High-entropy ceramics (HECs), defined as single-phase inorganic solid solutions comprising five or more principal elements in equimolar or near-equimolar ratios, have emerged as a frontier and hotspot in materials science over the past decade. Their expansive compositional space and diverse crystal structures open up new avenues for the design and performance regulation of ceramic materials. Initially, focused on proving the feasibility of entropy-stabilized phases, the field rapidly expanded into a vast, complex landscape of nonequimolar, multianionic, and medium-entropy compositions. This exploratory "great chaos" successfully validated the concept across diverse ceramic families and unlocked extraordinary properties, including ultrahigh temperature stability, exceptional radiation tolerance, ultralow thermal conductivity, and superior energy storage density. The realization of performance-tailored HECs fundamentally depends on rational compositional design and precise control of preparation processes, core challenges that remain at the heart of current research. However, a clear "scissors gap" has emerged between the rapid accumulation of experimental data and the lag in theoretical frameworks and data comparability. This review synthesizes a decade of research to chart a crucial transition "from chaos to order". It formulates emerging design paradigms for targeted applications such as oxidation-resistant ultrahigh temperature ceramics (UHTCs), thermal barrier coatings, durable nuclear materials, and high-performance energy storage and conversion materials. The analysis highlights the shift from discovery to quantitative efforts integrating computational thermodynamics, advanced characterization, and machine learning (ML). Despite remarkable progress, significant bottlenecks persist in processing, standardized characterization, and scaling from powder to component. The future roadmap emphasizes establishing robust structure–property relationships, fostering community-wide data standards, and advancing rational, physics-, and artificial intelligence (AI)-guided design to systematically realize the immense technological potential of HECs.
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With the growing prominence of electromagnetic pollution, the development of lightweight, flexible, and highly efficient electromagnetic wave (EMW) absorption materials has become an important research focus. Inspired by biological Turing structures, this study successfully prepares novel flexible ZrO2/C nanofibers with a spotted reaction-diffusion pattern via a controlled oxidation strategy from preformed ZrC/C nanofibers. The ZrO2/C nanofibers sample contains ZrO2 particles embedded within a carbon matrix, which contributes to the formation of numerous heterogeneous interfaces. Furthermore, both the ZrO2 and carbon matrix exhibit a mixed amorphous-nanocrystalline structure, thereby enhancing interfacial diversity and density. The ZrO2/C Turing structural characteristic enhances impedance matching in the nanofibers and significantly improves the polarization loss capability. The obtained novel nanofibers achieve a minimum reflection loss of −59.20 dB, a maximum effective absorption bandwidth of 5.84 GHz, and require a matching thickness of only 2.39 mm. Computer simulation technology (CST) simulations indicate a maximum radar cross-section reduction of 34.94 dB m2, highlighting the material’ s radar stealth capability. The study provides a new strategy for designing lightweight and high-performance fiber-based EMW absorption materials.
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Ultrasonic-assisted hot pressing (UAHP) has shown significant potential in enhancing both the densification and mechanical performance of metallic materials. However, the poor high-temperature stability of ultrasonic systems severely limits its application in the fabrication of high-melting-point materials. To fill this gap, UAHP was operated at temperatures exceeding 2000 °C and employed in the preparation of monolithic boron carbide (B4C) ceramics for the first time. The densification behavior, microstructure evolution, and mechanical properties of B4C fabricated via UAHP were systematically investigated and compared with those prepared by conventional hot pressing (HP). It was demonstrated that the introduction of high-frequency ultrasonic vibration in UAHP can not only accelerate the densification rate but also reduce the densification temperature and enhance the mechanical properties of B4C. Specifically, the relative density of B4C increased from 90.90% to 97.22% at 1900 °C under UAHP, which was comparable to that achieved by HP at 1950 °C, indicating a 50 °C reduction in densification temperature. In addition, a significant increase in densification efficiency by reducing the densification time during UAHP endowed B4C with both near-full density and superior mechanical properties. The B4C ceramics prepared by UAHP at 1950 °C for 20 min and at 2050 °C for 5 min exhibited flexural strengths of 669.3±19.4 and 688.3±32.5 MPa, respectively, and fracture toughnesses of 4.37±0.23 and 4.22±0.29 MPa·m1/2, respectively. These results suggest that UAHP is a promising strategy for efficient densification and optimization of the mechanical properties of B4C ceramic and opens a new avenue for the preparation of difficult sintering ceramics.
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Rapid Communication
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Oxide scales grown on carbides or borides based ultrahigh thermal protection materials during service play crucial roles in the safe operation of the systems in extreme environments, where advancing technologies are pushing temperature limits beyond 3000 °C, exceeding the melting points of all known nonradioactive oxides. Although cationic solid solutions offer a pathway to modulate melting behavior, conventional phase diagrams show that most solid solutions exhibit lower melting points than their parent components. The mechanisms underlying melting point elevation in oxides have remained unclear. Here, we demonstrate a cationic design strategy for ultrahigh melting point oxides based on simultaneous control of the valence electron concentration, cation size, orbital overlap, coordination number and crystallographic symmetry. Using this approach, we developed a Ta-doped HfO2 solid solution with a melting point of 3006 °C, the highest reported nonradioactive oxide, which represents an increase of nearly 150 °C over the parent oxide. This approach should be universally applicable to designing various ceramics with high or ultrahigh melting points.
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CrB2 crystallizes in an AlB2-type crystal structure, and the chemical bonding in CrB2 includes B sp2‒B sp2 covalent bonds in the graphite-analogous six-numbered B ring, B pz‒Cr 3d covalent‒ionic bonds, and Cr‒Cr metallic bonds from theoretical calculations. However, the crystal structure and chemical bonding properties have not been experimentally validated. To fill this research gap, herein, the crystal structure and chemical bonding of CrB2 were evaluated for the first time via aberration-corrected transmission electron microscopy (AC-TEM) coupled with electron energy loss spectroscopy (EELS). Combined with first-principles calculations based on density functional theory (DFT), CrB2 is confirmed to have an AlB2-type structure, where Cr bonds to each other in the (001) plane via metallic bonding and where B bonds in the form of a graphite-like six-membered ring in the (002) plane through sp2 hybridization, whereas Cr‒B ionic‒covalent bonding is formed in the (110) plane. A detailed analysis of the experimental and calculated results of the EELS of CrB2 shows that the hybridization of Cr 3d and B has a significant effect on the EELS of transition metal borides (TMB2). In addition, the hysteresis loop of CrB2 was tested for the first time on the basis of theoretical calculations, and the molar susceptibility of CrB2 was approximately 5.77×10−4 emu/mol. The present work is helpful for understanding the structure‒property relationships, which are essential for tailoring the properties from a crystal structure and chemical bonding point of view and promoting the practical application of TMB2 in extreme aerospace environments.
Open Access
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CrTaO4 and CrNbO4, rutile structured ternary scales formed on refractory high-entropy alloys (RHEAs), protect the RHEAs from oxidation and thermal attack. However, the Vickers hardness (12.20/10.20 GPa for CrTaO4 and CrNbO4, respectively) is lower than that of YSZ (14 GPa), making them prone to erosion. In addition, further reduction of thermal conductivity (1.31/1.09 W·m−1·K−1 for CrTaO4 and CrNbO4, respectively) benefits to protect the substrate materials from thermal attack. As such, optimizing their properties is urgently needed. To enhance the mechanical properties and further reduce the thermal conductivity of rutile-type ternary oxides CrTaO4 and CrNbO4, herein we designed a CrTa0.5Nb0.5O4 solid solution based on the mechanism of solid solution strengthening, and systematically investigated its phase composition, microstructure, mechanical and thermal properties. The HAADF and ABF-STEM analyses confirmed the rutile-structure of CrTa0.5Nb0.5O4, while minor impurities of rutile-structured CrNbO4 and CrO2 were also identified. The elastic modulus, bulk modulus, and shear modulus of CrTa0.5Nb0.5O4 are 201, 119, and 175 GPa, respectively. Notably, the mechanical properties of CrTa0.5Nb0.5O4 have been significantly improved via solid solution strengthening, with the Vickers hardness of 13.01 ± 0.2 GPa, fracture toughness of 2.07 ± 0.017 MPa·m1/2, and flexural strength of 201 ± 12 MPa. The measured melting point of CrTa0.5Nb0.5O4 is 2073 ± 20 K, with an average thermal expansion coefficient of (5.91 ± 0.52) × 10⁻6 K⁻1. The room-temperature thermal conductivity of CrTa0.5Nb0.5O4 is 1.07 W·m⁻1·K⁻1, which decreases to 0.57 W·m⁻1·K⁻1 at 1473 K, being lower than most of the well-known thermal barrier coating materials. In terms of thermal expansion coefficient matching, CrTa0.5Nb0.5O4 is a qualified thermal barrier material for refractory metals and their alloys and ultra-high temperature ceramics. Therefore, this study has not only successfully developed a thermal barrier coating material with excellent mechanical properties and low thermal conductivity, but also provided new ideas for the research and development of materials in high-temperature fields from the perspective of material design.
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Research Article
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Cr–Nb-containing refractory high-entropy alloys (RHEAs) have high strength above 1200 °C but low density close to that of Ti-based alloys, which makes them promising for application in aero engines. However, oxidation is the bottleneck that limits their practical application. Recently, CrNbO4 has been found to effectively protect them from oxidation. Nevertheless, little is known about this oxide. To elucidate the protection mechanism of CrNbO4 and explore its properties, we report for the first time the microstructure, mechanical, and thermal properties of CrNbO4. Using atomic-resolution high-annular dark field (HAADF) and annular bright field (ABF) techniques, we confirmed the rutile-type structure of CrNbO4, identified the precipitation of Cr2O3, and observed Cr segregation at the interface boundary between CrNbO4 and Cr2O3. The Young’s modulus (E), shear modulus (G), and bulk modulus (B) of CrNbO4 are 253, 100, and 180 GPa, respectively, whereas the Vickers hardness (HV), flexural strength (σf), and fracture toughness (KIC) of CrNbO4 are 10.2±0.58 GPa, 205±8 MPa, and 1.54±0.12 MPa·m1/2, respectively. The measured melting point of CrNbO4 is 2053±20 K. The anisotropic thermal expansion coefficient (TEC) is αa = (5.38±0.09)×10−6 K−1, αc = (7.44±0.14)×10−6 K−1, and the average TEC is (6.07±0.12)×10−6 K−1, which is close to that of refractory metals and RHEAs. Interestingly, the room temperature thermal conductivity of CrNbO4 is 1.09 W·m−1·K−1 and decreases to 0.45 W·m−1·K−1 at 1473 K, which is lower than that of most of the currently well-known thermal insulation materials. Consequently, CrNbO4 can be considered a novel dual-functional scale on top of RHEAs to protect them from oxidation and thermal attack.
Open Access
Research Article
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Carbon fiber composites hold significant promise as electromagnetic wave (EMW)-absorbing materials. However, balancing lightweight materials with excellent mechanical properties, low thermal conductivity, and EMW absorption for multifunctional applications remains challenging. Herein, a novel hydrothermal carbon (HC)-coated three-dimensional (3D) needled carbon fiber-reinforced silicon–boron carbonitride (Cf/HC–SiBCN) composite was developed via an optimized precursor infiltration and pyrolysis (PIP) process combined with impregnation–filtration. By adjusting the precursor concentration and number of impregnation‒filtration cycles, a hierarchical Cf/HC–SiBCN composite with the density of 0.32 g·cm−3 was obtained, which exhibited remarkable mechanical properties, including flexural strengths of 14.75±0.43 MPa (xy-direction) and 14.45±0.66 MPa (z-direction), along with a compressive strength of 9.36±0.20 MPa (z-direction). It also demonstrated low thermal conductivity (0.145 W·m−1·K−1) and exceptional EMW absorption, with a minimum reflection loss (RLmin) of −58.13 dB and an effective absorption bandwidth (EAB) of 7.38 GHz. Owing to their combination of lightweight, enhanced mechanical properties, low thermal conductivity, and superior EMW absorption capabilities, Cf/HC–SiBCN composites are highly suitable for multifunctional applications.
Open Access
Research Article
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High-entropy nanolaminated materials, referred to as MAX phases, have exceptional potential in various fields, including physics, mechanics, and energy storage, owing to their diverse compositions and outstanding properties. However, synthesizing stable high-entropy phases presents significant challenges because of the considerable differences in the physical and chemical properties of complex elements. In this study, we added low-melting-point metal tin (Sn) as an additive to facilitate the formation of solid solutions. The cohesion energy and formation enthalpy of the Sn-containing system are negative, which maintains the thermodynamic stability of the system, and the incorporation of Sn decreases the mixing enthalpy of the target high-entropy MAX phase and inhibits the formation of competing phases. The addition of Sn increases the lattice parameter and improves the structural stability by increasing the lattice distortion of octahedral M6X and prism M6A, which facilitates the successful synthesis of single-phase high-entropy MAX bulk materials. In addition, the high-entropy MAX phases with added Sn retain good mechanical and physical properties. This study provides a novel approach for the synthesis and application of high-entropy MAX phase materials, which has the potential to contribute to advancements in multiple technological fields.
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Research Article
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The stacking structure of Nb2CSe2, a newly synthesized layered metal carbo-selenide, was elucidated by scanning transmission electron microscopy. Nb2CSe2 features Se−Nb−C−Nb−Se quintuple atomic layers. These layers are stacked in Bernal mode. In this mode, Nb2CSe2 crystallizes in a trigonal symmetry (space group P
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