Understanding the Hardness of Doped WB4.2Click to copy article linkArticle link copied!
- Kirill D. ShumilovKirill D. ShumilovDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Kirill D. Shumilov
- Zerina MehmedovićZerina MehmedovićDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Zerina Mehmedović
- Hang YinHang YinDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Hang Yin
- Patricia PothsPatricia PothsDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Patricia Poths
- Selbi NuryyevaSelbi NuryyevaDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Selbi Nuryyeva
- Ieva LiepuoniuteIeva LiepuoniuteDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Ieva Liepuoniute
- Chelsea JangChelsea JangDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Chelsea Jang
- Isabelle WinardiIsabelle WinardiDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Isabelle Winardi
- Anastassia N. Alexandrova*Anastassia N. Alexandrova*E-mail: [email protected]Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United StatesMore by Anastassia N. Alexandrova
Abstract
WB4.2 is one of the hardest metals known. Though not harder than diamond and cubic boron nitride, it surpasses these established hard materials in being cheaper, easier to produce and process, and also more functional. Metal impurities have been shown to affect and in some cases further improve the intrinsic hardness of WB4.2, but the mechanism of hardening remained elusive. In this work, we first theoretically elucidate the preferred placements of Ti, V, Cr, Mn, Zr, Nb, Mo, Hf, and Ta in the WB4.2 structure and show these metals to preferentially replace W in two competing positions with respect to the partially occupied B3 cluster site. The impurities avoid the void position in the structure. Next, we analyze the chemical bonding within these identified doped structures and propose two different mechanisms of strengthening the material, afforded by these impurities and dependent on their nature. Smaller impurity atoms (Ti, V, Cr, Mn) with deeply lying valence atomic orbitals cause the interlayer compression of WB4.2, which strengthens the Bhex–Bcluster bonding slightly. Larger impurities (Zr, Nb, Mo, Hf, Ta) with higher-energy valence orbitals, while expanding the structure and negatively impacting the Bhex–Bcluster bonding, also form strong Bcluster–M bonds. The latter effect is an order of magnitude more substantial than the effect on the Bhex–Bcluster bonding. We conclude that the effect of the impurities on the boride hardness does not simply reduce to structure interlocking due to the size difference between M and W but, instead, has a significant electronic origin.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 6 publications.
- Georgiy Akopov, Shanlin Hu, Kirill D. Shumilov, Spencer G. Hamilton, Lisa E. Pangilinan, Zerina Mehmedović, Hang Yin, Paul J. Robinson, Inwhan Roh, Abby Kavner, Anastassia N. Alexandrova, Sarah H. Tolbert, Richard B. Kaner. Hardening in Tungsten Tetraboride with the Addition of Carbon, Zirconium, and Silicon: Intrinsic vs Extrinsic Effects. Chemistry of Materials 2024, 36
(7)
, 3233-3245. https://doi.org/10.1021/acs.chemmater.3c03092
- Lisa E. Pangilinan, Shanlin Hu, Spencer G. Hamilton, Sarah H. Tolbert, Richard B. Kaner. Hardening Effects in Superhard Transition-Metal Borides. Accounts of Materials Research 2022, 3
(1)
, 100-109. https://doi.org/10.1021/accountsmr.1c00192
- David A. Strubbe. A computational materials science paradigm for a Course-based Undergraduate Research Experience (CURE). MRS Advances 2024, 9
(19)
, 1479-1485. https://doi.org/10.1557/s43580-024-00934-w
- Elena Bykova, Sergey V. Ovsyannikov, Maxim Bykov, Yuqing Yin, Timofey Fedotenko, Hendrik Holz, Stefan Gabel, Benoit Merle, Stella Chariton, Vitali B. Prakapenka, Natalia Dubrovinskaia, Alexander F. Goncharov, Leonid Dubrovinsky. Synthesis, crystal structure, and properties of stoichiometric hard tungsten tetraboride, WB
4. Journal of Materials Chemistry A 2022, 10
(37)
, 20111-20120. https://doi.org/10.1039/D2TA02268K
- Krati Joshi, Raghunath O. Ramabhadran. Studying the impact of diagonal-doping on thermal stability of main-group metal clusters via Born Oppenheimer molecular dynamics. Molecular Physics 2022, 120
(12)
https://doi.org/10.1080/00268976.2022.2088420
- Russlan Jaafreh, Yoo Seong Kang, Jung-Gu Kim, Kotiba Hamad. Machine learning guided discovery of super-hard high entropy ceramics. Materials Letters 2022, 306 , 130899. https://doi.org/10.1016/j.matlet.2021.130899
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.