Mechanical and Thermal Properties of Antiperovskite Ti3AlC Prepared by an In Situ Reaction/Hot-Pressing Route

Bulk Ti₃AlC ceramic containing 2.68 wt% TiC was prepared by an in situ reaction/hot-pressing route. The reaction path, microstructure, mechanical and thermal properties were systematically investigated. At room temperature Vickers hardness of Ti₃AlC ceramic is 7.8 GPa. The flexural strength, compressive strength, and fracture toughness are 182, 708 MPa, and 2.6 MPa·m^1/2, respectively. Its apparent Young's modulus, shear modulus, bulk modulus and Possion's ratio are 208.9, 83.4, 140.4 GPa, and 0.25 at room temperature. Apparent Young's modulus decreases slowly with the increasing temperature, and at 1210°C the modulus is 170 GPa. The average coefficient of thermal expansion of Ti₃AlC ceramic is about 10.1 × 10⁻⁶ K⁻¹ in the temperature range of 150°–1200°C. Both the molar heat capacity and thermal conductivity increase with an increase in the temperature. At 300 and 1373 K, the molar heat capacities are 87 and 143·J·(mol·K)⁻¹, while the thermal conductivities are 8.19 and 15.6 W·(m·K)⁻¹, respectively.     

In Situ Reaction Synthesis, Electrical and Thermal, and Mechanical Properties of Nb4AlC3

In this work, a bulk Nb₄AlC₃ ceramic was prepared by an in situ reaction/hot pressing method using Nb, Al, and C as the starting materials. The reaction path, microstructure, physical, and mechanical properties of Nb₄AlC₃ were systematically investigated. The thermal expansion coefficient was determined as 7.2 × 10⁻⁶ K⁻¹ in the temperature range of 200°–1100°C. The thermal conductivity of Nb₄AlC₃ increased from 13.5 W·(m·K)⁻¹ at room temperature to 21.2 W·(m·K)⁻¹ at 1227°C, and the electrical conductivity decreased from 3.35 × 10⁶ to 1.13 × 10⁶Ω⁻¹·m⁻¹ in a temperature range of 5–300 K. Nb₄AlC₃ possessed a low hardness of 2.6 GPa, high flexural strength of 346 MPa, and high fracture toughness of 7.1 MPa·m^1/2. Most significantly, Nb₄AlC₃ could retain high modulus and strength up to very high temperatures. The Young's modulus at 1580°C was 241 GPa (79% of that at room temperature), and the flexural strength could retain the ambient strength value without any degradation up to the maximum measured temperature of 1400°C.     

Thermal Expansion, Compressibility, and Polymorphism in Hafnium and Zirconium Titanates

Using X-ray diffraction techniques, thermal expansion and compressibility were measured on the orthorhombic compounds HfTiO₄, Hf_1.26Ti_0.74O₄, and ZrTiO₄ (both quenched and cooled slowly from 1300°C). The thermal expansion of HfTiO₄ is highly anisotropic; the thermal expansion coefficients along the crystallographic axes are α _a =+(8.7±0.5)×10⁻⁶°C⁻¹, α _b =−(5.2±0.5)×10⁻⁶°C⁻¹, and α _c =+ (5.3±0.5)×10⁻⁶°C⁻¹. The thermal expansion of Hf_1.26Ti_0.74O₄ was similar to that of HfTiO₄ but that of ZrTiO₄ was markedly less anisotropic. The compressibilities of HfTiO₄ and ZrTiO₄ also differed markedly. All compounds investigated, however, behaved similarly in exhibiting a polymorphic transition to a high-pressure phase having the monoclinic baddeleyite (ZrO₂) structure. The polymorphism can be explained qualitatively on the basis of crystal structure.     

Characterization of Material for Low-Temperature Sintered Multilayer Ceramic Substrates

The sintering temperature of multilayer ceramic substrates must decrease to 1000° or below to avoid melting the conductors (Pd-Ag, Au, or Cu) during sintering. In this study, SiO₂, CaO, B₂O₃, and MgO were used as additives to Al₂O₃ to decrease the firing temperature by liquid-phase sintering. Compositions with 18.0 and 22.5 wt% B₂O₃ were sintered at around 1000° in an air atmosphere to yield dense ceramics with good properties: relative dielectric contant between 6 to 7 (1 MHz), tan δ≤× 3 × 10⁻⁴ (1 MHz), insulating resistivity > 10¹⁴ω cm, coefficient of thermal expansion ∼ 7.0 × 10⁻⁶/°, and thermal conductivity ∼ 4.1 W/(m · K).     

Relationship between the Mesoporous Intermediate Layer Structure and the Gas Permeation Property of an Amorphous Silica Membrane Synthesized by Counter Diffusion Chemical Vapor Deposition

An amorphous silica membrane with an excellent hydrogen/nitrogen (H₂/N₂) permselectivity of >10 000 and a He/H₂ permselectivity of 11 was successfully synthesized on a γ-alumina (γ-Al₂O₃)-coated α-alumina (α-Al₂O₃) porous support by counter diffusion chemical vapor deposition using tetramethylorthosilicate and oxygen at 873 K. An amorphous silica membrane possessed a high H₂ permeance of >1.0 × 10⁻⁷ mol·(m²·s·Pa)⁻¹ at ≥773 K. The dominant permeation mechanism for He and H₂ at 373–873 K was activated diffusion. On the other hand, that for CO₂, Ar, and N₂ at 373–673 K was a viscous flow. At ≥673 K, that for CO₂, Ar, and N₂ was activated diffusion. H₂ permselectivity was markedly affected by the permeation temperature, thickness, and pore size of a γ-Al₂O₃ mesoporous intermediate layer.     

Preparation and Characterization of Aluminum Borate

Aluminum borate, 9Al₂O₃·2B₂O₃ or Al₁₈B₄O₃₃, was synthesized by the reaction of stoichiometric amounts of α-Al₂O₃ and B₂O₃. The Al₁₈B₄O₃₃ material was formed into a dense ceramic by pressureless sintering with CaO, MgO, or CaAl₂B₂O₇ additives. The material was characterized by low bulk density, moderate coefficient of thermal expansion (3 × 10⁻⁶/°C to 5 × 10⁻⁶/°C), moderate strength (210 to 324 MPa), and low dielectric constant.     

Thermal Expansion of the Low-Temperature Form of BaB2O4

Thermal expansion of the low-temperature form of BaB₂O₄ (β-BaB₂O₄) crystal has been measured along the principal crystallographic directions over a temperature range of 9° to 874°C by means of high-temperature X-ray powder diffraction. This crystal belongs to the trigonal system and exhibits strongly anisotropic thermal expansions. The expansion along the c axis is from 12.720 to 13.214 Å (1.2720 to 1.3214 nm), whereas it is from 12.531 to 12.578 Å (1.2531 to 1.2578 nm) along the a axis. The expansions are nonlinear. The coefficients A, B , and C in the expansion formula L _t = L ₀(1 + At + Bt ²+ Ct ³) are given as follows: a axis, A = 1.535 × 10⁻⁷, B = 6.047 × 10⁻⁹, C = -1.261 × 10⁻¹²; c axis, A = 3.256 × 10⁻⁵, B = 1.341 × 10⁻⁸, C = -1.954 × 10⁻¹²; and cell volume V, A = 3.107 × 10⁻⁵, B = 3.406 × 10⁻⁸, C = -1.197 × 10⁻¹¹. Based on α _t = (d L _t /d t )/ L ₀, the thermal expansion coefficients are also given as a function of temperature for the crystallographic axes a , c , and cell volume V.     

Synthesis of MgAl2O4 Whiskers by an Oxidation-Reduction Reaction

Magnesium aluminate whiskers were synthesized by an oxidation—reduction reaction between MgO, C, and Al in a CO and CO₂ atmosphere. The oxygen partial pressure suitable for MgAl₂O₄ whisker growth ranged from 10^−12.1 to 10^−11.5 MPa. The average whisker diameter and length formed at 1500°C for 8 h were ∼3.1 μm and ∼4 mm, respectively. The whiskers grew in the [111] direction.     

Thermal Expansion Anisotropy of Ceria-Stabilized Tetragonal Zirconia

Ceria-stabilized tetragonal zirconia polycrystals were obtained by thermal treatment of amorphous powder prepared by the sol–gel method. Detailed XRD profile analysis was employed to study microstructural disorder and crystallite size and shape; in particular, no fluctuation of stoichiometry was found, the main cause of disorder being attributable to dislocations. Thermal expansion measurements were carried out by high-temperature XRD at 294, 473, 673, 873, and 1073 K using silicon as an internal standard. Thermal expansion coefficients are anisotropic and changes in the stabilizer content have little effect on them. A mean value, α _a = 10.6 × 10⁻⁶ (K⁻¹) and α _c = 13.5 × 10⁻⁶ (K⁻¹), can be assumed for Zr_{1− x} Ce _x O₂ with x in the range 0.12–0.18.     

Molten Glass Corrosion Resistance of Immersed Combustion-Heating Tube Materials in E-Glass

The corrosion resistance of molybdenum, molybdenum disilicide, and a SiC_{( p )}/Al₂O₃ composite to molten E-glass at 1550^deg;C was studied. Mo showed no tendency to oxidize as it was immersed in soda-lime silicate glass in a parallel study. MoSi₂ was corroded by soluble molecular oxygen, leaving a Mo₅Si₃ interface behind. The SiC_{( p )}/Al₂O₃ composite was corroded at a more rapid rate wherein the SiC component was oxidized to form amorphous silica and CO bubbles. Based on these results, the activity of soluble molecular oxygen in E-glass was determined to be in the range of 2.4 × 10^-14 to 2.0 × 10^-8.     

Microstructural and Thermoelectric Characteristics of Zinc Oxide-Based Thermoelectric Materials Fabricated Using a Spark Plasma Sintering Process

M-doped zinc oxide (ZnO) (M=Al and/or Ni) thermoelectric materials were fully densified at a temperature lower than 1000°C using a spark plasma sintering technique and their microstructural evolution and thermoelectric characteristics were investigated. The addition of Al₂O₃ reduced the surface evaporation of pure ZnO and suppressed grain growth by the formation of a secondary phase. The addition of NiO promoted the formation of a solid solution with the ZnO crystal structure and caused severe grain growth. The co-addition of Al₂O₃ and NiO produced a homogeneous microstructure with a good grain boundary distribution. The microstructural characteristics induced by the co-addition of Al₂O₃ and NiO have a major role in increasing the electrical conductivity and decreasing the thermal conductivity, resulting from an increase in carrier concentration and the phonon scattering effect, respectively, and therefore improving the thermoelectric properties. The ZnO specimen, which was sintered at 1000°C with the co-addition of Al₂O₃ and NiO, exhibited a ZT value of 0.6 × 10⁻³ K⁻¹, electrical conductivity of 1.7 × 10⁻⁴Ω⁻¹·m⁻¹, the thermal conductivity of 5.16 W·(m·K)⁻¹, and Seebeck coefficient of −425.4 μV/K at 900°C. The ZT value obtained respects the 30% increase compared with the previously reported value, 0.4 × 10⁻³ K⁻¹, in the literature.     

Vacuum Vaporization in the System MgO-Cr2O3

The vaporization of the system MgO-Cr₂O₃ was studied in a vacuum of 10⁻⁵ torr (10⁻³N/m²) at 1500° to 1700°C using the Langmuir and Knudsen methods. It was found that the phases in the system vaporize nearly congruently and the logarithm of the vaporization coefficient, α, of MgCr₂O₄ increases linearly with increasing reciprocal temperature. Alpha tends to unity at a temperature near the melting point (2525±23°C). The additivity rule can be applied to the Langmuir vaporization rates on the basis of the surface area ratios of the phases in the 2-phase system MgO-Cr₂O₃. The enthalpies of vaporization of MgCr₂O₄ were 695.0 and 549.2 kcaVmol for activated and equilibrium processes, respectively.     

Characterization of the Thermally Contracting Tungstates Ta22W4O67, Ta2WO8, and Ta16W18O94

An investigation of the properties of high-purity (>99 wt%) tantalum tungstates (Ta₂₂W₄O₆₇, Ta, WO₈, and Ta₁₆W₁₈O₉₄) included determination of density (bulk and theoretical), refined lattice constants, maximum use temperatures, micro-hardness, heat capacity, thermal expansion (contraction) and diffusivity, calculated thermal conductivity, and electrical resistivity. Usable to ∼ 1700 K in air or inert atmospheres, these tantalum tungstates have theoretical densities of 7.3 to 8.5 g/cm³, are relatively soft (120 to 655 kg/mm² hardnesses), and are electrical insulators (6× 10³ to 2× 10⁸Ω^.cm resistivities). The distinguishing properties of the materials are their thermal expansion (average CTE values from + 0.6×10⁻⁸/K to −5.1× 10⁻⁶/K at 293 to 1273 K), thermal expansion hysteresis with minimal observable microcracking, and thermal diffusivity     

Porous Glass-Ceramics with a Skeleton of the Fast-Lithium-Conducting Crystal Li1+xTi2−xAlx(PO4)3

Porous glass-ceramics with a skeleton of the fast-lithium-conducting crystal Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ (where x = 0.3–0.5) were prepared by crystallization of glasses in the Li₂O─CaO─TiO₂─Al₂O₃–P₂O₅ system and subsequent acid leaching of the resulting dense glass-ceramics composed of the interlocking of Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ and β-Ca₃(PO₄)₂ phases. The median pore diameter and surface area of the resulting porous Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ glass-ceramics were approximately 0.2 μm and 50 m²/g, respectively. The electrical conductivity of the porous glass-ceramics after heating in LiNO₃ aqueous solution was 8 × 10⁻⁵ S/cm at 300 K or 2 × 10⁻² S/cm at 600 K.     

Thermal Expansion Behavior of Titanium-Doped La(Sr)CrO3 Solid Oxide Fuel Cell Interconnects

La_0.8Sr_0.2Cr_0.9Ti_0.1O₃ perovskite has been designed as an interconnect material in high-temperature solid oxide fuel cells (SOFCs) because of its thermal expansion compatibility in both oxidizing and reducing atmospheres. La_0.8Sr_0.2Cr_0.9Ti_0.1O₃ shows a single phase with a hexagonal unit cell of a = 5.459(1) Å, c = 13.507(2) Å, Z = 6 and a space group of R -3 C . Average linear thermal expansion coefficients of this material in the temperature range from 50° to 1000°C were 10.4 × 10⁻⁶/°C in air, 10.5 × 10⁻⁶/°C under a He–H₂ atmosphere (oxygen partial pressure of 4 × 10⁻¹⁵ atm at 1000°C), and 10.9 × 10⁻⁶/°C in a H₂ atmosphere (oxygen partial pressure of 4 × 10⁻¹⁹ atm at 1000°C). La_0.8Sr_0.2Cr_0.9Ti_0.1O₃ perovskite with a linear thermal expansion in both oxidizing and reducing environments is a promising candidate material for an SOFC interconnect. However, there still remains an air-sintering problem to be solved in using this material as an SOFC interconnect.     

Properties of (Y)ZrO2–Al2O3 and (Y)ZrO2–Al2O3–(Ti or Si)C Composites

The effect of Al₂O₃ and (Ti or Si)C additions on various properties of a (Y)TZP (yttria-stabilized tetragonal zirconia polycrystal)–Al₂O₃–(Ti or Si)C ternary composite ceramic were investigated for developing a zirconia-based ceramic stronger than SiC at high temperatures. Adding Al₂O₃ to (Y)TZP improved transverse rupture strength and hardness but decreased fracture toughness. This binary composite ceramic revealed a rapid loss of strength with increasing temperature. Adding TiC to the binary ceramic suppressed the decrease in strength at temperatures above 1573 K. The residual tensile stress induced by the differential thermal expansion between ZrO₂ and TiC therefore must have inhibited the t - → m -ZrO₂ martensitic transformation. It was concluded that a continuous skeleton of TiC prevented grain-boundary sliding between ZrO₂ and Al₂O₃. In contrast, for the ternary material containing β-SiC in place of TiC, the strength decreased substantially with increasing temperature because of incomplete formation of the SiC skeleton.     

Synthesis, Structure Determination, and Aqueous Durability of Cs2ZrSi3O9

The structure of Cs₂ZrSi₃O₉ synthesized using a sol–gel method was determined from the Rietveld refinement of experimental powder X-ray diffraction data. The refinement confirmed that this compound was isostructural with wadeite: its structure was hexagonal (space group P 6₃/ m ), and its lattice parameters were a = 7.2303(2) Å and c = 10.2682(4) Å. The aqueous durability of Cs₂ZrSi₃O₉ varied, depending on the solution conditions. In modified leach tests with buffered (pH 7) and unbuffered solutions, the 7-d cesium release rates were <1.2 × 10⁻⁴ g·(m²·day)⁻¹, which indicated high aqueous durability. However, in unsaturated, unbuffered solutions with a pH of 9–10, the durability was much lower, with 7-d cesium release rates of 2.2 × 10⁻³ g·(m²·day)⁻¹. The ability of this material to retain cesium in aqueous environments can be explained by its condensed ring structure, in which the size of the channel openings is smaller than the diameter of a Cs⁺ ion. However, dissolution of the network silicate occurred at high pH, which resulted in the release of cesium.     

Formation of Al2O3/Metal Composites by the Directed Oxidation of Molten Aluminum-Magnesium-Silicon Alloys: Part I, Microstructural Development

The growth of α-Al₂O₃/metal composites by the directed oxidation of molten Al-Mg-Si alloys proceeds through four distinct stages. The first stage encompasses the early heating of the alloy ingot, melting, and continued heating to between 1123 and 1173 K. In this latter temperature range, the molten alloy surface rapidly oxidizes to form a MgO-covered MgAl₂O₄ layer. During further heating and initial soak at the composite growth temperature (1373 to 1573 K), the duplex layer slowly thickens (second stage). The start of the third stage, growth initiation, is marked by the spread of a metal-rich zone over the duplex layer; this metal-rich zone is believed to be connected to the molten alloy through microcracks in the thickened MgO/MgAl₂O₄ layer. Small nodules of the oxide/metal composite nucleate from the metal-rich layer. During the final rapid growth stage, the small composite nodules grow and coalesce to form a macroscopically planar growth front, which persists until growth is complete. Throughout the growth process, the external surface of the α-Al₂O₃/metal composite is covered by a thin MgO layer. Immediately under this external layer and separating it from the α-Al₂O₃ is a thin layer of molten metal.     

Barium Aluminosilicate Reinforced In Situ with Silicon Nitride

Advanced ceramic composite materials that exhibit high strength and toughness with good thermal shock resistance are needed for emerging high-temperature engineering applications. A recently developed in situ reinforced barium aluminosilicate glass-ceramic shows promise of meeting many of the requirements for these types of applications with the added benefit of low-cost fabrication through densification by pressureless sintering. The material is toughened through in situ growth of rodlike β-Si₃N₄ grains resulting from the α–β silicon nitride phase transformation. Microstructural development and material properties for temperatures up to 1400°C are discussed. When compared to monolithic barium aluminosilicate, barium aluminosilicate reinforced with 70% by volume of Si₃N₄ shows a significant increase in flexural strength (from 80 to 565 MPa) and fracture toughness (from 1.8 to 5.74 MPa·m^1/2) with a high resistance to thermal shock.