Abstract
Usually, mechanochemical reactions between solid phases are either gradual (by deformation-induced mixing), or self-propagating (by exothermic chemical reaction). Here, by means of a systematic kinetic analysis of the Bi–Te system reacting to Bi2Te3, we establish a third possibility: if one or more of the powder reactants has a low melting point and low thermal effusivity, it is possible that local melting can occur from deformation-induced heating. The presence of hot liquid then triggers chemical mixing locally. The molten events are constrained to individual particles, making them distinct from self-propagating reactions, and occur much faster than conventional gradual reactions. We show that the mechanism is applicable to a broad variety of materials systems, many of which have important functional properties. This mechanistic picture offers a new perspective as compared to conventional, gradual mechanochemical synthesis, where thermal effects are generally ignored.
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Acknowledgements
F.D. and S.G. are grateful to Prof. Stefano Enzo, Dipartimento di Chimica e Farmacia, Università degli Studi di Sassari, for his help in the quantitative analysis of XRD patterns. This material is partially based on work supported as part of the ‘Solid State Solar-Thermal Energy Conversion Center (S3TEC)’, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001299 (S.A.H.-B. and C.A.S.). The material is also partially supported by the Universities of Cagliari and Sassari (F.D. and S.G., respectively).
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F.D., S.G. and S.A.H.-B. designed and performed experiments; F.D., C.A.S. and S.A.H.-B. analysed the data and co-wrote the manuscript.
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Humphry-Baker, S., Garroni, S., Delogu, F. et al. Melt-driven mechanochemical phase transformations in moderately exothermic powder mixtures. Nature Mater 15, 1280–1286 (2016). https://doi.org/10.1038/nmat4732
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DOI: https://doi.org/10.1038/nmat4732
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