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Volume Effects of Alloying: A Thermodynamic Perspective

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Abstract

This study presents a thermodynamic analysis of volume change (Δ°Vm) accompanying alloy formation. Utilizing the thermodynamic identity connecting volume change with Gibbs energy (Δ°Gm) of mixing, Δ°Vm(x) = (∂Δ°Gm/∂p)T,x and closed-form analytical approximations are obtained for both enthalpy (Δ°Vm)h and entropy (Δ°Vm)s-based contributions to Δ°Vm. It is shown that both positive and negative volume change could be supported in a single alloy system in different composition regimes, depending on whether the effect of pressure on enthalpy is dominating over entropy effects of alloying or otherwise. Further, it is also established that entropy contribution to volume change is primarily influenced by volume expansion mismatch between solid solution and compositionally averaged end members. The thermodynamic analysis is supplemented by a phenomenological treatment of enthalpy contribution to volume change arising out of different microscopic contributions to mixing enthalpy. Possible thermodynamic justification of empirical polynomial representation of composition induced volume variation is also presented. An illustrative case study on volume effects accompanying the formation of bcc solid solution phase in U1−xZrx system is presented.

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Acknowledgements

The author acknowledges Dr. Balasubramanian Venkatraman, Director, IGCAR, for the encouragement, support and permission to publish this study. The benign influence of late Dr. Srikumar Banerjee, formerly the Chairman, DAE and Secretary to the Government of India, in nurturing and motivating the academic aspirations of the author, is gratefully recalled. This study is dedicated to the 75th anniversary of India’s independence.

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  1. Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam, 603102, India

    Subramanian Raju

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Raju, S. Volume Effects of Alloying: A Thermodynamic Perspective. Trans Indian Inst Met 75, 1031–1041 (2022). https://doi.org/10.1007/s12666-022-02550-4

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