Crystal structure and compressibility of a high-pressure Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81, isomorphous with cubic zirconia

Hexiong Yang, Jürgen Konzett, Robert T Downs

Research output: Contribution to journalArticle

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Abstract

A Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)∑=1.0O1.81, was synthesized at 8.8 GPa and 1600 °C using a multi-anvil apparatus. Its crystal structure at ambient conditions and compressibility up to 10.58 GPa were determined with single-crystal X-ray diffraction. This high-pressure phase is isomorphous with cubic zirconia (fluorite-type) with space group Fm3̄m and unit-cell parameters a=4.8830(5) Å and V=116.43(4) Å3. Like stabilized cubic zirconia, the structure of (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 is also relaxed, with all O atoms displaced from the (frac(1, 4), frac(1, 4), frac(1, 4)) position along 〈1 0 0〉 by 0.319 Å and all cations from the (0, 0, 0) position along 〈1 1 1〉 by 0.203 Å. No phase transformation was detected within the experimental pressure range. Fitting the high-pressure data (V vs. P) to a third-order Birch-Murnaghan EOS yields K0=164(4) GPa, K′=4.3(7), and V0=116.38(3) Å3. The bulk modulus of (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 is significantly lower than that (202 GPa) determined experimentally for cubic TiO2 or that (~210 GPa) estimated for cubic ZrO2. This study demonstrates that cubic TiO2 may also be obtained by introducing various dopants, similar to the way cubic zirconia is stabilized below 2370 °C. Furthermore, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 has the greatest ratio of Ti4+ content vs. vacant O2- sites of all doped cubic zirconia samples reported thus far, making it a more promising candidate for the development of electrolytes in solid oxide fuel cells.

Original languageEnglish (US)
Pages (from-to)1297-1301
Number of pages5
JournalJournal of Physics and Chemistry of Solids
Volume70
Issue number9
DOIs
StatePublished - Sep 2009

Fingerprint

Compressibility
zirconium oxides
Zirconia
Oxides
compressibility
Crystal structure
crystal structure
oxides
Fluorspar
fluorite
solid oxide fuel cells
anvils
Solid oxide fuel cells (SOFC)
bulk modulus
Electrolytes
phase transformations
Cations
Elastic moduli
Phase transitions
Positive ions

Keywords

  • A. Ceramic
  • B. Crystal growth
  • C. High pressure
  • D. Crystal structure
  • D. X-ray diffraction

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Chemistry(all)
  • Materials Science(all)

Cite this

Crystal structure and compressibility of a high-pressure Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81, isomorphous with cubic zirconia. / Yang, Hexiong; Konzett, Jürgen; Downs, Robert T.

In: Journal of Physics and Chemistry of Solids, Vol. 70, No. 9, 09.2009, p. 1297-1301.

Research output: Contribution to journalArticle

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title = "Crystal structure and compressibility of a high-pressure Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81, isomorphous with cubic zirconia",
abstract = "A Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)∑=1.0O1.81, was synthesized at 8.8 GPa and 1600 °C using a multi-anvil apparatus. Its crystal structure at ambient conditions and compressibility up to 10.58 GPa were determined with single-crystal X-ray diffraction. This high-pressure phase is isomorphous with cubic zirconia (fluorite-type) with space group Fm3̄m and unit-cell parameters a=4.8830(5) {\AA} and V=116.43(4) {\AA}3. Like stabilized cubic zirconia, the structure of (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 is also relaxed, with all O atoms displaced from the (frac(1, 4), frac(1, 4), frac(1, 4)) position along 〈1 0 0〉 by 0.319 {\AA} and all cations from the (0, 0, 0) position along 〈1 1 1〉 by 0.203 {\AA}. No phase transformation was detected within the experimental pressure range. Fitting the high-pressure data (V vs. P) to a third-order Birch-Murnaghan EOS yields K0=164(4) GPa, K′=4.3(7), and V0=116.38(3) {\AA}3. The bulk modulus of (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 is significantly lower than that (202 GPa) determined experimentally for cubic TiO2 or that (~210 GPa) estimated for cubic ZrO2. This study demonstrates that cubic TiO2 may also be obtained by introducing various dopants, similar to the way cubic zirconia is stabilized below 2370 °C. Furthermore, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 has the greatest ratio of Ti4+ content vs. vacant O2- sites of all doped cubic zirconia samples reported thus far, making it a more promising candidate for the development of electrolytes in solid oxide fuel cells.",
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T1 - Crystal structure and compressibility of a high-pressure Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81, isomorphous with cubic zirconia

AU - Yang, Hexiong

AU - Konzett, Jürgen

AU - Downs, Robert T

PY - 2009/9

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N2 - A Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)∑=1.0O1.81, was synthesized at 8.8 GPa and 1600 °C using a multi-anvil apparatus. Its crystal structure at ambient conditions and compressibility up to 10.58 GPa were determined with single-crystal X-ray diffraction. This high-pressure phase is isomorphous with cubic zirconia (fluorite-type) with space group Fm3̄m and unit-cell parameters a=4.8830(5) Å and V=116.43(4) Å3. Like stabilized cubic zirconia, the structure of (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 is also relaxed, with all O atoms displaced from the (frac(1, 4), frac(1, 4), frac(1, 4)) position along 〈1 0 0〉 by 0.319 Å and all cations from the (0, 0, 0) position along 〈1 1 1〉 by 0.203 Å. No phase transformation was detected within the experimental pressure range. Fitting the high-pressure data (V vs. P) to a third-order Birch-Murnaghan EOS yields K0=164(4) GPa, K′=4.3(7), and V0=116.38(3) Å3. The bulk modulus of (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 is significantly lower than that (202 GPa) determined experimentally for cubic TiO2 or that (~210 GPa) estimated for cubic ZrO2. This study demonstrates that cubic TiO2 may also be obtained by introducing various dopants, similar to the way cubic zirconia is stabilized below 2370 °C. Furthermore, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 has the greatest ratio of Ti4+ content vs. vacant O2- sites of all doped cubic zirconia samples reported thus far, making it a more promising candidate for the development of electrolytes in solid oxide fuel cells.

AB - A Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)∑=1.0O1.81, was synthesized at 8.8 GPa and 1600 °C using a multi-anvil apparatus. Its crystal structure at ambient conditions and compressibility up to 10.58 GPa were determined with single-crystal X-ray diffraction. This high-pressure phase is isomorphous with cubic zirconia (fluorite-type) with space group Fm3̄m and unit-cell parameters a=4.8830(5) Å and V=116.43(4) Å3. Like stabilized cubic zirconia, the structure of (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 is also relaxed, with all O atoms displaced from the (frac(1, 4), frac(1, 4), frac(1, 4)) position along 〈1 0 0〉 by 0.319 Å and all cations from the (0, 0, 0) position along 〈1 1 1〉 by 0.203 Å. No phase transformation was detected within the experimental pressure range. Fitting the high-pressure data (V vs. P) to a third-order Birch-Murnaghan EOS yields K0=164(4) GPa, K′=4.3(7), and V0=116.38(3) Å3. The bulk modulus of (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 is significantly lower than that (202 GPa) determined experimentally for cubic TiO2 or that (~210 GPa) estimated for cubic ZrO2. This study demonstrates that cubic TiO2 may also be obtained by introducing various dopants, similar to the way cubic zirconia is stabilized below 2370 °C. Furthermore, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81 has the greatest ratio of Ti4+ content vs. vacant O2- sites of all doped cubic zirconia samples reported thus far, making it a more promising candidate for the development of electrolytes in solid oxide fuel cells.

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KW - B. Crystal growth

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KW - D. Crystal structure

KW - D. X-ray diffraction

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