Mechanical behavior of zirconium diboride–silicon carbide ceramics at elevated temperature in air

The mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics were characterized from room temperature up to 1600 °C in air. ZrB₂ containing nominally 30 vol% SiC was hot pressed to full density at 1950 °C using B₄C as a sintering aid. After hot pressing, the composition was determined to be 68.5 vol% ZrB₂, 29.5 vol% SiC, and 2.0 vol% B₄C using image analysis. The average ZrB₂ grain size was 1.9 μm. The average SiC particles size was 1.2 μm, but the SiC particles formed larger clusters. The room temperature flexural strength was 680 MPa and strength increased to 750 MPa at 800 °C. Strength decreased to ～360 MPa at 1500 °C and 1600 °C. The elastic modulus at room temperature was 510 GPa. Modulus decreased nearly linearly with temperature to 210 GPa at 1500 °C, with a more rapid decrease to 110 GPa at 1600 °C. The fracture toughness was 3.6 MPa·m^½ at room temperature, increased to 4.8 MPa·m^½ at 800 °C, and then decreased linearly to 3.3 MPa·m^½ at 1600 °C. The strength was controlled by the SiC cluster size up to 1000 °C, and oxidation damage above 1200 °C.     

Microstructure and mechanical properties of superplastically deformed silicon nitride–silicon oxynitride in situ composites

Silicon nitride–silicon oxynitride in situ composites were fabricated by plane-strain-compressing dense silicon nitrides, starting from 93 wt.% ultrafine β-Si₃N₄ and 7 wt.% cordierite, at 1600 °C under a constant load of 40 MPa and subsequent annealing at 1750 °C for 30 min. The resulting composites featured a microstructure of elongated Si₂N₂O grains (∼0.64 μm in diameter and ∼5.5 in aspect ratio) dispersed in a fine-grained β-Si₃N₄ matrix (∼ 0.30μm in diameter and ∼3.5 in aspect ratio), with the amount of Si₂N₂O, which had relatively strong textures, being strain-dependent. The mechanical properties were found to be improved due to the development of elongated Si₂N₂O grains, the texture formation, and the coarsening of β-Si₃N₄. Fracture toughness, however, was still low (∼5.2 MPa m^1/2) for these composites in comparison to self-reinforced silicon nitrides, resulted from the strong Si₂N₂O-matrix interfacial bond and nearly equiaxed β-Si₃N₄ with a small grain size. Anticipated property anisotropies were clearly observed as a result of the textured microstructure.     

Boron nitride–silicon carbide interphase boundaries in silicon nitride–silicon carbide particulate composites

Interphase boundaries between SiC and h-BN grains in hot isostatically pressed Si₃N₄–SiC particulate composites made from both as-received powders and deoxidised powders, in which sub-micron size h-BN particles occur as a contaminant, have been characterised using transmission electron microscopy techniques. Most of the h-BN grains observed were aligned with respect to SiC grains so that (111) 3C SiC and (0001) α-SiC planes were parallel to (0001) h-BN planes. The h-BN–SiC interphase boundaries in the composites made from as-received powders were covered with thin silica-rich intergranular films, in contrast to the interphase boundaries in the composites made from deoxidised powders. These observations are discussed in the light of models for the formation of intergranular amorphous films in ceramic materials, geometric considerations for low interfacial energies and the possible bonding at h-BN–SiC interphase boundaries free of intergranular films.     

Processing of silicon carbide–boron carbide–aluminium composites

The aim of this work was to shed light on the wetting mechanism in the SiC–B₄C–Al system and to explore processing routes that enable infiltration of Al alloys into these ceramic powder mixtures without the formation of the deleterious reaction product Al₄C₃. For this purpose, powder mixtures consisting of SiC and pre-treated B₄C were pressureless infiltrated with Al alloys at relatively low temperatures under an inert gas atmosphere. Depending on the characteristics of the starting powders fully infiltrated composites were achieved in the temperature range of 935–1420 °C. It was observed that addition of pre-treated B₄C to SiC enabled complete infiltration of the ～0.6 cm thick preforms. The bulk density of all produced composites was >98% of the X-ray density. By controlling the surface chemistry and particle size of the starting powders as well as the processing conditions, the wetting behaviour and reaction kinetics of this system could be tailored so as to render fully dense SiC–B₄C–Al composites devoid of Al₄C₃.     

Effect of silicon carbide dispersion on the microwave absorbing properties of silicon carbide-epoxy composites in 2–40 GHz

In this study, silicon carbide powders were manufactured successfully by the method of preheating combustion synthesis in nitrogen atmosphere where it was introduced into an epoxy resin to produce a microwave absorber. The structure of the silicon carbide was characterized by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Composite based on the various loadings of silicon carbide and epoxy resin specimens were prepared and the reflection losses of these composite samples were studied using the free space method. Based on the microwave measurements, microwave absorber specimens of silicon carbide with thermal plastic resin at frequencies between 2 and 18 and 18–40 GHz could be obtained from a matching thickness of 2.0 mm by controlling the content of silicon carbide.     

Thermal properties of silicon carbide composites fabricated with chopped Tyranno® SiAlC fibres

Thermal diffusivity, a, and thermal conductivity, κ, between room temperature and 600 K were investigated for SiC composites containing 0–50 mass% of Tyranno^® SiAlC (SA) fibre (mean length: 394 μm) hot-pressed at 1800 °C for 30 min under a pressure of 31 MPa. The monolithic SiC specimen possessed κ of 32.1 W m⁻¹ K⁻¹ at room temperature; no significant changes were found for the SiC composite containing ≤20 mass% of SA fibre addition. However, further increases in the amount of SA fibre to 50 mass% improved κ to a maximum of 56.3 W m⁻¹ K⁻¹. The value of a for the SiC composite containing 40 mass% of SA fibre was 0.185 cm² s⁻¹ at room temperature and decreased to 0.120 cm² s⁻¹ at 600 K. In addition, SiC composites using 40 mass% of SA fibre with a carbon interface of approximately 100 nm were fabricated. The effect of this interface on a and κ was marginal.     

Creep behavior of a zirconium diboride–silicon carbide composite

Flexural creep studies of ZrB₂–20 vol% SiC ultra-high temperature ceramic were conducted over the range of 1400–1820 °C in an argon shielded testing apparatus. A two decade increase in creep rate, between 1500 and 1600 °C, suggests a clear transition between two distinct creep mechanisms. Low temperature deformation (1400–1500 °C) is dominated by ZrB₂ grain or ZrB₂–SiC interphase boundary and ZrB₂ lattice diffusion having an activation energy of 364 ± 93 kJ/mol and a stress exponent of unity. At high temperatures (>1600 °C) the rate-controlling processes include ZrB₂–ZrB₂ and/or ZrB₂–SiC boundary sliding with an activation energy of 639 ± 1 kJ/mol and stress exponents of 1.7 < n < 2.2. In addition, cavitation is found in all specimens above 1600 °C where strain-rate contributions agree with a stress exponent of n = 2.2. Microstructure observations show cavitation may partially accommodate grain boundary sliding, but of most significance, we find evidence of approximately 5% contribution to the accumulated creep strain.     

Mechanical and thermal properties of silicon carbide ceramics with yttria–scandia–magnesia

Two different SiC ceramics with a new additive composition (1.87 wt% Y₂O₃–Sc₂O₃–MgO) were developed as matrix materials for fully ceramic microencapsulated fuels. The mechanical and thermal properties of the newly developed SiC ceramics with the new additive system were investigated. Powder mixtures prepared from the additives were sintered at 1850 °C under an applied pressure of 30 MPa for 2 h in an argon or nitrogen atmosphere. We observed that both samples could be sintered to ≥99.9% of the theoretical density. The SiC ceramic sintered in argon exhibited higher toughness and thermal conductivity and lower flexural strength than the sample sintered in nitrogen. The flexural strength, fracture toughness, Vickers hardness, and thermal conductivity values of the SiC ceramics sintered in nitrogen were 1077 ± 46 MPa, 4.3 ± 0.3 MPa·m^1/2, 25.4 ± 1.2 GPa, and 99 Wm⁻¹ K⁻¹ at room temperature, respectively.     

Processing and mechanical properties of hot-pressed zirconium diboride – zirconium carbide ceramics

ZrB₂ was mixed with 0.5 wt% carbon and up to 10 vol% ZrC and densified by hot-pressing at 2000 °C. All compositions were > 99.8% dense following hot-pressing. The dense ceramics contained 1–1.5 vol% less ZrC than the nominal ZrC addition and had between 0.5 and 1 vol% residual carbon. Grain sizes for the ZrB₂ phase decreased from 10.1 µm for 2.5 vol% ZrC to 4.2 µm for 10 vol% ZrC, while the ZrC cluster size increased from 1.3 µm to 2.2 µm over the same composition range. Elastic modulus was ~505 GPa and toughness was ~2.6 MPa·m^½ for all compositions. Vickers hardness increased from 14.1 to 15.3 GPa as ZrC increased from 2.5 to 10 vol%. Flexure strength increased from 395 MPa for 2.5 vol% ZrC to 615 MPa for 10 vol% ZrC. Griffith-type analysis suggests ZrB₂ grain pullout from machining as the strength limiting flaw for all compositions.     

Crack healing in liquid-phase-pressureless-sintered silicon carbide–aluminum nitride composites

Crack healing in liquid-phase-pressureless-sintered SiC–AlN composites was investigated by introducing cracks into specimens and subsequently heat-treating the specimens. It was observed that cracks were healed and the strength was recovered. Cracks were filled with silica or mullite produced by the oxidation of the composites. It was shown that the healing temperature could be fixed in the range 1100–1300 °C and that large cracks up to about 300 μm could be healed completely. Our results imply that a simple oxidation heat-treatment can improve the reliability of silicon carbide–aluminum nitride components.     

Surface stress distribution in diamond crystals in diamond–silicon carbide composites

Diamond–silicon carbide composites were sintered at high temperature, up to 2273 K, and high pressure, up to 10 GPa. Raman microscopy was used to map stress distribution in diamond crystals on surfaces of the composites. Splitting of the triple degenerate band of diamond and frequency shifts of its components were used to calculate the magnitudes of stress. Those magnitudes varied with location and reached maximum values near crystals boundaries. Stress depended on the sintering temperature, pressure, and the crystal size and was attributed to differences in thermal expansion coefficients and bulk moduluses of diamond and silicon carbide.     

Micromechanics modeling of creep fracture of zirconium diboride–silicon carbide composites at 1400–1700 °C

The creep deformation of the ultra-high temperature ceramic composite ZrB₂–20%SiC at temperatures from 1400 to 1700 °C was studied by a micromechanical mode in which the real microstructure was adopted in finite element simulations. Based on the experiment results of the change of activation energy with respect to the temperature, a mechanism shift from diffusional creep-control for temperatures below 1500 °C to grain boundary sliding-control for temperatures above 1500 °C was concluded from simulations. Also, the simulation results revealed the accommodation of grain rotation and grain boundary sliding by grain boundary cavitation for creep at temperatures above 1500 °C which was in agreement with experimental observations.     

Temperature-dependent mechanical and long crack behavior of zirconium diboride–silicon carbide composite

Hot pressed ZrB2–20 vol.% SiC ultra-high temperature ceramic composites have been prepared for strength and fracture investigations. Two composites fabricated under differing hot pressing temperatures with (ZSB) and without (ZS) B4C sintering aids were selected for room temperature modulus of rupture (MOR) strength and single-edge-notch bend (SENB) fracture toughness experiments. Structure property relationships were examined for both composites. MOR and stiffness temperature dependence was also investigated up to 1500 °C. Long crack propagation studies were conducted up to 1400 °C using the double cantilevered beam geometry with half-chevron-notch initiation zones. Residual Boron-rich carbide maximum particle sizes were found to be strength limiting in ZSB billets while SiC controlled strength in ZS billets. Flexure strength decreased linearly with temperature from 1000 to 1500 °C with no visible plastic deformation prior to fracture. Similar stiffness decreases were observed with a transition temperature range of 1100–1200 °C. Long crack studies produced R-curves that show no significant toughening behavior at room temperature with some modest rising R-curve behavior appearing at higher temperatures. These studies also show the plateau toughness increases with temperature up to 1200 °C. This is supported by an observed transition from primarily transgranular fracture at room temperature to primarily intergranular fracture at high temperatures. Wake zone toughening is evident up to 1000 °C with K_R rise from 0.1 to 0.5 MPa√m. Beyond 1000 °C fracture mechanism transitions to include creep zone development ahead of crack tip with wake zone toughening vanishing.     

Tensile properties of two-dimensional carbon fiber reinforced silicon carbide composites at temperatures up to 2300 °C

Carbon fiber reinforced silicon carbide (C/SiC) composites are of the few most promising materials for ultra-high-temperature structural applications. However, the existing studies are mainly conducted at room and moderate temperatures. In this work, the tensile properties of a two-dimensional plain-weave C/SiC composite are studied up to 2300 °C in inert atmosphere for the first time. The study shows that C/SiC composite firstly shows linear deformation behavior and then strong nonlinear characteristics at room temperature. The nonlinear deformation behavior rapidly reduces with temperature. The Young’s modulus increases up to 1000 °C and then decreases as temperature increases. The tensile strength increases up to 1000 °C firstly, followed by reduction to 1400 °C, then increases again to 1800 °C, and lastly decreases with increasing temperature. The failure mechanisms being responsible for the mechanical behavior are gained through macro and micro analysis. The results are useful for the applications of C/SiC composites in the thermal structure engineering.     

Mechanical and dielectric properties of porous Si2N2O–Si3N4 in situ composites

Mechanical and dielectric properties of porous Si₂N₂O–Si₃N₄ in situ composites fabricated for use as radome by gel-casting process were investigated. The flexural strength of the Si₂N₂O–Si₃N₄ ceramics is 230.46 ± 13.24 MPa, the complex permittivity of the composites varies from 4.34 to 4.59 and the dissipation factor varies from 0.00053 to 0.00092 from room temperature to elevated temperature (1150 °C) at the X-band. In the porous regions, some Si₂N₂O fibers (50–100 nm in diameter) are observed which may improve the materials properties.     

Additive manufacturing of continuous carbon fiber–reinforced silicon carbide ceramic composites

A material extrusion (MEX) technology has been developed for the additive manufacturing of continuous carbon fiber–reinforced silicon carbide ceramic (C_f/SiC) composites. By comparing and analyzing the rheological properties of the slurries with different compositions, a slurry with a high solid loading of 48.1 vol% and high viscosity was proposed. Furthermore, several complex structures of C_f/SiC ceramic composites were printed by this MEX additive manufacturing technique. Phenolic resin impregnation–carbonization process reduces the apparent porosity of the green body and protects the C_f. Finally, the reactive melting infiltration (RMI) process was used to prepare samples with different C_f contents from 0 to 2 K (a bundle of carbon fibers consisting of 1000 fibers). Samples with C_f content of 1 K show the highest bending strength (161.6 ± 10.5 MPa) and fracture toughness (3.72 ± 0.11 MPa·m^1/2) while the thermal conductivity of the samples with the C_f content of 1 K reached 11.0 W/(m·K). This study provides a strategy to prepare C_f/SiC composites via MEX additive manufacturing and RMI.     

Effect of carbon and oxygen on the high-temperature properties of silicon carbide–hafnium carbide nanocomposite fiber

The polymer-derived ceramics (PDCs) technique enables relatively low-temperature fabrication of Si-based ceramics, with silicon carbide fiber as a representative product. Polycarbosilane (PCS) has Si-C backbone structures and can be converted to silicon carbide. In the PDCs method, residual or excess carbon is generated from the precursor (C/Si ratio = 2 for polycarbosilane). Because of the non-stoichiometry of SiC, the physicochemical properties of polymer-derived SiC are inferior to those of conventional monolithic SiC. Herein, a silicon carbide-hafnium carbide nanocomposite fiber was optimized by crosslinking oxygen into the PCS fiber by regulating the oxidation curing time. During pyrolysis, carbothermal reduction, and sintering, carbon was removed by reaction with hydrogen and cross-linked oxygen. Non-destructive techniques (X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and high-temperature thermomechanical analysis) were used to investigate the effects of excess carbon. The microstructure of the near-stoichiometric SiC-HfC nanocomposite fiber was more densified, with superior high-temperature properties.     

Improved ablation resistance of C–C composites using zirconium diboride and boron carbide

Zirconium diboride and boron carbide particles were used to improve the ablation resistance of carbon–carbon (C–C) composites at high temperature (1500 °C). Our approach combines using a precursor to ZrB₂ and processing them with B₄C particles as filler material within the C–C composite. An oxyacetylene torch test facility was used to determine ablation rates for carbon black, B₄C, and ZrB₂–B₄C filled C–C composites from 800 to 1500 °C. Ablation rates decreased by 30% when C–C composites were filled with a combination of ZrB₂–B₄C particles over carbon black and B₄C filled C–C composites. We also investigated using a sol–gel precursor method as an alternative processing route to incorporate ZrB₂ particles within C–C composites. We successfully converted ZrB₂ particles within C–C composites at relatively low temperatures (1200 °C). Our ablation results suggest that a combination of ZrB₂–B₄C particles is effective in inhibiting the oxidation of C–C composites at temperatures greater than 1500 °C.     

Oxidation,mechanical and thermal properties of hafnia–silicon carbide nanocomposites

Dense nanocomposites constituted from 70/30 vol% of hafnia–silicon carbide and were prepared by spark plasma sintering. Silicon carbide suppresses grain growth. The fracture strength of as prepared composites is 400–600 MPa. Oxidation up to 1600 °C in air for 10 h has minor influence on the mechanical strength, which is ascribed to the dense nature of the oxidation scale. The high density of the oxidation scale is attributed to a volume increase when silicon carbide oxidizes and reacts with hafnia to form hafnium silicate. The composite has a thermal conductivity of 14 W m⁻¹ K⁻¹ at room temperature. Design approaches for further enhancement of ultrahigh temperature properties of oxide/non-oxide composites are discussed.     

Dispersants for silicon carbide in water—A comparative study

The present work describes a comparative study on a pool of 12 dispersants for the de-agglomeration and stabilization of silicon carbide in aqueous suspensions with solids loading relevant for dip coating applications. As silicon carbide slurries may include sintering aids, different functional groups, molecular weight, and stabilization mechanisms were considered for the dispersants to be able to stabilize both slurry components. Additionally, pH effect, toxicity, additive compatibility, and foaming properties were considered, giving all the necessary information for developing new aqueous formulation of SiC suspensions, including advantages and disadvantages of the different candidates. Different de-agglomeration procedures, powder surface area, and calcination temperature were also considered to study the effect of the SiC surface properties. The outcome is that slurry stabilization provided by an alkaline environment at pH larger than 8‒9 is significantly more effective than slurry stabilization by any of the tested dispersants. Alkaline environments facilitate a negative surface charge on SiC particles and provide a stable electrostatic stabilization mechanism not observed in neutral or acidic environments. One among the dispersant candidates (FA 4404) seems to broaden slightly the range of stability toward the acidic regime. Anionic surfactants or block co-polymers tested exhibited no significant interaction with the SiC particles.