Structural formation of hybrid siloxane-based polymer monolith in confined spaces.

Structural deformation of phase-separated methylsiloxane gel under the influence of a surface has been studied. Competitive wetting of siloxane gel phase on a surface during phase formation is found to significantly affect the final morphology in a confined space. When the spinodal wavelength is sufficiently shorter than the size of the available space, a uniform bicontinuous structure forms in confined geometry. However, gel skeletons in the vicinity of a surface are elongated with decreasing size of the space, and finally when the size of the space becomes shorter than the spinodal wavelength, all the gel phase wets on a surface, showing a "wetting transition". Homogeneous bicontinuous methylsiloxane gels were successfully prepared, avoiding such structural deformation, in a long cylindrical fused silica capillary and used for capillary HPLC. The capillary gels exhibited excellent separation efficiency of nitrobenzenes and it was found that the surface character can be altered by incorporating surfactants, which will enable more advanced and extended control of surface character, depending on the analytes.