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Original article
Abstract
A layer of TiO2 nanoparticle 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 treatment
was 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 TiO2 is precipitated in the presence of PET
fabric and deposited on the surface of fiber via the hydrothermal process. The thin film is constituted of sphere
nanoparticles of an average size 3.0 nm, which is grafted onto the fiber surface by chemical reaction. For the TiO2coated fiber, the onset decomposition temperature decreases, but the exothermic temperature increases as compared
with the untreated fiber. Owing to the shrinkage of fabric size, the breaking load and tensile strain in warp and weft
directions increase. The TiO2-loaded PET fabric can absorb more ultraviolet radiation even after being washed for 30
times. The water absorbency is also slightly increased. The capability of photocatalytic degradation of methyl orange dye
is obtained.
Keywords
PET fabric, hydrothermal method, TiO2 nanoparticle
Introduction
Among various methods for the preparation of titanium dioxide (TiO2) photocatalyst, including the thermal hydrolysis, the sol-gel, the template process, the
chemical-precipitation, the thermal oxidation and the
microemulsion process, the hydrothermal processing
is a simple and eective 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 homogeneity and controlled particle morphology.4 It has
been reported that the structure and morphological
characteristics of TiO2 particles are markedly inuenced by the process conditions. The shape, size, crystalline form, photocatalytic activity and some relevant
properties of TiO2 particles can be controlled by altering the reaction temperature and time, the pH, the ratio
of reactants and so on.5 The precursors for the fabrication of TiO2 particles are mainly focused on titanium
trichloride (TiCl3), titanium tetrachloride (TiCl4), titanium 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 photocatalytic activities. Both anatase and brookite are metastable and transform to rutile when they are heated.6
Some researchers have carried out the synthesis of TiO2
by the hydrothermal method. For instance, nanosized
748
immobilized on polypropylene fabric by the hydrothermal method so as to obtain the highly active buoyant
photocatalysts. It was conrmed 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 in
the literature related to the TiO2-coated fabric with
photocatalytic activity prepared by the hydrothermal
method. In this paper, we synthesized TiO2 nanoparticles immobilized on a polyethylene terephthalate (PET)
ber surface to evaluate the potential applicability to
functional fabrics. Nanosized TiO2 was deposited in the
presence of PET fabric using titanium sulfate and urea
in the sealed aqueous solution. The morphology, microstructure, thermal stability and optical properties of
PET fabric before and after treatments were characterized by scanning electron microscopy (SEM), X-ray
diraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetry (TG), dierential
scanning calorimetry (DSC) and UV-Vis reectance
spectroscopy. The properties of tensile, water absorption and photocatalytic degradation of methyl orange
were also investigated.
Experimental
Materials
The undyed plain woven PET fabric was used for precipitating TiO2 nanoparticles. The linear densities of
ends and picks were identical (7.3 tex). The numbers
of ends and picks were 410 and 290 per 10 cm, respectively. 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.
Zhang et al.
749
mw mc
100%
mc
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 specic time
intervals. The degradation rate was calculated from
equation (2).
D
A0 At
100%
A0
750
(a)
(b)
(c)
(d)
Figure 1. SEM pictures of the surface of PET fiber. (a) 5000 and (c) 30000 before treatment; (b) 5000 and (d) 30000 after
treatment with titanium sulfate and urea.
XRD analysis
FT-IR analysis
Figure 3 shows the FT-IR spectra of PET fabric before
and after treatment with titanium sulfate and urea. It is
Intensity
20
30
40
50
60
70
80
2q /
Figure 2. X-ray patterns of PET fabric (a) before and (b) after
treatment with titanium sulfate and urea.
Zhang et al.
751
1577
1505
2966
1341
Tsmittanceran/%
1410
1716
1016
1236 1093
1505
1234
723
1017
1659
45.9C
4.13 mW
2000
1500
1000
500
100
Figure 3. FT-IR spectra of PET fabric (a) before and (b) after
treatment with titanium sulfate and urea.
120
Relative Mass/%
80
60
40
(c)
20
0
100
200
300
(b)
(a)
400
endo
3.00 mW
250.8C
6.30 mW
Wavenumbers/cm-1
100
exo
618
1116
3000
463.4C
1.38 mW
418.5C
722
4000
251.2C
4.67 mW
1401
3129
532.8C
0.36 mW
872
Heat Flow/mW
3432
437.4C
0.46 mW
500
Temperature/C
The corresponding bending band at 1659 cm1 is identied. The peak at 1410 cm1 caused by the benzene
skeleton vibration is intensied and shifted to
1401 cm1. The peak at 1093 cm1 (COC anti-symmetrical stretching vibration) is also intensied and
shifted to 1116 cm1. At the same time, the new absorption 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 ber.
TG analysis
Figure 4 displays the TG curves of PET fabric before
and after treatment with titanium sulfate and urea. The
200
300
400
Temperature/C
500
600
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 45.9 C 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 250.8 C changed only
a little (251.2 C) when the PET fabric was treated with
titanium sulfate and urea. The melting enthalpies of
PET ber before and after treatment calculated by integration of the DSC curve in the temperature range
250 10 C are 10.2 J/g and 14.8 J/g, respectively. The
exothermic peaks at 418.5 C and 463.4 C are increased
to 437.4 C and 532.8 C, respectively. This signies the
thermal pyrolysis of PET ber and phase transition of
anatase TiO2 to rutile.27
752
100
100
Degradation rate/%
80
Reflectance/%
80
60
40
20
0
200
60
(a) Untreated PET fabric
40
20
0
0
300
400
500
600
Wavelength/nm
700
20
800
40
60
80
Irradiation time/min
100
120
Table 1. The results of density and tensile properties of PET fabric before and after treatment with titanium sulfate and urea
Density/thread10 cm1
Breaking load/N
warp
weft
warp
weft
warp
weft
410
436
290
321
583.3
593.0
362.3
373.3
19.6
20.1
19.5
22.5
Tensile strain/%
PET fabric
Untreated
TiO2-coated
Zhang et al.
753
Photodegradation effect
Figure 7 shows the eect of UV irradiation time on the
degradation rate of methyl orange dye for PET fabric
before and after treatment. It is found that the degradation 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 irradiated for 90 min. The experimental results demonstrate
that the TiO2 nanoparticles precipitated onto PET ber
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 TiO2 nanoparticles, which provides a great opportunity for the treatment of industrial dye euents.
Conclusions
A thin layer of TiO2 nanoparticles was well precipitated
onto the surface of PET ber by the hydrothermal
method, using titanium sulfate and urea. From the
results of SEM and XRD, it is found that the lm of
TiO2 nanoparticles has the anatase phase. The TiO2
particle is constituted of the agglomerated nanoparticles with an average size of 3.0 nm or so. FT-IR results
show that the TiO2 nanoparticles are grafted onto PET
ber. TG and DSC results indicate that the thermal
stability of PET ber is decreased after being treated
with titanium sulfate and urea by the hydrothermal
process. The PET fabric loaded with the TiO2 nanoparticles exhibits an excellent UV absorption ability. Due
to the shrinkage of fabric size in warp and weft directions, 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) in
China.
Funding
This research received no specic grant from any funding
agency in the public, commercial, or not-for-prot sectors.
References
1. Ren CJ, Zhong BH, Zhou DL, Liu H, Li DC and Gong
JH. Research advances for preparation of highly-active
TiO2 photocatalyst with hydrothermal method. Chinese J
Rare Metal 2004; 28(5): 903907.
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