High-pressure behaviour of Ca-rich C2/c clinopyroxenes along the join diopside-enstatite (CaMgSi2O6-Mg2Si2O6)

An in situ high-pressure (HP) X-ray diffraction investigation of synthetic diopside and of the Ca0.8Mg1.2Si2O6 clinopyroxene (Di(80)En(20)) was performed up to respectively P=40.8 and 15.1 GPa, using high brilliance synchrotron radiation. The compression of the cell parameters is markedly anisotropic, with beta (b) much greater than beta (c) > beta (a) > beta (asin beta) for any pressure range and for both diopside and Di(80)En(20). The compressibility along the crystallographic axes decreases significantly with pressure and is higher in Di(80)En(20) than in diopside. The beta cell parameter decreases as well with pressure, at a higher rate in Di(80)En(20). The cell volume decreases at almost the same rate for the two compositions, since in diopside a higher compression along a* occurs. A change in the mechanism of deformation at P higher than about 5-10 GPa is suggested for both compositions from the analysis of the strain induced by compression. In diopside at lower pressures, the deformation mainly occurs, at a similar rate, along the b axis and at a direction 145 degrees from the c axis on the (0 1 0) plane. At higher pressures, instead, the deformation occurs mostly along the b axis. In Di(80)En(20) the orientation of the strain axes is the same as in diopside. The substitution of Ca with Mg in the M2 site induces at a given pressure a higher deformation on (0 1 0) with respect to diopside, but a similar change in the compressional behaviour is found. Changes in the M2 polyhedron with pressure can explain the above compressional behaviour. A third-order Birch-Murna-ghan equation of state was fit to the retrieved volumes, with K = 105.1(9) GPa, K' = 6.8(1) for diopside and K = 107.3(1.4) GPa, K' = 5.7(3) for Di(80)En(20); the same equation can be applied for ally pressure range. The elasticity of diopside is therefore not significantly affected by Mg substitution into the M2 site, in contrast to the significant stiffening occurring for Ca substitution into Mg-rich orthopyroxenes.