Polymer Degradation and Stability 86 (2004) 467e471 www.elsevier.

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Oxidation of natural rubber-based magnetorheological elastomers
Mattias Lokandera, Torbjorn 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 The rheological properties of magnetorheological (MR) materials can be changed continuously, rapidly and reversibly by an applied magnetic field. Magnetorheological fluids, where magnetically polarisable particles 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). 0141-3910/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.polymdegradstab.2004.05.019

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

and they were randomly distributed in the oven. counts/min 35000 30000 0% 21 % 25000 20000 15000 10000 0 5 10 15 20 4% 27 % 37 % 9% Time (h) Fig.468 M. A Mettler Toledo AE100 balance and a Mettler density determination kit 33360 were used for the measurements. Sweden. 6 phr zinc oxide (ZnO). with peak sensitivity in the region 400e450 nm. 0. The number of counts per minute is a measure of the reaction rate. .5 phr sulphur. and 0. 3. and riron is the density of iron = 7. Natural rubber was chosen as the matrix because it has been successfully used in magnetorheological rubbers [4. Chemiluminescence curves at 120  C for materials with different content of ASC300 particles. were made from three different materials: without iron particles. The stressestrain properties of the materials were evaluated using an Instron 5566 tensile testing machine. The volume percentage of iron particles was calculated according to: ciron ¼ rtot ÿ rrubber riron ÿ rrubber where rtot is the density of the whole material. The time for the CL curves to reach this maximum is plotted in Fig. The measurements were performed at constant temperature. The iron particles were mixed into the rubber together with the vulcanisation system in a Brabender internal mixer. which causes the signal to be weaker when the iron content increases although the reaction is actually faster. 3. Results and discussion Chemiluminescence curves at 120  C for materials with different content of ASC300 particles are shown in Fig. Some materials were stabilised by addition of 2 phr Irganox 1076. Density In order to confirm the iron particle content of the samples the density of each sample was measured before the measurements. The different samples were hanging in cotton threads without contact with each other or any metal parts in the oven. 2. rrubber is the density of the matrix material. As can be 40000 2.11]. 3. Lokander et al.4. and because it is known to give a good chemiluminescence signal when oxidised [18]. Chemiluminescence Chemiluminescence (CL) measurements were performed on a CLD100 CL-Detector from Tohoku Electronic Industrial Co. 120  C or 90  C. The maximum in the CL curve corresponds to the formation of a visible oxidised skin [18].5 phr MBT (phr Z grams per hundred grams rubber). Experimental 2. The inverse of this time could be seen as a measure of the rate of the skin formation. The dependence of this rate on the iron concentration is shown in Fig. Materials The iron particles used were irregularly shaped pure iron particles from Hoganas AB. As can be seen. the oxidative stability of natural rubber-based magnetorheological elastomers has been studied by chemiluminescence and oven ageing. The recipe was 100 phr rubber. or spherical carbonyl iron CM from BASF (particle size 10 mm). The density was calculated applying the Archimedes principle according to: Density ¼ Mass in air !Density of ethanol Buoyancy in ethanol 2.3. and filled with about 9 and 37% by volume. ASC300 ¨ ¨ (particle size !60 mm). The instrument is sensitive to wavelengths between 280 and 650 nm. The matrix material was conventionally cured natural rubber. SMR GP. Density of ethanol = 0. 2. The sample weight was chosen so the amount of matrix material was about 3 mg. with an airflow of 50 ml/min through the test chamber. 1. 1.9 g cmÿ3.2.1. Samples were vulcanised at 140  C for 40 min under a pressure of approximately 12 MPa.5 phr stearine. ‘‘Dog bones’’ with a cross-section of approximately 2 ! 3 mm. the time to reach the peak of the CL curve is shorter for the materials with iron. 2. Five samples of each material were evaluated at each ageing time.79 g cmÿ3. but the iron particles shields some of the light emitted. The crosshead speed was 500 mm/min. Oven ageing and tensile testing Ageing was carried out in an oven at 90  C or 70  C. / Polymer Degradation and Stability 86 (2004) 467e471 In this paper.

1 0 0 10 20 30 40 50 0 5 10 15 iron content (% ) Fig. and the fraction of monosulfidic crosslinks is higher.8 NR NR+9%ASC300 NR+37%ASC300 NR+AO NR+AO+9%ASC300 NR+AO+37%ASC300 1/(time to max.55 0. / Polymer Degradation and Stability 86 (2004) 467e471 30 469 Modulus 10 9 8 7 20000 18000 16000 14000 12000 10000 8000 6000 0 50 100 150 Time to CL-max (h) 25 20 E (MPa) 15 10 5 0 0 10 20 30 40 50 6 5 4 3 2 1 0 iron content (%) Fig. but also in faster degradation within the sample. it has been reported that incorporation of large amounts of aluminium particles. 2. ageing time (h) Fig. Rate of skin formation (1/time to CL max) as a function of iron content. The oven ageing tests confirm that the peak of the CL curve corresponds to the formation of the oxidised skin. does not decrease the oxidative stability [20].3 0. For the unfilled material. Time to CL max versus iron content. Lokander et al. However.7 0. which leads to a lower minimum modulus of the material due to which more oxygen has time to diffuse into the material [19]. The conventional sulphur vulcanisation system used is sensitive to reversion. There are some possible explanations for the increase in oxidation rate due to incorporation of large amounts of iron particles into the rubber. the antioxidant prolongs the time to form the oxidised skin. 4. before it increases rapidly due to the formation of the crosslinked oxidised skin. This will influence the oxidative behaviour of the materials [22]. 5). which could lead to faster degradation of the matrix. Minimum modulus related to original modulus versus the ageing time to reach the minimum value. 4). Yet another explanation could be that the particles are covered with a thin layer of iron oxide. thus. This is seen as a larger relative decrease in the modulus before it starts to increase for the iron filled materials.85 0.5 E min / E 0 0. should 0. If the minimum value of the modulus. and should be the same for iron particles. whereas the stress at break and tensile modulus initially decreases due to chain scission within the matrix. 5. Another explanation could be that the increased heat transfer will influence the vulcanisation reactions.9 0. Modulus after different ageing times. smaller particles. This is the case for aluminium particles [21]. The mechanical strain at break decreases with increasing ageing time. ageing time (days) Fig. The incorporation of iron particles into the rubber not only results in faster formation of the oxidised skin. which also increases the heat transfer through the material. CL counts/min . (h)) 0.6 0. with larger surface area.6 0. The antioxidant in these cases decreases both the degradation within the material and the rate of the skin formation.4 0.2 0. In such cases. 3. the crosslink density in the iron filled materials could be somewhat lower than that in the unfilled materials.M. related to the original value. seen the rate increases linearly with increasing iron concentration.75 0. is plotted versus the ageing time to reach this value.65 0. some interesting aspects can be seen (Fig. and chemiluminescence curve at 90  C for natural rubber filled with about 9% of ASC300. The iron particles will increase the heat transfer through the material.5 0. The minimum of the stress at break and modulus correspond well to the maximum in the CL curve (Fig.

8 0. Conventional antioxidants can be used to prolong the lifetime of magnetorheological elastomers. 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. Lokander et al. 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. The shielding of the light is very efficient for the smaller particles. 7.15]. and maybe most probable. related to the properties of unaged material. Conclusions The oxidative stability of natural rubber decreases dramatically when large amounts of iron particles are incorporated in the matrix. Another group of stabilisers that could be interesting to use in these materials is the recently developed organotellurium antioxidants [28].2 0 0 5 10 15 NR (strain) MR (strain) NR (stress) MR (stress) NR (Modulus) MR (Modulus) counts/min. metal deactivators. Mechanical properties after ageing at 70  C. but in order to get acceptable lifetime of the materials a careful selection of the antioxidant system. If the curves are normalised to their maximum and minimum (Fig. For NR and other general-purpose elastomers. such a test was performed on stabilised natural rubber and iron filled natural rubber. decrease the stability even more than large particles. is one group of stabilisers that should be investigated.470 M. which leads to a very weak signal. About 75% of the strain. This is probably due to the catalytic effect of iron ions on the decomposition of hydroperoxides. As can be seen. 20000 18000 16000 14000 12000 10000 8000 0 5 10 CM ASC300 Time (h) Fig. CL curves of materials with 27% of ASC300 and carbonyl iron CM at 120  C are shown in Fig. explanation is that iron ions catalyse the decomposition of hydroperoxides and thereby accelerate the oxidation [14. 6. 1 Normalised CL-signal 0. 8. and the large amounts of oxygen on the surface of the particles.2 1 0.8 0. for the iron filled samples a more efficient antioxidant system has to be chosen.4 0. and 85% of the stress at break remains after 14 days. which form complexes with the metal ions and thereby inhibit the catalysis of the oxidation. has to be made. Thus. Such diffusion of metal ions into the matrix would provide an efficient catalyst of the oxidation.4 24000 aged material / unaged material 22000 1. Ageing time (days) Fig. If this is the main reason for the acceleration of the oxidation.4 0. . As mentioned. 7). Chemiluminescence curves at 120  C of materials with 27% of ASC300 and carbonyl iron CM. which should include some metal deactivator. The mechanical properties. The last.  The European Commission is gratefully acknowledged for financial support (Contract no: G5RD-CT1999-00125). / Polymer Degradation and Stability 86 (2004) 467e471 1. Normalised chemiluminescence curves at 120 C of materials with 27% of ASC300 and carbonyl iron CM. 8.2 0 0 5 10 ASC300 CM Acknowledgements Time (h) Fig. However. as related to the values of unaged samples are shown in Fig. 4.24e26]. the antioxidant Irganox 1076 is a reasonable choice for natural rubber. ageing conditions of 7e14 days at 70  C have become commonplace in product specifications and in antioxidant evaluations [27]. The iron ions may be able to diffuse from the particle surfaces into the rubber.6 0. 6. It has been shown that copper ions are able to diffuse into a polymer matrix from a copper surface [23].6 0. complex forming metal deactivators may be used for decreasing the oxidation rate of MR solids [14.

Whitehouse RB.7(11):613e22. Stenberg B. Stenberg B. Kaut Gummi Kunstst 2002. Liauw CM. Oxidation of synthetic rubbers catalyzed by metallic ions. Stenberg B. Mechanism of oxidative degradation.36:541e6. Penetration of copper ions in the polyethylene matrix.5(5): 607e14. In: Brostow W. J Intell Mater Syst Struct 1996.67: 1308e15. Eriksson P. II.42:2553e7. [14] Kuzminskii AS. [8] Davis LC. ozone and high energy radiation. [11] Lokander M.64:197e205. [5] Jolly MR. J Polym Sci Polym Chem Ed 1976. Phang KW.M. Persson S. Lokander M.22(6):677e80. p. Varghese S. Oxford: Oxford University Press. [4] Ginder JM. The magnetic fluid clutch. Mattson B. [10] Kari L. Model of magnetorheological elastomers.55(12):1e5. The magneto˜ viscoelastic response of elastomer composites consisting of ferrous particles embedded in polymer matrix. Allen NS. Elie LD. Al-Maharik N. 1988. Kuriakose B.63(1):23e31. [28] Shanks D. Pascale JV. Chan MG. Mechanisms of inhibition against the copper-catalyzed oxidation of polyethylene: structures and catalytic reactivities of copper-inhibitor complexes. Smart Mater Struct 1996. AIEE Trans 1948. Jolly MR.14:93e104. Zaitsev VD. Carlson JD.25:109e15. Stacy CL. Tardiff JL. Aging studies on redox polymers: effect of iron. Meek RL.58:637e52. Natural rubber science and technology: oxidative ageing. Ind Eng Chem 1950. Polym Test 2003. Improving the magnetorheological effect in isotropic magnetorheological rubber materials. SPIE 1999.75: 405e12. Briggs TH. [18] Forsstrom D. A model of the behaviour of ˜ magnetorheological materials. [23] Allara DL. Nichols ME. Polym Test 2003. Polym Degrad Stab 2003. / Polymer Degradation and Stability 86 (2004) 467e471 471 References [1] Rabinow J. Munoz BC. White CW. Applications of chemiluminescence in rubber research. Kuriakose B. et al. MR fluid. Smart Mater Struct 2003. Effect of aluminium powder on filled natural rubber composites. Stenberg B. Reitberger T. Munich: Carl Hanser Verlag. In: Roberts AD. ¨ Terselius B. Rubber Chem Technol 1992. [17] Keller RW. [3] Carlson JD. Malmstrom J. 553e74. Tardiff JL. [12] Zhou GY. editor. Martin WM. Kron A. [13] Parks CR. Suppression of the activity of metal ions in the oxidation of rubber.14:1857e76.3675:131e8. Rubber Chem Technol 1990. foam and elastomer devices. [7] Nichols ME. Correlation of physico-chemical changes. Effect of metallic salts and metal deactivators on the oxidation of polybutadiene. [21] Vinod VS. De Benedictis T . Gonzalez-Sanchez R.10: 1717e24. 2001. Performance of ˜ plastics: composites with field responsive rheology. Engel RG. Structure-borne sound properties of isotropic magneto-rheological rubber. Ostman E. [2] Munoz BC. Engman L. Carlson JD. [9] Lokander M. [15] Lee L-H. Russell CA. Varghese S. The influence of cure and carbon black on the high temperature oxidation of natural rubber: I. Engel RG. [24] Lee L-H. Thermoanalytical studies of rubber oxidation catalyzed by metallic ions. Polym Degrad Stab 1999. Cole JO. J Polym Sci A 1964. Stenberg B. Improved antioxidant formulations for polymeric materialsdsynergistic protective effectsin combinations of organotellurium compounds with phenolic antioxidants or thiols.74:236e48. Rubber Chem Technol 1985. J Appl Phys 1999. p. J Appl Polym Sci 1966. Thermochim Acta 1978. Mechanisms of oxidative degradation. Performance of isotropic magnetorheological rubber materials. Lokander et al. II. editor. I. 621e78. ¨ Stenberg B.65:736e43. Orlando. Alex R. [16] Goh SH. D’Ianni JD. [27] Barnard D. Jolly MR. [26] Allara DL. 1999. ¨ [19] Mattson B. The dynamic mechanical behaviour of magnetorheological elastomers. Elie LD. Lewis PM.12:139e46. [22] Edge M. Mechatronics 2000. Lezhnev NN. J Appl Polym Sci 1966. Ginder JM. Degradation behaviour of natural rubberealuminium powder composites: effect of heat. Thermo-oxidative degradation of thick-walled rubber materials studied by IRtechnique and computed X-ray tomography scanning. Florida.2:587e609. Inhibition of the copper-catalyzed oxidation of polypropylene.10:1699e715. [25] Hansen RH. Rubber Chem Technol 2001. Munoz BC. [6] Jolly MR. . J Polym Sci Polym Chem Ed 1976. Stacy CL. In: 156th ACS Rubber Division Meeting.22(3):245e51. Magnetorheological elastomers: properties and applications. Bullions TA. Oxidation and ozonation of rubber. [20] Vinod VS. Polym Degrad Stab 2002. Shear properties of a magnetorheological elastomer. Read SJ. Rubber Chem Technol 1963.10:555e69.81(2):261e71.85(6):3348e51. Mechanism of oxidation at a copperepolyethylene interface.

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