Equation of State and Amorphization of Ca9R(VO4)7 (R = La, Nd, Gd): A Combined High-Pressure
X‑ray Diffraction and Raman Spectroscopy Study
Posted on 2018-10-11 - 14:06
Ca9R(VO4)7 (R = rare earth) multicomponent
oxides of a whitlockite-related structure are under consideration
for applications in optoelectronics. In this work, the Czochralski-grown
Ca9R(VO4)7 crystals were investigated
as a function of pressure by powder X-ray diffraction and single-crystal
Raman spectroscopy. The diffraction experiments were performed at
the ALBA synchrotron under pressures ranging up to 9.22(5), 10.7(1),
and 8.55(5) GPa for R = La, Nd, and Gd, respectively, to determine
the third order equation of state (EOS) parameters. Fitting of the Birch–Murnaghan
EOS provided the isothermal bulk moduli K0 = 63(4), 63(2), and 61(5) GPa for these three orthovanadates. These
values are apparently lower than that reported for structurally related
tricalcium vanadate Ca3(VO4)2. The
compressibility anisotropy was observed; the lattice is markedly stiffer
in [001] than in [100] direction. For Ca9Nd(VO4)7, the variation of the diffractograms just above 10
GPa provides an indication on the beginning of amorphization process;
during pressure release the whitlockite-like structure is recovered. Raman spectroscopy measurements
for single crystals of the above-mentioned rare-earth vanadates and
Ca9Y(VO4)7 were performed (the maximum
pressures achieved were 16.3(1), 21.2(1), 15.3(1), and 18.6(1) GPa
for R = Y, La, Nd, and Gd, respectively). These measurements reveal
a partially reversible phase transition interpreted as amorphization,
with an onset at the pressure of ∼9–10 GPa, characterized
by broadening of the peaks and their shift to lower energies.
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Kosyl, Katarzyna M.; Paszkowicz, Wojciech; Ermakova, Olga; Wlodarczyk, Damian; Suchocki, Andrzej; Minikayev, Roman; et al. (2018). Equation of State and Amorphization of Ca9R(VO4)7 (R = La, Nd, Gd): A Combined High-Pressure
X‑ray Diffraction and Raman Spectroscopy Study. ACS Publications. Collection. https://doi.org/10.1021/acs.inorgchem.8b01182
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AUTHORS (11)
KK
Katarzyna M. Kosyl
WP
Wojciech Paszkowicz
OE
Olga Ermakova
DW
Damian Wlodarczyk
AS
Andrzej Suchocki
RM
Roman Minikayev
JD
Jaroslaw Z. Domagala
AS
Alexei N. Shekhovtsov
MK
Miron Kosmyna
CP
Catalin Popescu
FF
François Fauth
KEYWORDS
Raman spectroscopy measurementspowder X-ray diffractionEOSwhitlockite-like structurebulk moduli K 0amorphization process10 GPawhitlockite-related structureRaman Spectroscopy Studypressure releaseorder equationALBA synchrotronGdmulticomponent oxidessingle-crystal Raman spectroscopyNdphase transitionrare-earth vanadates7 crystalsVO 4compressibility anisotropytricalcium vanadateLadiffraction experiments