The new complex high-entropy metal boron carbonitride: Microstructure and mechanical properties

In this contribution, the ternary BCN anion systems of high-entropy ceramics (HEC) are consolidated by hot-pressing sintering and the impacts of sintering temperature and the content of amorphous BCN addition on microstructural evolution and mechanical performance were evaluated. Results confirmed that high-entropy, oxide, and BN(C) phases were precipitated for (Ta_0.2Nb_0.2Zr_0.2Hf_0.2Ti_0.2)(B, C, N) ceramics after sintering at 1900°C. With the decrease of BCN addition, a new phase of MiB₂ (Mi representing the metal atoms) occurred. The Vickers hardness, bending strength, elastic modulus, and fracture toughness of the optimized bulk HECs were investigated, obtained at 24.5 ± 2.3 GPa, 522.0 ± 2.6 MPa, 478.9 ± 11.1 GPa, and 5.36 ± 0.56 MPa m^1/2, respectively.     

Novel single phase (Ti0.2W0.2Ta0.2Mo0.2V0.2)C0.8 high entropy carbide using ball milling followed by reactive spark plasma sintering

Single phase novel (Ti_0.2W_0.2Ta_0.2Mo_0.2V_0.2)C_0.8 high entropy carbide (HEC) compacts were successfully synthesized by reactive spark plasma sintering of ball milled metal-carbon elemental mixture at temperatures of 1400−1800 °C. X-ray diffraction and element distribution maps indicated single phase carbide formation with lattice parameter ranging from 4.307 Å to 4.312 Å with small amount of TiO₂. X-ray energy dispersive spectroscopy (EDS) mapping showed uniform distribution of the transition metals in the carbide phase. The microhardness, elastic modulus, fracture toughness, electrical resistivity and thermal expansion coefficient (25 °C–600 °C) of the compact sintered at 1800 °C were found to be 25.8 ± 2.8 GPa, 461 ± 36 GPa, 3.7 ± 0.4 MPa.m^1/2, 7 × 10⁻⁴ Ω/m² and 7 × 10^-6 K⁻¹ respectively.     

Densification and joining of a (HfTaZrNbTi)C high-entropy ceramic by hot pressing

A bulk (Hf_0.2Ta_0.2Zr_0.2Nb_0.2Ti_0.2)C high-entropy ceramic (HEC) with a high density was prepared by hot pressing (HP), and through a robust joining technique, large-sized piece was fabricated. A hot-pressed carbide HEC with a single-phase and homogeneous composition was obtained at the sintering temperatures from 1800 to 1950 °C for 30 min under a pressure of 30 MPa. The influence of sintering temperature on the mechanical properties of the HEC was investigated, and the flexural and compressive strengths were reported. Additionally, the feasibility of active brazing of this HEC was studied and solid joints with high shear strength were obtained by atomic diffusion and chemical reaction at the interface, providing a key approach to fabricate complex components of HECs.     

The significant influence of carbon content on mechanical and thermal properties of (VNbTaMoW)0.5Cx high entropy carbides

The high-entropy formation possibility of (VNbTaMoW)_0.5C_x was first analyzed by phase diagram and then a series of single-phase (VNbTaMoW)_0.5C_x was fabricated by SPS. We investigated the mechanical properties and thermal conductivity of (VNbTaMoW)_0.5C_x as C stoichiometry is varied. As C stoichiometry is increased from 0.345 to 0.35, multi-phase evolves into a single rock-salt phase. The high entropy phase formation depends on C atoms and vacancies, which increase the total number of microscopic states, and then increases the overall configuration entropy and lattice distortion energy. A highly carbon-deficient condition (C=0.345) leads to FCC structure disintegration and drives metal rich Mo₂C phase evolution. As the carbon stoichiometry increases from 0.35 to 0.5, the nanohardness and flexure strength of (VNbTaMoW)_0.5C_x first increase and reach the peak values of 48 GPa and 410 MPa ((VNbTaMoW)_0.5C_0.4), then decrease. The point defects concentration in (VNbTaMoW)_0.5C_x drastically change with carbon stoichiometry, which affects the structure, mechanical properties and thermal conductivity of high-entropy (VNbTaMoW)_0.5C_x. The thermal conductivity of (VNbTaMoW)C_x first decreases and then gradually increases with an increase in carbon content. Low carbon content (VNbTaMoW)C with primarily metallic bonding is electronically thermal conductivity. As the carbon content increase, the high-entropy (VNbTaMoW)C is covalent bonding and phonon contribution to thermal conductivity plays a great role.     

Densification behaviour and physico-mechanical properties of porcelains prepared using spark plasma sintering

Porcelain powder was consolidated using spark plasma sintering (SPS) at a constant heating rate of 100°C?min^?1 to peak temperatures ranging from 1000 to 1200°C and was observed to sinter at relatively low temperature ～920°C under the SPS conditions while conventional sintering requires ～1050°C. SPS produced densification rates about 10 times greater than conventional sintering. The dwelling step at the optimal peak temperature was negligible due to rapid flow of the molten glass assisted by applied pressure. SPSed samples exhibited denser microstructures, resulting in improved physico-mechanical properties compared with conventionally sintered samples such as apparent bulk density improved from 2.38 to 2.48?g?cm^?3, Vickers hardness improved from 3–5 to 6–7?GPa, and fracture toughness improved from 2–3 to 4–6?MPa?m^1/2.     

Properties of Si3N4–TiN composites fabricated by spark plasma sintering by using a mixture of Si3N4 and Ti powders

Si₃N₄–TiN composites were successfully fabricated via planetary ball milling of 70 mass% Si₃N₄ and 30 mass% Ti powders, followed by spark plasma sintering (SPS) at 1250–1350 °C. The sintering mechanism for SPS was a hybrid of dissolution–reprecipitation and viscous flow. The electrical resistivity decreased with increasing sintering temperature up to a minimum at 1250 °C and then increased with the increasing sintering temperature. The composites prepared by SPS at 1250–1350 °C could be easily machined by electrical discharge machining. Composite prepared by SPS at 1300 °C showed a high hardness (17.78 GPa) and a good machinability.     

Microstructural,electrical, and mechanical properties of conductive SiC ceramics fabricated by spark plasma sintering

Nitrogen (N)-doped conductive silicon carbide (SiC) of various electrical resistivity grades can satisfy diverse requirements in engineering applications. To understand the mechanisms that determine the electrical resistivity of N-doped conductive SiC ceramics during the fast spark plasma sintering (SPS) process, SiC ceramics were synthesized using SPS in an N₂ atmosphere with SiC powder and traditional Al₂O₃–Y₂O₃ additive as raw materials at a sintering temperature of 1850–2000°C for 1–10 min. The electrical resistivity was successfully varied over a wide range of 10⁻³–10¹ Ω cm by modifying the sintering conditions. The SPS-SiC ceramics consisted of mainly Y–Al–Si–O–C–N glass phase and N-doped SiC. The Y–Al–Si–O–C–N glass phase decomposed to an Si-rich phase and N-doped Y_xSi_yC_z at 2000°C. The Vickers hardness, elastic modulus, and fracture toughness of the SPS-SiC ceramics varied within the ranges of 14.35–25.12 GPa, 310.97–400.12 GPa, and 2.46–5.39 MPa m^1/2, respectively. The electrical resistivity of the obtained SPS-SiC ceramics was primarily determined by their carrier mobility.     

Effect of temperature on the structure and mechanical properties of SiC–TiB2 composite ceramics by solid-phase spark plasma sintering

SiC composite ceramics have good mechanical properties. In this study, the effect of temperature on the microstructure and mechanical properties of SiC–TiB₂ composite ceramics by solid-phase spark plasma sintering (SPS) was investigated. SiC–TiB₂ composite ceramics were prepared by SPS method with graphite powder as sintering additive and kept at 1700 °C, 1750 °C, 1800 °C and 50 MPa for 10min.The experimental results show that the proper TiB₂ addition can obviously increase the mechanical properties of SiC–TiB₂ composite ceramics. Higher sintering temperature results in the aggregation and growth of second-phase TiB₂ grains, which decreases the mechanical properties of SiC–TiB₂ composite ceramics. Good mechanical properties were obtained at 1750 °C, with a density of 97.3%, Vickers hardness of 26.68 GPa, bending strength of 380 MPa and fracture toughness of 5.16 MPa m^1/2.     

Effects of ZrB2 reinforcement on microstructure and mechanical properties of a spark plasma sintered mullite-CNT composite

A high density 10 wt% ZrB₂ and 1 wt%. CNT-reinforced mullite-based composite was prepared by spark plasma sintering (SPS) at temperature of 1350 °C, average heating rate of 60 °C/min and a soaking time of 5 min. Under these conditions, the sintered composite obtained a high hardness (16.24 ± 0.12 GPa), fracture toughness (4.18 ± 0.51 MPa m^1/2) and flexural strength (488 ± 21 MPa). The results of FESEM images showed a uniform distribution of the reinforcement particles in the composite. The resulting CNTs survived the sintering process and did not undergo any transformation. A transgranular fracture was predominantly observed in the fractured surface micrographs of the composite. The CNTs pullout and crack-bridging toughening mechanisms were also observed in the composite, which could have a significant contribution to the fracture energy and the interfacial adhesion.     

Low‐Temperature Sintering of HfC/SiC Nanocomposites Using HfSi2‐C Additives

HfC/SiC nanocomposites were fabricated via the reactive spark plasma sintering (R‐SPS) of a nano‐HfC powder and HfSi₂‐C sintering additives. The densification temperature decreased to 1750°C as the additive content increased. XRD analysis indicated the formation of pure HfC–(19.3–33.8 vol%) SiC within the sintered composites without residual silicide or oxide phases or secondary nonoxide phases. Ultrafine and homogeneously distributed HfC (470 nm) and SiC (300 nm) grains were obtained in the dense composites using nano‐HfC powder through the high‐energy ball‐milling of the raw powders and R‐SPS. Grain growth was further suppressed by the low‐temperature sintering using R‐SPS. No amorphous phase was identified at the grain boundary. The maximum Vickers hardness, Young's modulus, and fracture toughness values of the HfC/SiC nanocomposites were 22 GPa, 292 GPa, and 2.44 MPa·m^1/2, respectively.     

Bending strength and microstructure of Al2O3 ceramics densified by spark plasma sintering

Al₂O₃ ceramics were superfast densified using spark plasma sintering (SPS) by heating to a sintering temperature between 1350 and 1700°C at a heating rate of 600°C/min, without holding time, and then fast cooling to 600°C within 3 min. High-density Al₂O₃ ceramics could be achieved at lower sintering temperatures by SPS, as compared with that by conventional pressureless sintering (PLS). The bending strength of Al₂O₃ superfast densified by SPS in the range of sintering temperature between 1400 and 1550°C reached values as high as 800 MPa, almost twice that obtained by the PLS. SEM observations indicated that intragranular fracture was the preponderant fracture mode in these samples, resulting in these excellent bending strength values.     

Spark plasma sintering and pressureless sintering of SiC using aluminum borocarbide additives

Aluminum borocarbide powders (Al₃BC₃ and Al₈B₄C₇) were synthesized, and the ternary powders were used as a sintering additive of SiC. The densification of SiC was nearly completed at 1670 °C using spark plasma sintering (SPS) and pressureless sintering was possible at 1950 °C. The sintering behavior of SiC using the new additive systems was nearly identical with that using the conventional Al–B–C system, but grain growth was suppressed when adding the borocarbides. In addition, oxidation of the fine additive powders did not intensively occur in air, which has been a problem in the case of the Al–B–C system for industrial application. The hardness, Young's modulus and fracture toughness of a sintered SiC specimen were 21.6 GPa, 439 GPa and 4.6 MPa m^1/2, respectively. The ternary borocarbide powders are efficient sintering additives of SiC.     

Spark plasma sintering of polycrystalline La0.6Ce0.3Pr0.1B6–ZrB2 composites

This paper has studied the densification, microstructure, and properties of polycrystalline La_0.6Ce_0.3Pr_0.1B₆–ZrB₂ composites prepared by spark plasma sintering (SPS). The highest relative density of 98.7% is obtained at the SPS condition of axial mechanical pressure 50 MPa, sintering temperature 1900°C and holding time 5 min. The Vickers hardness decreases linearly from the maximum value of 21.49 GPa to the value of 8.24 GPa with the tested temperature increased from room temperature to 1000°C. The effects of crack deflection and bridging have resulted in the fracture toughness of 4.56 MPa m^1/2 of dense polycrystalline La_0.6Ce_0.3Pr_0.1B₆–ZrB₂ composite. The J_1kV of 7.02 A/cm² obtained at 1600°C, the work function of 2.743 eV determined by ultraviolet photoelectron spectroscopy, and the good oxidation resistance below 1100°C in air have revealed that the dense polycrystalline La_0.6Ce_0.3Pr_0.1B₆–ZrB₂ composite has a good potential to be a promising hot cathode material.     

Preceramic paper-derived Ti3Al(Si)C2-based composites obtained by spark plasma sintering

The paper describes the structure and properties of preceramic paper-derived Ti₃Al(Si)C₂-based composites fabricated by spark plasma sintering. The effect of sintering temperature and pressure on microstructure and mechanical properties of the composites was studied. The microstructure and phase composition were analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. It was found that at 1150 °C the sintering of materials with the MAX-phase content above 84 vol% leads to nearly dense composites. The partial decomposition of the Ti₃Al(Si)C₂ phase becomes stronger with the temperature increase from 1150 to 1350 °C. In this case, composite materials with more than 20 vol% of TiC were obtained. The paper-derived Ti₃Al(Si)C₂-based composites with the flexural strength > 900 MPa and fracture toughness of >5 MPa m^1/2 were sintered at 1150 °C. The high values of flexural strength were attributed to fine microstructure and strengthening effect by secondary TiC and Al₂O₃ phases. The flexural strength and fracture toughness decrease with increase of the sintering temperature that is caused by phase composition and porosity of the composites. The hardness of composites increases from ~9.7 GPa (at 1150 °C) to ~11.2 GPa (at 1350 °C) due to higher content of TiC and Al₂O₃ phases.     

Sintering behavior and mechanical properties of spark plasma sintering SiO2-MgO ceramics

SiO₂-MgO ceramics containing different weight fractions (0, 0.5, 1, 2, and 4 wt%) of SiO₂ powder were prepared by mixing nano MgO powder, and the powder mixtures were densified by spark plasma sintering (SPS). The effect of SiO₂ addition and SPS method on the sintering behavior, microstructure and mechanical properties were investigated. Results were compared to specimens obtained by conventional hot pressing (HP) under a similar sintering schedule. The highest relative density, flexural strength and hardness of 2 wt% SiO₂-MgO ceramics reached 99.98%, 253.99 ± 7.47 MPa and 7.56 ± 0.21 GPa when sintered at 1400 °C by SPS, respectively. The observed improvement in the sintering behavior and mechanical properties are mainly attributed to grain boundary "strengthening" and intragranular "weakening" of the MgO matrix. Furthermore, the spark plasma sintering temperature could be decreased by more than 100 °C as compared with the HP method, SPS favouring enhanced grain boundary sliding, plastic deformation and diffusion in the sintering process.     

Fabrication and characterization of medium-entropy carbide ceramics in low temperature sintering

The medium-entropy carbide (W,Ti,V)C_0.8 ceramics were prepared by sparking plasma sintering at temperatures between 1400 and 1700°C. The effects of sintering temperature on the microstructure and mechanical properties of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics were investigated. X-ray diffraction, scanning electron microscope, and energy dispersive spectrometer were used to confirm the formation of single-phase face-centered cubic (FCC) solid solution of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics prepared at a sintering temperature of 1600°C. It was found that the mechanical properties of the material were improved by solid solution strengthening during the formation of single-phase FCC solid solution, and the best overall performance of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics was achieved at 1600°C, when the hardness value was 22.3 ± 1.8 GPa, the fracture toughness was 5.7 ± 0.8 MPa·m^1/2, the flexural strength was 605 ± 4 MPa, and the compressive strength was 1.84 GPa. Most importantly, the addition of TiC_0.4 promoted the diffusion among the elements of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics, which contributed to the formation of single-phase FCC solid solution and significantly reduced the sintering temperature of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics due to the effect of vacancies. This study provides a new idea for the preparation of medium-entropy carbide ceramics.     

Microstructure and ionic conductivity of Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte prepared by spark plasma sintering

In this paper, the microstructure and ionic conductivity of Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) solid electrolytes prepared by spark plasma sintering (SPS) were investigated by XRD, SEM, TEM and EIS, respectively. The results showed that as the sintering temperature was increased, both the relative density and the ionic conductivity of the sintered LAGP samples first increased and then decreased, achieving a maximum value of 97% and 2.12 × 10⁻⁴ S cm⁻¹ simultaneously at 700 °C. At the same time, the crystallinity of the sintered samples was improved, while a few impurity phases, such as AlPO₄ and GeO₂, appeared in the samples. It was also found that carbon contamination and oxycarbide gas was be brought in during SPS. Carbon contamination could produce an extra grain boundary impedance to the samples and could be removed by annealing at 500 °C in an air atmosphere. Oxycarbide gas could affect the relative density of the sintered LAGP samples and could be mitigated by choosing a suitable SPS process. Moreover, the shear modulus of the sintered LAGP was measured to be 49.6 GPa, which exceeded the minimum value of 8.5 GPa that was necessary to suppress Li dendrite growth.     

Unlubricated sliding wear of B4C composites spark-plasma sintered with Si aids and of their reference B4C monoliths

Two fully-dense B₄C–SiC composites were fabricated by spark-plasma sintering (SPS) from B₄C+Si powders, one superhard (i.e., ～28.7(8) GPa) with abundant SiC by SPS of B₄C+20vol%Si at 1400 °C and the other ultrahard (i.e., ～35.1(4) GPa) with little SiC by SPS of B₄C+4.28vol%Si at 1800 °C, and their unlubricated sliding wear was investigated and compared with those of the reference B₄C monoliths. It was found that the two B₄C–SiC composites underwent mild tribo-oxidative wear with preferential removal of the oxide tribolayer, with the one SPS-ed at 1400 °C from B₄C+20vol%Si being, despite its lower hardness and greater proneness to form oxide tribolayer, only slightly less wear resistant than the one SPS-ed at 1800 °C from B₄C+4.28vol%Si (i.e., ～1.0(5)·10⁷ vs 1.37(8)·10⁷ (N?m)/mm³). The reference B₄C monolith SPS-ed at 1400 °C is comparatively two orders of magnitude less wear resistant (i.e., ～1.70(6)·10⁵ (N?m)/mm³), attributable to its undergoing severe purely mechanical wear by microfracture-dominated three-body abrasion due to its very poor sintering (i.e., high porosity of ～33.5 %), poor grain cohesion, and low hardness (i.e., ～3.1(5) GPa). The reference B₄C monolith SPS-ed at 1800 °C, while equally or less hard (i.e., ～28.4(9) GPa) and slightly porous (i.e., ～5.3 %), is somewhat more wear resistant (～1.8(3)·10⁷ (N?m)/mm³) than the B₄C–SiC composites, attributable to its undergoing only mild purely mechanical wear by plasticity-dominated two-body abrasion without porosity-induced grain pull-out, but it requires SPS temperatures well above 1400 °C. Finally, relevant implications for the ceramics and hard-materials communities with interests in tribological applications are discussed.     

Mechanical properties and thermal conductivity of dense β-SiAlON ceramics fabricated by two-stage spark plasma sintering with Al2O3-AlN-Y2O3 additives

Fully dense β-SiAlON ceramics with excellent mechanical properties and good thermal conductivity were fabricated by two-stage spark plasma sintering (SPS) processes without and with applying pressure respectively, using α-Si₃N₄ powder and 6 Al₂O₃-3 AlN-6 Y₂O₃ (in wt.%, label with 636), 424 and 422 additives. In the first stage SPS process without pressure, the relative dense β-SiAlON ceramics with interlock microstructures of elongated grains and density of 3.14˜3.18 g cm⁻³, hardness of 14.00˜14.82 GPa and fracture toughness of 6.00˜6.63 MPa m^1/2 were obtained by sintering at about 1600 °C for 20 min. In the second stage SPS process at about 1425 °C for 5 min under pressure of 24 MPa, the fully dese β-SiAlON ceramics with density of 3.22˜3.24 g cm⁻³, high hardness of 15.68˜15.95 GPa, high fracture toughness of 6.38˜7.03 MPa m^1/2 and thermal conductivity of 13.5˜19.6 Wm^-1K^-1 were obtained. The reaction between the samples and the graphite mold can be avoided in this fabrication method.     

Spark plasma sintering of Sm2O3-doped aluminum nitride

The high sintering temperature required for aluminum nitride (AlN) at typically 1800 °C, is an impediment to its development as an engineering material. Spark plasma sintering (SPS) of AlN is carried out with samarium oxide (Sm₂O₃) as sintering additive at a sintering temperature as low as 1500–1600 °C. The effect of sintering temperature and SPS cycle on the microstructure and performance of AlN is studied. There appears to be a direct correlation between SPS temperature and number of repeated SPS sintering cycle per sample with the density of the final sintered sample. The addition of Sm₂O₃ as a sintering aid (1 and 3 wt.%) improves the properties and density of AlN noticeably. Thermal conductivity of AlN samples improves with increase in number of SPS cycle (maximum of 2) and sintering temperature (up to 1600 °C). Thermal conductivity is found to be greatly improved with the presence of Sm₂O₃ as sintering additive, with a thermal conductivity value about 118 W m⁻¹ K⁻¹) for the 3 wt.% Sm₂O₃-doped AlN sample SPS at 1500 °C for 3 min. Dielectric constant of the sintered AlN samples is dependent on the relative density of the samples. The number of repeated SPS cycle and sintering aid do not, however, cause significant elevation of the dielectric constant of the final sintered samples. Microstructures of the AlN samples show that, densification of AlN sample is effectively enhanced through increase in the operating SPS temperature and the employment of multiple SPS cycles. Addition of Sm₂O₃ greatly improves the densification of AlN sample while maintaining a fine grain structure. The Sm₂O₃ dopant modifies the microstructures to decidedly faceted AlN grains, resulting in the flattening of AlN–AlN grain contacts.