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Keywords = Kauzmann paradox

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14 pages, 3984 KiB  
Article
New Interpretation of X-ray Diffraction Pattern of Vitreous Silica
by Shangcong Cheng
Ceramics 2021, 4(1), 83-96; https://doi.org/10.3390/ceramics4010008 - 13 Mar 2021
Cited by 7 | Viewed by 4862
Abstract
The striking feature of X-ray diffraction pattern of vitreous silica is that the center of its intense but broad ring is located at nearly the same position as the strongest diffraction ring of β-cristobalite. Two fundamentally different explanations to the diffraction patterns were [...] Read more.
The striking feature of X-ray diffraction pattern of vitreous silica is that the center of its intense but broad ring is located at nearly the same position as the strongest diffraction ring of β-cristobalite. Two fundamentally different explanations to the diffraction patterns were appeared about 90 years ago, one based on the smallest crystals of β-cristobalite and the other based on the non-crystalline continuous random network. This work briefly outlines the facts supporting and objecting these two hypotheses, and aims to present a new interpretation based on a medium-range ordering structure on the facets of clusters formed in the glass transition process. It will be shown that the new interpretation provides a more satisfactory explanation of the diffraction pattern and physical properties of silica glass, and offers considerable valuable information regarding the nature of glass and glass transition. Full article
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7 pages, 1534 KiB  
Proceeding Paper
A New Perspective on the Kauzmann Entropy Paradox: A Crystal/Glass Critical Point in Four- and Three-Dimensions
by Caroline S. Gorham and David E. Laughlin
Proceedings 2020, 46(1), 23; https://doi.org/10.3390/ecea-5-06677 - 17 Nov 2019
Viewed by 1615
Abstract
In this article, a new perspective on the Kauzmann point is presented. The “ideal glass transition” that occurs at the Kauzmann temperature is the point at which the configurational entropy of an undercooled metastable liquid equals that of its crystalline counterpart. We model [...] Read more.
In this article, a new perspective on the Kauzmann point is presented. The “ideal glass transition” that occurs at the Kauzmann temperature is the point at which the configurational entropy of an undercooled metastable liquid equals that of its crystalline counterpart. We model solidifying liquids by using a quaternion orientational order parameter and find that the Kauzmann point is a critical point that exists to separate crystalline and non-crystalline solid states. We identify the Kauzmann point as a first-order critical point, and suggest that it belongs to quaternion ordered systems that exist in four- or three-dimensions. This “Kauzmann critical point” can be considered to be a higher-dimensional analogue to the superfluid-to-Mott insulator quantum phase transition that occurs in two- and one-dimensional complex ordered systems. Such critical points are driven by tuning a non-thermal frustration parameter, and result due to characteristic softening of a `Higgs’ type mode that corresponds to amplitude fluctuations of the order parameter. The first-order nature of the finite temperature Kauzmann critical point is a consequence of the discrete change of the topology of the ground state manifold of the quaternion order parameter field that applies to crystalline and non-crystalline solids. Full article
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32 pages, 665 KiB  
Article
Glass Transition, Crystallization of Glass-Forming Melts, and Entropy
by Jürn W. P. Schmelzer and Timur V. Tropin
Entropy 2018, 20(2), 103; https://doi.org/10.3390/e20020103 - 1 Feb 2018
Cited by 46 | Viewed by 10444
Abstract
A critical analysis of possible (including some newly proposed) definitions of the vitreous state and the glass transition is performed and an overview of kinetic criteria of vitrification is presented. On the basis of these results, recent controversial discussions on the possible values [...] Read more.
A critical analysis of possible (including some newly proposed) definitions of the vitreous state and the glass transition is performed and an overview of kinetic criteria of vitrification is presented. On the basis of these results, recent controversial discussions on the possible values of the residual entropy of glasses are reviewed. Our conclusion is that the treatment of vitrification as a process of continuously breaking ergodicity with entropy loss and a residual entropy tending to zero in the limit of zero absolute temperature is in disagreement with the absolute majority of experimental and theoretical investigations of this process and the nature of the vitreous state. This conclusion is illustrated by model computations. In addition to the main conclusion derived from these computations, they are employed as a test for several suggestions concerning the behavior of thermodynamic coefficients in the glass transition range. Further, a brief review is given on possible ways of resolving the Kauzmann paradox and its implications with respect to the validity of the third law of thermodynamics. It is shown that neither in its primary formulations nor in its consequences does the Kauzmann paradox result in contradictions with any basic laws of nature. Such contradictions are excluded by either crystallization (not associated with a pseudospinodal as suggested by Kauzmann) or a conventional (and not an ideal) glass transition. Some further so far widely unexplored directions of research on the interplay between crystallization and glass transition are anticipated, in which entropy may play—beyond the topics widely discussed and reviewed here—a major role. Full article
(This article belongs to the Special Issue Residual Entropy and Nonequilibrium States)
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