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To examine the effects of chemical composition on thermal expansion in the pyroxene mineral group, X-ray diffraction data have been collected from room temperature to ~925 °C on a chemically diverse group of 13 pyroxenes including four orthorhombic and nine monoclinic samples. Additionally, resulting unit-cell volumes computed from the XRD data have proven to be good tests for a large number of thermal expansion models; the physical model by Kroll and coworkers and the empirical one by Fei have been found to be especially useful. Modeling also has allowed the connection of present data, collected at temperatures above 25 °C, to the volume data of other workers for much lower temperatures, well below 0 °C, and also extrapolation of values for volume and thermal expansion well beyond the measurement range.We have found for orthopyroxenes that Fe2+-Mg2+ substitution has little effect on thermal expansion coefficients for volume. For clinopyroxenes, however, greater thermal expansion occurs in Ca2+-(diopside, augite, hedenbergite, johannsenite) than in Li+-(spodumene) or Na+-bearing members (jadeite, aegirine, kosmochlor). Present data support the observation that differences in volume thermal expansion relate primarily to differences in expansion along the b crystallographic axis. This apparently is due to the greater concentration of M1 polyhedra along the b crystallographic axis, where expansion differences can be related to the shared O1-O1 polyhedral edge and inter-oxygen repulsion that is made easier by divalent, as opposed to trivalent, cation occupancy of the M1 crystallographic site.

The effect of the substitution of Ca with Co, on the phase transition and on the extension of the miscibility gap, was studied to model the general mechanism of phase transitions and solid solutions in (Ca,M 2+ )M 2+ Si 2 O 6 pyroxenes. Eleven pyroxenes with composition Ca 1−x Co 1+x Si 2 O 6 , (0 ≤ × ≤ 1) were therefore synthesized by piston cylinder at P = 3 GPa, and T between 1100 and 1350 °C. The samples were characterized by SEM-EDS, XRD powder diffraction, and TEM. The results were compared with those of Ca-Fe and Ca-Mg pyroxenes. The phase diagram of Ca-Co pyroxenes is similar to that of Ca-Fe and Ca-Mg ones, with a wide asymmetric miscibility gap, and higher solubility in the Ca-rich side of the gap. The solubility on the Ca-rich side of the gap is related to the radius of the cation substituting. The cell parameters of the Ca-Co pyroxenes undergo a sudden change at the composition of about 0.4 Ca apfu, due to the C 2/ c – P 2 1 / c phase transition. The change in volume with composition follows an ideal trend, in the C 2/ c phase, dictated by the ionic size of the substituting cation. Deviation from the C 2/ c behavior are instead observed in the P 2 1 / c field and ascribed to volume strain. The same turnover was found in Ca-Mg, Ca-Fe, and Ca-Mn pyroxenes. The C 2/ c – P 2 1 / c transition occurs with decreasing the M2 average cation radius, down to a critical value between 0.85 and 0.88 A, depending on the series. A stabilization of the C 2/ c phase related to crystal field in Ca-Fe and Ca-Co pyroxenes is suggested by the analysis of the volume strain in the P 2 1 / c field. A key finding is that a miscibility gap may develop either by lattice strain related to cation substitution, within a series where all end-members have the same structure, or for the combined effect of lattice strain and a phase transition, as is the case for pyroxenes.