Peroxide and Radiation Cured Compounds Filled with Reinforcing Fine Particle Silica

There are indications that the chemical reaction involved in bound rubber formation proceeds via a free-radical mechanism for compounds filled with reinforcing hydrated fine-particle silica, as well as in the case of carbon black as filler. The high potential of silica as a rubber reinforcer is indicated by its bound rubber formation. This potential was realized by the extent of filler-polymer interaction developed in silica-filled vulcanizates cured by peroxide and by high-energy radiation, respectively. Both these relatively simple curing systems are postulated to effect crosslink formation via a free-radical mechanism. The value, after cure, of the ratio of the crosslink density of the filled compound to the crosslink density of the respective unfilled compound, η/η0, was taken to be a logical measure of the ability to reinforce. In natural rubber compounds filled with silica (30 vol.), the values of η/η0 obtained were 1.6–1.9 for peroxide-cured material, and 3.6 for radiation-cured material. Comparisons are made with similarly cured HAF black-filled stocks. Sulfur-cured natural rubber stocks filled with HAF black (30 vol.) generally exhibit η/η0 values in the range of 1.5 to 2.0. Comparative effects of antioxidants are described.