First-principles study,fabrication, and characterization of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramic

The formation possibility of (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy ceramic (HHC-1) was first analyzed by the first-principles calculations, and then, it was successfully fabricated by hot-pressing sintering technique at 2073 K under a pressure of 30 MPa. The first-principles calculation results showed that the mixing enthalpy and mixing entropy of HHC-1 were −0.869 ± 0.290 kJ/mol and 0.805R, respectively. The experimental results showed that the as-prepared HHC-1 not only had an interesting single rock-salt crystal structure of metal carbides but also possessed high compositional uniformity from nanoscale to microscale. By taking advantage of these unique features, it exhibited extremely high nanohardness of 40.6 ± 0.6 GPa and elastic modulus in the range from 514 ± 10 to 522 ± 10 GPa and relatively high electrical resistivity of 91 ± 1.3 μΩ·cm, which could be due to the presence of solid solution effects.     

Synthesis,mechanical, and thermophysical properties of high-entropy (Zr,Ti,Nb,Ta,Hf)C0.8 ceramic

Two high-entropy carbides, including stoichiometric (Zr,Ti,Nb,Ta,Hf)C and nonstoichiometric (Zr,Ti,Nb,Ta,Hf)C_0.8, were prepared from monocarbides and ZrH₂. Their sinterability, microstructures, mechanical properties, thermophysical properties, and oxidation behaviors were systematically compared. With the introduction of carbon vacancy, the sintering temperature was lowered up to 300°C, Vickers hardness was almost unaffected, whereas the strength decreased significantly generally due to the decrease of covalent bonds. The thermal conductivity shows a 50% decrease for nonstoichiometry high-entropy carbide, which is a major consequence of the lower electrical conductivity. The oxidation resistance in high temperature water vapor was not sensitive to carbon stoichiometry.     

Synthesis of the ternary metal carbide solid-solution ceramics by polymer-derived-ceramic route

The polymer-derived-ceramic (PDC) route has been widely used to fabricate the transition-metal carbides (TMCs). Previously reported works focused mainly on the synthesis of the single or binary TMCs, while the synthesis of the ternary or more component TMCs was rarely reported. Herein, a class of the ternary TMCs, namely (Nb_1/3Zr_1/3Ta_1/3)C solid-solution ceramics, was successfully synthesized via PDC route for the first time. The as-synthesized ceramics exhibited the particle-like morphology with an average particle size of ~250 nm and showed a single rock-salt crystal structure of metal carbides. At the same time, they had high compositional uniformity from nanoscale to microscale. In addition, they possessed low-oxygen impurity content of 0.79 wt% and moderate-carbon impurity content of 8.98 wt%. Such work provides a novel route to fabricate the ternary or more component TMCs.     

Synthesis and characterization of (HfMoTiWZr)C high entropy carbide ceramics

(HfMoTiWZr)C high entropy carbides (HEC) were prepared from the commercial carbide powders of IVB (Hf, Ti, Zr) and VIB (Mo, W) group metals of the periodic table via high energy ball milling (HEBM) and spark plasma sintering (SPS). Metal carbide powders (HfC, TiC, ZrC, Mo₂C and WC) were HEBM’d for 3 h in a vibratory ball mill, and then SPS’d at different temperatures (1800, 1900, 2000 and 2100 °C). The HEBM’d powders and SPS’d ceramics were characterized in composition, density and microstructure using an X-ray diffractometer (XRD), a scanning electron microscope/energy dispersive spectrometer (SEM/EDS), a particle size analyzer and a pycnometer. Also, microhardness and sliding wear tests were conducted on the SPS’d ceramics. Based on the performed characterization, a single-phase FCC structure was observed at all sintering temperatures indicating a high entropy carbide ceramic, and they all have high hardness and wear resistance values.     

High-temperature oxidation behavior of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics in air

High-entropy metal carbides have recently been arousing considerable interest. Nevertheless, their high-temperature oxidation behavior is rarely studied. Herein the high-temperature oxidation behavior of (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy metal carbide (HEC-1) was investigated at 1573-1773 K in air for 120 minutes. The results showed that HEC-1 had good oxidation resistance and its oxidation obeyed a parabolic law at 1573-1673 K, while HEC-1 was completely oxidized after isothermal oxidation at 1773 K for 60 minutes and thereby its oxidation followed a parabolic-linear law at 1773 K. An interesting triple-layered structure was observed within the formed oxide layer at 1673 K, which was attributed to the inward diffusion of O₂ and the outward diffusion of Ti element and CO or CO₂ gaseous products.     

One-step synthesis of coral-like high-entropy metal carbide powders

The synthesis of high-entropy metal carbide powders is critical for implementing their extensive applications. However, the one-step synthesis of high-entropy metal carbide powders is rarely studied. Herein, the synthesis possibility of high-entropy metal carbide powders, namely (Zr_0.25Ta_0.25Nb_0.25Ti_0.25)C (ZTNTC), via one-step carbothermal reduction was first investigated theoretically by analyzing chemical thermodynamics and lattice size difference based on the first-principle calculations, and then the ZTNTC powders with particle size of 0.5-2 μm were successfully synthesized experimentally. The as-synthesized powders not only had a single rock-salt crystal structure of metal carbides, but also possessed high-compositional uniformity from nanoscale to microscale. More interestingly, they exhibited the distinguished coral-like morphology with the hexagonal step surface, whose growth was governed by a classical screw dislocation growth mechanism.     

(Ti,Mo,W,Ta,V,Nb)(C,N)多元陶瓷相的价电子结构

运用固体与分子经验电子理论(EET理论)计算了(Ti,Mo,W,Ta,V,Nb)(C,N)多元陶瓷相的价电子结构.结果表明,价电子结构参数(nA)随碳化物添加量的增加而增加.不同碳化物对价电子结构参数的影响不同,其中VC的影响最为显著.价电子结构参数(nA)可以用来评价金属陶瓷的力学性能,提出了相关的判据关系式.     

Local orders,lattice distortions,and electronic structure dominated mechanical properties of (ZrHfTaM1M2)C (M = Nb,Ti, V)

High-entropy carbides (HECs) are regarded as potential candidate structural materials with attractive mechanical properties due to their ultra-high hardness. It is essential to reveal the atomic and electronic basis for strengthening mechanism in order to develop the advanced HECs. In the present work, C (M = Nb, Ti, V) are selected as case studies. The effects of transition metals (M) on the lattice parameters, bulk modulus, enthalpy of formation, electron work function (EWF), and bonding morphology/strength of HECs are comprehensively studied by first-principles calculations. It is found that the lattice parameters, equilibrium volumes, and bulk modulus of HECs are improved with the increase of M atomic volumes. The atomic-size differences among various groups of elements not only result in the lattice mismatch/distortion but also contribute to the formation of weak spots. In the view of bonding charge density, the electron redistributions caused by the coupling effect of the lattice distortion and valance electron differences can be revealed obviously, which identify the different bonding strength. Moreover, in terms of EWF, the proposed power-law-scaled hardness of HECs is validated and matches well with those reported theoretical and experimental results, providing a strategy to design advanced HECs with excellent mechanical properties.     

Pressureless sintering and properties of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics: The effect of pyrolytic carbon

A novel (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy ceramic was successfully prepared by pressureless sintering at 2200 °C. With increasing content of resin-derived-carbon, the density, and mechanical and thermal properties increased up to a maximum content of 2～4 wt% resin addition, after which further addition was detrimental. All specimens showed high strength (≥347±36 MPa), with the highest value achieving 450±64 MPa, and fracture toughness significantly higher (>20 %) than those of the corresponding monocarbides and Ta_0.5Hf_0.5C, (Ta_1/3Zr_1/3Nb_1/3)C. The thermal conductivity was approximately equivalent to the lowest value of the corresponding mono-carbides, which was assumed to be due to the lattice distortion effect.     

Fabrication and characterization of polymer-derived high-entropy carbide ceramic powders

Polymer-derived ceramic (PDC) route has been widely used to fabricate various ceramics or ceramic-matrix composites in recent years. However, the synthesis of high-entropy ceramics via PDC route has rarely been reported until now. Herein, we successfully synthesized a class of high-entropy carbides, namely (Hf_0.25Nb_0.25Zr_0.25Ti_0.25)C (HEC-1), via PDC route. The polymer-derived HEC-1 ceramics consisted of numerous superfine particles with the average particle size ~800 nm. Meanwhile, they possessed a rock-salt structure of metal carbides and high-compositional uniformity from nanoscale to microscale. In addition, the as-obtained HEC-1 ceramics had a low oxygen impurity content of 0.51% and a low free carbon impurity content of 2.56%. This work will open up a new research field on the fabrication of high-entropy ceramics or high-entropy ceramic-matrix composites via PDC route.     

Temperature-dependent elastic and thermodynamic properties of ZrC,HfC, and their solid solutions (Zr0.5Hf0.5)C

Zirconium carbide (ZrC) and hafnium carbide (HfC) have been identified as ultrahigh temperature ceramics with excellent thermal conductivity performance. The temperature profiles of ZrC and HfC have been studied; however, the temperature-dependent of solid solution of (Zr_0.5Hf_0.5)C is still lacking. Herein, we report the temperature-dependent elastic and thermodynamic properties of (Zr_0.5Hf_0.5)C using first-principles calculations. The covalent characters of ZrC, HfC, and (Zr_0.5Hf_0.5)C are weakened at high temperatures by analyzing their respective electronic structures. In addition, the equilibrium volumes at different temperatures can be determined from the energy–volume (E–V) curves under the quasi-harmonic approximation. Throughout the temperature ranges studied, the HfC material shows the highest bulk modulus and lowest thermal expansion. When T > 1000 K, (Zr_0.5Hf_0.5)C exhibits better shear and Young's modulus performance close to HfC and shows the highest anisotropy. The lattice thermal conductivity decreased as temperature increased for ZrC, HfC, and (Zr_0.5Hf_0.5)C, and (Zr_0.5Hf_0.5)C has the smallest lattice thermal conductivity. These results provide fundamental and useful information for the practical application of ZrC, HfC, and (Zr_0.5Hf_0.5)C.     

Effects of Nb/TiC/TaC/VC and Co addition on the microstructure and properties of WC-based cemented carbides

A series of WC-based cemented carbides with Nb/TiC/TaC/VC and Co was prepared through spark plasma sintering (SPS) at a low sintering temperature of 1300°C, and their microstructures and mechanical properties were investigated. The nonstoichiometric multicomponent carbide Nb/TiC/TaC/VC with a rock-salt structure ($Fm\overline{3}m$) has a high atomic solution capacity. In the sintering process, partial WC and Co may dissolve in Nb/TiC/TaC/VC. With a high concentration of carbon vacancies, Nb/TiC/TaC/VC plays a beneficial role as a mass transfer intermediary. Good mass transfer facilitates the formation of a more accommodating and stable bonding between WC, Nb/TiC/TaC/VC, and Co, thereby preserving the hardness of the sintered bulks and preventing the initiation and propagation of cracks. When 6 wt.% Nb/TiC/TaC/VC and 4 wt.% Co are added to WC, the sintered bulk with fine grains exhibits superior hardness (23.27 ± .63 GPa) and toughness (10.45 ± .56 MPa·m^1/2).     

Synthesis and characterization of (Fe3O4/MWCNTs)/ epoxy nanocomposites

A sonochemical technique is used for in situ coating of iron oxide (Fe₃O₄) nanoparticles on outer surface of MWCNTs. These Fe₃O₄/MWCNTs were characterized using a high‐resolution transmission electron microscope (HRTEM), X‐ray diffraction, and thermogravimetric analysis. The as‐prepared Fe₃O₄/MWCNTs composite nanoparticles were further used as reinforcing fillers in epoxy‐based resin (Epon‐828). The nanocomposites of epoxy were prepared by infusion of (0.5 and 1.0 wt %) pristine MWCNTs and Fe₃O₄/MWCNTs composite nanoparticles. For comparison purposes, the neat epoxy resin was also prepared in the same procedure as the nanocomposites, only without nanoparticles. The thermal, mechanical, and morphological tests were carried out for neat and nanocomposites. The compression test results show that the highest improvements in compressive modulus (38%) and strength (8%) were observed for 0.5 wt % loading of Fe₃O₄/MWCNTs. HRTEM results show the uniform dispersion of Fe₃O₄/MWCNTs nanoparticles in epoxy when compared with the dispersion of MWCNTs. These Fe₃O₄/MWCNTs nanoparticles‐infused epoxy nanocomposite shows an increase in glass transition (T_g) temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhanced high-temperature strength in textured (Ti1/3Zr1/3Hf1/3)B2 medium-entropy ceramics via strong magnetic field

This study prepared textured (Ti_1/3Zr_1/3Hf_1/3)B₂ medium-entropy ceramics for the first time that maintain enhanced flexural strength up to 1800°C using single-phase (Ti_1/3Zr_1/3Hf_1/3)B₂ powders, slip casting under a strong magnetic field, and hot-pressed sintering methods. Effects of WC additive and strong magnetic field direction on the phase compositions, orientation degree, microstructure evolution, and high-temperature flexural strength of (Ti_1/3Zr_1/3Hf_1/3)B₂ were investigated. (Ti_1/3Zr_1/3Hf_1/3)B₂ grain grows along the a,b-axes, resulting in a platelet-like morphology. Pressure parallel and perpendicular to the magnetic field direction can promote the orientation degree and hinder the texture structure formation, respectively. Reaction products of W(B,C) and (Ti,Zr,Hf)C between (Ti_1/3Zr_1/3Hf_1/3)B₂ and WC additive can efficiently refine the (Ti_1/3Zr_1/3Hf_1/3)B₂ grain size and promote grain orientation. (Ti_1/3Zr_1/3Hf_1/3)B₂ ceramics doped with 5 vol.% WC yielded a Lotgering orientation factor of 0.74 through slip casting under a strong magnetic field (12 T) and hot-pressed sintering at 1900°C. Furthermore, cleaning the boundary by W(B,C) and introducing texture can enhance the grain-boundary strength and improve its high-temperature flexural strength. The four-point flexural strength of textured (Ti_1/3Zr_1/3Hf_1/3)B₂-5 vol.% WC ceramics was 770 ± 59 MPa at 1600°C and 638 ± 117 MPa at 1800°C.     

Thermal and electrical properties of a high entropy carbide (Ta,Hf, Nb,Zr) at elevated temperatures

The thermal and electrical properties were measured for a high entropy carbide ceramic, consisting of (Hf, Ta, Zr, Nb)C. The ceramic was produced by spark plasma sintering a mixture of the monocarbides and had a relative density of more than 97.6%. The resulting ceramic was chemically homogeneous as a single-phase solid solution formed from the constituent carbides. The thermal diffusivity (0.045–0.087 cm²/s) and heat capacity (0.23–0.44 J/g•K) were measured from room temperature up to 2000°C. The thermal conductivity increased from 10.7 W/m•K at room temperature to 39.9 W/m•K at 2000°C. The phonon and electron contributions to the thermal conductivity were investigated, which showed that the increase in thermal conductivity was predominantly due to the electron contribution, while the phonon contribution was independent of temperature. The electrical resistivity increased from 80.9 μΩ•cm at room temperature to 114.1 μΩ•cm at 800°C.     

Diffusion bonding of (Hf0.2Zr0.2Ti0.2Ta0.2Nb0.2)C high-entropy ceramic with metallic Ni foil

To prepare large-sized and complex-shaped components, the feasibility of direct diffusion bonding of (Hf_0.2Zr_0.2Ti_0.2Ta_0.2Nb_0.2)C high-entropy ceramic (HEC) and its diffusion bonding with a metallic Ni foil was investigated, and the interfacial microstructure and mechanical properties of HEC/HEC and HEC/Ni/HEC joints were analyzed. For the direct diffusion bonding, reliable joints with a shear strength of 146 MPa could be achieved when the bonding temperature reached 1500 °C under a pressure of 30 MPa. By introducing a metallic Ni foil as the interlayer, the HEC was successfully bonded at the diffusion temperatures from 1150 °C to 1250 °C under 10 MPa through the formation of Ti₂Ni compound phase. Meanwhile, the HEC(Ni) phase formed by the diffusion of Ni into HEC and Ni(s, s) bulks precipitated in the bonding transition zone. The maximum joint shear strength of 151 MPa was obtained by optimizing the Ni-foil thickness, bonding temperature, and holding time.     

Low-temperature synthesis and oxidation resistance of random combination of Hf,Nb, and Ta carbides microcuboids

Based on the dissolution-precipitation mechanism, this article successfully synthesized binary and ternary transition metal carbide microcuboids with random combinations of Hf, Nb, and Ta by annealing monocarbides/cobalt powders. Accelerated mass transport rate through the flow of molten alloys (Co-Hf-Nb-Ta) instead of slow solid diffusion made the low-temperature pressureless sintering technique (1500°C) a reality. Furthermore, the equilibrium morphology was driven by the gradient Gibbs potential of carbides induced by the different local curvature of powders and anisotropic interfacial energy. (Hf_0.5Ta_0.5)C possessed the optimal oxidation resistance among all mentioned carbides, even competed with (Hf_1/3Nb_1/3Ta_1/3)C. During the isothermal oxidation at 800∼1200°C, the doping of Nb and Ta in carbides assisted the monoclinic-orthorhombic HfO₂ transition at ambient pressure, besides, TaC can also restrain the orthorhombic-monoclinic transition of Nb₂O₅. Moreover, oxidation kinetics parameters concluded that the addition of HfC and TaC contributed to the decreasing reaction order and the increasing activation energy, respectively.     

Dielectric Properties and Relaxation in (1−x)BiScO3–xBa(Mg1/3Nb2/3)O3 Solid Solutions

The dielectric properties and frequency dispersion associated with a dielectric relaxation were evaluated within the perovskite (1− x )BiScO₃– x Ba(Mg_1/3Nb_2/3)O₃ solid solution systems (0.7 ≤ x ≤ 1). With increasing BiScO₃, the room-temperature dielectric permittivity at low frequency (100 Hz) increased up to 115 at x = 0.7, and a dielectric relaxation phenomenon was evident. Relaxation parameters were analyzed using several Arrhenius-type equations, and the microwave dielectric property measurement using rectangular wave-guide method enabled confirmation of the extrapolated value of the Arrhenius plot. The result of the microwave dielectric property measurement was also checked with J -function fitting based on the frequency-dependent Gaussian distribution of the associated dielectric loss data at low frequency.