Real-Space Distribution of Local WO4 Ordering in Negative Thermal Expansive ZrW2O8
Abstract
Solids usually expand when they are heated. This is quite common behavior of solids; however, there are some exceptions. Zirconium tungstate (ZrW2O8) is a prototype material among them, because it has the highest degree of negative thermal expansion (NTE) over broad temperature range. Intensive investigation of NTE mechanisms has suggested the importance of metal–oxygen polyhedra. However, most of the studies have been done with volume-averaged techniques, and microscopic information has been lacking. Here, our electron microscopy observations have unraveled the real-space distribution of local WO4 tetrahedra ordering for the first time. We have found that (i) the WO4 ordering is partly inverted; (ii) WO4 is disordered on the nanoscale; and (iii) doping with scandium enhances the WO4 disordering. These findings led to construction of a microstructure model for ZrW2O8, providing a new structural perspective for better understanding of local structure and its role in phase transitions.
Cited By
This article is cited by 10 publications.
- Andrea Sanson . Toward an Understanding of the Local Origin of Negative Thermal Expansion in ZrW2O8: Limits and Inconsistencies of the Tent and Rigid Unit Mode Models. Chemistry of Materials 2014, 26 (12) , 3716-3720. https://doi.org/10.1021/cm501107w
- Chang Zhou, Yongxiao Zhou, Qiang Zhang, Qingyu Meng, Lianyu Zhang, Equo Kobayashi, Gaohui Wu. Near-zero thermal expansion of ZrW2O8/Al–Si composites with three dimensional interpenetrating network structure. Composites Part B: Engineering 2021, 211 , 108678. https://doi.org/10.1016/j.compositesb.2021.108678
- Chang Zhou, Qiang Zhang, Xin Tan, Sihao Deng, Kewen Shi, Cong wang, Gaohui Wu. Fully-dense Mn3Zn0.7Ge0.3N /Al composites with zero thermal expansion behavior around room temperature. Materialia 2019, 6 , 100289. https://doi.org/10.1016/j.mtla.2019.100289
- Sudipta Mondal, Chandan Mazumdar, R. Ranganathan. Transverse vibration driven large uniaxial negative and zero thermal expansion in boron bridged REPt 3 B framework materials. Physical Chemistry Chemical Physics 2018, 20 (21) , 14876-14883. https://doi.org/10.1039/C8CP00934A
- Xiaozhi Yan, Xiangting Ren, Guangai Sun, Dong Li, Xin Li, Duanwei He, Wenge Yang. Kinetics of a first-order crystalline-amorphous transformation in zirconium tungstate. Physical Review B 2017, 95 (22) https://doi.org/10.1103/PhysRevB.95.224205
- R. Mendonça, W. Paraguassu, J. Mendes Filho, B. A. Marinkovic, A. G. Souza Filho, M. Maczka, P. T. C. Freire. Pressure-induced structural transformations in In 2-x Y x (MoO 4 ) 3 systems. Journal of Raman Spectroscopy 2016, 47 (3) , 350-356. https://doi.org/10.1002/jrs.4814
- Xiaohui Liu, Janine George, Stefan Maintz, Richard Dronskowski. β-CuN 3 : die übersehene Grundzustandsmodifikation des Kupferazids mit heterographenartigen Schichten. Angewandte Chemie 2015, 127 (6) , 1977-1982. https://doi.org/10.1002/ange.201410987
- Xiaohui Liu, Janine George, Stefan Maintz, Richard Dronskowski. β-CuN 3 : The Overlooked Ground-State Polymorph of Copper Azide with Heterographene-Like Layers. Angewandte Chemie International Edition 2015, 54 (6) , 1954-1959. https://doi.org/10.1002/anie.201410987
- Leiming Fang, Xiping Chen, Guangai Sun, Bo Chen, Shuming Peng. Synthesis hexagonal ZrW 2 O 8 and its thermal properties. High Pressure Research 2013, 33 (4) , 760-767. https://doi.org/10.1080/08957959.2013.847931
- Leighanne C. Gallington, Karena W. Chapman, Cody R. Morelock, Peter J. Chupas, Angus P. Wilkinson. Orientational order-dependent thermal expansion and compressibility of ZrW2O8 and ZrMo2O8. Physical Chemistry Chemical Physics 2013, 15 (45) , 19665. https://doi.org/10.1039/c3cp52876f