Polymer Degradation and Stability 91 (2006) 2213e2219

www.elsevier.com/locate/polydegstab

Preparation of PANIeTiO2 nanocomposites and their solid-phase

photocatalytic degradation
Liuxue Zhang, Peng Liu, Zhixing Su*
Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000, PR China
Received 28 November 2005; received in revised form 23 December 2005; accepted 4 January 2006
Available online 28 February 2006

Abstract

A series of polyanilineeanatase TiO2 (PANIeTiO2) nanocomposite powders with different PANI:TiO2 ratios were prepared by ‘in-situ’
deposition oxidative polymerization of aniline hydrochloride using ammonium persulfate (APS) as oxidant in the presence of ultrafine grade
powder of anatase TiO2 cooled in an ice bath. And the solid-phase photocatalytic degradation of PANIeTiO2 nanocomposites was investigated
under the ambient air in order to assess the feasibility of developing photodegradable polymers. The photodegradation of the composite powders
was compared with that of pure PANI powders by performing weight loss monitoring, elemental analysis, FT-IR and UVevis spectroscopy and
X-ray photoelectron spectroscopy (XPS). The PANIeTiO2 nanocomposite powders showed highly enhanced photodegradation and the photo-
degradation increased with decreasing ratios of PANI:TiO2. A weight loss of about 6.8% was found for the PANIeTiO2 (1:3) nanocomposite;
however, the weight loss of the PANIeHCl powder was only 0.3% after being irradiated for 60 h under air. The photocatalytic degradation of the
nanocomposite powders accompanied the peak intensity decrease in the FT-IR spectra at 1235 cm
1, attributed to CeN stretching mode for
benzenoid unit, and the depigmentation of the powders due to the visible light scattering from growing cavities. The elemental analysis and
XPS analysis of the composite showed that the bulk and surface concentrations of N decreased with irradiation. A possible mechanism for
the photocatalytical oxidative degradation was also mentioned.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Polyanilineeanatase TiO2 nanocomposite; Preparation and characterization; Solid-phase photocatalytic degradation; UV irradiation; Mechanism

1. Introduction Heterogeneous-conducting polymer nanocomposites, espe-

It is well known that nanocrystalline TiO2 will produce
electronehole pairs under illumination of UV light. TiO2
photocatalyst has been successfully used to purify water and
air, to degrade the organic pollutants and to kill bacteria [1e
3]. Previous studies on the TiO2 photocatalytic degradation
of polymers mainly dealt with liquid-phase reactions, such
as photocatalytic degradation of polyvinylchloride (PVC) par-
ticles in TiO2 suspension aqueous solution [4]. Recently, there
are a few studies on the solid-phase photocatalytic degradation
of polymereTiO2 composite. The polymer matrices are
mainly polyolefins, such as polystyrene (PS) [5], PVC [6]
and so on.
* Corresponding author. Tel.: þ86 931 8912391; fax: þ86 931 8912582.
E-mail address: suzx@lzu.edu.cn (Z. Su).
cially for organic/inorganic nanocomposite, have drawn the at-
tention of scientists over the last few years [7]. Most recently,
as one of the most intensively studied conducting polymers in
the last 20 years, polyaniline (PANI) has attracted consider-
able attention for the preparation of its composites with inor-
ganic particles to improve their processability, such as
conducting polyanilineeBaTiO3 composite [8], polyanilinee
molybdenum trisulfide composite [9], conducting polya-
nilineeinorganic salt composite [10] and polyanilineeV2O5
composite [11]. Besides conducting materials, polyanilinee
inorganic particles were also investigated for their applications
in electrorheological ER fluids [12] and high-density informa-
tion storage material [13].
TiO2 has also been studied to prepare its composite with
conducting polymers [14,15]. Although there are so many can-
didates for polymeric matrix, one particular interest is the

0141-3910/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2006.01.002
2214 L. Zhang et al. / Polymer Degradation and Stability 91 (2006) 2213e2219
integration of inorganic nanoclusters with conducting poly-
mers because the resulting nanocomposites may possess
unique electrical and optical properties. Because of the
combination of electrical conductivity of polyaniline and
UV-sensitivity of anatase TiO2, such nanomaterials are
expected to find applications in electrochromic devices, non-
linear optical system and photoelectrochemical devices.
In this study, a series of polyanilineeanatase TiO2 (PANIe
TiO2) nanocomposite powders with different PANI:TiO2 ratios
from 3 to 0 were prepared and their photocatalytic degradation
under the ambient air atmosphere was investigated. It demon-
strates that the PANIeTiO2 composite has a potential viability
to be used as a photodegradable product. The photocatalytic
degradation in the solid polymer matrix proceeded much faster
than the direct photolytic degradation under air. A possible
mechanism for the photocatalytical oxidative degradation
was also mentioned.
2. Experimental
2.1. Materials and reagents
Aniline (ANI) (AR, Beijing Chemical Reagent Co., China)
was distilled under reduced pressure and stored below 4  C
under nitrogen atmosphere prior to use. Nanocrystalline
TiO2 (anatase, 27 nm, Zhoushan Mingri Nanomaterials Ltd.
Co., Zhejiang, China), 38% hydrochloric acid (AR), ammo-
nium persulfate (NH4)2S2O8 (APS, AR), ether (AR) and etha-
nol (AR) were used as received.
2.2. Preparation of PANIeTiO2 nanocomposites
The PANIeTiO2 nanocomposites were prepared according
to the following steps: 0e3.0 g of nanocrystalline TiO2 parti-
cles, 1 mL of aniline and 90 mL of 1.0 M HCl aqueous solution
were introduced into the reaction vessel. The solution was me-
chanically stirred for 1 h to obtain a uniform suspension con-
taining TiO2 particles, in an ice-water bath. The mixture was
deoxygenated by bubbling oxygen-free nitrogen into the reac-
tion vessel. After that, 100 mL of a precooled 1.0 M HCl aque-
ous solution containing 2.5 g of APS was added dropwise to the
above cooled mixture over a period of approximately 60 min,
and the resulting mixture was allowed to react in the ice bath
for 4 h. During the polymerization, N2 purging rate was kept
constant. The precipitated dark green-colored PANIeTiO2
nanocomposite powder was filtered and washed with large
amount of deionized water, then with 50 mL of ethanol and
30 mL of ether, after that the powder was extracted with ethanol
in order to remove the oligomers till the extracted solution be-
came colorless. Finally, the product was dried at 80  C till the
constant mass was reached. The samples were signed as PANIe
TiO2 (X ), where X is the ratio of ANI to TiO2 in nominal.
2.3. The photocatalytic performances
The photocatalytic degradation reactions were carried out
under atmospheric condition in a box reactor using a 300 W
high-pressure mercury lamp (qe6, lmax ¼ 365 nm, Osram
Corporation, Germany) as the irradiation source. The relative
humidity was 40% and the temperature was 30  C in the reac-
tion box. All samples were a 1.00 g round mat placed in a cul-
ture dish with about 78.5 cm2 area. The irradiation distance
between the lamp and the sample was 15 cm. Each sample
was weighed three times before and after irradiation to mea-
sure the weight loss of PANI by the photocatalytic degradation
as the function of irradiation time.
2.4. Analysis and characterizations
The elemental analysis was carried out using Elementar
Vario EL instrument. Fourier transform infrared (FT-IR)
spectra of the polymers in KBr pellets were recorded on
a Nicolet Avatar 360 FT-IR spectrometer (Nicolet Corp.,
USA). The spectra were collected from 4000 to 400 cm
1,
with a 4 cm
1 resolution over 20 scans. Thermogravimetric
analysis (TGA) was carried out for the measurement of
thermal degradation of the polyanilineeanatase TiO2
(PANIeTiO2) nanocomposite powders, performed with
a PerkineElmer TGA-7 system at a scan rate of 10  C min
1
to 800  C in N2. X-ray diffraction (XRD) was used for the
identification of the crystalline phases. The XRD patterns
were recorded in the range of 2q ¼ 10e80  by step scanning
with a Shimadzu XRD-6000 X-ray diffractometer. Nickel-fil-
ter Cu Ka radiation (l ¼ 0.15418 nm) was used with a genera-
tor voltage of 40 kV and a current of 30 mA. The UVevis
absorption spectra were recorded on a UVevis spectrometer
(Lambda 35, PerkineElmer Corporation, USA) with an inte-
grating sphere and 2 nm spectral resolutions at room tempera-
ture in the range of 190e1100 nm, and BaSO4 was used as
a reference. X-ray photoelectron spectroscopy (XPS) was per-
formed on an XSAM 800 X-photoelectron spectrometer with
a Mg Ka X-ray source. In the data analysis, the binding energy
of the core level C1s was set at 284.8 to compensate for sur-
face-charging effects. The microstructures of the nanocompo-
sites were analyzed with a JEOL JXA-8800R electron-probe
microanalyser (EPMA; Japan Electronic Corporation, Japan)
at an accelerating voltage of 15 keV and with a beam diameter
of 2 mm. Data were reduced with the Bence and Albee correc-
tion method.
3. Results and discussion
3.1. Preparation and characterizations of PANIeTiO2
For the polyanilineeanatase TiO2 (PANIeTiO2 (1:3))
nanocomposite powders, the elemental analysis (Table 1)
showed that the organic/inorganic (PANIeTiO2) weight ratio
was near to 1:2.5. The loss of TiO2 may be caused by the dis-
persed TiO2 in the solution. This indicated that the addition of
a mass of TiO2 had little influence on the conversion of
aniline.
The FT-IR spectra of PANI doped with HCl and PANIe
TiO2 composites are shown in Fig. 1. All characteristic bands
of PANI in the PANIeHCl (Fig. 1a) before UV irradiation,
 L. Zhang et al. / Polymer Degradation and Stability 91 (2006) 2213e2219
Table 1
Elemental analysis results of the PANIeTiO2 (1:3) nanocomposites
Samples C (%)
Before UV irradiation 23.04
After UV irradiation for 60 h 18.40
PANIeHCl (Fig. 1b) after UV irradiation and PANIeTiO2
(1:3) (Fig. 1c) were observed. The main characteristic peaks
of doped PANI are assigned as follows: the band at 3457 and
3230 cm
1 can be attributed to the free (non-hydrogen bonded)
NeH stretching vibration and hydrogen-bonded NeH bond be-
tween amine and imine sites [16], C]N and C]C stretching
modes for the quinonoid and benzenoid units occur at 1560
and 1483 cm
1, the bands at 1297 and 1235 cm
1 have been
attributed to CeN stretching mode for benzenoid unit, while
the band at 1112 cm
1 to quinonoid unit doped PANI, and
the peak at 793 cm
1 is associated with CeC and CeH for
benzenoid unit. The characteristic peaks of TiO2 at 1103 and
452 cm
1 were also found in the spectrum of PANIeTiO2
nanocomposite. The characteristic peaks from the PANI around
1297, 1483 and 1560 cm
1, corresponding to the stretching
modes of CeN and C]N bonds, reveal the presence of leucoe-
meraldine and pernigraniline components. After titania was in-
troduced, all peaks shifted to higher wavenumbers: 1299, 1491
and 1573 cm
1. Meanwhile, the characteristic peak of NeH
stretching mode at 3457 cm
1 of PANI shifted to a lower
wavenumber (3432 cm
1) in the PANIeTiO2 composite, and
the hydrogen bond absorption at 3230 cm
1 is strengthened af-
ter TiO2 was introduced. These findings reveal that the hydrogen
bonding in the PANI complex became stronger after complexing
with TiO2. The results also suggest that there is strong interac-
tion between the polyaniline and nanocrystalline TiO2 [17,18].
The UVevis absorption spectra of the PANIeTiO2 com-
posites with various aniline:TiO2 weight ratios prepared with
the proposed method are shown in Fig. 2. Clearly, the prepared
(b)
3230
3457
(a)
1560
Transmittance
1483
1491
1573
3230
(c)
1299
3432
1235
4000 3600 3200 2800 2400 2000 1600
Wavenumber (cm-1)
Fig. 1. FT-IR spectra of PANIeHCl (a) before, (b) after UV irradiation for 60 h
and (c) PANIeTiO2 (1:3).
2215
PANIeTiO2 composites not only can strongly absorb the UV
light but can also absorb the visible and near-IR light. The hy-
H (%) N (%) brid samples present characteristic bands of polyanilinee
2.380 4.356 emeraldine salt at w320 nm, w415 nm and w650e690 nm,
1.689 2.691 which are attributed to pep* transition of benzenoid ring, po-
laronep* and pepolaron exaction transition of the quinonoid
rings, respectively [19], whereas electronic spectra of PANIe
TiO2 composites exhibited bands at 415 and 650 nm presum-
ably due to the formation of new composite [20]. And the peak
at about 650 nm is shifted to higher wavelengths of 690 nm
with the increase in TiO2:aniline weight ratio. This result indi-
cates that there is strong interaction between polyaniline and
nanocrystalline TiO2 [20].
X-ray diffractions of the TiO2, PANI and PANIeTiO2 (1:3)
composites are presented in Fig. 3. It can be seen from Fig. 3a
that the titania powder was anatase crystal, and the positions of
all peaks are in good agreement with the results reported by
Tang et al. [21]. In the pattern of PANI (Fig. 3b), the Bragg
diffraction peaks of 2q w 9.4, 14.0, 15.7, 16.9, 26.5 and
27.4  can be found. It indicated that the pure PANI was in par-
tial orthorhombic structure [22]. The other two broad peaks
centered at 2q w 20.8 and 25.4  are ascribed to the periodicity
parallel and perpendicular to the polymer chain and indicated
that the pure PANI was in semi-crystalline phases [23]. In the
pattern of PANIeTiO2 (1:3) composite, the peaks of 2q w 9.4,
14.0, 15.7, 16.9 and 27.4  of PANI disappeared and the peak
at 20.8  of PANI became weaker. The result suggests that the
addition of nanocrystalline TiO2 hampers the crystallization of
the polyaniline molecular chain. This is because when
the deposited polyaniline is absorbed onto the surface of the
nano-TiO2 particle, the molecular chain of absorbed polyani-
line is tethered, and the degree of crystallinity decreases [20].
The thermal behavior of the PANIeTiO2 (1:3) composite
sample was investigated by thermogravimetric analysis
(TGA), and the result is shown in Fig. 4. From Fig. 4a, it is ev-
ident that the release of ethanol and water (from both the titania
Absorbance (a.u)
1112
1297
793
(d)
(c)
452
(b)
(a)
1103
1200 800 400 200 400 600 800 1000 1200
Wavelength (nm)
Fig. 2. UVevis absorption spectra of the PANIeTiO2 nanocomposites with
different PANI:TiO2 ratios; (a) 10:1, (b) 5:1, (c) 1:1 and (d) 1:3.
2216 L. Zhang et al. / Polymer Degradation and Stability 91 (2006) 2213e2219

spectra (Fig. 5) that the peak intensity at 1235 cm
1 attributed

to CeN stretching mode for benzenoid unit decreased with the
increase in irradiation time and disappeared after a UV irradi-
ation time of 60 h. The FT-IR spectrum in Fig. 5b also showed
the existence of C]O bond by a peak at 1680 cm
1 [25]. The
peak intensity at 1097 and 448 cm
1 attributed to the charac-
Intensity (a.u.)

teristic peaks of TiO2 was strengthened by increasing the UV

10 20 30 40 50
2 Theata (deg)
Fig. 3. X-ray diffraction patterns of the different particles: (a) titania, (b)
PANIeHCl, PANIeTiO2 (1:3) (c) before and (d) after UV irradiation for 60 h.
and polymer surface) occurs from 50 to 100  C, and thereafter
a plateau appears up to about 210  C. The mass loss occurred
between 210 and 245  C with an exothermic peak probably
due to the expulsion of the dopant [24]. In the temperature
range of 330e650  C, a strong weight loss occurred, which
is attributed to the degradation of the skeletal polyaniline chain
structure [24]. The amount of polyaniline (28.7%) in the
PANIeTiO2 (1:3) composite sample estimated by CHN ele-
mental analysis (Table 1) is close to that stipulated by the
weight loss in the 330e650  C range (26.0%) on TGA curves.
3.2. Solid-phase photocatalytic degradation and possible
mechanism
For the PANIeTiO2 (1:3) nanocomposite, that had the
highest inorganic/organic ratio, it was found in the FT-IR
irradiation time. This observation indicated that the character-
istics of TiO2 increased and the characteristics of PANI de-
creased as the irradiation time increased due to the
(b) degradation of PANI in the composite sample. However, for
(c) the FT-IR spectra of the PANIeHCl (Fig. 1a and b), the
(d) peak intensity at 1235 cm
1 changed little with the UV irradi-
ation and the FT-IR spectra were almost same before and after
(a) UV irradiation. The experiment result indicated that the CeN
60 70 80 bonds of the benzenoid unit had been photocatalytically oxida-
tively degraded in the presence of the photocatalyst of nano-
TiO2 in the PANIeTiO2 nanocomposites, but the changes in
the pure PANI sample were little.
The evidence for degradation and erosion of PANI in the
PANIeTiO2 nanocomposites was obtained by electron-probe
microanalyser (EPMA). The surface morphologies of the com-
posite before and after irradiation are shown in Fig. 6. It can be
seen that after irradiation for certain time, the cavities formed
on the surface of the composite particles, and the surface be-
came more coarse. With the prolonging of the UV irradiation,
the nanocomposites’ structure was destroyed, and the chalking
phenomenon took place [5]. This indicates that TiO2 nanopar-
ticles will greatly enhance the photocatalytic degradation of
the PANI material. It can also be found that the PANIeTiO2
(1:3) sample after UV irradiation for 60 h had poorer
thermo-stability than that before UV irradiation (Fig. 4b).
The organic compounds had been decomposed completely at
the temperature range of 330e640  C. The weight loss of
sample after UV irradiation was lower than that before UV
irradiation. Accordingly, the C, N and H elemental contents
in the composites decreased after UV irradiation (Table 1).

100
1235

95 (a)
1680

90 (b)
1493
1580

1303
3237

85
3430
Weight (%)

Transmittance

80
463

75
(b)

70
1101

65
(a)
60
100 200 300 400 500 600 700 800 4000 3600 3200 2800 2400 2000 1600 1200 800 400
Temperature (deg) Wavenumbers (cm-1)

Fig. 4. TGA curves of the PANIeTiO2 (1:3) before (a) and after (b) UV irra- Fig. 5. FT-IR spectra of the PANIeTiO2 (1:3) (a) before and (b) after UV ir-
diation for 60 h. radiation for 60 h.
 L. Zhang et al. / Polymer Degradation and Stability 91 (2006) 2213e2219 2217

Fig. 6. EPMA images of the PANIeTiO2 nanocomposite (1:3) before (a) and after UV irradiation for (b) 30 h, (c) 60 h.

All these results indicated that parts of PANI in the composites
had been photodegraded.
The UVevis absorbances of the PANIeTiO2 (1:3) compos-
ites after different UV irradiation times were measured and the
results are shown in Fig. 7. Clearly, the adsorption of UV light,
visible and near-IR light of the PANIeTiO2 (1:3) nanocompo-
site increased with the prolonging of UV irradiation time. It re-
sulted from the cavities formed not only on the surface, but
also inside the nanocomposites due to photodegradation of
PANI. Since the cavities formed as a result of the photocata-
lytic degradation scattered visible light, depigmentation of
the irradiated composites was observed.
The XRD analysis also showed that the Bragg diffraction
peak at 20.8  of PANI which is ascribed to the periodicity
parallel and perpendicular to the polymer chain became weaker
after irradiation under UV for 60 h (Fig. 3c and d). This indi-
cates that chain scission in the backbone of polymer has taken
place by 60 h of photocatalytic degradation, and it resulted in
the vanishing of the crystalline phase in the PANI polymer.
The photoinduced weight losses of the samples with differ-
ent PANI:TiO2 ratios for different UV irradiation times up
to 60 h are shown in Fig. 8. The weight losses increased
with the decrease in PANI:TiO2 ratio and the weight loss rates
of the PANIeTiO2 composites were much higher than that of
2218 L. Zhang et al. / Polymer Degradation and Stability 91 (2006) 2213e2219

2.0 Table 2
The surface compositional data of PANIeTiO2 (1:3) nanocomposites from
XPS
1.8 Samples XPS analysis (at.%)
Ti O C N
Absorbance (a.u.)

Before UV irradiation 4.53 66.74 19.21 9.52

1.6
After UV irradiation for 60 h 1.72 67.17 31.11 0

1.4
1.2
1.0
200 400 600 800
Wavelength (nm)
Fig. 7. The UVevis absorption spectra of the PANIeTiO2 (1:3) composites
after different UV irradiation times. (a) 10 h, (b) 20 h, (c) 30 h, (d) 40 h, (e)
60 h.
the PANIeHCl particles. The weight of the nanocomposite
PANIeTiO2 (1:3) steadily decreases with irradiation under
air and led to the total of 6.8% reduction in 60 h; however,
the PANIeHCl particles showed only 0.3% weight loss under
the identical experimental condition. It indicated that the more
nano-TiO2 added, the higher absorption in UV region (Fig. 2),
and the faster photocatalytical oxidative degradation rate were
achieved. The above weight loss data implied that some deg-
radation products volatilized into the air.
The elemental analysis showed that the C, N and H elemen-
tal contents of the samples decreased after the UV irradiation
and N elemental content was the fastest to decrease (Table 1).
The surface compositional data of the PANIeTiO2 (1:3) from
XPS also showed that the surface N elemental content had
been decreased to 0 and that of C and O elements increased
after UV irradiation for 60 h (Table 2). And the surface Ti el-
emental content had been also decreased.
7 radation in the solid polymer matrix proceeded much faster
6 mechanism for the photocatalytical oxidative degradation
Weight loss (%)
(e) So a mechanism for the solid-phase photocatalytical oxida-
(d) tive degradation is emerged as following: TiO2 particles that
(c) absorbed light with energy higher than 3.2 eV under UV irra-
(b) diation generate electronehole pairs in the conduction bond
(a) (CB) and valence bond (VB), respectively. Subsequent reac-
tions with O2 lead to the formation of active oxygen species
1000 1200
such as hydroxyl radical and hydroperoxyl radical. The active
oxygen species attacked neighboring polymer chains, the Ce
N bonds of the benzenoid unit were broken up and the PANI
chains had been cut up into pieces with end-group of hydroxy-
benzene hydroxyl groups originating from the CeN bonds of
the benzenoid unit, and this caused the decrease in the surface
N elemental content to 0, vanishing of the crystalline phase in
the PANI polymer and appearance of 1680 cm
1 peak in FT-
IR spectra. The chain pieces cleaved were absorbed onto the
surfaces of nano-TiO2 and then oxidised to p-benzoquinone
[25,26], to quinone and to CO2 and H2O finally [25,27]. The
adsorbtion of cleaved chain pieces onto the surface of nano-
titania caused a significant increase in the concentration of car-
bon atoms and decrease in Ti element.
4. Conclusions
The polyanilineeTiO2 (PANIeTiO2) composites with dif-
ferent inorganic/organic ratios prepared by an in situ polymer-
ization method could be degraded by photocatalytic oxidation
under UV irradiation. The present study reveals that photoca-
talytic method can be effective for solid-phase PANI degrada-
tion and the PANIeTiO2 composite has a potential viability to
be used as a photodegradable product. The photocatalytic deg-
(a)(1:3) than the direct photolytic degradation under air. A possible
emerged from the analytical results of the elemental analysis,

5 FT-IR and XPS.

(b)(1:1)
4
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