在碳化物陶瓷中构筑金属原子层分相共生结构

doi:10.15541/jim20240284

无机材料学报 ›› 2025, Vol. 40 ›› Issue (1): 17-22.DOI: 10.15541/jim20240284 CSTR: 32189.14.10.15541/jim20240284

在碳化物陶瓷中构筑金属原子层分相共生结构

鲍伟超¹(), 郭晓杰¹, 辛晓婷¹^,³, 彭湃², 王新刚¹, 刘吉轩², 张国军², 许钫钫¹()

1.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050
2.东华大学功能材料研究中心, 纤维材料改性国家重点实验室, 上海 201620
3.中国科学院大学材料科学与光电子功能中心, 北京 100049

收稿日期:2024-06-11 修回日期:2024-07-15 出版日期:2025-01-20 网络出版日期:2024-07-26
通讯作者: 许钫钫, 研究员. E-mail: ffxu@mail.sic.ac.cn
作者简介:鲍伟超(1988-), 男, 副研究员. E-mail: baoweichao@mail.sic.ac.cn
基金资助:
国家自然科学基金(52032001);国家自然科学基金(52102081);上海市无机非金属材料分析测试表征专业技术服务平台(19DZ2290700)

Establishment of Symbiotic Structure with Metal Atomic-layer Phase-separation in Carbide Ceramics

BAO Weichao¹(), GUO Xiaojie¹, XIN Xiaoting¹^,³, PENG Pai², WANG Xingang¹, LIU Jixuan², ZHANG Guojun², XU Fangfang¹()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Institute of Functional Materials, Donghua University, Shanghai 201620, China
3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-06-11 Revised:2024-07-15 Published:2025-01-20 Online:2024-07-26
Contact: XU Fangfang, professor. E-mail: ffxu@mail.sic.ac.cn
About author:BAO Weichao (1988-), male, associate professor. E-mail: baoweichao@mail.sic.ac.cn
Supported by:
National Natural Science Foundation of China(52032001);National Natural Science Foundation of China(52102081);Shanghai Technical Platform for Testing and Characterization on Inorganic Materials(19DZ2290700)

摘要/Abstract

摘要：

在保持结构陶瓷高硬度的同时提高其韧性和塑性, 可以显著拓展其在极端环境中的应用前景, 其中微结构设计是一项重要策略。本工作研究了在碳化物陶瓷中构筑金属单原子层分相共生结构的可行性。以过渡金属单质、石墨和少量Al为原材料, 采用放电等离子体烧结工艺在1900 ℃和30 MPa压力下制备不同组元数的过渡金属碳化物陶瓷, 发现只有高熵(TiZrHfNbTa)C陶瓷形成了Al原子层分相共生结构。该结构不是长程序的单相化合物(如MAX相), 而是一种无周期性的碳化物和金属单原子层交叉堆叠的复合物。通过纳米至原子尺度的球差校正透射电子显微镜和能谱表征, 揭示了少量Al单原子层无周期性地嵌入高熵碳化物面心立方结构的{111}面。结合第一性原理计算, 发现形成原子层分相共生结构的关键因素不是Al在不同碳化物晶格中的扩散差异, 而是高熵带来的热力学稳定性、晶格畸变和迟滞扩散效应等。本研究有助于推动结构陶瓷中原子尺度微结构的设计和调控, 从而获得硬度-强度-韧性综合力学性能优异的结构陶瓷。

关键词: 结构陶瓷, 高熵碳化物陶瓷, 金属原子层分相, 共生结构

Abstract:

Microstructural design is a promising strategy to enhance the toughness and plasticity of structural ceramics while maintaining their inherently excellent hardness, which can facilitate their applications in extreme environments. In this work, the possibility of establishing a symbiotic structure with metal atomic-layer phase-separation (MALPS) in carbide structural ceramics was investigated. The carbide ceramic samples were synthesized from raw materials comprising transition metals with different component numbers, graphite powders, and a small amount of aluminum by spark plasma sintering at 1900 ℃ and under a pressure of 30 MPa. It was found that Al-MALPS structure was observed exclusively in the high-entropy (TiZrHfNbTa)C ceramic, which was not a MAX phase with long-range-order but rather a composite featuring a non-periodic cross-stacking of single metal atomic layers within the carbide matrix. Characterization by spherical aberration correction transmission electron microscopy and energy dispersive spectroscopy from nanometer to atomic scales revealed that the single Al atomic layers were sparsely embedded onto the {111} planes of the carbide face-centered cubic structure. Combined with the first-principles calculations, the formation of MALPS structure was found to be driven by thermodynamic stability, lattice distortion, and sluggish-diffusion effect of high entropy, rather than the differential diffusion of Al in various carbide lattices. This work could promote the design and regulation of atomic-scale microstructures in structural ceramics, aiming for high performance with synergetic high hardness-strength-toughness.

Key words: structural ceramic, high-entropy carbide ceramic, metal atomic-layer phase-separation, symbiotic structure

中图分类号:

TQ174
P575

鲍伟超, 郭晓杰, 辛晓婷, 彭湃, 王新刚, 刘吉轩, 张国军, 许钫钫. 在碳化物陶瓷中构筑金属原子层分相共生结构[J]. 无机材料学报, 2025, 40(1): 17-22.

BAO Weichao, GUO Xiaojie, XIN Xiaoting, PENG Pai, WANG Xingang, LIU Jixuan, ZHANG Guojun, XU Fangfang. Establishment of Symbiotic Structure with Metal Atomic-layer Phase-separation in Carbide Ceramics[J]. Journal of Inorganic Materials, 2025, 40(1): 17-22.

图/表 6

图1 (TiZrHfNbTa)C高熵陶瓷样品的微观结构表征

Fig. 1 Microstructure characterization of (TiZrHfNbTa)C high-entropy ceramic sample (a) High angle annular dark field (HAAFD) image and EDS elemental mappings; High-resolution electron microscope (HREM) images of (b) face-centered cubic carbide phase and (c) hexagonal MAX phase with Fourier transformed patterns at the top right corners

图2 (TiZrHfNbTa)C高熵陶瓷样品中碳化物晶粒的精细结构表征

Fig. 2 Fine structure characterization of carbide grains in (TiZrHfNbTa)C high-entropy ceramic sample (a) TEM bright field image; (b) HREM image; (c-e) Fourier transformed patterns of corresponding areas marked by yellow, green and gold squares in (b). Colorful images are available on website

图3 (TiZrHfNbTa)C高熵陶瓷样品中碳化物晶粒的ACTEM表征

Fig. 3 ACTEM characterization of carbide grains in (TiZrHfNbTa)C high-entropy ceramic sample (a) HAADF image and EDS elemental mappings; (b) HAADF atomic image; (c) EDS line scan of the yellow line in (b). Colorful images are available on website

图4 (TiZrHfNbTa)C高熵陶瓷样品中碳化物晶粒的HAADF图像

Fig. 4 HAADF images of carbide grains in (TiZrHfNbTa)C high-entropy ceramic sample (a) Low-magnification HAADF image; (b) HAADF atomic image; (c) HAADF atomic image of a grain boundary area. The grain boundary is marked by red arrows and planar defects are marked by arrows of other colors. Colorful images are available on website

图5 不同单元碳化物陶瓷的形成能及其结构中Al间隙的形成能和迁移能垒

Fig. 5 Formation energies of different single carbides, and formation energies and migration barriers of Al interstitials in these carbides

图6 HfC, (TiHf)C和(TiHfTa)C陶瓷样品的TEM表征

Fig. 6 TEM characterization of HfC, (TiHf)C and (TiHfTa)C ceramic samples (a1, a3, b1, b3, c1, c3) Bright field images; (a2, a4, b2, b4, c2, c4) HREM images

参考文献 20

[1]	DONG S, WANG J, NI D. Structural ceramics—the cornerstone of human civilization. Journal of Inorganic Materials, 2024, 39(6): 569.
[2]	QIN Y, LIU J X, LIANG Y, et al. Equiatomic 9-cation high-entropy carbide ceramics of the IVB, VB, and VIB groups and thermodynamic analysis of the sintering process. Journal of Advanced Ceramics, 2022, 11(7): 1082.
[3]	YANG Q, WANG X, BAO W, et al. Influence of equiatomic Zr/(Ti, Nb) substitution on microstructure and ultra-high strength of (Ti, Zr, Nb)C medium-entropy ceramics at 1900 ℃. Journal of Advanced Ceramics, 2022, 11(9): 1457.
[4]	XIN X T, BAO W C, WANG X G, et al. Reduced He ion irradiation damage in ZrC-based high-entropy ceramics. Journal of Advanced Ceramics, 2023, 12(5): 916.
[5]	WYATT B C, NEMANI S K, HILMAS G E, et al. Ultra-high temperature ceramics for extreme environments. Nature Reviews Materials, 2024, 9: 773.
[6]	BUBAN J P, MATSUNAGA K, CHEN J, et al. Grain boundary strengthening in alumina by rare earth impurities. Science, 2006, 311(5758): 212. PMID
[7]	CUI J, ZHENG X, BAO W, et al. Coexistence of superhardness and metal-like electrical conductivity in high-entropy dodecaboride composite with atomic-scale interlocks. Nano Letters, 2023, 23(20): 9319. DOI PMID
[8]	DING H, LI M, LI Y, et al. Progress in structural tailoring and properties of ternary layered ceramics. Journal of Inorganic Materials, 2023, 38(8): 845.
[9]	ZHANG Z, DUAN X, QIU B, et al. Preparation and anisotropic properties of textured structural ceramics: a review. Journal of Advanced Ceramics, 2019, 8(3): 289.
[10]	LIN Z, ZHUO M, ZHOU Y, et al. Microstructures and theoretical bulk modulus of layered ternary tantalum aluminum carbides. Journal of the American Ceramic Society, 2006, 89(12): 3765.
[11]	CAI F Y, NI D W, DONG S M. Research progress of high-entropy carbide ultra-high temperature ceramics. Journal of Inorganic Materials, 2024, 39(6): 591.
[12]	NI D W, CHENG Y, ZHANG J P, et al. Advances in ultra-high temperature ceramics, composites, and coatings. Journal of Advanced Ceramics, 2022, 11(1): 1.
[13]	LIU T, LEI L, ZHANG J, et al. Unveiling the transporting mechanism of (Ti_0.2Zr_0.2Nb_0.2Hf_0.2Ta_0.2)C at room temperature. Crystals, 2023, 13(4): 708.
[14]	KRESSE G, FURTHMÜLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B, 1996, 54(16): 11169.
[15]	BLÖCHL P E. Projector augmented-wave method. Physical Review B, 1994, 50(24): 17953. DOI PMID
[16]	KRESSE G, JOUBERT D. From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 1999, 59(3): 1758.
[17]	PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865. DOI PMID
[18]	HENKELMAN G, UBERUAGA B P, JÓNSSON H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. Journal of Chemical Physics, 2000, 113(22): 9901.
[19]	BAO W C, WANG X, DING H J, et al. High-entropy M₂AlC-MC (M=Ti, Zr, Hf, Nb, Ta) composite: synthesis and microstructures. Scripta Materialia, 2020, 183: 33.
[20]	WANG X H, ZHOU Y C. Layered machinable and electrically conductive Ti₂AlC and Ti₃AlC₂ ceramics: a review. Journal of Materials Science & Technology, 2010, 26(5): 385.

在碳化物陶瓷中构筑金属原子层分相共生结构

Establishment of Symbiotic Structure with Metal Atomic-layer Phase-separation in Carbide Ceramics

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 20

相关文章 4

编辑推荐

Metrics

本文评价

[1]	薛伟江, 谢志鹏. 低温环境下结构陶瓷的相变、断裂机理与性能的研究进展[J]. 无机材料学报, 2014, 29(4): 337-344.
[2]	刘峰, 陆毅青, 李永祥. 铋层状共生结构铁电体Bi₇Ti₄NbO₂₁的第一性原理计算[J]. 无机材料学报, 2014, 29(1): 38-42.
[3]	郭景坤. 关于先进结构陶瓷的研究[J]. 无机材料学报, 1999, 14(2): 193-202.
[4]	张宝林,庄汉锐,Sajalkik P. 层状结构陶瓷复合材料[J]. 无机材料学报, 1997, 12(6): 769-773.