Crystal structures and formation mechanisms of boron-rich tungsten borides

Gu, Chao; Liang, Yongcheng; Zhou, Xuefeng; Chen, Jian; Ma, Dejiang; Qin, Jiaqian; Zhang, Wenqing; Zhang, Qiang; Daemen, Luke L.; Zhao, Yusheng; Wang, Shanmin

doi:10.1103/physrevb.104.014110

Crystal structures and formation mechanisms of boron-rich tungsten borides

Journal Article · Thu Jul 22 00:00:00 EDT 2021 · Physical Review B

DOI:https://doi.org/10.1103/physrevb.104.014110· OSTI ID:1818658

Gu, Chao ^[1]; ^[2]; Zhou, Xuefeng ^[1]; ^[1]; Ma, Dejiang ^[1]; ^[3]; Zhang, Wenqing ^[1]; ^[4]; Daemen, Luke L. ^[4]; ^[1]; ^[1]

Southern Univ. of Science and Technology, Shenzhen (China)
Donghua Univ., Shanghai (China)
Chulalongkorn Univ., Bangkok (Thailand)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Boron-rich tungsten borides tend to adopt mechanically unfavorable layered structures but experimentally exhibit excellent mechanical properties rivalling traditional superhard solids. Unravelling the contraindicated structure-property relationship, however, has been impeded by their structural ambiguities because of the difficulty in probing boron and atomic deficiency of these borides. Here, we study crystal structures of boron-rich tungsten borides WB_3+x and WB_2+x by neutron diffraction based on high-quality samples prepared by a high-pressure method, leading to definitive structural resolutions for both borides with unique compositions of WB_5.14 and WB_2.34. Combined with theoretical calculations, their structural stability is revealed to be closely related to atomic deficiency, which is governed by the valence-band filling with an optimal valence-electron concentration of ~10 per cell. The presence of interstitial boron trimers at the vacant W : 2b sites in WB_5.14 alters the crystal symmetry, making the Wyckoff 2d site more favorably occupied by W, rather than the 2c site, as previously misassigned. Here, the staggered planar boron layers and wrinkled boron bonding in WB_2.34 are identified to be crucial for stabilizing its structure. These findings unveil the longstanding structural mysteries of boron-rich tungsten borides and offer powerful insights for rational design of borides by defect chemistry.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1818658

Journal Information:: Physical Review B, Journal Name: Physical Review B Journal Issue: 1 Vol. 104; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (57)

Advancements in the Search for Superhard Ultra-Incompressible Metal Borides Levine, Jonathan B.; Tolbert, Sarah H.; Kaner, Richard B. Advanced Functional Materials, Vol. 19, Issue 22 https://doi.org/10.1002/adfm.200901257	journal	November 2009
Transition Metal Borides: Superhard versus Ultra-incompressible Gu, Qinfen; Krauss, Günter; Steurer, Walter Advanced Materials, Vol. 20, Issue 19 https://doi.org/10.1002/adma.200703025	journal	October 2008
WB ₅₋ _x : Synthesis, Properties, and Crystal Structure—New Insights into the Long‐Debated Compound Kvashnin, Alexander G.; Rybkovskiy, Dmitry V.; Filonenko, Vladimir P. Advanced Science, Vol. 7, Issue 16 https://doi.org/10.1002/advs.202000775	journal	July 2020
A General Solution Route toward Metal Boride Nanocrystals Portehault, David; Devi, Sarala; Beaunier, Patricia Angewandte Chemie International Edition, Vol. 50, Issue 14 https://doi.org/10.1002/anie.201006810	journal	February 2011
Bor-reiche Wolframboride Nowotny, H.; Haschke, H.; Benesovsky, F. Monatshefte für Chemie - Chemical Monthly, Vol. 98, Issue 3 https://doi.org/10.1007/BF00901362	journal	May 1967
Critical assessment and thermodynamic calculation of the binary system boron-tungsten (B-W) Duschanek, H.; Rogl, P. Journal of Phase Equilibria, Vol. 16, Issue 2 https://doi.org/10.1007/BF02664852	journal	April 1995
Crystal Structure of W1−x B3 and Phase Equilibria in the Boron-Rich Part of the Systems Mo-Rh-B and W-{Ru,Os,Rh,Ir,Ni,Pd,Pt}-B Zeiringer, I.; Rogl, P.; Grytsiv, A. Journal of Phase Equilibria and Diffusion, Vol. 35, Issue 4 https://doi.org/10.1007/s11669-014-0291-0	journal	March 2014
Structure of poorly crystalline MoS2 — A modeling study Liang, K. S.; Chianelli, R. R.; Chien, F. Z. Journal of Non-Crystalline Solids, Vol. 79, Issue 3 https://doi.org/10.1016/0022-3093(86)90226-7	journal	February 1986
The crystal structure of the molybdenum boride Mo1−xB3 Lundström, Torsten; Rosenberg, Ingvar Journal of Solid State Chemistry, Vol. 6, Issue 2 https://doi.org/10.1016/0022-4596(73)90194-1	journal	February 1973
Lattice constants and nonstoichiometry of WB2-x Otani, Shigeki; Ohashi, Haruo; Ishizawa, Yoshio Journal of Alloys and Compounds, Vol. 221, Issue 1-2 https://doi.org/10.1016/0925-8388(94)01486-8	journal	April 1995
Unexpectedly hard and highly stable WB3 with a noncompact structure Liang, Yongcheng; Gou, Yanpeng; Yuan, Xun Chemical Physics Letters, Vol. 580 https://doi.org/10.1016/j.cplett.2013.06.059	journal	August 2013
Sulfur-catalyzed phase transition in MoS2 under high pressure and temperature Wang, Shanmin; Zhang, Jianzhong; He, Duanwei Journal of Physics and Chemistry of Solids, Vol. 75, Issue 1 https://doi.org/10.1016/j.jpcs.2013.09.001	journal	January 2014
A facile one-step route to nanocrystalline TiB2 powders Chen, Luyang; Gu, Yunle; Qian, Yitai Materials Research Bulletin, Vol. 39, Issue 4-5 https://doi.org/10.1016/j.materresbull.2003.12.005	journal	April 2004
Boron-Rich Molybdenum Boride with Unusual Short-Range Vacancy Ordering, Anisotropic Hardness, and Superconductivity Tang, Hu; Gao, Xiang; Zhang, Jian Chemistry of Materials, Vol. 32, Issue 1 https://doi.org/10.1021/acs.chemmater.9b04052	journal	December 2019
Nonrandomly Distributed Tungsten Vacancies and Interstitial Boron Trimers in Tungsten Tetraboride Dong, Juncai; Li, Haijing; Wang, Jiaou The Journal of Physical Chemistry C, Vol. 123, Issue 48 https://doi.org/10.1021/acs.jpcc.9b08621	journal	November 2019
New Tungsten Borides, Their Stability and Outstanding Mechanical Properties Kvashnin, Alexander G.; Zakaryan, Hayk A.; Zhao, Changming The Journal of Physical Chemistry Letters, Vol. 9, Issue 12 https://doi.org/10.1021/acs.jpclett.8b01262	journal	June 2018
Superhard Tungsten Tetraboride Films Prepared by Pulsed Laser Deposition Method Rau, Julietta V.; Latini, Alessandro; Teghil, Roberto ACS Applied Materials & Interfaces, Vol. 3, Issue 9 https://doi.org/10.1021/am200927q	journal	August 2011
Exploring Hardness and the Distorted sp ² Hybridization of B–B Bonds in WB ₃ Tao, Qiang; Zheng, Dafang; Zhao, Xueping Chemistry of Materials, Vol. 26, Issue 18 https://doi.org/10.1021/cm5021806	journal	September 2014
Electronic structure of transition-metal borides with the AlB2 structure Burdett, Jeremy K.; Canadell, Enric.; Miller, Gordon J. Journal of the American Chemical Society, Vol. 108, Issue 21 https://doi.org/10.1021/ja00281a020	journal	October 1986
Toward Inexpensive Superhard Materials: Tungsten Tetraboride-Based Solid Solutions Mohammadi, Reza; Xie, Miao; Lech, Andrew T. Journal of the American Chemical Society, Vol. 134, Issue 51 https://doi.org/10.1021/ja308219r	journal	December 2012
A New Molybdenum Nitride Catalyst with Rhombohedral MoS ₂ Structure for Hydrogenation Applications Wang, Shanmin; Ge, Hui; Sun, Shouli Journal of the American Chemical Society, Vol. 137, Issue 14 https://doi.org/10.1021/jacs.5b01446	journal	April 2015
Icosahedral packing of B12 icosahedra in boron suboxide (B6O) Hubert, Hervé; Devouard, Bertrand; Garvie, Laurence A. J. Nature, Vol. 391, Issue 6665 https://doi.org/10.1038/34885	journal	January 1998
Ionic high-pressure form of elemental boron Oganov, Artem R.; Chen, Jiuhua; Gatti, Carlo Nature, Vol. 457, Issue 7231 https://doi.org/10.1038/nature07736	journal	January 2009
Polyphony in B flat Zhang, Zhuhua; Penev, Evgeni S.; Yakobson, Boris I. Nature Chemistry, Vol. 8, Issue 6 https://doi.org/10.1038/nchem.2521	journal	April 2016
Polytypism in superhard transition-metal triborides Liang, Yongcheng; Yang, Jiong; Yuan, Xun Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep05063	journal	May 2014
Discovery of elusive structures of multifunctional transition-metal borides Liang, Yongcheng; Wu, Zhaobing; Yuan, Xun Nanoscale, Vol. 8, Issue 2 https://doi.org/10.1039/C5NR06404J	journal	January 2016
Unexpected stable phases of tungsten borides Zhao, Changming; Duan, Yifeng; Gao, Jie Physical Chemistry Chemical Physics, Vol. 20, Issue 38 https://doi.org/10.1039/C8CP04222E	journal	January 2018
Phase stability and mechanical properties of tungsten borides from first principles calculations Zhao, Erjun; Meng, Jian; Ma, Yanming Physical Chemistry Chemical Physics, Vol. 12, Issue 40 https://doi.org/10.1039/c004122j	journal	January 2010
Origin of hardness in WB4 and its implications for ReB4, TaB4, MoB4, TcB4, and OsB4 Wang, Mei; Li, Yinwei; Cui, Tian Applied Physics Letters, Vol. 93, Issue 10 https://doi.org/10.1063/1.2977760	journal	September 2008
Peculiar structure and tensile strength of WB ₄ : nonstoichiometric origin Gou, Huiyang; Li, Zhiping; Wang, Li-Min AIP Advances, Vol. 2, Issue 1 https://doi.org/10.1063/1.3696721	journal	March 2012
Radial x-ray diffraction of tungsten tetraboride to 86 GPa under nonhydrostatic compression Xiong, Lun; Liu, Jing; Bai, Ligang Journal of Applied Physics, Vol. 113, Issue 3 https://doi.org/10.1063/1.4775482	journal	January 2013
Interstitial-boron solution strengthened WB ₃₊ _x Cheng, Xiyue; Zhang, Wei; Chen, Xing-Qiu Applied Physics Letters, Vol. 103, Issue 17 https://doi.org/10.1063/1.4826485	journal	October 2013
Unexpected structural softening of interstitial boron solid solution WB3+x Wu, Hao; Sun, Hong; Chen, Changfeng Applied Physics Letters, Vol. 105, Issue 21 https://doi.org/10.1063/1.4902388	journal	November 2014
Large-volume cubic press produces high temperatures above 4000 Kelvin for study of the refractory materials at pressures Zhou, Xuefeng; Ma, Dejiang; Wang, Lingfei Review of Scientific Instruments, Vol. 91, Issue 1 https://doi.org/10.1063/1.5128190	journal	January 2020
Tungsten tetraboride, an inexpensive superhard material Mohammadi, R.; Lech, A. T.; Xie, M. Proceedings of the National Academy of Sciences, Vol. 108, Issue 27 https://doi.org/10.1073/pnas.1102636108	journal	June 2011
Structure of superhard tungsten tetraboride: A missing link between MB ₂ and MB ₁₂ higher borides Lech, Andrew T.; Turner, Christopher L.; Mohammadi, Reza Proceedings of the National Academy of Sciences, Vol. 112, Issue 11 https://doi.org/10.1073/pnas.1415018112	journal	March 2015
Low-compressibility of tungsten tetraboride: a high pressure X-ray diffraction study Liu, Chenji; Peng, Fang; Tan, Ning High Pressure Research, Vol. 31, Issue 2 https://doi.org/10.1080/08957959.2011.582871	journal	June 2011
Neutron scattering lengths and cross sections Sears, Varley F. Neutron News, Vol. 3, Issue 3 https://doi.org/10.1080/10448639208218770	journal	January 1992
Unravelling the structure and strength of the highest boride of tungsten WB 4.2 Gong, Weiguang; Liu, Chang; Song, Xianqi Physical Review B, Vol. 100, Issue 22 https://doi.org/10.1103/PhysRevB.100.220102	journal	December 2019
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Low-compressibility and hard materials Re B 2 and W B 2 : Prediction from first-principles study Hao, Xianfeng; Xu, Yuanhui; Wu, Zhijian Physical Review B, Vol. 74, Issue 22 https://doi.org/10.1103/PhysRevB.74.224112	journal	December 2006
Thermodynamic identification of tungsten borides Liang, Yongcheng; Yuan, Xun; Zhang, Wenqing Physical Review B, Vol. 83, Issue 22 https://doi.org/10.1103/PhysRevB.83.220102	journal	June 2011
Exploring the high-pressure behavior of superhard tungsten tetraboride Xie, Miao; Mohammadi, Reza; Mao, Zhu Physical Review B, Vol. 85, Issue 6 https://doi.org/10.1103/PhysRevB.85.064118	journal	February 2012
Unexpectedly low indentation strength of WB 3 and MoB 3 from first principles Zang, Chenpeng; Sun, Hong; Chen, Changfeng Physical Review B, Vol. 86, Issue 18 https://doi.org/10.1103/PhysRevB.86.180101	journal	November 2012
Electronic and Structural Origin of Ultraincompressibility of 5 d Transition-Metal Diborides M B 2 ( M = W , Re, Os) Chen, Xing-Qiu; Fu, C. L.; Krčmar, M. Physical Review Letters, Vol. 100, Issue 19 https://doi.org/10.1103/PhysRevLett.100.196403	journal	May 2008
Stability and Strength of Transition-Metal Tetraborides and Triborides Zhang, R. F.; Legut, D.; Lin, Z. J. Physical Review Letters, Vol. 108, Issue 25 https://doi.org/10.1103/PhysRevLett.108.255502	journal	June 2012
Global Structural Optimization of Tungsten Borides Li, Quan; Zhou, Dan; Zheng, Weitao Physical Review Letters, Vol. 110, Issue 13 https://doi.org/10.1103/PhysRevLett.110.136403	journal	March 2013
Anomalous Stress Response of Ultrahard WB n Compounds Li, Quan; Zhou, Dan; Zheng, Weitao Physical Review Letters, Vol. 115, Issue 18 https://doi.org/10.1103/PhysRevLett.115.185502	journal	October 2015
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
Composition and crystallographic data for the highest boride of tungsten Romans, P. A.; Krug, M. P. Acta Crystallographica, Vol. 20, Issue 2 https://doi.org/10.1107/S0365110X6600063X	journal	February 1966
Computational materials discovery: the case of the W–B system Cheng, Xi-Yue; Chen, Xing-Qiu; Li, Dian-Zhong Acta Crystallographica Section C Structural Chemistry, Vol. 70, Issue 2 https://doi.org/10.1107/S2053229613027551	journal	January 2014
Synthesis of group IV and V metal diboride nanocrystals via borothermal reduction with sodium borohydride Zoli, Luca; Galizia, Pietro; Silvestroni, Laura Journal of the American Ceramic Society, Vol. 101, Issue 6 https://doi.org/10.1111/jace.15401	journal	January 2018
Tungsten Diboride: Preparation and Structure Woods, H. P.; Wawner, F. E.; Fox, B. G. Science, Vol. 151, Issue 3706 https://doi.org/10.1126/science.151.3706.75	journal	January 1966
An unexpected softening from WB ₃ to WB ₄ Liang, Yongcheng; Fu, Zhao; Yuan, Xun EPL (Europhysics Letters), Vol. 98, Issue 6 https://doi.org/10.1209/0295-5075/98/66004	journal	June 2012
The Crystal Structures of Molybdenum and Tungsten Borides. Kiessling, Roland; Wetterholm, Allan; Sillén, Lars Gunnar Acta Chemica Scandinavica, Vol. 1 https://doi.org/10.3891/acta.chem.scand.01-0893	journal	January 1947

Similar Records

Modeling Tungsten Boride Neutronics in ORIGEN for Z-Facility

Technical Report · Mon Apr 01 00:00:00 EDT 2024 · OSTI ID:2429964

Atomic site preferences and its effect on magnetic structure in the intermetallic borides M{sub 2}Fe(Ru{sub 0.8}T{sub 0.2}){sub 5}B{sub 2} (M=Sc, Ti, Zr; T=Ru, Rh, Ir)

Journal Article · Fri Dec 14 23:00:00 EST 2012 · Journal of Solid State Chemistry · OSTI ID:22149927

Formation of tungsten borides studied by field ion microscopy

Journal Article · Wed Jul 01 00:00:00 EDT 1987 · J. Vac. Sci. Technol., A; (United States) · OSTI ID:6423363

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
Chemical synthesis
Crystal structures
First-principles calculations
Interstitials
Neutron diffraction
Point defects
Structural properties
X-ray diffraction

Crystal structures and formation mechanisms of boron-rich tungsten borides

Citation Formats

References (57)

Similar Records

Related Subjects