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 solution-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.
2007 Elsevier Ltd. All rights reserved.
Keywords: Polyvinyl alcohol; Silica; Nanocomposite; Thermal degradation

1. Introduction
The thermal resistance is one of the most dominative properties for polymer materials, as it ultimately governs the mechanical properties, durability, spectral stability, shelf lives,
and life cycles of polymers [1e4]. Once the degradation begins, the above properties will gradually deteriorate.
The widely recognized polymers with inherent thermal resistance 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 incorporating 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.: 86 759 2286933; fax: 86 759 2221586.
E-mail address: zhengpeng8@yahoo.com (Z. Peng).
0141-3910/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2007.02.012

into the polymer chains can enhance the thermal stability of

polymers [6]. By introducing inorganic nano-fillers into polymers, 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 substantial decrease in the degradation rate [9]. Hence, the thermal 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 resistance 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 example, previous work seldom reported the kinetic aspects and

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 approaches to reveal the thermal degradation mechanisms of
the polymer hosts of PINs. Fourier transform infrared/thermogravimetric analysis (FTIR/TGA) allows simultaneous
quantification and identification of evolved degradation products, 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 nanocomposite, 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 recombination, 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 gaseous 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 powerless to identify the low concentration degradation products
due to its inherent limitation of sensibility. Therefore, pyrolysis-gas chromatography/mass spectrometric analysis (Py-GC/
MS) has been used to collect more detailed information for understanding 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 cyclization reactions. Although it has been demonstrated in our
previous work [3,13,23] that SiO2 reinforced PVA nanocomposites 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 envisage a thermal degradation mechanism of PVA/SiO2 nanocomposite 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 process to prepare PVA/SiO2 nanocomposites by combining solution compounding with self-assembly technique. Firstly, the
negatively charged SiO2 nanoparticles act as templates to adsorb positively charged PAH molecular chains through electrostatic 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 nanocomposite films. The key procedure of this process is the encapsulation of the SiO2 nanoparticles with PAH and PVA layers,
aiming at suppressing the self-aggregation of SiO2 nanoparticle 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 measurement 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 under 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 residual 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 degradation 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 chromatograph 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 conducted on TGA analysis. The carrier gas was high-purity nitrogen 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

GCeMS interface was set at 230  C. Mass spectra were

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

There are two distinct and well-separated turns (300e

450  C and 450e550  C) in the thermogravimetric (TG)
curves (Fig. 1a) and two corresponding weight-loss peaks in
derivative thermogravimetric (DTG) curves for the pure PVA
(Fig. 1b). Therefore, the thermal degradation of PVA can be
roughly regarded as a two-step-degradation. Due to the presence of SiO2, the TG/DTG curves of the nanocomposite shift
to higher temperatures (Fig. 2). Therefore, the PVA/SiO2
nanocomposite is more thermally stable than the pure PVA.
Correspondingly, at a given temperature, the degradation rate
of the nanocomposite is significantly lower. Under a given
100

80

60

40

80

Weight % (%)

3.1. Thermal degradation process

Weight % (%)

100

60

40

20
TG
0
200

300

400

500

600

Temperature (C)
-48
Step 1: Tp = 1.09 + 384.6

Derivative Weight % (%/min)

3. Results and discussion

1063

-38

Step 1

Step 2: Tp = 0.75 + 479.3

Step 2

-28

-18

-8

2
200

DTG

300

400

500

600

Temperature (C)
20

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.

TG

0
200

300

400

500

600

Temperature (C)
-48

Derivative Weight % (%/min)

Step 1: Tp = 1.68 + 355.6

Step 2: Tp = 0.64 + 467.8

Step 1

-38

Step 2

-28

-18

-8

2
200

DTG

300

400

500

600

Temperature (C)
Fig. 1. TG (a) and DTG (b) curves of PVA in nitrogen with different heating
rates: B 10  C/min; O 20  C/min; , 30  C/min; > 40  C/min; C 50  C/
min.

heating rate, the TG curve of the nanocomposite is situated

at a higher temperature than that of the pure PVA. Here, we
take one of the most important degradation temperatures, the
peak degradation temperature with maximum weight loss
rate (Tp), as an example to quantitatively investigate the difference in degradation temperatures between pure PVA and
nanocomposite.
As the thermal degradation in this study was conducted with
a temperature-scanning model, the heating rate (b) has a strong
effect on the degradation. To truly identify the difference
between the degradation of pure PVA and PVA/SiO2 nanocomposite, the influence of heating rates was eliminated with a
multi-heating rate method [13,24]. From Figs. 1b and 2b, it was
found that degradation temperature Tp for both PVA and nanocomposite linearly increases with the heating rate.
The linear increase of thermal degradation temperatures
with heating rate is caused by the heat hysteresis, i.e. the inner
part of the samples cannot follow the program temperature
when the temperature increases too fast. Theoretically, the
slower the heating rate, the more accurate the degradation

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

1064

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

min, the equilibrium peak thermal degradation temperature
(Tp ) can be identified from equations in Figs. 1b and 2b.
The Tp of the PVA/SiO2 nanocomposite increase to 29.0  C
which is 11.5  C over the pure PVA at the first and second degradation steps, respectively.
In addition to the increase of thermal degradation temperatures, the difference in the degradation process between the
pure PVA and nanocomposite is also obviously observed in
the DTG curves (Figs. 1b and 2b). Due to the improvement
in thermal resistance, the whole degradation process of the
nanocomposite is protracted, which is confirmed by the
DTG curves where the degradation peak of nanocomposite
is obviously wider than that of pure PVA. More importantly,
there is a significant change in the shape of the degradation
peak of DTG. There are two obvious degradation peaks (a
side peak accompanies the main peak) in the first degradation
step of the nanocomposite, while there is only one degradation
peak for the pure PVA (Figs. 1b and 2b). According to others
work [20e22], at the first degradation step, the thermal degradation of PVA mainly involves the elimination reactions, and
correspondingly there is only one peak in the DTG curve.
The split of the first degradation peak in TG/DTG curves implies that the degradation mechanism of the nanocomposite
differs from that of pure PVA. The side peak at lower temperature can be caused by the elimination reactions, while the
main peak can be the overlap of the continual eliminations
and chain-scission reactions which need more energy and
occur at a higher temperature.
3.2. Thermal degradation kinetics
The kinetic analysis provides information on the energy
barriers of the process and clues to the degradation mechanism
for polymers. The challenge for the study of thermal
degradation kinetics is to find a reliable approach. As singleheating-rate methods have identified shortcomings [25], multiheating-rate methods have been extensively used to study the
thermal degradation kinetics for polymers due to their reliability [14,26]. In this study, CoatseRedfern model [24] based on
the multi-heating rate method is employed to obtain reliable
kinetic information on the thermal degradation of PVA/SiO2
nanocomposite and pure PVA.
The reaction kinetic parameters are obtained by processing
TG data in Figs. 1a and 2a. By integrating the reaction kinetic
equation
da=dt k1  a

and Arrhenius equation,

k Ae

E=RT

and




1  a
1  2RT=EAR
E
n 1


ln
ln  ln
T2
bE
RT

where n is the reaction order, a the reaction degree, T the absolute temperature, b the heating rate, E the reaction activation
energy, R the gas constant and A the frequency factor. When
n s 1, a line can be obtained from the plot of ln1
1  a1n =T 2 1  n versus 1/T, where the slope is E=R,
and the intercept is ln1  2RT=EAR=bE. When n 1,
a line can be obtained from the plot of lnln1  a=T 2  versus 1/T, of which the slope is E=R, and the intercept is
ln1  2RT=EAR=bE. Adopting the least square fitting
method with different n, the n with maximum correlation coefficient (r) is the apparent reaction order, and the corresponding E is the reaction activation energy.
Table 1 lists various kinetic parameters of the first thermal
degradation step for both PVA and nanocomposite. At the first
degradation step, the average value of n of PVA is 3.6, which
is 0.8 lower than that of the nanocomposite. The reaction activation energy increases with the heating rate. Using the leastsquare linear regression method, E of the pure PVA and the
nanocomposite can be described as E 0.66 b 129.9 and
E 0.70 b 135.6, respectively. Eliminating the influence
of heating rates, i.e. b 0  C/min, the apparent reaction activation energy (E0) for the pure PVA is 129.9 kJ/mol, and
135.1 kJ/mol for the nanocomposite, respectively. At the second thermal degradation step, the average value of n for
both PVA and nanocomposite are 1.6 and 2.6, correspondingly. The E for PVA and nanocomposite are E 1.24
b 145.6 and E 1.02 b 156.4, respectively (Table 2).
With the addition of SiO2, the thermal degradation mechanism tends to be more complex, the n for the nanocomposite
is, therefore, higher than that of the pure PVA. Due to the retardant effect of PVA/SiO2 char, the nanocomposite, compared
to the pure PVA, is more difficult to be degraded, and more reaction activation energy is required during the reaction
process.
The enhanced thermal resistance attributes to the introduction of SiO2 nanoparticles. As illustrated in our previous work
[3,13,23], when 5 wt% SiO2 is added to PVA, SiO2 nanoparticles are homogenously distributed throughout the PVA matrix as nano-clusters with an average size less than 30 nm.
Because the size of SiO2 clusters is far below 100 nm, these
SiO2 nano-clusters with a huge relative surface area and great
potential energy strongly interact with the PVA molecular
Table 1
Kinetic parameters of the first thermal degradation step
B ( C/min)

the following CoatseRedfern equations [24] can be obtained:



1n
1  1  a
1  2RT=EAR
E
ln
ns1
3
ln

bE
RT
T 2 1  n

10
20
30
40
50

PVA

Nanocomposite

E (kJ/mol)

E (kJ/mol)

3.4
3.6
3.6
3.7
3.6

131.5
147.0
153.7
155.5
160.0

4.6
4.4
4.3
4.2
4.6

140.3
151.3
157.0
166.5
167.5

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

Table 2
Kinetic parameters of the second thermal degradation step
B ( C/min)

10
20
30
40
50

PVA

3.5

Nanocomposite

E (kJ/mol)

E (kJ/mol)

1.6
1.4
1.6
1.6
1.7

163
167.0
176.7
198.7
209.3

2.3
2.8
2.8
2.9
2.2

169.8
174.6
184.7
200.2
209.1

2.5

1.5

0.5

-0.5

chains through various effects, such as branching effect, nucleation, size and surface effects. Thus, the diffusion of decomposition products from the bulk polymer to gas phase is slowed
down. Consequently, the nanocomposite has a pronounced improvement in thermal resistance compared to the pure PVA.
Another reason for this enhancement is the formation of
PVA/SiO2 char. While being heated, the SiO2 nanoparticles,
due to their relatively low surface potential energy, migrate
to the surface of the composites to form a SiO2/PVA char,
which acts as a heating barrier to protect the PVA inside. Similarly, Gilman et al. [12] and Vyazovkin and Sbirrazzuoli [25]
observed that a clay/polymer char greatly enhances the thermal resistance of host polymers.
However, the above theories seem somewhat weak to explain why and how the PVA/SiO2 nanocomposite has much
better thermal resistance than the pure PVA. To give a more
illustrative insight into the thermal degradation, the degradation chemistry was studied by identifying degradation
products.

4000

3500

3000

2500

2000

1500

1000

3500

3000

2500

2000

1500

1000

3500

3000

2500

2000

1500

1000

Absorbance

0.060

0.040

0.020

0.000
4000
0.024

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/
TGA and Py-GC/MS from two degradation steps as described
in Section 2.

0.000
4000

Wavenumber (cm-1)
Fig. 3. FTIR spectra of degradation products at different temperatures: (a)
110  C; (b) 350  C; (c) 470  C.

3.3.1. The first degradation step

Elimination reactions: The elimination reactions of linear
and aliphatic polymers including polyvinyl chloride (PVC)
OH
OH

1065

OH

OH

OH

Elimination of nH2O

HO

Scheme 1. Elimination reaction of H2O.

+
HO

H2O

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

1066

HO

HO

O
O

CH3

CH3

Elimination of H2O

Elimination of acetate groups

O
H3C

CH3

HO

HO

H2O

Scheme 2. Dehydration and eliminations of residual acetate groups.

and PVA in the first stage of thermal degradation mainly form

polyene structures via dehydrochlorination [27,28] or dehydration [20e22]. Therefore, dehydration should be one of the major reactions involved in the first degradation step of the PVA/
SiO2 nanocomposite, which well explains why a big amount of
water is present in the FTIR/TGA analysis during the first degradation step of the nanocomposite (Fig. 3). Theoretically, if
a high-hydrolyzed PVA is employed, the dehydration of
PVA/SiO2 nanocomposite should generate two polyene structures: conjugated polyenes and non-conjugated polyenes
(Scheme 1).
However, as the present study employs a low hydrolyzed
(86.7e88.7%) PVA and a big amount of acetate groups remain
in PVA molecular chains, the eliminations of the PVA/SiO2
nanocomposite should occur in the form of Scheme 2, where
the elimination of H2O and residual acetate groups occurs simultaneously as the acetate groups are randomly inserted between hydroxyl groups. Therefore, in addition to water, a big

Table 3
Identification of degradation products at 330  C for PVA/SiO2 nanocomposite
Retention
time (min)

Compound

1.35

Acetaldehyde

Molecular
formula
O
H3C

Molecular
weight

Content (%)

44

18.0

58

3.1

68

2.3

60

64.1

8.0

CH
O

1.52

Acetone

1.74

Furan

H3C

CH3

1.82e2.05

Acetic acid
H3C

44.87

Polyenes

OH

amount of acetic acid is also observed during the first degradation step. This is testified by the FTIR/TGA spectra (Fig. 3b)
where narrow and acute peaks at 3550 cm1 and 1760 cm1
belong to the stretching vibration peaks of OeH and C]O
of gaseous acetic acids [13], respectively. Another evidence
is given by Py-GC/MS analysis, as Table 3 indicates that the
content of acetic acid accounts for more than 64% of the gaseous degradation products.
The high-molecular-weight polyenes presented in Scheme
2 do not appear in the FTIR/TGA (Fig. 3b) and Py-GC/MS
spectra (Fig. 4), due to their relatively high-molecular weights.
The degradation temperature of the first degradation step is not
high enough to break all the backbone chains of these polyenes into low-molecular-weight polyenes. Most of these polyene structures will act as intermediate products and be further
degraded into other products with lower molecular weights at
the next degradation step. Therefore, only a small amount of
low-molecular-weight polyenes is observed in the MS spectra
(Table 3).
As the hydroxyl group is protonated under acidic conditions to form a substituent, namely eOH
2 , that in turn gives
rise to a more favourable leaving group, i.e. H2O, the first
stage of PVA degradation can be catalyzed by acetic acid.
From this point of view, the highly hydrolyzed PVA has better
thermal stability than PVA with a low degree of hydrolysis,
and the addition of a compound with basic groups seems to
be suitable for improving the thermal stability.
Chain-scission reactions: Gilman et al. [21] and Alexy et al.
[20] found that the first degradation step of PVA mainly contains the elimination reactions. In this study, it is however
found that the chain-scission reactions are also intensively involved at this stage when SiO2 nanoparticles are introduced
into PVA host. That is why the DTG curves of the first degradation of nanocomposite present two degradation peaks
(Fig. 2b). The first one occurs at lower temperatures and corresponds to elimination reactions, while the other one at higher

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

650000

1067

1.35

550000
450000

1.82
1.95

350000
250000

1.15

1.52

2.05
1.60 1.74

150000
1.20
120000

1.60

2.00

2.40

2.80

44

100000
80000
60000
40000
20000

28

34

20
16000

94

78

40
40

60

80

100

43

12000
8000
58

4000
34 37 39

28
20
200000
170000

46

55

64

40

66

77

60

80

29

44

140000
110000
80000
50000

26

20000

31

42
40
40

33
30

13000

46

55

51
50

64

78
70

60

41

10000
70

7000
4000

27
20

65000

50

32 36

1000

81

57

40

60

94
80

100

45

60

50000
35000
20000
29

5000
20

68

52
40

60

105

78
80

100

122
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.

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

1068

HO

HO

Chain-Scission

CH
HO

H3C
HO

Chain-Scission
O

H3C

CH

+H
H3C

H3C

Scheme 3. Chain-scission reactions in the first degradation step.

temperature corresponding to the overlap of elimination and

chain-scission reactions. As the introduction of SiO2 nanoparticles greatly improves the thermal resistance of the nanocomposite, the first thermal degradation step of the nanocomposite
occurs at a higher temperature (Figs. 1 and 2), which enables
the chain-scission reactions.
Tsuchiya and Sumi [29] reported that the dehydration of
PVA leads to the formation of the conjugated polyene structures. However, we believe that the conjugated and nonconjugated polyenes are simultaneously formed during the
degradation of PVA/SiO2 nanocomposite (Scheme 2). At the
temperatures of first degradation step, the conjugated polyenes
are unlikely to be degraded due to their relatively stable structures, which are highly regular. However, the non-conjugated
polyenes seem to be more likely degraded under this condition
(Scheme 3). After the elimination reactions, lots of hydroxyl
groups still anchor on the polyene molecular chains to form

OH
Intramolecular dehydration

OH
Chain-Scission

+
O

Scheme 4. Formation of furan.

non-conjugated polyene structures. These hydroxyl groups destroy the structural regularity of polyenes and act as weak
links, from where the non-conjugated polyenes can be snipped
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
(Table 3).
Gilman et al. [21] proposed similar conjugated and nonconjugated polyene structures, and described the degradation
mechanism of non-conjugated polyenes into cis and trans
methyl-terminated polyenes via chain-scission reaction. However, we envisage a different mechanism in the chain scission
of the nanocomposite at the first degradation step (Scheme 3).
The non-conjugated polyenes are not directly degraded into
low-molecular-weight polyenes, but form some intermediates:
methyl-terminated non-conjugated polyenes and carbonyl-terminated 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 characteristic peak of methyl terminal group around 1370 cm1 is
clearly observed in the FTIR spectra of degradation products
(Fig. 3b and c).
Other subsidiary reactions also contribute to the chain scission. The appearance of a small amount of furan in the gaseous
degradation products (Fig. 4e) can be explained by the formation of furan rings via intramolecular cyclizations. The dehydration reaction of two intramolecular hydroxyl groups
proceeds under the catalysis of acetate acid produced by the
elimination of residual acetate groups (Scheme 4). As forementioned reason, the first degradation step of the nanocomposite occurs at relatively high temperatures, some of the
chain scissions occur at the position of ortho-diol. This chain
scission will generate some acetaldehyde and acetone structures as indicated in Scheme 5.
3.3.2. The second degradation step
The degradation products of the second degradation step are
acetaldehyde, acetic acid, polyenes, benzenoid derivatives and
a small amount of furan (Table 4). As the second step of thermal
degradation occurs at higher temperatures compared to the first
step, it becomes more complex. At this step, the degradation is
dominated by the chain-scission reactions, side-reactions and
cyclization reactions. A continual degradation of residual
acetate groups is also found.
The acetic acid is generated from the continued degradation
of residual acetate groups as described in Scheme 2, while the
acetaldehyde and acetone are attributed to the continual chainscission reaction presented in Schemes 3 and 5. Furan, similar
to the first degradation step, is formed by intramolecular cyclizations (Scheme 4).
After the first step of degradation, the residuals from elimination reactions mainly include high-molecular-weight polyenes, which are further degraded to low-molecular-weight
polyenes via chain-scission reactions (Scheme 6). That is
why around 16% polyenes are found in the gaseous degradation products (Table 4) and characterization peaks of polyenes

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

OH
OH

OH
OH

OH

OH
CHO
OH

CH3

OH

OH

OH
H3C

CH

1069

H3C

OH
CH3

Scheme 5. Chain-scission reactions.

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

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 PVAs molecular structure is very similar to PVC,
that is, they are all linear and aliphatic polymers, the cyclization 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
time (min)

Compound

1.25

Acetaldehyde

Molecular
formula
O
H3C

1.34

H3C

1.51

Content (%)

44

24.0

58

5.8

68

5.6

60

30.6

CH
O

Acetone

Molecular
weight

4. Conclusion
The PVA/SiO2 nanocomposite exhibits a significantly improved 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 twostep 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 elimination 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 furan are produced. The reactions in the second degradation step
are dominated by chain-scission reactions. Some side-reactions such as cyclization reactions and a continual degradation

CH3

Furan
O

1.78

Acetic acid
H3C

Chain-scission

+H

OH

1.92e6.08

Low molecular
polyenes

16.1

4.40e9.98

Benzenoid
derivatives

15.1

H3C
+

H3C

Scheme 6. Chain-scission reaction of polyenes.

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

1070

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 degradation products of this step are acetaldehyde, low-molecularweight 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 Laboratory 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.
References
[1] Cho HJ, Jung BJ, Cho NS, Lee J, Shim HK. Synthesis and characterization of thermally stable blue-light-emitting polyfluorenes containing
siloxane bridges. Macromolecules 2003;36:6704.
[2] Jin JY, Smith DW, Topping CM, Suresh S, Chen SR, Foulger SH, et al.
Synthesis and characterization of phenylphosphine oxide containing perfluorocyclobutyl aromatic ether polymers for potential space applications. Macromolecules 2003;36:9000.
[3] Peng Z, Kong LX, Li SD, Spiridonov P. Polyvinyl alcohol/silica nanocomposite: its morphology and thermal degradation kinetics. Journal of
Nanoscience and Nanotechnology 2006;12:3934.
[4] Xia R, Heliotis G, Campoy-Quiles M, Stavrinou PN, Bradley DDC,
Vak D, et al. Characterization of a high-thermal-stability spiroanthracenefluorene-based blue-light-emitting polymer optical gain medium. Journal of Applied Physics 2005;98. Art. No. 083101.

[5] Zhang HQ, Farris RJ, Westmoreland PR. Low flammability and thermal
decomposition behavior of poly(3,30 -dihydroxybiphenylisophthalamide)
and its derivatives. Macromolecules 2003;36:3944.
[6] Lin SH, Li FM, Cheng SZD, Harris FW. Organo-soluble polyimides:
Synthesis and polymerization of 2,20 -bis(trifluoromethyl)-4,40 ,5,50 -biphenyltetracarboxylic dianhydride. Macromolecules 1998;31:2080.
[7] Ji XL, Hampsey JE, Hu QY, He JB, Yang ZZ, Lu YF. Mesoporous silicareinforced polymer nanocomposites. Chemistry of Materials 2003;15:
3656.
[8] Tsai TY, Li CH, Chang CH, Cheng WH, Hwang CL, Wu RJ. Preparation
of exfoliated polyester/clay nanocomposites. Advanced Materials
2005;17:1769.
[9] Kong LX, Peng Z, Li SD, Bartold PM. Nanotechnology and its role in
the management of periodontal diseases. Periodontology 2000
2006;40:184.
[10] Vyazovkin S, Dranca I, Fan XW, Advincula R. Kinetics of the thermal
and thermo-oxidative degradation of a polystyrene-clay nanocomposite.
Macromolecular Rapid Communications 2004;25:498.
[11] Choi J, Kim SG, Laine RM. Organic/inorganic hybrid epoxy nanocomposites from aminophenylsilsesquioxanes. Macromolecules 2004;37:99.
[12] Gilman JW, Jackson CL, Morgan AB, Harris R, Manias E, Giannelis EP,
et al. Flammability properties of polymer-layered-silicate nanocomposites, polypropylene and polystyrene nanocomposites. Chemistry of Materials 2000;12:1866.
[13] Peng Z, Kong LX, Li SD. Thermal properties and morphology of poly
(vinyl alcohol)/silica nanocomposite prepared with self-assembled monolayer technique. Journal of Applied Polymer Science 2005;96:1436.
[14] Vyazovkin S. Modification of the integral isoconversional method to account for variation in the activation energy. Journal of Computational
Chemistry 2001;22:178.
[15] Li SD, Peng Z, Kong LX, Zhong JP. Thermal degradation kinetics and
morphology of natural rubber/silica nanocomposites. Journal of Nanoscience and Nanotechnology 2006;6:541.
[16] Zhu J, Morgan AB, Lamelas FJ, Wilkie CA. Fire properties of polystyreneeclay nanocomposites. Chemistry of Materials 2001;13:3774.
[17] Jang BN, Wilkie CA. The effects of clay on the thermal degradation
behavior of poly(styrene-co-acrylonitirile). Polymer 2005;46:9702.
[18] Sundarrajan S, Surianarayanan M, Srinivasan KSV, Kishore K. Thermal
degradation processes in polysulfide copolymers investigated by direct
pyrolysis mass spectrometry and flash pyrolysis-gas chromatography/
mass spectrometry. Macromolecules 2002;35:3331.
[19] Chen K, Susner MA, Vyazovkin S. Effect of the brush structure on the
degradation mechanism of polystyreneeclay nanocomposites. Macromolecular Rapid Communications 2005;26:690.
[20] Alexy P, Bakos D, Crkonova G, Kolomaznik K, Krsiak M. Blends of
polyvinylalcohol with collagen hydrolysate thermal degradation and
processing properties. Macromolecular Symposia 2001;170:41.
[21] Gilman JW, VanderHart DL, Kashiwagi T. In: Nelson GL, editor. Fire
and Polymers II: Materials and tests for hazard prevention. Washington,
DC: American Chemical Society; 1994. p. 161.
[22] Zhao WW, Yamamoto Y, Tagawa S. Radiation effects on the thermal
degradation of poly(vinyl chloride) and poly(vinyl alcohol). Journal of
Polymer Science Part A Polymer Chemistry 1998;36:3089.
[23] Peng Z, Kong LX, Li SD. Non-isothermal crystallisation kinetics of selfassembled polyvinylalcohol/silica nano-composite. Polymer 2005;
46:1949.
[24] Peng Z, Li SD, Huang MF, Xu K. Thermogravimetric analysis of methyl
methacrylate-graft-natural rubber. Journal of Applied Polymer Science
2002;85:2952.
[25] Vyazovkin S, Sbirrazzuoli N. Kinetic methods to study isothermal and
nonisothermal epoxyanhydride cure. Macromolecular Chemistry and
Physics 1999;200:2294.
[26] Brown ME, Maciejewski M, Vyazovkin S, Nomen R, Sempere J,
Burnham A, et al. Computational aspects of kinetic analysis. Part A:
The ICTAC kinetics project-data, methods and results. Thermochimica
Acta 2000;355:125.
[27] Millan JL, Martinez G, GomezElvira JM, Guarrotxena N, Tiemblo P. Influence of tacticity on the thermal degradation of PVC. 8.

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

A comprehensive study of the local isotactic GTTG() conformation
dependence of the mechanism of initiation. Polymer 1996;37:219e30.
[28] Starnes WH, Wallach JA, Yao HY. Six-center concerted mechanism for
poly(vinyl chloride) dehydrochlorination. Requiescat in pace? Macromolecules 1996;29:7631e3.
[29] Tsuchiya Y, Sumi K. Thermal decomposition products of poly(vinyl alcohol).
Journal of Polymer Science Part A-1: Polymer Chemistry 1969;7:3151.

1071

[30] Garrigues C, Guyot A, Tran VH. Thermal dehydrochlorination

and stabilization of polyvinylchloride in solution. 9. Dialkyltin
maleates e DielseAlder reaction. Polymer Degradation and Stability
1994;43:307.
[31] German K, Kulesza K. The effect of poly(ethylene terephthalate) and
polyethylene as admixtures in, on dehydrochlorination of, poly(vinyl
chloride). Polimery 1999;44:548.