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    http://trj.sagepub.com/Textile Research Journal

    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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    What is This?

    - Oct 19, 2011OnlineFirst Version of Record

    - Mar 7, 2012Version of Record>>

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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

    Reprints and permissions:

    sagepub.co.uk/journalsPermissions.nav

    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

    748 Textile Research Journal 82(8)

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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.

    Zhang et al. 751

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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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