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Polymer Degradation and Stability 86 (2004) 467e471

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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


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

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

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

1,4
24000

aged material / unaged material


22000 1,2
20000
1
counts/min.

NR (strain)
18000 CM MR (strain)
0,8
16000 ASC300 NR (stress)
MR (stress)
14000 0,6
NR (Modulus)
12000 0,4 MR (Modulus)

10000
0,2
8000
0 5 10 0
0 5 10 15
Time (h)
Ageing time (days)
Fig. 6. Chemiluminescence curves at 120  C of materials with 27% of
ASC300 and carbonyl iron CM. Fig. 8. Mechanical properties after ageing at 70  C, related to the
properties of unaged material.

decrease the stability even more than large particles. CL


curves of materials with 27% of ASC300 and carbonyl commonplace in product specifications and in antioxi-
iron CM at 120  C are shown in Fig. 6. The shielding of dant evaluations [27]. Thus, such a test was performed
the light is very efficient for the smaller particles, which on stabilised natural rubber and iron filled natural
leads to a very weak signal. If the curves are normalised rubber. The mechanical properties, as related to the
to their maximum and minimum (Fig. 7), it is clear that values of unaged samples are shown in Fig. 8. As can be
the peak of the signal for the small carbonyl iron seen, the antioxidant Irganox 1076 is a reasonable
particles comes earlier than for the larger ASC300 choice for natural rubber. About 75% of the strain, and
particles. This indicates that the decrease in oxidative 85% of the stress at break remains after 14 days.
stability is due to the surface of the particles. However, for the iron filled samples a more efficient
The last, and maybe most probable, explanation is antioxidant system has to be chosen. The stress and
that iron ions catalyse the decomposition of hydro- strain at break for this material has decreased to about
peroxides and thereby accelerate the oxidation [14,15]. 35% of the original value after only 7 days at 70  C. As
The iron ions may be able to diffuse from the particle mentioned, metal deactivators, which form complexes
surfaces into the rubber. It has been shown that copper with the metal ions and thereby inhibit the catalysis of
ions are able to diffuse into a polymer matrix from the oxidation, is one group of stabilisers that should be
a copper surface [23]. Such diffusion of metal ions into investigated. Another group of stabilisers that could be
the matrix would provide an efficient catalyst of the interesting to use in these materials is the recently
oxidation. If this is the main reason for the acceleration developed organotellurium antioxidants [28].
of the oxidation, complex forming metal deactivators
may be used for decreasing the oxidation rate of MR 4. Conclusions
solids [14,24e26].
For NR and other general-purpose elastomers, The oxidative stability of natural rubber decreases
ageing conditions of 7e14 days at 70  C have become 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
1
hydroperoxides, and the large amounts of oxygen on the
surface of the particles. Conventional antioxidants can
Normalised CL-signal

0,8
be used to prolong the lifetime of magnetorheological
0,6
elastomers, but in order to get acceptable lifetime of the
ASC300 materials a careful selection of the antioxidant system,
0,4
CM which should include some metal deactivator, has to be
made.
0,2

0 Acknowledgements
0 5 10
Time (h) The European Commission is gratefully acknowl-
Fig. 7. Normalised chemiluminescence curves at 120 C of materials  edged for financial support (Contract no: G5RD-CT-
with 27% of ASC300 and carbonyl iron CM. 1999-00125).
M. Lokander et al. / Polymer Degradation and Stability 86 (2004) 467e471 471

References [17] Keller RW. Oxidation and ozonation of rubber. Rubber Chem
Technol 1985;58:637e52.
[1] Rabinow J. The magnetic fluid clutch. AIEE Trans 1948;67: [18] Forsström D, Kron A, Mattson B, Reitberger T, Stenberg B,
1308e15. Terselius B. Applications of chemiluminescence in rubber
[2] Muñoz BC, Jolly MR. In: Brostow W, editor. Performance of research. Rubber Chem Technol 1992;65:736e43.
plastics: composites with field responsive rheology. Munich: Carl [19] Mattson B, Stenberg B, Persson S, Östman E. Thermo-oxidative
Hanser Verlag; 2001. p. 553e74. degradation of thick-walled rubber materials studied by IR-
[3] Carlson JD, Jolly MR. MR fluid, foam and elastomer devices. technique and computed X-ray tomography scanning. Rubber
Mechatronics 2000;10:555e69. Chem Technol 1990;63(1):23e31.
[4] Ginder JM, Nichols ME, Elie LD, Tardiff JL. Magnetorheological [20] Vinod VS, Varghese S, Kuriakose B. Degradation behaviour of
elastomers: properties and applications. SPIE 1999;3675:131e8. natural rubberealuminium powder composites: effect of heat,
[5] Jolly MR, Carlson JD, Muñoz BC, Bullions TA. The magneto- ozone and high energy radiation. Polym Degrad Stab 2002;75:
viscoelastic response of elastomer composites consisting of ferrous 405e12.
particles embedded in polymer matrix. J Intell Mater Syst Struct [21] Vinod VS, Varghese S, Alex R, Kuriakose B. Effect of aluminium
1996;7(11):613e22. powder on filled natural rubber composites. Rubber Chem
[6] Jolly MR, Carlson JD, Muñoz BC. A model of the behaviour of Technol 2001;74:236e48.
magnetorheological materials. Smart Mater Struct 1996;5(5): [22] Edge M, Allen NS, Gonzalez-Sanchez R, Liauw CM, Read SJ,
607e14. Whitehouse RB. The influence of cure and carbon black on the
[7] Nichols ME, Ginder JM, Tardiff JL, Elie LD. The dynamic high temperature oxidation of natural rubber: I. Correlation of
mechanical behaviour of magnetorheological elastomers. In: physico-chemical changes. Polym Degrad Stab 1999;64:197e205.
156th ACS Rubber Division Meeting, Orlando, Florida; 1999. [23] Allara DL, White CW, Meek RL, Briggs TH. Mechanism of
[8] Davis LC. Model of magnetorheological elastomers. J Appl Phys oxidation at a copperepolyethylene interface. II. Penetration of
1999;85(6):3348e51. copper ions in the polyethylene matrix. J Polym Sci Polym Chem
[9] Lokander M, Stenberg B. Performance of isotropic magneto- Ed 1976;14:93e104.
rheological rubber materials. Polym Test 2003;22(3):245e51. [24] Lee L-H, Stacy CL, Engel RG. Mechanism of oxidative
[10] Kari L, Lokander M, Stenberg B. Structure-borne sound degradation. II. Effect of metallic salts and metal deactivators
properties of isotropic magneto-rheological rubber. Kaut Gummi on the oxidation of polybutadiene. J Appl Polym Sci 1966;10:
Kunstst 2002;55(12):1e5. 1717e24.
[11] Lokander M, Stenberg B. Improving the magnetorheological [25] Hansen RH, Russell CA, De Benedictis T , Martin WM,
effect in isotropic magnetorheological rubber materials. Polym Pascale JV. Inhibition of the copper-catalyzed oxidation of
Test 2003;22(6):677e80. polypropylene. J Polym Sci A 1964;2:587e609.
[12] Zhou GY. Shear properties of a magnetorheological elastomer. [26] Allara DL, Chan MG. Mechanisms of inhibition against the
Smart Mater Struct 2003;12:139e46. copper-catalyzed oxidation of polyethylene: structures and
[13] Parks CR, Cole JO, D’Ianni JD. Aging studies on redox catalytic reactivities of copper-inhibitor complexes. J Polym Sci
polymers: effect of iron. Ind Eng Chem 1950;42:2553e7. Polym Chem Ed 1976;14:1857e76.
[14] Kuzminskii AS, Zaitsev VD, Lezhnev NN. Suppression of the [27] Barnard D, Lewis PM. In: Roberts AD, editor. Natural rubber
activity of metal ions in the oxidation of rubber. Rubber Chem science and technology: oxidative ageing. Oxford: Oxford
Technol 1963;36:541e6. University Press; 1988. p. 621e78.
[15] Lee L-H, Stacy CL, Engel RG. Mechanisms of oxidative [28] Shanks D, Al-Maharik N, Malmström J, Engman L, Eriksson P,
degradation. I. Oxidation of synthetic rubbers catalyzed by Stenberg B, et al. Improved antioxidant formulations for poly-
metallic ions. J Appl Polym Sci 1966;10:1699e715. meric materialsdsynergistic protective effectsin combinations of
[16] Goh SH, Phang KW. Thermoanalytical studies of rubber oxidation organotellurium compounds with phenolic antioxidants or thiols.
catalyzed by metallic ions. Thermochim Acta 1978;25:109e15. Polym Degrad Stab 2003;81(2):261e71.