Phase Transitions and Equations of State of Alkaline Earth Fluorides CaF2 SrF2 and BaF2 to Mbar Pressures
Phase transitions and equations of state of the alkaline earth fluorides CaF{sub 2}, SrF{sub 2}, and BaF{sub 2} were examined by static compression to pressures as high as 146 GPa. Angle-dispersive x-ray diffraction experiments were performed on polycrystalline samples in the laser-heated diamond-anvil cell. We confirmed that at pressures less than 10 GPa all three materials undergo a phase transition from the cubic (Fm3{sup -}m) fluorite structure to the orthorhombic (Pnam) cotunnite-type structure. This work has characterized an additional phase transition in CaF{sub 2} and SrF{sub 2}: these materials were observed to transform to a hexagonal (P6{sub 3}/mmc) Ni{sub 2}In-type structure between 63-79 GPa and 28-29 GPa, respectively, upon laser heating. For SrF{sub 2}, the Ni{sub 2}In-type phase was confirmed by Rietveld refinement. Volumes were determined as a function of pressure for all high-pressure phases and fit to the third-order Birch-Murnaghan equation of state. For CaF{sub 2} and SrF{sub 2}, the fluorite-cotunnite transition results in a volume decrease of 8-10%, while the bulk modulus of the cotunnite-type phase is the same or less than that of the fluorite phase within uncertainty. For all three fluorides, the volume reduction associated with the further transition to the Ni{sub 2}In-type phase is {approx}5%. The percentage increase in the bulk modulus ({Delta}K) across the transition is greater when the cation is smaller. While for BaF{sub 2}, {Delta}K is 10-30%, {Delta}K values for SrF{sub 2} and CaF{sub 2} are 45-65% and 20-40%. Although shock data for CaF{sub 2} have been interpreted to show a transition to a highly incompressible phase above 100 GPa, this is not consistent with our static equation of state data.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE SC OFFICE OF SCIENCE (SC)
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 1042119
- Report Number(s):
- BNL-97797-2012-JA; TRN: US1202745
- Journal Information:
- Physical Review. B, Condensed Matter and Materials Physics, Vol. 81, Issue 17
- Country of Publication:
- United States
- Language:
- English
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