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Title: Isotropic Low Thermal Expansion over a Wide Temperature Range in Ti 1–xZr xF 3+x (0.1 ≤ x ≤ 0.5) Solid Solutions

Abstract

TiF 3 exhibits a rhombohedral to ReO 3-type cubic phase transformation at ~340 K. Here we report that, by introducing ZrF 4 into TiF 3, the cubic phase is stabilized at least down to 123 K in the Ti 1–xZr xF 3+x compounds. All compounds exhibit low thermal expansion (LTE) between 123 and 623 K, and a nearly zero thermal expansion (ZTE) was obtained in Ti 0.7Zr 0.3F 3.3L = 0.91 ppm/K). The analysis of pair distribution function reveals that the cation-centered octahedra are partially changed to pentagonal bipyramids in Ti 1–xZr xF 3+x due to the excess fluorines relative to the case of TiF 3. Therefore, the cooperative rotation of the polyhedra tends to be restricted, and the cubic phase is thus stabilized. The restrained polyhedral rotations compete against the lattice softening caused by the introduction of Zr 4+, giving rise to the LTE. Lastly, our present strategy is applicable to other rhombohedral metal trifluorides for the design of new isotropic ZTE materials.

Authors:
ORCiD logo [1];  [2];  [2];  [1];  [3];  [1];  [3]; ORCiD logo [4];  [4];  [5]
  1. Chinese Academy of Sciences, Hefei (People's Republic of China); Univ. of Science and Technology of China, Hefei (People's Republic of China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Chinese Academy of Sciences, Hefei (People's Republic of China)
  4. Chinese Academy of Sciences, Shanghai (China)
  5. Chinese Academy of Sciences, Hefei (People's Republic of China); Chinese Academy of Sciences, Hefei (People's Republic of China)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1487256
Report Number(s):
BNL-209761-2018-JAAM
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 22; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Yang, Cheng, Zhang, Yugang, Bai, Jianming, Tong, Peng, Lin, Jianchao, Tong, Haiyun, Zhang, Lei, Wen, Wen, Zhang, Xingmin, and Sun, Yuping. Isotropic Low Thermal Expansion over a Wide Temperature Range in Ti1–xZrxF3+x (0.1 ≤ x ≤ 0.5) Solid Solutions. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b02593.
Yang, Cheng, Zhang, Yugang, Bai, Jianming, Tong, Peng, Lin, Jianchao, Tong, Haiyun, Zhang, Lei, Wen, Wen, Zhang, Xingmin, & Sun, Yuping. Isotropic Low Thermal Expansion over a Wide Temperature Range in Ti1–xZrxF3+x (0.1 ≤ x ≤ 0.5) Solid Solutions. United States. doi:10.1021/acs.inorgchem.8b02593.
Yang, Cheng, Zhang, Yugang, Bai, Jianming, Tong, Peng, Lin, Jianchao, Tong, Haiyun, Zhang, Lei, Wen, Wen, Zhang, Xingmin, and Sun, Yuping. Wed . "Isotropic Low Thermal Expansion over a Wide Temperature Range in Ti1–xZrxF3+x (0.1 ≤ x ≤ 0.5) Solid Solutions". United States. doi:10.1021/acs.inorgchem.8b02593.
@article{osti_1487256,
title = {Isotropic Low Thermal Expansion over a Wide Temperature Range in Ti1–xZrxF3+x (0.1 ≤ x ≤ 0.5) Solid Solutions},
author = {Yang, Cheng and Zhang, Yugang and Bai, Jianming and Tong, Peng and Lin, Jianchao and Tong, Haiyun and Zhang, Lei and Wen, Wen and Zhang, Xingmin and Sun, Yuping},
abstractNote = {TiF3 exhibits a rhombohedral to ReO3-type cubic phase transformation at ~340 K. Here we report that, by introducing ZrF4 into TiF3, the cubic phase is stabilized at least down to 123 K in the Ti1–xZrxF3+x compounds. All compounds exhibit low thermal expansion (LTE) between 123 and 623 K, and a nearly zero thermal expansion (ZTE) was obtained in Ti0.7Zr0.3F3.3 (αL = 0.91 ppm/K). The analysis of pair distribution function reveals that the cation-centered octahedra are partially changed to pentagonal bipyramids in Ti1–xZrxF3+x due to the excess fluorines relative to the case of TiF3. Therefore, the cooperative rotation of the polyhedra tends to be restricted, and the cubic phase is thus stabilized. The restrained polyhedral rotations compete against the lattice softening caused by the introduction of Zr4+, giving rise to the LTE. Lastly, our present strategy is applicable to other rhombohedral metal trifluorides for the design of new isotropic ZTE materials.},
doi = {10.1021/acs.inorgchem.8b02593},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 22,
volume = 57,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
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