Abstract
The thermodynamic properties of nanometer-sized particles have been studied in a large variety of sample configurations, and by many different experimental techniques. Much of this work has focussed on the size dependence of the melting temperature, and has included studies of nearly free particles prepared in the form of discontinuous vapor deposited films, as well as confined particles in granular and porous materials. These studies have shown that the melting temperature is generally reduced with respect to the corresponding bulk value by an amount that is approximately proportional to the inverse particle size. Similar size dependent reductions in the latent heat of fusion have also been observed. In each case the experimentally observed behavior is in qualitative agreement with classical thermo- dynamic treatments of melting when surface effects are explicitly accounted for.
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It is worth noting that an unambiguous determination of melting temperatures based on the disappearance of crystalline diffraction peaks arising from a distribution of different particle sizes is not trivial. Because the intensity of the crystalline peaks themselves depends on the temperature through the Debye-Waller factor, it is necessary to separate this effect from the intensity reduction arising from the melting of the smallest particles in the sample. Different approaches to separating these effects led to melting temperatures of the smallest particles that differed by several hundred degrees (see ref. 6).
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Unruh, K.M., Sheehan, J.F. (1994). Thermodynamics of Finite Systems. In: Hadjipanayis, G.C., Siegel, R.W. (eds) Nanophase Materials. NATO ASI Series, vol 260. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-1076-1_40
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DOI: https://doi.org/10.1007/978-94-011-1076-1_40
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