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Free radical formation in oriented polybutadiene during mechanical deformation below Tg
Authors:W. T. Mead  P. E. Reed
Abstract:The tensile behavior of oriented polybutadiene at 83°K is systematically studied as a function of strain rate and pre-test orientation. Electron spin resonance studies of radical formation are made in conjunction with the mechanical tests. Three different modes of mechanical behavior are observed (brittle, crazing and a second ductile behavior without crazing), depending on test conditions. Radical formation is observed in association with the two ductile modes of behavior. The ESR spectra obtained are attributed to a combination of allyl radicals formed by chain scission between the α-methylene groups and peroxy radicals. The relative quantity of the two radical species present is thought to be related to the ratio of cis/trans-isomerism. Stability of the radicals observed with time and with an increase in temperature is studied. Further studies are made of the quantity of environmental test gases absorbed during crazing.
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