Maria Chiara Domeneghetti

The high-temperature P21/c-C2/c phase transition in Fe-free pyroxene (Ca0.15Mg1.85Si2O6): structural and thermodynamic behavior

Abstract A high-temperature in situ single-crystal X-ray diffraction study was performed from room T to 1150 °C on two crystals of Fe-free P21/c clinopyroxenes of composition Ca0.15Mg1.85Si2O6 [cell parameters at room T: a = 9.651(2) Å, b = 8.846(2) Å, c = 5.202(1) Å, b = 108.38(2)°, V = 421.4 (2) Å3] synthesized by isothermal annealing for 624 h at T = 1370 °C, P = 1 atm. A first order P21/c-C2/c phase transition was found slightly below 1000 °C [Tc = 926(39) °C]. The transition was revealed by discontinuous changes in intensities and cell parameters. Prolonged heating at high temperature induced a non-reversible increase in the transition temperature up to more than 1150 °C, without apparent changes in the order of the phase transition. Coupling with strain due to incipient exsolution in a formerly almost defect-free sample is suggested to be responsible for increase in Tc. TEM observations of a sample from the same starting material after further annealing for 72 h at T = 1050 °C, P = 1 atm are consistent with the proposed incipient exsolution model. Annealing was found to induce the formation of a mottled texture oriented parallel to (101). Results from structure refinement of data collected below the transition at T = 25, 500, 650, 800, and 1000 °C showed only minor changes in the chain configurations, which are highly differentiated up to 1000 °C, confirming the strong first-order character of the transition.

A new micro-furnace for in situ high-temperature single-crystal X-ray diffraction measurements

A new micro-furnace equipped with an H-shaped resistance heater has been developed to conduct in situ single-crystal X-ray diffraction experiments at high temperature. The compact design of the furnace does not restrict access to reciprocal space out to 2θ = 60°. Therefore, unit-cell parameters and intensity data can be determined to a resolution of 0.71 A with Mo radiation. The combined use of mineral phases with well characterized lattice expansion (e.g. pure Si and SiO2 quartz) and a small-diameter (0.025 mm) K-type thermocouple allowed accurate temperature calibration from room temperature to about 1273 K and consequent evaluation of thermal gradients and stability. The new furnace design allows temperatures up to about 1273 K to be reached with a thermal stability better than ±5 K even at the highest temperatures. Measurements of the lattice thermal expansion of pure silicon (Si), pure synthetic grossular garnet (Ca3Al2Si3O12) and quartz (SiO2) are presented to demonstrate the performance of the device. Its main advantages and limitations and important considerations for using it to perform high-temperature diffraction measurements are discussed.