FUNDAMENTAL CONDITION OF GLASS FORMATION*

Kuan‐Han Sun

Journal of the American Ceramic Society · 1947 · 603 citations · 4 references

Concepts

TL;DR

Glass formation requires strongly bonded, extended atomic networks that inhibit ordered arrangement near the melting point, allowing the liquid structure to persist upon cooling until long‑range atomic motion ceases. The study identifies that achieving long atomic chains or networks demands very strong bonds, minimal small‑ring formation, appropriate atomic ratios for continuous configurational chains, and low coordination numbers to maintain bond strength. The authors apply a general framework to oxide glasses, calculating and tabulating the bond strengths of all M–O single‑bond linkages. They find glassformers possess bond strengths above 80 kcal/mol, intermediates 60–80 kcal/mol, and modifiers below 60 kcal/mol, with a continuous transition that renders the classification into glassformers, intermediates, and modifiers arbitrary.

Abstract

A bstract The fundamental condition for glass formation is the existence of strongly bonded large networks or long chains of atoms in the liquid. Such chains or networks prevent or hinder the orderly orientation of atoms in the chains or networks themselves and also that of atoms, not in the networks in the liquid, near the melting point or liquidus temperature. A liquid structure will persist when the liquid is cooled below the melting point or liquidus temperature and will continue until free, long‐range movement of atoms becomes impossible. In order to obtain such long chains or large networks, it is necessary that (1) the bond strength of atoms in the chains or networks be very strong; (2) the small ring formation of these strongly bonded atoms be at a minimum; and (3) the relative numbers of various atoms in the chains or networks be such that at least a continuous chain is configuratively and structurally possible; at the same time, the coordination numbers of the glassforming atoms should be as small as possible to keep the bond strong. The general treatment is applied to all kinds of glasses, particularly oxide glasses. The bond strengths of all M—O single‐bond linkages in these glasses are calculated and tabulated here for the first time. The bond strength of all the glassformers was found to be greater than 80 kilocalories per Avogadro bond, that of the intermediates between 60 and 80, and that of the modifiers below 60; the transition is continuous, and the division into glassformers, intermediates, and modifiers is arbitrary.

References

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