不同化学计量碳化钛的离子辐照损伤行为研究

doi:10.15541/jim20250228

无机材料学报 ›› 2026, Vol. 41 ›› Issue (3): 322-330.DOI: 10.15541/jim20250228 CSTR: 32189.14.jim20250228

不同化学计量碳化钛的离子辐照损伤行为研究

石金瑜¹^,²(), 雷一明¹, 王晨旭³, 张洁¹(), 王京阳¹

1.中国科学院金属研究所, 沈阳 110016
2.中国科学技术大学材料科学与工程学院, 沈阳 110016
3.北京大学核物理与核技术全国重点实验室, 北京 100871

收稿日期:2025-05-26 修回日期:2025-07-14 出版日期:2025-07-31 网络出版日期:2025-07-31
通讯作者: 张洁, 研究员. E-mail: jiezhang@imr.ac.cn
作者简介:石金瑜(1996-), 男, 博士研究生. E-mail: jyshi19s@imr.ac.cn
基金资助:
国家自然科学基金(52372071);国家自然科学基金(U2441266)

Ion Irradiation Damage Behavior in Titanium Carbide with Different Stoichiometry

SHI Jinyu¹^,²(), LEI Yiming¹, WANG Chenxu³, ZHANG Jie¹(), WANG Jingyang¹

1. Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2. School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3. State Key Laboratory of Nuclear Physics and Technology, Peking University, Beijing 100871, China

Received:2025-05-26 Revised:2025-07-14 Published:2025-07-31 Online:2025-07-31
Contact: ZHANG Jie, professor. E-mail: jiezhang@imr.ac.cn
About author:SHI Jinyu (1996-), male, PhD candidate. E-mail: jyshi19s@imr.ac.cn
Supported by:
National Natural Science Foundation of China(52372071);National Natural Science Foundation of China(U2441266)

摘要/Abstract

摘要：

第四代核反应堆服役环境苛刻, 高温和强辐照对结构材料提出了更高的要求, 亟需开发新型抗辐照材料。碳化钛(TiC_x)陶瓷因其高熔点、优异的力学性能、良好的耐腐蚀性而成为先进核反应堆中极具潜力的结构材料。本研究采用3 MeV Au²⁺对不同化学计量TiC_x薄膜进行辐照实验, 系统研究了TiC_x结构缺陷、表面形貌和力学性能在不同辐照通量下的变化规律。结果表明: 随着辐照通量的增加, 近化学计量TiC_x晶格无序化程度加剧, 而亚化学计量TiC_x辐照后的结构稳定性优异。亚化学计量TiC_x辐照后表面粗糙度无明显变化且未产生辐照裂纹。此外, TiC_x辐照后的硬度和模量均呈现增加趋势, 其中亚化学计量TiC_x的抗辐照硬化能力优于近化学计量TiC_x。这主要是由于亚化学计量TiC_x的本征碳空位有效抑制了辐照缺陷的累积, 从而维持了良好的稳定性。本研究为理解化学计量与过渡金属碳/氮化合物辐照损伤之间的关系, 以及设计新型抗强辐照陶瓷新材料提供了重要的参考依据。

关键词: 碳化钛薄膜, 离子辐照, 结构分析, 表面形貌, 力学性能

Abstract:

Gen IV nuclear reactors operate in extreme service environments characterized by high temperature and intense irradiation, imposing stringent demands on structural materials and thus necessitating the development of novel irradiation resistant materials. Titanium carbide (TiC_x) ceramic is considered as promising structural material for advanced nuclear reactors, attributed to its high melting point, excellent mechanical properties, and excellent corrosion resistance. In this study, TiC_x films with different stoichiometries were irradiated with 3 MeV Au²⁺, aiming to systematically investigate irradiation-induced changes in structural characteristics, surface morphology and mechanical properties under different irradiation fluences. The results revealed that structural disorder of TiC_x intensified with increasing irradiation fluence, while the substoichiometric TiC_x maintained superior structural stability after irradiation. Surface roughness of substoichiometric TiC_x showed no significant variation after irradiation, with no irradiation-induced crack. Additionally, both hardness and elastic modulus of TiC_x exhibited an increasing trend after irradiation, demonstrating that substoichiometric TiC_x enhanced resistance to irradiation compared to near-stoichiometric counterparts. The native carbon vacancies in substoichiometric TiC_x effectively suppress accumulation of irradiation-induced defects, thereby preserving excellent stability. This study provides critical insights into the relationship between stoichiometry and irradiation damage in TiC_x, while offering valuable guidance for designing new classes of irradiation-resistant ceramic materials.

Key words: titanium carbide film, ion irradiation, structural analysis, surface morphology, mechanical property

中图分类号:

TB43

石金瑜, 雷一明, 王晨旭, 张洁, 王京阳. 不同化学计量碳化钛的离子辐照损伤行为研究[J]. 无机材料学报, 2026, 41(3): 322-330.

SHI Jinyu, LEI Yiming, WANG Chenxu, ZHANG Jie, WANG Jingyang. Ion Irradiation Damage Behavior in Titanium Carbide with Different Stoichiometry[J]. Journal of Inorganic Materials, 2026, 41(3): 322-330.

图/表 8

图1 (a~c)不同辐照通量(3 MeV Au2+)辐照后样品(a) TiC0.62、(b) TiC0.72、(c) TiC0.98的辐照损伤剂量和Au2+浓度随深度的变化; (d) 2×1016 cm-2辐照通量下样品的辐照损伤剂量随深度的变化

Fig. 1 (a-c) Damage dose and Au2+ concentration profiles induced by 3 MeV Au2+ irradiation in (a) TiC0.62, (b) TiC0.72, and (c) TiC0.98 at various fluences; (d) Damage dose profiles of samples at a fluence of 2×1016 cm-2 Colorful figures are available on website

图2 制备态及不同辐照通量辐照后TiCx薄膜的拉曼谱图

Fig. 2 Raman spectra of TiCx films before and after irradiation with various fluences (a) TiC0.62; (b) TiC0.72; (c) TiC0.98

图3 制备态及不同辐照通量辐照后TiCx薄膜的AFM表面二维形貌及三维形貌图

Fig. 3 Surface two-dimensional morphologies and three-dimensional morphologies obtained by AFM of as-deposited and irradiated TiCx films with various fluences

图4 不同辐照通量下TiCx薄膜的(a)粗糙度及(b)相对粗糙度

Fig. 4 (a) Roughness and (b) relative roughness of TiCx films under different fluences Colorful figures are available on website

图5 不同辐照通量下TiCx薄膜的高倍表面形貌

Fig. 5 High-magnification surface morphologies of TiCx films under different fluences

图6 辐照前后TiCx薄膜的(a)硬度和(b)弹性模量随辐照损伤剂量的变化

Fig. 6 (a) Variations of hardness and (b) elastic modulus of as-deposited and irradiated TiCx films with damage dose

表S1 制备态及不同辐照通量辐照后TiCx薄膜的拉曼光谱峰位

Table S1 Raman peak positions of as-deposited and irradiated TiCx films under different fluences

Sample	Fluence	Peak position/cm^-1
Sample	Fluence	TA	LA	TO
TiC_0.62	Virgin	273.69	418.55	605.78
	1×10¹⁴ cm^-2	273.58	418.32	605.83
	1×10¹⁵ cm^-2	273.52	418.33	605.80
	1×10¹⁶ cm^-2	273.60	418.22	605.81
	2×10¹⁶ cm^-2	273.55	418.55	605.79
TiC_0.72	Virgin	279.69	415.58	604.19
	1×10¹⁴ cm^-2	275.49	415.65	604.28
	1×10¹⁵ cm^-2	274.86	415.32	604.54
	1×10¹⁶ cm^-2	273.69	415.27	604.81
	2×10¹⁶ cm^-2	273.80	415.55	604.54
TiC_0.98	Virgin	277.29	416.55	595.40
	1×10¹⁴ cm^-2	275.49	416.55	598.87
	1×10¹⁵ cm^-2	273.69	416.62	604.07
	1×10¹⁶ cm^-2	271.89	416.55	605.81
	2×10¹⁶ cm^-2	270.09	416.78	605.81

图S1 不同辐照通量下TiCx薄膜的低倍表面形貌

Fig. S1 Low-magnification surface morphologies of TiCx films under different fluences

参考文献 27

[28]	LI Q, WEI Y, DING X, et al. Enhanced resistance to He ions irradi-ation damage of nanocrystalline SiC coating. Journal of Advanced Ceramics, 2025, 14: 9221067.
[29]	CHEN C C, LIANG N T, TSE W S, et al. Raman spectra of titanium nitride thin films. Chinese Journal of Physics, 1994, 32: 205.
[30]	KLEIN M V, HOLY J A, WILLIAMS W S. Raman scattering induced by carbon vacancies in TiC_x. Physical Review B, 1978, 17(4): 1546.
[31]	WARD Y, YOUNG R J, SHATWELL R A. Application of Raman microscopy to the analysis of silicon carbide monofilaments. Journal of Materials Science, 2004, 39(22): 6781.
[32]	WIPF H, KLEIN M V, WILLIAMS W S. Vacancy-induced and two-phonon Raman scattering in ZrC_x, NbC_x, HfC_x, and TaC_x. Physica Status Solidi(b)-Basic Solid State Physics, 1981, 108(2): 489.
[33]	LANG E, BEECHEM T, MCDONALD A, et al. Defect structures as a function of ion irradiation and annealing in LiNbO₃. Thin Solid Films, 2023, 768: 139719.
[34]	HU J, LI H, LI J, et al. Super-hard and tough Ta_1-_xW_xC_y films deposited by magnetron sputtering. Surface and Coatings Technology, 2020, 400: 126207.
[35]	LI H, ZHANG L, ZENG Q, et al. Structural, elastic and electronic properties of transition metal carbides TMC (TM=Ti, Zr, Hf and Ta) from first-principles calculations. Solid State Communications, 2011, 151(8): 602.
[36]	WANG R, LI B, LI P, et al. Effect of low-dose Xe²⁰⁺ ion irradiation on the deformation behavior of the magnetron sputtered Cr coatings under nanoindentation. Surface and Coatings Technology, 2021, 428: 127907.
[37]	ZHANG Y, LI B, REN Y, et al. Evolution of structural and magnetic properties of NiFe/NiO exchange biased bilayer with medium energy C⁺ ion irradiation. Journal of Alloys and Compounds, 2025, 1018: 179180.
[38]	YANG J, LU S, YANG J. Irradiation response of microstructure and mechanical properties of NbMoVCr multi-principal element alloy coatings. Surface and Coatings Technology, 2024, 492: 131209.
[39]	ZHANG W, DENG J, ZHONG Y, et al. Microstructure response and LBE corrosion behavior of the FeCrAlY coating after Au-ions irradiation. Corrosion Science, 2024, 241: 112521.
[40]	ZHONG Y, ZHANG W, YANG J, et al. Study on LBE corrosion failure of FeAl/Al₂O₃ coatings after ion irradiation. Materials & Design, 2024, 242: 113019.
[41]	FU T, ZHU Y, PAN H, et al. Irradiation softening in a uranium containing NbTiZrU high entropy alloy induced by Xe ion implantation. Materials Today Communications, 2025, 42: 111231.
[42]	MONNET G. Multiscale modeling of irradiation hardening: application to important nuclear materials. Journal of Nuclear Materials, 2018, 508: 609.
[43]	HUANG Q, LEI G, LIU R, et al. Microstructure, hardness and modulus of carbon-ion-irradiated new SiC fiber (601-4). Journal of Nuclear Materials, 2018, 503: 91.
[44]	PELLEGRINO S, CROCOMBETTE J P, DEBELLE A, et al. Multi-scale simulation of the experimental response of ion-irradiated zirconium carbide: Role of interstitial clustering. Acta Materialia, 2016, 102: 79.
[1]	DONG D, GUAN J, WANG Z, et al. Current status and trends of nuclear energy under carbon neutrality conditions in China. Energy, 2025, 314: 134253.
[2]	OUYANG Q, WANG Y F, XU J, et al. Research progress of SiC fiber reinforced SiC composites for nuclear application. Journal of Inorganic Materials, 2022, 37(8): 822.
[3]	ZINKLE S J, SNEAD L L. Designing radiation resistance in materials for fusion energy. Annual Review of Materials Research, 2014, 44(1): 241.
[4]	ZINKLE S J, BUSBY J T. Structural materials for fission & fusion energy. Materials Today, 2009, 12(11): 12.
[5]	杜进隆, 徐川, 付恩刚. 基于界面和纳米析出相材料的抗辐照损伤机制研究进展. 科学通报, 2023, 68(9): 1125.
[6]	HAN W Z, DEMKOWICZ M J, FU E G, et al. Effect of grain boundary character on sink efficiency. Acta Materialia, 2012, 60(18): 6341.
[7]	HAN W, DEMKOWICZ M J, MARA N A, et al. Design of radiation tolerant materials via interface engineering. Advanced Materials, 2013, 25(48): 6975.
[8]	YU K Y, BUFFORD D, KHATKHATAY F, et al. In situ studies of irradiation-induced twin boundary migration in nanotwinned Ag. Scripta Materialia, 2013, 69(5): 385.
[9]	DU J, JIANG S, CAO P, et al. Superior radiation tolerance via reversible disordering-ordering transition of coherent superlattices. Nature Materials, 2023, 22(4): 442.
[10]	XUE J X, ZHANG G J, GUO L P, et al. Improved radiation damage tolerance of titanium nitride ceramics by introduction of vacancy defects. Journal of the European Ceramic Society, 2014, 34(3): 633.
[11]	魏博鑫. 高抗辐照损伤容限ZrC_x陶瓷的制备与环境损伤行为. 哈尔滨: 哈尔滨工业大学博士学位论文, 2018.
[12]	陈丽娜. 先进核能系统用碳化锆陶瓷涂层的制备与性能研究. 合肥: 中国科学技术大学博士学位论文, 2021.
[13]	SHI J, CHEN L, LEI Y, et al. Irradiation damage of zirconium carbide with different stoichiometry. Vacuum, 2025, 239: 114355.
[14]	AGARWAL S, KOYANAGI T, BHATTACHARYA A, et al. Neutron irradiation-induced microstructure damage in ultra-high temperature ceramic TiC. Acta Materialia, 2020, 186: 1.
[15]	NOSEK A, CONZEN J, DOESCHER H, et al. Thermomechanics of candidate coatings for advanced gas reactor fuels. Journal of Nuclear Materials, 2007, 371(1/2/3): 288.
[16]	TANG C, STUEBER M, SEIFERT H J, et al. Protective coatings on zirconium-based alloys as accident-tolerant fuel (ATF) claddings. Corrosion Reviews, 2017, 35(3): 141.
[17]	AGARWAL S, TROCELLIER P, VAUBAILLON S, et al. Diffusion and retention of helium in titanium carbide. Journal of Nuclear Materials, 2014, 448(1/2/3): 144.
[18]	WEINBERGER C R, THOMPSON G B. Review of phase stability in the group IVB and VB transition-metal carbides. Journal of the American Ceramic Society, 2018, 101(10): 4401.
[19]	LIPATNIKOV V N, KOTTAR A, ZUEVA L V, et al. Ordering effects in nonstoichiometric titanium carbide. Inorganic Materials, 2000, 36(2): 155.
[20]	GAVARINI S, MILLARD-PINARD N, GARNIER V, et al. Elaboration and behavior under extreme irradiation conditions of nano-and micro-structured TiC. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 2015, 356/357: 114.
[21]	PELLEGRINO S, TROCELLIER P, THOMÉ L, et al. Raman investigation of ion irradiated TiC and ZrC. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 2019, 454: 61.
[22]	SHI J, LEI Y, WANG C, et al. Microstructure evolution in titanium carbide with different stoichiometry under 3 MeV Au²⁺ ion irradiation. Journal of Nuclear Materials, 2025, 606: 155609.
[23]	徐川, 付恩刚. 北京大学1.7 MV串列静电加速器的离子注入/辐照实验系统. 原子核物理评论, 2021, 38(4): 410.
[24]	WEBER W J, ZHANG Y. Predicting damage production in monoatomic and multi-elemental targets using stopping and range of ions in matter code: challenges and recommendations. Current Opinion in Solid State and Materials Science, 2019, 23(4): 100757.
[25]	JIANG M, XIAO H Y, ZHANG H B, et al. A comparative study of low energy radiation responses of SiC, TiC and ZrC. Acta Materialia, 2016, 110: 192.
[26]	HANSON W A, PATEL M K, CRESPILLO M L, et al. Ionizing vs collisional radiation damage in materials: separated, competing, and synergistic effects in Ti₃SiC₂. Acta Materialia, 2019, 173: 195.
[27]	KITAJIMA M. Defects in crystals studied by Raman scattering. Critical Reviews in Solid State and Materials Sciences, 1997, 22(4): 275.

不同化学计量碳化钛的离子辐照损伤行为研究

Ion Irradiation Damage Behavior in Titanium Carbide with Different Stoichiometry

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