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Title: Atomic Linkage Flexibility Tuned Isotropic Negative, Zero, and Positive Thermal Expansion in MZrF 6 (M = Ca, Mn, Fe, Co, Ni, and Zn)

The controllable isotropic thermal expansion with a broad coefficient of thermal expansion (CTE) window is intriguing but remains challenge. Herein we report a cubic MZrF 6 series (M = Ca, Mn, Fe, Co, Ni and Zn), which exhibit controllable thermal expansion over a wide temperature range and with a broader CTE window (–6.69 to +18.23 × 10 –6/K). In particular, an isotropic zero thermal expansion (ZTE) is achieved in ZnZrF 6, which is one of the rarely documented hightemperature isotropic ZTE compounds. By utilizing temperature dependent high-energy synchrotron X-ray total scattering diffraction, it is found that the flexibility of metal···F atomic linkages in MZrF 6 plays a critical role in distinct thermal expansions. The flexible metal···F atomic linkages induce negative thermal expansion (NTE) for CaZrF 6, whereas the stiff ones bring positive thermal expansion (PTE) for 6. Thermal expansion could be transformed from striking negative, to zero, and finally to considerable positive though tuning the flexibility of metal···F atomic linkages by substitution with a series of cations on M sites of MZrF 6. In conclusion, the present study not only extends the scope of NTE families and rare high-temperature isotropic ZTE compounds but also proposes a new method to designmore » systematically controllable isotropic thermal expansion frameworks from the perspective of atomic linkage flexibility.« less
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [3] ;  [1] ;  [3] ;  [1]
  1. Univ. of Science and Technology Beijing, Beijing (China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Chines Academy of Sciences, Beijing (China)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 44; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1393263

Hu, Lei, Chen, Jun, Xu, Jiale, Wang, Na, Han, Fei, Ren, Yang, Pan, Zhao, Rong, Yangchun, Huang, Rongjin, Deng, Jinxia, Li, Laifeng, and Xing, Xianran. Atomic Linkage Flexibility Tuned Isotropic Negative, Zero, and Positive Thermal Expansion in MZrF6 (M = Ca, Mn, Fe, Co, Ni, and Zn). United States: N. p., Web. doi:10.1021/jacs.6b08746.
Hu, Lei, Chen, Jun, Xu, Jiale, Wang, Na, Han, Fei, Ren, Yang, Pan, Zhao, Rong, Yangchun, Huang, Rongjin, Deng, Jinxia, Li, Laifeng, & Xing, Xianran. Atomic Linkage Flexibility Tuned Isotropic Negative, Zero, and Positive Thermal Expansion in MZrF6 (M = Ca, Mn, Fe, Co, Ni, and Zn). United States. doi:10.1021/jacs.6b08746.
Hu, Lei, Chen, Jun, Xu, Jiale, Wang, Na, Han, Fei, Ren, Yang, Pan, Zhao, Rong, Yangchun, Huang, Rongjin, Deng, Jinxia, Li, Laifeng, and Xing, Xianran. 2016. "Atomic Linkage Flexibility Tuned Isotropic Negative, Zero, and Positive Thermal Expansion in MZrF6 (M = Ca, Mn, Fe, Co, Ni, and Zn)". United States. doi:10.1021/jacs.6b08746. https://www.osti.gov/servlets/purl/1393263.
@article{osti_1393263,
title = {Atomic Linkage Flexibility Tuned Isotropic Negative, Zero, and Positive Thermal Expansion in MZrF6 (M = Ca, Mn, Fe, Co, Ni, and Zn)},
author = {Hu, Lei and Chen, Jun and Xu, Jiale and Wang, Na and Han, Fei and Ren, Yang and Pan, Zhao and Rong, Yangchun and Huang, Rongjin and Deng, Jinxia and Li, Laifeng and Xing, Xianran},
abstractNote = {The controllable isotropic thermal expansion with a broad coefficient of thermal expansion (CTE) window is intriguing but remains challenge. Herein we report a cubic MZrF6 series (M = Ca, Mn, Fe, Co, Ni and Zn), which exhibit controllable thermal expansion over a wide temperature range and with a broader CTE window (–6.69 to +18.23 × 10–6/K). In particular, an isotropic zero thermal expansion (ZTE) is achieved in ZnZrF6, which is one of the rarely documented hightemperature isotropic ZTE compounds. By utilizing temperature dependent high-energy synchrotron X-ray total scattering diffraction, it is found that the flexibility of metal···F atomic linkages in MZrF6 plays a critical role in distinct thermal expansions. The flexible metal···F atomic linkages induce negative thermal expansion (NTE) for CaZrF6, whereas the stiff ones bring positive thermal expansion (PTE) for 6. Thermal expansion could be transformed from striking negative, to zero, and finally to considerable positive though tuning the flexibility of metal···F atomic linkages by substitution with a series of cations on M sites of MZrF6. In conclusion, the present study not only extends the scope of NTE families and rare high-temperature isotropic ZTE compounds but also proposes a new method to design systematically controllable isotropic thermal expansion frameworks from the perspective of atomic linkage flexibility.},
doi = {10.1021/jacs.6b08746},
journal = {Journal of the American Chemical Society},
number = 44,
volume = 138,
place = {United States},
year = {2016},
month = {10}
}