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  • 1
    Electronic Resource
    Electronic Resource
    s.l. ; Stafa-Zurich, Switzerland
    Advances in science and technology Vol. 45 (Oct. 2006), p. 759-768 
    ISSN: 1662-0356
    Source: Scientific.Net: Materials Science & Technology / Trans Tech Publications Archiv 1984-2008
    Topics: Natural Sciences in General , Technology
    Notes: Organic-inorganic hybrid monoliths with well-defined macropores and/or mesopores havebeen synthesized by a sol-gel process accompanied by polymerization-induced phase separation.Using aklyltrialkoxysilanes and alkylene-bridged alkoxysilanes, two different categories oforgano-siloxane networks have been characterized in view of macroporoisity based on phaseseparation as well as mesoporosity based on supramolecular templating by surfactants. Thealkyl-terminated polysiloxane network exhibited substantial surface hydrophobicity together with themechanical flexibility. On the other hand, the alkylene-bridged network behaved much moresimilarly to those prepared from tetraalkoxysilanes with regard to surface hydrophilicity, mechanicalrigidness and mesopore-forming ability. Supramolecular templating of mesopores embedded in thegel skeletons comprising well-defined macroporous network has proven to give wide variety ofhierarchically designed macro-mesoporous organic-inorganic hybrid materials
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  • 2
    Electronic Resource
    Electronic Resource
    Westerville, Ohio : American Ceramics Society
    Journal of the American Ceramic Society 81 (1998), S. 0 
    ISSN: 1551-2916
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Macroporous titania (TiO2) films have been prepared via a sol-gel dip-coating method from a titanium tetraisopropoxide solution that contains poly(ethylene glycol) (PEG). The macroporous morphology-i.e., the size, distribution, and shape of the macropores-is controlled by varying the content and molecular weight of PEG, the withdrawal speed, and the temperature of the dipping solution. The morphology of the TiO2 film is determined by competitive contributions of the following factors: (i) decrease in fluidity, because of the evaporation of solvent; (ii) network formation by polycondensation reactions; and (iii) domain formation during phase separation into gel phases and solvent phases.
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  • 3
    ISSN: 1551-2916
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Phase separation in a sol–gel process of SiO2–ZrO2 in the presence of polyethylene oxide is investigated. An amorphous gel with interconnected macroporous morphology is obtained when phase separation and sol–gel transition concur to fix a transitional structure of spinodal decomposition. Macropore size, together with connectivity of the pores and gel skeleton, can be controlled precisely by selecting an appropriate starting composition for preparation at a zirconium content ≤11.7 mol%. The macroporous gel retains additional mesopores 〈4 nm and exhibits typical bimodal pore size distribution. The addition of ZrO2 in SiO2 improves the thermal stability of both macroporous and mesoporous structures.
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  • 4
    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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  • 5
    ISSN: 1573-4846
    Keywords: silica ; poly(ethylene oxide) ; light scattering ; spinodal decomposition ; initial stage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Domain formation kinetics in gelling alkoxy-derived silica solutions containing polyethylene oxide (PEO) has been investigated. The time-resolved light scattering measurement was performed for the polymerizing solutions which underwent phase separation in the length scale of micrometer. Domain formation processes which resulted in various sizes of inter-connected morphology were examined, focusing mainly on the initial stage. For all the samples, the scattering intensity grew exponentially with time forming a single peak at a fixed wave-number in the first few tens seconds, which is the characteristic of the linearized regime of the spinodal decomposition. An analysis based on the linearized theory proposed by Cahn gave a reasonable description of the kinetic parameter of phase separation induced in various stages of the sol-gel transition.
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  • 6
    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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  • 7
    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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  • 8
    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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  • 9
    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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  • 10
    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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