Role of Rare Earth Oxide Modification in Strengthening ZrB2-SiC Composites Against Oxidation and Cyclic Ablation

Mengen Hu, Xian Dang, Chengwan Yang, Kewei Li, Hanwen Zhang, Zhen Wang, Shuxin Li, Yuebin Li, Xiaoye Hu, Yue Li, Abdumutolib Atakhanov, Zhulin Huang, Guowen Meng

Extreme Materials ›› 2026

Extreme Materials ›› 2026 DOI: 10.1016/j.exm.2025.12.001

作者信息 +

Role of Rare Earth Oxide Modification in Strengthening ZrB2-SiC Composites Against Oxidation and Cyclic Ablation

Author information +
文章历史 +

Abstract

ZrB2-20SiC (ZS20) composite and its derivatives doped with 5 vol% Sc2O3, Y2O3, and La2O3 were densified using hot press sintering to investigate the influence of rare earth oxides on their high temperature oxidation and ablation behavior. Isothermal oxidation testing at 1773 K indicate that rare earth oxides modification lowers activation energy and slightly accelerates weight gain during the initial phase. As oxidation progresses, the weight gain of ZS20 increases sharply. The sample doped with La2O3 (ZS20L5) exhibits the lowest oxidation weight gain, with a porosity of only 1.8% after oxidation. Cyclic ablation tests at the middle-low temperature zones indicate that ZS20L5 exhibits the lowest linear and mass ablation rates. Thermodynamic analyses demonstrate that La2O3 preferentially reacts with SiO2 to form La2Si2O7, which demonstrates a more effective oxygen barrier property compared to ZrSiO4. Additionally, La2O3 enhances the fluidity of the glass phase, effectively filling cracks, sealing pores, and blocking the penetration of oxygen.

Key words

ZrB2-SiC composites / rare earth / doping modification / oxidation resistance / ablation resistance

引用本文

导出引用
Mengen Hu, Xian Dang, Chengwan Yang, . [J]. Extreme Materials. 2026 https://doi.org/10.1016/j.exm.2025.12.001
Mengen Hu, Xian Dang, Chengwan Yang, et al. Role of Rare Earth Oxide Modification in Strengthening ZrB2-SiC Composites Against Oxidation and Cyclic Ablation[J]. Extreme Materials. 2026 https://doi.org/10.1016/j.exm.2025.12.001

参考文献

[1]
Z.H. Wen, Y.W. Liu, J. Yang, Y.H. Chen, Y.M. Fu, L. Zhuang, H.L. Yu, Y.H. Chu, Exceptional Oxidation Resistance of High-Entropy Carbides up to 3600 °C, Adv. Mater. ( 2025) 2507254, https://doi.org/10.1002/adma.202507254.
[2]
Y.R. Lin, T. Koyanagi, D.J. Sprouster, C.M. Petrie, W. Fahrenholtz, G.E. Hilmas, Y. Katoh, Response of 11B enriched ZrB2 ultra-high temperature ceramic to neutron irradiation at elevated temperatures, Acta Mater. 276 ( 2024) 120111, https://doi.org/10.1016/j.actamat.2024.120111.
[3]
C. Fang, S. Dong, X.H. Zhang, Y.C. Zhou, Breaking the 3000 °C melting temperature barrier of oxide ceramics, J. Adv. Ceram. ( 2025), https://doi.org/10.26599/JAC.2025.9221193.
[4]
B.R. Golla, A. Mukhopadhyay, B. Basu, S.K. Thimmappa, Review on ultra-high temperature boride ceramics, Prog. Mater Sci. 111 ( 2020) 100651, https://doi.org/10.1016/j.pmatsci.2020.100651.
[5]
Q.Y. Deng, P.F. He, C. Sun, Y. Li, Y. Xing, Y.J. Wang, J.L. Li, X.B. Liang, X. Wang, Y.J. Zhou, Y.J. Cai, High speed laser cladding as a new approach to prepare ultra-high temperature ceramic coatings, J. Adv. Ceram. 13 ( 2024) 143-154, https://doi.org/10.26599/jac.2024.9220827.
[6]
D.W. Ni, Y. Cheng, J.P. Zhang, J.X. Liu, J. Zou, B.W. Chen, H.Y. Wu, H.J. Li, S.M. Dong, J.C. Han, X.H. Zhang, Q.G. Fu, G.J. Zhang, Advances in ultra-high temperature ceramics, composites, and coatings, J. Adv. Ceram. 11 ( 2022) 1-56, https://doi.org/10.1007/s40145-021-0550-6.
[7]
N.P. Padture, Advanced structural ceramics in aerospace propulsion, Nat. Mater. 15 ( 2016) 804-809, https://doi.org/10.1038/nmat4687.
[8]
K.W. Li, Z.L. Huang, J.Y. Yuan, X.Y. Li, Z. Wang, M.E. Hu, T.X. Wang, X.Y. Hu, Y. Li, X.H. Zhang, Synthesis and growth mechanism of highly crystalized multi-branched HfB2 microrods with self-toughening effect, Mater. Des. 244 ( 2024) 113196, https://doi.org/10.1016/j.matdes.2024.113196.
[9]
X. Dang, Z.L. Huang, J.Y. Yuan, K. Li, M.G. Hu, Z.M. Xie, H.R. Song, B.S. Chen, X.Y. Li, M. Li, X.Y. Hu, Y. Li,Improved spectral emissivity and mechanical properties of high-entropy (Ti0.2Zr0.2Nb0.2Mo0.2Hf0.2)B2 derived from boro/carbothermal reduction, J. Eur. Ceram. Soc. 44 ( 2024) 4410-4424, https://doi.org/10.1016/j.jeurceramsoc.2024.01.091.
[10]
R. Naraparaju, K. Maniya, A. Murchie, W.G. Fahrenholtz, G.E. Hilmas, Effect of moisture on the oxidation behavior of ZrB2, J. Am. Ceram. Soc. 104 ( 2021) 1058-1066, https://doi.org/10.1111/jace.17500.
[11]
B.C. Wyatt, S.K. Nemani, G.E. Hilmas, E.J. Opila, B. Anasori, Ultra-high temperature ceramics for extreme environments, Nat. Rev. Mater. 9 ( 2024) 773-789, https://doi.org/10.1038/s41578-023-00619-0.
[12]
Z. Wang, Y. Cheng, K.W. Li, M.G. Hu, H.W. Zhang, X. Dang, M. Li, X.Y. Li, Z.L. Huang, Y. Li, X.Y. Hu,Growth mechanism and sintering properties of high crystallinity Archimedean polyhedral (Zr0.5Hf0.5)B2 nanoparticles, J. Eur. Ceram. Soc. 45 ( 2025) 117251, https://doi.org/10.1016/j.jeurceramsoc.2025.117251.
[13]
Z.Y. Tang, Z.H. Wen, L. Zhuang, H.L. Yu, Y.H. Chu, Enhanced oxidation resistance of high-entropy diborides by multi-component synergistic effects, Sci. China Mater. 67 ( 2024) 3392-3400, https://doi.org/10.1007/s40843-024-3045-4.
[14]
F.C. Liu, B.W. Chen, D.W. Ni, Q. Wang, F.Y. Cai, C.J. Liao, H.D. Wang, Y.S. Ding, S.M. Dong, Cyclic ablation mechanisms of the YB4-CrSi2 surface-modified Cf/ZrB2-SiC composites at 2600 °C, Corros. Sci. 255 ( 2025) 113091, https://doi.org/10.1016/j.corsci.2025.113091.
[15]
L.Y. Yang, S. Dong, T.Y. Cui, J.Q. Xin, G.Q. Chen, C.Q. Hong, X.H. Zhang, Novel gradient ZrB2-MoSi2-SiC dense layer with enhanced emissivity and long-term oxidation resistance at ultra-high temperatures, Rare Met. 44 ( 2025) 2043-2058, https://doi.org/10.1007/s12598-024-02959-4.
[16]
C. Young, C. Zhang, A. Loganathan, P. Nautiyal, B. Boesl, A. Agarwal, Densification and oxidation behavior of spark plasma sintered Hafnium Diboride-Hafnium Carbide composite, Ceram. Int. 46 ( 2020) 14625-14631, https://doi.org/10.1016/j.ceramint.2020.02.263.
[17]
T.A. Parthasarathy, R.A. Rapp, M. Opeka, R.J. Kerans, Effects of Phase Change and Oxygen Permeability in Oxide Scales on Oxidation Kinetics of ZrB2 and HfB2, J. Am. Ceram. Soc. 92 ( 2009) 1079-1086, https://doi.org/10.1111/j.1551-2916.2009.03031.x.
[18]
S.B. Sun, H.B. Wang, X.M. Liu, C. Liu, H. Lu, Z.R. Nie, X.Y. Song, Outstanding anti-oxidation performance of boride coating under high-temperature friction, Corros. Sci. 179 ( 2021) 109133, https://doi.org/10.1016/j.corsci.2020.109133.
[19]
M.M. Chen, X.Y. Yao, G.H. Feng, Y. Guo, Anti-ablation performance of La2O3-modified ZrB2 coating on SiC-coated carbon/carbon composites, Ceram. Int. 46 ( 2020) 28758-28766, https://doi.org/10.1016/j.ceramint.2020.08.038.
[20]
S.K. Thimmappa, B.R. Golla, V.V.B. Prasad, Oxidation Behavior of Silicon-Based Ceramics Reinforced Diboride UHTC: a Review, Silicon 14 ( 2022) 12049-12074, https://doi.org/10.1007/s12633-022-01945-8.
[21]
S.J. Sun, Z. Ma, Y.B. Liu, L. Liu, F.C. Wang, X.T. Luan, Ablation mechanism and properties of SiO2 modified ZrB2-SiC coatings fabricated on C/C composites via plasma spraying technology, Surf. Coat. Technol. 381 ( 2020) 125132, https://doi.org/10.1016/j.surfcoat.2019.125132.
[22]
Y.X. Liu, H. Wang, J.C. Hao, Y.H. Cheng, S. Dong, P. Hu, W.B. Han, X.H. Zhang, Key materials for extreme high-temperature environments: Ultra-high-temperature ceramics and their composites, Extreme Mater. 1 ( 2025) 38-66, https://doi.org/https://doi.org/10.1016/j.exm.2025.01.001.
[23]
J. Binner, M. Porter, B. Baker, J. Zou, V. Venkatachalam, V.R. Diaz, A. D'Angio, P. Ramanujam, T.L. Zhang, T. Murthy, Selection, processing, properties and applications of ultra-high temperature ceramic matrix composites, UHTCMCs-a review, Int. Mater. Rev. 65 ( 2020) 389-444, https://doi.org/10.1080/09506608.2019.1652006.
[24]
X.R. Ren, H.L. Shi, W.H. Wang, H.A. Chu, P. Chen, P.Z. Feng, L.T. Guo, Z.Y. Li, Influence of the ZrB2 content on the anti-oxidation ability of ZrB2-SiC coatings in aerobic environments with broad temperature range, J. Eur. Ceram. Soc. 40 ( 2020) 203-211, https://doi.org/10.1016/j.jeurceramsoc.2019.10.006.
[25]
Z. Kovácová, L. Orovcík, J. Sedlácek, L. Baca, E. Dobrocka, M. Kitzmantel, E. Neubauer, The effect of YB4 addition in ZrB2-SiC composites on the mechanical properties and oxidation performance tested up to 2000 °C, J. Eur. Ceram. Soc. 40 ( 2020) 3829-3843, https://doi.org/10.1016/j.jeurceramsoc.2020.03.060.
[26]
H. Yang, H.S. Zhao, T.W. Wang, X.X. Liu, K.H. Zhang, Z.Q. Li, Y. Gao, B. Liu, A multi-layered SiC coating to protect graphite spheres from high temperature oxidation in static air, Corros. Sci. 183 ( 2021) 109325, https://doi.org/10.1016/j.corsci.2021.109325.
[27]
Y. Lyu, B.H. Du, G.Q. Chen, G.D. Zhao, Y. Cheng, S.B. Zhou, Q.R. Lv, X.H. Zhang, W.B. Han, Microstructural regulation, oxidation resistance, and mechanical properties of Cf/SiC/SiHfBOC composites prepared by chemical vapor infiltration with precursor infiltration pyrolysis, J. Adv. Ceram. 11 ( 2022) 120-135, https://doi.org/10.1007/s40145-021-0521-y.
[28]
J.S. Lv, W. Li, T. Li, B. Gao, J.C. Li, Y.Q. Fu, L.X. Guo, Y.L. Zhang, Multicomponent (Hf-Zr-Ta)B2 coatings for carbon/carbon composites and structural optimization enabling superior ablation resistance, J. Mater. Sci. Technol. 204 ( 2025) 115-126, https://doi.org/10.1016/j.jmst.2024.03.050.
[29]
X.R. Ren, P.P. Wang, Y.X. Chen, W. Xie, X. Ji, Z.C. Shang, C.S. Ji, J. Zhao, H.Q. Liu, G.Z. Lv, P.Z. Feng, Advances in ultra-high-temperature ceramic coatings with enhanced oxidation resistance for carbon-based composites, Extreme Mater. 1 ( 2025) 9-43, https://doi.org/https://doi.org/10.1016/j.exm.2025.07.003.
[30]
B.W. Chen, D.W. Ni, W.C. Bao, C.J. Liao, W. Luo, E.R. Song, S.M. Dong, Engineering Cf/ZrB2-SiC-Y2O3 for Thermal Structures of Hypersonic Vehicles with Excellent Long-Term Ultrahigh Temperature Ablation Resistance, Adv. Sci. 10 ( 2023) 2304254, https://doi.org/10.1002/advs.202304254.
[31]
L. Silvestroni, H.T. Liu, D. Sciti, X.G. Wang, G.J. Zhang, Rare earth-doped ZrB2-MoSi2 ceramics: Densification and oxidation behavior, J. Eur. Ceram. Soc. 45 ( 2025) 116992, https://doi.org/10.1016/j.jeurceramsoc.2024.116992.
[32]
H. Lin, Y.Y. Liu, W.P. Liang, Q. Miao, S.Y. Zhou, J.Y. Sun, Y. Qi, X.G. Gao, Y.D. Song, K. Ogawa, Effect of the Y2O3 amount on the oxidation behavior of ZrB2-SiC-based coatings for carbon/carbon composites, J. Eur. Ceram. Soc. 42 ( 2022) 4770-4782, https://doi.org/10.1016/j.jeurceramsoc.2022.05.006.
[33]
M.G. Hu, L. Liu, Z. Wang, X. Dang, C.W. Yang, X.Y. Li, M. Li, X.Y. Hu, Y. Li, Z.L. Huang, X.H. Zhang, La2O3 stabilized WB2-SiC composites with remarkable ablation resistance up to 2273 K, J. Eur. Ceram. Soc. 45 ( 2025) 117298, https://doi.org/10.1016/j.jeurceramsoc.2025.117298.
[34]
D.Y. Qian, Y.X. Chen, X.R. Ren, L.Y. Wang, J.P. Chen, Y. Zhao, D.L. Shi, Y. Li, H.B. Du, P.Z. Feng, Effect of La2O3 content on the oxygen barrier ability of the HfB2-SiC coating at 1973 K, J. Am. Ceram. Soc. 106 ( 2023) 2155-2168, https://doi.org/10.1111/jace.18876.
[35]
B. Liu, J. Sun, L.X. Guo, H.L. Shi, G.H. Feng, L. Feldmann, X.M. Yin, R. Riedel, Q.G. Fu, H.J. Li, Materials design of silicon based ceramic coatings for high temperature oxidation protection, Mater. Sci. Eng. R 163 ( 2025) 100936, https://doi.org/10.1016/j.mser.2025.100936.
[36]
H.C. Ma, Q. Miao, W.P. Liang, Y.Y. Liu, H. Lin, H.R. Ma, S.W. Zuo, L. Xue, High temperature oxidation resistance of Y2O3 modified ZrB2-SiC coating for carbon/carbon composites, Ceram. Int. 47 ( 2021) 6728-6735, https://doi.org/10.1016/j.ceramint.2020.11.015.
[37]
S. Stemmer, Thermodynamic considerations in the stability of binary oxides for alternative gate dielectrics in complementary metal-oxide-semiconductors, J. Vac. Sci. Technol. B 22 ( 2004) 791-800, https://doi.org/10.1116/1.1688357.
[38]
M.E. Hu, Z.L. Huang, X.Y. Li, Y. Cheng, Z. Wang, K.W. Li, T.X. Wang, X.Y. Hu, Y. Li, X.H. Zhang, Ultrafine ZrB2 Ceramic Powders Prepared by a Sol-Gel Method Synergized with a Carbothermic Reaction and Their Improved Sintering Performance, ACS Appl. Eng. Mater. 1 ( 2023) 769-779, https://doi.org/10.1021/acsaenm.2c00195.
[39]
A. Vinci, L. Zoli, P. Galizia, D. Sciti, Influence of Y2O3 addition on the mechanical and oxidation behaviour of carbon fibre reinforced ZrB2/SiC composites, J. Eur. Ceram. Soc. 40 ( 2020) 5067-5075, https://doi.org/10.1016/j.jeurceramsoc.2020.06.043.
[40]
Muksin D.H. Yoon K. Raju, Effects of Sc2O3 sintering aid for the densification and mechanical properties of SiC-ZrB2 composites, Ceram. Int. 42 ( 2016) 7300-7308, https://doi.org/10.1016/j.ceramint.2016.01.126.
[41]
W. Xu, L. Shi, Y.H. Zheng, Transient analysis of nuclear graphite oxidation for high temperature gas Cooled reactor, Nucl. Eng. Des. 306 ( 2016) 138-144, https://doi.org/10.1016/j.nucengdes.2016.04.029.
[42]
Z.H. Wen, Z.Y. Tang, H. Meng, Y.H. Chu, A promising new class of high-entropy ceramics: High-entropy oxycarbides with good oxidation resistance, Corros. Sci. 207 ( 2022) 110574, https://doi.org/10.1016/j.corsci.2022.110574.
[43]
Z.H. Wen, Z.Y. Tang, H. Meng, L. Zhuang, H.L. Yu, Y.H. Chu, Ultrafast synthesis of high-entropy carbides up to 3,273 K for superior oxidation resistance, Cell Rep. Phys. Sci. 5 ( 2024) 101821, https://doi.org/10.1016/j.xcrp.2024.101821.
[44]
Y.Q. Li, T. Qiu, Oxidation behaviour of boron carbide powder, Mater. Sci. Eng. A 444 ( 2007) 184-191, https://doi.org/10.1016/j.msea.2006.08.068.
[45]
W.N. Tan, M. Adducci, R. Trice, Evaluation of Rare-Earth Modified ZrB2-SiC Ablation Resistance Using an Oxyacetylene Torch, J. Am. Ceram. Soc. 97 ( 2014) 2639-2645, https://doi.org/10.1111/jace.12991.
[46]
T.A. Parthasarathy, R.A. Rapp, M. Opeka, M.K. Cinibulk, Modeling Oxidation Kinetics of SiC-Containing Refractory Diborides, J. Am. Ceram. Soc. 95 ( 2012) 338-349, https://doi.org/10.1111/j.1551-2916.2011.04927.x.
[47]
J. Zhou, C.X. Ren, C.L. Tian, M. Omran, J. Tang, F. Zhang, G. Chen, The phase-stabilized behavior of Sc2O3-Y2O3 co-doped ZrO2 nanopowders by co-precipitation synthesis, Ceram. Int. 50 ( 2024) 24823-24834, https://doi.org/10.1016/j.ceramint.2024.04.218.
[48]
H. Jeon, I. Lee, Y. Oh, Changes in high-temperature thermal properties of modified YSZ with various rare earth doping elements, Ceram. Int. 48 ( 2022) 8177-8185, https://doi.org/10.1016/j.ceramint.2021.12.020.
[49]
Z.T. Tabari, S.Z. Heris, Heat Transfer Performance of Milk Pasteurization Plate Heat Exchangers Using MWCNT/Water Nanofluid, J. Dispersion Sci. Technol. 36 ( 2015) 196-204, https://doi.org/10.1080/01932691.2014.894917.
[50]
W. Xie, Q.G. Fu, C.Y. Cheng, N.N. Yan, Experimental and theoretical study on the effect of different rare-earth oxides on the high-temperature stability of SiO2 glass at 1973K, Ceram. Int. 46 ( 2020) 24371-24378, https://doi.org/10.1016/j.ceramint.2020.06.219.
[51]
M. Chromcíková, A.A. Osipov, L.M. Osipova, B. Hruska, J. Michálková, A. Nowicka, J.A. Peterson, M. Liska, Thermodynamic model and Raman spectra of binary barium borate glassforming melts, J. Therm. Anal. Calorim. 142 ( 2020) 945-951, https://doi.org/10.1007/s10973-020-09329-z.
[52]
Y.X. Zhang, H.R. Li, S.Y. Liu, N.N. Wu, S.L. OuYang, Raman spectroscopic study of irregular network in the process of glass conversion to CaO-MgO-Al2O3-SiO2 glass-ceramics, J. Non-Cryst. Solids 563 ( 2021) 120701, https://doi.org/10.1016/j.jnoncrysol.2021.120701.
[53]
D.Y. Qian, Y.X. Chen, X.R. Ren, L.Y. Wang, J.P. Chen, Y. Zhao, D.L. Shi, Y. Li, H.B. Du, P.Z. Feng, Effect of La2O3 content on the oxygen barrier ability of the HfB2-SiC coating at 1973 K, J. Am. Ceram. Soc. 106 ( 2023) 2155-2168, https://doi.org/10.1111/jace.18876.

脚注


Accesses

Citation

Detail

段落导航
相关文章

/