Synthesis of Non-siliceous Glasses and Their Structural Characterization by Solid-State NMR
Sol-gel glasses are an attractive area for both fundamental and applied research owing to their potential and actual use as catalysts, bioactive materials, photonic devices, and solid electrolytes. As some of these applications cannot be realized with glasses prepared by traditional melt cooling, a fundamental understanding of structure-property relations in this research field is an important research objective. Nuclear magnetic resonance (NMR) spectroscopy offers an element-selective, inherently quantitative, and experimentally very flexible approach for the structural elucidation of noncrystalline materials. The present chapter introduces the basic concepts of this technique, highlighting the use of advanced NMR methodology for characterizing short- and intermediate-range order in these systems. The current state of the literature on the structural characterization of the most prominent non-siliceous glasses, based on the network former species Al2O3, B2O3, and P2O5, is reviewed. By monitoring the structural evolution occurring during the sol-> gel-> glass transformations, NMR can yield important mechanistic information, which is useful for optimizing the synthesis parameters. In addition, detailed structural studies as a function of glass composition reveal the underlying principles of glass formation in these systems.
This chapter features work done during the course of the Schwerpunkt program “Vom Molekül zum Material,” funded under grants Ec168/4-1 and Ec168/4-2 from 2000 to 2007 by the Deutsche Forschungsgemeinschaft. Thanks are also due to the NRW Graduate School of Chemistry, funded from 2000 to 2009 at the WWU Münster by the State of North Rhine Westphalia. I wish to thank Professor Dr. Long Zhang (now at the Shanghai Institute of Optics and Fine Mechanics) for pioneering the aluminum lactate sol-gel process during his postdoctoral stay in my laboratory from 2001 to 2006. Thanks are further due to Professor Dr. Jinjun Ren (now at the Shanghai Institute of Optics and Fine Mechanics), Professor Dr. J. C. C. Chan (now at National Taiwan University, Taipei), Dr. Carla Araujo, Dr. Rashmi Deshpande, Dr. Tobias Uesbeck, and Dr. Lars Hoyer, for their invaluable contributions to the work being reviewed here, made during the course of PhD and postdoctoral work during the time period 2000–2015. The author further wishes to thank the late Professor Dr. Günther Heinz Frischat (formerly TU Clausthal) and Professor Dr. Dominik Eder (formerly WWU Münster, now TU Wien) for fruitful collaborations. Further support by the Brazilian funding agencies São Paulo Research Foundation FAPESP (CEPID Project 2013/07793-6, grant 2013/23490-3) and CNPq (Universal Project 477,053/2012-2) is most gratefully acknowledged.
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