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Title: Distortion-stabilized ordered structures in A2BB’O7 mixed pyrochlores

Abstract

Abstract Pyrochlore oxides (A 2 B 2 O 7 ) are interesting for a number of technological applications, including radiation damage tolerance and as ionic conductors. Mixed pyrochlores—containing two A and/or two B site cations—provide even more flexibility for tailoring properties owing to the diverse chemical and configurational degrees of freedom accessible within this chemical space. Here, we examine relative stability of different cation orderings in one model double pyrochlore Gd 2 (Zr x Ti 1− x ) 2 O 7 , as a function of Zr content x . Our results show that, in the presence of some very specific local cation arrangements, certain cation-ordered compositions in this system are highly stabilized as a result of large oxygen relaxation displacements, leading to the formation of an ordered ‘double’ pyrochlore structure. The origins of these anomalous oxygen relaxations are traced back to both the local cation symmetry and a strong chemical preference of Zr atoms towards adopting a 7-fold coordination environment, as opposed to a 6-fold coordination available in a regular pyrochlore structure. Subsequently, we examine the stability of this type of ordering in 131 other pyrochlore compositions. Implications of our findings are discussed in relationmore » to the observed composition-dependent ionic conductivity in these systems and connections with previously reported experimental findings are made.« less

Authors:
; ; ORCiD logo
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1619624
Alternate Identifier(s):
OSTI ID: 1542823
Report Number(s):
LA-UR-18-26270
Journal ID: ISSN 2057-3960; 7; PII: 144
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Published Article
Journal Name:
npj Computational Materials
Additional Journal Information:
Journal Name: npj Computational Materials Journal Volume: 5 Journal Issue: 1; Journal ID: ISSN 2057-3960
Publisher:
Nature Publishing Group
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Pilania, Ghanshyam, Puchala, Brian, and Uberuaga, Blas P. Distortion-stabilized ordered structures in A2BB’O7 mixed pyrochlores. United Kingdom: N. p., 2019. Web. doi:10.1038/s41524-018-0144-1.
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Pilania, Ghanshyam, Puchala, Brian, & Uberuaga, Blas P. Distortion-stabilized ordered structures in A2BB’O7 mixed pyrochlores. United Kingdom. https://doi.org/10.1038/s41524-018-0144-1
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Pilania, Ghanshyam, Puchala, Brian, and Uberuaga, Blas P. Mon . "Distortion-stabilized ordered structures in A2BB’O7 mixed pyrochlores". United Kingdom. https://doi.org/10.1038/s41524-018-0144-1.
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@article{osti_1619624,
title = {Distortion-stabilized ordered structures in A2BB’O7 mixed pyrochlores},
author = {Pilania, Ghanshyam and Puchala, Brian and Uberuaga, Blas P.},
abstractNote = {Abstract Pyrochlore oxides (A 2 B 2 O 7 ) are interesting for a number of technological applications, including radiation damage tolerance and as ionic conductors. Mixed pyrochlores—containing two A and/or two B site cations—provide even more flexibility for tailoring properties owing to the diverse chemical and configurational degrees of freedom accessible within this chemical space. Here, we examine relative stability of different cation orderings in one model double pyrochlore Gd 2 (Zr x Ti 1− x ) 2 O 7 , as a function of Zr content x . Our results show that, in the presence of some very specific local cation arrangements, certain cation-ordered compositions in this system are highly stabilized as a result of large oxygen relaxation displacements, leading to the formation of an ordered ‘double’ pyrochlore structure. The origins of these anomalous oxygen relaxations are traced back to both the local cation symmetry and a strong chemical preference of Zr atoms towards adopting a 7-fold coordination environment, as opposed to a 6-fold coordination available in a regular pyrochlore structure. Subsequently, we examine the stability of this type of ordering in 131 other pyrochlore compositions. Implications of our findings are discussed in relation to the observed composition-dependent ionic conductivity in these systems and connections with previously reported experimental findings are made.},
doi = {10.1038/s41524-018-0144-1},
journal = {npj Computational Materials},
number = 1,
volume = 5,
place = {United Kingdom},
year = {Mon Jan 14 00:00:00 EST 2019},
month = {Mon Jan 14 00:00:00 EST 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1038/s41524-018-0144-1
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Cited by: 15 works
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Figures / Tables:

Fig. 1 Fig. 1: Calculated mixing energies (i.e., formation energies relative to the pure single pyrochlore end point compositions with x = 0 and x = 1) per primitive unit cell (with 22 atoms, containing two effective pyrochlore formula units) for the entire set of 704 unique configurations enumerated within the Gd2(ZrxTi1−x)2O7more » chemistries. The DFT predicted convex hull is represented as a solid line. The atomistic structures for the identified ground-state ordered structures on the convex hull are illustrated. While Gd and O atoms are represented by purple and red spheres, Ti and Zr polyhedra are depicted in blue and green colors, respectively« less
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