Vapor phase infiltration of zinc oxide into thin films of cis-polyisoprene rubber

Elastomers are an important class of polymers for many applications. Often, additives are added to the polymer matrix of elastomers to promote vulcanization or enhance physical or chemical properties. In this study, vapor phase infiltration (VPI) is investigated for transforming unvulcanized cis-polyisoprene (from natural rubber) into an organic/inorganic hybrid material. Specifically, we examine single-cycle infiltration with diethylzinc (DEZ) and water to form infiltrated zinc oxide species. Interestingly, low-temperature pre-heating of the cis-polyisoprene acutely affects the processes of infiltration, including diffusivity, maximum solubility, and chemical reactivity. We attribute these effects to a combination of film relaxation and oxidation. Independent of thermal pre-treatments, all infiltration processes exhibited consistent zinc oxide loading irrespective of purge time between the DEZ and water doses, indicating the presence of a strongly bound intermediate state between the DEZ precursor and the cis-polyisoprene polymer. Increasing infiltration process temperature accelerates diffusion and lowers the maximum solubility, in accordance with Fick's law and gas phase sorption equilibrium. Resulting organic–inorganic hybrid films show enhanced resistance to dissolution in toluene, a good solvent for the pure polymer.