes in the specific heat
and magnetic rate of metallic nanoparticles. However,
although many studies have been conducted, Kubo’s effect
remains unverified. And although magnetic nanoparticles
attracted great attention for various applications, and in
spite of excellent properties and characteristics, magnetic
nanoparticles failed to be used. This is for several reasons:
magnetic nanoparticles have unstable properties, it is difficult to obtain a large volume of uniform magnetic particles
at low cost, and it is difficult to handle magnetic particles,
as they are active and easily coagulate.
Thereafter, Hayashi’s ultrafine particle project, ERATO,
was established in 1981. In the project, the conditions of
nanoparticles could be checked successfully much more
precisely with an electron microscope having high performance and resolution. In particular, the dynamic observation of gold nanoparticles by Iijima is well known and
helped the later discovery of carbon nanotube. Regarding
handling, a nanoparticle gas transportation technology
called the gas deposition method was developed and has
since been improved. In addition, advanced research was
conducted on two-dimensional arrays of nanoparticles, the
conversion of an organic compound into nanoparticles, and
magnetotactic bacteria that contain magnetic nanoparticles.
At the time, fine ceramics were attracting much attention
and many fine ceramic particles were prepared by various
methods, greatly contributing to the development of the
electronic ceramics industry. However, when the new
materials boom ended, research on nanoparticles faded.
Since President Clinton’s nanotechnology policy in
2001, nanoparticle research has become active again. Figure 1 shows the number of hits upon searching Science
Direct, Japanese patents,2) and US patents3) using the keywords “nano” and “particle,” revealing a rapid increase
since 2001. Figure 2 shows the breakdown of international
journals on materials and US patents by country (areas) in
2004. In Korea and China, the number of journals is large
but that of US patents is small, reflecting the United States’
emphasis on patents. Japan used to hold the lead in nanotechnology research but perhaps no longer.
According to a 2002 report,4) about 320 companies in
the world are manufacturing the primary products of nanomaterials: nanoparticles (160), nanotubes (55), nano-multi-
Japanese patents
US patents
Count
International journals
Year
Fig. 1 Number of hits when searching international journals, Japanese
patents, and U.S. patents with the keywords “nano” and “particle”.
US patents
Ratio (%)
International journals
USA Japan Europe Korea China Taiwan Other
Fig. 2 Breakdown of international journals and US patents by country
(areas) in 2004.
77
pore materials (22), fullerene (21), quantum dots (19),
nanomaterials (16), nanofibers (9), nanocapsules (8),
nanowires (6), and dendrimers (5). The numerals in parentheses are numbers of companies. As shown by the growing number of US patents in Figure 2, many companies are
US venture firms which are ready to provide users with
various nanoparticles.
According to a questionnaire conducted by Nikkei
Shimbun on 1700 companies (535 responses) from October
to November,5) the main focus of technology development
in Japan is micromachining (72 companies), followed by
nanoparticles (70 companies). The number of companies
involved in micromachining is over 100 if those companies
now considering research are included. However, Japan is
considered to be lagging behind the United States in terms
of pricing and variety.
At present, the major markets for nanoparticles (including fine particles of up to 250 nm) are automotive catalysts
(11,500 tons), abrasives (9,400 tons), magnetic recording
materials (3,100 tons), and sun-screen materials (1,500
tons).4) The numerals in parentheses indicate the final product quantities. Table 1 lists the ratios of companies developing products that use nanoparticles.4) The efforts in the
medical and pharmaceutical industry, such as for drug
delivery, are particularly noteworthy.
3. Subjects
Nanoparticles are of zero dimension but can be used as
fine lines in one dimension, as films in two dimensions,
and as bulk materials in three dimensions. Issues concerning nanoparticle fabrication technologies are: 1) particle
size control, 2) morphological and interface control for stable nanoparticles, and 3) low-cost mass production. In
order to produce quantum effects in particular, sharp particle size control (up to tens of nanometers) is necessary. As
nanoparticles easily coagulate, technologies to modify the
surfaces of nanoparticles and arrange and integrate the
nanoparticles on a substrate are needed.1)-6) Depending on
the particle generation phase, nanoparticle synthesis can be
classified into solid, liquid, and gas phase methods. So far,
the fabrication of nanoparticles has been done mainly by
experimentation. Technical problems are expected to be
solved by in-situ observation of the generation process, by
the introduction of colloidal and aerosol science and engineering, and by better simulation. The known requirements
for nanoparticle utilization are stabilization processing, dispersion processing, microspace use, nano-order composite,
formation of a film of generated particles, and advanced
handling for bulk formation. Theoretical work is necessary
to utilize conventional metals, ceramics, and polymers
beyond the framework of materials and for the fusion of
genetic engineering and materials, such as the use of DNA.
Regarding the process of converting ceramic nanoparticles
into bulk materials, the previous new materials boom
showed the importance of pre-sintering process science for
solving problems of surface contamination with particles
and particle coagulation, including its resultant inhomogeneous formation. Some researchers are therefore studying a
colloidal process based on a colloidal science technique
and bio-inspired processing.
4. Conclusion
Japan used to hold the lead in the nanoparticle field but
is being outstripped by the United States with advanced
technologies and by China and Korea with existing technologies. However, Japan still maintains technical superiority in manufacturing equipment, and so collaboration with
Japanese companies is indispensable for production. To
ensure the current demand continues and is not a temporary
boom, further systematic academic studies are required.
The risks and social influences of nanoparticles are
emerging mainly in Europe and America. In particular,
there is concern about the influence of nanoparticles on
health and the environment because they may be taken into
the human body during production, utilization, and disposal. Therefore, not only the advantages but also the disadvantages of nanoparticle applications should be
researched.7)
Table 1 Ratios of companies developing products using nanoparticles.
References
Medical and pharmaceutical
Chemical applied products
Information and communications
Energy
Automobile
Space and aeronautics
Textile
Agriculture
78
30 (%)
29
21
10
5
2
2
1
1) M. Koizumi, K. Okuyama and Y. Sakka: Latest Technologies of
Nanoparticle Manufacture, Application, and Equipment (CMC
Publishing) (2002) (in Japanese).
2) http://www1.ipdl.ncipi.go.jp/FP1/cgi-bin/
3) http://www.uspto.gov/
4) M. J. Pitkethly, Nanotoday, December, 36 (2003).
5) Nikkei Sangyo Shimbun (Dec. 1, 2003) (in Japanese).
6) Z. Tang and N. A. Kotov, Adv. Mater., 17, 951 (2005).
7) Asahi Shimbun (Mar. 30, 2005) (in Japanese).
01 Nanomaterials
Section 3. Quantum Dots
Nobuyuki Koguchi
Nanodevice Group, Nanomaterials Laboratory, NIMS
Since a zero-dimensional artificial nanostructure made
of semiconductor (the so-called quantum dot) shows quantum size effects, new functions not available from bulkstate semiconductor may emerge. Various countries have
been researching quantum dots in the expectation that using
such materials will produce devices having much higher
performance than the conventional silicon-based semiconductor devices whose performance seems to have reached a
plateau.
Based on the results of searching a database of academic
papers (SCI Expanded), this chapter summarizes the trends
in research on quantum dots. From all papers published
since 1970, papers containing a term meaning quantum dot
in their title, abstract, or keywords were searched and sorted, including those containing a term meaning bottom-up
or top-down fabrication. The number of papers published
by year and the transition by country was summarized.
Also, the transition in research regarding bottom-up applications is summarized by country.
Number of papers (Total)
Number of papers (Major countries)
Year
major countries. Figure 2 shows the transition in the number of papers published about quantum dots, containing a
term meaning top-down or bottom-up fabrication.
In 1982, the concept of the quantum dot was proposed
for the first time by Arakawa and Sakaki of the University
of Tokyo, with respect to application to an advanced semiconductor laser. 1) This triggered much nanotechnology
research.
Fewer than 20 papers were published annually in 1989
and earlier years, but the number increased quickly from
1990 and now more than 2,000 papers are published every
year. To date, over 16,000 papers have been published, a
number that is almost the same as that of papers on carbon
nanotubes on which research started at about the same
time. This indicates intensive research on quantum dots
throughout the world. Among papers related to quantum
dots, ones from Japan account for about 16%, ranking
about second with Germany after the United States and
verifying the global importance of research in Japan. It is
also noteworthy that the number of papers from China is
quickly increasing recently, and will exceed that of Japan
or Germany in the near future.
The number of papers related to quantum dots, containing a keyword meaning top-down or bottom-up fabrication,
was not more than two a year until 1989 but increased
quickly from 1990, and now more than 900 such papers are
issued every year (including more than 800 papers contain-
Quantum dot
Top-down/Bottom-up
Bottom-up
Bottom-up
Number of papers
1. Introduction
Top-down
Bottom-up
Fig. 1 Numbers of papers on quantum dots.
2. Trends in research
Figure 1 shows the transition in the number of papers
published about quantum dots, both worldwide and in
Year
Fig. 2 Number of papers on quantum dots and papers containing a
keyword meaning top-down or bottom-up fabrication.
79
Year
Fig. 3 Application of quantum dots to laser and light emitting devices.
Number of papers
ing a keyword meaning bottom-up fabrication). The number of published papers shows a similar tendency as the
total number of papers on quantum dots.
In1985, the CNRS group reported the formation of
three-dimensional nanostructures in the semiconductor
thin-film fabrication process.2) However, the above data
clearly indicate that there was little research on quantum
dots and few papers were published until 1989, because
there were no effective methods of fabrication. The proposal of top-down and bottom-up fabrication techniques for
quantum dots in 1990 triggered today’s active research on
quantum dots. Of these fabrication techniques, the droplet
epitaxy method proposed by the National Research Institute for Metals (presently the National Institute for Materials Science) in 19903) and the technique proposed by the
University of California and others in 1993 4) that uses
nano-size islands structure based on the Stranski-Krastanow (S-K) growth mechanism manifested during thinfilm formation were pioneering bottom-up fabrication techniques for quantum dots, while the selective growth
method proposed by NTT in 19905) was a pioneering topdown fabrication technique for quantum dots. These techniques are frequently used to fabricate quantum dots for
various semiconductor materials.
For quantum dots, the bottom-up fabrication techniques
will be popular. Compared with the technique based on the
S-K growth mechanism, the droplet epitaxy method could
not be established soon after it was proposed, so a technique based on the S-K growth mechanism is now usually
used. Unlike this technique, however, the droplet epitaxy
method6) allows quantum dots to be fabricated from even
combinations of materials called lattice matching, which is
not possible by the technique based on the S-K growth
mechanism, and also allows the shapes of quantum dots to
be controlled.7) Thanks to these features, the droplet epitaxy
method will develop further as a major bottom-up fabrication technique for quantum dots.
Year
Fig. 4 Application of quantum dots to infrared detectors and light
receiving devices.
1. Application of quantum dots to light emitting devices
(1,942 papers since 1982)
2. Application of quantum dots to infrared detectors and
light recieving devices (245 papers since 1991)
3. Application of quantum dots to single-electron effect
devices (1,772 papers since 1989)
4. Application of quantum dots to quantum information
processing (429 papers since 1995)
5. Application of quantum dots to spin electronics (35
papers since 1999)
6. Application of quantum dots to artificial atoms and molecules (386 papers since 1992)
7. Application of quantum dots to biological labeling (86
papers since 1998)
80
Quantum dot research started based on a few principles
but without clear applications, but the directions and applications of much research are now converging.
3. Outlook
Year
Fig. 5 Application of quantum dots to single-electron effect devices.
Figures 3 to 9 show the transition in the number of published papers by major country. Only papers employing the
bottom-up fabrication technique are counted here because
it is considered the technique will become increasingly
important.
Number of papers
Number of papers
Year
Year
Year
Fig. 8 Application of quantum dots to artificial atoms and molecules.
Number of papers
Fig. 6 Application of quantum dots to quantum information processing.
Year
Fig. 7 Application of quantum dots to spintronics.
Fig. 9 Application of quantum dots to biological labeling.
These figures show that Japan, the USA, and Europe
(mainly Germany) are competing in research. Regarding
“Application of quantum dots to light emitting devices”
that triggered quantum dot research, the number of published papers leveled off or started to decline in all countries since 2000. This is probably because the quantum dot
laser has now almost reached a practical level 8) and
research in this field has begun to shift to production. In
this field, standardization will be particularly important.
Regarding “Application of quantum dots to infrared
detectors and light receiving devices”, Japan tends to publish fewer papers than the United States and other countries, perhaps because Japanese research focuses on application to civil equipment.
Regarding “Application of quantum dots to artificial
atoms and molecules,” there is not much research aimed at
specific devices, yet this is very important from the basic
viewpoint of clarifying and controlling the unique properties of nanostructures.
Regarding research on application to single-electron
effect devices, quantum information processing, and spintronics, the number of published papers is growing steadily
and research will continue. Particularly concerning quantum information processing and spintronics, the total num-
ber of published papers is still small but is starting to rise
rapidly, and the trend needs to be monitored.
Although different from application to solid elements in
1 to 6, research on the application of quantum dots of II-VI
group compound semiconductors like CdSe to biological
labeling is being stepped up, especially in the United
States.
Research trends can also be investigated by searching
for papers on quantum dots published in the 5-year period
from 2000 for papers that are cited often. From the papers
published in each year, 10 papers are selected in descending order of citation frequency. By checking the contents of
the selected papers, we see that the percentages of papers
on “Application to quantum information processing” and
“Application to biological labeling” are very high. Of the
50 papers (total number of citations: 6,111) here, 14 papers
were on “Application to quantum information processing”
and were cited 2,424 times in total, 19 papers were on
“Application to biological labeling” and were cited 2,142
times in total.
81
4. Conclusion
Research on quantum dots may lead to the development
of devices far superior to the conventional semiconductor
devices of mainly silicon, which have nearly reached their
performance limit.
Regarding quantum dot applications related to solid
devices, the quantum dot laser that triggered quantum dot
research and the single-electron memory for room-temperature use9) that uses polysilicon have nearly reached a practical level, although more than 20 years have passed since
the first papers were published. Application to biological
labeling has started to some extent, following years of
intensive research on fine particles. For the application of
quantum dots to various practical purposes, ongoing
research is necessary in each field, especially for the fabrication and characterization of nanostructures.
This paper used the academic paper database “SCI Expanded” of ISI and the data is based on the search results as of
March 11, 2005. The keywords used for the quantum dot
search were “quantum dot*, quantum-size* dot*, quantum
well box*, quantum box* and multidimensional quantum
well* ”. (* means that some characters may be added after
the word.)
82
The author would like to thank Ms. W. Yamada for her
assistance in searching and sorting the database.
References
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01 Nanomaterials
Section 4. Nanodevices
Tsuyoshi Hasegawa
Atomic Electronics Group, Nanomaterials Laboratory, NIMS
1. Introduction
Semiconductor transistors, which underpin today’s
sophisticated information-oriented society, have been integrated and enhanced by reducing the device size. New
materials are now being employed and structures are being
optimized to improve the performance even further. However, once the minimum feature size enters the nano-scale,
the leakage current generated by the tunneling effect
becomes obvious and conventional semiconductor devices
no longer function properly,1) so a new technology is needed to enhance the performance of electronic devices. A
global strategy for semiconductor device development, the
International Technology Roadmap for Semiconductors
(ITRS), has therefore focused attention on nanodevices and
is now studying the performance and size of devices, and
also manufacturing costs and materials to realize nanodevices.2) Figure 1 compares semiconductor devices and nanodevices by ITRS. Since nanodevices have various characteristics depending on their type, optimum ones should be
selected according to the intended product. Fierce competition is underway throughout the world to replace semiconductor devices with electronic devices of higher performance based on these nanodevices.
This chapter reports the current status of nanodevice
development by introducing those of single-electron
devices in which single electrons are controlled using quan-
tum effects, and atomic or molecular devices in which single atoms or molecules are used as a device component.
In many cases, nanodevice R&D began with basic scientific research, then demonstration of the principle became
possible due to the nanotechnology advances. Some of the
nanodevices are now at the stage of being researched for
practical use, where integration techniques are being developed. For example, basic research on quantum effects such
as the metallic particle charging effect (Kubo’s effect)
announced in the 1960s led to the proposal of single-electron devices in the 1980s.3) By using a micro fabrication
technique and a scanning probe microscope, the basic
structure of the single-electron devices was constructed and
their operations were confirmed.
Meanwhile, molecular devices use molecules as device
components. It was theoretically shown that one organic
molecule could function as a diode in 1974,4) and various
research has been conducted.
Research on a new type of device that controls atom
transfer instead of electron transfer has started. With the
invention of the scanning tunneling microscope, individual
atoms could be observed and manipulated, and hence a
device for controlling atom transfer was achieved at last.
Today, all the nanodevices mentioned above are being
researched to clarify their individual performance and also
to integrate them and form circuits for practical use.
As nanotechnology advances, various kinds of nanodevices and their applications are being proposed and
researched. Due to limited space, this chapter introduces
the characteristics, development status, and potential of
nanodevices, and examines the significance of using new
materials in developing new nanodevices.
2. Research trends
Fig. 1 Comparison of semiconductor devices and nanodevices.
A single-electron device is a nanodevice that controls
the transfer of single electrons by using quantum effects.
As the quantum dot size becomes smaller, the electrostatic
energy changes by a greater amount when electrons go in
and out. Therefore, if small quantum dots are used, single
electrons can be controlled easily without operation error
due to the thermal effect. When developing a single-electron device, it is important to fabricate quantum dots that
are small and of uniform size.
83
Initially, metallic and semiconductor quantum dots were
made by using the conventional micro fabrication technique, which is a top-down technique. However, this was
impractical because only quantum dots with an operating
temperature lower than that of liquid helium could be fabricated.5) Therefore, more practical bottom-up techniques
such as using the self-organization of materials have been
employed. These techniques are now being used to produce
single-electron transistors, 6) single-electron memory
devices,7) and even logic circuits using the single-electron
effects.8) Indeed, integration technologies for some of these
are now being developed for practical applications. For
example, prototyping of a 128M-bit memory device using
polycrystalline silicon9) has already been fabricated.
Single-electron devices positively employing new nanomaterials are also being researched. This is because using
nanomaterials that are uniform in size and characteristics
enables reducing the quantum dot size to make single-electron devices of higher performance. Specifically, singleelectron devices have been fabricated by using carbon nanotube,10) fullerene, and single atoms11) as quantum dots. The
single-electron transistor using carbon nanotube has
already been verified to function normally at room temperature,12) paving the way for early actualization of a singleelectron device.
Figure 2 shows the transition in the number of papers on
single-electron transistor by year. The figure reveals that
the number has increased remarkably since the latter half of
the 1990s, and the number from Japan is as great as those
from Europe and the United States, indicating that research
in Japan is active.
Molecular devices are one of the nanodevices where
most intensive research is being done, boosted by the fact
that the scanning probe microscope has enabled not only
characterization of individual molecules to be measured but
also manipulation of the molecules themselves, and that a
monomolecular film can now be formed thanks to
advanced research on self-organizing films.
Molecular devices can be classified into one type that
uses single molecules as the functional parts (operational
elements) of a nanodevice and another type that controls
the reactions between molecules and uses the resultant
functions as operational elements and wires. Regarding the
former, a molecular switch using rotaxane molecules is
being researched. A two-terminal device using conductivity
that changes by molecule oxidization was also formed and
a logic circuit using the device was also reported. 13)
Research on the latter includes the utilization of electronic
state changes by the polymerization of porphyrin molecules, diacetylene molecules,14) and fullerene.15)
For a molecular device, the reversibility or irreversibility
of phenomena used for operations, such as oxidation-reduction reaction and polymerizing reaction, greatly influences
applicability of the device. A recent experiment by a group
of the National Institute for Materials Science that proved
the reversibility of the polymerizing reaction for fullerene
molecules is thus of particular interest.
A device using atom transfer is also under development.
Though the atom transfer speed is lower than the electron
transfer speed; for a nanodevice whose transfer distance is
84
Fig. 2 Numbers of papers on single-electron transistor by years.
of nano-scale, the transfer time or the time necessary for
device operation is shorter than a nanosecond, which is the
same level as the operation time of an electronic device. On
the contrary, using atoms not lost by the tunneling effect
may enable the fabrication of a device having higher performance than the conventional device that controls electrons.
A nanodevice controlling atom transfer was verified first
under a scanning tunneling microscope.16) A rare gas atom
was transferred between the probe of the scanning tunneling microscope and the surface of a sample to vary the conductivity between the probe and sample. Thereafter, a
device where a metal atomic bridge appears and disappears
between two electrodes was developed. To control the
appearance and disappearance of an atomic bridge, a scanning tunneling microscope was used first but a technique
using an electrochemical reaction was developed later. The
latter can be classified into a method using liquid electrochemical reaction17) and another using solid electrochemical reaction; 18) the latter is considered to be practical
because it can be easily adapted to the existing semiconductor device fabrication process. In fact, research is not
limited to element verification but has already been extended to logic circuit fabrication19) and integration20) by introducing new materials called mixed electronic and ionic
conductors to device fabrication.
3. Outlook
So far, research on nanodevices has been merely basic
research. This is because improvement of device performance meant that of semiconductor devices regarding practical devices. However, as the improvement of the performance of semiconductor devices has almost reached its
limit, work is progressing on developing practical nanodevices. Researchers are attempting to develop an integrated
circuit using nanodevices and to construct an architecture
utilizing the characteristics of nanodevices that operate
according to a different principle from that of conventional
semiconductor devices.
For single-electron devices, architectures utilizing the
Switch resistance (Ω)
4. Conclusion
Atomic switch
Switch size
Fig. 3 Switch size and ON resistance.
single-electron device characteristics are being researched,
as well as the conventional logic architecture based on
Boolean algebra. The new architectures include Cellular
Automaton21) and Binary Decision Diagram,22) and devices
based on these architectures are now being prototyped.
For molecular devices, logic circuits 13) and memory
devices23) are being prototyped, as well as switches, transistors, and other basic element structures. In addition, new
architectures24) are being studied using their characteristics.
Molecular devices are expected to be applied to sensors by
using molecular characteristics and there is growing
demand for devices that cannot be created with conventional semiconductor devices. Organic molecules are already
being used for liquid crystal displays and seem to be easy
to put to practical use as materials.
With this background, research on practical atomic
devices will accelerate because atomic devices may solve
almost all the problems inherent in semiconductor devices.
For example, the ON resistance of conventional semiconductor devices increases as they become finer. Even if a
nano-scale semiconductor device is developed successfully,
integration is thought to be impossible due to power consumption. On the contrary, atomic devices using metals are
free of such problems (see Figure 3). These characteristics
enable the development of electronic devices for new types
of products that cannot be realized with conventional semiconductor devices. For example, research has started on
developing programmable devices indispensable for highperformance mobile terminals in the ubiquitous information-oriented society.25)
Device development using solid electrolytes is not limited to nanodevices and is already reaching a practical level.
In the United States, for example, device manufacturers are
now developing memory devices using metallic bridges,
indicating that companies are trying to shake themselves
free from device development that is dependent solely on
semiconductor devices.
Using nanodevices not only enhances the performance
of conventional electronic devices but enables new electronic devices and products to be developed. As an example of using molecular switches, a defect-tolerant architecture of a crossbar structure 26) has been proposed. This
architecture is also applicable to other molecular switches.
Single-electron devices and atomic devices can also be
used to construct neural networks, which may lead to
remarkable development in the field of electronics.
This chapter examined single-electron, molecular, and
atomic nanodevices and described their development status
and future progress. As semiconductor devices reach a
development plateau, nanodevice development is shifting
from the basic level to the practical level.
Nanodevices not only enhance the performance of electronics using semiconductor devices but also enable new
electronic products and computer architectures to be developed that cannot be attained with conventional semiconductor devices. As the examples in this chapter show, the
key to nanodevice development is how the new functions
of materials can be used in device operations. Therefore,
the development of materials for new functions will continue to play a crucial role in nanodevice development, as will
the development of practical circuits and integration techniques.
References
1) P. Gelsigner, Tech. Dig. 2001 IEEE Int. Solid-State Circuits Conf.,
San Francisco, p. 22.
2) ITRS web site: http://public.itrs.net/Nanodevices are handled as
emerging technology.
3) D. V. Averin and K. K. Likharev, Mesoscopic Phenomena in
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Publishers, (1991) Chap. 6.
4) A. Aviram and M. A. Ratner, Chem. Phys. Lett., 29, 277 (1974).
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Today, No. 109, 30. Science (2002).
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Int. Solid-State Circuits Conf., p. 266 (1996).
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9) K. Yano, T. Ishii, T. Sano, T. Mine, F. Murai, T. Kure and K. Seki,
IEEE Int. Solid-State Circuits Conf. p. 344 (1998).
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86
Chapter 2.
Superconducting Materials
Section 1. Oxide Materials
Hiroaki Kumakura
Superconducting Materials Center, NIMS
1. Introduction
There are many kinds of oxide superconducting materials, among which the high-temperature oxide superconducting materials of bismuth-based oxides and
YBa2Cu3Oz(Y-123) are now being studied in detail toward
practical use. Two bismuth-based oxides are
Bi2Sr2CaCu2Ox(Bi-2212) and Bi 2Sr2Ca2Cu3Oy(Bi-2223).
Figure 1 shows the transition in the number of papers published about these three superconducting materials in the
past decade; many are published every year on all of these
materials, indicating the active state of research.
This section introduces research on wires and tapes
made of these high-temperature oxide superconducting
materials. The powder-in-tube (PIT) method is the most
popular for making wires of both bismuth-based oxides
Bi2Sr2CaCu2Ox(Bi-2212) and Bi 2Sr2Ca2Cu3Oy(Bi-2223).
Oxide superconducting materials have a problem of weak
coupling between crystalline grains. To avoid this problem,
it is necessary to orient the crystalline grains of oxide
superconductor, which greatly improves the coupling
between crystalline particles and allows a large superconducting current. All oxide superconductors have layered
crystalline structures. The crystalline grains of bismuth
oxides are relatively easy to orientate because the materials
have strong anisotropy (two-dimensionality). However, the
technique of orientation differs between Bi-2212 and Bi2223: heat treatment by partial melting and gradual cooling
is used for Bi-2212, with the Bi-2212 heated just beyond
the melting point and then cooled slowly.1) In contrast, Bi2223 is oriented by a combination of machining and heat
treatment.2)
Compared with the bismuth-based oxides, YBa2Cu3Oy
(Y-123) has much smaller two-dimensionality and its critical current characteristic at the temperature of liquid nitrogen (77 K) is far superior. To overcome the problem of
weak coupling, however, uniaxial orientation (c-axis orientation) alone is insufficient; biaxial orientation is also necessary. 3) Therefore, the vapor method is mainly used
throughout the world to deposit a thick film of Y-123 on a
metallic substrate tape. The product is usually called coated
conductor.4) There are two main methods for achieving
biaxial orientation, one of which is called Ion Beam Assisted Deposition (IBAD). This method deposits a film on a
non-oriented metallic substrate tape of hastelloy or other
material. The key technique is the deposition of biaxially
oriented intermediate layer of yttria stabilized zirconia
(YSZ). The biaxially oriented Y-123 film is epitaxially
grown on the oriented intermediate layer by pulsed laser
deposition (PLD). The other method is called rolling assisted biaxially textured substrate (RABiTS); a metallic substrate of Ni or other metal is oriented by machining and a
Y-123 film is deposited on the substrate through an intermediate layer.
Number of papers
2. Global trends
Year
Fig. 1 Numbers of papers on Bi-2212, Bi-2223, and Y-123.
This section examines the trends in R&D on wires and
tapes in major countries. Research is most advanced in the
United States where many companies, universities, and
national laboratories are engaged in research, with the good
links among them perhaps being a factor for success. The
United States has several national projects on the application of oxide superconducting materials. There is an established system whereby companies are in charge of wire and
tape development and universities and national laboratories
are in charge of related basic research.
Regarding Bi-2212, Oxford has been developing wires
87
and tapes and recently began to fabricate high-performance
wires in lengths of several kilometers. Regarding the characterization of Bi-2212 tapes and wires, Florida State University is conducting research with Oxford. The university
is also researching the application of Bi-2212 to high magnetic fields. The National Renewable Energy Laboratory is
proceeding with tape research by the coating method and
Wisconsin University is also researching Bi-2212 although
on a small scale.
A Bi-2212 wire and tape show far superior characteristics to metallic wires at low temperature in a high magnetic
field, and so a high-field magnet is one promising application of Bi-2212 wire. The National High Magnetic Field
Laboratory, Florida University plans to fabricate high-field
magnets from Bi-2212 wires. They have already fabricated
a small coil from a 2 km long Bi-2212 tape and installed
the coil in a normal-conduction magnet of 19.85 Tesla to
generate 5.20 Tesla, achieving a magnetic field of 25.05
Tesla in total.
Regarding Bi-2223, American Superconductor (AMSC)
is the world-leader in the development of Bi-2223 tapes of
practical lengths. As the world’s leading producer of Bi2223 tape, the company has fabricated many tapes of several kilometers length for national projects, and their Bi-2223
tapes are also used in the test coils of Japan’s Maglev,
which will be mentioned later. Meanwhile, Wisconsin University is actively conducting basic research and supporting
AMSC, which is further supported by the Los Alamos
National Laboratory (LANL) and the Argonne National
Laboratory (ANL).
Since as-cold rolled tapes have large pore in the core of
a Bi-2223 tape, the Bi-2223 filling factor was not large and
needed to be improved. US Wisconsin University recently
developed a high-pressure thermal treatment method that
improves the filling factor of Bi-2223 core and increases Jc
greatly.5) This high-pressure heat treatment method also
reduces the percentage of Bi-2212 and other impurities,
thus increasing Jc. Geneva University of Switzerland and
Sumitomo Electric Industries are also conducting similar
research.
Regarding coated conductors, such national laboratories
as LANL, Oak Ridge National Laboratory (ORNL), and
ANL are powerfully promoting national projects. LANL
adopted the IBAD method and ORNL adopted the RABiTS
method to produce long tapes. ANL is proceeding with
research by a method called Inclined Substrate Deposition
(ISD). The relationship between microstructure and superconductivity is under intensive research by Wisconsin University, which is the center of basic wire research in the
United States, including metallic wires. IGC-Superpower
and AMSC are also making progress, such as fabricating
high-performance coated conductors.
Many organs are conducting research also in Europe, but
the links among them seem to be weaker than in the United
States. In Germany, Gottingen University has long been
researching superconducting wires and tapes and is now
focusing on coated conductors. In Switzerland, Geneva
University is conducting research to solve various materials
science problems concerning Bi-2223 and Y-123 tapes. In
the UK, IRC in Superconductivity of Cambridge University
88
is conducting basic research on Bi oxide wires and tapes. In
France, Nexans is engaged in the research of Bi-2212 wires
and fabricating wires of several kilometers length. In Spain,
the Institut de Ciencia de Materials de Barcelona is
researching coated conductors. In Austria, Vienna University of Technology is making progress in research on the
irradiation effects of superconducting wires and other subjects.
In Australia, the University of Wollongong has the Institute for Superconducting and Electronic Materials where
Bi-2223 wires and coated conductors are being researched
intensively in relation to microstructure and superconductivity. The institute has close links with Australian Superconductors in the country.
In Asia, Innova Superconductor Technology, which was
recently established in China, successfully fabricated 1-km
Bi-2223 tapes and is now setting up a supply system.
Regarding the critical current characteristic, the company
still lags behind others, but is anticipated to improve the
characteristic in the near future and will then become a
strong competitor for Bi-2223 tape manufacturers in Japan
and the United States. Note that this company has close
links with the Applied Superconductivity Research Center
of Tsinghua University, where basic research is being done
on Bi-2223 tapes. The Institute of Electrical Engineering is
also conducting applied research on Bi-based oxides but
their basic research on materials may not be enough.
In Korea, oxide superconducting materials are now
being developed intensively and the Korea Institute of
Machinery and Materials is conducting research to enhance
the performance of Bi-2223 wires and also on coated conductors. In addition, Seoul National University is researching coated conductors.
3. Domestic trends
In Japan, much research on oxide superconducting wires
and tapes is underway and the general research activities
are similar to those in the United States. The main organs
conducting research on Bi-2212 are the University of
Tokyo, Hitachi Limited, Hitachi Cable, Showa Electric
Wire & Cable, and NIMS. The University of Tokyo is conducting research on the Pb substitution of Bi-2212 and
other basic studies, rather than on wire fabrication itself.
Hitachi Limited and Showa Electric Wire & Cable have
been developing Bi-2212 multicore round wires which are
advantageous for practical use. Hitachi Limited successfully achieved 100 m-long round wires and Showa Electric
Wire & Cable attained 500 m-long round wires. Meanwhile, Hitachi Cable succeeded in the experimental fabrication of 2 km-long round wires with no thermal treatment.
These companies are conducting basic research with
NIMS. Regarding applications, Chubu Electric Power and
Showa Electric Wire & Cable are developing coils for
Superconductive Magnetic Energy Storage (SMES) by
using Showa’s Bi-2212 round wires. In addition, Showa
Electric Wire & Cable is manufacturing assembled conductors, called Rutherford cables, from Bi-2212 round wires
and delivering them to the US Lawrence Berkeley National
Laboratory.
Regarding Bi-2223 wires, Sumitomo Electric Industries
is the central manufacturer. The company has already
developed tapes of several kilometers length and has started supplying tapes by participating in the US superconducting cable project. In addition, Furukawa Electric and
Showa Electric Wire & Cable are proceeding with R&D
for Bi-2223 tapes. Regarding basic research, Kyoto University is conducting research on the relationship between
microstructure and characteristics and also conducting
model analysis and research on stress effects. Meanwhile,
Kyushu University and Kyushu Institute of Technology are
actively researching electromagnetic characteristics. However, for Bi-2223 tapes, in general the links among manufacturers, universities, and national laboratories are not
strong. The most popular application of Bi-2223 is power
transmission cables. The Central Research Institute of Electric Power Industry is performing various characteristic
tests on 500-m power transmission cables experimentally
produced by Furukawa Electric. By using Bi-2223 tapes,
coils for magnetically levitated trains (Toshiba and JR
Tokai) and superconducting transformers (Kyushu University) are also being prototyped and tested.
Regarding coated conductors, the Superconductivity
Research Laboratory is performing research through a
national project with domestic companies and universities,6) with the participation of Fujikura, Sumitomo Electric
Industries, Showa Electric Wire & Cable, Furukawa Electric and other firms, and is promoting R&D mainly on the
IBAD method and Metal Organic Deposition (MOD)
method. In addition, Fujikura is proceeding with unique
R&D. In this field, Japan is in fierce competition with the
United States. In basic research, Kyoto University is studying the fabrication process, while Kyushu University and
Yokohama National University are conducting precision
analyses of the critical current characteristic and evaluations of the AC loss. Regarding length, the recent successful fabrication of 100-m tape having good characteristics
put Japan one step ahead of the United States.
Coated conductors used to have a problem that it takes a
long time to form an intermediate layer by the IBAD
method, but the Superconductivity Research Laboratory of
Japan recently found that a CeO2 layer having a higher
degree of grain orientation than the intermediate layer
could be quickly obtained if the CeO2 film is further evaporated on the intermediate layer as the cap layer by the PLD
method (self orientation). If a Y-123 layer is deposited on
this CeO2 layer, a Y-123 film having high orientation can
be obtained for very high Jc.
Compared with the above PLD method, an easier application method (MOD method) is being researched and a
high Jc characteristic can now be obtained. Since no vacuum chamber is necessary, this method can be easily scaled
up and industrialized to enable tapes to be fabricated at low
cost.
tion mainly by the PIT method and the dip coating method.
NIMS has already developed the partial melting and slow
cooling method for the c-axis orientation of crystalline
grains and the Pre-Annealing & Intermediate Rolling
(PAIR) method, thus successfully achieving the world’s
highest critical current density Jc. The partial melting and
slow cooling method is now used worldwide as the standard heat treatment for Bi-2212 wires and tapes. Compared
with the conventional metallic superconductors, Bi-2212
wires produce much higher Jc especially in a high magnetic
field, which is extremely promising for application to high
magnetic field generation. Nano-level structural control is
also useful. For example, the oxygen partial pressure upon
heat treatment changes the grain boundary structure and Jc.
Research is also underway on the microstructure and characteristics, such as biaxial orientation by temperature gradient heat treatment and the resultant enhancement of Jc
characteristic. NIMS is also conducting joint research with
Showa Electric Wire & Cable to increase Jc of Bi-2212
multicore round wires. NIMS recently found that slow
cooling from a narrow temperature range just above the
partial melting temperature of Bi-2212 greatly improves Jc,
probably because Bi-2212 filaments do not become irregular or coarse, and they have attained the world’s highest Jc
for round wires.
Regarding applications, NIMS is proceeding with
research to enhance the magnetic field generated by a
superconducting magnet using Bi-2212 wires and tapes. By
using Bi-2212 tapes small test coils were fabricated jointly
with Hitachi Limited and Hitachi Cable, and were then
installed at the center of existing superconducting magnets
system to increase the magnetic fields by the Bi-2212
coils.7) NIMS attained a total magnetic field of 21.8 Tesla
with coils by the dip coating method and 23.4 Tesla with
coils by the PIT method, the latter being the world’s highest magnetic field generated by a superconducting magnet
system. When small magnets fabricated from Bi-2212
wires were cooled by a cryocooler not requiring liquid helium, the magnetic field was high enough and the magnets
were thermally stable at temperatures around 20 K. So
there are high expectations for superconducting magnets
made of Bi-2212 wires which can be cooled very efficiently by a cryocooler.
In addition to the above application research, NIMS has
been searching for new superconducting materials and also
developed high-pressure equipment. With these devices,
NIMS immediately started searching for new high-temperature superconductors under high pressure and successfully
found more than half of the existing oxide superconductors
that had a transition temperature exceeding 100 K. Through
a chemical oxidation process, NIMS obtained a hydrated
cobalt oxide superconductor (NaxCoO2/yH2O).8) Its Tc is
not higher than about 5 K, however, this is the first cobalt
oxide that showed superconductivity. This discovery provides a new direction for superconducting materials
research and may help clarify the mechanism of superconductivity of high-temperature oxides.
4. Current status of NIMS and research by NIMS
NIMS is proceeding with Bi-2212 wire and tape fabrica89
5. Outlook
Bi-2223 and Bi-2212 wires and tapes having high J c
were recently produced in various studies both within and
outside Japan but have not yet reached a practical level. In
various experiments, both Bi-2223 and Bi-2212 wires and
tapes locally showed sufficiently high Jc for practical use,
so both materials offer good potential. Actual bismuthbased wires and tapes, however, have many defects that
hinder a superconducting current, such as voids, impurities,
and misorientation, and so a sufficient superconducting
transport current cannot be obtained. There are also
unknown mechanism in terms of materials, such as the
transfer mechanism of a superconducting current at the
crystalline grain boundary.
To solve these problems, R&D on a new technique
seems indispensable. The basic parameters that characterize superconducting materials include coherence length.
Since this parameter is on the nanometer level, structural
control of the nanometer level may be effective for improving the characteristics. For example, it will be important to
use nanoparticle starting materials, to modify layered crystalline and grain boundary structures, and to introduce
nanometer particles. Through such techniques, Jc of Bi2212 should be improved at 4.2 K and 20 K and that of Bi2223 should be improved also at 77 K.
Meanwhile, coated conductors showing excellent Jc
characteristics on short tapes have been developed. For
practical use in future, technologies for creating tapes of
several kilometers length and reducing the manufacturing
cost are needed. In both cases, close links among companies, universities, and national laboratories will be crucial
for efficient R&D.
To enhance characteristics by nanostructure control, it is
important to establish a technology for evaluating the
microstructure of wires and tapes and the distribution of
superconducting current densities on the nanometer level
90
and to feed back such information to the wire and tape fabrication process. For this nanometer-level analysis, we will
establish a technique of analyzing the microstructure and
properties of a micro-area with a scanning SQUID magnetic microscope for the two-dimensional analysis of current
distribution and a microwave STM, as well as a transmission electron microscope.
Meanwhile, research on new superconductors having
better characteristics than the existing oxide superconductors will be important not only academically but also for
applications. For new materials synthesis, synthesis in a
special environment (ultrahigh pressure, ultrahigh gas pressure, and soft chemistry) may be promising. We should
promote R&D on these techniques to obtain new superconductors as the seeds for next-generation superconducting
materials.
References
1) H. Kumakura, Bismuth-based High-Temperature Superconductors,
Eds. H. Maeda, K. Togano, Marcel Dekker, Inc., New York (1996)
451.
2) Y. Yamada, Bismuth-based High-Temperature Superconductors,
Eds. H. Maeda, K. Togano, Marcel Dekker, Inc., New York (1996)
289.
3) D. Dimos, P. Chaudhari, J. Mannhart and F.K. LeGoues, Phys. Rev.
Lett., 61, 219 (1988).
4) Y. Shiohara and N. Hobara, Adv. Superconductivity XII (2000) p.
567.
5) Y. Yuan, R. K. Williams, J. Jiang, D. C. Larbalestier, X. Y. Cai, M.
O. Rikel, K. L. DeMoranville, Y. Huang, Q. Li, E. Thompson, G.
N. Riley and Jr., E. E. Hellstrom, Physica C 372-376, 883 (2002).
6) Y. Shiohara: Cryogenic Engineering, 39, 511 (2004).
7) M. Okada, K. Tanaka, T. Wakuda, K. Ohata, J. Sato, T. Kiyoshi, H.
Kitaguchi, H. Kumakura, K. Togano and H. Wada, Advances in
Superconductivity, XI (1999) 851.
8) Y. Sakurai, K. Takada, and E. Muromachi: Appl. Phys., 74, 22
(2005).
02 Superconducting Materials
Section 2. Metallic Materials
Takao Takeuchi
Metallic Wire Group, Superconducting Materials Center, NIMS
Among thousands of kinds of superconducting materials
discovered, only the four kinds of metallic superconducting
materials (Nb-Ti alloy and Nb3Sn, Nb3Al, and MgB2 compounds) listed in Table 1 are already in service or expected
to be used, along with one kind of Y-type oxide superconductor and two kinds of Bi-type oxide superconductors.
Compared with oxide superconductors, metallic superconducting materials are low both in critical temperature Tc
and critical field B c2, and so metallic superconducting
materials may be replaced with practical oxide superconducting materials in future. Regarding superconducting
applications (Table 1), oxide superconductors cannot be
used yet because of poor mechanical characteristics and the
difficult superconducting joint, so the performance of
metallic superconductors still needs to be improved.
To review the trends in R&D of metallic superconductors, an academic database was searched for papers that
contain materials names in their titles. Figure 1 shows the
number of published papers by year. The number of papers
on MgB2 just discovered in 2001 is far larger than those on
other metallic superconducting materials. This reflects the
high expectations for the new MgB2 material which features the highest T c and low-cost metallic materials.
Regarding comparisons of Nb-Ti, Nb 3Sn, and Nb 3Al,
research on their bulk state properties was completed in the
1960s and 1970s, and the research was shifted to the practical form of wires and thin films in the 1990s. A search of
the academic paper database revealed that papers containing wires or thin films in their titles (gray) accounted for
about 20 to 30% of the total number of papers on MgB2,
which was about 1.5 to 2 times the number of papers on
Nb3Sn. Figure 1 shows that research on MgB2 has been
particularly active in the past few years but the number of
papers on other metallic superconductors has not
decreased. This may be because many MgB2 researchers
have returned from the field of oxide superconductors.
According to OST’s unique survey,1) Nb-Ti and Nb3Sn
accounted for most of the world’s output of superconducting materials by weight in FY2004 (Figure 2(a)). Of 1,100
tons in total, Nb-Ti accounted for 97.8%, followed by
Nb3Sn with 1.5%. The rest, just 0.7%, is Bi-type oxide
superconductor. According to statistics on wire sales by
equipment type in FY2004 (Figure 2(b)), magnetic reso-
Number of papers
1. Introduction
Year
Fig. 1 Numbers of papers on metallic superconductors (Source: Web of
Science).
Table 1 Comparison of main metallic superconductors.
Nb-Ti alloy
Critical temperature Tc 9.6 K
Critical field Bc2 (4.2 K) 11.5 T
Ductility (Handling: Easy)
Feature
Low cost
10 T or less
Medical MRI
Superconduction
NMR
application
Accelerator
Magnetic levitated train
Nb3Sn
18 K
26-28 T
Strain sensitivity: High
Nb3Al
17.5-18.5 K
26-30 T
Strain sensitivity: Low
MgB2
35-39 K
10-50 T
20 K run
Lightweight
High-field NMR•MRI
Coil for properties research
Accelerator
Fusion reactor
Fusion reactor
Liquid hydrogen coolant
High-field NMR•MRI Magnetic levitated train
Accelerator
Space environment
Coil for properties research
91
Other
Big Physics
Total annual output: 1,100 tons
Wire sales (2004): 185 million dollars
Fig. 2 (a) Wire output by materials, (b) Wire sales by application type1)
in 2004.
nance imaging (MRI) apparatuses and nuclear magnetic
resonance (NMR) spectrometers account for about 60% of
wire sales, for which Nb-Ti and Nb3Sn are employed. The
total number of MRI and NMR units sold annually is
increasing at the rate of 8 to 10% and much research is
being done to enhance the performance of Nb-Ti and
Nb3Sn and to reduce their cost.
2. Global trends
Advanced medical institutes in and outside Japan are
experimentally using MRI apparatuses of which the magnetic field is as high as almost 10 Tesla. To enable such
high-field MRI to be widely used in medical hospitals in
future, we need to develop a low-cost Nb3Sn (or Nb3Al)
wire available for the R&W method that winds a coil after
forming the Nb3Sn phase. With a view to achieving highperformance analysis of protein structures, Japan, the US,
and Europe are strategically developing 1 GHz (23.5 Tesla)
NMR, for which the high-field superconducting materials
Nb3Sn and Nb3Al are key to success. For large-scale applications, the performances of Nb-Ti, Nb3Sn, and Nb3Al need
to be improved continuously. Metallic superconductor
research was led by the CERN accelerator (LHC) and
fusion reactor (ITER) in the mid 1990s, and by the nextgeneration accelerator and other large projects since 2000.
The total demand for superconducting materials for ITER
magnets is as large as 550 tons for Nb3Sn or 250 tons for
Nb-Ti. Production facilities need to be built to produce and
deliver the materials within a few years after the start of
construction.
The keys to raising the performance of Nb3Sn are to
increase the amount of Sn which contributes to the diffusion reaction and to control microstructures on the nanolevel. Consequently, the critical current density per cross
section excluding stabilizing copper (non-Cu Jc) at 12 Tesla
and 4.2 K was doubled to 3000 A/mm2 in the past decade.
In other words, the bronze method increased the Sn concentration in Cu to the solubility limit (16%) to make the
grain finer and thus increase Jc. However, it is difficult to
raise the Sn concentration of bronze further. Meanwhile,
the internal Sn diffusion method uses a Cu matrix containing not only Nb filaments but also Sn as cross-sectional
92
components. This method has been actively studied in
Japan, the US, and Europe (Mitsubishi Electric, Outokumpu, Bochvar, and Alstom) because it allows the Sn
content to be increased, thus raising J c, although the
method is inferior to the bronze method in terms of AC
loss. Recently, OST in the US made further improvements
to satisfy the high Jc specification for the next-generation
accelerator. By minimizing the Cu ratio, they successfully
achieved a high non-Cu Jc of 3000 A/mm2 at 4.2 K and 12
Tesla. To overcome the problem of low mass-production, a
dummy salt placeholder was adopted instead of Sn so as to
allow the hot extrusion of large 200 kg multi-billets. Immediately after extrusion, the salt is substituted with Sn and
processed by cold wire drawing to attain adequate unit
lengths and low cost. In future, it will be important to
improve the stability (Cu contamination with Sn), AC loss
characteristic, and mechanical characteristics that have
been sacrificed in order to achieve high Jc. The Northwest
Institute for Non-ferrous Metal Research of China recently
started large-scale production not only of Nb-Ti but also
Nb3Sn by the internal Sn diffusion method. Although the
Institute’s products are inferior in the Jc characteristic, the
prices are low for the global market and so the situation
should be monitored. SMI of Europe improved the powderin-tube (PIT) method; NbSn2 powder filled diffusion-reacts
with an Nb tube to form Nb3Sn, which is advantageous for
attaining high Jc. With cooperation from EAS, SMI successfully extended the unit-length by large billets (50 kg).
This has an advantage of less Sn contamination of the Cu
stabilizer placed outside Nb.
As mentioned later, Nb3Al is mainly being developed in
Japan.2) In the United States, Ohio State University, OST,
IGC, and Supercon have been developing rapid-quenched
Nb 3 Al for the next-generation accelerator. Recently,
EURATOM-ENEA of Italy also started research on rapidquenched Nb3Al.
Although other metallic superconductors require liquid
helium as a coolant, MgB2 has a high critical temperature
and so the cooling costs can be greatly reduced if environment-friendly liquid hydrogen – a possible future energy
source – is used as the coolant for superconductor. Because
of its lightweight characteristic, MgB2 is expected to be
used for magnetically levitated trains and space applications. When discovered, MgB2 had a problem of low Bc2
for high Tc. However, the trace oxygen soluble thin film
developed by Wisconsin University and the SiC nanoparticles added by the University of Wollongong, Australia,
greatly improved Bc2 by substituting C with B, thus proving
the immense potential of the material as wires for high
magnetic fields. Intensive research is now in progress in
Japan, the US, Europe, and Australia to produce MgB2
wires by the PIT method. Compared with other metallic
superconductors, however, MgB2 is still at an early stage of
research. Wires of 1000-m class have already been fabricated, suggesting that the length can be increased easily, as
expected. As shown by a collection of data3) comparing the
non-Cu Jc characteristic between various superconducting
wires, the Jc values of MgB2 long wires are still low.
3. Trends in Japan
Regarding Nb-Ti, Furukawa Electric produced and
delivered 92 tons in total to CERN in Europe as a conductor for the LHC accelerator from 2000 to 2003. CERN
bestowed an award on Furukawa Electric for higher quality
of the products than other overseas manufacturers, demonstrating the high technical power and competitiveness of
Nb-Ti wires.
Regarding Nb3Sn,4) note that Kobe Steel produced highSn-content bronze-route Nb3Sn wires for the first time in
the world. Now Kobe Steel, Furukawa Electric, and Hitachi
Cable are developing high-Sn-content bronze-route Nb3Sn
wires for high-field NMR. The high-Sn-content bronzeroute Nb3Sn is about to be used not only for NMR but also
ITER. The wires of the ITER fusion reactor require both
low hysteresis and high J c. Like the internal Sn Nb 3Sn
wires of which inter-filament coupling is suppressed, the
high-Sn-content bronze Nb3Sn wires with high Jc are very
promising materials for fusion uses. The Ta-Sn PIT Nb3Sn
wires jointly developed by Tokai University and Kobe
Steel are attracting attention as new candidate wires for
high-field NMR. Regarding the development of Nb3Sn
wires of high Jc for the next-generation accelerator, Japan
lags behind the United States because wire development
programs used to be led by the US. Recently, however,
Mitsubishi Electric started developing wires featuring
improved the internal Sn Nb 3Sn wire, and this work is
worth monitoring.
Regarding Nb3Al, the Japan Atomic Energy Agency has
been developing Nb3Al wires by the low-temperature diffusion method jointly with Sumitomo Electric Industries by
noting lower strain sensitivity and hence better strain tolerance. By using a trial manufactured Nb3Al coil with the
R&W technique, a high current as large as 46 kA was successfully achieved at 13 Tesla in 2003. However, the values of Bc2 and Jc of the low-diffusion processed Nb3Al are
lower than those of rapidly quenched Nb3Al. Since the
magnetic field required by the next-generation fusion reactor will increase from 13 Tesla to 16–20 Tesla, low-temperature diffusion processed Nb3Al will not be able to satisfy
the requirement and thus the rapid-heating, quenching and
transformation (RHQT) processed Nb3Al will be developed
jointly with NIMS. The High Energy Accelerator Research
Organization started developing RHQT Nb3Al for the nextgeneration accelerator jointly with Hitachi Cable and
NIMS.
Regarding MgB2,5) JR Tokai and Hitachi Limited started
developing MgB2 wires by considering application to coils
for magnetically levitated trains and to MRI. By the ex-situ
method that fills MgB2 powder directly into a Cu/Fe composite pipe, they fabricated a small coil experimentally
from a single-core wire of about 50 m and succeeded in
generating a magnetic field. Future issues are to make long
lengths of wire, to increase the number of filaments to suppress instability in a low magnetic field, and to develop a
superconducting joint technique. By mixing indium metallic powder of a low melting point into raw MgB2 powder,
Tokai University successfully improved the connectivity
between MgB2 particles and greatly increased Jc.
Regarding the RHQT Nb3Al initiated in 1996, NIMS has
been collaborating with Hitachi Cable to develop it as a
candidate wire for the insert coil of high-field NMR now
under development at the Tsukuba Magnet Laboratory.
Nb/Al precursor wires are rapidly heated and quenched to
prepare a supersaturated bcc solid solution once and then
transformed into Nb 3Al by additional heat treatment.
Unlike the low-temperature diffusion method, this method
produces stoichiometric and fine microstructures and features high non-Cu Jc over the whole range of magnetic field
up to 20 Tesla or more. Excellent strain tolerance is not
lost. NIMS is also developing wires jointly with the High
Energy Accelerator Research Organization, Japan Atomic
Energy Agency, and National Institute for Fusion Science
for the next-generation accelerator and fusion reactor as
well as for high-field NMR. Regarding making long-length
wire, a Nb/Al precursor wires of 2.5 km long were successfully manufactured. Techniques for rapidly heating and
quenching such long wires, and also for stabilizing the
wire, need to be developed urgently. NIMS is now developing a method of mechanical cladding after RHQ operation for NMR uses, an internal stabilization technique of
dispersing Nb-jacketed Ag-rods for accelerators and fusion
uses, and also a copper ion plating/electroplating method. It
will also be necessary to take measures against a flux jump,
to pin the flux line by nano-scale microstructure, and to
optimize the transformation processing conditions to
enhance non-Cu Jc.
Regarding Nb 3Sn, NIMS started research in 2003 to
raise Jc by a new method using a Cu-Sn compound (ε
phase, η phase) having a higher Sn concentration than
bronze as the starting material. The future tasks are to
enhance and stabilize the Jc characteristic and to extend the
length. Regarding the bronze-route Nb3Sn, a basic study
was also started to convert the residual bronze into copper
by selective oxidization of Sn, after the Nb3Sn-formation
heat treatment.
Regarding MgB2, NIMS started fabricating wires by the
PIT method immediately after Aoyama Gakuin University
discovered its superconductivity in 2001. NIMS used the
ex-situ method that fills MgB2 compound power into a
metallic tube and the in-situ method that fills Mg and B
blended powder into a metallic tube and generates MgB2 by
heat treatment. In the latter method, we used MgH2 powder
instead of Mg powder because the surface of commercially
available Mg powder was found to be partially oxidized
and this suppressed reaction between Mg and B. Since
MgH2 was decomposed at around 450˚C and became Mg
powder having an active surface, and thereby the dense
MgB 2 cores were achieved and J c was successfully
increased. It became clear that adding SiC nanoparticles to
the mixed powder of MgH2 and B improves the high magnetic field characteristic and raises Bc2 at 4.2 K to 23 Tesla,
about equal to that of Nb3Sn. The compound Jc at 20 K is
600 A/mm2 at 3 Tesla, which is far too low for practical
purposes. From thin film and other data, a grain boundary
was proved to be an effective flux-pinning center. In future,
one research approach to improve Jc dramatically will be to
93
reduce the grain size to the scale of single- or double-digit
nanometers. NIMS also began to develop a method that
uses Mg2Cu instead of MgH2 as the starting material. When
Mg2Cu is used as the starting material, MgB2 formation is
promoted and high Tc can be obtained by short-time heat
treatment at low temperature.
Regarding alloy-type superconducting materials, NIMS
began to study a constitute-element diffusion method that
does not require the melting and casting process.
5. Future outlook
Compared with compound-type superconducting materials, alloy-type superconducting materials are very easy to
handle and allow easy coil rewinding, for example. Therefore, many magnet designers wish to build equipment that
partially uses Nb3Sn all with alloy-type superconducting
materials if a high magnetic field becomes available for
such alloy-type wires. It is therefore important to raise the
available magnetic fields with Nb-Ti and other alloy-type
superconducting wires. One effective way to increase Jc of
alloy-type superconducting materials remarkably is to
introduce nano-size artificial pins, which are being investigated by Tokyo Metropolitan University and other institutes, but costs will need to be reduced for practical use.
Regarding Nb3Sn, Tokai University has been developing
a new method that superimposes a Sn sheet made of Ta-Sn
compound powder on an Nb sheet and inserts them into an
Nb tube, and will now start research on lengthening and
stabilizing.
Regarding MgB2, currently Cu, Fe, SUS, and steel are
used as sheath materials but magnetic sheathing materials
are not favorable for precision magnetic field or AC applications. For wire drawing, hard materials are preferable for
94
high filling density. In relation to making a multifilamentary structure, incorporating stabilizers, and developing the
superconducting joint technique, the selection of sheathing
materials will be important. Since it is essential to improve
Jc, the introduction of effective pinning centers is a matter
of some urgency.
In addition, it will probably be important to develop
superconducting materials supporting low induced radioactivity with a view to a post-ITER fusion demonstration
reactor. The lightweight superconductor MgB 2 has low
induced radioactivity even against neutron irradiation. The
development of a lightweight V-base conductor is also
worth noting.
In 2005, a paper from the user’s perspective rather than
the manufacturer’s appeared in an academic journal on
superconductors and attracted much attention. This paper6)
discussed how superconducting material costs for the nextgeneration accelerator should be determined and what multiple of the raw material cost would be an appropriate price
for such materials. Research on metallic superconductors,
aimed at achieving a balance between high performance
and low cost, will surely become more active.
References
1) K. Marken, 2004 Appl. Supercond. Conf., Jacksonville, 2MW05.
2) The Japan Institute of Metals 68, No. 9 (2004) “Superconducting
Materials - Materials Science to Practical Use”.
3) http://www.asc.wisc.edu/plot/plot.htm
4) Cryogenic Engineering 39, No. 9 (2004) “Current Status and Future
Outlook of Nb 3 Sn Wires - Commemorating 50 Years after
Recovery”.
5) Cryogenic Engineering 38, No. 11 (2003) “Development of MgB2
Materials”.
6) L. D. Cooley et al., Supercond. Sci. Technol. 18, R51, (2005).
Chapter 3.
Magnetic Materials
Kazuhiro Hohno
Fellow, NIMS
1. Introduction
Magnetic materials are key industrial materials that are
used in various applications such as magnets, inductor
cores, sensors, data storage media, and recording heads.
Components made of magnetic materials are used in various industrial areas including electrical communication,
power electronics, and transportation. The scale of industrial applications of magnetic materials is much larger than
that of superconducting materials, but their importance
appears to be underestimated in the materials science community probably because the research field is regarded as
fully matured. As mobile electrical communication equipment becomes more and more compact, the magnetic materials for data storage and electronic circuits are required to
exhibit even better properties for downsizing. The improvement of the performance of the permanent magnets for
motors and generators, and that of soft magnetic materials
for power electronics transformers would result in significant energy savings.
Japan was once a leader in the fields of permanent magnets, soft magnetic materials, and magnetic recording
industries. Around 1985, researchers of magnetic materials
were observing research trends in Japan. After the 1990s,
however, Japan quickly lost its competitive edge and the
United States gained strength in the magnetic recording
industry. The research and manufacture of permanent magnets is now shifting to China. Since magnetic materials
have a great industrial impact as mentioned above, industry, universities, and governmental labs need to make a
strategic research plan on magnetic materials research,
which will in turn increase Japan’s industrial competitiveness.
the past 20 years, no new magnetic materials superior to
the Nd2Fe14B compound have been found and the increase
in energy product is becoming saturated.
There are two approaches for achieving another breakthrough in the future. The first one is to discover a completely new ferromagnetic compound that surpasses
Nd2Fe14B, but there are no guidelines for this approach.
Compositional search without guiding principles has an
extremely small chance of success; there is no way to find
new materials other than predicting compounds having
high magnetocrystalline anisotropy and saturation magnetic
flux density using a computational materials science
approach. The second one is nanostructure control. The
coercive force of the current Nd2Fe14B sintered magnet is
no more than about 15% of the ideal coercive force, the
anisotropic magnetic field HA, which can be estimated from
the coherent rotation of fully isolated single-domain particles. Increasing the coercivity to 50% of HA, for example,
would greatly improve the performance of the magnets. To
do so, we must understand why the current magnet materials cause magnetization reversal at only 15% of HA. The
magnetization reversal of a sintered magnet is considered
to occur when a reverse magnetic domain is nucleated from
a locally low anisotropy area at grain boundaries. The
nanostructure control of the grain boundary structure with
an understanding of this mechanism may significantly
improve the performance of permanent magnet materials.
According to recent theoretical predictions, the maximum
energy product that is higher than that of single-phase magnet can be obtained by the nanocomposite of a hard magnetic phase with a high magnetocrystalline anisotropy and a
soft magnetic phase with a high saturation magnetic flux
density. Based on this theoretical calculation, nanocomposite magnets are now actively investigated. Thus, controlling
2. Permanent magnet materials
2.1 Research trends
Figure 1 shows the annual trend in the maximum energy
product of permanent magnet material. Approximately
every 20 years, there were breakthroughs in the maximum
energy product corresponding to the developement of new
compounds for permanent magnets. The most recent breakthrough was the invention of the Nd2Fe14B sintered magnet
by Sagawa of Sumitomo Special Metals in 1982. Since
then, optimization of the microstructure constantly
improved the maximum energy product. However, during
Fig. 1 Annual changes of the energy products of permanent magnets. 1)
95
the nanostructure of magnet materials may give breakthrough in the performance of permanent magnets.
2.2 Future outlook
Permanent magnet materials are mainly used for industrial motors. In Japan, the power consumption of motors is
estimated to be about 53% of the total power consumption.
Therefore, development of a high-performance magnet that
can improve motor power efficiency by 1% was estimated
to save electric power equivalent to one small-scale nuclear
power plant.2) This is just one example of the potential
impact of development of a higher performance permanent
magnet. Since the Kyoto Protocol was enacted, automotive
manufacturers have been working to achieve fuel savings
and to suppress carbon dioxide emissions by reducing vehicle body weights. About 25 to 30 motors are used on each
automobile, so enhancing the permanent magnet performance would significantly reduce the vehicle weight. For
environmental friendliness, automobiles will change to
hybrid cars and then eventually to electric cars. For this
transition, permanent magnets usable at 200°C are essential. Figure 2 shows the energy product, coercive force, and
basic alloy composition of commercial Nd2Fe14B permanent magnets. The motor of an electric automobile requires
coercive force as high as 30 kOe at room temperature
because the coercivity decreases as temperature reaches the
operating temperature of the motors of hybrid cars. The
current Nd-Fe-B sintered magnets on the market contain
the heavy rare earth element Dy to increase the coercive
force. However, this addition has the serious disadvantage
of reducing magnetization, thereby decreasing the maximum energy product. A large amount of Dy is added to the
magnet for an electric car, which secures coercive force but
reduces the energy product. The natural resource of Dy is
quite limited and China alone accounts for almost the entire
world production. If Nd magnets with Dy contents beyond
the natural abundance are supplied in large quantities for
electric car manufacturing in Japan, the Dy market price
will soar and electric car manufacturing in Japan will be
affected by the supply of Dy raw materials. To avoid this
situation, development of a permanent magnet that can produce coercive force without Dy addition is strongly
desired.
Theoretically, the nanocomposite magnets that are composed of exchange coupled hard and soft phases are expected to achieve maximum energy products that are higher
than those of conventional sintered magnets. However, the
Nd-Fe-B nanocomposite magnets that were recently commercialized do not exhibit higher performance than the sintered magnets because they are isotropic magnets. Since
the rare earth content is lower than that for sintered magnets, the Nd-Fe-B nanocomposite magnets are only used as
medium-performance permanent magnets with low cost
and good corrosion resistance.3) However, if the crystal orientation of the hard magnetic phase can be aligned to a certain direction, an anisotropic magnet with higher maximum
energy product may be achieve. In fact, it has been demonstrated that an energy product that is higher than the theoretical limit of a single-phase magnet can be achieved by
fabricating the ideal anisotropic nanocomposite microstructure in a multilayer thin film.4)
There is a strong demand for developing thin film magnets of approximately 100 µm thick for various applications in portable information devices and MEMS. Since
the nucleation of a reverse magnetic domain occurs from
the surface processed layer, the coercivity of magnets is
lost when bulk magnets are processed to less than 100 µm
thick,. Therefore, there is a growing interest in developing
an industrial production method of high performance thin
film magnets .
These days, the number of university laboratories that
study permanent magnet materials are decreasing in Japan.
If this trend continues, universities will no longer be able to
conduct fundamental research to support the industrial
research and development of permanent magnets, which
will seriously affect permanent magnet research in Japan.
Since the development of high-performance permanent
magnets is expected to give large industrial and environmental impact, it is necessary to promote national projects
whereby scientists from universities, public research sectors and industries can participate in research and development of high performance permanent magnets.
Energy product (MGOe)
3. Soft magnetic materials
MRI, speaker
HD, CD, DVD, MD, VCR, digital camera, headphones
ABS sensor
OA/FA motor
Servomotor
Air-conditioner motor
Robot motor
Generator
Electric car motor
Coercive force (kOe)
Fig. 2 Characteristics, uses, and compositions of Nd-Fe-B sintered
magnets (by Sagawa).
96
3.1 Research trends
Soft magnetic materials can be roughly classified into
those used for transformers and those used as inductor
cores of electronic circuits. For the former, electric steel
had been used for a long time in large quantities. Although
there were attempts to use amorphous alloys as transformer
cores in the 1980s, Japan quickly gave then up because of
international patent disputes. Since environmental problems have become a major issue today, transformers with
magnetic cores made of amorphous alloys have begun to
appear on the market. In 1988, Yoshizawa from Hitachi
Metals invented the Fe-Si-B-Nb-Cu nanocrystalline soft
magnetic material. Since the Fe contents of the nanocrystalline soft magnetic materials are higher than those of
amorphous soft magnetic alloys, higher saturation magnetic
flux density is achieved. With their high magnetic flux den-
sity and extremely high permeability, the new material is
being used for magnetic cores for choke coils and small
transformers.5) The nanocrystalline soft magnetic material
is inferior to silicon steel in magnetic flux density but has
extremely high permeability. Both the permeability and
magnetic flux density are superior to those of amorphous
alloys. Recently, Co is added for high induced magnetic
anisotropy to improve the material as a magnetic material
that can be used in the high frequency range. Unlike amorphous soft magnetic materials, the magnetic properties of
nanocrystalline soft magnetic materials are sensitive to
their microstructures. Thus, the mechanism of nanocrystalline microstructure formation by amorphous crystallization has also been actively investigated.6) More recent studies are clarifying the origin of induced magnetic
anisotropy.7)
With the recent increase in the size of data communication in mobile phones, the frequencies of electronic information devices have reached the GHz band. In addition, the
miniaturization of mobile equipment is causing electromagnetic interference in electronic circuits of high mounting
density. This is hampering further miniaturization and
transfer to higher frequencies. Thus, the development of
soft magnetic materials that can be used in the GHz band is
required. Under these circumstances, nanogranular soft
magnetic materials are being developed by dispersing
nanoscale ferromagnetic particles in oxide matrixes.8)
Soft magnetic materials are also being investigated for
the applications to magnetic recording heads or as soft
magnetic underlayer for perpendicular recording media.
For a recording head to generate a large magnetic field, a
material of high magnetic flux density is necessary.
Numerous research activities have been performed on iron
nitrides, with the expectation that they might have huge saturation magnetic flux densities. However, due to poor
reproducibility of experimental results, recent studies cast
doubt on the possibility of achieving a large magnetic
moment. Therefore the research is shifted to more practical
level such as how to enable Fe65Co35 alloy that has the
largest saturation magnetic flux density to be processed as
soft magnetic thin film. Since coercivity of lower than 10
Oe is sufficient for the application to a recording head, soft
magnetism is achieved by hybridization of the Fe65Co35
alloy with Permalloy and nanocrystallization by nonelectrolytic plating.
3.2 Future outlook
One of the breakthroughs in soft magnetic materials is
the development of Fe-base nanocrystalline soft magnetic
materials by Yoshizawa in 1988. Although there have been
no further breakthroughs since then, development of higher
performance soft magnetic materials is still required to
meet various demands for the advanced electric communication devices and for increasing the areal density of magnetic recording. Since the frequency range of electrocommunication is increasing to transfer large digital amounts of
information, the development of high resistance soft magnetic materials that can be used in the GHz range is
required. The enhancement of recording density is reducing
the recording bit size to the nanoscale dimension, which
requires the use of recording media having high magnetocrystalline anisotropy to maintain the thermal stability of
the magnetization of ferromagnetic nanoparticles. As a
result, the coercivity of future recording media will become
very high, and new materials with saturation magnetic flux
densities beyond 2.4 T, which is the upper limit of the current FeCo alloy, will be required for recording heads.
Searching this kind of material without any guiding principle will be extremely difficult. Exploring such materials
with higher magnetization will only be possible with the
aid of the prediction based on computational materials science. Many investigations reported that FeCo thin films
show soft magnetic properties if they are grown on a
Permalloy or as multilayer with soft magnetic materials,
but the mechanism of this is not yet understood. Understanding this mechanism will also provide a guideline for
developing even better soft magnetic materials.
4. Magnetic recording media
4.1 Research trends
The magnetic recording system of a hard disk drive
(HDD) can be classified into longitudinal recording and
perpendicular recording, and is now changing from the former to the latter. The longitudinal recording method uses a
thin film of Co-Cr base alloy where easy axes are oriented
in the plane. When a Cr underlayer is deposited on a glass
substrate by the sputtering method, the (011) plane, the
densely packed plane of a bcc metal, is preferentially oriented. When a Co-Cr base alloy of an hcp structure is sput–
tered on the textured Cr underlayer, the (1011) plane grows
epitaxially. In addition, the preferred orientation of the Cr
(001) plane develops under an appropriate condition, which
makes the c-axis of the hcp Co-Cr completely in the plane
of the film. If the Co-Cr based alloy film is deposited on
heated substrates of about 300°C, phase separation progresses according to the miscibility gap of the hcp phase in
the Co-Cr system, and Cr is segregated at grain boundaries.
Because of the formation of Cr-rich grain boundary phase,
Co-rich grains are magnetically isolated from each other,
making the microstructure that is suitable for recording
media. The current longitudinal recording media contain Pt
to enhance anisotropy and Ta to promote Cr phase separation. In the longitudinal magnetic recording method, ferromagnetic grains are magnetized in the in-plane direction by
a leakage field from a ring head. For longitudinal magnetic
recording, reduction of film thickness is required because
of the increasing demagnetizing field between the recording bits as the recording density increases. Since the head
signal become weak accordingly, the recording limit is
expected to be around 100 Gbit/in2.
On the other hand, the perpendicular magnetic recording
method uses the media structure having the easy axis perpendicular to the plane. Magnetization opposite to the vertical direction becomes stable by magnetostatic interaction
even when the bit size becomes nanoscale. In 1979, Iwasaki at Tohoku University proposed the perpendicular magnetic recording method that can enhance the recording density much higher than the limit for the longitudinal record97
Fig. 3 3D nanostructure of CCP-CPP spindle valve. 15, 16)
ing method. After about 25 years, the perpendicular recording method is about to be used commercially.9) In the perpendicular magnetic recording media, the c-axis of hcp
must be oriented perpendicular to the plane. Cr is segregated at the grain boundaries using the same principle as the
longitudinal recording method, which decouple the ferromagnetic particles magnetically. Current research interest
in perpendicular magnetic recording media is directed to
granular-type media, in which CoCrPt columnar grains are
isolated by the SiO2 matrix.9) To achieve 1 Tbit/in2 magnetic recording in the future, the size of magnetically isolated
ferromagnetic particles is estimated to be approximately 5
nm in the granular media having the bit size of about 65 nm
and the distance between the head and media is 5 nm.
However, such a recording system would be extremely difficult to achieve. Due to various technical restrictions, the
upper limit of the perpendicular recording method is estimated to be 600 Gbit/in.10) Therefore, a completely new
recording method must be developed to achieve a recording
density of 1 Tbit/in2.
To ensure a bit size of about 65 nm and an adequate S/N
ratio at a recording density of 1 Tbit/in2, the media must be
composed of 5 nm isolated ferromagnetic particles. For a
higher density of about 10 Tbit/in2 in future, magnetic
information must eventually be written to individual ferromagnetic particles, then the thermal stability of the magnetization of the nanoparticles will become a serious problem.
If the magnetocrystalline anisotropy is Ku and the volume
of crystalline particles is V, the thermal barrier becomes
KuV. If the thermal barrier is 60 times the thermal energy
kBT, the recording information could be maintained for 10
years. To achieve the recording density of Tbits, therefore,
a ferromagnetic phase of sufficiently high Ku must be
selected as the recording media material. Ku of L10-FePt is
one order of magnitude higher than that of hcp Co. This is
why FePt is regarded as the most promising recording
media. Nd 2Fe14B, SmCo 5, and other permanent magnet
materials also have high magnetocrystalline anisotropy but
are not suitable as media because they are inferior in corrosion resistance. Therefore, the research interest in the magnetic properties of FePt, SmCo5, and other high Ku materials thin films has increased recently.
However, most research activities are concerned with
the perpendicular magnetic anisotropy and high coercive
force of continuous films of high Ku materials and are far
from the stage of application to media. In the future, more
research efforts are needed to process the thin-film struc98
tures that are suitable for magnetic recording media using
the high Ku materials. The films as recording media must
have the following features: (1) magnetically isolated particles of approximately 5 nm with narrow size distribution,
(2) c-axes must be oriented in the direction normal to the
film plane, (3) FePt particles must be fully ordered to the
L10 structure without high temperature annealing, and (4)
the switching field must be reduced for writable media
while maintaining the energy barrier. All of these are challenging problems and it may take more than 10 years to
solve then. Since the switching field of FePt particles is
much higher than the magnetic filed that can be generated
from the current write head materials, a new recording
method such as heat assisted recording will have to be
introduced. Since FePt media are expected to be seriously
considered when the areal density of the current perpendicular recording method reaches its highest limit, there is still
sufficient time for further research.
4.2 Future outlook
To increase the recording density by the perpendicular
magnetic recording method, a media material having a high
coercive force is becoming necessary, and recording by the
current heads is becoming extremely difficult. Therefore,
an oblique recording system with high Ku materials oriented obliquely12) and nanocomposite media with exchange
coupled soft and hard phases 13) is proposed. Materials
research to attain these media structures will become
active.
As a recording method to be employed after the perpendicular recording method has reached the limit, the thermal
assist method using FePt self-assembled nanoparticles is
proposed. 11) However, there are still many issues to be
resolved for adapting FePt to a media structure that is suitable for the thermal assist method, such as the process to
order FePt nanoparticles to the L1 0 structure, the twodimensional arrangement of nanoparticles, the suppression
of the coalescence of particles by thermal treatment for
ordering, and the alignment of the easy axis of FePt
nanoparticles.
5. Materials for magnetoresistance devices
5.1 Research trends
The conventional hard disk drives employed magnetoresistive heads using the anisotropic magneto-resistance
effect of Permalloy. Since MR head sensitivity is given by
the voltage output per unit track width, the output decreases
as the recording density becomes higher and the track
width becomes smaller. To overcome this problem, IBM
employed a GMR head for a hard disk drive for the first
time in 1997. The GMR device uses the giant magnetoresistance phenomenon that was discovered by Fert for the
first time with an Fe/Cr/Fe artificial lattice in 1988. If a
multilayer film of Fe/Cr/Fe is fabricated by changing the
Cr film thickness, the antiferromagnetic coupling of two Fe
layers with an appropriate Cr layer thickness reverses the
direction of magnetization. Applying a unidirectional magnetic field to this film makes Fe magnetization parallel. If a
current is applied to this kind of element, electrons cause
spin-dependent scattering with a relative magnetization
change of Fe, and the electric resistance changes according
to the magnetic field. However, if an antiferromagnetic
coupling is used, a large magnetic field is necessary for
magnetization reversal. To allow the magnetization reversal in a lower magnetic field, an element called a spin valve
was developed. If FeNi or similar soft magnetic layers are
used for ferromagnetic film and a soft magnetic layer on
one side with a nonmagnetic field in between is pinned by
an antiferromagnetic phase, such as L10-FeMn, the magnetic field sensitivity of electric resistance change becomes
extremely high because magnetization reversal occurs at a
low magnetic field.
Thanks to the improved sensitivity of the GMR head,
the recording density of HDDs has increased to 4 Gbit/in2.
However, to achieve areal density exceeding 10 Gbit/in2, a
GMR head of a simple configuration is not sufficient.
Because of this limitation of the read heads, the rate of
increase of recording density is slowing down. For an areal
density over 40 Gbit/in2, a GMR head of higher sensitivity
is required. The GMR head so far is of the current-in-plane
type in which the current flows in parallel to the multilayers. A current-perpendicular-plane (CPP) spin valve is
expected to show a greater regenerative output because the
electron scattering occurs not only at the interface but also
within the ferromagnetic electrode layers. The CPP spin
valve with the current-confined path (CCP) structure is
expected to exhibit an even higher MR value. A metallic
nanobridge is self-organized in an oxide layer of several
nanometers thick and the current is constricted in the
nanobridge to increase the MR value. This kind of device
has a complicated three-dimensional nanostructure as
shown in Figure 3 and detailed nonstructural information
cannot be acquired only by cross-sectional TEM observations. Now that the properties of magnetoresistive devices
are dominated by the three-dimensional nanostructures, a
highly sophisticated nanostructure analysis technique must
be employed for device development.
The GMR structure has a metallic nonmagnetic layer
between two ferromagnetic layers. If the two ferromagnetic
layers are separated by an oxide layer, electron transport
occurs by tunneling. Since spin-dependent scattering
occurs even in the case of electron tunneling, a MR effect
appears. This type of MR is called tunneling magnetoresistance (TMR). TMR is electron conduction by tunneling and was considered unsuitable for applications to a read
head because of large electric resistance. Recently, however, a TMR junction of low electric resistance with a MR
value of 230% was developed.17) The TMR value is considered to follow Julliere’s formula, TMR = 2P1P2/ (1–P1P2),
where P1 and P2 are spin polarization of ferromagnetic
materials. If a half metal with P=1 is used as the ferromagnetic electrode, an infinite value of TMR is predicted. This
is the reason why tunnel junctions with half-metal electrodes receive so much research interest now. Although
there are various types of half-metals like oxides and
alloys, Heusler alloys are considered to be most promising
materials as ferromagnetic electrode for TMR junctions
because some of the Heusler alloys have Curie tempera-
tures that are higher than room temperature. Nevertheless,
only TMR values of less than 16% have been obtained so
far even from the TMR junctions with the Heusler alloy
electrodes whose spin polarization are theoretically predicted to be 1.18) To achieve high TMR values from the TMR
junctions using the Heusler alloy electrodes, the spin polarization of the ferromagnetic electrodes must be determined
experimentally, as high spin polarization was predicted
from fully ordered L21 phase. Since sputtering is a highly
nonequilibrium process, it is very unlikely that equilibrium
L21 phase is formed from the as-sputtered conditions. In
many previous investigations, the structure of electrode
films has not been characterized thoroughly and the spin
polarization was estimated from the TMR values experimentally measured from the TMR junctions. To achieve a
large TMR value in the near future, the characterization of
electrode phase and the analysis of interface structure are
necessary in addition to TMR measurements.
While many groups have been trying to realize large
TMR values with half-metal tunnel junctions, Yuasa et al.
at the Agency of Industrial Science and Technology successfully manufactured a Fe(001)/MgO(001)/Fe(001) tunnel junction with rigorous interface control at the atom
level and demonstrated a TMR value as great as 88% at
room temperature.19) This is because the MgO single crystal
has a spin filtering effect, so that the MR value can be
enhanced. The electrodes were then changed to amorphous
FeCoB to achieve TMR as great as 230%17) and are now
expected to be applicable to MRAM in the future.
Although TMR devices were considered unsuitable for
read head applications because of their large electric resistance, the electric resistance was successfully reduced with
the TMR junction using an ultrathin MgO single crystalline
insulator layer.
5.2 Future outlook
The bottleneck in increasing the areal density of magnetic recording is the development of an read head. A GMR
element of higher sensitivity is always necessary. The conventional simple multilayer film structure is not sufficient
to achieve high magnetoresistance and GMR devices are
becoming complex 3D nanostructures in which electron
paths are constricted in narrow metal paths. Head manufacturers are fiercely competing in development, and largescale film deposition and microfabirication facilities are
necessary for the development of GMR devices. Device
development and application can no longer be competitive
subject among universities or national laboratories. In the
future, collaborative research programs for industry, academia, and governmental labs are necessary, and universities
and national labs should share the research effort toward
understanding basic principles and characterization of highly complicated nanostructures.
The largest TMR so far reported was acquired from the
TMR junctions using coherent MgO insulators. Half-metal
TMR should theoretically produce a large TMR value and
further research is necessary. Since the research method of
manufacturing a tunnel junction first and measuring its MR
values has reached its limit, the research direction should
be changed to acquire better understandings of the process99
ing conditions for half-metal electrodes. We also need a
technique for measuring the spin polarization of ferromagnetic films directly. Thereafter, we should try to fabricate
junctions from the electrodes that have been confirmed to
have high spin polarization. Before device development,
we should understand the intrinsic properties of electrode
materials.
6. Current status and future activities of NIMS
As part of the 5-year project on “Development of new
advanced nanohetero metallic materials” supported by the
Special Coordination Funds on Science and Technology,
NIMS coordinated the collaborative research program for
industry, university, and governmental labs. In this program, NIMS carried out fundamental researches on the
characterization of nanostructures of magnetic materials,
such as nanocomposite magnets, nanocrystalline soft magnetic materials, nanogranular soft magnetic materials, and
FePt thin films. The nanostructure analysis results were
used to optimize the nanostructures of the materials to
obtain improved properties.20)
As to nanocomposite magnets, NIMS systematically
studies the effects of adding alloying elements on
nanocomposite microstructure and magnetic properties
with NEOMAX and has greatly contributed to their development of medium-performance permanent magnet materials. To verify the possibility of surpassing the properties of
the current sintered magnet by nanostructure control, NIMS
fabricated a [Sm(Co,Cu)5/Fe]6 anisotropic nanocomposite
thin film and proved that it could realize an energy product
that is higher than the theoretical limit of a single-phase
SmCo5 magnet. Regarding nanocrystalline soft magnetic
materials, NIMS proposed a nanostructure control method
for the Co-added Fe-Si-B-Nb-Cu type nanocrystalline soft
magnetic materials with Hitachi Metals, and contributed to
the development of soft magnetic materials with high frequency properties. By clarifying the mechanism of induced
magnetic anisotropy of stress-annealing, NIMS established
a guiding principle for achieving the nanocrystalline
microstructure that is suitable for high frequency applications. As to the nanogranular soft magnetic materials, soft
magnetic properties and induced magnetic anisotropy were
explained from the viewpoint of the nanostructures.
Regarding the FePt thin films as a potential ultrahigh-density magnetic recording media of the next generation, the
mechanism of ordering by low temperature annealing was
clarified and the size dependence of ordering was discovered. In addition, it was demonstrated that the switching
field could be lowered remarkably by nanocomposite
media without impairing the thermal stability of the
nanoparticles. Some of the nanostructures observed in the
magnetic materials were modeled by the phase-field
method in the computational materials science group, and
the conditions required to optimize the nanostructure for
better magnetic properties were predicted.
In the next 5-year plan starting from FY2006, NIMS
aims at establishing a guideline for developing nanostructured magnetic materials for the ubiquitous society from
100
the viewpoint of materials science through the project
“Development of high performance nanostructured magnetic materials by nonstructural control.” To achieve this
goal, experimentally fabricated magnetic materials and
spintronics materials will be studied in view of nanostructure and magnetic properties, and their relationships will be
established. The nanostructures of the following materials
will be thoroughly characterized with atom scale resolution: Application to magnetic recording techniques – (i)
thin film for high-density magnetic recording media, (ii)
soft magnetic materials of high magnetic flux density for
recording heads, (iii) CPP-GMR spin valve for HDD heads,
and (iv) half-metal thin film for TMR devices; application
to an electromagnetic noise absorber for small mobile
equipment – (v) nanogranular soft magnetic thin film for
high frequency; application to magnetoelectric microsystems (MEMS) – (vi) thin-film permanent magnet materials.
Based on the acquired knowledge, data storage techniques
and nanomagnetic materials for GHz band electronics will
be developed to establish a guideline for materials science
for the corporate development of magnetic device systems.
7. Conclusions
Since it is not possible to cover all of various magnetic
materials, this article reviewed the current status and future
trends in the fields related to NIMS research activities. So
far, NIMS has not made serious effort in the research and
development of magnetic materials. However, NIMS will
set clear goals for the research of magentic materials in the
next 5-year plan. Among various magnetic materials,
NIMS will put its emphasis on the materials whose properties are expected to improve through nanostructure control.
NIMS is devoted to research on magnetic materials that are
necessary for developing devices and systems because it is
not practical to compete with industry research in the
development of magnetic devices and their applications.
While strengthening the linkage between industry, universities, and governmental labs as far as possible, NIMS will
proceed with basic research in its strongest field. NIMS has
the potential to conduct complementary research with
industries in the fields of nanostructure characterization,
understanding mechanisms, predicting microstructure evolution, and measuring magnetic properties using high magnetic field facilities.
References
1) M. Sagawa, Proc. 18th Inter. Workshop on High Performance
Magnets and Their Applications, Annecy, France (2004) pp. 7
2) Subsidized general research in FY2000 Interim report of “Research
for the fabrication of new metallic materials by clarifying the
function manifestation mechanism of nano-hetero metals”
subsidized by the Science and Technology Fund in 1999
3) S. Hirosawa, Trans. Magn. Soc. Jpn, 4, 101 (2004)
4) J. Zhang, Y.K. Takahashi, R. Gopalan, and K. Hono, Appl. Phys.
Lett., 86, 122509 (2005)
5) http://www.hitachi-metals.co.jp/prod/prod02/p02_21.html
6) K. Hono, M. Ohnuma, D.H. Ping and H. Onodera, Acta. Mater, 47,
997 (1999)
7) M. Ohnuma, K. Hono, T. Yanai, H. Fukunaga and Y. Yoshizawa,
Appl. Phys. Lett., 83, 2859 (2003)
8) H. Shimada, The Magnetic Society of Japan, 26, 135 (2002)
9) http://www.toshiba.co.jp/about/press/2004_12/pr_j1401.htm
10) T. Shimatsu, H. Sato, T. Oikawa, Y. Inaba, O. Kitakami, S.
Okamoto, H. Aoi, H. Muraoka and Y. Nakamura, IEEE Trans.
Mag., 40, 2483 (2004)
11) D. Weller, IEEE Distinguished Lecturer (2004)
12) K. Gao and H. Bertram, IEEE Trans. Magn., 38, 3675 (2002)
13) R.H. Victora and H. Shen, IEEE Trans. Magn., 41, 537 (2005)
14) O. Kitakami, Jpn. J. Appl. Phys., 42, L455 (2003)
15) H. Fukuzawa, H. Yuasa, S. Hashimoto, K. Koi, H. Iwasaki, M.
16)
17)
18)
19)
20)
Takagishi, Y. Tanaka and M. Sahashi, IEEE Trans Magn., 40, 9464
(2004)
H. Fukuzawa, H. Yuasa, K. Koi, H. Iwasaki, Y. Tanaka, Y.K.
Takahashi and K. Hono, J. Appl. Phys., 97, 10C509 (2005)
D.D. Djayaprawira, K. Tsunekawa, M. Nagai, H. Maehara, S.
Yamagata, N. Watanabe, S. Yuasa and K. Ando, INTERMAG.,
CA-01 (2005)
K. Inomata, S. Okamura, R. Goto, and N. Tezuka, Jpn. J. Appl.
Phys., 42, L419 (2003)
S. Yuasa, A. Fukushima, T. Nagahama, K. Ando and Y. Suzuki,
Jpn. J. Appl. Phys., 43, L588 (2004)
http://www.nims.go.jp/apfim/nanohetero_j.html
101
Chapter 4.
Semiconductor Materials
Toyohiro Chikyow
Nanomaterials Configuration Group, Nanomaterials Laboratory, NIMS
1. Introduction
The history of semiconductor materials as electronic
materials can be traced back to 1833 when Faraday found
that the electrical resistance of AgS changes as the temperature changes.1) Later, the rectification theory was proposed
by using such materials and sulfide and copper dioxide to
deepen understanding of the semiconductor band structure
based on quantum theory. During such research, it was
found that semiconductors could be classified by type of
impurity into n type and p type and that electrical conductivity can be controlled by the impurity density. Russell
Ohl of Bell Labs developed a Ge semiconductor in 1939
and then a high-frequency diode using Ge. These achievements led to the development of a point-contact diode by
Bardeen and Brettin of Bell Labs in 1946 and a junction
transistor by Shockley in 1948.1)
After the War, Teal of Texas Instruments announced a
Si transistor in 1954, triggering the modern development of
semiconductor devices. In particular, Kilby created an integrated circuit (IC) in 1958, Homy announced the first planar transistor using photolithography in 1959, then Hofstein and Heyman of RCA developed the MOS field-effect
transistor (MOSFET) in 1961. Through this series of
achievements, the basic technology for the current Si-type
integrated circuits was completed. Since then, circuits have
been further integrated with related materials, mainly Si
(substrate and gate), SiO2 (gate oxide film and interlayer
dielectric), and Al (electrode and interconnection).
With the advance of integration, however, Moore’s Law
concerning the pace of integrated circuit development,
began to show its limit. Attempts are now being made to
extend this limit with new materials.2)
This chapter outlines the changes and future trends in
SiMOSFET related materials which account for 90% or
more of all semiconductor devices, as well as the trends in
organic materials and compound semiconductor materials.
2. Research trends
2.1 Current status of SiMOSFET and future materials
For gates, the current Si devices use hp 65 nm nodes
(hp: half pitch; the actual gate width is 30 nm, about half).
The width will finally be reduced to about 10 nm and the
post-scaling generation will begin to emerge around 2015.2)
SiMOSFET related research includes many subjects
102
regarding materials, such as gate dielectric materials (highk materials), metal gate materials, interlayer dielectric
materials (low-k materials), channel materials, and interconnecting materials.
i) Gate dielectric materials (high-k materials)
Existing gate dielectric materials are made of SiON but
materials of greater permittivity will be needed for the
next-generation MOSFET. These are called high-k materials. Research on gate dielectrics began to accelerate around
1996. For gate dielectrics, amorphous materials noncrystallized by adding SiO2 or Al2O3 to high-permittivity oxide
HfO2 are regarded as promising. The next dielectrics will
be expected to have higher permittivity, to offer excellent
electrical matching (low interface states) with Si, to not
form SiO2 with Si and to withstand high-frequency operation. The probable gate oxides of the next generation are
rare earth oxides based on La2O3 that has f electrons. Considering MOSFET operations, the permittivity of gate
dielectrics may be limited to about 30. Since this value is
difficult to achieve with amorphous materials, gate
dielectrics made by epitaxial growth or similar structures
will emerge eventually.
ii) Gate materials
The conventional gate materials are made of polycrystalline Si metallized by doping impurities to high densities.
As integration advances, metals may be used as they are.
The requirements are reduction of resistance and control of
work function; research is underway on metallic nitrides
(TiN and other) and metallic silicides (alloys with Si) as
possible candidates. In terms of electrical resistance, however, materials of even lower resistance are expected.
Regarding control of work function, there is a growing
number of reports on intermetallic compounds, metallic
nitrides of excess metals, and various metallic silicides. For
continuous control of work function, an entirely solid solution is preferable. If the work function is fixed for selfmatching, however, alloys having many intermetallic compounds may become advantageous. Research on metal gate
began to take off around 2003 and is still on the increase.
iii) Interlayer dielectric materials (low-k materials)
For high-speed signal operation, materials of low permittivity (low-k) are expected for interlayer dielectrics of
multilayer interconnection. The required permittivity is
e=2.7 or less but it is difficult to find bulk materials satisfy-
ing this condition, so the interlayer dielectrics SiO2 is made
hollow to create a multipore structure of low permittivity.
As next-generation low-k materials, carbon-type and
organic materials of low permittivity are attracting attention and research took off around 1995. However, employing a multipore structure or organic materials results in
inadequate structural strength. Integrated circuits also have
a serious problem of inadequate strength because they are
polished during the chemical mechanical polishing (CMP)
process to make the interlayer dielectrics uniform.2) For
future interlayer dielectrics, composite materials should be
developed from organic materials of low permittivity and
reinforcing materials (structural materials) having mechanical strength. These trends are summarized in Figure 1.
Si-type MOSFET related materials
150
High-k
Low-k
metal gate
100
50
0
1980
1985
1990
1995
2000
vi) Other related materials
Magnetic random access memory (MRAM), combined
from magnetic metal films and insulation layers, is now
attracting attention as a material to replace today’s flash
memory. However, MRAM still has many unresolved
issued, such as magnetic intermetallic insulating materials
and large power consumption.
Perovskite oxide materials have a wide range of characteristics from conductor to insulator and also dielectric and
magnetic functionalities. Judging from these characteristics, perovskite oxide materials will certainly be used as
semiconductor related materials in future. Resistance random access memory (RRAM) that writes and erases data
by voltage is now also being developed on the basis of perovskite oxide materials, and such research will pick up
pace. Figure 3 shows the trend.
NRAM and RRAM
2005
Fiscal year
Fig. 1 Trend of Si-type MOSFET related materials.
iv) Channel materials
The next-generation devices are expected to operate
faster at high frequency. Therefore, studies are now underway on varying the effective mass of a carrier and changing
the carrier mobility by straining the channel area and introducing Ge of large mobility into the channel layers of Si
devices.
100
Number of papers
Number of papers
200
of even lower resistance will be necessary. In future, optical interconnecting materials will also be incorporated.3)
For gate interconnection, metallic silicides are formed
on polycrystalline Si gates by self-matching. Recently,
research was started on the full silicide (FUSI) of this polycrystalline Si area (see Figure 2).
80
MRAM
RRAM
60
40
20
0
1990
1995
2000
2005
Fiscal year
Fig. 3 Trend of NRAM and RRAM.
v) Interconnection materials
Al used to be the main interconnection material for integrated circuits. For high-speed signal operation, however,
low-resistance materials were investigated and plated Cu
interconnection is now becoming popular. This material
will also pose a problem of an increase in resistance due to
fine patterning. For higher speed, interconnection materials
vii) Organic materials
Research and papers on organic devices have also been
increasing since around 1995. Organic devices may be used
for display elements and other limited purposes because
they are driven by current control and their electron mobility is far less than that of Si. Since organic materials do not
Organic devices
Electrode and wiring materials
100
Number of papers
Number of papers
1000
100
10
0
1980
silicide
FUSI
Cuinterconnection
1985
1990
1995
2000
2005
80
Organic Tr
organic display
60
40
20
0
1980
1985
1990
Fiscal year
Fig. 2 Trend of Si device wiring materials.
1995
2000
2005
Fiscal year
Fig. 4 Trend of organic devices.
103
2.2 Compound semiconductors
The typical material for compound semiconductors is
GaAs, which has been used for light emitting devices and
high-speed transistors (HEMT). Research in this field has
been active since the 1980s and many studies have been
performed. In 1992 and 1993, research intensified probably
because new structures, such as quantum wires and quantum dots, were proposed and III-V diluted magnetic semiconductors emerged.
However, GaAs research began to diminish in 1998 and
GaN research has been increasing instead. In 2000, the InN
band gap was reported to be 0.7 eV, indicating the possibility of achieving a wide range of light wavelength from red
to blue by controlling GaInN composition. In addition,
GaN-HEMT for the hundred-GHz band using the strong
field resistance of GaN was proposed. Thus, research
seems to be shifting from GaAs to GaN. Figure 5 shows the
trend.
Last year, an LED using ZnO was announced by
Tohoku University and attracted great attention. Ultraviolet
LEDs made by ZnO are expected to become a new source
of white light replacing the fluorescent lamp. In terms of
resources and costs, ZnO is superior to GaN.
Compound semiconductors
Number of papers
6000
5000
4000
GaN
InN
GaAs
3000
2000
1000
0
1980
1985
1990
1995
2000
and drain and also lead-free solder for mounting.
Si devices will then enter the post-scaling generation
and their device structures and materials will change.
Three-dimensional devices having vertical structures in
narrow areas may emerge to replace the conventional twodimensional ones. FinFET and Tri-Gate transistors are
examples featuring structures.
CNT transistors
25
Number of papers
produce great environmental loads and can be bent, they
may be applied to devices having different functions (see
Figure 4).
20
CNT Tr
15
10
5
0
1990
1995
2000
2005
Fiscal year
Fig. 6 Trend of CNT transistors.
Among them, MISFET using carbon nanotube (CNT) is
attracting attention. CNT is superior to other materials in
that a large ON current can be acquired, the field strength is
greater than that of Si, and impurities can be incorporated
into CNT without reducing the mobility due to scattering of
the impurities. Stanford University created an experimental
transistor using CNT and verified its operation, and
research on CNT transistors is growing each year (see Figure 6).
A future issue is how to integrate nanodevices. Toshiba
proposed an attempt to integrate MOSFET having vertical
and surrounded gates.4) Such research may lead to the postscaling generation of Si devices.
Atomic switches and other devices of atomic-level operations are also expected to emerge in future.5)
2005
Fiscal year
4. Conclusion
Fig. 5 Trend of compound semiconductors.
3. Future development
It is predicted that ArF excimer laser and immersion
technologies can integrate Si semiconductors up to the hp
gate node of 22 nm (actual gate width: 10 nm) by around
2015. Until that time, Si devices will surely be the main
type of semiconductor devices. However, many new materials have begun to enter the process. Si-type electronic
devices have so far achieved high speed and functionality
by integration, and this trend will be maintained by changing materials and structures. The tendency toward faster
processing speed while maintaining the current process will
not change for the time being. Although MOSFET related
materials were mainly introduced in this report, it is necessary to develop other materials, including carbon nanotube
as a plug material for vertical interconnection from source
104
Si-based electronic devices have been further integrated
by micromachining to achieve higher processing speeds
and functions, a tendency that will not change even in the
post-scaling generation, and so Si will remain the dominant
basic material for the time being. MISFETs using Ge or
CNT, high-frequency transistors using GaN, and optical
interconnection will also be packaged on a single chip to
realize a multifunctional single-chip device. Gate
dielectrics, dielectrics between organic layers, and many
new related materials will be developed and will need to be
integrated by gathering knowledge from many fields.
Compound semiconductors can be classified into GaAs
materials applicable to quantum devices of quantum dots;
GaN materials applicable to light emitting devices, lighting
instruments, and high-frequency transistors; and oxide
materials (oxide electronics) to deliver characteristic functions.
In 2010, a ubiquitous society will emerge in which all
equipment and systems are networked through high-speed
data communication networks. Semiconductor materials
are becoming increasingly important as an infrastructure to
support society, and materials that make many functions
possible will need to be developed accordingly.
References
1) “Semiconductor Engineering” (By K. Takahashi).
S. M. Sze, “Physics of Semiconductor Device”, “High-Speed
Semiconductor Device”, “Semiconductor Device”, and others.
2) About Semiconductor Technology Roadmap of Japan http://strjjeita.elisasp.net/strj/
3) About Si Optics: http://developer.intel.com/technology/silicon/sp/
index.htm and other.
4) T. Endoh, M. Suzuki, H. Sakuraba and F. Masuoka, IEEE Trans.
Electron Devices, 48, 1599-1603 (2001).
5) K. Terabe, T. Hasegawa, T. Nakayam and M. Aono, Nature, 433,
7021 (2005).
105
Chapter 5.
Biomaterials
Section 1. Materials for Artificial Organ and Tissue
Engineering
Hisatoshi Kobayashi
Artificial Organ Materials Group, Biomaterials Center, NIMS
For the next generation of medical treatment which is
safe and kind for both people and the environment, it is
essential to develop biomaterials having biological functions that can control the manifestation of functions from
cells and tissues (aggregates of cells and extracellular
matrix). The interaction between organism and materials
begins with the adsorption of biomolecules to nanostructural surfaces and their structural changes, and then progresses
to microic and macroic high-degree functions and spaces
with such additional factors as cell adhesion, proliferation,
and differentiation and intercellular action. This series of
reactions starts with the mechanism of a nanostructured
receptor on a cell membrane recognizing a material and
transducing a signal into the cell. This mechanism plays a
key role in determining a biological reaction. The recent
implementation of nanotechnologies as tools has enabled
detail research on the interaction between materials and
cells. From the “nano-bio” area which is a fusion between
nanotechnology and biotechnology, new scientific knowledge is being acquired successively and a new knowledge
infrastructure is starting to be built. Based on this knowledge, R&D has started on new functional materials of
microstructure and macrostructure control, devices, and
cell-material composites.
This section first discusses research on biomaterials,
artificial organ materials, and regenerative materials by
examining the transition in the number of papers, and then
looks at the medical applications of biomaterials as the
product of R&D in the same way. It also discusses the position of nanotechnologies in pharmaceuticals related
research, including tissue engineering and drug delivery
systems which are recently attracting attention as applications of biomaterials research. Then the research trends in
the nano-bio fusion area of each materials field is discussed
by examining the number of papers, and the research status
for each type of material is reviewed. In addition, the past
research trends are surveyed based on the number of biomaterials studies by each organ. Lastly, the section introduces some advanced research activities in related areas,
discusses the future directions of these areas, and describes
106
subjects for future research.
2. Research trends
2.1 Transition in number of papers
In the current survey, we examined papers published in
science magazines from 1970 until 2004. By using keywords related to this section, we searched a database using
SCI Expander as a search engine for papers containing the
above keywords in their titles or abstracts.
First, a materials search with Bio* and a biomaterials
search (Biomaterial*) were clearly distinguished from each
other. Then the following rough search was performed to
check the research trends and the implications between
nanotechnologies and nanomaterials. Figure 1 shows the
results of searched papers for the combinations of Bio*,
Nano*, and Biomaterial* each with Material*. Regarding
papers containing both the terms Bio and Material, the
1. Introduction
Year
Fig. 1 Number of papers containing the combinations of Bio*, Nano*,
and Biomaterial* each with Material*.
estimate: 660 papers), Technolog* in 82 papers (annual
estimate: 328 papers), and Device* in 83 papers (annual
estimate: 332 papers), and so by the end of 2005 the number of papers will reach about 1.3 or 2.0 times that in 2004.
These results suggest that practical research on functional
materials and devices will accelerate.
Figure 3 shows the results of an AND search for Medic*
(medical care) and Therap* (therapy), meaning the fields of
application of biomaterials, with Nano* for analysis from
the aspect of application. Papers containing the term
Medic* (for Medicine or Medical) with Nano* began to
appear in 1988. The number of papers increased at an
annual rate of over 10% until 2001, showed a three-digit
increase in 2002, and reached an annual output of about
180 in 2004, totaling about 800. The number of papers containing Therap* (for Therapy or Therapeutic) with Nano*
also showed the same tendency, reaching an annual output
of about 400 in 2004, totaling about 1,600. This indicates
that research on the application of nanotechnology to medical treatment has taken off quickly. Among medical
research fields, the regenerative area is growing remarkably
and attracting much attention as a future medical treatment.
Figure 4 shows the results of searching papers for the combinations of Tissue*, Engineer*, and Regenerative medicine each with Nano* to check the situation of regenerative
medicine and related research. The number of papers related to regeneration started increasing around 1995 and
reached an annual output of about 1,800, totaling about
8,700. In this area, however, the number of papers related
to Nano* reached double digits in 2002 and the aggregate
number until 2004 was only about 220, indicating that
research has just started in this Nano area. Pharmaceuticals
research represented by DDS and scaffolding materials
(Scaffold*) research related to tissue engineering are the
main targets of biomaterials research. Figure 5 shows the
results of searching for the combinations of Drug* and
Scaffold* each with Nano* to check the research trends in
this area. Regarding research on Nano* and pharmaceuti-
number of papers started increasing explosively in 1990
and reached about 6,500 in the year 2004, totaling 60,300.
The number of papers containing the term Biomaterial also
started increasing in 1990 and reached about 1,200 in the
year 2004, totaling 8,500. This indicates that the range of
materials research expanded to encompass the bio field,
and that about 20% of materials research directly concerns
medical applications. Papers were also searched for Nano*
and Material* to extract materials research for nanotechnology applications and nano-sizes. The number of papers
started increasing dramatically in 1990 and reached about
5,500 in the year 2004. To check the fusion of nanoresearch and bioresearch which are rapidly growing areas,
papers were searched for the terms Nano*, Bio*, and Material*. The results showed that research in this field started
in 2000. This indicates that the fusion of the areas began to
pick up speed 10 years after the start of each area. About
370 papers were published in 2004, totaling 1,250. To gather additional information, the annual number of papers was
checked as of March 2005; the number of published papers
had already reached 165, so the number at the end of 2005
is estimated to be about double that in 2004, indicating that
this area has started quickly.
technologies, materials, and devices in the fusion area of
Nano* and Bio*. In this area, the number of papers started
increasing remarkably in 1990 and reached 2,700 in the
year 2004, totaling 11,100. Of the papers, the number containing the term Material* as a keyword reached about 370
in 2004, totaling 1,250 as mentioned before. The number of
papers containing the term “Technolog*” as a keyword
reached an annual output of about 250, totaling about 810.
The number of papers containing the term “Device*” as a
keyword reached an annual output of about 270, totaling
about 790. This indicates that R&D on materials and
devices has just started in the fusion area of Nano* and
Bio*. When the annual output of papers by March 2005
was surveyed, Material* was found in 165 papers (annual
Year
Fig. 2 Number of papers containing Material*, Technology, and
Device* in the fusion area of Nano* and Bio*.
Year
Fig. 3 Number of papers containing Medic* (medical treatment) and
Therap* (therapy) with Nano*.
107
ber of papers started to surge in 2000, and in 2004 the number was about 300 (1,000 in total) in the field of metallic
materials, about 130 (520 in total) in the field of inorganic
materials, and about 180 (515 in total) in the field of composite materials. In 2005, the number of papers is estimated
to reach about 1.5 to 2.0 times that in 2004, indicating that
the scope of research is extending in each field of materials
to cover bio and nano.
Figure 7 shows the results of searching papers for the
combinations of Fiber* or Fibr*, Particle* or Sphere*, and
Tube* or Tubular* each with Nano* and Bio* to check the
transition in the number of papers by materials. In the
fusion field of nano and bio, research using particles is taking the lead, quickly followed by research on fibrous materials. Due to papers on the application of carbon nanotube
to the nanobio area, the number of papers on tubular fibers
is increasing but more slowly than those about fibers and
particles.
Lastly, we checked the total number of papers by
applied organs of the body to examine artificial organ
research. Figure 8 shows the results of searching papers for
cals, papers began to appear in 1990. The number of papers
has been increasing and reached an annual output of 700 in
2004, totaling 3,470. Papers related to regenerative scaffolding and Nano* began to appear in 2000. The number of
papers reached an annual output of 150 in 2004, totaling
about 370. This indicates that regeneration related research
started even later than pharmaceuticals research. The annual number of papers as of March 2005 was 63, and so the
number of papers is estimated to reach 250 by the end of
the year, indicating quick fusion with Nano*.
Figure 6 shows the results of searching papers for the
combinations of Inorg* (inorganic), Metal*, and Polym*
(polymer) each with Nano* and Bio* to examine research
trends by materials. Research using polymer materials
began to be published actively in 1990. The number of
papers reached three digits in 1999 and an annual output of
600 in 2004, totaling 2,150. In 2005, the annual output is
estimated to be about 900, indicating active research. This
data reveals that research in the fields of inorganic, metallic, and composite materials has started about 5 years later
than in the field of polymer materials. However, the num-
Year
Year
Fig. 5 Number of papers containing Scaffold* (for regenerative
medicine) and Drug* with Nano*.
108
Fig. 6 Number of papers containing Inorg* (inorganic), Metal*, Polym*
(polymer), and Composite* in the fusion area of Nano* and Bio*.
Fig. 4 Number of papers containing terms about regenerative medicine
and tissue engineering (Tissue, engineer*) with Nano* and about their
fusion research.
Year
Year
Fig. 7 Number of papers by material types (fiber, particle, and tube) in
the fusion area of Nano* and Bio*.
combinations of the major organs and related terms each
with Bio* and Material*. There is clearly a positive
approach toward various organs, with active research on
tissues and organs of comparatively simple functions, such
as blood, vessel, bone, cartilage, joint, tendon, ligament,
and others. Further research is necessary on organs having
multiple advanced functions such as the liver and pancreas.
So far, we have discussed research trends based on the
number of papers. Next, we look at the circumstances of
research.
In Japan, the framework of nanomedical research is
expanding in each ministry or agency with the rapid
advance of genome analysis and nanotechnology. In the
Nanomedicine Project, the Ministry of Health, Labour and
Welfare is conducting research to enhance diagnostic technology in the direction of preventive medicine. The Ministry of Economy, Trade and Industry is developing organs
by using technology for integrating cell functions for
regenerative medicine and conducting R&D for industrialization, targeting medical treatment for elderly people. In
the Core Research for Evolutional Science and Technology, the Japan Science and Technology Agency is mainly
developing polymer materials, DNA, protein nano-tissues,
function-integrated chips, and diagnostic technologies to
create nanostructures where self-organization and other
molecular-order arrangements are controlled on the nanolevel.
Regarding global research, nano-tissue, micro-tissue,
and macro-tissue structural materials are being researched
individually, without a systematic approach to the interaction between materials and cells. Regenerative medicine is
the most advanced medical technology and there is fierce
global competition on its supporting biomaterials and cell
composition technology. For medical applications, however, reproducibility, stability, and precision are key issues to
be solved. An urgent research topic throughout the world is
the safety of nano-materials: rapid progress in nano-materials research is producing a succession of high-function
materials, but research on the biocompatibility and environmental compatibility of these materials lags far behind. As
national policies, the US and Europe are tackling the bioEsophagus, stomach,
intestines, bladder
Kidney
Pancreas
logical expansion of nanomaterials and evaluation of their
safety by public institutes. In particular, the area of fusion
with bio may be greatly affected by safety issues. Also
from the viewpoint of safety evaluation, nanobio is a crucial area of research.
2.2 Examples of advanced research in related fields
The nanobio research area includes not only direct
research on artificial organs and regeneration which has
been considered in this section, but also research on an
imaging tool to monitor intercellular information transmission and status, research on early high-precision diagnosis
of various diseases by quantitatively capturing ultra-trace
quantities of biomolecules, and research on nanomedical
equipment. Examples of leading research in these related
research fields are introduced below.
i) Imaging technology
Paul Alivisatos of the University of California in Berkley
developed a technology for staining cells with CdSe-CdS
shell particles by applying quantum dot technology and
industrialized the research results.1)
Quantum Dot Corporation (California)
http://www.qdots.com/live/index.asp
ii) Nanomedical equipment
C.D. Montemagano of Cornell University created a new
biomotor-driven nanomechanical device that drives the
pump and valve of a micro-fluid device by converting ATP
synthesis and hydrolytic reaction into mechanical kinetic
energy. To apply this research, they are now developing
nanomedical equipment.2)
iii) New concept of nanodiagnosis
IBM and the University of Basel developed a nanomechanical cantilever array. Biomolecules are fixed on the surface
of the cantilever of the probe microscope. This array system senses kinetic changes generated by molecule recognition.3)
iv) Tissue engineering
David J. Mooney of Michigan University introduced
nanoparticles sealing arterialization factors as a vascularizing technology indispensable for regenerative medicine and
developed cellular scaffolding materials.4)
v) Safety of bionanomaterials
As an environmental project, DuPont is addressing the biological safety of nanomaterials. By using the SWCNT pulmonary toxicity screening test, they showed that a large
dosage (5 mg/kg) could cause 15% of patients to die.5)
Liver
Heart
3. Conclusion
Lung and trachea
Cornea, lens, retina, ear
Nerve
Vessel, blood
Skin
Muscle, tendon, ligament
Bone, joint, cartilage
Number of papers
Fig. 8 Total number of papers about biomaterials by organ.
In the fields of artificial organs and regenerative medicine, materials research will be diverse, making it difficult
to assess global research trends. However, research will
likely vary from basic materials research in the following
respects or by techniques given below to applied research,
such as device creation for clinical application. The key
aspects and techniques for research are as follows:
1. Research to create super-biocompatible materials that
allow active control of cell differentiation and function
manifestation by controlling their nano-level structures
109
to avoid foreign-body and immune reactions against the
materials.
2. Materials research to create an environment similar to
extracellular matrix by using the inorganic-organic composition technology and the phenomenon of self-organization.
3. Research to clarify the optimum conditions of spatial
nanostructures in terms of cell differentiation or proliferation inducing materials, using the levels of gene and
protein manifestation as indexes, by immobilizing (coordinate bond, covalent bond, and hydrogen bond) cell
adhesion molecules.
4. Research on microstructure and macrostructure control
technologies to promote the penetration and activation
of cells and capillaries.
5. Development of various devices using the above materials.
6. Development of cell group formation control technology
to fully utilize the functions of cells (intercellular
actions).
7. Development of medical technologies using cells and
cell materials having composite functions for artificial
organs.
8. Research on technologies to evaluate the physiochemical characteristics of biomaterials, the surface characteristics of materials, biological molecular adsorption and
cell adhesion, and their functional changes under a biological or similar environment.
9. Research to create systems and devices for materials
research to clinical applications, including materials and
biological information sensing systems to recognize and
measure biological function molecules.
To develop the next generation of medical materials
which are kind to both people and the environment, complementary and comprehensive efforts are needed in these
research fields. For practical applications, materials must
behave safely in human bodies. The current survey of
research trends clarified that various materials are being
110
developed rapidly. However, nanobiomaterials are a double-edged sword, for if they are used without adequate
safety considerations, public trust will be lost. If skepticism
about the safety of nanobiomaterials is spread by incorrect
instructions or uses, non-scientific reasoning, or mere
rumor, then research on nanobiomaterials which have such
great potential will be severely affected. We must accumulate the academic knowledge and technology necessary for
creating highly functional, biocompatible, and safe materials and draw up basic guidelines for materials design for
safe nanobiomaterials.
Notes:
1) Keywords marked * in the text refer to all words containing the keywords. The author set the keywords to
minimize noise during the search, but note that noise
could not be entirely eliminated.
2) For biomaterials, various keywords are set depending
on their uses. Since the author attempted to grasp the
general trend in this survey, note that many searches
failed.
3) One paper may be counted in multiple items because
duplications were not eliminated.
References
1) M. Bruchez, Jr., M. Moronne, P. Gin, S. Weiss and A. P.
Alivisatos, Science, 25, 2013 (1998).
2) J. Z. Xi, J. J. Schmidt, C. D. Montemagno, Nature Mater., 4, 180
(2005).
3) Y. Arntz, J. D. Seelig, H. P. Lang, J. Zhang, P. Hunziker, J. P.
Pamseyer, E. Meyor, M. Hegner and C. Gerber, Nanotechnology,
14, 86 (2003).
4) T. P. Richardson, M. C. Peters, A. B. Ennett and D. J. Mooney,
Nature Biotechnol., 19, 1029 (2001).
5) A. A. Shvedova, V. Castranova, E. R. Kisin, D. Schwegler-Berry,
A. R. Murray, V. Z. Gandelsman, A. Maynard, P. Baron and J. of
Toxicology and Environmental Health Part A, 66, 1909 (2003).
05 Biomaterials
Section 2. Bioelectronics
Yuji Miyahara
Bioelectronics Group, Biomaterials Center, NIMS
1. Introduction
The micro electro mechanical system (MEMS) technology now being researched for application to analytical
chemistry, molecular biology, medicine, and the chemical
industry has established a new field called micro total
analysis system (µ-TAS) or “lab-on-a-chip”. This is a
chemical analysis system which combines fluid control elements (channels, pumps, and valves) fabricated by semiconductor micromachining technology and analysis elements (detectors, sensors, and electronics). The basic concept is to integrate all functions necessary for sample pretreatment, reagent mixing, chemical reaction, and detection
onto a single chip for thorough processing in the fields of
chemistry, biology, and medicine. Compared with the conventional biological and chemical analyzers, such a system
features: (1) smaller size and lower price, (2) lower running
costs and less environmental load because smaller quantities of samples and reagents are used, and (3) shorter analysis time because of localized chemical reaction fields.
Miniaturization and integration with microsensors and signal processing circuits will enable new styles of use, such
as high throughput analysis by parallel processing, bedside
clinical testing, and on-site environment monitoring. In the
µ-TAS field, technological development is progressing
rapidly. Based on silicon, glass, polymer, and other materials as well as micrometer- to nanometer-scale machining
technologies, µ-TAS is being studied for application to a
wide range of biological and chemical analyses, including
electrophoresis, DNA chips, chromatography, flow injection, biochemical analysis, protein analysis, and cell analysis. Research on µ-TAS is focusing on application to fields
where the µ-TAS features of miniaturization, parallel processing, and function integration can be exhibited or to new
fields.
The author surveyed research trends by searching an
academic paper database (Web of Science) for keywords
and counting the number of papers contributed to the Micro
Total Analysis System (µ-TAS), a major international conference in the field of bioelectronics. This report summarizes the results. From papers published since 1990, those
containing specific terms (µ-TAS, lab-on-a-chip, electrophoresis chip, DNA chip, and DNA microarray) in their
abstracts or keywords were extracted and sorted by years to
identify research trends. To predict the future of research in
this field, the number of recent papers on biodevices using
nanotechnologies was also checked.
2. Research trends
As the initial research on µ-TAS, Stanford University
reported an example of a gas chromatograph in 1979. The
gas chromatograph consists of a sample injection valve, a
separation column, and a thermal conductivity detector
integrated on a single silicon substrate. This technology
was systemized with a small gas cylinder and commercialized as a portable gas chromatograph. In 1990, Dr. Manz
proposed the concept of µ-TAS and introduced a chip integrated with a liquid chromatograph separation column and
an electric conductivity detector.1) At the time, micromachining technology was maturing and fields of application
were being sought. When it was shown that the technology
could be applied to the chemical and biological fields,
many researchers converged on µ-TAS and the research
took off rapidly. Figure 1 shows the transition in the number of papers on µ-TAS and lab-on-a-chip. Since the proposal in 1990, the number of papers has increased, reflecting the growth in research. At the initial stage of research
on µ-TAS, many papers were published on micropumps,
valves, and other fluid control elements having moving
parts. However, these devices had complicated structures
and so technical problems such as withstanding pressure
and long-term stability arose for practical applications.
Therefore, the electrophoresis chip and DNA chip/microarray which had no moving parts were at first used in practice.
electrophoresis chips. Papers began to appear at the same
time as the µ-TAS proposal and have increased quickly
since 2000. This is probably because the need for highthroughput DNA analysis rose as the human genome project progressed. Figures 3 and 4 show the transition in the
number of papers on DNA microarrays and DNA chips,
respectively. In both cases, the number started increasing
quickly around 2000 just as DNA microarray and DNA
chip technologies started to become established. Research
was initiated to clarify the genetic functions mainly by
expression analysis and is still continuing. At first, many
papers focused on DNA microarray creation and data processing methods, but are now turning to applied research,
such as research on disease-related genes and the expres111
Fig. 1 Number of papers in the µ-TAS and lab-on-a-chip fields.
Fig. 3 Number of papers on DNA microarrays.
Fig. 2 Number of papers on electrophoresis chips.
Fig. 4 Number of papers on DNA chips.
sion analysis of specific genes, for which DNA microarrays
and DNA chips are essential tools. In the µ-TAS and labon-a-chip fields, research was conducted from the 1990s
until early 2000 mainly in Europe and the US. Especially in
the United States, research spanning from basic to applied
was conducted, including industrialization. Element
devices based on various principles were proposed and
some were actually created. In particular, electrophoresis
chips and DNA chips/microarrays were researched actively
as genetic functional analysis progressed, and are now
essential tools for genetic functional analysis, pharmaceutical creation, and clinical research.
In Japan, systematic research started in the µ-TAS and
lab-on-a-chip fields only recently, but is accelerating
thanks to competitive funds from NEDO under the Microanalysis and Production System Project and the Advanced
Nanobiodevice Project. Figure 5 shows the number of
papers by country accepted at the µ-TAS International Conference in the last two years.2, 3) The conference was held in
Nara in 2003 and in Malmo, Sweden in 2004. The number
of papers from Japan increased quickly in the last two years
and reached the top in 2004, surpassing the United States.
It is noteworthy that the numbers of papers from Korea,
Taiwan, and other Asian countries are increasing. Recently,
the themes of research are extending from genes to proteins
and even to cell analysis. In addition, device performance
has been evaluated under conditions closer to the actual
environment of use and many studies geared to practical
applications have been reported. Meanwhile, nanotechnology applications are being promoted, and both molecular
measurement and microdroplet operation control are noteworthy new trends.
112
3. Future outlook
An organism is composed of micrometer-scale cells and
a cell is an aggregate of protein, lipid, nucleic acid, and
other nanometer structures. Research is underway on
achieving target functions and high-sensitivity measurement of biomolecules by controlling the structures, forms,
and chemical properties of biomaterials at the nanometer
level. High-sensitivity detection technology is being developed from biomolecular reaction specificity, molecular
recognition, and micromachining to detect biomolecules by
controlling the surface and interface functions and nanostructures. In particular, high-sensitivity biomolecular measurement technology using nanomachining technology and
devices is a noteworthy future trend. The author surveyed
technologies mainly for measuring DNA and proteins with
high sensitivity by effectively combining the unique properties of biomolecules and the characteristics of nanostructures. Nanopillars, nanopores, cantilevers, nanogaps, thin
films (field effect), and nanowires and nanotubes have been
developed as characteristic nanostructures, and their interactions with biomolecular reaction specificity, superstructure, charge, and base sequence are now being studied.
biomolecular measurement devices using nanotechnologies.
UK 19
Korea
22
2003
Contributed
papers:
460
Adopted
papers:
323
USA
104
Number of papers
Other
83
Japan
95
(a) 2003
Other
113
Germany 20
2004
Contributed
papers:
652
Adopted
papers:
432
Sweden
23
Denmark
33
USA
117
Japan
124
(b) 2004
Fig. 5 Number of papers at µ-TAS international conference by country.
A micrometer- to nanometer-scale pole structure having
a large aspect ratio formed on a substrate is called a
nanopillar. This structure is mainly used in separation
analysis technologies, such as electrophoresis and liquid
chromatography. If nanopillars are integrated in a micrometer-scale channel (µ-fluidics) and biomolecules are let
through, the biomolecules are sieved by size. In other
words, small biomolecules can move fast but large ones are
slowed down by the steric hindrance effect of the nanopillars. This molecule sieving effect of nanopillars spatially
separates the biomolecules in a sample by size. Nanopillars, which do not require the conventional polymer matrix
or similar separation matrix, are being applied to the electrophoresis for long-stranded DNA.
A through pore (nanopore) having a nanometer-scale
opening is formed into a thin film and the space is partitioned into two chambers. A voltage is then applied
between two electrodes installed in each chamber and biomolecules passing the nanopore are detected as changes in
current.4) If a phospholipid double layer is used for the thin
film and a nanopore is formed by using the self-organization of the α-Hemolysin (α-HL) protein, a channel
(nanopore) of 1.8 nm in aperture and 5 nm in length is
formed. When a DNA molecule passes through the
nanopore, the current flow in the nanopore is blocked and
the current drops quickly. Once the DNA molecule has
passed through, the current flowing through the nanopore
rises again to its original value. By analyzing the value of
current and the time of current drop, information can be
acquired about the interaction between the DNA molecule
and nanopore and the configuration (secondary structure,
length, and base sequence) of the DNA molecule.
By using silicon micromachining technology, the beam
thickness was reduced from micrometer to nanometer scale
Year
Fig. 6 Number of papers on biomolecular measurement devices using
nanotechnologies.
to fabricate a cantilever that reacts sensitively to surface
stress.5) Silicon or silicon nitride (SiN) is mainly used for
the cantilever. A bio-related material is fixed on the surface
of the free end of the cantilever and the deflection of the
cantilever by the formation of composite containing the target molecule is detected by the light beam deflection
method. The biomaterial to be fixed is long-stranded DNA
or protein that uses hybridization with complementary
DNA, antigen-antibody reaction, and other specific reactions for high-sensitivity biomolecular detection.
Through a nanometer-scale gap, a pair of conductive
electrodes is fabricated. A biomolecule is trapped between
the nanogap electrodes for high-sensitivity biomolecular
measurement. Electrodes having a gap of 50 nm were fabricated from polysilicon and a DNA molecule trapped in the
gap was analyzed.6) A single-stranded DNA (poly T or poly
G) of 35 bases, composed of thymine or guanine only, was
fixed on the nanogap electrode surface and the inter-electrode capacitance was measured. Consequently, hybridization with complementary DNA was found to reduce the
inter-electrode capacitance by 70%. This is because the
comparatively flexible single-stranded DNA gains a double
spiral structure by hybridization and the effective length
and the dielectric relaxation characteristic change.
Research is now being conducted on using a nanotube or
nanowire for high-sensitivity biomolecular detection. By
using a carbon nanotube as a channel, a back-gate fieldeffect transistor was fabricated to detect specific biomolecular bindings.7) The side of a carbon nanotube was coated
with a polymer, such as polyethylene glycol (PEG) (< 10
nm), and biotin was fixed on the surface to monitor
changes in electrical characteristic due to reaction with
streptoavidin. When biotin was fixed on the carbon nanotube for reaction with streptoavidin, the current showed an
extreme drop in the area of negative gate voltage. Biomolecular detection using Si nanowire was also reported.6) An
113
SiO2/Si substrate was doped with boron and a monocrystal
Si nanowire was formed on it. Then metallic electrodes
were connected to both ends to create a field-effect transistor structure with the Si substrate as the back gate. The Si
nanowire surface was treated with aminosilane and various
biomolecules were fixed to monitor changes in conductivity of the Si nanowire by the specific biomolecular bindings.
The number of papers on each device above began to
increase around 2003, especially regarding biomolecular
measurement using nanotubes and nanopores. Since these
technologies are effective for high-sensitivity biomolecular
measurement, single molecule detection, and local measurement, new knowledge may emerge and we are monitoring the future trend.
Since the µ-TAS and lab-on-a-chip technologies are
effective for attaining compact biomolecular detection
techniques, there are expectations that a portable clinical
testing system will be developed. By combining these systems with Internet or wireless communication technologies,
the concept of remote medicine and home care was proposed and demonstrated in some areas. The former Ministry of Health and Welfare set up a remote medicine
research group in the information technology development
research project funded by a subsidy for scientific research.
The group collected data on the model remote medicine as
of 1998. Figure 7 shows the breakdown of the cases of
remote medicine by field,8) although the data is as of 1998,
which is somewhat outdated in view of the rapid progress
of information communication technologies. However,
since the number of cases is as great as 229 and the medical
items do not change as drastically as communication technologies, the data is still useful for checking the fields of
application of remote medicine. Of the 229 cases, 29 are in
the field of pathological diagnosis, 97 in radiological imaging, 40 in home care, 6 in ophthalmology, 3 in dentistry, 44
in medical imaging, and 10 in other fields. In most cases,
excluding those in home care, image information is mutually exchanged between medical institutions. In the field of
home care, communication is done between medical institution and private home, or between medical institution and
aged people’s home. From the patient’s side, images may
be transmitted by the patient or a visiting nurse or automatically from a monitor.
Dentistry Other
10
3
Ophthalmology
6
Pathological
diagnosis
29
Home care
40
Radiological
imaging
97
Medical
imaging
44
Fig. 7 Breakdown by fields of remote medicine.
114
For home care, not only images but also various biological information are collected, including body temperature,
pulse, blood pressure, electrocardiogram, body weight,
aspiration, pressure in respiratory tract, oxygen saturation,
and heart rate (including fetus). Home care is intended for
aged people, terminal-care patients, patients undergoing
rehabilitation after apoplexy or cardiac infarction, patients
undergoing dialysis for chronic renal failure, and pregnant
women. Image transmission is used not only for oral medical examination or rehabilitation guidance by videophone
but also for monitoring catheter status and observing dialyzate.
To meet the growing medical needs in the aged society,
home care will become much more important. This style of
home care is still not popular and its problems are now
being studied. To collect information about more biological
items, quickly provide information which is useful for
diagnosis, and develop an easy-to-use inspection system,
the µ-TAS and lab-on-a-chip technologies hold the key.
4. Conclusion
New technologies of nanometer scale and molecular
level are quickly emerging to decode all the base sequences
of the human genome in the human genome project, to
develop microfabrication by lithography or self-organization, and to develop a means of controlling molecules by
using nanotube or nanowire. Technologies are rapidly
merging beyond the existing framework of academic disciplines. Bioelectronics technologies such as µ-TAS and labon-a-chip are applied to various fields and some will be
proven while others will be weeded out. The nanobio
fusion area has just started, but new breakthrough technologies are expected in the medical and pharmaceutical fields
in the 21st century. This is an area which is worth keeping
an eye on.
References
1) A. Manz, N. Graber, H. M. Widmer, Sensors and Actuators B, 1,
244 (1990).
2) S. Shoji, IEEJ Trans. SM, 123, 98 (2003).
3) T. Torii, IEEJ Trans. SM, 125, 102 (2005).
4) A. Meller, L. Nivon and D. Branton, Phys. Rev. Lett., 86, 3435
(2001).
5) J. Fritz, M. K. Baller, H. P. Lang, H. Rothuizen, P. Vettiger, E.
Meyer, H-J. Guntherodt, Ch. Gerber and J. K. Gimzewski, Science,
288, 316 (2000).
6) J. S. Lee, S. Oh, Y. K. Choi and L. P. Lee, Micro Total Analysis
System, 1, 305 (2002).
7) A. Star, J-C. P. Gabriel, K. Bradley, G. Gruner, Nano Letters, 3, 4,
459 (2003).
8) http://square.unim.ac.jp/enkaku/97/Proj/EnkProj-Idx.html (Updated
August 1998).
Chapter 6.
Ecomaterials
Section 1. Environmental Function Materials (Photocatalytic
and Environment Purification Materials)
Jinhua Ye and Tetsuya Kako
Eco-Function Materials Group, Ecomaterials Center, NIMS
Hirohisa Yamada
Eco-Circulation Processing Group, Ecomaterials Center, NIMS
1. Introduction
The global environmental problems and ecological
changes in the 20th century were brought by the rapid
expansion of human and industrial activities. In order to
solve them and survive in the 21st century, it is essential
for us to convert the present society to an environmentfriendly sustainable society. Under these circumstances,
one of the research targets is the development of environmental function materials. Environmental function materials are identified newly in the Ecomaterials Center, NIMS,
as eco-function materials, which are environment purification materials with smart functions, that is, high sensitivity
and intelligent response to harmful pollutants. The production of eco-function materials for improving environmental
quality can take two approaches. One strategy is to tailor
the material as a catalyst for decomposing polluting products, that is, to make a new photocatalyst. The second one
is to establish an effective adsorbent and separator for the
remediation process and correcting already polluted environments. This section reviews the current status and future
outlook of photocatalytic materials and other environment
purification materials.
2. Photocatalytic materials
2.1 Introduction
Photocatalysts have attracted extensive interest since
Honda and Fujishima introduced the water decomposition
phenomenon (Honda-Fujishima Effect) of a photoelectrochemical cell using a titanium-oxide photo electrode and a
Pt counter electrode in Nature in 1972.1)
At that time, the Oil Shock and other global energy
crises triggered global research on producing hydrogen by
decomposing water using a semiconductor photocatalyst.
However, the conversion efficiency remains low and many
hurdles must be overcome before the technology can be put
to practical use. Nevertheless, many researchers, especially
those in Japan, are still making continuous efforts towards
achieving the ultimate goal of the chemical conversion of
solar energy using a photocatalyst.
Meanwhile, a group from the University of Tokyo, in
collaboration with many enterprises, began to explore the
application of a titanium oxide photocatalyst in the field of
environmental purification from the 1990s. The photoinduced hydrophilicity2) discovered in 1994 by the group
revealed promising potential for practical application. The
self-cleaning function, which is combined from the oxidization function and hydrophilicity function of titanium
oxide photocatalyst, is now used widely for building walls,
window panes, antifogging mirrors, etc. Products using the
deodorizing and antibacterial effects of titanium oxide photocatalyst are also being developed.3)
Photocatalysts are like a magic material that can be used
not only to decompose and remove harmful organic chemical substances, but also to produce hydrogen from water,
by the strong oxidizing and reducing power of photo-excited holes and electrons.
2.2 Research trends
Figures 1 and 2 show the transition in the number of
photocatalyst-related papers and patents throughout the
world in the 30 years from 1971 to 2001. The figures show
that Japan is leading the world in both aspects. In contrast
to the steady increase of papers, the number of patents
grew slowly until the 1990s. When the photo-induced
hydrophilicity effect was discovered in 1994, the number
of patent applications jumped. In terms of countries, the
number of patent applications from Japan is overwhelming,
while about half of the patent applications even in the US
and Europe are by Japanese people.
Accompanying the development of applications of photocatalysis technology, photocatalytic materials are expected to be highly activated. To decompose and remove various organic harmful substances quickly under the weak
ultraviolet rays of natural light and artificial light from
lighting devices, research efforts have been concentrated on
115
Number of papers
Number of papers (World)
Year published
Japan
USA
Europe
China
Korea
Total
Number of applications
Fig. 1 Number of photocatalyst-related papers in the world (Source: Patent-applied Technology Trend. Report 2003 by Patent Office).
Year of claim for priority
Application to Japan
Registration in USA
Application to Europe
Total of three
Fig. 2 Number of photocatalyst-related patents in Japan, USA, and Europe (Source: Patent-applied Technology Trend Report 2003 by Patent Office).
increasing the specific surface area of titanium oxide, creating a porous structure, and combining with other
absorbents.4),5) In recent years, research interest is shifting
largely from the control of ultraviolet-supporting TiO2 photocatalyst to the development of visible light responsive
materials that can utilize more light because the spectra of
solar light and indoor light (fluorescent lighting) is mostly
composed of visible light.
Visible light responsive materials can be developed by
two approaches: one is to convert existing UV sensitive
materials into visible light responsive ones by modification,
and the other is to develop new materials. Most researchers
are working on the former. The conventional method of
producing a visible light responsive material is to dope a
different kind of metal (Cr or V) into TiO2. However, since
photo-induced electrons and holes tend to re-combine
together again in the doped level, visible light activation
can seldom be expected. Instead of cation doping, recent
researches showed that partial substitution of oxygen ions
by nitrogen can successfully activate TiO2 to be capable of
decomposing acetaldehyde or other organic matter under
116
visible light, as reported by a group from Toyota Central
R&D Labs.6) In addition to N, the doping effects of S and C
are now also being researched. Since the doping amount
must be minimal to maintain the crystalline structure of
titanium dioxide, however, the visible-light activation
effect is limited (up to about 500 nm).
For response to a wider range of visible light, a new visible light sensitive photocatalyst should be developed
beyond the framework of titanium oxide. Non-oxide semiconductors (cadmium sulfide, cadmium selenide, etc.) having a small band gap and adsorption capability in the visible light area attracted attention but were found to have
many problems such as photo-corrosion caused by the
photo-generated holes in the valence band, and thus prevent stable functioning. For practical purposes, a comparatively stable oxide photocatalyst is required. Recently, a
group from the Tokyo Institute of Technology developed
oxynitride7) and a group from the Science University of
Tokyo developed BiVO48) as new photocatalysts. These
materials can generate hydrogen and oxygen from aqueous
solutions containing an electron donor sacrificial agent
(methanol) and an electron acceptor sacrificial agent
(AgNO3) under visible light, but fail to decompose pure
water. Up to now, only a few materials have been reported
to be capable of splitting pure water under visible light irradiation. Among them, In1-xNixTaO4 photocatalyst9) jointly
developed by the Agency of Industrial Science and Technology (AIST) and the National Institute for Materials Science (NIMS) attracted much attention for the world’s first
successful decomposition of water into hydrogen and oxygen at the stoichiometric ratio of 2:1 under visible light.
Recently, NIMS also succeeded in developing several composite oxide photocatalysts that could produce hydrogen
and decompose various organic harmful substances under
visible light.10)-12)
2.3 Future outlook
Photocatalysis technology is now mainly used for outdoor applications, such as exterior and road materials. Air
cleaners using photocatalysts also enjoy strong demand as a
solution to “sick house syndrome” in recent years. The
market is expected to grow continuously for improving the
living environment particularly in the construction materials industry. In addition to these products, the fusion of
photocatalyst technology and environment-related technology is predicted to produce a large market. For example, an
environment-related public works technology that decomposes harmful substances and germs in the atmosphere,
water, and soil by solar or indoor light will create a huge
market for photocatalysts, and the photo-induced
hydrophilicity effect of a photocatalyst will possibly be
used for global warming prevention. In the near future,
photocatalysis technology will be applied to energy-related
fields, such as the commercial production of hydrogen by
the photodecomposition of water.
With the expansion of applications, basic research is
needed on clarifying the mechanism of the photocatalytic
reaction underlying photocatalyst technology, improving
the activity, controlling responsiveness to visible light, and
stabilizing the reaction. For the time being, the most important subject is to develop a highly efficient visible light sensitive photocatalyst to extend the capabilities of photocatalysis technology and bring the material to practical application.
2.4 Conclusion
Photocatalysis technology originated in Japan, and Japan
leads the world in the number of papers, the number of
patents, and market scale. However, competition from the
United States and Europe is growing, as well as from China
and Korea. To ensure competitiveness in the international
market, efforts in improving the reliability of photocatalyst
related products while maintaining technological development superiority are indispensable. Working groups from
industry, academia, and the government of Japan are now
actively involved in standardization of the performance
evaluation of photocatalysts.
References
1) A. Fujishima and K. Honda, Nature, 238, 37 (1972).
2) R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, A.
Kitamura, M. Shimohigoshi and T. Watanabe, Nature, 388, 431
(1997).
3) A. Fujishima, K. Hashimoto and T. Watanabe: “Mechanism of
Photocatalyst” (in Japanese), Nippon Jitsugyo Publishing (2000).
4) T. Sasaki, S. Nakano, S. Yamauchi and M. Watanabe, Chem.
Mater., 9, 602(1997).
5) S. Chu, K. Wada and S. Inoue, Adv. Mater., 14, 1752 (2002).
6) R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki and Y. Taga, Science,
293, 269 (2001).
7) M. Hara, K. Domen: Functional Materials (in Japanese), 22, 25
(2002).
8) A. Kudo, O. Omori, H. Kato and J. Am. Chem. Soc., 121, 11459
(1999).
9) Z. Zou, J. Ye, K. Sayama and H. Arakawa, Nature, 414, 625
(2001).
10) J. Yin, Z. Zou, J. Ye and J. Phys. Chem. B., 107, 4936 (2003).
11) J. Tang, Z. Zou and J. Ye, Angew. Chem. Int. Ed., 43, 4463 (2004).
12) J. Tang, Z. Zou and J. Ye, Chem. Mater., 16, 1644 (2004).
3. Environment purification materials
3.1 Introduction
Environmental problems are caused by harmful chemical substances (dioxins, etc.), harmful heavy metals (Cd-,
Cr-ions, etc.), water contaminants (NH4+, PO43–, A5O33–),
groundwater contaminants (trichloroethylene and tetrachloroethylene), volatile organic compounds (VOC),
atmospheric contaminants (NO x, SO x, SPM, etc.), and
radioactive waste. To solve these problems and create a
sustainable society, we must remove the contaminants
accumulated so far and control further contamination.
Since even trace quantities of environmental contaminants
have a large impact, a very specific and highly sensitive
sensing technology is necessary.
3.2 Research trends
To promote environmental purification and conservation, materials have been created to adsorb, separate,
decompose, and remove harmful contaminants selectively.
Because of organophilic property as well as adsorption and
catalytic capabilities, clay minerals such as smectites have
been used to adsorb, decompose, and remove harmful substances since ancient times. High selectivity has not been
achieved yet, despite recent reports on the adsorption of
dioxin on pillared smectite and that of aromatics by
organophilic smectite.1)-4) Zeolite is a microporous material,
having regular nano-pores, a large specific area, and cationexchange capacity, and has attracted attention as an adsorbent or a catalyst support. 5, 6) Natural zeolites found in
abundance have been used to remove ammonia which is
the main contaminant of closed water systems, lakes and
marshes, and rivers arising from household drainage. However, natural zeolites do not have high selectivity for
adsorbing cadmium, arsenic, and other heavy metal ions.
Since the 1940s, synthetic zeolites developed by Union
Carbide, Mobil, and others have been used as an industrial
catalyst and a detergent builder. Since the 1970s, the development of novel zeolites with a unique pore structure have
117
enabled many new industrial catalyst processes. However,
the synthetic zeolites do not have enough selectivity for
adsorbing or removing heavy metal ions and chemical stability. Furthermore, the microporous structure is unsuitable
for adsorbing and fixing large molecules.
In the early 1990s, mesoporous silica was developed
independently by the Waseda University – Toyota Central
R&D Labs group and Mobil. Mesoporous materials with
large specific surface areas and uniform and regular mesopores have been greatly expected to adsorb and remove
organic metal complexes and organic matter that cannot be
adsorbed by microporous materials.7)-9) However, their
functions and chemical stability are not yet adequate for
applications.
Under these circumstances, the development of materials to separate, decompose, and remove harmful chemical
substances very selectively has been demanded. AIST has
developed mesoporous materials with a selective pore diffusion function and inorganic-, organic- and hybrid-type
nanospace materials with a high selective adsorption function. AIST has also developed nano-metal particles for
highly active catalysts. By combining these materials,
AIST is constructing a multifunctional integrated system
with catalyst functions for adsorbing and decomposing
harmful chemical substances.10, 11) In addition, high-sensitivity environmental sensors have been developed by modifying the quartz crystal microbalance with biomaterials.12)
NIMS is currently promoting 1) Research on the removal
of heavy metals and ammonia and the management of
radioactive waste by using nanopore materials (zeolite,
etc.) and nanoparticles (boehmite, etc.),13) 2) Development
of chemical sensor using ultrathin films prepared by the
Langmuir-Blodgett technique,14) 3) Development of a magnetic separation system using a superconducting magnet for
chemical-adsorbing of target substances (arsenic, bisphenol
A, dioxin, etc.),15) and 4) Research for fixing biopolymers
using mesoporous silica or mesoporous carbon, and removing VOC and harmful organic substances.16) Mesoporous
carbon is a new material produced by using mesoporous
silica as a template and is expected to be applied to catalysts, adsorbents, electrodes, and capacitors.
3.3 Future outlook
In order to separate, decompose and remove the specific
harmful substances, we have to create novel materials with
high-selectivity and sensing functions by using nanotechnologies, self-organization, and template reactions. To
apply nanomaterials to environmental purification, we also
need to clarify the chemical stability of nanomaterials in
118
water, soil, and other environments and the desorption
capability, chemical stability, and catalytic activity of
nanomaterials after fixing harmful chemical substances.
This will require the creation of materials by fusion beyond
the traditional frameworks of inorganic, organic, and polymer materials.
3.4 Conclusion
To overcome various complex environmental problems,
the technologies should be shifted to be more precise and
flexible. It is necessary to improve the functions and characteristics of materials through nano-level structural control
utilizing nanotechnologies. It is also important to create
environment-purifying nanomaterials based on recycling of
resources with less environmental load. This cannot be
achieved without widely linked research beyond the fields
of material science, chemistry, environment science, and
biology. Furthermore it is necessary to develop a new environment purification system considering the self-cleaning
ability in nature.
References
1) S. A. Boyd, J. F. Lee and M. M. Mortland, Nature, 333, 345 (1988).
2) S. A. Boyd, S. Shaobai, M. M. Mortland, Clays Clay Miner., 36,
125 (1988).
3) L. J. Michot and T. J. Pinnavaia, Clays Clay Miner., 38, 634 (1991).
4) R. K. Kukkadapu and S. A. Boyd, Clays Clay Miner., 43, 318
(1995).
5) J. Weitkamp, Solid State Ionics, 131, 175 (2000).
6) K. Meyer, P. Lorenz, B. Bohlkun and P. Klobes, Cryst. Res.
Technol., 29, 903 (1994).
7) T. Yanagisawa, T. Shimizu, K. Kuroda and C. Kato, Bull. Chem.
Soc. Jpn., 63, 988 (1990).
8) C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and J. S.
Beck, Nature, 359, 710 (1992).
9) S. Inagaki, Y. Fukushima and K. Kuroda, J. Chem. Soc., Chem.
Commun., 680 (1993).
10) K. Kosuge, T. Murakami, N. Kikukawa and M. Takemori, Chem.
Mater., 15, 3184 (2003).
11) A. K. Sinha, S. Seelan, S. Tsubota and M. Haruta, Angew. Chem.
Int. Ed., 42, 1546 (2004).
12) S. Kurosawa, H. Aizawa, S. Pak, S. Wakita and S. Niki,
“Biosensing Micromachine Using Crystal Resonator” Industrial
Technology Service Center, p. 542 (2002).
13) Y. Watanabe, H. Yamada, J. Tanaka, Y. Komatsu and Y.
Moriyoshi, Sep. Sci. Technol., 39, 2091 (2004).
14) K. Tamura, H. Sato, S. Yamashita, A. Yamagishi and H. Yamada,
J. Phys. Chem. B, 108, 8287 (2004).
15) T. Ohara, T. Watanabe, S. Nishijima, H. Okada and N. Saho, Oyo
Butsuri, 171, 57 (2002).
16) M. Miyahara, A. Vinu, T. Nakanishi and K. Ariga, Kobunshi
Ronbunshu, 61, 623 (2004).
06 Ecomaterials
Section 2. System Element Type Ecomaterials - Supporting
New Energies and Energy Conservation:
Materials for Hydrogen Energy and Fuel Cells
Chikashi Nishimura
Eco-Energy Materials Group, Ecomaterials Center, NIMS
Year
Fig. 1 Number of papers on hydrogen energy.
Number of papers (total)
Expectations for the hydrogen energy age are growing
and fuel cell technology is progressing rapidly.1) Fuel cells
have more than a 100-year history of research and development, yet they have been applied to spacecraft and other
limited uses only. For example, the fuel-cell automobiles of
Toyota and Honda were leased to the government in
December 2002 and a stationary fuel cell was installed in
the Prime Minister’s Office. In reality, however, fuel cells
are still at the prototype stage and there remain many problems concerning output, stability, cost, infrastructure, and
so forth. Research and development on conventional large
fuel cells and automotive or stationary fuel cells is based on
engineering considerations, such as how a system should
be created from existing materials. This is the current global trend of fuel cell research and development. However, if
only this engineering-oriented research toward early application continues, it will be difficult to use the fuel cells in
automobiles or medium-scale generators. Therefore, there
is a growing perception of the need to return to basics and
give priority to materials research.2)
This report examines the field of materials for hydrogen
energy and fuel cells where research and development is
progressing quickly. To grasp the trends accurately, the
author investigated the recent transition in the number of
papers by searching a database of academic papers (SCI
Expanded) for the period 1980 to 2004 containing the
terms “hydrogen energy,” “fuel cell,” and “hydrogen permeation” in their titles or keywords, and counting the
resulting papers in each year.
1. Introduction
2. Research trends
hydrogen energy throughout the world and in each major
country. The number started increasing rapidly around
1996. It was soon after the 10th World Hydrogen Energy
Congress was held in Cocoa Beach, USA (1994), and WE-
Year
Fig. 2 Number of papers on polymer electrolyte fuel cells (PEFC).
NET I (1993-1998) was started in Japan. Research is now
active in the United States, Japan, and China, with the
119
growth in China being especially remarkable.
polymer electrolyte fuel cells (PEFC) for which expectations are highest among fuel cells. The total number of
papers from 1980 to 2004 is about 500. Papers started
increasing globally around 1990 and reached an annual output of 100 in 2004. With about 29% of the world’s total
number of papers, Japan holds the lead, far ahead of the US
(21%) ranking second and Germany (13%) ranking third.
solid oxide fuel cells (SOFC). The number in the last 25
years was about 1,800, nearly four times that on polymer
electrolyte fuel cells. Papers on solid oxide fuel cells also
started increasing rapidly around 1990. Regarding the total
number of papers in the last 25 years, Japan accounts for
25% of the world’s total, higher than that of the US (21%)
ranking second and Germany (10%) ranking third. For the
last decade, the annual number of papers from Japan has
been stable at about 50, but the number from the United
States has been increasing and surpassed that of Japan in
Year
Fig. 3 Number of papers on solid oxide fuel cells (SOFC).
Year
Fig. 4 Number of papers on fuel cells of the molten carbonate type
(MCFC), phosphoric acid type (PAFC), and alkaline type (AFC).
120
2003, and the gap is widening. This may be partly because
the United States is discussing a combined power generation system with coal fired power at a national level.
So far, we have examined the transition in papers on
polymer electrolyte fuel cells and solid oxide fuel cells. For
comparison, Figure 4 shows the other main types of fuel
cell: molten carbon type (MCFC), phosphoric acid type
(PAFC), and alkaline type (AFC). The number of papers
also showed a global rapid increase around 1990. However,
the increase leveled off around 1996 and the annual output
has been stable at about 120 to 140. This is a contrast to the
dramatic increase in papers on polymer electrolyte fuel
cells (Figure 2) and solid oxide fuel cells (Figure 3).
Fuel cells run on hydrogen, and the trend of hydrogen
production is as follows. Hydrogen does not exist independently in nature and is generally produced from fossil fuels
by the steam reforming method, the partial oxidization
method, or the auto-thermal method which is a combination of both. Polymer electrolyte fuel cells, which is undergoing intensive research for practical application, uses a
platinum-type electrocatalyst. Since the catalyst loses activity in this kind of fuel cell operated at low temperatures, it
is necessary to suppress the CO concentration in reformed
gas to 10 ppm or less, so a CO removal process is usually
added. Metallic membrane materials for hydrogen separation can be laminated up to tens of microns thick with no
pinholes. Research is underway on combining these with a
reforming reaction vessel to produce a new reaction vessel
(membrane reformer or membrane reactor) that can concurrently shift the chemical equilibrium to the product side,
lower the reaction temperature, and generate high-purity
hydrogen. Figure 5 shows the transition in the number of
papers. The total in the last 25 years is about 1,500. The
number started increasing rapidly around 1990, and for the
last several years the annual output is about 150. Japan is
vying for the world’s top position with the United States,
Germany, and China.
As the key material for the membrane reformer, membrane materials for hydrogen separation are also the subject
of intense research and development. Figure 6 shows the
results of searching papers for the keyword “hydrogen permeation” with additional conditions “Pd” and “Nb/V or
amorphous.” Basic research has been conducted on hydrogen permeation since around 1980, and on the application
of hydrogen separating membranes since around 1990. The
numbers of papers on Pd, Nb/V are increasing in line with
the total number of papers on materials. Papers on non-Pd
(Nb/V or amorphous) are increasing slightly faster than
those on Pd. Figure 7 shows the total number of papers by
country in the last 25 years. Japan ranks first with about
22%, closely followed by the US ranking second with 18%
but far ahead of the remaining countries.
In addition to searching papers, the author also investigated web pages related to the Ministry of Economy, Trade
and Industry and the Ministry of Education, Culture,
Sports, Science and Technology for Japan’s research projects on hydrogen energy and fuel cells.
Concerning projects related to the Ministry of Economy,
Trade and Industry (including NEDO), huge research funds
have been invested in projects related to hydrogen and fuel
Japan
Year
Fig. 5 Number of papers on membrane reformers and membrane
reactors.
Year
Fig. 6 Number of papers on hydrogen permeation.
cells for over 10 years. R&D was carried out comprehensively in WE-NET I (1993-1998, 10 billion yen total) to
develop a large-scale hydrogen infrastructure technology
and WE-NET II (1999-2002, 5.8 billion yen in total) to
develop a hydrogen infrastructure technology mainly for
fuel cells. WE-NET was succeeded by “Development of
infrastructure technology for the safe use of hydrogen.” In
this project from FY2003 to FY2007, research is focused
on two areas: the safe use of hydrogen, and practical application. The working expenses in FY2004 were 6 billion
yen. Two other projects were carried out simultaneously
from FY2000 to FY2004: “Technical Development Project
for Polymer Electrolyte Fuel Cell System” aimed at
enhancing and systemizing polymer electrolyte fuel cells
for future full-scale use and dissemination, and “Infrastructure Establishment Project for Polymer Electrolyte Fuel
Cells” aimed at establishing an infrastructure for disseminating polymer electrolyte fuel cells. The working expenses
in FY2004 were 4.1 billion and 2.4 billion yen, respectively. In FY2005, a 5-year project “Strategic Technical Development for Practical Polymer Electrolyte Fuel Cells” started, with a first-year budget of 5.5 billion yen, aiming at
USA
India China
UK Germany Taiwan Italy France
Canada
Rank
Fig. 7 Top 10 countries by number of papers on hydrogen permeation
(1980-2004).
developing elemental and systemizing technologies for
practical application and dissemination. To deepen understanding of the basic mechanisms of fuel cells, the Agency
of Industrial Science and Technology is analyzing phenomena and has established a research system for this purpose,
“Entrusted Research Expenditures for Fuel Cell Advanced
Science,” with the FY2005 budget of 1 billion yen.
Other projects related to solid oxide fuel cells are
“Research and Development of Solid Oxide Fuel Cell
(SOFC)” (FY2001-2004, FY2004 budget: 1 billion yen)
and “Technical Development of Solid Oxide Fuel Cell
(SOFC) System” (FY2004-2007, FY2004 budget: 1.5 billion yen).
Meanwhile, the Japan Science and Technology Agency
(JST) is conducting ground-breaking research on developing catalysts and new materials in the Core Research for
Environmental Science and Technology (CREST) funded
by the Ministry of Education, Culture, Sports, Science and
Technology. The individual topics are “Pseudo 3D Interface Design for Electric Energy Conversion” (2000-2005)
in the area of resources recycling, “Fabrication of Energy
Conversion Device Using Composite Structure of Highlevel Regular Array” (2002-2007) and “Fabrication of
High-function Nanotube Materials and Application to
Energy Conversion Technology” (2002-2007) in the area
of high-level energy use. In the area of nanostructure control catalysts, the topics are “New Environmental Catalyst
Function of Surface-optimized Carbon Nanofiber” (20022007) and “Fabrication of Nanocatalyst of Precise Universal Control” (2002-2007). The average annual budget is
just under 100 million yen for each topic. The project,
“Development of Low-temperature Oxide Electrolyte Fuel
Cell” (2002-2004) was conducted with the FY2004 budget
of 130 million yen funded from promotion and coordination expenses. In the leading project, “Next-generation Fuel
Cell Project” (FY2003-2007, FY2004 budget: 290 million
yen) now in progress, electrode catalysts for polymer electrolyte fuel cells are being designed.
121
As described, huge funds are being invested in research,
particularly on the polymer electrolyte fuel cell which is
regarded as very promising. Despite the investments, however, fuel cells have not yet reached a practical level in
terms of cost and lifespan. While considering practical use,
we must return to the basics of materials.
Concerning papers on solid oxide fuel cells, Figure 8
compares the transition in the number of papers on YSZ
(partially stabilized zirconia) which is used in nearly practical systems and papers on non-YSZ materials. A comparison of the increases in the last three or four years shows
that the number of papers without YSZ is greater, reflecting
a return to materials research and basic research.
3. Future outlook
Year
4. Conclusion
As outlined above, the number of papers on hydrogen
energy, fuel cells, and hydrogen permeation started increasing rapidly around 1990. In the last 10 years or more, Japan
has invested heavily in research in this field and ranks first
or near the top in each item in terms of the number of
papers published. However, large obstacles remain before
fuel cells can enter widespread use. While continuing with
research toward early application, we must return to the
basics of materials and conduct research on improving the
characteristics based on fine analysis and tissue and structure control.
122
Fig. 8 Number of papers on solid oxide fuel cells, containing or not
containing YSZ as a keyword.
References
1) Science and Technology Foresight Center, National Institute of
Science and Technology Policy, Ministry of Education, Culture,
Sports, Science and Technology: Forefront of Hydrogen Energy
(Illustrated), Kogyo Chosakai (2003).
2) T. Honma and T. Kudo: Ceramics 40, 369-373 (2005).
06 Ecomaterials
Section 3. Ecomaterials of Lifecycle Design
Hideki Kakisawa
Eco-Circulation Processing Group, Ecomaterials Center, NIMS
Kohmei Halada
Ecomaterials Center, NIMS
1. Introduction
Ecomaterials of lifecycle design refer to materials
designed to reduce environmental loads throughout their
lifecycle, from manufacture to disposal. While the aforementioned two kinds of ecomaterials address specific environmental problems by performance, lifecycle design type
materials are based on the design concept “environmentfriendly materials (and materials technologies)”.
The environmental load BL of materials is the sum of the
environmental load BP during production, environmental
load BU during use, and environmental load BE upon disposal, minus the value BR upon recycling (BL = BP + BU +
BE – BR). The eco-efficiency Ee, which indicates the ratio
of service SU provided by the materials to the environmental load, is defined by:
SU
Ee ＝ B +B +B –B
P
U
E
R
(1)
To create materials of small environmental load, the values
of BP, BU, and BE must be designed to be small while those
of SU and BR must be designed to be large. The ecomaterials of lifecycle design can thus be classified into four categories:1)
1) High materials efficiency (Large SU, small BU)
2) Green environmental profile (Small BP)
3) Free of hazardous substances (Small BE)
4) High recyclability (Large BR)
This classification is certainly not strict, and some ecomaterials may have characteristics of more than one category.
1) and 2) often follow the trend of conventional research
(e.g. high specific strength, long life, efficient process,
energy-saving, etc.). Since these materials are explained in
other chapters, this section discusses the recent trends and
future outlook for materials free of harmful substances and
materials of high recycling efficiency. The technique for
evaluating lifecycle design conformance is also introduced.
2. Free of hazardous substances
The electronics industry enriches life with products but
also discharges many harmful substances into the environment. It is a typical industry that incurs large environmental
loads. Therefore, much of the research on materials free of
hazardous substances focuses on the electronics industry.
In particular, the enforcement of the Home Appliance
Recycling Law in Japan and that of WEEE and ROHS in
the EU made it a matter of urgency to remove heavy metals
and other harmful elements. Since this affects electronic
mounting the most, lead-free solder alloys (not containing
lead) and electronic mounting techniques using the alloys
are being developed throughout the world.
2.1 Global trends
The National Center for Manufacturing Science (NCM)
of the United States started developing lead-free solder by
the Lead-Free Solder Project in the early 1990s, followed
by Improved Design Life and Environmentally Aware
Manufacturing of Electronics Assemblies by Lead-Free
Soldering (IDEAL) of the EU. This led to active research
and development mainly within industry in Japan. Since it
is difficult to make lead-free solder which is able to withstand high temperatures, this solder was exempted from
legislation in the United States. Considering the results of
the WEEE/ROHS bill in the EU and the research for promoting practical application in Japan, the United States
organized an industry-academia-government research system again by The National Electronics Manufacturing Initiative (NEMI). In the EU, the practical use of mediumtemperature solder (Sn-Ag-Cu solder) was verified in the
above IDEALS Project. In practice, however, the solder
has various problems hindering practical use and the
COST351 Project (EU COST Initiative) and the Interconnection Materials for Environmentally Compatible Assembly Technologies (IMECAT) Project are now in progress.
Figure 1 shows past projects related to lead-free mounting
in Europe and the US.
2.2 Domestic trends
Stimulated by the NCMS Lead-Free Solder Project,
Japanese industry went ahead with research and development. NEDO executed a project from 1997 to 2000.
Recently, a medium-temperature solder (Sn-Ag-Cu solder)
123
RQHS Command
Fig. 1 Projects related to lead-free mounting in the world.
standardizing project was carried out mainly by The Japan
Welding Engineering Society and Japan Electronics and
Information Technology Industry Association (JEITA), the
latter project being followed by a low-temperature solder
development project. These projects in Japan are organized
mainly by industrial groups and not industry-academiagovernment organizations as in the United States and
Europe. The electronic industry is an important pillar of
Japan but academic organs, especially national institutions,
are much less aware of problems and less willing to participate compared with those in Europe and the US. Although
much practical data has been acquired, Europe and the US
have the lead in intellectual property rights because Japan
has no academic infrastructure.
2.3 Current status of NIMS and research by NIMS
NIMS has only an individual-level research system for
lead-free mounting and no research system driven by a
national laboratory as in the United States. Recently, however, members of the Ecomaterials Center began to participate in the JEITA project and the industrial sector and
organizations are now expecting the former national laboratories to join.
2.4 Noteworthy research outside NIMS and future outlook
Research outside NIMS is mainly conducted between
industry and universities (partially national universities)
and the JEITA project of low-temperature lead-free solder
technology is attracting attention. So far, only the mediumtemperature Sn-Ag-Cu solder has entered practical use. To
achieve entirely lead-free mounting, high-temperature and
low-temperature solder alloys and their peripheral technologies are required. In particular, no substitute solder has
been found for the high-temperature Pb-5Sn solder that is
used for LSI packaging. For future research, an R&D system led by an academic institute is needed. Bonding without solder alloy, such as conductive bonding (already partially achieved), will be another research trend. Each country has started work on standardizing lead-free mounting
related technologies and international competition in standardization will surely become fierce. As a national strategy, therefore, industry, academia, and government must
124
immediately encourage the standardization of technologies
established so far and related technologies to be developed
in future.
3. Supporting recycling
However far process technologies might advance, it may
never be possible to melt unsorted piles of scrap and to
extract the various constituent materials of the same quality
as before disposal. The keys to building a recycling system
are therefore to improve the social system through legislation, establishment of recovery channels, and thorough
sorting, as well as to design products that are easy to disassemble for recycling. However, approaches based on technology and materials still have a very important role to
play. For example, one technological approach is to develop a recycling process that can permit impurities, while a
materials approach is to enhance the recycling efficiency of
materials themselves. In addition, materials technologies
make a significant contribution to product designs that
assist recycling.
3.1 Recycling process technology
There is no doubt that scraps from used products will
increase in all countries, irrespective of the kind of materials. To cope with this problem, we need to develop recycling technologies, particularly for plastics, metallic structure materials, and concrete because of the large volumes
of such scrap. The United States, Japan, and Europe have
many research projects targeted at the three kinds of scraps,
and in the United States there are many FRP recycling projects involving the military.
In most cases, products have already undergone some
compound treatment for usage, but this makes quality control difficult and mixes foreign components. Process technologies for removing artificially mixed impurities are still
not satisfactory, so cascade recycling of materials of lower
grades than the original ones is unavoidable. Research
should attempt not only to enhance separation and refining
technologies but also to develop processing technologies
that permit or use impurities. This tendency is evident from
the recent international congresses on ecomaterials2), 3) and
papers on ecomaterials in international materials journals.4)5) From this point of view, research on recycling
processes can be classified as follows (for details, refer to
the above documents):
(1) Making impurities harmless: Clarifying the mechanism
of impurities that adversely affect the process and immobilizing the impurities during the process
(2) Materials design using impurities: Controlling the present form and distribution of impurities appropriately to
utilize them as effective added elements
(3) Solid-phase recycling: Recycling scraps in the solid
phase, instead of melting and refining.
3.2 Recyclable materials design
While devising the recycling of scraps, we need to
design marketing materials that are easy to recycle after
use, especially for composite materials. Recyclable materials designs can be classified into:
(1) Structure-controlled recyclable design: Design not to
enhance properties by added elements but to produce various properties from materials of simple compositions by
controlling microstructure.
(2) New composite materials: Design combining materials
of the same chemical composition but different properties
with easy-to-disassemble interfaces.
3.3 Materials technologies for recyclable product design
Easy-to-disassemble design is one of the important elements of product ecodesign (environment-harmonious
design) based on lifecycle engineering. The basis of this
design is to facilitate separation and its importance is now
widely recognized. Instead of time-consuming screws, various quick clamps are being proposed and new types of connections such as shape-memory springs6) and shape-memory screws that lose threads, are being developed. New
adhesives for resin bonding include thermoplastic adhesives that soften when heated to make separation easy, ones
that are liquefied or produce foams when heated to debond
interfaces, and ones that debond upon absorbing water or
receiving ultraviolet irradiation. It is also proposed to use
yeast and biodegradable plastics for connections. In this
unique method, water is added to the plastics to grow yeast
for separation. For metallurgical connections, it is proposed
to use materials of low melting points for interfaces, to
condense degraded elements at interfaces by using the diffusion of atoms and ions, and to use hydrogen brittleness.
Recently, NIMS developed a method of diffusing a lowmelting-point metal on an interface for easy separation.
Connections designed for easy separation are still at a
primitive stage and future development is expected.
3.4 Future outlook
There is no doubt that materials research conscious of
recycling will increase in future. However, research in this
field only has value when actually used. As well as R&D
for the future, it is equally important to develop individual
technologies jointly with industry from the outset of
research by considering various scales of recycling.
4. Technology for evaluating lifecycle materials design
To improve ecomaterials of lifecycle design, not only
the evaluation of conventional materials characteristics but
also the correct evaluation of lifecycle design compatibility
is important. The representative evaluation indexes are lifecycle assessment (LCA), materials flow accounting (MFA),
eco-efficiency, and resource productivity.
4.1 Index by environmental load
LCA is a technique dedicated to the evaluation of products and services from the environmental aspect based on
the concept of lifecycle. A product lifecycle can roughly be
divided into the stages of manufacture, use, and disposal.
Environmental loads are accumulated at each stage. Much
research on LCA methods and database construction is
being done worldwide. The main LCA software overseas is
the
Bousted
Model
(http://www.bousteadconsulting.co.uk/products.htm). There is sufficient inventory data in Japan, and NIMS offers an inventory database
containing iron, steel, and nonferrous materials on its website
(http://www.nims.go.jp/
emc/).
4.2 Index by materials flow
MFA is a technique of quantifying and grasping systematically the materials balance in units of country, area, or
industrial field. Since the late 1990s, surveys and research
have been particularly active in Europe. In Japan,
Moriguchi and co-workers of the National Institute for
Environmental Studies7) are conducting advanced research.
Tohoku University is conducting MFA research in East
Asia with cooperation from Nagoya University, Waseda
University, and NIMS, the purpose of which is to propose
an MFA technique conforming to overseas trends and
available for international comparison while compiling
existing MFA results of Japan. [JST RISTEX “Materials
flow as sustainability index”]
Total material requirement (TMR) is a technique focusing on hidden flows (or ecological knapsack). This technique was proposed as a powerful means of expressing
environmental stress factors related to materials use. As the
material input per service (MIPS), this is given importance
also in “Guideline for Environment-compatible Design” 8)
by the US Department of Environment. In Japan, NIMS is
performing approximate calculations of the total material
requirements of metals.9)
Indexes generally called “recycling rate” are based on
materials and product flows. However, the definition and
method of calculating “recycling rate” differ between
industries and products, and many indexes focus on part of
recycling. The Eco Material Forum is proposing a high
recycling index10) based on an overall view of the materials
flow as a guideline, and the index can be regarded as a
common language for discussing recycling. Future discussions on the recycling rate are expected to be based on this
guideline.
4.3 Index considering service
The above index is attracting attention also from the
125
viewpoints of eco-efficiency and resources productivity.
On the product level, eco-efficiency is calculated by comparing the service provided by the product with the environmental load of the product. Eco-efficiency concerns
how the service provided by the product and the environmental load of the product should be expressed. The aforementioned LCA is one technique of evaluating the environmental load. Resources productivity is the eco-efficiency
when the environmental load is expressed as a function of
the resources consumed. Japan’s Basic Project for Recycling Society divides the gross domestic product (GDP) by
the natural resources input (total amount of domestic and
imported natural resources and imported products) to calculate the resources productivity. However, this is still at
the research stage and no index definitions or calculation
methods have been established for evaluating materials or
products.
126
References
1) K. Halada and R. Yamamoto, Mater. Res. Soc. Bull., 11, 871
(2001).
2) J. Adv. Sci. 13 (2002).
3) Trans. Mater. Res. Soc. Jpn., 29 (2004).
4) Mater. Trans., 43 (2002).
5) Mater. Trans., 44 (2003).
6) J. D. Chiodo, E. H. Billett and D. J. Harrison, EcoDesign 99: First
Intern. Symp. on Environmentally Conscious Design and Inverse
Manufacturing, 590 (1999).
7) Y. Moriguchi, J. Mater. Cycles and Waste Management, 1, 2
(1999).
8) US Environmental Protection Agency, “Design for the
Environment”, Tomio Umeda, Kogyo Chosakai (1997).
9) K. Halada, K. Ijima, N. Katagiri and T. Okura, Jpn. Inst. Metals,
65[7]564-570 (2001).
10) Eco Materials Forum, “High Recycling Index Guideline” (2004).
Chapter 7.
High Temperature Materials for Jet
Engines and Gas Turbines
Hiroshi Harada
High Temperature Materials Group, Materials Engineering Laboratory, NIMS
1. Introduction
To reduce energy-generated CO2 and curb global warming, it is necessary to develop high-efficiency combinedcycle power stations and next-generation jet engines. The
most effective way to raise the efficiency of the thermal
engines is to increase the temperature on the high-temperature side of the Carnot cycle. High temperature materials
that can withstand such temperature increases are now
being researched intensively, and platinum-group metals
appear to be the key to development.
This paper introduces research trends in the application
of platinum-group metals to high temeperature alloys,
focusing on Ni-base superalloys with platinum-group metals additions, and refractory superalloys based on platinumgroup metals. It also examines the outlook for traditional
refractory alloys.
2. The future of refractory materials
At takeoff, the turbine inlet gas temperature of the
engines of modern civil aircraft exceeds 1600˚C. Since
next-generation engines will operate at higher temperature
for higher efficiency, Ni-base superalloys having greater
heat resistance are required. For the 250-seater Boeing 787
to enter service in 2008 and other new models, GE Corporation of the US and Rolls Royce of the UK started to
develop high-efficiency engines (Figure 1) and are now
considering using next-generation Ni-base single crystal
superalloys for the blades and vanes of thier high-temperature turbines.
In Japan, the Ministry of Economy, Trade and Industry
started developing a regonal jet plane and in 2003 initiated
a project to develop an environment-friendly small jet
engine. Thus, much work is being done on the development
of high-performance engines both within and outside Japan
and there is growing demand for advanced superalloys that
could be used in such engines.
In the field of power generation, a combined-cycle
power-generation gas turbine of ultrahigh efficiency is
indispensable at a turbine inlet gas temperature of 1700˚C
or higher and higher thermal efficiency of 56% in order to
substitute coal-firing thermal power plants and to reduce
CO2 effectively. Here too, there is a need for high temperature materials for turbine blades and vanes. In addition, the
gas turbine needs to be made more efficient in cogenerations for local power systems with higher electricity/heat
ratios.
Turbine blades are manufactured with a hollow interior
by precision investment casting. The metal temperature is
adjusted by internal air cooling so that the blades can be
used in a gas flow that is hotter than the melting point of
the metal. Since air cooling lowers the thermal efficiency,
however, the temperature capability must be maximized
and the cooling air must be minimized.
3. Development trends for Ni-base superalloys
Fig. 1 Boeing 787 to enter service in 2008; a new high-efficiency engine
under simultaneous development.
An Ni-base superalloy can be made to exhibit excellent
temperature resistance by the coherent precipitate of 60 to
70 vol% γ’ (L12 ordered phase whose basic composition is
Ni3Al) in the γ matrix (Ni solid solution) where the interphase interface provides a barrier to dislocations, and by
increasing the solution strengthening elements in both
phases by adding Re, W, and Ta. Figure 2 shows a typical
microstructure.
Ni-base superalloys have evolved from forged alloys to
conventionally cast alloys, directionally solidified alloys,
and single-crystal alloys. Single-crystal alloys have also
been evolving from first-generation alloys to second-generation alloys containing about 3 wt% rhenium (Re), third127
Table 1 Compositions (wt%, remaining Ni) of single-crystal (SC) Ni-base superalloys for turbine blades.
(The fourth-generation and fifth-generation SC superalloys contain Ru, a platinum-group element.)
Alloy
Composition
generation alloys containing about 5 to 6 wt% Re, and
fourth-generation alloys containing a platinum-group
metal, such as ruthenium (Ru) or iridium (Ir). Figure 3
shows the background of enhancement in temperature
Temperature for 1000-hour creep at 137 MPa stress
Fig. 2 Typical microstructure of Ni-base superalloy.
Development goal
Single crystal
Generation
capability during this period.1) “Target” in the figure means
the goal of development in the High Temperature Materials
21 Project. Table 1 lists the compositions of typical singlecrystal Ni-base superalloys.
The development of fourth-generation single-crystal
superalloys with platinum-group metals additions is being
undertaken by GE in the US2) and the High Temperature
Materials 21 Project3) in Japan. The addition of platinum
group metals can couse the microstructure stability which
is a disadvantage of third-generation single-crystal alloys,
thus improving the creep strength. This is a common characteristic of fourth-generation alloys.
In the High Temperature Materials 21 Project, the
fourth-generation single-crystal alloy TMS-1384) which can
withstand 1083˚C and the fifth-generation single-crystal
alloy TMS-1625) which can withstand 1100˚C have been
developed. The development methods are to stabilize the
microstructure by adding Ru or Ir and to refine the misfit
dislocation networks at the boundary interface by controlling the γ/γ’ misfit when an element (e.g. Mo) is added.
Figure 4 shows a microstructure observed in a transmission
electron microscope: very fine dislocation networks are
formed on the interface.
Regarding the fourth-generation alloy TMS-138 (with 2
wt% Ru) developed in the High Temperature Materials 21
Project, a demonstration test of the alloy being used as a
Directionally solidified
Common cast
Dislocation networks at γ / γ’ interface
γ phase
Forged
γ ’phase
Year
Fig. 3 Heat resistance improvement of Ni-base superalloy. (○: forged
alloy, □: conventionally cast alloy, △: directionally solidified alloy, ◇:
single-crystal alloy; the solid symbols indicate alloys developed by the
National Institute of Materials Science (NIMS) and its joint research
companies).
128
Fig. 4 Misfit dislocation networks formed at the γ/γ’ interface of Ni-base
superalloy during creep at high temperature.
high-temperature high-pressure turbine blade material was
performed in the supersonic engine project of the Ministry
of Economy, Trade and Industry in collaboration with a
Japanese jet engine manufacturer, Ishikawajima-Harima
Heavy Industries. Figure 5 shows the test. The material will
be used in the first-stage turbine blade of Japan’s civil jet
engine, an environment-friendly small jet engine now being
developed by the Ministry of Economy, Trade and Industry.
Ru costs up to about 5,000 $/kg, lower than other precious metals. If about 2 wt% is added, however, the average cost of raw materials will increase about 50% and the
cost of the completed turbine blades will rise by about
20%. Nevertheless, the metal will certainly be used in nextgeneration aircraft engines to improve the engine efficiency
and specific fuel consumption.
If one turbine blade is assumed to weigh 300 g and a
superalloy containing about 2 wt% Ru is used, about 500 g
of Ru will be necessary for one engine. If Ru is used for
twin engines on 1,000 planes, the necessary amount of Ru
will be about 1 ton in total. If Ni-base superalloy containing Ru is progressively used on other aircraft engines, then
an even larger amount may be needed. However, the annual amount of Ru traded globally is no more than 10 tons, so
it will be important to set up a stable supply system by
establishing a technology for recycling used components
and remaining materials in the manufacturing processes.
As the gas temperature increases and the running conditions become severe, turbine blades and vanes, combustors,
and other Ni-base superalloy components that are exposed
to very high temperatures are usually coated for corrosion
resistance, oxidization resistance, and heat shielding. Traditionally, coating against corrosion and oxidation was done
by diffusion coating using chrome or aluminum, but Pt-Al
coating as well as MCrAlY coating are now widely used.
The High Temperature Materials 21 Project developed
coating materials of a new concept6) having long-term stability and compatibility with Ni-base superalloys.
4. Development trends for refractory superalloys
Unlike Ni-base superalloys, refractory metals and their
alloys are expected to be used for turbine blades without
cooling. Therefore, alloys based on Nb, Mo, W, and Ta
have long been developed. However, high-temperature
strength still cannot be achieved with oxidization resistance
Fig. 6 Phase diagrams and microstructures of Ni-base superalloys and
Ir-base refractory superalloys.
Stress(MPa)
Fig. 5 Single-crystal turbine blade made of a fourth-generation singlecrystal superalloy TMS-138 and its ground test on a supersonic engine.
or toughness, so these alloys are limited to applications in a
protective environment such as vacuum or inert gas.
In the High Temperature Materials 21 Project, refractory
superalloys of the same γ/γ’ stracture as Ni-base superalloys are being developed based on platinum-group metals
having excellent oxidation resistance.7) Regarding Ni-base
superalloys and Ir-base refractory superalloys, Figure 6
shows the phase diagrams and typical microstructures of
their prototype binary alloys (Ni-Al and Ir-Nb). From the
figure, we see that an alloy based on Ir with a melting point
of 2447˚C has crystallographically the same microstructures suitable for enhancing the creep strength as Ni-base
superalloys. However, the melting points are about 1000˚C
higher than those of Ni-base superalloys.
The resultant Ir-base refracrtory superalloys showed
excellent strength: the 2% deformation time was about 100
hours in a compressive creep test at 1800˚C and 137 MPa.8)
Figure 7 compares the creep strength with those of other
refractory alloys by using the Larson-Miller parameter.
From this figure, we see that the Ir-base refractory superalloys withstand the highest temperature among refractory
alloys, far beyond those of Ni-base superalloys.
The research by the Materials Engineering Laboratory
has triggered the development of refractory superalloys
Larson-Miller's parameter
Fig. 7 Comparison of creep strength between Ir-base refractory
superalloys and other refractory alloys.
(The Ir-base superalloys withstand 675˚C higher than the Ni-base
single-crystal superalloys and have higher creep strength than Nb, Ta,
and W alloys.)
129
based on platinum-group metals in South Africa, Germany,
the USA, the UK, and other countries.9) Regarding Pt-Al
type superalloys, for example, the γ’ phase (L12 phase) is
known to be unstable and transform to a different structure
at comparatively low temperature. Therefore, the addition
of third and fourth elements is now being attempted to stabilize the γ’ phase.
Platinum-group metals generally have much higher oxidization resistance than Nb, Mo, W, and Ta, and so refractory superalloys based on them are promising ultra-high
temperature use. However, many issues remain to be
solved, such as high cost, large specific gravity (Ir alloys:
about 20), and insufficient ductility (Ir-base).
For Ir-base refractory superalloys, new approaches to
material design are being attempted. For example, Ni-base
superalloys are mixed to optimize the cost performance,10)
while Pt-base refractory superalloys are mixed to increase
the ductility.11)
If γ solid solutions produced by mixing Ni, Co, Ir, Rh,
Pt, and other FCC-type metallic elements are used as base
metals for refractory superalloys, then Ni-base superalloys
to platinum-group refractory superalloys, including their
intermediate products, can be selected for materials according to cost performance, ductility, and oxidization resistance. Therefore, research is expected to proceed in this
direction.
In the High Temperature Materials 21 Project, research
is being conducted in a wide range of other areas, spanning
from basic research on refractory materials to practical
research through corporate linkage. 12) Such research
includes the development of next-generation turbine disk
materials, highly ductile chrome alloys, and other new
alloys; the development of material design techniques as
the basis for various new materials; microstructure analysis
by three-dimensional atom probe and in-situ observation of
creep deformation under an electron microscope; and the
development of virtual gas turbine/Jet engine systems by
linking materials design and system design.
The overseas bases developing superalloys for jet
engines and gas turbines are GE – Michigan University
(USA), Rolls Royce – Cambridge University (UK), SNECMA (France)-ONERA (France).
130
5. Conclusion
To save fossil fuels, mitigate CO2 emission, and prevent
global warming, jet engines and various thermal engines
are expected to have higher performance and so the
demand for enhanced high temperature materials is growing.
To meet this demand, fourth and fifth generation Nibase single-crystal superalloys with platinum-group metals
additions are starting to be used for jet engines. In addition,
refaractory superalloys based on platinum-group metals
have been proposed in NIMS as new materials that may
surpass Ni-base superalloys in future. The new superalloys
are now subject to global research and development, and
coating materials are also being developed.
In the field of refractory alloys, the importance of platinum-group metals is growing. In future, we expect that
new superalloys based on platinum-group metals will be
increasingly used through linkage and cooperation in materials research and recycling and other process research to
contribute to global environmental conservation and to the
international competitiveness of Japanese industry with jet
engines and gas turbines of high efficiency.
References
1) H. Harada and T. Yokokawa: MATERIA, 42, No. 9, 621-625
(2003).
2) K.S. O’hara, W.S. Walston, E.W. Ross and R. Darolia: U.S. Patent
5,482,789A (1996).
3) Y. Koizumi, T. Kobayashi, T. Yokokawa, H. Harada, Y. Aoki, M.
Arai, S. Masaki and K. Chikugo, High Temperature Materials 2001,
May 31-June 2, 30-31 (2001).
4) J.X. Zhang, T. Murakumo, Y. Koizumi, T. Kobayashi, H. Harada
and S. Masaki, JR: Met. and Mat. Trans. A, 33A, 3741-3749
(2002).
5) Y. Koizumi, K. Chou, T. Kobayashi, T. Yokokawa, H. Harada, Y.
Aoki and M. Arai: MRS Bulletin, 67, No. 9, 468-471 (2003).
6) H. Harada, A. Sato and K. Kawagishi: Patent pending, a paper
accepted for publication in Met. and Mat. Trans. A.
7) Y. Mitarai, Y. Ro, S. Nakazawa and H. Harada: MRS Bulletin, 64,
No. 11, 1068-1075 (2000).
8) Y. Yamabe-Mitarai, Y. Gu and H. Harada, Met. and Mat. Trans. A,
34A, No. 10, 2207-2215 (2003).
9) L.A. Cornish, B. Fischer and R. Volkl, MRS Bulletin, 28, No. 9,
632-638 (2003).
10) X.H. Yu, Y. Yamabe-Mitarai, Y. Ro and H. Harada, Met. and Mat.
Trans. A, 31A, 173-178 (2000).
11) C. Huang, Y. Yamabe-Mitarai, K. Nishida and H. Harada,
Intermetallics, 11, 917-926(2003).
12) http://sakimori.nims.go.jp/
Chapter 8.
Metals
Section 1. Steel - Steel Technology for Strong, Safe
Structures
Toshiyasu Nishimura,
Corrosion Resistant Design Group, Steel Research Center, NIMS
1. Global research trends
The demand for steel materials is growing to combat
global issues such as environmental problems, shortages of
resources and energy, and aging of social infrastructure.
Especially in East Asia, the explosive economic development is stimulating the demand for steel materials that can
withstand earthquakes attributable to geographical factors
and also atmospheric corrosion and so forth. Therefore,
steel research in East Asia has been carried out under
national projects. In China, the 10-year NG Steel Project
(Fundamental Research on New Generation of Steel Materials in China) was started in 1999. In the first five years,
40 organs including many universities conducted steel
research, with the main themes being ultrafine-grain steel,
delayed fracture, and nanodeposition in casting and rolling.
In Korea, the 10-year HIPERS21 Project (High Performance Structural Steels for the 21st Century) was started in
1998. In the first five years, basic research was conducted
on ultrafine-grain steel, coastal weather resistant steel,
ultrahigh-strength bolts, welding technology, and structural
design. In China and Korea, the projects have entered the
second term. Researchers are now shifting the acquired
basic science technologies toward applications, and are
making progress in using structural materials designed for
high strength and safety.
Thus, steel research is particularly active in East Asia
and many international conferences are held in this area.
Related to the steel-related projects noted above, the
International Conference on Advanced Structural Steels
(ICASS) provides a forum for academic discussion on steel
research in Japan, China, and Korea and is growing as an
international conference to discuss the future of steel
research. ICASS was held in Tsukuba in 2002 and in
Shanghai in 2004 and is scheduled to be held in Geongju,
Korea in 2006. Many researchers from industry, academia,
and the government are planning to participate.
2. Key trends in Japan
The Council for Science and Technology Policy
announced “Promotion of Industrial Exploitation in the
Field of Nanotechnologies and Nanomaterials” in July
2003. To develop a bridge structure that is “earthquake
resistant, corrosion resistant, light weight, and low cost” in
the innovative materials industry according to the above
policy, ministries and agencies concerned initiated a linked
project “New bridge structure” in 2004 for the purpose of
constructing safe social infrastructure and strengthening the
international competitiveness of the materials industry. At
the Committee for Surveying the Utilization of Steel in
Civil Engineering and Architecture of the Japanese Society
of Steel Construction, many researchers gathered from civil
engineering laboratories, architecture laboratories, NIMS,
universities, JR, JH, and private enterprises with specific
design proposals for new structures using steels and their
bonding technologies (welding, bolts, etc.). Based on the
results of surveys conducted by the Japanese Society of
Steel Construction, the Committee will promote the evaluation of characteristics of steel structures from FY2005,
focusing on automotive road bridges using steel, highstrength bolts, and the corrosion evaluation of weatherresistant steel bridges. Materials and structure researchers
should be encouraged to collaborate on future developments, based on the great vitality of university researchers
specialized in civil engineering and architecture.
3. Research by NIMS
NIMS has long led the world in steel research and is also
highly respected for its leading position in the Asian project noted above. The Steel Project is now in its second
term. Based on the principles of increasing the strength and
weather resistance by microcrystallization acquired in the
first term, steel having high strength and corrosion resistance (steel factor of 4) available for use in cities was fabricated. Its chemical stability against corrosion was evaluated
by thermodynamic calculation, and Al and Si satisfying the
two requirements of resource conservation and easy recycling were selected as weather-resistant elements to replace
Ni and Cu. Since steel having high Al and Si contents is
not tough enough when the grains are of ordinary size, the
toughness was dramatically improved by microcrystallization. Microcrystallization has an advantage of increasing
131
the strength without needing to add special elements. As Al
and Si are ferrite generating elements, a ferrite phase was
generated at welded sections, which prevented curing and
enhanced the weldability. Thus, NIMS successfully developed a material of excellent strength, toughness, and corrosion resistance, supporting LCA and LCC. For steel structures of high strength and safety, the novel material offers
overall excellence and is highly rated.
The principle of fabrication was established successfully
to enable the production of large or component-shaped
steel materials. NIMS also successfully solved the issue of
creating steel-welded structures by ultra-narrow bevel
GMA welding and large-output pulse-modulated CO 2
welding developed in the first term, and the issue of producing bolts of 2000-MPa class strength. Many of these
achievements have been reported in academic journals and
at conventions both within and outside Japan, and have
attracted worldwide respect. Regarding joint work with
civil engineering and architecture researchers on innovative
structural design using steel materials, progress is reported
systematically at the steel workshop held every year.
4. Future outlook and actions
In the field of structural steel materials, various global
issues remain and can often be solved most efficiently
through international cooperation. Therefore, it will be
increasingly important to solve specific problems through
linkage and cooperation by concluding MOUs with the
world’s key research institutes. In China, for example, the
Steel Research Center (SRC) concluded an MOU with The
Central Iron & Steel Research Institute (CISRI) in 2002
and with The Institute of Material Research (IMR) in 2004.
In India, SRC has already concluded an MOU with Anna
University. In partnership with the institutes, SRC intends
to conduct joint research in the field of corrosion. In 2003,
SRC concluded an MOU with MPA (Staatliche Materialprufungsanstalt) of Germany in the field of materials evaluation, jointly with the Materials Information Technology
Station. In 2004, SRC concluded an MOU with MPIE
(Max Planck Institut fur Eisenforschung) of Germany to
extend the range of cooperation in the field of steel. In
2003, SRC concluded an MOU with VUZ (Výskumný
132
ústav zváraèský) of Slovakia in the field of welding. By
concluding MOUs with research institutes all over the
world, SRC is constructing a global network to solve common problems related to steel.
Meanwhile, it is important to increase international competitiveness in the field of steel. SRC is proceeding with
studies to enhance materials characteristics and is committed to grasping characteristics as a practical basis. Next, it
is important to exploit technologies for practical utilization.
Specifically, we need an environment that enables us to use
developed materials in the quickly growing Asian market.
Since East Asia is subject to frequent earthquakes and has a
hot, humid climate that aggravates corrosion, all
researchers in East Asia need to make steel materials resistant to earthquakes and corrosion. As the leader in the field
of atmospheric corrosion, Japan should guide other countries toward solving the specific problems of high temperature and humidity, coastal environments, and acid rain for
the whole of Asia, and should set up an Asian code on
maximizing the use of high-function materials. Currently,
SRC is discussing and creating a specific plan with those
institutes with which it has signed MOUs and other Asian
research institutes.
Japan has been able to retain its world-leading position
in the field of steel through elemental research. Japan used
to have high levels of research on fracture, welding, and
corrosion, but as no attractive steel materials were proposed for a long time, the intellectual curiosity of the
younger generation could not be stimulated, causing universities to lose interest in steel. To solve this great problem, SRC is considering sharing the knowledge obtained so
far by steel research and pending issues with universities to
maintain the basic power of science in steel. For example,
we would like to request university researchers to share
steels and structures and discuss them from their professional points of view to stimulate steel research. SRC has
already started working toward this goal and will step up
such activities in future.
References
1) The 9th Steel Workshop Proceedings, 9 (2005) p.1.
2) “Survey and Research about New Structural Design for Utilizing
Steel,” FY2004 report by The Iron and Steel Institute of Japan.
08 Metals
Section 1. Steel - Steel Technology for High-Efficiency
Energy
Fujio Abe
Heat Resistant Design Group, Steel Research Center, NIMS
1. Introduction
Heat-resistant steel that can be used for a long time at
high temperature is the key to developing thermal and
nuclear power generation, chemical plants, power generation from wastes, automobiles, and industries. During the
last decade, great progress was made in developing heatresistant steels of high strength and corrosion resistance at
even higher temperature, and in evaluating materials in
terms of the welding joint characteristics necessary for constructing plants, creep strength, and service life, for example, under social pressure to reduce CO2 emissions, dioxins
and other environmentally hazardous gases.
In five years from 1999 to 2004, major international
conferences on heat-resistant steels were held twice in each
of Japan, Europe, and the US, making six times in total.
Figure 1 shows the number of reports presented at the conferences by countries and the contents presented at the
international conference held in the United States in 2004.
Japan, Europe, and the US are about equal in the number of
reports, which have focused on materials development, oxidization, and corrosion.
2. Research trends on heat-resistant steels of high
strength and corrosion resistance
In the field of thermal power generation, the upper limit
of temperature was about 620˚C for the conventional ferritic heat-resistant steels. However, Japan, the US, and
Europe made progress in the research and development of
high-strength 9-12Cr ferrite heat-resistant steels for largediameter and thick boiler steel pipes and turbines that can
be used for a long time in a 650˚C ultra super critical
(USC) power plant. By adding W or other elements,
austenitic heat-resistant steels for boiler superheater tubes
has been enhanced from 18Cr-8Ni to 20Cr-25Ni and then
to high Cr - high Ni to withstand steam temperatures of up
to 700˚C. In the field of nuclear power, oxide dispersion
strengthened 9Cr ferrite steel, which is excellent both in
high-temperature creep strength and irradiation resistance,
was developed for cladding tubes for 650˚C fast breeder
reactors. Regarding hydrogen refining equipment in chemical plants, the temperature and pressure were 454˚C and 17
MPa in the early 1990s when reaction chambers were made
of 2.25Cr-1Mo steel, but the subsequent development of
high-strength 3Cr-1Mo-V steel and 2.25Cr-1Mo-V steel
raised the temperature and pressure to 482˚C and 24 MPa
by 1995. These figures are now about to reach 510˚C and
24 MPa. Regarding power generation from wastes, the
development of austenitic heat-resistant steels having high
corrosion resistance enabled the boiler steam temperature
to be raised from about 300˚C at conventional plants up to
about 500˚C. In the automotive field, exhaust manifolds
used to be made of cast iron to withstand exhaust heat.
However, as the exhaust gas temperature rose with
improved engine performance, higher strength was
required and so 18Cr-2Mo-Nb and other steels were developed, raising the exhaust gas temperature to 900˚C or higher.
Recent research on enhancing the creep strength of
650˚C class ferritic heat-resistant steels has revealed that:
- microstructure observation and creep deformation behavior analysis clarified that the formation of even a partially
weak microstructure near a grain boundary promotes local
creep deformation and causes premature fracture, and
- some guidelines on materials design showed that fine
microstructure could be maintained near a grain boundary
for a long time.
Based on these guidelines, NIMS proposed: a steel for
the long-term stabilization of M23C6 carbides near grain
boundaries by adding a high concentration of boron; a steel
for stabilizing microstructure near grain boundaries with
nano-size MX-type nitrides only; and a steel having only
Fe 2(Mo,W)-Laves phase and other intermetallic compounds without using carbonitrides. The world is monitoring the results of long-term creep tests which are still continuing and the microstructure stability.
Regarding corrosion resistance, the resistance in hightemperature steam has been increased greatly. This resistance depends on the Cr concentration. Since the Cr concentration of ferritic heat-resistant steels is generally as low
as 12% or less, an oxide scale rich in Fe is generally produced on the surface. Therefore, the main issue used to be
how to suppress the growth of this thick oxide scale of Fe
by adding alloy elements or by other means. On the contrary, NIMS recently found that, even when the Cr concentration is about 9%, by adding about 0.5% Si and perform133
ing pre-oxidation treatment, a nanometer-thick Cr2O3 protective scale can be formed to improve the oxidation resistance remarkably. This finding caused great interest in
Cr2O3 protective scale also in Europe and the US. Regarding the exfoliation characteristic of surface scale, a test
method needs to be established. Surface coatings are also
being researched but there are problems of complicated
process and cost.
3. Trends of research on the strength of welded joints
If a welded structure made of ferritic heat-resistant steels
is used under high temperature and low stress (about 600˚C
and 100 MPa or less), brittle creep fracture or so-called
Type IV fracture progresses at the weld heat-affected zone
(HAZ). This causes the serious problem of short creep life
compared with the base material. In Japan, Europe, and the
US, therefore, 9-12Cr ferritic heat-resistant steels are being
studied to clarify the mechanism of Type IV fracture, to
analyze the fracture dynamics of brittle creep fracture, and
to prevent Type IV fracture.
Regarding the mechanism of Type IV fracture, the HAZ
grain refinement model and HAZ softening model were
proposed, of which the former is becoming dominant. In
other words, heating up to about Ac3 changes the HAZ
region to fine grains and reduces the life. Regarding fracture dynamics analysis, a high-temperature creep crack
propagation test using CT specimens of welded joints was
conducted and the analysis results clarified that highstrength 9-12Cr steels are subject to cracking in HAZ
regions. By analyzing stresses in welded joints by the finite
element method (FEM), with the creep strength parameters
of the welded metal region, HAZ region, and base material,
cracking positions could be accurately predicted. FEM
codes were also developed to simulate the generation of the
creep void ahead of the crack tip and the progress of the
crack. Regarding the prevention of Type IV fracture, the
aforementioned high-boron 9Cr steel of NIMS was reported to be free of grain refinement in the HAZ region and
therefore resistant to Type IV fracture. This is attracting
attention in Europe and the US.
in a lath-block microstructure having high dislocation density. Japan and Europe are now competing fiercely to clarify the phenomenon in which re-dissolution of nano-size
M2X and MX during creep promotes the formation of Z
phase (Cr(V,Nb)N type composite nitride), which is thermodynamically more stable and rough, and the creep
strength drops quickly.
For predicting long-term life, the Larson-Miller method
and other time-temperature parameter (TTP) methods used
to be used widely. However, it gradually became clear that
the conventional TTP methods could not evaluate longterm creep life correctly but tended to overestimate it. To
solve this problem, new analysis techniques were proposed:
- Classifying creep rupture data by temperature dependence
or areas having the same activation energy.
- Splitting the area of creep rupture data with half the 0.2%
yield strength of the tensile test as the criterion and analyzing only data in the low-stress area because time-independent plastic deformation at loading under high stress affects
greatly the subsequent creep deformation behavior.
These techniques have improved the accuracy of long-term
life prediction to about 100,000 hours.
5. Future outlook
As plant temperatures are raised to improve energy efficiency, it is becoming important to establish the foundation
of heat-resistant steels that can be used safely for a long
time without showing deterioration of creep strength.
Researchers are now interested in clarifying the transition
process of nano-precipitates during high-temperature use,
the long-term strength at high temperature, the generation
and exfoliation of a nanometer-thick surface protective
scale, and the brittle fracture behavior of a welded joint in
terms of fracture dynamics.
Other countries:
28 reports, 8.3%
Life Assessment:
7 reports, 12.1%
USA:
75 reports, 22.2%
Weld & Fracture:
7 reports, 12.1%
Components:
9 reports, 15.5%
4. Trends of research on predicting long-term creep life
In Japan and Europe, high-strength 9-12Cr steels were
found to suffer quick loss of creep strength at 550˚C or
higher temperature often after prolonged use. This quick
loss of creep strength is now actively being analyzed even
with the latest energy filter type of transmission electron
microscope to clarify the microstructure degradation factors. High-strength 9-12Cr steels are usually produced by
normalizing-tempering heat treatment. This heat treatment
reforms steel to a microstructure of high precipitation
strength where fine (about 100 nm) M23C6 carbides and
nano-size M2X and MX-type carbonitrides are precipitated
134
Japan:
115 reports, 34%
Oxidation &
Corrosion:
17 reports, 29.3%
Europe:
120 reports, 35.5%
Materials &
Alloy Development:
18 reports, 31.0%
Intern. Conf., 1999-2004
(338 reports in total)
4th EPRI Conf. (2004)
(58 reports in total)
Fig. 1 Number of reports made at six international conferences on heatresistant steels in Japan, Europe, and the USA in the 5-year period from
1999 to 2004 and the contents of reports made at the conference in the
USA.
08 Metals
Section 1. Steel - Steel Technology for Hydrogen Utilization
Eiji Akiyama
Corrosion Resistant Design Group, Steel Research Center, NIMS
1. Introduction - Global trends
There are high expectations worldwide for hydrogen
fuel as a clean energy solution to global warming and pollution (NOx, particulate matter (PM), etc.). However, the
safety of the entire hydrogen system that produces, stores,
transports, and utilizes hydrogen, a material that is explosive and not widely used, requires detailed study. More
specifically, it is important to ensure the safety of materials
used for storage tanks, hydrogen tanks on hydrogen fuel
cell cars, pipes, valves, joints, compressors, and so forth.
Structural measures to prevent hydrogen leakage and sensing technologies are also necessary.
Regarding the global trends in hydrogen fuel cells, the
use of fuel cells on the Apollo and space shuttle while in
space drove technological development in the United
States. In 1993, President Clinton proposed that fuel cells
be used for vehicles, triggering intensive research on such
applications. Even after the Bush Administration took over,
the policy on fuel cell development was strengthened. In
Freedom CAR 9 led by the Department of Energy (industry-government partnership between Ford, GM, Daimler
Chrysler and the government until 2010),1) technological
development is being promoted with an emphasis on technologies related to hydrogen fuel cell cars. In the State of
the Union address at the end of January 2003, President
Bush declared that the United States would lead the world
in the development of clean hydrogen fuel cars and proposed a total budget of 1,700 million dollars for 5 years
from 2004 to develop a hydrogen cell from the hydrogen
initiative and Freedom CAR, the foundation of the hydrogen industry, and advanced automotive technologies.2)
In the EU, fuel cells and related technologies are being
developed in the Framework Program,3) which is a comprehensive R&D project led by the Directorate-General for
Research and (Research DG) and Directorate-General for
Science, Research and Development (DG12) at the European Commission,4) fuel cell development began in the 3rd
Framework Program (FP3) starting in 1992. From FP5
(1998-2002), more than half the budget for fuel cells and
hydrogen energy has been allocated to technological development for transportation. In FP6 for the five years from
2002, technologies are being studied to reduce the costs of
stationary and automotive fuel cells, to develop advance
materials for fuel cells, and to construct infrastructure for
producing and supplying hydrogen. In relation to this, the
Clean Urban Transport System for Europe (CUTE)5) and
the Ecological City Transport System (ECTOS)6) are now
demonstrating hydrogen fuel cell buses.
Since hydrogen fuel cells are targeted at automobiles
that appear on the international market, Western countries
are keen to have their own standards adopted internationally.2)
2. Domestic trends
At EXPO 2005 AICHI in Nagoya, hydrogen fuel cell
hybrid buses traveled among the pavilions and a hydrogen
station was exhibited. This indicates people’s keen interest
in hydrogen infrastructure, such as hydrogen fuel cars and
their hydrogen stations, in Japan as well as in Europe and
America.
Japan’s international clean energy system project for
hydrogen utilization “WE-NET” 7) was started in 1993
under the New Sunshine Project, and the New Energy and
Industrial Technology Development Organization (NEDO)
has promoted research.7-9) In the first term (FY1993-1998),
the low temperature materials R&D group selected austenite stainless steels which are widely used for cryogenic vessels and Al alloys used for LNG tankers as candidate materials and tested them as base materials and welded joints in
liquid hydrogen and low-temperature hydrogen gas. In the
second term (FY1999-2002), the development of hydrogen
supply stations, automotive hydrogen storage materials,
and solid molecular fuel cells with pure hydrogen supply,
and hydrogen diesel engines was planned in order to spread
the hydrogen system in society. The low temperature materials R&D group promoted research with a view to developing elemental technologies for optimum bonding materials and methods.
The R&D contents and achievements are summarized
below.8,9)
• Selection of candidate materials and welding methods:
As candidate materials, the aforementioned austenite
stainless steels and Al alloys were selected. For stainless
steel welding, CO2 laser welding, reduced pressure electron beam welding (RPEB), and friction stir welding
(FSW) were used, as well as tungsten inert gas welding,
metal inert gas welding, and submerged arc welding.
135
• Introduction of test equipment into liquid nitrogen
atmosphere: Test equipment was fabricated for tensile
strength, fracture toughness, and fatigue tests in a cryogenic atmosphere.
• Large-scale liquid transportation and evaluation of characteristics of stored materials: Thick plates of the candidate materials were welded, and the welded metal joints
were evaluated for their cryogenic characteristics and
again after hydrogen charging of about 10 ppm. The
Japan Atomic Energy Research Institute developed a
complete γ-type welding material (12Cr-14Ni-10Mn5Mo-N steel) featuring high toughness and excellent solderability. When this material was welded by the conventional method, the welded joints showed sufficient
cryogenic toughness and did not crack at high temperature, showing that the welding method is effective for
large tankers and tanks. For welding very tough and
thick plates, RPEB and FSW are promising. SUS304L,
SUS316L, and SUS316LN showed sufficient fatigue life
both as base materials and welded joints. For welding Al
alloys, FSW and RPEB are effective.
• Research on hydrogen embrittlement: The results of tensile tests on austenite stainless steels in a hydrogen
atmosphere and a helium gas atmosphere indicated that
brittleness sensitivity to a hydrogen environment
increases as the temperature falls below room temperature. After reaching a maximum value at about 200 K,
the sensitivity dropped quickly and the influence of
hydrogen was lost at about 150 K or lower. Therefore,
criteria for selecting austenite stainless steels could be
set from the fact that the phenomenon is related to the
generation of strain induced martensite and the sensitivity decreases as the austenite phase becomes more stable.
In addition, fundamental research was conducted on the
conditions of hydrogen permeation into materials and
the local fracture toughness in a hydrogen gas environment, and also on the influences of coolant on mechanical properties at 20 K. From the test results, a database
was constructed.
These R&D results were used in the next 5-year project
of NEDO, “Development of Safe Utilization and Infrastructure of Hydrogen” from FY2003 to 2008. In this project, safety and technologies for implementing hydrogen
energy are being developed to ensure the smooth introduction and implementation of polymer electrolyte fuel cells
(PEFC). WE-NET was mainly for materials research at low
temperature and in a liquid hydrogen atmosphere. The
materials research in this project, however, is intended to
construct a safe infrastructure in a liquid hydrogen environment. The research includes further development of hydrogen stations that supply hydrogen to fuel cell cars by using
PEFC and development of technologies for high-pressure
hydrogen tanks to be mounted on cars.9,10)
For fuel cell cars and stationary fuel cells to become
reality, basic safety data needs to be accumulated for reinspection and standardization, with demonstration tests.
Therefore, this is a common basic technology for the
hydrogen infrastructure, vehicle-related equipment, and
stationary systems. The theme “Basic property research on
hydrogen materials” is classified into materials properties
136
in “Safety technology” above. As common and basic safety
measures for hydrogen, the basic properties of hydrogen
materials are being researched. The main candidate materials are stainless steel SUS316L and Al alloy A6061T6. In
FY2003 and FY2004, strength, fatigue, and other basic
property data were collected for materials to be used for
35-MPa class high-pressure hydrogen equipment. The specific items are as follows:8-11)
• Lining materials for high-pressure hydrogen tanks (Al
alloy, stainless steel, etc.)
• Enhancing the durability of high-pressure hydrogen
pumps (stainless steel, etc.)
• Materials for high-pressure hydrogen accumulators (CrMo steel, etc.)
• Materials for high-pressure valves and joints (stainless
steel, etc.)
• Structural materials for liquid hydrogen (stainless steel,
etc.)
• Basic properties of nonmetallic materials for hydrogen
(FRP, etc.)
• Survey of properties of materials for hydrogen and database creation
• Development of hydrogen characteristic test equipment
and basic property evaluation (low strain speed test,
fatigue test, and evaluation of fatigue crack propagation
characteristics) of hydrogen materials with the equipment
• Research on materials properties in a cryogenic gas
environment
• Evaluation of hydrogen-absorbing characteristics
• Evaluation of metallic materials for hydrogen stand
• Fatigue and tribology evaluation of hydrogen materials
in a hydrogen environment
The research themes in FY2005 to FY2007 are to extend
the collected basic property data of materials used for automotive tanks, stationary tanks, pipes, valves, and other elemental equipment and to develop practical materials and
technologies suitable for use in various high-pressure
hydrogen environments. To achieve these themes, industry,
academia, and the government set up a linked research system.
Since the mounting of hydrogen tanks on vehicles was
deregulated in April 2001, the method of storing hydrogen
for fuel cell cars changed from hydrogen absorbing alloy to
compressed hydrogen, and practical fuel cell cars are now
quickly becoming reality. The High Pressure Gas Safety
Law is now limiting hydrogen tanks to a maximum pressure of 350 bars (about 35 MPa). For a hydrogen fuel cell
car to achieve the target cruising distance of 500 km, about
equal to a gasoline vehicle, the filling pressure will need to
be even higher. Therefore, research is now being conducted
on a compressed hydrogen method using a vehicle-mounted ultrahigh-pressure tank for up to 700 bars and the liquid
hydrogen method. Related technologies being studied for
such pressure include: hydrogen compressors, dispensers,
flowmeters, couplings, and filling control technologies,
while technologies for liquid hydrogen include: liquid
hydrogen containers, boosters, and pumps.12,13) For these
diverse elemental equipment, new practical steel materials
are needed.
In the first term of WE-NET (FY1993-1998), the
National Research Institute for Metals (present National
Institute for Materials Science: NIMS) evaluated cryogenic
materials jointly with Chugoku National Industrial
Research Institute8,9) on the “Development of cryogenic
materials technologies” related to “Hydrogen transportation
and storage technologies,” entrusted by The Japan
Research and Development Center for Metals (JRCM). The
National Research Institute for Metals conducted research
on low temperature brittleness and the Chugoku National
Industrial Research Institute conducted research on hydrogen embrittlement.
In the second term (FY1999-2002): (1) To clarify the
mechanisms of hydrogen embrittlement and cryogenic
embrittlement, JRCM, the National Institute of Advanced
Industrial Science and Technology, NIMS, and the Materials Testing Institute University of Stuttgart (MPA) conducted joint research. (2) Regarding welding technologies,
The Welding Institute (TWI) of UK conducted joint
research with JRCM.
For “Basic property research of hydrogen materials”
(from FY2003) in “Development of Safe Utilization and
Infrastructure of Hydrogen,” the Hydrogen Materials
Development Committee was set up in JRCM and a
research entity was organized consisting of experts from
the National Institute of Advanced Industrial Science and
Technology, NIMS, Kyushu University, Aichi Steel Corporation, Nippon Steel Corp., and Sumitomo Metal Industries, Ltd.9,10) NIMS is sharing the theme of “Research on
materials characteristics in a cryogenic gas environment.”
The fatigue test, Charpy impact test, and tensile test here in
a cryogenic environment are also used to create data sheets
on the strength of aeronautical materials.
In addition, NIMS is examining the influence of hydrogen gas on the fatigue strength of various materials jointly
with Professor Murakami of Kyushu University to confirm
the importance of hydrogen trapped in inclusions for superlong life fatigue fracture, and to ensure the long-term safety
of a fuel cell system. (“Influences of hydrogen on gigacycle
fatigue fracture mechanism and establishment of fatigue
strength reliability enhancement method” (FY2002 to
FY2006, funded by a science research subsidy and represented by Prof. Yukitaka Murakami, Kyushu University).
Hydrogen can cause delayed fracture of high-strength
steel, so research is underway to clarify the mechanism of
such fracture, to develop a method of evaluating the
delayed fracture characteristics, to study the influences of
microstructure on delayed fracture, to fabricate highstrength materials having excellent resistance to delayed
fracture characteristics, to clarify the hydrogen trap site in
steel, and to study a design guideline for hydrogen traps.
Research is currently focusing on high-strength bonding
materials for architecture and not directly targeted at materials related to hydrogen energy. However, the knowledge
obtained can be applied to materials related to hydrogen
energy. Other activities include joint research with KAIST
(Korea) on the hydrogen induced deterioration of low-alloy
materials for pressure vessels14) and research on the hydro-
gen embrittlement of iron-base alloys.15)
4. Key research by organizations other than NIMS and
future outlook
For “Targeted Support for Creating World-level
Research and Education Bases” (21st Century COE) in
FY2003, the Ministry of Education, Culture, Sports, Science and Technology selected “Integration Technology of
Mechanical System for Hydrogen Utilization” of Kyushu
University. Accompanying this, the Research Center for
Hydrogen Utilization Technology was inaugurated.16) This
is the world’s sole institute for general technological
research on hydrogen utilization, covering a wide range of
research from the atomic level to large structures. Regarding the strength of metallic materials, for example, the loss
of strength caused by hydrogen entry into metal and metal
fatigue are being researched. There are also various other
research themes, such as bearing damage by wear, friction,
seal deterioration, and hydrogen entry and hydrogen leakage. To take the advantage of the fact that there are many
automobile manufacturers for producing fuel cell cars and
companies holding byproduct hydrogen, the Fukuoka Strategy Conference for Hydrogen Energy was set up by industry, academia, and the government in Fukuoka Prefecture
in August 2004. As of February 28, 2005, the conference is
participated in by 91 corporate members, 78 university
staff, 12 research and support institutes, and 8 administrative organizations. The main activities of this conference
are to create industry-academia-government projects headed by the Research Center for Hydrogen Utilization Technology, to perform various demonstrations with the new
campus (Hydrogen Campus) of Kyushu University and
Kitakyushu Eco-town District serving as experimental
mini-societies, and to train human resources.
The COE program “Establishment of COE on Sustainable Energy System” of Kyoto University has four pillars,
one of which is “Construction of hydrogen energy technology”.17) In future, research at such large bases will be the
driving force behind materials research to realize a hydrogen energy society.
At present, hydrogen fuel cell cars are being demonstrated by test runs and hydrogen stations are being constructed
both within and outside Japan, suggesting that they may
soon enter practical use. It is therefore becoming increasingly important to develop and select reliable items and
evaluate them accurately. To extend the cruising distance
to the same level as that of a gasoline vehicle, the hydrogen
stored in fuel cell cars will be compressed further12,13) and
yet the weight of storage tanks and car bodies needs to be
reduced. Therefore, a high-strength steel which is safe to
use in hydrogen gas environments and which has excellent
pressure resistance will need to be developed.
References
1) http://www.eere.energy.gov/vehiclesandfuels/
2) Fuel Cell Project Team Report - Japan’s first Project X
137
3)
4)
5)
6)
7)
8)
9)
10)
138
“Developing an engine for earth reproduction” - Fuel Cell Project
Team of Vice Ministers’ Conference (2002).
http://fp6.cordis.lu/fp6/home.cfm
NEDO Overseas Report No. 906-908, 910 (2003).
http://europa.eu.int/comm/energy_transport/en/cut_en.html
http://www.newenergy.is/
http://www.enaa.or.jp/WE-NET/
NEDO Achievement Report Database http://www.tech.nedo.go.jp/
JRCM News, No. 204, 205 (2003).
Polymer Electrolyte Fuel Cell/Hydrogen Energy Utilization
Program “Basic Plan for Development of Safe Utilization and
Infrastructure of Hydrogen” NEDO Hydrogen Energy Technology
Development Section. http://www.nedo.go.jp/hab/project.html
11) “Development of Safe Utilization and Infrastructure of Hydrogen”
(Interim evaluation) Reference material for the first subcommittee
meeting 5-2, 6-4.
12) Y. Tamao and T. Ogata, Science & Technology Trends, February
issue (2003).
13) Y. Tamao and R. Omori, Materia., 44, 188 (2005).
14) X. Wu, Y. Katada, S. G. Lee and I. S. Kim, Metall. Mater. Trans.
A, 35A, 1477 (2004).
15) Y. Tateyama and T. Ohno, Phys. Rev., B67, 174105 (2003).
16) http://www.f-suiso.jp/, http://www.kyushu-u.ac.jp/magazine/
kyudai-koho/No. 36/36_18.html
17) http://energy.coe21.kyoto-u.ac.jp/
08 Metals
Section 1. Steel - Reliability of Steel Materials
Koichi Yagi
Materials Technology Information Station, NIMS
1. Introduction
Before structural materials can be used for machines or
plants, the total reliability and safety characteristics of the
materials must be clarified. This makes it necessary to
accumulate an enormous amount of laboratory data, to
accumulate understanding and knowledge about characteristics, and verify the materials by preliminary use. Therefore, it takes a long time from research and development of
materials until the materials are actually used in machines,
plants, and other products. Since damage still occurs, however, it is necessary to evaluate the strengths of materials
and modify designs to ensure the appropriate use of materials.
Structural materials have various characteristics but the
characteristics must maintain the product performance of
machines and plants and ensure safe use for a long time.
The important characteristics are high-temperature creep,
fatigue, and corrosion that depend on time. The timedependent characteristics are especially important because
it takes a long time to acquire such data and the characteristics are difficult to understand. Based on the results of a
recent survey and the reference materials for research and
survey, this report explains the importance of research on
long-term data accumulation and life evaluation for
enhancing the reliability of heat-resistant steels; the
requirements for acquiring long-life fatigue data because
long-life fatigue is related to the development of highstrength materials and clarifying the fracture mechanism; a
new metallic structure analysis technique for understanding
fatigue characteristics, and a risk-based thinking for making effective use of optimum materials.
less steels and many materials have been proposed. As data
is accumulated from long-term creep tests on high-Cr ferrite steels, however, researchers are beginning to notice that
the creep strength remarkably decreases after a long time at
550˚C or higher and that the strength value estimated by
conventional short-time creep test data is not necessarily
reliable. Damage has also been reported at welded joints of
structural components made using such materials.
By acquiring long-term creep strength data of high-Cr
ferrite steels, the drop in strength after a long time was
studied. This research clarified that the recovery of tempered martensite differs between high and low stresses and
produces a non-uniform metallic microstructure at low
stress after a long time where only the neighborhood of the
prior austenite grain boundary has recovered. In addition,
progress has been made in research on the mechanism by
which the creep strength of high-Cr ferrite steels is manifested.1) High-Cr ferrite steels develop high dislocation
densities by thermal treatment and strengthened precipitation by the dispersion of fine precipitates. Precipitates
become coarse during creep, the pinning force of dislocation goes down, and the creep strength drops quickly.
After this mechanism was clarified, a method of predicting life modified from the conventional one was proposed.
NIMS proposes a method in which the area of creep fracture data is split with half the 0.2% proof stress of the tensile test as the criterion and only data in the low-stress area
2. Research characteristics
2.1 Creep characteristic of heat-resistant steel
Since 1980, the temperatures of thermal power plants
and petrochemical plants have been raised to save energy
and mitigate global environmental problems, and so heatresistant steels have been actively developed. By considering not only high-temperature creep strength but also the
suppression of thermal stress which is generated during
non-stationary operation, high-Cr ferrite steels having high
strength are attracting attention instead of austenitic stain-
Fig. 1 Long-life prediction of modified 9Cr-1Mo steel by the area
splitting method.
139
is analyzed.2) Figure 1 shows the results of applying the
area splitting method to the modified 9Cr-1Mo steel; the
experimental data matches the predicted value well. This
method has been used to review the allowable stress of
high-Cr ferrite steel for thermal power plants.3)
2.2 Fatigue characteristics of structural materials
Fatigue fracture was found to occur even in a long-life
area exceeding 107 cycles which had been considered the
fatigue limit of steels; this phenomenon is called gigacycle
fatigue. This super-long-life fatigue is unique to highstrength steels and characteristic of the origin of an internal
fracture. The influences of various factors on super-longlife and the fracture mechanism are being researched within
and outside Japan.4)
NIMS is also acquiring data on super-long-life fatigue
and conducting research based on it. About 20 years ago,
NIMS (the former National Research Institute for Metal)
started collecting data about up to 108 cycles by considering the problem of fatigue in the long-life area and studied
the presence or absence of a fatigue limit and also internal
fractures. NIMS thus reported that a fatigue limit could not
be determined by 108 cycles. Meanwhile, industry strongly
demanded the collection of long-life fatigue data to ensure
reliability in the long-life area for using high-strength materials to reduce weight. Therefore, NIMS initiated a project
to acquire long-life fatigue test data for up to about 1010
cycles from high-strength steels and titanium alloys. For
the fatigue test of 1010 cycles, it takes three years at the
cyclic speed of 100 Hz, so data is being collected simultaneously by a 20-kHz ultrasonic fatigue test machine.
Figure 2 shows the long-life fatigue test results of spring
steel SUP7.5) The results of the rotating bending fatigue test
and the ultrasonic fatigue test matched those of the longlife fatigue test. This means that reliable data can be
acquired by the ultrasonic fatigue test if care is taken. In the
super-long-life area, a fracture originates from an internal
Al2O3 inclusion. The weak bonding between this inclusion
and the matrix is considered to be the cause of internal
fracture. The influence of danger volume on the internal
fracture characteristic is also studied.
A fatigue fracture often occurs from a crack in a non-
continuous region. Many studies used to follow a mechanical engineering approach, but since the super-long-life
fatigue characteristic depends on the metallic microstructure of the material as mentioned above, research on superlong-life fatigue requires a materials approach. Thermal
treatment produces various metallic microstructures from
steel materials and achieves the requested strength characteristic. As metallic microstructures produced by thermal
treatment affect the fatigue characteristic, the characteristic
should be evaluated in relation to fine metallic structure
information. Therefore, researchers are recently conducting
nano level structure analysis by using an intoratomic force
microscope (AFM), and nano-meso-macro multilevel
strength analysis linking with nano-level strength and
fatigue strength evaluation by ultra-small hardness testing
procedure.
As Figure 3 shows, a high-Cr ferrite steel shows a complicated metallic microstructure produced by thermal treatment. To evaluate its fatigue characteristic, a quantitative
understanding of the metallic microstructure is necessary,
and so a nano-scale structure analysis method with AFM is
used.6) By this method, the non-uniformity of microstructures was evaluated quantitatively and its relation between
high-temperature fatigue characteristic and metallic structure was clarified.
2.3 Material strength and risk-based engineering
Many of the recently developed structural materials are
used nearly at their strength limits and under extremely
severe conditions for the materials. Therefore, the life evaluations and deterioration diagnoses of materials need to be
even more accurate. However, it is impossible to reduce the
failure probability to zero because of the dispersions of
material characteristic values and the inaccuracies of life
predictions and deterioration diagnoses. As long as materials are used, therefore, there is always the possibility of
fracture. When selecting materials, we should not only
determine the product, system, technology, or materials
based on the possibility of an accident by fracture, but also
by considering the scale of a disaster or damage caused by
the accident or fracture. This is called risk assessment.
To establish risk-based engineering that uses risks as
Packet boundary
Block boundary
Lath boundary
Prior γ grain boundary
Fig. 2 Long-life fatigue strength of spring steel SUP7.
140
Fig. 3 Multilevel structure of martensite.
indexes, we need to create a database or acquire knowledge
from accident information, to establish a risk evaluation
technique, and to study risk recognition and communication in society. As well as this research, risk evaluations on
actual machines and plants are also often reported.7) To
provide necessary information for future risk evaluations
from the viewpoint of materials, NIMS is proceeding with
R&D on creating a materials risk information platform in
collaboration with research institutes, universities, and
enterprises.8)
make best use of research results through information
exchanges. Safety is critical for constructing a society
based on science and technology and it is important to
ensure that the results of reliability research are of benefit
to society. NIMS is expected to strengthen information
exchanges and cooperation with enterprises, to grasp needs
appropriately, and to help inform the world of design
strength values derived in Japan.
References
3. Future outlook
Research on the reliability of structural materials
requires a great investment in research equipment and facilities. One institute alone cannot tackle such research, but
requires assistance from domestic and overseas research
institutes, research groups, and enterprises. NIMS is conducting research on the reliability of structural materials by
linking the structural materials data sheet project at the
Materials Information Technology Station with materials
creation at the Steel Research Center. Comprehensive
activities like this are rare even outside Japan and will need
to be expanded in future. In addition, we need to create a
system whereby such activities can be connected to domestic and overseas activities physically and effectively to
1) F. Abe., Bulletin of The Iron and Steel Institute, Japan, 10, 302
(2005).
2) K. Kimura, H. Kushima and T. Abe, Journal of The Society of
Materials Science, Japan, 52, 57 (2003).
3) Japan Power Engineering and Inspection Corporation: FY2004
report “Investigation of Conformance to Technical Standard for
Long-term Creep Strength Drop of High-chrome Steel”, March
2005.
4) Y. Ochi and T. Sakai, Journal of The Society of Materials Science,
Japan, 52, 433 (2003).
5) Y. Furuya, T. Abe and S. Matsuoka, Fatigue Frac. Engin. Mater.
Struc., 26, 786 (2003).
6) M. Hayakawa and S. Matsuoka, Materia Japan, 43, 717 (2004).
7) K. Yagi, Journal of The Japan Society of Mechanical Engineers,
107, 597 (2004).
8) K. Yagi, Journal of The Japan Institute of Metals, 66, 1264 (2002).
141
08 Metals
Section 2. Nonferrous Alloys
Hiroshi Harada*, Toshiji Mukai**, Masuo Hagiwara*, Toshiyuki Hirano*,
Youko Yamabe-Mitarai*, Satoshi Kishimoto*, Yoshihisa Tanaka*,
Akira Ishida*, Takahiro Sawaguchi*
*Materials Engineering Laboratory,NIMS
**Ecomaterials Center, NIMS
1. Aluminum alloys
1.2 Research trends
Figure 1 shows the history of strength improvement of
rolled materials for aircraft.1) Despite the improvement
from the 2000 series to the 7000 series, even stronger materials are needed to reduce aircraft weight. These alloy
development projects are mainly led by US aluminum alloy
manufacturers. Since the greater strength of the 7000 series
is offset by stress corrosion cracking, it is necessary to add
more Zn and other elements to suppress stress corrosion
cracking.
Likewise, alloys having a good balance with fracture
toughness are being developed. As Figure 2 shows, new
alloys offer both the fracture toughness of the 2000 series
alloys and excellent proof stress of the 7000 series alloys.2)
142
Yield strength (MPa)
Goal
1.1 Introduction
Reducing the weights of aircraft, rolling stock, and automobiles is effective for saving energy and curbing CO2.
Therefore, aluminum alloys are being researched through
both alloy development and process development and their
application areas are expanding.
Aluminum alloys can roughly be classified into rolled
materials (sheets, foils, sections, tubes, bars, wires, and
forging) and cast materials (casting and die casting). Rolled
materials can further be classified into pure aluminum
(1000 series), Al-Mn (3000 series), Al-Si (4000 series), AlMg (5000 series), Al-Cu-Mg (2000 series), Al-Mg-Si
(6000 series), and Al-Zn-Mg (7000 series). Cast materials
can further be classified into Al-Si, Al-Mg, Al-Cu-Si, AlCu-Mg-Si, and Al-Mg-Si.
Alloy development is particularly active for the 2000series and 7000-series rolled materials, which are most
important for transportation equipment such as aircraft.
Regarding process development, the application of the
6000 series to airframes by laser welding is being studied.
In addition, the Friction Stir Welding (FSW) method developed in the UK as a new bonding technique is being used
for a broadening range of applications. These research
trends are outlined below.
Aluminum alloy application timing (year)
Fig. 1 History and goal of aluminum alloy development for aircraft.
Fig. 2 Trend of improvements in material characteristics of highstrength Al alloys.
Two methods are under research, one is to enhance the
toughness of the 7000 series at the sacrifice of strength, and
the other is to enhance the strength from the 2000 series by
increasing the solute.
For the past 10 years, NIMS has conducted atomisticlevel research on the aging and precipitation phenomena,
which are crucial for strengthening rolled aluminum
alloys.3) The 6000 series is attracting attention as alloys for
1)
2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
H. Taira, Materials Science, 35, 220 (1998)
T. Tsuzuki, Materia, 43, 396 (2004)
K. Takarano, Metals, 73, 201 (2003)
M. Murayama and K. Hono, Acta Mater., 47, 1359 (1999)
L. Reich, M. Murayama and K. Hono, Acta Mater., 46, 6053 (1998)
T. Honma, S. Yanagita, K. Hono, Y. Nagai and M. Hasegawa, Acta
Mater., 52, 1997 (2004)
T. Yokokawa, N. Taira and H. Harada, Spring Convention of The
Japan Institute of Metals (2005) 434. (submitted)
H. Sasaki, K. Kita, J. Nagahora and A. Inoue, Mater. Trans., 42,
1561 (2001)
T. Sato, Materia., 43, 400 (2004)
http://www.airbusjapan.com/media/a380_technical.asp
http://www.twi.co.uk/j32k/unprotected/band_1/tffricst.html
2. Magnesium alloys
2.1 Introduction
Magnesium has been used mainly for the bodies of
mobile electronic equipment because it is the lightest metal
for structures. To meet the demand for conserving energy
and resources and reducing exhaust emissions and other
environmental loads, research has started on using magnesium for automobiles and other moving devices, and
indeed, magnesium is now being used for an increasing
number of automotive parts. Magnesium production has
been increasing every year: in 2003, output reached about
380,000 tons, up 8% over the previous year. Of the total
output, about 40% is used as structural materials, and this
percentage is still increasing every year. This section summarizes the recent research trends in magnesium based on
the results of searching an academic paper database (SCI
Expanded).
2.2 Research trends
magnesium worldwide and by major country.
Papers are generally increasing although the rate of
increase varies among countries, with a particularly rapid
increase from 2000. There are more papers from Japan than
any other country, with a remarkable increase in 2003
probably because it was the last year of national academic
Total number
of papers
Number of papers by country
1.3 Future outlook
The cost performance of CFRP and other competitive
composite alloys may enable aluminum alloys to be used
for aircraft and other advanced transportation equipment
due to the light weight and high specific strength of such
alloys. For the Boeing 787, a next-generation mediumsized civil aircraft now under development, for example,
the target weight ratio of composite materials in the airframe is set to 50% (25% for the Boeing 777). For aluminum alloys to win the competition and be chosen for
advanced transportation equipment, it is important not only
to improve the materials property and the processability,
but also to make better use of the advantage of aluminum
alloys in recycling.
References
Total number of papers
automotive body panels but the greatest obstacle to practical application is the delay effect of artificial aging by natural aging. To overcome this, the mechanism of the delay
effect has been researched by the 3D atom probe method,
the positron annihilation method, and other nano-level
analysis techniques.4) Based on these results, an important
guideline was created for the heat treatment design for the
6000-series alloys. This guideline helped to clarify the agehardening phenomenon in the mechanism of Mg-Ag addition to Al-Cu-Mg-Ag alloy among the 2000-series materials now being used for aircraft5) and to clarify the atom
cluster formation, and aging and precipitation of Weldalite
alloys which are aeronautical materials having excellent
weldability.6) This guideline is now used for alloy design
throughout the world.
NIMS statistically analyzed the alloy compositions and
strength characteristics of the 2000 series and 7000 series.
Under the conditions of solution and aging processing (T6),
for example, the relationship between alloy composition
and mechanical properties (yield stress, tensile strength,
and elongation) was formulated as one equation for both
the 2000-series and 7000-series alloys.7) This equation will
be useful for optimizing alloy compositions.
Since grain refinement is effective for improving both
strength and toughness, refining processes by liquid
quenching and warm rolling have been researched intensively in the Supermetal Project and other projects.8) This
research was succeeded by the Nanometal Project and is
now focusing on precipitation control to achieve strength
and ductility at the same time.9)
For the super-large Airbus 380 aircraft due to enter service in 2006, the 6000-series alloys which are weldable by
laser process were selected instead of the 2000- or 7000series alloys which need to be riveted. The new process is
faster and is attracting much attention.10)
The Friction Stir Welding (FSW) method11) developed
by The Welding Institute on the outskirts of Cambridge in
the UK is being used for an ever-broader range of applications. Compared with the conventional MIG and other
melting methods, this method produces few bonding
defects, and so the method will be applied to vehicles and
other fields. It may also be used for aircraft eventually, but
strict reliability evaluations and research on material
strength are necessary.
Year
Fig. 1 Number of papers in the past 10 years.
143
project, “Platform Science and Technology for Advanced
Magnesium Alloys”, selected as the priority area of Grantin-Aid from the Ministry of Education, Science, Sports and
Culture, Japan. The number of papers from China is now
growing remarkably and reached the top in 2004. This is
probably because the country is not only producing magnesium metal but also keen to promote research and development under a national initiative.
Research is mainly focused on so-called cast alloys,
including die cast ones, as shown in Figure 2. Since 2002,
the ratio of wrought alloys, including rolled, extruded, and
severe-plastically deformed ones, has increasing rapidly.
Researchers tend not to be devoted to the research and
development of cast materials not only applicable to actual
casting but to future large members; key research themes
are grain refinement, accompanying the increase of
research in rolled materials. As to alloy designs, a growing
number of designs feature the addition of rare earth elements which increase the heat resistance and strength. The
number of “nano-aware” research papers is also increasing
dramatically. Nanostructured materials made by the addition of rare earth elements is another recent research trend.
Regarding material characteristics, research is focusing
on corrosion and corrosion protection as shown in Figure 3,
followed by creep. Papers on fracture, bonding, and fatigue
Number of papers
Number of papers
Year
Number of papers
Fig. 2 Number of papers by material types and microstructures.
Year
Fig. 3 Number of papers by material characteristics.
144
are also increasing, as well as on formability and ductility.
Hence, it would appear that materials research is shifting
toward larger structures and higher safety in line with the
growing research and development of rolled materials.
2.3 Future outlook
From the transition in the number of papers, R&D on
magnesium is predicted to keep increasing globally
because its application to large automotive members will
help reduce weight. BMW’s announcement of a 6-cylinder
engine block made of a magnesium alloy last year may
accelerate the development of new alloys offering excellent
high-temperature strength and creep resistance. Like twin
roll casting which has been actively researched since
around 2002, low cost sheet is also expected to be mass
produced in future. As an increasing number of new alloys
are designed with rare earth elements, R&D on nanostructure analysis and control to optimize the dispersion may
also increase.
3. Titanium alloys
3.1 Titanium industry within and outside Japan and information trends
In Japan, the shipment of titanium materials has
increased steadily for the last 20 years, reaching 13,838
tons in 2003 and predicted to reach 30,000 tons in 2009.
The world’s shipment in 2003 was 60,601 tons, and so
Japan accounted for about 24%. The United States shipped
23,600 tons in 2003, about double that of Japan.
At the World Conference on Titanium held in Germany
in July 2003, Japan ranked second with 77 papers after the
sponsor nation Germany (89). The United States (62)
ranked third and China (51) ranked fourth, followed by the
UK (44), France (34), Russia (18), and Korea (17).
3.2 Titanium research and development trends
For about 10 years after the collapse of the bubble economy, various ways of reducing cost were studied, such as
improving the efficiency of the manufacturing process,
manufacturing parts by powder metallurgy, and developing
alloys composed of only low-cost elements such as Al and
Fe. At that time, new fields of application other than aircraft were sought, and new demand was exploited in construction materials, sporting goods, daily necessities, and
accessories. In these latter fields, commercial-grade pure
titanium is mainly used.
Fortunately, in recent years in Japan, the situation has
been gradually turning more positive. Specifically, there
are some changes being seen which appear to favor a vast
expansion of the usage of titanium alloys. Namely, 1)
Japan has plans to produce medium-sized aircrafts using
Japanese own technologies, 2) Adoption of Ti alloy parts in
commercial cars (Toyota, VW), 3) Demand for biomedical
applications due to the growing population of elderly peoples.
Under these circumstances, the Titanium Forum of The
Iron and Steel Institute of Japan (chaired by M. Hagiwara,
NIMS) attempted to identify the main current research
trends, as well as ones required in future and promising
trends, in the fields of refining and melting, machining
technology, property database, structural alloys, functional
alloys, and uses. Subjects concerning alloy development
are as follows:
i) Alloy development (structural uses)
(1) Titanium alloys having high strength and great
plastic deformation capability for aircraft
(2) Heat-resistant titanium alloys having high strength
and toughness for next-generation aircraft engines
(3) Titanium alloys having high strength and low elastic modulus for biological uses and automotive
springs
(4) Titanium alloys having low-cost compositions for
welfare equipment and automotive connecting rods
ii) Alloy development (functional uses)
(1) Shape memory titanium alloys for high temperature application
(2) Shape memory titanium alloys for biomedical uses
The required characteristics in the new fields of structural and functional uses are satisfied by body centered cubictype titanium alloys (bcc phase or B2 phase) which offers
excellent deformation performance.
3.3 Research by NIMS
As mentioned above, demand for titanium alloys will be
great for next-generation aircraft engines and substitute
materials for biological hard tissues. Since existing titanium alloys cannot easily satisfy the required characteristics
in these new fields of application, new alloys must be
developed.
Therefore, NIMS is now developing new types of body
centered cubic-type high-strength titanium alloys suitable
for aircraft engines and biomedical applications. For aircraft engines, NIMS focuses on the Ti2AlNb (O phase)based alloy and its composite materials that shows excellent high temperature mechanical properties at 600˚C or
higher. For biomedical uses, NIMS is developing a titanium alloy having high strength and low Young’s modulus
from the nanostructured body centered cubic-type Ti(Ta,Nb)-Cu-Ni-Si alloy by compositional modification,
such as substituting harmful Ni with Fe, Co, or Cr.
3.4 Key research by other than NIMS
Toyota Central Laboratory developed a body centered
cubic-type Ti3(Ta+Nb+V)+(Zr,Hf,O) alloy (named “Gum
Metal”) showing far superior mechanical properties (high
plastic deformation capability, low Young’s modulus, and
superelasticity) than the conventional titanium alloys, and
the new alloy is expected to be used in other fields. Niinomi and co-workers of Toyohashi University of Technology
are developing a new titanium alloy having low Young’s
modulus and high strength for biomedical uses and proposed an alloy of the Ti-29Nb-13Ta-4.6Zr composition.
Meanwhile, Ikeda and his group of Kansai University are
developing an alloy having low-cost composition for welfare equipment. In addition, there is much university-led
research on body centered cubic-type shape memory alloys
and superelastic alloys.
4. Porous alloys
4.1 Introduction
Porous materials, which have many pores inside, are
used in various fields, such as biotechnology, fuel cells,
catalysts, and gas adsorption. Though research field of on
porous materials covers very wide fields such as inorganic,
organic, and physiochemical fields, solid state physics, etc.,
this paper reports on research on mult-functional lightweight porous materials.
4.2 Research trends
Porous materials can be roughly classified into metallic
porous materials, inorganic (ceramics) porous materials,
organic porous materials, metallic complex materials,
wooden materials and carbon materials. According to function, the materials can be also classified into biomaterials,
fuel cell electrodes, catalysts, gas adsorbents and sensors
using them, solar battery materials, energy absorbing materials, lightweight structural materials, etc. Regarding the
structural materials, solids containing small pores are called
porous materials, and the materials which have high porosity that is actively used are called cellular structural materials. Recently, these cellular materials are attracting attention because their uniform-size cells are arranged regularly.
According to the structure, structure materials, it is using
to fabricate lightweight structural materials. Lightweight
cell structural materials can be divided into the open cellular material that has no cell walls and the closed cellular
material in which each cell is surrounded by cell walls. The
open-cellular materials include ceramics for filtering materials and open cellular metals for shock absorbing materials. The closed cellular structural materials include foamed
metals, sintered hollow shollow spears and honeycomb
structure materials. These materials are fabricated by gas
foaming, sintering hollow spears and regularly bonding
geometrically bent plates. These closed-cellular structures
are lightweight and have excellent shock-absorbing capability. So, applications of these cellular materials for shockabsorbing structural materials of automobiles are being
developed.
4.3 Future outlook
Because the safety of transportation equipment is so
important, cellular structural materials are expected to be
developed as strong and lightweight structural materials,
shock absorbing and damping materials. Structural materials having multiple functions are also expected to be developed. Other researches to produce new functional materials
and hybrid materials using cellular structural materials also
need to be developed.
4.4 Conclusion
Metallic closed cellular materials which are one of
porous materials were introduced. These materials will be
lightweight structural materials having large shock absorbing and damping properties.
145
References
1) L. J. Gibson and M. F. Ashby, Cellular Solids, Pergamon Press
(1988)
2) Handbook of Cellular Materials, Hans-Peter Degischer and
BrigittebKriszt, Wiley-VCH (2002)
5. Intermetallic compounds
5.1 Research trends within and outside Japan
After several stages of research since 1950, full-scale
research on structural intermetallic compounds started in
the 1980s or later. Research and development are now
focusing on the aluminide type (TiAl, Ni3Al, FeAl, etc.)
and silicide type (Nb3Si, Mo5Si3, etc.) for application to aircraft, automotive engines, power generation turbines, and
space shuttles. This transition is clear from the reports
made at the 11th MRS Convention in the autumn of 2004, a
convention which has been held every two years since
1984.
Regarding TiAl which is lightweight and has excellent
heat resistance, Japan, the US, and Europe competed with
large projects in the 1990s. This fueled research and development on alloy composition, microstructures, characteristics, and manufacturing technology. In 1999, a unique precision casting technology developed in Japan enabled TiAl
to be used for turbochargers in actual automotive engines
on the market for the first time in the world. The turbochargers have reached the production level and European
automobiles are about to follow. The current issues are to
enhance the heat resistance and durability for diesel
engines. Automotive engine valves and low-pressure turbine rotor blades have also been fabricated experimentally
and verified by performance tests, but issues of reliability
enhancement and cost reduction remain. Compared with
these cast materials, wrought materials are difficult to manufacture and expensive, and thus innovative compositions,
microstructure control and machining technology are needed. Regarding Ni3Al and FeAl, research on the composition
and microstructure control and manufacturing process has
advanced. In the United States, Ni3Al is now being used in
heating element fixtures, high-temperature dices, and
valves for heat treat furnaces, while FeAl is being used in
heating elements to some extent. Other materials were
proved to have heat resistance characteristics exceeding
those of Ni-base heat-resistant alloys; basic research is
underway and is expected to progress.
Since intermetallic compounds show peculiar properties
originating from ordered structures, they have been
researched as thermoelectric materials, catalytic and electrode materials, magnetic materials, shape memory materials, and superconductive materials. Many of them are in
practical use. These days, intermetallic compounds of Ni
and Pt are attracting attention and being researched as catalytic and electrode materials for fuel cells.
For Ni3Al, fabrication technologies of the cold-rolled
foils and honeycomb structures were developed for the first
146
time in the world and Ni3Al foils were found to have a catalytic effect for decomposing methanol and generating
hydrogen. To develop the foils as both a catalyst and a
structural vessel, R&D is being promoted to clarify the
characteristics and create a reformer and an exhaust gas
purifier for fuel cells.
5.3 Future outlook
Intermetallic compounds started being used as practical
structural materials at the end of the 20th century, and the
applications and types of intermetallic compounds will
expand. Therefore, cost reduction is essential and technological development is necessary for enhancing the ductility and toughness, and improving and varying the manufacturing technology.
These days, finely-distinguished characteristics of both
structural and functional materials are requested, and intermetallic compounds are expected to satisfy such requests.
While needs-oriented research and development are
underway, there are estimated to be thousands of intermetallic compounds whose characteristics and functions
are unknown or not used. To use these compounds, basic
and fundamental research will continue for seeds research.
6. Refractory alloys
Ni-base superalloys are high-temperature materials used
under severe conditions such as in jet and rocket engines.
To raise the thermal efficiency of a gas turbine or aircraft
engine, a high-temperature material that withstands temperatures over the temperature capability (1500˚C) of Ni-base
superalloy is expected. For this, refractory metals (Nb, Mo,
etc) and platinum group metals (Ir, Ru, Rh, Pt, etc) having
melting points of 2000˚C or higher are attracting attention.
Researchers are very interested in materials beyond Nibase superalloys. In 2003, US MRS introduced Pt-Al alloys
and Mo and Nb silicides (Si compounds) in a feature
“Ultrahigh-Temperature Materials for Jet Engine.1)” TMS,
another materials society of the United States, held a symposium on the theme of “Beyond Ni-Based Superalloys” in
March 2004 and published a special issue in an academic
journal in 2004.2) Not only Pt-Al alloys but also the potential of platinum-group metal base alloys using Ir3Nb, RuAl,
IrAl, and other platinum-group intermetallic compounds
were introduced in the special issue.
NIMS is actively researching platinum-group metals. Of
the platinum-group metals, Ir has an especially high melting point, and NIMS is developing Ir- base alloys for use
around 1950˚C. These alloys are expected to be applicable
for very severe aeronautical and space uses, such as the
attitude control thrusters of satellites. In addition, PtTi,
IrTi, and other intermetallic compounds based on platinumgroup metals were found to have potential use as shape
memory alloys at 1000˚C or higher. Since the conventional
shape memory alloy NiTi can be used only near room temperature, these intermetallic compounds could be used as
new high-temperature shape memory alloys for gas turbines, high-temperature sensors, and actuators.
6.3 Future outlook
These ultrahigh-temperature structural materials are
used only under highly specific condition. However,
despite demand, they are not being systematically
researched. Then, supply of the ultrahigh-temperature
materials is insufficient. Such uses require not only adequate strength but also oxidization, resistance, corrosion
resistance, manufacturability, and various other conditions.
Therefore, materials development requires advanced technologies. By clarifying the purposes of application and targeting research on them, these materials will start to be
used for space and aeronautical applications.
ing a market of 3 billion dollars. Research is also being
stepped up in China.
In the field of shape memory alloys, continuous efforts
are being made to extend the application range of alloys to
meet emerging needs. New applications for medical materials, smart materials, safe materials, MEMS materials, and
high-temperature shape memory alloys are being studied.
As more applications emerge, researchers have started to
develop new shape memory alloys to replace the TiNi
alloy, such as biologically harmless Ni-free shape memory
alloys, composite materials fusing the functions of different
kinds of materials, thin films made of shape memory alloys
by the semiconductor process, iron-base shape memory
alloys that can be mass-produced at low cost, high-temperature shape memory alloys for turbines, and ferromagnetic
shape memory alloys having a quick response by magnetic
fields.
References
1) J-C. Zhao and J. H. Westbrock, Mater. Res. Soc. Bull., 9, 622
(2003)
2) D. A. Alven, JOM, 9, 27 (2004)
7. Shape memory alloys
The TiNi shape memory alloy discovered in the United
States in 1963 spawned many successful products, from the
valves of coffee makers to women’s underwear, thanks to
the production technology established in the 1980s and a
new materials boom. In the 1990s, the application range
was extended to the antennas of cellular materials and biomaterials, riding on the IT wave and high-grade medical
technology. With an overwhelming number of researchers
and enterprises, Japan has been leading the world in both
basic and applied research (see Figure 1). Research on
shape memory alloys is an important part of domestic
materials societies. Japan is also playing a leading role in
international academic societies. In the United States, much
development is focused on medical applications, with
stents used for the treatment of myocardial infarction hav-
Finland
Other
51
56
42
13
68
Japan
14
Fe
base
15
France
TiNi alloy
14
11
12
Ukraine
9
9
Cu
base
UK
China
Medical
materials
Other
Ferromagnetic
materials
29
19
20
16
23
Spain
Russia
TiNi base
Germany USA
Composite
materials
Microactuators
Damping
materials
Fig. 1 Number of participants at an international conference on
martensite transformation (ICOMAT ’02) by country (many from
Finland, the sponsor country) and number of reports at an international
conference on the application of shape memory alloys (SMST ’01) by
material.
NIMS has announced important research results on thin
films of shape memory alloys used for microactuators and
iron-base shape memory alloys used for large members.
Thin films of shape memory alloys are expected to be
used for as MEMS actuators of great force. The number of
papers published was about 2 a year around 1990 when
NIMS embarked on research, but began to increase around
1995. Now, nearly 50 papers are published a year and the
number is still rising. The University of California and
Karlsruhe are promoting the application of TiNi alloy to
microdevices. Materials development, however, is led by
NIMS which has a wealth of data on characteristics and
unique evaluation techniques, as well as Tsukuba University.
Meanwhile, the Fe-Mn-Si base alloy discovered in Japan
in 1982 is about to be used as a low-cost material for bonding large pipes. NIMS recently succeeded in the development of an NbC-added Fe-Mn-Si base alloy not requiring
training and is now promoting joint research with domestic
and overseas research institutes and enterprises for application of the alloy to reinforcing bar bonding materials and
concrete reinforcing fibers. NIMS is also studying use of
the alloy, which has damping properties, as a damping
material.
7.3 Future outlook
Compared with other materials, shape memory alloys
are comparatively new. The successful application of TiNi
alloy triggered new materials development for extending
the application range of shape memory alloys. With the
development of new industries for which there is great
social demand, such as nanotechnologies, biomaterials, and
safe materials, the development of materials and processing
methods is advancing. Shape memory alloys will therefore
be applied to more fields as intelligent materials having
multiple sensor, actuator, damping, and superelasticity
functions.
147
08 Metals
Section 3. Protective Coating for Severe Environments
Seiji Kuroda, Hideyuki Murakami
Thermal Spray Group, Materials Engineering Laboratory, NIMS
1. Thermal BarrierCoating
Thermal barrier coating (TBC) is an essential surface
treatment for the blades and vanes of jet engines and turbines for thermal power generation. As Figure (a) shows,
TBC produces a multilayer structure consisting of i) a base
material made of Ni-base superalloy, ii) a metallic bond
coat layer enriched in Al, iii) a thermally grown oxide
(TGO) layer formed by the surface oxidization of the bond
coat, and iv) a top coating layer of oxide ceramics with low
thermal conductivity (in general, yttria stabilized zirconia:
YSZ).
To meet the recent demand for CO 2 reduction, it is
important to improve the thermal efficiencies of internal
combustion engines or to raise the operating temperatures.
In various countries throughout the world, several research
projects organized by industry, academia, and the government are in progress to enhance the TBC system for keeping the temperature of the substrate material hundreds of
degrees lower than that of the combustion gas. The main
projects are the HIPERCOAT Project,1) an international
joint program by the NSF in the US and the EC, and
Japan’s Nanostructure Coating Project2) following the main
theme of NEDO’s Nanotechnology Program.
The key aspects of TBC technological innovation are
high temperature operation and long life. Until recently,
most researchers had been interested in the design of top
coat materials and the development of coating processes.
As Figure (b) shows, however, the life of coated components greatly depends on i) the peeling of the top coat layer
on the bond coat attributable to TGO and ii) the deposition
of harmful phase in the substrate material attributable to the
mutual diffusion of alloying elements between the substrate
material and bond coat. In other words, the highest priority
for attaining long life is to develop bond coat materials
offering slow and stable growth of TGO and to suppress
microstructural changes of the substrate material.
Researchers are therefore shifting attention to the bond
coat.
Ahead of these global trends, NIMS has been conducting research since 2000 to develop novel bond-coat alloys
using Ir as a base element, because Ir has low diffusivity
into Ni-base alloys with excellent resistance to high-temperature oxidization and corrosion.3-5) In FY2005, NIMS
was appointed as a collaborative institute for the Specially
148
Promoted Research project “Fabrication of diffusion-barrier bond coating to realize long-life, high-reliability thermal
barrier coatings” subsidized by Grants-in-Aid for Scientific
Research. Thus, NIMS is attracting national and international attention for its achievements.
With a research group leading the world in the design
and development of Ni-base superalloys, NIMS is the sole
research institute in Japan that has the full research potential necessary for developing TBC coating materials, such
as the capabilities of developing ceramic top coat materials
and processes. In future, closer linkage between researchers
is expected to enable the development of unique turbine
blades made entirely within Japan.
TGO growth
→Peeling of top coating
Top coat
Bond coat
Substrate (Ni-base superalloy)
Inter diffusion of alloying elements
→Precipitation of harmful phase
Fig. (a) Thermal barrier coating and (b) deterioration mechanism.
References
1) http://www.materials.ucsb.edu/TBC/index.php
2) http://www.nedo.go.jp/nanoshitsu/project/pro06/index.htmlFFor
achievement reports by years, search NEDO’s achievement report
database (http://www.tech.nedo.go.jp/Index.htm) with “nanocoating”
3) P. Kuppusami and H. Murakami, Surf. and Coat. Technol., 186,
377-388 (2004).
4) P. Kuppusami, H. Murakami and T. Ohnuma, J. Vac. Sci. Technol.,
A22, 1208-1217 (2004).
5) H. Murakami, A. Suzuki, F. Wu, P, Kuppusami, H. Harada,
Superalloys 2004, Eds. K. A. Green, T. M. Pollock, H. Harada, T.
E. Howson, R. C. Reed, J. J. Schirra and S. Walston, TMS (2004),
pp. 589-596.
2. Thermal Spraying
Thermal spraying is a surface coating process used to
form coatings of 100 micron or thicker. This process can
produce coatings from various materials such as metals,
ceramics, composite materials, and plastics. The process is
industrially very attractive for high-speed large-area coating and field work, and can be classified into various types
by the heat source (combustion flame or electric energy)
and the form of raw materials (powder or wire). In the
1910s, wire arc spraying and flame spraying were developed and mainly applied to metal spraying. In the 1960s,
plasma spraying was put to practical use for coating ceramics of high melting points. Low-pressure plasma spraying
developed in the 1970s enabled the formation of a very
dense, less oxidized metallic coating. This process became
widely used for turbine engines and other high-tech fields.
High velocity oxy-fuel (HVOF) spraying was developed in
the 1980s. At 500 m/s or higher spray particle speed, this
process can stack unmolten spray materials on a substrate
by kinetic energy. In particular, the process can form dense
coatings of carbide-type cermet materials while suppressing decarbonization. Cold spraying and aerosol deposition
were recently developed as other processes using kinetic
energy, and are carried out almost at room temperature.
The former mainly forms a coating from a metallic powder
in the atmosphere while the latter feeds submicron ceramics particles into a decompressed chamber and forms a
coating by a high-speed impact.
The Thermal Spray Group of NIMS has developed corrosion-resistant dense metallic coatings by optimizing the
spray particle speed and temperature of the HVOF process,
and verified them by demonstration tests in a coastal environment and the like. These days, it has become possible to
form dense coatings of titanium and other materials that are
otherwise difficult to make dense in the air atmosphere.
NIMS is carrying out basic research on the mechanism of
spray coating adhesion and a method of evaluating it, and
the result is attracting international attention.
The trend toward high speed and low temperature will
continue in process development because the process can
maintain the microtissues of raw materials and powerfully
form coatings from materials having nanostructures.
Regarding nano-structured spray coatings, interesting
reports have been published on the enhancement of wear
resistance and adhesiveness. For industrial use, the application of spray coatings to automotive engine blocks is of
particular interest. Automotive manufacturers worldwide
are discussing the replacement of cast-iron cylinder liners
with iron-type sprayed coatings and a manufacturer in
Europe has established a production line. This technology
enables weight reduction and greater cooling efficiency by
reducing the lining thickness drastically, but the problem of
controlling the quality of the coating remains. To solve
this, nondestructive coating inspection is important and a
method using thermography is attracting attention.
As the environment of materials use becomes harsher
year by year, thermal spraying is becoming more recognized as an important technology that offers many choices
for adding environmental performance to the surfaces of
materials. Since clarification of the basic phenomena in
these processes has been delayed somewhat, research and
development in advanced countries are often driven by
research institutes and university laboratories.
References
1) J. Akedo, Surface Science 25, 25 (2004).
2) J. Kawakita, S. Kuroda, T. Fukushima and T. Kodama, Sci.
Technol. Adv. Mater., 4, 281 (2003).
3) M. Gell, E. H. Jordan, Y. H. Sohn, D. Goberman, L. Shaw and T.
D. Xiao, Surface and Coatings Technol., 146 –147, 48 (2001).
149
Chapter 9.
Ceramic Materials
Section 1. Non-oxides - Carbon
Hisao Kanda
Super Diamond Group, Advanced Materials Laboratory, NIMS
1. Introduction
Upon making bonds with each other, carbon atoms gain
various structures and become materials having various
properties. The most typical ones are diamond monocrystals consisting of carbon atoms arranged regularly by sp3
bonds and graphite monocrystals arranged regularly by sp2
bonds. Among the many carbon materials, the most famous
ones recently found are fullerene and nanotube. These have
remarkably extended the world of carbon materials, which
can be classified by the style of bonds, size, and form as
follows:
Diamond type: Monocrystal or polycrystal sintered compact, thin film, and nanodiamond. Nanodiamond is a
nanoparticle of tens of nanometers, which is a form of thin
film when produced by vapor phase processes or is in dispersion when produced by the explosion process.
Graphite type: Monocrystal, polycrystal, thin film, particulate, porous form, fiber, nanotube, nanofiber, and fullerene.
The graphite-type carbon materials are of sp2 bonds but
vary widely from amorphous to highly crystalline ones in
terms of X-ray diffraction.
Between diamond and graphite is diamond-like carbon
(DLC). This is an amorphous thin-film material mixed with
sp2 bonds and sp3 bonds.
Regarding nanotechnologies now popular, not only
nano-size carbon units but also nano-size voids in porous
carbon are attracting attention.
Modifications with other atoms are also possible. Diamond can be doped with impurities and there are also carbon materials having surfaces modified with hydrogen or
other different molecules. Graphite can be intercalated with
other atoms or molecules between layers.
Some boron nitrides produced by replacing carbon with
boron and nitrogen atoms have structures and forms similar
to those of the above carbon materials, and so they may
have similar characteristics and functions. Here, the boron
nitrides are also partly introduced.
These carbon materials of various structures also have a
wide variety of properties. This section summarizes the
recent research trends by properties.
Data on recent research trends was collected from academic journals, particularly the two international academic
journals specializing in carbon materials: “Diamond Relat150
ed Materials” and “Carbon” (both published by Elsevier).
In 2004, these journals carried about 300 and 500 papers,
respectively. The domestic academic journals “Tanso (Carbon)” and “NEW DIAMOND” were also referenced.
Research achievements may also be reported in magazines
and at academic meetings in the fields of physics, chemistry, and biology but such areas were not checked.
2. Research trends
2.1 Mechanical properties
The most widely-known characteristic of diamond is
that it has the highest hardness of any material. Thanks to
this hardness, diamond is widely used for machining tools
and abrasives. Graphite is also useful as a structural material. As a composite, carbon fiber is widely used for golf
clubs, fishing rods, and aircraft. In these fields, carbon fiber
is now at the stage of industrialization.
With the emergence of new carbon materials, new
research on mechanical characteristics has started. The
research activities include the synthesis of thin films from
diamond, DLC, and other amorphous carbon materials by
using plasma technology and also the evaluation of their
characteristics. The objectives of these activities are to
apply the materials to micro electro mechanical systems
(MEMS), protective films of magnetic disks and artificial
joints, and bearings and seals for oil-free machines.
Research is focused on high hardness, great abrasion resistance, and low friction.
The high tensile strength and other mechanical characteristics of carbon nanotube are also interesting in the field
of nanotechnologies.
2.2 Electrical and optical properties
Diamond is a wide-gap semiconductor having a bandgap of 5.5 eV; it shows the highest thermal conductivity
and excellent light transmittance over a wide range of
wavelength. Active research is underway in expectation of
producing new electronic devices based on these characteristics. Diamond has the potential to be used for high-frequency high-power transistors, ultraviolet light emitters
and detectors, thermistors, particle detectors, electron emitters, optical windows, X-ray windows, and X-ray mono-
chromators for synchrotron radiation. Research is currently
focused on electron emitting devices. Japan is conducting a
national project “Advanced Diamond Device Project”
(NEDO: 2003 - 2005) with the goal of developing electron
emitting devices. Carbon nanotube, nanodiamond, and
DLC are also being studied as electron emitting devices.
To use diamond as a semiconductor, it is essential to
produce p-type and n-type characteristics. This has been
done by doping with boron and phosphorus, respectively,
although the characteristics are not yet satisfactory for
practical purposes. Mainly in Japan and Europe, basic
research on electrical conductivity and mobility is being
continued in terms of synthesis and characterization.
Research papers clearly oriented toward specific electronic materials deal with not only electron emitting
devices but also high-frequency transistors, ultraviolet light
emitting devices, ultraviolet light detection devices, and
particle detection devices.
Many papers on graphitic carbon are related to electrodes, dealing with negative electrode materials for lithium
batteries, electrodes for fuel cells, and electrical doublelayer capacitors. For these uses, the small pore size and
large specific area of carbon are important characteristics,
in the same way that the characteristics of activated carbon
have long been used. In relation to recent nanotechnologies, research on energy conservation and environmental
problems has been very active.
Diamond is also useful for electrochemical electrodes
because it has chemical inertness and wide potential window. Boron-doped semiconducting diamond is now being
applied to electrodes to decompose waste water. Selective
detection is now possible for bio-related substances, such
as various molecules (dopamine, uric acid, etc.) contained
in body fluid.
This may lead to the development of fuel cell electrodes.
Technologies for removing NOx and other environmental
contaminants have also been reported.
Diamond is chemically stable but known to form a ptype semiconducting layer once hydrogen is adsorbed on
the surface. By using this conductive layer, field-effect
transistors (FET) and DNA detectors are being researched.
If reduced to nano-size, diamond seems to display special
reactions and has even been reported to acquire the ability
to kill cancer cells.
Although not chemical properties, fine pores may enable
carbon to be used as a molecular sieve to separate hydrogen
and carbon monoxide or other substances. The DLC coating of a PET container is also known to suppress gas permeation.
2.3 Magnetic properties
According to a paper published several years ago,
pyrolytic graphite and polymerized fullerene show ferromagnetism. It is interesting to note that magnetic bodies are
composed of nonmagnetic atoms. However, some questions must be solved to verify the paper, and it was reported
last year that proton irradiation of carbon produces magnetism. This proves that the magnetism of carbon is not attributable to contamination with a magnetic substance.
2.6 Thermal properties
Diamond has the highest thermal conductivity. By using
this characteristic, diamond can be used for heat spreading
boards for laser diodes and other electronics devices. On
the contrary, a carbon fiber aggregate shows great thermal
insulation and also very high heat resistance. As a heatinsulating material, the carbon fiber composite is applied to
the heat-insulating members of rocket engines. Thus, the
thermal characteristics are another excellent advantage of
carbon but no papers on its thermal characteristics were
found.
2.4 Chemical properties
As a chemical application of graphite-type carbon, activated carbon which has long been used as a deodorant is
well known. Graphite-type carbon, however, is still being
researched intensively for application to many fields related to nanotechnology by utilizing the characteristics of carbon, large specific area and small pore size.
Many studies are in progress to purify water and suppress bacteria generation in water with various kinds of
activated carbon and to immobilize marine organisms with
carbon fibers. Affinity with blood, such as cohesiveness
between the DLC surface and blood platelets, is also being
researched. By nickel or another metal supported on carbon, hydrogen-added reaction (e.g. reaction from butene to
butane) and other catalytic effects are also being examined.
2.5 Jewelry
Although jewelry may not be directly related to science,
research on diamond is also attracting attention in the
world of jewelry. As jewelry, natural diamond is treasured
but synthetic diamond has begun to enter the jewelry market. Jewelry-level synthetic diamond can now be produced
from gas phase using a chemical vapor deposition (CVD)
technique as well as under high pressure, and the CVD synthetic diamond is now about to be sold as jewelry. A technology has also been developed to enhance the quality of
brown low-quality natural diamond by high temperature
and pressure treatment. However, the emergence of these
synthesizing and processing technologies produces the
problem of how to distinguish natural diamond valuable as
jewelry from artificial diamond. A new discrimination
technology is expected to be established, and research on
the characterization of diamond for raising the level of discrimination is underway.
2.7 Vibration properties
Diamond conveys sound at the highest speed, and so has
been applied to thin-film speakers and surface acoustic
wave devices. However, there have been few research
papers on this aspect.
2.8 Topics in 2004
Last year, the journal “Nature” reported rather unexpected noteworthy discoveries.
One is the superconductivity of diamond. Diamond containing boron has long been known to show electrical conductivity. However, the doping of boron as high as 2% was
found to synthesize superconducting diamond. First, a
151
Russian research group discovered this phenomenon with
high-pressure synthetic diamond. The phenomenon was
then confirmed with CVD diamond in a joint study by
NIMS and Waseda University. Although the critical temperature is about 10 K, this is interesting because it is diamond, which may be in another category of superconductors.
The other is 215-nm deep-ultraviolet laser oscillation
from hexagonal boron nitride (hBN), which was achieved
by NIMS. Ultraviolet light emission of GaN is well known
but the wavelength of the deep-ultraviolet laser of hBN is
much shorter. hBN has long been known but never been
considered as an electronic material. NIMS successfully
synthesized monocrystals of high purity and crystallinity
by using a special solvent, resulting in its success.
152
3. Conclusion
As outlined above, carbon has a wide range of applications as mechanical and structural materials, electronic
materials, and chemical materials. Recently, however, carbon is actively being researched for application to the fields
of bio and environment from the viewpoint of nanotechnology, and such research looks set to continue.
Carbon materials for new fields are also expected to be
developed. It was only one year ago that the superconductivity of diamond was discovered unexpectedly. The magnetism of carbon is another interesting subject worth
researching in detail.
09 Ceramic Materials
Section 1. Non-oxides -Carbides, Nitrides, and Borides
Hidehiko Tanaka
Non-oxide ceramics Group, Advanced Materials Laboratory, NIMS
Carbides, nitrides, and borides are not produced naturally with some exceptions, so powders are synthesized from
metals or oxides and sintered into materials. The main
materials are silicon carbide (SiC), silicon nitride (Si3N4)
and sialon (Si 3N4-AlN-Al2O3 solid solution), aluminum
nitride (AlN), boron nitride (BN), boron carbide (B4C), and
zirconium boride (ZrB 2 ) and other metallic borides.
Because of their excellent heat resistance, strength, elasticity and hardness (wear resistance), corrosion resistance, and
thermal conductivity, these materials are used for refractory
and structural (engineering) ceramics.
SiC polycrystal materials were developed in the UK
around 1970 as substitute materials for metals in internal
combustion engines to raise the yield temperature and
enhance the energy efficiency. This was a pioneering
approach. Regarding materials development, an SiC powder sintering process was developed in the United States in
1975 and the Si3N4 sintering process in Japan in 1975 to
1977. In 1976, nitride ceramics were developed in the UK
and in Japan. These findings had a great impact on science
and technology and established non-oxide ceramics as
materials.
With this background, global policies for conserving
energy led to national projects being started in the US,
Europe, and Japan. First in the United States, the Ceramic
Application in Gas Turbine Engine (CATE) Project (19701980) was started and the Department of Energy (DOE)
and the Detroit Diesel Allison (DDA) of GM researched
ceramics for gas turbines of buses and trucks. This was
succeeded by the Advanced Gas Turbine Project (19791987) and then the ATTAP Project (1987-1992). Both projects were carried out by DOE, GM, and Garret Ford.
Automotive gas turbine components were developed in
West Germany (1974-1982, by BMFT Ministry of
Research and Technology, VW, DM, and MTU), the projects for ceramic gas turbines in the UK (1985-1989, by
RR), and for ceramic gas turbines aircraft and vehicles in
France (1985-1989, by ONERA), and the KTT project in
Sweden (by United Turbine and Volvo).1)
Internal combustion engines made of ceramics became
technically possible but were not implemented due to
issues concerning economy and reliability, since when
R&D on structural ceramics has not been active. In the
United States, however, work on developing aeronautic and
space ceramic materials became very active. Key materials
are Ceramic Matrix Ceramic Fiber Reinforced Materials
(CMC) which are composites of carbon (C) fiber reinforced
carbon matrix and SiC fiber reinforced SiC(Si3N4) matrix.
The former is already used for the heat insulation on the
space shuttle. Raw materials in these ceramic products are
mostly supplied from Japan. Japan is taking the lead in
manufacturing and the United States in evaluation and utilization.
2. Domestic trends
Regarding non-oxide engineering ceramics, the Ministry
of International Trade and Industry (MITI) conducted
research on fine ceramics under the basic technology for
future industry (1981-1992). Mainly for Si 3N4 and SiC,
work has focused on developing advanced basic technologies for raw-material powder synthesis, powder processing,
and sintering and component creation to raise the efficiency
of internal combustion engines. This boosted the ceramics
manufacturing technologies of Japan remarkably. MITI
then initiated the Synergy Ceramics Project (1994-2003) to
develop new ceramics by fusing various characteristics and
functions and started materials development by using
sophisticated nano-micro structure control technologies.
This resulted in the development of new Si3N4 and SiC
(including oxides) materials featuring high strength, toughness, elasticity, thermal shielding, and grinding resistance
and also high (low) thermal conductivity, enabling the next
generation of materials to be developed. The concept of
nanoceramics was proposed to strengthen ceramics by dispersing nanoparticles.
The developed process technologies were inherited by
the Ceramics Gas Turbine Technology Development
(CGT) Project of NEDO of MITI (1998-1999) and produced a practical ceramic gas turbine for 300-kW class
cogenerators. Eventually, the target thermal efficiency of
42% (the world’s highest) could be achieved. For hightemperature regions, Si3N4 ceramics having high strength
and toughness was used.2,3)
Supported by various projects, Japan’s fine ceramics
industry gained international competitiveness, and currently about 70% of the world’s ceramic parts are estimated to
153
Sales (100 million yen)
Fine ceramics production
(including functional ceramics)
AlB2 added amount (mass %, 2%C was added.)
Eu2+ solid-solution sialon
Excitation
Illumination
Wavelength
Year
Market scale by structural material
(Total: 116.5 billion yen in 2003)
Other
Aluminum
nitride
Silicon
carbide
Silicon
nitride
Alumina
Zirconia
Shipment by structural materials
(Total: 23 billion yen in 2004)
Other
Catalytic
BN tools
carriers
Diamond
tools
Heat-resistant
materials
Tools
Wear-resistant and
corrosion-resistant materials
Fig. 1 Fine ceramics market trends (Source: References4,5)).
As the main demand for non-oxide engineering ceramics
in Japanese industry is for precision equipment, semiconductor-related equipment, environment and energy, and
optoelectronics, NIMS has been proceeding with materials
development accordingly.
For application to semiconductor-related equipment,
carbides require an easy densification process for obtaining
large ceramics and cost reduction. Therefore, NIMS devel154
Sintering
density
Strength
come from Japan. Aluminum nitride (AlN), a material of
high thermal conductivity, was developed by enhanced
technologies of synthesizing and sintering a high-purity
powder, and they were applied to heat sinks for power
devices. B4C has been used for abrasives. Since the normalpressure sintering process was developed, B 4C is now
attracting attention as a lightweight and very hard material.
Other metallic borides and nitrides (TiC, WC, TiN, TiB2,
and ZrB2) and their composites (B4C-TiB2, TiB2-CoB6, and
TiB2-W2B5) have been well researched as materials having
high melting points and great hardness.
Figure 1 shows the market trends in fine ceramics. In
Japan, “fine ceramics” means refined functional and structural ceramics. Carbides, nitrides, and borides hold important positions among fine ceramics.
Sintering temperature (˚C)
Fig. 2 Recent major achievements by NIMS.
Upper: Low-temperature SiC sintering process.
Lower: Sialon phosphor.
oped a low-cost easy sintering process for SiC ceramics.
The Al-B-C phase relation was clarified and the high-temperature liquid phase Al8B4C7 was identified. By using this
phase as a sintering additive, NIMS developed a technology for complete densification at a temperature 200 to
250˚C lower than before. Materials having high specific
elasticity, specific strength, and resistance applicable to
semiconductor-related equipment will be supplied for
wafer tables (Fig. 2, upper). By using high-purity organic
matter as the starting raw materials, an SiC powder of
ultrahigh purity was developed through sol-gel precursor
synthesis and organic-inorganic conversion. The powder
provides materials for high-purity reaction furnaces essential in the semiconductor industry. Meanwhile, the effect of
material transportation activated by phase transition and
metallic solution was discovered and applied to grain
growth in manufacturing a porous SiC material, which can
be used for catalytic carriers for environmental purification.
Regarding nitrides, a Lu2O3 added Si3N4 ceramic which
suffers no loss of strength at 1400 to 1500˚C was manufactured for gas turbines in the New Century Heat-resistant
Materials Project. We should also note the discovery of a
new sialon phosphor. Sialon easily dissolves other metallic
elements. By dissolving optically active rare earth ions in
sialon, blue, green, yellow, and red phosphor can be
obtained (Fig. 2, lower). White LEDs were successfully
produced by combining the yellow phosphor with the blue
LED, and so application to white backlighting is greatly
expected. The sialon phosphor, which are thermally stable,
are also promising for next-generation plasma displays.
Boron nitrides (BN) were mentioned in the section on
“Carbons.” Recently, a new material having excellent electron emission performance was found by laser plasma
CVD. CVD under laser emission grew a new needle-like
material, 5H-BN. The electron emission characteristic was
found to be 1,000 times or greater than that of nanotube.
This material can be applied to RGB displays and DVD
recording devices in combination with phosphor.
The development of single-crystal metallic borides as
electron emission materials was started by the National
Institute for Research in Inorganic Materials (present:
Advanced Materials Laboratory of NIMS) a long time ago.
Recently, NIMS succeeded in synthesizing high-quality
single-crystal ZrB2. Since the coefficient of thermal expansion is compatible, ZrB2 was found to be the substrate of
GaN-LED. All of the above materials were developed by
NIMS and have huge potential markets as electronic and
optical materials.
4. Key research by organizations other than NIMS and
future outlook
SiC porous honeycomb materials are now used for
diesel engine particle filters (DPF). In Europe, diesel vehicles are becoming popular as privately-owned cars, but regulations on graphite particulates are being tightened
accordingly. The particulates are removed by filtering and
burning with SiC porous honeycomb filter already mounted
in automobiles. The materials will also have to comply
with tougher exhaust gas regulations but demand for them
will grow.
Single-crystal SiC is now undergoing rapid development
for semiconductor power devices. Since SiC is a semiconductor having a wide band gap, single-crystal SiC can be
used for power devices of high frequencies and withstanding voltages and large currents. The material can be applied
widely from power generators to automobiles and motor
inverters. Since there are still cost and quality problems to
be solved, single-crystal SiC has not yet entered practical
use but is still an important material as a partial substitute
for Si semiconductor.6)
Sm-Fe-N, Fe-N magnetic substance, and (In)GaN semiconductor, and other nitride electronic materials are
promising. The use of GaN blue LEDs is growing quickly.7) In addition, boride MgB2 superconducting material is
attracting attention. Intensive research is now in progress
on both materials toward practical use.
The trends in carbide, nitride, and boride ceramics will
depend on peripheral materials for semiconductor manufacturing, environmental materials, and optical and electronic
materials.
References
1) Research and development of basic technology for future industry,
“Report on the Development of Elemental Technologies for
Petroleum Gasifying Ceramics Turbine and Composite Fine
Ceramics Technology”, Shinko Research Co. (2000).
2) Joint research consortium of synergy ceramics, “Synergy Ceramics
II,” Gihodo Publishing Co. (2004).
3) NEDO (New Energy and Industrial Technology Development
Organization), “300kW Class Ceramic Gas Turbine Research
Results”, (1999).
4) Ceramics Japan, Bull. Ceram, Soc. Japan, 39, 706 (2004).
5) FC Report, 23, 44 (2004).
6) High-temperature Ceramic Materials 124th Committee of Japan
Society for the Promotion of Science: H. Suzuki, T. Izeki, H.
Tanaka, “New Materials of SiC Ceramics”, Uchida Rokakuho Co.
(2001).
7) TIC Editing Department, “Nitride Ceramics for New Age”, TIC
Co., 465 (2001).
155
Section 2. Oxides - Alumina, Zirconia, and Magnesia
Keijiro Hiraga
Fine Grained Refractory Materials Group, Materials Engineering Laboratory, NIMS
Noriko Saito
Electroceramics Group, Advanced Materials Laboratory, NIMS
1. Introduction
The materials listed in the title are typical fine ceramics
that are widely used for various machines, chemical plants,
that energy equipment such as generators and engines
thanks to their heat resistance, corrosion resistance, high
hardness and strength. These materials may thus be regarded as “matured” materials. These oxides, however, are still
expected to have many potential functions that may be
exploited through controlling the geometry, size, distribution, localized structures and chemistry of grain boundaries, inter- and intra-grain particles and pores. To clarify
research trends quantitatively, the titles, abstracts and keywords of papers published between 1991 and 2004 were
searched in an academic paper database (SCI Expanded).
Of about 45,000 papers concerned with alumina, zirconia
and/or magnesia, 95% or more were written in English.
Examination of the searched papers revealed the following
research trends on these materials.
2. Research trends
Figure 1 shows the annual number of papers on alumina
(Al 2O 3), zirconia (ZrO 2), and/or magnesia (MgO). The
number of papers increases every year, indicating that these
materials are potential research subjects. In 2004, the total
number of papers on the materials became more than double the number in 1991. Most papers concern Al2O3 that
has often been regarded as the most matured material. The
ratio of total paper number is about 68, 29 and 3 for Al2O3,
ZrO 2 and MgO, and this ratio almost holds true every
searched year.
Figure 2 shows the annual number of papers on typical
research subjects for Al2O3, ZrO2, and MgO (black line in
Figure 1). Although the data do not distinguish these materials, the ratio of the paper number was similar to that noted
above. The main subjects are catalysts (catalytic functions
and carriers), syntheses (powder processing, molding, and
sintering), composite materials (fabrication techniques and
properties), coating (techniques and characteristics), energy
(fuel cells and nuclear power plants) and biomaterials (syntheses and characteristics).
Figure 3 shows the annual number of papers published
from some selected countries. Papers from the US, Europe
Alumina
Zirconia
Magnesia
Year
Fig. 1 Annual change in the number of papers on alumina, magnesia,
zirconia, and magnesia.
156
Catalyst
Total
Synthesis
Composite
materials
Coating
Energies
Organisms and bio
Year
Fig. 2 Change in research themes on alumina, zirconia, and magnesia.
USA
Japan
China
Korea
Europe 2
Russia
Syntheses
processes
Porous
materials
Multilayer and
orientation
Year
Year
USA
Europe 1
Japan
Europe 2
Korea
Russia
Number of papers (by country)
China
Year
Fig. 5 Number of papers on typical research themes in the nano-area.
Nano area
(By country)
Europe
Number of papers
Fig. 3 Number of papers on alumina, zirconia, and magnesia by country.
Nano area (Total)
Composite
materials
Nano area
Number of papers
Europe 1
Total
Number of papers (By country)
China
USA
Japan
Korea
Russia
Year
Fig. 4 Number of papers in the nano area by country.
Fig. 6 Number of research activities in the nano-area by country.
1 (Germany, France and the UK) and Japan account for the
majority. The total paper number for other EU countries
(noted as Europe 2 for Italy, Spain, Austria, Holland, Sweden, etc.) is about 50% of the number of Japan. Papers
from Russia (including Ukraine) gradually increases, but
the total number is about one-fifth the number of the United States. Since 2000, the paper number of the US, Japan,
and Europe tended to saturate, whereas the paper number
of China increased quickly, and caught up with the number
of the United States in 2004. A rapid increase from 2000
also appears in Korea.
Of the 45,000 searched papers, about 10% (4,480) of
papers relate to the nanostructure area that includes raw
materials, syntheses, characterization and properties. The
fraction of this area increased quickly from 1% in 1991 to
about 10% in 2000 and to about 20% in 2004, indicating a
shift to nanostructure-oriented subjects. As shown in Figure
4, this tendency appears commonly in all countries examined. In China and Korea, the papers of this area have also
increased drastically since 2000, and the paper number of
China exceeded the number of the US, Europe 1 or Japan.
Figure 5 shows the annual change in typical topics
appearing in the 4,480 papers relating to the nanostructure
area. Most papers focus on the structural characterization
and property evaluation of nanocomposites, porous materials and multilayered or oriented materials and on the synthesizing processes (powder synthesis, molding and sintering) of these materials. The number of papers in this field is
increasing every year and this tendency has strengthened
particularly since 2000 for composites, porous materials
and synthesizing processes. As shown in Figure 6, the
number of papers published from Europe (the sum of
Europe 1 and Europe 2) is the greatest, and the number of
the United States and Japan follows the former. As shown
in Figures 3 and 4, papers from China and Korea increased
quickly since around 2000 and reached a level similar to
the United States and Japan in 2004.
Figure 7 shows the annual number of papers concerned
with basic research on the nanostructure area. Main subjects are the experimental analysis of nanostructures, theoretical evaluations of stable atomic sites and chemical
bonding using molecular dynamics and molecular orbital
calculations, and the relationships between nanostructures
and electric, magnetic, thermal and mechanical properties.
Although the number of papers is less than one-third of the
number given in Figure 5, the annually increasing number
suggests strongly that research in this field is essential for
exploiting new functions. Figure 8 shows the annual num157
Nanostructure
and
characteristics
Structure and
strength, fracture
Structure analysis and
calculation
Number of papers
Number of papers
Nanostructure
Structure and
physical characteristics
Superelasticity
Nano-multilayer
and orientation
Electric conductivity,
elasticity,
and strength
Structure, electric conductivity,
and thermal expansion
Year
Year
Fig. 7 Annual change in the number of fundamental papers in the
nanostructure area.
Fig. 8 Annual change in the number of papers on research themes, in an
incubation stage.
ber of papers relating to research in an incubation stage.
The subjects concern multifunctions, namely the combination of such properties as electric conductivity, elasticity,
thermal expansion and strength. The subjects also concern
multilayered or oriented structures and superelasticity.
Europe, the US and Japan have been ahead of the research
fields shown in Figures 7 and 8: these countries have published 90% or more of the papers.
In materials relating to Al2O3, ZrO2 or MgO, new functions or multifunctions associated with nanostructures have
mainly been discovered and developed in Europe, the US
and Japan. A typical example of such research in Japan is
CuAlO2: the first success in developing a p-type semiconductor in transparent oxides.1) This is based on the discovery that 12CaO•7Al2O3 (C12A7) has a nanobasket structure
that can include various ions.2) For requirements for multifunctions, typical examples are found in the development
of a transparent MgO film for plasma display electrodes
(requiring translucency, insulation, and durability under
discharge phenomenon) and a transparent Mg2SiO4 substrate for microwave (requiring high Q value and low
dielectric constant). Another example is transparent YAG
polycrystals synthesized by using rare-earth elements,3) the
transparency of which enables the polycrystals to be used
for high-energy lasers and arc tubes.
proceed together.
Under such circumstances, NIMS has developed new
functional materials and synthesizing techniques: the synthesis of MgO, YAG, Y2O3, ZnO, TiO2,4) Mg2SiO4, CaZrO3
and other microparticles from water solutions, a new
process using pulse-modulated RF thermal plasma generation, the synthesis of TiO2 nanoparticles by controlling the
saturation of gas phases,5) the synthesis of highly oriented
oxide thin films using symmetric control of a plasma-magnetic field, colloidal processing that can control the crystal
orientation and lamination using an external field6) and the
synthesis and modification of nanometer-sized porous
structures using anode oxidization.7) With the support of
the synthesizing techniques and the analysis of nanometersized structures, NIMS has also synthesized transparent
polycrystals of Mg2SiO4, YAG3), Y2O3,8) and MgO, substantially superplastic alumina and apatite and high-strainrate superplastic composites.9) In the next half decade,
NIMS will extend the fundamentals relating to these
research fields and will develop new processing techniques
and multifunctional materials using electric and magnetic
fields, thermal plasma, anode oxidation, molecular mixing
and superplasticity.
4. Conclusion
3. Future outlook and research by NIMS
The searched results described above indicate the importance of designing and controlling the nanometer-sized
structures of grains, grain boundaries, inter- and intra-grain
phases and pores for exploiting new functions and multifunctions in Al2O3, ZrO2, MgO and related complex oxides.
This tendency should become stronger in the near future.
We should also note that countries achieving success in this
research field have simultaneously conducting the basic
research shown in Figure 7: analysis, characterization and
theoretical calculations of nanometer-sized structures and
chemistry, structure–property relationships and new synthesizing techniques. This situation indicates that the development of new functions and basic research are linked and
158
Al2O3, ZrO2, and MgO and related complex oxides have
extensively been studied in the last decade, since these
oxides have been expected to possess many potential functions. To exploit new functions and optimize the combinations of the functions, further research is necessary on the
control of nanostructures, theoretical calculations of
nanometer-sized local structures and chemistry and the
nanostructure-property relationships. The US, Europe and
Japan have been ahead of this research field and are expected to lead the research. NIMS will extend the ability for
analyzing and controlling nanometer-sized local structures
and chemistry in order to develop new functional materials
for the next generation.
References
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4) D. Li, H. Haneda, N. Ohashi and S. Hishita, Catalysis Today, 95,
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(2001).
159
Section 2. Oxides - 3d Transition Metal Oxides
Hideo Kimura
Piezo Crystals Group, Materials Engineering Laboratory, NIMS
Xiaobing Ren
Materials Physics Group, Materials Engineering Laboratory, NIMS
Shunichi Hishita
Electroceramics Group, Advanced Materials Laboratory, NIMS
1. Introduction
“3d transition metals” generally refer to the nine elements from Sc to Cu. However, in view of its importance
Zn is included here, making 10 elements in total.1)
As representative correlated electron systems, the 3d
transition metal oxides show drastic changes in magnetic
and electrical properties with temperature, lattice constant,
carrier density and so on. Microscopically, the double
exchange interaction that produces a colossal magnetoresistance effect (CMR effect) and the superexchange interaction that produces ferromagnetism or antiferromagnetism
play important roles. Spins, charges, and lattices are closely
related in the 3d transition metal oxides, and ferromagnetism, superconduction, optical response, and other properties appear to have a close relation.
This section describes the recent trends (2000 to 2004)
concerning the oxides of individual elements.
Optics
Photocatalyst
Solar battery
Other optical functions
Catalyst
Ferroelectrics
Dielectrics
Piezoelectrics
Sensor
Electrode
Electrochemical
Semiconductor
Other electronic characteristics
Other
2. Trends within and outside Japan
2.1 Scandium oxide
Since scandium has the smallest ion radius among the
homologous rare earth elements, it is often used in studies
for verifying the size effect of added rare earth elements.
Furthermore, due to its comparatively high permittivity (ca.
13), thermal stability with Si, and large band gap (> 6 eV),
the application of scandium oxide for gate insulating films
and transparent films2) is attracting attention.
2.2 Titanium oxide
Titanium oxide is actively being studied as one of the
most important materials for the global effort to create a
sustainable society and clean environment. Research on
titanium oxide is especially active for photocatalysts and
solar batteries that use light energy. Furthermore, titanate
compounds such as perovskite are the subject of many
studies for application to piezoelectric and ferromagnetic
160
Fig. 1 Research fields of papers on titanium oxide.
Breakdown of 7,422 papers published from 2000 to 2004.
materials. These trends are evident also in the number of
papers published. More than 8,000 papers were published
on titanium oxide in the 5-year period from 2000 to 2004.
Of them, more than 2,500 papers were on optical functions,
such as photocatalysts and solar batteries. Nearly 2,000
papers were on electrical characteristics, such as ferroelectrics, sensors, and electrode materials. There is also
much research on titanium oxide as a (thermo)catalytic
material. Figure 1 shows the details.
2.3 Vanadium oxide
Vanadium oxide has been researched traditionally as a
catalytic material, and now it is attracting attention for
application to sensors and electrode materials.
2.4 Chromium oxide
Chromium oxide is under research not only as an anticorrosive material, fuel cell electrode material, and catalytic
material but also as a secondary battery electrode material.
2.5 Manganese oxide
Since manganate shows a colossal magnetoresistance,
many studies are underway on its electro-magnetism. In the
5-year period from 2000 to 2004, over 1,100 papers were
published on manganese oxide. The number of papers on
magnetism is the greatest with over 300 papers, followed
by more than 150 papers on the electrochemical characteristics for electrodes, etc., and more than 120 papers on catalytic properties.
2.6 Iron oxide
Magnetism is a popular theme of research these days.
More than 2,100 papers were published on iron oxide in the
5-year period from 2000 to 2004, of which over 600 were
on magnetism. In particular, papers on superparamagnetism
accounted for the greatest part of about 1/4. There were
also about 200 papers on catalysts, of which about 10%
concerned photocatalysts. Figure 2 shows the details. From
the viewpoint of structural character, more than one-quarter
of the papers were about nanostructures.
Magnetism
Ferromagnetism
Ferrimagnetism
Superparamagnetism
Paramagnetism
Spin
Phase transition
Catalyst
Photocatalyst
Optical functions
Electronic characteristics
Other
lished from 2000 to 2004, over one-quarter were on superconduction, followed by 20% on electrical and magnetic
characteristics and 10% on catalytic characteristics.
2.10 Zinc oxide
Among more than 3,800 papers published on zinc oxide
from 2000 to 2004, the most popular theme was catalytic
effect (about 6%), followed by varistor (4%), luminescence
(4%), photocatalyst (2%), and sensor (1%). As we can see,
the target characteristics vary widely. From the viewpoint
of specimen shapes, over 30% of the papers were on thin
films, followed by 20% on nanostructures. This indicates
that function manifestation by shape control is the focus of
zinc oxide research.
3. Research by NIMS
Regarding scandium oxide, NIMS is attempting to synthesize a nanopowder for transparent sintered compacts by
solution synthesis.2)
Regarding titanium oxide, NIMS is creating nanostructures such as nanotube,4) nanosheet,5) and nanorod6) and
researching their characteristics. Visible-light driven photocatalysts7) are also being examined. Regarding titanate,
NIMS has proposed a new piezoelectric mechanism based
on the nano-symmetry of point defects and has demonstrated it on BaTiO3.8) Figure 3 shows its outline. A ferromagnetic material, Pb-free titanate compound,9) is also being
studied.
As double oxide materials, V, Cr, and Mn oxides have
been actively researched for lithium secondary battery electrode materials.10-12) Manganese oxide is being studied for
creating new nanostructures13) and for creating proteincomposite films.14)
Iron oxide is being studied for synthesizing nanocrystals
having giant coercive force15) and photocatalytic nanorod
arrays.16)
Regarding cobalt, the NIMS discovery of a hydrated
cobalt oxide superconductor 3) is greatly contributing to
superconductor research. Composite perovskite oxide with
Nb17) is also under research as a visible-light driven photo-
2.7 Cobalt oxide
Cobalt oxide is mainly researched as a magnet, electrode, and catalyst. These days, layered cobalt oxide compound is attracting attention as a non-Cu oxide superconducting material.3)
2.8 Nickel oxide
Nickel oxide is mainly researched as a magnetic material, electrode material, and catalytic material. In particular,
research on nanostructures for electrodes is noteworthy.
2.9 Copper oxide
Copper oxide has been researched as a superconducting
material in many projects. Of more than 1,700 papers pub-
Field-induced strain ε (%)
Fig. 2 Research fields of papers on iron oxide .
Breakdown of 2,131 papers published from 2000 to 2004.
1st cycle
2nd cycle
th
4 cycle
Aged Fe-BaTiO3 single crystal
PZN-PT
single crystal
PZT
ceramics
Electric field (V/mm)
Fig. 3 Giant electro-strain by nano-symmetry property of point defects.
161
catalyst.
Regarding nickel oxide, nanoparticles embedded in an
insulator (silica)18) are being synthesized.
Copper oxide will be described in a separate section
because many superconducting materials have been created.
Zinc oxide is now the subject of intensive research by
NIMS. From the viewpoint of functions, NIMS is researching the electronic,19) catalytic,20) and luminescence characteristics. 21) From the viewpoint of synthesis, NIMS is
researching the MBE synthesis of thin films,22) self-organization of a zinc oxide mono-particulate film (Figure 4) by
the solution method, and a patterning technique.23) For
details on zinc oxide research, refer to the document.24)
Fig. 4 Zinc oxide mono-particulate film.
4. Conclusion
Because of their various physical and chemical properties, the 3d transition metal oxides are the subject of intense
research worldwide as materials for environmental purification, low environmental load, energy, information &
communications, and electronic & optical materials. Under
these circumstances, NIMS is developing new synthesizing
techniques for promoting new applications and clarifying
basic material properties with enhanced functions and
exploited new characteristics.
162
References
1) Dictionary of Physics and Chemistry (Third enlarged edition),
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(2004).
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Dilanian and T. Sasaki, Nature, 422, 53 (2003).
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www.nims.go.jp/piezo/
10) K. Ozawa, M. Eguchi and Y. Sakka, J. Europ. Ceram. Soc., 24, 405
(2003).
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and M. Watanabe, J. Electrochem. Soc., 150, A157 (2003).
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Rusling, Langmuir, 16, 8850 (2000).
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(2005).
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Chem. Mater., 13, 233 (2001).
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18) H. Amekura, N. Umeda, Y. Takeda, J. Lu and N. Kishimoto, Appl.
Phys. Lett., 85, 1015 (2004).
19) N. Ohashi, K. Kataoka, T. Ohgaki, T. Miyagi, H. Haneda and K.
Morinaga, Appl. Phys. Lett., 83, 4857 (2003).
20) D. Li, H. Haneda, N. Ohashi, S. Hishita and Y. Yoshikawa, Catal.
Today, 93-95, 895 (2004).
21) I. Sakaguchi, S. Hishita and H. Haneda, Appl. Surf. Sci., 237, 358
(2004).
22) T. Ohgaki, N. Ohashi, H. Kakemoto, S. Wada, Y. Adachi, H.
Haneda and T. Tsurumi, J. Appl. Phys., 93, 1961 (2003).
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1461 (2001).
24) ISSN 1347-3212. AML/NIMS Reports, No. 8, 2003.
Section 2. Oxides - Niobate, Tantalate, and Rare Earth Oxide
Kenji Kitamura
Opto-Single Crystal Group, Advanced Materials Laboratory, NIMS
1. Introduction
The National Institute for Materials Science (NIMS) is
currently focusing on lithium niobate (LiNbO3:LN) and
lithium tantalate (LiTaO3:LT) which are related to recent
information & communications and optical technologies.
An octahedral structure, composed of six oxygen ions with
a d0 ion such as Nb (4d transition metal) or Ta (5d transition metal) at the center, tends to become asymmetric due
to orbital hybridization. This hybridized binding energy
becomes low as the octahedron is deformed (low symmetry). When the temperature goes down, therefore, deformation produces a ferroelectric phase having no center of
symmetry and a spontaneous polarization.
Ferroelectric materials were first applied mainly to surface acoustic wave elements as electronic ceramics or
piezoelectric elements, but full-scale development is now
targeting applying ferroelectric thin films to memory elements and single crystals to optical devices. Applications
are mostly in the emerging fields of communication and
optical technologies where Japan is again taking the lead in
production.
The main application of rare earth oxide is crystals for
solid lasers. In 1960, red pulses having a wavelength of
694.3 nm were oscillated successfully with a ruby Crystal.
Up to 1965, laser oscillations with ions of various rare
earth elements (Nd, Pr, Eu, Ho, Er, Tm, Yb, and Gd) were
reported, since when almost all candidate materials seem to
have appeared. The development of transparent ceramics
for solid state laser materials is now attracting global attention, and NIMS was closely involved at the outset of development.
Due to lack of space, this section focuses on the trends
in research on LN and LT single crystals and ceramics laser
materials.
2. Research trends
2.1 Research trends in LN and LT
Lithium niobate (LN) and lithium tantalate (LT) are typical ferroelectric single crystal materials. According to a
report by Matthias and Remeika in 1949,1) both have a
pseudo-ilmenite structure and show a trigonal ferroelectric
phase of space group R3c with no center of symmetry at
room temperature. The successful growth of large single
crystals by Ballman et al. using the Czochralski (CZ)
method2) quickly clarified the properties. There are not
many oxide single crystals that have such excellent piezoelectric, electro-optical, and nonlinear optical characteristics and that have been researched in detail in so many
fields.
In general, many ferroelectric crystals show complicated
phase transitions and it is considered difficult to grow large
and homogenous single crystals. In contrast, LN and LT
are considered to be stable materials because they have
only 180-degree polarization and phase transition points at
high temperature. Therefore, research has concentrated on
producing larger and more homogenous crystals from the
materials. During the enhancement of crystal homogeneity
by the CZ method, the phase diagrams of LN and LT were
researched in detail and the [Li]/[Nb] and [Li]/[Ta] ratios
of these crystals were found to show wide ranges of composition (nonstoichiometry) at high temperature.3-5)
At high temperature, the nonstoichiometry of LN and
LT extends mainly to the Nb or Ta component excess side
but not to the Li component excess side. Therefore, the
congruent composition is on the Nb or Ta component
excess side and the Li:Nb or Li:Ta ratio is about 48.5:51.5.
The ordinary CZ method cannot produce homogenous single crystals without a melt of congruent composition. Since
growth by Ballman, large crystals have always had congruent compositions. This indicates that the composition is
determined by restrictions on growth. In the congruent
composition, however, as much as a few percent of Nb or
Ta excess ions substitute Li ions (nonstoichiometric defect)
and produce vacancies of several percent at the sites of Li
ions.6)
To grow and evaluate stoichiometric LN and LT (SLN
and SLT; CLN and CLT for congruent LN and LT) by controlling the nonstoichimetric defect density, the improvements of various characteristics have been reported.7-10)
Once again, NIMS played a major role in this work.
with LN in the title (source: Web of Science). Since around
1975, more than 100 papers have been published annually.
The main application in the 1980s was optical elements,
such as optical modulators, optical integrated elements, and
holograms, and the number gradually increased until 1990.
From 1990 to 1992, the number of papers started
163
Number of papers
Number of papers
Year
Year
Fig. 1 Number of papers with lithium niobate in the title, by year (Red:
Total, Green: Papers on non-stoichiometric defects).
Fig. 2 Number of papers with lithium tantalite in the title, by year
(Green: Total, Blue: Nonstoichiometric defects).
increasing quickly, partly because the digital hologram
became available as a means of storing information using
LN and attracted attention. The hologram was mainly used
to store 3D images and execute information processing
operations but was extended to the digital hologram for
storing digital information and triggered a surge in interest.
In 1990, it was reported that the inversion of polarization
can be patterned by an electric field. This enabled application to wavelength conversion and optical deflection elements and fueled further research. Application to communication devices also increased quickly as investment in the
IT revolution boomed.
In 1992, the National Institute for Research in Inorganic
Materials (the present NIMS) announced the aforementioned problem of nonstoichiometric defect and the single
crystal growth method for controlling the problem. The
green columns in Figure 1 indicate the transition in the
number of papers with stoichiometry in the title. Papers
dealing with stoichiometry began to appear in 1992 and are
now increasing.
with LT in the title. Up to 1990, the application of LT to
optical elements had been limited mainly to collector sensors and some manufacturers’ SAW filters for TV and
video. Since 1990, however, the number of papers has been
increasing quickly because the application of LT to SW filters of cellular elements boosted the demand, and wavelength conversion by the inversion of polarization began to
attract attention.
The blue columns in Figure 2 indicate the number of
papers on nonstoichiometry. NIMS has also been publishing papers after starting LN research later. Accompanying
the increase in the total number of papers, papers in this
field started increasing quickly. Most of these papers dealt
with application to wavelength conversion elements by the
periodic inversion of polarization, and this field may grow
dramatically in future.
2.2 Research trends in ceramics laser
As already mentioned, crystalline materials for solid
lasers were all identified at a rather early stage. However,
the transition in laser use or system to high output, semiconductor excitation, and microchip processing is changing
the materials of interest. Nd-doped YAG(Y3Al5O12) laser is
still a dominant solid laser but the density to which activated Nd ions can be doped is limited, and so Nd-doped YVO4
was studied. Since Nd-doped YVO4 has a large coefficient
of absorption and a large cross section of induced emission,
it was developed actively and is already marketed as a
microchip or compact solid laser material.11,12) However,
YVO 4 has low thermal conductivity, low mechanical
strength, and short life of fluorescence. The compound also
has the disadvantage that it is difficult to grow large single
crystals of high quality.
There has also been research on the application of transparent ceramics to laser host systems, which was initiated
by the National Institute for Research in Inorganic Materials (the present NIMS).
Number of papers
Year
Fig. 3 Number of papers with ceramic laser in the title.
164
YAG ceramics produced by the sintering method allow
high doping of Nd into ceramics to achieve a large absorption characteristic. Since the dispersion of grain boundaries
can be almost controlled and the characteristics are more
excellent than those of the conventional microcrystal, this
material is ideal for microchip lasers.
with ceramics laser in the title. The number quickly started
increasing in 1990. Materials range widely from YAG, and
future developments should be monitored. The application
to laser is at a very high level. Once the technology has
been established, single crystals will be substituted in many
fields.
References
2) A. A. Ballman, J. Am. Ceram. Soc., 48, 112 (1965).
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Growth, 22, 230 (1974).
5) S. Miyazawa and H. Iwasaki, J. Crystal Growth, 10, 276 (1971).
6) N. Iyi, K. Kitamura, F. Izumi, S. Kimura and J. K. Yamamoto, J.
Solid State Chem., 101, 340 (1992).
7) K. Kitamura, Y. Furukawa, Y. Ji, M. Zgonik, C. Medrano, G.
Montemezzani and P. Guenter, J. Appl. Phys., 82, 1006 (1997).
8) T. Fujiwara, M. Takahashi, M. Ohama, A. J. Ikushima, Y.
Furukawa and K. Kitamura, Electron. Lett., 35, 499 (1999).
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Phys. Lett., 72, 1981 (1998).
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51, 1885 (1987).
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1955 (1991).
1) B. T. Matthias and J. P. Remeika, Phys. Rev., 76, 1886 (1949).
165
Section 3. Glass
Satoru Inoue
Functional Glass Group, Advanced Materials Laboratory, NIMS
1. Introduction
Glass materials are used widely for both traditional
wares and products for daily living, such as window panes,
bottles, and tableware, and there are also functional glass
materials which are used for optical equipment lenses,
computer hard disks, and computer displays, for example.
In particular, a type of glass now the subject of much
research is a functional glass called nanoglass, which can
be made to offer new functions by high-grade tissue control.
Figure 1 shows the basic concept of nanoglass. The first
generation is ordinary functional glass where atomic or
ionic active spots are dispersed in the glass matrix at random. Fluorescent emission materials belong to this group.
Research is conducted by varying glass compositions to
search for new compositions having useful properties. The
second generation is nanoglass where particulate active
points composed of several atoms or ions are dispersed in
the glass matrix at random. The glass properties are dominant. Semiconductor particulate dispersed glass, which is
expected to be used as a nonlinear optical material, belongs
to this group. The third generation is nanoglass where the
active spots are somewhat larger and are dispersed regularly in the glass matrix. With this type, crystal properties
begin to appear. This glass manifests the functions of photonics crystals for nonlinear optical materials, and so intensive global research is underway on the third generation of
nanoglass. Chemically, the third-generation state is glass
1st generation
2nd generation
3rd generation
Active spot size
Submicron to
several nm
1 to 10 nm
10 to 100 nm
Dispersed status
Uniform dispersion
Particulate aggregate dispersion
Nanoglass
Fig. 1 Basic concept of nanoglass.
166
High-degree periodic
structure array
Photonic crystals
but is about to show crystal-equivalent properties. About
18 years ago, glass researchers proposed the concepts of
amostal,1) conjugate glass,1) and polling technology2) to produce glass states of the second and third generations. The
current nanoglass is based on these ideas and research is
ongoing to achieve higher precision and functionality.
2. Research trends
This section outlines the main functional glass and nanoglass fabrication technologies now being researched worldwide.
2.1 Vapor phase synthesis3)
There are two main gas synthesis processes. The chemical vapor deposition (CVD) process causes a chemical
reaction between raw material gases and deposits the reactant on a substrate. The sputtering process makes ions
impinge upon the same material (target) as the object substance to drive out the target ions and deposit them on the
substrate. To form active spots or nanostructures, materials
are repetitively deposited by masking or self-cloning. This
process has excellent precision and stability.
2.2 Laser-induced structuring process4)
A femtosecond laser beam is narrowed through a lens
into glass to induce a structural change in the irradiated
region and to form a region having a high refractive index.
Not only spots but also lines or optical waveguides can be
formed. This simple process has excellent controllability.
Unlike a nanosecond-order pulse laser beam, a femtosecond-order laser beam is known to cause a permanent structural change (induced structure) by irradiation into glass
where electron state changes of ions other than the heating
effect are involved. This laser is optimum for irradiation
because high-output irradiation hardly causes irradiation
damage called abrasion on the surface of materials. To
date, ion reduction and ionization of silver and other substances, and diffraction grating by forming an index pattern
have been achieved. The possible uses are high-density 3D
optical recording, micro illumination source, and micro diffraction grating.
2.3 Etching process5)
The etching process, which is used in photolithography
in semiconductor manufacturing, offers excellent precision
and stability. A glass film deposited by vapor phase synthesis is bored regularly by precision machining technology to
fabricate the world’s first practical photonic crystals. The
crystal atoms correspond to pneumatic pillars and the
matrix corresponds to glass. There is also a technique of
direct etching by abrasion using an electron beam or highoutput excimer laser beam and a technique of etching a
damaged region after irradiation by SOR-X-ray or highspeed accelerated baryon ion beam. Pores are used because
they are very effective for creating a difference in refractive index and the grain boundary can be finished very
neatly.
2.4 Anodic oxidization process6)
Figure 2 shows the formation process. A conductive film
is formed on a glass surface and then an aluminum thin
film is formed on the conductive film by evaporation or
sputtering. This unique process for fabricating functional
glass was developed by NIMS. Anode oxidization changes
an aluminum thin film into an amorphous-alumina porous
thin film of nanopores vertically arranged on the glass surface. The conductive film is an electrode to allow the anode
oxidization of the aluminum to the last. An oxide film on a
glass surface has an aluminum film (barrier layer) at the
bottom of pores which is thinner than the film on the side,
so the barrier layer can be eliminated completely by etching. However, this is not possible for a general anodic-oxidized film of aluminum. Since the self-organization process
is used, a nanometer-order porous tissue can be formed.
Pores of a wide diameter ranging from several to 1000 nm
An aluminum film is
deposited on the
glass plate covered
with a thin
conductive film.
Aluminum
Glass plate
Aluminum
oxide
Conductive
film
can be fabricated. Into the pores, a chemical compound or
metal can be entered by the sol-gel process or the electrodeposition process to add various functions to the nanotissue. By using the difference of solubility between the
amorphous alumina and the compound which enters the
pores, the alumina can be removed to form a nanorod or
nanotube array. This process is expected be used for photocatalysts using titanium dioxide, high-density magnetic
recording media using magnetic materials, and pseudophotonics crystals using dielectrics.
2.5 Crystallization process and phase splitting process
The crystallization process that deposits nanosize crystals in glass is used to manufacture transparent crystalline
glass. In general, two-stage heating is used for glass crystallization. Glass is heated first in the crystal nucleation
temperature area and then heated to a higher temperature to
grow a nucleus of deposition for adjusting the crystal size.
In one study, second harmonics were generated from nanoglass using regular crystal deposition7) by a laser beam trigger. Another study attempted to deposit crystals and manifest functions on a glass surface where deposition is easy.
Takahashi8) systematically fabricated transparent crystalline
glass by B 2O 3-GeO 2 or other glass formation systems,
found that ferromagnetic crystals are orientation-deposited,
and thus successfully generated second harmonics.
The phase splitting process9) uses the phenomenon of
liquid-liquid phase splitting that separates a liquid into two
(stable immiscible liquids) or the phenomenon of potential
phase splitting at the liquidus temperature. By the nucleation and growth mechanism, this process uses the phase
splitting area where phase splitting deposits droplets. A
homogenous melt is produced by heating beyond the phase
slitting limit called the immiscibility temperature, cooling
down to the immiscibility temperature area, and holding for
a specified time to allow phase splitting. Finally, the melt is
quickly cooled to produce phase-split grain dispersed nanoglass or nanoglass of the second generation. During quick
cooling, the melt may be expanded or compressed to flatten
the phase-split grains and give anisotropy to the properties.
This process can be applied to alkali-earth silicates, alkali-
Small pores are
bored in the glass
surface with the
progress of
electrolysis
Small pore
A thin film of
aluminum oxide
with nanometer-size
pores is formed.
High-speed
automatic weighing
Parallel melting
Quick cooling
and observation
Determination of glass forming area
Automatic
measurement
Determination of dependence of
properties on compositions
Synthesis
research
Through
small pore
Parallel synthesis
When the aluminum
oxide is oxidized
with an acid, the
pores are slightly
enlarged and reach
the conductive film.
Properties
research
High-speed specimen
fabrication and parallel
thermal treatment
Fig. 2 Formation of nanostructure on glass surface by anodic
oxidization.
Crystallization
judgment
Automatic optical
measurement
Determination of dependence
on thermal treatment
Fig. 3 Concept of combinatorial glass research system.
167
earth borates, iron silicates, and titanium silicates. A rareearth oxide, if added as the third component, is condensed
in the phase-split grains, so only the compositions of phasesplit grains can be varied with priority to manifest functions.
2.6 High-speed glass search
To search for new glasses by varying glass compositions, NIMS is pioneering a glass research system based on
the combinatorial techniques.10) This system can search for
new glasses more than 100 times faster than before. Figure
3 shows the concept of the system. Specimen synthesis and
properties measurement are processed at high speed by parallel operations to increase the speed of research. Comprehensive research will lead to the discovery of new functional glass.
3. Future outlook
The functional glass fabrication processes introduced
here have unique characteristics and no single process can
be said to be better; they are used according to the type of
glass to be developed. The vapor synthesis process, laserinduced structuring process, and etching process are suitable for regular 2D and 3D dispersions but are not good in
terms of productivity. The anodic oxidization process is
suitable for producing comparatively large nanoglass having a regular structure with high efficiency. The crystallization process using the deposition phenomenon and the
phase splitting method both offer excellent productivity but
are not good at regular crystal dispersion.
Materials research and development by the processes
introduced here will proceed in parallel and yield practical
functional glass reflecting the features of each process.
Combined research techniques will be developed and rolled
out to research systems at enterprises to accelerate the
development of new materials.
168
4. Conclusion
New glass materials will be actively developed by combining various synthesizing processes with combinatorial
research techniques. The demand for glass materials is
especially large in the fields of the environment, energy,
and information, and research in these fields will be promoted. Since the glass industry consumes large quantities
of energy, it is a matter of urgency to develop energy-saving production technologies for curtailing CO2 emissions.
With the enhancement of recycling technologies, research
and development on industrial glass manufacturing
processes will proceed based on new ideas.
References
1) H. Yamashita: “Materials and Devices of New Photonics Age” TIC,
p. 281 (2000).
2) For example: R. H. Stolen and H. W. K. Tom, Opt. Lett., 12, 585
(1987).
3) For example: S. Kawakami, T. Kawashima and T. Sato, Appl. Phys.
Lett., 74, 463 (1999).
4) K. Miura: “Materials and Devices of New Photonics Age” TIC, p.
284 (2000).
5) For example: M. E. Zoorob, M. D. B. Charlton, G. J. Parker and J.
J. Baumberg, M. C. Netti, Nature, 404, 740 (2000).
6) S. Inoue, S. Z. Chu, K. Wada, D. Li and H. Haneda, Sci. Technol.
Adv. Mater., 4, 269 (2003).
7) T. Honma, Y. Benino, T. Fujiwara, R. Sato and T. Komatsu, J.
Ceram. Soc. Japan, 110, 398 (2002).
8) Y. Takahashi, Y. Benino, T. Fujiwara and T. Komatsu, J. Appl.
Phys., 89, 5282 (2001).
9) S. Inoue, A. Makishima, H. Inoue, K. Soga, T. Konishi and T.
Asano, J. Non-Cryst. Solids, 247, 1 (1999).
10) S. Inoue, S. Todoroki, T. Konishi, T. Araki and T. Tsuchiya, Appl.
Surf. Sci., 223, 233 (2004).
Chapter 10. Composite Materials
Yutaka Kagawa
Composite Materials Group, Materials Engineering Laboratory, NIMS
Specific rigidity
Tensile strength [MPa]
By tracing back the history of R&D on composite materials, we see that the operating temperature has been going
up with the development of composite materials from rubbers to plastics, metals, and ceramics. In addition to
reviewing the history, this section describes the future of
R&D on composite materials focusing on materials characteristics. So far, composite materials have been researched
mainly in terms of mechanical properties because composite materials satisfy the requirements of lightweight and
high strength for aircraft and vehicles. Figure 1 shows the
relationship between specific strength and specific modulus
for main metals, ceramics, polymers, and composite materials. Composite materials are the only ones that can have
both characteristics.
Fiber reinforced plastics (FRP), which are the most
widely used polymer materials among composite materials,
are considered to have almost reached their highest performance. Figure 2 shows the relationship between the tensile
strength and tensile modulus of carbon fibers. There are
high-strength carbon fibers of 7000 MPa or greater tensile
strength and high-modulus carbon fibers of 900 GPa or
greater tensile modulus. However, for users, composite
materials require knowledge about how to use them, yet
their practical application range is expanding. There are
various problems that seem to have been solved but have
actually yet to be solved, such as interfacial debonding,
joint structure with different materials and its reliability,
and the assurance of environmental resistance to shock and
water.
Metal matrix composites have also been the subject of
much research, seeking materials that may have high specific modulus and can withstand the high operating temperature of a metal which is used as a matrix. Since applications are difficult to find, however, R&D is not so active.
Nevertheless, metal matrix composites have a low coefficient of thermal expansion that is not available with metalonly materials. Among ceramic matrix composites, particle-dispersed and whisker-dispersed ones could not achieve
a fracture toughness of 10 MPam1/2 or higher. Ceramic
matrix composites of a textile type woven from continuous
fibers are being studied not to enhance the strength but to
produce high-temperature materials having great fracture
resistance.
For all composite materials, it is comparatively easy to
understand the mechanisms of reinforcement and manifestation of functions, because more than 90% of the existing
phenomena can be understood based on past knowledge.
Macro-mechanical function design and non-mechanical
function design do not offer such great potential as new
materials will be constructed by extension from existing
Specific strength
Fig. 1 Relationship between specific rigidity and specific strength of
various materials.
Tensile modulus [GPa]
Fig. 2 Relationship between tensile strength and tensile modulus of
carbon fibers.
169
materials and composite guidelines.
2. Trends within and outside Japan
This section summarizes the recent important composite
technologies.
2.1 Concept of composite materials
Research on existing composite materials has intensified, and many reports outlining new composite materials
are being published. In particular, the term “composite
materials” now means nano-order composite and tissue
control, far beyond the conventional framework of materials. In Japan, no uniform concept has been established
because of the vertical organization of academic societies.
2.2 Metal matrix composites
About 30 years ago, metal matrix composites attracted
great attention as a reinforcing mechanism for overcoming
the problem of dislocations. Ceramic fibers and whiskers
were then developed in Japan, and various attempts were
made to use these new materials. However, the materials
failed to become popular except for particular special uses,
because these composite materials offered no advantages
above those of metallic materials. In the field of metal
matrix composites, it is hard to search for new materials.
Further research is necessary in the particular fields of low
thermal expansion and high modulus.
2.3 Polymer matrix composites
Figure 3 shows the demand (including prediction) for
carbon fibers, which are the developing type of reinforcing
fibers of FRP. Figure 3 (a) shows the demand by country
and (b) shows the demand by industry. As the space-race
took off in the latter half of the 1960s, carbon fibers began
to emerge, and Japan has an overwhelmingly share of this
field.
The fields of application of FRP having specific modulus and strength are continuing to expand. The ratio of FRP
in aircraft is growing, but neither the universities and
research institutes are developing the inspection technologies needed for companies to ensure the safety of practical
materials nor conducting research on optimum manufacturing processes. Although many researchers are examining
Intelligent Materials and Smart Technologies for FRP, the
basic concept has already been developed. In Japan, very
few researchers are conducting research of the Western
type where FRP is always being studied as an old yet new
subject whereas the majority of researchers are heading in
the same direction. This is another characteristic of domestic research on classic polymer composite materials.
In the world of polymers, nanocomposite materials are
also undergoing active research. Self-organization and
nanostructure are the themes of various research activities
but not beyond the materials level.
2.4 Ceramic matrix composites
Regarding materials dispersed with particles and ones
dispersed with whiskers, the first stage of research has been
completed. In particular, fiber-based materials are now
entering practical use because they have high fracture resistance that is not available with ceramic materials. However,
there are still new issues to be solved before composite
materials can be used in practice, such as surface composite
materials based on a new concept and environmental resistance coatings. Due to such delays, Japan may lag far
behind Europe and the US.
All papers published since 1985 in an academic paper
database (SCI Expanded) were searched for those containing both the keywords “nano” and “composite materials”.
Figure 4 summarizes the number of papers published every
year by country. The total number of papers started increasing in 1993 and has been increasing especially fast since
2000. The percentage of papers from Japan is 14%, the
greatest proportion after the United States and China. The
growth of China, which is faster than that of the United
States, is noteworthy. In terms of the number of papers,
Korea ranks high after France and Germany. Figure 5 classifies the contents of papers published in 2004 into poly-
Aeronautics and space
Japan
Europe
USA
(a) Demand by country
Fig. 3 Demand for carbon fibers.
170
Carbon fiber demand (tons)
Carbon fiber demand (tons)
Asia
Sports
General industry
(b) Demand by industry
mers, metals, and ceramics. Over 60% of the papers are on
polymer nanocomposite materials. The nanocomposite
materials of this type are attracting great attention because
they not only have enhanced mechanical characteristics but
manifest multiple function, including optical characteristics, electrical conductivity, thermal radiation, and attenuation characteristics.
The Composite Materials Group of NIMS, which is
involved in the field of nanocomposite materials, has started researching nanoparticle-dispersed polymer and ceramic
composite materials. Such nanocomposite materials are
being studied for composite materials that can not only be
downsized to the nano level but also produce peculiar
nanoeffects thanks to composite effects. Our group is
examining whether characteristics such as modulus, thermal expansion, electrical conductivity, and thermal conductance can be obtained beyond the conventional range of
macro-composite effects. Regarding the phenomenon of
interaction between light and electromagnetic waves,
deformation and fracture, we are studying whether unexpected nano-unique composite effects can be obtained. In
order to use nano-effects, we also started multiscaling by
biomimetics for hybridization using nanocomposite materials.
These procedures are being researched beyond the borders of polymers, metals, and ceramics. We have also started developing measurement and evaluation technologies
for the nanomaterials technologies. The concept of
nanocomposite materials has expanded widely in the last
few years and now includes even polymer materials composed of different molecular structures. In the field of conventional composite materials, however, we have not
achieved noteworthy R&D results, but in the field of
nanocomposite materials, we successfully manifested new
functions and obtained characteristics not available with
conventional composite technologies. For example, the
inclusion of clay, silica, or other nanoparticles was reported
to increase the modulus of polymer materials by 1.5 to 3
times. These days, composite materials dispersed with carbon nanotubes are also undergoing active research for very
peculiar mechanical characteristics and low densities.
However, these excellent characteristics and the mechanisms of nanocomposite effects have yet to be clarified.
Regarding polymer and ceramic composite materials
that are expected to be applied to a wide range of uses,
NIMS is working to secure the necessary human resources
and to extend the research fields. The first stage of personnel organization has been completed, and NIMS now plans
to initiate full-scale research on composite materials, making best use of the personnel belonging to the organization.
4. Future outlook
Composite materials are at a turning point in research.
Instead of the conventional handling by reinforcing materials, matrix, interface, and other parameters, the control and
design of microstructures of materials themselves and at
interfaces will become necessary, because new development can no longer be extended from conventional technologies. Great efforts are necessary for composite materials research by the nanostructural control of matrix and
interface and by positively employing the nano-order differences in the modulus and the coefficient of thermal
expansion. As a result, materials research is expected not
merely to downsize the current composite materials but
also to utilize nano-level interactions.
In addition to creating new materials, it is necessary to
solve the problems involving composite materials. For
example, the tasks of ensuring the quality and reliability of
composite materials and inspecting adhesive bonded joints
are addressed by know-how in practical application. The
recent advances in computer and electronic technologies
will enable different approaches even in similar research to
that in the past. As explained above, the following challenges are strongly demanded in composite materials
research:
(a) Seeking new effects of composites by positively using
nanomaterials technologies,
(b) Solving old but new important pending problems, such
Other
China
Total number
of papers
Japan
Germany
Fig. 4 Number of papers on nanocomposite materials.
Total number
USA
Metals
Total number
of papers:
2,542
Polymers
Ceramics
Fig. 5 Breakdown of papers on nanocomposite materials published in
2004.
171
as the development of testing and measuring technologies
by positively using recent advances in science and technology
From the viewpoints of i) Mechanical composite materials and ii) Non-mechanical composite materials, materials
research in the future is likely to consider the following.
i) Mechanical composite materials:
Composite materials offer the great feature that microfractures can be accumulated in composite materials, irrespective of the matrix type. The micro-damage of the current composite materials are fiber breaking, matrix cracking, and interfacial debonding but they are of the order of
tens of microns. As these micro-fractures accumulate, the
compliance increases, causing dimensional changes of the
materials. The recent materials technologies allow nanometer-order tissue control for metallic, ceramic, and polymer
materials. The positive employment of such nanotissue
control for composite materials is another subject to be
solved. Users of composite materials require a science and
technology review of the conventional know-how based
solutions to the subjects of reliability assurance and life
prediction.
ii) Non-mechanical composite materials:
Inclusion of fibers and particles can effectively enhance
the coefficient of thermal expansion. This phenomenon is
172
already used for many materials but not particularly for
composites. Theoretical analysis is now almost at the stage
of predicting structure-insensitive materials characteristics
from the volume fraction ratios of components. Because of
interface effects, electrical conductivity and thermal conductance are difficult to predict accurately but can be estimated roughly from the characteristics of components.
Regarding functional materials, members employing the
materials will be further downsized in future. In the fields
of micromachines, bio, and devices, for example, the materials themselves will inevitably be downsized to the micron
order, whereupon the conventional composite materials
may pose the problems of heterogeneity and anisotropy and
become inapplicable to these fields. Thus, there are high
expectations for nanometer-order composite technologies.
References
1) The Materials Selector on CD-ROM ver. 2.1, Norman A. Waterman
and Michael F. Ashby.
2) Report on “Growth Opportunities in Carbon Fiber Market 20042010”, published by E-Composites, Inc. (2004).
3) T. Sun and J. M. Garces, Adv. Mater., 14, 128 (2002).
4) On-line Database, Web of Science, Science Citation Index
Expanded (2005).
Chapter 11. Polymer Materials
Izumi Ichinose
Macromolecular Function Oxides Group, Advanced Materials Laboratory, NIMS
1. Introduction
In parallel with metallic and inorganic materials, polymer materials are playing an important role. As industrial
infrastructure materials, polymers are widely applied to
plastics, rubbers, adhesives, photoresists, separation membranes, gels, biomaterials, and so forth. If fibers, packaging
styrofoam, and paper are included, it is clear that polymers
are closely interwoven with today’s various complicated
industrial structures.
The global chemical industry, excluding the medical
field, is estimated to be worth 144 trillion yen and its major
products are polymers. Internationally-renowned polymerrelated companies are, for example, DuPont, Dow Chemical, Bayer, and BASF.
The annual consumption of plastics per person has now
reached 90 to 100 kg in West Europe, the US, and Japan
(statistics of FY2001), while the consumption in Asia (13
kg/person in FY2001), including India, is predicted to
increase rapidly in future and cause environmental and
energy related problems.
This section outlines the situation concerning polymers
since 2000 and also the research trends within and outside
Japan.1-3)
2. Global situation concerning polymer materials
The American Chemical Society surveys and publishes
the sales, profits, and R&D expenditure of the 50 top-ranking global companies in the chemical industry. First, the
journal of the Society (C&E News, issued on July 18,
2005) was checked for the trends. Table 1 gives the
FY2004 data of major chemical companies. The top three
companies by sales are Dow Chemical, BASF, and
DuPont, with sales exceeding 30 billion dollars each.
BASF spent a total of 1,459 million dollars on R&D, 3.8%
of sales. R&D expenditure in FY2004 was 6.2% higher
than in FY2003. Although not shown in Table 1, petrochemical sales showed a remarkable increase in 2004. For
example, the sales of Royal Dutch/Shell exceeded 29.4 billion dollars, approaching those of DuPont. The petrochemical industry seems to be raising the profit ratio of the entire
chemical industry. From Japan, the four companies of Mitsubishi Chemical, Mitsui Chemicals, Sumitomo Chemical,
and Toray rank among the world’s top 20, and their sales
increased from 12% in 2003 to 28%. The world’s top 50
chemical companies include 8 Japanese companies, the
total sales of which account for 13.2% (78,000 million dollars) of the sales of the top 50 companies.
According to C&E News, the profit ratio on chemical
products was 8.1% in 2004, up from 5.5% in 2003. The
ratio of R&D expenditure to sales is 2.1% on average,
down from the past five years.
Table 1 Sales and R&D expenditure of polymer-related
global companies.
Company
Chemical Sales
($ Millions)
Chemical R&D
Spending
% of
Sales
Dow Chem.
40161.0
1022.0
2.5
BASF
38189.1
1459.0
3.8
DuPont
30130.0
1333.0
4.4
Bayer
18088.3
1138.1
6.3
Mitsui Chem.
11350.0
322.7
2.8
Sumitomo Chem.
9883.0
417.9
4.2
DSM
9641.8
355.7
3.7
Clariant
6862.4
220.4
3.2
Rohm & Hass
6471.0
265.0
4.1
Ciba Specialties
5653.3
231.7
4.1
(Source: C&E News, July 18, 2005)
In the field of polymers, the focus of R&D is changing
from the provision of general-purpose materials to that of
functional materials and customer-oriented solutions. In
addition, the most important management strategy is clearly shifting from M&A to the expansion of core business
(organic growth) and priority investments are extending to
Asia including China.
As of the end of March 2005, the price of crude oil on
the NY market was over 55 dollars/barrel. Considering that
the price was around 32 dollars one year ago and had been
stable around 20 dollars for the last decade, this represents
a remarkable sudden rise. The world’s chemical companies
may be engaged in oil and gas refining or the energy business, and the dependence on natural gas is high in the US.
Under these circumstances, the impact of crude oil prices
on polymer research are too complex to be determined, but
there is no doubt that the price is a huge long-term threat,
as are environmental problems.
173
Fig. 1 Transition of R&D expenditure in Japan’s chemical industry (excluding the medical field).
Statistical data: “Survey Report on Science and Technology Research in Japan”, Statistics Bureau, Ministry of Public Management, Home
Affairs, Posts and Telecommunications; and “Industrial Statistics”, Industry Division, Ministry of Economy, Trade and Industry.
Figure 1 shows the transition in R&D expenditure in
Japan’s chemical industry. The data was compiled by The
Society of Polymer Science, Japan (SPSJ) based on various
statistical materials of the government. The R&D expenditure in FY2000 was 801.8 billion yen, accounting for about
4% of total sales. Despite the economic stagnation since
FY1990, this value has been constant. The facility investment for R&D has been decreasing since peaking in
FY1992. The facility investment in FY2000 was not more
than 60% (about 1 trillion yen) of the peak. According to
data of the Statistics Bureau of the Ministry of Internal
Affairs and Communications, the total sales of Japan’s
chemical industry in FY2004 were 21.6 trillion yen and the
operating profit was about 1,430 billion yen. The expenditure on R&D was 890 billion yen, 4.1% of the total sales.
For details, see: http://www.stat.go.jp/data/kagaku/.
3. Environment and polymer materials
In Japan, technological development related to “green
sustainable chemistry” is being promoted under the leadership of the Japan Chemical Innovation Institute (JCII), and
this is now a global trend of polymer materials research.
For example, propanediol synthesized from corn starch is
used as a raw material for polyester, and the conversion
from fossil fuels to cost-competitive biomass materials has
been already started. To reduce environmental loads, halogen-free fire retardants and water-soluble polymer coatings
not containing volatile organic compounds (VOC) have
been developed. Current research ranges widely from water
treatment using polymer membranes and energy-saving
technologies, such as lightweight polymer composite materials, to polymer membranes for fuel cells and other energy-related purposes and recyclable carpets.
The Society of Polymer Science, Japan featured environment-supporting polymer technologies in the March
2005 issue of its bulletin “KOBUNSHI”. Key technologies
include a non-phosgene process for manufacturing polycar174
bonate from CO2 (Asahi Kasei), self-extinguishing epoxy
resins (NEC and Sumitomo Bakelite), and a recycle coating
system (Nippon Paint).
4. Research trends in Japan and the US
Japan’s polymer research is extremely active and
advanced compared with those of Western countries. For
example, The Society of Polymer Science, Japan has the
largest number of members (12,500) of any polymer-related societies in the world, much more than that in the polymer chemistry division (7,500) of the American Chemical
Society.
Figure 2(a) shows the number of papers published in the
January to March 2005 issues of the most influential polymer-related journal “Macromolecules” (American Chemical Society, IF:3.621) by country. The number of papers
from Japan is 33, the second highest after the United States.
In 2003, the journal carried 240 Japanese papers, 17.5% of
the total (1372). Figure 2(b) shows the number of papers
published in the journal “Macromolecular Rapid Communications” (IF:3.236) of Wiley (Germany) in 2004. In terms
of the number of papers, Japan ranks third after China and
the United States, above Germany. These results indicate
the advanced level of Japan’s polymer research.
Figure 3 shows the number of papers reported at the
54th Annual Meeting of The Society of Polymer Science,
Japan (SPSJ) held in May 2005 by field. In this meeting,
2,276 general papers were reported. By field, 481 were in
the field of “polymer chemistry” dealing with polymer synthesis (radical polymerization and polycondensation), dendrimer and other special structure polymers, polymer reactions, and new polymerization processes; 715 in the field of
“structures and physics of polymers” dealing with the molecular properties of polymers, solid properties, solution
properties, surface properties (rheology, gel, and tribology),
thin films, and molecular aggregates; 600 in the field of
“polymer functions” dealing with optical characteristics,
Fig. 2 Number of papers published on polymer-related journals by country.
(a) Total from January 2005 to March 2005 issues of “Macromolecules”. (b) Total from “Macromolecular Rapid Communications” 2004.
electric, electronic, and magnetic characteristics, separation, recognition, and catalytic characteristics, highly
strong and elastic polymers, properties in ultimate conditions, and liquid crystals; 348 in the field of “biopolymers
and biomolecules” dealing with proteins, enzymes, DNA,
carbohydrate polymers, biomembranes, biomimetics, bioengineering, DDS, and biomaterials; 113 in the field of
“environment and polymers”; and 13 in the field of “polymer industry and engineering”.
Polymer chemistry (481)
Structures and physics of polymers (715)
Polymer functions (600)
Biopolymers and biomolecules (348)
Environment and polymers (113)
Polymer industry and engineering (19)
Invitations and awards (39)
Fig. 3 Number of papers reported at the 54th Annual Meeting of The
Society of Polymer Science, Japan, by field.
The number of general papers reported at the SPSJ’s
Annual Meeting was 1,890 in 2000 (Nagoya), 1,940 in
2001 (Osaka), 2,028 in 2002 (Yokohama), 2,081 in 2003
(Nagoya), and 2,251 in 2004 (Kobe). This annual increase
indicates that polymer materials are closely related to a
wide range of domestic industries and that researchers’
interest is growing.
At the 229th National Meeting (San Diego) of the American Chemical Society held in March 2005, 9,200 papers
were reported at 930 chemistry-related sessions. The number of papers was greater than the approximately 8,500
papers at the 225th National Meeting (New Orleans) in
2003, and 8,000 papers at the 227th National Meeting
(Anaheim) in 2004. In relation to polymers, a total of 972
papers were reported in the Division of Polymer Chemistry
(POLY) and Division of Polymeric Materials: Science &
Engineering (PMSE).
For special sessions at POLY, six themes were selected:
“Biological and Synthetic Macromolecules for Emerging
Nanotechnologies”, “Carbon Nanotubes, Polymers, and
Complex Fluids”, “Polymer Surfaces and Interfaces”, “Bio-
Table 2 Polymer-related papers reported at ACS National Meeting (San Diego) in March 2005.
Special Sessions
POLY
PMSE
Biological and Synthetic Macromolecules for Emerging Nanotechnologies
Papers
74
Carbon Nanotubes, Polymers, and Complex Fluids
38
General Papers
156
Polymer Surfaces and Interfaces
85
Biomimetic Polymers
41
Degradable Polymers and Materials
66
Smart Polymer Films, Composites, and Devices
42
Awards
51
Others
52
New Concepts in Polymeric Materials
33
Polymers and Medical Devices
22
Application of Polymers in Manufacturing of Integrated Circuits
11
Polymer Nanocomposites
33
Polymeric Semiconductors for Thin-Film Electronics
37
Confinement Effects on Relaxation Properties of Polymers
27
Bionanotechnology – The Interface Between Biology and Polymer Science
31
Toward Noninvasive Delivery and Diagnostics: Proteins, Genes and Cells
8
Awards
23
Others
142
175
mimetic Polymers”, “Degradable Polymers and Materials”,
and “Smart Polymer Films, Composites, and Devices”. For
special sessions at PMSE, “New Concepts in Polymetric
Materials”, “Polymers and Medical Devices”, “Application
of Polymers in Manufacturing of Integrated Circuits”,
“Polymer Nanocomposites”, “Polymer Semiconductors for
Thin-Film Electronics”, “Confinement Effects on Relaxation Properties of Polymers”, “Bionanotechnology – The
Interface Between Biology and Polymer Science”, and
“Toward Noninvasive Delivery and Diagnostics: Proteins,
Genes and Cells”. Table 2 lists the numbers of papers
reported.
From the titles of the sessions at the POLY divisions,
polymer materials are clearly important elements for nanotechnologies and as infrastructure materials indispensable
for the environment, safety, and medicine. From the sessions at the PMSE divisions, polymer materials are closely
related to various industries, such as IT, biotechnology, and
devices.
and materials. Before the emergence of biotechnologies
and nanotechnologies, polymer materials spanned many
other fields in order to establish the current solid position
as infrastructure materials. These features of polymer materials will not change regardless of the future direction of
science and technology. In other words, polymer materials
will remain important for supporting sustainable growth by
resolving various problems concerning the environment,
safety, health, and energy.
Lastly, the major terms identified in the current survey
of research trends are the following: (1) Bio-based material
design, (2) Nanocomposites, (3) Microstructure control of
capsules and coatings, (4) Optical materials and new catalysts, (5) Reduction of environmental load, (6) Organic
growth, and (7) Quick rise of crude oil price. These will be
important keywords when considering the future of polymers.
References
5. Conclusion
Despite several uncertainties regarding the current situation, the numbers of papers reported at R&D sessions of
companies and academic societies suggest that polymer
materials are steadily gaining in importance. From the outset, polymer science has grown in harmony with chemistry
176
1) January 2005 and March 2005 issues of “KOBUNSHI” of The
Society of Polymer Science, Japan (Guide to the 54th Annual
Meeting of The Society of Polymer Science, Japan).
2) January 10, 2005 issue, February 21, 2005 issue, and July 18, 2005
issue of “Chemical & Engineering News” of the American
Chemical Society (Guide to the 229th ACS National Meeting).
3) Statistical materials from “KOBUNSHI DOYUKAI” of The
Society of Polymer Science, Japan.
Chapter 12. Analysis and Assessment Technology
Section 1. Nanoscale Measurement
Tomonobu Nakayama
Electro-nanocharacterization Group, Nanomaterials Laboratories, NIMS
1. Introduction
In order to construct nanoelectronics which will support
an advanced information and communications-oriented
society, nanostructures having atomic-level precision must
be widely used. To achieve this, it is necessary to address
not only the locality of measurement but also the enlargement of circuit size as circuit density increases. Nanoscale
quantum phenomena need to be detected using advanced
instruments and techniques to support the development of
nanodevices and integrated circuits. Research in an interdisciplinary field of biotechnology and nanotechnology
will flourish in the future, but its success or failure depends
upon the development of nanoscale measurement technologies which can be applied to biomaterials.
2. Research trends
The widely-used instruments having atomic-level spatial
resolution are the electron microscope (EM) and scanning
probe microscope (SPM). Nanomeasurement using an EM
has been established for evaluating synthesized materials,
and is also widely used in industries. However, there is
now fierce competition to develop ultrahigh resolution
imaging and elemental analysis at the monoatomic level
and a next-generation nanomeasurement technology concerning light elements such as carbon. An SPM-related
technique achieves interesting nanomeasurements, since it
also enables us to create ultimate materials by manipulating
atoms one by one (an atom manipulation technology). The
purposes of nanomeasurement by a proximity probe vary
widely, and the detection of electric, magnetic, optical,
dynamic and chemical nano-scale properties has been realized. Therefore, various probe microscopes such as the
scanning tunneling microscope, atomic force microscope,
scanning near-field optical microscope and scanning magnetic-force microscope have been developed. However,
SPM technologies for measuring magnetic and chemical
information on the nanometer scale have not yet been adequately developed, and much R&D in this field is expected
in the future. One of the technological trends is to convert
an SPM into a multiple-scanning-probe microscope
(MPSPM). SPM manufacturers in Japan and abroad as well
as research groups and organizations around the world such
as IBM, Pittsburgh University, Tokyo University, Toyota
University of Technology, and NIMS are working hard on
this conversion. Since the application of individual nanostructures to devices has not reached full-scale practical
implementation yet, an MPSPM measurement technology
is still at the research stage before practical implementation.
3. Situation and trends of NIMS
Concerning nanomeasurement using an electron microscope, NIMS has been carrying out a variety of distinguishing development activities, such as the development of an
electron microscope for realizing elemental analysis at the
atomic scale, and an ultrahigh resolution electron microscope. NIMS is also establishing an Internet electron
microscope environment. Regarding nanomeasurement
related to a scanning probe microscope, NIMS has also
produced a remarkable outcome in developing and operating an instrument using an extreme field control technology, as will be described later in this chapter. Moreover,
NIMS has succeeded in converting an SPM into a MPSPM
ahead of any other country, and is the only research institute that has completed several MPSPMs which allow
entirely independent driving in two to four scanning
probes, enabling nanomeasurements such as length-dependent electrical resistance measurement of individual
nanowires, which was impossible in the past. NIMS is also
conducting research (entrusted by the Ministry of Education, Culture, Sports, Science and Technology) on an integrated control system for multiple-scanning-probe instruments that assumes a variety of multiple-scanning-probe
measurements in the future.
4. Conclusion
The scanning tunneling microscope and atomic force
microscope have established the basis of nanotechnology
today because they can deal with various materials. However, the recent nanomeasurement work tends to focus on
assessing particular materials and to lack generality. If
177
researchers continue to develop techniques only for individual materials, it will become difficult to use research
resources effectively. It is thus necessary to develop
nanomeasurement instruments and techniques having generality and versatility. Researchers also need to study and
develop a nanomeasurement technology which can be used
for assessing a large-scale integrated circuit built up with
178
precision at the atomic level, and which can be used for
assessing biomaterials. The multi-probe measurement technology will become a nano-manufacturing and measurement technology that offers even greater precision and
scale, beyond the framework of individual nanomeasurement, by developing a multiprobe into a superparallel
large-scale multiprobe.
12 Analysis and Assessment Technology
Section 2. Extreme Field Measurement
Daisuke Fujita
Extreme Field Nano Functionality Group, Nanomaterials Laboratories, NIMS
1. Introduction
In recent years, technology for analyzing and assessing
the size effect and quantum effect peculiar to extremely
small areas has become important as research on substances and materials at the nano-level has stepped up.
Much of the new functionality of nanodevices and nanomaterials is a quantum-mechanical effect that typically
appears in an extreme-field environment combined with an
ultralow temperature, a high magnetic field, or an ultrahigh
vacuum. Since thermal disturbance decreases in an ultralow
temperature environment, a quantum effect in which an
electron wave is involved can be clearly measured. For
example, the interference of a low-dimensional electron
wave, the Kondo effect, a single electron effect, inelastic
tunneling phenomena, and so forth can be measured. A
high magnetic field plays an important role in spin control,
superconducting state control, Landau quantization observation, etc. An ultrahigh vacuum environment is essential
for creating clean surfaces at an atomic level and
monoatomic manipulation. In order to clarify the precise
mechanism by which a quantum effect due to an extremely
small structure appears and to verify new useful functionality, a physical-properties measurement technology by a
nanoprobe in a combined extreme-field environment which
is precisely controlled is required. Physical quantities and
nano-information to be measured include: atomic structure,
local density of states (LDOS), band structure, a Fermi surface, spin, interatomic force, magnetic force, friction force,
potential, work function, photon, and atomic vibration.
Such measurements of physical quantities and quantum
Spin control
Superconducting control
Landau level
Nano
probe
Interference of an electron wave
Kondo effect
Single electron effect
Inelastic tunneling phenomenon
Photon
Ultraclean surface
Atomic manipulation
Molecular manipulation
Interference effect of
an electron wave
Single spin
Time axis
Fig. 1 Investigation of functional physical-properties by extreme-field
environment nanomeasurement.
effects on a nano-scale under such a combined extremefield environment by means of time resolving are expected
to boost the investigation of new nanofunctionality and
physical properties (Fig. 1).
2. Research trends
Although the transmission electron microscope (TEM)
and scanning probe microscope (SPM) are important for
nano-analysis, the SPM technique allows a variety of physical properties to be measured and a combined extremefield environment to be created. This section examines the
research trend of atomic-resolution SPM measurement
technology in a combined extreme-field environment
where development competition is fierce.
The most important among SPM techniques having a
wide range of applications are the scanning tunneling
microscope (STM) and the non-contact atomic force microscope (NCAFM). STM is a probe in a local atomic state,
and can measure multiple physical properties such as
LDOS, band state, tunneling electron inductive luminescence, spin polarization tunnel, and inelastic vibration excitation. NCAFM performs imaging by scanning a probe or a
specimen while controlling the approach distance using a
probe top atom and a specimen surface atom. Like STM,
NCAFM has true atomic resolution and can also be used
for insulators. Mainly, the physical quantities of interatomic force, magnetic force, friction force, potential, work
function, etc. can be measured. SPM can be downsized
comparatively easily, and can measure so many physical
properties and functions that its application to combined
extreme-field environments has been developed in SPMleading countries since the latter half of the 1990s.
Japan, the US and Germany are leading other countries
in the development of an ultralow temperature, strong magnetic field and ultrahigh vacuum STM, and an atomic-resolution image in a temperature range of 1 K or less has been
obtained by a 3He cryostat or dilution-refrigerating method
in these countries. In the US, for example, Davis and his
group succeeded in developing an ultralow temperature (15
mK) and strong magnetic field (9 T) STM based on a dilution-refrigerating method, and has been using it to clarify
the superconducting state. In Germany, Wiesendanger and
his group completed an ultralow temperature (300 mK) and
179
strong magnetic field (14 T) STM based on a 3He cryostat
method in 2004, and are using it to clarify spintronics and
Landau quantization. In the development of an NCAFM in
a combined extreme-field environment, on the other hand,
Japan, Switzerland and Germany are leading other countries. An ultralow temperature at a 5 K level, strong magnetic field and ultrahigh vacuum NCAFM based on a He
cryostat method have been developed. In Switzerland, for
example, Güntherodt and his group of Basel University
have succeeded in developing an ultralow temperature (6
K) and strong magnetic field (7 T) NCAFM, and have
achieved measurement by an atomic-resolution NCAFM
and a magnetic force microscope (MFM). In Germany,
Wiesendanger and his group have succeeded in developing
an ultralow temperature (5.2 K) and strong magnetic field
(5 T) NCAFM.
Concerning Japanese progress in SPM nano-analysis in
combined extreme-field environments, STM is introduced
below first. In Japan, leading research on an atomic-resolution STM technology combined with three extreme-field
environments of ultralow temperature, high magnetic field
and ultrahigh vacuum is being carried out in Tokyo University and NIMS. Fukuyama and his group of Tokyo University have developed an ultralow temperature (126 mK) and
strong magnetic field (6 T) UHV-STM based on a dilutionrefrigerating method, and have used it to investigate nanomaterials at a low temperature level. On the other hand,
Morita and Sugawara and their group of Osaka University
have been taking the lead in developing an atomic-resolution NCAFM in a combined extreme-field environment,
and have successfully developed an ultralow temperature
(5 K) UHV-NCAFM and atomic-resolution imaging.
Moreover, Sugawara and others started developing an
ultralow temperature (5 K) and strong magnetic field (10
T) UHV-NCAFM in 2001, and recently succeeded in atomic-resolution imaging.
The development of an extreme-field environment SPM
in NIMS was started from a low temperature atomic-resolution UHV-STM in the 1990s. NIMS then began to develop an atomic-resolution STM in an extreme-field environment in 2001, and has succeeded in developing an ultralow
temperature (400 mK) / high magnetic field (vertical direction, maximum 11 T) / ultrahigh vacuum (in the order of
10-10 Pa) atomic-resolution STM.1) NIMS has its own technology called “ultrahigh vacuum creation technology,” and
by combining it with a technique for creating a clean surface, has also succeeded in the atomic-resolution measurement of a surface that no other groups could observe. In
particular, it is noteworthy that NIMS has succeeded in the
atomic-resolution STM measurement of a Si (100) surface
and an Au (111) reconstructed surface at an ultralow temperature of 1 K or less for the first time. NIMS has thus
already reached world-class standards in the development
of a combined extreme-field environment STM.
future as the investigation of new functionality at the nanolevel and the clarification of a quantum effect will become
important.
In combined extreme-field environment STM measurement, an atomic-resolution STM technology combined
with extreme fields of an ultralow temperature of 0.5 K or
less, high magnetic field of 10 T or more, and ultrahigh
vacuum of 10-8 Pa is currently the world’s highest standard.
Research groups which have reached this standard exist in
Japan, Germany and the US, and they are leading the
development of an extreme-field environment STM measurement technology. In particular, the higher the magnetic-field intensity, the more likely that new materials and
functionality will appear, and so development competition
in this area will continue. Since NIMS has a high magnetic
field, it is in an advantageous position compared with other
research institutes. Another important technology to be
developed is an ultrahigh vacuum environment and a highprecision tunneling spectroscopy measurement technology.
Meanwhile, an extreme-field environment NCAFM is
being developed mainly in Japan, Switzerland and Germany, but no research group is currently attempting such
an extreme-field environment that would be required for
STM. This is partly because atomic-resolution measurement by an optical method NCAFM involves very complex
technology in an extreme-field environment. If a simple
new high-resolution probe is developed, then development
of an extreme-field environment NCAFM will surely take
off. If atomic-resolution measurement similar to that by
STM can be accomplished by a combined extreme-field
environment NCAFM, then it will be possible to measure
multiple physical properties and functionality of the surface
of various substances including insulators.
4. Conclusion
Concerning measurement technology in extreme-field
environments, this section has outlined mainly an atomicresolution SPM measurement technology in an ultralow
temperature, high magnetic field and ultrahigh vacuum
environment where there is global development competition is intense. In order to develop such a highly-advanced
measurement technology, precision measurement and
extreme-field environment creation technologies are indispensable, thus testing overall technical capabilities. Such a
world-class measurement technology would be a powerful
tool for clarifying how the functions of nanostructures
appear and the mechanisms of their physical properties,
and may lead to the discovery of entirely new nano-functionality and quantum effects. For such new “creation of
intelligence,” international cooperation is vital, and an
international core-research institute for substances and
materials should take the lead in this particular field of
R&D.
References
Competition in high-precision SPM nano-analysis in
extreme-field environments is expected to intensify in the
180
1) Daisuke Fujita and Keisuke Sagisaka, Microscopy, 40, 14 (2005).
Section 3. Electron Transport Modeling in Surface Analysis
Shigeo Tanuma
Fundamental Chemical Analysis Group, Materials Analysis Station, NIMS
1. Introduction
In spectroscopies in which electrons are used for the
incident probe or detected signals, such as in surface electron spectroscopy (including Auger electron spectroscopy
(AES), and X-ray photoelectron spectroscopy (XPS)), electron probe microanalyzer (EPMA), secondaryelectron
microscope (SEM), many researchers are trying to expand
from two-dimensional analysis to three-dimensional analysis. Depth direction analysis with ion sputtering and specimen depth analysis in which a cross-section is made by
focused ion-beam (FIB) used to be the mainstream, but
now research is focusing on the method of inferring the
three-dimensional composition and structure of the neighborhood of a surface from small changes in an observed
spectrum (such as the shape of a peak and background) and
a two-dimensional image. While many materials are made
in complex shapes at the nano-level today, researchers are
trying to assess the structure and characteristics of materials through three-dimensional simulation of spectra and
imaging after clarifying the structure and characteristics of
materials. In order to identify the two-dimensional and
three-dimensional elemental distribution and structure
accompanied with metrological “uncertainty” from spectrum measurement, modeling based on precise findings as
to the exact physical quantity which describes the interaction between electrons and solid, and its transport phenomenon is required.
2. Present status of physical quantity databases
In spectroscopy using a low-energy electron as an incident probe, it is conventional to trace a multiple scattering
process of electrons and to clarify the interaction thereof
based on the Monte Carlo (MC) method. This method
requires: (a) elastic scattering cross section, (b) inelastic
scattering cross section, and (c) stopping power. For EPMA
and SEM, (d) inner-shell ionization cross section, (e) fluorescence quantum yield, and (f) secondary electron yield
are also required. In reality, the elastic scattering database
of (a) in which a free atom is calculated using the DiracHartree-Fock potential has been published by NIST, and is
replacing the previous elastic scattering database in which a
free atom is calculated using the Thomas-Fermi-Dirac
potential. However, problems remain as to its accuracy
under 1,000 eV. The inelastic scattering database of (b),
which is calculated from the general equation TPP – 2M or
the optical dielectric functions, are commonly used, but it
has not yet been fully verified based on comparisons with
experimental values. In particular, the importance of
exchange correction in a low-energy region has been pointed out, but this has not been taken into consideration in the
above mentioned calculatiens. In the stopping power of (c),
the Bethe equation ia used over 10 keV, but there is no definite database for the range under 10 keV. Concerning (f)
which is important for SEM quantitative analysis, the variation of secondary electron yield is so large (reaching
around 200%) that it has become a serious problem. Other
databases for the low-energy range have not been sufficiently established either, and so simulations lack accuracy.
3. Development of a simulator
For SEM, the accurate measurement of length is essential in industry. An electron beam of 200 eV or less is considered desirable to reduce the edge effect. Since it is difficult to calculate such a low-energy region with high accuracy by the MC method, effective modeling of this area has
been studied, and it has been pointed out that it would be
more effective to use a elasfic scathering electron which
can easily control depth than a secondary electron.
On the other hand, the spectrum simulators* of the AES
and XPS, which have lately been developed assuming the
three-dimensional structure, can be produced the shapes of
main peaks and the background of photo-electrons even
though they could be applied to the limited systems and
elements. However, AES spectra have a problem for predicting the shape of a peak. In reality, the surface excitation
effect and elastic scattering effect, which greatly affect
spectra, cannot be adequately included for electron transport modeling, and it is difficult to use the spectrum simulator in practice because the system is limited and quantitative accuracy is not enough. At present, the spectrum simulator can be used only for depth-direction analysis of elements. It is possible, however, to calculate a combined high
level of physical quantity of a transport cross section which
is required for electron spectroscopy, and it is useful as a
database for basic physical quantities of surface analysis.
181
*SESSA (NIST SRD 100), QUASES (http://www.quases.
com)
References
“Workshop on Modeling Electron Transport for Applications in
Electron and X-ray Analysis and Metrology,” Abstracts, NIST
(November 2004).
182
Section 4. Advancee Transmission Electron Microscope
Masaki Takeguchi
In situ Characterization Group, High Voltage Electron Microscopy Station, NIMS
Koji Kimoto
High-resolution Characterization Group, High Voltage Electron Microscopy Station, NIMS
1. Introduction
A transmission electron microscope (TEM) is indispensable and one of the most widely used tools for research on
nanomaterials in view of its capability of not only atomic
resolution imaging in real space but also simultaneous
analyses of structure and composition in the sub-nanometer
area. One of the key characteristics of nanomaterials is that
they have unique structures and physical properties different from those of the bulk, and so analyzing such structures
and physical properties at high resolution and high precision allows nanosubstances and nanomaterials to be accurately controlled. Today, the development of next-generation TEM technology is focusing on enhancing the resolution and precision of the TEM itself, adding a function of in
situ measurement of nano-physical properties, and developing it into a three-dimensional characterization technology.
This section summarizes research and development for:
improving the resolution and precision of the TEM; a technology for analyzing in situ nano-physical properties; and a
technology for three-dimensional characterization.
Table 1 High-performance TEM development projects.
TEAM project
(USA, 2000 –)
An overall project centering on five US national
research institutes (ANL, BNL, LBNL, ORNL,
FSMRL). This project is not only developing a TEM
but also organizing its industrial applications. The
budget for the project is $100 million, and an
instrumentation development contract is to be
concluded with FEI (USA).
Super STEM project
(UK, 2000 –)
A project centering on Leeds University, Cambridge
University and Liverpool University in the UK
concerning enhancing the performance of a
scanning TEM (STEM) and it public utilization.
SESAM project
(Germany, 1999 –)
An electron microscope development project
centering on a corporation (Carl Zeiss). The project
is being promoted in three phases (I, II, and III),
and it is in the third phase at present. Resolution of
0.08 nm was announced in 2005.
Table 2 Research on electron beam monochromatization.
Delft University of Technology
(Netherlands) + FEI Inc.
Development and application of a monochromator for TEM
Graz University of Technology
Application of a monochromator for TEM
(Austria)
Tohoku University + JEOL Ltd. Development of a monochromator for TEM
SESAM project (Germany)
Refer to Table 1.
IBM (USA) + Delft University
of Technology (Netherlands)
Development of a monochromator suitable
for a scanning TEM
2. Research trends
2.1 Improvement of high resolution and high precision of
TEM
Until around 1990, the main approach to improve the
resolution of the TEM was to reduce spherical aberration in
designing the objective lens polepiece, but in the 1990s
attempts were made to eliminate the spherical aberration by
computer processing such as image processing, and an
aberration correcting lens was developed around 2000.
More recently, since the resolution limits of TEM have
finally reached the information limit of TEM, research on
improving the overall performance of TEM such as stabilization of TEM, monochromatization of the electron beam,
and correction of aberration of lenses has been carried out
as projects among some countries (Table 1).
Concerning the monochromatization of an electron
beam, research and development are being promoted not
only to improve the resolution but also to enhance the pre-
Table 3 Main functions for in situ
nano-physical properties measurement.
Electron holography/
Lorentz microscopy
Quantitative measurement of electric and magnetic
fields inside and outside a specimen is possible.
Since the resolution is almost the same as that of a
TEM, these techniques are effective for measuring
physical properties such as nanodevices.
SPM in TEM
The probe can be brought into contact with a
nanomaterial using piezoelectric driving, and
electrical characteristics and mechanical
characteristics can be measured while being
observed with a TEM. The part of a specimen that is
being observed with the TEM can be observed with a
STM/AFM at the same time. The use of multiple
probes is expected to become possible in future.
It is possible to assess luminescent characteristics
while assessing a location and a defect in
semiconductor nanomaterials by TEM. One problem
is that the lens must contain space to accommodate
a condenser mirror.
Cathode
luminescence
in TEM
High resolution
wavelength
dispersive X-ray
spectrometry
It is possible to measure valence state density by
high resolution Xray emission spectrometry, but the
problem of improving detection efficiency remains.
183
cision of chemical analyses (Table 2). Through the monochromatization of an electron beam, it becomes possible to
know the detailed electric state of interatomic bonding in
nanomaterials.
2.2 In situ nano-physical properties measurement function
Measuring nano-physical properties inside a TEM in
addition to observing the structure and analyzing the composition of nanomaterials allows electron microscopy to
explore the appearance of nano-physical properties using
electron microscopy. Therefore, various functions have
been added to TEMs in recent years. Table 3 shows the
main functions for measurement of nano-physical properties.
2.3 Three-dimensional characterization function
Although a projected image of a specimen is observed in
conventional TEM, a three-dimensional image can be
obtained by using the tomography technique. Researchers
are aiming to apply this TEM tomography technique to
nanomaterials research by improving the resolution of
three-dimensional imaging. Cambridge University (UK)
and Arizona State University (USA) are developing the
184
technology of three-dimensional elemental analysis and
three-dimensional nano-physical property measurement by
combining the tomography technique with a two-dimensional composition map and electron holography.
3. Conclusion
High-performance and new-functional TEM will
become increasingly important in the research of nanomaterials. New breakthroughs in TEM instrumentation and
analytical technology have been made since 2000, and in
order to take the initiative in the research of nanomaterials,
it is important to establish these fundamental and elemental
technologies of TEM.
References
1) Transmission Electron Energy Loss Spectrometry in Materials
Science and the EELS Atlas, 2nd ed., Ed. C. C. Ahn, John Wiley
&Sons Inc., New Jersey (2004).
Section 5. Standardization of Assessment Methods
Takashi Kimura, Shinji Itoh
Fundamental Chemical Analysis Group, Materials Analysis Station, NIMS
1. Introduction
Concerning methods of analyzing and assessing various
substances and materials, ISO/IEC provides international
standards and JIS (Japanese Industrial Standards) provides
national standards. The “Guideline for Coordination
between JIS and International Standards” was revised in
accordance with the revision of the ISO/IEC Guide 21
(adoption of international standards as regional national
standards) in 1999, and work to coordinate national standards is now underway.
A new criterion called “uncertainty” for indicating the
reliability of measured data has been used since the 1990s.
Since the concept of error and accuracy was not unified
among technical fields and countries, the International
Committee of Weights and Measures unified the method of
assessing and expressing the reliability of measured data.
The “Guide to the Expression of Uncertainty in Measurement (GUM)” was published in 1993. In the GUM, uncertain components are sought either by (1) A-type assessment
based on ordinary statistical analysis which calculates a
standard deviation, or (2) B-type assessment which infers
the size corresponding to a standard deviation from various
information other than data, and uncertainty as a whole is
then determined by combining these components. The
assessment of uncertainty is essential in order to comply
with the standards of ISO 9000 (quality management system) and ISO 17025 (general requirements for the ability of
calibration and testing laboratries).
2. Research trends
A primary standard assessment method is a traceable
analytical method in SI units; such methods for chemical
analysis include the gravimetric method, coulometry, and
isotope dilution-mass spectrometry. The isotope dilutionmass spectrometry adds a spike of an element to be analyzed whose density is already known (which has an isotope composition different from the naturally occurring
one) to an unknown specimen, and then analyzes its mass.
This analysis method, when combined with the barium-sulfate gravimetric method, can attain accurate results, as
shown in the examples of quantitative analysis of sulfur (S)
in iron and lead (Pb) in iron. Accurate quantitative analysis
of single ppm content of Si in iron and steels has been
obtained by an inductively-coupled plasma mass spectrometry (ICP-MS) using gel absorption and separation and an
isotope dilution method. Likewise, determination of Fe and
Cr, which are the main components of Fe-Cr binary alloy,
has also been conducted by ICP-MS. In connection with
environmental problems, the development of an analytical
method without using a chlorine-based organic solvent
which is a harmful reagent has been studied, and work is
underway to develop a coprecipitation separation method,
an ion exchange separation method, a solid-phase extraction method, etc., so national and international standards
are being steadily reviewed.
The ISO standards concerning surface analysis were discussed and established in TC201 (surface chemical analysis) and TC202 (microbeam analysis). The target of TC201
is Auger electron spectroscopy (AES), secondary ion mass
spectrometry (SIMS), X-ray photoemission spectroscopy
(XPS), glow discharge spectroscopy (GDS), scanning
probe microscopy (SPM), and total reflection fluorescent
X-ray spectroscopy (TXRF). Not only the definition of
each method but also the parameters, energy axis, precision
in the x, y and z axes which determine the basic performance of an instrument, and the standards concerning the
method of calibrating each instrument as well as the standards concerning the method of determining a relative sensitivity coefficient and of using it have been drawn up. The
standards concerning the properties which a specimen
should have and the method of selecting and using them
have also been drawn up. TC201 provides a standard concerning the accuracy of quantification of depth profile by a
sputtering method.
On the other hand, TC202 establishes standards concerning procedures for qualitative and quantitative analysis
by a wavelength dispersive spectrometer (WDS) electron
probe X-ray microanalyzer (EPMA) and its applicability,
the energy calibration and resolution of an electron energy
loss spectrometer (EELS) by an analytical electron microscope (AES), the magnification calibration and spatial resolution of a scanning electron microscope (SEM), and the
instrument specifications and analytical method of an energy dispersive spectrometer (EDS).
185
3. Conclusion
In recent researches, both speed and accuracy are crucial, and the time spent for verification experiments and
analysis has been getting shorter. In order to ensure the
reproducibility and traceability of analysis results, it is necessary to produce guidelines concerning analysis and to
clarify the targets to be analyzed and discussed. Standardization and the establishment of standards are thus becoming increasingly more important.
186
References
1) JSCA News, Japanese Industrial Standards, International
Standardization Committee for Surface Chemical Analysis (JSCA),
17, 2005, pp. 1-22.
Chapter 13. High Magnetic-Field Generation
Technology and Its Applications
Section 1. The Aim of Developing a High Magnetic Field
NMR Facility
Tadashi Shimizu
NMR & Chemistry Group, High Magnetic Field Center, NIMS
1. Introduction
Of the various analytical technologies which are expected to greatly assist nanobiology research, national research
institutes should put priority on large special instruments,
such as a synchrotron radiation system, high-voltage electron microscope, high-field NMR system, and neutron diffractometer. Theses instruments have different characteristics, and nanobiological analysis will not be completed
until all of these complementary analytical technologies are
provided.
Concerning the synchrotron radiation system, a highvoltage electron microscope and a neutron diffractometer,
their effectiveness is already universally known. The effectiveness of high magnetic-field NMR lies in being able to
clarify a local three-dimensional chemical structure (the
geometrical structure of a molecule, and the kind and size
of a chemical bond) even for substances which other analytical technologies are not suitable for, such as amorphous
materials and compounds. There are many important prob-
Fig. 1 90% of the elements of the periodic table can be analyzed by
NMR (blue, red and yellow in the drawing). However, only three
elements (H, C and N) can be analyzed by conventional NMR. 75% of
the elements which can be analyzed by NMR are quadrupole nuclei (red
in the drawing). Quadrupole nuclei can be analyzed only by high
magnetic-field NMR.
lems that can be solved by high magnetic-field NMR in
such fields as catalysts, glasses, slag, fuel cells, solar cells,
and living substances.
It has long been known that NMR is theoretically advantageous for analyzing amorphous materials and compounds. However, since NMR used to have only a low
magnetic field, its effectiveness was limited to particular
substances such as organic substances. When a magnetic
field of 20 T or more became possible, the effectiveness of
NMR rose dramatically. While NMR should be able to analyze 90% of the elements in the periodic table, its magnetic
field was so low in the past that it could not analyze more
than three elements such as hydrogen and carbon (Fig. 1).
2. The trend of high-field NMR
NMR is a striking analytical technology that has produced five Nobel Prize winners, and yet it still involves
many cutting-edge developments and is still being
improved. The sixty-year history of NMR is the history of
producing a high magnetic field with a magnet (Fig. 2), and
each increase in magnetic field has led to an innovation in
NMR. When the electromagnet (2 T) was changed to a
superconducting magnet (5 T) about 40 years ago, it
became possible to use NMR for chemical analysis (structural analysis of low molecules). When the 10 T superconducting magnet based on Nb3Sn was achieved about 20
years ago, the structural analysis of protein became possible. In today’s ultra-20T era, even inorganic substances can
be analyzed for the first time. This is because the high resolution measurement of quadrupole nuclei which are necessary for analyzing inorganic substances can be achieved for
the first time by a high magnetic field of 20 T or more.
Today, 40 T-class magnetic fields are feasible by using a
hybrid magnet. In the US, France, and the Netherlands, the
main purpose of developing high magnetic-field magnets
including hybrid magnets is for the analysis of nanobiological materials by high magnetic-field NMR.
187
Magnetic field (NMR frequency MHz)
Hybrid magnet
USA – 40 T
NIMS – 35 T
1000
Superconducting
magnet
17.5T magnet
in NIMS
100
920 MHz,
21.6 T magnet
in NIMS
Electromagnet
5.5 T magnet in the US
1950
1960
1970
1980
1990
2000
2010
Year
Fig. 2 History of NMR magnet.
A high magnetic field is required not only for NMR but
also for MRI and the analysis of various physical properties. However, since these applications are limited to fundamental research fields, the market is too small to drive the
development of high magnetic-field magnets. Instead, magnets for NMR require higher performance than magnets
used for other purposes, and so if such magnets can be
developed, they may be applied to other fields. Developing
a high magnetic-field NMR is the most effective way of
powering the overall development of magnets.
3. Future development and conclusion
General users who require a conventional NMR magnet
typically cannot afford to purchase a high magnetic-field
188
NMR magnet because of the huge costs required for developing and maintaining such magnets. Instead, it would be
more appropriate to install a high magnetic-field NMR
magnet in one or two research facilities in Japan and make
them available to domestic users.
The highest-risk technology in developing high magnetic-field NMR is the magnet. The High Magnetic Center of
NIMS is the only high magnetic-field institution having all
kinds of magnetic-field generation instruments such as
ultra-20 T superconducting magnets (930 MHz, 920 MHz)
and a 40 T-class hybrid magnet. In order to develop the
technical basis of NIMS in the most efficient manner,
NIMS needs to develop a system including a group of
devices based on the magnets as a core. The NMR facilities
with high magnetic-field magnets of NIMS are expected to
be useful for researchers engaged in nano-research in universities and industry.
The main magnet to be developed is a high magneticfield magnet such as a power-source driving type superconducting magnet (1.2 GHz class) and a hybrid magnet (1.5
GHz class). In terms of the strength of magnetic field, a
hybrid magnet is more advantageous, but in terms of the
development and maintenance cost, a power-source driving
type superconducting magnet is more suitable when used
exclusively for NMR for a long time. Hybrid magnets will
likely be used only for materials which cannot be analyzed
in a lower magnetic field.
Since the magnetic field of these new-type NMR magnets is less stable than that of superconducting magnets of
persistent-current operation by at least one order of magnitude, it is necessary to develop a technology that allows
high resolution NMR measurement even when the magnetic field is not so stable. Such a technology has two aspects,
that is, developing equipment for making a magnetic field
stable, and the software aspect of developing the measuring
technique. As these peripheral technologies are not
required for low magnetic-field magnets which are widespread among general users, they must be independently
developed in NIMS.
High magnetic-field NMR may soon become as widespread as today’s synchrotron radiation and neutron diffraction.
13 High Magnetic-Field Generation Technology and Its Applications
Section 2. Development of High-Field Whole-Body MRI
Tsukasa Kiyoshi
Magnet Development Group, High Magnetic Field Center, NIMS
1. Introduction
MRI (Magnetic Resonance Imaging) uses an NMR phenomenon, and by dividing an object to be analyzed into
small volume elements and incorporating a technique for
simultaneously analyzing from which element a signal is
obtained, MRI carries out imaging at an arbitrary sliced
plane of the object. The Nobel Prize in Physiology or Medicine of 2003 was awarded to P. Lauterbur and P. Mansfield for their development of the magnetic resonance
imaging technique.
MRI has the advantage that the inside of the brain,
spinal cord, etc. can be clearly diagnosed because MRI
causes no radiation exposure and is not affected by bone or
air. In Japan, more than 500 MRI instruments are at work
in hospitals and the like. Today, there is a trend toward specialization in two types of MRI. One type uses a donutshaped superconducting magnet which generates 1.5 T, and
the other type is called “open MRI” and uses an inexpensive permanent magnet of about 0.3 T, which is designed to
avoid stress during diagnosis.
2. Merits of high magnetic fields
Theoretically, the sensitivity of NMR increases in proportion to the power of 3/2 of the magnetic field. It is possible to improve the S/N ratio of an image and make an
image finer by increasing the magnetic field. Accordingly,
the Ministry of Health, Labor and Welfare has already
given its approval for an MRI instrument using a 3 T magnet, which is now being introduced for clinical diagnosis.
Almost all conventional MRI instruments are used for
anatomical morphological measurement (distribution of
water states by measurement of 1H), but MRI is expected to
be used for functional measurement as well in the future,
and so the development of a high magnetic-field MRI
instrument is now being promoted. In MRS (Magnetic Resonance Spectroscopy) which analyzes metabolism using
information concerning chemical shifts, the nuclei that play
an important role for metabolism such as 31P and 13C can be
measured as the magnetic field increases. In fMRI (functional MRI) which is used to observe susceptibility changes
in blood flow in the brain occurring due to a stimulus, a
map of the active part of the brain is made. The susceptibility effect increases with magnetic fields. High-field MRI is
being used mainly to clarify brain functions at present.
3. Global trend
A 7 T whole-body MRI instrument has been installed in
the Brain Research Institute of Niigata University in Japan.
In the US, high-field MRI instruments have been actively
introduced, and 7 to 8 T whole-body MRI instruments have
already been installed in a number of leading institutes. A
9.4 T (400 MHz in the resonance frequency of 1H) MRI
instrument that features the highest magnetic field available
today has been installed in the University of Illinois and
University of Minnesota.
In France, the construction of “NeuroSpin” (Intense
Field Neuro-Imaging Center) is being promoted by CEA
(Commissariat à l’énergie atomique).1) Under this plan, the
Intense Field Neuro-Imaging Center is built within the
premises of CEA Saclay near Paris, in which today’s
highest-level MRI technologies including magnets are to be
installed, and these MRI technologies will be used for
research of human brain functions. Although the plan is
flexible, the original plan includes the following.
• 3 T wide bore MRI for clinical studies
• 11.7 T (500 MHz) wide bore MRI for clinical studies
• 11.7 T MRI for anaesthetized and awake monkey studies
• 17 T small bore MRI for rodent studies
4. Materials development for high-field MRI
The field quality almost equivalent to that of an NMR
spectrometer is required for the superconducting magnet of
whole-body MRI, but the space required to generate a magnetic field quite differs between the two. An NMR spectrometer generates a magnetic field in a space of 51 to 89
mm in diameter, whereas a whole-body MRI instrument
needs to generate a magnetic field in a space of 0.7 to 1 m
in diameter, which is about ten times as large. As a result,
the stress applied to the superconducting conductor increas189
es. NMR spectrometers had reached a turning point for the
11.7 T (500 MHz) NMR spectrometer, by using Nb3Sn
conductor which has excellent high-field characteristics in
addition to NbTi conductor which has excellent mechanical
characteristics. For the 11.7 T MRI instrument, it has yet to
be decided whether to use only NbTi conductor by employing superfluid helium cooling, or a combination of other
conductors such as Nb3Sn conductor. However, NbTi conductor cannot be used in magnetic fields over 12 T by
itself, so Nb 3 Sn and Nb 3 Al conductors which have
improved mechanical characteristics need to be developed.
190
References
1) http://www.meteoreservice.com/neurospin/
13 High Magnetic-Field Generation Technology and Its Applications
Section 3. Mass Spectrometry
Ken Takazawa
NMR & Chemistry Group, High Magnetic Field Center, NIMS
1. Introduction
Mass spectrometry is a fundamental analytical technique
that has been used in a wide range of research fields such
as atomic and molecular science and gas analysis. In recent
years, it has been used for the analysis of biological molecules such as proteins and nano-clusters such as fullerene,
and has become an indispensable analytical technique in
the fields of biological science and nanotechnology. This
section describes mass spectroscopy as an application of a
high magnetic field.
As the importance of mass spectrometry in biological
science and nanotechnology has rapidly risen, many
attempts will be made to improve the performance of FTICR. In fact, the Korean Basic Science Institute has
announced the joint development of an FT-ICR spectrometer using a 15 T-class superconducting magnet (aiming at
completion by 2007) with the US National High Magnetic
Field Laboratory (in Tallahassee, Florida).3)
Meanwhile, the High Magnetic Field Center of NIMS
has developed a high-magnetic-field TOF-MS spectrometer
which is a TOF-MS spectrometer built into the bore of a
superconducting magnet. FT-ICR is mass spectrometry
using a magnetic field, whereas high-magnetic-field TOFMS is mass spectrometry of a substance under a magnetic
field. Since this spectrometer (TOF-MS spectrometer) can
carry out both mass spectrometry and spectroscopic measurement in a high magnetic field at the same time, it is
possible to perform mass-selected spectroscopy of a substance in a high field. The high-magnetic-field TOF-MS is
expected to be developed further as a new measuring technology for observing a high-magnetic-field effect on biological molecules and nanomaterials.
2. Research trends
As the applicability of mass spectrometry expands to
substances whose mass is large and which have a complicated structure, the mass resolution and mass range which
can be analyzed need to be improved. In mass spectrometry, a gas substance to be analyzed is ionized and mass is
determined from its mass-to-charge ratio (m/z). For the
measurement of mass-to-charge ratio, various techniques
such as time-of-flight mass spectrometry (TOF-MS) and
quadrupole mass spectrometry (Q-MS) are used, but the
development of Fourier transform ion cyclotron resonance
mass spectrometry (FT-ICR) has been promoted in recent
years because it can, theoretically, obtain high mass resolution in comparison with other techniques. In FT-ICR, an
ionized gas sample is introduced into a magnetic field and
is run under cyclotron motion (circular motion). When a
high-frequency voltage conforming to the frequency of
cyclotron motion is applied from outside, the ion absorbs
energy, and the revolution radius of the motion increases.
Since the frequency of cyclotron motion differs according
to the mass-to-charge ratio of the ion, the mass-to-charge
ratio can be measured by detecting the absorption of the
high frequency voltage. The mass resolution in FT-ICR
improves in accordance with the increase in strength of the
magnetic field used. Mass spectrometers using 5 T to 10 Tclass superconducting magnets have been developed in
Japan and the US and are already in use.1), 2)
4. Conclusion
The importance of mass spectrometry in fundamental
science is clear from the fact that two Nobel Prizes were
awarded for research achievements in this field in the past
ten years.4), 5) Mass spectrometry is considered to be one of
the most important applications of a high magnetic field to
analytical technology.
References
1) S. Maruyama, L. R. Anderson, R. E. Smalley and Rev. Sci.
Instrum., 61, 3686 (1990).
2) A. G. Marshall and Int. J. Mass Spectro., 200, 331 (2000).
3) Homepage of National High Magnetic Field Laboratory
(http://www.magnet.fsu.edu/).
4) 1996 Nobel Prize in Chemistry (Discovery of fullerene).
5) 2002 Nobel Prize in Chemistry (Analytical method of
biomolecules).
191
Chapter 14. Nanosimulation Science
Takahisa Ohno, Xiao Hu and Hidehiro Onodera
Computational Materials Science Center, NIMS
1. Introduction
The peak performance of the Earth Simulator, the fastest
computer in Japan, is 40 TFLOPS (40 tera floating operations per second). It was ranked as the fastest computer in
the world, but recently fell to the third following the Blue
Gene (91 TFlops) and Columbia (60 TFlops) in the US.
Such rapid increase of the computer speed makes us possible to perform larger and more accurate simulations in the
computational materials science, and our targets are now
not only simple atoms, molecules or solids, but also more
complicated systems having so-called “nano-scaled” structures.
In Fig. 1, several computational methods in materials
science are shown and categorized with respect to the system size and time-scale of the phenomena of our targets.
They are first-principles calculations, which consider the
electronic structures as well as the atom movements; classical molecular dynamics (MD) and Monte Carlo simulations
(MC), which treat the collective motion of the atom or molecules; finite element methods (FEM) and statistical thermodynamics calculations, whose targets are bulk materials;
and the phase-field method which deals with meso-scale
systems connecting between micro and macro.
Today’s information and communications based society
is built on silicon technologies. Many researchers predict
that we will have a problem of reaching the limit of downsizing in the near future. The target we need to work on is
in the nano-scale region, which requires micro analysis and
Macro-scale
Finite element method
Statistical thermodynamics method
Time
Meso-scale
Phase-field method
Cellular automaton method
Atomic-scale
Molecular dynamics method
Monte Carlo method
Atomic state
Quantum mechanics
Space
Fig. 1 Time and space scales of computational science.
192
control and in which unknown functions are being investigated. As the phenomena in this area cannot be clarified by
experiments only, there are great expectations for computational science to employ the efficient way of research. It is
expected that simulations would first predict the phenomena in this region, and then, for selected targets, experimental verification would be made. This section describes the
present situation and outlook for simulation techniques
which are the key to the computational science.
2. First-principles simulation
The electron wave function, which determines the nature
of a material, is governed by Schrödinger’s equation. It
used to be difficult to solve Schrödinger’s equation of a
multi-electron system numerically. The Density Function
Theory (DFT) proposed by Hohenberg and Kohn in 1964,
shows that the ground state of a system can be described by
a total electron density instead of multi-electron wave functions and that the problem can be ascribed to a single electron problem. 1), 2) DFT enables us to get the electronic
structure from the atomic information alone, and calculations based on this theory are called first-principles simulations. Due to the development of a linearization technique,
pseudopotential methods, etc. and the improvement of
computing power in recent years, it has become possible to
precisely calculate the electronic structures of several hundred atom systems. For the exchange-correlation part, a
more accurate method such as the Generalized Gradient
Approximation3) (GGA) has been developed instead of the
original Local Density Approximation (LDA) from about
1990, and theoretical predictions have become possible for
strongly correlated systems, such as ferromagnetic materials, molecules and so on.
For strongly correlated systems, quantum Monte Carlo
methods which directly solve multi-electron wave functions numerically using Schrödinger’s equation have been
proposed, and the variational Monte Carlo method, the diffusion Monte Carlo method, etc. have been developed. In
the variational Monte Carlo method,4) the electronic structure of a multi-electron system is approximated by a wave
function including an adjustment parameter, and the adjustment parameter is optimized by the variational method to
calculate the total energy. The diffusion Monte Carlo
method deals with Schrödinger’s equation of a multi-electron system with an imaginary time. In the time evolution
of an imaginary time, the ground state of the multi-electron
system is obtained using the fact that any arbitrary initial
wave functions converge to the ground state after a long
time simulation. Maezono and co-workers5) have applied
this technique to the metallic Na and obtained more accurate cohesive energy and the bandwidth than those obtained
by the LDA calculation.
Towards the large-scale simulations, order-N methods,
hybrid methods, and so forth have been proposed since the
1990s. Nano-scaled materials, such as DNA and biomolecules, contain several thousand atoms or more. However, it
was difficult to apply conventional first-principles simulation techniques to such a large system including more than
several hundred atoms because the computational time
increases as N3 with the number of atoms N in the system.
The order-N method is a computational technique in which
the computational cost is proportional to the number of
atoms N, and so offers great potential for large-scale simulations. Order-N methods can be classified into two kinds.
One is the moment expansion method, which includes the
Fermi operator expansion method and the Bond order
potential method, and the linearity of computational cost is
achieved by using a finite number in the moment expansion
of energy or force. The other is based on the variational
principle, which includes the density matrix method6) and
the localized orbital method.7) Linear scaling is achieved by
using localization of a density matrix and the Wannier
function. Recently, Miyazaki and Ohno have started to
apply the order-N method based on the density matrix
method to an actual system, and proved the possibility of
its application to a Ge cluster-system (including about
10,000 atoms) on the surface of Si (001). We expect the
order-N method can be used for various fields such as the
surface nanostructures, catalytic activity of a metallic cluster, and oxygen reaction of a biomolecule.
been proposed. The hybrid methods have been applied to
various systems, such as the mechanical characteristics of
crack propagation, dynamical process to the surface, oxygen reaction in a biomolecule system, etc. Ohno and
Tateyama recently made public their Quantum – Classical
Hybrid Method Program, CAMUS.
For nano-scaled materials, it is extremely important to
analyze and predict the physical properties and their functionalities, and to clarify the relationship between the structures and the functionalities. This is the key for the advance
of the nanotechnologies. Electron transport is one of the
important functions displayed by nanomaterials. In a
CMOS transistor, the thickness of the SiO2 insulating gate
film is only several nm (nanometer), and leakage current
through the film causes a serious problem. In addition, the
use of single molecules or atomic wires has been proposed
to make electronic devices smaller. For the numerical
analysis of electron transport, we need a theoretical technique to treat the electronic structure in an open system,
which is different from the usual one for periodic systems.
For this, the method using the Lippmann-Schwinger equation and the method using the Non Equilibrium Green
Function (NEGF) have been proposed. Nara and Ohno
developed the Lippmann-Schwinger method 8) and the
NEGF method,9) and have investigated the properties of
electron transport in an atomic wire, nanotube, organic
molecule, and so on. They have clarified the dependence of
the conductance upon the point-of-contact structure as well
as on the electrode materials. On the other hand, Kino and
Ohno10) calculated the electronic state of DNA and have
shown theoretically that when hydrating water is removed
(dried) from metallic ions, such as Mg and Zn around a
DNA chain, positive-hole carriers are introduced into the
DNA chain, resulting in electronic conduction. From the
result, they have proposed the possibility of a next-generation nano device using DNA.
Fig. 2 Ge cluster on Si (001) (calculated up to atom 9263 maximum).
Fig. 3 Transfer of hole from metallic ions to DNA chain.
The hybrid method is one of the multi-scale techniques.
The method divides a large system into several regions spatially, applies a most suitable technique for each region,
and analyzes the whole system simultaneously. For a
region requiring analysis of electronic state, we apply the
first-principles MD or the Tight Binding (TB) MD methods. For a region in which there is little change in electronic state and sufficient description by classical interatomic
potential is possible, the classical MD method is applied.
We can use the finite element method for a macro region
where the continuum approximation is sufficient. In order
to seamlessly merge the different techniques at the boundary of different regions, several connecting schemes have
The dielectric response of a material changes depending
upon its frequency, and in the operating frequency area (1
MHz to several hundred GHz) of CMOS, both electronic
states and phonons contribute to the polarization of the
materials. Most of the high-dielectric materials studied as a
candidate of the insulating gate film for the next-generation
CMOS, are highly-ionic materials, like metal oxides and
metal silicates. The polarization due to the phonons is large
for these materials. Thus, we need to analyze both contributions from the electronic part and phonon part to calculate the dielectric response of the materials. We can calculate the contribution from the electronic part using the
193
time-dependent perturbation method, and the contribution
from the phonon part by calculating the phonon frequencies
and by using the Berry phase polarization theory.11)
In principle, DFT can describe the ground states of
materials correctly, and has been highly successful with the
use of LDA or GGA. However, one of its major drawbacks
is that the energy gaps of semiconductors or insulators are
underestimated by about 50%. In the GW method proposed
by Louie et al. in 1985, quasiparticle energies are calculated by evaluating the self-energy with the screened
Coulomb interaction, and the energy gaps can be calculated
more accurately.12) However, as the computational cost is
very large, this method can be applied only to small systems with a few tens of atoms. The Time-Dependent DFT
(TDDFT) method formulated by Gross in 1984 has been
applied with the linear response theory to the calculation of
the adsorption spectra of various gas molecules, and the
results turned out to be very accurate.13) Moreover, using
TDDFT, we can calculate the real-time dynamics of a system after an electron excitation, including both electronic
and atomic dynamics. Tateyama, Oyama and Ohno applied
this method to the photoisomerization reaction of a photochromic molecule, which is a candidate for a future optical switch or memory. The results agree well with experimental results.
Some of the calculation techniques to analyze the structure and functionality of materials shown in the above are
open to public as the outcomes of the IT program project
“Frontier Simulation Software for Industrial Science” of
the Ministry of Education, Culture, Sports, Science and
Technology.
References
1) P. Hohenberg and W. Kohn, Phys. Rev., 136, B864 (1964).
2) W. Kohn and L. J. Sham, Phys. Rev., 140, A1133 (1965).
3) J. P. Perdew, K. Burke and M. Ernzerhof, Phys. Rev. Lett., 77,
3865 (1996).
4) W. M. C. Foulkes, L. Mitas, R. J. Needs and G. Rajagopal, Rev. of
Modern Phys., 73, 33 (2001).
5) R. Maezono, M. D. Towlor, Y. Lee and R. J. Needs, Phys. Rev., B
68, 165103 (2003).
6) T. Miyazaki, D. R. Bowler, R. Choudhury and M. J. Gillan, J.
Chem. Phys., 121, 6186 (2004).
7) T. Ozaki and H. Kino, Phys. Rev., B 69, 195113 (2004).
8) J. Nara, W. T. Geng, H. Kino, N. Kobayashi and T. Ohno, J. Chem.
Phys., 121, 6485 (2004).
9) H. Kondo, H. Kino and T. Ohno, Phys. Rev., B 71, 115413 (2005).
10) H. Kino, M. Tateno, M. Boero, J. A. Torres, T. Ohno, K. Terakura
and H. Fukuyama, J. Phys. Soc. Jpn., 73, 2089 (2004).
11) T. Yamamoto, H. Momida, T. Hamada, T. Uda and T. Ohno, Thin
Solid films, 2005 (in press).
12) M. S. Hybertsen and S. G. Louie, Phys. Rev. Lett., 55, 1418 (1985).
13) E. Runge and E. K. U. Gross, Phys. Rev. Lett. 52, 997 (1984)
electric and magnetic fields, density and temperature,
which are crucial for nano technologies with low energy
consumption. The search and control of these systems are
therefore not only of academic interests but also of application importance. Hot topics include studies on new superconductivity phenomena, nano-ferromagnetism, spintronics, and polymer-based materials.1)-13)
As a macroscopic quantum phenomenon, superconductivity has remained a central subject in condensed matter
physics since its discovery. The well-known equipment
MRI (magnetic resonance imaging) for observing into
brains in clinical practice is actually based on the advantage of the quantum interference property of superconductivity in measuring a tiny magnetic field. Today, researches
on making full usage of the potential of superconductivity
phenomenon are going on worldwide. For example, the
implementation of quantum bits and quantum calculation
using the so-called Josephson junctions offers a better scalability than other competing techniques.2) Another effort is
to excite laser of tunable terahertz frequency based on single crystals of the so-called high-Tc cuprate superconductors.3)
The clarification of the thermodynamically stable states
of interlayer Josephson vortices is an important research
theme since it lays the basis for the above-mentioned laser
radiation. In superconductivity state, the magnetic field
penetrating into the sample is quantized into tiny pieces,
known as the flux quantum or quantum vortex. Flexibility
of Josephson vortex lines because of thermal fluctuations,
anisotropic interaction between vortex lines and the commensuration effect between the vortex alignment and the
underlying layer structure of high-Tc cuprate superconductors produce rich physics, which is not experienced in conventional systems. Hu and Tachiki were the first to find a
novel thermodynamic state of interlayer Josephson vortices, in which vortex lines within same layers exhibit
quasi-long-range order, while those in different layers show
short-range order (Fig. 4).5), 10)
Japan is one of the top runners in the pace of developing
quantum bits and quantum calculation using Josephson
junctions as well as terahertz laser radiation based on highTc superconductors. In the former topic, NEC and NTT
3. Strong coupling modeling
Much recent attention has been focused on the investigation of strongly correlated systems. Because of the effects
of many-body correlations, a system may exhibit a large
response to a small variation of external conditions, such as
194
Fig. 4: Left-top: schematics of interlayer Josephson vortex line. Leftbottom: Structure factors for the lattice and the novel phases. Right:
Magnetic field vs. temperature phase diagram of interlayer Josephson
vortices obtained by large-scale Monte Carlo simulations.
have succeeded in the implementation and control of two
quantum bits. In the latter topic, a theoretical proposal was
made by Tachiki et al., and research based on large-scale
numerical calculation by the Earth Simulator is going on.
Concerning the new state of the interlayer Josephson vortices proposed by Hu and Tachiki, two research groups in
the US and France are planning to carry out experiments in
order to confirm the theoretical proposal and to map out the
total phase diagram.
References
1) S. Murakami, N. Nagaosa and S. C. Zhang, Science, 301, 1348
(2003).
2) Y. Nakamura et al., Nature, 398, 786 (1999).
3) M. Tachiki et al., Phys. Rev. B, 71, 134515 (2005).
4) X. Hu, S. Miyashita and M. Tachiki, Phys. Rev. Lett., 79, 3498
(1997).
5) X. Hu, M. Tachiki, Phys. Rev. Lett., 85, 2577 (2000).
6) X. Hu, Phys. Rev. Lett., 87, 057004 (2001).
7) Y. Nonomura and X. Hu, Phys. Rev. Lett., 86, 5140 (2001).
8) A. Tanaka and X. Hu, Phys. Rev. Lett., 88, 127004 (2002).
10) X. Hu and M. Tachiki, Phys. Rev. B, 70, 064506 (2004).
11) X.G. Wan, M. Kohno and X. Hu, Phys. Rev. Lett., 94, 087205
(2005).
12) X. G. Wan, M. Kohno and X. Hu, Phys. Rev. Lett., 95, 146602
(2005).
of thermodynamic data, the realistic approach is to predict
the thermodynamic parameters based on the first principles
calculation which can be used as a part of the database of
the CALPHAD method.5)
Concerning a stable phase in an equilibrium state, accurate prediction has become possible. However, for the prediction and control of materials microstructure, information
on the equilibrium structures based on a phase diagram is
insufficient, and we need a technique for predicting time
dependent microstructure evolution. The phase-field
method6) is a hopeful technique to analyze the time dependent process of the microstructure formation. Here, the
shape of microstructure is expressed by variables such as
the chemical compositions and the order parameters and
the time development of microstructure is obtained by solving their evolution equations. Koyama7)-10) and his group
have successively clarified the dynamics of various
microstructure-forming processes in real materials based on
the phase field method, and it is becoming possible to predict microstructure in practical alloy systems (Fig. 5).
The phase-field method can handle sizes from nano to
4. Prediction of nano-structures and properties
Phase diagrams are indispensable for materials development, and they have been determined by experiments for
many systems. Because it is not possible to determine all
phase diagrams of multi-component systems by experiments, a phase-diagram calculation technique called CALPHAD (CALculation of PHAse Diagram) has greatly
advanced in recent years owing to the sophistication of
thermodynamic modeling1) and the higher performance of
computers. Commercial software packages such as Thermo-calc,2) ChemSage, P*A*C*T, and Pandat are sold as
systems equipped with a thermodynamic database, an equilibrium calculation function, and a construction function,
and such software is being used for the development and
analysis of materials because they can reproduce, with high
precision, phase diagrams of complicated multi-component
alloy systems for practical use.
Now, one of the important targets here is to expand the
thermodynamic database, and a database indispensable for
developing advanced materials such as Pb-free solder
alloys3) has been developed. Great advances have been
made concerning thermodynamic modeling. Kikuchi 4)
developed the Cluster Variation Method (CVM) in which
the distribution of atoms is considered not as a point but as
a pair of atoms and units of a triangular cluster. The CVM
can deal with the short range order existing in a solid solution alloy. The phase diagram calculation based on first
principles is academically important but requires enormous
computation. Therefore, when there is no measured value
Fig. 5 Two-dimensional simulation of γ’ precipitation process in Ni-Al
alloy based on phase-field method (973 K isothermal aging).
meso scale, and in order to handle the scale of an actual
products, it must be coupled with some other techniques
such as the finite element method. In NAREGI, which is a
national project of the Ministry of Education, Culture,
Sports, Science and Technology, a multi-scale simulation
technique is now being developed.
In analyzing changes of internal microstructure using
FEM as the core method, materials parameters such as
recrystallization rate constant and the recovery velocity are
missing. If these materials parameters can be theoretically
obtained as a function of chemical compositions based on
the phase-field method, the MD method, etc., then the prediction of macro-structure will progress dramatically. Concerning the prediction of mechanical properties, too, various techniques have been developed in order to model the
deformation process after describing the elementary
process of plastic deformation, and it is possible to analyze
the deformation process of polycrystalline materials including the dislocation distribution inside a grain and the formation of sub-grains by the homogenization method, the
crystal plasticity theory, and the diffusion equation of dis195
locations.
5. Conclusion
The ultimate goal for nano-bio materials is to achieve
innovative functions and to design and control such functionalities. It is necessary to develop advanced nano-simulation techniques which enable us to clarify the relationships between the electronic structures, physical properties
and functions of these materials. Developments and
improvements of the simulation techniques for very largescale simulations, multifunctional analysis (multi-physics),
strongly-correlated modeling and multi-scale techniques
are urgently needed.
196
References
1) T. Abe and B. Sundman, CALPHAD, 27, 403 (2003).
2) B. Sundman, B. Jansson and J. O. Andersson, CALPHAD, 9, 153
(1985).
3) I. Ohnuma, M. Miyashita, K. Anzai, X. J. Liu, H. Ohtani, R.
Kainuma and K. Ishida, J. Electron Mater., 29, 1137 (2000).
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(2004).
6) R. Kobayashi and Bull. Jpn. Sco. Ind. Appl. Math., 1, 22 (1991).
7) M. Ode, S. G. Kim, W. T. Kim and T. Suzuki, ISIJ Int., 45, 147
(2005).
8) T. Koyama and H. Onodera, Metals and Mater. Int., 10, 321 (2004).
9) T. Koyama and H. Onodera, Mater. Trans., JIM, 44, 1523 (2003).
10) T. Koyama and H. Onodera, Mater. Trans., JIM, 44, 2503 (2003).
Chapter 15. Technologies New Materials Creation
Section 1. Particle-Beam Technologies
Naoki Kishimoto
Nanofunction Group, Nanomaterials Laboratory, NIMS
Kazutaka Mitsuishi
In-situ Characterization Group, High Voltage Electron Microscopy Station, NIMS
1. Introduction, world trend
Particle-beam technologies with ions, electrons and neutral atoms for creating nanostructures have greatly
advanced in recent years. This section starts with ion
implantation and irradiation technology. The authors analyzed the recent research trend by counting papers devoted
to various topics at the IBMM-14 (conference on Ion Beam
Modification of Materials, US in September 2004) 1) which
is one of the most important international conferences in
this field. Among 343 papers in total, the largest number
was on radiation damage (22.7%), followed by semiconductor applications (20.7%), nanoparticles and nanostructures (16.6%), plasma-immersion implantation (16.3%),
biological applications (6.4%), high-energy ions (5.2%),
and beam lithography. Other papers, such as beam-solid
interactions (2.9%) and magnetism applications (2.3%),
were reported but in small numbers. It is not surprising that
radiation damage and semiconductor applications dominated, occupying first and second place in the number of
papers, because of their long history. What is noteworthy is
the third place occupied by the field of nanoparticles and
nanostructures, which has rapidly advanced in the last 5 to
10 years. This rising field offers the potential of using the
nonequilibrium processes and excellent controllability of
ion implantation. Research institutes active in this field are
Oak Ridge National Laboratory, Vanderbilt University,
Alabama A & M University (all in the US), FOM (the
Netherlands), FZ Rossendorf (Germany), Padova University (Italy), Australian National University (Australia), and
NIMS. Plasma-immersion implantation in fourth place is
an emerging field, but it should be regarded as a processing
technology or a parts-making technology which is different
from a genuine technology for creating new materials and
will not be considered further in this section.
One technology which has attracted attention in recent
years is beam-induced chemical vapor deposition which is
advantageous for creation of nanostructures. The technique
for introducing a precursor gas such as an organic metal
into the neighborhood of a specimen and irradiating a
focused beam onto it 2)-5) enables three-dimensional nanos-
tructures to be made with a high degree of freedom, with
low penetrability of ions. In this technique, structures such
as a wineglass of about 2 µm in diameter and a nanobellows have been made. A structure with a minimum size of
about 100 nm has been achieved by a ion beam whose
diameter is about 7 nm.6) Electron beam-induced deposition
aims to make even finer structures by using an electron
beam which can be focused more finely, and this technique
has been widely studied for various gases based on the
method of introducing a gas into a scanning electron microscope.7)-10) In this technique, structures such as a nanodot of
about 10 nm and a needle-like structure of about 15 nm
have been made using an electron beam of about 1 nm. A
research group at Delft University of Technology in the
Netherlands has recently been carrying out both theoretical
and experimental research in this area.11)
Lithography is an excellent technology for mass-producing nanometer elements, but conventional exposure sources
concerning an electron beam are subjected to various problems such as transmission and scattering, diffraction, and
space charge. On the contrary, a low-speed atom beam
such as metastable atoms (He*, Ne*, Ar*) has no problems
with transmission; its limit of diffraction as a material wave
is very small as the mass is large; and it is neutral and has
no divergence without the space charge effect. Therefore, it
has ideal characteristics as an exposure source for nanolithography. Since Berggren and other researchers 12) proposed
neutral atom-beam lithography in 1995, research on it has
been advancing in the US, Germany and Australia. A selfassembled monolayer film (SAM), a hydrocarbon or silicon
polymerized film, and a passivation layer on the substrate
surface are used as a resist.
2. Domestic trend
Ion implantation technology: The main application is
surface modification of materials. Research reports on
improving adaptability of artificial biological materials to a
living body 13) have been published, in addition to industrial
applications such as (a) improvement of crystallinity of
197
YBCO and DLC films by plasma-immersion implantation
in the case of inorganic materials and (b) improvement of
gas barrier properties in the case of organic materials. Concerning nanoparticles, attempts have been made to create
metal nanoparticle (Au, Ag) monolayers in a silicon oxide
film with the aim of making a single electron device.14)
Beam induced vapor deposition: Matsui and his group
are studying creating nanostructures by ions, and have
actually made structures such as a switch and a coil.6) In
making nanostructures using an electron beam, Hiroshima
and his group have made nanostructures using a scanning
electron microscope of up to 30 kV.10)
Atomic beam lithography: In Japan, only the atomic
beam lithography system is developed at NIMS, but creative research on the related technology of atom-beam
holography is underway.15) This technology forms a pattern
with an ultra-slow Ne* atom beam whose monochromaticity is increased by laser cooling passes through a hologram,
and is a promising technique for maskless lithography.
3. Current status and research activities of NIMS
Ion implantation technology: NIMS is promoting the
creation, control, and evaluation of nanoparticles in insulators using a high-current/heavy-ion accelerator. NIMS has
succeeded in controlling nanoparticle precipitation by
wavelength-selective laser irradiation after ion implantation, and in creating oxide nanoparticles, such as ZnO, with
thermal oxidation of implanted substrates. In-situ optical
spectroscopy during formation of nanoparticles, evaluation
of the optical nonlinearity of metal nanoparticles, and the
application to an optical device are in progress.
Beam induced vapor deposition: NIMS has made a finer
structure using a scanning transmission electron microscope (STEM) of 200 kV, which has triggered interest
worldwide.16) With such a powerful electron microscope,
NIMS has succeeded not only in making a nanodot of 4 nm
or less and a three-dimensional structure of 10 nm or less
by an electron beam of 1 nm or less, but also in making a
nanodot of 1.5 nm by controlling the degree of vacuum.17)
Atom-beam lithography: NIMS has succeeded in transferring a pattern onto a gold thin film with the edge width
of 40 nm using an alkanethiol SAM as a resist and using a
He* atom beam as an exposure source.18) Researchers at
NIMS are systematically studying optimum conditions in
accordance with the difference in the length of a normal
chain, and evaluating the transferred pattern. They have
found solarization of the contrast of a transferred pattern in
the process of such research, and clarified that the contrast
of a transferred pattern depends on the length of a normal
chain. They are currently working to clarify the exposure
process by observing desorbed ions by He* irradiation.19)
Moreover, since the spin dependence of desorption probability has been clarified by a spin polarized He* atomic
beam, they are examining the behavior of surface electron
spin.
198
4. Future trend
Concerning the creation of nanoparticles and nanostructures using nonequilibrium processes and good spatial controllability inherent in ion implantation technology, it is
expected that various new nanostructures including not
only metal nanoparticles but also metal oxides and
nanorods will continue to be created. To enhance functionality of the nanomaterials, development of (one- or two
dimensional) nanoparticle-array structures, instead of randomly distributed nanoparticle structures, is indispensable.
Hybridization of beam technology with micro-scale procesing or laser treatment is very important.
Electron-beam induced vapor deposition has adequate
capability for making nanostructures in terms of size and
position controllability, but it is also necessary to develop a
technology for identifying the structures obtained and to
improve physical properties such as crystallinity of nanomaterials obtained.
In atom-beam lithography, a report has been published
concerning a method of depositing an evaporated atom
beam on a substrate while controlling its position and forming structures without a mask or etching treatment, which is
entirely different from conventional lithography. An evaporated atom beam of Na, Cr, Al, etc. is focused by dipole
interaction with the electric field of a standing wave of
light which deviates slightly from the absorption line of the
evaporated atom. Three-dimensional doping has been also
proposed,20) and it is predicted that this technique will be
developed to cover all the elements constituting devices.
References
1) Abstract book, 14th Intern. Conf. on Ion Beam Modification of
Mater., Monterey, California, USA, (2005) Sept.
2) T. Minafuji, Mater. Sci., 38, 184 (2001).
3) J. Fujita, M. Ishida, T. Sakamoto, Y. Ochiai, T. Kaito and S.
Matsui, J. Vac. Sci. Technol., B19, 2834 (2001).
4) G. M. Shedd, H. Lezec, A. D. Dubner and J. Melngailis, Appl.
Phys. Lett., 49, 1584 (1986).
5) S. Matsui, T. Kaito, J. Fujita, M. Komuro, K. Kanda and Y.
Haruyama, J. Vac. Sci. Technol. B., 18, 3181 (2000).
6) S. Matsui, Appl. Phys., 73, 445 (2005).
7) H. W. P. Koops, J. Kretz, M. Rudolph, M. Weber, G. Dahm and K.
L. Lee, Jpn. J. Appl. Phys., 33, 7099 (1994).
8) H. W. P. Koops, R. Weiel, D. P. Kern and T. H. Baum, J. Vac. Sci.
Technol. B., 6, 477 (1988).
9) P.C. Hoyle, J. R. A. Cleaver and H. Ahmed, J. Vac. Sci. Technol.
B., 14, 662 (1996).
10) H. Hiroshima, N. Suzuki, N. Ogawa and M. Komuro, Jpn. J. Appl.
Phys., 38, 7135 (1999).
11) N. Silivis-Cividjian, C. W. Hagen, P. Kruit, M. A. J. v.d. Stam and
H. B. Groen, Appl. Phys. Lett., 82, 3514 (2003).
12) K. K. Berggren, A. Bard, J. L. Wilbur, J. D. Gillaspy, A. G. Helg, J.
J. McClelland, S. L. Rolston, W. D. Phillips, M. Prentiss and G. M.
Whitesides, Science, 269, 1255 (1995).
13) F. Saito, T. Yotoriyama, Y. Nagashima, Y. Suzuki, Y. Itoh, A.
Goto, M. Iwaki, I. Nishiyama and T. Hyodo, Proc. Mater. Sci.
Forum, 445-6, 340 (2004).
14) H. Tsuji, N. Arai, T. Matsumoto, K. Ueno, Y. Gotoh, K. Adachi, H.
Kotaki and J. Ishikawa, Appl. Surf. Sci., 238, 132 (2004).
15) J. Fujita, S. Mitake and F. Shimizu, Phys. Rev. Lett., 84, 4027
(2000).
16) K. Mitsuishi, M. Shimojo, M. Han and K. Furuya, Appl. Phys.
Lett., 83, 2064 (2003).
17) M. Tanaka, M. Shimojo, M. Han, K. Mitsuishi and K. Furuya,
Surface and Interface Analysis, 37, 261 (2005).
18) X. Ju, M. Kurahashi, T. Suzuki and Y. Yamauchi, Jpn. J. Appl.
Phys., 42, 4767 (2003).
19) Y. Yamauchi, T. Suzuki, M. Kurahashi and X. Ju, J. Phys. Chem.
B., 107, 4107 (2003).
20) T. Schulze, T. Muther, D. Jurgens, B. Brezger, M. K. Oberthaler, T.
Pfau and J. Mlynek, Appl. Phys. Lett., 78, 1781 (2001).
199
15 Technologies New Materials Creation
Section 2. Applied Technology of Vacuum Process
Masahiro Tosa
Micro-nano Component Materials Group, Materials Engineering Laboratory, NIMS
1. Introduction
2. Research trend
Fabrication of a new material by controlling the configuration and structure of atoms constituting the material at the
atomic level based on a design drawing is one of the ultimate approaches. In order to treat a material at a
monoatomic or monomolecular level it is necessary to minimize the absorption of gaseous molecules which cause
contamination at the same level. By using an extremely
high vacuum (atmospheric pressure of 10-10 Pa or less) in
which only a few to tens of gaseous molecules exist per 1
mm3, an ultraclean ultimate environment is generated in
which contamination due to surface absorption can be
neglected even at a monoatomic size. Moreover, by constructing an extremely highly integrated process which
consecutively carries out all the multistage operations such
as making the surface of the sample substrate ultraclean,
preparing the film, processing, analyzing the characteristics, and evaluating the performance in an extremely high,
ultraclean vacuum, it is expected to lead to a material
development process which can fabricate new materials at
the atomic or molecular level.
In such a large-type vacuum process, however, there
exist many gas desorption sources which deteriorate the
ultraclean vacuum atmosphere, such as the walls of the
vacuum chamber, the filaments of the vacuum gauge electron system, and the evacuation system. In particular, in a
sample movement-based source in a meter, not only gas
desorption but also generation of dust such as microparticles might occur due to the increase of friction and abrasion
peculiar to a vacuum environment, and in the worst case,
the driving mechanism might seize up by friction and
become inoperable.
To eliminate the friction which can contaminate this
ultraclean space during sliding, it is essential to develop a
non-contact floating transport system which is not accompanied by sliding for a substrate transport-based source, for
which long-haul high-speed transportation is required.
The next section looks at research on the construction of
a magnetic-levitation type extremely highly integrated
process that NIMS is working on to achieve an extremely
high, ultraclean vacuum space for fabrication of materials
at the atomic level.
Japanese universities and research institutes have outdistanced many other countries in research on an ultrahigh
vacuum which is the key technology of an extremely high
vacuum process, especially research on a high-performance
evacuation technology for generating an extremely high
vacuum environment, a technology for reforming a material whose gas absorption is hard and its surface, and an elemental technology for measuring ultra-low atmospheric
pressure with high precision. The results of these studies
have been widely used for the development, etc. of singlefunction measuring and analyzing equipment such as various electron microscopes and surface analyzers as well as a
large high energy accelerator system.
A multi-chamber integrated process has been much used
for developing semiconductors, analyzing the surface of
compounds, etc. However, as a contact-type driving system
was used for moving a substrate in all of the processes,
contamination of the surface of a substrate due to gas desorption following sliding could not be avoided.
In recent years, NIMS has developed a magnetic-levitation type of mechanism for transport in an extremely high
vacuum, as shown in the photo. In this transport system,
the movable body which carries a substrate is made to float
using electromagnetic force and so can travel long distances by using a driving mechanism with a linear motor.
Since there exists no contact part that suffers friction or
seizing up during driving, almost no dust particles and no
gas desorption are generated that would damage the ultraclean, extremely high vacuum environment and ultraclean
substrate surface. By installation of an electromagnetic-levitation type transportation mechanism which can perform
long-distance levitation transportation in a main line as a
transportation device, and also by installation of an oxide
superconductive levitation transportation mechanism offering tough positioning power required for a branch line that
receives and delivers substrates between the main line
transportation system and a vacuum apparatus to be connected, it is possible to receive and deliver substrates while
keeping the substrate surface ultraclean at an atomic and
molecular level between each vacuum apparatus connected
such as film-preparation apparatus and surface analysis
apparatus. This system is the extremely high vacuum integrated process unprecedented in the world.
200
Electromagnetic-levitation
transportation system.
Superconducting magneticlevitation transportation.
Photo: Extremely high vacuum integrated process equipped with
magnetic levitation type transportation systems.
to a nano scale. This will be highly promoted by the
increase in performance of the extremely high vacuum integrated process that provides consistent operations at each
process in an extremely high, ultraclean vacuum environment at the atomic or molecular level, which will contribute to the fabrication of next-generation new advanced
materials and micro-nano devices.
4. Conclusion
Elemental technologies which can use an extremely high
vacuum or an ultraclean environment at an atomic level
have almost fully come out, and the extremely high vacuum integrated process which has been constructed by integrating the elemental technologies is expected to exhibit its
true value in the creation and fabrication of new advanced
materials and devices by establishing transportation accuracy and reliability.
3. Future trend
Although the extremely high vacuum integrated process
developed by NIMS receives and delivers ultraclean substrates, control of the transportation positioning is sometimes not so accurate, and so reliability of the system needs
to be improved. In fabrication of next-generation LSI
devices, research will focus on downsizing from a semiconductor-based material in which gas absorption on the
surface of a substrate is hard, to a metal-based material in
which such gas absorption is easy, or from a micron scale
References
1) M. Tosa and K. Yoshihara, J.Vacuum Society of Japan, 40, 156
(1997).
2) M. Tosa, A. Kasahara, K. Lee and K. Yoshihara, J.Vacuum Society
of Japan, 42, 443 (1999).
3) M. Tosa, K. S. Lee, A. Kasahara and K. Yoshihara, Vacuum, 60,
167 (2001).
4) M. Tosa, K. S. Lee, Y. S. Kim, A. Kasahara and K. Yoshihara,
Appl. Surf. Sci., 169, 689 (2001).
201
Chapter 16. Acquisition and Transmission of
Materials Information Data and
Information
Section 1. Structural Materials Data Sheets
Saburo Matsuoka
Materials Information Technology Station, NIMS
1. Introduction
In order to secure the reliability of machines, structures,
plants, etc., materials data are indispensable. NIMS has
accumulated materials data related to creep, fatigue, corrosion, and space use; publishes about ten data sheets every
year; and has distributed them to about 1,000 organizations
inside and outside Japan. NIMS has almost a 40-year history of working on creep and fatigue data sheets, and its data
sheets including those on corrosion and space use materials
are highly valued inside and outside Japan. These data
sheets are based on ISO9001 “Quality Management System”. The achievements of each data sheet and research
trend are summarized below.
2. Creep data sheets
We published three volumes of creep data sheets in
FY2004, which are 1) base metal, weld metal and welded
joint of hot rolled stainless steel SUS316-HP (18Cr-12NiMo-middle N-low C) (No.45A), 2) alloy steel tube for a
power boiler KA-STBA27 (9Cr-2Mo) (No.46A), and 3)
metallographic atlas of long-term crept materials on three
types of 2.25Cr-1Mo steels (No. M-4). By FY2004, we had
published 132 volumes of creep data sheets, including four
volumes of metallographic atlas. We have also obtained
708 creep test data for long durations exceeding 100,000
hours (about 11.4 years) including data for which experiments are still underway.
We clarify the mechanism of degradation occurring in
accordance with prolonged use at high temperature, and
study methods of predicting long-term creep strength using
the valuable long-term creep test data which we have accumulated over about 40 years. Regarding high-strength highCr ferrite heat-resistant steel which has recently been used
to improve the efficiency of thermal-power generation
plants, a drop in strength was found with long-term use that
could not have been predicted based on past knowledge,
202
and in fact an accident occurred. Based on creep data
sheets, we therefore proposed an easy and precise method
for predicting long-term creep strength (NIMS method) and
for analyzing and evaluating long-term creep strength using
half of the 0.2% offset yield stress as an index. In FY2004,
based on long-term creep strength analysis by the NIMS
method, we reviewed the allowable tensile stress regulated
in the national standard. The creep data sheets have contributed greatly to improved safety in high-temperature
plants such as power generation and petrochemical plants.
We have focused on creep fracture in the past creep data
sheets, but will systematically acquire creep deformation
data and publish creep deformation data sheets in the
future. We are also planning to acquire creep data on an Al
alloy, Mg alloy, etc. which is in great demand for energy
saving in transportation equipment such as automobiles as
well as creep data on light-weight nonferrous metals.
3. Fatigue data sheets
In FY2004 we published 1) giga-cycle fatigue data
sheets (No. 97) for carbon steel S40C (0.4C), and 2) gigacycle fatigue data sheets (No. 98) for a titanium alloy Ti6Al-4V (1100-MPa class). Among 98 volumes of fatigue
data sheets, there have been as many as 14 volumes of
high-cycle fatigue data sheets which we started publishing
in 1997 on high-temperature fatigue and welded joint
fatigue characteristics in addition to room-temperature
fatigue and titanium-alloy fatigue.
In recent years, the issues of long-term use of structures
and extension of life have emerged as problems to be
solved, and the trend of fatigue research has been shifting
toward clarifying fatigue fracture at ultrahigh cycle of 107
or more, especially internal fractures, for which data have
not been obtained to date. Therefore, the published longterm fatigue data sheets are well-timed data sheets. In particular, NIMS has developed an ultrahigh cycle fatigue testing method using a 20-kHz ultrasonic fatigue tester for
accelerated fatigue testing, and has developed a test method
which can obtain data on fractures of up to 1010 cycles in a
short time. These data sheets, which focus on fatigue that
causes internal fracture to occur from an intermediary as a
starting point newly named “giga-cycle fatigue”, are very
useful for engineering and are highly valued in industry.
Concerning welded joints, we have also obtained data of up
to 108 cycles in a large-type joint test, and are striving to
interpret a new welded joint fatigue strength that has not
existed before. In addition, we are undertaking epoch-making research, for example, on a new method of observing
metallic structures using an atomic force microscope
(AFM) and associating micro and macro structures and
hardness based on the measurement of nano-hardness.
High-cycle fatigue data sheets are well underway and
data have been steadily published, but we are planning to
advance toward new materials and fields of new test conditions such as: giga-cycle characteristics in an average stress
state and a thickness effect in welded joints; systematic
study of notch effects; and high-temperature characteristics
of Ni-base superalloys.
4. Corrosion data sheets
Corrosion is a chemical phenomenon which changes
endlessly according to the combination of material and
environment. NIMS’s corrosion data sheets cover atmospheric corrosion phenomena among a variety of corrosion
phenomena available at the moment. About seven years
have passed since we started an atmospheric exposure test
on the binary alloys of Fe-Ni and Fe-Cr systems in 1998 in
order to acquire basic data on corrosion-resistant low-alloy
steel in a coastal environment and establish development
guidelines for it. Concerning the atmospheric corrosion of
these steel materials, we gathered all data together three
years after starting the exposure test, and published corrosion data sheets No. 1A in FY2002. We collected data on
the atmospheric corrosion of binary alloys of Fe-Al and FeSi systems and published corrosion data sheets No. 2 in
FY2004.
We are also working toward issuing corrosion data sheet
materials in March 2006 which will include photographs on
the external appearance of test pieces, influences of alloy
elements and weather factors upon durability, etc. that we
could not include in No. 1A and No. 2.
There has been an immense reaction since corrosion
data sheets No. 1A was issued, and we have since received
opinions from many people requesting us to issue corrosion
data concerning various materials and environments. We
will positively study these opinions, reflect them in future
research for corrosion data sheets, and aim to issue corro-
sion data sheets that will be increasingly useful.
From now on, we will evaluate the corrosiveness of various materials including practical materials in an atmospheric corrosive environment, and enrich basic data concerning atmospheric corrosion phenomena.
5. Data sheets on strength of materials for space use
We started to produce data sheets on the strength of
materials for space use after the LE-7 engine of H-II Rocket No. 8 was raised from 3,000 meters down on the seabed
west of the Bonin Islands in January 2000. It was pointed
out while searching for the cause of the accident that there
was almost no strength data on the materials of domestically-made rockets, that data of NASA in the US had been
used to design the rocket, and that information about
microstructure and fracture surface, which were indispensable for analyzing the accident and resolving defects during
all development stage, had not been well prepared. As
NIMS had developed test technologies concerning these
matters, NIMS was requested to prepare data. While NIMS
prepared materials strength characteristics data jointly with
the Japan Aerospace Exploration Agency, NIMS published
data sheets on the strength of materials for space use based
on the past data sheet results, with the aim of not only
obtaining data and providing it for the design, but also providing data to the public to be widely used and to help
those who handle similar materials, thus improving the reliability of materials themselves.
Starting with the data sheets from the liquid hydrogen
fuel turbo pump (FTP) and engine materials of the H-IIA
Rocket, we published data sheets one after another for titanium alloys, Alloy 718, and superalloys, and we published
1) data sheets (No. 5) on the destruction toughness of an
Alloy 718 forged material and high-cycle fatigue characteristics, and 2) data sheets (No. 6) on the destruction toughness of an A286 forged material and high-cycle fatigue
characteristics, thus contributing to the successful launch of
the H-IIA.
In the process of acquiring the materials strength data
for publication of such data sheets, we obtained many useful findings for improving the characteristics and reliability
of future materials such as the influence of grain size upon
fatigue characteristics at low temperature, the occurrence of
accompanying internal cracks, and the influence of notch
effects.
We will continue to publish collections of data sheets on
fractures and fatigue crack progress characteristics for
which demand is strong, in addition to strength characteristics data, and will study the acquisition of other engine
materials and important structural materials.
203
16 Acquisition and Transmission of Materials Information Data and
Information
Section 2. Materials Databases
Masayoshi Yamazaki
Materials Database Group, Materials Information Technology Station, NIMS
1. Introduction
Basic data and information on science and technology
have been edited in the form such as dictionaries, encyclopedia, handbooks, manuals, and data books, which have
been in general use for a long time. When large generalpurpose computers became widespread in the 1990s, the
possibility of digitizing huge quantities of data was studied,
and a wide variety of databases have since been constructed as information processing equipment has progressed.
Since the 1990s, people around the world have been able to
share data and information over the Internet thanks to the
rapid diffusion of the world wide web.
Materials data can be classified into the following two
categories: 1) High-quality basic data whose universality is
high (such as physical constants, spectrum information,
nuclear data, structure-independent characteristics, crystal
structures, and phase diagrams), and 2) Fundamental engineering data (various characteristics on practical materials
which are the basis of design and safety assessment). Highquality basic data is made useful data by linking it with
engineering data.
This section describes the situation of the materials databases made public on the Internet at present, as well as
associated problems.
2. Research trends
As an example of high-quality basic data, basic physical
constants were revised greatly and officially announced
toward the end of 1999 after a lapse of over ten years by
the Task Group on Fundamental Constants which was
founded under the Committee on Data for Science and
Technology of the International Council for Science
(CODATA) of the International Council of Scientific
Unions (ICSU).1) The corresponding organization in Japan
is the CODATA sectional meeting of the Science Council
of Japan and the CODATA sectional meeting of the Japan
Society of Information and Knowledge. In Japan, the
National Institute of Advanced Industrial Science and
Technology, an independent administrative institution, has
made spectrum data of organic compounds available to the
204
public.2) Nuclear data is included in the nuclear materials
database of the National Institute for Materials Science,
another independent administrative institution, and crystal
structure information and phase diagrams are included in
the basic crystal structure database (Pauling file) and electronic structure database.3) Concerning such database-making activity, it is important to construct databases efficiently through international tie-ups while avoiding the duplication of similar work, and to establish databases as public
goods to be used all over the world.
Fundamental engineering data and information are indispensable not only for researchers and technical experts but
also for designers of equipment. Such data is used for
materials design and various simulations. It is also used for
selecting materials for equipment design and optimum use
of materials. There are two ways of gathering fundamental
engineering data. One is to collect brochures of materials
manufacturers, make a database of the data, and distribute
it. The other is to accumulate measured data obtained by
various research institutes by carrying out materials tests or
data collected from scientific reference materials and compile them into a database. Therefore, a database containing
characteristic values as well as information on the manufacturing process of a material, measuring equipment,
shape, size and test conditions of a test sample, and test
organizations needs to be constructed to enable fundamental engineering data to be used in industry. However, there
is no research institute in the world that collects data systematically, compiles databases therefrom and makes the
databases publicly available. The only data available in the
world is data on creep, fatigue, corrosion, and space use
materials strength in the structural materials databases of
NIMS. The largest database of brochures of materials manufacturers is MatWeb, which is the most popular and is
accessed by 16,000 persons a day.4) In Europe, handbooks
and databooks published by publishers are the traditional
format, but CD-ROM versions have been made recently.
As a database on structural materials, the European Commission Joint Research Center (JRC) gathers data of the
EU countries together and distributes it.5)
Reliability (quality) is crucial in a materials database,
but comprehensiveness (quantity) is necessary, too. Moreover, a database must not only gather data but also offer a
retrieval function which can promptly display the data and
information required by a user. However, there is a limit to
the volume of data and information which one organization
can transmit, so Granta Design Ltd. of the UK has developed and made public MATDATA.net, which combines
publicly available databases on substances and materials on
the Internet, and the data of each database can be retrieved
by category of material (ceramic, composite, fiber & particulate, foam, metal, natural and polymer).6) At present, 12
database sites are connected to MATDATA.net, of which
the substances and materials database of NIMS is one. Figure 1 shows the top page of the substances and materials
database of NIMS, and Table 1 shows the materials database connected to MATDATA.net.7)
Concerning universal and high-quality basic data on
materials, research which promotes the accumulation of
data in international tie-ups in order to discover substances
and materials through data informatics will be actively promoted. Accordingly, the representatives of database construction organizations in Japan, the US, and Europe will
study the standardization of XML and MatML to enable
data-sharing, at the materials sectional meeting of the
CODATA.
Concerning fundamental engineering databases, strategic development investment by the government (national
institute) is required. The materials procurement and globalization of manufacturing factories in industry is
inevitable in Asia as seen in the EU. It will become increasingly important to collect, accumulate and transmit data
and fundamental information concerning materials to maintain the quality of products.
4. Conclusion
Fig. 1 Materials Databases of NIMS. http://mits.nims.go.jp
Table 1 Databases Connected to MATDATA.net.
Source
References
Database
Organization
ASM Handbook
ASM Alloy Center
ASM Micrograph Center
ASM International/Granta Design
Ltd.
Ltd.
Ltd.
Past databases were used only by groups engaged in
development, and many of them disappeared as the development budget was curtailed and no data was added when
the R&D period came to an end. Databases must be continuously accumulated by grasping the needs of users and
“usable databases” must be constructed.
Country
USA/
UK
USA/
UK
USA/
UK
PGM Database
Platinum group metals (PGMs)
USA/
UK
IDES Resin Source
IDES Inc.
USA
MatWeb
Automation Creations, Inc.
USA
Metals Universe.com
National Metals Technology Center
UK
MIL-HDBK-5H
Granta Design Ltd.
UK
NIMS Materials Database
NIMS
NPL MIDS
National Physical Laboratory
UK
Steel Spec II
UK Steel
UK
TWI JoinIT
The Welding Institute
UK
1)
2)
3)
4)
5)
6)
7)
1) http://physics.nist.gov/cuu/Constants/Citations/Search.html
http://www.aist.go.jp/RIODB/riohomej.html
http://mits.nims.go.jp
http://www.matweb.com/index.asp?ckck=1
http://odin.jrc.nl/
http://matdata.net/index.jsp
K. Yagi, Problems and Future Perspectives of Materials Database,
Sci. &Tech. Tendency, No. 42, pp. 22 to 33 (2004).
Japan
205
Chapter 17. International Standard
Section 1. Standard Materials
Shigeo Tanuma
Fundamental Chemical Analysis Group, Materials Analysis Station, CNIMS
1. Introduction
In order to promote fair and smooth national trade, it is
necessary to quantitatively evaluate the international equivalence of measured and analyzed values of substances and
materials, and their reliability. In people’s daily lives, the
equivalence and reliability of analyzed values in the fields
of environment, food, health, and so are also very important. This requires the traceability of those values to be
kept. Traceability is called “sourceability” or “retroactivity,” and means “the ability to trace the source of something.” In other words, it means that a measured value is
associated with an international standard or can be traced to
an international standard with some degree of uncertainty.
That is, the accuracy and trueness of standard equipment
used to perform a test or a standard substance on which a
test is performed are associated with international measurement standards and whether they can be traced to the
International System of Units (SI) based on the international definition in the Meter Convention.
(CCEM), 2) Photometry and radiometry (CCPR), 3) Temperature scale (CCT), 4) Length (CCL), 5) Time and frequency (CCTF), 6) Ionizing Radiation (CCRI), 7) Unit
(CCU), 8) Mass and Related Quantities (CCM), 9) Amount
of a Substance (CCQM), and 10) Acoustics, ultrasound,
and vibration (CCAUV). Of these fields, CCQM deals with
chemical quantity standards using an amount of a substance
(mol) as a basic unit, and is closely related to the material.
The consultative committees develop various standard samples which serve as a scale for measurement chemical substances and component standards which are used to calibrate measument methods and measument equipments. In
recent years the consultative committees have been energetically preparing standard materials and standard measument methods jointly with the World Health Organization
and the International Food Standards Committee. Meanwhile, as the field of materials (particularly including the
measurement and analysis of substances on the nano scale)
cannot be covered by the ten fields specified above, it has
been proposed that a Consultative Committee on Materials
Metrology (CCMM) be newly established.
2. Certified standard materials and development trend
Standard materials are developed to adjust the needs of
communities, social structures, corporations, organizations,
etc., but ultimately they should also be valid globally.
Therefore, “certified” standard materials or high-ranking
standard materials are important. The strict definition of
these standard materials is described in ISO Guide 30, but
for certified values of characteristics, international equivalence based upon traceability is the most important, and so
it is necessary to make traceability to the SI units as certain
as possible.
As described above, it is indispensable to be able to
mutually validate analyzed and measured values on a global basis, and the International Committee of Weights and
Measures (CIPM) has 10 consultative committees in addition to the International Bureau of Weights and Measures
(BIPM), and its mission is to unify international unit systems and measurement standards (standard materials and
standard measurements methods) of basic quantities in
each field. The fields with which the consultative committees deals are as follows: 1) Electricity and Magnetism
206
3. Certified standard materials for surface and microarea analysis
Standard materials are used in such a wide range of
fields that it is difficult to give an overview of all fields.
Thus, this section describes only certified standard samples
in nano-scale analysis (which is limited to the method of
measument a substance of 100 nm even in one axis out of
three-dimensional measurement). Table 1 shows these certified standard materials. As can be seen, the number of
certified high-ranking standard materials in this particular
field is very small. It is hoped that secondary standards and
practical standards to enable materials measurement on site
will be promptly developed in this field.
References
1) Masaaki Kubota, “Standard Substances – For Securing Reliability
of Analysis and Measurement”, Kagaku Nipposha (1998).
2) ISO Guide 30, 31; ISO 14606, 156969.
3) Koichi Chiba, Bunseki, 125 (2005).
4) “Auger Electron Spectroscopy” ed., J. Japanese Society of Surface
Science, Maruzen (2001).
Table 1. Examples of certified standard substances in surface analysis.
Name of
Thickness
Certifying
Name of
Distributing
material
(mm)
organization
product
organization
1
Ta2O5/Ta
30 and 100 (4) IRMM
No. 261
BCR2
3
Ni/Cr
66/53 (8)
NIST
NIST
2135c
multilayer film
AlAs/GaAs
NIMC4
25/25 (4)
SASJ5
multilayer
Cr/CrO
NIST
NIST
2136
29 – 30
Ta2O5/Ta
KRISS6
KRISS5
03-04-10
30/30 (6)
multilayer film
Certified values are thickness. Numerical values in ( ) are the number
of layers.
1: Institute for Reference Materials and Measurements
2: Community Bureau of Reference
3: National Institute for Standards and Technology
4: National Institute of Materials and Chemical Research
5: Surface Analysis Society of Japan
6: Korea Research Institute of Standards and Science
207
17 International Standard
Section 2. International Standardization Research, VAMAS
Toshio Ogata
Cryogenic Materials Group, Materials Information Technology Station, NIMS
1. Introduction
International standardization research in NIMS aims at
developing new evaluation methods required for the application and practical implementation of new materials
through a pre-standardization activity and promoting
international standardization thereof. In particular, the following are important in international standardization
research: 1) making newly-developed materials and new
evaluation methods known to the public, 2) increasing
Japan’s contribution to international standardization activities, and 3) contributing to the general public through
internationalization activities.
VAMAS (Versailles Project on Advanced Materials and
Standards) is one of the international research cooperation
projects agreed upon at the 1982 Group of Seven summit,
and its purpose is to promote international standardization
through international cooperation concerning advanced
materials and to stimulate foreign trade in advanced technical products.1), 2) The steering committee of VAMAS is
made up of senior officials of governmental organizations
in the seven summit countries and ISO who are engaged in
materials and standards. VAMAS, which currently has 30
technical working areas (TWA, experts’ sectional meetings), terminates the activities of the TWA once it has
achieved its goal, and continually keeps its activities up to
date in line with the needs agreed upon by each country.
Each TWA is composed of national research institutes, universities, and private enterprises of each country. Concerning the TWA sectional meeting marked with an asterisk (*)
shown in Fig. 1, a researcher at NIMS acts as chairman of
that TWA sectional meeting, thus taking the leadership in
that field.
2. Merits and outcomes of VAMAS
Steering Committee
Seven summit countries + EU
(Director General-class officials
of research institutes)
UK (chairman), Japan, USA, Canada, France,
Germany, Italy, EU, and ISO (observer)
Technical Working Areas (TWA)
01 Wear test methods
02 Surface chemical
analysis
03 Ceramics for structural
applications
05 Polymer composites
10 Computerised
materials data*
13 Low-cycle fatigue
16 Superconducting
materials*
17 Cryogenic structural
materials*
18 Statistical techniques
for interlaboratory
studies and related
projects
20 Measurement of
residual stress
Japan VAMAS Committee
21 Mechanical
measurement for hard
metals
22 Mechanical property
measurements of thin
films and coatings
24 Performance related
properties for electroceramics
25 Creep/fatigue crack
growth in components
26 Optical measurement
of stress and distortion
27 Characterization
methods for ceramic
powders and green
bodies
28 Quantitative mass
spectrometry of
synthetic polymers
29 Nanomaterials
30 Tissue engineering*
Fig. 1 Organization and Technical Working Areas of VAMAS.
208
Much remains to be established in the evaluation of
advanced materials and there are major differences among
organizations, so the first mission of VAMAS is to determine measuring and evaluating methods which can be used
VAMAS activities
ISO International Standards Procedure
Proposal of new work items (NWIP)
Working draft (WD)
Final working draft
Technical transfer
assessment report
(proposal of tests
and measuring
methods)
1st
Committee draft (CD)
Final
Partially agreed
standards (PAS)
committee draft (FCD)
Draft of international
standards (DIS)
Final draft
Technical
standards
of international standards (FDIS)
International
standards
Fig. 2 International Standards Process of ISO and Liaison with
VAMAS.
as standard ones. By participating in an international
round-robin test of VAMAS and comparing measured
results obtained on common samples with the results of
other organizations, it is possible to improve the evaluation
technology and reliability of the participating organizations.
The achievements obtained through VAMAS activities
become international standards by being submitted to ISO
and IEC. It takes several years to establish international
standards, so some successes first emerged ten years after
activities on them first started. These have contributed to
the creation of about 60 standards of the ISO and the
American Association of Test and Materials (ASTM).
Since the international round-robin test is held at the convenience of the organization which carries out the test, it is
not easy to collect the results as scheduled. Moreover, it
takes a long time to gather international standards together
because the opinions of people in many countries are
solicited, collected by each country, and are then distributed and adjusted. Although circumstances differ according
to each TWA, the steady establishment of international
standards is one of the great achievements of VAMAS.
In recent years, as VAMAS has gained international
repute, its liaison with ISO has been strengthened, and their
respective achievements are now mutually respected.
Under such circumstances, the registration of achievements
of VAMAS in the ISO standards has been promoted, and
by collecting and organizing the results of the international
round-robin test of VAMAS (a test in which common samples are distributed to each participating organization and
test results are compared) and proposing the organized
results as technical transfer assessment documents (TTA
documents), it has become possible to speed up the discussions, as shown in Fig. 2.
NIMS has organized a Domestic VAMAS Committee
consisting of a VAMAS steering committee member and
experts involved in international standards, and NIMS will
arrange domestic standardization activities, deliberate
Japan’s contribution in the field of VAMAS international
joint research, and propose new TWA(s). Research
achievements and cooperative relationships obtained from
positive activities toward new materials and international
standardization of the methods of testing them in cooperation with VAMAS will boost Japan’s influence in ISO and
IEC, thus enabling Japan to easily propose standards of
which it takes the lead. This is because in order to propose
international standards, adequate supporting research data
and the development of international cooperative relationships are necessary; even if an international standard is
suddenly proposed to the ISO, it will be difficult to gain
consent even to consider the proposal.
tionally, but this requires the accumulation of data as the
basis of standards through the international round-robin test
in cooperation with researchers both inside and outside
Japan. It is also necessary to obtain the understanding and
approval of many people concerning the proposed test
method.
Since international standards are established by obtaining positive approval through lengthy discussions and the
work of many countries, such standards have a greater
impact than is generally imagined, and can trigger the proposal of other standards. The larger the impact of international standards, the more difficult it is to balance the merits and demerits of many countries. Moreover, since the
number of proposal achievement is related to the appointment (or acceptance) of a lead manager country, and this
increases the power of persuasion in the ISO and IEC and
makes it easy to arrange a prior agreement, it is necessary
to emphasize and highly appreciate steady activities.
International standards of materials evaluation are
important technologies pertaining to not only the promotion of foreign trade related to shipment inspections but
also the safety and reliability evaluation of materials and
the prediction of remaining life of existing infrastructures
from a national interest point of view. If foreign technology
and standards are introduced too easily, then the people
engaged in such work may use the technology or standards
without knowing the basis of them; they may not know the
technology which is involved until the technology or standards are established, or techniques for evaluating the technology or standards may disappear. Unless Japanese
researchers have underlying data for standards and the
potential to counter foreign researchers, and promote
international standardization activities positively, then various standards including design standards and safety standards will be dominated by other countries, and Japan will
not be able to leave technologies and markets to the next
generation. By promoting international standardization
activities positively and proposing international standards,
the research institutes and industrial world that participate
therein can maintain the same technical level as in other
countries.
Judging from the fact that many countries include nanomaterials in their national policies and are beginning to
compete in international standardization, the international
standardization activities of VAMAS will clearly rise in
importance in government and industry. Since it takes five
to ten years to propose and establish international standards
which are binding internationally starting from the proposition and verification of our own method of assessing characteristics, it is essential to increase the appreciation of
research in order to foster successors.
3. Importance of VAMAS international standardization
activities
References
One of the clear means of using the achievements
obtained in substances and materials research for the common good of society is to establish international standards
(an international law) which have binding power interna-
1) Tetsuya Saito, VAMAS in International Standardization, Bulletin of
Jpn. Soc. of Machin., 102, 302 (1999).
2) Toshio Ogata, Yoshitaka Tamao, Current Conditions and Issues of
International Strategy from the Viewpoint of International
Standardization of Materials, Science and Technology Trend, No.
28, 19 (2003).
209
17 International Standard
Section 3. Standardization of Nanotechnology and Risk
Management
Daisuke Fujita
Extreme Field Nano Functionality Group, Nanomaterials Laboratory, NIMS
1. Introduction
As investment in nanotechnology R&D has grown
rapidly worldwide, it has become crucial to secure the permanence of nanotechnology as a basic industrial technology for the next generation. Accordingly, public trust in nanotechnology must be gained by scientifically evaluating
both the positive and negative aspects of nanotechnologies.
To avoid the risks of nanotechnology and secure international competitiveness, a movement toward international
standardization of nanotechnology became conspicuous in
the US and leading European countries in 2004, and moves
toward nanotechnology standardization simultaneously
started in Japan, too. One often-cited example of the risks
of nanotechnology is carbon nanomaterials. The technology of mass-synthesizing nanometer-scale new-functional
substances such as carbon nanotubes and fullerene has lately been developed, and these nanomaterials will start being
used in various products in large quantities. The main entity of such carbon-based nanostructures is a fine powder
similar to soot. However, the main component of diesel
exhaust particles (DEP) contained in the exhaust gas from
diesel engines is carbon and is of a nanoscale size. Since
there are concerns over the harmful health effects of DEP,
it is necessary to scientifically evaluate the toxicity and
risks to the human body of fullerene and carbon nanotubes
which are carbon-based substances of a similar size. The
toxicity of nanoparticles is deemed to be the main potential
risk of nanotechnology, but various other social influences
have been also raised.
As the application of nanotechnology in industry has
advanced, the necessity of international standardization of
nanotechnology has become clear in order to maintain the
industrial competitiveness of nanotechnology in the same
way as in other existing industries. Japan is highly dependent on foreign trade, so industrial competitiveness and
international standardization are closely related to each
other. For products to gain international market share, global product compatibility is essential and standardization of
the product by the manufacturer itself is important. The
WTO/TBT (Trade Barrier Treaty) came into force in 1995,
and the treaty member countries were obligated to use
international standards when establishing technical criteria
210
(such as standards). As a result, establishing international
standards and international specifications in favor of industrial technologies of one’s own country is linked to the
higher competitiveness of products in the world market. As
a natural consequence, the importance of acquiring international standards (de jure standards) in the ISO and IEC,
which are organizations establishing international standards, is now recognized. In fact, for strengthening industrial competitiveness, European countries have rapidly
begun to reflect the predominance of their industrial technologies to international standards such as ISO and IEC.
2. Research trends
This section describes world and domestic trends in the
standardization of nanotechnology. Efforts toward the standardization of nanotechnology have started not only in
Europe and the US but also in Japan and Asia. As an
international framework, the International Dialogue on
Responsibility for Research and Development of Nanotechnology, which has the mission of promoting the research
and development of nanotechnology as a national policy,
has been held since 2004.
In the US, ANSI (American National Standard Institute)
and ASTM International have begun to tackle the standardization of nanotechnology. ANSI established the Nanotechnology Standard Panel (ANSI-NSP) in 2004, and ANSINSP has determined the following order of priority for the
standardization of nanotechnology:
(1) Generic terminology in nanotechnology science
(2) Systematic terminology concerning the composition
and characteristics of materials
(3) Evaluation of influence and risks of toxic effect on
the environment
(4) Measuring methods, analyzing methods and standard
testing methods
Various risks of nanotechnology are cited as important
priorities in this list. On the other hand, ASTM agreed in
October 2004 to promote the standardization of nanotechnology, and Nanotechnology Committee (E56) was established in 2005. E56 consists of industrial, governmental
and academic people, particularly in the US, who are
actively involved in the field of nanotechnology. E56 is
supposed to develop concrete standards and guidelines and
adjust various matters with relevant organizations with a
view to international cooperation.
In Europe, CEN (European Committee for Standardization) has begun a new movement of promoting the standardization of nanotechnology. The technical board (BT) of
CEN decided to establish a working group concerning nanotechnology (CEN/BTWG 166) in March 2004. The main
task of this group is to analyze the necessity of standardization activities in this new field, develop strategies, and start
various related activities.
In Asia, the Asia Nanotech Forum (ANF) summit was
held in 2004 under the initiative of the Ministry of Economy, Trade and Industry and the National Institute of
Advanced Industrial Science and Technology (AIST) of
Japan as a common ground to discuss the research and
development of nanotechnology among Asian countries.
ANF is considered to be a common ground for comprehensive discussions including on the social influences of nanotechnology at the moment, and ANF is important as a
common ground for discussing nanotechnology in Asia as a
whole from the viewpoint of promoting national policies.
In the ISO, which is an international standardization organization, a committee concerning nanotechnology (TC: For
example, TC201 Surface Chemical Analysis) has carried
out standardization activities individually, but the UK has
now proposed that a new TC concerning nanotechnology
be established.
The movement toward the standardization of nanotechnology in Japan started promptly in 2004 in accordance
with the trend in Europe and the US. The Nanotechnology
Standardization Survey Committee was established with
the Japanese Standards Association as its secretariat under
the initiative of the Ministry of Economy, Trade and Industry in November 2004. The purpose of this committee is to
present a policy for drawing up specifications for the standardization of nanotechnology in Japan and a policy for
submitting proposals to the ISO.
Concerning the nanotechnology standardization activities in NIMS, both ISO activities as international standardization and VAMAS as international joint research survey
activities for standardization are being promoted in parallel.
In the ISO activities, NIMS is working closely with TC201
(surface chemical analysis). It was decided in 2004 to
establish a subcommittee concerning a scanning probe
microscope which is particularly important for nano analysis (SC9), and accordingly NIMS provided committee
members and has proposed new working items, etc. Meanwhile, in the ISO activities, an independent administrative
institution as a neutral organization should gather the opinions of experts from private enterprises and universities,
and in the case of ISO/TC201, NIMS is positively cooperating with AIST to promote standardization. Regarding the
VAMAS activities, on the other hand, NIMS promotes
international joint research for pre-standardization in cooperation with the international standardization activities of
the ISO. The VAMAS has decided to establish a new committee concerning nanomaterials measurement (TWA29).
These actions demonstrate that standardization is being
actively studied.
3. Future trend
Standardization of nanotechnology is indispensable to
guarantee the permanence of the nanotechnology industry,
and standardization activities are set to make rapid progress
for several years to come. Speed is of the essence. Before
the US and European countries solidify the general frameworks and important matters, Japan should take the initiative in the international standardization activities of the
ISO, etc. to take the lead in the standardization of nanotechnology. Concerning the position of NIMS, it is important for NIMS to get involved in formulating de jure standards which Japan is promoting because this will yield
many benefits for NIMS. By strategically combining intellectual property rights such as patent rights and standardization, various effects can be expected such as the
strengthening of tie-ups between industrial enterprises, universities and NIMS, and the promotion of intellectual
international contribution by NIMS’ fundamental research.
4. Conclusion
Nanotechnology is expected to boost international competitiveness and new industries as a key technology for creating a society in the 21st century. In the second-term science and technology basic plan, national resources have
been allocated preferentially to nanotechnology, and the
industrialization and practical implementation of research
achievements are strongly desired. Accordingly, it is vital
to promote the industrialization of nanotechnology in close
cooperation with industry, universities and the government,
as well as standardization for securing international competitiveness ahead of the US and European countries. As a
neutral and core independent administrative research institution, NIMS has a major role to play in leading the standardization of nanotechnology.
211
Acknowledgements
We would like to acknowledge that some of the articles published in this book refer to database
products of Web of Science® which is published by Thomson Corporation Ltd. and ScienceDirect®
which is published by Elsevier Science Ltd.
Web of Science® was used as a source for the following figures:
Yoshio Bando, Fig. 1, p. 74, Fig. 2, p. 75
Nobuyuki Koguchi, Figs. 1-2, p. 79, Figs. 3-5, p. 80, Figs. 6-9, p. 81
Hiroyuki Kumakura, Fig.1, p. 87
Takao Takeuchi, Fig. 1, p. 91
Toyohiro Chikyow, Figs. 1-4, p. 103, Fig. 5-6, p. 104
Hisatoshi Kobayashi, Fig. 1, p. 106, Figs. 2-3, p. 107, Figs. 4-7, p. 108, Fig. 8, p. 109
Yuji Miyahara, Figs. 1-4, p. 112, Fig. 6, p. 113
Chikashi Nishimura, Figs. 1-2, p. 119, Figs. 3-4, p. 120, Figs. 5-7, p. 121, Fig. 8, p. 122
Hiroshi Harada, Toshiji Mukai, Masuo Hagiwara, Toshiyuki Hirano, Youko Yamabe-Mitarai,
Satoshi Kishimoto, Yoshihisa Tanaka, Akira Ishida, Takahiro Sawaguchi,
Fig. 1, p. 143, Figs. 2-3, p. 144
Keijiro Hiraga, Noriko Saito, Figs. 1-2, p. 156, Fig. 3-6, p. 157, Fig. 7-8, p. 158
Hideo Kimura, Xiaobing Ren, Shuichi Hishita, Fig. 1, p. 160, Fig. 2, p. 161
Kenji Kitamura, Figs. 1-3, p. 164
Yutaka Kagawa, Figs. 4-5, p. 171
ScienceDirect® was used as a source for the following figures:
Yoshio Sakka, Figs. 1-2, p. 77
Date of publication: March 1, 2006
Tomoaki Hyodo
Publication Secretariat of the Materials Science Outlook
International Affairs Office
1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
Tel: 81-29-859-2749
Fax: 81-29-859-2049
E-mail: [email protected]
http://www.nims.go.jp
S If you have any opinions or questions about this book, please contact the above.
© 2005 National Institute for Materials Science, Printed in Japan. All rights reserved.

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