Professional Documents
Culture Documents
INTRODUCTION The concept of appropriately combining two or more different polymers to obtain a new material system with the desirable features of its constituents is not new. Over the years, numerous systems based on the chemical combination of different monomers through random, block and graft copolymerization methods have been developed with this goal in mind. For similar reasons, the coatings and rubber industries have blended together different polymers and particularly over the last decade the interest in polymer blend systems as a way to meet new market applications with minimum development cost has rapidly increased. This approach has not been without its difficulties and has not developed as rapidly as it might, in part because most physical blends of different high-molecular-weight polymers prove to be immiscible. That is, when mixed together, the blend components are likely to separate into phases containing predominantly their own kind. This characteristic, combined with the often low physical attraction forces across the phase boundaries, usually causes immiscible blend systems to have poor mechanical properties. Even *To whom correspondenceshould be addressed tPresent address: Rubber Research Institute of India, Kottayam 686009, Kerala, India 0032-3861/93/163428-09 1993 Butterworth-Heinemann Ltd.
for immiscible pairs, proper control of phase morphology during processing and addition of compatibilizing agents can improve the interfacial situation. In recent years the technical literature on this subject has expanded greatly, as evidenced by the appearance of several research papers, books and proceedings of various conferences 1-6. Martuscelli et al. 7"8 have reported on the thermal behaviour and morphology of rubber-plastic blends. According to them, fundamental information about the miscibility of blends and the phase diagram of the components in the molten state could be obtained from these studies. Locke and Paul 9 studied the dynamic mechanical properties, thermal behaviour, adhesion characteristics and morphology of ternary blends to examine the effectiveness of a third component as a blend modifier. Kuriakose and De 1 and Thomas et al. l l have also investigated morphology, miscibility and mechanical properties of various thermoplastic elastomer blends. Recently, blends of natural rubber (NR) and ethylene-vinyl acetate copolymer (EVA) have gained a lot of interest. These materials combine the excellent ageing and flex crack resistance of EVA and the good mechanical properties of NR. In this laboratory, we have already studied the mechanical properties, vulcanization kinetics, rheological behaviour and ageing properties of these blends 12-16. The present study explores the miscibility, morphology, crystallization and dynamic
Effect of blend ratio and cross~inking on properties of NR-EVA blends. A. T. Koshy et al.
mechanical properties of NR-EVA blends with special reference to the effects of blend ratio and crosslinking systems.
EXPERIMENTAL
Materials
Natural rubber (NR) conforming to ISNR 5 was supplied by the Rubber Research Institute of India. Ethylene-vinyl acetate (EVA Exxon 218) was supplied by the Exxon Chemical Company, Houston. The vinyl acetate content of EVA is 18% by weight, its melt flow index is 1.7 g per 10 min and the Vicat softening point is 64C. All other additives such as dicumyl peroxide (DCP), zinc oxide (ZnO), sulfur, and dibenzthiazyl disulfide (MBTS) were of commercial grade.
X-ray study
In order to find out the degree of crystallinity and the amorphous content of different blends, X-ray diffraction patterns of the samples were recorded with an X-ray diffractometer using Ni-filtered CuK~ radiation from a Philips X-ray generator. The angular range was 5 to 40 (20). Samples of the same thickness and the same area were exposed. The operating voltage and the current of the tube were kept at 55 kV and 190 mA, respectively, throughout the course of the investigation. The X-ray diffraction patterns of the samples were separated into two parts, crystalline and amorphous, by taking natural rubber as fully amorphous. The areas under the crystalline and amorphous portions were measured in arbitrary units, and the degree ofcrystallinity X c and the amorphous content X a of the samples were calculated using the relations
X c-
Blend preparation
The blends were prepared in a laboratory model intermix (Shaw Intermix KO) set at a temperature of 80C and a rotor speed of 60 r.p.m. NR was masticated for 2 rain and then blended with EVA for 2.5 min. The final temperature of the blend inside the intermix was in the range 110-125C, depending upon the blend ratio. The blends contained 0, 30, 40, 50, 60, 70 and 100% by weight of EVA and were designated A, D, E, F, G, H and J, respectively. The blends were compounded in a two-roll laboratory mill as per the test recipes given in Table 1. The compounds which contained the sulfur cure system were designated A1, Dx and F1 and those with DCP as A 2, D2, F2, Hz and J2. Compounds which contained the mixed cure system consisting of sulfur and DCP were designated as A 3, D3, F3, H3 and J3. The proportions of sulfur and DCP in the mixed cure system did not correspond to the proportions of NR and EVA in the blend because their distribution in these two elastomers can be different12. As given in Table 1, the mixed cure system contained the sum of the curatives used for the sulfur and DCP systems. The objective of taking these three cure systems was to study the responses of polysulfidic, carbon-carbon and mixed crosslinks towards thermal and dynamic mechanical effects. The compounded blends were vulcanized to optimum cure in a steam-heated hydraulic press at 160C to get the required test samples. The blends with 50% or more of EVA could not be vulcanized fully with the sulfur system and hence could not be evaluated for physical properties. The blends were characterized by differential scanning calorimetry (d.s.c.), X-ray, scanning electron microscopy (SEM) and dynamic mechanical thermal analysis (d.m.t.a.).
Table 1 Formulations of mixes in g per 100 g of rubber Sulfur system 100.0 5.0 1.5 1.0 0.8 2.5 DCP system 100.0 5.0 1.5 1.0 4.0 Mixed system 100.0 5.0 1.5 1.0 0.8 4.0 2.5
Ic + Ia
Ia
X a-
la + l~
where I~ and I a represent the integrated intensities corresponding to the crystalline and amorphous phases, respectively, i.e. the areas under the respective curves.
Ingredients Polymer Zinc oxide Stearic acid Styrenated phenol antioxidant Dibenzthiazyl disulfide Dicumyl peroxide (40% active ingredient) Sulfur
3429
Effect of blend ratio and crosslinking on properties of NR-EVA blends: A. T. Koshy et al.
Table 2
Thermal properties of NR-EVA blends Uncrosslinked blend Properties Heat of fusion A H (cal g - 1 ) Peak temperature Tm (C) Onset of glass transition (C) Glass transition ~ N R phase
[
Crosslinked blend" J D1 5.2 86.7 -35.7 27.0 1.9 85.3 -69.1 - 58.0 . 11.6 . F1 3.6 85.0 -67.9 - 54.6 . 22.2 D2 1.9 81.0 -65.7 - 63.8 . 11.5 . 28.4 F2 4.6 81.5 -65.4 - 62.7 . 1--I 2 3.9 79.4 -65.0 - 63.0 . 24.1 D3 1.9 81.4 -64.4 - 57.1 . 11.7 29.0 26.6 F3 4.7 81.6 -65.5 - 53.4 Ha 4.3 82.0 -66.0 - 43.8
A _ -67.4 - 65.3 . .
29.0
32.1
The subscripts 1, 2 and 3 stand for sulfur, peroxide and mixed cure systems, respectively
Thermal properties The thermal properties of NR, EVA, and crosslinked and uncrosslinked blends were analysed by d.s.c. The melting temperatures T,~, fractional crystallinities Xc, heats of fusion AH and glass transition temperatures Tg of the blends are reported in Table 2. D.s.c. results for the uncrosslinked and crosslinked blends are given in Figures 1 and 2, respectively. The peak point temperature of the thermogram was taken as the melting point Tin. It is interesting to note from Table 2 that in the case of uncrosslinked and sulfur-crosslinked blends, Tm is almost independent of composition. However, a slight decrease in melting point is observed in the case of peroxide-cured and mix-cured blends. The area of the melting endotherm is also calculated and reported as the heat of fusion AH. The fractional crystallinities of EVA in the blends are calculated from the AH values on the basis that EVA has an 18% vinyl acetate content 17. It is seen that the fractional crystallinity Xc and heat of fusion values decrease with increase in rubber content for similar conditions of crystallization. The crystallinity of EVA was found to be 32%. With gradual incorporation of NR, the crystallinity of EVA comes down to 29.0% for 30:70 NR:EVA, 13.3% for 50:50 NR:EVA and 11.6% for 70:30 NR:EVA blends. Martuscelli 8 has shown that crystallinity is affected by blend composition and crystallization conditions such as temperature, pressure, orientation, molecular weight and diluent. The crystallization of the EVA segments is controlled by the segmental diffusion rate of the other polymeric chains. The separation is enhanced as the NR content is increased. Incomplete crystallization thus leads to a decrease in AH and, hence, crystallinity. The glass transition temperatures T, as obtained from the d.s.c, measurements are reported in Table 2 for crosslinked and uncrosslinked NR-EVA blends. The Tg values of pure NR and EVA are found to be -65.3C and -27.0C, respectively. In the case of uncrosslinked NR-EVA blends, the glass transition temperature of NR was found to be -66C. It is interesting to note that the T, value of the NR phase remains almost constant with increasing composition. The Tg of the EVA phase could not be detected in the blends using d.s.c. However, d.m.t.a. (see later) could detect the T, of EVA. It seems that the T, values of the two phases in the uncrosslinked blends do not undergo substantial shifts. These observations, coupled with the fact that Tmremains more or less constant with increase in NR content,
TEMPERATURE C
Figure l
D.s.c. thermograms
of uncrosslinked NR-EVA
blends
He
^i ,,=,~
N
-g000
-70.00
-SO00
1000
3000
5000
?0.00
Figure 2
D.s.c. thermograms
of crosslinked NR-EVA
blends
indicate the fact that the blends are incompatible or immiscible 18. It is interesting to note that in the case of crosslinked blends, depending on the type of crosslinking system used (sulfur, peroxide or mixed) the Tg of the NR phase undergoes a substantial shift from its normal position to a higher temperature (Table 2). Generally, the introduction of crosslinks increases the Tg value due to the restriction of the segmental motion of the polymer by the crosslinks. When sulfur is used as the crosslinking
3430
Effect of blend ratio and crossfinking on properties of NR-EVA blends. A. T. Koshy et al.
system, the N R phase is preferentially crosslinked. D C P crosslinks both the phases. In the mixed system, sulfur crosslinks the N R phase and D C P crosslinks both the phases. In the case of the 70:30 N R : E V A blend, the Tg values of the N R phase in the blend for the sulfur, peroxide and mixed crosslink systems are - 5 8 . 0 , - 6 3 . 8 and - 5 7 . 1 C , respectively. The Tg of the natural rubber phase in the uncrosslinked 70:30 N R : E V A blend is - 6 6 . 3 C . This suggests that the increase in the Tg of the N R phase is at its m a x i m u m when the mixed system is used as the crosslinking agent. A similar behaviour was observed for 50:50 and 30:70 N R : E V A blends. Therefore, it can be concluded that the mixed system predominantly crosslinks the N R phase and the crosslinking efficiency of the three systems in the N R phase varies in the order mixed > sulfur > peroxide. Since Table 3 Crystallization characteristics of the blends Sample reference Uncrosslinked Sample D Sample F Crystallinity Xc (%) 10.3 24.6 d values (~,) 4.164 3.799 2.499 4.164 3.796 2.493 4.164 3.786 2.483 4.164 3.776 2.473 4.165 3.800 2.494 4.164 3.797 2.493 4.164 3.799 2.495 4.165 3.798 2.493 4.165 3.777 2.473 4.166 3.800 2.495 4.164 3.799 2.495 4.165 3.776 2.473
Sample H
26.5
Sample J
36.4
Crosslinked" Sample D 1
7.6
Sample F 1
20.1
Sample D 2
7.6
T
Sample F 2
35
20.4 22.6
Sample H 2
co
Sample D 3
7.7 20.4
s.oo
~o.'oo
ls'.oo
2c;.oo
51
.00
30.03
3500
4000
Sample F 3
Sample H 3
22.1
"The subscripts 1, 2 and 3 stand for sulfur, peroxide and mixed cure systems
the resolution of the equipment used for the study was only up to 15 nm, the Tg corresponding to the EVA phase could not be detected and therefore the extent of crosslinking in the EVA phase could not be derived.
[
C
X-ray diffraction analysis Figures 3 and 4 depict the X-ray diffraction patterns of
uncrosslinked and crosslinked blends. The results of the X-ray analyses of the samples are given in Table 3. F r o m the table it can be seen that the degree of crystallinity X c of EVA is 36.4%. This is higher than that obtained by d.s.c, measurements. The value of Xc depends very much on the method of preparation of the sample and the technique of measurement 19. The decrease in crystallinity caused by natural rubber is due to the addition of an a m o r p h o u s component which migrates into the crystalline phase of pure EVA, reducing the crystalline domains of the pure EVA sample. The introduction of crosslinks further reduces the crystallinity of the system. This is due to the fact that the crosslinking system arrests the regular arrangement of the crystalline
10
P O L Y M E R , 1993, V o l u m e 34, N u m b e r 16
3431
Effect of blend ratio and cross/inking on properties of NR-EVA blends: A. T. Koshy et al. regions within the sample 14. The interplanar distances (d values) are reported in Table 3. With the addition of natural rubber there was a tendency for the d value to increase in most systems. This suggests the migration of the NR phase into the interchain spaces of EVA. Similar observations have been reported in the case of N R - P E blends by Roychoudhury et al. 18. the NR phase and the lower melt viscosity of the EVA phase 14. The photomicrograph of the 30:70 EVA:NR blend shows aggregates of EVA domains lying on the benzene-extracted surface (Figure 5d), indicating that phase inversion has occurred in the blend and EVA forms the dispersed phase at this blend ratio. Thus, the morphology of uncrosslinked EVA-NR blends appears to be such that the EVA forms the dispersed phase when its proportion is below 40% and NR forms the dispersed phase when its proportion is 40% or below. In the range of 40:60 and 50:50 EVA:NR both the polymers remain as continuous phases to give an interpenetrating structure.
Figure 5 (a) Photomicrographof blend G. (b) Photomicrographof blend F. (c) Photomicrographof blend E. (c) Photomicrographof blend D
3432
Effect of blend ratio and crosslinking on properties of NR-EVA blends." A. T. Koshy et al.
12 0
A D F g ~. 30
A~
24
D
A
0.96
D, F,
0.72
18
048
.o cl.2 t~ F-
0.24
0,6
0.00 -80
-30 TEMPERATURE, C
20
0.0 -80
~.--~y.~,
,-~.~-,
-30
T E M P E R A T U R E , C
, o---~,--,-~
20
10' ,
10 ~
10~
=-|
10=
10'
I0'
--10~
~J
I0'
10S
10'
-80
-30
TEMPERATURE, oC
20
-80
-30
TEMPERAIURE
20
109
109
10'
#_
uJ
g.
w 10'
- - 107
\
~o
~]
/
106
10=
F H J
v *
-80
-30
TEMPERATURE,C
20
1
of
-S0
-30 TEMPERATURE, C
20
on
the
storage
modulus
on
the
storage
modulus
of
3433
Effect of blend ratio and crosslinking on properties of NR-EVA blends." A. T. Koshy et al.
3.0 , Az
D2
3.0 o
A
A~
D~ 2.4 /,-=~
FJ Ha
D
A
+
2.4
Fz H=
J3
1.8
,,o cl.2
/\
"\ \
_
1.8
~2 c 1.:
0.6
! f \ \xo.
0.0 -80
0.0 -80
-30
TEMPERATURE,C
20
-30
TEMPERATURE, C
20
10lo
101
10'
10+
10~
\~.\._
---.~-~
#_ m
10+ . ~
* + +
#_
--10'
106
10'
F=
"""---0
10s
F~ R=
H2 J= -80
-3 TEMPERATURE, o c
-1
; ,
20
on
the
storage
modulus
of
10j
101
= 101
------o.....
10'
10'
10'
#_
w
107
10 S
Fz
Ha
10+
H3
Jz -80
+
i
J3
-30 TEMPERATURE, o c 20 -80
-~
TEMPERATURE,
20
3434
Effect of blend ratio and crosslinking on properties of NR-EVA blends: A. T. Koshy et al.
Table 4 Dynamic mechanical properties
Sample reference Sample A (0:100) Sample D (70:30) Sample F (50:50) Sample H (30:70) Sample J (100:0) Sample A1 Sample D 1 Sample F 1 Sample A 2 Sample D 2 Sample F 2 Sample H 2
Sample Sample Sample Sample J2 m3 D 3 F 3
Ts, NR phase (C) -46.3 -46.3 -50.0 -51.7 -42.0 --42.3 --43.6 --45.0 --46.0 - 48.0 --47.5
-
tan 61,,=x NR phase 0.856 0.400 0.165 2.200 1.020 0.880 2.200 1.040 0.440 0.224 2. I00 0.184 0.475 0.240 -
E (kJ mo1-1) 211.12 205.50 178.45 191.29 204.62 170.89 161.46 209.84 218.23 176.05 216.35 192.73 186.57 228.01 237.65 -
tan 62max EVA phase 0.200 0.200 0.144 0.280 0.224 0.400 0.251 0.304 0.264 0.250
E" peak temperature of NR transition (C) -55.0 -51.0 -51.0 -51.0 - 51.1 -48.0 -45.0 - 53.1 -52.6 - 50.0 -46.3 - 48.7 -42.6 - 41.0 - 40.0 -
Sample H 3
Sample J3
two t r a n s i t i o n s c o r r e s p o n d i n g to the N R a n d E V A phases, which indicates the i n c o m p a t i b i l i t y of the two c o m p o n e n t s . As c o m p a r e d to the d.s.c, results, the d y n a m i c m e c h a n i c a l analysis (d.m.a.) t h e r m o g r a m s exhibit t r a n s i t i o n s at higher t e m p e r a t u r e s . This shows the difference in r e s p o n s e of the m o l e c u l a r segments of the s a m p l e t o w a r d s d.m.a, a n d d.s.c, analysis c o n d i t i o n s . It can be seen t h a t the t a n 6mx due to the N R p h a s e decreases as the E V A c o n t e n t increases, a n d the decrease is m u c h s h a r p e r w h e n the E V A c o n t e n t is 5 0 % o r m o r e , where E V A forms a c o n t i n u o u s phase. As expected, the loss m o d u l i (Figure 7) s h a r p l y increase in the t r a n s i t i o n zone until they a t t a i n m a x i m a ; they then decrease with increasing t e m p e r a t u r e . T h e Tg values o b t a i n e d from the E" versus t e m p e r a t u r e p l o t s are always lower t h a n those o b t a i n e d from t a n 6max (Table 4). T h e s h a r p loss p e a k s indicate t h a t the system c o m p o n e n t s are i n c o m p a t i b l e . Figure 8 shows the elastic m o d u l u s E' for v a r i o u s b l e n d s o v e r a wide r a n g e of t e m p e r a t u r e . T h e curves for all the c o m p o s i t i o n s have three distinct regions: a glass region, a t r a n s i t i o n r e g i o n (leathery region), a n d a r u b b e r y region. Since the e x p e r i m e n t was n o t p e r f o r m e d a b o v e 20C, the h i g h - t e m p e r a t u r e viscous region was n o t o b t a i n e d . It is seen t h a t the s t o r a g e m o d u l u s decreases with increasing t e m p e r a t u r e d u e to the decrease in stiffness of the sample. T h e decrease is s h a r p in the case of h i g h - N R blends. T h e d y n a m i c m e c h a n i c a l p r o p e r t i e s of c r o s s l i n k e d systems are s h o w n in Figures 9 to 17. T h e i m p o r t a n t p r o p e r t i e s are listed in Table 4. It is seen that, as c o m p a r e d to the u n c r o s s l i n k e d blends, the Tg values of the N R p h a s e increase s h a r p l y in the case of sulfur-crosslinked a n d m i x - c r o s s l i n k e d systems. F o r e x a m p l e , the Tg of u n c r o s s l i n k e d , p u r e N R is - 4 6 . 3 C . The c o r r e s p o n d i n g values for sulfur-cured, p e r o x i d e cured a n d m i x - c u r e d systems are - 4 2 . 0 , - 4 6 . 0 a n d
- 39.8C, respectively. Similarly, for the 70:30 N R : E V A b l e n d the Tg values of the N R p h a s e in the u n c r o s s l i n k e d , sulfur-cured, p e r o x i d e - c u r e d a n d m i x - c u r e d systems are - 46.3, - 4 2 . 3 , - 46.0 a n d - 37.5C, respectively. This suggests t h a t the degree of crosslinking of the N R phase is at a m a x i m u m in the case of the m i x e d crosslinking system. H o w e v e r , the Tg of E V A d o e s n o t show a s u b s t a n t i a l shift with respect to crosslinking. This further suggests that in N R - E V A blends the extent of c r o s s l i n k i n g of the N R p h a s e is s u b s t a n t i a l l y higher t h a n t h a t of the E V A phase. This is a s s o c i a t e d with the faster curing n a t u r e of the N R phase as a result of the high level of u n s a t u r a t i o n in the i s o p r e n e units. In s o m e recent studies on similar systems it was i n t e r p r e t e d t h a t the shift in Tg values is d u e to interface c r o s s l i n k i n g which results in s o m e type of c o m p a t i b i l i z a tion 2. H o w e v e r , in the case of the N R - E V A system all the crosslinked systems show two t r a n s i t i o n s corres p o n d i n g to the E V A a n d N R phases. Therefore, the c r o s s l i n k e d system c o m p o n e n t s are i n c o m p a t i b l e . H o w e v e r , the o b s e r v e d shift in the Tg of the N R p h a s e as seen from d.s.c, a n d d.m.t.a, studies m a y be a s s o c i a t e d with the p r e d o m i n a n t crosslinking of t h a t p h a s e a n d n o t due to the c o m p a t i b i l i z i n g action. The t a n 6max values of b o t h the N R a n d E V A phases increase with crosslinking (Figures 9, 12 a n d 15). The i n t r o d u c t i o n of crosslinks also increases the s t o r a g e m o d u l i of the b l e n d s (Figures 11, 13 a n d 17). T h e a c t i v a t i o n energy E of the t r a n s i t i o n of the N R phase has been c a l c u l a t e d from the A r r h e n i u s e q u a t i o n by p l o t t i n g log(frequency) a g a i n s t the r e c i p r o c a l of a b s o l u t e t e m p e r a t u r e a n d finding o u t the slope of the straight line o b t a i n e d . These d a t a are given in Table 4. It can be n o t i c e d t h a t in m o s t cases, except for the m i x - c u r e d system, the a c t i v a t i o n energy decreases with increasing E V A content.
3435
Effect of blend ratio and cross/inking on properties of NR-EVA blends: A. T. Koshy et al.
CONCLUSIONS The thermal behaviour, morphology, crystallinity and dynamic mechanical properties of blends of natural rubber and ethylene-vinyl acetate have been investigated with special reference to the effect of blend ratio and crosslinking systems. The d.s.c, and d.m.t.a, results show that the blend components are incompatible in the crosslinked and uncrosslinked states. The predominant crosslinking of the natural rubber phase as a result of the addition of sulfur or mixed crosslinking agents can be analysed by the shift in the glass transition temperature of the natural rubber phase towards higher temperatures. The addition of natural rubber to EVA decreases the crystallinity of the samples, as endorsed by d.s.c, and X-ray analysis. The morphology of the blends, as studied by scanning electron microscopy, consists of a two-phase structure in which the natural rubber phase is dispersed into domains at its lower proportions. In 40:60 and 50: 50 EVA :NR blends both phases exist as continuous phases. Phase inversion is observed when the proportion of EVA is less than 40%. REFERENCES 1 2 Bruins,P. F. (Ed.) Appl. Polym. Symp. 1970, 15 Platzer,N. A. J. (Ed.) Adv. Chem. Ser. 1971, 99 3 4 5 6 7 8 9 10 11 12 13 14 16 17 18 19 20 Sperling,L. H. (Ed.) 'Recent Advances in Polymer Blends, Grafts and Blocks', Plenum Press, New York, 1974 Kempler,D. and Frisch, K. C. (Eds) 'Polymer Alloys: Blends, Blocks, Grafts and Interpenetrating Networks', Plenum Press, New York, 1977 Paul,D. R. and Newmann, S. (Eds) 'Polymer Blends', Vols I and II, Academic Press, New York, 1978 Roland, C. M. in 'Handbook of Elastomers' (Eds A. K. Bhowmick and H. L. Stephens), Marcel Dekker, New York, 1988, Ch. 6 Martuscelli.E., Riva, F., Sellitti, C. and Silvestre, C. Polymer 1985, 26, 270 Martuscelli,E. Polym. Eng. Sci. 1984, 24, 563 Locke,C. E. and Paul, D. R. Polym. Eng. Sci. 1973, 13, 108 Kuriakose, B. and De, S. K. Polym. Eng. Sci. 1985,25(10), 630 Thomas, S., Gupta, B. R. and De, S. K. J. Vinyl Technol. 1987, 9, 71 Koshy, A. T., Kuriakose, B. and Thomas, S. Indian J. Nat. Rubber Res. 1990, 3(2), 87 Koshy, A. T., Kuriakose, B. and Thomas, S. Polym. Degr. Stab. 1992, 36, 137 Koshy, A. T., Kuriakose, B., Thomas, S. and Varghese, S. J. Appl. Polym. Sci. in press Koshy, A. T., Kuriakose, B., Thomas, S. and Varghese, S. Kausch Gummi Kunststoffe 1992, 45, 852 Gilby, G. W. (Ed.) 'Developments in Rubber Technology', Vol. III, AppliedSciencePublishers, London, 1982,pp. 101-144 Roychoudhury,N., Chaki, T. K., Dutta, A. and Bhowmick, A. K. Polymer 1989, 30, 2047 Herman, P. H. and Weidinger, A. Makromol. Chem. 1961,24, 44 Tinker,A. J. Rubber Chem. Technol. 1990, 63, 503
3436