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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 19 (2000), S. 65-70 
    ISSN: 1573-4846
    Keywords: porous material ; phase separation ; microporous crystals ; chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Recent progress in the sol-gel science concerning the porous gels made by phase separation has been reviewed. Based on the principle and technique explored for monoliths, the material shape has been extended to a macroporous thick film and a macroporous gel in a confined space such as capillary, both of which are expected to find useful applications in the chromatography. The modifiable size range of the additional porosity within the micrometer-sized gel skeleton has been broadened from micropores by zeolite, mesopores by surfactant templates to macropores by intensive hydrothermal treatments. A detailed investigation of 3D interfacial structure in real space has been performed using the laser scanning confocal microscope, which enabled quantitative comparison of the structure with those of other phase-separating systems.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 19 (2000), S. 553-557 
    ISSN: 1573-4846
    Keywords: dip coating ; phase separation ; macroporous film ; alkylsiloxane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Macroporous silicate thick films were prepared by the sol-gel dip-coating method accompanied by the phase separation using the composition of methyl-trimethoxysilane (MTMS), nitric acid and dimethylformamide (DMF). The morphology of the film varied to a large extent depending on the time difference between hydrolysis and dipping of the coating solution. The films prepared by early coating had inhomogeneous submicrometer-sized pores on the surface of the film. At increased reaction times, relatively narrow sized internal macropores were observed and their size gradually decreased with the increase of reaction time.
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  • 3
    ISSN: 1573-4846
    Keywords: porous silica gel ; light scattering ; phase separation ; spinodal decomposition ; Cahn's theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The investigation of phase separation processes induced by polymerization reactions of tetramethoxysilane (TMOS) was attempted by a time-resolved light scattering method for TMOS-formamide-water system under the acid-catalyzed condition. Since the early stage of the phase separation exhibits very fast kinetics and weak scattering intensity, the experimental set-up was designed so as to reduce the experimental error and to obtain higher time resolution by using a laser beam expander. For the gels whose morphologies are ‘interconnected structure’ and ‘aggregates of particles,’ it was experimentally found that the wavelength of the concentration fluctuation in the early stage of phase separation was time-independent and its amplitude grew exponentially with time. This suggests that these samples phase-separate by spinodal decomposition mechanism. In the later stages of phase separation, the coarsening process and the following structure-freezing process by gel-network formation were observed.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 8 (1997), S. 547-552 
    ISSN: 1573-4846
    Keywords: silicon alkoxide ; phase separation ; double pore structure ; liquid chromatography ; Van Deemter equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Silica gels retaining double pore structure in the size ranges of micrometer and nanometer have been applied to the rod-shaped monolithic column for liquid chromatography. The macropore structure was designed by controlling the phase separation process induced by the hydrolysis and polycondensation of alkoxysilane, whereas the mesopore structure was tailored by the solvent exchange treatments on wet gels. The size exclusion chromatograms on polystyrene standards exhibited almost similar features for octadecyl-modified rod and conventional packed beads columns. The dependence of plate height on the velocity of mobile phase determined for amylbenzene was by far weaker in the rod column than in the packed beads column, suggesting that additional geometrical factors should be considered in describing the separation mechanism in the rod column.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 1 (1993), S. 35-46 
    ISSN: 1573-4846
    Keywords: Flory-Huggins' theory ; phase separation ; spinodal decomposition ; sol-gel method ; porous silica gel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Silica gels with well-defined pores both in micrometer and nanometer ranges were obtained by acid-catalyzed hydrolysis and polymerization of tetramethoxysilane in the presence of formamide. The micrometer-range structures of these gels are studied in terms of the phase diagram of the quasi two-component system, namely solvent-rich and silica-rich end compositions. The resulting interconnected structures and aggregates of particles are related to the occurrence of spinodal phase separation. The composition region that gave interconnected structures for the present system was much more limited and their characteristic sizes were much smaller than those for the previously reported systems containing an organic polymer. These results could be explained qualitatively by the effect of the degree of polymerization on the Flory-Huggins' type free energy change of mixing.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 13 (1998), S. 163-169 
    ISSN: 1573-4846
    Keywords: silica gels ; phase separation ; pore size distribution ; liquid chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Utilizing the concurrence of polymerization-induced phase separation and sol-gel transition in the hydrolytic polycondensation of alkoxysilanes, a well-defined macroporous structure is formed in a monolithic wet gel. By exchanging the fluid phase of the wet gel with an appropriate external solution, the nanometer-range structure of the wet gel can be reorganized into structures with larger median pore size essentially without affecting the macroporous framework. The double-pore structure thus prepared is characterized by open pores distributed in discrete size ranges of micrometers and nanometers. A new type of chromatographic column (silica rod) has been developed using monolithic double-pore silica instead of packed spherical gel particles. Typical silica rod columns had significantly reduced pressure drops and improved analytical efficiencies which do not deteriorate even at higher sample flow rates, both arising from a greater macropore volume than particle packed columns.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 17 (2000), S. 7-18 
    ISSN: 1573-4846
    Keywords: organic-inorganic interaction ; in situ observation of sol-gel reaction ; phase separation ; meso scale structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Growth behavior of silica in an acid catalyzed sol-gel process from silicon alkoxide in the presence of poly(ethylene oxide), PEO, was investigated by in situ small angle X-ray scattering, SAXS, and 29Si NMR measurements. The results of SAXS, that aggregation and gel formation behaviors of silica were affected by the presence of PEO, suggested a strong attractive interaction between silica oligomers and PEO. A possible reaction scheme of silica in the presence of PEO is as follows; (1) PEO and small silica oligomers coexist in the solution without specific interaction just after hydrolysis of the silicon alkoxide. (2) With the progress of condensation, a ramified aggregated complex between PEO and silica oligomers is formed, which is characterized by larger apparent value of radius of gyration and smaller fractal dimension than in the PEO-free system. (3) After gelation, the fractal dimension of scatterers remains to be smaller than that in the PEO-free system, because PEO associated with the silica network inhibits aggregation within the gel networks. Furthermore, PEO inhibits the condensation in the aging and in the drying process, leading to less strongly crosslinked dry gel. A temporal maximum in the time evolution of Rg was observed for the samples separated into two phases with their characteristic domain size being larger than several micrometers. This is considered to be a phenomenon related to increase and divergence of correlation length near and at the critical point.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 17 (2000), S. 191-210 
    ISSN: 1573-4846
    Keywords: silica ; phase separation ; pore structure ; mesopores ; chromatography columns
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract By inducing a phase separation parallel to the sol-gel transition of alkoxy-derived silicate systems, gels with well-defined macroporous structure can be prepared. Depending on the post-gelation treatment such as aging and solvent exchange, the final pore structure in the nanometer range of dried and heat-treated gels exhibits a considerable variation. With an aim of completely controlling the hierarchical pore structure in the discrete size ranges of nanometers and micrometers, systematic experimental studies have been performed. The macroporous nature of the wet gels allows an efficient solvent exchange process compared with conventional gels only with mesopores. In addition, the surface chemistry of the wet gel skeleton affects the mesopore formation process by the solvent exchange to a great extent. The median size of mesopores larger than 5 nm can be controlled by adjusting the basic solvent exchange conditions such as pH value, temperature and bath ratio for any kind of macroporous silica gel. On the other hand, the control of pore volume independent of the mesopore size is possible only in the system incorporated with the micelle-forming surfactant. Some examples of the effects of controlled mesopores on the analytical performance of monolithic-type chromatographic columns are also presented.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 19 (2000), S. 337-341 
    ISSN: 1573-4846
    Keywords: macroporous silica ; phase separation ; membrane emulsification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A macroporous silica glass membrane with continuous cylindrical pores was prepared by a sol-gel process using phase separation. The applicability of the sol-gel derived macroporous silica to the membrane emulsification process was evaluated in comparison with a conventional SPG (Silasu Porous Glass) membrane. Aqueous colloidal silica in one side of the membrane was emulsified through the pores under an applied pressure to a toluene bath containing surfactant. With the sol-gel and SPG membranes with respective median pore diameters of 0.6 and 1.0 μm, emulsions with almost the same droplet size centered around 3 μm were obtained. The permeation rate of the sol-gel derived membrane was about 1.6 times faster than SPG, which reflected higher pore volume of the former one.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 19 (2000), S. 371-375 
    ISSN: 1573-4846
    Keywords: phase separation ; silica ; capillary column ; HPLC ; CEC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Continuous macroporous silica gel networks were prepared in a fused silica capillary, and evaluated in reversed-phase liquid chromatography. Under pressure-driven conditions, considerable dependence of column efficiency on the linear velocity of the mobile phase was observed in spite of the small size of the silica skeletons. A major source of band broadening in the pressure-driven mode was found in the A-term of van Deemter equation. The performance of the continuous silica capillary column in the electro-driven mode was much better than that in the pressure-driven mode.
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