Hostname: page-component-cd9895bd7-hc48f Total loading time: 0 Render date: 2024-12-23T15:33:10.343Z Has data issue: false hasContentIssue false
  • English
  • Français

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]
Get access Rights & Permissions [Opens in a new window]

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 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

Associate Editor: Peter Leverett

References

Aroyo, M.I., Perez-Mato, J.M., Orobengoa, D., Tasci, E., de la Flor, G. and Kirov, A. (2011) Crystallography online: Bilbao Crystallographic Server. Bulgarian Chemical Communications, 43, 183–197.Google Scholar
Aroyo, M.I., Kirov, A., Capillas, C., Perez-Mato, J.M. and Wondratschek, H. (2006 a) Bilbao Crystallographic Server II: Representations of crystallographic point groups and space groups. Acta Crystallographica Section A, 62, 115–128.CrossRefGoogle ScholarPubMed
Aroyo, M.I., Perez-Mato, J.M., Capillas, C., Kroumova, E., Ivantchev, S., Madariaga, G., Kirov, A. and Wondratschek, H. (2006 b) Bilbao Crystallographic Server I: Databases and crystallographic computing programs. Zeitschrift für Kristallographie, 221, 1, 15–27.Google Scholar
Belik, A.A., Naumov, P., Kim, J. and Tsuda, S. (2011) Low-temperature structural phase transition in synthetic libethenite Cu2PO4OH. Journal of Solid State Chemistry, 184, 3128–3133.Google Scholar
Blessing, R.H. (1995) An empirical correction for absorption anisotropy. Acta Crystallographica Section A, 51, 33–38.Google Scholar
Blessing, R.H., Coppens, P. and Becker, P. (1974) Computer analysis of step-scanned X-ray data. Journal of Applied Crystallography, 7, 488–492.CrossRefGoogle Scholar
Burns, P.C. and Hawthorne, F.C. (1995) Rietveld refinement of the crystal structure of olivenite: a twinned monoclinic structure. Canadian Mineralogist, 33, 885–888.Google Scholar
Carpenter, M.A., Salje, E.K.H., Graeme-Barber, A., Wruck, B., Dove, M.T. and Knight, K.S. (1998 a) Calibration of excess thermodynamic properties and elastic constant variations associated with the alpha-beta phase transition in quartz. American Mineralogist, 83, 2–22.Google Scholar
Carpenter, M.A., Salje, E.K.H. and Graeme-Barber, A. (1998 b) Spontaneous strain as a determinant of thermodynamic properties for phase transitions in minerals. European Journal of Mineralogy, 10, 621–691.Google Scholar
Fei, Y. (1995) Thermal expansion. Pp. 29–44 in: Mineral Physics and Crystallography – A Handbook of Physical Constants. (Ahrens, T. J., editor). AGU reference shelf 2, American Geophysical Union, Washington.Google Scholar
Gaines, R.V., Skinner, H.C.W., Foord, E.E., Mason, B. and Rosenzweig, A. (1997) Dana's New Mineralogy. The System of Mineralogy of James Dwight Dana and Edward Salisbury Dana. 8th Edition. John Wiley & Sons, Inc., 1819 pp.Google Scholar
Huminicki, D.M.C. and Hawthorne, F.C. (2002) The crystal chemistry of phosphate minerals. Pp. 123–253. In: Phosphates – Geochemical, Geobiological and Materials Importance (Kohn, M.L., Rakovan, J. and Hughes, J.M., editors). Mineralogical Society of America, Washington, D.C. and the Geochemical Society, St. Louis, Missouri, USA.Google Scholar
Ibers, J.A. and Hamilton, W.C. (1974) International Tables for X-ray Crystallography. Kynoch Press, Birmingham, UK, vol. 4 [pp. 99–101].Google Scholar
Landau, L.D. and Lifshitz, E.M. (1958) Statistical Physics. Addison Wesley, Reading, Massachusetts, USA.Google Scholar
Lehman, M.S. and Larsen, F.K. (1974) A method for location of the peaks in step-scan measured Bragg reflections. Acta Crystallographica Section A, 30, 580–584.CrossRefGoogle Scholar
Li, C., Yang, H. and Downs, R.T. (2008) Redetermination of olivenite from an untwinned single-crystal. Acta Crystallographica Section E, 64, i60–i61.Google Scholar
Mills, S.J., Kampf, A.R., Poirier, G., Raudsepp, M. and Steele, I.M. (2010) Auriacusite, Fe3+Cu2+AsO4O, the first M3+ member of the olivenite group, from the Black Pine mine, Montana, USA. Mineralogy and Petrology, 99, 113–120.Google Scholar
North, A.C.T., Phillips, D.C. and Mathews, F.S. (1968) A semi-empirical method of absorption correction. Acta Crystallographica Section A, 24, 351–359.Google Scholar
Orobengoa, D., Capillas, C., Aroyo, M.I. and Perez-Mato, J.M. (2009) AMPLIMODES: symmetry-mode analysis on the Bilbao Crystallographic Server. Journal of Applied Crystallography, 42, 820–833.Google Scholar
Perez-Mato, J.M., Orobengoa, D. and Aroyo, M.I. (2010) Mode Crystallography of distorted structures. Acta Crystallographica Section A, 66, 558–590.Google Scholar
Robinson, K., Gibbs, G.V. and Ribbe, P.H. (1971) Quadratic elongation, a quantitative measure of distortion in co-ordination polyhedra. Science, 172, 567–570.Google Scholar
Schneider, H. and Eberhard, E. (1990) Thermal expansion of mullite. Journal of the American Ceramic Society, 73, 2073–2076.Google Scholar
Sheldrick, G.M. (2003) SADABS. University of Göttingen, Germany.Google Scholar
Sheldrick, G.M. (2015) Crystal structure refinement with SHELXL. Acta Crystallographica Section C, 71, 3–8.Google Scholar
Tarantino, S.C., Zema, M., Pistorino, M. and Domeneghetti, M.C. (2003) High-temperature X-ray investigation of natural columbites. Physics and Chemistry of Minerals, 30, 590–598.CrossRefGoogle Scholar
Tarantino, S.C., Giannini, M., Carpenter, M.A. and Zema, M. (2016) Cooperative Jahn-Teller effect and the role of strain in the tetragonal-to-cubic phase transition in MgxCu1–xCr2O4. IUCrJ, 3, 354–366.Google Scholar
Toman, K. (1977) The symmetry and crystal structure of olivenite. Acta Crystallographica Section B, 33, 2628–2631.Google Scholar
Ventruti, G., Zema, M., Scordari, F. and Pedrazzi, G. (2008) Thermal behavior of a Ti-rich phlogopite from Mt. Vulture (Potenza, Italy): An in situ X-ray single-crystal diffraction study. American Mineralogist, 93, 635–643.Google Scholar
Zema, M., Tarantino, S.C. and Montagna, G. (2008) Hydration/dehydration and cation migration processes at high temperature in zeolite chabazite. Chemistry of Materials, 20, 5876–5887.Google Scholar
Zema, M., Tarantino, S.C. and Callegari, A.M. (2010) Thermal behavious of libethenite from room temperature up to dehydration. Mineralogical Magazine, 74, 553–565.Google Scholar
Zema, M., Tarantino, S.C., Boiocchi, M. and Callegari, A.M. (2016) Crystal structure of adamite at high temperature. Mineralogical Magazine, 80, 901–914.CrossRefGoogle Scholar
Supplementary material: File

Tarantino et al. supplementary material

Supplementary Material

Download Tarantino et al. supplementary material(File)
File 978.1 KB