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.     

Thermal Oxidation Kinetics of MoSi2-Based Powders

The oxidation process of MoSi₂ is very complex, and controversial results have been reported, especially for the early-stage oxidation before the formation of passive SiO₂ film. Most oxidation studies have been carried out on bulk consolidated samples, and the early stage of oxidation has not been studied. In this investigation, very fine MoSi₂ powder with an average particle size of 1.6 μm was used. Such a fine particle size makes it easier to study the early stages of oxidation since a significant portion of the powder is oxidized before the formation of passive SiO₂ film. The oxidation kinetics of commercial MoSi₂-SiC and MoSi₂-Si₃N₄ powder mixtures were also studied for comparison. Weight changes were measured at discrete time intervals at 500° to 1100°C in 0.14 atm of oxygen. X-ray diffraction was used to identify the phases formed during oxidation. Our results show the formation of MoO₃ phase and an associated weight gain at low temperatures (500° and 600°C). At temperatures higher than 900°C, Mo₅Si₃ phase formed first and was subsequently oxidized to solid SiO₂ and volatile MoO₃, resulting in an initial weight gain followed by subsequent weight loss. A model based on the assumption that oxidation kinetics of both MoSi₂ and Mo₅Si₃ are proportional to their fractions in the system describes the experimental data well.     

Reactive Hot Pressing of SiC/MoSi2 Nanocomposites

Dense SiC/MoSi₂ nanocomposites were fabricated by reactive hot pressing the mixed powders of Mo, Si, and nano-SiC particles coated homogeneously on the surface of Si powder by polymer processing. Phase composition and microstructure were determined by methods of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy-dispersive spectrometry. The nanocomposites obtained consisted of MoSi₂, β-SiC, less Mo₅Si₃, and SiO₂. A uniform dispersion of nano-SiC particles was obtained in the MoSi₂ matrix. The relative densities of the monolithic material and nanocomposite were above 98%. The room-temperature flexural strength of 15 vol% SiC/MoSi₂ nanocomposite was 610 MPa, which increased 141% compared with that of the monolithic MoSi₂. The fracture toughness of the nanocomposite exceeded that of pure MoSi₂, and the 1200°C yield strength measured for the nanocomposite reached 720 MPa.     

Simultaneous Synthesis and Densification of MoSi2 by Field-Activated Combustion

A method to simultaneously synthesize and consolidate MoSi₂ from powders of Mo and Si was investigated. Combustion synthesis was carried out under the combined effect of an electric field and mechanical pressure. Highly dense molybdenum silicide up to (99.2%) was produced from elemental powders in one step. Minor amounts of Mo₅Si₃ were present at the boundaries of MoSi₂ grains in the interior of samples made from stoichiometric reactants. The addition of 2.5 mol% Si excess, however, resulted in Mo₅Si₃-free, dense MoSi₂ products.     

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.     

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.     

High-Temperature Oxidation of Molybdenum Disilicide

The oxidation of MoSi₂ in air at atmospheric pressure was studied by electron diffraction, X-ray diffraction, and thermogravimetric analyses. The oxidation process occurs in two parts: (1) formation of MoO₃ and SiO₂ at temperatures below the boiling point of MoO₃, and (2) formation of Mo₅Si₃ and SiO₂ at higher temperatures. Evidence is presented which indicates that oxygen permeation through a silica layer, which may be of a mixed crystalline-glassy nature, controls reaction rate at high temperatures and that Mo₅Si₃ is present directly beneath the protective oxide. The activation energy for oxidation of MoSi₂ above 1200°C was calculated as 81.3 kcal mole⁻¹.     

Aluminum Infiltration into Molybdenum Silicide Preforms

The presence of Mo₅Si₃ in MoSi₂ preforms hinders the reactive infiltration of aluminum. To understand the role of Mo₅Si₃, the kinetics of aluminum infiltration into pure Mo₅Si₃ is studied. Irrespective of the initial composition (MoSi₂ or Mo₅Si₃) of the preform, the final product always contains Mo(Al,Si)₂. However, the aluminum content in the two cases is different: when the preform is MoSi₂, the aluminum content is 14–18 at.%, and, when the preform is Mo₅Si₃, the aluminum content is 25–27 at.%. The activation energy for the reactive infiltration of aluminum into the Mo₅Si₃ preform is ∼26 kJ/mol.     

Mo5Si3-Boron Composites Fabricated by Induction Plasma Deposition and Their High-Temperature Oxidation Resistance

Induction plasma spraying was used to produce freestanding parts of Mo₅Si₃-boron (Mo₅Si₃-B) composite materials. Four different Mo₅Si₃-B compositions were prepared and oxidized isothermally at 1210°C in air at atmospheric pressure. The high-temperature oxidation performance of these materials was dependent strongly on the boron content in the specimens. The composite that contained 2.0 wt% boron exhibited excellent resistance to oxidation, as indicated by the almost-zero change in specimen mass after oxidation for 24 h.     

Reaction-Bonding Preparation of Si3N4/MoSi2 and Si3N4/WSi2 Composites from Elemental Powders

Si₃N₄/MoSi₂ and Si₃N₄/WSi₂ composites were prepared by reaction-bonding processes using as starting materials powder mixtures of Si-Mo and Si-W, respectively. A presintering step in an At-base atmosphere was used before nitriding for the formation of MoSi₂ and WSi₂; the nitridation in a N₂-base atmosphere was followed after presintering with the total stepwise cycle of 1350°C × 20 h +1400°C × 20 h +1450°C × 2 h. The final phases obtained in the two different composites were Si₃N₄ and MoSi₂ or WSi₂; no free elemental Si and Mo or W were detected by X-ray diffraction.     

Hot-Pressed MoSi2-Particulate-Reinforced α-SiAlON Composites

MoSi₂-particulate-reinforced α-SiAlON ceramic composites containing 10, 20, 25, and 30 vol% were prepared by hot pressing at 1750°-1800°C. The α-SiAlON matrix was of the composition (Y_0.48Si_10.00A1_2.30O_1.17N_15.29). The hardness for the fully dense samples changed from HV10 = 22.5 to 15.3 GPa and the toughness from 3.2 to around 5.2 MPa^.m^1/2 when up to 30 vol% MoSi₂ was present. Two interesting microstructural features have been found. First, with an increasing amount of MoSi₂ a pronounced coalescence of MoSi₂ particles formed a "dual phase" material. The second effect was the growth of elongated α-SiAlON grains in the matrix with 10 vol% MoSi₂ added. The oxidation resistance has been determined to be unaffected by the addition of 2hd vol % MoSi₂ at 1250°C in oxygen gas of l atm pressure.     

Phase Relations in the System Al2O3─Ce2Si2O7 in the Temperature Range 900° to 1925°C in Inert Atmosphere

Equilibrium relationships in the system Al₂O₃-Ce₂Si₂O₇ in inert atmosphere have been investigated in the temperature range 900° to 1925°C. A simple eutectic reaction was found at 1375°C and 51 mol% Ce₂Si₂O₇. A high-low polymorphic transformation in Ce₂Si₂O₇ was observed at 1274°C. New XRD patterns are suggested for both polymorphs of cerium pyrosilicate. The melting point of Ce₂Si₂O₇ was found to be 1788°C. A value for ΔH°_m,Ce2Si2O7 of 36.81 kJ/mol was calculated from the initial slope of the experimentally determined liquidus in equilibrium with the pyrosilicate phase.     

Processing Temperature Effects on Molybdenum Disilicide

A series of MoSi₂ compacts were fabricated at increasing hot-pressing temperatures to achieve different grain sizes. The materials were evaluated by Vickers indentation fracture to determine room-temperature fracture toughness, hardness, and fracture mode. From 1500° to 1800°C, MoSi₂ had a constant 67% transgranular fracture and linearly increasing grain size from 14 to 21 μm. Above 1800°C, the fracture percentage increased rapidly to 97% transgranular at 1920°C (32-μm grain size). Fracture toughness and hardness decreased slightly with increasing temperature. MoSi₂ processed at 1600°C had the highest fracture toughness and hardness values of 3.6 MPa.m^1/2 and 9.9 GPa, respectively. The effects of SiO₂ formation from oxygen impurities in the MoSi₂ starting powders and MoSi₂–Mo₅Si₃ eutectic liquid formation were studied.     

The System Si3N4-SiO2-Y2O3

Subsolidus phase relations were established in the system Si₃N₄-SiO₂-Y₂O₃. Four ternary compounds were confirmed, with compositions of Y₄Si₂O₇N₂, Y₂Si₃O₃N₄, YSiO₂N, and Y₁₀(SiO₄)₆N₂. The eutectic in the triangle Si₃N₄-Y₂Si₂O₇-Y₁₀(SiO₄)₆N₂ melts at 1500°C and that in the triangle Si₂N₂O-SiO₂-Y₂Si₂O₇ at 1550°C. The eutectic temperature of the Si₃N₄-Y₂Si₂O₇ join was ∼ 1520°C.     

Fabrication and Microstructures of MoSi2 Reinforced–Si3N4 Matrix Composites

Details of the fabrication and microstructures of hot-pressed MoSi₂ reinforced–Si₃N₄ matrix composites were investigated as a function of MoSi₂ phase size and volume fraction, and amount of MgO densification aid. No reactions were observed between MoSi₂ and Si₃N₄ at the fabrication temperature of 1750°C. Composite microstructures varied from particle–matrix to cermet morphologies with increasing MoSi₂ phase content. The MgO densification aid was present only in the Si₃N₄ phase. An amorphous glassy phase was observed at the MoSi₂–Si₃N₄ phase boundaries, the extent of which decreased with decreased MgO level. No general microcracking was observed in the MoSi₂–Si₃N₄ composites, despite the presence of a substantial thermal expansion mismatch between the MoSi₂ and Si₃N₄ phases. The critical MoSi₂ particle diameter for microcracking was calculated to be 3 μm. MoSi₂ particles as large as 20 μm resulted in no composite microcracking; this indicated that significant stress relief occurred in these composites, probably because of plastic deformation of the MoSi₂ phase.     

High-Temperature Chemistry and Oxidation of ZrB2 Ceramics Containing SiC, Si3N4, Ta5Si3, and TaSi2

The effect of Si₃N₄, Ta₅Si₃, and TaSi₂ additions on the oxidation behavior of ZrB₂ was characterized at 1200°–1500°C and compared with both ZrB₂ and ZrB₂/SiC. Significantly improved oxidation resistance of all Si-containing compositions relative to ZrB₂ was a result of the formation of a protective layer of borosilicate glass during exposure to the oxidizing environment. Oxidation resistance of the Si₃N₄-modified ceramics increased with increasing Si₃N₄ content and was further improved by the addition of Cr and Ta diborides. Chromium and tantalum oxides induced phase separation in the borosilicate glass, which lead to an increase in liquidus temperature and viscosity and to a decrease in oxygen diffusivity and of boria evaporation from the glass. All tantalum silicide-containing compositions demonstrated phase separation in the borosilicate glass and higher oxidation resistance than pure ZrB₂, with the effect increasing with temperature. The most oxidation-resistant ceramics contained 15 vol% Ta₅Si₃, 30 vol% TaSi₂, 35 vol% Si₃N₄, or 20 vol% Si₃N₄ with 10 mol% CrB₂. These materials exceeded the oxidation resistance of the ZrB₂/SiC ceramics below 1300°–1400°C. However, the ZrB₂/SiC ceramics showed slightly superior oxidation resistance at 1500°C.     

Synthesis of Celsian (BaAl2Si2O8) from Solid Ba-Al-Al2O3-SiO2 Precursors: I, XRD and SEM/EDX Analyses of Phase Evolution

An intimate Ba-Al-Al₂O₃-SiO₂ powder mixture, produced by high-energy milling, was pressed to 3 mm thick cylinders (10 mm diameter) and hexagonal plates (6 mm edge-to-edge width). Heat treatments conducted from 300° to 1650°C in pure oxygen or air were used to transform these solid-metal/oxide precursors into BaAl₂Si₂O₈. Barium oxidation was completed, and a binary silicate compound, Ba₂SiO₄, had formed within 24 h at 300°C. After 72 h at 650°C, aluminum oxidation was completed, and an appreciable amount of BaAl₂O₄ had formed. Diffraction peaks consistent with hexagonal BaAl₂Si₂O₈, BaAl₂O₄, β-BaSiO₃, and possibly β-BaSi₂O₅ were detected after 24 h at 900°C. Diffraction peaks for BaAl₂O₄ and BaAl₂Si₂O₈ were observed after 35 h at 1200°C, although SEM analyses also revealed fine silicate particles. Further reaction of this silicate with BaAl₂O₄ at 1350° to 1650°C yielded a mixture of hexagonal and monoclinic BaAl₂Si₂O₈. The observed reaction path was compared to prior work with other inorganic precursors to BaAl₂Si₂O₈.     

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.     

Sintering Mechanisms of Zirconium and Hafnium Carbides Doped with MoSi2

The microstructure of two pressureless-sintered ultra-high-temperature ceramics, namely ZrC+20 vol% MoSi₂ and HfC+20 vol% MoSi₂, was characterized by scanning and transmission electron microscopy. With regard to the ZrC–MoSi₂ system, Zr _x Si _y compounds and SiC were detected. In the HfC–MoSi₂ system, a mixed phase was detected at the triple points and identified as (Mo,Hf)₅Si₃. For both the systems investigated, the high wettability of the silicide-based phases on the matrix grains suggests that sintering is assisted by a liquid phase. This contribution reports for the first time on the sintering mechanisms of early transition metal carbides doped with MoSi₂ as a sinter additive, on the basis of the microstructural evolution observed upon sintering and in the light of phase diagrams and thermodynamical calculations.     

Phase Equilibria in the System Si3N4-SiO2-BeO-Be3N2

The 1780°C isothermal section of the reciprocal quasiternary system Si₃N₄-SiO₂-BeO-Be₃N₂ was investigated by the X-ray analysis of hot-pressed samples. The equilibrium relations shown involve previously known compounds and 8 newly found compounds: Be₆Si³N₈, Be₁₁Si₅N₁₄, Be₅Si²N₆, Be₉Si₃N₁₀, Be₈SiO₄N₄, Be₆O₃N₂, Be₈O₅N₂, and Be₉O₆N₂. Large solid solubility occurs in β-Si₃N₄, BeSiN₂, Be₉Si₃N₁₀, Be₄SiN₄, and β-Be₃N₂. Solid solubility in β-Si₃N₄ extends toward Be₂SiO₄ and decreases with increasing temperature from 19 mol% at 1770°C to 11.5 mol% Be₂SiO₄ at 1880°C. A 4-phase isotherm, liquid +β-Si₃N₄ ( ss )Si₂ON₂+ BeO, exists at 1770°C.