HT-XRD study of synthetic magnesian ferrispodumene: The effect of site dimension on the P21/c . C2/c phase transition.

Ferrian magnesian spodumene was synthesized in the MLFSH system at P ¼ 0:4 GPa, T ¼ 700 C, fO2 ¼ NNO þ 2:3. The space group at room T is P21=c [a ¼ 9:638ð3Þ A ? , b ¼ 8:709ð2Þ A ? , c ¼ 5:258ð2Þ A ? , b ¼ 109:83ð3Þ, V ¼ 415:2 A? 3]. 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 crystalchemical composition was determined combiningEMP , SIMS and single-crystal XRD analysis, yielding M2(Li0:85Mg0:09Fe2+ 0:06) M1(Fe3+0:85Mg0:15) Si2O6. Li is orderedat the M2 site and Fe3+ is ordered at the M1 site,whereas 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 had 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 Mgsubstitutin g after Li), in keepingwith the results obtained for ferromagnesian P21/c pyroxenes. The effects of all the chemical substitutions must be considered when modellingtransition temperatures and thermodynamic behaviour in clinopyroxenes.