CNT - DLR

Neuere Entwicklungen
auf dem Gebiet der
CNT-Herstellung und Nutzung
im Faserverbundleichtbau
E0601A
Wissenschaftstag 2008
Nanotechnoscience in Faserverbundleichtbau und Adaptronik
BMS-CAS-INN-CNT
Dr. Helmut Meyer
9.10.2008 Braunschweig
Corporate History
• 1863 Company founded by F. Bayer and J.F. Weskott
• 1912 Corporate headquarters established in Leverkusen
E0629A
• 1951 Re-establishment of Farbenfabriken Bayer AG
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 2
as at December 31, 2005
Bayer Group
326 Gesellschaften
Forschungsausgaben
2,6 Mrd. Euro
106.200
Mitarbeiter**
E0602B
Umsatz 2007:
32,4 Mrd. Euro
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 3
* Stand: 31.12.2007
** Mitarbeiter auf Vollzeitkräfte umgerechnet.
E0604A
Bayer: Science For A Better Life
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 4
Bayer MaterialScience:
Facts and Figures 2007
Produktionsstandorte
ca. 30
Mitarbeiter
ca. 15.400 *
Umsatz
ca.
10,4 Mrd.
Euro
Absatz
ca.
9,7 Mio.
Tonnen
F&E-Investitionen
ca. 340 Mio. Euro **
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 5
* Stand 31.12.2007, Vollzeit-Äquivalente
** inkl. kundennahe Entwicklungen
Bayer MaterialScience:
Sales in 2007 by Business Units
Thermoplastic
Polyurethanes
Basic Chemicals
Others 1%
2%
4%
Coatings, Adhesives,
Specialties
15%
EUR
10.4 billion
Polycarbonates
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 6
27%
51%
Polyurethanes
Carbon Nanotubes
Alt bewährt und Material der Zukunft
Properties of Carbon Nanotubes
Tear strength
E-modulus
Thermal conductivity
Electrical conductivity
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 7
> 10 GPa
> 1 TPa
> 2000 W/mK
> 104 S/cm
Mechanical Strength
www.montrealhockey.com
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 8
Carbon Nanotubes
•
•
Single-Wall Carbon Nanotubes (SWNT):
–
Diameter: 0,4 - 3 nm
–
Ideal structure, low defects
–
Complex manufacturing process, high prices
(current medium term target >1000 $/kg)
–
High catalyst residue if CVD process is applied
–
High carbon black residue
50% if arc-discharge process is applied)
20 nm
25 nm
(up to
BTS
Multi-Wall Carbon Nanotubes (MWNT):
–
Diameter : 5 - 100 nm
–
High defects, high aspect ratio
–
Low cost process possible (CCVD)
–
(high yield, low catalyst residue)
–
Already in use in polymers in order to promote
electrical conductivity
20 nm
BTS
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 9
Catalytic Chemical Vapor Deposition
„Expanding Universe“
Dp = 80 μm
Mechanism
ρ = 2000 kg·m-3
Agglomerated catalyst particles
Scheme of the metalcatalyzed growth of a
carbon nanofiber from
gaseous hydrocarbons
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 10
Dp = 1200 μm
ρ = ca. 150 kg·m-3
CNT-Agglomerate
Movie Source: Stig Helveg et al., Atomic-scale imaging of
carbon nanofiber growth, Nature 427 (2004), 426-429
CNT Synthesis: CCVD / Fluidized Bed
Filter &
Incineration
• High carbon yields of catalyst
H2, inert gas
• High space-time yield
• Agglomerated / entangled product
easy to handle
• Product agglomerates must be
disentangled during processing
Catalyst
Heating
Agglomerates of CNT
( > 95 % C-purity)
Agglomerated
primary catalyst
particles
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 11
CNT-Agglomerate
Hydrocarbons /
H2 / inert gas
CNT Synthesis: CVD / Fluidized Bed
Magnification
X1300
73,7 : 1
B096501RE101
500µm
Particle-Size Distribution
c u m u la tiv e v o lu m e tric c o n te n t Q 3 [% ]
100
90
93910 : 1
200nm
80
70
CNT-Agglomerate
(> 95 % purity)
100µm
60
50
40
30
20
10
0
0,1
1
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 12
10
100
1000
10000
Production Scale Up – Fluidized Bed
Bench Scale
in operation
Pilot Scale-1
2006/07
in operation
ID = 0.1 m reactor
3-5 tons p.a.
Reactor 1
30 tons p.a.
Reactor 2
30 tons p.a
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 13
Pilot Scale-2
2009
In realization
Fluidized bed
200 tons p.a.
Production Scale
Vision 2012?
design and planning
Fluidized bed
3000 tons p.a.
Baytubes® - Properties
• Multi-wall carbon nanotubes agglomerates
of very high purity
• Low fraction of catalyst residues enables
immediate application in most polymers
without costly purification processes
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 14
Baytubes® - Polymer Applications
Electrical conductivity
• Antistatic behaviour
•Automotive parts
•Automotive fuel lines
• Electrostatic painting
•Car body panels
•Mirror housings
• Electrical conductivity
•IC trays, carrier tapes
•Intermediate container
• Electromagnetic shielding
•Mobile phones
•Housings
Mechanical strength
• Sporting goods
• Aircraft parts
• Lightweight construction
• Adhesives
• Polymer fibers
• Coatings
• Electronic components
• Elastomers
Thermal conductivity
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 15
Dispersion
Achieved complete
dispersion of original
agglomerates by
optimizing dispersion in
twin screw extruder or
three roll calander
Techniques
•In-situ polymerisation
•Melt impregnation
•Solvent impregnation
0,05 w.-% CNT
PC
PC
BMS-CAS-INN-CNT
Polyol
PA
200 nm
Dr. Helmut Meyer • Page 16
0,01 w.-% CNT
200 nm
200 nm
Baytubes® Electrical Conductivity in Polymers
Quelle: Hyperion
Baytubes® carbon nanotubes show higher conductivity at lower
loadings compared to high end conductive carbon blacks
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 17
Baytubes®
Comparison with Carbon Black
Surface Resistivity [Ohm/sq]
1,E+11
Baytubes C150P
1,E+10
High End Conductive CB
1,E+09
1,E+08
1,E+07
1,E+06
1,E+05
1,E+04
1,E+03
Polymer: Makrolon 2805
Dispersion machine: ZSK 26Mc
Screw speed: 400 1/min
Torque: 80%
Temperature profile: 280 °C (standard)
Parts Injection Moulded
1,E+02
1,E+01
1,E+00
0
2
4
6
Baytubes content [wt%]
8
10
Baytubes® show higher conductivity at lower loadings compared
to high end conductive carbon black in polycarbonate.
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 18
12
Baytubes® - Electrical Conductivity
PC – Influence of Processing Conditions
Surface Resistivity [Ohm/sq]
1,E+11
Pressed Plaque
1,E+10
Injection Moulding - Standard
Condition for PC
1,E+09
Polymer: Makrolon 2805
Additive: Baytubes C150P
Dispersion machine: ZSK 26Mc
1,E+08
Injection Moulding - Optimized
Condition for PC/ Baytubes
1,E+07
1,E+06
Optimization
of IM process
1,E+05
1,E+04
1,E+03
1,E+02
1,E+01
1,E+00
0
1
2
3
4
5
6
7
CNT-content [wt%]
Processes and processing conditions show strong influence on the
surface resistivity of the final part.
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 19
8
Baytubes® - Electrical Conductivity
PBT Injection Molding
1,0E+11
PBT B 1600
1,0E+10
Tp = 230 - Tw = 120
Tp = 260 - Tw = 120
1,0E+09
Surface resistivity [ Ω/ Œ‰]
PBT B 1600
Baytubes C150P
5 Gew.-% CNT
ZSK 26Mc
Tp = 290 - Tw = 120
1,0E+08
Vergleich PC 2805
1,0E+07
Tp = 340 - Tw = 120
1,0E+06
1,0E+05
1,0E+04
1,0E+03
1,0E+02
1,0E+01
1,0E+00
0
20
40
60
80
100
Injection speed [mm/s]
PBT-CNT composites show improved conductivity with
increased molding temperature and reduced feed rate
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 20
120
Baytubes® Applications in Thermoplastics
Addition of Baytubes results in
• improved electrical conductivity
• improved mechanical strength
• at low CNT loadings
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 21
Baytubes®
Colour of Composite Material
0,05 w.-% CNT
0,01 w.-% CNT
ƒ Compounded material likely to be black
ƒ Certain transparency achievable at low loading level
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 22
Baytubes® Electrical Conductivity in Epoxies
Epoxide: Araldite564/ HY2954
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 23
Baytubes® Mechanical Strength in Epoxies
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 24
Baytubes® - Mechanical Strength
Applications in Sporting Goods
„The worlds toughest Hockey Stick“
„lightest
and
strongest
xc-ski to
day“
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 25
Ultra-light weight Exel sticks
Baytubes® - Low Weight and
Proper Flexural Response in Epoxies
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 26
Baytubes®
Use in Lightweight Construction
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 27
Baytubes® - Concrete Reinforcement
Application Potentials in Construction
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 28
Health & Safety
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 29
HSEQ Activities
BMBF Project
T R A C E R
Start 01/06
€ 720.000 (AG), applied for 50% grant
HSEQ Project
BAYTUBES
Start 9/05
End 12/07
€ 200.000 (BMS)
PACTE Project
Producers Association of Carbon NanoTubes in
Start 8/05 Europe (PACTE) - Sector Group within Chemical
Industry Association
Key objectives: Science – Advocacy - Dialogue
2 0 0 5
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 30
2 0 0 6
2 0 0 7
2 0 0 8
Baytubes® Internal Testing Profile
•
•
Ecotoxicology
;:
No Acute aquatic toxicity (Daphnia, Algae, Fish)
;:
No Bacterial toxicity (activated sludge)
;: performed (GLP studies conducted
according to OECD Guidelines)
…: ongoing/planned (2007)
Toxicology
;:
No Acute toxicity (dermal, oral)
;:
No Acute local irritation (Eye & Skin); No Sensitization (Skin)
;:
No Mutagenicity (Ames test and in vitro cytogenicity test)
;:
Acute inhalation toxicity: LC50 rat: > 241 mg/m³ (micronised Baytubes)
ƒ
ƒ
ƒ
…:
Concentrations ≥11 mg/m³ cause a poorly soluble particle effect
Pulmonary toxicity of Baytubes and Quartz are markedly different
No extrapulmonary effects
Planned: Sub-chronic inhalation toxicity
All standard studies performed so far with Baytubes® show no relevant
adverse effect at realistic exposure level (GLP studies according to OECD
Guidelines). Results continuously published
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 31
No Exposure during Use of End-products
ƒ Baytubes are firmly embedded in matrix of polymer or coatings
ƒ Key branches are automotive, electronics and sport industry
ƒ E.g. sport articles (hockey, baseball bat), rotor blade for wind
turbine or antistatic packaging for computer chips
ƒ End-products can be safely used
ƒ Product categories foreseen for Baytubes® all have a low
potential of exposure
* Report to the European Parliament IP/A/ENVI/ST/2006-41
“Nanomaterials in Consumer Products” (April 2007)
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 32
Communication for Baytubes®
•
Scientific presentations of (eco)-toxicological results
–
Clean ecotoxicity profile at SETAC-UK (London, 2007-09)
www.sebiology.org/Documents/Meetings/Nanoparticles/nano_abstracts.pdf
–
Clean genotoxicity profile presented EEMS (Basel, 2007-09)
www.eems-2007-basel.ch/eems/files/EEMS2007
Basel_ultimaVersion_04.09.07.pdf
–
•
Acute Inhalation Study with Baytubes at SOT
Annual Meeting (Seattle, 2008-03)
Product Stewardship at BMS for
Nanomaterials
–
BayCare Webpage
www.baycareonline.com
(Free registration, see “What’s new” section)
–
Baytubes Webpage
www.baytubes.com
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 33
2008
The Winning Team
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 34
E0631A
Closing Motif
BMS-CAS-INN-CNT
Dr. Helmut Meyer • Page 35