Polymer Degradation and Stability 95 (2010) 2555e2562

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Effect of organo-modified clay on accelerated aging resistance of hydrogenated

nitrile rubber nanocomposites and their life time prediction
Anusuya Choudhury a, Anil K. Bhowmick a, *, Matthias Soddemann b
a
Rubber Technology Centre, Indian Institute of Technology Kharagpur, Kharagpur 721302, India
b
LANXESS Deutschland GmbH, 41538 Dormagen, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Organically modified clay e reinforced hydrogenated nitrile rubber vulcanizate was subjected to accel-
Received 3 April 2010 erated heat aging to estimate its long-term thermo-oxidative stability and its useful lifetime was compared
Received in revised form with that of the virgin polymer for the first time. Changes in technical properties such as tensile strength,
18 July 2010
modulus and elongation at break were studied as a function of time and temperature of aging. The infrared
Accepted 28 July 2010
Available online 5 August 2010
spectroscopic analysis of the degraded products revealed that under aerobic hot aging conditions,
hydrogenated nitrile rubber (HNBR) compounds undergo cross-linking reactions that lead to embrittle-
ment and ultimately failure. Incorporation of clay filler, however, resulted in significant improvement of
Keywords:
Hydrogenated nitrile rubber
the degradation profile of the nanocomposite at elevated temperatures. Loss of ductility during aging of
Organically modified nanoclay the nanocomposite was also milder, relative to the unfilled polymer, indicating a restricted degradation by
Accelerated heat aging the clay filled rubber, thus prolonging the durability. From the scanning electron microscopy and atomic
Life time prediction force microscopy studies, it was found that nanofillers protected the elastomer from surface rupture that
took place on oxidation. Life prediction of both virgin elastomer and the nanocomposite indicated a three-
fold increase in the effective service temperature range of the HNBR using 8 parts organically modified
nanoclay.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction packaging [3e8]. Though many organic or inorganic additives can be

The ability of an elastomeric composition to perform at elevated
temperature for an extended period of time is a paramount
requirement for a large number of applications. The introduction of
hydrogenated nitrile rubber has provided elastomers with superior
resistance to degradation even in hot air environment and a good
temperature performance up to the range of about 150
C, combined
with good oil and fluid resistance, [1,2]. Nevertheless, industry still
sees the need to extend the upper operating range of the polymer.
Increasing the heat resistance of a composition would indeed allow
it to be used at higher operating temperatures, or alternatively, it can
be used at a particular temperature expectedly with a longer useful
lifetime. The useful service life of an elastomer at elevated temper-
ature can be extended with the addition of an inorganic filler.
Polymer nanocomposites have long been a crucial topic for
advanced scientific research and industrial development, presenting
a variety of applications in transportation, construction and food
* Corresponding author. Present address: Indian Institute of Technology, Patna
800013, India. Tel.: þ91 3222 283180/91 612 2277380; fax: þ91 3222 220312/91 612
2277384.
E-mail addresses: anilkb@rtc.iitkgp.ernet.in, director@iitp.ac.in (A.K. Bhowmick).
incorporated for the reinforcement of a polymer, clay is considered to
be an optimum choice because of its small particle size and interca-
lation properties from the view of modification efficiency and product
cost [3,9,10]. Besides, economic and environmental factors, its natural
abundance, high mechanical strength and chemical resistance make
clay a suitable filler for polymer composites. Moreover, it is believed
that the superior properties of the elastomereclay nanocomposites
are not only because of the nanoscale dispersion of clay particles
within the elastomer matrix, but are also the result of a strong inter-
action between the elastomer matrix and the clay layers.
The clay mostly used is montmorillonite (MMT) which belongs to
the general family of 2:1 layered silicates. These are composed of
regular staking of two-dimensional plate like layers bound together
with weak inter-atomic forces. In fact, MMT-nanocomposite was the
first successful example of a polymereclay nanocomposite [11e22].
Natural Na-montmorillonite is hydrophilic in nature and is not
compatible with most of the organic polymers. However, sodium
cations in the interlayer space of montmorillonite can be exchanged
with organic cations to yield organophilic montmorillonite (e.g.,
Cloisite 30B, used in this study), which is compatible with such
polymers. The formation of polymer-filler nanocomposite affects the
thermal behaviour of the matrix because well dispersed nanofillers

0141-3910/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2010.07.032
2556 A. Choudhury et al. / Polymer Degradation and Stability 95 (2010) 2555e2562
result in the modification of their degradation pathways. Previously,
several reports have shown that presence of nanoclay improves the
degradation temperature of plastics, viz. nylon 6, polylactides,
polystyrene, polypropylene [23e27]. Bhowmick et al. have done
extensive work to improve the thermal stability of polymers like
polybutadiene rubber (BR), acrylonitrile butadiene rubber (NBR),
styrene butadiene rubber (SBR), fluoroelastomer (FKM) and nylon
6 by using different types of nanoclay [28e30]. The thermal
degradation pathway of virgin HNBR has also been studied by other
researchers [31,32]. However, any detailed information regarding
the aging mechanism of HNBR-clay nanocomposite at elevated
temperature is still lacking. Nevertheless, there is a shortage of
information about the long-term thermal stability of HNBR-clay
nanocomposite. It has also not yet been suggested how the use of
nanoclay can improve the lifetime of an article.
Along with the development of science and technology, there has
been an increased demand for materials with higher temperature
classification and excellent thermal performance. Performance
during outdoor application is a critical issue for the commercial
exploitation of the end products. The useful life time of an article, at
a given service temperature, is often assessed by determining the
time required for a particular property of interest to degrade to
a critical value [1,26]. The properties of rubber are subject to changes
ultimately to the point where the material is no longer capable of
fulfilling its functions. The life of a rubber component is of critical
importance in many applications and hence it becomes necessary to
predict its longevity. The comparative prediction of the full life time
of an article is often based on accelerated aging tests, conducting
characterizations at ordinary time interval of exposure. In this way,
change in bulk properties can be recorded quickly.
The present work aimed to develop a better understanding of the
effect of clay on the aging performance of HNBR nanocomposite. The
focus of this research is to study the effect of thermal aging in air, at
different time intervals and temperatures, on the physico-mechan-
ical properties of HNBR and its nanocomposite. The present article
reports, for the first time, a comparison of the predicted life span of
unfilled and nanoclay-filled rubbers. The results are explained in
terms of morphology analysis of the aged sample by scanning elec-
tron microscopy and atomic force microscopy. Such type of analysis
is also reported for the first time. The aging mechanism of the
elastomer and its nanocomposite has further been investigated by
FTIR studies.
2. Experimental
2.1. Materials
Therban C3467, having an acrylonitrile content of 34%, diene
content of 5.5%, Mooney Viscosity, ML(1þ4) at 100
C [where, M
stands for Mooney number, L indicates the use of large (i.e., stan-
dard) rotor, 100
C is the test temperature, sample preheating time
before the start of shearing is 1 min and shearing duration is 4 min]
of 68 and specific gravity of 0.95 were obtained from Lanxess,
Germany. The clay used was Cloisite 30B (produced by ion exchange
of a methyl tallow bis-2-hydroxy quaternary ion) purchased from
Southern Clay Products, Gonzales, Texas, USA. Designation of the
nanofiller is reported in Table 1. Solvents used in this study were
supplied by Merck Limited, Mumbai, India.
2.2. Preparation of rubbereclay nanocomposites
2.2.1. Vulcanized sample
The rubber was first dissolved in chloroform (10% rubber solu-
tion w/v). 8 phr of clay was dispersed in methyl ethyl ketone (MEK),
by sonicating in an ultrasonicator for 30 min. (1 g in 50 ml) at 25
C.
Table 1
Designation and characteristics of the rubber and clay.
Sample name Designation Characteristics
Therban C3467 S1 e
Cloisite 30B 30B Substituted dimethyl
dihydrogenated tallow
(w65% C18; 30% C16; w5% C14,
like stearic acid) quaternary
ammonium. Cation-Exchange
Capacity (CEC) ¼ 0.90 mequiv/g.
Moisture content ¼ 2%
Di cumyl peroxide (DCP) x e
Therban C3467 þ 1 phr DCP S1-1x e
Therban C3467 þ 8 phr S1-30B-8-1x e
Closite 30B þ 1 phr DCP
1 phr of dicumyl peroxide dispersed in MEK was then added into
the rubber solution. The amount of the filler and the solvent was
selected from the knowledge of our earlier studies [33,34]. The filler
dispersion was then poured into the prepared rubber solution and
stirred for 3 h in a magnetic stirrer at room temperature followed
by 30 min vigorous stirring with a mechanical stirrer to make
a homogenous mixture. The solution was finally cast on a Petri
dish to get a thin film. The solvent was allowed to evaporate at
room temperature and dried in a vacuum oven at 50
C, till there
was no weight variation. The samples were then cured at 150
C for
1 h under 5 MPa pressure in a hydraulic press to prepare 1 mm
thick sheets. The designation of rubber, nanofiller and their nano-
composites vulcanizate is represented in Table 1.
2.3. X-ray diffraction (XRD)
For the characterization of the nanocomposites, XRD studies
were performed on a PHILIPS X-PERT PRO diffractometer in the
range of 2e9
(2q) using Cu target (l ¼ 0.154 nm). The d-spacing of
the clay particles was calculated using the Bragg’s law.
2.4. Transmission electron microscopy (TEM)
The samples for TEM analysis were prepared by ultra-
cryomicrotomy with a Leica Ultracut UCT (Leica Microsystems
GmbH, Vienna, Austria). Freshly sharpened glass knives with cutting
edges of 45
were used to obtain cryosections of about 100 nm
thickness at e90
C. The cryosections were collected individually
in sucrose solution and directly supported on a copper grid of
300 mesh size. Microscopy was performed with JEOL 2100, Japan.
Transmission electron microscope was operated at an accelerating
voltage of 200 kV.
2.5. Scanning electron microscopy (SEM)
The surface morphology of the samples was studied by using
JEOL JSM-800 scanning electron microscope (JEOL JSM-800, Tokyo,
Japan) operating at an accelerating voltage of 20 kV. The samples
were sputter coated with gold before analysis.
2.6. Atomic force microscopy (AFM)
Multi Mode Scanning Probe Microscope model with a Nanoscope
IIIa controller by Digital Instruments Inc. (Veeco Metrology Group),
Santa Barbara, CA, USA, was used for the AFM studies. The AFM
measurements were carried out in air at ambient conditions (25
C),
using tapping mode probes with constant amplitude (40 mV). The
rotated tapping mode-etched silicone probe (RTESP) [square
pyramid in shape with a spring constant of 20 N/m, nominal radius
of curvature of 10 nm] with resonance frequency of 270 kHz was
 A. Choudhury et al. / Polymer Degradation and Stability 95 (2010) 2555e2562
Fig. 1. a) Tensile strength and b) elongation at break vs. time of ageing at 70
C.
used. Height and phase images were recorded simultaneously at the
resonance frequency of the cantilever with a scan rate of 1Hz
and a resolution of 512 samples per line. This allowed the resolution
of individual primary particle measurements. The images were
analyzed using a nanoscope image processing software (5.30r1).
2.7. Roughness analysis
The root-mean-square roughness, RRMS is defined as the stan-
dard deviation feature height, Z, within a given area is represented
in Equation (1) as follows-
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P
ðZi  ZAV Þ2
RRMS ¼ (1)
N
The mean surface level is defined as the line about which
roughness is measured. ZAV is the average Z values and Zi is the
current Z value and N is the number of points within the given area.
Roughness has been calculated from the images of same scan size.
2.8. Mechanical properties
Tensile specimens were punched out from the cast sheets using
ASTM Die-C. The tests were carried out as per the ASTM D 412-98
method in a Universal Testing Machine (Zwick/Roell Z010) at
a crosshead speed of 500 mm/min at 25
C. The average of three
tests is reported here. The error was 2% in the measurements of
tensile strength and modulus and 5% for elongation at break.
2.9. Fourier transform infrared (FTIR) spectroscopic analysis
Attenuated total reflection (ATR)-FTIR spectra of the samples were
taken at room temperature using an infrared spectrophotometer
Fig. 2. a) Tensile strength and b) elongation at break vs. time of ageing at 135
C.
2557
Nicolet Nexus, USA in the range 650 to 4000 cm1 at a resolution of
4 cm1. The average of three scans for each sample was taken for peak
identification.
2.10. Aging studies
Air aging was performed with three sets of tensile specimens in
an air circulating oven [Blue M Electric Co., IL, USA] at three pre-
determined temperatures for various time periods (24 h, 48 h, 72 h,
96 h, 120 h and 168 h at 70
C, 24 h, 48 h, 72 h, 96 h, 120 and 168 h
at 100
C and 24 h, 48 h, 72 h and 96 h at 135
C). Lifetime was
predicted from these data following ISO Standard 11346.
3. Results and discussion
The aging properties of neat HNBR and HNBR-filler nano-
composites were studied at various temperatures over different
periods. Plots of the change in properties with aging time at
a particular temperature (70
C, 100
C or 135
C) for both the
samples are shown in Figs. 1 and 2. The properties of neat HNBR
on aging at longer times are observed to be affected with drastic
reduction in tensile strength and elongation at break. It can be
visualized from Fig. 1a, b that at 70
C, the neat HNBR shows marginal
change in properties at the early stage of degradation. A marginal
increase in tensile strength is observed up to 24 h of aging (Fig. 1a),
beyond which there is a continuous decrease in properties of the neat
elastomer. At 168 h of aging, the tensile strength reduces to as much
as 40% of its original value. These results can be explained as follows:
Partial cross-linking of the elastomer backbone at the initial stage of
aging takes place [31,35]. On further aging for prolonged time period
at 70
C, the main chain starts degrading, which results in drastic
reduction of strength and elongation properties, as reflected in
Fig. 1a, b. These are also apparent from the FTIR studies (discussed
2558 A. Choudhury et al. / Polymer Degradation and Stability 95 (2010) 2555e2562

Fig. 3. SEM surface picture (in 5 mm) of a) S1-1x and b) S1-30B-8-1x before ageing and c) S1-1x and d) S1-30B-8-1x after ageing.

Fig. 4. AFM phase images of a) S1-1x, b) S1-30B-8-1x (before ageing) c) S1-1x and d) S1-30B-8-1x (after ageing).
 A. Choudhury et al. / Polymer Degradation and Stability 95 (2010) 2555e2562
Table 2
Quantitative parameters determined from roughness and power spectral density
analysis of unfilled elastomer and nanocomposite before and after ageing.
Sample Ra(nm) Rq(nm) Total power Equivalent
(nm2) RMS (nm)
S1-1x Before ageing 3.4 4.2 18.9 4.3
After ageing 16.1 18.8 368.0 19.2
S1-30B-8-1x Before ageing 8.7 12.9 123.0 11.0
After ageing 9.9 16.2 280.0 16.6
later). No significant change in these properties of the nanocomposite
is observed under the same above conditions. A similar trend is
observed at an aging temperature of 100
C (Figure not shown here).
Up to 24 h of aging, tensile strength of the neat elastomer increases
to 30%, while no such change is observed in the properties of the
nanocomposite. The overall reduction in properties for the neat
elastomer at 100
C for 168 h is 80%, whereas the nanocomposite
retains almost all its properties even under similar aging conditions.
On aging at 135
C, a remarkable drop in strength and elongation
properties for the neat elastomer takes place even at the early stage of
aging (24 h). In fact, S1-1x (unfilled elastomer vulcanizate) loses
its rubber-like properties within 24 h of aging at this temperature,
which can be clearly visualized from Fig. 2a, b. On the other hand, no
significant change in properties is observed, at this initial stage of
aging, for the nanocomposite. As reflected in Fig. 2a, b, the nano-
composite retains its properties up to 72 h of aging. However, beyond
this period, deterioration in properties of the nanocomposite takes
place. Thus, Figs. 1 and 2 explain the better retention of tensile
strength and elongation at break of the nanocomposite over the neat
elastomer upon aging in air. The stabilizer used in this study is BKF,
which is a Bi-Cresol derivative, and the amount present in Therban
C3467 is 0.1 phr. In order to find out the effect of clay without the
stabilizer, the stabilizer is removed from the rubber by ethanol
extraction and the rubber is then mixed with 8 phr of clay. Low
temperature (ageing at 135
C for 48 h) degradation study is carried
out in absence of the stabilizer. The result showed that the unfilled
elastomer loses 90% of its properties upon ageing at 135
C, while the
nanoclay-filled elastomer loses 15% of its properties. These figures are
85% and 10% respectively for the samples with stabilizer. From these
results, it can be inferred that, the presence of the stabilizer has the
same effect on the degradation of HNBR. Only the speed of the
Fig. 5. Power spectral density of a) S1-1x, b) S1-30B-8-1x (before ageing) c) S1-1x and d) S1-30B-8-1x (after ageing) (The full scale is 1 mm).
2559
degradation is faster in the sample without the stabilizer. Or in the
other words, the clays do not destabilize the polymer by deactivating
the stabilizer. A similar observation is made when the samples have
been heated up to 800
C in the furnace of the Perkin Elmer TGA
Instrument, under air atmosphere at a heating rate of 20
C/min.
(not shown here).
This marked change in properties upon aging for the neat
elastomer is due to cross-linking and degradation of the rubber
as explained in detail later. Furthermore, changes in the surface
morphology of the system, on aging, reflect such remarkable drop in
properties of the neat elastomer. The surfaces of both HNBR and its
nanocomposite, subjected to different degrees of aging, have been
studied by scanning electron microscopy (SEM) and atomic force
microscopy (AFM). The surface morphology of the unaged sample of
S1 and its nanocomposite is similar before aging as shown in Fig. 3a,
b (SEM photograph). However, upon aging, a dramatic change on
surface morphology is observed as depicted in Fig. 3c, d. The surface
of the unfilled elastomer is cracked due to oxidative attack (Fig. 3c),
while the nanoclay protects the rubber surface (Fig. 3d). As the
nanoclays are not observed in the SEM photograph, further inter-
pretation is done using AFM.
The phase images of the neat elastomer and the filled elastomer
vulcanizate are shown in Fig. 4a, b. In the case of clay filled sample
some distinct bright features are observed, which are absent in the
unfilled sample. This suggests that the filler appears as white
bright features (average dimension of 60 nm) in the rubber matrix
[33,34,36,37]. Fig. 4c, d represents the phage image of the unfilled
and the filled elastomer vulcanizates aged at 100
C for 7 days.
A distinct change in surface morphology of the neat elastomer is
observed on aging when compared with that of the unaged gum
rubber. There are cracks as well as bright features probably due to
oxidized hard surfaces. However, for the clay-filled elastomer,
no significant change in surface morphology is observed. In order to
determine the change in surface topography quantitatively, the
root-mean-square (RMS) roughness calculation is used. The RMS
(Rq and Ra) values of the gum and filled sample before and after
aging are included in Table 2. Before quantifying, the images were
flattened using first-order flattening. In the case of the neat rubber,
RMS (Rq and Ra) value is found to be 4.2 nm and 3.4 nm. In the case
of the clay filled elastomer vulcanizate, these values are 12.9 nm
and 8.7 nm. The higher value of Rq and Ra for S1-30B-8-1x vulca-
nizate as compared to neat elastomer confirms the presence of filler
2560 A. Choudhury et al. / Polymer Degradation and Stability 95 (2010) 2555e2562

Fig. 6. a) S1-1x and b) S1-30B-8-1x before ageing (left) after ageing at 135
C for 48 h
(right).

particles on the surface. It is further observed from the Table that Rq Fig. 8. Ageing coefficient vs. time of ageing at 70
C.
and Ra values of the unfilled elastomer after aging are increased to
18.8 nm and 16.1 nm respectively. Thus, there is a drastic change in
clay-filled elastomer vulcanizates before and after aging conducted
roughness taking place upon aging for the neat elastomer which
at 135
C. The S1 vulcanizate before aging shows a sharp peak at
confirms the oxidative attack at the surface. For the nanocomposite,
720 cm1 due to the presence of an ethylene moiety. Another peak at
however, only a slight change in roughness is observed on aging
970 cm1 is primarily due to di-substituted double bond. The sharp
(Rq and Ra values increased to 16.2 nm and 9.9 nm respectively) as
peaks that appear at 1460 cm1 and 2900 cm1 respectively corre-
shown in Table 2. This observation further confirms that nanofillers
spond to the eCH2e and CeH groups present in the matrix.
protect the surface of the matrix from oxidative attack.
The small peak at 1720 cm1 is due to the typical carbonyl range and
Power spectral density (PSD) analysis is another tool that
finally, the one at 2237 cm1 is the characteristic peak of acrylonitrile
provides valuable information not only on the height deviation of
group. In the case of the nanocomposite, two sharp peaks are
the roughness profile, but also on its lateral profile. The 2DPSD of
observed at 1032 cm1 and 920 cm1, mainly due to the SieO
the gum and the filled elastomer vulcanizate before and after aging
vibration. On aging at 135
C for 48 h, a major increase in peak
are shown in Fig. 5a, d. The total power and the equivalent
intensity at 1721 cm1, 1367 cm1 and 1163 cm1 is noted for
RMS (square root of the total power) values are shown in Fig. 5 a,
the unfilled elastomer vulcanizate. The first prominent peak at
d and Table 2. These values are much higher after aging for both the
O
unfilled and the filled samples. However, the changes in the value
1721 cm1 is due to the asymmetric and symmetric
before and after aging are much smaller for the nanocomposite.
It can be further visualized that the unfilled rubber vulcanizate stretching vibrations of vinyl carbonyl which is formed from
undergoes colour change from brown to black upon aging due to hydroperoxide with loss of a water molecule at this temperature. The
thermo-oxidative reaction (Fig. 6), while the nanocomposite mechanism of degradation of HNBR has been discussed by Bender
changes from light brown to deep brown. et al. [32]. The mechanism shows how vinyl carbonyl is formed from
In order to study the nature of this reaction, representative ROOH with loss of a water molecule. It is further clear from the
samples were analyzed at 100
C and 135
C, using FTIR spectros- mechanism that oxygen attacks the diene part of the elastomer and
copy. Fig. 7 represents the FTIR spectra of the unfilled and the causes oxidative degradation. The peaks at 1171 and 1017 cm1 are
assigned to the asymmetric and symmetric stretching vibration of

Fig. 7. FTIR photography of S1-1x and S1-1x-30B-8-1x on ageing at 135
C for 48 h. Fig. 9. Arrhenius plot of log t vs. 1/T for S1-1x and S1-30B-8-1x.
 A. Choudhury et al. / Polymer Degradation and Stability 95 (2010) 2555e2562
Table 3
life time of HNBR and its nanocomposite at 40
C.
Samples Life time (years)
S1-1x 15
S1-30B-8-1x 45
the ester group (eCeOeC). This implies that during aging (at 135
C),
additional ester links are formed in the case of unfilled HNBR. This is
in accordance with the mechanism suggested by Bender et al. [32].
The peak at 1367 cm1 is due to the CeH bending vibration of the
saturated carbon chain. The peak at 970 cm1, however, disappears
in the aged unfilled sample due to the utilization of the double bond
during the thermo-oxidative reaction. Bender et al. also noted that
during ageing of HNBR, abstraction of the allylic hydrogen leads to
the formation of delocalized radical which is more stable than alkyl
radical. Oxygen molecules as diradical can react with the polymer
radicals. On the other hand, the more stable peroxy radical in the
presence of oxygen abstracts a hydrogen atom from another
polymer chain to form a hydroperoxide and a new peroxy radical at
high temperature. Hydroperoxide can undergo number of reactions
leading to higher oxidized moieties such as ketones, carboxylic acids
and alcohols. The alcohol then undergoes oxidation and forms ester
link. As a consequence, the properties of the unfilled elastomer
reduce tremendously at this temperature of aging (Fig. 2a, b).
Addition of nanoclay protects the sample from oxidative reaction
and as a result formation of ester and carbonyl linkages is inhibited,
which has been confirmed from the FTIR spectrum of S1-30B-8
vulcanizate. This is the reason why, on addition of nanoclay, physico-
mechanical properties of the elastomer are retained as depicted in
Figs. 1a, b and 2a, b.
The half life period of dicumyl peroxide at 150
C is 27 min.
As the sample is cured at 150
C for 1 h, it can be assumed that no
residual peroxide is left after complete curing of the rubber sample.
For further confirmation, we carried out IR study of the HNBR
vulcanizate (not shown here). A sharp peak appeared at 1025 cm1
due to the peroxide linkage which is absent in the cured rubber.
This indicates that no residual peroxide is left and the effect of clay
is not due to adsorption and deactivation of the peroxide residues.
3.1. Lifetime prediction
The estimated lifetime of a polymer to failure can be defined as
the time when the properties of the polymer reach 50% of its
original value.
Fig. 10. a) X-Ray diffraction of nanoclay filled elastomer vulcanizate before and after ageing and b) TEM photograph of S1-30B-8-1x.
2561
The logarithmic form of the Arrhenius equation with the
constant terms combined in B is:
lnti ¼ E=RTi þ B (2)
1
where, ti ¼ reaction time (min); E ¼ Activation energy (Jmol );
R ¼ Gas constant (8.314 Jmol1 K1); Ti ¼ Absolute temperature.
A plot of log(time) verses 1/T gives a straight line with the slope E/R,
and is known as an ‘Arrhenius plot’. However, over the last few decades
many degradation studies have dealt with the complexity of polymer
life time prediction and extrapolation [38]. Perhaps the key weakness
in testing linear Arrhenius behaviour is often the limited availability
of experimental data. Although there is no exact correspondence
between the actual life and predicted life, this is the standard proce-
dure followed by the rubber industry and the methodology for carrying
out this procedure is described in the ISO Standard 11346.
Fig. 8 represents a plot of aging coefficient (ratio of tensile
strength of aged samples over tensile strength of unaged sample)
vs. time of aging (in hours).
In order to predict the life of clay-filled and unfilled elastomer
vulcanizate, the Arrhenius graph of log(time) against 1/T (Equation
(1)) has been plotted. The time taken to reach 50% of the original
value (aging coefficient) was determined for each temperature from
Fig. 8 either directly or by extrapolation. Fig. 9 represents the plot of
log (time) vs. 1/T for the unfilled and the nanoclay-filled elastomer
vulcanizate The error in the measurement of log t varies from 1.5%
to 3.0%. Extrapolating the line, life time of the articles at 40
C can
be calculated from the slope of the straight line, as shown in Table 3.
Cloisite 30B, being an organically modified clay, is quite
compatible with organic polymers. The X-ray diffractograms of the
unaged nanocomposite vulcanizate and the samples aged at
different times and temperatures are shown in Fig. 10a. No peak is
observed for the nanocomposite. This indicates a complete break-
down of the layered structure of the clay, leading to its exfoliation.
The absence of any (00l) reflection peak in the 2q ¼ 2e10
range,
further confirmed that morphology does not change on aging. It is
a conventionally known fact that complete dispersion achieved by
an exfoliated system provides superior physico-mechanical prop-
erties. Adequate dispersion of the nanoclay within the bulk of the
matrix is further confirmed from the TEM photograph of S1-30B-8-
1x vulcanizate (Fig. 10b). Incorporation of the tallow quaternary
ammonium ions expands the gallery gap between the clay layers of
30B. S1, having 34% acrylonitrile content (bulky in size), easily enters
the clay gallery space and finally breaks the layer structure to attain
an exfoliated morphology. Moreover, modification of the clay with
a polar surfactant further facilitates the interaction between the clay
2562 A. Choudhury et al. / Polymer Degradation and Stability 95 (2010) 2555e2562
and the polar elastomer. Here, improvement in the properties takes
place due to intercalation of polymer chains within the clay layers
along with H-bond formation between the CN groups of the rubber
and the OH groups present on the clay surface and surfactant.
The favourable formation of nanocomposite between the poly-
mer and 30B has been explained thermodynamically using the
mean-field lattice-based description of polymer melt intercalation
in our earlier paper [34]. It is observed that for both the unaged and
aged samples, DeV is negative (0.2 nm1), while Dsv is close to
zero, hence, ΔGS is negative for all the samples. It is a well known
fact that mixing of two components is most favourable when free
energy change (ΔGS) of the system is negative.
4. Conclusions
This article addressed the long-term thermo-oxidative stability
and useful lifetime of the nanocomposite compared to those of the
virgin polymer. The material was subjected to accelerated heat aging
test at 70
C, 100
C and 135
C over different time periods. Addition of
organically modified clay improved the retention of physico-
mechanical properties of the elastomer by disrupting the oxidative
process. As a result useful service life of the nanocomposite was
increased from 15 yrs to 45 yrs. From the SEM and AFM studies, it was
found that nanofillers protected the elastomer from surface rupture
that took place on oxidation. It was further concluded from the FTIR
study that nanofillers protected the elastomer from oxidative cross-
linking reaction that lead to embrittlement and ultimately to failure.
From the X-ray diffractogram and the TEM photograph, it was found
that 30B had undergone full exfoliation within the bulk of the matrix,
and thus provided excellent aging resistance to the matrix.
Acknowledgement
The authors are indebted to LANXESS, Germany for funding the
project at IIT Kharagpur.
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