Polymer Degradation and Stability 92 (2007) 1061e1071

www.elsevier.com/locate/polydegstab

A thermal degradation mechanism of polyvinyl alcohol/silica

nanocomposites
Zheng Peng a,b,*, Ling Xue Kong b
a
Chinese Agricultural Ministry Key Laboratory of Natural Rubber Processing, Agricultural Product Processing Research Institute at Chinese
Academy of Tropical Agricultural Sciences, Zhanjiang 524001, Guangdong, China
b
Center for Advanced Manufacturing Research, University of South Australia, Mawson Lakes SA 5095, Australia
Received 9 November 2006; received in revised form 26 January 2007; accepted 15 February 2007
Available online 21 February 2007

Abstract

The thermal degradation mechanism of a novel polyvinyl alcohol/silica (PVA/SiO2) nanocomposite prepared with self-assembly and solu-
tion-compounding techniques is presented. Due to the presence of SiO2 nanoparticles, the thermal degradation of the nanocomposite, compared
to that of pure PVA, occurs at higher temperatures, requires more reaction activation energy (E ), and possesses higher reaction order (n). The
PVA/SiO2 nanocomposite, similar to the pure PVA, thermally degrades as a two-step-degradation in the temperature ranges of 300e450  C and
450e550  C, respectively. However, the introduction of SiO2 nanoparticles leads to a remarkable change in the degradation mechanism. The
degradation products identified by Fourier transform infrared/thermogravimetric analysis (FTIR/TGA) and pyrolysis-gas chromatography/
mass spectrometric analysis (Py-GC/MS) suggests that the first degradation step of the nanocomposite mainly involves the elimination reactions
of H2O and residual acetate groups as well as quite a few chain-scission reactions. The second degradation step is dominated by chain-scission
reactions and cyclization reactions, and continual elimination of residual acetate groups is also found in this step.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Polyvinyl alcohol; Silica; Nanocomposite; Thermal degradation

1. Introduction
The thermal resistance is one of the most dominative prop-
erties for polymer materials, as it ultimately governs the me-
chanical properties, durability, spectral stability, shelf lives,
and life cycles of polymers [1e4]. Once the degradation be-
gins, the above properties will gradually deteriorate.
The widely recognized polymers with inherent thermal re-
sistance are linear single-strand polymers having a sequence of
cyclic aromatic or heterocyclic structures, ladder polymers,
and inorganic or semiorganic polymers [5]. It is found that in-
corporating highly stable, rigid aromatic, or heterocyclic rings
* Corresponding author. Chinese Agricultural Ministry Key Laboratory of
Natural Rubber Processing, Agricultural Product Processing Research Institute
at Chinese Academy of Tropical Agricultural Sciences, Zhanjiang 524001,
Guangdong, China. Tel.: þ86 759 2286933; fax: þ86 759 2221586.
E-mail address: zhengpeng8@yahoo.com (Z. Peng).
into the polymer chains can enhance the thermal stability of
polymers [6]. By introducing inorganic nano-fillers into poly-
mers, thermal resistance of polymer hosts has recently been
dramatically improved [7,8]. Compared to virgin polymers,
polymeric/inorganic nanocomposites (PINs) usually degrade
at significantly higher temperatures, and demonstrate a sub-
stantial decrease in the degradation rate [9]. Hence, the ther-
mal resistance of polymer hosts can be markedly enhanced,
even if only a small amount of nano-fillers is loaded [10].
The contribution of inorganic nano-fillers to thermal resis-
tance of PINs has commonly been described as a barrier
model, which suggests that the thermal resistance is enhanced
because of a strong polymeric-inorganic char [11e14]. This
char is built up on the surface of the polymers as a mass
and heat transfer barrier, and limits the passage of degradation
products from the matrixes. However, the detailed mechanism
of such a remarkable effect is not well understood yet. For ex-
ample, previous work seldom reported the kinetic aspects and

0141-3910/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2007.02.012
1062 Z. Peng, L.X. Kong / Polymer Degradation and Stability 92 (2007) 1061e1071
chemistry of the thermal degradation which are critical for
understanding the processing energy barriers and degradation
mechanisms [12,15].
Thermal analysis coupling systems provide powerful ap-
proaches to reveal the thermal degradation mechanisms of
the polymer hosts of PINs. Fourier transform infrared/ther-
mogravimetric analysis (FTIR/TGA) allows simultaneous
quantification and identification of evolved degradation prod-
ucts, offering valuable information on thermal degradation
of polymers [16]. Jang and Wilkie [17] studied the thermal
degradation of poly(acrylonitrile-co-styrene) and its clay
nanocomposites using TGA/FTIR. It was found that the nano-
composite, compared to the pure poly(acrylonitrile-co-styrene),
contains additional degradation steps: extensive random chain
scission, evolving additional compounds that have an odd
number of carbons in the chain backbones, and radical recom-
bination, producing head-to-head structures. However, TGA/
FTIR is not sufficient to investigate every aspect of thermal
degradation. Particularly when a large number of organic gas-
eous species are generated, it is hard to use FTIR to identify
the structures for all degradation products due to intensive
overlap of characterization peaks. Moreover, FTIR is power-
less to identify the low concentration degradation products
due to its inherent limitation of sensibility. Therefore, pyroly-
sis-gas chromatography/mass spectrometric analysis (Py-GC/
MS) has been used to collect more detailed information for un-
derstanding the thermal degradation mechanisms [18]. Chen
et al. [19] combined Py-GC/MS and FTIR/TGA methods to
perform a comparative degradation study of polystyrene (PS)
and polystyreneeclay composite. The results demonstrated
that the degradation mechanism of the PS/clay composite
differs from that of virgin PS and an unusually high yield of
a-methylstyrene indicates that intermolecular radical transfer
reactions are found in the nanocomposite.
The thermal degradation of polyvinyl alcohol (PVA) has
been initially investigated with thermal analysis [20e22]. It
was found that PVA thermally degrades in two steps. The first
degradation step mainly involves the elimination reactions,
while the second one is dominated by chain-scission and cycli-
zation reactions. Although it has been demonstrated in our
previous work [3,13,23] that SiO2 reinforced PVA nanocom-
posites have improved thermal resistance, the impact of SiO2
nanoparticles on the thermal degradation of nanocomposites
has not been comprehensively studied. To understand how
the PVA/SiO2 nanocomposite exactly degrades, we will envis-
age a thermal degradation mechanism of PVA/SiO2 nanocom-
posite by combing three major experimental techniques TGA,
FTIR/TGA and Py-GC/MS.
2. Experimental section
2.1. Materials
Polyvinyl alcohol (PVA) (average molecular weight: 67,000;
polymerization degree: 1400; hydrolysis rate: 86.7e88.7 mol%),
silica nanoparticles (average diameter: 14 nm; surface area:
200  25 m2/g) and polyallylamine hydrochloride (PAH)
(average molecular weight: 70,000) were purchased from
Sigma-Aldrich. All experimental materials were used as
received.
2.2. Synthesis of PVA/SiO2 nanocomposite
In our previous work [3,13,23], we developed a novel pro-
cess to prepare PVA/SiO2 nanocomposites by combining solu-
tion compounding with self-assembly technique. Firstly, the
negatively charged SiO2 nanoparticles act as templates to ad-
sorb positively charged PAH molecular chains through electro-
static adsorption. PVA molecular chains are then assembled on
the surface of SiO2 nanoparticles through hydrogen-bonding
interaction between hydroxyl groups of PVA and amino
groups of PAH. Finally, the SiO2 nanoparticles covered with
PAH and PVA molecules are uniformly distributed in the
bulk PVA matrix, which is dried to form PVA/SiO2 nanocom-
posite films. The key procedure of this process is the encapsu-
lation of the SiO2 nanoparticles with PAH and PVA layers,
aiming at suppressing the self-aggregation of SiO2 nanopar-
ticle caused by strong particleeparticle interactions. The
nanocomposite contains 5 wt% SiO2.
2.3. Characterization
A Perkin Elmer TGA-7 thermogravimetric analyzer was
used for the thermogravimetric analysis (TGA). The measure-
ment of the films (ca. 10 mg) was carried out from 100 to
600  C with heating rates of 10, 20, 30, 40 and 50  C/min un-
der nitrogen with a flow rate of 80 ml/min.
Fourier transform infrared/thermogravimetric analysis
(FTIR/TGA) was performed on a combined Perkin Elmer
Spectrum Gx-I FTIR and TGA-7 system. The decomposition
gases from each degradation step were transferred from
TGA analyzer to FFIR/TGA interface, and measured by
FTIR spectrometer with 4 cm1 resolution and 4000e
600 cm1 scanning wave number range. To avoid the overlap
of evolved gases from different degradation steps, the samples
were heated at three temperature points, respectively. Firstly,
the samples were heated at 110  C for 5 min to eliminate re-
sidual water. The samples were then heated around the peak
degradation temperature (Tp) of the first degradation step
(350  C) that is obtained from TGA analysis till the degrada-
tion was completed. Finally, the samples were heated around
Tp of the second degradation step (470  C) till the degradation
was finished.
Pyrolysis-gas chromatography/mass spectrometric analysis
(Py-GC/MS) was carried out with a Japan Analytical Industry
JHP-3S Curie Point Pyrolyzer coupled to a HP6890 gas chro-
matograph linked to a 5973 Quadrupole mass spectrometer.
The samples were pyrolyzed at 330  C for 10 s and 530  C
for 15 s to simulate the two degradation steps that were con-
ducted on TGA analysis. The carrier gas was high-purity nitro-
gen at a flow rate of 50 ml/min. The GC column was a HP-5
fused silica capillary column. The GC column temperature
was initially held at 50  C for 2 min; then at a rate of 5  C/
min, it was raised to 280  C and held there for 30 min. The
 Z. Peng, L.X. Kong / Polymer Degradation and Stability 92 (2007) 1061e1071 1063

GCeMS interface was set at 230  C. Mass spectra were 100

recorded under the electron impact ionization energy of a
70 eV. The total flow was split at a ratio of 50:1. The mass
of each sample was 0.10e0.20 mg. 80

Weight % (%)
3. Results and discussion 60

3.1. Thermal degradation process

40
There are two distinct and well-separated turns (300e
450  C and 450e550  C) in the thermogravimetric (TG)
20
curves (Fig. 1a) and two corresponding weight-loss peaks in TG
derivative thermogravimetric (DTG) curves for the pure PVA
(Fig. 1b). Therefore, the thermal degradation of PVA can be 0
200 300 400 500 600
roughly regarded as a two-step-degradation. Due to the pres-
Temperature (°C)
ence of SiO2, the TG/DTG curves of the nanocomposite shift
to higher temperatures (Fig. 2). Therefore, the PVA/SiO2 -48
nanocomposite is more thermally stable than the pure PVA. Step 1: Tp = 1.09 β + 384.6 b
Step 1
Correspondingly, at a given temperature, the degradation rate Step 2: Tp = 0.75β + 479.3

Derivative Weight % (%/min)

of the nanocomposite is significantly lower. Under a given -38

-28 Step 2
100
a

80 -18
Weight % (%)

60 -8
DTG

40 2
200 300 400 500 600
Temperature (°C)
20
TG Fig. 2. TG (a) and DTG (b) curves of PVA/SiO2 nanocomposite in nitrogen
with different heating rates: B 10  C/min; O 20  C/min; , 30  C/min; >
40  C/min; C 50  C/min.
0
200 300 400 500 600
Temperature (°C)
heating rate, the TG curve of the nanocomposite is situated
-48 at a higher temperature than that of the pure PVA. Here, we
Step 1: Tp = 1.68β + 355.6 b take one of the most important degradation temperatures, the
Step 2: Tp = 0.64β + 467.8 Step 1 peak degradation temperature with maximum weight loss
Derivative Weight % (%/min)

-38
Step 2 rate (Tp), as an example to quantitatively investigate the differ-
ence in degradation temperatures between pure PVA and
-28
nanocomposite.
As the thermal degradation in this study was conducted with
a temperature-scanning model, the heating rate (b) has a strong
-18 effect on the degradation. To truly identify the difference
between the degradation of pure PVA and PVA/SiO2 nanocom-
DTG
posite, the influence of heating rates was eliminated with a
-8 multi-heating rate method [13,24]. From Figs. 1b and 2b, it was
found that degradation temperature Tp for both PVA and nano-
composite linearly increases with the heating rate.
2
200 300 400 500 600 The linear increase of thermal degradation temperatures
Temperature (°C) with heating rate is caused by the heat hysteresis, i.e. the inner
Fig. 1. TG (a) and DTG (b) curves of PVA in nitrogen with different heating part of the samples cannot follow the program temperature
rates: B 10  C/min; O 20  C/min; , 30  C/min; > 40  C/min; C 50  C/ when the temperature increases too fast. Theoretically, the
min. slower the heating rate, the more accurate the degradation
1064 Z. Peng, L.X. Kong / Polymer Degradation and Stability 92 (2007) 1061e1071

presents. Therefore, by assuming the heating rate equals 0  C/ and

min, the equilibrium peak thermal degradation temperature    
(Tp ) can be identified from equations in Figs. 1b and 2b. ð1  aÞ ð1  2RT=EÞAR E
ln  ln ¼ ln  ðn ¼ 1Þ ð4Þ
The Tp of the PVA/SiO2 nanocomposite increase to 29.0  C T2 bE RT
which is 11.5  C over the pure PVA at the first and second deg-
radation steps, respectively. where n is the reaction order, a the reaction degree, T the ab-
In addition to the increase of thermal degradation tempera- solute temperature, b the heating rate, E the reaction activation
tures, the difference in the degradation process between the energy, R the gas constant and A the frequency factor. When
pure PVA and nanocomposite is also obviously observed in n s 1, a line can be obtained from the plot of ln½1
the DTG curves (Figs. 1b and 2b). Due to the improvement ð1  aÞ1n =T 2 ð1  nÞ versus 1/T, where the slope is E=R,
in thermal resistance, the whole degradation process of the and the intercept is ln½ð1  2RT=EÞAR=bE. When n ¼ 1,
nanocomposite is protracted, which is confirmed by the a line can be obtained from the plot of ln½lnð1  aÞ=T 2  ver-
DTG curves where the degradation peak of nanocomposite sus 1/T, of which the slope is E=R, and the intercept is
is obviously wider than that of pure PVA. More importantly, ln½ð1  2RT=EÞAR=bE. Adopting the least square fitting
there is a significant change in the shape of the degradation method with different n, the n with maximum correlation co-
peak of DTG. There are two obvious degradation peaks (a efficient (r) is the apparent reaction order, and the correspond-
side peak accompanies the main peak) in the first degradation ing E is the reaction activation energy.
step of the nanocomposite, while there is only one degradation Table 1 lists various kinetic parameters of the first thermal
peak for the pure PVA (Figs. 1b and 2b). According to others’ degradation step for both PVA and nanocomposite. At the first
work [20e22], at the first degradation step, the thermal degra- degradation step, the average value of n of PVA is 3.6, which
dation of PVA mainly involves the elimination reactions, and is 0.8 lower than that of the nanocomposite. The reaction ac-
correspondingly there is only one peak in the DTG curve. tivation energy increases with the heating rate. Using the least-
The split of the first degradation peak in TG/DTG curves im- square linear regression method, E of the pure PVA and the
plies that the degradation mechanism of the nanocomposite nanocomposite can be described as E ¼ 0.66 b þ 129.9 and
differs from that of pure PVA. The side peak at lower temper- E ¼ 0.70 b þ 135.6, respectively. Eliminating the influence
ature can be caused by the elimination reactions, while the of heating rates, i.e. b ¼ 0  C/min, the apparent reaction acti-
main peak can be the overlap of the continual eliminations vation energy (E0) for the pure PVA is 129.9 kJ/mol, and
and chain-scission reactions which need more energy and 135.1 kJ/mol for the nanocomposite, respectively. At the sec-
occur at a higher temperature. ond thermal degradation step, the average value of n for
both PVA and nanocomposite are 1.6 and 2.6, correspond-
ingly. The E for PVA and nanocomposite are E ¼ 1.24
3.2. Thermal degradation kinetics b þ 145.6 and E ¼ 1.02 b þ 156.4, respectively (Table 2).
With the addition of SiO2, the thermal degradation mecha-
The kinetic analysis provides information on the energy nism tends to be more complex, the n for the nanocomposite
barriers of the process and clues to the degradation mechanism is, therefore, higher than that of the pure PVA. Due to the re-
for polymers. The challenge for the study of thermal tardant effect of PVA/SiO2 char, the nanocomposite, compared
degradation kinetics is to find a reliable approach. As single- to the pure PVA, is more difficult to be degraded, and more re-
heating-rate methods have identified shortcomings [25], multi- action activation energy is required during the reaction
heating-rate methods have been extensively used to study the process.
thermal degradation kinetics for polymers due to their reliabil- The enhanced thermal resistance attributes to the introduc-
ity [14,26]. In this study, CoatseRedfern model [24] based on tion of SiO2 nanoparticles. As illustrated in our previous work
the multi-heating rate method is employed to obtain reliable [3,13,23], when 5 wt% SiO2 is added to PVA, SiO2 nanopar-
kinetic information on the thermal degradation of PVA/SiO2 ticles are homogenously distributed throughout the PVA ma-
nanocomposite and pure PVA. trix as nano-clusters with an average size less than 30 nm.
The reaction kinetic parameters are obtained by processing Because the size of SiO2 clusters is far below 100 nm, these
TG data in Figs. 1a and 2a. By integrating the reaction kinetic SiO2 nano-clusters with a huge relative surface area and great
equation potential energy strongly interact with the PVA molecular
n
da=dt ¼ kð1  aÞ ð1Þ
Table 1
Kinetic parameters of the first thermal degradation step
and Arrhenius equation,
B ( C/min) PVA Nanocomposite
E=RT
k ¼ Ae ð2Þ n E (kJ/mol) n E (kJ/mol)
10 3.4 131.5 4.6 140.3
the following CoatseRedfern equations [24] can be obtained: 20 3.6 147.0 4.4 151.3
1n   30 3.6 153.7 4.3 157.0
1  ð1  aÞ ð1  2RT=EÞAR E 40 3.7 155.5 4.2 166.5
ln ¼ ln  ðns1Þ ð3Þ
T 2 ð1  nÞ bE RT 50 3.6 160.0 4.6 167.5
 Z. Peng, L.X. Kong / Polymer Degradation and Stability 92 (2007) 1061e1071 1065

Table 2 3.5 a
Kinetic parameters of the second thermal degradation step
B ( C/min) PVA Nanocomposite
2.5
n E (kJ/mol) n E (kJ/mol)
10 1.6 163 2.3 169.8
20 1.4 167.0 2.8 174.6 1.5
30 1.6 176.7 2.8 184.7
40 1.6 198.7 2.9 200.2
50 1.7 209.3 2.2 209.1 0.5

-0.5
chains through various effects, such as branching effect, nucle-
ation, size and surface effects. Thus, the diffusion of decompo- 4000 3500 3000 2500 2000 1500 1000
sition products from the bulk polymer to gas phase is slowed
down. Consequently, the nanocomposite has a pronounced im- b
provement in thermal resistance compared to the pure PVA. 0.060
Another reason for this enhancement is the formation of
PVA/SiO2 char. While being heated, the SiO2 nanoparticles,

Absorbance
due to their relatively low surface potential energy, migrate 0.040
to the surface of the composites to form a SiO2/PVA char,
which acts as a heating barrier to protect the PVA inside. Sim-
ilarly, Gilman et al. [12] and Vyazovkin and Sbirrazzuoli [25] 0.020
observed that a clay/polymer char greatly enhances the ther-
mal resistance of host polymers.
However, the above theories seem somewhat weak to ex- 0.000
plain why and how the PVA/SiO2 nanocomposite has much 4000 3500 3000 2500 2000 1500 1000
better thermal resistance than the pure PVA. To give a more
illustrative insight into the thermal degradation, the degrada- 0.024 c
tion chemistry was studied by identifying degradation
products.
0.016

3.3. Thermal degradation chemistry of PVA/SiO2

nanocomposite 0.008

To develop a degradation mechanism of the nanocomposite,

the gaseous degradation products are characterized by FTIR/ 0.000
TGA and Py-GC/MS from two degradation steps as described
4000 3500 3000 2500 2000 1500 1000
in Section 2. Wavenumber (cm-1)

3.3.1. The first degradation step Fig. 3. FTIR spectra of degradation products at different temperatures: (a)
110  C; (b) 350  C; (c) 470  C.
Elimination reactions: The elimination reactions of linear
and aliphatic polymers including polyvinyl chloride (PVC)

OH OH

OH OH OH

Elimination of nH2O

+ + H2O
HO HO

Scheme 1. Elimination reaction of H2O.

1066 Z. Peng, L.X. Kong / Polymer Degradation and Stability 92 (2007) 1061e1071

HO O HO O

CH3 CH3
O O

Elimination of H2O
Elimination of acetate groups

+
HO HO

O
+ H3C C CH3
+ H2O

Scheme 2. Dehydration and eliminations of residual acetate groups.

and PVA in the first stage of thermal degradation mainly form amount of acetic acid is also observed during the first degrada-
polyene structures via dehydrochlorination [27,28] or dehydra- tion step. This is testified by the FTIR/TGA spectra (Fig. 3b)
tion [20e22]. Therefore, dehydration should be one of the ma- where narrow and acute peaks at 3550 cm1 and 1760 cm1
jor reactions involved in the first degradation step of the PVA/ belong to the stretching vibration peaks of OeH and C]O
SiO2 nanocomposite, which well explains why a big amount of of gaseous acetic acids [13], respectively. Another evidence
water is present in the FTIR/TGA analysis during the first deg- is given by Py-GC/MS analysis, as Table 3 indicates that the
radation step of the nanocomposite (Fig. 3). Theoretically, if content of acetic acid accounts for more than 64% of the gas-
a high-hydrolyzed PVA is employed, the dehydration of eous degradation products.
PVA/SiO2 nanocomposite should generate two polyene struc- The high-molecular-weight polyenes presented in Scheme
tures: conjugated polyenes and non-conjugated polyenes 2 do not appear in the FTIR/TGA (Fig. 3b) and Py-GC/MS
(Scheme 1). spectra (Fig. 4), due to their relatively high-molecular weights.
However, as the present study employs a low hydrolyzed The degradation temperature of the first degradation step is not
(86.7e88.7%) PVA and a big amount of acetate groups remain high enough to break all the backbone chains of these poly-
in PVA molecular chains, the eliminations of the PVA/SiO2 enes into low-molecular-weight polyenes. Most of these poly-
nanocomposite should occur in the form of Scheme 2, where ene structures will act as intermediate products and be further
the elimination of H2O and residual acetate groups occurs si- degraded into other products with lower molecular weights at
multaneously as the acetate groups are randomly inserted be- the next degradation step. Therefore, only a small amount of
tween hydroxyl groups. Therefore, in addition to water, a big low-molecular-weight polyenes is observed in the MS spectra
(Table 3).
As the hydroxyl group is protonated under acidic condi-
Table 3 tions to form a substituent, namely eOHþ 2 , that in turn gives
Identification of degradation products at 330  C for PVA/SiO2 nanocomposite rise to a more favourable leaving group, i.e. H2O, the first
Retention Compound Molecular Molecular Content (%) stage of PVA degradation can be catalyzed by acetic acid.
time (min) formula weight From this point of view, the highly hydrolyzed PVA has better
1.35 Acetaldehyde O 44 18.0 thermal stability than PVA with a low degree of hydrolysis,
H3C CH and the addition of a compound with basic groups seems to
O be suitable for improving the thermal stability.
1.52 Acetone 58 3.1
H3C C CH3 Chain-scission reactions: Gilman et al. [21] and Alexy et al.
[20] found that the first degradation step of PVA mainly con-
1.74 Furan 68 2.3 tains the elimination reactions. In this study, it is however
O found that the chain-scission reactions are also intensively in-
volved at this stage when SiO2 nanoparticles are introduced
O
1.82e2.05 Acetic acid 60 64.1 into PVA host. That is why the DTG curves of the first degra-
H3C C OH dation of nanocomposite present two degradation peaks
(Fig. 2b). The first one occurs at lower temperatures and cor-
44.87 Polyenes e e 8.0
responds to elimination reactions, while the other one at higher
 Z. Peng, L.X. Kong / Polymer Degradation and Stability 92 (2007) 1061e1071 1067

1.35
650000 a
550000

450000
1.82
350000 1.95

1.15 2.05
250000 1.52
1.60 1.74
150000

1.20 1.60 2.00 2.40 2.80

120000 b 44
100000
80000
60000
40000
20000 28
34 40 78 94
20 40 60 80 100

16000 c 43

12000

8000
58
4000
28 34 37 39 66
46 55 64 77
20 40 60 80

200000 29
d
170000
44
140000
110000
80000
50000 31 42
20000 26
33 40 46 51 55 64 78
30 40 50 60 70

e 41
13000

10000

70
7000

4000
27
32 36 50 57 81 94
1000
20 40 60 80 100

65000 45
f
60
50000

35000

20000

5000 29 68 105 122

52 78
20 40 60 80 100 120

Fig. 4. Pyrogram of the nanocomposite at (a) 330  C and the MS spectra at different retention times: (b) 1.15 min; (c) 1.35 min; (d) 1.52 min; (e) 1.74 min; (f) 1.82 min.
1068 Z. Peng, L.X. Kong / Polymer Degradation and Stability 92 (2007) 1061e1071

non-conjugated polyene structures. These hydroxyl groups de-

HO HO stroy the structural regularity of polyenes and act as weak
links, from where the non-conjugated polyenes can be snipped
Chain-Scission
into low molecular structure via chain-scission reaction at
a relatively low degradation temperature. Therefore, a small
amount of polyenes are observed in the degradation products
H3C
(Table 3).
CH
+ Gilman et al. [21] proposed similar conjugated and non-
HO O HO conjugated polyene structures, and described the degradation
mechanism of non-conjugated polyenes into cis and trans
methyl-terminated polyenes via chain-scission reaction. How-
ever, we envisage a different mechanism in the chain scission
of the nanocomposite at the first degradation step (Scheme 3).
Chain-Scission The non-conjugated polyenes are not directly degraded into
low-molecular-weight polyenes, but form some intermediates:
O methyl-terminated non-conjugated polyenes and carbonyl-ter-
+ H3C CH minated polyenes. The methyl-terminated polyenes are then
snipped into acetaldehyde and polyenes with carbocations.
These polyenes are further degraded into cis and trans
methyl-terminated polyenes via additional reactions. The char-
+H
acteristic peak of methyl terminal group around 1370 cm1 is
H3C clearly observed in the FTIR spectra of degradation products
+ H3C (Fig. 3b and c).
Other subsidiary reactions also contribute to the chain scis-
Scheme 3. Chain-scission reactions in the first degradation step. sion. The appearance of a small amount of furan in the gaseous
degradation products (Fig. 4e) can be explained by the forma-
temperature corresponding to the overlap of elimination and tion of furan rings via intramolecular cyclizations. The dehy-
chain-scission reactions. As the introduction of SiO2 nanopar- dration reaction of two intramolecular hydroxyl groups
ticles greatly improves the thermal resistance of the nanocom- proceeds under the catalysis of acetate acid produced by the
posite, the first thermal degradation step of the nanocomposite elimination of residual acetate groups (Scheme 4). As fore-
occurs at a higher temperature (Figs. 1 and 2), which enables mentioned reason, the first degradation step of the nanocom-
the chain-scission reactions. posite occurs at relatively high temperatures, some of the
Tsuchiya and Sumi [29] reported that the dehydration of chain scissions occur at the position of ortho-diol. This chain
PVA leads to the formation of the conjugated polyene struc- scission will generate some acetaldehyde and acetone struc-
tures. However, we believe that the conjugated and non- tures as indicated in Scheme 5.
conjugated polyenes are simultaneously formed during the
degradation of PVA/SiO2 nanocomposite (Scheme 2). At the 3.3.2. The second degradation step
temperatures of first degradation step, the conjugated polyenes The degradation products of the second degradation step are
are unlikely to be degraded due to their relatively stable struc- acetaldehyde, acetic acid, polyenes, benzenoid derivatives and
tures, which are highly regular. However, the non-conjugated a small amount of furan (Table 4). As the second step of thermal
polyenes seem to be more likely degraded under this condition degradation occurs at higher temperatures compared to the first
(Scheme 3). After the elimination reactions, lots of hydroxyl step, it becomes more complex. At this step, the degradation is
groups still anchor on the polyene molecular chains to form dominated by the chain-scission reactions, side-reactions and
cyclization reactions. A continual degradation of residual
acetate groups is also found.
OH
The acetic acid is generated from the continued degradation
Intramolecular dehydration
of residual acetate groups as described in Scheme 2, while the
acetaldehyde and acetone are attributed to the continual chain-
OH O
scission reaction presented in Schemes 3 and 5. Furan, similar
to the first degradation step, is formed by intramolecular cycli-
Chain-Scission
zations (Scheme 4).
After the first step of degradation, the residuals from elim-
ination reactions mainly include high-molecular-weight poly-
enes, which are further degraded to low-molecular-weight
+ polyenes via chain-scission reactions (Scheme 6). That is
O
why around 16% polyenes are found in the gaseous degrada-
Scheme 4. Formation of furan. tion products (Table 4) and characterization peaks of polyenes
 Z. Peng, L.X. Kong / Polymer Degradation and Stability 92 (2007) 1061e1071 1069

OH OH

OH OH OH

O OH
OH
CHO
+ CH3
OH

O OH
OH
O
H3C CH3 +
+ H3C CH
OH

Scheme 5. Chain-scission reactions.

at 16,400e1660 cm1 are observed in FTIR spectra during the 4. Conclusion

second degradation step (Fig. 3c).
The Py-GC/MS results show that there are quite an amount
of benzenoid derivatives (15.1%) in the degradation products
(Table 4), which is also evidenced by the FTIR/TGA as peaks
at 3050e3100 cm1 and 1610e1630 cm1 corrseponding to
the benzenoid derivatives are observed in the FTIR spectra
(Fig. 3c). These benzenoid derivatives are generated from
the cyclization reactions. DielseAlder reaction was frequently
found in the thermal degradation of polyvinyl chloride (PVC)
[30,31]. As PVA’s molecular structure is very similar to PVC,
that is, they are all linear and aliphatic polymers, the cycliza-
tion reaction of PVA should be the same as PVC (Scheme 7).
Another intramolecular cyclization reaction proposed by
Gilman et al. [21] is also involved (Scheme 8).
Table 4
Identification of degradation products at 530  C for PVA/SiO2 nanocomposite
Retention Compound Molecular Molecular
time (min) formula weight
1.25 Acetaldehyde O 44
H3C CH
The PVA/SiO2 nanocomposite exhibits a significantly im-
proved thermal resistance. In comparison with the pure PVA,
degradation temperatures of the nanocomposite are markedly
higher, while its degradation rates at different degradation
stages, correspondingly, are significantly lower; the thermal
degradation of the nanocomposite possesses higher reaction
energy and reaction order.
Similar to the pure PVA, the thermal degradation of the
PVA/SiO2 nanocomposite can be roughly regarded as a two-
step degradation. However, the introduction of SiO2 into the
PVA matrix leads to a change of degradation mechanism
from that of pure PVA. In the first degradation step, the elim-
ination of H2O and residual acetate groups generates water,
non-conjugated polyenes and acetic acid; as the PVA/SiO2
nanocomposite degrades at a higher temperature, different
from the pure PVA, quite a few chain-scission reactions are
also found in this step in which acetaldehyde, acetone and fu-
Content (%) ran are produced. The reactions in the second degradation step
are dominated by chain-scission reactions. Some side-reac-
24.0 tions such as cyclization reactions and a continual degradation

1.34 Acetone O 58 5.8

H3C C CH3

1.51 Furan 68 5.6

O

1.78 Acetic acid O 60 30.6 Chain-scission +H

H3C C OH

1.92e6.08 Low molecular e e 16.1 H3C

polyenes

4.40e9.98 Benzenoid e e 15.1 + H3C

derivatives
Scheme 6. Chain-scission reaction of polyenes.
1070 Z. Peng, L.X. Kong / Polymer Degradation and Stability 92 (2007) 1061e1071
Diels-Alder Reaction
Aromatization
-4H
Scheme 7. Cyclization reaction I.
Intra-molecular
Cyclization
Aromatization
-2H
Scheme 8. Cyclization reaction II.
of residual acetate groups are also involved. The main degra-
dation products of this step are acetaldehyde, low-molecular-
weight polyenes, benzenoid derivatives, furan, acetone and
acetic acid.
Acknowledgment
We thank Prof. S.D. Li at Guangdong Ocean University,
P.R. China, Prof. H.P. Yu at Agriculture Ministry Key Labora-
tory of Natural Rubber Processing, P.R. China and Dr. P.
Spiridonov in Center for advanced Manufacturing Research
at the University of South Australia for their helpful comments.
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