Densification,microstructure and properties of ultra-high temperature HfB2 ceramics by the spark plasma sintering without any additives

Ultra-high temperature HfB₂ ceramic with nearly full densification is achieved by using gradient sintering process of SPS without any additives. The effect of the sintering temperature on the densification behavior, relative density, microstructure, mechanical and thermionic properties is systematically investigated. The results show that the fast densification of HfB₂ ceramic occurs at the heating stage, and the highest relative density of 96.75% is obtained at T =1950 °C, P = 60 MPa and t =10min. As the temperature is increased from 1800 to 1950 °C, the grain size of HfB₂ increases from 6.12 ±1.33 to 10.99 ± 2.25 μm, and refined microstructure gives the excellently mechanical properties. The highest hardness of 26.34 ±2.1GPa, fracture toughness of 7.12 ± 1.33 MPa m^1/2 and bending strength of 501 ±10MPa belong to the HfB₂ ceramic obtained at T =1950°C. Moreover, both the Vickers hardness and fracture toughness obey the normal indentation size effect. HfB₂ ceramic also exhibits the thermionic emission characterization with the highest current density of 6.12 A/cm² and the lowest work function of 2.92 eV.     

Effect of LaB6 addition on compressive creep behavior with simultaneous oxide scale growth of spark plasma sintered ZrB2-SiC composites

A study has been carried out to examine the effect of LaB₆ addition on the compressive creep behavior of ZrB₂-SiC composites at 1300–1400°C under stresses between 47 and 78 MPa in laboratory air. The ZrB₂-20 vol% SiC composites containing LaB₆ (10% in ZSBCL-10 and 14% in ZSBCL-14) besides 5.6% B₄C and 4.8% C as additives were prepared by spark plasma sintering at 1600°C. Due to cleaner interfaces and superior oxidation resistance, the ZSBCL-14 composite has exhibited a lower steady-state creep rate at 1300°C than the ZSBCL-10. The obtained stress exponent (n ∼ 2 ± 0.1) along with cracking at ZrB₂ grain boundaries and ZrB₂-SiC interfaces are considered evidence of grain boundary sliding during creep of the ZSBCL-10 composite. However, the values of n ∼ 1 and apparent activation energy ∼700 kJ/mol obtained for the ZSBCL-14 composite at 1300–1400°C suggest that ZrB₂ grain boundary diffusion is the rate-limiting mechanism of creep. The thickness of the damaged outer layer containing cracks scales with temperature and applied stress, indicating their role in facilitating the ingress of oxygen causing oxide scale growth. Decreasing oxidation-induced defect density with depth to a limit of ∼280 μm, indicates the predominance of creep-based deformation and damage at the inner core of samples.     

Microstructural evolution,mechanical and thermal properties of LaB6 embedded in Si-B-C-N prepared by spark plasma sintering

Si-B-C-N monoliths with 5 wt% LaB₆ additives were prepared by spark plasma sintering at 1250–2000 °C and 50 MPa using a mechanically alloyed mixture of graphite, c-Si, h-BN and LaB₆ powders as the starting materials. Microstructural evolution, mechanical and thermal properties of the as-prepared La/Si-B-C-N monoliths were investigated. The densification of the ceramics starts at 1160° and ends at 1800 °C with the formation of La-containing compounds coupled with SiC and BN(C) phases. La-containing BN(C) grains develop into a lamellar structure at 1900 °C offering improved fracture toughness and decreased Vickers hardness, flexural strength and elastic modulus. The formation of lamellar BN(C) is also responsible for a high thermal expansion coefficient of 4.2×10⁻⁶ /°C.     

Synthesis,microstructure, and mechanical properties of TiC-SiC-Ti3SiC2 composites prepared by in situ reactive hot pressing

In this work, TiC-SiC-Ti₃SiC₂ composites were synthesized by in situ reactive hot pressing using β-SiC, graphite, and TiH₂ powders as initial materials. Microstructure and mechanical properties of as-prepared dense composites were systematically investigated. It was found that by increasing the initial SiC content the final SiC content in the composites increased in contrast to the decrease in TiC and Ti₃SiC₂ contents. In the dense composites, TiC and Ti₃SiC₂ grains exhibited transgranular fracture, whereas SiC particles showed intergranular fracture. The composite containing 77 vol.% TiC, 4 vol.% SiC, and 19 vol.% Ti₃SiC₂ had the highest flexural strength of 706.6 MPa. The composite consisting of 44 vol.% TiC, 49 vol.% SiC, and 7 vol.% Ti₃SiC₂ exhibited the highest Vickers hardness of 22.3 GPa and the highest fracture toughness of 6.0 MPa·m^1/2.     

Spark plasma sintering of LaB6-(Ti,Zr)B2 composites

The LaB₆-(Ti_, Zr)B₂ composite was fabricated from LaB₆, TiB₂ and ZrB₂ powders by spark plasma sintering (SPS) at 1600–1900°C holding for 5?min under 40?MPa. The densification behaviour, microstructure, mechanical properties were investigated. The complete solid solution phase of (Ti, Zr)B₂ was identified. The morphologies of LaB₆ and (Ti, Zr)B₂ grains were equiaxed and elongated, respectively. The highest relative density of 98.43% and Vickers hardness of 19.56?GPa were obtained at 1900°C. The fracture toughness of 4.43?MPa?m^1/2 was obtained at 1800°C.     

Microstructure,mechanical properties and thermal conductivity of (Ti0.5Nb0.5)C–SiC composites

A series of (Ti_0.5Nb_0.5)C-x wt.% SiC (x = 0, 5, 10, 20) composites were prepared by spark plasma sintering. Dense microstructures with well‐dispersed SiC particles were obtained for all composites. With the increment of SiC content, the Vickers hardness, Young's modulus and fracture toughness increase monotonically. An optimized flexural strength of 706 MPa was achieved in (Ti_0.5Nb_0.5)C-5 wt.%SiC composite. (Ti_0.5Nb_0.5)C-20 wt%SiC composite exhibits the highest fracture toughness of 6.8 MPa m^1/2. The crack deflections and the suppression of grain growth were the main strengthening and toughening mechanisms. Besides, (Ti_0.5Nb_0.5)C-20 wt%SiC composite exhibit the highest thermal conductivity of 45 W/m·K at 800 °C.     

Microstructure and mechanical properties of carbon-precursor-added B4C and B4C−SiC ceramics subjected to pressureless sintering

Organic-carbon-precursor-added B₄C and B₄C–SiC ceramics were subjected to pressureless sintering at various temperatures. The carbon precursor increased the densification of the B₄C and B₄C–SiC ceramics sintered at 2200 °C to 95.6 % and 99.1 % theoretical density (T.D.), respectively. The pyrolytic carbon content of the B₄C–SiC composite decreased with increasing SiC content. The graphitization degree of pyrolytic carbon decreased slightly with the amount of carbon precursor and content of SiC. The 95 wt. % B₄C–5 wt. % SiC composite added with 7.5 wt. % carbon precursor and sintered at 2200 °C outperformed the other B₄C–SiC composites, and its sintered density, flexural strength, Young’s modulus, and microhardness were 98.6 % T.D., 879 MPa, 415 GPa, and 28.5 GPa, respectively. These values were higher than those of composites prepared via pressureless sintering and comparable to those of composites fabricated via hot pressing and/or using metal or oxide additives.     

Effect of LaB6 additions on densification,microstructure, and creep with oxide scale formation in ZrB2-SiC composites sintered by spark plasma sintering

A comparative study has been carried out on densification, microstructure, and creep with oxide-scale formation in ZrB₂-20 vol.% SiC-(7, 10 or 14 vol.%) LaB₆ composite containing B₄C and C as additives, and prepared by spark plasma sintering at 1800 °C under 70 MPa ram pressure. Addition of LaB₆ has promoted densification of composites by scavenging oxygen impurity, thereby increasing their hardness. Constant load compressive creep tests at 1300 °C under 47 and 78 MPa stresses have shown the lowest creep rate in the 10 vol.% LaB₆ composite. The stress exponents obtained for composites having 10 vol.% LaB₆ (～1.3 ± 0.1) and 14 vol.% LaB₆ (～2.6 ± 0.2) suggest respectively, grain boundary diffusion with intergranular glassy phase formation and dislocation glide as operating mechanisms. Intergranular cracking caused by grain boundary sliding appears as the damage mechanism. Oxide scales formed during creep exhibit greater thickness and defect concentration than those by isothermal exposure at 1300 °C within similar duration.     

The influence of different SiC amounts on the microstructure,densification, and mechanical properties of hot-pressed Al2O3-SiC composites

The hot pressing process of monolithic Al₂O₃ and Al₂O₃-SiC composites with 0-25 wt% of submicrometer silicon carbide was done in this paper. The presence of SiC particles prohibited the grain growth of the Al₂O₃ matrix during sintering at the temperatures of 1450°C and 1550°C for 1 h and under the pressure of 30 MPa in vacuum. The effect of SiC reinforcement on the mechanical properties of composite specimens like fracture toughness, flexural strength, and hardness was discussed. The results showed that the maximum values of fracture toughness (5.9 ± 0.5 MPa.m^1/2) and hardness (20.8 ± 0.4 GPa) were obtained for the Al₂O₃-5 wt% SiC composite specimens. The significant improvement in fracture toughness of composite specimens in comparison with the monolithic alumina (3.1 ± 0.4 MPa.m^1/2) could be attributed to crack deflection as one of the toughening mechanisms with regard to the presence of SiC particles. In addition, the flexural strength was improved by increasing SiC value up to 25 wt% and reached 395 ± 1.4 MPa. The scanning electron microscopy (SEM) observations verified that the increasing of flexural strength was related to the fine-grained microstructure.     

Electromagnetic wave absorption properties of hot-pressed Si3N4-SiC ceramic nanocomposites

High-density Si₃N₄-SiC ceramic nanocomposites have exceptional mechanical properties, but little is known about their electromagnetic wave absorption (EMA) capabilities. In this paper, the effects of sintering temperature and starting material compositions on the dielectric and EMA properties of hot-pressed Si₃N₄-SiC ceramic nanocomposites were investigated. The real and imaginary permittivities of Si₃N₄-SiC ceramic nanocomposites increase with increasing sintering temperature or SiC content, particularly at the sintering temperature of 1850°C and SiC content of 50 wt.%. This is primarily due to the improvement of interfacial and defect polarizations, which is caused by the doping of nitrogen into the SiC nanocrystals during the solution-precipitation process. The real and imaginary permittivities of Si₃N₄-SiC ceramic nanocomposites show decreasing trends as sintering aid content increases. Si₃N₄-SiC ceramic composites have both good EMA and mechanical properties when they are sintered at 1850°C with 30 wt.% SiC and 5–8 wt.% sintering aids. The minimum reflection loss and maximum flexural strength reach -58 dB and 586 MPa, respectively. Materials with multilayered structural designs have both strong and broad EMA properties.     

Densification and high-temperature oxidation behavior of SiC sintered with multicomponent rare-earth additives

This study examined the effects of rare-earth (RE) elements such as Sc, Y, Ce, and Yb on the densification and oxidation of SiC. After adding binary or ternary RE nitrates in liquid form to β-SiC, hot pressing was performed at 1750 °C for 2 h under 20 MPa. RE nitrate was transformed into RE oxide and formed a liquid phase during sintering by a reaction with SiO₂ present on the SiC surface, where the total amount of RE oxide was fixed at 5 wt%. RE-based silicate melts acted as sintering additives without decomposing SiC at high sintering temperatures. SiC containing Sc–Y as an additive showed a much higher density (≥ 99%) than SiC containing the conventional Al–Y additive (∼95%). The multicomponent RE additive with a melting point (T_m) < 1550 °C had a relatively lower density than that with a higher T_m, owing to the evaporation of the additive at 1750 °C. The density of SiC also depended on the additive composition. The oxidation test, conducted at 1300 °C for up to 168 h in air, exhibited a parabolic weight gain. The SiC sample sintered with the Sc–Yb additive achieved the highest resistance of 3.23 × 10⁻⁵ mg/cm⁴·s.     

Preparation and characterization of porous,biomorphic SiC ceramic with hybrid pore structure

Bio-carbon template (charcoal) was prepared by carbonizing pine wood at 1200 °C under vacuum, and was impregnated with phenolic resin/SiO₂ sol mixture by vacuum/pressure processing. Porous SiC ceramics with hybrid pore structure, a combination of tubular pores and network SiC struts in the tubular pores, were fabricated via sol–gel conversion, carbonization and carbothermal reduction reaction at elevated temperatures in Ar atmosphere. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM) were employed to characterize the phase identification and microstructural changes during the C/SiO₂ composites-to-porous SiC ceramic conversion. Experimental results show that the density of C/SiO₂ composite increases with the number of impregnation procedure, and increases from 0.32 g cm⁻³ of pine-derived charcoal to 1.5 g cm⁻³ of C/SiO₂ composite after the sixth impregnation. The conversion degree of charcoal to porous SiC ceramic increases as reaction time is lengthened. The resulting SiC ceramic consists of β-SiC with a small amount of α-SiC. The conversion from pine charcoal to porous SiC ceramic with hybrid pore structure improves bending strength from 16.4 to 42.2 MPa, and decreases porosity from 76.1% to 48.3%.     

Preparation,mechanical and ablation properties of a C/C-TaB2-SiC composite

A C/C-TaB₂-SiC composite was successfully prepared by high-solid-loading slurry impregnation combined with polymer infiltration and pyrolysis. The composite had a density of 3.46 g/cm³ and consisted of pyrolyzed carbon, carbon fibers, TaB₂ particles, and precursor-derived SiC with their mass fractions of 7.8 %, 13.0 %, 58.6 %, and 20.6 %, respectively. The C/C-TaB₂-SiC composite possessed a flexural strength of 248.2 ± 16.8 MPa and a fracture toughness of 13.7 ± 1.6 MPa·m^1/2, and demonstrated a non-brittle fracture behavior. After exposure to oxyacetylene flame with a heat flux of 4.18 MW/m² for 120 s, the ablation temperature of the sample surface reached a maximum of 2263 °C, and the mass and line ablation rates were 2.24 mg/s and 12.92 µm/s, respectively. The ablation resistance mainly comes from the hindrance of oxygen diffusion by the oxide layer composed of tantalum oxide and a small amount of SiO₂.     

Effect of ZrB2 powders on densification,microstructure, mechanical properties and thermal conductivity of ZrB2-SiC ceramics

With the view to improve the densification behaviour and mechanical properties of ZrB₂-SiC ceramics, three synthesis routes were investigated for the production of ZrB₂, prior to the fabrication of ZrB₂-20 vol. % SiC via spark plasma sintering (SPS). Two borothermal reduction routes, modified with a water-washing stage (BRW) and partial solid solution of Ti (BRS), were utilised, alongside a boro/carbothermal mechanism (BRCR) were utilised to synthesise ZrB₂, as a precursor material for the production of ZrB₂-SiC. It was determined that reduction in the primary ZrB₂ particle size, alongside a diminished oxygen content, was capable of improving densification. ZrB₂-SiC ceramics, with ZrB₂ derived from BRW synthesis, exhibited a favorable combination of high relative density (98.6%), promoting a marked increase in Vickers hardness (21.4 ± 1.7 GPa) and improved thermal conductivity (68.7 W·m^-1K^-1).     

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.     

Development of a new composite ceramic membrane from mullite,silicon carbide and activated carbon for treating greywater

In this experimental research, it is aimed at evaluating a novel composite ceramic membrane for treating and recycling on-site greywater. Therefore, three types of tubular microfiltration ceramic membrane including Mullite, Mullite/SiC and Mulite/SiC/AC composite were fabricated and sintered at a relatively low temperature (1250 ^°C) under N₂ atmosphere. Field Emission Scanning Electron Microscopy (FE-SEM) and Atomic Force Microscopy (AFM) analyses showed that the presence of silicon carbide and activated carbon can improve the surface roughness. Besides, the changes in open porosity, radial and longitudinal shrinkage, mean pore size and mechanical strength were measured and compared for the pure Mullite and composite membranes to determine the most appropriate membrane for the treatment of greywater. The highest pure-water permeability of 3954 kg/m²h.br was associated with the Mullite/SiC/AC membrane with the highest porosity of 64.7% and an acceptable appropriate mechanical strength (17.2 MPa approx.). Furthermore, the highest removal efficiency was related to Mullite/SiC/AC in comparison with Mullite and Mullite/SiC membranes. It was observed that using the Mullite/SiC/AC membrane, the removal efficiencies for chemical oxygen demand (COD), biochemical oxygen demand (BOD), total sulfate, total nitrate, phosphate, and detergent (ABS) were 88.0%, 87.0%, 71.5%, 86.5%, 94.3%, and 40.4%, respectively.     

Consolidation and high-temperature strength of monolithic lanthanum hexaboride

In this study we explored the densification, microstructure evolution, and high-temperature properties of bulk lanthanum hexaboride. LaB₆ bulks were consolidated using spark-plasma sintering only in the temperature range between 1400°C and 1700°C. We adopted flash spark plasma sintering (SPS) of LaB₆ using a direct current heating without a graphite die. We observed a peculiar grain-size gradient when coarse grains exceeding 300 μm were observed on the top side of the specimen, while the bottom side had a grain size of 15–20 μm. Such large grain was not observed using SPS at 2000°C, suggesting that these might originate from a local overheating. Based on the three-point flexural tests, it was observed that the toughness and strength of the LaB₆ were acceptable at room-temperature (3.1 ± 0.2 MPa m^1/2, 300 ± 20 MPa). However, at 1600°C, these parameters would decrease to 1.3 ± 0.1 MPa m^1/2 and 120 ± 40 MPa, respectively.     

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.     

Mechanical and tribological properties of SiC whisker-reinforced SiC composites via oscillatory pressure sintering

SiC whisker (SiCw)-reinforced SiC composites were prepared by an oscillatory pressure sintering (OPS) process, and the effects of SiCw content on the microstructure and mechanical and tribological properties of such composites were investigated. The addition of SiCw could promote the formation of long columnar α-SiC, and the aspect ratio of α-SiC grains first increased and then decreased with the increase of SiCw content. When the SiCw content was 5.42 wt%, the relative density of the SiC–SiCw composite reached up to 99.45%. The SiC–5.42 wt% SiCw composite possessed the highest Vickers hardness, fracture toughness, and flexural strength of 30.68 GPa, 6.66 MPa·m^1/2, and 733 MPa, respectively. In addition, the SiC–5.42 wt% SiCw composite exhibited the excellent wear resistance when rubbed with GCr15 steel balls, with a friction coefficient of .76 and a wear rate of 4.12 × 10⁻⁷ mm³·N⁻¹·m⁻¹. This could be ascribed to the improved mechanical properties of SiC–SiCw composites, which enhanced the ability to resist peeling and micro-cutting, thereby enhancing the tribological properties of the composites.     

Reactive hot pressing route for dense ZrB2-SiC and ZrB2-SiC-CNT ultra-high temperature ceramics

The in-situ exothermic reactions between ZrC_0.8, B₄C and Si have assisted densification and allowed to obtain fully dense ZrB₂-31 wt.%SiC ultra-high temperature ceramics within 6 min at 1750 °C. The use of zirconium carbide instead of metallic zirconium in the green body obviated the possibility of in-situ SHS process and allowed to apply the pressure at low temperatures. The latter provided a first densification stage just above 1050 °C. A slight carbon excess was created in the green body to preserve the carbon nanotubes. The developed reactive hot pressing route (1830 °C, 3 min, 30 MPa) has been successfully used to obtain ZrB₂-SiC ceramics containing 8 vol.% of multi-wall carbon nanotubes (MW-CNT). The carbon nanotubes survived the thermal cycle and could be clearly observed in the sintered ceramics. The CNT addition improved the fracture toughness of the composite from 4.3 MPa m^1/2 for ZrB₂-31 wt.%SiC to 6.8 MPa m^1/2 for ZrB₂-29 wt.%SiC-CNT.