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  • Articles  (114)
  • Chemistry and Pharmacology  (114)
Collection
  • Articles  (114)
Journal
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 8 (1997), S. 71-76 
    ISSN: 1573-4846
    Keywords: silica-zirconia ; poly(ethylene oxide) ; spinodal decomposition ; light scattering
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Gels with interconnected domain morphologies in the micrometer-range have been prepared in the silica-zirconia system. The domain formation kinetics in the gelling solution have been examined. Growth of an ordered structure on the length scale of micrometers, for which the kinetics are interpreted as spinodal decomposition, was observed by time-resolved light scattering measurements. The remarkable feature of the silica-zirconia system was that a time-dependent decrease of the wavelength of compositional fluctuations was observed. This occurred in the early stage, probably because the fast condensation reaction which was induced by the addition of zirconia, lead to a substantial change in quench depth on a timescale similar to that of the growth of concentration fluctuations. In the following stage, the coarsened domain structure was frozen-in by the sol-gel transition as the permanent morphology.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 8 (1997), S. 71-76 
    ISSN: 1573-4846
    Keywords: silica-zirconia ; poly(ethylene oxide) ; spinodal decomposition ; light scattering
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Gels with interconnected domain morphologies in the micrometer-range have been prepared in the silica-zirconia system. The domain formation kinetics in the gelling solution have been examined. Growth of an ordered structure on the length scale of micrometers, for which the kinetics are interpreted as spinodal decomposition, was observed by time-resolved light scattering measurements. The remarkable feature of the silica-zirconia system was that a time-dependent decrease of the wavelength of compositional fluctuations was observed. This occurred in the early stage, probably because the fast condensation reaction which was induced by the addition of zirconia, lead to a substantial change in quench depth on a timescale similar to that of the growth of concentration fluctuations. In the following stage, the coarsened domain structure was frozen-in by the sol-gel transition as the permanent morphology.
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  • 3
    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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  • 4
    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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  • 5
    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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  • 6
    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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  • 7
    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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  • 8
    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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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Journal of sol gel science and technology 19 (2000), S. 769-773 
    ISSN: 1573-4846
    Keywords: silica ; macropores ; deposition ; silicalite-1 ; microporous crystals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Microcrystalline silicalite-1 was formed on the inner surface of macroporus silica glasses prepared by the sol-gel process. By heating a homogeneous precursor solution at 100°C under a hydrothermal condition, 2–5 μm of plate-like particles of silicalite-1 were deposited. With an increase of mixing time of the precursor solution, the number of silicalite-1 particles increased, accompanied by the relative decrease of the particle size. Depending on the temperature and the duration of the heat-treatment of the macroporous silica, the amount of deposited silicalite-1 varied. Below 1000°C, the amount increased with the heat-treatment temperature, as a result of the competition between the precipitation of silicalite-1 and the dissolution of silica from the macroporous silica glass under a strongly basic condition. On the other hand, above 1000°C the amount of deposited silicalite-1 decreased in accordance with the decrease of the macropore diameter by the heat-treatment, because of the limited transport of the dissolved silicate species through the smaller macropores.
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  • 10
    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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