The Effect of Composition on the High-Pressure Behavior of Rare-Earth Phosphate Minerals

A comprehensive study on the effect of composition on the structural and elastic properties of MPO4 (M = Ce3+, Gd3+, Tb3+, Y3+, Sc3+) compounds has been completed. CePO4 and GdPO4 are isostructural with monazite (P21/n), and TbPO4, YPO4, and ScPO4, are isostructural with xenotime (I41/amd). Raman spectra are consistent with previous studies and high-pressure spectra showed no phase transitions up to 10 GPa under hydrostatic conditions. The spectra were used to develop Kieffer-type lattice vibrational models to calculate heat capacities of CePO4 and YPO4 and the results lie within 1-3% of experimental values. Equations of state were calculated from high-pressure single-crystal X-ray diffraction data. Bulk moduli (K0) determined from a 3rd-order Birch-Murnaghan equation of state are: 109(3) GPa for CePO4, 128.1(8) GPa for GdPO4, 141(1) GPa for TbPO4 and 166(1) GPa for ScPO4. The inverse relationship observed between K0 and the ionic radius of the RE3+ is shown to be linear. This equation can be used to predict K0 for other rare-earth phosphates. Comparison of these studies, performed under hydrostatic conditions, with previous studies show that MPO4 structures are sensitive to shear stresses created from non-hydrostatic environments. The first structural study of a monazite, GdPO4, is also reported. Compression mechanisms are comprised of "squishing" the GdO9 polyhedra and inter-polyhedral movement. This study and the axial compressibility data for Ce-, Tb-, Gd- and ScPO4 suggest that the compression mechanisms favored by MPO4 compounds are those which remain rigid parallel to polyhedral chains.

Name thesis:degree_name

Master of Science

Level thesis:degree_level

masters

Discipline thesis:degree_discipline

Geosciences

Department dc:contributor.department

Geosciences

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2016

Author dc:creator

• Heffernan, Karina May

Chair dc:contributor.committeechair

• Ross, Nancy L.

Committee members dc:contributor.committeemember

• Tracy, Robert J.
• Caddick, Mark J.
• Slebodnick, Carla
• Michel, Frederick Marc

• Monazite
• Xenotime
• High-Pressure
• Diffraction
• Raman

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

vt_gsexam:8500

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/81910