Abstract
IN earlier papers1–4 we developed a free-volume model for the amorphous phase according to which the liquid and glassy states of a given substance together comprise a single, thermodynamically well-defined phase. In this model the transition to the glass state results ideally from the freezing out of the free volume, and hence the configurational entropy of the liquid3. This transition should occur in all classical liquids, including monatomic ones, provided crystallization is by-passed2. Implicit in these ideas is the hypothesis that the glassy state is truly metastable and not unstable; consequently, by the Nernst theorem, it would have vanishing entropy at 0° K. For the hypothesis to be true, each microscopic structural unit of the glass must lie at a position of static equilibrium, the totality of which is randomly distributed. If one such structure exists there must be a large number of similar random structures of equal energy. Nevertheless, the entropy of each is zero, because all these structures are mutually inaccessible. One particular structure would be picked out in a given cooling process, and the system would remain in that structure. The increase of entropy on heating back into the liquid state would then occur because the equivalent random structures become mutually accessible5.
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These results are analogous to those obtained by Gibbs and DiMarzio (J. Chem. Phys., 28, 373; 1958) with a lattice model specifically applicable to molecularly complex systems.
(a) Rice, O. K., J. Chem. Phys., 12, 1 (1944). (b) Scott, G. D., Nature, 188, 908 (1960). (c) Bernal, J. D., and Mason, J., Nature, 188, 910 (1960).
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Stillinger, F. H., DiMarzio, E. A., and Kornegay, R. L., J. Chem. Phys., 40, 1564 (1964).
Rahman, A., Argonne National Laboratory (private communication).
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COHEN, M., TURNBULL, D. Metastability of Amorphous Structures. Nature 203, 964 (1964). https://doi.org/10.1038/203964a0
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DOI: https://doi.org/10.1038/203964a0
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