Skip to main content Accessibility help

T-induced displacive phase transition of end-member Pb-lawsonite

  • Martin Ende (a1), Bernd Wunder (a2), Monika Koch-Müller (a2), Thoma. Pippinger (a1), Gernot Buth (a3), Gerald Giester (a1), Christian L. Lengauer (a1) and Eugen Libowitzky (a1)...


Pb-lawsonite, PbAl2[(OH)2|Si2O7]·H2O, space group Pbnm, was synthesized as crystals up to 15 μm × 5 μm × 5 μm in size by a piston cylinder technique at a pressure of ∼4 GPa and a temperature of 873 ± 10 K. Temperature-dependent powder and single-crystal X-ray diffraction (XRD) analyses partly using synchrotron radiation as well as Raman spectroscopic investigations reveal a phase transition around 445 K resulting in the Cmcm high-temperature structure. The transformation temperature is considerably higher than that of lawsonite around 273 K, which is characterized predominantly by proton order/disorder. The transition is confirmed using principal component analysis and subsequent hierarchical cluster analysis on both the powder XRD patterns and the Raman spectra. Furthermore, a non-uniform change is observed around 355 K, which is not as pronounced as the 445 K transition and apparently comes from enhanced hydrogen bonding, which stops the atom shifts in Pb-lawsonite. These are the same bonds that mainly characterize the phase transition in lawsonite around 273 K. In contrast, the structural transition of Pblawsonite at 445 K seems to originate from the interaction of the SiO4 tetrahedra and AlO6 octahedra framework with the Pb2+ cation. The structural environment of Pb2+ can be described by a 12-fold coordination above 445 K, which changes towards irregular ten-fold coordination below this temperature. An assignment of the O–H stretching Raman bands confirms moderately strong H bonds in Pb-lawsonite, whereas both strong and weak H bonds exist in lawsonite. Therefore, a further phase transition of Pblawsonite, similar to that of lawsonite around 273 K, is not expected.

    • Send article to Kindle

      To send this article to your Kindle, first ensure is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about sending to your Kindle. Find out more about sending to your Kindle.

      Note you can select to send to either the or variations. ‘’ emails are free but can only be sent to your device when it is connected to wi-fi. ‘’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

      Find out more about the Kindle Personal Document Service.

      T-induced displacive phase transition of end-member Pb-lawsonite
      Available formats

      Send article to Dropbox

      To send this article to your Dropbox account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Dropbox.

      T-induced displacive phase transition of end-member Pb-lawsonite
      Available formats

      Send article to Google Drive

      To send this article to your Google Drive account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Google Drive.

      T-induced displacive phase transition of end-member Pb-lawsonite
      Available formats


Copyright © The Mineralogical Society of Great Britain and Ireland 2016 This is an Open Access article, distributed under the terms of the Creative Commons Attribution license. (, which permits unrestricted re-use, distribution, and reproduction in any medium, provided the original work is properly cited.

Corresponding author


Hide All
Armbruster, T., Oberhänsli, R., Bermanec, V and Dixon, R. (1993) Hennomartinite and kornite, two new Mn +rich silicates from the Wessels Mine, Kalahari, South Africa. Schweizerische Mineralogische und Petrographische Mitteilungen, 73, 349355.
Brovarone, A.V. and Beyssac, O. (2014) Lawsonite metasomatism: a new route for water to the deep Earth. Earth and Planetary Science Letters, 393,275284
Carpenter, M.A. (2006) Elastic properties of minerals and the influence of phase transitions. American Mineralogist, 91,229246
Carpenter, M.A., Meyer, H.W., Sondergeld, P., Marion, S. and Knight, K.S. (2003) Spontaneous strain variations through the low temperature phase transitions of deuterated lawsonite. American Mineralogist, 88, 534546.
Cattell, R.B. (1966) The scree test for the number of factors. Multivariate Behavioural Research, 1, 245276.
Coelho, A.A. (2007) TOPAS academic version 4.1. Coelho software, Brisbane, Australia.
Császár, A.G., Czakó, G., Furtenbacher, T., Tennyson, J., Szalay, V., Shirin, S.V., Zobov, N.F. and Polyansky, O.L. (2005) On equilibrium structures of the water molecule. Journal of Chemical Physics, 122,214305.
Daniel, L., Fiquet, G., Gillet, P., Schmidt, M.W. and Hanfland, M. (1999) P-V-T equation of state of lawsonite. Physics and Chemistry of Minerals, 26, 406–14.
Dörsam, G., Liebscher, A., Wunder, B., Franz, G. and Gottschalk, M. (2011) Synthesis of Pb-zoisite and Pb-lawsonite. Neues Jahrbuch für Mineralogie — Abhandlungen, 188,99110
Farmer, V.C. (1974) The Infrared Spectra of Minerals. Mineralogical Society, London.
Frost, R.L., Bouzaid, J.M. and Reddy, B.J. (2007) Vibrational spectroscopy of the sorosilicate mineral hemimorphite Zri4(OH)2Si2O7'H2O. Polyhedron, 26, 24052412.
Gabelica-Robert, M. and Tarte, P. (1979) Synthesis, X-ray diffraction and vibrational study of silicates and germanates isostructural with kentrolite Pb2Mn2Si2O9. Journal of Solid State Chemistry, 27, 179190.
Hahn, T. (2005) International Tables for Crystallography Volume A: Space-group Symmetry. Corrected reprint of the fifth edition, Wiley, New York.
Hofmeister, A.M., Hoering, T.C. and Virgo, D. (1987) Vibrational spectroscopy of beryllium aluminosili-cates: heat capacity calculations from band assign¬ments. Physics and Chemistry of Minerals, 14, 205224.
Kawachi, Y and Coombs, D.S. (1996) Noélbensonite, a new BaMn silicate of the lawsonite structure type, from Woods mine, New South Wales, Australia. Mineralogical Magazine, 60, 369374.
Kieffer, S.W. (1979) Thermodynamics and lattice vibra¬tions of minerals: 3. Lattice dynamics and an approximation for minerals with application to simple substances and framework silicates. Reviews of Geophysics and Space Physics, 17, 3559
Kieffer, S.W. (1980) Thermodynamics and lattice vibra-tions of minerals: 4. Application to chain and sheet silicates and orthosilicates. Reviews of Geophysics and Space Physics, 18,862886
Kozlova, S.G. and Gabuda, S.P. (2013) Single-crystal 1H NMR data and hydrogen atom disorder in lawsonite, CaAl2[Si2O7](OH)2-H2O. Journal of Structural Chemistry, 54, 146151.
Larson, A.C. and Von Dreele, R.B. (1994) General Structure Analysis System (GSAS), Los Alamos National Laboratory Report, 86-748.
Lazarev, A.N. (1972) Vibrational Spectra and Structure of Silicates. Consultant Bureau, New York.
LeBail, A., Duroy, H. and Fourquest, J.L. (1988) Ab initio structure determination of LiSbWO6 by X-ray powder diffraction. Materials Research Bulletin, 23,447452
Le Cléac'h, A. and Gillet, P. (1990) IR and Raman spectroscopic study of natural lawsonite. European Journal of Mineralogy, 2, 4353.
Libowitzky, E. (1999) Correlation of O-H stretching frequencies and O-H O hydrogen bond lengths in minerals. Monatshefte für Chemie, 130,10471059
Libowitzky, E. and Armbruster, T. (1995) Low-tempera¬ture phase transitions and the role of hydrogen bonds in lawsonite. American Mineralogist, 80, 12771285
Libowitzky, E. and Armbruster, T. (1996) Lawsonite-type phase transition in hennomartinite, SrMn2[Si2O7] (OH)2-H2O. American Mineralogist, 81, 918.
Libowitzky, E. and Rossman, G.R. (1996) FTIR spec-troscopy of lawsonite between 82 and 325 K. American Mineralogist, 81, 10801091.
Liebscher, A., Dörsam, G., Franz, G., Wunder, B. and Gottschalk, M. (2010) Crystal chemistry of synthetic lawsonite solid-solution series CaAl2[(OH)2/ Si2O7]-H2O-SrAl2[(OH)2/Si2O7]-H2O and th. Cmcm-P21/m phase transition. American Mineralogist, 95, 724735.
Mejía-Uriarte, E.V., Sato-Berru, R.Y., Navarrete, M., Kolokoltsev, O. and Saniger, J.M. (2012) Determination of phase transition by principal compo¬nent analysis applied to Raman spectra of poly crystal¬line BaTiO3 at low and high temperature. Journal of Applied Research and Technology, 10, 5762.
Mevel, C. and Kienast, J.R. (1980) Chromian jadeite, phengite, pumpellyite, and lawsonite in a high-pressure metamorphosed gabbro from the French Alps. Mineralogical Magazine, 43,979984
Meyer, H.W., Marion, S., Sondergeld, P., Carpenter, M.A., Knight, K.S., Redfern, S.A.T.. and Dove, M.T. (2001) Displacive components of the low-temperature phase transitions in lawsonite. American Mineralogist, 86, 566577.
Miyajima, H., Matsubara, S., Miyawaki, R. and Ito, K. (1999) Itoigawaite, a new mineral, the Sr analogue of lawsonite, in jadeitite from the Itoigawa-Ohmi district, central Japan. Mineralogical Magazine, 63, 909916.
Novak, A. (1974) Hydrogen bonding in solids. Correlation of spectroscopic and crystallographic data. Structure and Bonding (Berlin), 18, 177216.
Origlieri, M.J., Yang, H., Downs, R.T., Posner, E.S., Domanik, K.J. and Pinch, W.W. (2012) The crystal structure of bartelkeite, with a revised chemical formula, PbFeGeVI(Ge2 vO7)(OH)2-H2O, isotypic with high-pressur. P21/m lawsonite. American Mineralogist, 97, 18121815.
Pavlov, S.V. (2013) A phenomenological model of phase transitions in lawsonite. Moscow University Physics Bulletin, 68, 139142.
Pawley, A.R. and Allan, D.R. (2001) A high-pressure structural study of lawsonite using angle-dispersive powder-diffraction methods with synchrotron radi-ation. Mineralogical Magazine, 65, 4158.
Pearson, K. (1901) On lines and planes of closest fit to a system of points in space. Philosophical Magazine, 2, 559572.
Pechini, M.P. (1967) Method of preparing lead and alkaline earth titanates and niobates and coating method using the same to form a capacitor. US Patent 3,330,697.
Pefficek, V., Dušek, M. and Palatinus, L. (2006) JANA2006. Institute of Physics, Prague.
Raab, S. (2010) Synthese und Charakterisierung nanos-kaliger hydraulisch hochreaktiver Phasen des Portland- und Tonerdezements. PhD thesis, Martin-Luther-Universität Halle-Wittenberg, Germany.
Rietveld, H.M. (1967) Line profiles of neutron powder-diffraction peaks for structure refinement. Acta Crystallographica, 22,151152
Salje, E.K.H.. and Carpenter, M.A. (2011) Thermally activated proton hopping in lawsonite, the ferroelectric transition at 125 K, and the co-elastic phase transition at 270 K. Journal of Physics: Condensed Matter, 23,112208.
Salje, E.K.H.., Crossley, S., Kar-Narayan, S., Carpenter, M.A. and Mathur, N.D. (2011) Improper ferroelectri-city in lawsonite CaAl2Si2O7(OH)2-H2O: hysteresis and hydrogen ordering. Journal of Physics: Condensed Matter, 23,222202.
Sato-Berru, R.Y., Mejía-Uriarte, E.V., Frausto-Reves, C., Villagrán-Muniz, M., Murrieta, S.H. and Saniger, J.M. (2007) Application of principal component analysis and Raman spectroscopy in the analysis of polycrys-talline BaTiO3 at high pressure. Spectrochimica Acta, A66, 557560.
Schmidt, M.W. and Poli, S. (1994) The stability of lawsonite and zoisite at high pressures: experiments in CASH to 92 kbar and implications for the presence of hydrous phases in subducted lithosphere. Earth and Planetary Science Letters, 124,105118
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751767.
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112122
Sherlock, S.C. and Okay, A.I. (1999) Oscillatory zoned chrome lawsonite in the Tavganh Zone, northwest Turkey. Mineralogical Magazine, 63,687692
Sondergeld, P., Schranz, W., Tröster, A., Armbruster, T., Giester, G., Kityk, A. and Carpenter, M.A. (2005) Ordering and elasticity associated with low-temperature phase transitions in lawsonite. American Mineralogist, 90, 448456.
Tasci, E.S., de la Flor, G., Orobengoa, D., Capillas, C. and Perez-Mato, J.M. (2012) An introduction to the tools hosted in the Bilbao Crystallographic Server. EPJ Web of Conferences, 22, 122.
Toby, B.H. (2001) EXPGUI, a graphical user interface for GSAS. Journal of Applied Crystallography, 34, 210213.
Wondraschek, H. and Müller, U. (2010) International Tables for Crystallography Volume A1: Symmetry Relations Between Space Groups. Second edition, Wiley, New York.



Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed