Spark plasma sintering of silicon nitride/barium aluminum silicate composite

Si₃N₄ based composites were successfully sintered by spark plasma sintering using low cost BaCO₃, SiO₂ and Al₂O₃ as additives. Powder mixtures were sintered at 1600–1800 °C for 5 and 10 min. Displacement-temperature-time (DTT) diagrams were used to evaluate the sintering behavior. Shrinkage curve revealed that densification was performed between 1100 and 1700 °C. The specimen sintered at 1700 °C showed the maximum relative density (99.8±0.1%), flexural strength (352±16 MPa), Vickers harness (11±0.1 GPa) and toughness (5.6±0.05 MPa m^1/2).     

Densification behaviour and mechanical properties of B4C–SiC intergranular/intragranular nanocomposites fabricated through spark plasma sintering assisted by mechanochemistry

High-performance B₄C–SiC nanocomposites with intergranular/intragranular structure were fabricated through spark plasma sintering assisted by mechanochemistry with B₄C, Si and graphite powders as raw materials. Given their unique densification behaviour, two sudden shrinkages in the densification curve were observed at two very narrow temperature ranges (1000–1040 °C and 1600–1700 °C). The first sudden shrinkage was attributed to the volume change in SiC resulting from disorder–order transformation of the SiC crystal structure. The other sudden shrinkage was attributed to the accelerated densification rate resulting from the disorder–order transformation of the crystal structure. The high sintering activity of the synthesised powders could be utilised sufficiently because of the high heating rate, so dense B₄C–SiC nanocomposites were obtained at 1700 °C. In addition, the combination of high heating rate and the disordered feature of the synthesised powders prompted the formation of intergranular/intragranular structure (some SiC particles were homogeneously dispersed amongst B₄C grains and some nanosized B₄C and SiC particles were embedded into B₄C grains), which could effectively improve the fracture toughness of the composites. The relative density, Vickers hardness and fracture toughness of the samples sintered at 1800 °C reached 99.2±0.4%, 35.8±0.9 GPa and 6.8±0.2 MPa m^1/2, respectively. Spark plasma sintering assisted by mechanochemistry is a superior and reasonable route for preparing B₄C–SiC composites.     

Microstructures and mechanical properties of B4C–SiC intergranular/intragranular nanocomposite ceramics fabricated from B4C,Si, and graphite powders

B₄C–SiC intergranular/intragranular nanocomposites with high hardness and high toughness were fabricated through mechanochemical processing with B₄C, Si, and graphite powders and subsequent hot pressing without any sintering aid. The milled powders are composed of stacking-disordered SiC and nanocrystalline B₄C. Most nano/micron-sized SiC particles are homogeneously dispersed in B₄C matrix, and some nano-sized SiC and B₄C particles are embedded into B₄C grains to form an intergranular/intragranular structure. The disordered characteristic of the milled powders is the essential factor for the formation of the intragranular structure, sudden densification within the narrow temperature range (1700–1900 °C), and the preparation of dense samples under a relatively low temperature (1900 °C). The relative density, Vickers hardness, and fracture toughness of the samples sintered at 1950 °C are 98.6%, 34.3 GPa, and 6.0 MPa m^1/2, respectively. The intergranular/intragranular structure plays an important role in improving fracture toughness and hardness of the composites.     

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.     

Enhancing the sinterability and fracture toughness of Al2O3–TiN0.3 composites

We introduce a new and effective method for improving the fracture toughness of Al₂O₃-based composites through the addition of a nonstoichiometric material. Al₂O₃–TiN_0.3 composites were sintered by spark plasma sintering with different TiN_0.3 content at temperatures between 1300 and 1600 °C for 10 min and a micro-region diffusion phenomenon was observed at the Al₂O₃–TiN_0.3 interface. Ti atoms from TiN_0.3 diffused into Al₂O₃ to occupy Al sites, which led to the formation of Al vacancies that enabled the transport of aluminum by a vacancy mechanism. The optimal densification temperature of the Al₂O₃–30vol% TiN_0.3 composite was approximately 1400 °C. The maximum fracture toughness measured was 6.91 MPa m^1/2, from the composite with 30 vol% TiN_0.3 sintered at 1500 °C.     

Mechanical properties of LaFeO3 ceramics

The fracture strength, fracture toughness and apparent Young’s modulus of LaFeO₃ ceramics in the temperature region 25–800 °C are reported. The fracture strength of the material was observed to increase from 202 ± 18 MPa at room temperature to 235 ± 38 MPa at 800 °C. The room temperature fracture toughness was 2.5 ± 0.1 MPa m^1/2. The fracture toughness decreased to 2.1 ± 0.1 MPa m^1/2 at 600 °C, followed by an increase to 3.1 ± 0.3 MPa m^1/2 at 800 °C. The temperature dependence of the fracture toughness correlates well with the crystallographic strain, |(a−c)|/(a+c), and ferroelastic toughening of LaFeO₃ materials is inferred. Non-elastic stress–strain behaviour of the LaFeO₃ materials due to ferroelasticity was confirmed by cyclic compression experiments, and residual strain was observed in the material after unloading.     

Pressureless sintered self-reinforced Y-α-SiAlON ceramics

Y-doped α-SiAlONs, where the level of aluminum and oxygen was varied, have been successfully densified by pressureless sintering. The effect of parameters such as starting composition, morphology of grains and sintering temperature on densification and mechanical properties of Y-SiAlON ceramics were study. It was found that Y-α-SiAlONs with different compositions could be pressureless sintered in excess of 98% theoretical density at temperatures ranging from 1750 to 1920 °C. The typical microstructure of the SiAlON investigated consists of elongated α-SiAlON grains uniformly distributed in a matrix of equiaxed grains. Fracture toughness of 6.2 MPa m^1/2 and hardness of 17.6 GPa were found for Y_0.667Si_8.5Al_3.5O_1.5N_14.5 (m = 2.0, n = 1.5) sintered at 1850 °C. The results indicate that both crack deflection and crack bridging mechanisms of toughening operate in the materials, with the latter being the dominant one.     

Effect of FeAl3 on properties of (W,Ti)C–FeAl3 hard materials consolidated by a pulsed current activated sintering method

Using a pulsed current activated sintering (PCAS) method, the densification of (W,Ti)C and (W,Ti)C–FeAl₃ hard materials was accomplished within 3 min. The advantage of this process is not only rapid densification to near theoretical density, but also prevention of grain growth in nano-structured materials. Highly dense (W,Ti)C and (W,Ti)C–FeAl₃ with a relative density up to 99% were obtained within 3 min by PCAS under a pressure of 80 MPa. The average grain size of the (W,Ti)C was less than 100 nm. Hardness and fracture toughness of the dense (W,Ti)C and (W,Ti)C–FeAl₃ produced by PCAS were also investigated. The fracture toughness and hardness values of (W,Ti)C, (W,Ti)C–5 vol.% FeAl₃, and (W,Ti)C–10 vol.% FeAl₃ consolidated by PCAS were 7.5 MPa m^1/2 and 2650 kg/mm², 10.5 MPa m^1/2 and 2480 kg/mm², 11 MPa m^1/2 and 2300 kg/mm², respectively.     

Preparation and characterization of Si3N4-based composite ceramic tool materials by microwave sintering

Si₃N₄-based composite ceramic tool materials with (W,Ti)C as particle reinforced phase were fabricated by microwave sintering. The effects of the fraction of (W,Ti)C and sintering temperature on the mechanical properties, phase transformation and microstructure of Si₃N₄-based ceramics were investigated. The frictional characteristics of the microwave sintered Si₃N₄-based ceramics were also studied. The results showed that the (W,Ti)C would hinder the densification and phase transformation of Si₃N₄ ceramics, while it enhanced the aspect-ratio of β-Si₃N₄ which promoted the mechanical properties. The Si₃N₄-based composite ceramics reinforced by 15 wt% (W,Ti)C sintered at 1600 °C for 10 min by microwave sintering exhibited the optimum mechanical properties. Its relative density, Vickers hardness and fracture toughness were 95.73 ± 0.21%, 15.92 ± 0.09 GPa and 7.01 ± 0.14 MPa m^1/2, respectively. Compared to the monolithic Si₃N₄ ceramics by microwave sintering, the sintering temperature decreased 100 °C,the Vickers hardness and fracture toughness were enhanced by 6.7% and 8.9%, respectively. The friction coefficient and wear rate of the Si₃N₄/(W,Ti)C sliding against the bearing steel increased initially and then decreased with the increase of the mass fraction of (W,Ti)C., and the friction coefficient and wear rate reached the minimum value while the fraction of (W,Ti)C was 15 wt%.     

The processing and properties of (Zr,Hf)B2–SiC nanostructured composites

(Zr, Hf)B₂–SiC nanostructured composites were fabricated by high energy ball milling and reactive spark plasma sintering (RSPS) of HfB₂, ZrSi₂, B₄C and C. Highly dense composites with homogeneously intermixed ultra-fine (Zr, Hf)B₂ and SiC grains (100–300 nm) were obtained after RSPS at 1600 °C for 10 min. The densification was promoted by high energy ball milling and ZrSi₂ additive. The additives were almost completely transformed into ZrB₂ and SiC during densification. The improvement of flexural strength and fracture toughness (641 MPa and 5.36 MPa m^1/2, respectively) was achieved. The relationships between the ultra-fine microstructure and mechanical properties were discussed.     

SiC–AlN Particulate Composite

A SiC–AlN composite was fabricated by mechanical mixing of SiC and AlN powders, hot pressed under 40 MPa at 1950°C in Ar atmosphere. The object of this attempt was to achieve full density and a little solid solution formation. Fine microstructure and crack deflection behaviour are to improve the mechanical properties of the SiC–AlN composite. The bending strength and fracture toughness were achieved 800 MPa and 7·6 MPa m^1/2 at room temperature, respectively. The fracture toughness of the SiC–AlN composite shows minimal change between room temperature and 1400°C. Post-HIP improves the surface densification of the SiC–AlN composite resulting in an increase of the strength and the ability to resist oxidization. The bending strength of SiC–AlN composite increases from 800 to 1170 MPa after HIP treatment for 1 h under 187 MPa at 1700°C in N₂ atmosphere.     

Toughening of SiC matrix with in-situ created TiB2 particles

SiC–TiB₂ composites with up to 50 vol% TiB₂ were fabricated by in-situ reaction between TiO₂, B₄C and C. The densification of the uniaxially pressed samples was done using pressureless sintering in the presence of sintering aids consisting of Al₂O₃ and Y₂O₃. The influence of the volume fraction of TiB₂ and sintering temperature on density and fracture toughness was examined. It was found that fracture toughness is strongly affected by the volume fraction of TiB₂. The presence of TiB₂ particles suppresses the grain growth of SiC and facilitates different toughening mechanisms to operate which, in turn, increases fracture toughness of the composite. The highest value for fracture toughness of 5.7 MPa m^1/2 was measured in samples with 30 vol% TiB₂ sintered at 1940 °C.     

Preparation and properties of an Al2O3/Ti(C,N) micro-nano-composite ceramic tool material by microwave sintering

One kind of Al₂O₃/Ti(C,N) micro-nano-composite ceramic tool material with acceptable properties was prepared by microwave sintering. Effects of sintering temperature and holding time on densification, mechanical properties and microstructure were studied. The optimal relative density, fracture toughness and Vickers hardness were 98.4±0.30, 6.72±0.28 MPa m^1/2 and 18.42±0.59 GPa, respectively, which were obtained at 1550 °C for 10 min. Compared to the conventional sintering, the sintering temperature and holding time of microwave sintering were reduced by 14% and 89%, respectively. The microwave sintering made the sizes of some particles keep in nano-scale, which leaded to the formation of intragranular structures. The residual stress in the intragranular structures increased the ratio of grain boundary toughness to grain toughness of matrix (K_cb/K_cg), and thus the micro-Al₂O₃ grains were more inclined to transgranular fracture.     

Spark plasma sintering and characterization of ZrC-TiB2 composites

ZrC-based composites were consolidated from ZrC and TiB₂ powders by the Spark Plasma Sintering (SPS) technique at 1685 °C and 1700 °C for 300 s under 40-50-60 MPa. Densification, crystalline phases, microstructure, mechanical properties and oxidation behavior of the composites were investigated. The sintered bodies were composed of a (Zr,Ti)C solid solution and a ZrB phase. The densification behaviors of the composites were improved by increasing the TiB₂ content and applied pressure. The highest value of hardness, 21.64 GPa, was attained with the addition of 30 vol% TiB₂. Oxidation tests were performed at 900 °C for 2 h and the formation of ZrO₂, TiO₂ and B₂O₃ phases were identified by using XRD.     

Microwave sintering of fine grained HAP and HAP/TCP bioceramics

The effect of microwave sintering conditions on the microstructure, phase composition and mechanical properties of materials based on hydroxyapatite (HAP) and tricalcium phosphate (TCP) was investigated. Fine grained monophase HAP and biphasic HAP/TCP biomaterials were processed starting from stoichiometric and calcium deficient nanosized HAP powders. The HAP samples microwave (MW) sintered for 15 min at 900 °C, with average grain size of 130 nm, showed better densification, higher density and certainly higher hardness and fracture toughness than samples conventionally sintered for 2 h at the same temperature. By comparing MW sintered HAP and HAP/TCP samples, it was concluded that pure HAP ceramics have superior mechanical properties. For monophase MW sintered HAP samples, the decrease in the grain size from 1.59 μm to 130 nm led to an increase in the fracture toughness from 0.85 MPa m^1/2 to 1.3 MPa m^1/2.     

Densification,microstructure, elastic and mechanical properties of reactive hot-pressed ZrB2–ZrC–Zr cermets

In this study, cermets composed of zirconium diboride and zirconium carbide with intergranular zirconium were sintered by reactive hot-pressing. Relative density exceeding 97% was obtained for the sintered cermets having four distinct compositions varying in concentration of excess Zr. Their densification behaviour was examined by monitoring displacement during sintering. The microstructure was characterized by scanning electron microscopy and X-ray diffraction, and the elastic and mechanical properties were evaluated at room temperature. The effects of Zr concentration on the densification and mechanical properties were assessed. The ZrB₂ and ZrC micron-grains coarsened with increasing amount of Zr starting material. In addition, the cermets exhibited high flexural strength (546–890 MPa) and fracture toughness (6.63–10.24 MPa m^1/2), which simultaneously increased with increasing Zr concentration. However, the elastic moduli and hardness (11–18 GPa) decreased with increasing Zr. The shear modulus and Young's modulus were in the range of 150–190 GPa and 360–440 GPa, respectively.     

Additive-free superhard B4C with ultrafine-grained dense microstructures

A unique combination of high-energy ball-milling, annealing, and spark-plasma sintering has been used to process superhard B₄C ceramics with ultrafine-grained, dense microstructures from commercially available powders, without sintering additives. It was found that the ultrafine powder prepared by high-energy ball-milling is hardly at all sinterable, but that B₂O₃ removal by gentle annealing in Ar provides the desired sinterability. A parametric study was also conducted to elucidate the role of the temperature (1600–1800 °C), time (1–9 min), and heating ramp (100 or 200 °C/min) in the densification and grain growth, and thus to identify optimal spark-plasma sintering conditions (i.e., 1700 °C for 3 min with 100 °C/min) to densify completely (>98.5%) the B₄C ceramics with retention of ultrafine grains (∼370 nm). Super-high hardness of ∼38 GPa without relevant loss of toughness (∼3 MPa m^1/2) was thus achieved, attributable to the smaller grain size and to the transgranular fracture mode of the B₄C ceramics.     

Pressureless sintering and tribological properties of WC–ZrO2 composites

In a recent work [Basu, B., Lee, J. H. and Kim, D. Y., Development of WC-ZrO₂ nanocomposites by spark plasma sintering. J. Am. Ceram. Soc. 2004 87(2), 317–319], the processing of ultrahard WC–ZrO₂ nanocomposites using spark plasma sintering is reported. In the present work, we investigate the processing and properties of WC–6 wt.% ZrO₂ composites, densified by pressureless sintering route. The densification of the WC–ZrO₂ composites was performed in the temperature range of 1500–1700 °C with varying time (1–3 h) in vacuum. The experimental results indicate that significantly high hardness of 22–23 GPa and moderate fracture toughness of ∼5 MPa m^1/2 can be obtained with 2 mol% Y–stabilized ZrO₂ sinter-additive, sintered at 1600 °C for 3 h. Furthermore, the friction and wear behavior of optimized WC–ZrO₂ composite is investigated on a fretting mode I wear tester. The tribological results reveal that a moderate coefficient of friction in the range from 0.15 to 0.5 can be achieved with the optimised composite. A transition in friction and wear with load is noted. The dominant mechanisms of material removal are tribochemical wear and spalling of tribolayer.     

Effect of sintering temperature on microstructure and mechanical properties of zirconia-toughened alumina machinable dental ceramics

This study investigated the effect of sintering temperature on the microstructure and mechanical properties of dental zirconia-toughened alumina (ZTA) machinable ceramics. Six groups of gelcast ZTA ceramic samples sintered at temperatures between 1100 °C and 1450 °C were prepared. The microstructure was investigated by mercury intrusion porosimetry (MIP), X-ray diffraction (XRD), and scanning electron microscopy (SEM) techniques. The mechanical properties were characterized by flexural strength, fracture toughness, Vickers hardness, and machinability. Overall, with increasing temperature, the relative density, flexural strength, fracture toughness, and Vickers hardness values increased and more tetragonal ZrO₂ transformed into monoclinic ZrO₂; on the other hand, the porosity and pore size decreased. Significantly lower brittleness indexes were observed in groups sintered below 1300 °C, and the lowest values were observed at 1200 °C. The highest flexural strength and fracture toughness of ceramics reached 348.27 MPa and 5.23 MPa m^1/2 when sintered at 1450 °C, respectively. By considering the various properties of gelcast ZTA that varied with the sintering temperature, the optimal temperature for excellent machinability was determined to be approximately 1200–1250 °C, and in this range, a low brittleness index and moderate strength of 0.74–1.19 µm^−1/2 and 46.89–120.15 MPa, respectively, were realized.     

Microstructure and mechanical properties of the spark plasma sintered Ta2C ceramics

Single phase hexagonal α-Ta₂C ceramics were synthesized by spark plasma sintering and using TaC and Ta as the starting powders. Effects of sintering temperatures and holding times on the densification process, phase formation, microstructure development, and mechanical properties of the α-Ta₂C ceramics were investigated. Densification occurred in the temperature range of 1520–1675 °C in less than 2.5 min. But completion of the Ta₂C formation took about 40 min at 1500 °C, and 5 min at 1900 °C. The materials sintered at 1500 °C consisted of fine equiaxed grains. The Ta₂C grains grew anisotropic to form an elongated self-toughening microstructure at 1700 °C. At 1900 °C, the neighboring Ta₂C individual crystals coalesced to form large Ta₂C blocks to entrap the residual pores. Although higher flexural strength and fracture toughness were reached at 1700 °C, the unstable microstructures of the Ta₂C materials indicated limited applications at high temperatures.