Oxidation Behavior of Boron-Modified Mo5Si3 at 800°–1300°C

Mo₅Si₃ shows promise as a high-temperature creep-resistant material. The high-temperature oxidation resistance of Mo₅Si₃ has been found to be poor, however, limiting its use in oxidizing atmospheres. Undoped Mo₅Si₃ exhibits pest oxidation at 800°C. Mass loss occurs in the temperature range 900°–1200°C due to volatilization of molybdenum oxide, indicating that the silica scale that forms does not provide a passivating layer. The addition of boron results in protective scale formation and parabolic oxidation kinetics in the temperature range of 1050°–1300°C. The oxidation rate of Mo₅Si₃ was decreased by 5 orders of magnitude at 1200°C by doping with less than 2 wt% boron. Boron doping eliminates catastrophic pest oxidation at 800°C. The mechanism for improved oxidation resistance of borondoped Mo₅Si₃ is viscous sintering of the scale to close pores that form during the initial transient oxidation period, due to volatilization of molybdenum oxide.     

Al-B-C Phase Development and Effects on Mechanical Properties of B4C/Al-Derived Composites

B₄C/A1 offers a family of engineering materials in which a range of properties can be developed by postdensiflcation heat treatment. In applications where hardness and high modulus are required, heat treatment above 600°C provides a multiphase ceramic material containing only a small amount of residual metal. Heat treatment between 600° and 700°C produces mainly A1B₂; 700° and 900°C results in a mixture of A1B₂ and A1₄BC; 900° and 980°C produces primarily A1₄BC; and 1000° to 1050°C results in A1B₂₄C₄ with small amounts of A1₄C₃ if the heating does not exceed 5 h. Deleterious A1₄C₃ is avoided by processing below 1000°C. All of these phases tend to form large clusters of grains and result in lower strength regardless of which phase forms. Toughness is also reduced; the least determinal phase is A1B₂. The highest hardness (88 Rockwell A) and Young's modulus (310 GPa) are obtained in Al₄BC-rich samples. AlB₂-containing samples exhibit lower hardness and Young's modulus but higher fracture toughness. While the modulus, Poisson's ratio, and hardness of multiphase B₄C/A1 composites containing 5–10 vol% free metal are comparable to ceramics, the unique advantage of this family of materials is low density (>2.7 g/cm³) and higher than 7 MPa-m^1/2 fracture toughness.     

Molybdenum Oxycarbide and Tungsten Oxycarbide Coatings on Silicon Carbide Fibers

The strength and toughness of fibrous composites depend on the interface properties which control the bonding between the fibers and matrices. One method of controlling the interface involves coating the fiber with an appropriate material. In a previous study, it was found that there is a definite advantage in using low coating temperatures to prevent fibers from degrading. We therefore were interested in a report that Mo₂C could be deposited from Mo(CO)₆ at temperatures as low as 300° to 475°C. Our studies indicated that the material was not Mo₂C, but an oxycarbide, which, with an analogous tungsten oxycarbide coating, was applied to SiC yarns. Both oxycarbides could be converted to the metals by heat-treating in N₂.     

High-Temperature Strength and Creep Behavior of Melt-Infiltrated SiC-Mo≤5Si3C≤1 Composites

Molybdenum carbosilicide composites (SiC-Mo_≤5Si₃C_≤1) were fabricated via the melt-infiltration process. The fracture behavior of the composites was studied from room temperature up to 1800°C in 1 atm (∼10⁵ Pa) of argon. The bend strength of the composites slightly increased at ∼1200°C, because of the brittle-ductile transition of the intermetallic phase. The composites retained ∼90% of their room-temperature strength, even at 1700°C. Compressive creep tests were performed over a temperature range of 1760°-1850°C and a stress range of 200–250 MPa. The creep rate of the SiC-Mo_≤5Si₃C_≤1 composites was approximately an order of magnitude higher than that of reaction-bonded SiC.     

Co2+-Substitution Effect in Ce-TZP/La M-type Hexaferrite Composites

A Ce-TZP/platelike La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composite was synthesized in situ while sintering from a mixture of Ce-TZP, La(Fe_0.9Al_0.1)O₃, Fe₂O₃, Al₂O₃, and CoO powders. Platelike La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ crystals were grown in a dense Ce-TZP matrix after sintering at temperatures of 1200°–1350°C. The temperature range for sintering Ce-TZP/La(Fe,Al)₁₂O₁₉ composites was expanded widely by substituting Co²⁺ ions for Fe²⁺ ions in its structure. The highest value of the bending strength of the Ce-TZP/La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composites was 880 MPa, which was higher than that of the Ce-TZP/La(Fe,Al)₁₂O₁₉ composite (780 MPa) and Ce-TZP (513 MPa). The saturation magnetization of the Ce-TZP/La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composite was a constant value of 7.7 emu/g after the composite was sintered at 1200°–1350°C.     

Oxidation Kinetics and Composite Scale Formation in the System Mo(Al,Si)2

The oxidation kinetics of hot-pressed Mo(Al_0.01Si_0.99)₂ and Mo(Al_0.1Si_0.9)₂ were measured at 480°C, and between 1200° and 1600°C. The qualitative oxidation of arc-melted Mo(Al_0.1Si_0.9)₂, Mo(Al_0.3Si_0.7)₂, Mo(Al_0.5Si_0.5)₂, and Mo₃Al₈ was examined after 600°C for 1000 h in air. At all temperatures, the compositional difference between the materials yielded very different oxidation rates and scale microstructures. At 1400° and 1500°C, microstructural evolution of the oxide scales resulted in improved oxidation resistance at long times (>400 h). At these temperatures, a significant reduction in the long-time oxidation kinetics was correlated with the in situ formation of an inner mullite scale. At 480° and 600°C, oxidation resistance improved significantly with increasing aluminum concentration. Contrary to the behavior of MoSi₂, samples of Mo(Al_0.01Si_0.99)₂ did not demonstrate catastrophic oxidation, and samples of Mo(Al_0.1Si_0.9)₂ were very oxidation resistant.     

Microcellular Al2O3 Ceramics from Wood for Filter Applications

Microcellular biomorphous Al₂O₃ was produced by Al-vapor infiltration in pyrolyzed rattan and pine wood-derived biocarbon preforms. At 1600°C the biocarbon preforms reacted with gaseous aluminum to form Al₄C₃. After oxidation in air at temperatures between 1550° and 1650°C, for 3 h, the biocarbon preforms were fully converted into α-Al₂O₃. Owing to the high anisotropy of biomorphous Al₂O₃, the compressive strength behavior was strongly dependent on the loading direction. The compressive strength of the specimens (0.1–11 MPa) is strongly dependent on their overall porosity and their behavior could be explained using the Gibson–Ashby model. The Darcian permeability ( k ₁), as well as the non-Darcian permeability ( k ₂), increased with an increase of the total porosity. The Darcian permeability of biomorphous Al₂O₃ was found to be in the range of 1–8 × 10⁻⁹ m², which is in the order of magnitude of gas filters, and, therefore, suitable for several technological applications.     

Synthesis, Microstructure, and Mechanical Properties of Al3BC3

In situ synthesis of bulk Al₃BC₃ was achieved via a reactive hot-pressing method using Al, B₄C, and graphite powders at 1800°C for 2 h. The reaction path for synthesizing Al₃BC₃ was investigated. It was found that Al₃BC₃ formed via the reaction of C, B₄C, and Al₄C₃ above 1180°C. Dense Al₃BC₃ was prepared with a little B₄C and graphite remained. Microstructure observations revealed the plate-like morphology of Al₃BC₃ grains. Moreover, the mechanical properties of Al₃BC₃ were characterized (Vickers hardness of 11.1 GPa, bending strength of 185 MPa, fracture toughness of 2.3 MPa·m^1/2, and Young's modulus of 163 GPa). Young's modulus decreased slowly with increasing temperature, and at 1600°C remained 79% of that at ambient temperature. These results show that Al₃BC₃ is a promising lightweight high temperature structural material.     

Fabrication and High-Temperature Phase Stability of Mo(Al,Si)2—MoSi2 Intermetallics

A two-step processing technique was used to make dense, homogeneous intermetallics in the Mo(Al,Si)₂—MoSi₂ system. A variation of self-propagating high-temperature synthesis was used, in which starting pellets were nucleated at room temperature to make intermetallic powders from metallic precursors, followed by uniaxial hot pressing at 1600°—1800°C to achieve densification. The samples were held at the hot-pressing temperatures for several hours; therefore, this study also provided qualitative phase-stability information. The solubility limit of Al for Si in MoSi₂ was <5% at 1800°C. Samples that had 10% Al substituted for Si yielded approximately equal amounts of MoSi₂ and Mo(Al,Si)₂.     

Mechanical Properties and Fracture Toughness of α-Al2O3-Platelet-Reinforced Y-PSZ Composites at Room and High Temperatures

YPSZ/Al₂O₃-platelet composites were fabricated by conventional and tape-casting techniques followed by sintering and HIPing. The room-temperature fracture toughness increased, from 4.9 MPa·m^1/2 for YPSZ, to 7.9 MPa·m^1/2 (by the ISB method) for 25 mol% Al₂O₃ platelets with aspect ratio = 12. The room-temperature fiexural strength decreased 21% and 30% (from 935 MPa for YPSZ) for platelet contents of 25 vol% and 40 vol%, respectively. Al₂O₃ platelets improved the high-temperature strength (by 110% over YPSZ with 25 vol% platelets at 800°C and by 40% with 40 vol% platelets at 1300°C) and fracture toughness (by 90% at 800°C and 61% at 1300°C with 40 vol% platelets). An amorphous phase at the Al₂O₃-platelet/YPSZ interface limited mechanical property improvement at 1300°C. The influence of platelet alignment was examined by tape casting and laminating the composites. Platelet alignment improved the sintered density by >1% d _th , high-temperature strength by 11% at 800°C and 16% at 1300°C, and fracture toughness by 33% at 1300°C, over random platelet orientation.     

Lower-Temperature Modifications of Nb2C and V2C

The orthorhombic, low-temperature α-modification of Nb₂C has a structure similar to that of ζ-Fe₂N (a = 12.36 A, b = 10.89₅ A, c = 4.96₈ A) and transforms at ∼1200°C into the hexagonal ε-Fe₂N type. A second transition at approximately 2500°C is associated with the destruction of long range order in the carbon sublattice. Alpha-divanadium carbide (orthorhombic, a = 11.49 A, b = 10.06 A, c = 4.55 A) is isostructural with α-Nb₂C and transforms at ∼800°C into the hexagonal high-temperature modification. The structures of α-V₂C and α-Nb₂C are distorted modifications related to the ε-Fe₂N type.     

In Situ Processing and High-Temperature Properties of Ti3Si(Al)C2/SiC Composites

Ti₃SiC₂ has many salient properties including low density, high strength and modulus, damage tolerance at room temperature, good machinablity, and being resistant to thermal shock and oxidation below 1100°C. However, the low hardness and poor oxidation resistance above 1100°C limit the application of this material. The poor oxidation resistance at temperatures above 1100°C was because of the absence of protective layer in the scale and the presence of TiC impurity phase. TiC impurity could be eliminated by adding a small amount of Al to form Ti₃Si(Al)C₂ solid solutions. Although the high-temperature oxidation resistance was significantly improved for the Ti₃Si(Al)C₂ solid solutions, the strength at high temperatures was lost. One important way to enhance the high-temperature strength is to incorporate hard ceramic particles like SiC. In this article, we describe the in situ synthesis and simultaneous densification of Ti₃Si(Al)C₂/SiC composites using Ti, Si, Al, and graphite powders as the initial materials. The effect of SiC content on high-temperature mechanical properties and oxidation resistance were investigated. The mechanisms for the improved high-temperature properties are discussed.     

Near-Net-Shape Fabrication of Ti3AlC2-Based Composites

A porous ceramic preform was fabricated by printing a powder blend of TiC, TiO₂, and dextrin. The presintered preforms contained a bimodal pore size distribution with intra-agglomerate pores ( d ₅₀≈0.7 μm) and inter-agglomerate pores ( d ₅₀≈30 μm), which were subsequently infiltrated by aluminum melt spontaneously in argon above 1050°C. A redox reaction at 1400°C resulted in the formation of dense Ti–Al–O–C composites mainly composed of Ti₃AlC₂, TiAl₃, Al, and Al₂O₃, which attained a bending strength of 320 MPa, a Young's modulus of 184 GPa, and a Vicker's hardness of 2.5 GPa.     

Spark Plasma Sintering of Nano-Sized TiN Prepared from TiO2 by Controlled Hydrolysis of TiCl4 and Ti(O-i-C3H7)4 Solution

Nano-sized TiO₂ powders were prepared by controlled hydrolysis of TiCl₄ and Ti(O-i-C₃H₇)₄ solutions and nitrided in flowing NH₃ gas at 700°–1000°C to form TiN. Nano-sized TiN was densified by spark plasma sintering at 1300°–1600°C to produce TiN ceramics with a relative density of 98% at 1600°C. The microstructure of the etched ceramic surface was observed by SEM, which revealed the formation of uniformly sized 1–2 μm grains in the TiCl₄-derived product and 10–20 μm in the Ti(O-i-C₃H₇)₄-derived TiN. The electric resisitivity and Vickers micro-hardness of the TiN ceramics was also measured.     

High-Temperature Behavior of MoSi2 and Mo5Si3

The high-temperature stability and behavior of MoSi₂ was studied by heating dense sintered specimens under a vacuum of 10⁻⁵ mm Hg in the temperature range 1700° to 2000°C. The resulting material was examined using physical measurements, X-ray analysis, and metallographic techniques. The decomposition of MoSi₂ into Mo₅Si₃ is described. The Mo₅Si₃-MoSi₂ eutectic temperature was determined as 1900° C, and the melting points of MoSi₅ and Mo₅Si₃ were determined as 1980° and 2085° C, respectively.     

Elevated-Temperature Toughness and Hardness of a Hot-Pressed Al2O3—WC—Co Composite

The fracture toughness and hardness of an Al₂O₃80WC10Co composite were investigated in air at elevated temperatures. The primary phases in the composite were WC, α-Al₂O₃, and Co₃W₃C, but small amounts of Co and C (graphite) appeared at elevated temperatures, related to decomposition of the Co₃W₃C phase. The fracture toughness of the composite was constant with increasing temperature up to 330°C and then increased in the range 400° to 550°C. A transition of brittle to ductile behavior occurred at about 700°C. The enhancement of fracture toughness at elevated temperature is attributed to the decomposition of Co₃W₃C to Co and C, and enhanced crack deflection and bridging. Decreases in hardness with increasing temperature are attributed to the softening of WC matrix and decomposition of Co₃W₃C.     

Phase Relations in the Garnet Region of the System Y2O3–Fe2O3–FeO–Al2O3

Liquidus equilibrium relations for the air isobaric section of the system Y₂O₃–Fe₂O₃–FeO–Al₂O₃ are presented. A Complete solid-solution series is found between yttrium iron garnet and yttrium aluminum garnet as well as extensive solid solutions in the spinel, hematite, orthoferrite, and corundum phases. Minimum melting temperatures are raised progressively with the addition of alumina from 1469°C in the system Y–Fe–O to a quaternary isobaric peritectic at 1547°C and composition Y _0.22 Fe _1.08 Al _0.70 O _2.83* Liquidus temperatures increase rapidly with alumina substitutions beyond this point. The thermal stability of the garnet phase is increased with alumina substitution to the extent that above composition Y _0.75 Fe _0.65 Al _0.60 O ₃ garnet melts directly to oxide liquid without the intrusion of the orthoferrite phase. Garnet solid solutions between Y _0.75 Fe _1.25 O ₃ and Y _0.75 Fe _0.32- Al _0.93 O ₃ can be crystallized from oxide liquids at minimum temperatures ranging from 1469° to 1547°C, respectively. During equilibrium crystallization of the garnet phase, large changes in composition occur through reaction with the liquid. Unless care is taken to minimize temperature fluctuations and unless growth proceeds very slowly, the crystals may show extensive compositional variation from core to exterior.     

Tribological Behavior of Mo5Si3-Particle-Reinforced Silicon Nitride Composites

The tribological behavior of Mo₅Si₃-particle-reinforced silicon nitride (Si₃N₄) composites was investigated by pin-on-plate wear testing under dry conditions. The friction coefficient of the Mo₅Si₃–Si₃N₄ composites and Si₃N₄ essentially decreased slowly with the sliding distance, but showed sudden increase for several times during the wear testing. The average friction coefficient of the Si₃N₄ decreased with the incorporation of submicrometer-sized Mo₅Si₃ particles and also as the content of Mo₅Si₃ particles increased. When the Mo₅Si₃–Si₃N₄ composites were oxidized at 700°C in air, solid-lubricant MoO₃ particles were generated on the surface layer. Oxidized Mo₅Si₃–Si₃N₄ composites showed self-lubricating behavior, and the average friction coefficient and wear rate of the oxidized 2.8 wt% Mo₅Si₃–Si₃N₄ composite were 0.43 and 0.72 × 10⁻⁵ mm³ (N·m)⁻¹, respectively. Both values were ∼30% lower than those for the Si₃N₄ tested in an identical manner.     

The Study on Carbon Nanofiber (CNF)-Dispersed B4C Composites

Carbon nanofiber (CNF)-dispersed B₄C composites have been synthesized and consolidated directly from mixtures of elemental raw powders by pulsed electric current pressure sintering (1800°C/10 min/30 MPa). A 15 vol% CNF/B₄C composite with ∼99% of dense homogeneous microstructures (∼0.40 μm grains) revealed excellent mechanical properties at room temperature and high temperatures: a high bending strength (σ_b) of ∼710 MPa, a Vickers hardness ( H _v) of ∼36 GPa, a fracture toughness ( K _{I C} ) of ∼7.9 MPa m^1/2, and high-temperature σ_b of 590 MPa at 1600°C in N₂. Interfaces between the CNF and the B₄C matrix were investigated using high-resolution transmission electron microscopy, EDS, and electron energy-loss spectroscopy.     

Zirconium Aluminum Carbides: New Precursors for Synthesizing ZrO2–Al2O3 Composites

ZrO₂–Al₂O₃ nanocrystalline powders have been synthesized by oxidizing ternary Zr₂Al₃C₄ powders. The simultaneous oxidation of Al and Zr in Zr₂Al₃C₄ results in homogeneous mixture of ZrO₂ and Al₂O₃ at nanoscale. Bulk nano- and submicro-composites were prepared by hot-pressing as-oxidized powders at 1100°–1500°C. The composition and microstructure evolution during sintering was investigated by XRD, Raman spectroscopy, SEM, and TEM. The crystallite size of ZrO₂ in the composites increased from 7.5 nm for as-oxidized powders to about 0.5 μm at 1500°C, while the tetragonal polymorph gradually converted to monolithic one with increasing crystallite size. The Al₂O₃ in the composites transformed from an amorphous phase in as oxidized powders to θ phase at 1100°C and α phase at higher temperatures. The hardness of the composite increased from 2.0 GPa at 1100°C to 13.5 GPa at 1400°C due to the increase of density.