Service Life Prediction of Rubber Compound by Accelerated Ageing and Mechanical Properties

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SERVICE LIFE PREDICTION OF RUBBER COMPOUND

BY ACCELERATED AGEING AND MECHANICAL
PROPERTIES
Chandresh Dwivedi1*,
K Rajkumar1,
Maninee Vibhande2,
Nikhil Shinde2,
Shrutika Sankhe2
1
Indian Rubber Manufactures Research Association, Thane

2
Dept. of Chemical Engineering, SOJE Thane
ABSTRACT
Generally, the useful life of a rubber component is governed by its susceptibility to failure by
either mechanical or chemical deterioration. There are well established tests to address the failure
properties of elastomers fracture mechanism toinvestigate mechanical durability and also
accelerated aging tests for chemical degradation. This paper is presented to experimentally estimate
the life span of the rubber blend comprising NR and SBR in a ratio of 3:1 at accelerated ageing
conditions. The specimens are subjected to ageing at different temperatures mainly at 900C, 1000C,
1200C and 1500C. The changes estimated at these temperatures were then understood with the help
of the concept of Arrhenius theory and were compared to the rubber sample at ordinary conditions
and the retention in physical properties was assessed.
Keywords: Service Life, Ageing, Mechanical Properties, Arrhenius Law.
INTRODUCTION
Rubber is a widely used material in many applications. Products made from rubber have a
flexible and stable three dimensional chemical structure and are able to withstand under force large
deformations. For example the material can be stretched repeatedly to at least twice its original
length and, upon immediate release of the stress, will return with force to approximately its original
length. Under load the product should not show creep or relaxation. Besides these properties the
modulus of rubber is from hundred to ten thousand times lower compared to other solid materials
like steel, plastics and ceramics. This combination of unique properties gives rubber its specific
applications like seals, shock absorbers and tires.
46
International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976
6480(Print), ISSN 0976 6499(Online), Volume 5, Issue 11, November (2014), pp. 466-60 IAEME
An elastomeric component may be said to reach the end of its life when it fails to function
properly as in seal leakage or a loose elastomeric bushing or when its appearance or some other
o
aspect of its behavior leads to failure of an inspection. Either way, longer more assured lives are
being expected of rubber components at the same time as other demands such as: reduced space
and increased operating temperature. Rubber has a tendency
cy to degrade after a certain period of time.
[1]
There are many factors that lead to degradation of rubber . The four main types of causes that leads
to degradation of rubber are, fatigue causing mechanical aspects, environmental factors, rubber
formulation and consecutive behavior.
A tire compound when subjected to mechanical loading under specific conditions is likely to
rupture after a certain period of time. The appraisal of this life span proves beneficial in
understanding the concept of life prediction
predictio of the rubber compound[2].
With time, we observe specific changes in the rubber sample
sample collectively termed as Aging.
Aging
ing means change in the physical properties
p
of rubber. Thermal aging
ing concerns with the change of
physical properties with respect to various temperature change. Elevated temperature has a
deleterious effect on rubber, both on crack nucleation life, and on fatigue crack growth rate.
Temperature effects occur independently of any chemical changes that may occur due to aging or
continued vulcanization[2,3]. Temperature has a large effect on the rate of these chemical processes,
which can result in additional degradation of fatigue life at elevated temperatures,
temperatures, or over long
period.
THERMAL AGING
Rubber materials are sensitive to temperature and this is particularly evident at low
temperatures. This is a reversible situation as the temperature is increased well above the glass
transition temperature the material recovers its elastomeric characteristics. In a laboratory study
chemical degradation can be accelerated by aging the compound at temperatures higher than the
intended service temperature. This testing involves finding degradation rate and stability of rubber
sample exposed to accelerate to thermal condition to predict
predict the life of rubber sample[3,4]. For some
time period, degradation behavior is studied to life of sample expected for long time, long
temperature explore with quantitative prediction of life of sample. There is established model that
describe the relationship
ationship between reaction rate and temperature.
47
The condition of short period of time with an elevated temperature is useful to yield
predictions of the property degradation expected in the long run with quantitative predictions of
lifetimes obtained from the use of Arrhenius relation[6,7,8] So this method assumes that the chemical
deterioration induced in the lab testing is the factor determining the service life in the field. Although
oxidation of rubber is fairly complex, thermally activated processes can be described using the
Arrhenius equation if certain conditions apply.
Assumption for Arrhenius theory
1. The rate of each chemical step involved in the oxidation process (initiation, oxygen uptake,
termination) must respond the same to changes in temperature.
2. The oxidation proceeds uniformly throughout the material.
Mathematical Representation
Arrhenius theory is originally derived from Thermodynamics. When these assumptions hold,
the rate of oxidative aging, at the use temperature T1, can be determined from the aging rate
measured in the lab at a test temperature T2 from Arrhenius equation [7,8]given by,

K =

1
1
= exp

Where,
K = Overall rate constant of aging process.
= pre exponential factor
= reaction rate at temperature

= reaction rate at temperature
.
Ea. = activation energy. J/molK or cal/molK

R = gas constant (8.314 J/molK or 1.987 cal/molK)
Effectiveness
Arrhenius behavior will be more effective even when the thermal degradation process is more
complicated. In this case the measured Ea. is only an effective activation energy, but nevertheless
still useful for predictions [11]. Although fracture mechanics and Arrhenius extrapolations are both
firmly based on well understood principles, service life predictions are reliable only to the extent that
the relevant failure mechanisms are identified, all contributing factors accounted for, and the samples
used for laboratory test are representative.
Activation Energy
Activation Energy is the minimum Energy by which the colliding molecules of sample must
have in order to bring about the degradation reaction. Lower the value of activation energy, higher
will be the rate at which the degradation will proceed. Higher value of activation energy, lower will
be the rate at which deterioration proceed [8].
48
Graphically Determination Using Arrhenius Plot

If concentration dependency of rate is not known, degradation rate against Temperature data

plotted in the graph, slope will be equal to { }. So, activation energy is determined

experimentally by carrying out reaction at several temperature. The reaction rate at any temperature
is obtained from the change in the selected property with the exposure time at that temperature[7,9].

Ln r = + ln "

Fig: Arrhenius Plot

Four cut samples are then exposed to different temperature 800C to 120 continuously in hot
air oven. Sample is then taken out and conditioned at room temperature. A condition of the rubber
(e.g. brittleness or hardness) is assumed that corresponds to a degree of deterioration likely to cause
product failure. The service life is then estimated as the time for the material to reach this condition
at the service temperature. This can be extrapolated to determine life to the service temperature (TS)
property[13,8,7].
Methodology
1. Before we began, the number of sets of samples required for each tests (for Tensile,
Abrasion, flexing and tearing) which were supposed to be conducted at different temperature
and time period were prepared.
2. Respective number of samples were then exposed to different temperatures (i.e. at 80oC,
90oC, 100oC, 120) continuously in the hot air oven.
3. Then sample was taken out periodically at room temperature according to test plan.
4. The property of the rubber (e.g. brittleness or hardness) was assumed that corresponds to a
degree of degradation likely to cause product failure. The service life was then estimated as
the time for the material to reach this condition at the service temperature.
The service life can be easily changed by choosing a different property, end-point criterion or
test-piece geometry. To improve the accuracy of the prediction, more test temperatures and a greater
number of samples should be tested. Exposed samples are conditioned at room temperature and
analyzed by spectrophotometer. Spectrum will be analyzed by software to study the quantitative
changes in cracks of the sample i.e. variation in the crack length of the samples.
49
Temperature ranges (80, 90,110,120

90,110,120)
There arises a question in our mind that why the selected temperature range is from 80oC to
120 for thermal aging of given rubber sample.[8]
sample.
When sample is subjected to higher temperature, rate of degradation rapidly goes on
changing. So, as wee have discussed earlier, it is easier to estimate the activation energy at
higher temperature.
As the temperature tends to increase it becomes more feasible to estimate the degradation
behavior in a short period of time.
time But, in case of lower temperatures
temperature the process is little
procrastinating
inating as it requires more time for the sample to degrade.
Mechanical Test
2) Tensile strength test
The properties that are typically determined during a tensile test are tensile strength,
elongation at break, stress at a given elongation, elongation at a given stress, stress at yield, and
elongation at yield.. The tensile testing is carried out by applying longitudinal or axial load at a
specific extension rate to a standard tensile specimen with known dimensions (gauge length and
cross sectional area perpendicular to the load direction) till failure.
Dumbbell shaped Specimen
3) Crescent tear test:

This test also measures the force required to propagate a nick already produced in the test
piece, and the rate of propagation is not related to the jaw speed. Nick the test piece to a depth 0.5
mm by a single stroke of the blade[9]
blade
4) Angle tear test:
This test is a combination of tear initiation and propagation. Stress is built up at the point of
the angle until it is sufficient to initiate a tear and then further stresses propagate this tear. However,
50
it is only possible to measure the overall force required to rupture the test piece, and, therefore, the
force cannot be resolved in two components producing initiation and propagation[9,12]
EXPERIMENATL DETAIL
Sample Requirement
In order to calculate the total quantity of the rubber material required, we need to know the
total number of specimens we want to conduct a particular test. Therefore, the following table gives
us the information regarding the number of sets that were needed for the experiment.
Condition
Unaged
90C
100C
120C
150C
Total set of
samples
Duration(in days)
1
1
1
1
3
3
3
3
5
5
5
5
10
10
10
20
-------
Total Number of sets
1
6
5
4
3
19
Formulation:
Sample formulation is the gist of all the ingredients present in the given compound with their
quantities.
CONTENT
BASIC FORMULATION (pphr)
NR(RSS 3)
75
SBR
25
Carbon Black HAF 330
60
Oil
ZnO (activator)
Stearic Acid(activator)
TDQ (antioxidant)
6PPD antoX (antioxidant)
42
Sulphur (curing agent)
2.5
CBS (accelerators)
0.7
Total content
218.2
Molding
Compression, transfer, and injection-molding techniques are used to shape the final product.
Once in the mold, the rubber compound is vulcanized at temperatures ranging from 100 to 200C.
51
The cure time and the temperature are determined beforehand with a curemeter,
curemeter, such as the
oscillating disk rheometer.
The compounded sample is sent to the rheometerat 150C with a cure time of $% obtained
from an oscillating disc rheometer (MDR 2000) according to ASTM D2084 is 8.82min. Then the
samples were molded by compression molding, as per the need.
CALCULATIONS
S AND GRAPHICAL ANALYSIS
1. Life Estimation
A. By Tensile Strength.
Tensile
ensile strength retention in % with respect to time period in hour
Time period
in Hr.
Property reten.
at 90C
Property reten.
at 100C
Property reten.
at 120C
Property reten.
at 150C
90.73
95.14
100
100
24
100
100
51.49
35.3
72
94.59
79.35
39.57
9.36
120
89.19
58.7
30.21
240
67.95
45.75
480
50.58
Graph1:: Tensile Strength (T.S.) Retention at 90C

The above plot of tensile strength retention against time period can give time required for any
% retention value for the particular
icular temperature curves shown in graph-1
graph
52
For 55% retention,

Temperature(C)
90
100
120
150
Time(Hr.)
357.4
133.1
28.4
15.46
Arrhenius Data:
For degradation, we consider first order reaction, so the term ln(k) is taken as ln(1/ t in sec)
and hence Arrhenius data is predicted in the following table.
Temp
1/T (in kelvin)
Time(Hr.)
ln(1/ t in sec)
90
0.0028
357.4
-14.07
100
0.0027
133.1
-13.08
120
0.0025
28.4
-11.25
150
0.0024
15.46
-10.93
Graph 2:
2 Arrhenius plot for 55% retention of T.S.
In the above plot, we obtain a linear nature and using this we can find out the time period (life
span) at ambient temperature.
At, ambient temperature i.e. T= 298K
298
(x=1/T=0.00335) in the graph, we get the value of
If wee trace the value of temperature (x=1/T=0.00335)
function f(x).
F(x) = ln (1/sec) = -18.415
Time at 298k or Life span = 99433536.1sec = 3.2 years.
53
For 60% retention,
Graph 3:
3 Arrhenius plot for 60% retention of T.S.
F(x) = -18.1875
Therefore, Life span for 60% retention of T.S. = 2.78 years
Similarly, we have estimated the life using other testing properties
properties by graphical analysis
B. Abrasion Index
Graph 4:
4 Abrasion property retention graph
54
Arrhenius data:
Graph For 55% retention,
Graph 5: Arrhenius plot for 55% retention of Abrasion Index

F(x) = -18.5726
Therefore, Life span for 55% retention of Abrasion Index = 3.36 years
For 60% retention
Graph 6: Arrhenius plot for 60% retention of Abrasion Index

F(x) = -18.2627
0% retention of Abrasion Index = 2.9years
Therefore, Life span for 60%
55
C. Angle Tear Strength-
Graph 7: Angle Tear Strength Retention at 900C, 1000C, 1200C and 1500C
Arrhenius data:
For 55% retention,
Graph 8: Arrhenius plot for 55% retention of Tear strength retention

F(x) = -17.6343
Therefore, Life span for 55% retention of Angle tear strength = 3years.
56
For 60%
0% retention of tear strength,

F(x) = -17.7215
Therefore, Life span for 60% retention of Angle tear strength = 2.56years.
D. Crescent Tear Strength-
Graph 10:
10 Crescent Tear Strength Retention
57
Arrhenius data:
For 55% retention,
F(x) = -18.2939
Therefore, Life span for 55% retention of Crescent tear strength = 3.1years.
For 60% retention of crescent tear strength,
F(x)= -18.2757
Therefore, Life span for 60%
% retention of Crescent tear strength = 2.8
58
RESULTS AND DISCUSSION

We have made a tread tire compound (NR-SBR) with 3:1 proportion of their standard range
of properties. Further, the samples were subjected to ageing at different temperatures in order to get a
retention percentage. We have selected the temperatures 900C, 1000C, 1200C and 1500C. The
selection of these temperatures weredone in order to complete this experiment of life prediction in a
short duration where current tests available in the industries require longer time. So we have taken a
maximum time period of 20days for aging at 90C as degradation rate is slow at low temperatures
and retention falls up to 50%. A whole month was taken for successful completion of all the tests in
predefined time. This time period had been decided to get a property retention upto 50 %. From
graphs (1,4, 7, 10) we observe that at 90oC and 100C, the retention gradually decreases with time.
Where as in case of 120C it falls rapidly and a steep curve is obtained as compared to 900 C and
1000C and at 150C graph of retention falls immediately. So, the Retention of these mentioned
properties decrease with increase in temperature as well as time.
Using this temperature range and then plotting time retention as well as Arrhenius graph, we
have obtained a range of values for life spans of our rubber blend for 55% and 60% retention of
property which are shown below:
Tests
Life span (in year)

for 55% retention
for 60% retention
Tensile Test
3.2
2.78
Abrasion Index Test
3.36
2.9
Angle Tear Test
2.56
Crescent Test
3.1
2.86
We can observe that life span for 55% retention is more as compared to 60% retention for
each test. This shows that as time for ageing a sample increases the rate of degradation also
increases, which proves that our data obtained from the experiment is correct. Thus life span values
at 55% retention 3 to 3.4 year and at 60% retention 2.6 to 2.9 years respectively.
So for overall life of compound we can assume the minimum value at this specified retention i.e. for
55% retention life is 3 years. And for 60% retention life is 2.6years
CONCLUSION
NR-SBR a tread tire compound is widely used in the tire industries and NR is ubiquitous in
India. SBR is the most economical and environmental friendly rubber. Natural rubber is often used
in heavy vehicles. A blend of this rubber compound.This project helps is in studying the life
prediction techniques for life span of a compound. As we are considering the minimum value for
Life span, life of our compound 2.6years to for 55 and 3years for 60% retention which is allowable.
REFERENCE
[1]
[2]
Y. S. RohanaYahya, A. R. Azura. And Z. Ahmad.(2011). Effect of curing system on

thermal degradation behaviour of NR, Journal of Physical Science, vol-22(2), 1-14.
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polymerphysics.net.
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[3]
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V. A. Coveney, (2013). Service life Prediction- Process and Challenge, Woodhead
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Maria D. Ellul. Mechanical Fatigue, Advanced Elastomer System.
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ASTM D624, (2001). Std. test method for Tear strength of conventional vulcanized Rubber
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60

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International

ISSN 0976 - 6480 (Print)

SERVICE LIFE PREDICTION OF RUBBER COMPOUND

Indian Rubber Manufactures Research Association, Thane

 = reaction rate at temperature 

Ea. = activation energy. J/molK or cal/molK

Graphically Determination Using Arrhenius Plot

Fig: Arrhenius Plot

Temperature ranges (80, 90,110,120

3) Crescent tear test:

Total Number of sets

BASIC FORMULATION (pphr)

Carbon Black HAF 330

6PPD antoX (antioxidant)

Sulphur (curing agent)

Graph1:: Tensile Strength (T.S.) Retention at 90C

For 55% retention,

1/T (in kelvin)

For 60% retention,

Graph 5: Arrhenius plot for 55% retention of Abrasion Index

Graph 6: Arrhenius plot for 60% retention of Abrasion Index

C. Angle Tear Strength-

Graph 8: Arrhenius plot for 55% retention of Tear strength retention

Graph 9: Arrhenius plot for 60% retention of Tear strength retention

RESULTS AND DISCUSSION

Life span (in year)

for 60% retention

Abrasion Index Test

Angle Tear Test

Y. S. RohanaYahya, A. R. Azura. And Z. Ahmad.(2011). Effect of curing system on

G. K. Kannan, L. V. Gaikwad, L. Nirmala, and N. C. Kumar, (2010). Thermal Aging

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= reaction rate at temperature