Liquid fragility and the glass transition in water and aqueous solutions.

In a review of the present title, the first requirement is to ensure that the title words are understood. While the term “glass” is broadly familiar, and the origin of the “glass transition” in terms of the crossing of system and experimental time scales is generally agreed upon, there are at least three different definitions of the material property “glass transition temperature” (Tg) in current use.1,2 Furthermore, these may differ from each other by as much as 50 K in certain higher Tg cases. The difference is a consequence of the magnitude of the “glass transformation range” within which the Tg is variously defined. This magnitude, the “width of the glass transition”, can vary greatly from system to system, for reasons discussed below. Since the quantity Tg will recur frequently in this review, it is necessary to deal adequately with the definition problem, and this will be done by reference to Figures 1 and 2 below. Depending on the liquid in question, glass transitions may be observed occurring over an enormous range in temperature, from below 50 K to above 1500 K. The reason for this range is clearly to do with the strength of the interparticle interactions, i.e., the “bonds” that are being broken as the particles rearrange. However, the reason that some glass transitions are “sharp” (meaning narrow glass transformation range, or “transition width”) and others very spread out in temperature is not so clear. It is largely to do with the “fragility” of the glassformer, but may C. A. Angell was born in Canberra, Australia, and studied chemistry and metallurgy at the University of Melbourne. After working on molten salts with J. O’M Bockris at the University of Pennsylvania for two years, he became the Stanley Elmore Fellow at Imperial College of Science, London, where he completed his Ph.D. under the direction of John W. Tomlinson. There he was awarded the Armstrong medal for graduate research 1959− 1961. He returned to Australia as lecturer in chemical metallurgy but after two years came back to the U.S. as a post-doc with Dieter Gruen at Argonne National Laboratory. In 1966, he joined Purdue University as Assistant Professor, becoming full Professor in 1971. In 1989, he moved to Arizona State University where he is now Regents’ Professor of Chemistry and Biochemistry. He has enjoyed and profited from sabbatical leaves at the University of Amsterdam, the Australian National University, Institute Laue-Langevin, Grenoble, the Ecole de Physique et Chemie Industrielle, Paris, University of Rennes-Beaulieu, Sydney University, and the University of Rome. His research interests range from rechargeable lithium batteries and fuel cells, through the phenomenology of the glass transition and the origin of fragility in liquids, to the anomalous properties of water and geochemical fluids and their relation to polyamorphism. Currently, he is focusing on the annealing behavior of hyperquenched liquids and solutions, particularly denatured protein solutions, with a sideline on nanoporous network glasses as gas storage media. 2627 Chem. Rev. 2002, 102, 2627−2650