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.     

Densification behavior and microstructure evolution of hot-pressed SiC–SiBCN ceramics

Densification behavior and microstructure evolution of hot-pressed SiC–SiBCN ceramics were studied between 1660 °C and 1830 °C. Polyborosilazane was chosen as the SiBCN precursor and pyrolyzed at 1000 °C in inert atmosphere before use. Samples with SiBCN contents of 10% and 20% in weight were prepared. During the sintering, at temperatures <1660 °C, the density of all the samples showed a minor increase because of solid state particles rearrangement. Above 1660 °C, the density increased rapidly because of the grain boundary sliding with a non-Newtonian viscous boundary phase. After grain boundary sliding, grain-boundary diffusion enhanced by B and C elements from the SiBCN material was responsible for the further densification. The microstructure of the samples hot pressed at 1660 °C appeared particle packing state. The two samples can achieve almost full density when they were hot pressed at 1830 °C/40 MPa for 90 min.     

Densification,microstructure and mechanical properties of ZrB2–SiCw ceramic composites

ZrB₂–SiCw composites were prepared through hot-pressing at a low temperature of 1800 °C, and Al₂O₃ plus Y₂O₃ were added as sintering aids. Analysis revealed that additives may react with impurities (i.e. surface oxygen impurities and residual metallic impurities) to form a transient liquid phase, thus promote the sintering and densification of ZrB₂–SiCw composites. The content of additives was found to have a significant influence on the sinterability, microstructure and mechanical properties of ZrB₂–SiCw composites. ZrB₂–SiCw composite prepared with a small amount of additives (3 vol.%) provided the optimal combination of microstructure (relative density of 98.3%) and excellent properties, including flexural strength of 783 MPa and fracture toughness of 6.7 MPa m^1/2. With further addition of additives, SiC whiskers were inclined to gather together and be enveloped by excessive liquids to form core-rim-like structures, which lead to little decrease in mechanical properties.     

Preparation,microstructure and mechanical properties of ZrB2–ZrO2 ceramics

ZrB₂–ZrO₂ ceramics with ZrO₂ content varied from 15 to 30 vol.% were prepared by hot pressing. The content of ZrO₂ was found to have an evident effect on the preparation, phase constitution, microstructure as well as the mechanical properties of ZrB₂–ZrO₂ ceramics. ZrB₂–30 vol.% ZrO₂ provided the optimal combination of dense microstructure (2.6 μm, as the average grain size) and excellent properties, including the flexural strength of 803 MPa, and the hardness of 22.7 GPa tested under 9.8 N. The highest t-ZrO₂ transformability of 35.2 vol.% during fracture for ZrB₂–30 vol.% ZrO₂ brought the best toughness of 6.5 MPa m^1/2 compared with any other ceramic. In addition, the dependence of toughness on the test method as well as the hardness on the indentation load was also investigated.     

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.     

Densification,mechanical and thermal properties of ZrC1 − x ceramics fabricated by two-step reactive hot pressing of ZrC and ZrH2 powders

Densification behavior, mechanical and thermal properties of ZrC_1 ? x ceramics with various C/Zr ratios of 0.6–1.0 have been investigated by two-step reactive hot pressing of ZrC and ZrH₂ powders at 30 MPa and 1500–2100 °C. The two-step reactive hot pressed ZrC_1 ? x ceramic has a higher relative density (> 95.3%) than that (91.9%) of stoichiometric ZrC sintered at 2100 °C. A cubic Zr₂C-type ordered phase forms in the ZrC_1 ? x sample obtained at a ZrC/ZrH₂ molar ratio of 0.6 at a relatively low temperature of 1100 °C. The decrease in C/Zr ratio is beneficial to densification of ZrC_1 ? x ceramic, however, excess grain growth occurs after sintering above densification temperature. The elastic modulus and Vickers hardness decrease with decreasing the C/Zr ratio. With decreasing the C/Zr ratio, both thermal conductivity and specific heat decrease due to the enhanced scattering of conducting phonons and electrons by carbon vacancies.     

Fabrication and mechanical properties of laminated HfC–SiC/BN ceramics

Laminated HfC–SiC/BN ceramics were successfully fabricated by tape casting and hot pressing. Fully dense HfC–SiC ultra-high temperature ceramics with homogeneous structure were obtained. The introduction of the weak BN layer resulted in a slight decrease of the flexural strength but significantly improved the fracture toughness compared with monolithic HfC–SiC ceramics. The fracture toughness of laminated HfC–SiC/BN ceramics in the parallel direction peaked at 8.06 ± 0.46 MPa m^1/2, which increased by 115% than that of monolithic HfC–SiC ceramics. The composites showed non-catastrophic fracture behaviors in both parallel and perpendicular directions. It indicates that laminated structure design is a promising approach to obtain full density HfC–SiC ceramics with high fracture toughness.     

Effects of SiC content on the densification,microstructure, and mechanical properties of HfB2–SiC composites

To investigate the effects of SiC on microstructure, hardness, and fracture toughness, 0, 10, 20, and 30 vol% SiC were added to HfB₂ and sintered by SPS. Upon adding SiC to 30 vol%, relative density increased about 4%; but HfB₂ grain growth had a minimum at 20 vol% SiC. This may be due to grain boundary silicate glass, responsible for surface oxide wash out, enriched in SiO₂ with higher fraction of SiC. By SiO₂ enrichment, the glass viscosity increased and higher HfO₂ remained unsolved which subsequently lead to higher grain growth. Hardness has increased from about 13 to 15 GPa by SiC introduction with no sensible variation with SiC increase. Residual stress measurements by Rietveld method indicated high levels of tensile residual stresses in the HfB₂ Matrix. Despite the peak residual stress value at 20 vol% SiC, fracture toughness of this sample was the highest (6.43 MPa m^0.5) which implied that fracture toughness is mainly a grain size function. Tracking crack trajectory showed a mainly trans-granular fracture, but grain boundaries imposed a partial deflection on the crack pathway. SiC had a higher percentage in fracture surface images than the cross-section which implied a weak crack deflection.     

Effects of high-temperature annealing on the microstructure and properties of C/SiC–ZrC composites

C/SiC–ZrC composites were prepared by a combining slurry process with precursor infiltration and pyrolysis, and then annealed from 1200 °C to 1800 °C. With rising annealing temperature, their mass loss rate increased, and the flexural strength and modulus decreased from 227.9 MPa to 41.3 MPa and from 35.3 GPa to 22.7 GPa, respectively. High-temperature annealing, which elevated thermal stress and strengthened interface bonding, was harmful to the flexural properties. However, it improved the ablation properties by increasing the crystallization degree of SiC matrix. The mass loss rate and linear recession rate decreased with increasing annealing temperature and those of the samples annealed at 1800 °C were 0.0074 g/s and 0.0011 mm/s respectively. Taking mechanical and ablation properties into consideration simultaneously, the optimum annealing temperature was 1600 °C.     

Hot-pressed ZrB2–SiC composite ceramics: Effect of various Ta-containing additives on the microstructure and mechanical properties

The ZrB₂–SiC composites have been commercially used at ultrahigh temperatures, but it often failed due to their poor toughness. In order to solve this problem, four types of Ta-containing additives (Ta, TaC, TaB₂ and TaSi₂) were used as the “third phase” to regulate the microstructure, so as to enhance the mechanical properties of hot-pressed ZrB₂–20SiC-based ceramics (in vol. %). The incorporation of the additives generated a core–shell structure, which comprised of a ZrB₂ core and a (Zr, Ta)B₂ solid solution shell. The additives helped refine the ZrB₂ grains in addition to the metallic Ta and release the internal stress field generated by the thermal misfit. The interfacial structure was modified by the formation of the coherent core/shell interface and the semi-coherent interface of adjacent ZrB₂ grains and the semi-coherent ZrB₂/(Zr, Ta)C interface in the TaC-additive composite. The addition of TaB₂ or TaC hardened the ZrB₂–20SiC ceramics, whereas the addition of Ta or TaSi₂ reduced the hardness. The fracture toughness was enhanced by the formation of the Ta-containing phases. These phases reduced the stress intensity factor of the crack tip, which was proportional to the intrinsic residual stress. However, the crack-propagation mechanism would be changed by the incorporation of various Ta-containing additives. The decrease in the crack deflection, which was induced by the stronger interfacial bonding force and the significant consumption of SiC, resulted in relatively low toughness in the Ta- and TaC-included samples. The weaker interfacial bonding force in the TaB₂- and TaSi₂-included samples caused an increase in deflection and generated branching, which enhanced the toughness of the TaSi₂-included composites to ～4.72 MPa?m^1/2.     

R-curve behavior,mechanical properties and microstructure of sintered ZrB2–SiCp–ZrO2f ceramics

In this paper, zirconium diboride based ceramics added with 20 vol.% silicon carbide particle and 15 vol.% zirconia fiber (Z20S_p15Z_f) were prepared by hot-pressing at 1850 °C for 60 min under a uniaxial load of 30 MPa in Ar atmosphere. R-curves for Z20S_p15Z_f ceramics were studied using the indentation-strength in bending technique and the envelope method. The results indicated that these two testing methods were consistent and viable for estimating R-curve. Z20S_p15Z_f ceramics had high resistance to crack growth and damage tolerance with the 6.8 MPa m^1/2 of steady-state toughness. The toughening mechanism was fiber debonding, fiber pull-out, crack bridging, crack branching, crack deflection and transformation toughening.     

High temperature mechanical properties of laminated ZrB2–SiC based ceramics

Two laminated ZrB₂-SiC based ceramics were prepared by tape casting and subsequent hot pressing, with BN (LZB) and graphite (LZG ) as interface layers. The LZB specimen presents flexural strength of 381 MPa at room temperature and 111 MPa at 1500 °C; while the LZG specimen shows flexural strength of 414 MPa at room temperature and 377 MPa at 1500 °C. In addition, the flexural strength of LZG specimen is always higher than that of the LZB specimen in the temperature range from room temperature to 1500 °C. Such higher strength is attributed to the healing of surface microcracks and pores by the SiO₂ glass phase, producing less glass phase in graphite interface layers at high temperature.     

Effect of NiO additive on microstructure,mechanical behavior and electrical properties of 0.2PZN–0.8PZT ceramics

A NiO-added Pb((Zn_1/3Nb_2/3)_0.20(Zr_0.50Ti_0.50)_0.80)O₃ system is prepared and investigated. The results reveal that Ni doping induces a phase transformation from the morphotropic phase boundary to the tetragonal phase side. Above the solubility limit of 0.3 wt% in NiO form, excess Ni ions segregate at the grain boundaries and triple junctions, which facilitate the formation of a liquid phase with excess PbO and lead to remarkable grain growth. The mechanical behavior (Vickers hardness (H_v) and fracture toughness (K_IC)) can be tailored by controlling the content of additive; this is accompanied by a transition in the fracture mode changed from transgranular without NiO additive to intergranular with 1.0 wt% NiO additive. Moreover, the NiO addition weakens the dielectric relaxor behavior and improves the piezoelectric properties simultaneously. The 0.2PZN–0.8PZT with 0.5 wt% NiO addition shows good transduction coefficient (d₃₃·g₃₃ = 10,050 × 10^?15 m²/N) and large fracture toughness (K_IC = 1.35 MPa m^1/2).     

Synthesis,microstructure, and mechanical properties of WC–TiC–Co ceramic composites

A ceramic composite constituting the formula 78 wt% WC–16 wt% TiC–6 wt% Co denoted as the 78WC–16TiC–6Co ceramic composite was fabricated using a powder metallurgy process, by utilising commercially available WC and Co powders, and laboratory produced TiC powders. TiC powders were produced from machining chips of Grade 4 Titanium. Five different procedures were followed for the manufacturing process by altering the amount of the binding agent (stearic acid) and/or compacting pressure and/or sintering regime (temperature and time) and/or mixing process (dry mixing and mechanical alloying). Characterisation investigations conducted on the sintered samples revealed that stearic acid as the binding agent resulted in the decrease of the relative density while mechanical alloying (MA) induced finer microstructures. The 78WC–16TiC–6Co composites manufactured from commercially available and laboratory produced TiC powders using similar process procedures (including MA) exhibited similar characteristics in terms of relative density, hardness, and wear performance.     

Mechanical behaviour and microstructure of Cf/ZrC,Cf/SiC and Cf/ZrC – SiC composites

Cf/ZrC, Cf/SiC and Cf/ZrC–SiC composites were successfully prepared by polymer infiltration and pyrolysis (PIP) using polycarbosilane and a liquid ZrC precursor. The densification process, mechanical properties and microstructures were studied in a view of comparison. After the same total 20 PIP cycles, the Cf/ZrC, Cf/SiC and Cf/ZrC–SiC composites had flexural strengths of 50.1±5.3, 285.7±22.6, 141.5±13.1?MPa respectively; elastic moduli of 7.8±0.9, 57.1±3.2 and 45.1±2.6?GPa respectively; and fracture toughness of 2.5±0.2, 10.4±0.9 and 10.9±1.1?MPa m^1/2 respectively. With the introduction of high modulus SiC phase into the ZrC matrix, the densification and modulus of the matrix were improved; as a result, the Cf/ZrC–SiC composite showed higher mechanical properties compared to Cf/ZrC.     

Densification behavior and properties of alumina–chrome ceramics: Effect of TiO2

Highly dense alumina–chrome bodies with low porosity are usually used as corrosion and thermal resistant refractories. Alumina–chrome refractory with molar ratio 1:1 was developed using chemical grade hydrated alumina and chromium (III) oxide by conventional sintering route. Batch materials were attrition milled, isostatically pressed and sintered in the temperature range from 1000 °C to 1700 °C with 2 h soaking at peak temperature. Phase development of the sintered materials with temperature was studied by X-ray diffraction. Sintering temperature, sintering condition and addition of sintering aid (TiO₂) have immense effect on the densification of the alumina–chrome refractory. Highly dense alumina–chrome refractory with almost nil apparent porosity was developed at 1500 °C in reducing atmosphere. Flexural strength of the sintered materials at room temperature and at 1200 °C was also measured. 1 wt% TiO₂ gives the optimum result with respect to densification and flexural strength.     

In situ synthesis,physical and mechanical properties of ZrB2–ZrC–WB composites

In this study, two composition ZrB₂–ZrC–WB composites were synthesized by reactive hot-pressing of Zr + B₄C + WC powder mixtures at 1900 °C. The microstructure of the resulting composites was characterized by a combination of scanning electron microscopy and X-ray diffraction. It is seen that highly-dense ZrB₂–ZrC–WB composites with a homogenous fine-microstructure were obtained after the sintering. The mechanical behavior of the composites was evaluated using by testing under four-point bend testing at room and high temperatures. The results show that the high-temperature strength of the ZrB₂–ZrC–WB composites was substantially improved, compared to ZrB₂–ZrC-based composites without WB. In addition, the elastic properties, electrical conductivity, hardness and fracture toughness of the composites were measured at room temperature. The results reveal that these properties were comparable to those of ZrB₂–ZrC-based composites without WB.     

Fabrication and properties of ZrB2–SiC–BN machinable ceramics

ZrB₂–SiC–BN ceramics were fabricated by hot-pressing under argon at 1800 °C and 23 MPa pressure. The microstructure, mechanical and oxidation resistance properties of the composite were investigated. The flexural strength and fracture toughness of ZrB₂–SiC–BN (40 vol%ZrB₂–25 vol%SiC–35 vol%BN) composite were 378 MPa and 4.1 MPa m^1/2, respectively. The former increased by 34% and the latter decreased by 15% compared to those of the conventional ZrB₂–SiC (80 vol%ZrB₂–20 vol%SiC). Noticeably, the hardness decreased tremendously by about 67% and the machinability improved noticeably compared to the relative property of the ZrB₂–SiC ceramic. The anisothermal and isothermal oxidation behaviors of ZrB₂–SiC–BN composites from 1100 to 1500 °C in air atmosphere showed that the weight gain of the 80 vol%ZrB₂–20 vol%SiC and 43.1 vol%ZrB₂–26.9 vol%SiC–30 vol%BN composites after oxidation at 1500 °C for 5 h were 0.0714 and 0.0268 g/cm², respectively, which indicates that the addition of the BN enhances oxidation resistance of ZrB₂–SiC composite. The improved oxidation resistance is attributed to the formation of ample liquid borosilicate film below 1300 °C and a compact film of zirconium silicate above 1300 °C. The formed borosilicate and zirconium silicate on the surface of ZrB₂–SiC–BN ceramics act as an effective barriers for further diffusion of oxygen into the fresh interface of ZrB₂–SiC–BN.     

Highly-efficient preparation of anisotropic ZrB2–SiC powders and dense ceramics with outstanding mechanical properties

Highly-dense ZrB₂–SiC ceramics with excellent mechanical properties including Vickers hardness of 24.5 GPa and fracture toughness of 4.8 MPa/m^1/2 were successfully prepared, by spark plasma sintering of the raw powders synthesized by a novel molten-salt and microwave co-assisted boro/carbothermal reduction (MSM-BCTR) method. Compared with the processing conditions required for synthesizing ZrB₂–SiC by conventional reduction method, the present MSM-BCTR method possessed a variety of significant merits including the smaller material cost, lower processing temperature (1200°C), and remarkably higher efficiency (soaking time as short as 20 minutes). More importantly, the ZrB₂–SiC powders, resultant from MSM-BCTR treatment, were verified to have single-crystalline nature and uniform well-grown anisotropic morphologies (rod-like ZrB₂ and sheet-like SiC) as well as great potential in promoting the mechanical properties of their bulk counterparts. This great achievement was mainly ascribed to the specific MSM-BCTR conditions characterized by microwave heating and molten-salt medium.     

Effect of PyC interphase thickness on mechanical and ablation properties of 3D Cf/ZrC–SiC composite

Three-dimensional (3D) C_f/ZrC–SiC composites were successfully prepared by the polymer infiltration and pyrolysis (PIP) process using polycarbosilane (PCS) and a novel ZrC precursor. The effects of PyC interphase of different thicknesses on the mechanical and ablation properties were evaluated. The results indicate that the C_f/ZrC–SiC composites without and with a thin PyC interlayer of 0.15 µm possess much poor flexural strength and fracture toughness. The flexural strength grows with the increase of PyC layer thickness from 0.3 to 1.2 µm. However, the strength starts to decrease with the further increase of the PyC coating thickness to 2.2 µm. The highest flexural strength of 272.3±29.0 MPa and fracture toughness of 10.4±0.7 MPa m^1/2 were achieved for the composites with a 1.2 µm thick PyC coating. Moreover, the use of thicker PyC layer deteriorates the ablation properties of the C_f/ZrC–SiC composites slightly and the ZrO₂ scale acts as an anti-ablation component during the testing.