Asseref. P. M *, G. Rajesh*, S. Syamala Devi & G.

Rohini Devi
Elastomers Division, HTCC, Advanced Systems Laboratory, DRDO, Hyderabad

ABSTRACT
Aerospace systems employ large number of rubber
components in the form of seals, gaskets, liners, vibration
isolators etc. The service life of these systems is governed
by the useful life of elastomeric materials used in different
subsystems. Defence equipments are expected to have
long storage life. Hence the rubber components should
have long life when stored in different environments
prevalent in the actual field of application. Rubber
components can get degraded when exposed to oxygen,
ozone, sunlight, UV radiations and also due to mechanical
stress in the assembled conditions. A study has been
conducted to predict the life of different rubber
components by accelerated ageing of compositions at
different temperatures both by Hot air oven ageing and
also by Compression stress relaxation studies. In this work
three types of Acrylonitrile Butadiene rubber (NBR)
compositions, Na tura l Rubber (NR) composition,
Chloroprene Rubber, Ethylene Propylene Diene Rubber
(EPDM) compositions are studied for a geing
characteristics. Sam ples were exposed to high
temperatures in hot air oven and in compression stress
relaxation tester. The aged and unaged samples were
periodically tested for physico-mechanical properties.
Experiments were continued till 50 % reduction in
properties. Based on the accelerated test data Arrhenius
methodology is adopted to predict the life at ambient
temperature. Time taken for 50% drop in elongation at
different temperatures in case of hot air oven ageing and
in compressive stress in case of compression stress
relaxation were monitored for each composition. Log of
Time Vs. 1/T (Absolute temperature) was plotted. From
these plots life at ambient temperatures is predicted for
different rubber compositions.
Keywords: Accelerated ageing, Stress relaxation, Life
prediction of Rubber, Arrhenius Methodology.

1. INTRODUCTION
Defence equipments are expected to have long service
life in variety of hostile environments such as hot, dry,
dusty deserts, extremely low temperatures, hot and
humid coastal plains and sometimes in sea water
environments also. The materials selected for various
sub systems should have long life when stored under
the above mentioned environmental conditions.
Aerospace systems consist of many subsystems
*

Corresponding author: pm_ashraf@rediffmail.com

raj15779@yahoo.co.in

assembled with different types of elastomeric seals,

gaskets, liners, vibration isolators etc. Assembled
system is expected to have a life of at least 10 years.
Rubber components used in various sub-systems are
prone to degradation and the designer has to ensure
a minimum life for all the category of seals. One of
the methods to determine the life of the rubber
components is to store the rubber samples at room
temperature and test them at regular intervals [1].
This method requires long time of the order of 2 to 10
years where as accelerated ageing test methods can
be successfully employed to predict the life of rubber
components in few weeks or months.
Rubber polymers like Natural Rubber (NR),
Acrylo-Nitrile Butadiene Rubber (NBR), Chloroprene
Rubber (CR) and Ethylene Propylene Diene Rubber
(EPDM) are often used to develop rubber components
to meet the expected performance of sealing in
aerospace systems [2, 3]. Depending on the polymer
structure and the level of unsaturation, the rubber
polymers can be categorized into three broad groups.
Unsaturated Rubbers, Saturated Rubbers and
Speciality Rubbers. The unsaturated category are
based on a diene monomer and as a consequence have
unsaturated groups repeated along the polymer
chain. Members of this class include Natural Rubber,
Polychloroprene, Acrylonitrile butadiene copolymers
etc [4]. The inherent reactivity of the unsaturated
groups in diene rubbers make them particularly prone
to oxidative degradation. The presence of air, heat and
light cause rapid deterioration of these polymers
unless preventive measures are taken. Oxygen from
the atmosphere ie air decomposes into free radicals
in presence of heat and light and these radicals cause
chain scission giving rise to aldehyde and ketone
groups.
The saturated rubbers include Ethylenepropylene
copolymers,
Butyl
rubbers,
Chlorosulphonated polyethylene etc which are not
prone to oxidative degradation. These materials
contain a small percent of diene constituent to provide
cross linking sites. Ethylene-propylene diene rubber
and butyl contain very low unsaturation. The third

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I J M E M S: 5(1) 2013

category includes the speciality rubbers like

Fluorocarbons, Silicone, Flurosilicone, Acrylate,
Hydrin rubbers which possess high temperature
properties and good oil resistance. They are relatively
expensive materials and are used only for critical
applications. These special rubbers do not degrade
and are expected to have indefinite life [5]. Rubber
compositions filled with carbon Black are less
susceptible to ultra violet degradation and the major
cause of degradation is thermal oxidation.
The factors which can influence ageing are listed
below:
Temperature

: Thermo-oxidation, additive
migration, cross linking
UV light
: Photo-oxidation
Photo-oxidation
: Radio-oxidation, cross
linking
Fluids (gas, organic or : Chemical degradation,
swelling,
extraction,
cracking inorganic liquids,
vapors)
Mechanical stress,
: Fatigue, creep stress
pressure :
relaxation, set, abrasion
Oxidative degradation is generally considered to
be the most serious problem for rubbers at high
temperature. Degradation is relatively slow at ambient
temperatures. Short wave UV and sunlight cause
damage to the rubber components exposed to outdoor
environment. Temperature accelerates the rate of any
chemical reaction. While most photo chemical reactions
are not temperature sensitive, any subsequent chain
reaction usually is temperature dependent [6].
In this present work three types of Nitrile rubber
compositions, Natural rubber, Chloroprene and
EPDM compositions were considered for ageing
studies and life prediction. These compositions were
selected based on its importance and usage in defence
systems. The details of these compositions are
discussed in Experimental part.
2. THEORY AND METHODOLOGY
The properties of rubbers are subject to change as a
result of degradation, ultimately to the point where
the material is no longer capable of fulfilling its
functions. The degree of ageing is dependent on many
factors including Polymer type, formulation, test
product geometry, environmental conditions etc. [7].
2.1 Causes for Chemical Degradation
The chemical degradation of rubber essentially takes
places via radical reaction, these radicals being

initiated by energy sources such as heat, ultraviolet

radiation and presence of oxygen. Radical reaction is
also influenced by species acting as chain transfer
agents and terminators. The form of the reaction for
a given rubber compound therefore varies according
to the behaviour of particular polymer and additives.
2.1.1 Thermo-Oxidative Degradation
Generally, in the absence of radiation, the degradation
of rubber takes places by thermo- oxidative
mechanism. In addition to the factors which usually
affect free radical reaction this type of degradation
depends upon the oxygen density which in turn
depends upon the solubility, rate of dispersion and
rate of oxidation [8].
The general mechanisms by which thermooxidative degradation occur are given below:
(A) When a sufficient supply of oxygen is present
Initiation

Initiator (I)
I + RH
Chain Reaction R + O2
ROO + RH
Termination
2ROO
Reaction

I
IH +R
R OO
R + ROOH
Deactivated
material

Where: RH = rubber
(B) When there is no oxygen present
Initiation

Initiator (I)
I + RH
Chain Reaction R +RH
(Containing
a double bond)
Chain Transfer R +RH
Reaction
Beta scission
R
reaction
Termination
2 R
Reaction

I
IH + R
RRH
(a form of
cross linking)
RH + R
R1 + R2
R-R
Deactivated
material

2.2 Parameters to Monitor Degradation

2.2.1 Tensile Stress Strain Properties
The tensile stressstrain properties are universally
selected as test parameters for ageing. Tensile test
piece is stretched at constant speed to breaking point,
and the force and elongation are measured
simultaneously. These tests are relative simple and
several useful parameters are obtained from one test.
Thin test specimens are used in the test which
minimizes the oxygen diffusion problem [9].

Prediction of Life of Rubber Components by Accelerated thermal Ageing by Hot Air...

Tensile stressstrain properties were determined

experimentally in accordance with the standard
ASTMD 412. Adequate numbers of dumbbell shaped
samples were exposed to elevated temperatures like
120, 110, 100, 90, 80 & 70 C in hot air ovens (as per
ASTM D 573). Five samples were removed at equal
intervals of time (depending upon the exposure
temperature). These samples were tested for tensile
properties. The variation in tensile strength with
respect to ageing is found to be cyclic whereas the %
Elongation at break is linear. Percentage elongation
is found to be sensitive to ageing and is one of the
important characteristics of elastomers. Hence time
taken for 50% drop in percentage Elongation has been
selected to predict the life using Arrhenius approach
[10].
2.2.2 Stress Relaxation
When a constant strain is applied to a rubber sample,
the force that is necessary to maintain that strain is
not constant, but decreases with time and this
behaviour is called stress relaxation. At ambient or
low temperatures (for a short period of time) stress
relaxation is dominated by physical process, while at
high temperatures (for a long period of time) chemical
processes are dominant. It is a critical parameter for
rubber seals and gaskets which are under constant
compression. Hence stress relaxation measurements
in compression are used to measure sealing efficiency.
The standard methods for determination of sealing
force are given in ISO 3384 [11] . The method consists
of compressing cylindrical specimens between platens
under constant strain of 25% and the force exerted by
the test piece is measured continuously or at equal
intervals of time.
Continuous measuring type of stress relaxation
tester made by Elastocon (Sweden) is used for present
study. It consists of three small rigs with load cells.
Three different samples with different temperatures
are used simultaneously. For testing at elevated
temperatures the rig is placed in a cell oven and for
testing at room temperature it is placed in a box
maintained at room temperature, as temperature
stability is of great importance for this test. The
systems are connected to a data acquisition computer
that stores the force and temperature data
continuously. The continuous stress relaxation graphs
are plotted as shown in figure 1.
2.3 Arrhenius Methodology (ISO 11346)
With rise in temperature, there will be an
enhancement in reaction rate of any chemical reaction.
For many organic reactions, a temperature rise of 100C
leads to double or triple the reaction rate. This

63

Relaxation Index
1.0
0.9
0.8

70C
85C

0.7
100C

0.6
0.5
0.4
0.3
0.2

t3

0.1
0.0

10

50

100

t2

500 1000

t1
5000 1000

Figure 1: Continuous Stress Relaxation Graphs

temperature dependence of chemical reaction can be

described by the Arrhenius equation [12].
K (T) = A eE/RT

(1)

Where : K (T) = Reaction rate constant (min), A = Preexponential factor (min), E = Activation energy
(J/mol), R = Gas constant (8.314 J/mol K) and
T = Absolute temperature (K)
The state of a chemical reaction is given by
relation:
Fx (t) = K (t) . t

(2)

Where: Fx (t) = function of the state of the reaction x

and t = reaction time (min)
Due to different reaction rates Ki, at different
temperatures Ti the same threshold value Fa of a
reaction will be reached by different reaction times ti
(equal-value times), e.g. t1 to t3 (Figure 3):
Fa (ti) = K (Ti) . ti

(3)

The Arrhenius equation (1) can be substituted in

equation (3) as follow
Fa (ti) = A eE/RT . ti
Or in logarithmic form with the constant terms
combined in B
In ti = E / RTi + B
A plot of log (time) verses 1/T gives a straight
line with the slope E/R, and is known as an Arrhenius
plot (Figure 3 A). Arrhenius plot is however normally
presented with log 10 times against 1/T. The
activation energy is assumed to be constant over a
temperature range in which the major ageing
reactions are same. The plot is extrapolated to the
value corresponding to ambient temperature or at
required temperature where rubber parts are stored
to predict the life at that particular temperature. This
methodology limits the extrapolation to 30-40C from

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I J M E M S: 5(1) 2013

last data point. The temperature range for ageing is

selected in such a way that at maximum temperature
the sample has to withstand minimum 100 Hrs and
at minimum temperature the sample has to withstand
more than 1000 Hrs.
3. EXPERIMENTAL
Six types of rubber compositions; three Nitrile,
Natural Rubber, Chloroprene & EPDM compositions
were considered for this study. The details of these
compositions are given in table 1. The cure
characteristics were measured by using Tech Pro
ODR as per ASTM D2084 and results are given in table
2. Test slabs (150 X 150 X 2 mm3) and compression
stress relaxation buttons ( 12.5 X 6) were moulded
by means of compression moulding hydraulic presses
with proper cure temperature and time. Dumbbell
specimens of length 115 mm (ASTM D 412 Type C)
were cut from the moulded test slabs by using
specimen cutting press. Five numbers of specimens
were tested for stressstrain properties by means of
R&D Universal testing machine for initial ambient
properties. The physico-mechanical properties are
given in Table 3.
Table 1
Details of Rubber Compositions
Rubber Composition

Remarks

1.

Nitrile 1

Medium ACN content, Black filled,

Semi efficient cure system.

2.

Nitrile 2

Medium ACN content, White filled,

Without Anti-oxidant, Conventional
cure system

3.

Nitrile 3

Medium ACN content, White filled,

With Anti-oxidant, Conventional cure
system

4.

Natural Rubber

ISNR 5, Low Hardness, Less amount of

curatives, Low shear modulus.

5.

Chloroprene

Black filled, Metal oxide cure

6.

EPDM

Black filled, Sulphur cure

Table 3
Physico-mechanical Properties
Properties

Nitrile Nitrile Nitrile Natural Chloro EPDM

1
2
3 Rubber prene

Tensile Strength
(MPa)
Elongation at
break (%)
Hardness (Shore A)
Specific gravity
Compression set %*

19.65 20.51 17.84

323

643

754

71-73 71-73 70-72

1.21 1.12 1.18
9.37 26.2 24.8

11.5 17.38
1100

16.54

242

475

28-30 68-70
1.01 1.40
17.0
15

73-75
1.03
15.43

* Compression set test is done at 70 C, 22 Hrs of exposure.

Around 150 Nos. of dumbbell specimens were cut

and subjected to accelerated ageing at different
temperatures in the range of 70C to 130C (within
accuracy of 2C). The specimens were removed at
periodic intervals and change in tensile properties
(UTS & % Elongation at Break) were measured.
Ageing at a given temperatures was continued till
percentage elongation at break falls to 50% of the
initial value. The methodology is adopted for all the
six compositions. Figure 2 gives typical example for
hot air oven ageing trend for Nitrile (2 & 3) with and
without antioxidant. The time taken for elongation
drop for each composition at different temperatures
is given in table 4. Based on these data Arrhenius
graphs are plotted as given in Figure 3 A to F.

Figure 2: Hot Air oven Ageing Trend for Nitrile 2 & 3

Table 2
Cure Characteristics
Properties
Cure Temperature
(C)
Cure Time t90
(Minutes)
Scorch Time ts2
(Minutes)
Maximum torque
(1b-1n)
Minimum torque
(1b-1n)

Table 4
t1/2 Period for Hot Air oven Ageing

Nitrile Nitrile Nitrile Natural Chloro EPDM

1
2
3 Rubber prene
150

150

4.65

150

130

150

160

6.0 12.82

34.40 12.30

12.83

1.0

3.1

7.3

12.62

1.14

1.79

110.8

95.5

78.0

28.4

93.1

70.8

24.65 22.57 16.40

8.9

10.7

15.70

Time required for 50% drop in % elongation (Days)

Exposure
Temp. (C)
130
120
110
100
95
90
80
70

Nitrile
1

Nitrile
2

5
11

34
118
286

5
15

25
96

Nitrile Natural
3 Rubber

10
18

34
200

8
15
38
154

Chloro EPDM
prene

5
9
46

71
185
336

4
23
42
56

Prediction of Life of Rubber Components by Accelerated thermal Ageing by Hot Air...

3 A (Nitrile 1)

3 B (Nitrile 2)

3 C (Nitrile 3)

3 D (Natural Rubber)

3 E (Chloroprene)

3 F (EPDM)

Figure 3: Arrhenius Plots for Hot air oven Ageing

For compression stress relaxation, button

specimens of size 12.5 6 were compressed by 25%
of initial thickness. Initial force (F0) was recorded. The
drop in force (F) was continuously monitored (every
1 minute) till it reaches 50% of F0. Relative stress decay
(F/F0) is plotted against time. Typical stress decay
curve for Nitrile 1 is given in Figure 4. The time taken
for 50% stress decay for each composition at different
temperatures is given in table 5. Based on the data
Arrhenius graphs are plotted as given in Figure 5A
to E.
Figure 4: Stress Decay Curves for Nitrile 1

65

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I J M E M S: 5(1) 2013
Table 5
t1/2 Period for Compression Stress Relaxation

Exposure Temp. (C)

120
110
100
90
85
80
70
60

Nitrile 1
16.3
32.6
57.7
94.5

189.3

Time required for 50% Decay in Compressive Stress (Days)

Nitrile 2
Nitrile 3
Natural Rubber

6.7
10.2
38
121

3.0
9.3

30.6
67.0

2.8

9.7
39.2

5 A (Nitrile 1)

5 B (Nitrile 2)

5 C (Nitrile 3)

5 D (Natural Rubber)

5 E (Chloroprene)
Figure 5: Arrhenius Plots for Stress Relaxation

Chloroprene

21
36
60

105

Prediction of Life of Rubber Components by Accelerated thermal Ageing by Hot Air...

4. RESULTS AND DISCUSSIONS

From Arrhenius plots of hot air oven ageing data and
stress relaxation data, time required for 50% decay in
property at lower temperature say 40 C (typical
deployment temperature) for different rubber
compositions have been extrapolated. Table 6 gives
the life of rubber compositions at different ageing
environments.
Table 6
Predicted Life of Rubber Compositions
Rubber composition

Nitrile 1
Nitrile 2
Nitrile 3
Natural Rubber
Chloroprene
EPDM

Life predicted at 40C (Years) by

Hot air oven
ageing

Compression Stress
relaxation

40
23
36
28
33
56

14
5.1
6.2
10
8
--

The life of rubber compositions not only depends

upon the type of polymer, filler and cure systems used
but also on the type of mechanical stress to which
rubbers are subjected. From table it is evident that
life of all the compositions is very very low at loaded
condition compared to ageing under no load
condition. Compression stress relaxation is an
important property for application involving critical
sealing.
From the results it is seen that Nitrile rubber
composition (Nitrile 1) when filled with carbon black
and semi-efficient cure system has exhibited higher
life (ie 74% more) compared to the other two
compositions (Nitrile 2 & 3) which are filled with silica
based white filler and conventional cure system. This
composition has behaved well under compression
also. From the results of Nitrile 2 & 3 it is found that,
composition with Antioxidant have given better life
(ie 56% more) than the composition without
antioxidant.
Natural rubber formulation with low sulphur cure
system and black filler, designed to meet low shear
properties gives a life of 28 years with hot air oven
ageing and 10 years under compression. Chloroprene
composition gives a life of 33 years by hot air oven
ageing but a lesser life under compression, even lower
than that of Natural rubber. Even though chloroprene
is considered to have a better life than that of Natural
rubber it gives a lesser life under compression. This
is due to the Metal oxide cure system used for this
composition. EPDM gives a better life of 56 years
which expected due to the presence of saturated

67

polymer chain thereby high inactivity of this

copolymer to degrading agents.
General practice of categorizing the rubbers for
life prediction based only on the polymer type may
not be true. From the results it is clearly seen the type
of filler, cue system and type of antioxidant play a
critical roll in imparting ageing resistance to rubber
compositions.
5. CONCLUSIONS
Accelerated ageing of different rubber compositions
were carried out by hot air oven ageing and
continuous compression stress relaxation methods
and life of each composition was predicted at 40 C
by Arrhenius approach. The life of rubber components
not only depends on the type of polymer used but
also on the type of filler (black or non-black), the cure
systems and the type of antioxidant used in the
respective compositions. This effect is reflected both
in hot air oven ageing and compression stress
relaxation studies. The life predicted by hot air oven
ageing can be considered for assigning shelf life of
rubber components, where as the life predicted by
Stress relaxation can be considered for assigning life
in the assembled condition especially for seals and
gaskets. The Arrhenius approach is found to be
extremely useful in prediction the life of different
rubber compositions in relatively short time based on
accelerated ageing data. However while assigning the
actual life, many other parameters like actual storage
/service conditions, storage environment, presence
or absence of hydraulic oils, corrosive chemicals,
exposure to any other gases or vapors and special
functional requirements the rubber components
actually have to perform have to be judiciously
considered.
References
[1]

Natural Ageing of Rubber, Cha nges in Physical

Properties over 40 years. Roger P. Brown, and T. Butler,
RAPRA Technology Ltd. 2000.

[2]

Rubber Technology Compounding and Testing for

Performance by John S. Dick. Published by Hanser.

[3]

Rubbery Materials and their Compounds by J.A.

Brydson Elsevier Publication 1988.

[4]

Rubber Technology and Manufacture by C. M. Blow

and C. Hepburn. 2nd Edition. Published by Plastics and
Rubber Institute.

[5]

Rubber Compounding-Chemistry and Applications

edited by Brendan Rodgers 2004.

[6]

Ageing of Rubber by Roger P. Brown, T. Butler and S.

W. Hawley. RAPRA Technology Ltd. 2001.

[7]

Failure of Plastics and Rubber Products-causes, Effects

& Case Studies Involving Degradation by David Wright,
RAPRA Technology Ltd. 2001.

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I J M E M S: 5(1) 2013

[8]

Addressing Durability of Rubber Compounds by N. M.

Huntik Rubber Chemistry and Technology, Volume 77.

[9]

Practical Guide to the Assessment of the Useful Life of

Rubbers by Roger P. Brown, RAPRA Technology Ltd.
2001.

[10] Long Term and Accelerated Ageing Test on Rubbers

by R. P. Brown, M. J. Forrest & Soulanget G. (2000)
RAPRA Review Reports 110, 2001.
[11] Rubber, Vulcanized or Thermoplastic-Determination of
Stress Relaxation in Compression at Elevated and
Ambient Temperatures, ISO 3384.

[12] Rubber, Vulcanized or Thermoplastic-Estimation of

Lifetime and maximum Temperature of use from an
Arrhenius Plot, ISO 11346.
[13] Optimizing the Heat Resistance of EPDM and NBR by
Bob Ohm, et al. Presented at a Meeting of Rubber Division.
American Chemical Society 2000.
[14] Ageing of Rubber-Accelera ted Hea t Ageing Test
Results by R. P. Brown, T. Butler and S. W. Hawley
RAPRA Technology Ltd. 2001.
[15] Application of Statistics to Rubber Testing BS: 5324.