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 Title: Multinuclear NMR Investigations of Sol-Gel Systems Author(s): Irwin, Alan Dale Doctoral Committee Chair(s): Jonas, Jiri Department / Program: Chemistry Discipline: Chemistry Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Chemistry, Analytical Abstract: The inorganic polymeric materials known as oxide glasses are normally prepared by the fusion of refractory oxides, followed by rapid cooling to avoid devitrification. A topic of current interest in materials research is the preparation of oxide glasses by the hydrolysis and polymerization of metal alkoxides in solution to form a gel, which may then be fired to form a glass. This so-called sol-gel process represents the synthesis of an inorganic polymer in a manner analogous to that in which organic polymers have traditionally been prepared.Much work has been and continues to be done toward preparing specific materials by the sol-gel process, and toward determining the physical characteristics of sol-gel derived materials. However, there remains a great need for basic understanding of the chemistry involved. The effects of processing variables such as starting reagents, temperature, pressure, pH, etc. cannot be optimally controlled or exploited without a knowledge of the chemistry of polymer-forming metal alkoxide systems.Recent advances in instrumentation and methods have made pulse Fourier transform nuclear magnetic resonance (NMR) spectroscopy a powerful technique for studying the chemistry of inorganic oxide systems in both the liquid and solid states. This thesis describes the application of these NMR techniques to the sol-gel systems SiO$\sb2$, B$\sb2$O$\sb3$-SiO$\sb2$, Al$\sb2$O$\sb3$-SiO$\sb2$ and Na$\sb2$O-Al$\sb2$O$\sb3$-SiO$\sb2$.It is demonstrated that in the borosilicate system, borosiloxane bonds do not result from co-polymerization in the sol; rather they are formed during heat treatment above 150$\sp\circ$C, after water has been driven out. The degree of cross-linking in SiO$\sb2$ gels prepared under different catalytic conditions is monitored during heat treatment. While the initial gels vary greatly in their degree of cross-linking, the products after heating to 800$\sp\circ$C are very similar. In aluminosilicate gels, aluminosiloxy bonds are formed by the time of gelation, the aluminum occupying tetrahedral (AlO$\sb4$) $\sp-$ sites which are charge balanced by octahedral cationic aluminum species. The addition of sodium as a counter ion enables the octahedral aluminum to convert to (AlO$\sb4$) $\sp-$. The aluminum environment is also shown to be dependent on the type of aluminum starting alkoxide employed. Issue Date: 1987 Type: Text Description: 102 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987. URI: http://hdl.handle.net/2142/70388 Other Identifier(s): (UMI)AAI8803078 Date Available in IDEALS: 2014-12-15 Date Deposited: 1987
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