Densification,microstructure and mechanical properties of hot pressed ZrB2–SiC ceramic doped with nano-sized carbon black

The effect of nano-sized carbon black on densification behavior, microstructure, and mechanical properties of zirconium diboride (ZrB₂) – silicon carbide (SiC) ceramic was studied. A ZrB₂-based ceramic matrix composite, reinforced with 20 vol% SiC and doped with 10 vol% nano-sized carbon black, was hot pressed at 1850 °C for 1 h under 20 MPa. For comparison, a monolithic ZrB₂ ceramic and a ZrB₂–20 vol% SiC composite were also fabricated by the same processing conditions. By adding 20 vol% SiC, the sintered density slightly improved to ~93%, compared to the relative density of ~90% of the monolithic one. However, adding 10 vol% nano-sized carbon black to ZrB₂–20 vol% SiC composite meaningfully increased the sinterability, as a relatively fully dense sample was obtained (RD=~100%). The average grain size of sintered ZrB₂ was significantly affected and controlled by adding carbon black together with SiC acting as effective grain growth inhibitors. The Vickers hardness, flexural strength and fracture toughness of SiC reinforced and carbon black doped composites were found to be remarkably higher than those of monolithic ZrB₂ ceramic. Moreover, unreacted carbon black additives in the composite sample resulted in the activation of some toughening mechanisms such as crack deflections.     

Influence of graphite nano-flakes on densification and mechanical properties of hot-pressed ZrB2–SiC composite

Hot pressed monolithic ZrB₂ ceramic (Z), ZrB₂–20 vol% SiC composite (ZS₂₀) and ZrB₂–20 vol% SiC–10 vol% nano-graphite composite (ZS₂₀G_n10) were investigated to determine the influence of graphite nano-flakes on the sintering process, microstructure, and mechanical properties (Vickers hardness and fracture toughness) of ZrB₂–SiC composites. Hot pressing at 1850 °C for 60 min under 20 MPa resulted in a fully dense ZS₂₀G_n10 composite (relative density: 99.6%). The results disclosed that the grain growth of ZrB₂ matrix was efficiently hindered by SiC particles as well as graphite nano-flakes. The fracture toughness of ZS₂₀G_n10 composite (7.1 MPa m^1/2) was essentially improved by incorporating the reinforcements into the ZrB₂ matrix, which was greater than that of Z ceramic (1.8 MPa m^1/2) and ZS₂₀ composite (3.8 MPa m^1/2). The fractographical observations revealed that some graphite nano-flakes were kept in the ZS₂₀G_n10 microstructure, besides SiC grains, which led to toughening of the composite through graphite nano-flakes pull out. Other toughening mechanisms such as crack deflection and branching as well as crack bridging, due to the thermal residual stresses in the interfaces, were also observed in the polished surface.     

The fabrication and mechanical properties of SiC/ZrB2 laminated ceramic composite prepared by spark plasma sintering

Laminated SiC/ZrB₂ ceramic was fabricated by roll-compaction and spark plasma sintering at 1600 °C. A maximum fracture toughness of 12.3 ± 0.3 MPa m^1/2 was measured for the sintered SiC/ZrB₂ laminated ceramic. This significant improvement in fracture toughness can be attributed to the crack deflection along the interfacial layer and the presence of residual stresses in the sample. The effect of interlayer composition on the residual stresses was discussed in detail. It is observed that the residual thermal stress could be reduced by addition of ZrB₂ particles to the SiC interlayer. The bending strength can be increased to 388 ± 44 MPa with the addition of 20 vol% ZrB₂ to the SiC interlayer.     

Particle size effect of starting SiC on processing,microstructures and mechanical properties of liquid phase-sintered SiC

Dense SiC (97.3–99.2% relative density) of 1.1–3.5 μm average grain size was prepared by the combination of colloidal processing of bimodal SiC particles with sintering additives (Al₂O₃ plus Y₂O₃, 2–4 vol%) and subsequent hot-pressing at 1900–1950 °C. The fracture toughness of SiC was sensitive to the grain boundary thickness which was controlled by grain size and amount of oxide additives. A maximum fracture toughness (6.2 MPa m^1/2) was measured at 20 nm of grain boundary thickness. The mixing of 30 nm SiC (25 vol%) with 800 nm SiC (75 vol%) was effective to reduce the flaw size of fracture origin, in addition to a high fracture toughness, leading to the increase of flexural strength. However, the processing of a mixture of 30 nm SiC (25 vol%)–330 nm SiC (75 vol%) provided too small grains (1.1 μm average grain size), resultant thin grain boundaries (12 nm), decreased fracture toughness, and relatively large defect of fracture origin, resulting in the decreased strength.     

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.     

Microstructure development,hardness, toughness and creep behaviour of pressureless sintered alumina/SiC micro–nanocomposites obtained by slip-casting

Al₂O₃–SiC micro–nanocomposites are much more resistant materials than monolithic alumina regarding some mechanical properties. In order to study the possibility of obtaining creep resistant alumina/SiC micro–nanocomposites using inexpensive forming methods, alumina 1 and 5 vol% SiC materials were produced by slip-casting and pressureless sintering. Well-densified alumina–SiC pressureless sintered materials were obtained at 1700 °C for 2 h and attained 97–99% of the theoretical density. The microstructure, hardness and toughness were examined and 4-point flexure creep tests were performed at 1200 °C and 100 MPa in air. Compared with pure alumina materials, the creep resistance, toughness and hardness were enhanced drastically in materials containing 5 vol% of SiC.     

Silicon carbide–titanium diboride ceramic composites

The effect of TiB₂ content on mechanical properties of silicon carbide–titanium diboride ceramic composites was studied. The hardness of the ceramics decreased from 27.8 GPa for nominally pure SiC to 24.4 GPa for nominally pure TiB₂. In contrast, fracture toughness of the ceramics increased from 2.1 MPa m^1/2 for SiC to ～6 MPa m^1/2 for SiC with TiB₂ contents of 40 vol.% or higher. Flexure strengths were measured for three composites containing 15, 20, and 40 vol.% TiB₂ and analyzed using a two parameter Weibull analysis. The Weibull modulus increased from 12 for 15 vol.% TiB₂ to 17 for 20 and 40 vol.% TiB₂. Microstructural analysis revealed microcracking in the ceramics containing 20 and 40 vol.% TiB₂. The ceramic containing 40 vol.% TiB₂ had the best combination of properties with a fracture toughness of 6.2 MPa m^1/2, hardness of 25.3 GPa, Weibull modulus of 17, and a strength of 423 MPa.     

Influence of in-situ synthesized Zr-Al-C on microstructure and toughening of ZrB2-SiC composite ceramics fabricated by spark plasma sintering

Zr-Al-C was in-situ synthesized as a toughening component in ZrB₂-SiC ceramics by spark plasma sintering (SPS) ball-milled ZrB₂-based composite powders with SiC and graphite powders. The phase composition of Zr-Al-C toughened ZrB₂-SiC (ZSA) composite ceramics fabricated through the two-step process (ball milling and SPS) did not change dramatically with varying content of Zr-Al-C which shows a major phase of Zr₃Al₄C₆. With increasing Zr-Al-C content, the fracture toughness of the ZSA ceramics initially increased and then decreased when the content reached 40 vol%. The ZSA ceramic with 30 vol% Zr-Al-C exhibited a maximum fracture toughness value of 5.96 ± 0.31 MPa m^1/2, about 22% higher than that of the ZSA ceramic with 10 vol% Zr-Al-C. When the Zr-Al-C content goes beyond 30 vol%, the higher open porosity and component agglomeration led to the relatively lower fracture toughness. Crack deflection and bridging resulted from the weak interface bonding between Zr-Al-C and matrix phases and the weak internal layers of Zr-Al-C crystals, leading to longer crack paths and, hence, the toughened ZSA composite ceramics. Compared to the one-step in-situ synthesis process of Zr-Al-C and the direct incorporation process of synthesized Zr-Al-C grains, the two-step in-situ synthesis process not only led to the more uniform distribution of different components but also resulted in a much larger size of Zr-Al-C grains with a large aspect ratio causing longer crack propagation path as the result of crack deflection and bridging. The larger Zr-Al-C grains combined with the more homogeneous microstructure achieve the most substantial toughening of the ZSA composite ceramics. This work points out a promising approach to control and optimize the microstructure and improve the fracture toughness of ZrB₂-SiC composite ceramics by selecting the incorporation process of compound reinforcement components.     

Effects of plasma gas composition on bond strength of hydroxyapatite/titanium composite coatings prepared by rf-plasma spraying

The effects of plasma gas composition on the bond-strength of HA/Ti composite coatings were investigated. HA/Ti composite coatings were deposited on titanium substrates by a radio-frequency (rf) thermal plasma spraying method with input powers of 10–30 kW. The ratio of the HA and Ti powders supplied into the plasma was precisely controlled by two microfeeders so as to change the coating's composition from Ti-rich at the bottom to HA-rich at its upper layer. The bond (tensile) strength of the obtained HA/Ti composite coatings was 40–65 MPa when sprayed with plasma gas containing N₂ (i.e., Ar–N₂). On the other hand, HA/Ti composite coatings prepared with plasma gas containing O₂ (i.e., Ar–O₂) had significantly lower bond strength (under 30 MPa). XRD patterns of Ti coatings without HA showed that titanium nitride and titanium dioxide formed, respectively, on titanium deposits sprayed with Ar–N₂ and Ar–O₂ plasma. Scanning electron microscopic (SEM) observation showed an acicular texture on the Ti deposits prepared with Ar–N₂ plasma. SEM observations implied that, when sprayed with Ar–O₂ plasma, a thin TiO₂ layer formed at the interfaces between the Ti splats in the deposits.     

Pressureless sintered SiC matrix toughened by in situ synthesized TiB2: Process conditions and fracture toughness

This paper reports the fabrication of SiC toughened by in situ synthesized TiB₂ based on pressure-less sintering technique using TiO₂, B₄C, C and SiC as starting materials. The process conditions were investigated in detail, including the pre-sintering temperatures, carbon contents, differently sized TiO₂ powders, TiB₂ volume contents, final sintering temperature and time. These conditions were found to have great influence on the TiB₂ toughened SiC in terms of relative density, TiB₂ particle size and fracture toughness. Homogeneous dispersion of in situ synthesized TiB₂ secondary phase was confirmed to enhance the K_IC of the SiC matrix. The K_IC of SiC toughened by in situ synthesized TiB₂ (15 vol%) reaches 6.3 MPa m^1/2, which is among the highest values reported so far on TiB₂ reinforced SiC composites based on the pressure-less sintering technique using TiO₂ as Ti source.     

A high strength alumina-silicon carbide-boron carbide triplex ceramic

A ceramic particulate composite composed of oxide, and carbide ceramics was found to have high strength, hardness, and fracture toughness values. A composition consisting of Al₂O₃ with 15 vol% SiC and 15 vol% B₄C additions was produced by hot-pressing at 1650 °C for 30 min, with full density reached after ~5 min at temperature. Both WB and WB₂ were observed, with the W source presumably an impurity from WC milling media, and Al₁₈B₄O₃₃ was also detected following densification. Strength was ~880 MPa, which is greater than values reported for comparable composites of Al₂O₃ containing 30 vol% SiC or B₄C. Vickers hardness was ~21 GPa, and fracture toughness was ~4.5 MPa m^½, comparable to values reported for the binary mixtures. The calculated critical flaw size of the material was similar to the size of the SiC/B₄C clusters and microcracking at grain boundaries. The latter resulting from thermal expansion mismatch between the Al₂O₃ matrix and SiC/B₄C reinforcing phases.     

Microstructure,hardness and fracture toughness of spark plasma sintered ZrB2–SiC–Cf composites

The combined effects of SiC particles and chopped carbon fibers (C_f) as well as sintering conditions on the microstructure and mechanical properties of spark plasma sintered ZrB₂-based composites were investigated by Taguchi methodology. Analysis of variance was used to optimize the spark plasma sintering variables (temperature, time and pressure) and the composition (SiC/C_f ratio) in order to enhance the hardness of ZrB₂–SiC–C_f composites. The sintering temperature was found as the most effective variable, with a significance of 83%, on the hardness. The hardest ZrB₂-based ceramic was achievable by adding 20 vol% SiC and 10 vol% C_f after spark plasma sintering at 1850 °C for 6 min under 30 MPa. Fracture toughness improvement were related to the simultaneous presence of SiC and C_f phases as well as the in-situ formation of nano-sized interfacial ZrC particles. Crack deflection, crack branching and crack bridging were detected as the toughening mechanisms. A Vickers hardness of 14.8 GPa and an indentation fracture toughness of 6.8 MPa m^1/2 were measured for the sample fabricated at optimal processing conditions.     

Reactive hot pressing of SiC-ZrC composites at low temperature

SiC-ZrC composites with relative density in excess of 99% were prepared by reactive hot pressing (RHP) of SiC and ZrH₂ at 1800 °C for 1 h. The reaction between SiC and ZrH₂ resulted in the formation of ZrC_1-x. The formation process and densification behavior during RHP process were investigated. Low temperature densification of SiC-ZrC composites is attributed to the formed nonstoichiometric ZrC_1-x and the removal of SiO₂ impurity on the surface of SiC particles. As reinforced phase, ZrC_1-x has inhibiting effect on the abnormal grain growth of SiC, resulting in homogeneous microstructure of fine SiC grains. Adding 10 wt% ZrH₂ to SiC, the formed SiC-4.62 vol% ZrC composite exhibited better mechanical properties (Vickers hardness of 27.6 ± 0.7 GPa, flexure strength of 448 ± 38 MPa, fracture toughness of 6.0± 0.3 MPa·m^1/2, respectively) than monolithic SiC ceramic.     

Microstructure,mechanical properties and machining performance of spark plasma sintered Al2O3–ZrO2–TiCN nanocomposites

The effect of addition of nanocrystalline ZrO₂ and TiCN to ultrafine Al₂O₃ on mechanical properties and microstructure of the composites developed by spark plasma sintering (SPS) was investigated. The distribution of the nanoparticles was dependent on their overall concentration. Maximum hardness (21 GPa) and indentation toughness (5.5 MPa m^1/2) was obtained with 23 vol% nanoparticles, which was considered as the optimum composition. The Zener pinning criteria were also satisfied at this composition with grain size of the restraining nanoparticles ～63–65 nm. Hardness of the composites follows the rule of mixtures; crack deflection and crack arrest by nanoparticles at grain boundaries along with mixed fracture mode led to high toughness in the nanocomposites. Cutting tool inserts were developed by SPS with the optimized composition and their machining performance was compared with commercial alumina based inserts. Increased toughness in the nanocomposite inserts reflects in the machining performance as the tool life improves drastically compared to that of the commercial inserts at high cutting speeds ≥500 m min^?1. This was attributed to differences in their failure modes; the commercial inserts fail catastrophically by fracture due to their low toughness whereas the nanocomposite inserts reach the tool failure criteria by crater wear at all machining conditions.     

Improved mechanical properties of Al2O3 ceramic by in-suit generated Ti3SiC2 and TiC via hot pressing sintering

Al₂O₃ multi-phase composites with different volume fractions of SiC varying from 0 vol% to 30.0 vol% were fabricated by vacuum hot pressing sintering at 1600 °C under the pressure of 30 MPa for 2.0 h. The aim of this work was to investigate the effect of SiC content on the morphology and mechanical properties of the Al₂O₃ multi-phase composite. The results show that the addition of SiC and Ti can produce new strengthening and reinforcing phases include Ti₃SiC₂, TiC, Ti₅Si₃, which would hamper the migration of grain boundaries and promote sintering. The mechanical performances could reach the comprehensive optimal values for 20.0 vol% SiC, delamination and transgranular fracture being the major crack propagation energy dissipation mechanisms.     

Microstructure,mechanical, thermal,and oxidation properties of a Zr2[Al(Si)]4C5–SiC composite prepared by in situ reaction/hot-pressing

The microstructure, mechanical and thermal properties, as well as oxidation behavior, of in situ hot-pressed Zr₂[Al(Si)]₄C₅–30 vol.% SiC composite have been characterized. The microstructure is composed of elongated Zr₂[Al(Si)]₄C₅ grains and embedded SiC particles. The composite shows superior hardness (Vickers hardness of 16.4 GPa), stiffness (Young's modulus of 386 GPa), strength (bending strength of 353 MPa), and toughness (fracture toughness of 6.62 MPa m^1/2) compared to a monolithic Zr₂[Al(Si)]₄C₅ ceramic. Stiffness is maintained up to 1600 °C (323 GPa) due to clean grain boundaries with no glassy phase. The composite also exhibits higher specific heat capacity and thermal conductivity as well as better oxidation resistance compared to Zr₂[Al(Si)]₄C₅.     

UHTC–carbon fibre composites: Preparation,oxyacetylene torch testing and characterisation

Current generation carbon–carbon (C–C) and carbon–silicon carbide (C–SiC) materials are limited to service temperatures below 1800 °C and materials are sought that can withstand higher temperatures and ablative conditions for aerospace applications. One potential materials solution is carbon fibre-based composites with matrices composed of one or more ultra-high temperature ceramics (UHTCs); the latter are intended to protect the carbon fibres at high temperatures whilst the former provides increased toughness and thermal shock resistance to the system as a whole. Carbon fibre–UHTC powder composites have been prepared via a slurry impregnation and pyrolysis route. Five different UHTC compositions have been used for impregnation, viz. ZrB₂, ZrB₂–20 vol% SiC, ZrB₂–20 vol% SiC–10 vol% LaB₆, HfB₂ and HfC. Their high-temperature oxidation resistance has been studied using a purpose built oxyacetylene torch test facility at temperatures above 2500 °C and the results are compared with that of a C–C benchmark composite.     

High temperature erosion behavior of spark plasma sintered ZrB2-SiC composites

Damage of structural components of hypersonic vehicles by atmospheric particles demands thorough understanding on their wear behavior. In the present work, dense ZrB₂-SiC (10, 20, and 30 vol%) composites are prepared by spark plasma sintering at 55 MPa in two stages: 1400 °C for 6 min followed by 1600 °C for 2 min. With increase in SiC content, microstructures of sintered composites reveal strongly bonded ZrB₂ grains with SiC particles. A combination of maximum hardness of 23 GPa, elastic modulus of 398 GPa and fracture toughness of 5.4 MPa m^1/2 are obtained for the composite containing 30 vol% SiC particles. It is found that cracks are bridged or deflected by SiC particles in the composites. When the composites are subjected to SiC particle erosion at 800 °C, a 14% decrease in erosion rate is obtained with increase in SiC content from 10 to 30 vol%. The formation of large extent of boro-silicate rich viscous surface on eroded surfaces is attributed to reduced fracture or removal of ZrB₂ grains of the composites with increased SiC content.     

Developing high toughness and strength Al/TiC composites using ice-templating and pressure infiltration

We prepared Al/TiC composites with different ceramic volume fractions (15, 25 and 35 vol%) using ice-templating and pressure infiltration. The thickness of the lamellar layer and the porosity in the ceramic layer of the TiC scaffolds were controlled by varying the slurry concentration. The Al/15 vol%TiC composite had a thick metal layer and a low-density ceramic layer, which effectively dissipated the stress at the crack tip and fractured in a multiple-crack-propagation mode, giving bending strength of 355±3 MPa and fracture toughness of 81±2 MPa m^1/2. However, the Al/25 vol%TiC and Al/35 vol%TiC composites had much higher bending strength (417−500 MPa) but lower fracture toughness (46−33 MPa m^1/2) as compared to the Al/15 vol%TiC composite, and they fractured in a single-crack-propagation mode. In addition, an increase in the brittle TiAl₃ phase with increasing ceramic volume at the fracture surface greatly deteriorated the toughness of the Al/TiC composites. Finally, the relationship between cracking mode and structure features in the laminated composites was discussed to account for the toughening mechanism.     

Vacuum brazing Nb and BN-SiO2 ceramic using a composite interlayer with network reinforcement architecture

A novel composite interlayer with a reinforced network was designed using a SiC ceramic with a network structure and Ti-Ni-Nb composite filler foils, to which the Nb and BN-SiO₂ ceramic were successfully brazed under vacuum. For a brazing temperature of 1160 °C and holding time of 10 min, the interfacial microstructure of the Nb/BN-SiO₂ ceramic joint was Nb/(βTi,Nb)-TiNi eutectic structure+(βTi,Nb)₂Ni+SiC+TiC/TiN+Ti₂N+TiB+Ti₅Si₃+TiO/BN-SiO₂ ceramic. In addition, the shear strength and nano-hardness were analyzed to evaluate the effect of the composite interlayer with a network reinforcement architecture on the mechanical properties of the joint. During brazing, the Ti-Ni-Nb filler metal infiltrated and reacted with the SiC to form the network reinforcement architecture, resulting in the residual stress being relieved and the mechanical performance of the joint being significantly improved. A maximum shear strength of 102 MPa was achieved, which was 60 MPa (142%) higher than that of the joint brazed without the network reinforcement architecture. A reduction in the residual stress on the BN-SiO₂ ceramic side from 328 MPa to 210 MPa was observed with the network reinforcement architecture, and the fracture path of the joint changed from the surface of the BN-SiO₂ ceramic to the interfacial reaction zone.