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Condensed matter

Too hot to melt

Nature volume 404, pages 134–135 (2000)Cite this article

Melting is a familiar process not expected to show surprises — the melting of ice in a cocktail is expected to produce cooling not heating. Yet just such an effect — inverse melting — has been seen in a polymeric system, as reported by Rastogi et al.1 in Macromolecules . Their findings are relevant for a wide range of systems (not just polymeric ones), and have implications not only for the structural changes involved in melting, but also for the formation of solid amorphous (or glassy) states.

In interpreting their results, Rastogi et al. have revisited much earlier work1,2. In his classic Kristallisieren und Schmelzen (1903), the great inorganic chemist Gustav Tammann devoted some 20 pages to melting, including speculation that it might sometimes be inverted3. In later works4,5,6 he reduced the emphasis on inverse melting — presumably through lack of experimental support — but retained the key concept. Liquids typically have higher volume per unit mass, but also higher compressibility, than their crystalline counterparts; so, at higher pressure, a liquid may have the same volume per unit mass as a crystal. Similarly, liquids typically have higher heat content (enthalpy, H), but also have higher specific heat, than the corresponding crystals; so, at lower temperature, the enthalpy difference may become zero.

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Figure 1: Tammann's universal pressure and temperature phase diagram5,6.
Figure 2: A simplified phase diagram of a polymeric system based on the structural2 and calorimetric1 results of Rastogi and colleagues.

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  1. Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street , Cambridge, CB2 3QZ, UK

    A. Lindsay Greer

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Greer, A. Too hot to melt. Nature 404, 134–135 (2000). https://doi.org/10.1038/35004689

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