PolymerDegradationand Stability 62 (1998) 471-477

PII:

1998 Elsevier Science Limited. All rights reserved

Printed in Northern Ireland
0141-3910/98/S--see front matter

S0141-3910(98)00030-5

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
ratios o f E P D M rubber. The physico-mechanical
properties after and before thermal ageing, at
various temperatures, were evaluated.

Butyl rubber (IIR) is most noted for its excellent

resistance to air permeation and, hence, is widely
used in the production o f inner tubes 1 and tire
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 temperature conveyor belt application, 4 mainly for
carrying hot coal. Various properties o f a heat
resistant conveyor belt cover c o m p o u n d based on
E P D M blends, have been reported. 5,6
With the increased emphasis on weight reduction
and the resulting downsizing of the automobile,
additional demands are put on. the elastomeric
components. 7 Butyl and E P D M rubbers are often
used in m a n y applications among which are engine
mounts, body mounts, transaxle mounts and
bushing o f various types.
The problem with blending is that it is often difficult consistently to obtain parts with the same
properties on a batch-to-batch basis. The inconsistency in properties can be attributed to a different degree of mixing in the blend system. A
heterogeneous blend usually results when two chemically dissimilar rubbers are mixed. Several
investigators have examined this morphology. 8-12
M a n y scientists have established the factors which
are important in determining the mechanical
properties o f such blends. 13 other researchers have
investigated the compatibility o f rubber blends. 14-16

2 EXPERIMENTAL

2.1 Materials
Butyl rubber:IIR-268
E P D M rubber types:
Buna R AP-447:ethylene-propylene-ENa terpolymer, unsaturation b 8, ethylene content
70% (from Enie Chem. Elastomer).
Vistalon-5600:ethylene-propylene-EN terpolymer, unsaturation 9, ethylene content 65%
(from ESSO CHIMIE).
Vistalon-6505:ethylene-propylene-EN terpolymer, unsaturation 9, ethylene content 55%
(from ESSO CHIMIE).
Keltan-820:ethylene-propylene-DCPD c terpolymer, unsaturation 4.5, ethylene content
60% (from DSM):
(a) Ethylidene norbornene;
(b) Unsaturation (DB/IO00C);
(c) Dicyclopentadiene.
471

S.H. Botros

472

Compounding ingredients: they are of pure

grade and customarily used in industry.
2.2 Techniques
1. The rubber mixes were blended on a tworoll mill of 460 m m diameter and 3 0 0 m m
working distance. The speed of slow roll
was 16rev/min, and the gear ratio was
1:1.25.
2. The rheometric characteristics of the rubber
mixes were determined using a Monsanto
Oscillating Disc Rheometer R-100 according
to a standard method. 17
3. The rubber mixes were vulcanized in a
hydraulic press at 172+1C for their optim u m cure time (tc90).
4. Mechanical properties of the rubber vulcanizates were measured using a tensile testing
machine Zwick-1101 according to a standard
method. TM
5. The rubber vulcanizates were subjected to
thermal ageing w in an air-circulating oven at
temperatures as stated, for different periods.
The retained values, %, in tensile strength,
elongation at break and 100% modulus of the
vulcanizates were calculated.

Table 1. Vulcanizing systems, rheometric characteristics and

physico-mechanical properties of IIR vulcanizates
Sample no.

S1

$2

$3

IIR
Neoprene-w
MBT
TMTD
ZDEDC
S
P h e n o l f o r m a l d e h y d e resin

100
-0.6
1.2
-1
--

100
---2
2
--

100
8
----12

53
10
13
3.5
10.5

58
12
17
2
6.7

30
9
34
6
3.6

Rheometric characteristics
M a x i m u m torque, d N m
M i n i m u m torque, d N m
Cure time tc90, rain
Scorch time ts2, rain
Cure rate index (CRI), min -1
Physico-mechanical properties
100% modulus, M P a
Tensile strength, M P a
Elongation at break, %

0.88 0.92 0.90

14
13 11.2
700 650 700

However, the cure time (tC9o) and the scorch

time (ts2) of resin cured vulcanizate are longer
than S cured vulcanizates. It can be noticed that
the 100% modulus and the elongation at break
for the three vulcanizates, under investigation
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
The rubber mixes were prepared in an open two
roll mill. The rubber blend compositions are shown
in Table 1. The base recipe contains: rubber 100,
ZnO 5 phr, stearic acid 1.5 phr, SRF carbon black
40 phr and processing oil 5 phr.
3.1 Effect of the vulcanizing systems on the heat
resistance of IIR vulcanizates
In order to study the thermal stability of IIR
vulcanizates, three vulcanizing systems were used:
(1) MBT/TMTD/S; (2) Z D E D C / S and (3) neoprene-w/phenolformaldehyde resin-1054. The formulations are indicated in Table 1.

3.1.1 Rheometric and physico-mechanical

characteristics
The rheometric and physico-mechanical data are
shown in Table 1. It is clearly seen that the
m a x i m u m and minimum torques of resin cured IIR
are lower than those obtained by S cured IIR.

3.1.2 The physico-mechanieal properties after

thermal ageing
The three vulcanizates under investigation were
subjected to thermal oxidative ageing at 90C for
various periods up to 7 days. The retained values
of tensile stregth, elongation at break and 100%
modulus were calculated and plotted versus the
ageing time (Figs 1-3, respectively). Those values
are taken as a measure for the heat resistance of
IIR vulcanizates. It is clear from Figs 1 and 2 that
resin cured IIR retains tensile strength and elongation at break to a higher extent than S cured IIR
(S1 and $2). Also $3 shows moderate values of
100% modulus u p o n ageing as shown in Fig. 3.
Therefore, it can be concluded that resin cured IIR
has superior performance to the other vulcanizing
systems used, against thermal ageing. The heat
resistance of the vulcanizates can be arranged
according to the vulcanizing systems used, in a
descending order, as follows:
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

3.2 Effect of E P D M types on the heat resistance of
I I R / E P D M vulcanizates

In order to select the suitable type of EPDM which

improves the thermal ageing resistance of IIR,

120

51
052
x $3

100
"

80

60

40
|

1
2
3
4
5
6
7
Ageing t i m e at 9 0 ' C , d a y s

473

various types of EPDM were blended with IIR,

then the other compounding ingredients were
added to the blend.

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
their vulcanizates are given in Table 2. It is clearly
seen that blending of IIR with Keltan-820 does not
affect the rheological characteristics of IIR. However, blending of IIR with Vistalon-5600, Vistalon-6505 and Buna AP-447, results in increasing
maximum torque and decreasing minimum torque, cure time and scorch time. It can be also
noticed from Table 2 that blending IIR with Vistalon-5600 and Vistalon-6505 produces vulcanizates with lower tensile strength and elongation at
break than does Keltan-820. Blending IIR with
Vistalon-6505 and Buna AP-447 results in
increasing of 100% modulus of the blend vulcanizates. Therefore, Keltan-820 shows no adverse
effect on characteristics of the vulcanizates.

Fig. 1. Retained tensile strength versus ageing time of IIR

with various vulcanizing systems: S1 (S/TMTD/MBT), $2 (S/
ZDEDC) and $3 (Ph. resin).

3.2.2 The physico-mechanical properties after

thermal ageing
IIR/EPDM vulcanizates with various types of
EPDM were subjected to thermal ageing at elevated
200,

120

51
o 52
x53

Sl

o S2
180

53

100
160
.-e*

uJ

E
tw

,I

140 /

x~

120~

oL
4_~
0

I , I
1
2
Ageing

I
I
I
I
I
3
4
5
6
7
time at 9 0 ' C , d a y s

J
8

Fig. 2. Retained elongation at break versus ageing time of IIR

with various vulcanizing systems: S1 (S/TMTD/MBT), $2 (S/
ZDEDC) and $3 (Ph. resin).

1
2
Ageing

3
time

,,ii,

4
5
6
7
at 9 0 " C , d a y s

Fig. 3. Retained 100% modulus versus ageing time of IIR

with various vulcanizing systems: S1 (S/TMTD/MBT), $2 (S/
ZDEDC) and $3 (Ph. resin).

S . H . Botros

474

temperature (120C) for periods up to 7 days. It

should be noted, here, that the ageing temperature
exceeds that of the previous step (90C).
The retained values in tensile strength and
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
the best performance against thermal ageing;
since it retains tensile strength and elongation at
break to a higher extent than do the other types
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 descending order as follows:

oil 5 phr, Neoprene-W 8 phr and phenolformaldehyde resin--1045 12 phr.

It is noticed from Table 3 that the maximum
torque decreases gradually as the Keltan-820 content

120
4- ~

100

8O

Keltan-820 > B u n a R A p - 447

60

> Vistalon-5600 and 6505.

053
$4
"55

40
3.3 Effect of IIR/EPDM blend composition on heat
resistance of the vulcanizates

In order to produce I I R / E P D M vulcanizate with

outstanding heat resistance a partial replacement
of IIR with various proportions of Keltan-820 was
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

$3

$4

$5

$6

$7

IIR
Keltan-820
Vistalon-5600
Vistalon-6505
Buna R AP-447

100
---.
.

80
20
---

80

80

20

80
-20
-.

-20

Rheometric characteristics
Maximum torque, dNm
Minimum torque, dNm
Cure time tC9o, rain
Scorch time ts2, min
Cure rate index (CRI)

30
9
34
6
3.6

28
9
34
6
3.6

36
3
30
4
3.8

35
4
30
3.5
3.8

40
6
31
3.5
3.6

Physico-mechanical properties
100% modulus, MPa
0.9
Tensile strength, MPa
11.2
Elongation at break, %
700

0.8
11
720

0.83
7
600

1.1
9
600

1.2
10.5
650

1
2
3
z,
5
6
7
8
Ageing time at 120'C,days

Fig. 4. Retained tensile strength versus ageing time of IIR/

EPDM, with various types of EPDM: $4 (Keltan), $5 (Vista1on-5600), $6 (Vistalon-6505) and $7 (Buna AP-447).

20t

v 56
x 5 7

053
+54
55

100

Table 2. Rheometric characteristics and physico-mechanical

properties of IIR/EPDM vulcanizates, using various types of
EPDM
Sample no.

v S8
x S 7

LU

80

rr

60

z,0
l

I
2
3
&
5
6
7
Ageing time at 1 2 0 ' C , d a y s

Fig. 5. Retained elongation at break versus ageing time of

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

increases in the blend, while the minimum torque,
cure time (tc90), scorch time (ts2), 100% modulus
and tensile strength of the vulcanizates decrease at
high content of Keltan-820 (40 and 50 phr). On the
other hand the elongation at break is almost not
affected by increasing the content of Keltan-820 in
the blend.

From the results obtained, it can be concluded

that IIR/Keltan-820 vulcanizate ($8(70:30)) shows
a superior performance to the other blend compositions against thermal ageing at 140C for 7 days.
220

X ~ x ~ x

2O0

3.3.1 The physico-mechanical properties after

thermal ageing

180

IIR/Keltan-820 vulcanizates, with various compositions, were subjected to thermal ageing at an elevated temperature (140C) for periods up to 7
days. It should be noted here, that the ageing
temperature exceeds that of the previous step

160
140
,,., 120

(120C).

The retained values of tensile strength, elongation at break and 100% modulus were calculated
and plotted against the thermal ageing time as
illustrated in Figs 6-8, respectively. It is clear that
the retained values of tensile strength increase as
the Keltan-820 content increases in the blend. The
replacement of 30, 40 and 50 parts of IIR with
Keltan-820 shows similar but higher retained
values of elongation at break than those obtained
for IIR with and without replacement of 20 parts,
as shown in Fig. 7.
On the other hand, it is found from Fig. 8 that
100% modulus increases to a low extent (a desirable character) by replacement of 20 and 30 parts of
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 oxidation and cross-linking of EPDM during oxidative
ageing. Therefore, IIR/Keltan-820 vulcanizate $8
(70:30) is the least affected by thermal ageing.

475

100
80-

4-

~~+----~+

6O
402O

S 3

"

S 8

o S9
x S 10

0
0

Ageing time at 140"C , d a y s

Fig. 6. Retained tensile strength versus ageing time of IIR/
Keltan, with various compositions: $3 (100:0), $4 (80:20), $8
(70:30), $9 (60:40) and S10 (50:50).

$3

100

$9
$10

+ S4
/" S 8

Table 3. I I R / E P D M blend composition, rheometric characteristics and physico-mechanical properties

Sample no.

$3

S4

$8

$9

S10

IIR
Keltan-820

100
--

80
20

70
30

60
40

50
50

Rheometric characteristics
Maximum torque, d N m
Minimum torque, dNm
Cure time tc90, min
Scorch time ts2, min
Cure rate index (CRI)

30
9
34
6
3.6

28
9
34
6
3.6

26
9
34
6
3.6

24
5
32
3
3.4

23
4
30
3
3.7

0.9 0.8
11.2 11
700 720

0.8
9.8
730

0.7
7.3
730

0.7
5.7
740

Physico-mechanical properties
100% modulus, MPa
Tensile strength, MPa
Elongation at break, %

E
6O

40I

1
2
3
4
5
6
7
Ageing time at 1/,0 ' C , d a y s

Fig. 7. Retained elongation at break versus ageing time of

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 physicomechanical properties of IIR/Keltan-820 (70:30)

vulcanizate

oo]

A severe thermal ageing test was carried out in

order to evaluate the heat resistance of IIR/Keltan820 vulcanizate.
The prepared vulcanizates were subjected to
thermal ageing in an air-circulated oven at various
temperatures up to 200C for 48 h. Tensile strength
elongation at break and 100% modulus of the vulcanizates are illustrated in Fig. 9. It is clear that
tensile strength of the vulcanizate $8 (70:30)
increases as the ageing temperature increases up to
120-130C, then it decreases till the temperature
reaches 200C. It should be noted here that, at
165C, the vulcanizate $8 retains 100% of its original tensile strength value before ageing, while the
elongation at break decreases gradually as the
ageing temperature increases. On the other hand
100% modulus of that vulcanizate, increases as the
ageing temperature increases up to 165C. Further
increase of the ageing temperature results in a
decrease of 100% modulus. This can be attributed
to the cross-linking process that takes place till the
ageing temperature reaches 165C. However, a
chain scission process takes place as the temperature

400

300
E

n,-

200

S 3
+54

100

059
x 5 10

aSS

OL
0

,
,
1
2
Ageing

l
,
i
i
,
3
&
5
6
7
t i m e at 1 4 0 C , d a y s

,
5

Fig. 8. Retained 100% modulus versus ageing time of IIR/

Keltan with various compositions: $3 (100:0), $4 (80:20), $8
(70:30), $9 (60:40) and S10 (50:50).

1000

200
x T.S.

oE

~0

Mocl.

160

:E

600

120 0.~
:E

LIJ

400 -

80

20O -

40

x
0

40

80
120
Ageing t e m p . , C

160

200

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

increases over 165C. This result agrees with the

data obtained for the tensile strength.
From the above results it can be concluded that
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
165C for 48h.

4 CONCLUSIONS
The following conclusions can be extracted from
the observations and the data obtained.
1. Resin cured IIR is characterized by low maximum torque, longer cure and scorch times
and comparatively having the same physicomechanical properties as those for sulphur
cured IIR.
2. Resin cured IIR vulcanizate has superior performance to sulphur-cured vulcanizates,
against thermal ageing at 90C.
3. Of all EPDM types, Keltan-820 shows the
best performance against thermal ageing of
IIR/Keltan-820 vulcanizate at 120C.
4. Of all IIR/Keltan-820 blend compositions
investigated, 70:30 is superior because of good
retension of the tensile strength and the elongation at break of the vulcanizates, beside the
least increase of 100% modulus, upon the
thermal ageing at 140C for 7 days.
5. From severe thermal ageing test, indications
are that the IIR/Keltan-820 (70:30) vulcanizate has an outstanding thermal resistance,
since it retains 100% of its original tensile
strength, after ageing at 165C for 48h;
likewise; that vulcanizate undergoes scission

477

after ageing at temperatures above 165C.

Therefore, the stated vulcanizate can be recommended for high temperature application.

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