Sintering highly dense ultra-high temperature ceramics with suppressed grain growth

Grain coarsening normally occurs at the final stage of sintering, resulting in trapped pores within grains, which deteriorates the density and the performance of ceramics, especially for ultra-high temperature ceramics (UHTCs). Here, we propose to sinter this class of ceramics in a specific temperature range and coupled with a relatively high pressure. The retarded grain boundary migration and pressure-enhanced diffusion ensure the proceeding of densification even at final stage. A highly dense TaC ceramic (98.6 %) with the average grain size of 1.48 μm was prepared under 250 MPa via high pressure spark plasma sintering using a C_f/C die at 1850 °C. It was suggested that the final-stage densification is mainly attributed to grain boundary plastic deformation-involved mechanisms. Compared to the usual sintering route using a high temperature (>2000 °C) and normal pressure (<100 MPa), this work provides a useful strategy to acquire highly dense and fine-grained UHTCs.     

High pressure sintering of fully dense tantalum carbide ceramics with limited grain growth

In this work, TaC ceramics with a high density (98.6 %) and fine grains (1.42 µm) were fabricated by high pressure sintering. The as-sintered specimen possessed a high dislocation density of 1.9 × 10¹⁴ m⁻², which contributed to its high hardness of 16.26 GPa. In addition, the electrical conductivity was improved. The characterization results showed that high pressure greatly promoted densification and limited grain growth. The process provides valuable experiences and ideas for obtaining other fully dense structural ceramics with fine grains.     

Sintering dense boron carbide without grain growth under high pressure

Traditionally, densification and grain growth are two competing processes in sintering of ceramics. To improve the density, while limiting grain growth at the same time, an ultrahigh pressure (>1 GPa) is employed here and results in plastic deformation as the dominant densification mechanism during the sintering process. In this way, fully dense boron carbide (B₄C) structural ceramics without grain growth is prepared under the pressure of 4.5 GPa at low temperature of 1300°C in 5 minutes, while showing excellent mechanical properties such as Vickers hardness of 38.04 GPa, Young's modulus of 487.7 GPa, and fracture toughness of 3.87 MPa·m^1/2. This study should also facilitate the development of other structural ceramics for practical applications.     

Consolidation and characterization of highly dense single-phase Ta–Hf–C solid solution ceramics

Herein, Ta–Hf–C solid solution ceramics were consolidated from nano-scale Ta–Hf–C solid solution powders for the first time. Four different compositions (4TaC–1HfC, 1TaC–1HfC, 1TaC–3HfC, and 1TaC–4HfC) were prepared by hot-pressed sintering at 2100°C, 70 MPa pressure and a holding time of 30 minutes. The densification, formation of single-phase solid solution and mechanical properties of the samples were systemically investigated. Relative density >95% was achieved for all four compositions with some improvement when TaC content was increased. And the formation of single-phase Ta–Hf–C solid solution was strongly demonstrated by phase analysis and crystal measurement using XRD and TEM. A significant improvement of hardness up to ~30 GPa was achieved, which was much higher than that of pure TaC (18.9 GPa) and HfC (22.1 GPa), due to the high densification and solid solution strengthening mechanism.     

Mechanical properties and rapid consolidation of binderless nanostructured tantalum carbide

The rapid sintering of nanostructured TaC hard material was investigated with a focus on the manufacturing potential of high-frequency induction heated sintering process. The advantage of this process is that it allows very quick densification to near theoretical density and prohibition of grain growth in nanostructured materials. A dense pure TaC hard material with a relative density of up to 96% was produced with simultaneous application of 80 MPa pressure and induced current within 3 min. The finer the initial TaC powder size, the higher the density and the better mechanical properties. The fracture toughness and hardness values obtained from 10 h milled powder were 5.1 ± 0.3 MPa m^1/2 and 22 GPa, respectively, under 80 MPa pressure and 80% output of total power capacity (15 kW).     

Pressure-enhanced densification of TaC ceramics during flash spark plasma sintering

Flash spark plasma sintering (FSPS) offers extremely high heating rates to consolidate ceramics at a short time. However, significant grain growth sometimes occurs accompanied by rapid densification. In this work, a FSPS apparatus available for applying pressure was used to sinter TaC ceramics from powder compacts without preheating. It is found that the use of a higher pressure can efficiently promote densification and retard significant grain growth. Dense bulk TaC ceramics (95.18%) with average grain size of 4.09 μm were obtained in 90 seconds under 80 MPa. Such a process should facilitate the fast preparation of refractory ceramics with fine-grained microstructure.     

Sintering Mechanism and Microstructure of TaC/SiC Composites Consolidated by plasma-activated sintering

TaC/SiC composites with 5 wt% SiC addition were densified by plasma-activated sintering (PAS) at 1500–1800 °C for 5 min under 30 MPa. The effects of plasma-activated sintering on microstructures, densification and mechanical properties of the composites were investigated. The results showed that TaC/SiC composites achieved a relative density more than 99% of the theoretical density at 1600 °C. A low eutectic liquid phase generated by the oxide on the particle surface was observed in the composite to realize a relatively low temperature sintering densification. While the TaC particle size decreased insignificantly with increasing sintering temperature, the transformation of morphology of SiC particles changing from equiaxed to elongated grain was activated, accompanying with a slight particle size decreasing of the SiC phase, thus promoting a relatively high flexural strength of 550 MPa under 1800 °C. Besides, some ultra-fine 2 nm Ta₂Si was observed in the glassy pockets, strengthening the amorphous phase and thus increasing the flexural strength.     

Microstructure and mechanical properties of tantalum carbide ceramics: Effects of Si3N4 as sintering aid

Stoichiometric Tantalum carbide (TaC) ceramics were prepared by reaction spark plasma sintering using 0.333–2.50 mol% Si₃N₄ as sintering aid. Effects of the Si₃N₄ addition on densification, microstructure and mechanical properties of the TaC ceramics were investigated. Si₃N₄ reacted with TaC and tantalum oxides such as Ta₂O₅ to form a small concentration of tantalum silicides, SiC and SiO₂, with significant decrease in oxygen content in the consolidated TaC ceramics. Dense TaC ceramics having relative densities >97% could be obtained at 0.667% Si₃N₄ addition and above. Average grain size in the consolidated TaC ceramics decreased from 11 µm at 0.333 mol% Si₃N₄ to 4 µm at 2.50 mol% Si₃N₄ addition. The Young's modulus, Vickers hardness and flexural strength at room temperature of the TaC ceramic with 2.50 mol% Si₃N₄ addition was 508 GPa, 15.5 GPa and 605 MPa, respectively. A slight decrease in bending strength was observed at 1200 °C due to oxidation of the samples.     

Solid solution synthesis of tantalum carbide‐hafnium carbide by spark plasma sintering

Solid solutions of Tantalum carbide (TaC) and Hafnium carbide (HfC) were synthesized by spark plasma sintering. Five different compositions (pure HfC, HfC‐20 vol% TaC, HfC‐ 50 vol% TaC, HfC‐ 80 vol% TaC, and pure TaC) were sintered at 1850°C, 60 MPa pressure and a holding time of 10 min without any sintering aids. Near‐full density was achieved for all samples, especially in the HfC‐contained samples. The porosity in pure TaC samples was caused by the oxygen contamination (Ta₂O₅) on the starting powder surface. The addition of HfC increased the overall densification by transferring the oxygen contamination from TaC surface and forming ultrafine HfO₂ and Hf‐O‐C grains. With the increasing HfC concentration, the overall grain size was reduced by 50% from HfC‐ 80 vol% TaC to HfC‐20 vol% TaC sample. The solid solution formation required extra energy, which restricted the grain growth. The lattice parameters for the solid solution samples were obtained using X‐ray diffraction which had an excellent match with the theoretical values computed using Vegard's Law. The mechanical properties of the solid solution samples outperformed the pure TaC and HfC carbides samples due to the increased densification and smaller grain size.     

Effect of boron addition on microstructure,mechanical properties and oxidation resistance of TaC ceramics

TaC ceramics with 0.03–0.60?wt% of boron additions were prepared by hot pressing at 2100?°C for 1?h under a pressure of 40?MPa. Effects of boron content on densification, phase composition, microstructure, mechanical properties and oxidation resistance of the TaC ceramics were investigated. When the boron content was 0.12?wt% and above, full density was obtained due to reactions between boron and oxygen impurity at presence of TaC. Minor phases of TaB₂ and C were formed in the 0.24 and 0.60?wt% B compositions after gas-out of the oxygen impurity. Microstructure of the TaC ceramics was refined with increasing in boron content. The TaC ceramic with 0.24?wt% of boron showed the best mechanical properties with a Vickers hardness, flexural strength and fracture toughness of 17.7?GPa, 534?MPa and 4.6?MPa?m^1/2, respectively. When more boron was added, interfacial bonding of the TaC grains was strengthened causing a decrease in fracture toughness. Oxidation resistance of the TaC ceramics increased with boron content. Particularly, the 0.60?wt% B composition showed a weight gain of 0.0018?g/cm² after oxidization at 800?°C in air for 3?h.     

Influence of processing parameters on the densification and the microstructure of pure zinc oxide ceramics prepared by spark plasma sintering

Due to the sensitivity of nanopowders and the challenges in controlling the grain size and the density during the sintering of ceramics, a systematic study was proposed to evaluate the densification and the microstructure of ZnO ceramics using spark plasma sintering technique. Commercially available ZnO powder was dried and sintered at various parameters (temperature (400–900?°C), pressure (250–850?MPa), atmosphere (Air/Vacuum) etc.). High pressure sintering is desirable for maintaining the nanostructure, though it brings a difficulty in obtaining a fully dense ceramic. Whereas, increasing the temperature from 600 to 900?°C results in fully densified ceramics of about 99% which shows to have big impact on the grain size. However, a high relative density of 92% is obtained at a temperature as low as 400?°C under a pressure of 850?MPa. The application of pressure during the holding time seems to lower the grain size as compared to ceramics pressed during initial stage (room temperature).     

Densification,microstructure and mechanical properties of hot pressed tantalum carbide

Monolithic tantalum carbide (TaC) ceramics were prepared by hot pressing in order to investigate the effect of hot pressing temperature on the densification behavior, microstructure and mechanical properties of TaC. Monolithic TaC sample hot pressed at 2000 °C for 45 min under 40 MPa, with relative density value above 97%, Vickers hardness of 15.7 GPa and fracture toughness of 4.1 MPa m^1/2 was obtained. Fracture surfaces investigations of the samples, which were carried out using the SEM analysis, showed a significant grain growth by increasing the hot pressing temperature from 1700 to 2000 °C. Also, based on the X-ray diffraction pattern, a decrease in the lattice parameter of hot pressed TaC sample was observed.     

Microstructure and mechanical properties of TaC ceramics with 1–7.5 mol% Si as sintering aid

Metallic Si as sintering aid was effective in densifying tantalum carbide ceramic (TaC) by spark plasma sintering (SPS) at 1700°C. Full density was reached at 5.0 mol% Si addition (equivalent to 1.088% Si in weight) and above. Enhanced densification of TaC ceramic with Si was associated with decrease in oxygen content from ~0.24 wt% in TaC powder to ~0.03 wt% in consolidated specimen. Rest of the oxygen species was collected at multigrain conjunctions to form SiO₂‐based liquid at high temperatures. Upon cooling, Ta, Si, O, and C dissolving in the liquid precipitated minor phases of TaSi_x and SiC of low concentrations. Microstructure of TaC ceramics was refined by the Si addition, with average grain size decreasing from 11±8 μm at 1.0 mol% Si to 3±2 μm at 7.5 mol% Si addition. Ta solute in SiC and Si solute in TaC were evidenced. TaC ceramic containing 7.5 mol% Si had a relatively good flexural strength and fracture toughness of 646±51 MPa and 5.0 MPa·m^1/2, respectively.     

Synthesis,processing and properties of TaC–TaB2–C ceramics

Multi-phase ceramics in the TaC–TaB₂–C system were prepared from TaC and B₄C mixtures by reactive pressureless sintering at 1700–1900 °C. The pressureless densification was promoted by the use of nano-TaC and by the presence of active carbon in the reaction products. The presence of TaB₂ inhibited grain growth of TaC and increased the hardness compared to pure TaC. If a coarse TaC powder was used, the compositions did not densify. In contrast, pure nano-TaC was pressureless sintered at 1800 °C by the addition of 2 wt.% carbon introduced as carbon black or graphite. The introduction of carbon black resulted in fully dense TaC ceramics at temperatures as low as 1500 °C. The grain size of nominally pure TaC ceramics was a strong function of carbon stoichiometry. Enhanced grain size in sub-stoichiometric TaC, compared to stoichiometric TaC, was observed. Additional work is necessary to optimize processing parameters and evaluate the properties of ceramics in the TaC–TaB₂–C system.     

Pressureless sintering of silicon carbide ceramics containing zirconium diboride

SiC-5 wt.% ZrB₂ composite ceramics with 10 wt.% Al₂O₃ and Y₂O₃ as sintering aids were prepared by presureless liquid-phase sintering at temperature ranging from 1850 to 1950 °C. The effect of sintering temperature on phase composition, sintering behavior, microstructure and mechanical properties of SiC/ZrB₂ ceramic was investigated. Main phases of SiC/ZrB₂ composite ceramics are all 6H-SiC, 4H-SiC, ZrB₂ and YAG. The grain size, densification and mechanical properties of the composite ceramic all increase with the increase of sintering temperatures. The values of flexural strength, hardness and fracture toughness were 565.70 MPa, 19.94 GPa and 6.68 MPa m^1/2 at 1950 °C, respectively. The addition of ZrB₂ proves to enhance the properties of SiC ceramic by crack deflection and bridging.     

Densification mechanism and microstructure characteristics of nano- and micro- crystalline alumina by high-pressure and low temperature sintering

Fully dense ceramics with retarded grain growth can be attained effectively at relatively low temperatures using a high-pressure sintering method. However, there is a paucity of in-depth research on the densification mechanism, grain growth process, grain boundary characterization, and residual stress. Using a strong, reliable die made from a carbon-fiber-reinforced carbon (C_f/C) composite for spark plasma sintering, two kinds of commercially pure α-Al₂O₃ powders, with average particle sizes of 220 nm and 3 μm, were sintered at relatively low temperatures and under high pressures of up to 200 MPa. The sintering densification temperature and the starting threshold temperature of grain growth (T_sg) were determined by the applied pressure and the surface energy relative to grain size, as they were both observed to increase with grain size and to decrease with applied pressure. Densification with limited grain coarsening occurred under an applied pressure of 200 MPa at 1050 °C for the 220 nm Al₂O₃ powder and 1400 °C for the 3 μm Al₂O₃ powder. The grain boundary energy, residual stress, and dislocation density of the ceramics sintered under high pressure and low temperature were higher than those of the samples sintered without additional pressure. Plastic deformation occurring at the contact area of the adjacent particles was proved to be the dominant mechanism for sintering under high pressure, and a mathematical model based on the plasticity mechanics and close packing of equal spheres was established. Based on the mathematical model, the predicted relative density of an Al₂O₃ compact can reach ～80 % via the plastic deformation mechanism, which fits well with experimental observations. The densification kinetics were investigated from the sintering parameters, i.e., the holding temperature, dwell time, and applied pressure. Diffusion, grain boundary sliding, and dislocation motion were assistant mechanisms in the final stage of sintering, as indicated by the stress exponent and the microstructural evolution. During the sintering of the 220 nm alumina at 1125 °C and 100 MPa, the deformation tends to increase defects and vacancies generation, both of which accelerate lattice diffusion and thus enhance grain growth.     

Microstructure and mechanical properties of the spark plasma sintered TaC/SiC composites: Effects of sintering temperatures

TaC/SiC composites with 20 vol.% SiC addition were densified by spark plasma sintering at 1600–1900 °C for 5 min under 40 MPa. Effects of sintering temperatures on the densification, microstructures and mechanical properties of composites were investigated. The results showed the materials achieved >98% of theoretical density at a temperature as low as 1600 °C. While the TaC grains grew slightly with the sintering temperature increasing, the SiC particles in materials decreased in size. Equiaxed to elongated grain morphology transformation was observed in the SiC phase in the 1900 °C material to obtain a higher flexural strength and fracture toughness of 715 MPa and 6.7 MPa m^1/2, respectively. Lattice enlargement of the TaC phase in the 1900 °C material suggested possible Si diffusion into TaC grains. Ta was also detected in SiC grains by energy dispersive spectroscopy. Glassy pockets present at multi-grain junctions explained the enhanced densification.     

Strengthening Hf0.95Ta0.05B2 ceramic with ultrafine grains and high-density dislocations

Full densification and fine microstructures are the two key optimization targets of ceramic materials. Although fine Hf_0.95Ta_0.05B₂ powder (∼ 0.36 µm) has been synthesized, it was still difficult to obtain densified Hf_0.95Ta_0.05B₂ ceramics with ultrafine grains (< 1 µm) using conventional high temperature sintering. Increasing sintering pressure could provided higher densification driving force, but it usually negatively promoted grain growth for nanoceramics. Our strategy was to gain the fully dense Hf_0.95Ta_0.05B₂ ceramic under a high pressure at a selected temperature with retarded grain growth. In this work, fully dense Hf_0.95Ta_0.05B₂ ceramic was prepared at 1700 °C under a high pressure of 200 MPa. The limited grain growth was achieved with the average grain size of 0.6 µm. Therefore, the mechanical properties were significantly improved, including Vickers hardness (24.8 GPa) and fracture toughness (4.2 MPa.m^1/2), which were ascribed to Hall-Petch and dislocation strengthening mechanism.     

Enhancing the sintering ability of TiNx by introduction of nitrogen vacancy defects

Highly nitrogen-deficient non-stoichiometric TiN_x powders within nitrogen vacancy defects (0.3<x<0.5) were prepared by mechanical alloying and consolidated by high pressure sintering. The effects of nitrogen vacancy defects, sintering temperature and pressure on densification and grain growth of TiN_x were investigated for improving sintering ability and mechanical properties. Increasing nitrogen vacancy defects promoted densification and grain growth of TiN_x. Nitrogen vacancies accelerated material transport and diffusion during sintering and altered strong covalent bonding nature was believed to result in enhanced sintering ability. Densification of TiN_x was enhanced by increasing temperature and elevating pressure, grain growth was promoted by increasing temperature, whereas restrained by elevating pressure. TiN_x (x=0.32) ceramic with relative density of 99.4% and average grain size of 21 nm was obtained at 1200 °C, 5 GPa and 10 min. Vickers hardness of 22.6 GPa and fracture toughness of 5.0 MPa m^1/2 were achieved.     

The effect of SPS parameters on the production of yttria transparent ceramic

In this work, the spark plasma sintering (SPS) of commercial yttria nanopowder is investigated. The SPS parameters such as sintering temperature, applied pressure, and dwell time are varied. Densification without grain growth occurring at occurred up to a sintering temperature of 1400°C and grain growth without further densification taking place at the higher temperature. The optimum sample was obtained at a temperature of 1400°C with a pressure of 70 MPa and dwelling time of 15 minutes. The highest relative density of 99.8% and the average grain size of 1.26 μm were obtained at 1400°C. The yttria ceramic annealed at 1200°C had the in-line transmission of 5%-70% and 70%-82% in the visible and infrared wavelength region, respectively. The measurements of hardness and fracture toughness characteristics of the transparent yttria ceramic showed 9.2 GPa and 2.24 MPa.m^1/2, respectively.