DOI 10.

1007/s11223-019-00113-5
Strength of Materials, Vol. 51, No. 4, July, 2019

ACIDIC-THERMAL AGEING EFFECT

ON COMPRESSION STRESS RELAXATION OF SILICONE RUBBER

G. Li,a,1 J. M. Gong,b J. Z. Tan,b D. S. Zhu,a UDC 539.4

W. H. Jia,a and X. J. Lua

The compression properties of silicone rubbers used as gaskets in PEM fuel cells are studied. The
specimens are aged under different test conditions, viz, high temperature, humid air, and acidic
solutions, prepared to match real PEM fuel cell operation conditions. The compression and stress
relaxation tests are conducted. Temperature, humid air and acidic solution exert a serious effects
on the mechanical performance of silicone rubbers. All the three factors can ñàuse an increase in
the stress relaxation modulus and permanent compression deformation. The effects of high
temperature and an acidic solution are more pronounced. This can accelerate the deterioration of
mechanical properties and decrease the sealing efficiency of gaskets, which would influence the
durability of PEM fuel cells. It creates the basis for life prediction of silicone rubbers under
appropriate accelerated durability test conditions.

Keywords: stress relaxation, compression, silicone, fuel cell.

Introduction. The long-term stability of PEM fuel cells, which are very lucrative power sources, due to their
high efficiency and zero pollution, is critical. The performance of PEM fuel cell components under operation
conditions is in the focus of current research. In particular, polymer gaskets in PEM fuel cells are subjected to humid
air, acidic environment, and compression by assembling bolts to prevent leaking [1–6]. Polymeric materials,
including rubbers, are known to have viscoelastic properties. That is to say the relation between stress and strain
intensively relies on time. If the strain is held constant, the viscoelastic material will show stress relaxation behavior:
its stress drops with time at a constant strain [7–9]. The sealing force would decay with time due to the stress
relaxation of the gaskets after assembly in applications. Then, the gasket would lose its sealing functionality when
the stress in the gasket becomes lower than a certain value.
Therefore, many researchers focus on the chemical degradation and the mechanical properties of silicone
rubbers [2–15]. Elleuch and Taktak [10] have studied the monotonic tensile behavior and viscoelastic behavior such
as, creep and relaxation of the HDPE and found both elastic modulus and plastic flow stress displaying an increase
with displacement speed. Zhao et al. [12] have investigated the effect of the concentration of oxygen, temperature and
strain levels on the stress relaxation behavior of nitrile rubber in different test conditions. And it is found that at final
stage the stress rebound is mainly due to the thermos-oxidative cross-linking rather than chain scission. Fernandes
and De Focatiis [13] have obtained the tendency of stress relaxation varying with the deformation history of the
carbon-filled EPDM rubbers and found the stress relaxation is highly relying on strain levels under a constant load.
Liu et al. [14] have found that the stress relaxation rate has a linear correlation with the deformation rate in
different polymer glasses in cases of large-scale extension and compression and proposed the correlation between the
molecular mobility and nonlinear stress relaxation behavior. Li et al. [15] have developed a computational algorithm
a
College of Mechanical Engineering, Nanjing Institute of Technology, Nanjing, China (1liguoperfect@
163.com). bSchool of Mechanical and Power Engineering, Nanjing Tech University, Nanjing, China. Translated from
Problemy Prochnosti, No. 4, pp. 181 – 188, July – August, 2019. Original article submitted October 20, 2018.

660 0039–2316/19/5104–0660 © 2019 Springer Science+Business Media, LLC

of volume averaged for 3-D model for estimating the viscoelastic properties of composites and clarified the effect of
constructing method of the repeating unit cells with square, hexagonal, and random fiber packing.
Some researchers proposed an appropriate mode to fit the experimental data and predicted the service life of
the materials [16–22]. Such as, Rao et al. [16] have developed three types of SMEPs with different cross-linking
densities by curing an aromatic epoxy resin with aliphatic amines. The viscoelastic behavior of SMEPs were
obtained by creep-recovery test at a certain temperature and a three-parameter Zener model was employed to fit the
experimental data. The latter effectively described the viscoelastic behavior of SMEPs depending on test temperatures.
Pieczyska et al. [17] have found that the polymer deformation process intensively relies on the applied strain rate and
obtained a new constitutive model valid in a finite strain regime for polyurethane shape memory polymer, which is a
multifunctional new material described as a two-phase material comprised of hyperelastic rubbery phase and
elastic-viscoplastic glassy phase.
Rey et al. [18] have considered the effect of the temperature on the compressive mechanical behavior (such
as compression set, stress relaxation) of silicone rubber with and without fillers. The neo-hookean model was applied
to estimate the experimental data above-mentioned. Kömmling et al. [19] have obtained that the heterogeneous aging
leads to distortion of the whole performance involving the compression set and the compression stress relaxation in
compressed HNBR and EPDM O-ring seals. It is suggested that HNBR has better property than EPDM at 150°C but
which is not the case at 100°C. By applying the time–temperature superposition principle, the exemplary CS values
of 80% would be reached after approx. 29 years for HNBR and approx. 1100 years for EPDM, respectively.
Vaidyanathan et al. [20] have validated the predictive models of stress relaxation in selected dental polymers
and obtained the predictive models by using the master curves constructed from experimental data in a short time with
WLF time temperature superposition method. Maria et al. [21] have found that the nature of nanoclay can influence
the stress relaxation rate of the rubber/nitrile rubber nanocomposites. The organically modified clay could improve
the mechanical property. And the Maxwell–Weichert model was proposed and well to fit the experimental values.
Yamaguchi et al. [22] have studied the mechanical performance such as creep, stress relaxation and set recovery of
the cross-linked natural rubber without fillers in tension. A new method according to Boltzmann superposition
principle is applied to contrast the creep compliance to a measurement of its recovery after release from a series of
constant loads at different time. Cui et al. [7–9] have studied the mechanical performances of silicone rubber and
EPDM in simulated fuel cell environments and predicted the service life of by master curves and Maxwell model.
The present study is concerned with the compression set and the compression stress relaxation behavior of
the polymers in different test environment such as in ambient air, in wet conditions, in acidic solutions at elevated
temperatures and the strain level is set as 25%. This study is aimed to provide the experimental data for predicting
the lifetime of gaskets.
1. Material and Experiments.
1.1. Material and Preparation. The silicone rubber material has many advantages in sealing field. It
possesses the properties of elasticity and viscoelasticity and keeps the performance stable in a wide range from - 40
to 120°C. Due to this excellent and economic performance, it becomes a potential material for gaskets in all kinds of
sealing applications, including in the proton exchange membrane fuel cell application. Generally speaking, the
silicone rubber material is cross-linked by peroxides, and uses carbon black and calcium carbonate as its fillers.
Because of its good flexibility and weather resistance, the gaskets made from silicone rubbers are employed in the
PEM fuel cells. The gaskets are compressed at all times by the clamping force when the PEM fuel cells are
assembled to prevent the leakage of reactant gases. When the silicone rubber material is exposed to PEM fuel cell
operational conditions which is humid, acidic and at a high temperature, its chemical composition on the surface
could change over time and this will result in the damage of its bulk mechanical properties, especially the
compressive mechanical properties, such as the permanent compression set deformation and the stress relaxation
behavior related to its viscoelastic performance depending on the temperature.
In this research, a commercial silicone rubber in sheet form is acquired from the manufacturer in China and
shaped into cylindrical buttons with 13 mm in diameter (D) by 6.3 mm in height (H) as far as possible for
compression tests, according to the GB/T7759.1-2015 and GB/T1685-2008 standards [23, 24].

661
 Three solutions are used to age the materials. The first solution is just the deionized water with 18 MW
resistance. Because the reactant gases need to be humidified in the PEM fuel cells for producing a high current
density, so the gasket is under a humid condition. The second solution is composed with 12 ppm sulfuric acid
(H2SO4), 1.8 ppm hydrofluoric acid (HF) and deionized water, termed “RS” (short for regular solution). The PH
value is about 3~4, which is close to the real PEM fuel cell operational environment. The third solution is composed
with 1 M H2SO4, 12 ppm HF and deionized water, called “ADT.” Because this solution is prepared for accelerated
durability test. The PH value is less than one. Besides, the unaged samples and the samples exposed to air under
different temperatures are used to be compared.
The cylindered-shaped samples are prepared first and then they are put into different solutions individually.
The exposed specimens are taken out from the test bottles at a certain period of time according to the actual aging
process, about 7 days but not fixed, for all experiments.
1.2. Test Equipment. The compression set and the stress relaxation tester made by Mingzhu Co. Lt., China,
are put into use in the experiments. There are three independent testing rigs, which can test the samples at levels of
10, 15, and 25%, respectively. The third level is chose in this paper. The compression permanent deformation was
measured by the thickness tester. The stress relaxation was conducted, and the force at a constant strain level was
recorded with time throughout the whole test period by a computer.
1.3. Experimental. The specimens of silicone rubber materials were immersed in the air, in the DI water, in
the RS and in the ADT environments at temperatures of 30, 70, and 90°C, individually. Then the exposed samples
were detached for compression set test and stress relaxation test at 25% strain levels individually at room temperature
for every selected time. The test procedure follows the GB/T 7759.1-2015 and GB/T 1685-2008 standards.
The data obtained in this study may be used to investigate the effect of different operating conditions, acids,
water, and temperature on the compression mechanical properties of gasket seals, as well as lay a foundation to the
lifetime prediction in the future research.
2. Results and Discussion.
2.1. Compression Set. The samples immersed in DI water for different time were taken out for compression
set test. The samples were sandwiched by compression set tester at 25% strain level for three days. Then the
thickness of the samples were measured and compared to that of uncompressed samples. The results are displayed in
Figs. 1–3. The compressive deformation was calculated according to Eq. (1).

H - H¢
C= ´100%, (1)
H

where C is the compression permanent deformation, H and H ¢ are sample heights before and after compression,
respectively.
Figure 1 shows the compression permanent deformation versus time when the strain levels is 25% for
specimens exposed to DI water at two temperatures, namely 30 and 70°C. It can be seen that the compression
permanent deformation increases with the exposure time for the samples exposed to DI water both at 30 and 70°C.
The trends of both curves are similar to each other but the deformation of samples exposed to 70°C is higher than that
of samples exposed at 30°C at the same exposure times. The deformation reaches up to 5% when the exposure time is
over 100 days. The deformations are about 4.7% and 4.0% for samples exposed to 30 and 70°C for 30 days,
respectively. Larger deformations imply that the resilience of silicone rubbers gets worsened. However, the silicone
rubber is used as gasket material due to its excellent hyper- and viscoelastic properties. So this result indicates that
the mechanical property of the materials is deteriorated and the temperature contributes more than the DI water on
the deterioration of mechanical properties, which finding is consistent with other available reports. For example, Wu
et al. [25] have analyzed the rules of thermal-oxidative aging on the mechanical properties of aero-NBR. The
experimental results also show that the compression permanent deformation increases with time.
The compression permanent deformation for samples exposed to DI water and air at 70°C is present in Fig. 2.
In Fig. 2, the effect of the exposure environment (DI water) on the deformation is obvious, and the trends of the
curves are identical to those in Fig. 1. The compression permanent deformation of samples immersed into DI water is

662
 Fig. 1 Fig. 2
Fig. 1. Compression set of silicone rubbers exposed to DI water at 30 and 70°C.
Fig. 2. Compression set of aged silicone rubbers with or without DI water.

Fig. 3. Compression set of aged silicone rubbers in different test solutions.

a little larger than that of samples in the air at the same temperature. As compared to Fig. 1, it can be observed that
the DI water effect on the deformation is less than that of the temperature.
Figure 3 shows the compression permanent deformation versus time obtained from specimens exposed to DI
water, regular solution (RS), and the accelerated durability test solution (ADT) at 70°C. From Fig. 3, it can be seen
that the deformation of samples in DI water is close to that in RS, but the deformation of samples in ADT is larger
than that of the former two. The deformation increases to 6.5% in samples immersed into ADT solution for about 20
days but rises only by 5% in samples exposed to DI water for over 100 days. These results prove that the elastic
resilience of the silicone rubber deteriorated most in the higher concentration acid solution. This can be attributed to
the fact that HF and H2SO4 can strongly damage the chemical structure by decomposing the main chain Si-O-Si in
backbone to form Si-O and the hydrolyzing of cross-links [1, 2].
2.2. Stress Relaxation. The immersed samples were taken out for compression stress relaxation tests. The
test data were recorded by computer in the real-time scale (once per second).
Figure 4 shows the curves of time-dependent compression stress relaxation and the Young modulus obtained
at 25% strain levels for specimens in air at temperatures of 30, 70, and 90°C aged for 1 week. Not being identical, the
tendency of curves is similar. Besides, the curve of the unexposed sample is present for comparison. From this figure,

663
 Fig. 4 Fig. 5
Fig. 4. Compression stress relaxation modulus E of silicone rubber at temperatures 30, 70, and 90°C.
Fig. 5. Compression stress relaxation modulus E of silicone rubber exposed to test solutions at 70°C.

it can be seen that the Young modulus E decreases dramatically at first. After 10,000 s, it decreases steadily with
time. These results point out that the stress exponentially decays with time, which shows the stress relaxation
behavior of the silicone rubbers. the Young’ modulus represents the elasticity property of the materials. When the
gaskets made from the silicone rubbers relax at a constant strain, the sealing force will decrease and the seal
performance will become worse. This will lead to the leakage of reactant gases in PEM fuel cells result in the safety
problem and poor electrochemical performance. The increasing modulus indicates the large relaxation. From this
figure, the elastic properties of silicone rubber materials exposed to ambient air at 90°C are strongly deteriorated
during the first 6 h.
Figure 5 shows the stress relaxation modulus curves, which are highly related to time, at two exposure
conditions, RS and ADT, at temperature 70°C with 25% applied strain. It can be observed that the acid has a
significant effect on the elastic properties of silicone rubbers. The compression stress relaxation modulus E increases
with the acid concentration in the test solution. This result corresponds with the reference [8, 9]. The acid solution
can induce the degradation of the chemical structure. Then, changes in the chemical composition result in the damage
of the mechanical properties, especially in high-concentration acid environments.
Figure 6 shows the time dependent Young modulus curves for samples exposed to RS solutions at 70°C with
different exposure times, namely 1, 2, 3, and 4 weeks. It can be observed that the exposure time can gradually affect
the elasticity of silicone rubbers. The modulus increases with time, which indicates the loss of sealing properties
under the RS environment, which is close to the real PEM fuel cell operational conditions. This also proves that
durability of gaskets is critical for PEM fuel cell performance. The revealed patterns of compression relaxation
modulus variation are consistent with results of Cui [7–9], who constructed the master curve based on compression
relaxation modulus data via the time-temperature superposition principle. This research is also considered
instrumental in revealing mechanical performance changes and finding an optimal method to predict the lifetime of
silicone rubber gasket used in PEM fuel cell.
Generally speaking, temperature, acid, and exposure time jointly affect the compression mechanical
properties due to the chemical composition changes on the surface of samples exposed to these environments. In the
air, the chemical degradation is mainly due to the thermal-oxidative aging. In the acidic solution, it could attack the
chemical molecular backbone of silicone rubber and lead to chain scission, which results in the degradation of the
compression mechanical properties. In humid environment, water can affect the chemical composition of samples
can affect their mechanical behavior, just like acid solution. Higher temperatures and concentrations of acidic
solution can accelerate the ageing process and shorten the gasket material lifetime.

664
 Fig. 6. Compression stress relaxation modulus E of silicone rubber exposed to RS up to 4 weeks at 70°C.

Conclusions. This study presents experimental results on compression and stress relaxation behavior of
silicone rubbers in ambient air, DI water, and acid solutions at three different temperatures, under applied 25% strain
level. The results obtained prove that three factors, namely temperature, water/acid, and exposure time, jointly
influence the compression mechanical properties by increasing the compression permanent deformation and the
compression stress relaxation modulus. This strongly indicates that the above test conditions/environments deteriorate
the resilience and elasticity of silicon rubber, especially when samples are exposed to higher temperatures and
concentrations of acid solutions. These results are instrumental in accelerated identification of the optimal durability
test conditions and predicting the lifetime of silicone rubber gaskets used in PEM fuel cells.
Acknowledgments. This study was sponsored by the National Natural Science Foundation of China (Nos.
51505212, 51505211, and 11302097) and Open Research Fund of Jiangsu Collaborative Innovation Center for Smart
Distribution Network, Nanjing Institute of Technology, China (No. XTCX201609).

REFERENCES

1. G. Li, J. Z. Tan, and J. M. Gong, “Chemical aging of the silicone rubber in a simulated and three accelerated
proton exchange membrane fuel cell environments,” J. Power Sources, 217, 175–183 (2012).
2. J. Tan, Y. J. Chao, M. Yang, et al., “Degradation characteristics of elastomeric gasket materials in a
simulated PEM fuel cell environment,” J. Mater. Eng. Perform., 17, 785–792 (2008).
3. G. Li, J. Z. Tan, J. M. Gong, and W. H. Jia, “Degradation mechanism of the silicone rubber in simulated
PEM fuel cell environments,” J. Chem. Ind. Eng. (China), 65, No. 9, 3669–3675 (2014).
4. J. Tan, Y. J. Chao, M. Yang, et al., “Chemical and mechanical stability of a Silicone gasket material exposed
to PEM fuel cell environment,” Int. J. Hydrogen Energy, 36, 1846–1852 (2011).
5. Y. Chen, K. Hou, C. Lin, et al., “A synchronous investigation of the degradation of metallic bipolar plates in
real and simulated environments of polymer electrolyte membrane fuel cells,” J. Power Sources, 197,
161–167 (2012).
6. C. Lin, C. Chien, J. Tan, et al., “Chemical degradation of five elastomeric seal materials in a simulated and
an accelerated PEM fuel cell environment,” J. Power Sources, 196, 1955–1966 (2011).
7. T. Cui, C.-W. Lin, C. H. Chien, et al., “Service life prediction of seal in PEM fuel cells,” in: Proc. of the
SEM Annual Conf. (June 7–10, 2010, Indianapolis, Indiana, USA) (2010), https://doi.org/10.1007/978-1-
4419-9798-2_4.
8. T. Cui, Y. J. Chao, and J. W. Van Zee, “Stress relaxation behavior of EPDM seals in polymer electrolyte
membrane fuel cell environment,” Int. J. Hydrogen Energy, 37, 13478–13483 (2012).

665
 9. T. Cui, Y. J. Chao, and J. W. Van Zee, “Stress relaxation behavior of a liquid silicone rubber seal subjected
to temperature cycling,” J. Electrochem. Soc., No. 16, 1037–1037 (2011).
10. R. Elleuch and W. Taktak, “Viscoelastic behavior of HDPE polymer using tensile and compressive loading,”
J. Mater. Eng. Perform., 15, No. 1, 111–116 (2006).
11. D. Santiago, F. Ferrando and S. De la Flor, “Influence of holding time on shape recovery in a polyurethane
shape-memory polymer,” J. Mater. Eng. Perform., 23, No. 7, 2567–2573 (2014).
12. J. Zhao, R. Yang, R. Iervolino, et al., “The effect of thermo-oxidation on the continuous stress relaxation
behavior of nitrile rubber,” Polym. Degrad. Stabil., 115, 32–37 (2015).
13. V. A. Fernandes and D. S. De Focatiis, “The role of deformation history on stress relaxation and stress
memory of filled rubber,” Polym. Test., 40, 124–132 (2014).
14. J. Liu, P. Lin, X. Li, and S. Q. Wang, “Nonlinear stress relaxation behavior of ductile polymer glasses from
large extension and compression,” Polymer, 81, 129–139 (2015).
15. H. Li, B. Zhang, and G. Bai, “Effects of constructing different unit cells on predicting composite viscoelastic
properties,” Compos. Struct., 125, 459–466 (2015).
16. K. V. Rao, G. S. Ananthapadmanabha, and G. N. Dayananda, “Effect of cross-linking density on creep and
recovery behavior in epoxy-based shape memory polymers (SMEPs) for structural applications,” J. Mater.
Eng. Perform., 25, No. 12, 5314–5322 (2016).
17. E. A. Pieczyska, M. Maj, K. Kowalczyk-Gajewska, et al., “Mechanical and infrared thermography analysis
of shape memory polyurethane,” J. Mater. Eng. Perform., 23, No. 7, 2553–2560 (2014).
18. T. Rey, G. Chagnon, J.-B. Le Cam, and D. Favier, “Influence of the temperature on the mechanical
behaviour of filled and unfilled silicone rubbers,” Polym. Test., 32, No. 3, 492–501 (2013).
19. A. Kömmling, M. Jaunich, and D. Wolff, “Effects of heterogeneous aging in compressed HNBR and EPDM
O-ring seals,” Polym. Degrad. Stabil., 126, 39–46 (2016).
20. T. K. Vaidyanathan and J. Vaidyanathan, “Validity of predictive models of stress relaxation in selected
dental polymers,” Dent. Mater., 31, No. 7, 799–806 (2015).
21. H. J. Maria, N. Lyczko, A. Nzihou, et al., “Stress relaxation behavior of organically modified
montmorillonite filled natural rubber/nitrile rubber nanocomposites,” Appl. Clay Sci., 87, 120–128 (2014).
22. K. Yamaguchi, A. G. Thomas, and J. J. Busfield, “Stress relaxation, creep and set recovery of elastomers,”
Int. J. Nonlin. Mech., 68, 66–70 (2015).
23. GB/T 7759.1-2015. Rubber, Vulcanized or Thermoplastic – Determination of Compression Set – Part 1: At
Ambient or Elevated Temperatures, National Standards of People’s Republic of China (2015).
24. GB/T 1685-2008. Rubber, Vulcanized or Thermoplastic – Determination of Stress Relaxation in
Compression at Ambient and at Elevated Temperatures, National Standards of People’s Republic of China
(2008).
25. Y. Wu, D. Wang, W. Zhang, and J. Zhang, “Experimental research of thermal-oxidative aging on the
mechanics of aero-NBR,” J. Test. Eval., 42, No. 3, 568–572 (2014).

666