Bottom-up design of high-entropy ceramics is a promising approach for realizing materials with unique combination of high hardness and fracture-resistance at elevated temperature. This work offers a simple yet fundamental design criterion - valence electron concentration (VEC) > ~9.5 e-/f.u. to populate bonding metallic states at the Fermi level - for selecting elemental compositions that may form rocksalt-structure (B1) high-entropy ceramics with enhanced plasticity (reduced brittleness). Single-phase B1 (HfTaTiWZr)C and (MoNbTaVW)C, chosen as representative systems due to their specific VEC values, are here synthesized and tested. Nanoindentation arrays at various loads and depths statistically show that (HfTaTiWZr)C (VEC=8.6 e-/f.u.) is hard but brittle, whilst (MoNbTaVW)C (VEC=9.4 e-/f.u.) is hard and considerably more resistant to fracture than (HfTaTiWZr)C. Ab initio molecular dynamics simulations and electronic-structure analysis reveal that the improved fracture-resistance of (MoNbTaVW)C subject to tensile and shear deformation may originate from the intrinsic material's ability to undergo local lattice transformations beyond tensile yield points, as well as from relatively facile activation of lattice slip. Additional simulations, carried out to follow the evolution in mechanical properties as a function of temperature, suggest that (MoNbTaVW)C may retain good resistance to fracture up to ~900-1200K, whereas (HfTaTiWZr)C is predicted to remain brittle at all investigated temperatures.
Despite the continuous evolution on the performance of refractory ceramic products, monolithic materials still require special attention during their processing steps as various phase transformations may take place during the curing, drying and firing stages. Drying is usually the longest and the most critical process observed during the first heating cycle of refractory linings, as the enhanced particle packing and reduced permeability of the resulting microstructure may lead to recurrent explosive spalling and mechanical damage associated with dewatering and the development of high steam pre…
The development of thermal stresses inside refractory ceramics experiencing severe thermal shock is studied. The present analysis departs from the linear theory of thermal stresses as it accounts for temperature dependent thermal and mechanical material properties. Radiation surface heat exchange between the refractory component and its surroundings is included. A Finite Element Procedure is presented and a MATLAB code is developed. The nonlinear heat equation is solved for the temperature field and this solution is subsequently used in order to determine the stress field evolution. The finite…
Machine learning potential as a guide for eutectic in ultra-refractory multicomponent ceramics
Moscow Institute of Physics and Technology (National Research University)（莫斯科物理科学与技术大学）；Institute for High Pressure Physics, Russian Academy of Sciences（俄罗斯科学院高压物理研究所）；Joint Institute for Nuclear Research（苏联联合核研究所）
The main aim of this study is to scrutinize promising plasmonic materials by understanding their electronic structure and correlating them to the optical properties of selected refractory materials. For this purpose, the electronic and optical properties of the conductive ceramics TiC, ZrC, HfC, TaC, WC, TiN, ZrN, HfN, TaN, and WN are studied systematically by means of first-principles density functional theory. A full ab initio procedure to calculate plasma frequency from the electronic band structure is discussed. The dielectric functions are calculated by including electronic interband and …
High entropy materials, which include high entropy alloys, carbides, and borides, are a topic of substantial research interest due to the possibility of a large number of new material compositions that could fill gaps in application needs. There is a current need for materials exhibiting high temperature stability, particularly oxidation resistance. A systematic understanding of the oxidation behavior in high entropy materials is therefore required. Prior work notes large differences in the thermodynamic favorability between oxides formed upon oxidation of high entropy materials. This work use…
Improved toughness is a central goal in the development of wear-resistant refractory ceramic coatings. Extensive theoretical and experimental research has revealed that NaCl structure VMoN alloys exhibit surprisingly high ductility combined with high hardness and toughness. However, during operation, protective coatings inevitably oxidize, a problem which may compromise material properties and performance. Here, we explore the role of oxidation in altering VMoN properties. Density functional theory and theoretical intrinsic hardness models are used to investigate the mechanical behavior of cub…
Titanium diboride (TiB2) is a low-density refractory material belonging to the family of ultra-high temperature ceramics (UHTCs). This paper reports on the production and microstructural and optical characterization of nearly fully dense TiB2, with particular interest to its potential utilization as novel thermal solar absorber. Monolithic bulk samples are produced starting from elemental reactants by a two-step method consisting of the Self-propagating High-temperature Synthesis (SHS) followed by the Spark Plasma Sintering (SPS) of the resulting powders. The surface of obtained samples has-be…
Superlattice (SL) thin films composed of refractory ceramics unite extremely high hardness and enhanced fracture toughness; a material combination often being mutually exclusive. While the hardness enhancement obtained whentwo materials form a superlattice is well described by existing models based on dislocation mobility, the underlying mechanisms behind the increase in fracture toughness are yet to be unraveled. Here we provide a model based on linear elasticity theory to predict the fracture toughness enhancement in (semi-)epitaxial nanolayers due to coherency stresses and formation of misf…
Ultra-high-temperature ceramics (UHTCs) are candidate structural materials for applications that require resiliency to extreme temperature (>2000°C), high mechanical loads, or aggressive oxidizing environments. Processing UHTC transition metal carbides as standalone materials using additive manufacturing (AM) methods has not been fully realized due to their extremely slow atomic diffusivities that impede sintering and large volume changes during indirect AM that can induce defect structures. In this work, a two-step, reactive AM approach was studied for the formation of the ultra-high temperat…
Aiiso Yufeng Li Family Department of Chemical and Nano Engineering（加州大学圣地亚哥分校艾思友峰李家族化学与纳米工程系；材料科学与工程计划）；Program in Materials Science and Engineering, University of California San Diego
Recent years have witnessed considerable work on the development of lead-free piezoelectric ceramic materials and their structure-property correlations. The development of piezo response is a strong function of phase evolution in these materials. In this work, we report the effect of Ru doping and consequent phase evolution on maximization of piezoelectric response of polycrystalline lead-free barium titanate, depicted as Ba(RuxTi1-x)O3 (BRT). The samples were prepared in a narrow compositional range of using conventional solid-state reaction method. Ru doping increases the leakage current of …
Grain Growth Kinetics in (Cr,Mo,Ta,V,W)C1-δ High-Entropy Carbide Ceramics
Missouri University of Science and Technology（密苏里科技大学）；Pennsylvania State University（宾夕法尼亚州立大学）；Duke University（杜克大学）；University of California, Irvine（加州大学尔湾分校）
Refractory producers face many challenges in terms of producing MgO-containing castables due to the high likelihood of magnesia to hydrate in contact with water, resulting in Mg(OH)2 generation. The expansive feature of this transformation affects the performance of such refractories, as (i) if this hydrated phase is not accommodated in the formed microstructure, ceramic linings with cracks and low green mechanical strength will be obtained; and (ii) if crack-free pieces are prepared, they should present low porosity and reduced permeability, which require special attention when heating these …
A new type of compositionally complex (medium- or high-entropy) M5Si3 silicides is synthesized. Both (V1/5Cr1/5Nb1/5Ta1/5W1/5)5Si3 and (Ti1/5Zr1/5Nb1/5Mo1/5Hf1/5)5Si3 form single-phase homogenous solid solutions. Notably, (V1/5Cr1/5Nb1/5Ta1/5W1/5)5Si3 forms the hexagonal gamma (D88) phase, while all its five constituent binary silicides, V5Si3, Cr5Si3, Nb5Si3, Ta5Si3, and W5Si3, are stable in the tetragonal alpha (D8l) or beta (D8m) phases. Annealing at 1600C demonstrates that this hexagonal gamma phase is stable. Comparison of the experimental and calculated X-ray diffraction patterns, Rietve…
High entropy carbides (HECs) are a promising new class of ultra-high temperature ceramics that could provide novel material solutions for leading edges of hypersonic vehicles, which can reach temperatures above 3500C and experience extreme thermal gradients. Although the mechanical and thermal properties of HECs have been studied extensively at room temperature, few works have examined HEC properties at high temperatures or considered these materials' responses to thermal shock. In this work, we measure the thermal conductivity of a five-cation HEC up to 1200C. We find that thermal conductivit…
