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Melt-driven mechanochemical phase transformations in moderately exothermic powder mixtures

Nature Materials volume 15, pages 1280–1286 (2016)Cite this article

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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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Figure 1: Bi melts locally under impact.
Figure 2: Reaction kinetics are driven by liquid Bi.
Figure 3: There is a strong thermal component to reaction kinetics.
Figure 4: The reaction is partially propagated by the enthalpy of mixing.
Figure 5: The kinetics of phase formation are much faster than typical mechanochemical reactions.
Figure 6: Other elements that could melt under mechanochemical processing.

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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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Authors and Affiliations

  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Samuel A. Humphry-Baker & Christopher A. Schuh

  2. Department of Materials, Imperial College, London SW7 2AZ, UK

    Samuel A. Humphry-Baker

  3. Dipartimento di Chimica e Farmacia, Università degli Studi di Sassari, via Vienna 2, 07100 Sassari, Italy

    Sebastiano Garroni

  4. Dipartimento di Ingegneria Meccanica, Chimica e dei Materiali, Università degli Studi di Cagliari, via Marengo 2, 09123 Cagliari, Italy

    Francesco Delogu

Authors
  1. Samuel A. Humphry-Baker
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Contributions

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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Correspondence to Samuel A. Humphry-Baker.

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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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