Two new block copolymers containing dimethylsiloxane and semifluorinated styrene blocks (BSF6 and BSF8) were prepared using a polysiloxane azo-macroinitiator and corresponding semifluorinated styrene monomers StyF6 and StyF8. The thermal properties of the block copolymers were investigated by DSC, which showed the formation of a thermotropic mesophase in BSF8. This was attributed to the self-assembly of the semifluorinated side groups in microphase-separated domains of the incompatible polymer blocks. Coatings with 300 nm thicknesses had a root-mean-square roughness of 10 nm by atomic force microscopy. Using water and alcohols, wetting behavior was studied along with a model poly(dimethylsiloxane) (PDMS) network. High advancing (θ adv = 122°) and receding (θ rec = 82°) water contact angles were observed for BSF8. Using 2-propanol, BSF8 displayed oleophobicity (θ adv = 64° and θ rec = 45°) while a reference PDMS coating was completely wetted (θ adv = θ rec = 0°). Utilizing θ adv for a series of alcohols, a fit to a modified equation of state gave a low value for BSF8 surface tension (γ SV = 10.5 mN/m). Both the wetting behavior of BSF8 and surface dynamics associated with wetting are consistent with the presence of a well-ordered, liquid crystalline fluorocarbon surface domain. In contrast, BSF6 surfaces are swollen by alcohols and display a cycle-dependent wetting behavior in water. BSF6 surfaces are thus labile to surface reorganization and/or solvent adsorption.

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A new surface phenomenon is reported for hybrid nanocomposites comprising (1) a low Tg poly(dimethylsiloxane) (PDMS) phase cross-linked by (2) a siliceous phase (SP) generated by in situ hydrolysis/condensation of poly(diethoxysiloxane) (PDES), and (3) fumed silica nanoparticles (FSN). After ambient temperature cure, tapping mode atomic force microscopy (TM-AFM) easily reveals near-surface FSN. For nanocomposites with higher PDES content, FSN surprisingly "disappear" after a further cure at 100 degrees C. The observation is explained by further condensation of extant siliceous fragments creating an amorphous reticular phase, which acts as a mechanical barrier between the FSN and the AFM tip.