Journal of Polymer Science Part B: Polymer Physics, Vol.34, No.9, 1679-1689, 1996
Stability of Filled Poly(Dimethylsiloxane) and Poly(Diphenylsiloxane-Co-Dimethylsiloxane) Elastomers to Cyclic Stress at Elevated-Temperature
The response of aluminum oxide-filled poly(dimethyl siloxane) and poly(diphenylsiloxane) and poly(dimethylsiloxane-co-dimethylsiloxane) elastomers, containing 3-24 mol % diphenylsiloxane, to cyclic stress at elevated temperatures (dynamic creep) was evaluated. The materials could be divided into two classes, based on their response to the application of cyclic stress : no or low-diphenylsiloxane content elastomers in which substantial creep and a decrease in crosslink density were observed, and high diphenylsiloxane content (16-24 mol %) elastomers that showed decreased creep with increasing diphenylsiloxane content and an increase in crosslink density. It was suggested that the phenyl groups stabilize the siloxane bond in the polymer backbone, decreasing the rate of chain scission reactions as the diphenylsiloxane content increases and stabilizing the elastomer against creep. The balance of chain scission, chemical crosslinking, and cyclic formation reactions varies depending on diphenylsiloxane content, giving rise to the differences in dynamic creep behavior. An activation energy of 12.9 kcal/mol was measured for dynamic creep of poly(16 % diphenylsiloxane/84 % dimethyl siloxane), suggesting that a catalyzed degradation mechanism was responsible. The primary catalysts of the degradation reactions are postulated to be the filler particles.
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