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

doi:10.15541/jim20240284

Journal of Inorganic Materials ›› 2025, Vol. 40 ›› Issue (1): 17-22.DOI: 10.15541/jim20240284

• RESEARCH ARTICLE • Previous Articles Next Articles

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)

Abstract

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

CLC Number:

TQ174
P575

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.

Figures/Tables 6

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

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

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

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

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

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

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

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