Microstructure and mechanical properties of Ti (C,N) based cermets reinforced with different ceramic particles processed by spark plasma sintering

The addition effect of different ceramic particles such as TiB₂, TiN and nano-Si₃N₄ on the microstructure and mechanical properties of TiCN-WC-Co-Cr₃C₂ based cermets, which are prepared by spark plasma sintering, was studied. Microstructural characterization of the cermets was done by scanning electron microscope. X-ray diffraction was performed to study the crystal structures. Mechanical properties such as hardness and fracture toughness were measured for the different developed cermets. The hardness and fracture toughness of the TiCN-WC-Co-Cr₃C₂ cermets without TiN, TiB₂, and nano-Si₃N₄ were 8.4 GPa and 3.4 MPa m^1/2, respectively. It was found that 5 wt% TiB₂ addition alone improved the corresponding hardness and fracture toughness to 19.2 GPa and 6.9 MPa m^1/2, respectively. The addition of 5 wt% TiN, improved the hardness and fracture toughness to 16.7 GPa and 6.9 MPa m^1/2, respectively. With the combination of 5 wt% TiN and 5 wt% TiB₂, the hardness and fracture toughness were improved to 15.5 GPa and 6.6 MPa m^1/2, respectively. But, the addition of 5 wt% Si₃N₄ showed a balanced improvement in both hardness (17.6 GPa) and toughness (6.9 MPa m^1/2). Fracture toughness did not change much for all the above cermets with different ceramic inclusions.     

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.     

Fast preparation of ZTA-TiC-FeCrNi cermets by high-gravity combustion synthesis

ZTA-TiC-FeCrNi cermets are prepared by a fast and furnace-free way called high-gravity combustion synthesis. The synthesized cermet samples show the maximum relative density of 97.6% and a hierarchical microstructure with grain sizes from submicron to >50 µm. The content of TiC has a strong influence on the microstructure and mechanical properties of the cermet samples. A higher TiC content results in refined microstructure, improved hardness, and reduced coefficient of friction. With increasing TiC content, the strength and toughness of the samples first increase and then drops, and reach the maximum of 469±26 MPa and 11.3±0.2 MPa m^1/2 at 20% TiC. Compared with commercial polycrystalline Al₂O₃ ceramics, the ZTA-TiC-FeCrNi cermets exhibit better wear resistance, and the volume loss is lower by one magnitude than Al₂O₃ under the same condition.     

Effect of WC content on microstructure and mechanical properties of Ni3Al-bonded cermets

The effect of WC content on microstructure and mechanical properties of the TiC–Ni₃Al system cermets was investigated. Ni₃Al-bonded cermets showed a core–rim structure with carbide particle coupled with rim embedded in Ni₃Al binder. With WC content increasing, TiC grains were refined and the white rim became complete and got thicker gradually. Interface between core and rim showed a completely coherent relationship. The rim enriched in W constituted an ideal coherence between hard phase and Ni₃Al binder phase. With WC content increasing, the densification of cermets was enhanced, and hardness and TRS were increased firstly and then reduced, reaching peak values 90.9 HRA (HV₃₀ 15 GPa) and 1629 MPa, respectively in cermet N5 (25 wt% WC). Similarly, fracture toughness got a peak value (11.6 MPa m^1/2), at the composition with 20 wt% WC.     

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.     

Preparation and properties of B6O/TiB2-composites

B₆O/TiB₂ composites with varying compositions were produced by FAST/SPS at temperatures between 1850 and 1900 °C following a non-reactive or a reactive sintering route. The densification, phase and microstructure formation and the mechanical and thermal properties were investigated. The comparison to an also investigated pure B₆O material showed that the addition of TiB₂ in a non-reactive sintering route promotes the B₆O densification. Further improvement was obtained by sintering reactive B–TiO₂ mixtures which also results in materials with a finer grain size and thus in enhanced mechanical properties. The fracture toughness was significantly improved in all composites and is up to 4.0 MPa m^1/2 (SEVNB) and 2.6–5.0 MPa m^1/2 (IF method) while simultaneously a high hardness of up to 36 GPa (HV_0.4) and 28 GPa (HV₅) could be preserved. The high temperature properties at 1000 °C of hardness, thermal conductivity and CTE were up to 20 GPa, 18 W/mK and 6.63 × 10^?6/K, respectively.     

Influence of sol-gel derived ZrB2 additions on microstructure and mechanical properties of SiBCN composites

A simple method for introducing ZrB₂ using sol-gel processing into a SiBCN matrix is presented in this paper. Zirconium n-propoxide (ZNP), boric acid and furfuryl alcohol (C₅H₆O₂) (FA) were added as the precursors of zirconia, boron oxide and carbon forming ZrB₂ dispersed in a SiBCN matrix. SiBCN/ZrB₂ composites with different contents of ZrB₂ (5, 10, 15, and 20 wt%) were formed at 2000 °C for 5 min by spark plasma sintering (SPS). The microstructures were carefully studied. TEM analysis showed that the as formed ZrB₂ grains were typically 100–500 nm in size and had uniform distribution. HRTEM revealed clean grain boundaries between ZrB₂ and SiC, however, a separation of C near the SiC boundary was observed. The flexural strength, fracture toughness, Young's modulus and Vicker's hardness of composites all improved with the ZrB₂ contents and SiBCN matrix containing 20 wt% of ZrB₂ could reach 351±18 MPa, 4.5±0.2 MPa m^1/2, 172±8 GPa and 7.2±0.2 GPa, respectively. The improvement in fracture toughness can be attributed to the tortuous crack paths due to the presence of reinforcing particles.     

ZrB2-based composites toughened by as-received and heat-treated short carbon fibers

In order to improve the fracture toughness of ZrB₂ ceramics, as-received and heat treated short carbon fiber reinforced ZrB₂-based composites were fabricated by hot pressing. The toughening effects of the fibers were studied by investigating the relative density, phase composition, microstructure and mechanical properties of the composites. It was found that the densification behavior, microstructure and mechanical properties of the composites were influenced by the fibers’ surface condition. The heat treated fiber was more appropriate to toughen the ZrB₂-based composites, due to the high graphitization degree, low surface activity and weak interfacial bonding. As a result, the fracture toughness of the composites with heat-treated fiber is 7.62 ± 0.12 MPa m^1/2, which increased by 10% as compared to the composites with as-received fiber (6.89 ± 0.16 MPa m^1/2).     

High-strength ZrB2-based ceramics prepared by reactive pulsed electric current sintering of ZrB2–ZrH2 powders

Fully densified ZrB₂-based ceramic composites were produced by reactive pulsed electric current sintering (PECS) of ZrB₂–ZrH₂ powders within a total thermal cycle time of only 35 min. The composition of the final composite was directly influenced by the initial ZrH₂ content in the starting powder batch. With increasing ZrH₂ content, ZrB₂–ZrO₂, ZrB₂–ZrB–ZrO₂ and ZrB₂–ZrB–Zr₃O composites were obtained. The ZrB₂–ZrB–ZrO₂ composite derived from a 9.8 wt% ZrH₂ starting powder exhibited an excellent flexural strength of 1382 MPa combined with a Vickers hardness of 17.1 GPa and a fracture toughness of 5.0 MPa m^1/2. The high strength was attributed to a fine grain size and the removal of B₂O₃ through reaction with Zr. Higher ZrH₂ content starting powders were densified through solution-reprecipitation resulting in the formation of coarser angular ZrB₂–ZrB composites with a Zr₃O grain boundary phase with a fracture toughness of 5.0 MPa m^1/2 and an acceptable strength in the 852–939 MPa range.     

Mechanical properties of reactively processed W/Ta2C-based composites

The mechanical properties of reactively processed W/Ta₂C cermet composites were studied. Dense W/Ta₂C cermets with a nominal composition of 40.4 vol% W(Ta)ss, 48.9 vol% Ta₂C and 10.6 vol% Ta₂WO₈ were fabricated using a pressureless reactive processing method. Four-point bend strength, fracture toughness, elastic modulus, and microhardness were measured at room temperature. The average flexure strength was 584 MPa which is lower than for pure W; however the strength of pure Ta₂C is unknown. The fracture toughness was 8.3 MPa m^1/2 which fits a rule of mixtures between literature values for the fracture toughness of the W and Ta₂C phases. The elastic modulus was 476 GPa, and the microhardness was 13.4 GPa. Both Young's modulus and hardness were higher than values reported for other W-based cermets.     

The ablation behavior of ZrB2/Cu composite irradiated by high-intensity continuous laser

Ultra high temperature ceramics (UHTCs) based composite ZrB₂/20 vol.% Cu was prepared by spark plasma sintering (SPS) at 1650 C° for 3 min. The ablation behavior of composite irradiated for 2–20 s by 20 MW/m² high-intensity continuous laser was investigated. The phase and microstructure evolution of ZrB₂/20 vol.% Cu during ablation was demonstrated by XRD and SEM, respectively. The results reveal that no macroscopic damage but only one ablated layer with 40 μm in thickness is observed even after being ablated for 20 s. It implies that ZrB₂/20 vol.% Cu composite exhibits good ablation resistance against high-intensity continuous laser. The continuous Cu in composite evaporates preferentially, which impacts on the following ablation behavior. The generated ZrO₂ at the spot center shows different forms such as closely packed nano-ZrO₂, micron ZrO₂ or melting ZrO₂ for different ablation time. The melting ZrO₂ is helpful to promote the ablation resistance of ZrB₂/20 vol.% Cu.     

Fabrication of SiCw reinforced ZrB2-based ceramics

ZrB₂-based ceramics with SiC_w were produced by hot pressing at 1750 °C for 1 h from mixed powders after adding liquid polycarbosilane. The obtained ZrB₂-SiC_w composites had toughness up to 7.57 MPa m^1/2, which was much higher than those for monolithic ZrB₂, SiC particles reinforced ZrB₂ composites, and other ZrB₂–SiC_w composites directly sintered at high temperatures. The added liquid polycarbosilane could reduce the sintering temperatures and restrict the reaction of matrix with whisker, which led to fewer damages to the whisker and high fracture toughness.     

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.     

ZrB2–SiC composites prepared by reactive pulsed electric current sintering

Fully densified ZrB₂–20 vol% SiC composites were produced by reactive pulsed electric current sintering (PECS) of a powder mixture containing ZrH₂, B, SiC and B₄C within a total thermal cycle time of only 50 min. During the combined synthesis and sintering process, the ZrH₂ powder decomposed gradually from ZrH₂ into ZrH_m and finally metal Zr that reacted with elemental B to form the ZrB₂ matrix. Reducing the ZrH₂ particle size by attritor milling significantly enhanced densification and allowed initiation of self-propagating high temperature synthesis (SHS) during PECS. The PECS grades exhibited a slightly textured structure, with ≤17% of the ZrB₂ grains oriented with their (0 0 1) planes perpendicular to the direction of pressure and DC current. Because of the ZrB₂ grain orientation, anisotropic mechanical properties were observed. Ceramics prepared from attritor milled powders and PECS with a pressure applied after 5 min upon reaching 1900 °C achieved excellent flexural strengths of 901–937 MPa. The hardness and fracture toughness were respectively 19.7–19.8 GPa and 4.0–4.7 MPa m^1/2 in the direction parallel and 20.2–21.3 GPa and 3.8–3.9 MPa m^1/2 in the direction perpendicular to the applied pressure.     

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.     

SPS processing of bismuth-layer structured ferroelectric ceramics yielding highly textured microstructures

The spark plasma sintering (SPS) behaviour of nano-sized Bi₄Ti₃O₁₂ (BIT) and micron-sized CaBi₂Nb₂O₉ (CBNO) powders is described. The densification process of both powders is very rapid, i.e. the densification occurs within a very narrow time interval (2–3 min using a heating rate of 100 °C min⁻¹ and a pressure of 50 MPa). The BIT powder exhibits a lower densification onset temperature (∼650 °C) and higher maximum shrinkage rate (8.9 × 10⁻³ s⁻¹ at 780 °C) than that of the CBNO powder (∼825 °C and 4.5 × 10⁻³ s⁻¹ at 950 °C). Isothermal compaction studies revealed that fully dense nano-sized BIT compacts could be obtained within the temperature region 750 °C < T_iso < 850 °C while for T_iso > 850 °C compacts containing elongated platelet grains are formed. A new preparation route to produce highly textured compacts is described in detail. Appropriate pre-forms are prepared by spark plasma sintering (SPS) and these fully dense compacts are subject to superplastic deformation in the SPS unit to achieve a total compressive strain of ∼60%. This strain was achieved within a period of 1.5 min and with a maximum strain rates of 1.1 × 10⁻² s⁻¹ achieved at ∼840 °C and 1.3 × 10⁻² s⁻¹ at 1020 °C for the BIT and CBNO compacts, respectively. The X-ray studies showed that the Lotgering orientation factors of grains in the deformed BIT and CBNO compacts are 99% and 70%. The formation of highly textured compacts is suggested to be governed by a superplastic deformation-induced directional dynamic ripening mechanism.     

ZrB2–SiC laminated ceramic composites

The oxidation behavior for ZrB₂–20 vol% SiC (ZS20) and ZrB₂–30 vol% SiC (ZS30) ceramics at 1500 °C was evaluated by weight gain measurements and cross-sectional microstructure analysis. Based on the oxidation results, laminated ZrB₂–30 vol% SiC (ZS30)/ZrB₂–25 vol% SiC (ZS25)/ZrB₂–30 vol% SiC (ZS30) symmetric structure with ZS30 as the outer layer were prepared. The influence of thermal residual stress and the layer thickness ratio of outer and inner layer on the mechanical properties of ZS30/ZS25/ZS30 composites were studied. It was found that higher surface compressive stress resulted in higher flexural strength. The fracture toughness of ZS30/ZS25/ZS30 laminates was found to reach to 10.73 MPa m^1/2 at the layer thickness ratio of 0.5, which was almost 2 times that of ZS30 monolithic ceramics.     

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.     

Influence of silicon carbide addition on the microstructural development of hot pressed zirconium and titanium diborides

The influences of adding SiC on the microstructure and densification behavior of ZrB₂ and TiB₂ ceramics, hot pressed at 1850 °C for 60 min under 20 MPa, were investigated. The sintered samples were characterized by SEM, EDS and XRD methods. A fully dense TiB₂-based ceramic was obtained by adding 30 vol% SiC. The grain size of ZrB₂ or TiB₂ matrices in the final microstructures decreased with increasing SiC content. The XRD analyses, microstructural characterization as well as thermodynamical calculations proved the in-situ formation of TiC in the SiC reinforced TiB₂-based composites. The interfaces between ZrB₂ and SiC grains in the SiC reinforced ZrB₂-based composites were free of any impurities or tertiary interfacial phases such as ZrC. This result was consistent with the X-ray diffraction pattern and thermodynamics.     

Preparation of B4C composites toughened by TiB2-SiC agglomerates

High-performance B₄C composites toughened by TiB₂-SiC agglomerates were fabricated via reactive hot pressing with B₄C, TiC and Si as raw materials. The TiB₂-SiC composite serves as a composite toughening phase formed in the B₄C matrix through an in situ reaction; its agglomerates are composed of interlocked TiB₂ and SiC, which can remarkably improve the toughness of the B₄C composites. The Vickers hardness, flexural strength and fracture toughness of the B₄C-TiB₂-SiC composite reached 35.18 ± 0.45 GPa, 567 ± 14 MPa, and 6.38 ± 0.18 MPa m^1/2 respectively. The special toughening structure of the TiB₂-SiC composite introduced into B₄C ceramics was evaluated for the first time in this study.