AGING WITH APPLIED STRAIN OF A BLACK-FILLED NATURAL RUBBER VULCANIZATE. PART I: NETWORK CHANGES

Black-filled natural rubber. with an inefficient sulfur cure, was aged at 90 degrees C and 110 degrees C under nitrogen, with and without applied strain. Samples aged under strain became "double networks" and retained a residual extension ratio. The crosslink density of samples passed through a maximum with increasing severity of aging. Presumably this arises because the thermally labile, polysulfidic crosslinks break, and new crosslinks of lower rank form, resulting in increased crosslink density; but, when aged at 110 degrees C, this is offset by chain scission and other main-chain modifications. For double networks, it is proposed that a second network, which tends to keep samples extended, is formed at the expense of crosslinks in the original, first network. Unaged and single network samples were isotropic in tensile behavior and only slightly anisotropic in swelling behavior. For double networks, swelling and tensile properties were anisotropic, and there was some evidence that parallel specimens have increased ability to strain-crystallize. The observed anisotropies in double networks are proposed to arise from the chain orientation that persisted after double network formation.