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www.elsevier.com/locate/polydegstab
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
1062
80
60
40
80
Weight % (%)
Weight % (%)
100
60
40
20
TG
0
200
300
400
500
600
Temperature (C)
-48
Step 1: Tp = 1.09 + 384.6
1063
-38
Step 1
Step 2
-28
-18
-8
2
200
DTG
300
400
500
600
Temperature (C)
20
TG
0
200
300
400
500
600
Temperature (C)
-48
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.
1064
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)
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
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
0.008
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.
1065
OH
OH
OH
Elimination of nH2O
HO
+
HO
H2O
1066
HO
HO
O
O
CH3
CH3
Elimination of H2O
O
H3C
CH3
HO
HO
H2O
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
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.
1068
HO
HO
Chain-Scission
CH
HO
H3C
HO
Chain-Scission
O
H3C
CH
+H
H3C
H3C
OH
Intramolecular dehydration
OH
Chain-Scission
+
O
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
OH
OH
OH
OH
OH
OH
CHO
OH
CH3
OH
OH
OH
H3C
CH
1069
H3C
OH
CH3
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
1070
Diels-Alder Reaction
Aromatization
-4H
Intra-molecular
Cyclization
Aromatization
-2H
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.
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