Some Factors Affecting The Service Life of Natural Rubber Articles
Some Factors Affecting The Service Life of Natural Rubber Articles
The paper is mainly concerned with failure under repeated stressing (fatigue) and creep
behaviour.
Fatigue failure is a crack growth process from small naturally occurring flaws. A critical
minimum severity of strain is necessary to produce any mechanical crack growth at all and this
governs the 'fatigue limit', the strain below which the fatigue life is very great. Factors which
influence this minimum severity include the molecular structure of the vulcanisate, the presence
of oxygen and anti-oxidants and the minimum strain during the strain cycle. Ozone attack can
be very important in fatigue at low strains.
Creep and stress relaxation are due to a combination of physical and chemical effects. The
former is affected by humidity, pre-stressing and the nature of the vulcanising system, whereas
the latter depends on the chemical stability of the vulcanisate.
Many factors can influence the useful life of a in engineering applications as it may be rapid
rubber article in service. It may, for example, and catastrophic.
become excessively hard or soft or become As the failure is essentially a crack growth
mechanically weak due to chemical changes. process from small flaws, the crack growth be-
These effects are countered by suitable com- haviour of the rubber and the size of the initial
pounding to improve the chemical stability. flaw are the essential factors determining fa-
The present paper is mainly concerned with two tigue life.The crack growth characteristics of vul-
factors which are of particular concern in en- canised rubbers have now been quite extensive-
gineering applications: mechanical failure due ly studied (THOMAS, 1958; LAKE AND LINDLEY,
to repeated stressing (fatigue), and the creep (or 1964 and 1965). The form in which they have
stress relaxation) which occurs under a constant been expressed has been derived from earlier
load (or deformation). In both cases, chemical work on tear behaviour (RIVLIN AND THOMAS,
as well as physical processes are important. 1953; THOMAS, 1960). This approach considered
the energetics of crack propagation. If a crack
FATIGUE FAILURE of length c in a strained test piece grows by a
Under repeated stressing, rubber components small amount thus producing an area dA of
may eventually fail. If the stressing is vigorous new surface, the amount of energy (U) in the
and the component is large, failure may be due strained test piece is reduced by oU. This lost
to excessive heat build-up, as may happen in energy can be considered as the energy available
large tyres at high speed. In this paper, however, for driving the crack through the rubber, and a
cases where the temperature rise itself is a major quantity 3 UfoA can be denned which can loosely
factor are not being considered. Failure at nor- be described as the driving force trying to make
mal temperatures under repeated stressing is the crack grow. This quantity is known as the
due to the growth of small cracks across the tearing energy and is denoted by T. It has been
specimen until finally rupture occurs. This is a shown that T governs the magnitude of the
mode of failure which must be guarded against stresses around the tip of the crack (THOMAS,
COMMUNICATION 512
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Journal of the Rubber Research Institute of Malaya, Volume 22, Part 2, 1969
192
depends on the particular vulcanisate and the growing crack which does not disappear on
form of the strain cycle. By using Equation (4), partial relaxation and thus produces an effec-
which can be determined by crack growth mea- tive strengthening of the material. The effective
surements, instead of Equation (2) the fatigue value of To increases and the rate of crack
life in the presence of ozone can be predicted growth at T values above it decreases. The
and compared with experiment, as shown in effect of incomplete relaxation on fatigue is
Figure 4. The agreement, using the flaw size much less in a non-crystallising rubber such as
deduced from high strain measurements of SBR as Table 1 indicates (LAKE AND LINDLEY,
2.5 x 10~3 cm, is satisfactory. 1966).
In practice, most spring applications do not
allow the rubber to be completely relaxed. This
can greatly enhance the fatigue life. This en- TABLE 1. EFFECT OF STRAIN
hancement appears to be due to the presence of CYCLE ON FATIGUE LIFE
strain-induced crystallisation at the tip of the
Fatigue life (kilocycles)
Strain cycle
NR SBR
0-250 13
50-240 13 000
194
C. J. DERHAM et al.: Some Factors Affecting the Service Life of Natural Rubber Articles
surements in tension may suggest. A rubber straightforward. This question will be consi-
disc 2 cm diameter and 3 mm thick bonded to dered later.
metal on its major faces was compressed by Some of the factors affecting physical creep
16% and exposed to ozone at 600 parts per mil- and stress relaxation will now be considered.
lion for 25 hours. This is equivalent to about
fifty years at normal atmospheric concentra- (i) Humidity
tions. Although cracks grew, they penetrated It was apparent from stress relaxation mea-
only about 1 mm into the body of the rubber, surements carried out at room temperature that
equivalent to a rate of growth only about 450 the atmospheric humidity was influencing the
of that observed in tension. The reason is pro- results appreciably. A systematic study was
bably that the very small opening of the cracks therefore made. The sample, about 1 mm thick,
under this strain makes access of ozone difficult. was immersed in a suitable aqueous solution
This effect is fortunate as many rubber com- for at least 20 minutes, rapidly extended while
ponents for long term applications are used in still in the solution and the subsequent stress
compression. decay followed. The apparatus was thermo-
CREEP AND STRESS RELAXATION stated at 25°C.
Under constant load the deformation of a rub- Saturated aqueous solutions of various in-
ber sample increases steadily with time, the organic salts were used giving a range of relative
phenomenon of creep. At constant deformation humidities from 15% upwards. Check mea-
relaxation of stress occurs. The two effects are surements with air at various humidities showed
aspects of the same molecular processes and the that the salts themselves did not influence the
relation between them is governed by the force- relaxation and presumably did not enter the
deflection curve. If this is known, one can be rubber. Results for vulcanisates A (a conven-
calculated from the other (GENT, 1962a). tional CBS-accelerated sulphur mix given in the
Broadly speaking therefore, compounding and Appendix) and B (a peroxide vulcam'sate) are
other changes which improve one will improve shown in Figure 5 for 100 % extension. Varying
the other. the humidity has two effects:(a)the overall rela-
In springing and load-bearing applications xation rate increases with humidity; and (b) the
generally, creep is probably the main disadvan- shape of the curves varies systematically, those
tage of rubber as compared with steel, and in at high humidity curving upwards. It has been
severe conditions, such as at elevated tempera- reported that accelerated sulphur vulcanisates
tures, may limit the useful life. Understanding similar to this one give linear log(tkne) relations
of the phenomenon, prediction of the amount for physical relaxation (GENT, 1962a). It ap-
of creep over long periods and improvements pears that this is somewhat fortuitous and arises
in materials are thus of importance. because laboratory humidities are usually in
There are two components of creep: (i) a the range 30 -60% where this relation holds
physical effect which reflects the internal visco- approximately.
sity, and (ii) chemical effects which are due to The substantial magnitude of the effect of
cross-link and main chain scission. The physical humidity shows the desirability of control of
component contributes a term approximately this variable during testing and also the possible
proportional to the logarithm of the time after important effect of atmospheric humidity on
loading (GENT, 1962a) and thus gets progres- service performance.
sively less important at longer times. The chemi-
cal component is approximately proportional (ii) Vulcanising System
to the time, and at very long times becomes the Relaxation rates depend on the degree of
dominating effect (GENT, 1962b). The two com- cross-linking so that this must be held constant
ponents have different variations of rate with when other compounding variables are consi-
temperature so that extrapolation of creep rates dered (GENT AND MASON, 1963). The moduli of
to service temperatures is not completely the two rubbers shown in Figure 5 are similar,
195
5-O
*N
92%
jj > S/C BS
///
J/ / 66%
47%
//// / Peroxide
2-0
10 100
Time, minutes
Figure 5. Effect of relative humidity on physical stress relaxation for natural rubber SjCBS and
peroxide vulcanisates A and B respectively. The figures by each curve give the relative humidity.
C. J. DERHAM et al.: Some Factors Affecting the Service Life of Natural Rubber Articles
197
Journal of the Rubber Research Institute of Malaya, Volume 22, Part 2, 1969
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C. J. DERHAM et al.: Some Factors Affecting the Service Life of Natural Rubber Articles
DISCUSSION
Chairman: Dr. A. A. Watson
Dr. P.Thirion asked about the effect of humidity on stress relaxation and the time of recovery of the free strain.
Mr. Thomas replied that die humidity effect was due probablyto the non-rubbers rather than the polyisoprene
itself, because the diffusion of water into rubber was controlled by the non-rubbers present. Dr. C.E. Scott en-
quired if similar humidity effects were shown by synthetic cw-polyispprene whose non-rubber constituents were
greatly reduced. Mr. Thomas replied that humidity affected synthetic cw-polyisoprene as well as natural rubber,
but comparative data—especially on synthetic—were lacking. Mr. S.W. Shi asked if the effect of humidity
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Journal of the Rubber Research Institute of Malaya, Volume, 22, Part 2, 1969
could be due to water acting as a physical plastitiser. Mr. Thomas said that plasticisation often reduced stress
relaxation rates; perhaps water softened some components and imparted a stiffness dependent on time, which
would contribute to the creep. Mr. Thomas said that work was in progress on EV vulcanisation systems, which
Mr. J. Payne suggested would show less creep than the conventional use of sulphur; Dr, J.I. Cunneen added
that EV compounds should be better than conventional sulphur vulcanisates in long-term creep where chemical
effects were important, but the behaviour of EV systems and conventional vulcanisates were very similar in
short-term creep,
Mr. R.A. Billett said that lampblack—mentioned in the paper—was virtually unobtainable outside Britain.
Mr. Thomas said lampblack was the material used in the experiments, but any soft non-reinforcing black could
be used. Dr. P.M. Sorgo stated that carbon blacks were very specific in their applications and should not be
used indiscriminately. However, a black with the desired properties—such as large particles and non-rein-
forcing—could always be obtained. Dr. A.A. Watson considered that medium thermal black would provide a
good replacement if lampblack was not available. He asked if it was known what gave rise to the extra creep.
Mr. J. O'Connell commented that lampblack increased stiffness with minimum loading. Mr. Thomas informed
Mr. I.K. Yeo that creep behaviour in rubber under compression was under investigation.
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