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Monoclinic-to-orthorhombic phase transition in Cu2(AsO4)(OH) olivenite at high temperature: strain and mode decomposition analyses

Published online by Cambridge University Press:  28 February 2018

Serena C. Tarantino ,
Michele Zema ,
Athos M. Callegari ,
Massimo Boiocchi  and
Michael A. Carpenter
Serena C. Tarantino
Affiliation:
Dipartimento di Scienze della Terra e dell'Ambiente, Università di Pavia, via Ferrata 9, I-27100 Pavia, Italy CNR-IGG, Sezione di Pavia, via Ferrata 9, I-27100 Pavia, Italy
Michele Zema*
Affiliation:
Dipartimento di Scienze della Terra e dell'Ambiente, Università di Pavia, via Ferrata 9, I-27100 Pavia, Italy CNR-IGG, Sezione di Pavia, via Ferrata 9, I-27100 Pavia, Italy
Athos M. Callegari
Affiliation:
Dipartimento di Scienze della Terra e dell'Ambiente, Università di Pavia, via Ferrata 9, I-27100 Pavia, Italy
Massimo Boiocchi
Affiliation:
Centro Grandi Strumenti, Università di Pavia, via Bassi 21, I-27100 Pavia, Italy
Michael A. Carpenter
Affiliation:
Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ, UK
*
*Email: [email protected]
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Abstract

A natural olivenite single crystal was submitted to in situ high-temperature single-crystal X-ray diffraction from room temperature (RT) to 500°C. Unit-cell parameters were measured at regular intervals of 25°C, and complete datasets collected at T = 25, 50, 100, 150, 200, 250, 300, 400 and 500°C. Evolution of unit-cell parameters and structure refinements indicates that olivenite undergoes a structural phase transition from P21/n to Pnnm at ~200°C, and eventually becomes isostructural with the other members of the olivenite-mineral group. Volume expansion with temperature is larger in the monoclinic phase – where it follows a non-linear trend – than in the orthorhombic one. Axial and volume expansion coefficients of the orthorhombic olivenite phase are positive and linear and similar to those of the other Cu-bearing member of the mineral family, namely libethenite, but rather different from those of the Zn-analogue arsenate adamite.

Distortion of Cu polyhedra is quite high in the olivenite monoclinic phase at RT and goes towards a relative regularization with increasing T until the phase transition occurs. In the orthorhombic phase, no significant variation of the polyhedral distortion parameters is observed with increasing temperature, and maximum expansion is along the b direction and governed by corner-sharing. Landau potential provides a good representation of the macroscopic changes associated with the phase transition, coupling between the strains and the order parameter is responsible for the nearly tricritical character of the transition.

Keywords

olivenitephase transitionsthermal expansionstrainsingle-crystal X-ray diffraction
Type
Article
Information
Mineralogical Magazine , Volume 82 , Issue 2 , April 2018 , pp. 347 - 365
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2018 

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Footnotes

Associate Editor: Peter Leverett

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