Ferrian magnesian spodumene was synthesized in the MLFSH system at P = 0.4 GPa, T = 700 °C, fO2 = NNO + 2.3. The space group at room T is P21/c [a = 9.638(3) A, b = 8.709(2) A, c = 5.258(2) A, β = 109.83(3)°, V = 415.2 A3]. The structure is topologically equivalent to that of ferrian spodumene, LiFeSi2O6, and has two symmetrically independent tetrahedral chains, A and B, and two independent octahedral sites, M1 and M2. The crystal-chemical composition was determined combining EMP, SIMS and single-crystal XRD analysis, yielding M2 Mg (and Fe2+) distribute over both octahedral sites. Structure refinements done at different temperatures (25, 70, 95, 125, 150 and 200 °C) allowed characterization of a reversible displacive P21/ c → C2/ c transition at 106°C. Previous HT-XRD studies of Li-clinopyroxenes has shown that the transition temperature is inversely related to the size of the M1 cation. For the crystal of this work, the aggregate ionic radius at M1 is longer than that of ferrian spodumene, for which the transition temperature is -44°C. The higher transition temperature observed can only be explained on the basis of the shorter aggregate radius at the M2 site (due to the presence of Mg substituting after Li), in keeping with the results obtained for ferromagnesian P21/c pyroxenes. The effects of all the chemical substitutions must be considered when modelling transition temperatures and thermodynamics behaviour in clinopyroxenes.

HT-XRD study of synthetic ferrian magnesian spodumene : the effect of site dimension on the P21/c→C2/c phase transition / F. Cáḿara, G. Iezzi, R. Oberti. - In: PHYSICS AND CHEMISTRY OF MINERALS. - ISSN 0342-1791. - 30:1(2003 Feb), pp. 20-30.

HT-XRD study of synthetic ferrian magnesian spodumene : the effect of site dimension on the P21/c→C2/c phase transition

F. Cáḿara
;
2003

Abstract

Ferrian magnesian spodumene was synthesized in the MLFSH system at P = 0.4 GPa, T = 700 °C, fO2 = NNO + 2.3. The space group at room T is P21/c [a = 9.638(3) A, b = 8.709(2) A, c = 5.258(2) A, β = 109.83(3)°, V = 415.2 A3]. The structure is topologically equivalent to that of ferrian spodumene, LiFeSi2O6, and has two symmetrically independent tetrahedral chains, A and B, and two independent octahedral sites, M1 and M2. The crystal-chemical composition was determined combining EMP, SIMS and single-crystal XRD analysis, yielding M2 Mg (and Fe2+) distribute over both octahedral sites. Structure refinements done at different temperatures (25, 70, 95, 125, 150 and 200 °C) allowed characterization of a reversible displacive P21/ c → C2/ c transition at 106°C. Previous HT-XRD studies of Li-clinopyroxenes has shown that the transition temperature is inversely related to the size of the M1 cation. For the crystal of this work, the aggregate ionic radius at M1 is longer than that of ferrian spodumene, for which the transition temperature is -44°C. The higher transition temperature observed can only be explained on the basis of the shorter aggregate radius at the M2 site (due to the presence of Mg substituting after Li), in keeping with the results obtained for ferromagnesian P21/c pyroxenes. The effects of all the chemical substitutions must be considered when modelling transition temperatures and thermodynamics behaviour in clinopyroxenes.
Displacive phase-transition; HT-XRD; Li-clinopyroxene; Synthesis
Settore GEO/06 - Mineralogia
feb-2003
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/477849
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