PolymerDegradationand Stability 62 (1998) 471-477

© 1998 Elsevier Science Limited. All rights reserved

Printed in Northern Ireland
PII: S0141-3910(98)00030-5 0141-3910/98/S--see front matter
ELSEVIER

Thermal stability of butyl]EPDM rubber blend

vulcanizates
S. H. Botros
Polymers Department, National Research Centre, Dokki-Cairo, Egypt

(Received 8 November 1997; accepted 30 December 1997)

Butyl rubber has some disadvantages such as marginal green strength and only fair
heat and ozone resistance. These disadvantages can generally be overcome by the
partial replacement of butyl rubber (IIR) with ethylene propylene diene monomer
rubber (EPDM). EPDM has a highly saturated backbone which gives it excellent
resistance to the effect of oxygen and ozone. However, IIR has some unsaturation
due to the isopreneunits in its structure. In this investigation,data and observations
on the heat resistance behaviour of IIR/EPDM blend vulcanizates over a range of
compositions and temperatures are highlighted. The results show that blending of
IIR with EPDM is beneficialbecause of the enhancement of heat resistance of the
blend vulcanizates. © 1998 Elsevier Science Limited. All rights reserved

1 INTRODUCTION This paper concerns preparation of I I R / E P D M

rubber blend vulcanizates with various types and
Butyl rubber (IIR) is most noted for its excellent ratios o f E P D M rubber. The physico-mechanical
resistance to air permeation and, hence, is widely properties after and before thermal ageing, at
used in the production o f inner tubes 1 and tire various temperatures, were evaluated.
inner liners. 2,3 The fair heat resistance o f I I R can
be overcome by blending it with E P D M . The
blends obtained can also be used for high tem-
perature conveyor belt application, 4 mainly for 2 EXPERIMENTAL
carrying hot coal. Various properties o f a heat
resistant conveyor belt cover c o m p o u n d based on 2.1 Materials
E P D M blends, have been reported. 5,6
With the increased emphasis on weight reduction Butyl rubber:IIR-268
and the resulting downsizing of the automobile, E P D M rubber types:
additional demands are put on. the elastomeric
components. 7 Butyl and E P D M rubbers are often • Buna R AP-447:ethylene-propylene-ENa ter-
used in m a n y applications among which are engine polymer, unsaturation b 8, ethylene content
mounts, body mounts, transaxle mounts and 70% (from Enie Chem. Elastomer).
bushing o f various types. • Vistalon-5600:ethylene-propylene-EN terpo-
The problem with blending is that it is often dif- lymer, unsaturation 9, ethylene content 65%
ficult consistently to obtain parts with the same (from ESSO CHIMIE).
properties on a batch-to-batch basis. The incon- • Vistalon-6505:ethylene-propylene-EN terpo-
sistency in properties can be attributed to a differ- lymer, unsaturation 9, ethylene content 55%
ent degree of mixing in the blend system. A (from ESSO CHIMIE).
heterogeneous blend usually results when two che- • Keltan-820:ethylene-propylene-DCPD c terpo-
mically dissimilar rubbers are mixed. Several lymer, unsaturation 4.5, ethylene content
investigators have examined this morphology. 8-12 60% (from DSM):
M a n y scientists have established the factors which
are important in determining the mechanical (a) Ethylidene norbornene;
properties o f such blends. 13 other researchers have (b) Unsaturation (DB/IO00C);
investigated the compatibility o f rubber blends. 14-16 (c) Dicyclopentadiene.
471
472 S.H. Botros

Compounding ingredients: they are of pure Table 1. Vulcanizing systems, rheometric characteristics and
grade and customarily used in industry. physico-mechanical properties of IIR vulcanizates
Sample no. S1 $2 $3
2.2 Techniques IIR 100 100 100
Neoprene-w -- -- 8
1. The rubber mixes were blended on a two- MBT 0.6 -- --
roll mill of 460 m m diameter and 3 0 0 m m TMTD 1.2 -- --
working distance. The speed of slow roll ZDEDC -- 2 --
S 1 2 --
was 16rev/min, and the gear ratio was
P h e n o l f o r m a l d e h y d e resin -- -- 12
1:1.25.
Rheometric characteristics
2. The rheometric characteristics of the rubber
M a x i m u m torque, d N m 53 58 30
mixes were determined using a Monsanto M i n i m u m torque, d N m 10 12 9
Oscillating Disc Rheometer R-100 according Cure time tc90, rain 13 17 34
to a standard method. 17 Scorch time ts2, rain 3.5 2 6
3. The rubber mixes were vulcanized in a Cure rate index (CRI), min -1 10.5 6.7 3.6

hydraulic press at 172+1°C for their opti- Physico-mechanical properties

100% modulus, M P a 0.88 0.92 0.90
m u m cure time (tc90).
Tensile strength, M P a 14 13 11.2
4. Mechanical properties of the rubber vulcani- Elongation at break, % 700 650 700
zates were measured using a tensile testing
machine Zwick-1101 according to a standard
method. TM
5. The rubber vulcanizates were subjected to However, the cure time (tC9o) and the scorch
thermal ageing w in an air-circulating oven at time (ts2) of resin cured vulcanizate are longer
temperatures as stated, for different periods. than S cured vulcanizates. It can be noticed that
The retained values, %, in tensile strength, the 100% modulus and the elongation at break
elongation at break and 100% modulus of the for the three vulcanizates, under investigation
vulcanizates were calculated. are, almost, unchanged. But the tensile strength
of resin cured vulcanizate ($3) is lower than
those obtained for S cured vulcanizates (S1 and
S2).
3 R E S U L T S AND D I S C U S S I O N
3.1.2 The physico-mechanieal properties after
The rubber mixes were prepared in an open two thermal ageing
roll mill. The rubber blend compositions are shown The three vulcanizates under investigation were
in Table 1. The base recipe contains: rubber 100, subjected to thermal oxidative ageing at 90°C for
ZnO 5 phr, stearic acid 1.5 phr, SRF carbon black various periods up to 7 days. The retained values
40 phr and processing oil 5 phr. of tensile stregth, elongation at break and 100%
modulus were calculated and plotted versus the
3.1 Effect of the vulcanizing systems on the heat ageing time (Figs 1-3, respectively). Those values
resistance of IIR vulcanizates are taken as a measure for the heat resistance of
IIR vulcanizates. It is clear from Figs 1 and 2 that
In order to study the thermal stability of IIR resin cured IIR retains tensile strength and elonga-
vulcanizates, three vulcanizing systems were used: tion at break to a higher extent than S cured IIR
(1) MBT/TMTD/S; (2) Z D E D C / S and (3) neo- (S1 and $2). Also $3 shows moderate values of
prene-w/phenolformaldehyde resin-1054. The for- 100% modulus u p o n ageing as shown in Fig. 3.
mulations are indicated in Table 1. Therefore, it can be concluded that resin cured IIR
has superior performance to the other vulcanizing
3.1.1 Rheometric and physico-mechanical systems used, against thermal ageing. The heat
characteristics resistance of the vulcanizates can be arranged
The rheometric and physico-mechanical data are according to the vulcanizing systems used, in a
shown in Table 1. It is clearly seen that the descending order, as follows:
m a x i m u m and minimum torques of resin cured IIR
are lower than those obtained by S cured IIR. resin cure > S / Z D E D C > S / M B T / T M T D .
 Thermal s.tability of butyl/EPDM rubber blend vulcanizates 473

3.2 Effect of E P D M types on the heat resistance of various types of EPDM were blended with IIR,
I I R / E P D M vulcanizates then the other compounding ingredients were
added to the blend.
In order to select the suitable type of EPDM which
improves the thermal ageing resistance of IIR, 3.2.1 Rheometric and physico-mechanical
characteristics
The rheometric characteristics of the I R R / E P D M
blends and the physico-mechanical properties of
120 • 51 their vulcanizates are given in Table 2. It is clearly
052

100 x $3
seen that blending of IIR with Keltan-820 does not
affect the rheological characteristics of IIR. How-
ever, blending of IIR with Vistalon-5600, Vista-
lon-6505 and Buna AP-447, results in increasing
maximum torque and decreasing minimum tor-
que, cure time and scorch time. It can be also
80
noticed from Table 2 that blending IIR with Vis-
"

talon-5600 and Vistalon-6505 produces vulcani-

zates with lower tensile strength and elongation at
60 break than does Keltan-820. Blending IIR with
Vistalon-6505 and Buna AP-447 results in
increasing of 100% modulus of the blend vulcani-
40
zates. Therefore, Keltan-820 shows no adverse
effect on characteristics of the vulcanizates.
| I I I I I I I
1 2 3 4 5 6 7 8 3.2.2 The physico-mechanical properties after
Ageing t i m e at 9 0 ' C , d a y s thermal ageing
IIR/EPDM vulcanizates with various types of
Fig. 1. Retained tensile strength versus ageing time of IIR
with various vulcanizing systems: S1 (S/TMTD/MBT), $2 (S/ EPDM were subjected to thermal ageing at elevated
ZDEDC) and $3 (Ph. resin).

200,

120 • 51 * Sl
o 52 o S2
x53 180 x 53

100

160
.-e*
E
uJ tw

,°I 140 /

120~
j o x~ x

oL
4_~
0
I , I
1 2
I
3
I
4
I
5
I
6
I
7
J
8 0 1 2
Ageing
3
time
,,ii,
4 5 6
at 9 0 " C , d a y s
7 8
Ageing time at 9 0 ' C , d a y s

Fig. 2. Retained elongation at break versus ageing time of IIR Fig. 3. Retained 100% modulus versus ageing time of IIR
with various vulcanizing systems: S1 (S/TMTD/MBT), $2 (S/ with various vulcanizing systems: S1 (S/TMTD/MBT), $2 (S/
ZDEDC) and $3 (Ph. resin). ZDEDC) and $3 (Ph. resin).
474 S . H . Botros

temperature (120°C) for periods up to 7 days. It oil 5 phr, Neoprene-W 8 phr and phenolformalde-
should be noted, here, that the ageing temperature hyde resin--1045 12 phr.
exceeds that of the previous step (90°C). It is noticed from Table 3 that the maximum
The retained values in tensile strength and torque decreases gradually as the Keltan-820 content
elongation at break, after ageing, were calculated
and taken as a measure of the heat resistance of
vulcanizates, as seen in Figs 4 and 5. It is
obvious that IIR/Keltan-820 vulcanizate shows 120
the best performance against thermal ageing;
since it retains tensile strength and elongation at 4- ~ ÷
break to a higher extent than do the other types
100
of EPDM. This can be attributed to the low
unsaturation value of Keltan-820 (4.5 DB/
1000C). It can be concluded that heat resistance
of the vulcanizates can be arranged in a des- 8O
cending order as follows: Z
Keltan-820 > B u n a R A p - 447 60
> Vistalon-5600 and 6505.
053 v S8
÷ $4 x S 7
40 "55
3.3 Effect of IIR/EPDM blend composition on heat
t m i I i I l
resistance of the vulcanizates
0 1 2 3 z, 5 6 7 8
Ageing time at 120'C,days
In order to produce I I R / E P D M vulcanizate with
outstanding heat resistance a partial replacement Fig. 4. Retained tensile strength versus ageing time of IIR/
of IIR with various proportions of Keltan-820 was EPDM, with various types of EPDM: $4 (Keltan), $5 (Vista-
1on-5600), $6 (Vistalon-6505) and $7 (Buna AP-447).
carried out. Composition of the blends, rheometric
characteristics and physico-mechanical properties
of the vulcanizates are indicated in Table 3. The
base recipe contains: Rubber 100, Zn0 5 phr, stearic
acid 1.5 phr, SRF carbon black 40phr, processing
20t 053
+54
•55
v 56
x 5 7

Table 2. Rheometric characteristics and physico-mechanical 100

properties of IIR/EPDM vulcanizates, using various types of
EPDM
Sample no. $3 $4 $5 $6 $7
80
IIR 100 80 80 80 80 LU
rr
Keltan-820 -- 20 --
Vistalon-5600 -- -- 20
Vistalon-6505 -- -- -- 20 -- 60
Buna R AP-447 . . . . 20
Rheometric characteristics
Maximum torque, dNm 30 28 36 35 40
Minimum torque, dNm 9 9 3 4 6 z,0
Cure time tC9o, rain 34 34 30 30 31
Scorch time ts2, min 6 6 4 3.5 3.5 l I I I ! I | I
Cure rate index (CRI) 3.6 3.6 3.8 3.8 3.6 I 2 3 & 5 6 7 8
Physico-mechanical properties Ageing time at 1 2 0 ' C , d a y s
100% modulus, MPa 0.9 0.8 0.83 1.1 1.2
Tensile strength, MPa 11.2 11 7 9 10.5 Fig. 5. Retained elongation at break versus ageing time of
Elongation at break, % 700 720 600 600 650 IIR/EPDM, with various types of EPDM: $4 (Keltan), $5
(Vistalon 5600), $6 (Vistalon-6505) and $7 (Buna AP-447).
 Thermal stability of butyl/EPDM rubber blend vulcanizates 475

increases in the blend, while the minimum torque, From the results obtained, it can be concluded
cure time (tc90), scorch time (ts2), 100% modulus that IIR/Keltan-820 vulcanizate ($8(70:30)) shows
and tensile strength of the vulcanizates decrease at a superior performance to the other blend compo-
high content of Keltan-820 (40 and 50 phr). On the sitions against thermal ageing at 140°C for 7 days.
other hand the elongation at break is almost not
affected by increasing the content of Keltan-820 in 220
the blend.
2O0 X ~ x ~ x
3.3.1 The physico-mechanical properties after
thermal ageing 180
IIR/Keltan-820 vulcanizates, with various compo-
160
O
sitions, were subjected to thermal ageing at an ele-
vated temperature (140°C) for periods up to 7 140
days. It should be noted here, that the ageing
temperature exceeds that of the previous step ,,., 120
(120°C).
The retained values of tensile strength, elonga- 100 4-
tion at break and 100% modulus were calculated ~ ~~+----~+
80-
and plotted against the thermal ageing time as
illustrated in Figs 6-8, respectively. It is clear that 6O
the retained values of tensile strength increase as
the Keltan-820 content increases in the blend. The 40- • S 3 o S9
replacement of 30, 40 and 50 parts of IIR with + S 4 x S 10
Keltan-820 shows similar but higher retained 2O " S 8
values of elongation at break than those obtained 0
for IIR with and without replacement of 20 parts, 0 1 2 3 4 5 6 7 8
as shown in Fig. 7. Ageing time at 140"C , d a y s
On the other hand, it is found from Fig. 8 that
Fig. 6. Retained tensile strength versus ageing time of IIR/
100% modulus increases to a low extent (a desir- Keltan, with various compositions: $3 (100:0), $4 (80:20), $8
able character) by replacement of 20 and 30 parts of (70:30), $9 (60:40) and S10 (50:50).
IIR with Keltan-820, while it increases to a high
extent by replacement of 40 and 50 parts of IIR. This
can be attributed to the scission of IIR during oxi-
dation and cross-linking of EPDM during oxidative
• $3 o $9
ageing. Therefore, IIR/Keltan-820 vulcanizate $8
+ S4 x $10
(70:30) is the least affected by thermal ageing. 100 /" S 8

Table 3. I I R / E P D M blend composition, rheometric character-

istics and physico-mechanical properties
Sample no. $3 S4 $8 $9 S10
IIR 100 80 70 60 50
E
Keltan-820 -- 20 30 40 50 6O
Rheometric characteristics
Maximum torque, d N m 30 28 26 24 23
Minimum torque, dNm 9 9 9 5 4
40-
Cure time tc90, min 34 34 34 32 30
Scorch time ts2, min 6 6 6 3 3 I | I 1 I I I J
Cure rate index (CRI) 3.6 3.6 3.6 3.4 3.7 0 1 2 3 4 5 6 7 8
Physico-mechanical properties Ageing time at 1/,0 ' C , d a y s
100% modulus, MPa 0.9 0.8 0.8 0.7 0.7
Tensile strength, MPa 11.2 11 9.8 7.3 5.7 Fig. 7. Retained elongation at break versus ageing time of
Elongation at break, % 700 720 730 730 740 IIR/Keltan, with various compositions: $3 (100:0), $4 (80:20),
$8 (70:30), $9 (60:40) and S10 (50:50).
476 S. H. Botros

3.4 Effect of ageing temperature upon physico-

mechanical properties of IIR/Keltan-820 (70:30)
oo] vulcanizate

A severe thermal ageing test was carried out in

order to evaluate the heat resistance of IIR/Keltan-
400 820 vulcanizate.
The prepared vulcanizates were subjected to
thermal ageing in an air-circulated oven at various
temperatures up to 200°C for 48 h. Tensile strength
300 elongation at break and 100% modulus of the vul-
canizates are illustrated in Fig. 9. It is clear that
E tensile strength of the vulcanizate $8 (70:30)
n,-
200
increases as the ageing temperature increases up to
120-130°C, then it decreases till the temperature
reaches 200°C. It should be noted here that, at
165°C, the vulcanizate $8 retains 100% of its ori-
100 • S 3 059 ginal tensile strength value before ageing, while the
+54 x 5 10 elongation at break decreases gradually as the
aSS ageing temperature increases. On the other hand
100% modulus of that vulcanizate, increases as the
OL , , l , i i , ,
0 1 2 3 & 5 6 7 5 ageing temperature increases up to 165°C. Further
Ageing t i m e at 1 4 0 ° C , d a y s increase of the ageing temperature results in a
decrease of 100% modulus. This can be attributed
Fig. 8. Retained 100% modulus versus ageing time of IIR/ to the cross-linking process that takes place till the
Keltan with various compositions: $3 (100:0), $4 (80:20), $8 ageing temperature reaches 165°C. However, a
(70:30), $9 (60:40) and S10 (50:50). chain scission process takes place as the temperature

1000 200

t
x T.S.
oE
~0 • Mocl. 160

:E
600 120 0.~
:E
LIJ -

400 - 80

20O - 4 40

x
0 i I I I I I I 1 I 0 0
0 40 80 120 160 200
Ageing t e m p . , ° C

Fig. 9. Tensile strength, elongation at break and 100% modulus of IIR/Keltan (70:30) versus ageing temperature for 48 h.
 Thermal stability o f b u t y l / E P D M rubber blend vulcanizates 477

increases over 165°C. This result agrees with the after ageing at temperatures above 165°C.
data obtained for the tensile strength. Therefore, the stated vulcanizate can be recom-
From the above results it can be concluded that mended for high temperature application.
the IIR/Keltan-820 (70:30) blend vulcanizate
shows outstanding resistance to thermal ageing;
since it can retain 100% of its tensile strength
value, even after the exposure to thermal ageing at REFERENCES
165°C for 48h.
1. Jablonowski, T. L. and Faiman, D. T., J. Elastomers and
Plastics, 1991, 23, 199.
2. Jablonowski, T. L., Mitchell, J. M. and Suryanarayanan,
4 CONCLUSIONS B., The use of EPDM in butyl inner tubes for improved
performance. Presented at the 14th Rubber Conference of
the India Rubber Manufacturers Research Association,
The following conclusions can be extracted from January 1988.
the observations and the data obtained. 3. Morton, M., Rubber Technology, 3rd edn. Van Nostrand
Reinhold, New York, 1987, pp. 284-321.
1. Resin cured IIR is characterized by low max- 4. Bhaumik, T. K., Gupta, B. R. and Bhowmick, A. K.
J. Mater. Sci. 1987, 22, 4336-4342.
imum torque, longer cure and scorch times 5. Bhaumik, T. K., Bhowmick, A. K. and Gupta, B. R.,
and comparatively having the same physico- Plast. Rubber Process. Applic., 1987, 7, 43.
mechanical properties as those for sulphur 6. Bhaumik, T. K, Gupta, B. R. and Bhowmick, A. K.,
J. Adhesion, 1987, XX, 915.
cured IIR. 7. Trexler, H. E. and Lee, M. C. H., Kautschuk & Gummi
2. Resin cured IIR vulcanizate has superior per- Kunstoffe Jahrgang, 1987, 40, 945.
formance to sulphur-cured vulcanizates, 8. Waiters, M. H. and Keyte, D. N., Trans. Inst. Rubbers
Ind., 1962, 38, T 10.
against thermal ageing at 90°C. 9. Gardiner, J. B., Rubber Chem. Technol., 1970, 43, 370.
3. Of all EPDM types, Keltan-820 shows the 10. Kazhdan, M. V., Bakeyev, N. F. and Berestneva, Z. I.,
best performance against thermal ageing of J. Polym. Sci., 1972, 38, 443.
i 1. Corish, P. J., Rubber Chem. Technol., 1967, 40, 324.
IIR/Keltan-820 vulcanizate at 120°C. 12. Rehner Jr J. and Wei, P. F., Rubber Chem. Technol., 1969,
4. Of all IIR/Keltan-820 blend compositions 42, 985.
investigated, 70:30 is superior because of good 13. Hamed, G. R., Rubber Chem. Technol., 1982, 55, 151.
retension of the tensile strength and the elon- 14. Yehia, A. A., Helaly, F. M. and E1-Sabbagh, S. H., Mod-
eling Measurements and Control., 1992, 32, 53-64, AMSE
gation at break of the vulcanizates, beside the Press.
least increase of 100% modulus, upon the 15. Yehia, A. A., Abdel-Aal, N. S., Helaly, F. M. and E1-
thermal ageing at 140°C for 7 days. Sabbagh, S. M., Proceedings of the 2nd Arab International
Conference on Advances in Material Science & Engineer-
5. From severe thermal ageing test, indications ing (Polymeric Materials), Cairo-Fayom, Egypt, Sep 6-9,
are that the IIR/Keltan-820 (70:30) vulcani- 1993.
zate has an outstanding thermal resistance, 16. Yehia, A. A., Mansour, A. A. and Stoll, B., J. Thermal
Analysis, 1997, 48, 1299.
since it retains 100% of its original tensile 17. ASTM Designation D 2084 76T, 1972.
strength, after ageing at 165°C for 48h; 18. ASTM Designation D 412 66T, 1967.
likewise; that vulcanizate undergoes scission 19. ASTM Designation D 573 55T, 1968.