Polymer Degradation and Stability 72 (2001) 423439

www.elsevier.nl/locate/polydegstab

Studies on the thermal stability of natural rubber/polystyrene

interpenetrating polymer networks: thermogravimetric analysis
Aji P. Mathew a, S. Packirisamy b, Sabu Thomas a,*
a

School of Chemical Sciences, Priyadarshini hills PO, Mahatma Gandhi University, Kottayam 686 560, Kerala, India
b
PSC Division, VSSC, Thiruvananthapuram-22, India
Received 3 October 2000; accepted 14 November 2000

Abstract
The thermal degradation of natural rubber/polystyrene (NR/PS) interpenetrating polymer networks (IPNs) was studied and the
eects of blend ratio, crosslink level and initiating system were analysed. The thermogravimetric analysis (TGA) shows that the
IPNs are more stable than the pure components. The full-IPNs have better stability than semi-IPNs which is due to higher entanglement density of full-IPNs. The initial decomposition temperature and temperature for 50% decomposition (T50) increase with
increase in concentration and crosslinker level of the plastic phase. The kinetics of degradation were analysed using nine mechanistic equations. The kinetic parameters such as activation energy, Arrhenius parameter and entropy of activation were determined.
Thermal ageing studies of the samples were also conducted. The IPNs aged for 72 h at 100
C showed enhanced mechanical strength
due to crosslinking on post curing. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Thermal degradation; Interpenetrating polymer networks; Natural rubber; Polystyrene

1. Introduction
Blending of existing polymers is an important way of
getting new commercially useful materials having desired
properties [13]. Interpenetrating polymer networks are
a relatively new class of polymer blends where one/both
phases are crosslinked [46]. When one of the phases is
crosslinked pseudo or semi-IPNs will be formed [7,8].
When both phases are crosslinked full-IPNs are developed [9,10]. The IPNs are generally prepared by sequential, simultaneous or latex polymerisation techniques
[1113]. The properties of the nal product are dependent on phase behaviour, blend ratio and crosslinking
levels [14,15].
In recent years considerable progress has been made
towards a better understanding of the factors involved
in the miscibility of IPNs. The measurement of glass
transition temperature (Tg) is an important and convenient tool for miscibility studies [16,17]. A miscible
system exhibits a single and sharp glass transition

* Corresponding author. Tel.: +91-481-598303; fax: +91-481561190.

E-mail address: sabuthom@vsnl.com (S. Thomas).

temperature intermediate between the component polymers [18]. In heterogeneous system, Tgs of the individual
polymers will be present, though some shifting and
broadening are very often observed [19].
Usually ordinary blends exhibit phase separation to a
greater or lesser degree [20,21]. Through IPN synthesis
two crosslinked polymers are intimately and eectively
blended and a wide range of properties with controlled
morphology is obtained. Miscibility studies of IPNs are
of great interest since IPN synthesis is aimed at making
the system more miscible compared to ordinary blends,
grafts, blocks, etc.
Thermogravimetric analysis has proved to be a highly
successful technique for determining the thermal stability of polymeric systems. A knowledge of degradation
and mode of decomposition under the inuence of heat
is highly recommendable in the processing and fabrication procedures. The threshold decomposition temperature indicates the highest fabrication temperature. The
thermal stability of individual polymers can be manipulated to a great extent by blending with other polymers.
Interpenetrating networks, regardless of composition
have better thermal properties than corresponding
homopolymers [22,23]. This is usually, attributed to the
networking of the phases.

0141-3910/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(01)00042-8

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

The inuence of crosslink density on poly(ether urethane)/poly(ethyl methacrylate) IPNs was studied by
Hourston and Schafer [24]. TGA studies revealed
improved thermal properties for the IPNs with higher
crosslink density in the PUR network. IPNs based on
castor oil polyurethane (hydroxy ethyl methacrylate)
were characterised by Nayak et al. [25]. They found that
there is a rapid weight loss from 10 to 90% in the temperature range of 400500
C in these IPNs. In this
laboratory we have studied the thermal degradation
behaviour of dierent polymeric systems earlier [2628].
The useful properties of a material gradually deteriorate under the inuence of temperature. The eect of heat
on the performance of polymeric system can be studied
by thermal ageing. During ageing, scission of the main
chain, crosslink formation or crosslink breakage can take
place [29]. Sometimes existing crosslinks may be replaced
by new more stable crosslinks. All these factors contribute to the properties of the aged samples.
In the present paper, the thermal stability of the IPNs
from NR/PS was studied using thermogravimetric analysis. The eects of composition, crosslink density and
initiating system on thermal stability of IPNs were
investigated. The kinetic parameters like activation
energy, entropy of degradation and Arrhenius parameters of NR/PS IPN degradation were determined. The
eects of thermal ageing on the mechanical performance
of the samples are also examined by tensile strength
measurements. For this, samples aged in air ovens were
used.

2. Experimental
2.1. Materials used
2.1.1. Natural rubber
Natural rubber was of ISNR-5 grade, supplied by
Rubber Research Institute of India (RRII). Its physical
characteristics are given in Table 1.
2.1.2. Styrene monomer
Styrene monomer for IPN synthesis was supplied by
Merck, India. The monomer was made inhibitor free by
washing it with 1% NaOH and was dried before use.

Table 1
Characteristics of NR
Property

Isnr-5

Glass transition temperature ( C)

Density (g/cm3)
Solubility parameter (Jm3)1=2
Volatile matter (% ) max
Ash (%) max

72
0.97
16.2
0.50
0.40

2.1.3. Dicumyl peroxide

Dicumyl peroxide (40% active) was used as the vulcanising agent for rubber and as the initiator for the
polymerisation of styrene. It was supplied by Kishore
Rubber Products Pvt. Ltd, Pune.
2.1.4. Benzoyl peroxide
Benzoyl peroxide was obtained from BDH, India and
was used as initiator for styrene.
2.1.5. Azobis-iso-butyronitrile
AIBN was obtained from Sigma, India and was used
as the initiator.
2.1.6. Divinyl benzene (DVB)
Divinyl benzene was used as crosslinking agent for
styrene. It was supplied by E. Merck, Germany.
2.2. IPN preparation
The IPN was prepared by the sequential technique in
which NR is rst crosslinked using DCP followed by the
polymerisation and crosslinking of PS phase.
2.2.1. Crosslinking of NR phase
Natural rubber was masticated in a two roll mixing
mill at room temperature. Dicumyl peroxide (4 phr) was
added and mixed well with the rubber. The rheograph
of the mix was taken on a Monsanto Rheometer and the
optimum cure time was determined. The mix was vulcanised at 160
C on a hydraulic press to get crosslinked
NR sheet. Dierent series of IPNs were prepared using
dierent initiators.
2.2.2. Crosslinking of PS phase
The vulcanised NR sheets were weighed and kept
immersed in inhibitor free styrene monomer containing
initiator and 0, 2, 4 and 6% of divinyl benzene which
acts as crosslinker for PS phase. The NR sheets were
swollen to dierent time intervals to obtain varying
weight percentages of PS. The swollen samples were
kept at 0
C for few hours to achieve equilibrium distribution of styrene monomer in the matrix. The swollen
networks were heated at 80
C for 6 h and at 100
C for 2
h to complete the polymerisation and crosslinking of
styrene monomer. For the polymerisation of styrene
during IPN synthesis three dierent initiating systems
viz. 1% benzoyl peroxide, 1% dicumyl peroxide and
0.5% azo-bis-isobutyronitrile were used.
The hardened sheets, in all cases, were then kept in air
oven to eliminate unreacted styrene. The nal weight of
the sample was taken and the composition calculated.
In all the three series, NR/PS semi- and full-IPNs with
PS content up to 70% were prepared. A schematic
representation of the synthesis of semi- and full-IPNs is
given in Fig. 1.

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

Fig. 1. Schematic representation of the synthesis of semi- and full-IPNs.

biu

The IPNs are coded based on composition, initiating

system of PS and crosslinker content. The DCP, BPO
and AIBN initiated system are denoted by D, B and A
series, respectively. The DVB content was varied in
order to have varying levels of crosslinking. The blend
composition is denoted as N30, N50 and N70, where the
subscripts indicate the weight percentage of rubber. The
codings are given in Table 2.

where Mc is the molecular weight between crosslinks,

and


Mc p n 1=3 = ln1    2
2
where n is the molar volume of the solvent; p , the
density of the polymer; , the interaction parameter;
and , the volume fraction of the swollen sample.  is
given by the equation,

2.3. Crosslink density

The crosslink density was determined by the swelling
method using the equation [30],

v 1=2Mc



2
Vs
s  p
RT

where  is the lattice constant; Vs is the molar volume of

the solvent; s and p are the solubility parameters of the
solvent and polymer, respectively; R, the gas constant;

Table 2
Nomenclature of IPNs
Sample code

Initiator

NR/PS ratio

DVB content

A0N30, A0N50, A0N70

A1N30, A1N50, A1N70
A2N30, A2N50, A2N70
A3N30, A3N50, A3N70

0.5% (azo-bis-isobutyronitrile)
0.5% (azo-bis-isobutyronitrile)
0.5% (azo-bis-isobutyronitrile)
0.5% (azo-bis-isobutyronitrile)

30/70, 50/50, 70/30

30/70, 50/50, 70/30
30/70, 50/50, 70/30
30/70, 50/50, 70/30

0%
2%
4%
6%

B0N30,
B1N30,
B2N30,
B3N30,

B0N50, B0N70
B1N50, B1N70
B2N50, B2N70
B3N50, B3N70

1% (benzoyl peroxide)
1% (benzoyl peroxide)
1% (benzoyl peroxide)
1% (benzoyl peroxide)

30/70, 50/50, 70/30

30/70, 50/50, 70/30
30/70, 50/50, 70/30
30/70, 50/50, 70/30

0%
2%
4%
6%

D0N30,
D1N30,
D2N30,
D3N30,

D0N50, D0N70
D1N50, D1N70
D2N50, D2N70
D3N50, D3N70

1% (dicumyl peroxide)
1% (dicumyl peroxide)
1% (dicumyl peroxide)
1% (dicumyl peroxide)

30/70, 50/50, 70/30

30/70, 50/50, 70/30
30/70, 50/50, 70/30
30/70, 50/50, 70/30

0%
2%
4%
6%

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

and T, the absolute temperature. The value of  was

taken as 0.34.
The swelling of IPNs was carried out in toluene and
the crosslink density determined.

Between 200 and 300
C the molecular weight of

polystyrene drops, but no volatile products are given
out. Random scission of polymer chains occurs below
300
C in the following manner [35].

2.4. Scanning electron microscopy

The phase morphology of cryogenically fractured IPN
specimens was examined using a scanning electron
microscope. The fractured specimen was coated with
gold before examination. The samples were prepared for
the SEM analysis by the ebonite method [31].
2.5. Thermogravimetric analysis (TGA)
A Perkin-Elmer delta series TGA-7 was used for the
thermogravimetric analysis of the IPN samples. A small
amount (13 mg) of sample was taken for the analysis
and the samples heated from 40 to 500
C at a rate of
10
C/min in nitrogen. The TGA and DTG curves are
drawn for each sample.
2.6. Ageing studies
The dumbbell shaped tensile pieces from IPN sheets
were kept in an air oven for 72 h or 120 h at 100
C. The
aged samples were tested on a universal testing machine.
The strength values are compared with unaged samples.

3. Results and discussion

3.1. Thermogravimetric analysis
The TGA and DTG curves of vulcanised NR and pure
uncrosslinked PS are given in Figs. 2 and 3, respectively.
Dicumyl peroxide vulcanised NR starts degradation at
290
C and 67% residue remains at 396
C. In the case of
NR, below 250
C there is no degradation. In the temperature range of 250400
C about 85% of the material
is degraded. During this stage weight loss and volatilisation of degradation products take place rapidly.
Beyond 400
C the weight loss is about 67%.
According to Bolland and Orr in the temperature
range 200270
C, both scission and crosslinking occur
though no loss of unsaturation of the bulk rubber
occurs [32]. Madorsky and coworkers reported that NR
undergo thermal degradation in the temperature range
of 287400
C to give 39% isoprene, 13.2% dipentene
and small amounts of p-menthene [33,34]. In the temperature range 450800
C, dipentene is the major degradation product and isoprene is the major degradation
product in the temperature range 675800
C. In our case
at 300
C 67% weight loss is observed and at 400
C,
96% weight loss is observed. In the DTG curve the
major peak is at 364
C.

Literature shows that below 300
C no volatile product are formed and (A) and (B) undergo cage disproportionation to give (C) and (D) which are stable up
to 300
C. Polystyrene degrades into a mixture of styrene
(40%), toluene (2.4%), methyl styrene, etc. above 300
C
[36]. From Fig. 3 it was observed that polystyrene degradation occurs in a single step. The TGA curve shows that
PS is stable up to 250
C and after that degradation
occurs rapidly. The degradation starts at about 276

and at 385
C almost 96% degradation is complete.
Above 430
C no residue remains. The major peak in the
DTG curve is at 360
C. This corresponds to the chain
scission to give monomer along with some amount of
dimer, trimer, tetramer and pentamer.
Though the homopolymers degrade in this manner,
they behave in a slightly dierent way in the IPN system. NR is in the crosslinked stage and PS is crosslinked
or linear depending on whether it is a full or semi-IPN.
It could be seen that vulcanised NR and pure PS have
almost the same thermal stability which is clear from the
DTG peaks (Figs. 2 and 3). They both degrade in the
temperature range of 300400
C.
It can be seen that the chemical structure of NR and
PS consists of CClinkages alone. During vulcanisation of NR using dicumyl peroxide and polymerisation
and crosslinking of PS the crosslinks formed are also
CC linkages. The CC bond length is 1.54 A and
bond energy is 20.3 kJ/mol. The dierences in degradation behaviour in dierent IPNs are therefore dependent
on crosslinking level, blend ratio and initiating system,
rather than on the nature of linkages present. The
presence of interfacial crosslinks between NR and PS
phases also cannot be ruled out.
In the case of IPNs in the temperature range of 200
300
C there is no appreciable weight loss (Table 3).
Therefore, the IPNs are more resistant to thermal degradation compared to the component homopolymers.
However, the degradation behaviour varies from semi
and full-IPNs and is dependent on blend ratio, crosslink
density, etc. In semi-IPNs at 300
C, 1.54% weight loss

A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

Fig. 2. TGA and DTG curves of vulcanised NR.

Fig. 3. TGA and DTG curves of pure PS.

427

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

is observed and at 400
C the weight loss increases

dramatically. When we consider the eect of blend ratio
on thermal degradation it was observed that in B0N70
and B0N50 samples the weight loss is 6364% and for
B0N30 samples the weight loss is 48% at 400
C. The
TGA and DTG curves of B0N30, B0N50 and B0N70
samples are given in Figs. 46 respectively. The low
weight loss of N30 samples at 400
C denotes an increase
in thermal stability upon the addition of PS to NR. In
the case of full-IPNs the weight loss in the temperature
Table 3
Thermal degradation of IPNs at dierent temperatures
Sample
code

Percentage weight loss at

Crosslink
density104 (gmol/cc)

200 C

300 C

400 C

450 C

N0
N100

1
2.1

13.3
6.45

95
96.4

0.94

B0N30
B0N50
B0N70

0.5
0.7
0.28

3
3.5
1.42

48.8
64.2
62.5

93
91.6
91.1

7.06
5.54
3.24

D0N50
D1N50
D2N30
D2N50
D2N70
D3N50
B2N30

1
1.3
1.0
0.5
2.0
1.5
1.0

3.9
3.14
2.14
3.57
5.0
3.57
2.14

78.5
43.4
39.2
42.1
55.7
52.7
37.1

92.3
92.87
92.67
92.85
91.9
88.46
94.1

6.07
6.74
12.35
9.96
7.13
15.09
11.57

B2N50

0.75

2.85

50.0

87.8

8.87

A2N30
A2N50

1.0
2.0

3.92
4.28

39.3
50.0

90.39
90.29

12.92
9.17

range of 300400
C is low compared to that of semiIPNs in most cases. At 400
C and above the weight loss
is rapid and the weight loss is dependent upon the blend
ratio at all temperatures. The TGA and DTG curves of
D2N30, D2N50 and D2N70 samples are given in Figs. 79
respectively. It was observed that at 400
C the weight
loss for N30 sample is 39% while that of N50 sample is
42% and N70 sample is 56%. This shows that as PS
content increases the thermal stability is enhanced.
The crosslinking level of the PS phase in full-IPN was
varied by changing the amount of divinyl benzene. The
TGA curves of D0N50, D1N50, D2N50 and D3N50 show
the eect of crosslinking level on thermal decomposition
(Fig. 10). In D1N50, D2N50 and D3N50 about 4355%
weight loss is observed at 400
C. At 450
C D1N50 and
D2N50 are degraded to 93% whereas D3N50 degraded
up to 88%. Here it could be noticed that as the extent of
crosslinking increases thermal stability increases. In
D0N50 where the NR phase alone is crosslinked, a
weight loss of 78% is observed at 400
C and at 450
C
almost 92% degradation was observed. It may also be
noted that increasing the crosslink content of PS from 2
to 6% does not have much eect on the thermal stability. After 2% of crosslinker there is almost a levelling
o of thermal stability. In the DTG curve two peaks are
observed corresponding to NR and PS degradation
(Fig. 11). Also as we move to samples with higher crosslinked PS a minor peak is observed at about 515
C for
D1N50, D2N50 and D3N50. The peak intensity increases
as we move to higher crosslinking. In the semi-IPN

Fig. 4. TGA and DTG curves of B0N30.

A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

429

Fig. 5. TGA and DTG curves of B0N50.

Fig. 6. TGA and DTG curves of B0N70.

(D0N50) this peak is totally absent. Therefore, this peak

may be due to the degradation of residual divinyl benzene polymer. When we compare the degradation
behaviour of semi and full-IPNs it could be seen that in

semi-IPNs degradation occurs at lower temperatures

compared to full-IPNs. This is due to the fact that the
low crosslinking in semi-IPNs makes the rupture of
bonds easier. The crosslink density values of the samples

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

Fig. 7. TGA and DTG curves of D2N30.

Fig. 8. TGA and DTG curves of D2N50.

A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

Fig. 9. TGA and DTG curves of D2N70.

Fig. 10. TGA curve showing the eect of crosslinker content on thermal stability: (a) D0N50; (b) D1N50; (c) D2N50; (d) D3N50.

431

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

Fig. 11. DTG curve showing the eect of crosslinker content on thermal stability: (a) D0N50; (b) D1N50; (c) D2N50; (d) D3N50.

given in Table 3 support this explanation. The higher

crosslink density values of full-IPNs compared to semiIPNs resulted in the high thermal stability of full-IPNs.
The linear PS chain gets fragmented easily and subsequent volatilisation of the degradation products is
easier due to low entanglement density. In the case of
full-IPNs the compact network formed by interpenetration and physical entanglement of the two phases makes
the bond rupture dicult. The morphology of the system also aects the thermal stability. The scanning electron micrographs of D0N50, D1N50, D2N50 and D3N50
are given in Fig. 12. The IPN samples for the SEM studies were prepared by the ebonite method, where the
NR phase is highly crosslinked using sulphur. This
makes the NR phase appear dark and provides the
necessary contrast with the PS phase. The improved
interpenetration and phase mixing of the components
with increase in crosslinking level is clear from these
gures.
It was also observed that the thermal stabilities of the
semi and full-IPNs do not change appreciably with
change in the initiating system. The DTG curve for the
dicumyl peroxide, benzoyl peroxide and azo-bis-isobutyronitrile initiated N50 samples are shown in Fig. 13.
In all the cases about 23% weight loss is observed at
300
C and 50% weight loss is observed at 400
C. In
Table 3 the percentage weight loss at dierent temperature are tabulated. From the table it is clear that the

thermal stability increases with increase in PS content

and increase in PS crosslinking in most cases. Also an
increase is observed in degradation temperature of the
IPNs compared to pure components. It was reported
earlier by other researchers that the mixing of two
polymers improves thermal stability [37,38].
The initial decomposition temperature (T0) and temperature for 50% decomposition (T50) were calculated
from the TGA curves. The temperature of initial
decomposition, 50% decomposition and nal decomposition are given in Table 4. For the homopolymers the
T0 and T50 values are low compared to semi and fullIPNs. In the case of IPNs the T0 and T50 values depend
on blend ratio, initiating system and crosslinking level.
As PS content increases the decomposition temperature
increases. An increase in the extent of crosslinking also
enhances the thermal stability up to 4% of crosslinker
level. Above 4% there is a levelling o or a slight
decrease in thermal stability. The increase in decomposition temperature with increase in PS content for semiand full-IPNs is clear from Fig. 14. All the curves
exhibited a positive deviation from the additivity line.
This is indicative of the enhanced thermal stability of
the IPNs compared to the homopolymers.
When the semi- and full-IPNs are compared the initial
decomposition temperature is higher for full-IPNs
compared to semi-IPNs in most cases. The temperature
for 50% decomposition is higher for full-IPNs showing

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

Fig. 12. Scanning electron micrograph showing the eect of crosslinking on phase mixing: (a) D0N50; (b) D1N50; (c) D2N50; (d) D3N50.

that the degradation rate is rapid in semi-IPNs compared to full-IPNs. In the initial stage of decomposition
the random scission of polymer chains occurs.

Table 4
Initial, 50% and nal decomposition temperatures of degradation of
semi- and full-IPNs
Sample code

3.2. Kinetic parameter from thermal degradation

Decomposition temperature
Initial (T0)a

50% (T50)

Final

The overall decomposition rates are controlled by

three fundamental aspects namely, the laws of diusion,
nucleus formation and growth, and phase boundary
movements. The most prominent rate controlling process operating in a particular case is chosen and used for
deriving the rate equation. The integral rate equation
derived by Coats and Redfern is as follows [39].




2RT
E
2
ln g=T logAR=E 1 
4

E
2:303RT

N0
N100

276.5
290

352.8
360

385.9
396.7

B0N30
B0N50
B0N70

343.8
325.8
334.2

401.8
385.4
381.8

454.5
434.0
440.1

D0N50
D1N50
D2N30
D2N50
D2N70
D3N50

314.9
331.8
319.8
319.8
290.9
319.8

389.1
400.0
414.5
411.0
392.7
400.0

425.6
454.5
461.7
455.7
443.4
461.7

A2N30
A2N50

334.0
283.7

411.0
402.0

454.5
458.1

A straight line graph will be obtained if we plot the

left hand side (LHS) of this equation versus 1=T. The
slope and intercept of this graph are used for calculating
the kinetic parameters by the least squares method. The
goodness of t was tested by evaluating the correlation
coecient.
The entropy of activation can then be calculated using
the equation.

B2N30
B2N50

319.8
319.8

411.0
400.0

461.7
454.5

a
T0: temperature at which the rapid loss in weight occurs due to the
formation of volatile degradation products.

kTs S=R
e
h

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

where, k is the Boltzmann constant and h, the Planck

constant.
Several mechanistic equations have been derived by
dierent authors based on integral method to determine
the kinetic parameters of thermal decomposition.
Satava has chosen nine equations based on nine possible
mechanism [nine dierent forms of g] [40]. The form
of g which best represents the experimental data gives
the proper mechanism. The nine possible equations and
the rate controlling processes in each case are given in
Table 5.
In the case of NR/PS IPNs, the TG data were analysed using these nine equations and the eect of blend
ratio, crosslinking level and initiating system on kinetic

parameters were studied. The analysis of thermal

decomposition data showed that the best t curve was
obtained from Mampel equation irrespective of blend
ratio, crosslink density or initiating system. This leads
to the conclusion that NR/PS IPN degradation is based
on a random nucleation mechanism with one nucleus on
each particle which is the rate controlling process.
The kinetic parameters of two stage decomposition of
NR/PS IPNs with dierent blend composition are given
in Table 6. In all the three cases, the activation energy of
Stage II is greater than that of Stage I. The activation
energies increase gradually in both the stages as the PS
content increases. In the rst stage the activation energy
increases from 110 to 165.5 J/mol as the PS content

Fig. 13. DTG curve showing the eect of initiating system on thermal stability: (a) D2N50; (b) B2N50; (c) A2N50.

Table 5
Commonly used g forms for solid state reactions
Eq. no.

Form of g

Rate controlling process

(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)

 ln1  
1  1  1=2
1  1  1=3
 1   ln1  
1  2=3  1  2=3
ln 1   1=2
ln 1   1=3 
2
1  1   1=3
2


Random nucleation one nucleus on each particle Mampell equation

Phase boundary reaction, cylindrical symmetry
Phase boundary reaction, spherical symmetry
Two dimensional diusion
Three dimensional diusion spherical symmetryGinsthingBrounshtein equation
Random nucleation Avrami equation I
Random nucleation Avrami equation II
Three dimensional diusion, spherical symmetry Jander equation
One dimensional diusion

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increases from 30 to 70%. Similarly for the second stage

the activation energy increases from 336.7 to 414.7 J/
mol as the PS content increases from 30 to 70%. This

shows that the increase in PS phase makes the system

more resistant to thermal degradation. When the
D2N30, D2N50 and D2N70 samples were compared it

Fig. 14. Eect of blend ratio on initial decomposition temperature (T0) and 50% decomposition (T50) of semi- (B0 series) and full-IPNs (D2 series).

Table 6
Eect of blend ratio of NR/PS IPNs on kinetic parameters for the thermal decomposition
Sample

D2N30
D2N50
D2N70

Activation energy E (J/mol)

Arrhenius parameter A (s1)

Entropy of activation S (J/deg/mol)

Stage I

Stage II

Stage I

Stage II

Stage I

Stage II

165.5
163.8
110.0

414.7
350.3
336.7

2.8103
5.8103
42.0103

5.8
3.7
8.0

179.3
185.6
220.6

36.5
165.9
73.5

Table 7
Eect of crosslinking level of NR/PS IPNs on kinetic parameters for the thermal decomposition
Sample

D0N50
D1N50
D2N50
D3N50

Activation energy E (J/mol)

Arrhenius parameter A (s1)

Entropy of activation S (J/deg/mol)

Stage I

Stage II

Stage I

Stage II

Stage I

Stage II

22.9
173.3
163.8
195.0

140.1
216.2
350.3
313.0

4.4103
3.1103
5.8103
2.8103

2.4
2.6
3.7
5.6

136.5
176.9
185.6
160.0

84.4
153.9
165.9
94.1

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

Table 8
Eect of initiating system of NR/PS IPNs on kinetic parameters for the thermal decomposition
Sample

A2N50
B2N50
D2N50

Activation energy E (J/mol)

Arrhenius parameter A (s1)

Entropy of activation S (J/deg/mol)

Stage I

Stage II

Stage I

Stage II

Stage I

Stage II

176.3
138.4
163.8

326.7
305.1
350.3

2.8103
2.8103
5.8103

3.4
4.1
3.7

171.8
197.7
185.6

84.1
97.9
165.9

Table 9
Tensile strength and elongation at break of aged and unaged samples
Sample code

A1N50
A2N50
A3N50
B2N50
D3N30
D3N50

Tensile strength (MPa)

Elongation at break (%)

Unaged

Aged for 72 h

Aged for 120 h

Unaged

Aged for 72 h

Aged for 120 h

10.2
6.9
8.5
6.0
14.0
14.5

18.9
19.7
17.6
11.9
15.52
26.0

5.5
10.9
14.6
5.4
5.05
15.5

420.0
300.0
231.0
256.0
87.0
97.0

95.0
330.0
160.0
140.0
5.5
100.0

320.0
190.0
63.0
57.0
210.0
105.0

Fig. 15. Stressstrain curves for aged and unaged samples (D3N50).

A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

was observed that as the PS content increases the number of crosslinks increases making the system more
thermally stable. It is important to notice that the
higher activation energy in Stage II points to the fact
that crosslinked PS is more thermally stable than NR.
From the table, it is clear that the entropy of activation
has negative values. The magnitude of entropy is lower
in the second stage in all the cases.
The eect of crosslinking of PS on kinetic parameters
is made clear from Table 7. In this case also the activation energy of Stage II is higher than that of Stage I
showing that crosslinked PS is more stable towards
temperatures compared to NR. The activation energy of
Stage I increases from 22.9 to 195 J/mol as the crosslinker content increases from 0 to 6%. The activation
energy of Stage II also increases with increase in crosslinker content. This shows that the thermal stability is
enhanced on increasing the crosslinking of PS phase.
The entropy of activation is negative in all cases. The
increase in crosslink density with increase in crosslinker
content is the reason for this enhanced thermal stability.
At high crosslink density the energy required for bond
scission and volatilisation of products is higher.

437

The eect of initiating system on activation energy of

decomposition is shown in Table 8. The activation
energy of Stage II is higher than that of Stage I. The
activation energies of Stage I and II do not exhibit any
denite trend on comparing the initiating systems. The
entropy values are negative in this case also.
The kinetic study of thermal decomposition showed
the presence of two activation energy values for each
IPNs sample indicating phase separation. Each phase
decomposes separately at two dierent temperatures. It
was found that NR degrades rst followed by PS. The
low activation energy of rst stage of decomposition
compared to that of second stage shows that NR
degrades at lower temperatures and PS degrades at a
higher temperatures.
3.3. Ageing of IPNs
The tensile strengths of aged samples were determined
to study the eect of thermal ageing on the mechanical
performance. In Figs. 15 and 16 the stressstrain curves
of aged and unaged samples of D3N50 and D3N30
respectively are given. The stressstrain curves of D3N50

Fig. 16. Stressstrain curves for aged and unaged samples (D3N30).

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A.P. Mathew et al. / Polymer Degradation and Stability 72 (2001) 423439

clearly show the enhancement in properties after 72 h

of ageing. The decay of strength after 120 h of ageing
is also clear from Figs. 15 and 16. The values of tensile strength for dierent samples are tabulated in
Table 9.
It was observed that in almost all cases after 72 h of
ageing at 100
C the properties were enhanced. This may
be due to post curing of the samples, making the samples more tough and strong. However, after the thermal
ageing for 120 h at 100
C the mechanical strength dropped drastically. This indicates the degradation of the
samples on prolonged heating. The resistance to ageing
increases as PS crosslinking increases from 2 to 6%. For
A1N50 sample the tensile strength increases dramatically
after 72 h of ageing, but after prolonged ageing the
values drop drastically due to degradation. For A3N50
the tensile strength increases after 72 h of ageing, but
the magnitude is lower than that of A1N50 and A2N50.
However, after prolonged ageing the strength does not
fall drastically. For A2N50 the tensile strength is higher
than A1N50 and A3N50 after 72 h of ageing and drops
after prolonged ageing.

4. Conclusion
The thermal degradation behaviour of NR/PS semiand full-IPNs were studied as a function of blend ratio,
crosslinker level and initiating system using thermogravimetry. The vulcanised NR and pure uncrosslinked
PS exhibited almost comparable thermal stability and
both degraded around 360
C. The NR/PS semi- and
full-IPNs exhibited enhanced thermal stability compared to the homopolymers. In all the samples remarkable stability was observed up to 300
C, after which
there was a sharp decrease in weight. About 90% of the
sample gets degraded at about 450
C. Thermal decomposition temperature decreases as the rubber content,
increases. The N30 samples showed higher thermal stability than N50 and N70 samples. At 400
C about 60
80% of semi-IPNs degraded, while 3050% of full-IPNs
gets degraded at 400
C. This is because high entanglement density of full-IPNs restricts the rupture of bonds.
Above 4% of PS crosslinker content the thermal stability is not enhanced appreciably.
The kinetic parameters of thermal decomposition
were analysed using nine mechanistic equations. It was
found that the Mampel equation ts the experimental
data well which shows that the degradation is based on
random nucleation mechanism. The activation energy
increases with increase in PS content and PS crosslinking. The NR activation energy is lower than PS
activation energy in all the cases. The entropy of activation for both the stages of decomposition is negative.
The entropy values do not follow any systematic trend
depending on blend ratio or crosslinking level.

Ageing studies showed that thermal ageing for a period of 72 h increased the strength of IPNs, due to post
curing. However, on prolonged ageing degradation and
loss of mechanical strength was observed. The resistance
to ageing increased with increasing PS crosslinking.
Finally, it can be concluded that during IPN synthesis,
the physical entanglements due to networking of two
phases makes the system tough and thermally stable.

Acknowledgements
The authors are grateful to Third World Academy of
Sciences (TWAS) for nancial support and one of the
authors (A.P.M.) is grateful to the Council of Scientic
and Industrial Research (CSIR) for the senior research
fellowship. The authors are thankful to Mr. Madhu
N.T. and Mr. Vinod Kumar G.S. for helping with the
calculation of kinetic parameters.

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