Highly conductive SiC ceramics containing Ti2CN

Highly conductive SiC ceramics were fabricated by sintering β-SiC and TiN powder mixture in N₂ atmosphere. SiC ceramics exhibited decreased electrical resistivity (ρ) with increasing TiN content. X-ray diffraction data indicated that the specimens consisted of β-SiC grains without a detectible secondary phase for low TiN content (≤2 vol%) but contained a Ti₂CN phase as the TiN content increased. The temperature-dependent resistivity ρ(T) of specimens revealed semiconductor-like behavior for TiN content up to 10 vol% and metal-like behavior above 20 vol%. For the specimen with TiN content of 15 vol%, ρ(T) remained almost constant (2.06 ± 0.01 × 10⁻³ Ω cm) in the 4–300 K range. The resistivity of metal-like specimens were as low as 3.5 × 10⁻⁴ Ω cm for TiN content of 20 vol%. For semiconductor-like specimens, ρ(T) was primarily affected by N donors in the β-SiC grains. Metal-like specimens were primarily affected by metallic Ti₂CN clusters.     

Electrical and thermal properties of SiC-Zr2CN composites sintered with Y2O3-Sc2O3 additives

SiC-Zr₂CN composites were fabricated from β-SiC and ZrN powders with 2 vol% equimolar Y₂O₃-Sc₂O₃ additives via conventional hot pressing at 2000 °C for 3 h in a nitrogen atmosphere. The electrical and thermal properties of the SiC-Zr₂CN composites were investigated as a function of initial ZrN content. Relative densities above 98% were obtained for all samples. The electrical conductivity of Zr₂CN composites increased continuously from 3.8 × 10³ (Ωm)⁻¹ to 2.3 × 10⁵ (Ωm)⁻¹ with increasing ZrN content from 0 to 35 vol%. In contrast, the thermal conductivity of the composites decreased from 200 W/mK to 81 W/mK with increasing ZrN content from 0 to 35 vol%. Typical electrical and thermal conductivity values of the SiC-Zr₂CN composites fabricated from a SiC-10 vol% ZrN mixture were 2.6 × 10⁴ (Ωm)⁻¹ and 168 W/m K, respectively.     

Physical,thermal and ablative performance of CVI densified urethane-mimetic SiC preforms containing in situ grown Si3N4 whiskers

A two-step process has been developed for silicon carbide (SiC) coated polyurethane mimetic SiC preform containing silicon nitride (Si₃N₄) whiskers. SiC/Si₃N₄ preforms were prepared by pyrolysis/siliconization treatment at 1600 °C, of powder compacts containing rigid polyurethane, novolac and Si, forming a porous body with in situ grown Si₃N₄ whiskers. The properties were controlled by varying Si/C mole ratios such as 1–2.5. After densification using a chemical vapour infiltration, the resulting SiC/Si₃N₄/SiC composites showed excellent oxidation resistance, thermal conductivity of 4.32–6.62 Wm⁻¹ K⁻¹, ablation rate of 2.38 × 10⁻³ − 3.24 × 10⁻³ g cm⁻² s and a flexural strength 43.12–55.33 MPa for a final density of 1.39–1.62 gcm⁻³. The presence of a Si₃N₄ phase reduced the thermal expansion mismatch resulting in relatively small cracks and well-bonded layers even after ablation testing. This innovative two-step processing can provide opportunities for expanded design for using SiC/Si₃N₄/SiC composites being lightweight, inexpensive, homogeneous and isotropic for various high temperature applications.     

Electrical properties and microstructural evolution of ZrO2–Al2O3–TiN nanocomposites prepared by spark plasma sintering

Electroconductive ZrO₂–Al₂O₃–25 vol% TiN ceramic nanocomposites were prepared by spark plasma sintering at 1200 °C for 3 min. The electrical resistivity of the composites decreased from 4.5 × 10^?4 Ω m to 3 × 10^?5 Ω m as the Al₂O₃ content in the ZrO₂–Al₂O₃ matrix increased from 0 to 100 vol%. SEM images graphically presented the microstructural evolution of the composites and a geometrical percolation model was applied to investigate the relationship between the electrical property and the microstructure. The results indicated that the addition of Al₂O₃ to ZrO₂–TiN improved the electrical conductivity of the material by tailoring the structure from “nano–nano” type for ZrO₂–TiN to “micro–nano” type for ZrO₂–Al₂O₃–TiN.     

Mechanical and dielectric properties of SiCf/SiC composites fabricated by PIP combined with CIP process

2D KD-1 SiC fiber fabrics were employed to fabricate SiC_f/SiC composites by an improved polymer infiltration and pyrolysis (PIP) process, combined with cold isostatic pressing (CIP). The effect of CIP process on the microstructure, mechanical and dielectric properties of SiC_f/SiC composites was investigated. The infiltration efficiency was remarkably improved with the introduction of CIP process. Compared to vacuum infiltration, the CIP process can effectively increase the infiltrated precursor content and decrease the porosity resulting in a dense matrix. Thus SiC_f/SiC composites with high density of 2.11 g cm⁻³ and low porosity of 11.3% were obtained at 100 MPa CIP pressure, together with an increase of the flexural strength of the composites from 89 MPa to 213 MPa. Real part (ε′) and the imaginary part (ε″) of complex permittivity of SiC_f/SiC composites increase and vary from 11.7-i9.7 to 15.0-i12.8 when the CIP pressure reaches 100 MPa.     

Effects of polycarbosilane infiltration processes on the microstructure and mechanical properties of 3D-Cf/SiC composites

Three-dimensional braided carbon fiber-reinforced silicon carbide (3D-C_f/SiC) composites were prepared through eight cycles of infiltration of polycarbosilane (PCS)/divinylbenzene (DVB) and subsequent pyrolysis under an inert atmosphere. The effects of infiltration processes on the microstructure and mechanical properties of the C_f/SiC composites were investigated. The results showed that increasing temperature could reduce the viscosity of the PCS/DVB solution, which was propitious to the infiltration processes. The density and flexural strength of 3D-C_f/SiC composites fabricated with vacuum infiltration were 1.794 g cm⁻³ and 557 MPa, respectively. Compared to vacuum infiltration, heating and pressure infiltration could improve the infiltration efficiency so that the composites exhibited higher density and flexural strength, i.e., 1.944 g cm⁻³ and 662 MPa. When tested at 1650 °C and 1800 °C in vacuum, the flexural strength reached 647 MPa and 602 MPa, respectively.     

Electrically conductive SiC–(Nb,Ti)ss–(Nb,Ti)Css cermet

The present paper deals with the processing method of SiC–(Nb,Ti)_(ss)–(Ti,Nb)C_(ss) composites. The electrically conductive phases were formed by in situ reaction: NbC_(s) + Ti_(s) → (Nb,Ti)_(ss) + (Ti,Nb)C_(ss) that takes place during the reaction sintering by hot pressing. Prepared composites exhibit good compromise between electrical and mechanical properties and the present approach allows preparing a wide variety of compositions. For example composites containing 80 wt.% SiC and 20 wt.% {(Nb,Ti)_(ss)–(Ti,Nb)C_(ss)} have an electrical resistivity 2.6 × 10⁻⁴ Ω m, hardness 21.6 GPa and fracture toughness 6.3 MPa m^1/2.     

Physical characterization and arcjet oxidation of hafnium-based ultra high temperature ceramics fabricated by hot pressing and field-assisted sintering

For this study, HfB₂-based ultra high temperature ceramic (UHTC) samples were prepared by hot pressing and field-assisted sintering (FAS) with 10–20 vol.% SiC (baseline), 5 vol.% TaSi₂, and 5 vol.% iridium. Dense billets were tested for hardness and mechanical strength. When compared, the FAS method consistently yielded materials with a grain size 1.5–2 times finer than samples processed via hot pressing. In general, room temperature flexural strengths of these materials were found to be lower (～400 MPa) than similar fully dense HfB₂–SiC materials, with strengths between 500 and 700 MPa. Oxidation resistance testing of flat-face models was conducted in a simulated re-entry environment, at Q_{Cold Wall} ～250 W/cm² for 5 min. Samples processed by FAS had reduced oxide thickness and SiC depletion zones compared to the baseline HfB₂–20SiC material. In all cases oxide thickness was reduced by ～3× and SiC depletion zone thickness was reduced ～3× over the baseline.     

Densification and mechanical properties of cBN–TiN–TiB2 composites prepared by spark plasma sintering of SiO2-coated cBN powder

cBN–TiN–TiB₂ composites were fabricated by spark plasma sintering at 1773–1973 K using cubic boron nitride (cBN) and SiO₂-coated cBN (cBN(SiO₂)) powders. The effect of SiO₂ coating, cBN content and sintering temperature on the phase composition, densification and mechanical properties of the composites was investigated. SiO₂ coating on cBN powder retarded the phase transformation of cBN in the composites up to 1873 K and facilitated viscous sintering that promoted the densification of the composites. Sintering at 1873 K, without the SiO₂ coating, caused the relative density and Vickers hardness of the composite to linearly decrease from 96.2% to 79.8% and from 25.3 to 4.4 GPa, respectively, whereas the cBN(SiO₂)–TiN–TiB₂ composites maintained high relative density (91.0–96.2%) and Vickers hardness (17.9–21.0 GPa) up to 50 vol% cBN. The cBN(SiO₂)–TiN–TiB₂ composites had high thermal conductivity (60 W m⁻¹ K⁻¹ at room temperature) comparable to the TiN–TiB₂ binary composite.     

Effects of porous C/C density on the densification behavior and ablation property of C/C–ZrC–SiC composites

C/C–ZrC–SiC composites were prepared by precursor infiltration and pyrolysis process using a mixture solution of organic zirconium-containing polymer and polycarbosilane as precursors. Porous carbon/carbon (C/C) composites with density of 0.92, 1.21 and 1.40 g/cm³ were used as preforms, and the effects of porous C/C density on the densification behavior and ablation resistance of C/C–ZrC–SiC composites were investigated. The results show that the C/C preforms with a lower density have a faster weight gain, and the obtained C/C–ZrC–SiC composites own higher bulk density and open porosity. The composites fabricated from the C/C preforms with a density of 1.21 g/cm³ exhibit better ablation resistance with a surface temperature of over 2400 °C during ablation. After ablation for 120 s, the linear and mass ablation rates of the composites are as low as 1.02 × 10⁻³ mm/s and −4.01 × 10⁻⁴ g/s, respectively, and the formation of a dense and continuous coating of molten ZrO₂ solid solution is the reason for their great ablation resistance.     

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.     

Microstructure and densification of ZrB2–SiC composites prepared by spark plasma sintering

ZrB₂–SiC composites were prepared by spark plasma sintering (SPS) at temperatures of 1800–2100 °C for 180–300 s under a pressure of 20 MPa and at higher temperatures of above 2100 °C without a holding time under 10 MPa. Densification, microstructure and mechanical properties of ZrB₂–SiC composites were investigated. Fully dense ZrB₂–SiC composites containing 20–60 mass% SiC with a relative density of more than 99% were obtained at 2000 and 2100 °C for 180 s. Below 2120 °C, microstructures consisted of equiaxed ZrB₂ grains with a size of 2–5 μm and α-SiC grains with a size of 2–4 μm. Morphological change from equiaxed to elongated α-SiC grains was observed at higher temperatures. Vickers hardness of ZrB₂–SiC composites increased with increasing sintering temperature and SiC content up to 60 mass%, and ZrB₂–SiC composite containing 60 mass% SiC sintered at 2100 °C for 180 s had the highest value of 26.8 GPa. The highest fracture toughness was observed for ZrB₂–SiC composites containing 50 mass% SiC independent of sintering temperatures.     

Electrically conductive ZrO2–TiN composites

1.75 mol% Y₂O₃-stabilized ZrO₂–TiN composites could be fully densified by hot pressing for 1 h at 1550 °C in vacuum under a mechanical pressure of 28 MPa. Composites with 35–95 vol% TiN were investigated and the best mechanical properties, i.e., a Vickers hardness of 14.7 GPa, an indentation toughness of 5.9 MPa m^1/2 and an excellent bending strength of 1674 MPa were obtained with 40 vol% TiN. The active toughening mechanisms were identified and their contribution to the overall composite toughness as function of the TiN content was modelled, experimentally verified and discussed. Transformation toughening was found to be the primary toughening mechanism. The TiN grain size was found to increase with increasing TiN content, resulting in a decreasing hardness and strength. A maximum strength was obtained at 40 vol% TiN. The electrical resistivity of the composites decreases exponentially with increasing TiN content and correlates well with the Polder-Van Santen mixture rule. Thus at around 40 vol% TiN, the conductivity is high enough to allow EDM machining of the composite, therefore avoiding the expensive grinding operation for final shaping and surface finishing of components.     

Reactive hot-pressing of ZrB2-ZrC-SiC ceramics via direct addition of SiC

A series of ZrB₂-ZrC-SiC composites with various SiC content from 0 to 20 vol% were prepared by reactive hot-pressing using Zr, B₄C and SiC as raw materials. Self-propagating high-temperature synthesis (SHS) occurred, and ZrC grains connected each other to form a layered structure when the SiC content is below 20 vol%. The evolution of microstructure has been discussed via reaction processes. The composite with 10 vol% SiC presents the most excellent mechanical properties (four-point bending strength: 828.6±49.9 MPa, Vickers hardness: 19.9±0.2 GPa) and finest grain size (ZrB₂: 1.52 µm, ZrC: 1.07 µm, SiC: 0.79 µm) among ZrB₂-ZrC-SiC composites with various SiC content from 0 to 20 vol%.     

Effect of Nd-doping on structural,thermal and electrochemical properties of LaFe0.5Cr0.5O3 perovskites

The structural, thermal and electrochemical properties of the perovskite-type compound La_1−xNd_xFe_0.5Cr_0.5O₃ (x=0.10, 0.15, 0.20) are investigated by X-ray diffraction, thermal expansion, thermal diffusion, thermal conductivity and impedance spectroscopy measurements. Rietveld refinement shows that the compounds crystallize with orthorhombic symmetry in the space group Pbnm. The average thermal expansion coefficient decreases as the content of Nd increases. The average coefficient of thermal expansion in the temperature range of 30–850 °C is 10.12×10⁻⁶, 9.48×10⁻⁶ and 7.51×10⁻⁶ °C⁻¹ for samples with x=0.1, 0.15 and 0.2, respectively. Thermogravimetric analyses show small weight gain at high temperatures which correspond to filling up of oxygen vacancies as well as the valence change of the transition metals. The electrical conductivity measured by four-probe method shows that the conductivity increases with the content of Nd; the electrical conductivity at 520 °C is about 4.71×10⁻³, 6.59×10⁻³ and 9.62×10⁻³ S cm⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. The thermal diffusivity of the samples decreases monotonically as temperature increases. At 600 °C, the thermal diffusivity is 0.00425, 0.00455 and 0.00485 cm² s⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. Impedance measurements in symmetrical cell arrangement in air reveal that the polarization resistance decreases from 55 Ω cm⁻² to 22.5 Ω cm⁻² for increasing temperature from 800 °C to 900 °C, respectively.     

Extraction of jojoba seed oil using supercritical CO2+ethanol mixture in green and high-tech separation process

In this study, the extraction of jojoba seed oil obtained from jojoba seed using both supercritical CO₂ and supercritical CO₂+ethanol mixtures was investigated. The recovery of jojoba seed oil was performed in a green and high-tech separation process. The extraction operating was carried out at operating pressures of 25, 35 and 45 MPa, operating temperatures of 343 and 363 K, supercritical fluid flow rates of 3.33 × 10⁻⁸, 6.67 × 10⁻⁸ and 13.33 × 10⁻⁸ m³ s⁻¹, entrainer concentrations of 2, 4 and 8 vol.%, and average particle diameters of 4.1 × 10⁻⁴, 6.1 × 10⁻⁴, 8.6 × 10⁻⁴ and 1.2 × 10⁻³ m. It was found that a green chemical modifier such as ethanol could enhance the solubilities, initial extraction rate and extraction yield of jojoba seed oil from the seed matrix as compared to supercritical CO₂. In addition, it was found that the solubility, the initial extraction rate and the extraction yield depended on operating pressure and operating temperature, entrainer concentration, average particle size and supercritical solvent flow rate. The solubility of jojoba seed oil and initial extraction rate increased with temperature at the operating pressures of 35 and 45 MPa and decreased with increasing temperature at the operating pressure of 25 MPa. Furthermore, supercritical fluid extraction involved short extraction time and minimal usage of small amounts entrainer to the CO₂. About 80% of the total jojoba seed oil was extracted during the constant rate period at the pressure of 35 and 45 MPa.     

Improving the electrical properties of niobium-doped titania sputtering targets by sintering in oxygen-deficient atmospheres

Niobium-doped titania (TNO) film can be used as a transparent conductive oxide (TCO) film due to its excellent conductivity and visible transparency. The performances of TNO sputtering targets are thus critical issues in optimizing sputtered films. This study clarifies the influences of inert and reducing atmospheres on the microstructure, densification, crystal structure, and electrical properties of TNO sputtering targets. The results indicate that a sintering atmosphere of 90% Ar–10% H₂ can result in a lower sintered density, larger grain size, and lower resistivity than can an atmosphere of Ar, followed by one of air. Sintering in 90% Ar–10% H₂ or Ar obviously decreases the resistivity of TiO₂, from >10⁸ Ω cm to <10⁻¹ Ω cm, and the TNO target, from >10¹ Ω cm to <10⁻¹ Ω cm. The resistivity of TNO target sintered at 1200 °C in 90% Ar–10% H₂ is as low as 1.8×10⁻² Ω cm.     

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.     

Influence of SiC particle addition on the nucleation density and adhesion strength of MPCVD diamond coatings on Si3N4 substrates

It is generally accepted that SiC layers are often involved in the adhesion efficiency of chemical vapour deposition (CVD) diamond films on Si-containing substrates. Si₃N₄–SiC composite substrates with different amounts of SiC particles (0–50 wt%) were then used for diamond deposition. Samples were produced by pressureless sintering (1750°C, N₂ atmosphere, 2–4 h). The diamond films were grown on a commercial MPCVD reactor using H₂/CH₄ mixtures. Despite there being no special substrate pre-treatment, the films were densely nucleated when SiC was added (N_d≈1×10¹⁰ cm⁻²) with primary nanosized (∼100 nm) particles, followed by a less dense (N_d≈1×10⁶ cm⁻²) secondary nucleation. Indentation experiments with a Brale tip of up to 588 N applied load corroborated the benefit of SiC inclusion for a strong adhesion. The low thermal expansion coefficient mismatch between Si₃N₄ and diamond resulted in very low compressive stresses in the film, as proved by micro-Raman spectroscopy.     

The effect of calcium on the properties of SmBa1−xCaxCoCuO5+δ as a cathode material for intermediate-temperature solid oxide fuel cells

The effect of calcium on the properties of SmBa_1–xCa_xCoCuO_5+δ (x = 0.0–0.3) as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs) is evaluated systematically. Samples exhibit a highly crystalline double perovskite phase, and their cell volumes decrease as x is changed from 0.0 to 0.3. The oxygen content and average thermal expansion coefficient (TEC) of SmBa_1–xCa_xCoCuO_5+δ decreases as the calcium content increased. An average TEC of as low as 15.3 × 10⁻⁶ °C⁻¹ is obtained for SmBa_0.7Ca_0.3CoCuO_5+δ. The area specific resistances at 700 °C decrease by approximately 50% when the calcium content is increased from x = 0.0 (0.173 Ω cm²) to x = 0.3 (0.086 Ω cm²). The maximum power densities of SmBa_1−xCa_xCoCuO_5+δ-based single cells at 800 °C increase from 635 mW cm⁻² (x = 0.0) to 939 mW cm⁻² (x = 0.3).