Polymer Degradation and Stability 86 (2004) 467e471

www.elsevier.com/locate/polydegstab

Oxidation of natural rubber-based magnetorheological

elastomers
Mattias Lokandera, Torbjörn Reitbergerb, Bengt Stenberga,*
a
Department of Fibre and Polymer Technology, KTH, Teknikringen 56-58, SE - 100 44 Stockholm, Sweden
b
Department of Chemistry, Nuclear Chemistry, KTH, Teknikringen 56, SE - 100 44 Stockholm, Sweden
Received 1 April 2004; received in revised form 17 May 2004; accepted 31 May 2004

Abstract

The rheological properties of magnetorheological (MR) materials can be changed continuously, rapidly and reversibly by an
applied magnetic field. Solid MR materials consist of magnetically polarisable particles, generally iron, in an elastomer matrix. The
high iron concentrations required (about 30% by volume) in order to get a substantial magnetorheological effect should influence
the long-term stability of the materials. In this paper, the oxidative stability of natural rubber-based magnetorheological elastomers
has been studied by chemiluminescence and oven ageing. The results show that the oxidative stability of natural rubber decreases
dramatically when large amounts of iron particles are incorporated in the matrix. This is probably due to the large amounts of
oxygen on the surface of the particles. Conventional antioxidants can be used to prolong the lifetime of magnetorheological
elastomers, but in order to get acceptable lifetime of the materials a careful selection of the antioxidant system has to be made.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Magnetorheology; Natural rubber; Iron; Oxidation

1. Introduction [4e7]. However, although the particles have been

The rheological properties of magnetorheological
(MR) materials can be changed continuously, rapidly
and reversibly by an applied magnetic field. Magneto-
rheological fluids, where magnetically polarisable par-
ticles are dispersed in a carrier oil, were introduced by
Rabinow in 1948 [1]. Interest in solid analogues of
magnetorheological fluids, where the carrier oil is
replaced by a rubber or a gel, has increased recently.
The MR effect in MR fluids is seen as a field-responsive
yield stress, whereas in MR solids the shear modulus is
field-responsive [2,3]. In most MR solids, the polarisable
particles, generally pure iron, have been aligned by an
applied magnetic field prior to the curing of the matrix
* Corresponding author. Tel.: C46 8 790 8269; fax: C46 8 10 07 75.
E-mail address: stenberg@polymer.kth.se (B. Stenberg).
aligned, the iron concentration needed in order to get
a good MR effect is about 30% by volume [5,7,8]. It is
possible to achieve a good MR effect without aligning
the particles if the particles used have a relatively low
critical concentration (the concentration where the
particles are in touch with each other). In such cases,
the actual iron concentration in the material has to be
close to the critical concentration of the particles [9e11].
The largest magnetorheological effect in MR solids
reported so far is about 60% [12].
The high iron concentrations required in order to get
a substantial magnetorheological effect may influence the
long-term stability of the materials. The surface of ‘‘pure’’
iron particles is covered with a thin layer of iron oxides.
This results in large amounts of oxygen incorporated into
the material. Furthermore, iron ions are known to
enhance the oxidation of rubber materials [13e17].

0141-3910/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2004.05.019
468 M. Lokander et al. / Polymer Degradation and Stability 86 (2004) 467e471

In this paper, the oxidative stability of natural 2.4. Density

rubber-based magnetorheological elastomers has been
studied by chemiluminescence and oven ageing. Natural In order to confirm the iron particle content of the
rubber was chosen as the matrix because it has been samples the density of each sample was measured before
successfully used in magnetorheological rubbers [4,11], the measurements. The density was calculated applying
and because it is known to give a good chemilumines- the Archimedes principle according to:
cence signal when oxidised [18].
Mass in air
Density ¼ !Density of ethanol
Buoyancy in ethanol
Density of ethanol = 0.79 g cm3.
2. Experimental A Mettler Toledo AE100 balance and a Mettler
density determination kit 33360 were used for the
2.1. Materials measurements. The volume percentage of iron particles
was calculated according to:
The iron particles used were irregularly shaped pure
iron particles from Höganäs AB, Sweden, ASC300 rtot  rrubber
ciron ¼
(particle size !60 mm), or spherical carbonyl iron CM riron  rrubber
from BASF (particle size
10 mm). The matrix material
where rtot is the density of the whole material, rrubber is
was conventionally cured natural rubber, SMR GP. The
the density of the matrix material, and riron is the density
recipe was 100 phr rubber, 6 phr zinc oxide (ZnO),
of iron = 7.9 g cm3.
0.5 phr stearine, 3.5 phr sulphur, and 0.5 phr MBT
(phr Z grams per hundred grams rubber). Some materi-
als were stabilised by addition of 2 phr Irganox 1076.
3. Results and discussion
The iron particles were mixed into the rubber together
with the vulcanisation system in a Brabender internal
Chemiluminescence curves at 120  C for materials
mixer. Samples were vulcanised at 140  C for 40 min
with different content of ASC300 particles are shown in
under a pressure of approximately 12 MPa.
Fig. 1. As can be seen, the time to reach the peak of the
CL curve is shorter for the materials with iron. The
number of counts per minute is a measure of the reaction
2.2. Chemiluminescence
rate, but the iron particles shields some of the light
emitted, which causes the signal to be weaker when the
Chemiluminescence (CL) measurements were per-
iron content increases although the reaction is actually
formed on a CLD100 CL-Detector from Tohoku
faster. The maximum in the CL curve corresponds to the
Electronic Industrial Co. The instrument is sensitive to
formation of a visible oxidised skin [18]. The time for the
wavelengths between 280 and 650 nm, with peak
CL curves to reach this maximum is plotted in Fig. 2.
sensitivity in the region 400e450 nm. The measurements
The inverse of this time could be seen as a measure of the
were performed at constant temperature, 120  C or
rate of the skin formation. The dependence of this rate
90  C, with an airflow of 50 ml/min through the test
on the iron concentration is shown in Fig. 3. As can be
chamber. The sample weight was chosen so the amount
of matrix material was about 3 mg.
40000

0%
2.3. Oven ageing and tensile testing 35000

30000
Ageing was carried out in an oven at 90  C or 70  C.
counts/min

21 %
‘‘Dog bones’’ with a cross-section of approximately
25000 4%
2 ! 3 mm, were made from three different materials:
without iron particles, and filled with about 9 and 37% 20000
by volume. The different samples were hanging in 27 % 9%
cotton threads without contact with each other or any 15000 37 %
metal parts in the oven, and they were randomly
distributed in the oven. The stressestrain properties of 10000
0 5 10 15 20
the materials were evaluated using an Instron 5566
tensile testing machine. Five samples of each material Time (h)
were evaluated at each ageing time. The crosshead Fig. 1. Chemiluminescence curves at 120  C for materials with
speed was 500 mm/min. different content of ASC300 particles.
 M. Lokander et al. / Polymer Degradation and Stability 86 (2004) 467e471 469

30 Modulus
10 20000
25
Time to CL-max (h)

9
18000
20 8

CL counts/min
7 16000
15

10
5 3
0 1
0 10 20 30
iron content (%)
Fig. 2. Time to CL max versus iron content.
seen the rate increases linearly with increasing iron
concentration.
The oven ageing tests confirm that the peak of the CL
curve corresponds to the formation of the oxidised skin.
The mechanical strain at break decreases with increasing
ageing time, whereas the stress at break and tensile
modulus initially decreases due to chain scission within
the matrix, before it increases rapidly due to the
formation of the crosslinked oxidised skin. The mini-
mum of the stress at break and modulus correspond well
to the maximum in the CL curve (Fig. 4). If the
minimum value of the modulus, related to the original
value, is plotted versus the ageing time to reach this
value, some interesting aspects can be seen (Fig. 5). The
incorporation of iron particles into the rubber not only
results in faster formation of the oxidised skin, but also
in faster degradation within the sample. This is seen as
a larger relative decrease in the modulus before it starts
to increase for the iron filled materials. The antioxidant
in these cases decreases both the degradation within the
material and the rate of the skin formation. For the
unfilled material, the antioxidant prolongs the time to
form the oxidised skin, which leads to a lower minimum
modulus of the material due to which more oxygen has
time to diffuse into the material [19].
E (MPa)
6 14000
5
12000
4
10000
2
8000
40 50
0 6000
0 50 100 150
ageing time (h)
Fig. 4. Modulus after different ageing times, and chemiluminescence
curve at 90  C for natural rubber filled with about 9% of ASC300.
There are some possible explanations for the in-
crease in oxidation rate due to incorporation of large
amounts of iron particles into the rubber. The iron
particles will increase the heat transfer through the
material, which could lead to faster degradation of the
matrix. However, it has been reported that incorpora-
tion of large amounts of aluminium particles, which
also increases the heat transfer through the material,
does not decrease the oxidative stability [20]. Another
explanation could be that the increased heat transfer
will influence the vulcanisation reactions. This is the
case for aluminium particles [21], and should be the
same for iron particles. The conventional sulphur
vulcanisation system used is sensitive to reversion;
thus, the crosslink density in the iron filled materials
could be somewhat lower than that in the unfilled
materials, and the fraction of monosulfidic crosslinks is
higher. This will influence the oxidative behaviour of
the materials [22].
Yet another explanation could be that the particles
are covered with a thin layer of iron oxide. In such cases,
smaller particles, with larger surface area, should

0,9

0,85
0,6
0,8
0,5 NR
1/(time to max. (h))

E min / E 0

0,75 NR+9%ASC300
0,4 NR+37%ASC300
0,7
NR+AO
0,3
0,65 NR+AO+9%ASC300
0,2 NR+AO+37%ASC300
0,6
0,1 0,55

0 0,5
0 10 20 30 40 50 0 5 10 15
iron content (% ) ageing time (days)

Fig. 3. Rate of skin formation (1/time to CL max) as a function of iron Fig. 5. Minimum modulus related to original modulus versus the
content. ageing time to reach the minimum value.
470 M. Lokander et al. / Polymer Degradation and Stability 86 (2004) 467e471
24000
22000
20000
counts/min.
18000
16000
14000
12000
10000
8000
0 5
Time (h)
Fig. 6. Chemiluminescence curves at 120  C of materials with 27% of
ASC300 and carbonyl iron CM.
decrease the stability even more than large particles. CL
curves of materials with 27% of ASC300 and carbonyl
iron CM at 120  C are shown in Fig. 6. The shielding of
the light is very efficient for the smaller particles, which
leads to a very weak signal. If the curves are normalised
to their maximum and minimum (Fig. 7), it is clear that
the peak of the signal for the small carbonyl iron
particles comes earlier than for the larger ASC300
particles. This indicates that the decrease in oxidative
stability is due to the surface of the particles.
The last, and maybe most probable, explanation is
that iron ions catalyse the decomposition of hydro-
peroxides and thereby accelerate the oxidation [14,15].
The iron ions may be able to diffuse from the particle
surfaces into the rubber. It has been shown that copper
ions are able to diffuse into a polymer matrix from
a copper surface [23]. Such diffusion of metal ions into
the matrix would provide an efficient catalyst of the
oxidation. If this is the main reason for the acceleration
of the oxidation, complex forming metal deactivators
may be used for decreasing the oxidation rate of MR
solids [14,24e26].
For NR and other general-purpose elastomers,
ageing conditions of 7e14 days at 70  C have become
1
Normalised CL-signal
0,8
0,6
0,4
0,2
0 Acknowledgements
0 5
Time (h)
Fig. 7. Normalised chemiluminescence curves at 120 C of materials
with 27% of ASC300 and carbonyl iron CM.
1,4
aged material / unaged material
1,2
1
NR (strain)
CM MR (strain)
0,8
ASC300 NR (stress)
MR (stress)
0,6
NR (Modulus)
0,4 MR (Modulus)
0,2
10 0
0 5 10 15
Ageing time (days)
Fig. 8. Mechanical properties after ageing at 70  C, related to the
properties of unaged material.
commonplace in product specifications and in antioxi-
dant evaluations [27]. Thus, such a test was performed
on stabilised natural rubber and iron filled natural
rubber. The mechanical properties, as related to the
values of unaged samples are shown in Fig. 8. As can be
seen, the antioxidant Irganox 1076 is a reasonable
choice for natural rubber. About 75% of the strain, and
85% of the stress at break remains after 14 days.
However, for the iron filled samples a more efficient
antioxidant system has to be chosen. The stress and
strain at break for this material has decreased to about
35% of the original value after only 7 days at 70  C. As
mentioned, metal deactivators, which form complexes
with the metal ions and thereby inhibit the catalysis of
the oxidation, is one group of stabilisers that should be
investigated. Another group of stabilisers that could be
interesting to use in these materials is the recently
developed organotellurium antioxidants [28].
4. Conclusions
The oxidative stability of natural rubber decreases
dramatically when large amounts of iron particles are
incorporated in the matrix. This is probably due to the
catalytic effect of iron ions on the decomposition of
hydroperoxides, and the large amounts of oxygen on the
surface of the particles. Conventional antioxidants can
be used to prolong the lifetime of magnetorheological
elastomers, but in order to get acceptable lifetime of the
ASC300 materials a careful selection of the antioxidant system,
CM which should include some metal deactivator, has to be
made.
10
The European Commission is gratefully acknowl-
 edged for financial support (Contract no: G5RD-CT-
1999-00125).
 M. Lokander et al. / Polymer Degradation and Stability 86 (2004) 467e471
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