High-entropy ultra-high temperature ceramics (UHTCs) have garnered significant attention for outstanding designability and performance, yet existing strategies remain largely confined to cationic sublattice engineering, leaving the potential of anionic site manipulation unexplored. Herein, we extend the entropy- stabilization paradigm to the anion sublattice by designing a multi-anion Hf_0.8Zr_0.2B_0.1C_0.5N_0.4 solid solution. The resulting Hf_0.8Zr_0.2B_0.1C_0.5N_0.4 -SiC ceramic achieves negative ablation rates (-0.049 mg·s^-1; -0.287 μm·s^-1) under 2600 °C plasma flame exposure, markedly outperforming Hf_0.8Zr_0.2C-SiC. This exceptional ablation- resistant performance originates from the synergistic effects enabled by multi-anion sublattice engineering. The incorporation of B-C-N intrinsically enhances fracture toughness, while in-situ precipitation of hexagonal graphite during ablation extrinsically arrests cracks through interfacial shear, preventing catastrophic disintegration. Furthermore, the multi-anion matrix undergoes a sequential oxidation process, forming an HfZrBCNO interlayer that acts as an oxygen scavenger. Concurrently, h-BN precipitates at grain boundaries, serving as compliant diffusion barriers that impede oxygen ingress toward SiC. This dual-layer protection mechanism suppresses the active oxidation of SiC (SiC + O₂ ® SiO + CO) and promotes the formation of a dense, scouring-resistant HfZrO₂-SiO₂ composite barrier. By demonstrating simultaneous microstructural toughening and mesoscale oxidation management, this work establishes multi-anion sublattice engineering as a transformative platform for designing next-generation thermal protection materials beyond the limits of conventional entropy-stabilized ceramics.

Short carbon fiber reinforced ultrahigh temperature ceramic matrix composites (C_sf/UHTCMCs) are recognized as leading candidates for thermal structures owing to their precisely tailorable composition and enhanced tunability in structure and properties. Inspired by nature, the Bouligand structure—characterized by a gradual angular rotation between successive layers—exhibits remarkable load-bearing and thermal conductive capacity. In this study, the Bouligand structure was introduced into C_sf/ZrB₂-SiC by employing direct ink writing technology. The results indicate that the composite with a 30° interlayer Bouligand structure achieves a synergistic improvement in both mechanical performance and thermal diffusion uniformity. Specifically, enhancements of 42% in flexural strength and 35% in fracture toughness were achieved compared to conventional C_sf/ZrB₂-SiC. Meanwhile, the Z-axis thermal conductivity increased by 24.5%, along with a notable enhancement of in-plane thermal diffusion. These improvements can be attributed to the smaller deflection angles and more frequent unidirectional deflections within the 30° Bouligand structure, which promote more pronounced crack deflection. Furthermore, the small-angle rotational design improves in-plane thermal diffusion uniformity by leveraging the high intrinsic radial thermal conductivity of short carbon fibers. Hence, the bioinspired Bouligand structure design offers a promising strategy for the synergistic optimization of mechanical and thermal properties in C_sf/UHTCMCs.

C_f/Ta_xHf_1−xC–SiC composites are ideal thermal structural materials for service under extreme conditions of hypersonic vehicles. However, how to synthesize Ta_xHf_1-xC powders and efficiently fabricate C_f/Ta_xHf_1-xC–SiC composites still faces some challenges. Furthermore, mechanical properties and thermophysical properties of Ta_xHf_1−xC vary with the composition, but not monotonically. In-depth analysis of mechanical behaviors of the C_f/Ta_xHf_1−xC–SiC composites is extremely important for their development and applications. In this study, the Ta_xHf_1−xC powders (x = 0.2, 0.5, 0.8) were successfully synthesized via solid solution of TaC and HfC at a relatively low temperature of 1800 ℃, with a small amount of Si as an additive. Subsequently, the efficient fabrication of 2D-C_f/Ta_xHf_1–xC–SiC composites was achieved by slurry impregnation and lamination (SIL) combined with precursor infiltration and pyrolysis (PIP). In addition, the mechanical behavior of the composites was investigated systematically. It is demonstrated that the composites present remarkable non-brittle fractures, including a large number of fiber pull out and interphase debonding. Also, the fracture failure involves a complex process of microcrack generation and propagation, matrix cracking, and layer fracture. Moreover, the interfacial bonding between the fibers and the matrix is enhanced as the Ta∶Hf ratio decreases from 4∶1 to 1∶4. As a result, C_f/Ta_0.2Hf_0.8C–SiC composites exhibit exceptional flexural strength of 437±19 MPa, improved by 46% compared with C_f/Ta_0.8Hf_0.2C–SiC (299±19 MPa). This study provides a new perception of design and fabrication of ultra-high-temperature ceramic (UHTC) matrix composites with high performance.

Fiber damage and uniform interphase preparation are the main challenges in conventional short fiber reinforced ceramic matrix composites. In this work, we develop a novel processing route in fabrication of short carbon fiber reinforced ZrB₂-SiC composites (C_sf/ZrB₂-SiC) overcoming the above two issues. At first, C_sf preforms with oriented designation and uniform PyC/SiC interphase are fabricated via direct ink writing (DIW) of short carbon fiber paste followed by chemical vapor infiltration. After that, ZrB₂ and SiC are introduced into the preforms by slurry impregnation and reactive melt infiltration, respectively. Microstructure evolution and optimization of the composites during fabrication are investigated in detail. The as-fabricated C_sf/ZrB₂-SiC composites have a bulk density of 2.47 g/cm³, with uniform weak interphase and without serious fiber damage. Consequently, non-brittle fracture occurs in the C_sf/ZrB₂-SiC composites with widespread toughening mechanisms such as crack deflection and bridging, interphase debonding, and fiber pull-out. This work provides a new opportunity to the material design and selection of short fiber reinforced composites.

In this work, three-dimensional (3D) C_f/SiBCN composites were fabricated by polymer infiltration and pyrolysis (PIP) with poly(methylvinyl)borosilazane as SiBCN precursor. The 3D microstructure evolution process of the composites was investigated by an advanced X-ray computed tomography (XCT). The effect of dicumyl peroxide (DCP) initiator addition on the crosslinking process, microstructure evolution, and mechanical properties of the composites were uncovered. With the addition of a DCP initiator, the liquid precursor can cross-linking to solid-state at 120 ℃. Moreover, DCP addition decreases the release of small molecule gas during pyrolysis, leading to an improved ceramic yield 4.67 times higher than that without DCP addition. After 7 PIP cycles, density and open porosity of the final C_f/SiBCN composite with DCP addition are 1.73 g·cm^-3 and ~10%, respectively, which are 143.0% higher and 30.3% lower compared with the composites without DCP addition. As a result, the flexural strength and elastic modulus of C_f/SiBCN composites with DCP addition (371 MPa and 31 GPa) are 1.74 and 1.60 times higher than that without DCP addition (213 MPa and 19.4 GPa), respectively.

Using liquid poly(methylvinyl)borosilazanes (PMVBSZ) as precursor, carbon fiber reinforced SiBCN matrix composites (C_f/SiBCN) were fabricated by a modified polymer infiltration and pyrolysis (PIP) process. With dicumyl peroxide added as cross-linking agent, the PMVBSZ could be solidified at a low temperature of 120 ℃, leading to a high ceramic yield of ~70%. The cross-linking mechanism and ceramization processes of the precursor were investigated in detail. Moreover, a modified infiltration technology was developed, which improved the efficiency and protected the precursor against moist air during PIP. Consequently, the obtained C_f/SiBCN composites had an oxygen content of around 1.22 wt%. Benefiting from the high ceramic yield and high efficiency of the modified PIP, C_f/SiBCN composites with an open porosity of ~10% and uniform microstructure were obtained after only 7 cycles of PIP. The flexural strength and fracture toughness of the derived C_f/SiBCN composites were 371 MPa and 12.9 MPa·m^1/2, respectively. This work provides a potential route for the fabrication of high performance C_f/SiBCN composites.