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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b08746· OSTI ID:1393263
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  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)
+ Show Author Affiliations
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.
Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1393263
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 44 Vol. 138; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (13)

Enhancing Ligand‐Free Fe‐Catalyzed Aminocarbonylation of Alkynes by ZrF 4 journal March 2019
Spring-like motion caused large anisotropic thermal expansion in nonporous M(eim) 2 (M = Zn, Cd) journal January 2017
Crossover of thermal expansion from positive to negative by removing the excess fluorines in cubic ReO 3 -type TiZrF 7−x journal January 2018
Negative thermal expansion in molecular materials journal January 2018
Phonon spectrum attributes for the negative thermal expansion of MZrF 6 (M = Ca, Mn–Ni, Zn) journal January 2019
Inorganic–organic hybridization induced uniaxial zero thermal expansion in MC 4 O 4 (M = Ba, Pb) journal January 2019
Accordion and layer-sliding motion to produce anomalous thermal expansion behaviour in 2D-coordination polymers journal January 2019
Intrinsic zero thermal expansion in cube cyanurate K 6 Cd 3 (C 3 N 3 O 3 ) 4 journal January 2019
Controllable thermal expansion and magnetic structure in Er 2 (Fe,Co) 14 B intermetallic compounds journal January 2019
On the switching between negative and positive thermal expansion in framework materials journal May 2019
Negative thermal expansion behavior in M Zr F 6 ( M = Ca , Mg , Sr ) : Ab initio lattice dynamical studies journal July 2018
On the switching between negative and positive thermal expansion in framework materials text January 2019
On the switching between negative and positive thermal expansion in framework materials text January 2019

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