Polymer Testing 17 (1998) 131–137

 1998 Elsevier Science Ltd. All rights reserved

PII: S0142-9418(97)00039-1 Printed in Great Britain
0142-9418/98/$19.00

MATERIAL BEHAVIOUR

Effect of Aging and Carbon Black on the Mechanical

Properties of EPDM Rubber

S. S. Hamza
Physics Department, Faculty of Science, Cairo University, Giza, Egypt

(Received 12 June 1997; accepted 14 August 1997)

ABSTRACT

Tensile strength, hardness and elongation at break have been measured for ethylene–
propylene diene (EPDM) rubber loaded with different concentrations of HAF carbon
black. The effect of temperature and time of ageing on such properties has also been
investigated. It was found that tensile strength increases with carbon content while
it decreases with temperature and ageing time. On the other hand, the hardness was
found to increase with carbon black content and time of ageing, while elongation at
break exhibited an inverse behaviour. All results were attributed to the changes on
the backbone structure.  1998 Elsevier Science Ltd. All rights reserved

1 INTRODUCTION

In recent years, there has been great interest in the development of EPDM
rubber. This is due to its unusual ability to accept high loadings of fillers as
well as its extensive use in electrical power cables and white side walls of
tires.1–3 Moreover, the insulator compound used in solid propellant rocket
motors is based on ethylene–propylene diene (EPDM) rubber.
Although considerable research efforts have been directed towards ageing
of natural rubber and rubber vulcanizates,4,5 reports on ageing of synthetic
rubber are few. Only few investigations are devoted to ageing of EPDM rub-
ber.6–8 Baldwin8 studied the influence of new cross-links during ageing and
polysulfide linkage on high temperature compression testing. Deuri and Bhow-
mick9 studied the ageing of three grades of EPDM having the same diene

131
132 S. S. Hamza

content but different types of diene (namely, ENB, ECPD and HD). They
reported that the retention in properties of ENB–EPDM vulcanizate is the best.
Ageing of rubber vulcanizate changes the network structure considerably,
which in turn controls the technical properties. These changes are dependent
on both temperature and time of ageing. In previous work,10 the effect of
carbon black (HAF) on the electrical conductivity and creep characteristics of
EPDM rubber has been investigated. It was found that the hardening of the
rubber increased by addition of carbon black.
In the present study, tensile strength, hardness and elongation at break have
been studied for EPDM rubber loaded with different concentrations of HAF
carbon black. The effect of thermal and thermo-oxidation ageing on such
properties has also been studied at different periods of ageing up to a tempera-
ture of 180°C. Such study is important for rubbers to be used for critical appli-
cations.

2 EXPERIMENTAL

All samples were prepared in the Heliopolis Company for Chemical Industry,
Cairo, Egypt. The formulation of the samples is listed in Table 1.
Samples containing different quantities of HAF carbon black were cured at
150°C for 10 minutes. They were further aged in hot air at 120°C (for 12,
24 and 48 h), 150°C (for 24, 48 and 72 h) and at 180°C (for 2, 4 and 6 h).
Ageing has been carried out using a Heirious Heat Cycle Machine VM180/50
(normal oven method with air circulation). Tensile strength and elongation at
break were measured using a Tensile Testing Machine type 2092. The hard-

TABLE 1

Sample ingredients Quantity (phr)

Royalene 512 100

Zinc oxide 5
Stearic acid 2
MB (antioxident) 1·5
Sulphur 1·5
TMTD 1·0
MBT 1·5
Carbon black (HAF) 0, 10, 20, 30 and 50

HB = 2-Mercaptobenzimazole
MBT = 2-Mercaptobenzothiazole
TMTD = Tetra methyl thiuram disulphur
HAF = High abrasion furnace
 Effect of aging and carbon black on the mechanical properties of EPDM rubber 133

ness of the tested specimens was determined by means of a Shore Hardness

Tester of type HGIB.

3 RESULTS AND DISCUSSION

Figures 1(a), 2(a) and 3(a) illustrate the dependence of tensile strength on the
concentration of carbon black at different temperatures and different periods
of ageing. The results obtained show that tensile strength increases sharply
with carbon black content up to a maximum value at about 40 phr and then
starts to decrease at relatively high filler loading (50 phr). On the other hand,
for a given loading tensile strength decreases with the increase of both tem-
perature and ageing time.
The increase of tensile strength with carbon black content is due to the
reinforcing effect of carbon black as a result of the increase of cross-linking
density. After the cross-linking density has become fairly high, it begins to
restrict the orientation process. The higher the cross-link density, the smaller
the probability of orientation and the lower the strength.11
It is worth noting that the blank sample (without carbon black) has more
resistance towards ageing as compared with the loaded samples. This detect-
able resistance was decreased with increasing temperature and time of ageing

Fig. 1. Ageing at 120°C, the variation of the tensile strength, hardness and elongation at break
with the carbon black content at different ageing times.
134 S. S. Hamza

Fig. 2. Ageing at 150°C, the variation of the tensile strength, hardness and elongation at break
with the carbon black content at different ageing times.

Fig. 3. Ageing at 180°C, the variation of the tensile strength, hardness elongation at break
with the carbon black content at different ageing times.
 Effect of aging and carbon black on the mechanical properties of EPDM rubber 135

as shown in Fig. 4, which may be attributed to the fact that carbon black
accelerates the oxygen uptake of sulphur-cured rubber and the reaction is
accompanied by a rapid degradation of polymer. Howkins and Worthington12
reported that carbon black seems to be a catalyst for the direct oxidation of
antioxidants leading to their deactivation. Either effect would account for the
decrease in stability with increasing carbon black content.
At high temperatures, oxidative degradation develops very rapidly leading
to the marked decrease in tensile strength. On the other hand, as the number
of polysulfidic cross-links increases, the more the sample is susceptible to
oxidative ageing. Similar observations have been found in natural rubber,13
where ageing has reduced the number of polysulfidic cross-links and increased
the main chain modification.
Figures 1(b), 2(b) and 3(b) show the variations of the samples hardness
with carbon black concentrations at different temperatures and ageing times.
It is obvious that the hardness increases with carbon black content and with
increasing both the temperature and the ageing time. The concentration growth
of hardness (H) for both ageing time and ageing temperature may be best
fitted by the following empirical formula

H = ␣C + ␤(C* ⫺ C) + ␥

where ␣, ␤ and ␥ are fitting parameters and C* is a percolative concentration

after which there is a gradual change in H with C. It was found from Table
2 that all fitted parameters are dependent on both the temperature and age-
ing time.
Carbon black is known as a reinforcing filler which enhances the hardness
of the rubber. The mechanical properties of vulcanizates do not totally depend

Fig. 4. The variation of the tensile strength with the time of ageing at different ageing tempera-
tures for the blank sample.
136 S. S. Hamza

TABLE 2

Unaged Aged (48 h) Aged (72 h)

␣ 0·71 0·70 0·69

␤ 0·195 0·19 0·23
␥ 47 49·5 53
C* 29 30 20

on the degree of cross-linking but they also depend to a certain extent on the
way in which the vulcanizates, are cross-linked, i.e. the type of the cross-link
(C-C, C-S-C, CSx-c) where x > 2. On the other hand, during ageing of poly-
mers both chain scission and cross-links take place depending on the tempera-
ture and the time of ageing.
In the light of the above considerations, it seems that desulfurization of
polysulfidic cross-links occurs with the generation of additional cross-links.
In other words, with longer ageing time, polysulfidic cross-links are destructed
(since they are weak) to monosulfidic and disulfidic cross-links. Accordingly,
along with the possibility of forming new cross-links due to residual free
sulfur, this will increase the hardening of the rubber.
Figures 1(c), 2(c) and 3(c) show that the elongation at break decreases with
both carbon black content and the time of ageing. This may be due to the
increase of hardness as mentioned before.
These results show that the measured properties depend mainly on the back-
bone structure and its modification.

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 Effect of aging and carbon black on the mechanical properties of EPDM rubber 137

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