Materials Science and Engineering A 496 (2008) 464470

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Materials Science and Engineering A
j our nal homepage: www. el sevi er . com/ l ocat e/ msea
Assessment of mechanical properties of uoroelastomer and EPDM in a
simulated PEM fuel cell environment by microindentation test
Jinzhu Tan
a,b,1
, Y.J. Chao
b,
, J.W. Van Zee
c
, Xiaodong Li
b
, Xinnan Wang
b
, Min Yang
d,b
a
College of Mechanical and Power Engineering, Nanjing University of Technology, Nanjing, Jiangsu 210009, China
b
Department of Mechanical Engineering, University of South Carolina, Columbia, SC 29208, USA
c
Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA
d
School of Materials Science and Engineering, Shandong University, Jinan, Sandong 250061, China
a r t i c l e i n f o
Article history:
Received 11 November 2007
Accepted 29 May 2008
Keywords:
Fuel cell
Mechanical properties
Fluoroelastomer
EPDM
Microindentation
a b s t r a c t
The elastomeric materials used as seals/gaskets in Polymer Electrolyte Membrane (PEM) fuel cells are
exposed to acidic environment, humid air and hydrogen, and subjected to mechanical compressive load.
Bothsealing andelectrochemical performance of the fuel cell dependheavily onthe long-termmechanical
and chemical stability of these materials. In this paper, mechanical property degradation of two elas-
tomeric materials, Fluoroelastomer and EPDM, which are being considered as gasket materials for PEM
fuel cells, was investigated using microindentation. Test samples were subjected to various compressive
loads to simulate the actual loading in addition to soaking in a simulated PEMfuel cell environment. Two
temperatures, based on actual fuel cell operation, 80 and 60

C, were selected in this study. Mechanical

properties of the samples before and after exposure to the environment were assessed. Hysteresis loss
energy, indentation load, elastic modulus and hardness were obtained from the loading and unloading
curves. Indentation deformation was studied using Hertz contact model. It was found that the mechanical
properties of the Fluoroelastomer samples changed signicantly after exposure to the simulated environ-
ment over time. The exposure medium, temperature and applied compressive load contributed to the
degradation of the material. On the other hand, the change of mechanical properties for the EPDM sam-
ples was not apparent. It is concluded that EPDM is much more stable than Fluoroelastomer for PEM seal
applications.
2008 Elsevier B.V. All rights reserved.
1. Introduction
Polymer Electrolyte Membrane (PEM) fuel cell stack requires
elastomeric seals/gaskets in order to keep the reactant gases
(hydrogen and oxygen) within their respective regions. These
seal/gasket materials inPEMfuel cell are exposed to acidic environ-
ment, humid air and hydrogen, as well as mechanical compressive
load. If any part of gasket degrades or fails, the reactant gases (H
2
and O
2
) can leak overboard or mixed each other during operation
or standby. It not only affects the overall operation reducing perfor-
mance but also poses a safety concern. Furthermore, it may result
in short circuit between cathode and anode. To keep intimate con-
tact between all components in a complete cell, gaskets in fuel cells
must also be exible to allowcompression of the stack. If degraded

Corresponding author at: 300 Main Street, Columbia, SC 29208, United States.
Tel.: +1 803 7775869; fax: +1 803 7770106.
E-mail address: chao@sc.edu (Y.J. Chao).
1
Present address: University of South Carolina, Columbia, SC 29208, USA.
(e.g., hardened), the gasket may lose its function and affect the fuel
cell performance. Therefore, long-term mechanical and chemical
stability and durability of the gasket/seal materials in fuel cell are
crucial.
Fluoroelastomer and EPDM (Ethylene-propylene-diene-
monomer) rubbers have the inherent resistance to heat, light and
fuel/oil [1,2]. Thus, they are widely used as seals and gaskets in
many industrial applications including fuel cells [3,4]. In open
literatures, there are many reports discussing both thermal and
irradiative degradation of EPDM and Fluoroelastomer elastomeric
materials [510], as well as chemical degradation [1116]. On the
other hand, only a few studies [1719] focused on the degradation
of the mechanical properties of these elastomeric materials.
For Fluoroelastomer and EPDM specically, there is no study,
to the authors knowledge, concerning the mechanical property
degradation in PEM fuel cell environment.
Mechanical properties of elastomeric gasket materials used in
PEM fuel cells are very important indicators to their level of func-
tionality. Although there are various standard mechanical tests
used to assess the mechanical properties of elastomeric materials
0921-5093/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2008.05.052
J. Tan et al. / Materials Science and Engineering A 496 (2008) 464470 465
including tensile and compressive tests, compression set, Durom-
eter hardness and stress relaxation test, many of the standard
test methods require large size samples. For example, tensile test
requires a dumbbell sample with 6.4mm (width) 3.0mm (thick-
ness) 50.0mm (sample gage length) per ASTM D412 [20]. For
compressive stress relaxationtest, it requires a cylindrical disc sam-
ple with the dimensions 13.0mm (diameter) 6.3mm (thickness)
or 29.0mm (diameter) 12.5mm (thickness) or a washer sample
withthe dimensions 12.5mm(inside diameter) 19.0mm(outside
diameter) 2.0mm (thickness) per ASTM D6147 [21]. And, hard-
ness tests on elastomeric, polymeric materials are based on the
Shore test per ASTM D2240 [22]. The shore hardness value has no
obvious correlation with any fundamental mechanical property of
the material [23].
Indentation test has been widely used to measure the mechan-
ical properties of solids such as metals and ceramics because of its
ease and speed to carry out [24,25]. In recent years, indentation
tests have been conducted on rubber-like elastomeric materials
[23,2632]. For example, Limand Chaudhri [28] reported the study
on applying the indentation on elastic solids including rubber
materials using rigid cones. Indentation tests on Silicone rubbers
exposed to PEM fuel cell environment were reported recently by
Tan et al. [33,34].
In this paper, mechanical property degradation of two elas-
tomeric materials, Fluoroelastomer and EPDM, which are being
considered as gasket materials for PEM fuel cells, was investigated
using microindentation test. An Accelerated Durability Test (ADT)
solution and two temperatures were used in the accelerated aging
of the materials. In order to simulate the actual PEM fuel cell envi-
ronment, test samples were subjected to various compressive loads
in addition to being soaked in the ADT solution. Microindentation
method was used to assess the change of the mechanical properties
of the elastomeric gasket materials after exposure to the environ-
ment over time. The objectives of this study are to (1) evaluate
the mechanical properties (indentation resistance, elastic modulus
and hardness) of the Fluoroelastomer and EPDMsamples invarious
conditions using the microindentation, (2) identify the difference
inmechanical properties betweenthe tworubber material exposed
to the simulated fuel cell environment for PEMfuel cell application
screening, and (3) understand the effect of exposure medium, tem-
perature and compressive stress on the mechanical properties of
the materials over time.
2. Experiment
2.1. Materials and simulated fuel cell environment
Two elastomeric materials, Ethylene-propylene-diene-
monomer (EPDM) andFluoroelastomer were usedinthis study. The
EPDM rubber consists of ethylene and propylene co-monomers
having ENB as diene. The EPDM was chosen due to potential
low cost and its resistance to acid and heat for its saturated
hydrocarbon backbone. The Fluoroelastomer material used in our
study was a commercial grade rubber that consists of hexauoro
propylene and diuoro ethylene co-monomers. Fluoroelastomer
rubber was chosen because of its inherent resistance to acid
and heat due to its chemistry structure. The two elastomeric
materials are been considered for fuel cell applications and could
be most likely to meet the targeted 10 years durability of fuel cell
life.
In order to accelerate the short-termaging tests, an Accelerated
Durability Test (ADT) solution was used as the simulated fuel cell
environment for this study. 48% HF and 98% H
2
SO
4
were dissolved
in balance reagent grade water to make the ADT solution. The com-
Fig. 1. Schematic of the specimen preparation under compressive load and soaked
in the ADT solution.
position of the ADT solution is 1M H
2
SO
4
, 10ppm HF and reagent
grade water having 18M resistance as the exposure medium.
The test temperatures were 80 and 60

C which are close to the

operating temperatures of actual PEM fuel cells.
2.2. Aging test
Square-shaped samples of 10mm10mm were prepared from
the two materials. The thickness of the samples for the Fluoroelas-
tomer and EPDMis 2.0 and 1.6mm, respectively. The samples were
sandwiched between two Plexiglas plates or graphite plates. Dead
weight was applied to the sandwich to create uni-axial compres-
sive stress in the sample. Three stress levels were selected, namely,
0.18, 0.36and0.77MPa, correspondingtoa compressionof 10%, 20%
and 30%, respectively, that are close to typical seal applications. As
shown in Fig. 1, the sample and the plates were placed in a large
Polypropylene bottle containingADTsolutions. The large bottle was
then put in an oven exposed to 80

C and 60

C for 147 weeks.

To study the effect due to the compressive stress and exposure
medium, additional samples from the Fluoroelastomer and EPDM
materials exposed to the ADT solution at 80 and 60

C without any
load for 147 weeks were also prepared for comparison.
2.3. Microindentation test
All tests were conducted at room temperature (about 22

C),
relative humidity of 45% and using a load-depth sensing microin-
denter (CETR, Campbell, CA). All tests were performed at the rate
of 0.004mm/s under displacement-controlled mode. The microin-
denter monitors and records the load and displacement of the
indenter as shown in Fig. 2. An indentation loaddisplacement
curve can be obtained fromthe indentation test. The indenter tip is
a stainless steel ball with a radius of 1.98mm. The instrument has a
force resolution of 0.5mNand a displacement resolution of 0.1m.
A series of 34 indentations were performed for each sample.
Fig. 2. Schematic of the indentation test showing the contact between the indenter
tip (rigid ball) and the sample surface.
466 J. Tan et al. / Materials Science and Engineering A 496 (2008) 464470
Fig. 3. Load versus indentation displacement curves for Fluoroelastomer samples:
FL00 unexposed exposure: (a) loading, (b) unloading; FL60 after 47-week expo-
sure at 60

C: (c) loading, (d) unloading; FL80 after 47-week exposure at 80

C: (e)
loading, (f) unloading.
To avoid the inuence due to the remaining ADT solution on
the sample surface, the sample surface was carefully cleaned using
reagent grade water having 18Mresistance to remove the excess
acids and made dry at roomtemperature before the microindenta-
tion test.
3. Results and discussion
3.1. The loading and unloading behavior
Fig. 3 shows some typical indentation load versus displacement
curves, including both loading and unloading, from the Fluoroe-
lastomer samples before exposure and after 47-week exposure to
the ADT solution at 60 and 80

C without any applied load. The

FL00, FL60 and FL80 in Fig. 3 are from the Fluoroelastomer sam-
ples before exposure and after exposure to the ADT solution at 60
and 80

C, respectively. Fig. 4 shows load versus indentation dis-

placement curves, for the Fluoroelastomer samples after 47-week
exposure to the ADT solution at 60

C with an applied pressure of

0.18MPa (C10FL60) and 0.36MPa (C20FL60), and at 80

C with an
applied pressure of 0.36MPa (C20FL80). In Fig. 4, the C10FL and
C20FL represent the Fluoroelastomer samples subjected to applied
pressure of 0.18 and 0.36MPa, respectively. It can be seen from
Figs. 3 and 4 that the unloading curve does not coincide with their
respective loading curve, showing hysteresis character for the Fluo-
Fig. 4. Load versus indentation displacement curves for Fluoroelastomer samples
after 47-week exposure: C10FL60 with applied pressure of 0.18MPa at 60

C: (a)
loading, (b) unloading; C20FL60 with applied pressure of 0.36MPa at 60

C: (c)
loading, (d) unloading; C20FL80 with applied pressure of 0.36MPa at 80

C: (e)
loading, (f) unloading.
Fig. 5. Load versus indentation displacement curves for EPDM samples: EP00
unexposed exposure: (a) loading, (b) unloading; C30EP60 after 47-week exposure
at 60

C with applied pressure of 0.77MPa: (c) loading, (d) unloading.

roelastomer rubber material. Inaddition, all unloading curves come
back to its origin. Residual displacement was not observed within
experimental error after the unloading was completed, indicating
no plastic deformation in the loading and unloading process.
Figs. 5 and 6 showindentation load versus displacement curves
(loading and unloading) obtained from the EPDM samples before
exposure (EP00) and after 47-week exposure to the ADT solution
at 60

C with an applied pressure of 0.77MPa (C30EP60), and after

47-week exposure to the ADT solution at 60 and 80

C without any
pressure. In Figs. 5 and 6, EP00, EP60, EP80 and C30EP60 repre-
sent the EPDMsamples before exposure, after exposure to the ADT
solution at 60 and 80

C without any load, and after exposure at

60

C with an applied pressure of 0.77MPa, respectively. Compar-

ing Figs. 5 and 6 with Figs. 3 and 4, it is observed that the two
materials have similar loadingunloading deformation behavior.
Hysteresis represents the loss of energy and overheating in
elastomers [35] and it is caused by the viscoelastic nature of poly-
mer [36,37]. The amount of hysteresis can be calculated from the
loadingunloading curve as shown in Figs. 36. The area belowthe
loading curve (e.g., curve a in Fig. 3) corresponds to the energy
appliedintheloadingstage, andtheareabelowtheunloadingcurve
(e.g., curve b in Fig. 3) corresponds to energy recovered. The area
between the two curves (e.g., between curves a and b in Fig. 3)
represents the energy lost from the hysteresis. Figs. 7 and 8 show
the hysteresis loss energy obtained from Figs. 36 for Fluoroelas-
tomer and EPDM samples, respectively. It can be seen from Fig. 7
that the energy changed notably after exposure to the environ-
Fig. 6. Load versus indentation displacement curves for EPDM samples after 47-
week exposure: EP60 at 60

C without any pressure: (a) loading, (b) unloading;

EP80 at 80

C without any pressure: (c) loading, (d) unloading.

J. Tan et al. / Materials Science and Engineering A 496 (2008) 464470 467
Fig. 7. Hysteresis loss energy for the Fluoroelastomer samples: (A) before exposure,
(B) after 47-week exposure at 60

C, (C) after 47-week exposure at 80

C, (D) after
47-week exposure at 60

C with applied pressure of 0.18MPa, (E) after 47-week

exposure at 60

C with applied pressure of 0.36MPa, (F) after 47-week exposure at

80

C with applied pressure of 0.36MPa.

ment over time, and both the temperature and applied pressure
have signicant effect on the loss energy. The loss energy increased
with temperature (see Fig. 7AF) and the applied pressure (see
Fig. 7DF). It can also be observed from Fig. 8 that the hystere-
sis energy did not increase apparently for the EPDM samples after
exposure to the environment up to 47 weeks (see Fig. 8A versus
B, C and D). The results indicate that the viscoelastic property of
the Fluoroelastomer material (at least on the surface of the sam-
ple) changed signicantly after exposure to the simulated fuel cell
environment after 47 weeks while EPDM material did not.
3.2. Indentation load
Mechanical properties such as indentation resistance and elas-
tic modulus can be obtained from microindentation load versus
displacement data [24,26]. Fig. 9 shows the loading curves at the
peak indentation depth of 0.22mm for the Fluoroelastomer sam-
ples before exposure (a), 47-week exposure to the ADT solution at
60

C with an applied pressure of 0.18MPa (b) and 0.36MPa (c), 47-

weekexposuretotheADTsolutionat 80

Cwithanappliedpressure
of 0.36MPa (d), after 47-week exposure to the ADT solution at 60
(e), and 80

C (f) without any loads. Here, we use the load at the

peak indentation depth as a manifestation of the surface harden-
ing of the sample. Fig. 9 shows that the indentation load at a xed
displacement increasedwiththe appliedpressure andtemperature
(see Fig. 9ad).
Fig. 10 presents the bar charts of the indentationloadat the peak
indentation depth of 0.22mm for the Fluoroelastomer samples
Fig. 8. Hysteresis loss energy for the EPDM samples: (A) before exposure, (B) after
47-week exposure at 60

C, (C) after 47-week exposure at 80

C, (D) after 47-week

exposure at 60

C with applied pressure of 0.77MPa.

Fig. 9. Indentation load versus displacement curves at the indentation depth of
0.22mm for the Fluoroelastomer samples: (a) before exposure, (b) after 47-week
exposure at 60

C with the applied pressure of 0.18MPa, (c) after 47-week exposure

at 60

C with the applied pressure of 0.36MPa, (d) after 47-week exposure at 80

C
with the applied pressure of 0.36MPa, (e) after 47-week exposure at 60

C, (f) after
47-week exposure at 80

C.
before exposure (A), after 47-week exposure to the ADT solution
at 60

C with the applied pressure of 0.18MPa (B) and 0.36MPa

(C), after 47-week exposure to the ADT solution at 80

C with the
appliedpressure of 0.36MPa (D), andafter 47-week exposure to the
ADT solution at 60 (E) and 80

C (F) without any load. The results

show that (1) the sample exposed to the ADT solution at 80

C has
the largest indentation load, followed by the sample at 60

C and
then the unexposed sample (see Fig. 10F, E and A) without any load,
showing the effect from the exposure medium and temperature;
(2) at the same temperature, the sample subjected to the applied
pressure of 0.36MPa has higher indentation load compared to the
sample subjected to the applied pressure of 0.18MPa (see Fig. 10B
and C), indicating that the applied pressure hardened the mate-
rial; (3) at the same applied pressure, samples at 80

C showhigher
indentation load than those at 60

C (see Fig. 10Dversus C), indicat-

ing that the tenperature had signicant effect on the indentation
load.
In summary, the increase of the peak load at a xed indenta-
tion depth implies that the material hardened after exposure to
the environment over time. The exposedmedium, temperature and
mechanically applied pressure to the test samples all have signi-
cant effect on the surface hardening of the materials, i.e., the higher
the temperature, the more hardening to the materials.
Fig. 10. Bar charts of indentation load at the indentation depth of 0.22mm for the
Fluoroelastomer samples: (A) before exposure, (B) after 47-week exposure at 60

C
with the applied pressure of 0.18MPa, (C) after 47-week exposure at 60

C with the
applied pressure of 0.36MPa, (D) after 47-week exposure at 80

C with the applied

pressure of 0.36MPa, (E) after 47-weekexposure at 60

C, (F) after 47-weekexposure

at 80

C.
468 J. Tan et al. / Materials Science and Engineering A 496 (2008) 464470
Fig. 11. Indentation load versus displacement curves at the indentation depth of
0.2mm for the EPDM samples: (a) before exposure, (b) after 47-week exposure at
60

C, (c) after 47-week exposure at 80

C, (d) after 47-week exposure at 60

C with
the applied pressure of 0.77MPa.
Fig. 11 shows the indentation load versus displacement curves
for the EPDMsamples before exposure (a), and after 47-week expo-
sure to the ADT solution at 60 (b) and 80

C (c) without any loads,

and after 47-week exposure to the ADT solution at 60

C with a
pressure of 0.77MPa (d). The indentation loads at the peak inden-
tation depth of 0.2mm are shown in Fig. 12 for the EPDM samples
before exposure (A), after 47-week exposure at 60

C (B) and 80

C
(C) without any loads, and after 47-week exposure at 60

C with an
applied pressure of 0.77MPa (D). It can be seen fromFigs. 11 and 12
that the indentation loads did not change apparently for the EPDM
samples indicating EPDMdid not degrade after exposure to the fuel
cell environment up to 47 weeks.
3.3. Elastic modulus
Elastic modulus is one of the important mechanical properties
used to characterize the elastic deformation behavior of elas-
tomeric materials. Hertz contact theory was often used to obtain
the elastic modulus from the indentation loadindentation depth
curves [38]. Considering the contact between a rigid sphere (the
indenter tip) and a at surface as shown in Fig. 2, Hertz contact
model gives the radius of contact circle, a, as [38]
a =

3FR
4E

1/3
(1)
where F is the indenter load, R is the radius of indenter, E
*
is a
combination of the modulus of the indenter and the sample and is
Fig. 12. Bar charts of indentation load at a peak depth of 0.2mmfor EPDMsamples:
(A) before exposure, (B) after 47-week exposure at 60

C, (C) after 47-week exposure

at 80

C, (D) after 47-week exposure at 60

C with the applied pressure of 0.77MPa.

Fig. 13. Indentationloading curves obtained by microindentationand Hertz contact
model for EPDM sample after 47-week exposure at 60

C with the applied pressure

of 0.77MPa.
given as:
1
E

=
1
2
indenter
E
indenter
+
1
2
sample
E
sample
(2)
where E
indenter
and E
sample
are the elastic modulus of the indenter
and the sample, and
indenter
and
sample
are the Poissons ratios of
the indenter and the sample, respectively. The distance of relative
approach of the distant points in the indenter and sample, h, is
expressed as [38]
h =
a
2
R
(3)
The relationship of total displacement h and normal load F can
be written as
h =

9F
2
16RE

1/3
(4)
Eq. (4) can be rewritten as
E

=
3
4

R
Fh
1.5
(5)
When a rigid indenter compresses a soft at sample like the rubber
sample used in this study, h is the depth of the indent because
the steel indenters deformation is negligible relative to that of
the rubber sample. Eq. (4) was used to t the loadindentation
displacement curve. Fig. 13 shows the indentation loading curves
obtained by microindentation and Hertz contact model for the
EPDMsample exposed to ADT solutionat 60

Cand subjected to the

appliedpressure of 0.77MPa. It is seenthat the Hertz contact model
can t the experimental loaddisplacement curve well, especially
in the low displacement range.
Based on Eq. (5), load (F), and indentation displacement (h), the
elastic modulus of the samples can then be obtained. The elastic
modulus and Poissons ratio of the stainless steel indenter tip were
assumed as 2.010
11
Pa and 0.3, respectively [24]. The Poissons
ratio for the rubber samples was assumed as 0.49 [26]. Combining
Eqs. (5) and(2), the elastic moduli were calculatedandare shownin
Figs. 14 and 15 for the Fluoroelastomer and EPDMsamples, respec-
tively.
The results shown in Fig. 14 indicate that the elastic modu-
lus changed signicantly after exposure to the simulated fuel cell
environment. In addition, the following are observed.
(1) For those samples free of any applied load, the sample exposed
to the ADT solution at 80

C has the highest elastic modulus,

followedbythesampleat 60

C, andthentheunexposedsample
J. Tan et al. / Materials Science and Engineering A 496 (2008) 464470 469
Fig. 14. Elastic moduli for Fluoroelastomer samples: (A) before exposure, (B) after
47-week exposure at 60

C with the applied pressure of 0.18MPa, (C) after 47-week

exposure at 60

C with the applied pressure of 0.36MPa, (D) after 47-week exposure

at 80

C with the applied pressure of 0.36MPa, (E) after 47-week exposure at 60

C,
(F) after 47-week exposure at 80

C.
(see Fig. 14F, E and A). It indicates that the exposure medium
and high temperature elevates the elastic modulus.
(2) For those samples exposed at identical temperature, the sam-
ple subjected to the compressive stress of 0.36MPa has larger
elastic modulus than that for the sample subjected to the lower
compressive stress of 0.18MPa (see Fig. 14C versus B). It indi-
cates that the applied compressive load also elevates the elastic
modulus.
(3) For those samples subjected to identical compressive stress or
pressure (see Fig. 14C and D), the sample at 80

C exhibits larger
elastic modulus than that at 60

C, indicating that the tenper-

ature had signicant role in the change of the elastic modulus
with the applied load.
These results indicate that the elastic modulus increased with
the exposure medium, temperture, and applied pressure.
Fig. 15 shows the results of elastic moduli for EPDM samples
after 47-week exposure to the same environment. It can be seen
that the elastic modulus did not change for both samples with
and without compressive loads. The results indicate that the EPDM
material is more stable compared to Fluoroelastomer in the simu-
lated environment.
3.4. Hardness
Mean contact pressure or hardness is dened as the indentation
load divided by the projected contact area of indentation [39], i.e.,
how much load a material can support at a given displacement.
Fig. 15. Elastic moduli for EPDM samples: (A) before exposure, (B) after 47-week
exposure at 60

C, (C) after 47-week exposure at 80

C, (D) after 47-week exposure

at 60

C with the applied pressure of 0.77MPa.

Fig. 16. Mean contact pressure for Fluoroelastomer samples: (A) before exposure,
(B) after 47-week exposure at 60

C with the applied pressure of 0.18MPa, (C) after

47-week exposure at 60

C with the applied pressure of 0.36MPa, (D) after 47-week

exposure at 80

C with the applied pressure of 0.36MPa, (E) after 47-week exposure

at 60

C, (F) after 47-week exposure at 80

C.
From the indentation loaddisplacement curve, the mean contact
pressure (hardness), P, can be obtained as
P =
F
max
W
(6)
where F
max
is the indentation load at the peak indentation dis-
placement h
max
and W is the projected area. The projected area is
a function of contact depth h
c
, which is dened as the depth of the
indenter in contact with the sample under load. The contact depth
can be estimated fromthe loaddisplacement data given as [39,40]
h
c
= h
max

F
max
S
(7)
where is a geometric constant equal to 0.75 for a spherical inden-
ter [40]. S is the initial unloading contact stiffness, i.e., the slope of
the initial portion of the unloading curve.
The slope of the unloading curve can be determined from the
loaddisplacement data Eq. (8) near the maximum penetration,
h=h
max
(i.e., Eq. (9)) which is then the unloading contact stiffness.
F = f (h) (8)
S =

dF
dh

h=hmax
(9)
For anindenter witha knowngeometry, the projectedarea is the
function of the contact depth h
c
. The projected area for spherical
indenter is given as
W = [R
2
(R h
c
)
2
] (10)
where is a constant equal to 3.14.
Using Eqs. (6)(10) and the loadingunloading curves, the hard-
ness values can be obtained for the test samples. Fig. 16 shows the
hardness values (mean contact pressures) at the maximum inden-
tation depth of 0.22mm for the Fluoroelastomer samples before
exposure (A), after 47-week exposure to the ADT solution at 60

C
withappliedpressures of 0.18MPa (B) and0.36MPa (C), andat 80

C
withanappliedpressure of 0.36MPa (D), after 47-weekexposure to
the ADT solution at 60 (E) and 80

C (F) without any loads. The test

results indicate that (1) the hardness changed signicantly for the
Fluoroelastomer samples after exposure to the environment over
time; (2) exposure medium, temperartue andthe appliedcompres-
sive loadto the samples also have signicant effect onthe hardness.
The results are in agreement with those of the peak load and elastic
modulus shown in Figs. 10 and 14.
Fig. 17 shows the hardness values (mean contact pressures) at
the maximumindentation depth of 0.20mmfor the EPDMsamples
before exposure (A), after 47-week exposure to the ADT solution at
470 J. Tan et al. / Materials Science and Engineering A 496 (2008) 464470
Fig. 17. Mean contact pressure for EPDM samples: (A) before exposure, (B) after
47-week exposure at 60

C, (C) after 47-week exposure at 80

C, (D) after 47-week

exposure at 60

C with the applied pressure of 0.77MPa.

60 (B) and 80

C (C) without any load, and after 47-week exposure

to the ADT solution at 60

C with an applied pressure of 0.77MPa

(D). It is seen that the hardness value did not changed apparently
which is in agreement with the peak load and elastic modulus
shown in Figs. 12 and 15, indicating that EPDM is more stable than
Fluoroelastomer.
4. Conclusions
Mechanical properties of Fluoroelastomer and EPDM samples
before and after 47-week exposure to a simulated PEM fuel cell
environment withvarious compressive stresses appliedtothe sam-
ples were studied using a microindentation technique. Hysteresis
loss energy, indentation load, elastic modulus and hardness were
obtained fromthe microindentation loading and unloading curves.
Hertz contact model was used to derive the elastic modulus of
the materials. A good correlation between indentation load, elastic
modulus and hardness was found for the rubber materials in this
study.
Test results show that the surface hardening occurred and the
elastic modulus increased for the Fluoroelastomer samples over
time. The exposure medium, temperature and applied compressive
load contributed to the material degradation. For the EPDM sam-
ples, the mechanical properties (i.e., indentation resistance, elastic
modulus and hardness) did not have signicant change after expo-
sure to the simulated PEM fuel cell environment up to 47 weeks.
The results indicate that EPDMis more stable than Fluoroelastomer
under the test conditions.
The microindentation tests used in this study may provide a
simple way for assessing the mechanical properties of gasket mate-
rials and can be used to screen gasket materials for PEM fuel cell
applications.
Acknowledgements
The work was sponsored by the NSF Industry/University Coop-
erative Research Center for Fuel Cells at the University of South
Carolina. Encouragement from the industry partners and nancial
support from the center were greatly appreciated.
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