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http://trj.sagepub.com/content/82/8/747The online version of this article can be found at:
DOI: 10.1177/00405175114245262012 82: 747 originally published online 19 October 2011Textile Research Journal
Hui Zhang, Hong Zhu and Runjun Sunnanoparticle film on PET fabric by hydrothermal method2Fabrication of photocatalytic TiO
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Original article
Fabrication of photocatalytic TiO2nanoparticle film on PET fabricby hydrothermal method
Hui Zhang, Hong Zhu and Runjun Sun
Abstract
A layer of TiO2nanoparticle was immobilized on PET fiber using titanium sulfate and urea under hydrothermal condition.The TiO2-loaded fiber was characterized by scanning electron microscopy, X-ray diffraction, infrared spectroscopy,thermal gravimetry and differential scanning calorimetry analysis, respectively. PET fabric before and after treatmentwas also examined for the reflectance spectrum, tensile properties, water absorption and degradation of methyl orange
dye under UV irradiation. The results show that pure anatase nanocrystalline TiO2is precipitated in the presence of PETfabric and deposited on the surface of fiber via the hydrothermal process. The thin film is constituted of spherenanoparticles of an average size 3.0 nm, which is grafted onto the fiber surface by chemical reaction. For the TiO2-coated fiber, the onset decomposition temperature decreases, but the exothermic temperature increases as comparedwith the untreated fiber. Owing to the shrinkage of fabric size, the breaking load and tensile strain in warp and weftdirections increase. The TiO2-loaded PET fabric can absorb more ultraviolet radiation even after being washed for 30times. The water absorbency is also slightly increased. The capability of photocatalytic degradation of methyl orange dyeis obtained.
Keywords
PET fabric, hydrothermal method, TiO2 nanoparticle
Introduction
Among various methods for the preparation of tita-
nium dioxide (TiO2) photocatalyst, including the ther-
mal hydrolysis, the sol-gel, the template process, the
chemical-precipitation, the thermal oxidation and the
microemulsion process, the hydrothermal processing
is a simple and effective synthesis technique.1,2 The
resulting TiO2
particles have the desired size and
shape with homogeneity in composition as well as a
high degree of crystallinity.3 Its most important feature
is that it favors a decrease in agglomeration among
particles, narrow particle size distribution, phase homo-
geneity and controlled particle morphology.4 It has
been reported that the structure and morphological
characteristics of TiO2 particles are markedly influ-
enced by the process conditions. The shape, size, crys-
talline form, photocatalytic activity and some relevant
properties of TiO2particles can be controlled by alter-
ing the reaction temperature and time, the pH, the ratio
of reactants and so on.5 The precursors for the fabrica-
tion of TiO2 particles are mainly focused on titanium
trichloride (TiCl3), titanium tetrachloride (TiCl4), tita-
nium metal, organic titanate, titanium sulfate
(Ti(SO4)2) etc.2 The common crystalline forms of
TiO2 include anatase, rutile and brookite. Rutile is
the only stable form and has a high dielectric constant
and refractive index. The anatase phase has high photo-
catalytic activities. Both anatase and brookite are meta-
stable and transform to rutile when they are heated.6
Some researchers have carried out the synthesis of TiO2by the hydrothermal method. For instance, nanosized
School of Textile and Materials, Xian Polytechnic University, China.
Corresponding author:
Hui Zhang, School of Textile and Materials, Xian Polytechnic University,
Xian 710048, China
Email: [email protected]
Textile Research Journal
82(8) 747754
! The Author(s) 2012
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DOI: 10.1177/0040517511424526
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TiO2 catalysts with high photocatalytic activity under
visible light irradiation were obtained by using acetone,
alcohol and pyridine as the solvent under the hydro-
thermal conditions.7,8 They could also be obtained by
using titanium sulfate and urea as the raw materials and
EDTA as the control agent,9 or titanium oxysulfate as
the precursor and urea as the precipitation agent,10
or the low-cost meta-titanic acid as the starting reac-
tant and the monacid as the dressing agent.11
Nanocrystalline TiO2 particles co-doped with N, Fe
or Si were prepared using tetrabutyl titanate as the pre-
cursors,12,13 or using titanium oxysulfate as the precur-
sor.14 The pH conditions had a great effect on the
quantity of the surface hydroxyl absorbed by the syn-
thesized powders.15 The dispersion of the prepared
nanoparticles could be greatly improved by using tetra-
ethylammonium hydroxide as the solvent.16
Although nanocrystalline TiO2 shows a wide range
of applications in gas sensors, photovolatic cells and
photocatalysis, the dispersion of nanoparticles with a
narrow size distribution is very important for produc-
ing the advanced functional materials.17,18 Nanosized
particles are liable to agglomerate among them due to
their large surface area per unit mass and high specific
surface energy. The recovery and reuse of waste nano-
particles are usually restricted in the practical applica-
tion. Therefore, development of TiO2 based
photocatalysts anchored to supporting materials with
large surface areas would be of great significance. It can
not only avoid the disadvantages of filtration and sus-
pension of fine photocatalyst particles, but also lead to
high photodecomposition efficiency.19
More recently,TiO2 has been extensively explored as a coating mate-
rial for textiles to provide functions such as antibacter-
ial activity, UV protection, and self cleaning.
Immobilization of TiO2(or Au/TiO2) clusters on differ-
ent textiles has been currently realized showing the for-
mation of rutile or anatase crystals of small dimensions,
stably grafted onto fiber surfaces.19,2023 For example,
in order to obtain the self-cleaning activity effect under
visible light irradiation, cotton textiles were firstly acti-
vated by RF plasma, MW plasma and UV irradiation
respectively, and then (or directly) were immersed in the
TiO2
colloidal suspension, followed by heating at high
temperatures in air. It has been demonstrated that the
contamination from dirt, stains, and harmful microor-
ganisms attached on cotton fibers can be effectively
removed upon daylight irradiation. Nanosized TiO2was prepared by hydrothermal method at first, and
then the woven glass fabric was dipped in the TiO2suspension solution. Finally, the coated fabric was cal-
cined at different temperatures. It was found that the
TiO2 particle films coated on glass fabric, with high
photocatalytic activity for the NO oxidation, were
achieved.4 Different layers of TiO2 were also
immobilized on polypropylene fabric by the hydrother-
mal method so as to obtain the highly active buoyant
photocatalysts. It was confirmed that the degradation
of methyl orange dye solution under UV and visible
lights could be greatly improved compared with one
layer of anatase TiO2.24
Unfortunately, relatively little research is found inthe literature related to the TiO2-coated fabric with
photocatalytic activity prepared by the hydrothermal
method. In this paper, we synthesized TiO2 nanoparti-
cles immobilized on a polyethylene terephthalate (PET)
fiber surface to evaluate the potential applicability to
functional fabrics. Nanosized TiO2was deposited in the
presence of PET fabric using titanium sulfate and urea
in the sealed aqueous solution. The morphology, micro-
structure, thermal stability and optical properties of
PET fabric before and after treatments were character-
ized by scanning electron microscopy (SEM), X-ray
diffraction (XRD), Fourier transform infrared spec-
troscopy (FT-IR), thermal gravimetry (TG), differential
scanning calorimetry (DSC) and UV-Vis reflectance
spectroscopy. The properties of tensile, water absorp-
tion and photocatalytic degradation of methyl orange
were also investigated.
Experimental
Materials
The undyed plain woven PET fabric was used for pre-
cipitating TiO2 nanoparticles. The linear densities of
ends and picks were identical (7.3 tex). The numbersof ends and picks were 410 and 290 per 10 cm, respec-
tively. Chemicals including titanium sulfate (Ti(SO4)2),
urea ((NH2)2CO), acetone, anhydrous ethanol, methyl
orange dye, and distilled water were all of analytical
reagent grade.
Preparation of TiO2 nanoparticle film on PET fabric
The PET fabric was first scoured with an aqueous solu-
tion of 200 g/L NaOH for 30 min at 60C prior to use,
followed by rinsing with acetone and anhydrous etha-
nol solution at room temperature for 15 min, and then
was repeatedly washed, three times, with distilled water
at 60C. The hydrothermal process was employed to
modify PET fabric in the laboratory. First, 19.2 g of
titanium sulfate was added to 160 mLof distilled
water, with vigorous stirring, at a temperature of
60C. Subsequently, 9.6 g of urea was dissolved in the
above solution completely. At last, 2.4 g of pretreated
PET fabric was dipped in the mixture for 30 min, and
then was transferred to a 200 mLPTFE sealed can,
which was put into the stainless steel autoclave.
The autoclave was then placed in a furnace for the
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hydrothermal treatment. The temperature was heated
to 200C at a speed of 2C/min. After treatment for 3 h,
the PTFE sealed can was cooled down to room tem-
perature. The PET fabric was dried at 80C for 5 min in
an oven, and then was dipped in the acetone and eth-
anol solution twice for 10min, respectively, followed by
washing with distilled water for 10 min, and dried atambient condition. The weight of PET fabric before
and after treatment was measured by an AL54 analyt-
ical balance. The pick-up of TiO2nanoparticles depos-
ited on PET fabric, in weight, relative to the untreated
one was calculated.
Characterization and measurement
The surface morphologies of the samples were observed
with a JEOL JSM-6700 field emission scanning electron
microscope. XRD patterns were obtained by using Cu
Ka1 radiation ( 1.540562 A ), using a 7000 S diffrac-tometer at 40 kV and 40 mA with the angle of 2from
10 to 80 at a scan speed of 8 deg/min. The mean crys-
tallite size of the TiO2crystallite formed on the surface
of PET fabric was determined by the Scherrer equation.
FT-IR spectra of the samples were recorded using KBr
pellets in the range of 4004000 cm1, using a Bruker
TENSOR 27 spectrometer. The thermogravimetric
analyses were carried out on a TGA/SDTA851e ther-
mogravimetric/differential thermal analyzer (TG-DTA)
instrument according to GB/T 13464-2008. Percentage
weight change versus temperature was evaluated at a
heating rate of 10
/min with a nitrogen flush rate of10 mL/min over the range of 30550C. DSC analyses
were performed in a Sapphire apparatus at a rate of
10/min in flowing nitrogen gas at 10 mL/min from
30C to 600C.
The reflectance spectra of the samples in the 200
800 nm wavebands were tested at room temperature on
a U-3010 UV-VIS-NIR spectrometer with an integrat-
ing sphere (150 mm) at a scanning speed of 120 nm/
min. The tested sample was overlapped so that the
light could not transmit through the fabric sample.
The tensile properties of the samples were measured
on the YG(B)026D-500 electromechanical test instru-ment according to GB/T3923.1-1997. The initial
gauge length was 200 mmand the width was 50 mm.
The testing rate was 100 mm/min and the pre-tension
was 5 N.
The water absorption measurements were conducted
according to GB/T23320-2009 and were calculated
from equation (1).
Aw mw mc
mc 100% 1
Where Aw is the water absorption (%), mw is the wet
fabric weight (g), and mc is the dry fabric weight (g).
Five samples were tested and the average of the mea-
surements was given.
Photocatalytic experiments
The photocatalytic activities of PET fabric before and
after treatment were evaluated after exposure to UV
irradiation based on the decomposition of methyl
orange dye. The irradiation was carried out using
20 W (main wavelength 254 nm) quartz ultraviolet
lamp. 1.5 g of the fabric sample were dipped into
30 mL of methyl orange solution at a concentration of
20 mg/L at natural pH. The lamp was hung above the
solution at a distance of 10 cm. The absorbance of the
characteristic peak of methyl orange at the maximum
absorption wavelength (464 nm) was measured using a
UV-Vis spectrophotometer (Beijing Rayleigh
Analytical Instrument Corp. UV-1600) at specific time
intervals. The degradation rate was calculated from
equation (2).
D A0 At
A0 100% 2
Where D is the degradation rate (%), A0 is the initial
absorbance of the methyl orange solution, andAtis the
absorbance of the methyl orange solution irradiated for
t minutes.
Results and discussion
SEM analysis
Figure 1 shows the scanning electron pictures of PET
fibers before and after treatment with titanium sulfate
and urea. It can be seen that the surface of the
untreated PET fiber is clean and smooth. A few small
particles are induced by the attached substances
(Figure 1a). When PET fabric was treated with tita-
nium sulfate and urea by hydrothermal processing,
the surface of as-obtained fiber is covered with a layer
of homogeneous granular materials. Some large parti-
cles in the micrometer scale are formed on the fiber
surface because of the adhesion of agglomerated parti-
cles. The pick-up of TiO2nanoparticle is 1.1% (w/w). A
number of pits can also be observed on the fiber sur-
face, which is etched by the caustic solution (Figure 1b).
From the high resolution SEM picture of PET fiber, the
surface of the untreated PET fiber is compact (Figure
1c). For the TiO2-coated fiber, many irregular tiny par-
ticles are distributed on the fiber surface. The average
particle size is larger than 100 nm in given growth con-
dition (Figure 1d).
Zhang et al. 749
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XRD analysis
Figure 2 illustrates the XRD patterns of PET fabric
before and after treatment with titanium sulfate and
urea. It is clear that the intense diffraction peaks at
2 17.9, 23.0 and 26.3 are due to the typical PETphase. A series of characteristic peaks are observed in
the XRD pattern of the TiO2-coated PET fabric at 2
of 25.2, 37.5, 48.8, 53.7, 55.5, 62.4, 68.6, 70.6
and 75.5. These are related to the {101}, {004},
{200}, {105}, {211}, {204}, {116}, {220} and {215}
planes of TiO2 anatase structure (see Figure 2c).
From the width of the peaks at 2 25.2, 37.5 and
48.8, the crystallite sizes of the TiO2 particle are cal-
culated to be 2.4nm(101), 3.5nm(004) and
3.1 nm (200) using Scherrers equation DK/cos
(where D is the diameter of the particle, is the X-
ray wavelength, is the FWHM (full width at half
maximum) of the diffraction line, is the diffraction
angle, and K is a constant 0.89), respectively. These
data imply that the shape of the TiO2 nanoparticle is
spherical and is quite different from the particle size
estimated in SEM observation because of the agglom-
erating of nanoparticles.
FT-IR analysis
Figure 3 shows the FT-IR spectra of PET fabric before
and after treatment with titanium sulfate and urea. It is
evident that compared with the spectrum of the
untreated PET fabric (line (a)), the peaks at
3432 cm1 (C-H stretching vibration in benzene ring)
and 2966 cm1 (C-H stretching vibration of -CH2) are
negligible. The O-H band for the TiO2-coated fabric at
3129 cm1 is observed, which is attributed to the sur-
face absorbed water induced by TiO2 nanoparticles.
(b)(a)
(d)(c)
Figure 1. SEM pictures of the surface of PET fiber. (a) 5000 and (c) 30000 before treatment; (b) 5000and (d) 30000after
treatment with titanium sulfate and urea.
10 20 30 40
2q/
50 60 70 80
Intensity
(215)(204)(211)(105)(200)
(004)
(101)
(b) PET fabric treated with
Ti(SO4)2and Urea
(a) Untreated PET fabric
(116) (220)
(c) Anatase TiO2
Figure 2. X-ray patterns of PET fabric (a) before and (b) after
treatment with titanium sulfate and urea.
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The corresponding bending band at 1659 cm1 is iden-
tified. The peak at 1410 cm1 caused by the benzene
skeleton vibration is intensified and shifted to
1401 cm1. The peak at 1093cm1 (COC anti-sym-
metrical stretching vibration) is also intensified and
shifted to 1116 cm1. At the same time, the new absorp-
tion band at 618 cm1 is observed, which is assigned to
the characteristic stretching vibration of Ti-O-Ti band
around 650 cm1.25,26 So this result proves that the
TiO2 nanoparticle is grafted onto the PET fiber.
TG analysis
Figure 4 displays the TG curves of PET fabric before
and after treatment with titanium sulfate and urea. The
TG curve of TiO2 nanoparticle is also given, which is
prepared by using the same method but without adding
the PET sample. This result agrees with that displayed
by Mohamed et al.28 It is obvious that there is only one
onset of decomposition temperature at 376.7C for the
untreated PET fabric. The weight loss is 80.8% between
339.7C and 455.5C. For the TiO2-coated fabric, the
onset of decomposition temperature is increased to
379.7C, but not distinctly. The corresponding weightloss changes only a little (81.6%). This is ascribed to the
coating of TiO2 nanoparticles. So the hydrothermal
processing has little effect on the thermal properties
of PET fiber.
DSC analysis
Figure 5 exhibits the DSC curves of PET fabric before
and after treatment with titanium sulfate and urea. It is
clear that a small endothermic peak at 45.9C for the
TiO2-coated fabric is observed, which is mainly due to
the dehydration of absorbed water caused by TiO2
nanoparticle. Compared with the untreated PET
fabric, the endothermic peak at 250.8C changed only
a little (251.2C) when the PET fabric was treated with
titanium sulfate and urea. The melting enthalpies of
PET fiber before and after treatment calculated by inte-
gration of the DSC curve in the temperature range
250 10C are 10.2 J/g and 14.8 J/g, respectively. The
exothermic peaks at 418.5C and 463.4C are increased
to 437.4C and 532.8C, respectively. This signifies the
thermal pyrolysis of PET fiber and phase transition of
anatase TiO2 to rutile.27
100 200 300 400 500 600
endo
45.9C
4.13 mW463.4C1.38 mW
418.5C
3.00 mW
250.8C
6.30 mW
HeatFlow
/mW
Temperature/C
(a) Untreated PET fabric
(b) TiO2coated PET fabric
251.2C
4.67 mW
437.4C
0.46 mW
532.8C
0.36 mW
exo
Figure 5. DSC curves of (a) untreated and (b) TiO2-coated
PET fabrics.
501
723
872
1016
10931236
13411410
1456
1505
1577
1716
29663432
618
722
1017
1116
1234
1401
1505
1659
4000 3000 2000 1500 1000 500
Tsmittanceran/%
Wavenumbers/cm-1
3129
a. Untreated PET fabric
b. PET fabric treated with Ti(SO4)2and urea
Figure 3. FT-IR spectra of PET fabric (a) before and (b) after
treatment with titanium sulfate and urea.
100 200 300 400 500
0
20
40
60
80
100
120
(c)
(b)
(c) TiO2nanoparticle
(b) TiO2-coated PET fabric
Onset: 379.7C
Endset: 422.1C
Step: -81.6%
(a) Untreated PET fabric
Onset: 376.7
CEndset: 416.5C
Step: -80.8%
Temperature/C
RelativeMass/%
(a)
Figure 4. TG curves of (a) untreated, (b) TiO2-coated PET
fabrics and (c) TiO2 nanoparticles.
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Reflectance spectrum analysis
Figure 6 represents the diffuse reflectance spectra of
untreated, TiO2-coated and washed (30 times) PET fab-
rics. The absorption peak at 304 nm for the untreated
PET fabric is assigned to the p!p* electronic transi-
tion in the benzene ring. The enhancement of UVabsorption capability for the TiO2-coated PET fabric
suggests that the TiO2nanoparticle film can absorb UV
irradiation and visible light to some extent. As com-
pared with the untreated fabric, the average absorp-
tances of the TiO2-coated fabric are increased by
10.0% in the UV (200400 nm) region, and 16.4% in
the Vis (400800 nm) region, respectively. This is due to
the band gap transition of TiO2 nanoparticles. When
the TiO2-coated fabric was washed for 30 times accord-
ing to IWS TM31 standard, the average reflectances are
slightly increased 3.6% in UV (200400nm) region, and
9.3% in Vis (400800 nm) region with respect to the
TiO2-coated one. This implies that some TiO2nanopar-
ticles are washed off from the fiber surface.
Tensile property analysis
The fabric densities and tensile properties of PET fabric
before and after treatment are given in Table 1 in accor-
dance with GB/T3923.1-1997. Because PET fabric was
treated at high temperature for a long time, the densi-
ties are increased from 410 to 436 per 10 cm in warpdirection, from 290 to 321 per 10 cm in weft direction,
respectively. The corresponding shrinkages are about
6.3% and 10.7% in warp and weft directions. The
breaking loads and tensile strains in both directions
are increased to some extent due to the shrinkage of
fabric size.
Water absorption analysis
The water absorption data indicates that as compared
with the untreated PET fabric, the water absorption of
the TiO2-coated fabric is slightly increased from 11.7%
to 13.9%. This is attributed to the TiO2 nanoparticle
film loaded onto the surface of the PET fiber. The
decreased distance between adjacent yarns also makes
a substantial contribution to the water absorption.
0 20 40 60 80 100 120
0
20
40
60
80
100
Irradiation time/min
Degradationrate/%
(a) Untreated PET fabric
(b) TiO2-coated PET fabric
Figure 7. Effect of irradiation time on the degradation rate for
(a) untreated and (b) TiO2-coated PET fabrics.
200 300 400 500 600 700 8000
20
40
60
80
100
(c) Washed PET fabric 30 times
(b) TiO2-coated PET fabricReflectance/%
Wavelength/nm
(a) Untreated PET fabric
Figure 6. Reflectance spectroscopy of (a) untreated and (b)
TiO2-coated PET fabrics.
Table 1. The results of density and tensile properties of PET fabric before and after treatment with titanium sulfate and urea
PET fabricDensity/thread10cm1 Breaking load/N Tensile strain/%
warp weft warp weft warp weft
Untreated 410 290 583.3 362.3 19.6 19.5
TiO2-coated 436 321 593.0 373.3 20.1 22.5
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Photodegradation effect
Figure 7 shows the effect of UV irradiation time on the
degradation rate of methyl orange dye for PET fabric
before and after treatment. It is found that the degra-
dation rate of methyl orange is gradually increased by
increasing the irradiation time for both fabric samples.The TiO2-coated fabric possesses higher photocatalytic
activity than that of the untreated one. The degradation
rate of methyl orange is 87.8% for the untreated fabric
and 93.6% for the TiO2-coated fabric after being irra-
diated for 90 min. The experimental results demonstrate
that the TiO2nanoparticles precipitated onto PET fiber
accelerate the degradation of methyl orange under the
UV irradiation. Consequently, the preparation can be a
low-cost way of producing photocatalytic fabric loaded
with TiO2nanoparticles, which provides a great oppor-
tunity for the treatment of industrial dye effluents.
Conclusions
A thin layer of TiO2nanoparticles was well precipitated
onto the surface of PET fiber by the hydrothermal
method, using titanium sulfate and urea. From the
results of SEM and XRD, it is found that the film of
TiO2 nanoparticles has the anatase phase. The TiO2particle is constituted of the agglomerated nanoparti-
cles with an average size of 3.0 nm or so. FT-IR results
show that the TiO2nanoparticles are grafted onto PET
fiber. TG and DSC results indicate that the thermal
stability of PET fiber is decreased after being treated
with titanium sulfate and urea by the hydrothermalprocess. The PET fabric loaded with the TiO2nanopar-
ticles exhibits an excellent UV absorption ability. Due
to the shrinkage of fabric size in warp and weft direc-
tions, the breaking load and tensile strain are increased
to some extent. The water absorption is slightly
increased. As far as the photocatalytic performance is
concerned, the TiO2-coated PET fabric has the prospect
for decontamination of dye in waste water.
Acknowledgement
This study was supported by the key discipline construction
of higher education of Shaanxi province (the special fund) inChina.
Funding
This research received no specific grant from any funding
agency in the public, commercial, or not-for-profit sectors.
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