AI Chat Paper
Discover the SciOpen Platform and Achieve Your Research Goals with Ease.
Understanding the initial oxidation mechanism is critical for studying the oxidation resistance of high-entropy diborides. However, related studies are scarce. Herein, the initial oxidation mechanism of (Zr0.25Ti0.25Nb0.25Ta0.25)B2 high-entropy diborides (HEB2-1) is investigated by first-principles calculations at the atomic level. By employing the two-region model method, the most stable surface of HEB2-1 is determined to be (110) surface. The dissociative adsorption process of the oxygen molecule on the HEB2-1-(110) surface is predicted to proceed spontaneously, where OO bond breaks and each oxygen atom is chemisorbed on the most preferable hollow site. The adsorption energy and the diffusion barrier of the oxygen atom on the (110) surface of HEB2-1 are in the vicinity of the average level of the corresponding four individual diborides. In addition, ab initio molecular dynamics simulations indicate a high initial oxidation resistance of HEB2-1 at 1000 K. Our results are beneficial to further designing the high-entropy diborides with excellent oxidation resistance.
Rost CM, Sachet E, Borman T, Moballegh A, Dickey EC, Hou D, et al. Entropy-stabilized oxides. Nat Commun 2015;6:8485.
McCormack SJ, Navrotsky A. Thermodynamics of high entropy oxides. Acta Mater 2021;202:1–21.
Ma M, Han Y, Zhao Z, Feng J, Chu Y. Ultrafine-grained high-entropy zirconates with superior mechanical and thermal properties. J Materiomics 2023;9:370–7.
Gild J, Zhang Y, Harrington T, Jiang S, Hu T, Quinn MC, et al. High-entropy metal diborides: a new class of high-entropy materials and a new type of ultrahigh temperature ceramics. Sci Rep 2016;6:1–10.
Liu D, Wen T, Ye B, Chu Y. Synthesis of superfine high-entropy metal diboride powders. Scripta Mater 2019;167:110–4.
Liu D, Liu H, Ning S, Ye B, Chu Y. Synthesis of high-purity high-entropy metal diboride powders by boro/carbothermal reduction. J Am Ceram Soc 2019;102:7071–6.
Ye B, Wen T, Huang K, Wang CZ, Chu Y. First-principles study, fabrication, and characterization of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramic. J Am Ceram Soc 2019;102:4344–52.
Ye B, Wen T, Liu D, Chu Y. Oxidation behavior of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics at 1073-1473 K in air. Corrosion Sci 2019;153:327–32.
Wang F, Yan X, Wang T, Wu Y, Shao L, Nastasi M, et al. Irradiation damage in (Zr0.25Ta0.25Nb0.25Ti0.25)C high-entropy carbide ceramics. Acta Mater 2020;195:739–49.
Ye B, Wen T, Nguyen MC, Wu Y, Shao L, Nastasi M, et al. First-principles study, fabrication and characterization of (Zr0.25Nb0.25Ti0.25V0.25)C high-entropy ceramics. Acta Mater 2019;170:15–23.
Wang Y, Zhang B, Zhang C, Yin J, Reece MJ. Ablation behaviour of (Hf-Ta-Zr-Nb)C high entropy carbide ceramic at temperatures above 2100 ℃. J Mater Sci Technol 2022;113:40–7.
Ma M, Hu X, Meng H, Zhao Z, Chang K, Chu Y. High-entropy metal carbide nanowires. Cell Rep Phys Sci 2022;3:100839.
Liu SY, Zhang S, Liu S, Li DJ, Li Y, Wang S. Phase stability, mechanical properties and melting points of high-entropy quaternary metal carbides from first-principles. J Eur Ceram Soc 2021;41:6267–74.
Kumar A, Dragoe D, Berardan D, Dragoe N. Thermoelectric properties of high-entropy rare-earth cobaltates. J Materiomics 2023;9:191–6.
Liu D, Liu H, Ning S, Chu Y. Chrysanthemum-like high-entropy diboride nanoflowers: a new class of high-entropy nanomaterials. J Adv Ceram 2020;9:339–48.
Ma M, Ye B, Han Y, Chu Y. High-pressure sintering of ultrafine-grained high-entropy diboride ceramics. J Am Ceram Soc 2020;103:6655–8.
Zhang Z, Zhu S, Dai FZ, Xiang H, Liu Y, Liu L, et al. Theoretical predictions and experimental verification on the phase stability of enthalpy-stabilized HE TMREB2s. J Mater Sci Technol 2022;121:154–62.
Tallarita G, Licheri R, Garroni S, Barbarossa S, Orrù R, Cao G. High-entropy transition metal diborides by reactive and non-reactive spark plasma sintering: a comparative investigation. J Eur Ceram Soc 2020;40:942–52.
Kavak S, Bayrak KG, Mansoor M, Kaba M, Ayas E, Balcı-Çağıran Ö, et al. First principles calculations and synthesis of multi-phase (HfTiWZr)B2 high entropy diboride ceramics: microstructural, mechanical and thermal characterization. J Eur Ceram Soc 2023;43:768–82.
Wen Z., Meng H., Jiang S., Tang Z., Liu Y., Chu Y. Non-equimolar (Hf, Zr, Ta, W) B2 high-entropy diborides enable superior oxidation resistance. Sci China Mater 2023;66:3213–3222.
Kirnbauer A, Wagner A, Moraes V, Primetzhofer D, Hans M, Schneider JM, et al. Thermal stability and mechanical properties of sputtered (Hf, Ta, V, W, Zr)-diborides. Acta Mater 2020;200:559–69.
Qin M, Gild J, Wang H, Harrington T, Vecchio KS, Luo J. Dissolving and stabilizing soft WB2 and MoB2 phases into high-entropy borides via boron-metals reactive sintering to attain higher hardness. J Eur Ceram Soc 2020;40:4348–53.
Feng L, Fahrenholtz WG, Hilmas GE, Monteverde F. Effect of Nb content on the phase composition, densification, microstructure, and mechanical properties of high-entropy boride ceramics. J Eur Ceram Soc 2021;41:92–100.
Gild J, Wright A, Quiambao-Tomko K, Qin M, Tomko JA, bin Hoque MS, et al. Thermal conductivity and hardness of three single-phase high-entropy metal diborides fabricated by borocarbothermal reduction and spark plasma sintering. Ceram Int 2020;46:6906–13.
Backman L, Gild J, Luo J, Opila EJ. Part Ⅱ: experimental verification of computationally predicted preferential oxidation of refractory high entropy ultra-high temperature ceramics. Acta Mater 2020;197:81–90.
Guo R, Li Z, Li L, Liu Y, Zheng R, Ma C. Microstructures and oxidation mechanisms of (Zr0.2Hf0.2Ta0.2Nb0.2Ti0.2)B2 high-entropy ceramic. J Eur Ceram Soc 2022;42:2127–34.
Kresse G, Furthmüller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp mater sci 1996;6:15–50.
Blöchl PE. Projector augmented-wave method. Phys Rev B 1994;50:17953.
Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett 1996;77:3865.
Pan Yong, Pu Delin, Liu Gaihua, Wang P. Influence of alloying elements on the structural stability, elastic, hardness and thermodynamic properties of Mo5SiB2 from first-principles calculations. Ceram Int 2020;4:16605–11.
Monkhorst HJ, Pack JD. Special points for Brillouin-zone integrations. Phys Rev B 1976;13:5188.
Van de Walle A, Tiwary P, De Jong M, Olmsted DL, Asta M, Dick A, et al. Efficient stochastic generation of special quasirandom structures. Calphad 2013;42:13–8.
Liu SY, Zhang S, Liu S, Li DJ, Niu Z, Li Y, et al. Stability and mechanical properties of single-phase quinary high-entropy metal carbides: first-principles theory and thermodynamics. J Eur Ceram Soc 2022;42:3089–98.
Sun W, Dai F, Xiang H, Liu J, Zhou Y. General trends in surface stability and oxygen adsorption behavior of transition metal diborides (TMB2). J Mater Sci Technol 2019;35:584–90.
Xing H, Hu P, Li S, Zuo Y, Han J, Hua X, et al. Adsorption and diffusion of oxygen on metal surfaces studied by first-principle study: a review. J Mater Sci Technol 2021;62:180–94.
Heyden A, Bell AT, Keil FJ. Efficient methods for finding transition states in chemical reactions: comparison of improved dimer method and partitioned rational function optimization method. J Chem Phys 2005;123:224101.
Henkelman G, Uberuaga BP, Jónsson H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J Chem Phys 2000;113:9901–4.
Shuichi N. Constant temperature molecular dynamics methods. Prog Theor Phys Suppl 1991;103:1–46.
Yong P, Zhang X. Theoretical predict the structure, elastic anisotropy and thermodynamic properties of Al5W in Al-rich region. J Mater Res Technol 2023;24:1792–801.
Yu E, Pan Y. Catalytic properties of borophene/MoS2 heterojunctions for hydrogen evolution reaction under different stacking conditions. J Mater Chem 2022;10:24866–76.
Sun W, Liu J, Xiang H, Zhou Y. A theoretical investigation on the anisotropic surface stability and oxygen adsorption behavior of ZrB2. J Am Ceram Soc 2016;99:4113–20.
Sihvola A. Mixing rules with complex dielectric coefficients. Subsurf Sens Technol Appl 2000;1:393–415.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
