Oxyacetylene ablation of (Hf0.2Ti0.2Zr0.2Ta0.2Nb0.2)C at 1350 − 2050 °C

Ablation resistance of a multi-component carbide (Hf_0.2Ti_0.2Zr_0.2Ta_0.2Nb_0.2)C (HTZTNC) was investigated using an oxyacetylene flame apparatus. When the surface temperature of the HTZTNC was below 1800 °C, (Nb, Ta)₂O₅, (Hf, Zr)TiO₄, and (Hf, Zr)O₂ were found to be the main oxidation products, while at higher temperature, formation of (Hf, Zr, Ti, Ta, Nb)O_x was favored and its content gradually increased with the increase in ablation temperature. Based on the ablation results and thermodynamic simulation analysis, a possible ablation mechanism of HTZTNC was proposed. Active oxidation of TiC and outward diffusion of TiO were demonstrated to occur during the ablation process, which constitute the critical steps for the ablation of HTZTNC. These results can contribute to the design of ablation resistant ultra-high-temperature ceramics.     

Experimental determination of the 1300 °C and 1400 °C isotherms for CaO–SiO2–TiO2-10 wt% Al2O3 system in air

Phase equilibrium relations for the CaO–SiO₂–TiO₂-10 wt%Al₂O₃ system were studied at 1300 °C and 1400 °C by a high temperature equilibration and quenching method, with the purpose of extending the equilibrium phase information for the TiO₂-containing slag systems. Equilibrium phase assemblies and phase compositions were analyzed by Scanning Electron Microscopy (SEM) equipped with an X-ray Energy Dispersive Spectroscopy (EDS). The equilibrium solid phases of perovskite CaO·TiO₂, wollastonite CaO·SiO₂, rutile TiO₂, silica SiO₂ and sphene CaO·SiO₂·TiO₂ were confirmed to coexist with a liquid phase. Based on the experimental results, the 1300 °C and 1400 °C isotherms were constructed in the CaO–SiO₂–TiO₂-10 wt% Al₂O₃ quasi-ternary phase diagram. Significant discrepancies were found between the present results and the simulated results by FactSage and MTDATA databases, as well as the results from previous literature.     

Oxidation behavior characteristics of an aluminized Ni-based single crystal superalloy CM186LC between 900 °C and 1100 °C in air

Oxidation behavior of an aluminized Ni-based single crystal superalloy CM186LC was performed between 900 °C and 1100 °C in air. The oxidation kinetics approximately followed a parabolic oxidation law at 900 °C and 1100 °C. The mass gains were significantly increased owing to the formation of θ-Al₂O₃ during initial oxidation stage. After 100 h oxidation, the mass gain rates were then decreased due to the transformation from θ-Al₂O₃ to α-Al₂O₃. The microstructures after 500 h oxidation at all temperatures generally consisted of scale, coating layer, interdiffusion zone (IDZ), substrate diffusion zone (SDZ) accompanied with the topologically close-packed (TCP) and substrate.     

Synthesis of hexagonal boron nitride fibers within two hour annealing at 500 °C and two hour growth duration at 1000 °C

Several advantageous features like low density, large surface area, high porosity and tight pore size make the nanofiber suitable for a wide range of applications from medical to consumer products and industrial to high-tech applications. Present study concerns the synthesis of hexagonal boron nitride fibers (Ø=70–350 nm) from a mixture of Boron, Magnesium oxide and Iron oxide powders via a simple CVD technique. A relatively long annealing and growth duration of two hours at 500 °C and 1000 °C, respectively were utilized in this synthesis. The synthesized samples seem to have the BNFs of irregular curved human hair-like morphologies in lower resolution and solid cylinder-like structures in high resolution transmission electron microscopy. The presence of Boron and Nitrogen in the synthesized BNF's sample were confirmed via the B 1s peak at 190.7 eV and N 1s peak at 398.3 eV in the XPS survey whereas a major peak at 1370 (cm⁻¹) in the Raman spectrum corresponds to the vibration of E_2g mode in h-BN. The sharp peaks in the XRD pattern verify the h-BN phase and highly crystalline nature of the synthesized BNFs.     

Solid-state pressureless sintering of silicon carbide below 2000 °C

To date, solid-state pressureless sintering of silicon carbide powder requires sintering aids and high sintering temperature (>2100 °C) in order to achieve high sintered density (>95% T.D.). Two-step sintering (TSS) method can allow to set sintering temperature lower than that conventionally required. So, pressureless two-step sintering process was successfully applied for solid-state sintering (boron carbide and carbon as sintering additives) of commercial SiC powder at 1980 °C. Microstructure and mechanical properties of TSS-SiC were evaluated and compared to those obtained with the conventional sintering (SSiC) process performed at 2130 °C. TSS-SiC showed finer microstructure and higher flexural strength than SSiC with very similar density (98.4% T.D. for TSS-SiC and 98.6% T.D. for SSiC).     

Oxidation behavior of ZrB2-SiC-ZrC at 1700 °C

The oxidation behaviors of four compositions of ZrB₂-SiC-ZrC and one composition of ZrB₂-SiC were studied at 1700 °C in air and under low oxygen partial pressure. Volatility diagrams for ZrB₂-SiC-ZrC and ZrB₂-SiC were used to thermodynamically elucidate the oxidation mechanisms. SiO₂ and ZrO₂ layers formed on the surfaces of ZrB₂-SiC-ZrC and ZrB₂-SiC oxidized at 1700 °C. A SiC-depleted layer only formed on the surface of the ZrB₂-SiC oxidized under low oxygen partial pressure. The oxide layer thickened with increasing ZrC volume content during oxidation in air and under low oxygen partial pressure. The ZrB₂-SiC-ZrC oxide surface exploded in air when the ZrC volume content was more than 50%. Under low oxygen partial pressure, the oxide surfaces of all the ZrB₂-SiC-ZrC specimens bubbled.     

Temperature-stable dielectric properties from −20 °C to 430 °C in the system BaTiO3–Bi(Mg0.5Zr0.5)O3

Ceramics in the solid solution series (1 − x)BaTiO₃–Bi(Mg_0.5Zr_0.5)O₃ are single-phase tetragonal for compositions x ≤ 0.05, and cubic for x ≥ 0.1. Plots of relative permittivity (ɛ_r), versus temperature show double peaks for x = 0.03 and x = 0.05, changing to a single, frequency-dependent peak for compositions, x ≥ 0.1. A progressive decline in ɛ_r max with increasing x leads to near temperature-stable dielectric properties over a wide temperature range. For x = 0.3, ɛ_r = 570 ± 15%, from −20 °C to 430 °C, and tan δ ≤ 0.02 from 30 °C to 420 °C. For x = 0.4, ɛ_r = 600 ± 15% from 25 °C to 420 °C, and tan δ ≤ 0.02 from 55 °C to 280 °C (at 1 kHz). Values of dc resistivity were ∼10⁹ Ω m at 250 °C and ∼10⁶ Ω m at 400 °C. A piezoelectric strain of ∼0.25% (at 40 kV/cm) was recorded for composition x = 0.03.     

Ablation behavior and mechanism of C/C–ZrC–SiC composites under an oxyacetylene torch at 3000 °C

C/C–ZrC–SiC composites with continuous ZrC–SiC ceramic matrix were prepared by a multistep technique of precursor infiltration and pyrolysis process. Ablation properties of the composites were tested under an oxyacetylene flame at 3000 °C for 120 s. The results show that the linear ablation rate of the composites was about an order lower than that of pure C/C and C/C–SiC composites as comparisons, and the mass of the C/C–ZrC–SiC composites increased after ablation. Three concentric ring regions with different coatings appeared on the surface of the ablated C/C–ZrC–SiC composites: (i) brim ablation region covered by a coating with layered structure including SiO₂ outer layer and ZrO₂–SiO₂ inner layer; (ii) transition ablation region, and (iii) center ablation region with molten ZrO₂ coating. Presence of these coatings which acted as an effective oxygen and heat barrier is the reason for the great ablation resistance of the composites.     

Oxidation behaviors of ZrB2–SiC binary composites above 2000 °C

Rapid oxidation testing for monolithic ZrB₂ and ZrB₂–SiC binary composites with different SiC contents (0–30 vol%) was performed using an electric heating system above 2000 °C. The system used in this study achieved the high heating rate of 250 °C/s. The experimental results showed that the morphologies of the oxidized specimens depended strongly on the SiC content. The formation mechanism of SiC-depleted layers beneath the surface scale above 2000 °C differed completely from that below 2000 °C. Although the holding time was below 10 s, SiC-depleted layers were formed because the oxygen partial pressure of the air atmosphere was not enough to form SiO₂ by the oxidation of SiC. It was determined that ZrB₂–20 vol% SiC showed the best oxidation resistance above 2000 °C at high heating rates.     

Performance investigation of resin bonded ferro-silicon nitride-corundum refractories after creep at 1300 °C

Novel tempered resin bonded ferro-silicon nitride-corundum refractories containing 0 wt%, 15 wt% and 25 wt% ferro-silicon nitride were prepared respectively. Creep tests were performed under a load of 0.2 MPa at a temperature of 1300 °C for 50 h in air. The results showed that creep performance was significantly improved by the addition of ferro-silicon nitride. Ferro-silicon nitride-corundum containing 15 wt% ferro-silicon nitride initially presented a steady-state stage and was able to remain stable from the beginning of the holding time until 50 h of creep testing. All the specimens exhibited cold crushing strength more than 100 MPa both before and after creep testing. Phase composition and microstructure were analyzed following the creep experiments. The results showed that Si₂N₂O and O’-sialon crystals formed in situ during creep testing, in addition to the conversion of α-Si₃N₄ to β-Si₃N₄. Liquid Fe₃Si from the ferro-silicon nitride component accelerated the formation of the O’-sialon and prolonged the growth of β-Si₃N₄, which improved the creep performance significantly. Fe₃Si liquid migrated into the pores, and some Fe₃Si coexisted with residual carbon from the resin, which filled a part of pores and protected the specimens from severe oxidation.     

Phase relations in silicon and germanium nitrides up to 98 GPa and 2400°C

Phase relations in silicon and germanium nitrides (Si₃N₄ and Ge₃N₄) were investigated using a Kawai-type multianvil apparatus and a laser-heated diamond anvil cell combined with a synchrotron radiation. The pressure-induced phase transition from the β to γ (cubic spinel-type structure) phase was observed in both compositions. We observed the coexistence of the β and γ phases in Si₃N₄ at 12.4 GPa and 1800°C, while the appearance of single phase γ-Ge₃N₄ was observed at pressures above 10 GPa. Our observations under higher pressures revealed that γ-Si₃N₄ and γ-Ge₃N₄ have wide stability fields and no postspinel transition was observed up to 98 GPa and 2400°C in both compositions. Using the room-temperature compression curves of these materials, the bulk moduli (K₀) and their pressure derivatives (K′₀) were determined: K₀ = 317 (16) GPa and K′₀ = 6.0 (8) for γ-Si₃N₄; K₀ = 254 (13) GPa and K′₀ = 6.0 (7) for γ-Ge₃N₄.     

Crystal structure,mixture behavior,and microwave dielectric properties of novel temperature stable (1 − x)MgMoO4 − xTiO2 composite ceramics

Novel temperature stable MgMoO₄–TiO₂ microwave dielectric ceramics were prepared by a solid state reaction process at low temperature (950 °C). As TiO₂ content increases, the relative permittivity increases while the Q × f value decreases, and the variation mechanisms are proposed, respectively. The temperature coefficient of resonant frequency (τ_f) shifts to the positive direction as TiO₂ is added. The mixture mechanisms of τ_f value for two-phase composite materials are supposed. A near-zero τ_f value (3.2 ppm/°C) is obtained when x = 0.3, with ε_r = 9.13 ± 0.03 and Q × f = 11,990 GHz. The 0.7MgMoO₄–0.3TiO₂ composites are considered to be appropriate as a low temperature co-fired ceramic material for microwave wireless communication applications.     

Heteroepitaxial ZnO/sapphire (0 0 0 1) structure prepared by sol–gel process

ZnO thin films were grown on sapphire (0 0 0 1) substrates by sol–gel process and their structural and optical properties were characterized in detail. High-quality texture was obtained by using precursor solution of zinc acetate and ethanolamine in 2-methoxyethanol, pyrolyzed at 300 °C, then heated at 500 °C, and finally annealed at 750 °C. Highly c-axis oriented ZnO films were confirmed by X-ray θ–2θ scan. A relatively high transmittance in the visible spectra range and clear absorption edge of the film were observed. Epitaxial relationship between ZnO and sapphire and photoluminescence of the film were examined by using a X-ray pole-figure analysis and He–Cd laser. Near-band-edge emission with a deep-level emission was observed.     

Syndiospecific styrene polymerization by (tert-BuC5H4)TiCl2(O-2,6-iPr2C6H3) – borate catalyst system

(^tBuC₅H₄)TiCl₂(O-2,6-ⁱPr₂C₆H₃) (2) exhibited relatively high catalytic activity for syndiospecific polymerization of styrene at 25 °C if both [PhMe₂NH]B(C₆F₅)₄ and a mixture of AlⁱBu₃/Al(n-C₈H₁₇)₃ were used as the cocatalyst. Effects of both organoaluminum and organoboron compounds were explored, and the effect of cocatalyst was different from that observed in 1-hexene polymerization catalyzed by Cp*TiCl₂(O-2,6-ⁱPr₂C₆H₃) (1). Resultant syndiotactic polystyrene possessed narrow molecular weight distribution under the optimized conditions, and the M_w values were unchanged during the time course.     

Microstructure and mechanical properties of titanium aluminum carbides neutron irradiated at 400–700 °C

This work reports the first mechanical properties of Ti₃AlC₂-Ti₅Al₂C₃ materials neutron irradiated at ∼400, 630 and 700 °C at a fluence of 2 × 10²⁵ n m⁻² (E > 0.1 MeV) or a displacement dose of ∼2 dpa. After irradiation at ∼400 °C, anisotropic swelling and loss of 90% flexural strength was observed. After irradiation at ∼630–700 °C, properties were unchanged. Microcracking and kinking-delamination had occurred during irradiation at ∼630–700 °C. Further examination showed no cavities in Ti₃AlC₂ after irradiation at ∼630 °C, and MX and A lamellae were preserved. However, disturbance of (0004) reflections corresponding to M-A layers was observed, and the number density of line/planar defects was ∼10²³ m⁻³ of size 5–10 nm. HAADF identified these defects as antisite Ti_Al atoms. Ti₃AlC₂-Ti₅Al₂C₃ shows abrupt dynamic recovery of A-layers from ∼630 °C, but a higher temperature appears necessary for full recovery.     

HiPIMS induced high-purity Ti3AlC2 MAX phase coating at low-temperature of 700 °C

Ti₃AlC₂, one of Ti-Al-C MAX phases, has received extensive attention due to its unique nano-laminated structure and combined properties of metals and ceramics. However, ultra-high synthesis temperature exceeding 800 °C is a critical challenge for broad application of Ti₃AlC₂ coatings on temperature-sensitive substrates. In this study, Ti-Al-C coatings were deposited on Ti-6Al-4V substrates using high-power impulse magnetron sputtering (HiPIMS) and DC sputtering (DCMS) for comparison. Different from as-deposited amorphous Ti-Al-C coating by DCMS, nanocrystalline TiAl_x compound was achieved by HiPIMS deposition due to highly ionized plasma flux with high kinetic energy. Furthermore, HiPIMS promoted the generation of dense and smooth Ti₃AlC₂ phase coating after low-temperature annealing at 700 °C, while annealed DCMS coating only obtained Ti₂AlC. In-situ XRD demonstrated such Ti₃AlC₂ phase could be early involved in crystallization at 450 °C, lowest than synthesis temperature ever reported. The mechanical properties of Ti₃AlC₂ coating were also discussed in terms of structural evolution.     

Mesoporous CuO/TixZr1 − xO2 catalysts for low-temperature CO oxidation

Mesoporous CuO/Ti_xZr_1 − xO₂ catalysts were prepared by a surfactant-assisted method, and characterized by N₂ adsorption/desorption, TEM, XPS, in-situ FTIR and H₂-TPR. The catalysts exhibited high specific surface area (S_BET = 241 m²/g) and uniform pore size distribution. XPS and in-situ FTIR displayed that Cu⁺ and Cu²⁺ species coexisted in the catalysts. The CuO/Ti_xZr_1 − xO₂ catalysts presented obviously higher activity in CO oxidation reaction than the CuO/TiO₂ and CuO/ZrO₂ catalysts. Effect of molar ratios of Ti to Zr and calcination temperature on catalytic activity was investigated. The CuO/Ti_0.6Zr_0.4O₂ catalyst calcined at 400 °C exhibited excellent activity with 100% CO conversion at 140 °C.