The effect of nitrogen doping on the ablation resistance of zirconium carbide ceramics

Zirconium carbide, an ultra-high temperature ceramic, has garnered considerable interest recently as a structural material for conditions marked by severe erosion and elevated-temperature oxidation. However, poor oxidation resistance is the main drawback that impedes its application in extreme environments.

Recent investigations indicate that solid solution combinations of metal carbides and metal nitrides have considerable high-temperature stability. However, related research on the nitrogen doping of zirconium carbide ultra-high temperature ceramics and their ablation-resistant properties remains limited. A team of material scientists from the National University of Defense Technology in China, recently investigates a series of zirconium carbonitride and clarified probable ablation resistance mechanisms using experimental and ab initio molecular dynamics simulations, representing the first analysis of such ultra-high melting point ceramics from the perspective of structural development during the oxidation process. Transmission electron microscopy (TEM) analysis reveals the precipitation of nanocarbon and Zr-C-N-O phases at the interface between the oxidized and unoxidized regions following nitrogen doping. This study underscores nitrogen doping as a promising strategy to improve the ablation resistance of UHTCs, offering valuable insights for their application in demanding conditions.

The team published their work in Journal of Advanced Ceramics on March 27, 2025.

“This study investigates a series of zirconium carbonitride and elucidates the underlying ablative mechanisms using ab initio molecular dynamics simulations. Additionally, the composition and microstructural evolution of nitrogen-doped zirconium carbides during ablation process at 3000 ℃ are demonstrated. Notably, the ZrC_0.47N_0.53 sample exhibits exceptional ablation-resistant properties, positioning it as a promising candidate for applications in extreme environments.” said Si’an Chen, the corresponding author of the paper in the college of Aerospace Science and Engineering at National University of Defense Technology.

“We surprisingly discovered that the inner layer of the cross-section for the ablated samples, demonstrates remarkable adaptation with the substrate. Through TEM analysis, we discovered that the formation of a gradient oxide/carbide interface with nanocarbons and Zr-C-N-O phases helped mitigate the thermal expansion mismatch.” said Si’an Chen.

“AIMD simulations further uncovered a temperature-dependent oxidation mechanism: below 2700 K, nitrogen forms strong Zr-N bonds, creating a protective Zr-C-N-O network. Above 2700 K, some nitrogen atoms escape as gas, but the remaining oxide network maintains structural continuity through topological reconstruction, preventing mechanical spalling.” said Zheng Peng, the first author of the paper in the college of Aerospace Science and Engineering at National University of Defense Technology.

“The AIMD simulations reproduce essential processes derived from experiments, providing atomic-level validation and explanation for the improved thermostability and ablation resistance of ZrCN.” said Zheng Peng. This research provides a new atomic-scale design framework and theoretical support for developing advanced UHTCs for extreme environments.

However, more delicate research works are still needed to explore the suitability of ZrC_xN_y as a structural material for thermal protection systems. Additionally, Zheng Peng proposed an indispensable developmental direction: enhancing the thermal shock resistance of composites by incorporating whiskers and fibers to mitigate the inherent brittleness of ultrahigh-temperature ceramics.

Other contributors include Yingjie Cui and Zengsheng Ma from the School of Materials Science and Engineering at Xiangtan University in Hunan, China; Jianbo Song from the college of Aerospace Science and Engineering at National University of Defense Technology; Fuhua Cao from the School of Materials Science and Engineering at Central South University in Hunan, China.

This work was supported by the National Natural Science Foundation of China (52302128) and the Foundation of State Key Laboratory of Science and Technology on Advanced Ceramic Fibers and Composites (No. 6142907230303).

About Author

Zheng Peng has extensively researched high-temperature and ultra-high-temperature ceramic-based thermal protection composite materials at the National University of Defense Technology. She innovatively proposed and conducted research on nitrogen-doped carbon sublattice ceramic matrix composites to meet the urgent needs of the new generation of hypersonic vehicles for thermal protection systems, achieving breakthroughs in the design and preparation of new ultra-high melting point and ablation-resistant thermal protection materials.

About Journal of Advanced Ceramics

Journal of Advanced Ceramics (JAC) is an international academic journal that presents the state-of-the-art results of theoretical and experimental studies on the processing, structure, and properties of advanced ceramics and ceramic-based composites. JAC is Fully Open Access, monthly published by Tsinghua University Press, and exclusively available via SciOpen. JAC’s 2023 IF is 18.6, ranking in Top 1 (1/31, Q1) among all journals in “Materials Science, Ceramics” category, and its 2023 CiteScore is 21.0 (top 5%) in Scopus database. ResearchGate homepage: https://www.researchgate.net/journal/Journal-of-Advanced-Ceramics-2227-8508

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