Title: Atomic Linkage Flexibility Tuned Isotropic Negative, Zero, and Positive Thermal Expansion in MZrF₆ (M = Ca, Mn, Fe, Co, Ni, and Zn)

Abstract

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 frameworksmore » from the perspective of atomic linkage flexibility.« less

Authors:

Hu, Lei ^[1]; Chen, Jun ^[1]; Xu, Jiale ^[1]; Wang, Na ^[1]; Han, Fei ^[1]; Ren, Yang ^[2]; Pan, Zhao ^[1]; Rong, Yangchun ^[1]; Huang, Rongjin ^[3]; Deng, Jinxia ^[1]; Li, Laifeng ^[3]; Xing, Xianran ^[1]

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+ Show Author Affiliations

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:

2016-10-26

Research Org.:

Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:

National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division

OSTI Identifier:

1393263

Grant/Contract Number:  

AC02-06CH11357

Resource 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)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY