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Title: High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

Abstract

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2B 2O 7 pyrochlore (A = Eu, Dy; B = Ti, Zr) up to ~50 GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B = Ti and ~16 GPa B = Zr. But, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionic radii, i.e., A = Dy, proceeding faster than those with a larger ionic radii, i.e., A = Eu. Our results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B = Zr compositions, Raman modes for cotunnite couldmore » be observed, with more modes recorded for A = Eu than A = Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2Zr 2O 7 as compared with the initially defect-fluorite structured Dy 2Zr 2O 7.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [3];  [1];  [4]
  1. Stanford Univ., CA (United States). Dept. of Geological Sciences
  2. National Polytechnic Institute Saltillo Unit, Coahuila (Mexico)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
  4. Stanford Univ., CA (United States). Dept. of Geological Sciences; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1360963
Alternate Identifier(s):
OSTI ID: 1361754; OSTI ID: 1468338
Grant/Contract Number:  
AC02-76SF00515; SC0001089; NA0001974; FG02-99ER45775; AC02-06CH11357; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Applied Physics
Additional Journal Information:
Journal Volume: 121; Journal Issue: 4; Journal ID: ISSN 0021-8979
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Rittman, Dylan R., Turner, Katlyn M., Park, Sulgiye, Fuentes, Antonio F., Yan, Jinyuan, Ewing, Rodney C., and Mao, Wendy L. High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr). United States: N. p., 2017. Web. doi:10.1063/1.4974871.
Rittman, Dylan R., Turner, Katlyn M., Park, Sulgiye, Fuentes, Antonio F., Yan, Jinyuan, Ewing, Rodney C., & Mao, Wendy L. High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr). United States. doi:10.1063/1.4974871.
Rittman, Dylan R., Turner, Katlyn M., Park, Sulgiye, Fuentes, Antonio F., Yan, Jinyuan, Ewing, Rodney C., and Mao, Wendy L. Tue . "High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)". United States. doi:10.1063/1.4974871. https://www.osti.gov/servlets/purl/1360963.
@article{osti_1360963,
title = {High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)},
author = {Rittman, Dylan R. and Turner, Katlyn M. and Park, Sulgiye and Fuentes, Antonio F. and Yan, Jinyuan and Ewing, Rodney C. and Mao, Wendy L.},
abstractNote = {In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A2B2O7 pyrochlore (A = Eu, Dy; B = Ti, Zr) up to ~50 GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B = Ti and ~16 GPa B = Zr. But, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionic radii, i.e., A = Dy, proceeding faster than those with a larger ionic radii, i.e., A = Eu. Our results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B = Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A = Eu than A = Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu2Zr2O7 as compared with the initially defect-fluorite structured Dy2Zr2O7.},
doi = {10.1063/1.4974871},
journal = {Journal of Applied Physics},
issn = {0021-8979},
number = 4,
volume = 121,
place = {United States},
year = {2017},
month = {1}
}

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