Pressureless sintering of titanium carbide doped with boron or boron carbide

Titanium carbide ceramics with different contents of boron or B₄C were pressureless sintered at temperatures from 2100 °C to 2300 °C. Due to the removal of oxide impurities, the onset temperature for TiC grain growth was lowered to 2100 °C and near fully dense (>98%) TiC ceramics were obtained at 2200 °C. TiB₂ platelets and graphite flakes were formed during sintering process. They retard TiC grains from fast growth and reduced the entrapped pores in TiC grains. Therefore, TiC doped with boron or B₄C could achieve higher relative density (>99.5%) than pure TiC (96.67%) at 2300 °C. Mechanical properties including Vickers’ hardness, fracture toughness and flexural strength were investigated. Highest fracture toughness (4.79 ± 0.50 MPa m^1/2) and flexural strength (552.6 ± 23.1 MPa) have been obtained when TiC mixed with B₄C by the mass ratio of 100:5.11. The main toughening mechanisms include crack deflection and pull-out of TiB₂ platelets.     

Spark plasma sintering of TiC ceramic with tungsten carbide as a sintering additive

By adding a small amount of tungsten carbide (WC) as sintering aids, nearly fully dense TiC ceramics were obtained by spark plasma sintering at 1450–1600 °C. The results show that the densification temperature of TiC ceramic was significantly decreased with the addition of 3.5 wt% WC. Compared with the monolithic TiC, the densification temperature of TiC–3.5 wt% WC is lower by ～150 °C and no deterioration of mechanical properties is observed. The TiC composite sintered at 1600 °C exhibits full density, a Vickers hardness of 28.2 ± 1.2 MPa, a flexural strength of 599.5 ± 34.7 MPa and a fracture toughness of 6.3 ± 1.4 MPa m^1/2.     

Pressureless sintering of boron carbide with Cr3C2 as sintering additive

In this study, chromium carbide (Cr₃C₂) was selected as the sintering additive for the densification of boron carbide (B₄C). Cr₃C₂ can react with B₄C and form graphite and CrB₂ in situ, which is considered to be effective for the sintering of B₄C composites. The sintering behavior, microstructure development and mechanical properties of B₄C composites were studied. The density of B₄C composite increased with the increase of Cr₃C₂ content and sintering temperature. The formation of liquid phase could effectively improve the densification of B₄C composites. The abnormal grains began to appear at 2080 °C. The bending strength could reach 440 MPa for the 25 wt% and 30 wt% Cr₃C₂ samples after sintering at 2070 °C.     

Fabrication of dense ZrB2/B4C composites using pulsed electric current pressure sintering and evaluation of their high-temperature bending strength

ZrB₂/x·vol%B₄C (x = 30–90) composites were fabricated from ZrB₂ and amorphous B/C powders using pulsed electric current pressure sintering (PECPS) from 1600 °C to 1900 °C for 6.0 × 10² s (10 min) under 50 MPa in a vacuum, accompanied by self-propagating high-temperature synthesis (SHS). Since the B₄C phase was formed at 1600 °C, the relative density (D_r) was evaluated; the composites sintered at 1900 °C attained the highest D_r. Their D_r values increased gradually from 99.35% to 99.99% with increasing B₄C contents up to 60 vol% and showed a constant value above 60 vol%. At room temperature, the mechanical properties of Vickers hardness (H_v), fracture toughness (K_IC) and three-point bending strength (σ_b) were measured. H_v exhibited a monotonous increase from 20.3 to 32.7 GPa. On the other hand, K_IC and σ_b revealed the same behavior for each of the compositions; both exhibited the highest values, i.e., 10.2 MPa m^1/2 for K_IC and 870 MPa for σ_b, in the 60 vol%B₄C sample, and then the K_IC decreased gradually to 9.73 MPa m^1/2, and σ_b dropped suddenly from 850 MPa (70 vol%) to 340 MPa (80 vol%) and stayed as low σ_b in the 90 vol% B₄C sample. Next, the high-temperature σ_b values of the composites (40–70 vol%) were measured in Ar. The composites (40–60 vol%) revealed high σ_b (≥640 MPa) from R.T.~1600 °C; the maximum value of 803.5 MPa was observed for the 60 vol%B₄C composites at 1600 °C, and then the σ_b of all composites dropped to around 340 MPa at 1800 °C. From their stress-strain curves, elastic and plastic deformations were observed at 1600 °C and 1800 °C, respectively.     

Ultra-high temperature ceramics based on ZrB2 obtained by pressureless sintering with addition of Cr3C2, Mo2C,and WC

ZrB₂-MeC and ZrB₂-19 vol% SiC-Me_xC_y where Me=Cr, Mo, W were obtained by pressureless sintering. The capability to promote densification of ZrB₂ and ZrB₂-SiC matrices is the highest for WC and lowest for Cr₃C₂. The interaction between the components results in the formation of new phases, such as MeB (MoB, CrB, WB), a solid solution based on ZrC, and a solid solution based on ZrB₂. The addition of Cr₃C₂ decreases the mechanical properties. On the other hand, the addition of Mo₂C or WC to ZrB₂-19 vol% SiC composite ceramics leads increased mechanical properties. Long-term oxidation of ceramics at 1500 °C for 50 h showed that, in binary ZrB₂-Me_xC_y, a protective oxide scale does not form on the surface thus leading to the destruction of the composite. On the contrary, triple composites showed high oxidation resistance, due to the formation of dense oxide scale on the surface, with ZrB₂-SiC-Mo₂C displaying the best performance.     

Fine grained Al2O3/SiC composite ceramic tool material prepared by two-step microwave sintering

Fine-grained Al₂O₃/SiC composite ceramic tool materials were synthesized by two-step microwave sintering. The effects of first-step sintering temperature (T1), content and particle size of SiC on the microstructure and mechanical properties were studied. It was found that the sample with higher content of SiC was achieved with finer grains, and the incorporation of SiC particles could bridge, branch and deflect the cracks, thus improving the fracture toughness. Higher T1 was required for the densification of the samples with higher content of SiC (>5?wt%). The sample containing 3?wt% SiC particles with the mean particle size of 100?nm, which was sintered at 1600?°C (T1) and 1100?°C (T2) for 5?min had the fine microstructure and optimal properties. Its relative density, grain size, Vickers hardness and fracture toughness obtained were 98.37%, 0.78?±?0.31?μm, 18.40?±?0.24?GPa and 4.97?±?0.30?MPa?m^1/2, respectively. Compared to the sample prepared by single-step microwave sintering, although near full densification can be achieved in both two methods, the grain size was reduced by 36% and the fracture toughness was improved by 28% in two-step microwave sintering.     

Fabrication of in situ elongated β-Sialon grains bonded to tungsten carbide via two-step spark plasma sintering

In order to reduce the difficulty of preparing binder-less cemented carbide and further broaden its application prospects, tungsten carbide toughened by in situ elongated β-Sialon grains was developed via sintering ball-milled WC and α-Si₃N₄ powders using Al₂O₃–ZrO₂ as a sintering aid and transformation additive. The two-step spark plasma sintering of the mixture at 1650 °C with dwelling at 1500 °C for 10 min was conducted under 30 MPa uniaxial pressure, and the densification behaviors, phase transformations, mechanical properties, and microstructures of the produced composites were investigated. The addition of Al₂O₃–ZrO₂ reduced the initial temperature of the densification process by approximately 100 °C and its final temperature by 200 °C (compared with the densification temperatures of pure WC and Si₃N₄ materials) and fully transformed α-Si₃N₄ to Sialon (Si–Al–O–N) phases. Microstructural characterization data showed that the WC matrix contained homogeneously distributed equiaxed and elongated β-Si₅AlON₇ grains. The WC composites containing in situ elongated β-Sialon grains exhibited an optimal hardness of 18.93 ± 0.03 GPa and enhanced fracture toughness of 10.43 ± 0.27 MPa m^1/2. The toughening mechanism of the β-Sialon phase involved the pull-out of elongated grains and crack bridging.     

Fabrication of transparent Y2O3 ceramics by two-step spark plasma sintering

Transparent Y₂O₃ ceramics were successfully fabricated by spark plasma sintering applying a two-step pressure and heating profile. Through the shrinkage curve of the single-step SPS profile, it was confirmed that shrinkage occurred at 800°C–1250°C, and it was selected as the two-step pressure profile. After the first-step SPS stage at 1250°C, the second-step SPS stage, which had the highest real in-line transmittance, was completed at 1500°C. The two-step SPS profile improved the shrinkage behavior and was able to achieve sufficient densification without excessive coarsening. As a result, the normalized real in-line transmittance to 1 mm was 80.6% at 1100 nm, which is close to the theoretical transmittance of 81.6%. The two-step pressure and heating profile in the SPS process was a significant advantage in manufacturing ceramics that were transparent and had sufficient densification.     

Fabrication and mechanical properties of homogeneous and gradient nanocomposites by two-step sintering

Homogeneous and functional gradient nanocomposites were prepared using a two-step sintering process at a pressure of 30 MPa. The effects of macro –micro fracture morphologies and element distributions on the mechanical properties of the composites were studied. The results showed that the fracture toughness of the inner layers of the gradient material was almost the same as that of the corresponding homogeneous material. The composition content difference between the gradient layers had a significant influence on the bending strength and hardness. There was little Ni and Mo diffusion in the gradient nanocomposites because of the relatively low contents and suitable processing parameters. A gradient distribution of the metals was ensured. The surface layer thickness had little influence on the flexural strength of the gradient nanocomposite, but it had an obvious influence on the hardness and fracture toughness of the surface. The five-layered gradient composite with a surface layer thickness of 85 μm exhibited the best mechanical properties, including a flexural strength of 1021 ± 35 MPa, fracture toughness of 7.60 ± 0.21 MPa m^1/2 and surface hardness of 19.26 ± 0.62 GPa.     

Low temperature pressureless sintering of dense silicon nitride using BaO-Al2O3-SiO2 glass as sintering aid

Dense Si₃N₄ ceramic with BaO-Al₂O₃-SiO₂ low temperature glass powders as sintering aids were prepared by pressureless sintering techniques at a relatively low temperature (1550 °C). Four kinds of glass powders of compositions melting at 1120 °C, 1300 °C, 1400 °C and 1500 °C, respectively, have been introduced as sintering aids. XRD results demonstrate that the BaO-Al₂O₃-SiO₂ glass powders reacted with BaAl₂O₄ and converted into hexagonal celsian, which is a high-temperature phase with melting point of 1760 °C, so being beneficial to the high temperature properties of the materials. In addition, a portion of α-Si₃N₄ transformed to rod like β-Si₃N₄ with high aspect ratio as shown by XRD and SEM analysis. The bulk density increased with the rise of the melting temperature of the BaO-Al₂O₃-SiO₂ glass powders, the sample obtained with the BaO-Al₂O₃-SiO₂ glass powder melting at 1500 °C reaching a maximum density of 98.8%, an high flexural strength (373 MPa) and a fracture toughness (4.8 MPa m^1/2).     

Low-temperature reactive spark plasma sintering of dense SiC-Ti3SiC2 ceramics

SiC-based ceramics are of great interest for various advanced applications. However, its fabrication requires high-temperature treatment at ～2000 – 2100 °С. In this study, we developed an approach based on low-temperature reactive spark plasma sintering to produce dense SiC-based ceramics with superior mechanical properties. It was found that an SPS temperature of 1600 °C and introduction of 10 – 15 wt% of mechanically activated non-oxide Ti–Si–C additive is required to manufacture ceramics with a theoretical density of higher than 90%. Nonetheless, employing 5 – 15 wt% of the additive mixture and an SPS temperature of 1700 °C, the maximum density of ～ 98% was achieved. The controlled formation and decomposition of the in-situ Ti₃SiC₂ MAX phase enables the fabrication of the engineering ceramics with enhanced compressive strength (550 MPa), elastic modulus (485 GPa), and microhardness (32 GPa), which are comparable to the best-reported SiC ceramics. The study has a significant potential for practical application in the production of advanced SiC-based ceramics for various purposes and could be used for further understanding and development of the high-temperature sintering methods.     

Fabrication of transparent LaAlO3/t-ZrO2 nanoceramics through controlled amorphous crystallization

Transparent nanoceramics are attracting more and more interests recently, while it is practically difficult to prepare by conventional sintering process because of undesirable grain growth. In this study a new method of amorphous sintering followed by controlled crystallization (ASCC) was developed, and transparent LaAlO₃/t-ZrO₂ nanoceramics were prepared as examples. Glass powders from Al₂O₃-La₂O₃-ZrO₂ (ALZ) were synthesized, sintered, and then converted to nanoceramics by post-heat-treatment. The processes of hot pressing and controlled crystallization were investigated in detail. The heat-treatment performed at 1200 °C for 2 h produced a transparent LaAlO₃/t-ZrO₂ nanoceramic with an average grain size of 40 nm. Due to the nanoscale microstructure, the composite showed a transparency up to 55% at 800 nm (1 mm thick), Vickers hardness of 19.05 GPa, and fracture toughness of 2.64 MPa m^1/2, respectively. It is expected to be a promising candidate for window materials.     

Fabrication and mechanical properties of multi-walled carbon nanotubes doped AlN ceramics prepared by spark plasma sintering

In this study, multi-walled carbon nanotubes (MWCNTs) are uniformly dispersed in aluminium nitride (AlN) powders, and the MWCNTs-doped AlN ceramics are sintered at 1500 °C with a holding time of 5 min by spark plasma sintering using Y₂O₃ as the sintering additive. The effects of the MWCNTs content on the microstructure and mechanical properties of the as-obtained ceramic composites are investigated. The results reveal that many submicron pores are generated when protecting the structure of the CNTs, thereby reducing the density of the AlN ceramic. However, the gradual filling of the grain gap may compensate for the strengthening after CNT doping. The relative density and hardness reach the maximum values of 89.6% of the theoretical density and 7.0 ± 0.3 GPa, respectively, at the doping amount of 2.5 wt%.     

Fabrication and properties of dense silicon carbide ceramic via gel-casting and gas silicon infiltration

The dense Silicon Carbide (SiC) ceramics are fabricated by means of gel-casting and gas silicon infiltration (GSI) using carbon black and α-SiC as raw materials. We have successfully introduced a new initiator AIBA which is very suitable to aqueous gel-casting system containing carbon black, overcoming the problems posed by the conventionally used initiator. We have investigated the influences of the monomer acrylamide (AM) content, the ratio of the monomer to crosslinking agent AM/MBAM content, the particle size distribution and the solid content on the mechanical and structural properties of samples. The result show that, the linear shrinkage of the green body can be reduced to 1.0% and its bending strength can reach 59.2 MPa at the optimized gel-casting process that has an AM content of 25 wt%, an AM to MBAM ratio of 12, a SiC particle distribution of 3/2 and a solid content of 60 vol%. After the GSI process, the bending strength and elastic modulus of the final products from such green bodies can reach 245 MPa and 220 GPa respectively. The study highlights that the combined application of the gel-casting and the GSI processes can produce high-quality silicon carbide ceramics that are suitable in the space optical applications.     

Fabrication and microstructure of porous SiC ceramics with Al2O3 and CeO2 as sintering additives

In the present study, porous silicon carbide ceramics were prepared via spark plasma sintering at relatively low temperatures using Al₂O₃ and CeO₂ as sintering additives. Sacrificial template was selected as the pore forming mechanism, and gelcasting was used to fix the slurry in a short time. The evolution process of the microstructures during different steps was observed by SEM. The influence of the sintering temperature and sintering additives on the shrinkage and porosity of the samples was studied. The microstructures of different samples were characterized, and the mechanical properties were also evaluated.     

Microstructure and mechanical properties of B4C based ceramics with Fe3Al as sintering aid by spark plasma sintering

B₄C based ceramics were fabricated with different Fe₃Al contents as sintering aids by spark plasma sintering at relatively low temperature (1700 °C) in vacuum by applying 50 MPa pressure and held at 1700 °C for 5 min. The effect of Fe₃Al additions (from 0 to 9 wt%) on the microstructure and mechanical properties of B₄C has been studied. The composition and microstructure of as-prepared samples were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe microanalyzer (EPMA) equipped with WDS (wavelength dispersive spectrometry) and EDS. The mixtures of B₄C and Fe₃Al underwent a major reaction in which the metal borides and B₄C were encountered as major crystallographic phases. The sample with 7 wt% of Fe₃Al as a sintering aid was found to have 32.46 GPa Vickers hardness, 483.40 MPa flexural strength, and 4.1 MPa m^1/2 fracture toughness which is higher than that of pure B₄C.     

Preparation and mechanical properties of SiCw-reinforced WC-10Ni3Al cemented carbide by microwave sintering

SiC_w-reinforced WC-10Ni₃Al cemented carbide was prepared by microwave sintering method, and the effects of the sintering temperature and SiC_w content on the microstructure and mechanical properties of WC-10Ni₃Al cemented carbide were investigated; the promotion effect and strengthening mechanism of SiC_w were then analysed. The experimental results showed that the relative density, hardness, flexural strength and fracture toughness of WC-10Ni₃Al cemented carbide increased and then decreased with increasing SiC_w addition and sintering temperature. When the sintering temperature was 1500 °C and the content of SiC_w was 0.3 wt%, the sample reached the highest mechanical properties and had a relative density of 96.5%, hardness of 1570 HV, flexural strength of 1275 MPa and fracture toughness of 13.1 MPa mm^1/2, which were 4.0%, 23.1%, 12.5% and 8.1% higher than those of the sample without SiC_w, respectively. During microwave sintering of WC-Ni₃Al, the addition of an appropriate SiC_w content can increase the microwave absorption of the sample, and produce many micro-high-temperature regions within the sample, which can accelerate the generation of the Ni₃Al liquid phase. This promotes liquid phase flow to fill pores and rearrange the WC grains, thereby improving density and mechanical properties of the sample. The strengthening mechanisms of SiC_w on microwave sintered WC-Ni₃Al consist of promoting densification enhancement, fine-grained strengthening, and solid solution strengthening of Ni₃Al by Si atoms.     

Microstructure and properties of dense Tyranno-ZMI SiC/SiC containing Ti3Si(Al)C2 with plastic deformation toughening mechanism

In this paper, Ti₃Si(Al)C₂ was introduced into dense SiC/SiC to improve the mechanical and electromagnetic interference (EMI) shielding properties. In order to reveal the effect of Ti₃Si(Al)C₂, dense SiC/SiC-Ti₃Si(Al)C₂ and dense SiC/SiC without Ti₃Si(Al)C₂ were fabricated. Owing to the plastic deformation toughening mechanism of Ti₃Si(Al)C₂, SiC/SiC-Ti₃Si(Al)C₂ performs a new damage mode characterized by matrix/matrix (m/m) debonding. High interfacial shear strength (IFSS) due to large thermal residual stress (TRS) is weakened by m/m debonding. This new mode also brings high effective volume fraction of loading fibers and long path of crack propagation. Hence SiC/SiC-Ti₃Si(Al)C₂ exhibits higher flexural strength (503 MPa) and fracture toughness (23.7 MPa · m^1/2) than the dense SiC/SiC without Ti₃Si(Al)C₂. In addition, dense SiC/SiC-Ti₃Si(Al)C₂ shows excellent electromagnetic interference shielding effectiveness (EMI SE, 43.0 dB) in X-band, revealing great potential as thermo-structural and functional material.     

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.     

Two step sintering of a novel calcium magnesium silicate bioceramic: Sintering parameters and mechanical characterization

Two-step sintering (TSS) was applied to control the grain growth during sintering of a novel calcium magnesium silicate (Ca₃MgSi₂O₈ – Merwinite) bioceramic. Sol–gel derived nanopowders with the mean particle size of about 90 nm were sintered under different TSS regimes to investigate the effect of sintering parameters on densification behavior and grain growth suppression. Results showed that sintering of merwinite nanopowder under optimum TSS condition (T₁ = 1300 °C, T₂ = 1250 °C) yielded fully dense bodies with finest microstructure. Merwinite compacts held at T₂ = 1250 °C for 20 h had the average grain size of 633 nm while the relative density of about 98% was achieved. Mechanical testing was performed to investigate the effect of grain growth suppression on the hardness and fracture toughness. Comparison of mechanical data for samples sintered under two sintering regimes, including TSS and normal sintering (NS), showed TSS process resulted in significant enhancement of fracture toughness from 1.77 to 2.68 MPa m^1/2.