Thermodynamics Research Today is a free monthly online journal that collates and summarizes the latest research about Thermodynamics, including details on enthalpy, entropy, energy transitions.

A thermodynamically stable nanophase material.

Lin Z, Gilbert B, Liu Q, Ren G, Huang F

Laboratory of Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, National Engineering Research Center for Optoelectronic Crystalline Materials, Chinese Academy of Sciences, Fuzhou, People's Republic of China.

Nanoparticles are metastable relative to the equivalent bulk material due to the positive excess interfacial free energy (IFE). Previous studies have shown that, with increasing surface interaction strength, the IFE diminishes but remains positive. We describe an experimental multicomponent system in which a nanoscale ZnS material is thermodynamically favored and can be formed at the expense of bulk ZnS. In 17 M sodium hydroxide solution, at 230 degrees C, both 3 nm ZnS nanoparticles and bulk ZnS are transformed into sheetlike nanocrystals with a ZnS polytype structure. Our results are theoretically compatible with the concept of a negative IFE, although not with the assumption of constant interface composition. We clarify the meaning of an effective negative IFE and present the necessary conditions for strong chemical surface interactions to stabilize nanoscale inorganic materials relative to bulk matter. Our results show that synthesis methods employing thermodynamic controls can produce nanomaterials with novel morphology.

Published 3 May 2006 in J Am Chem Soc, 128(18): 6126-31.
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