Page 1 名古屋工業大学学術機関リポジトリ Nagoya Institute of

Title
Author(s)
Synthesis of TiO2 films and their Photocatalytic and
Hydrophilic Characterization チタニア薄膜の作製と光触媒
性能及び親水性評価に関する研究
羅, 莉
Citation
Issue Date
URL
2009
http://repo.lib.nitech.ac.jp/handle/123456789/607
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Synthesis
Films
of TiO2
Photocatalytic
and
LI
LUO
Their
Hydrophilic
Characterization
2009
and
Contents
chapter
General
I
Introduction
Structural
1.I.
･････････････････････････････････････････････････････････････････････････････････1
Characteristics
Processes
of TiO2.................................................................･･3
1.2･. Photoinduced
and
Applications...･････････････････････････････････････････5
Their
1.2.I. Photocatalysis･･････････････････････････････････････････････････････････････････････････････････････････････6
1.2.2.
1.3.
Photoinduce4 Superhydrophilicity
Methods
Synthetic
Phase
Purpose
･･････････････････････････････････････････････････15
Methods..................................................................................
Methods..........................i.................................,............................･23
1.3.3. Other
1.4.
Nanostructures
orTi02
Routes.........................................................................................16
1.3.I. Solution
1.3.2. Gas
(PSII),..............･..･･･････････････････････････････
of This Thesis
････････････････････････････････････････････････････････････････････････････････････23
References......................................................................................................
chapter
2
2.1.
Synthesis
and
Characterization
of TiO2
Films
onAlum叫um
Fibers･･30
Imtroduction..….….…....….…..…...∴.…..…..…...…...…...…..-.--.-....--..--31
2.2. Experimental･･････････････････････････････････････････････････････････････････････････････････････････････
2.2.I. Synthesis
ofTi02
Films
････････････････････････････････････････････････････････････････････････････32
2.2.2. Characterization.................................................................................･.･･
2.2.3.
2.3.
hvestigation
Results
and
Property････････････････････････････････････････････････39
of Photocatalytic
Discussion........................................................................･..･････････42
23.1.
XkDAnalysis..............................･..･･･.･･･････････････････････････････････････････
2.3.2.
Surface
Morphology
State and Compositional
2.3.3. Chemical
2.3.4. Photocatalytic
2.4.
Evaluation
(ⅩPS) ･･････････････････････:･･･47
Ability･････････････････････････････････････････････････････････････････････････････
Conclusion...........................................................................................･････
References
3
chapter
(SEM)...............･････････････････････････････････････････････････
････････････････････････i････････････････････････････････････････････････････････････････:･････････
Synthesis
Applications
of TiO2
Films
on
Glass
Substrates
for Hydrophilicity
･････････････････････････････････････････････････････････････････････････････････････
3.1.
Introduition................................................................................･.･
3.2.
Experi血ehtaI･･･i･･･････････････････････････････････`･････････････････････････････････････････････････････
3.2.1. Sample
Preparatidn････････････････････････････････････････････････････････････････････････
ー､＼
J
3.2.2. Characterization..................................................................................
3.3.
Results
Discussion....................................................................................64
and
3.3.1. TG･DTA
Analysis
….…...….…...…....…..….…........…….…...….….…...........…64
3.3.2. XRI)Analysis......................................................................................
3.3.3. SEM
Observation.................................................................................
3.3.4. UV-VisAnalysis..............................................･.･.･･･････.･............................67
3.3.5. XPSAnalysis............................................................･･....･.･･.................
3･3･6･
∬M
Observation･･･････-･･-･･･-･･-･･･∵････････-･･････-`････:･-･-･------69
Measurement..................................................................................69
3.3.7. WCA
3.4.
Conclusion.............................................................................................
Referenc?s ････････････････････････････････････････････････････････････････････････････････････････････････
4
Chapter
Preparation
Their
4･1･
Hydrophilic
Intro血ction
Phase
Polymer
4.2.2. Film
4･23･
and
Method......................................･....･･･.･76
ModirICation..................................................･.････････････78
PL
･････････････････････････････････････････････････････:･････････････････････････
Activity..................................................................･･.･･.･･.･
Discussion...............................................................................
Optimization
4.3.3. XPS
of Reaction Condition.......................................................79
Observation.....................................................................8
Characterization....................................................….............
Spectra.......................................................................................
4.3.5. tJV･Vis
Spectra..................................................................................
4.3.6. HydrophilicityAnalysis
4.4.
(LPD)
I)eposition.................................................................................
4.3.2. FE-SEM･EDX
4.3.4.
and
Characterization
Results
4.3.1.
(PMMA)
Application................................................................74
Deposition
Surface
4.2.4. Hydrophilic
4.3.
polymethylmethacrylates
Procedure..............................................................･･.････..･･････････78
Experimental
4.2.1.
on
･････-･･･--･:･････････---･-･-･･-････････････････-･･･････-･･-･--･･--･･75
4.1.1.Liquid
4.2.
Films
ofTi02
････････････.･････.･.･.....................................................86
Contusion..............................................................................................
References...................................................................................................
Chapter
h5.1.
5
Conclusions
Summary
AckJ10Wledgements
of This
･･････････････････････････････････････････････････････････････････････････････････････････････
Research
････････････････････････････････････････････････････････････････････････････92
････････････････････････････････････.･･･････････.･･･.･････････････････････････････････････
ii
List
of Publication...........................................................................................･････...･.....97
iii
Chapter
General
1
IntrodtICtion
1
From
beginning
the
commercially
of
produced
the
twentieth
as
used
and widely
discovered
the
ultraviolet
of
phenomenon
so
of
pbotolysis
(UV) light [6, 7]. Since
then,
【1】
and
pigments
[4],ointments,干oothpaste
[5],and
3], paints
dioxide
titanium
century,
on
water
enormous
in
additives
TiO2
a
have
efforts
such
pbotoactivation
(1) Gratzel
as:
solar
in which
semiconductor,
of organic
been
by
stimulated
a
wide
Japanese
many
been
leading
teclmological
and
a
activated by
solar energy
[10].(4)Antimicrobial activity: The
pboto血emistry.
hospitals
"environmental"
[11].These
categories, many
Tio2 material itself but also
inorganic
envi工Onm
h
and
also exhibitantimicrobial
applications
organic
canbe
the modifications
on
dyes)
and'on
not
only
of the TiO2
interactions
the
in Japan
of
on
now･
demonstrated･
recent
to
h
the
su血ces
discovery
that
at houses
"energy"and
the properties of the
material host
TiO2
of
has
application
roughly divided into
depend
of which
Producing
'activation
activity is useful
●
and
ln
(3) Hydropbilic
in
surfaces
●
bas00ntributed
States
of research
TiO2こbased self-cleamng
This
[9] are
acceleration
TiO2-based
as弧aCtive
revolution
innovations
United
the
to
the
applications
the
on
to
●
is employed
based
under
devoted
its efficiency
cleanup
Honda
and
promlSlng
self-clean1ng Surfaces:
researchers,
in Europe
work
TiO2
to enhance
modified
on
pollutants
to many
application,
for environmental
variety of TiO2-based
much
addition,
has been
TiO2
photo-oxidation
materials, leading
也 this
【8】:
cell
(2) Medium
electrical energy.
Thus,
of TiO2
【2,
electrode
●
researc血on
been
sunscreens
Fujishima
In 1972,
on･
has
(TiO2)
(e･g･,
with
materialswith
the
eat.
this introduction, structural
characteristics of TiO2, Photoinduced
2
process of TiO2
and
for TiO2
synthetic methods
I.1. Structural
Ti02
Characteristics
three
possible
is
often
possesses
brookite
structure
distorted
octahedral
by
surrounded
rutile.
while,
sharing
distorted
differentmass
and
a
shows
are
terms
so
larger,
edge
each
oxygen
sharing
each
a
two
distances
is
octahedron
octahedron
and
than
in
is in
contact
densities and electronic band
structures
3
between
with
corner
TheTi-Ti
those
ten
in
neighbor
oxygen
atoms),
eightneighbors (four
with
corner).These differences in
chains. In
s血orter也an
contact-
eight sharing
Ti4+ ion is
'the octahedron
orthorhombic.
are
the
differ in the
the octahedra
distortion; inanatase,
Ti･O
pairs
each
structures
crystal
patternof
is lower
whereas也e
The
These
(right)･
0Ctahedra, where
The
its symmetry
that
structure,
four
ions･
brookite.
and
(left)andanatase
of chains ofTi06
slightorthorhombic
structure,
(two sharing
edge
in
anatase,
investigations･ Fig･ 1 depicts
ofrutile
and by the assembly
in the anatase
an
characteristic
octahedron
therutile
octahedrons
for experimental
used
of six 02-
in anatase
h
forms:rutile,
octahedron
an
rutile, the octahedron
is slgnificantly
of TiO2
crystalline
symmetries
distortion of each
distances
not
be described
can
structures
Will be described briefly.
lattice structures
the two
forms
cause
ofTi02.
RutI[+
Anatafe
Fig. 1. Crystalstructure
and
(left)
ofrutile
are
ato皿S
Table
1. Some
bulk properties of
structtlre
(eV)
Anatase
3.20
TetragoTlal
3.02
Tetragonal
stable
bulk
at
low.Kinetically,
is
so
with
coarsenlng'the
planes
of
oxygen
rearrangement
proposed
of
mechanism
b
D.h14-p42/mmm
andrutile TiO2
The
but
enthalpy
0.937
2,51
0.4584
0.2953
0.644
are
Presented
of anatase
transformation
following
are
transformations
retained
titaniumand
implies
practically does
asrutile
oxygen
at least
seen:
close･packed
ions
occurs
spatialdisturbance
grained
is the
(nanoscale)
is
transformation
torutile phase
not
are
l･ Rutile
in Table
is commoninfine
anatase
c/a
C
0.3733
is stable, i･e･, its transformation
anatase
that the
slow
D.h19-l41/and
hightemperatures,
synthetic samplesI
naturaland
Spacegroup
a
of anatase
properties
phase
a7)d rut皿e TiO2
anatase
LatticeconstaJltS(Ⅱm)
System
Rlltile
gray, and oxygen
are
atoms
t121.
black
Bandgap
Crystal
some
Titanium
(right)I
anatase
intorutile
at room
temperature
On
heating
concomitant
occur･
anatase
a
planes,and
within
closed-packed
pseudo
this
co10Perative
con丘guration･
of the oxygen
The
ion framework
and
breaking
aminimum
of Ti10
bonds
Processes
and
as
result of surface
a
nucleation
and
growth
【13].
I.2. Photoinduced
Their
Fig. 2. Photoinduced
TiO2
energy
leads
and
to
a
a
to
the
charge
presence
of
a
hole
of the photogenerated
phenomena
processes,
is the dominant
they
can
and
due
to
of
an
photoinduced
are
electron
in fact take place
band
pair
because
by
photon
to
(VB).
even
if they
on
Input Of super-band
with
enoughenergy
band
the conduction
The
are
the
are
●
an
subseq血ent
(e--h'),determines
concomitantly
5
a
promotion
(h')inthe valence
process,
of
These
phenomena･
activated
Absorption
electron-hole
TiO2.
on
processes
phenomena
TiO2.
semiconductor
separation
generation
action
the
in Fig･ 2･Al1 photoinduced
depicted
gap
by
is characterized
Applications
same
which
(CB)
mode
of
of the
intrinsically different
TiO2
Surface･
This
excited
solar cells
special
cause
or
drive
be
either
can
electron
chemical
a
was
phenomenon
directly
used
discovered
recently
create
electricity
by
termed
Beside
(PV)
the'se,
i汀adiation, TiO2
UV
that, under也e
was
in photovoltaic
is called photocatalysis･
reaction, which
highwettabilitysurface, which
･a
to
a
Can
'photoinduced
Fujishima [14] as
superbydropbilicity'(PSH).
1.2.I.
Pbotocatalysis
1.2.I.I.
of Photocataly
Principle
overall,
reactions
pbotocatalyzed
two
simultaneously
reactants,
throughan
activation
photocatalytic
abso,ption
structures,
andrutile
410
react
nm
(Rdユ)&ds
pairs
photonic
ニーRcdl + Oxユ
electrons
When
(02)to
the absorption
with
water
produce
6
differences
superoxide
hydroxyl
correspohd
photo-generated
radical
anions
in
electronic
materials:anatase
thresholds
a
thanthe
shorter
(The
hol占s･
and
forms･) The
to produce
[16].
of wavelengths
for bulk
gaps
for the re.spectiveTi02
oxygen
reactions･
differences in densitiesand
Cause
difference in band
to a
holes･react
scheme
fillowing
TiO2
of
adsorb
^t･>ち
lightconsisting
with
[9,15].Therefore,
with molecular
a
●
of inataseandrutile
in wavelength
by
to
follows:
as
explain･ the prlnCiple of photocatalytic
can
it produces
leading
its capability
oxidized
reducedand
痴如tx:tor
irradiated
Was
3.02 eV
photo-generated
the
TiO2
thresholds,
lattice structures
band
Fig･ 3
preceding
be
(hv ≧ Eg)
efficient absorption
by
characterized
can
which
(OxI)ads+
The
be
may
to
3･20 eV
384and
electrons
(021),and the
as shownin
(･0=) radi占als
2. The
Table
two
kinds of reaction scheme
of TiO2
Photocatalysis
Ox
Fig･ 3･ Main
processes
oxidation of donor
on
occurring
a
(D);(c)reduction
semiconductor
particle: (a)electron-hole
(A);(d)and (e)electronJIOle
of a∝eptor
surface and in bulk, respectively
The
photocatalytic
absorption
properties, e･g･,
on
rates
oxidation
recombination
the
rate. A
leads to faster surface
surface
activity of
area,
the
by
surface
photocatalytic
higher the
the
area
spectrumand
electron
with
reaction
photocatalytic
a
and
rates･
h
activity. On
7
controlled
coefficient,
hole,
constant
recombination
O))
at
[17].
is largely
semiconductor
lightabsorption
surface
large
a
generation;
(iii)and
surface
this
sense,
the other
by
(i)the light
(ii)reduction
the
and
I
electron-hole
density of adsorbents
the larger the specific
hand,
the surface
is
a
defective
the larger
site; therefore,
the surface
fewer
higher the crystallinity,the
bulk
the
The
the faster the recombination･
area,
defects,
higherthe
the
and
photocatalytic
ノヽ･-
High
activity･
nanomaterials,
in
which
decrease
the
between
the physical
optimal
by
are
for
to
H20,
decomposed
into accountand
may
and
a
chemic早lly
h
to use･
and
reactio*s･
human
beings.
almost
TiO2
biologicallyinert,
they
should be
say, they
should be
addition,
Needless
catalyze
and
is
cells
as
well-known
large variety
harmless
including
by
to produceand
sunlightand
TiO2
cancer
be
to
(with sizes ranging
all of the above-mentioned
from
proberties
ideal photocatalyst･
an
bulk
fungi,algae,and
molecules
is complicated･
activities
considerations
and
the relation
conclusions,
general
TiO2
,of
nanoparticles
of small
photocatalytic
should
singlecrystals)possesses
de;ontaminationfor
co2,
above
these
taking
photocatalysts
envirorLment
to be
Nowadays,
to
the
the
stable, cheap'easy
both
large
thus close
and
aggregation
crystallinity
Application
activated by
harmless
by
the
the
case･
photocatalytically
clusters
JudgingfromJ
semiconductor
efficiently
caninduce
sought
improves
usually
propertiesand
1.2.I.2. Photocatalytic
ldeally,
tum
area.
surface
conditions
case
vary
treatment
temperature
of orgamics
[22,23], which
inorgamicanions･
several
photocatalytic
pollutants
such
can
a
photocatalyst
be totally degradedand
dioxine,
Heterogeneous
reactionTi02･
8
environmental
[18, 19], viruses [20],bacteria
In addition,
as
in
many
NOxand
of hard
Sox
[21],
mineralized
decomposed
canalso
be
photocatalytical reactions
canbe
out
carried
specific
Photoinduced
Ti02
phase,
gas
of them
each
suited
for
Superhydrophilicity肝SⅡ)
Surfaces
by Wang
effect
observed
deposited
from
seenthat,
after UV
become
promislng
Fig. 4.
a
a
colloidal
effort
devoted,
of
Whichwill
in
on
on
a
glass
UV
utilized
irradiation in
UV
TiO2
films
be
a
etC.
TiO2
light [10a].
for the characterization
property
of TiO2
makes
films
It canbe
air;仲)hydrophilic
in details in the followlng
of the PSH
TiO2
substrate･
the surface
This
effect,
the extraordinary
polycrystalline
droplets.
after irradiationwith
be introduced
4 shows
anti-fogging,self-cleaning,
before
is usually
the mechanism
Particles
many､､water
TiO2 films su血ce
measurement
a
contacting
droplets spread
water
instead
surface
[10a]. Fig1
of allataSe
for the application
fihs
ofTi02,
droplets
water
irradiation,the
(a)Ilydrophobic
Contactangle
etal. in Nature
suspension
water-layer
Candidate
effect
for
hydrophilicity
the UV･induced
studied tounderstand
arealso
first reported
was
wetting
and
or
solution
applications.
1.2.2.
which
in aqueous
either
is still under
of hydrophilic
Part. In spite of much
debate.
hl this thesis,
several
existing
will be
models
discussed,
a
and
new
in chapter
will be proposed
model
4.
ContactAngle
I.2.2.1･.
Tbe
Measurements
common
most
is
hydrophobicity
by
extensively reviewed
Tbe
drわp
sessile
horizontal su血ce
a
and
Young's
obeys
yLV is the surface
and
forces
often
contact
balance
involves
large
as
conditions,
incldding
others
contact
angle,
droplet
a
of
angle
liquid
of
been
has
which
method,
either directly or山一ougb
solidlliquid interaction
The
the surface･
a
onto
analysis of
the surface
at
･ysv- ysL
is the
The
surface
[25].Additionally,
tension between
in Fig･ 5･ At
dropletand
the water
between
the
surface
the surface and
the three;phase
interface･
of droplet contactangles
reportedangles,and
indicators
atmospheric
tension
measurement
variability of
qualitative
the interface between
surface
angle asーshoyn
considered.
among
the
rsL is the
is described.
a
placement
=
rsv
atmosphere,
0 is the
the
tension about
atmosphere,
surrounding
involves
Contact
(WCA)･
or
as:
equation
surrounding
t24]･
on
rLVCOSO
where
sessile drop
Good
hydropbilicity
Su血ce
angle
and
measuring
of the droplet
digital image
contact
the
using
Neumann
method
water
of
done
simply
fわr measurlng
method
theanalysis
are
measurements
●
direct
and
that
may
humidity,
vary
contactangle
surface
10
such
on
measurements
drastically with
and/or
measurements
droplet
below
and
the
the
the liquid,
the vector
a
surface
should be
experimental
contamination,
loo, sigmifying
a
surface,
super-hydrophilic
contact
suc血low
especially hard
are
forces present
the vector
angle
From
Synopsis
or PSH
the surv.ey
hydrophilic
et al.
photoinduced
surface
as
a
production
at the
solid liquidinterface. ne
contact
measured
(0)is shown.
massive
Surfaces,
as
of literature dealingwith
amount
three
the UV-induced
have
possible mechanisms
been
proposed
to
discussed below.
defect production
[10] first proposed
wetting
defects,known
thermal
of the
phenomena
(1)UV-Induced
Wang
to measure
Theory
effect onTi02
explain the PSH
to the inability
angles.
Fig. 5. Diagramof
1.2.2.2.
due
toanalyze
result
as
activation
effect･
of oxygen
･oxygen
areknown-
of adsorbed
-OH
the mechanism
This model
atom
vacancies
to
groups,
at the
involves
from
ejection
or
cause
which
the
water
are
ll
on
the
[26-28】and,
be hydrophilic
at
the
Fig･ 6･ The
shownin
produced
dissociation
knownto
as
of the
ions
of Ti3+
production
the lattice
Ti3+ sites, when
of the discovery
time
surface
by
thus,
the
in nature･Asa
result, this
was
first logical
a
hydrophilic
for the UV-induced
explanation
effect･
viiiiiii地
H
H
一
【OH,pl-)
●叫0
章
､Ti･:､
I.
,貰二.c､,=]
T.A,声丁慧R/Th
Hydrw触
4rl-. ZO22･
o7
--
Hy脚(由ぬ
Fig. 6 Mechanism
The
by
presented
defect
to be
However,
Density
Bouzoubaa
et
on
the order of
slgnificantly lower
half of
energy
formation
carried
out
defects somehow
[30] have
the
absence
produced
of
0
et
state
to
-
in causlng
al.,the
that
assuming
ground
4･5 eV,
by controlled
to
the surface
vacancy
0(3p)
an
also
were
hydrophobic.
ln
Vacuum
at
at
h'the
foranO
vacancy
If,
photochemically･
formation
vacチncy
On
the other
that
Henderson
and
0
concept
kinetics for adsorbed
●
annealing
irradiation
formation･
the
TiO2･
on
become
conditions
vacancy
possibility of UV-induced
the
contradicted.the
under
0
an
of
energy
also
desorption
defectsand
effect
recently
calculations
for vacancy
generated,
precluding
quantitatively
that UV
is generated
atom
the hydrophilicity
the thermal
●
confirm1ng
formation
7 eV
-
02(g)molecule
TiO皇(110),has
on
cause
compared
Cannot
and
formation
of
be responsible
●
decrease
would
vacancy
study,
a
the energy
forrutile surfaces,
energleS
photon
is calculated by
instead,
7 eV
-
(DFr)
Theory
Functional
directly
was
postulate
[68]･
of TiO2
superhydrophilicity
【29]show
al.
studies of Bouzoubaa
theoretical
defect
formation
HyEhph【由ic
…Hyd和Ph軌
of photoinduced
defect
UV-induced
investigated.
il
ic
叫It)Fh
Tiン
r+Ti--■･
where
on
water
the
850 i for 10 min･ It
a
vacancy
co-workers
TiO2(110)in
defects
was
hand,
have
found
been
that the
12
′
kinetics for undissociated
desorption
both
fbr也e血st
binding
of H20
energy
sites in the
Because
monolayers.
by
governed
influenced
by
are
the
the surface
contact
H20
to the
of
or
the
defect
subsequent
the
and
contact
that
13%
of about
molecules
that the
conclusions
indicates
in the first
is adsorbed
this result indicates
energy,
This
by the presence
between
angle
essentially identical,
were
surfaces
monolayers.
the H20
whether
defect sites, contrary
is
su血ce
not
anglewill
Fujishima and Hashimoto
be
and
【10,31, 32】.
their colleagues
There
surface,
the two
is not influenced
molecules
annealed
on
fわr subsequent
and
monolayer
H20
great disagreements
about
this theory,
so
that afurther
improvement
will be
【33]suggests
that the UV-in血ced
neCeSSary･
(2) UV-hduced
A
second
model
an
increased
proposed
b'y Sakai
proposed
effect is due
hydrophilic
to surface
the basis
XPS,
of
et al. in 2003
modifications,
of Ti-OH
surface coverage
on
ban°ing
of Ti-OH
mpture
as
groups
IR,and
which, in the presence
in' Fig･
shown
electrochemical
lead to
of H20,
7･ This
The
measurements･
was
model
authors
■
explain
coordination
to Ti atoms
singly
coordinated
et al.
[34]suggest
groups
in
this effect
that
are
each
a
●
following
the
are
to
similar
converted
Way:
by H20
-OH
adsorption
Further
their ownTiatom.
mechanism,
where
associated with dangling
bonds.
13
Ti10H
that
groups
into
XPS
groups
two
bound
are
-OH
groups
investigations
are
in
converted
done
2-fold
that
by
are
Gao
into Ti-OH
lA)
H
ー÷11沖ヱ
○ど
I.-/ll/) ･÷n3)
for TiO2
Fig. 7. Surface structuralmodels
bound
to
latticeoxygen,
TiO2
clean
hydrophobic
a
of
new
(C) (afterUV irradiatioh)
Surface
frequency
sum
investigate
wettability effects
the
Fourier
surface,
asIPrePared
measured
using SFG
as
atmosphere.Althoughnot
photocatalytic
schematic
under
removalof
picture
the droplet
while
proven
hydrocarbons
more
slowly
oxidized
are
groups
as
a
tO
be
in any
these
TiO2
on
done
by
[33].
Simply
involves
WaJlg
TiO2
experiment
authors
[35] has
etal･
notes
using
layers
as
inanambient
conducted
that the
UV-induced
for the wettability
of screening
to
technique
hydrocarbon
suggest
the
atomical1y
investigated
trace
in Fig･ 81 In this model,
because
The
films･ T山s work
cleanwhen
isthe explanation
14
at the
formed
surface-sensitive
(FTIR),contains
directly,
of this effect is shown
is
Work
appearlng
be expected
would
hole is trapped
photo-oXidation･
nanoparticulateanatase
in血ared spectroscopy
transform
by
(SFG)
generation
on
effect
monolayer
is hydrophilic･
produced
employed
that
hydrophilicity
hydrocarbon
10H
is
-Oli group
the
irradiation)
UV
layer
contaminant
for the UV-induced
third model
removal
and
(A) Pefore
the photogenerated
tra･)sitionstate)
of hydrophobic
(3) PhotQ･OXidation
A
(B) (atthe
vacancy,
oxygen
Su血ce･
the hydrocarbon
effect･ A
layer
of this interfacialreglOn
from
02
by the droplet･
Su仙n
HydrD￠■rt?On
Hydrwhilic
Efred
Ph触Id各tJoれOrl
hv
Fig. 8. Diagram
2,1･ヰ.4
e-V
for the measured
the mechanism
showlng
I
TiO2 Surfaces
Since
the publication
done
to
eyen
without
products
that
of those
a
developed
●
applications,
photochemistry
1.3. Synthetic
TiO2
on
self-clean1ng andanti-fogglng.
in commercial
surface
based
Canbe
【10],a
large
amount
large number
this teclmology,
including
The
lS
technology
particularly in Japan･Asa
●
now
of comm_ercial
windows
and
mirrors
●
being
result, this
been
effect. However,
hydrophilicity
a
has
of work
lnCreaSingly
used
of metal
oxide
area
has generated broad interest･
Methods
prepared
on
[36]･
of this phenomenQn,
clear understanding
have been
papers
hydrophilicity effect
photoinduced
for the UV-induced
elucidate the mechamism
●
are
early
duゥb}
¶Of
ofTi02
inthe formof
Nanostructure?.
powder,
15
crystals,
or
thin films･ Both
powders
and
films
built
canbe
･up
from
It should
mi_crometers･
be
that
noted
few
a
crystallites ranglng血om
to
crystallites tend
nqnosized
to
nanometers
several
If
agglomerate･
■
separate
Many･
nanosized
so
novel
particles
lead
methods
far, TiO2
to
the materials
desired,
are
usually
deagglomeration
fabricated
by
lS
step
neCeSSary･
deagglomeration
withoutanadditional
nanoparticles
are
a
o触n
solution
or
routes
gas
step･
phase
methods.
I.3.1.
For
is
Routes
Solution
films, liquid-phase
applications, especially the synthesis of thin
some
of the most
one
advantage
of
convenientand
the
over
control
of symthesis･ This
methods
utilized
stoicbiometry'producing
processing
method
has
the
homogeneous
materials,
of
composite
materials･
can
(but
▲
formation
allowlng
However,
there
expensive
The
most
complex
of
are
disadvantages
several
●
precursors, long
commonly
used
shapes,and
solution
among
times,
processlng
routes
preparation
and
which
the presehce
in the synthesis
of carbon
of TiO2
are
need
as
an
Presented
not)
be:･
impurity･
below･
1.3.I.1. SoI･geI Method
血e sol-Gel
TEOS,
process
in liquid solution of organometallic
occurs
Zr(rV)-Propoxide,Ti(IV)･Butoxide,etc･),which,
condensation
reactions, lead
M-0-良
to the
+
formation
H20
-
M-OH
a new
of
+
(bydrol
ysis)
16
氏-OH
by
phass
precursors
means
(Sol)･
(TMOS,
of hydrolysisand
M-OH
HO-M
+
M-0-M
-
H20
+
(watercondensation)
M-0-氏
+
HO-MーM-0-M
(alcoholcondensation)(M
The
Sol is made
liquid phase.
Then
widely
studied
required
to forma
ceramic
other
dopants
method
fibers
the
particles
is immersed
macromolecule
The
of solid particles
in
homogeneous
is used
that
are
Si, Zr,
Ti)
of few
hundred
new
(solvent).The
of thin films,
Fig. 9
[37].The
nm
where
in
suspended
in
a
which
sol-gel method
oxides
at the molecular
of
(Gel)
phase
intimate
has
solid
been
is
mlXlng
powders,
aerogel, ceramics
has
method
and
many
advantages
and
over
flexibility in introducing
●
stoichiometry
the ability to coat
'control,
large and complex
仙肋j&r
ease
of processlng,
areas･
Sol-Gセ1
Technologies
Fig. 9. Various
kinds of sol-gehechologies
17
a
level.
such a孟purity, homogeneity
in large concentrations,
the composition,and
a
multicomponent
for the synthesis
fabrication teclmiques
in
liquid phase
phase
shownin
≡
diameter
condense
a
for
particularly
a
of
R-OE
+
control
over
As
most
titanium
commonly
used.
I.3.1.2. Solution
when
are
Ti(i-OP)4 【39-42】,
and Ti(0-nBu)4 【43-45】
Ti(0-E)4 【38】,､
sources,
Deposition
considering
Techmiques
of thin films
the preparation
●
that
realize
developed
and
concepts,
so-called
in
low
to?mphasize
of waste,
common
as
modernchemistry
Japan), and
branch
major
"green
"sustainable
and
a
of science
(formal
(GSC;
(in Germany),
chemistry"
series
of
Italy;
nomenclature
derivatives
their
and
a
U･K･,
formal
be
generation
of
in USA,
nomenclature
sustainable chemistry"
basis
the
should
should
low
energy,
are
processes
industry
and
add
one
route,
chemical
materials
These
chemistry"
Japan),"green
raw
of
consumption
producer/userfriendliness･
in
name
a
through
as
such
▲
"environmentally
bemign
friendly
chemistryn'uenvironmentally
【46】.
cbemist工y"
for the synthesis
Techmiques
thin films from
of ceramic
aqueous
meet
teclmiques,
including
reaction
deposition
recently
immersion
●
changlng
and
with
(ED)
with
publish?d
bath
chemical
(SILAR),
a
liquid
The
article･ CBD
oxidation
selemide thin films, while
with
formation
states･
some
[47]
produce
kinetics
This teclmique
relatively
18
new
of
and
methods,
their variations,
main
electroless
in
､Tere
solid
th-e solid,
is used
low
ion layer adsorption
successive
(IRD)
can
＼血ove･
mentioned
(CBD),
deposition
catalyst, along
review
requlrementS
deposition
phase
throughcontrol of the
the metals･
the
of
some
at
solutions
●
temperatures
and
Hclean
or
chemistryn,
mainly
summariz占d
films
in
a-
a
single
typically without
to
deposit sulfide
reports involve preparation
of oxides
Unlike
【48].
ions
of metal
to
refers
the
in
complex
with
F- to
LPD
method
prepare
metal
the CBD
and
aqueous
other
oxides, such
methods
under
but
media
employ
always,
material.
The
morphology,
composition,
to
of
TiO2,
V205,
or
a
can
the hydrolysis
thin films and
method
metal-fluoride
(Al) metal
aluminum
accelerate
SiO2
for depositing
chemical
react
The
rate･
later used
was
to
FeOOH
(Fe203),and multicomponent
in aqueous
[51](hydrothermal method)
VO2,_
reactions
(solvothermalmethod)
self-produced
not
the hydrolysis
LPD
Methods
1.3.1.3. Solvothermal
organic
[49].The
adsorption
【50】.
oxide丘1ms
These
as
is added
altemating也e
solutions
(H3BO3)
acid
and
firs.tdeveloped
was
by
thin films
Boric
species
solid by
a
the corresponding
oxide
solution.
stable
generate
an
of
deposit
can
ions from
cationic
formation
an
SILAR
method,
a
temperatures
thermal
treatment
subsequent
solvothermaltreatment
crystalline
reaction
phase,
temperature,
could
and
(usuallyunder
is required
be
surface
pressure,
[51],butanol
methanol
low
at
pressures
as
such
useful
to
chemistry:
to
[52],toluene
250oC).
by
final
size, particle
the
solution
additives,and
agelng
regulating
solvent properties,
[53]
Generally,
crystallize the
control grain
or
time.
Assources
H2Ti409･0.25H20
ofTi02,
in hydrothermal
TiC14
【51],
TiOSO4
synthesis,
in acidic solution
examples.
19
[54],H2TiO(C204)2 [55],
[56],and Ti
powder
are
reported
as
Synthesis
1.3.1.4. Electrochemical
Electrochemical
epitaxial, superlattice,
states
characteristic
compounds
due
difficulties,
both
requires
solutions
to
an
and
electrolysis
varylng
can
pH
control
easily
the
by tarious Ti
films
TiO2
as
films.Althoughelectrodepositionof
TiCl3
[57],TiO(SO4) [58],and (NH4)2TiO(C204)2 [59] is reported,
is always
solutions
an
to overcome
oxygen-free
environment
this problem
【61】･
by
accompanied
Th'erefore,
of the lSalts to hydrolyze･
and
medium
option
an
in aqueous
salts
hightendency
the
acidic
represent
ones･Also,
nanoporous
films such
thin
advanced
density'temperature,
current
inorganic
titanium
of
use
prepare
of the
as
such
to
used
dotand
quantum
like potential,
parameters
be
may
synthesis
electrolysis
[60]･Non-aqueous
｢
Spray
I.3.I.5;
is
-SPD
The main
an
Pyrolysis
from
a
directly focus-sed
reaction
mainly
been
used
precursor
sample
heated
(1)an
instead of
in
are
substrates
a
pressure･
at
There
aerosol
are
of
preparation
of
names
20
while
is
of techniques
powders/films
is
aerosol
a
dominant
in CVD,
the character
droplet-to-particle
for this class
(mixed) - oxide
(2) The
several small derivatives
step of the aerosoland
synthesisand
(gas-to･particle
spectrum
pressure,
droplets)
of small
diffusion
whereas
ambient
(a mist
CVD･
to
related
powders
in CVD･
vapour
cases,
most
differing in the formation
broad
for
for thin films and
pyrolysis:
spray
solution
the
onto
substrate
atthe
confusingly, a
that in
(SPD)
teclmique
is under reduced
commonly
teclmique,
are
(3)The
processincvD.
set-up
deposition
aerosol
differences
is formed
Deposition
the
of this
of the
synthesis)･
has
evolved･ It has
and
uses甲OStly
metal-organic
or
compounds
thin-mms
deposition
low
reproducibility,
costs,
while
the films
I.3.2. Gas
For
methods,
exhibit
spray
most
physical
a
to
collect the produced
Vapour
I.3.2.1. Chemical
deposition
to
coatings
to
has
ofTi02
merits
large
as
such
areas
other
simplicity,
a
time,
short
,in
a
from
performed
of these
teclmiques
to
any
solid-phase
The
be
can
if
also synthesize powder,
main
techmiques
are:
(CVD)
in which
process
These
material.
alter the mechanical,
the gas phase. These
can
particles is employed.
Deposition
refers
fbm
Most
of nature.
are
routes
synthesis
or
condensed
pyrolysis
to
electrical and optical properties.
chemical
Vapor
Compared
【64】.
precursors
the possibility of depositing
and
good
as
salts
Methods
Phase
thin films,
method
metal
in
materials
are
processes
a
nomally
used
electrical, thermal, -optical, corrosion
are
state
vapor
to fbm
resistance,
and
ノ
′†
wear
resistance
free-standing
properties
bodies,
materials. Recently,
Vapor
deposition
reaction･
occurs,
thermal
deposition
reaction.
is awidely
have
processes
processes,
CVD
films,and
they
this
ofもarious
used
widely
usually
proc占ssis
energy
fibersand
been
heats
take
called
the
to
to fabricate
explored
place
to coat
21
a
within
vapor
in the
gases
are
also
infiltrate fabric
chemical
versatile techmique
They
substrates.
vacuum
large
various
If chemical
(CVD).
In
and
drives
chamber
areas
form
nanomaterials.
chamber.
surface
to
formcomposite
to
deposition
coating
used
in
a
CVD
short span
the
of
In industry,
time.
and
ceramic
to
according
differences
decomposition
a
of
1.3.2.2. Physical
In contract
if
no
temperature,
heated/cooled,
are
subst工ateS
In most
gas
cases,
canbe
placed
prevent
and
molecu-les
from
a
the
●
reduced
place under
of
pollution
the
pressure
deposited
from
thermal
a
crucible
method
and
or
deposited
ion
deposition,
laser surface
is the-al
technique
thermal
deposition
streamof
shadow
effects, which
are
not
substrate･
implantation,
[63].PVD
a
present
have
arrays
nanOWire
material follows
gaseous
a
onto
plating'ion
alloying･ TiO2
evaporation,
is
a
1n
to
The
sputtering,
been
so-called
line from
straight
in CVD･
22
pnmary
a
stable
be at
room
are
also possible･
collisions of
most
commonly
material is evaporated
PVD
methods
include
laser vaporization,
fabricated
by
a
simple
teclmique,
line-of-sight
source
are
set-ups, the
minimize
films･ The
Which
can
In most
but other arrangements
source,
that
The substrate
the requlrementS･
on
is called physical
substances
possiblewith
●
PVD
employed
or
reaction
chemical
this process
occurs,
the substrate･
depending
takes
evaporation
Compounds,
and precursors･
formed
reaction
is, therefore, only
straight above
out
split
and
【62】･
directed towards
and
is extensive
produce
(PVD)
chemical
(PVD). This
to
process
continuous
CVD
of
are
in the gas phase
I)eposition
Vapour
a
pressure,
oxides,
composite
i血the gas phase
or
family
in activation method,
precursor
with CVD,
deposition
vapor
to
metals
in
employed
films･ The
semiconductor
from
ranging
is of(en
this teclmique
to substrate･
and
PVD
i･e･･ the
This leads
to
1.3.3.
Methods
Other
There
several
are
deposition. Sputtering
direct
(eitherusing
[66] currents)is used quitefrequently
of argon
cohsisting
part of it,which
evaporating
a
teclmique
that
uses
material is deposited
leads
bigb quality丘1ms
to
Althoughthese
and
the feasibility
Thus,
temperatures.
economical
gas
or
is deposited
with control
a
to
pure
substrate.
ablate
parts
have
they
materials,
of TiO2
electrode made
beam
TiO2
a
plasma
uses
0r
[67]is
epitaxy
target･ The
Ceramic
or
atmosphere
Ti
This
plasma･
are
energy
should
to
the
contr占I
intensive
films
growth
involve
and
also be developed
inview
high
of
Thesis
is
property
environmental-friendly-materials.
commercialized.
techmique
at
TiO2
films
TiO2
ForTi02
low-temperatures
grown
Lof
one
is
films,
●
a
chapter
2, in order
to
factors
●
h
Candidate.
promlSlng
Al
for
fibers
a
of
and
been
the
applications･
coating
In this
plastics
non-heat-tolerant
investigated･
investigate the applicability ofTi02
23
is
fact, bulkTi02
of
variety
for
required
however,anestablishment
is indispensable
onto
key
the
bolymethylmethacrylates) and their applicatioJIS have
In
of
(RF)
frequency
radio
The technique
Molecular
the merit
for films processing
techniques
an
vapour-phase
the orientation.
over
physical methods
to obtain
orThis
Photocatalytic
thesis,
on
ions hit
on
aspects･
1.4. Purpose
already
Ar
inanargon/oxygen
the substrate
on
films･
to produceTi02
(pulsed) laser
a
(DC) [65] or
current
Accelerated
oxygen.
and
based
sophisticated thin-films teclmiques
other
coatings
on
flexible
metal
its coatings
substrates,
Investigations
(SEM)
and
NOx
removal
The
min.
revealed
From
bacterium,
be
Was
important
was
also
P･ aeruglnOSa,
for
better
a
were
lemOVal
carried
samples
to
confirmed
it was
the control
microscopy
electron
out･
the
promote
test for 340
photocatalytic
that the TiO2
For
and facaltative aerobe･
in oxygen
Based
Sample
aerobe
is considered
concentration
sterilization performa.nce･
by 95 %
NOx
removed
demonstrated
onanaerobe
as
sterilization,
after the life time
maintained
sterilization experiments,
as
such
(XPS)
that optimized
%
sterilization performance
good
showed
H202
of
addition
performance･
(ⅩRD), scanning
measurements
than 40
and
di放action
spectroscopy
ratio higher
No又
is dealt with･
method
on
photoelectron
x-ray
the removal
and
by x-ray
dip-coating
sol-gel
properties
pbotocatalytic
on也eir
their characterization
as
well
by
onAlfibers
these
on
results
to
on
ヽ
effects, applications
photocatalytic
of TiO2一占oatedAl
fibers
for air and
filters used
as
●
water
are
clean1ng Systems
3, in order
In chapter
●
PrOPOSed･
to
explore
the possibility for the low-temperature
Tio2
films possessing
the photo-induced
glass
substrates
Paste
to
and
hydrophilicity
the surface
samples
uslng
were
(TG-DTA),
spectrophotometer･
annealing
was
From
(uv-vis)
necesmiy
by
water
in detail by XRD,
characterized
thermalgravimetry
SOlution in spln-coating
analyses
property･
superhydrophilic
contact
SEM,
differential
this study, it w.as
of anatase
to
realize the superhydrophilicity
24
In addition
measurements,
therhal
analysis
phase,
and
high-tempefiture
that
concluded
thus
a
new
●
be proposed
on
(AFM), and UV-Visible
forcemicrpscope
atomic
for the formation
(WCA)
angle
XPS,
deposition
TiO2
attempted･
was
method
synthesis of
without form1nganataSe
Phase･
idea should
In
4,
chapter
the
(PMMA)
polymethylmethacrylates
property
is dealt
method
was
was
absorption
located
hydrophilicity;
hydrophilicity
for concentiator
could
photovoltaic
5, the summaryand
be
superhydrophilic
deposition
were
characterized
prepared
phase
in visible light reglOnand
60%
even
maintained
liquid
on
COatings
(LPD)
by
spectra exhibited that the films possessed
The
decreased.to
value
PMMA
thus
'TiO2
of
photo-induced
modified
films
1ightregion.
visible
WCA
was
that TiO2-coated
In chapter
ability of about
in
the
a
in detail･ UV-Vis
methods
the
possessing
this purpose,
and
proposed,
above-described
high
For
with.
fabrication
room-temperature
films
OoC
indoor
under
as
applied
that the absorption
after
lh
UV
envir9nment･
fresne1
the
exhibited
excellent
it
lens to prevent.dew
systems.
achlievement
25
of this study
are
edge
super
irradiationand
Thus,
described.
was
a
the
believed
condensation
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A･ Hiskia, E･ Papaconstantinou,
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Design,
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and P. Falaras: J. Photochemt.
c. Bernard
C･ Lathe: Nucl･
and
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alld Y･ Du:
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V. P. Tolstoy,
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【51].S.
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Y. V. Kolenko,
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Matsumoto,
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K. Kamada,
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[63].
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1547･
305･
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T･ Wu:
and R. Roddguez-Clem￠nte:
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H. C. Shih and W.
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Yao,
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359･
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J･ Electrochem･
Y･ Matsumoto:
[61].
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A･ V･ Garshev,
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Chem･,
(c) T･
883･
(2000)
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(2004)
C. D. P'arfitt:J. Colloid
Natarajanand
J･ Mater･
(2003)173･
Sci･, 39
388
(1998)
Solid State tonics, 135
and S･M･
Phys･Lett･,
(1997) 255･
Mizuhata:
13
J･ Mater/Res･,
197
J. H. Park
H･ Adachiand
M･
and
and T･ Sato: J･ Mater･
V. D. Maximov,
[56]. D.
A.
【64】.
M. Ab
K. Ota: J. Mater･
R. Chragulov:
Kajinami
and Y. Nagai:
Catal. A: Chem･,
B. K. Moon,
[53].
A･
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and
Fujishiro,J. Wu,
J. Mol.
Surf･ Sci･, 112
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(1999)
192･
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[66].
K. Okimura,
and G･ I. Rusu:
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【67].C.
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【68】.
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and A. ShLibala: Thin
and S. J. Wang:
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(2002)
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(2001) 47･
and A. 又eller: Pro基. Solid St. Cbem.,
29
(1996) 427.
32
(2004) 33.
C'hapter
Synthesis
and
Films
on
2
Characterization
Alumin血m
30
Fibers
of TiO2
2.1. Introduction
Indoor
alr
【1,2】sbowed也at
studies
bigber
in outdoor
than
80%
than
pollutants
quality,
often
[3]･ Pollutants,
source
namely
ungovernable
vehicular
might
from
inevitable
were
transport
even
increase
more
higher risk
carbon
are
●
are
methods
such
[5],building
sources
of
inhalation
of
(CO),mitrogen
can
and
to
improve
cleamng･
Source
Hong
than
more
POllution is one
Kong･
[6]and
the
indoor
air
is
control
instance,
For
use
Thus,
environment･
cause
of the tQP
of cooking
Increase
air pollutants･
outdoor
pollutantsfrom
as
materials
indoor
from
common
suggested
ventilationandair
is actually
spend
monoxide
(VOCs),
in metropolis
traffic
nearby
as
is because
This
environment
generally
identified indoor?1r
three
unavoidable
and
exhaust
[7, 8]
utensils
control,
a
such
compounds
[4].In general,
risk
environmental
people
contribute
which
health effects. In 1995, USEPA
adverse
in indoor
也 addition,
volatile organic
in the early 1990s･
attention
of pollutants
environment･
outdoors
(No又)and
oxides
level
the
in indoors,
their time
of
immens･e
has received
quality
ventilation
air
cle&ing
●
be
remains
to
method,
filter is
fiber
and
are
a
most
feasible option
very
Important
as
a
shown
substrate
material
in Fig.1
the specific surface
to
improve
to it is cheaper
in
our
ismeasured
31
be
to
air cleaning
●
a
the
The
-､photo
and
the SEM
fiber-s diameter
to be about
image
is_about
O･015m2/g･
●
promlSlng
andflexibility･ Thus, the Al fiber
work,and
of the fiber
h
air quality･
is considered
(a)and (b),respectively.
area
ihdoor
Part･AndAlfiber
for filtermaterials due
candidate
utilized
the
was
of the
100
pm,
Fig. 1.
In this study,Ti02
The
(a)Photo
films
were
photocatalytic
were
fiber,
coated
(b)SEM
by
characterized
the
and
XRD,
by
interrelationship
of su血ce
by
between
composition
XPS,
and
NOx
ofAlfiber
the sol-gel dip-coating
chelTlical
SEM
investigated
was
property
image
onAlfiber
structural properly
crystalproperty,
coatings
ofAl
on
photocatalytic
property, the optim或1 fabrication condition
the
By
sterilization･
crystal
morphology,
was
fabricated
respectively.And
removaland
investigating
of
method･
quality
and
identified･
2.2. ExperimetLtal
2.2.1.
h
Synthesis
this work,
ofTi02
the sol-gel dip-coating
and凸exibility
ofAlfiber,
phase
Titanium
method.
titania. Because
and
acids
thus
or
condensation
TiO2
method
films
are
and
to control,
rates
chelating
the chemical
ligands
was
difficult
Because
employed･
to
be coated
making
their sol-gel
modification
is co甲mOnly
used
was
of itwithalcohols,
to retard
32
by
gas
for
precursor
transformation
fast
very
chlorides,
the hydrolysISand
((CH3)2(CO)2CH2 (ACAC))
[9111]. Acetylacetone
of the shape
the fibers
on
(Ti(0-i-C3H7)4(TrIP))
tetra-isopropoxide
of it is easily hydrolyzed,
difficult
bases,
Films
acting
as
a
bidentate
TrIP
by
several
anesthetic
and
ACAC
and
acetylacetonate
monocharged
with
complexes
alkoxide
was
as
used
stabilizing
a
ACAC
for
reagent
was
used
as
solvent･
hydrolysisICOndensation
througha
titanium alkoxide
can上eact with
ligands
chelating
reaction
ACAC,
as
shownin
(1)【14】.
reaction
Ti(OC,H,)4
+
(CH3)2(CO)2CH2 -Ti(OC3H7)4-n[(CH3)2(CO)2CH2]n+
n
even
completely
precursor
water
and
temperature
(RT)
dip-coating
process･
A
nuhber
or
uslng
when
would
be
the
mixture
A触r
nanostnlCture.
ligand ACAC
of the cbelating
complexes
remove
growth･
(EtOH))
as
[12, 13]･ So,
thin films
TiO2
prepare
(CH3CH20H
ethanol
formtitamium
Tbe
to
authors
ligand, has been
a
given
Then,
slow
a
large quantity
and
mild,
was
solution
temperature),the
a
of samples
post heat
were
the samples
are
in mixture
shown
in Table
solution, aglng
l･
33
a
at
aged
solution
varylng
time,
and
-on
out
Parameters,
heat
the reaction
of
(room
temperature
certain
carried
by
to
and
the fabrication of TiO2
coated
was
was
●
ratio of chemicals
Thus,
of water･
bard
stable
very
benefits
which
treatment
fabricated
are
wi也Ti
(1)
C3H40H
n
treatment･
theAlfibers
for
TiO2
Such
The
as:
by
Crystal
molar
details of
Table
Sample
Parameters
Molar
ratio
SeriesI
A
1
ACAC
3
3
6
of TiO2
COatings fabrica(ed onAlfiber.
SeriesⅠⅠ
ト1
a
mP
H20
1.lmtroduction
Ⅰ-2
Ⅰト1
SeriesⅡⅠ
Ⅰト2 Ⅰト3 ⅢⅠ-1 Ⅰ1Ⅰ_2ⅡⅠ-3
A
1
1
9
12
EtOH
6
3
9
3
20
5
10
Se血sⅣ
A
Ⅳ-1
Ⅳ-3
C
B
Ⅴ-1
1
1
1-
3
3
3
3
3
15
20
3
Ⅴ_2
6
20
80
TempぐC)
Ⅳ-2
C
SeriesV
20
RT
RT
80
2w
30mi皿
Aging
Time
EZ5
30min
2w
3w
4w
I
Heat
treatment
Temp(oC)
Time(也)
(Note:Temp-temperature;
RT-Room
Temperature;
w-week;
450
45d
700
450
プoo
3
3
4
3
4
h-hour.)
34
2.2.2.
Characterization
The
(RINT-2000,
TiO2
CuKα
JSM-5600,
were
by
have
long
considered
throughthe
electron
scatterer.
A
Crystals
of electromagnetic
are
waves
regular
as
an
spherical
scattering,and
array
of scatterers
cancel
waves,
add
arrays
ocean
from
emanating
secondary
interference),they
(ⅩPS) (ESCA-5700ci,
emanating
a
produces
out
a
law
nよ
35
a
waves,
few
from
regular
in
most
array
canbe
pnmarily
lighthouseproduces
striking
the
of
knownas
spherical
directions
an
This
electron･
(or lighthouse)is
the electron
in
-
striking
X-rays
and
X-ray
scatter
that
structures
lighthouse,soanX･ray
waves
oneanother
from
atoms,
of
wave
the
co去structively
2dsinC
of X-rays
radiation･ Atoms
electrons. Just
regular
(JEOL
analysis
composition
spectroscopy
the elastic scattering
on
waves
Althoughthe占e
Bragg's
based
isknownas
phenomenon
of
(SEM)
microscopy
semi･quantitative
and
morphology
surface
(ⅩRD) Techniques
order･
produces
electron
pbotoemission
range
atomsT
The
scan･
measurement
Inc･)･
are
circular
secondary
state
X-ray
Diffraction
techniques
scanning
using
chemical
an
Electronics,
2.2.2.1. X-ray
xRD
The
30KV).
pe血med
Physical
observed
(XRD)
difEra9tion
0-20
normal
a
radiation)with
was
coating
identifiedウyX-ray
was
structure
crystal
the
waves･
(destructive
determined
specific directions,
by
is any
n
where
'pattern,
often
called
of atoms
Fig. 2. Principle of XRD:
a
with
The
within
incoming
of itsenergy
･small portion
a
separation d,these
spherical
case,
part of the incoming
as
the
beam
a
waves
beam
as
appear
X-ray
on
a
on
spots
diffraction
the diffraction
from
results
regular
array
of
upper
left)causes
an
(the
scatterers
crystal).
(coming
from
If scatterers
will be in synch
(add constructively)
only
is deflected byanangle
are
arranged symmetrically
in directions
In
multiple of the wavelengthん.
20, producing
to
scatterer
each
sphericalwave.
2d sin 0 equalsaninteger
their path-1engthdifference
where
Thus,
(the X-ray) impinging
aⅢ■angement
re-radiate
specific directions
reflections.
wave
electromagnetic
repeating
integer. These
a
that
in the
rePectionspot
di放action pattem.
2.2.2.2. Scanning
A
detailed
Microscopy
Electron
of how
explanation
(SEM)
typical SEMfunctions
a
follows
(referto
the diagram
below):
Source"
The.TVirtual
of monochromatic
The
streamis
I-coarse
the top represents
the electron gun,
producing
a. stream
electrons.
condensed
probe
the amount
at
by the first condenser
This
currentknob--)･
of current
in the beam.
lens
len芦is used
It works
36
to both
(usuallycontrolled
●
forp,the beamand
in coqunction
by the
limit
with the condenser
to
aperture
3.
beam
The
is then
4.
second-condenser
and
is usually controlled
from
A
selectable
user
by the ''fhe probe
coils then
of
thin,
a
user
beam
tight,coherent
currentknobH
further
high-angle
eliminates
''scanl'or
"sweepf'the
beam
on
for
of time
points
(usuallyin the microsecond
speed
when
electrons
period
in
a
grid
(like a
fashion
by
determined
the
scan
range)
●
the
beam
scannlng
the part
onto
of the
desired･
the
interactions
Before
a
Objective,focuses
final lens, the
specimen
beamstrike;the
occur
of
determined
process
entire pattem
and
is repeated
dwells
are
detected
dwell
display
a
point
pixel
until the grid scanis
scanned
on
reactions the
(themore
by this number
(and
and
its next
to
interactions
canbe
sample
inside the sample
the beammoves
number
This
into
the electrons
objectiveaperture
dwelling
television),
10.
(usu?llynot
aperture
the beam
set
The
condenser
high-angleelectrons
some
lens forms
The
A
by. the
constricted
eliminating
selectable),
the beam
high-angleelectronsfrom
eliminate the
30 timesper
37
for
a
with
various
these instruments
a
CRT
whose
instruments
count
the
intensity is
brighterthe pixel)･
finishedand
second･
fewmicroseconds)
then
repeated,
the
Fig･ 3･ The
2.2.2.3.
X･ray
XPS
on
excite
kinetic
These
Spectroscopy
chemical
information
from
valence
of the
energy
(p is the work
to
pbotoelectron
known
values.
against
EB.
from
XPS
XPS
XPS
using
Mg
Ka
X-rays
-EK
function
spectra
peaks
handbooks
environments･
hv
the parent
XPS
well
from
hydrogen
and
an
electron
energy
EK,
can
spectra
(300
were
W;
oxidation
helium･
COre
5
X-rays,
as
Orbital
It
nm･
and
Soft
analyzer,
measures
to
up
can
structural
of energy
in Fig. 4.
shown
atoms.
of surface
【15】:
-?
of the
be
traditionally
be
plotted
kV,
uslng
on
uslng
20
mA)
38
energy
the
measured
as
tabulated
chemical
a
VG
and
binding
composition
Scientic
a
other
photoelectron
●
identified
acquired
is the binding
calculated丘om
information
15
EB
spectrometer.
can
and
then
yielding
as
to the relationship
according
atom
are
depths
analysis
as
and
energies
EB=
where
with
ejectedelectron,
have
pbotoelectrons
apart
functions
(XPS)
materials
all elements
electrons
typical SEM
a
of
near-surface
quantitative
environments
The
the
analyses
provide
hv
Photoelectron
diagram
Escascope
hemispherical
slgnal
energy
and
of the
and
intensity
values
bonding
spectrometer
electron
energy
Data
analyser･
acquisition
VGS5250
manufacturer-svpplied
in the main
charge
was
c血amber
【16]丘ompump
During
software･
out
carried
*10
aト8
maintained
was
referencing
were
manipulation
and
against
out
carried
the pressure
acquisition of spectra,
9 Torr
lo ensure
a
Clean
su血ce･
sample
Is -284･8
(C
hydrocarbon
adventitious
uslng
eV)
oil contamination･
I
Ⅶ伽向
bd
ミ
■■●●●■●●●●●M■
●■●1
●■一■●●●●4
41
t●●
≠
i
5
和好
EコEコ⊆⊆EコEコ⊇
--●一トナ十●･一
軸w
壬
言t
I-.-･一-i.......
-
j
25.I
壬
-I-･･
ふこ㌻卜
1f
･..
壬
J
l■llt
i.
showlng
XPS
-.-.-.
---く=--..
Fin&l曲te
hitbJ蜘
Fig･ 4･ Schematic
壬
壬
binding energy
process･ EB is the electron
EK
and
is the electron
kinetic energy.
2.2.3.
In this study, the photocatalytic
sterilization.The
Property
of Photocatalytic
hvestigation
characterized
was
property
details of the measurements
NOx
introduced
were
process
by
removaland
follows･･
as
2.2.3.1. 対ox Removal
To
evaluate
equipment
uv
into
lamp
a
surface
was
used
reaction
of TiO2
as
shown
in Fig･ 5
in wavelength,
(350 nm
●
ability of fabricated samples
the
chamber.
This
layer, therefore
15
system
leads
[17]･TiO2
W),and
can
to
on
make
then
39
Al fiber,
coated
the wrapped
the NO
higher NO
the NOx,
removlng
gases
removal
was
samples
contact
efficiency
a
self-made
wrapped
were
on
a
inserted
with the entire
and
lower NO2
generation efficiency than that of JIS evaluation
Gas
20
with
reactor
byanalr
vessel
glOX20
cm.
reactor
The
2.23.2.
In
vessel,
kinds
of
hospital
to
were
at the
measured
is
vessel
exit of the
①:MFC (Mass
system.
vessel,
@:
UV
lamp,
@:
now
sample,
②: air pump,
Contro皿er),
@
:
gas chromatograph
the
pbotocatalytic
(anaerobe, aerobe
and
fabricated
of
In也e
property.
facultative
samples
aerobe)
were
also
measurement,血ee
that
usually
in
appear
employed.
Theanaerobe
Staphylococcus
coli
reactor
into
period.
sterilization performances
characterize
bacteria
The size of
Were
gas
flowed
then
vessel
Of Sterili2:ation Pmperty
experiment,
investigated
reactor
NO2
and
the reaction
mixture
of 1.5 Umin.
rate
of NO
gas removal
@:
into the gaseous
at the flow
during
MeasuremetLt
this
Input
Pump
of NOx
gaseousmixture
was
concentrations
continuously
Fig. 5. Schematic
@:
NO
ppm
[18].
method
(E･ coli)were
is bacterium
aureus
used
that does
(MRSA),
●
not
requlre
EnterococCus
in the experiment.
MRSA
40
oxygen
faecalis
lives
for growth.Anaerobes
of
(E･ faecalis)and Escherichia
on
the skin
or
in the
nose
of
a
,
that
person
has
that
organism
an
E.
also have
and
that
6, which
were
commonly
forming
colony
solution
Milli-Q
[20-22]･The
conditions
per
a
simultaneous
02
the
other
intestines
etcI
facultative
The
It
isan
The
aerobe
the
Pseudomonas
infects
which
experiment,
mammalsI
of mammalsI
example,
production･
canuse
aerobe
oxygen,
is Bacillus
sample
cereus
other
water
system
research
gas Supply
With
groups
shown
different
was
used
rate
of 6･2
as
in Fig･
experimental
density
with initialbacteria
solution
atthe
device
evaluated bythe
was
of lO51107
initialsolution･ The
1Jmin
by
a
circulation
of 250mIJmin･
Ultrasonics
appaTatlJS
Fig. 6. Apparatus
the
ilhess･
milliliter (CFU/ml)
circulated inthe
was
with
umits
by
For
the
of the films
used
lower
and
absorption
in
used
of energy
sterilization performance
food
etc･And
wounds
foodborne
cancause
in the
metabolism･
was
methods
anaerobic
@. cereus)that
based
of humans
tracts
and
to life-threatening
skin injections
minor
coli lives
processing
oxygen
bums,
tract,
pulmonary
pump
waste
(P. aeruginosa)
aeruginosa
from
of illnesses
inhabits the gastrointestinal
assistswith
actually
The
range
endocarditis.And
cancause
but
a
cause
E. faecalis
diseases.
It
can
of photocatalytic sterilization
41
for TiO2丘1ms
on
Al
fiber
[19】
initial
water
2.3. Results
2.3.1.
XRI)Analysis
better crystallinity of TiO2
Tbe
So,
the prepare
Maximum
was
shown
2･ It canbe
exhibited
anatase.
with
well
tbat也e
with
FWHM
data
to be
by
peak
that these
of peaks
of the
B
of anatase
and
bene丘t photocatalytic
XRD
peaks
FⅣHM
narrower
and
The
samples
the optimized
which
of the samples
ち and
samples
c.possessed
(A) and
Al
better
in JCPDS
C
C
peaks
are
crystallinity･
【23】.
(
○
き:::
Samples
Fig. 7. FWIIM
of
same
42
samples
in Table
XRD
samples
are
1.
bigber
of
shown
in
at
than
than
peaks
tb皿
patterns
are
narrower
The
at Half
in XRD
heat-treated
were
Band
application･
Full Width
and
series of fabricated samples.
in Fig･ 7 and Fig･ 8･And
observed
samples
stronger
respective
the intensities of peaks
implying
agree
are
samples
Table
and
Sample
from
chosen
is considered
firstly optimized
were
samples
(FⅣHM).
others
these
Discussion
and
450oC
others
others,
in Fig･ 8
こiJ
●
∋
●
cC
ヽ-′
h
/tj
班
己
B
a
40
:】0
(d喝.)
20
(a)SeriesI
1
-
≡:i=コ
S
L一
EZ
●
重j
冒
ci
ヽ_/
点､
塊
;∃
B
a
l
l!
め
I--･ノ､･-_I-----･ノ:
J't.
-I
Ill
川
川
N1.M,■-..へ.
･q._･･…-･･/
■ ▲_I_■
八
I■■
40
30
20
(deg)
@)Series I
43
-
-一-●●llr■-
ll
I
hL-●●●▲
u.I.."..._..I..
▲■
tl
[コ]
∫
▼一■■
-2
■■■■●●▼■ヽ一■■■
■■▼.■■■●
■一■t●●●●-■一■■■
?
●
c6
ヽ_/
ヨヨ
/ti
∽
白
B
【]
l■･･■
40
20
50
(deg.)
(c) series Ⅱ
.■■■ヽ
E:I
【:
J
｣=
主
ょ･
'宗
1=
iU
.≡
(d) Series Ⅳ
Fig. 8. XRDpatterns
ofsamplesinseries
Table 2. The experiment
I
,
I
and
Sample
conditions for 2 samples
B
C
1:3:6:20
1:3:3:20
Molarratio
mP:ACAC:H20:EtOH
Aging
RT/2week
80oCβOmi皿
Heattreatment
450oC/3br
44
N
2.3.2.
Based
on
V
series
12 show
that TiO2
and
V-2
treatment
ligand
observed
and
Morphology
Surface
results of XRD,
the
in Table
1,
the SEM
images
been
have
were
at 808c
for allthe
the thermal
for SEM
chosen
C
increases
films,
expansion
thismight be
and
the concentration
attributed
differences between
Fig. 9. SEM
image
45
to
and
ofsample
B
to
Fig･
-
observed
B
thickness of sample
be
of complex
are
many
the conple5
substrate
Fig1 9
figures, it canbe
which.might
There
belong
which
analysis･
The
V-1,
solution･
V-2)
XPS
these
theAlfibers･
that of sample
of
and
and
From
on
coated
Tiandviscosity
Vll
C,
observation
of 4 typICalsamples･
to initialsolution
with
(B,
4 samples
successfully
wasthickerthan
ACAC
(SEM)
TiO2
due.to
heat
of chelating
cracks
canbe
Shape ofAlfabers
COating･
Fig. 10. SEM
Fig. ll. SEM
image
image
46
ofsample
of sample
C
V-I
Fig1 12･ SEM
Chemical
2.3.3.
The
by
XPS,
Fig･
13
shows
0,
attributed toTi,
TiO2
tabulated in Table
of
samples
V-2
temperatures
from
substrate
CandAl･
XPS
to
according
handbook
and
V-1,
was
[24]･ The
theTi/Alratios
respectivcly･
V-land
V-2
(ⅩPS)
of samplesI
spectrum
Ti 2p3/2 peak
3.Asseen,
of sample
to
typICalXPS
V-2
of the fabricated coatings
the composition
stateand
of sample
Evaluation
Compositional
State and
chemical
image
located
Thismight
TiO2 coatings.
47
of
B and
be
due
investigated
peaks
eV,
implyingTi4+
the
4
at 458･9
higher, which
were
Theindexed
Ti/Alratios
of samples
were
C
were
tothe
canmake
samples
were
in
were
larger than that
heat
treatment
moreAldefuse
Table 3･ TheTi/Alratio
Sa皿p1￠
of4 saJnPles by XPS
AcoJnPany
Ti/A1
sent-quaJltitativc analyses.
C
Ⅴ-1
Ⅴ_2
3.1
2.2
1.6
2.4
I.6
ら
嘗
O
U
Binding
470
465
J60
Birldlng
Fig･ 13･ (a) XPS
spectra
Energy
Ertergy
of sample
(eV)
455
450
(eV)
a,
48
(b)XPS
spectra
ofTi2p
of5samples.
2.3.4.
Removal
2.3.4.I.
NOx
The
mechanism
Step
Ability
Photocatalytic
of No又
h'+
[25]:
hv
TiO2
-
(e-+h')
Ofrー･OH
+02→02
e
2･ Oxidation
follows
Of TiO2
1. PbotocatalysIS
Tio2+
Step
as
removalis
using
NO
hydroxyhadicals:
･OH
+H20
+2･OH-NO2
NO2
+
0Ⅹidation
NOx
+H'
･OH1.NO{
llSlng 'acti∇e oxygen':
NO
----一旦｣-
02
;
L-rtl111
L!＼:radlLL=tln
･い:lごhl
Fig･ 141 Schematic
The NO
removal,
NO2
generationand
diagram
of NOx
NOx
removal
49
removalpTOCeSS
are
calculated
as
follows:
InitialNOx
+
NOR
removal
efficiency
con°.
Final No∑
-
×100%
hitial No∑
5 typical samples
were
con°.
-
for the
selected
Table
4. The
of NOx
measurement
samples
con°.
removal,
for NOx
employed
as
Temperatureof
Sample
aging
ACAC
6
C
3
heat-treatment
EtOH
H20
B
4.
removal･
TbemoralratioofⅡ1iXture
mP
in Table
shown
80oC/30m血
450oCβ血
1
3
20
Ⅴ_1
3
Ⅴ_2
6
RT/2week
-700oC/4b
(a)Nor
ability of fabricated TiO2
removal
Photocatalytic
80oC/30m血
properties
Samples
of the fabricated TiO2
for the removal
coating
ofmitrogen
ー_･ノ1
are
oxide
of NOx
and
and 20
and
for the 4 samples
time
min
sample,
reaction,
and
69 min
B
sample
NOx
possessed
the
NOx
Ⅴ-1. The
of anatase.
samples
However,
B, C,
the NOx
B
and
samples
C
were
V-2
between
75%,
to
Ⅴ-1
26%,
shown
5%and
67%,
sustainable
post
heat treated
and
V-1
50
were
at
24%and
59%
14, 25
This
s山ggested
photocatalytic
property
450oC,
annealing
removal
after 120,
16%
abilities for 4 samples
removal
of NOx
ratio
in Table 5. After 15, 4,
V･2, respectively.
and
and
as
removal
the quantity
ratio of 97%,
removal
highest efficiency
removal.Asobserved,
figures, the maximum
be observed,
can
the maximum
for samples
reaction
these
the relation
achieved, then, this ratio decreased
were
>
for respective
reaction
9
Fig. 15 to Fig. 19. From
shownin
was
possessing
at 700oC,
B
>
V-2
that
for
C
>
singlephase
wbicb
resulted
in multiphase
removal
samples
min,
weeks･
and
The
V-2
fabricated from
were
B and
sample
V-2
C
showed
initial solution
V-1
and
were
C
B and
of sample
●
that of the sample
whereas,
better performance
that the slngleanatas.e phase benefits
imply
would
B
andrutil･ The
of anatase
for NOx
the photocaterlytic property･
heat
treated
better pbotocatalytic
80oC
temperatufe
at room
aged
at
property,
which
for 30
for 2
indicated
＼
ノ
of initial solution
that the heat-treatment
Thus,
it can
be concluded
photocatalysis
improve
can
the photocatalytic
of initial solution and
that heat treatment
anataseTi02
･
ノ■■ヽ
l
1.0
ヽ■■′
'3
>
○
己
O
0.8
0.6
ココ
粥
O
0.4
a
%
0.2
0
'B
く弓
仁弓
0.0
0
20
40
80
60
Time
Fig･ 15･ Photocatalytic removalNOx
51
1 00
1 20
(min)
of samplefrom
performance･
A company
favor
一■■■ヽ
J
1.0
＼_/
'a
0.8
>
0
己
巴
O16
粥
2
o･4
く+■
O
o.2
0
'B
a
o･o
0
20
40
80
60
Time
100
120
(min)
Fig. 16. Pbotocatalytic removal
NOx
of sample
B
ノ■■ヽ
⊥･1･O
I■■■■■
空o.8
0
≡
巴0･6
-く
2
o14
く.ト1
0
o.2
0
'=
a
o･o
0
10
Time
Fig. 17. Photocatalytic removal
52
･15
(min)
Nor
of sample
C
ノ
ー1.0
I
ヽ■■′′
Tc
o.8
>
O
g
o･6
t'<
a
o･4
a
the
o･2
0
●
l■■
i
p〈
O･O
0
10
15
25
20
(min)
Time
Fig･ 18･ Pbotocatalytic remわval
No∑ of sample
V-1
′-■■ヽ
1.0
I
ヽ_/
■l･･-■
cd
0.8
>
○
己
A)
Lコ
0.6
〉く
O
0.4
a
the
0.2
O
'B
cd
0.0
Fi
0
40
20
Time
￠0
(min)
Fig･ 19･ Photocatalytic removalNOx
Table
5･ Comparison
80
of sample
photocatalytic effect for 4 samples
Ⅴ_1
Ⅴ_2
4上
9
20
67
24
59
B
C
ThetimeofmaXimum.removalNOx(m血)
15
Themaximu甲ratioofremovalNOx(%)
■97
Sample
(b)Addition
of H202
In order to enhance
into NOx
V-2
removal
reaction
the photocatalytic effect, H202
53
is introduced when
sample
B
was
a
used
second
time. H202
is a metastable
highredox potential (1.77V),and
molecule
of
･OH
radical･
●
the formation
canpromote
free hydroxyl
The
is
reaction
followlngS
as
【26】:
The
effect
H202
+
TiO2
+
(也+)
TiO2
(e
H202
hv-TiO2
(e- + hT)
H20ad
) H202
+
on
increaslng
concentration
Table 6. Comparison
inv.estigated by
was
removal
6. The
ration of NOR
the
When
the ratio of NOx
is
uslng
increasedwith
removal
concentration
lower
1.2%,
than
time dependent
pbotocatalytic
bacterial solution is shownin
92%,and
performance,
15,
1.5
3
4.5
7.5
9
92
90
75
84
79
79
71
H202
added
of sample
20. TheL maximum
at
about
it is concluded
whichmight
of H202
1.2
property
the ratio still maintained
the result of Fig.
sustainable
Fig.
quantity
0.75
87
RatioofNOXremoVa1(%)
the added
removalabout
-o.3
TheconcentrationofH202(%)
with
NOx
OH
+
･OH
decreased.
thereafter
Tbe
the
H+
+
･OH
+
-TiO2
in Table
shown
were
+
-TiO2
concentration
B, the results
sample
the
of
TiO2
80%
that
ち with
NOx
after
the
150
radicals.
54
removal
min
addition
be due to the formation
0.75%
of
ratio
was
in
about
reaction. Compared
H202
enhances
of larger amount
the
of.OH
(a)sample
仲)sample
B
一oo
′ヽ
100
%
芸
)
80
a
_80
A
>
垂60
塞80
L
X
a
占
≡
m
Z
B and H2020･75%
こ=
ヽト
0
0
20
0
0
20
+∫
こコ
d
∝
a
∝
0
40
80
0
100
80
0
20
48
60
Fig･ 20･ Photocatalytic removal
2.3.4.2. Sterilization Effect ofTi02
The
The
sterilization
o.5 h, 1 h and
sterilization
B.
NTox of sample
investigated,
was
increased
120%
It isknown
radical
on
the
TiO2
that the
as
Su血ce
02
02
+H十-Hoュ
02
+
2HO2
02
-
The
O%
shows
coating
differences
(1)
-
(7),thus
within
02-
02
+
+
HO2
02-
of
can
55
and
accelerate
(1)
(3)
(4)
Ⅲ202
different
be explained
can
[26]･
+
O･5 h,
existed after 6 h
50%
benefits the generation
in Eqs.
TiO2
TiO2
in Fig･ 21･
shown
became
to about
the
are
(2)
Hoュ-
-
02
reaction
(e-)+
TiO2
of
shown
bactericidal ability of photocatalytic
h･ So,
of bacteria.
present
the results
decreased
24
within
effects for different kinds
follow:
160
B and H202
E･ faecalis
E. coli and
cereus,
6 h, respectively, P･ aeruglnOSa
then,
reaction,
140
Films
B
of the sample
ratio of MRSA,
survival
令0 一oo 120
Time(min)
Time(mid
as
･OH
the
HO2
+eJ
H202
+HO2
Ti02
At the
+ H202
(eー)
more
02 WOuld
more
and
aerobe bacterium,
the exist of
have
OnAl丘ber
aerobe.As
for aerobe
atmosphere
is considered
photos
may
02
･OH+
OI〔
+
+
(7)
･OH
be consumed
would
intheantibacterialprocess.
E･ coli and E･ faecalis nearly disappeared,
cereus,
Since P. AeruglnOSa
exist in solution but consumed.
02 beneGts
excess
The results of time dependent
coatlngS
B･
+
-TiO2
02
aRer about 6 h, MRSA,
Otherwise,
H20
-
beginning,theintroduced
However,
and
+H'-H202
bacterium
good
P･
as
such
be very
be it make
survivalratio
sterilization by
good
on
aeruglnOSa,
for obtaining
Important
two
and makes
the00ntrol
tier system･
Fig1 22
一oo
ち
く)
ヽヽ
B.
80
▼
I
-l
40
cereus
E.coli
at)rug;nosa
◆
l●
己
●
I
l■
l.
LB
20
EE)
-◆一P.
｡.
60
.≧
:⊃
-
L.･
O
Fj
E.faecalis
●
0
0
200
400
800
600
Time(m
1000
1400
h)
Fig. 2 1. The photocatalytlC Steri1izatlOnOfmicrobe5
56
1200
for TiO2 films
the
exhibited that the
MRSA
-●-
軍
result.
shows
lot a洗er sterilization.
a
y)
of oxygen
sterilization
of the bacterial solution before and aRer sterilization, which
bacteria decreased
TiO2
and facaltative
anaerobe
good
an
it increase.
that the prepared
suggested
sterilization performance
bacterium,
to
its reproduction
is
on
Al fiber
(b)24h
(a)Oh
Fig. 22. The
(也)after
and after sterilization.(a)beforesterilization and
of before
comparison
sterilization.
2.4. Condusion
ln
in order
this study,
treatment
SEM
the photocatalytic
of
of fabricated
sterilization)
Anatase
lS
efBciency
The
Bwith
sample
effect.
photocatalytic
fabrication condition for TiO2
XPS.Andthe
investigation
the
By
good
were
characterized
coating
was
optimized
(experimentalof
NOR
removaland
and
crystalquality
H202
introduction
on
by
by
highTicontent
into NOx
gas,
the best
shows
higher NOx
removal
achieved.
sterilization
system
with
(MRSA,
aerobe
(P. aeruginosa),respectively.
good
property
fabricated
was
samples･
photocatalytic
show
COating
Samples
method･
(sterilization,
effects
photocatalyst
photoactiveTi02
dip-coating
by the sol-gel
and
various
etal.) onAlfiber,
of exhaust,
flexibleAlfiber
XRD,
introduce
to
anaerobe
effect
of
E. faecalis, EL
sterilization perfo-ance
The
on
was
evaluated
facultative
COli),
results
suggest
anaerobeand
57
bythe
theTi02
solution
aqueous
aerobe
FBI CereuS)and
COatings
facaltative aerobe.As
on
Al
fiber
for aerobe
bacterium,
such
●
very
Important
as
P. aemglnOSa,也e
for obtaining
good
control
of oxygen
sterilization result･
58
atmosphere
is considered
as
References
[1].
P. Jones: Atmospheric
[2].
R. Niemalaand
H. Vaino:
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M.
[10].
W.
IL J. Oh,
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Ⅰ.Oja and M･ bunks:
Es-Souni,
T. Nguyen,
L･ Miao,
D･ Briggs,
M･
Chichester
(1992)･
[16].
･
Handbook
Mimesota
L. Luo,
11112
of
M･
271
Tanemura,
X-ray
P･ P･Lettici･
J･
J･ Robichaud:
(2004) 259･
99･100
S･ Toh･
K･
Kaneko
M･
and
(2004) 245･
et･al･:PracticalSurfaceAnalysis,
F. Stickle, P･ E･ Soboland
W.
J. F. Moulder,
D･ Bersani,
19･
Solid State Phenomena,
S･ Tanemura,
J. Crys. Growth,
P･ Seah,
(1999)
(2002) 255･
Kamasaki:
[15]･
[17].
P･ V･Ashrit,
S. Badilescu,
Djaoued,
Solid Films, 349
I^nglet:Thin
and M.
K･ D･ Bomben:
Spectroscopy･
Photoelectron
seconded･･
Wiley,
vol･1 John
In: Chastain,
Perkin-Elmer
J･
(Eds･),
Corpor?tion,
(1992).
L. Miao,
S. Tanemura,
M･
Tanemuraand
(2006)15.
59
M･
Kawasaki
:
AdvI
Mater･
Rest,
【18】.ファインセラ享ツクス一光触媒材料の空気浄化性能試験方法
[19].
L. Luo,
L. Miao,
S. Tanemuraand
M.
Tanemura
Mater･
Sci･ Eng･
10
(2003) 247･
:
B, 148(1･3)
(2008) 183･
M.
【20】.
Mrowetz,
C. Pirola and E. Selli: Ultrason･ Sonocbem･,
[21].
Z. Shirgaonkar
[22].
P. Theron,
1
[23].
and A. B･ Pandit: Ultrason･ Sonochem･,
(1998) 53･
P. Pichat, C. Guillard, C. Petrier and T･ Chopin:
Phys･ Chem･
Chem･
Phys･
(1999) 4663･
JCPDS-hternational
Center
for Diffraction
00-001-1180,
DOV
view,
(2004).
[24].
Perkin-Elmer
Corporation
Physical
[25].
S. Dalton,
Environ.
G.
【26】.
5
Rincon
Data,
Electronics
K. R. Hallam
(2002) 415
and C. Pulgarin: Appl.
Catal. B, 51
60
00-003-1122,
Division･
P. A. Janes, N. G. Jones, J. A. Nicholson,
Pollu., 120
000-001-0562,
PDF
(2004) 283･
and
G･ C･Allen:
Chapter
Synthesis
Substrates
of TiO2
3
Films
on
Glass
for Hydtophilicity
Applications
61
3.1. Introduction
photoinduced
the su血ce
wang
light irradiation
under
et
al.
[2]. Since
of both
viewpoints
after irradiated
self-cleaning,
and
vapor
their synthesis,
by
PSH･
UV
heat
have
films
vapor depositionand
of applications, this drawback
range
be
should
from
be used
can
is usually required
treatment
mach
change
to
hydrophobicity
synthesized
spray
pyrolysis
a
from
attention
been
and
overcome,
by
reported
for anti-wetting,
for better PSH
across
spreads
water
was血stly
･attracted
films
TiO2
[3, 4]･ TiO2
anti-fogging
Su血ces
have
light,which
deposition, Chemical
a
of TiO2
Surfaces
photocatalystand
hydrophilicity
physical
PS辻
【1-4】.
TiO2
then,
effect in which
(PSH)享sthe
superhydrophilicity
anti-frost,
by
mainly
deposition･ In
For
property･
chemical
a
wider
coating
route,
on
quartz
●
as
such
spin-coating
In this chapter,
method,
Polymer
TiOdOrganic
using
temperature
on
SOlution･
films
Hybrid
[5-7]were
●
●
substrate
a
glVeS
maybe
Paste
in spin-coating
SOlution
hydrophilic
the photo-induced
The
method･
synthesized
effect
heat-treatment
of
films
TiO2
of the prepared
property
was
also discussed.
3.2. Experimental
3.2.1.
Sample
Preparation
Titanium
lactate, isopropyl
titania source,
solvent and
surfactant,
maintained
to
and伊A
room
was
temperature
(RT) and,
alcohol
be
31:57
(IPA)and urethane
respectivelyJ
in
weight.
then, stirred at RT
62
acrylic oligomer
ratio of titanium
The quantity
The
mixed
for lh to yield
were
was
solution
a
clearand
used
as
lactate
prepared
homogeneous
at
solution･
60
The
s･
it
Then,
was
films
precursor
organic
residuals･
without
post･anneal
The
coating
3.2.2.
Ch血racterization
The
crystalline phase
composition
and
UV-Vis
surface
and Thermal
The surface hydrophilicity
angle
(WCA),
commercial
illumination
wavelength
ias
which
contact
was
the
angle
camied
of 365nm
out
and也e
distance
by
(TG-DTA)
The
and
sample
post-annealed
Handy
between
63
of prepared
was
force
the UV
samples
Surface
The
Science
AFM
microscope
by
analyzed
Differential
after drying.
of the water
variation
conditions
UV
The
temperature･
lamp
using
the
with
the sample
was
a
(UV)
ultraviolet
(LUV-6)
light and
contact
(i.e.,298K)
dataphysics). The
(OCA20,
Kα radiation･
Cu
room
at
atomic
by the in-time
atambient
9W
then
(SSX-100,
by
solution
reaction
a
the solvent
times･
were
properties
XPS
observed
was
performed
10
with
(V-570, JASCO)
evaluated
using
optical
measured
meter
films
prepared
The
Gravimetry
was
for
repeated
for
rpm
for 3h in the air, respectively.
byl SEM.
were
to remove
studied by XRD
was
morph6logy
(JEOL, JSPM-5200TM).And
ThermalAnalysis
films
The
at 3000
spln-coating
for 10 min
process
A･
sample
spectra
Ti/0
of
heating
by
substrate
at 200oC
(sample C)
of TiO2
ratio
Instruments).The
as
observed
by
investigated
were
and
500oC
was
glass
preheated
is named
surface of sample
quartz
were
(sample B)and
at 400oC
on
coated
10
wave
cm･
3.3. Results
3.3.1.
Ann)ysis
TG-DTA
We
know
can
Discussion
and
(1) From
thirLgSfrom
some
OoC
200oC,
to
there
only isopropyl alcohol
maybe
(2) From
200Oc
to
that organic
presume
450oC,
was
Fig. 1:
is little change
there
(3) From
450oC
that there is no
to
mass
the
big change
of titanium
constituents
500oC,
two
are
that
range･
of the
lactateand
It explains
of TG.
curve
volatilized inthe temperature
volatilized in the temperature
were
of the
of TG･
curve
We
can
acrylic oligomer
urethane
range.
of TG
curve
changed
loss. In other word, there is no
to
a
horizontalline.
It explains
volatilization.
>
20
5
<
;≡
riE
1X
0
1 00
2血
300
400
500
Temp.(℃)
Fig. 1. TG-DTA
3.3.2.
XRD
Analysis
In order to
samplesare
aJIalysis of TiO2 SOlution
analyze
shownin
the crystalline quality, XRD
Fig. 2. Sample
A
without
64
was
carried
out･
Ⅹm
hightemperature treatment
patterns
shows
of
only
a
broad peak,
101
implying
004 peaks
and
According
400oC
and
sample
A
anatase
of
to the
500oC,
at
the contrary,
B
sample
C
and
s血ow也e
phase.
result of TG-DTA,
so
annealed
phase. On
amorphous
some
peaks of sample
500oC･And
organic
it also
annealed
at 400oC
are
very
than that of
weaker
there is
explain that why
can
volatizing between
are
compounds
no
in sample
peak
tboug血TG-DTA.
Eu
●
壬コ
エ
≡コ
J=
PJ
‡∃
B
a
30
50
60
20(d蒜ree)
Fig. 2 XRD
3.3.3.
SEM
During
formed
fabrication process,
the
(a)sample
A,仲)
the
onlyTi02
followlng
cuⅣe-shaped
B, and
sample
the
in sample
in this way.
The
Was
of heat
change
A･ May
same
leaved.
be
some
conclusion
Ti-0-Ti
network-like
[7]･And then, throughhigh-temperature
●
shrank
of TiO2 films.
C
(c)sample
Observation
volatilized and
changed
patterns
The
surface
treatment
material
as
morphology
shown
could
be getting
can
65
organic
processing,
not
from
of
compounds
TiO2
in Fig1 3. The
be volatilized
the DTA-TG
firstly
was
metaloxane
are
films
was
surface
is
at 200oC
figure.
and
a
(a)SEM
image
sample
P)
of
A
SEM
of
Image
sample
(c)
B
SEM
血age
sanplc
Fig. 3. SEM
images
66
of samples･
of
C
3.3.4.
UV-VisAnalysis
Fig･ 4 shows
from
the
250
to 700
nm
for all three
same
th9
UV-Vis
in the
Same
sharpest,
The
nm.
For
attribute
wbi血sbould
in thevisible
the two
wavelength
whole
The
it should
and
wavelengths
range
(> 500 nm)
is almost
C, the absorbance
absorption
bigber
the
in'the
lightrange
B
samples
range.
to
films
preparedTi02
absorbance
samples.
A is the smoothest,
sample
of three
spectra
edge
of
is almost
C
sample
quality of crystallization. And
be due to its lowest quality
is the
that of
of crystallization･ These
7J
with the result of XRD.
agree
So血e
quality
of crystallization
in且uence the UV-Vis
can
absorption.
According也e
equation,
E
band
the optical
3.17
eV
and
gaps
3.19
eV,
(eV)
≡
of samples
1240/i(nm)
A, B and
C calculated
from UV-Vis
is 3.1 eV,
spectra
respectively.
100
500
600
700
Waveleng也(nm)
Fig. 4. UV-Vis
3.3.5.
of samples
XPSAnalysis
In order
prepared
spectra
to
TiO2
insightinto
films, XPS
the c,hemical
is utilized.
bonding
To
statesand
exclude
67
chemical
the influent of
compositions
contamination
in the
on
xps
measurement.
clearly
were
due
to
0 of sample
be attributed
seen也at
much
0
A
an.d C
are
0
(1s)were
of sample
seen
to
agree well
which
C
The
with
that
C
higher quality
for Ti
XPS
should
of Ti
th,an that of sample
of crysta11ization･ The
after heat treatment
2･0, suggesting
than
smaller
atom
and
(3･0),
A
for Ti
465･OeV
according
5(b)･
Fig･
(1s)peaks
C
TiO2
is smaller that that of sample
was
5(a) and
and
(2p3/2)
of Ti4'in
the volatilization of residual organics
C
before
min
the spln Orbit components
stronger
are
C has
the ratio of sample
vacancy
observed.
459･3 eV
of sample
1.7, which
was
in Fig･
samples,
peaks
the sample
for 5
shown
at
peaks
ions
●
For both
two
as
[8].TheTi(2p)
handbook
and
b.y Ar+
(1s),Ti (2p) and
C
(2pl/2),respectively,
be
sputtered
the residual organics･
origiⅡate加m
may
were
spectra
to
peaks･assigned
(2p) state
films
TiO2
these
surface,
XPS
to
A, which
ratio of Ti
this
might
at 500oC･
It is
that there might
be
existed in the films.
EJ
蔓】
i
班
◆J
d
a
1 200
800
1 000
600
Bindi皿g Energy
400
200
0
(eV)
′■ヽ
蔓j
i
め
■■■
F]
a
450
●55
480
Binding
Fig. 5. XPS
spectra of TiO2丘1ms
(sampleA
Energy
and
C)･(a)survey spectra,仲)high
for Ti(2p)region
68
46S
(eV)
-
resolution spectra
AFM
33.6.
Surface
lxl岬12,
The
of the films
morphology
A
sample
Observation
and
C
sample
the surface
sample
A
possessed
spherical
that post-annealing
Increases
The
UV
shown
WCA
can
be
and
C
is 96
particle
50
size
of
n皿,
30
about
the shape
(b)sample
area
of
respectively.
So, it canbe
nm.
changes
A and
of(a) sample
that, in scanned
nmand
size of 80
of the samples
images
found
particle
the particles size of and
images
AFM
nm･-And
concluded
of particles･
C･
Measurement
hydrophilic
effect
irradiation. The
in Table
of sample
films
of UV
400oC
reduced
(B)
from
investigated by WCA
were
irradiation
Fig･ 7･ Before
at
A
of TiO2
effects
land
(A), post-annealed
WCA
61 It
particleswith
particleswith
Fig･ 6･ AFM
3.3.7.
AFM.
A
of sample
oval-like
by
observed
in Fig･
shown
roughness
C hadthe
sample
are
was
and
time
WCA
on
irradiation,the WCA
500oC
70o into 60o
69
(C)
are
70o,
af【er 60min
measurement
of prepared
of filmswithout
30o, 25o,
UV
under
samples
post-anneal
respectively.
irradiation,
are
implying
The
that
irradiation
did
the WCA
of sample
UV
the
decrease
irradiatioh,
the
bydropbilicity
it can
PSE
oxidative
by
is mainly
with
The
induced
H20,
Of
presenQl.e
related
in chapter 1
better
The
better
ち
Ilo, respectively･
be
for
loo
C･ Combine
<
TiO2
anatase
pairs･ The
at the
and
TiO2
boles
hydrophilicity
lead
by
generated
is due
effect
surface
toanincreased
a
namely
mecbanisms,
and
C･
The
titanium
to surface
coverage
are
arise from
formed
oxide
is
organic
by redox
reactions
UV
i汀adiation･
under
Ti-OH
in the
which,
modifications,
of
the
decomposition
to decompose也e
able
radicals
XPS,
and
pbotocatalytic
both
oxidative
photocatalytic
the
min
better hydrophilicity･
hydrophilicity, which
These
60
B
samples
show
are
a鮎r
And
the results of XRD
with
films
(02 ･,0Ⅲ) which
Surface･
both
irradiation
UV
30min
15o and
photo-induced
radicals
groups
that
was
【9,
10】.
crystallization
irradiation, hence,
why
to
<
two
on
to
and/or photo induced
oxidizing
pbotoelectrons
phpto
to be A
of electron-hole
active
C
and
reduced
based
decomposition
adsorbed
compounds
B
However,
effect･
obviously
that well crystallized
photo-generation
caused
show
was
is obseⅣed
be found
Tbe
WCA
not
the active
benefits
oxidizing
the
crystallization results in
a
generation
radicals
of electron-hole
(02-, ･oH). These
better bydrophilicity･
70
pairs
might
under
be the
UV
reason
∼0
(⊃
ヽ-/
4)
㌢o
cd
岩40
【]
O
O20
一...一
q)
■■■■■■■
く勺
声0
0
Fig. 7. Water
contact
10
20
30
50
(min)
angle variations following
A,
Table. 1 Images
Sample
40
UV illuminationtime
O))sample
showing
irradiation time for the films.
the UV
Band
(c)sample
effect of UV
BeforeUVirradiation
▲､
(a)sample
C
irradiation on
WCA
AflertJVirradiationforlh
､l
:/!:,i/
j!^v(∴二
A
60
ヨ■■ー､.㌔
転;遜義盛速惑溢ヲ男■忘去§ごi三3,k遠3J泌遠品
B
.∴､.ごー■■ー■⊥三.′′
匿叫､.L璽....-...-.-.wy-整■
I..v/R>
L-ー､.ゝ二丁∵l.机.ll
､∨...I.
I;::
C
{T-^山王血:ごn'm7*ーユY^/､ンハ●r-､iv&J}】ンち
3.4.
Conclusion
h
this study,
quartz
substrate
crystal1ineTi02
using
Paint
filmswith.
spin-COating
hydrophilic
method.
71
XRDand
were
properties
XPS
prepared
results indicated
on
that
filmswith
uv-vis
a
spectrum
sharpest,
which
was
should
at
post-annealed
showed
500oC
that
concluded
phase,
without
fbmlng
and
anatase
that the
attribute
absorptionedge
to
higher
the
has better hydrophilic
bigb-temperature
thus
(500oC)
heat-treatment
high temperature
a new
idea should
pbase･
72
of
better crystallization･
post-annealed
crystallization･
the other samples･
was
be proposed
●
anataSe
of sample
quality
than
annealing
exhibit
necessary
to realize
From
fb∫ the
The
at 500oC
The
is
sample
it
this study,
fb-ation
of
the superbydropbilicity
References
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Y. F. Gao,
[2].
R. Wang,
K. Hashimoto,
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K. Hashimoto,
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20
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388
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3188･
Kojima,
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[8].
Perkin-Elmer
[9].
N. Sakai,
Corporation
A.Fujishima, T.
Physical
Watanabe
Electronics
Division･
and K. Hashimoto:
J･ Phys･ Chem･
1028.
[10].
Y. F. Gao,
Y. Masudaand
Langmuir,
K. Koumoto:
73
20
(2004) 3188･
B, 107
(2003)
4
Cb.apter
Preparation
of TiO2
Films
on
polymethylmethacrylates'(PMMA)
Their
Hydrophilic
74
Application
and
4.1. Imtrod廿Ction
The
wettability is
controllable
of the most
one
significant
of solid surfaces･
properties
●
It is
important
an
and
adhesion,
the
use
surface
(uv)
light, they
[7]and
self-cleaning
described
Asis
formatioh
indispensable･
to
phase
make
concentrator
PMMA
point
be
one
for
IS
Preferable･
In this chapter,
used
as
this
substrate
(CPV)
as
the
been
coated
angle
of ultraviolet
to
candidates
promising
better
on
for
glasses
and
control in wettability, the
thus
to
the heat
is
treatment
low-temperature
however,
process,
solve this dilemma,
of the fb皿ation
idea
new
of anatase
is dealt with･
subject
for TiO2
COating･ The
transmit up
lens
shownin
This wil■1induce the formation
75
contact
the
[8]･
independent
ofglassand it can
system
[5]･ Since
(water
most
it has
In order
of the ideal materials forfresnel
is hydrophobic･
the
example,
supe血ydropbilicity
half of the density
photovoltaic
including
reported,
the illumination
under
of
of applications,
process
was
been
microsctructure
is the prerequisite for TiO2,
pbotoinduced
it one
to
chapter,
previous
view
should be proposed･
is less than
PMMA
a
surface
mirr9rS for anti-togging
phase
From
In this chapter,
which
･in the
room-temperature
realize也e
of
[6] for TiO2 films
tbougbt
car
it have
"superhydrophilicity
wettability･ For
on
ofanatase
al.
been
the controllable
achieve
ideally
have
et
Printing,
anti-fogglng,
[1],the application of?1ectricfields [2,3], chemical
[4], and the control
Wang
self-clean1ng,
fわr achievlng
of methods
photoinduced
so-cよIled
Oo)" by
-
as
Such
areas
gradients
modification
of
ln
Variety
coating･
of temperature
demonstration
(WCA)
technology
to
density
98%
of PMMA
of visible
for instance,
(Fig.1(b)),
Fig･
1(a)･However,
of water
drops,
light,
used
in
the surface
of
such
as
dew
and
resulting in scattering
fog,
superhydrophilic
surface
lS
self-cleaning
light and
of
which
the■ transmittance･lfthe
functions
the
possesses
it, this problemwill
on
achievable
decreasing
thus
of
anti-fogglng
and
be solved･
(h)
Fig. 1.
4.I.1.Liquid
PMMA
(a)Photo
Phase
possesses
sol-gel
method,
usually
poor
solvothermal
require
aJld
The-
method
of boric
acid
+
2H20
BO33-
+
4F-
(1)is described
Gas
type･
dissolves
and
phase
high-puritytargets
of
as
a
methods
h
TiO2
6H'→
BF4-
in detail by the following
76
solution
2) 【12-16],
+
requlrean
staring
soluble titamiumfluoride
land
6F
3H20
three equations:
So,
addition, they
at low
scavenger
4H'+
+
as
afluoride
Equation
easily.
utilized for polymer
successfully
(H3BO3)
令
+
used.
thin films i皿aqueOuS
in the following
TiF62-
or
hydrolysis
the
utilizes
right(as portrayed
Equation
TiO2
dome
line･of･sight
production.
to
has been
which
to deposit
(TiF621)inthepresence
tothe
be
high-vapor-pressurechemicals
￠mployed
LPD
limited
are
it swells
as
solvents,
cannot
method
In this chapter, Ⅰ.PD method,
was
【9-11],
to
offresnel
Method
(LPD)
resistance
Photo
@)
system,
Deposition
investment
expensive
ofCPV
lenswith
materials･
surfaces
temperature･
complex
to shift hydrolysis
TiF62-
+
TiF6_A(OH)n2-+ (6-n)PHTi(OH)62TiF62-
aqueous
(BO,31) as
H,BO,
side. TiO2
the
and
pH,and
the
attachment
shown
shown
in Eq.
deposition
(2) to
displace
as
the temperature,and
heterogeneous
orpreexisting
in FI concentration
a
obtained
of
titania
titania particles
particles
can
in
an
di岳places the
by
scavenged
(1),(3) and (4)to theright-hand
by
of
tuning
theinvolved
The
Ti(OH)62-I
of the feed
of the titanium
on
degree
the super-saturation
concentration
onthe
result, the deposition
nucleation
FI
produced
the Eqs.
is deliberately
of the solution
(Ti(OH)621)
ions
complex
Eq.･(5),and thus
in
depend
TiO2
of
hydroxide
side, however,
&omTi(OH)62rate
(5)
20H-
(3) and (4)Ihcrease
left-hand
the
+
(4)
6F-
Ti(OH)62- +
-
2H20
+
titanium
in Eq.
(4) to
formed
Was
supersaturation
via
as
solution
(1),(3) and
Eqs.
into
changes
gradually
TiO2
-
(3)
+ nFTiF6_a(OH)n21
-
noH-
films
ratio, the
is initiated
surface
the
or
[17]･
ーーL+匡蓋纂-.→抑
L-i遜
トーーー■
=･
--
:l●
･r
Fig1 2･ Fabrication
lmthis
ambient
work,Ti02
condition,and
thin丘1ms
the
were
deposition
prog-ess
deposited
parameters
77
of LPD
on
PMMA
were
method
by
LPD
optimized･
method
h
near
under
additions
to
the
stmctural
and
bydropbilic
and
properties
investigated.
were
4.2. Experimental
4.2.I.
Polymer
Procedure
were
fabricated
films
in chapter 3･ The
●
layer
prlmary
is low
underlayer
by
coated
were
difference
to increase
PMMA
and
as
agent.
After
achieved. Thus,
was
for thefunctionalization
alcohol, similar
below
of TiO2
the adhesion
the
in this work･
PMMA,
because
and
films
to
lOOoC
this coating
these
layer･ The
.
prlmary
a
isopropyl
isthe drying temperature;
self-crosslinking binding
TiO2
●
PMMA
on
diluting titanium lactate with
helpful
was
temperature
highadhesion of
films
hybrid
polymer
films
The
ModiTICation
Surface
TiO2-Orgamic
an
optical
compositional血aracterization,也e
of prlmary
it
layer,
will be applicable
as
in
the
of plastic surface.
4.2.2. 'Film Deposition
To
deposit
TiO2
films,
solution that contained
reaction
[21], the
deposition
concentration
optimized
was
Tables
1 and
4.2.3.
Characterization
The
the
pre-treated
PMMA
H3BO3and
(NH4)2TiF6.From
ratio of
H3BO3
in
of the concentration,
terms
tO
substrates
(NH4)2TiF6
0f
pHand
immersed
were
the results of Deki
3:1
was
et al.
The
employed.
temperature
as
shown
2.
crystalline
structure
of TiO2
films
was
78
determined
by
X-ray
di飴action
(m)
in
Morphological
CuKa
(RINT-2000,
●
were
(PL)
photoluminescence
spectrometer
The
325nm
a
hydrophilicity
performed
effect
of TiO2
of 365nm
films
and
4.3. Results
was
carried
out
4.3.1.
Optimization
For
the deposition
a
of
Water
evaluated･
value
a
using
9 W
sessile
droplets
X-ray
Instruments)･
SPEX
1702/04
the
of
prepared
temperature･
at room
Handy
UV
variation of the WCA,
drop
at
placed
the
as
5 different positions
contact
angle･ The
(LUV-6)with
lamp
lightand the sample
angle
the superhydrophilic
method,
were
which
contact
commercial
a
using
recorded
was
the UV
the distance between
and
(i･e･,
298K)
means
the average
sampleand
was
properties
by the in-time
evaluated
conditions
atambient
By
(ocA20, dataphysics).
illumination
a
using
(V-570, JASCO)
spectra
by
obtained
Science
laser･ Optical
Further
JEOL)･
was
77K
at
measured
He-Cd
was
meter
for each
(JSM-7001FF,
Surface
an
equlPPedwith
microscope
Activity
Hydrophilic
surface
was
by
investigated by UVIVis
were
samples
4.2.4.
excited
electron
(SSX-100,
were
spectra
of the sample
analyses
of the films surfaces
state
(XPS)
spectroscopy
photoelectron
scann.1ng
(FE-SEM-EDX)
bonding
of the chemical
compositional
■
field emission
x-rayanalyzer
energy-dispersive
information
a
uslng
performed
and
radiation)･
was
10
a
UV
wavelength
cm･
Discussion
of Reaction
ofTi02
If the solution supersaturation
0n
lCondition
PMMA,
is too
a
suitable
supersaturated
high,precipitation
79
takes
place
solution
dominantly
is needed･
through
homogeneous
However,
substrates･
ratio
the deposition
solution,
at 30oC
results
are
shown
was
shows
onto
the
infhenced
by
the
deposition
a
obtain
be carefully
deposited
seriously
concentrations,
to
be
not
temperature,
suitable
supersaturated
controlled･
different
turbiditywith
Thus,
the influence
respect
deposition time
to the
of concentration
investigated by fixing the ratio of H3BO3:
Table
1. Influence
on
of concentration
(NI14)2TiF6at
1-2(也) 2-3(也)
･0-1(也)
3-4(也)
0.005
clear
clear
clear
clear
0.03
0.01
clear
clear
clear
tuⅢltOturbid
0.06
0.02
clear
clear
turntoturbid
0.09
0.03
clear
clear
turntoturbid
0.15
0.05
clearー
0.3
0.1
turbid
0.45
0.15
turbid
is oflmportant
is difficult
difficult. However,
cannot
adhere
on
H3BO3
0.15M
were
3:1. The
solution turbidity
0.015
suppersaturation
solution
Pbenomenonofsolutionfbuowdepositiontime
(NE4)2TiF6
concentration
on
1.
Concentration(M)
The
is
Therefore,
pH.
of reactors.
in Table
H3BO3
solution
conditions should
concentration
turbidity
and
can
Particles
supersaturation
the
as
such
solution generally
the
and
TiO2
sohtion
(NH4)2TiF6nl3BO3
of
The
the
conditions
experimental
hence
and
nucleation
to
be
for films
achieved,
highconcentration
spbstrate･From
considered
turntoturbid
Table
to be
deposition. At
making
results
in
the
80
low
formation
large and
1, the concentrations
optimum.
turbid
of
heavy
concentration,
of TiO2
the
Particles
particles which
(NH4)2TiF6 0･05M
and
Table
the influence
2 shows
3.5
results, pH
of pH
Table
From
this
be the best･
thought to
was
at 30oC･
turbidity
the solution
on
value
2. Influence
solution turbidity
on
of pH
phenomenonofsolutionfollowdepositiontime
pH
0-1(h)
In
addition,
the
accelerate
Thus
clear
clear
clear
clear
1.0
clear
clear
clear
clear
3.0,
clear
clear
3.5
clear
it is found
optimal
H3BO3
0･15M,
pH
4.3.2.
FE.SEM･EDX
seen.
cracks
expansion
about
25
30oC, which
the
to
would
of
evaporation
highertemperatures･
determined
was
condition
Of films
to
be
(NH4)2TiF6 0･05M･
●
are
in followlng
employed
be
From
The
FE-SEM･
(Fig･3a),non-uniformgrains
might
during
induced
by
observed
were
low magnification
constants.
anuniformsize
at
due
be
might
70oC
50oCand
tO
temperature
that
process,
rapid reaction
non-uniformgrains
might
turbid
experiments.
Observation
=
The
●
increaslng
that
reaction
3･5and
morphologleS
in Fig. 3. From
as
tumtoturbid
turntoturbidL
turbidity
solution
the
The
3-4(也)
0.5
(H20), as well
solvent
2-3(也)
1-2(也)
be
drying
to
attributed
due
proce;s
the
to
SEM
and
images
are
cracks
some
the difference
are
clearly
observed･
nm.
81
The
diameter
be
can
special growthmode･
highmagnification (Fig･3b),individual spherical
distribution
shown
The
in thermal
grains
with
●
of grain
Size measured
Tbe
Not
of the films wereanalyzed
compositions
only
films. The
strong
N and
0
and
Tipeaks
F should
Fig. 3. FE-SEMmicrographs
be
butalso
weak
from
originated
ofTi02
thin films.
82
by EDX,
N
and
as
shown
Fpeaks
were
in Fig1 4 and
detected
Table
in the TiO2
(N丑4)2TiF6･
(a)low
magnification.
O))highmagnification
3･
Energy
Fig･ 4･ EDX
4.3.3.
XPS
_
xps
was
located
at 459.6
were
thin films
N
0
F
at.%
6.5
63.58
18.22
that
was
an
The-I C
investigate the composition
to
to Ti,
attributed
eV,
(XRD)analysis
organic
of TiO2
element
performed
peaks
deposited･
(at.%)
PMMA
on
Ti
1I.7
Characterization
indexed
suggested
of TiO2 fnms
spectra
3. Composition
Table
(Rev)
identi鮎d
amorphous
Is peak
inter layer･ The
at
FIs
C, N
films
285･4
eV
peak
at
or
TiO2
a
due
was
685 eV
83
no
to
peak
films
was
of low
Ti 2p3/2
the X-ray
observed･
to
peak
These
hydrocarbon
thefluorine
was
di缶action
results
crystalline quality
the adventitious
corresponded
Fig･ 5･ The
shownin
The
A地ougb
【18】.
for the samples,
TiO2
as
F elements･
and
Ti4十state in TiO2
as
performed
0,
of films,
was
from
ions, which
was
from
originated
N
to
assignable
of TiOF2
the compound
from
atoms
molecularly
N
[19,20]･And
Is peak
N-containing
adsorbed
at 402･4
eV
(NH3
compounds
was
and
NOx)【19】.
1000
800
-h
'G
貞
6
B
a
4
0
200
400
Binding
Fig. 5 XPS
4.3.4.
PL
Spectra
The
PL
techmique
trapping,
shows
the PL
the oxygen
assigned
mlgrationand
spectrum
vacancy
to the oxygen
is widely
survey
transfer,
to understand
and
of the prepared
with
two
trapped
vacancywith
one
of TiO2
investigate
TiO2
trapped
84
films.
the
efficiency
of
the fate of electron-hole
films. Peak
electrons,
800
(eV)
energy
spectra
to
used
600
i.e., F
(1)at
center.
electron, i.e.,F+
465
nm
Peak
center
charge
carrier
palrS･ Fig･ 6
is attributed to
(2) at 525
[21,22].
nm
is
′-■ヽ
●
∋
●
CI
ヽ-/
b
'G
∈】
B
a
Fig･ 6 the PL
UV･Vis
Spectra
optical
absorption
4.3.5.
The
films･ The
prepared
and
the
PMMA
a
lS
TiO2
films
substrate
sigmificantly absorbed
455
to
transparent
in visible
of UV
nm,
incorporation
about
was
not
This
ligDt･
N
of
or
F
into
detected･
The
90%･
It is well-known
TiO2
by
pre-coated
50%.
85
absorption
the
edge
is
absorption
visible
organic,
and
deposition,
films
are
be
due
thoughto
of
7, the
of the film
edge
TiO2
absorb
film
the TiO2
that the pure
absorption
[23]･And
After
samples
in Fig･
it did not
affected
significantly
sh泊of
the pre-coated
while
lightregion',
lightregion was
in visible reglOn･
visible
UV
of the substrate,
of the
properties
photochemical
investigated･Asshown
were
increasedabove
reglOn
for
Critical
spectra
absorption
absorption
thin films in low temperature･
for TiO2
spectra
property
UVIVis
i?tleincrease
.enhanced
(nm)
coatedwith
the absoq)tion
about
500
Wavelength
samples
lightregion. The
only
450
visibleregion
was
nearly
to
the
was
100
90
$0
′
ヽ
㌔
70
ヽ■■/
60
亡
○
●
50
ll■
⊂=
Gil
40
h
O
a
30
i
20
10
0
200
300
400
600
500
Wavelength
Fig. 7 Absorption
4.3.6.
hydrophilicity
4. The
Table
It
WCA
darkand indoor
sample
C2,
(nm)
(c)uncoated
layer and
irradiation under
up
to
73.3o
evolution
UV
PMMA
substrate･
of WCA
that of C2
was
films
lamp), referred
are
the
to as
time.
low,
A鮎r
about
30
WCA
The
films
deposited
sa甲Ples
stored
were
sample
Cland
in Fig.
days, WCA
The
in Fig.
shown
16.4o.
during storage. is shown
stored
75o.
about
was
implying
in Fig･ 8
shown
were
the irradiated
stillvery
86
as
irradiation
UV
lh,
Thereafter,
WCA,
samples
as-prepared
lightfor
increasedwith
samples
while
fo;the
(underfluorescence
environment
by
pre-coated
TiO2 films under
that the WCA
the two
investigated
was
PMMAand
of prepared
respectively･ The
WCAsof
increased
of both
excellent superhydrophilicity.
possessed
The
found
Oo after
to
reduced
in
be
can
films
of prepared
hydrophilicperformances
8(A).
$00
IIydrophilicityAnalysis
The
and
(a)TiO2 films,仲)Primary
of
700
8(B).
of Cl
14.8o,indicating
the
deposited
films
suggested
that thevisible
This
agreed
were
re-irradiated
well
to Oo
reduced
indicating
by
the
can
results
lightand
UV
irradiation
after lh
that
light
the
with
hydrophilicity
long-time
possessed
hydrophilicity
enl1anC戸the
(Fig･7)･After
in UV-Vis
the results
are
that of Cl
and
superhydrophilicity
photoinduced
of the deposited
filmsI
two
8(C)A The
the
of
samples
WCA
4.lo after 4hrs
to
reduced
results
storing, the
in Fig･
shown
light･The
visible
under
of C2
irradiation,
films
deposited
was
repeatable･
Asinvestigated
visible
light
of N
or
vacancies.
recombination,
acidityare
films.
addition,
butalso
knownto
enhance
enhance
Table
not
convert
only
N
and
Ti4+ toTi3+
acidity･ The
surface
of OCA
This
many.applicationsI
to the
attributed
F will
create
to reduce
conversionTistate
incorporation
surface
oxygen
the electron-hole
and
the surface
[24-26]
A
coTrOrding
C1(73.3o)
Af[er30days
be
under
superhydrophilicity
for
of both
hydrophilicity
4･ the photos
exhibited
lightregion would
Incorporation
Fwill
films
advantageous
quite
invisible
activity
F intoTi02
h
is
This
region.
superhydrophilic
TiO2
the prepared
above,
to the polntS
in Fig･ 8
C2(14.8o)
…ミ毒…≧;-:,妻;;;号I:..こ.
法…車;≡,
;,}÷㌧もノこJ
･1.Ji;Lこv,j
storing
C1(4.1o)
C2(Oo)
法要.書一戸…j巻雲をゝ′ノミ≡
Re-irradiatedby
･こ､こ､､ミ,:≡:…5/三ま':;:_
I.......I.I
UVlight
87
80
｢70
1Dg6D
芯50
P40
t∇
ち30
S20
0
010
0
O.0
0,2
0.6
0.4
0.8
5
10
IrradiationTirne (h)
Fig. 8. WCA
of TiO2
darkness
films taken under
different
after step A.
and in indoor
15
25
20
30
2
4
irradiation･ (B) in
UV
(A) under
conditions.
(C) u)der
3
lrradiationTime (h)
Storage Time (day)
UV
irradiation after the step B.
at
low
4.4. ComlllSion
films
TiO2
controllable
decreases
WCA
was
hydrophilic
edge
to Oo
after lh
increased
activity
films･
the increased
films
The
irradiation.
to
Visible
75o･
LPD
oxygen
This
implies
spectra
lightregion,maybe
vacancies
88
ions
that
the
found
to the
visible
lightand
for 30
days,
films
that the
incorporation
by
the
the
possess
absorption
of N
lightregion is thoughto
induced
the
possessed
under
in darkness
also
due
in visible
andTi3+
andF.
of -16o
storage
clearly
hydrophilicity
temperatures
WCA
Afterthe
■reg10n. UV･Vis
in visible
observed
surface
by
films maintainedthe
UV
up
ln
PMMA
on
wettability. The
of deposited
into TiO2
to
deposited
or
F
be due
the incorporated
N
References
F. Heslot, S. M.
[1].
M.
Cazabat,
[2].
M.
Schneemilch,
W.
and P･ Charles: Nature,
Troian
J. J. Welters,
R･ A･
(1990)
346
and J･ Ralston:
Hayes
824･
16
Langmuir,
(2000)
2924.
T. D. Blake, A. Clarke
[4].
M. K. Chaudhury
[5].
M.
Wang,
Science, 256
and G. M. Whitesides:
K.
2928･
(2000)
(1992) 1539･
P. N. Bartlett, T･ Kelf and J･ Baumberg:'I･angmuir,
E. Abdelsalam,
[6]. R.
16
and E. H･ Stattersfield: I･angmuir,
[3].
llashimoto,
A･
M･
Fujishima,
Chikuni,
E･
(2005)
21
Kojima,
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Chapter
Conclusions
91
5
5.1. Summary
ln
this
1.
2.
The
2･
and
hydrophilic
TiO2
films
Alfibers
by the sol-gel
For
removal
for
that
the removal
min.
fb∫ better
The
Based
these
on
as別ters used
to be
forair
and
on
are
as
on
of TiO2
Was
flexible
phase
OPtimized･
%
was
Was
NOx
by
after the life time
maintained
also
也
property･
removed
samples
heat
property･
pbotocatalytic
optimized
the
and
the better photocatalytic
40
H202
it was
on
to
confirmed
for
a
cleaning
that the TiO2
demonstrated
facaltative
anaerobeand
the
aeruglnOSa,
the
promote
control
in
S?mPle
aerobe･
oxygen
For
showed
aerobe
concentration
is
better sterilization performance･
photocatalytic
water
chapter 3, photo-induced
results
P･
important
results
in
investigated
･
sterilization performance
considered
of
addition
good
as
tht
higher than
ratio
sterilization experiments,
Such
fabricated
prepared
single
anatase
of
important
are
From
bacterium,
with
method･
formation
the
measurements
340
were
LOf anatase
phase
revealed
% and
The
were
onAlfibers
sterilization,the synthesis condition
and
photocatalytic performance
The
single
NOx
removal
fabricated･
films
apblications･
grown
of the coatings,
test
h
films
fact, the better the crystalinity
95
4.
a
with
of initial solution
treatment
for environmental
of TiO2
TiO2
processes,
were
properties
dip-coating
demonstrated
was
chemical
follows:
as
results are
NOR
simpl.e
and
applications
Photoactive
It
3.
cost
be promising
thought to
photocatalyst
Chapter
Research
low
photocatalytic
were
The
using
work,
excellent
samples
of This
effects,?pplicationsof TiO2-COatedAlfibers
Systems
are
PrOPOSed･
hydrophilicity of TiO2 films
follows:
92
coated
on
quartz
was
st止died･
1.
Crystalline
TiO2
films
●
using
treatment
at 400oCand
ⅩRD,
treatment
TiO2-Organic
on
500oC
induced
were
properties
prepared
hybrid
polymer
the structural
onglass
change
films･
of TiO2
Heat
films丘om
to anatase･
amorpbous
2･
heat
substrate
hydrophilic
with
UV-Vis
ⅩPS弧d
results indicated也at
the big血tbe
tempera叫re,
annealing
the better the crystallinity.
The bigber
3.
From
this study,
the formation
The
a
idea
new
anataSe
was
be proposed
should
for TiO2
films
films
coated
Phase
UV-Vis
and
and
detected
wsre
materials
TiO2
necessary
for
to realize
the
at
low
synthesized
films
lightand
suggested
Since
are
deposition
(LPD)
under ambient
the absorption
XPS
was
edge
at low
PMMA
for coating
used
TiO2
condition.
highabsoq)tion of
located
in the
EDX
and
was
method
that the films exhibited
by
on
follows:
as
of PMMA
ofTi02
in
60%
about
in visible light region･
films which
might
be
N
from
･
exhibited
after irradiation for
visible
phase
showed
light region
F
results
the surface
spectra
precursor
The
on
hydrophilicity
The
liquid
modified
visible
4･
form1ng
without
studied.
was
thin films
3･
thus
and
4, photo-induced
temperature
2.
phase,
high-temperatureannealing
that
concluded
properties.
erature
In Chapter
1.
it was
of anatase
superhydrophilicity
temp
the better tbe血ydropbilic
the crystallinity,
1 hour.
increased
The
to
that the hydropbilicity
the low-temperature
hydrophilicity; the WCA
excellent
WCA
was
after it was
75o
was
maintained
stored
decreased
at about
in dark
16o
for 30
even
days.
to
OoC
under
These
activated by visible light.
synthesizedTi02
93
films
were
amorphous
in crystalline
●
the observed
nature,
or
Thus,
F atoms
it
preveht dew
By
into TiO2
believed
was
super
superhydrophilic
Their optimization
their
and
attributable
PMMA
be
could
to
applied
for concentrator
photovoltaic
systems･
concentration,
transparent
TiO2
photocatalitic
is my
was
the incorporated
N
fresnel
to
films.
thatTi02-coated
condensation
controlling
hydrophilicity
properties
further work･
94
will
be
films
realized
on
as
●
possesslng
lens
both
plastic substrates･
Acknowledgements
like
I would
followlng
To
my
to
Peoples
express
him;
encouragement
(Nrr),
his understanding
To
for
and
hboratory
Tanemura,
constructive
criticism
in my
Sakae
Dr.
School
the
of Nano-Functional
an
me
course
to
opportunity
help,
great
guidance,
throughout the
Nagoya
of Engineerlng,
in offering
toilsome
advice･
to
appreciation
of this dissertation･
success
for his generosity
his invaluable
and patience
Professor
the
deepest
and
of Frontier Materials, Graduate
Institute of Technology
with
to
Dr･ Masaki
Professor
supervisor:
gratitude
have contributed
who
Materials, Department
study
sincere
my
warm
study; also for
of my
shortcomlngS･
Tanemura,
R&D
Materials
Japan
Laboratory,
Fine
l
ceramics
centre
and
guidance
of Engineering,
ToAssociate
.
hstitute
To my
Nagoya
study･
Iwamoto,
teachings
experiment
invaluable
and
･
of Frontier Materials,
Department
(Nrr),
Institute of Technology
School
Graduate
for his invaluable
guidance
study.
Professor
Department
of
invaluable
Yuji
in my
coⅡ皿entS
Materials,
Dr.
for his technical
in my
comments
To Professor
and
(JFCC),
on
Teclmology
guidanceand
Dr.
Yasuhiko
Hayashi,
of Frontier Materials,
Prr),
cornnents
for
his
in my
dear f礼血ly and friends,without
of NanoIFunctional
Graduate
hboratory
School
of Engine.erlng,
techmicalteachings
on
Nagoya
experimentand
study･
your
careand
support, I cannot
and
present
members
hold onuntil
thelast.
To
Dr.Lei
Miao,andthe
Nano-FunctionalMaterials,
past
Department
'of Environmental
95
of
hboratory
Technology
&
of
Urban
Plannlng,
Tbanks
Graduate
again丘om
School
of Engineerlng,
N汀.
my
heart f♭rall of也e
96
above.
List of Publication
(1)学術誌
1.
L. Miao,
M.
S. Tanemura,
Fibern
Sol-Gel
Study
photocatalytic
M･
S. Tanemura,
S･ Toh,
Applied
20 Suppl.1,
Tanemura
Coatings
of TiO2
Tanemura
Method
Sci. Technol., Vol.
J. Mater.
L. Miao,
2.過,
M･
Nguyen,也,
: uAnAlternative
Kawasaki
scale
T.H.
K･ Kaneko
Coating
TiO2
to
and
onAl
(2004) 89-92･
M･
and
: "Comparative
Kawasaki
Res･
Adv･ Mater･
onAlFibern
Vols･
ll-12
(2006) 15-18.
S. Tanemuraand
L. Miao,
3.過,
Substrates
Glass
Research
for
TiO2
Hydrophilicity
Films
S. Tanemura
Coated
and
Fiber",
AI
on
`Tanemura:"Synthesis
Transations
Applications"
Films
of TiO2
Materials
the
of
on
32[3] (2007) 721-723･
SocietyofJapan
L. Miao,
4.也,
M･
M･
Tanemura
Materials
"Photocatalytic
:
Science
and
Sterilization of
Engineering
B
films
PMMA"
148(1-3)
(2008) 183-186･
Induced
al., "Visible-light
5･辿et
Hydrophilicity
of TiO2
on
(翠
備中)
(2)学会発表
1.轟垂,苗膏,種村柴､種村真幸,河崎正弘:"アルミファイバ上二酸化チタ
｢平成18年春季
ンコーティングの光触媒効果によるNOx除去率の向上"
第53回応用物理学関係連合講演会｣講演予詩集p654.
(3)国際会意
1.
L.
Miao,ら‥‥!血o,
砧Photocatalytic
rproceeding
(Nagoya,Japan,
Tanemura,
S.
Removal
the 22nd
of
of
M･
No又
by
International
23124 Noyember,
Tanemura,
TiO2
97
Coating
Japan-Korea
2005) 1771180･
Y･
Z･
Mori,
onAluminum
Seminar
on
Yamada
:
FiberM
Ceramics
J
L.
2.叫o,
Miao,
S. Tanemura
plastic Substrate:Application
国際会議｣
Tio2
Film
worksbop
Solar
on
M.
Tanemura:
Cell
"Synthesis
of TiO2
Film
on
｢再生可能エネルギー2006
System"
p309.
L. Miao,
3.也,
and
on
on
名古屋(2006)
S. Tanemura
Various
Advanced
,
Abstract
and
Substrates
Ceramics
M.
Tanemura:
for Hydrophilicity
"Lew
Temperature
ApplicationH
Synthesis
of
rlnternational
｣
(先進セラミックスに関する国際ワークショップ)
p131.
98