ORDER FORMATION OF INORGANIC SOL-GEL SYSTEM IN CONFINED SPACES

在片状、细柱状和短柱状的小受限空间中合成了二氧化硅或有机-无机杂化体系中的大孔凝胶样品。在厚度达到30微米的板状受限空间中，无论是在二氧化硅还是在杂化体系中，冻结在凝胶结构中的相分离的特征尺寸都随着受限空间厚度的减小而变得粗糙。在疏水容器壁上，在杂化情况下观察到了皮肤层的形成，并伴随着容器壁附近的耗尽层和柱状相分离的区域。通过激光扫描共聚焦显微镜的三维观察对这些结构进行了详细的分析，发现相分离受到引起表面旋节波的壁的存在的影响。由于共连续的磁畴结构和层状表面诱导结构的叠加，形成了耗尽层和柱状形变磁畴。另一方面，在亲水容器壁上，凝胶域被化学结合，而不形成皮肤层。观察到了与疏水壁相似的耗尽层和柱状形变磁区。然而，在这种情况下，耗尽层是由于凝胶结构域与壁之间的排斥相互作用和含硅醇壁上的结构域化学锚定之间的妥协而形成的。当受限空间的尺寸与相分离区域的尺寸相同时，观察到独特的非常精细的相分离结构。

Macroporous gel samples in the systems of silica or siloxane-based organic-inorganic hybrid were synthesized in small confined spaces of slab, thin columnar and short columnar shapes. In the slab shaped confined spaces with the thickness up to 30 microns, the characteristic size of phase separation frozen in the gel structure became coarser with a decrease in the thickness of the confined space both in silica or hybrid systems. On hydrophobized container walls, the formation of skin layer was observed in the case of hybrid composition, which was accompanied by the depletion layer and columnar phase separated domains in the vicinity of the container walls. Detailed analysis of these structures by 3-D observation with laser scanning con focal microscopy revealed that the phase separation was affected by the presence of walls that cause surface-spinodal wave. As a result of superposition of the co-continuous domain structure and the layer-like surface-induced structure, the depletion layer and the columnar deformed domains were formed. On the other hand, on hydrophilized container walls, the gel domains were chemically bonded without forming the skin layer. Depletion layers and columnar deformed domains similar to the case of hydrophobized walls were observed. However, in this case, the depletion layers were formed as a result of compromise between repulsive interaction between gel domains and walls and chemical anchoring of the domains on the silanol-containing walls. Unique very fine phase separated structures were observed when the confined space was in the same dimension as the size of phase separated domains.