ORDER FORMATION OF INORGANIC SOL-GEL SYSTEM IN CONFINED SPACES

密闭空间中无机溶胶-凝胶体系的有序形成

• 批准号: 12450268
• 负责人: NAKANISHI Kazuki
• 金额: $ 7.94万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12450268/
• 关键词: confined space; sol-gel method; phase separation; porous structure; chromatography; organic-inorganic hybrid; wetting; silica

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.

在硅基或正庚烷基有机-无机杂化体系中，合成了板状、细柱状和短柱状的小受限空间的大孔凝胶样品。在厚度达30微米的板状受限空间中，在二氧化硅或混合体系中，随着受限空间厚度的减小，冻结在凝胶结构中的相分离的特征尺寸变得更粗。在疏水化的容器壁上，在混合组合物的情况下观察到表皮层的形成，其伴随着容器壁附近的耗尽层和柱状相分离域。通过激光扫描共聚焦显微镜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。由于共连续畴结构和层状表面诱导畴结构的叠加，形成了耗尽层和柱状变形畴。另一方面，在干燥的容器壁上，凝胶域化学键合而不形成皮层。观察到类似于疏水化壁的情况的耗尽层和柱状变形域。然而，在这种情况下，耗尽层的形成是由于凝胶域和壁之间的排斥相互作用和域在含硅烷醇的壁上的化学锚定之间的折衷。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。