Effect of ultraviolet/ozone treatment on the surface and bulk properties of poly(dimethyl siloxane) and poly(vinylmethyl siloxane) networks

We present a comparative study aiming at comprehending the effect of ultraviolet/ozone treatment on the modification of poly(dimethyl siloxane) (PDMS) and poly(vinylmethyl siloxane) (PVMS) silicone elastomers networks (SENs). Both PDMS and PVMS SENs undergo dramatic changes in their properties when exposed to UVO. The surface chemical composition of both PDMS and PVMS at long UVO treatment times changes substantially and features a high density of hydrophilic groups. There are two major differences in behavior in the two classes of materials. First, relative to PDMS, the PVMS-based SENs get modified throughout the entire bulk. Second, the physico-chemical changes detected in PVMS take place on much shorter time scale relative to PDMS. These results are in accord with our earlier reports that indicated that when exposed to UVO, the topmost ≈5 nm of PDMS gets converted into a silica-like material, which then acts as a barrier for diffusion of atomic oxygen. In this case, the bulk of PDMS maintains its elasticity. In contrast, both the surface and bulk of PVMS films undergo substantial changes in properties when exposed to UVO. First, the surface modification of PVMS SENs takes place after only a few seconds of the UVO treatment. In addition, we register substantial modification of bulk properties, including the complete densification accompanied with increased bulk modulus. Likely, the susceptibility of the vinyl bonds to radical reactions is responsible for this effect.