Thermal Stability of Low-Oxygen Silicon Carbide Fiber (Hi-Nicalon) Subjected to Selected Oxidation Treatment

Low-oxygen silicon carbide fibers (Hi-Nicalon) were oxidized at temperatures from 1073 to 1773 K under an oxygen partial pressure of 0.25 atm. The strength of the unoxidized core was practically unaffected by the oxidation temperatures. The strength of the as-oxidized fibers with an SiO₂ film decreased markedly with increasing oxidation temperature. When exposed subsequently to 1773 K in argon, the fibers with a SiO₂ film of 0.3–0.5 μm thickness had the best thermal stability.     

Thermal Stability of Polycarbosilane-Derived Silicon Carbide Fibers under Reduced Pressures

Three types of polycarbosilane-derived SiC fibers—Nicalon, Hi-Nicalon, and Hi-Nicalon S—were exposed at temperatures of 1573–1773 K under a reduced pressure of 1.3 Pa. The thermal stability of the fibers was investigated through examinations of the gas evolution, grain growth, specific resistivity, fiber morphology, and tensile strength. The thermal decomposition of the silicon oxycarbide phase began at 1523 K; then, active oxidation of the β-SiC crystallites occurred at >1673 K. The active oxidation caused serious damage to the fiber structure, which resulted in significant degradation of the fiber strength. Hi-Nicalon had a tensile strength of ∼0.5 GPa after exposure at 1773 K, although Nicalon and Hi-Nicalon S fibers completely lost their strength, even after exposure at 1673 K. Hi-Nicalon fiber had relatively good thermal stability under reduced pressure.     

Suppression of Active Oxidation of Polycarbosilane-Derived Silicon Carbide Fibers by Preoxidation at High Oxygen Pressure

Three types of polycarbosilane-derived SiC fibers (Nicalon, Hi-Nicalon, and Hi-Nicalon S) with different SiO₂ film thicknesses ( b ) were subjected to exposure tests at 1773 K in an argon-oxygen gas mixture with an oxygen partial pressure of 1 Pa. The suppression effect of a SiO₂ coating on active oxidation was examined through TG, XRD analysis, SEM observation, and tensile tests. All the as-received fibers were oxidized in the active-oxidation regime. The mass gain and the SiO₂ film development showed a suppression of active oxidation at b values of ≧0.070 μm for Nicalon, ≧0.013 μm for Hi-Nicalon, and ≧0.010 μm for Hi-Nicalon S fibers. Considerable strength was retained in the SiO₂-coated fibers. For Hi-Nicalon fibers, the retained strength was 71%–90% of the strength in the as-received state (2.14–2.69 GPa).     

先驱体转化法制备含硼SiC纤维

通过二甲基胺硼烷（dimethylamine borane,DMAB）与低分子量聚碳硅烷（low-molecular mass polycarbosilane,LPCS）反应合成硼溶胶,将硼溶胶与高分子量聚碳硅烷（high-molecular mass polycarbosilane,HPCS）共混制备含硼聚碳硅烷先驱...     

Thermal and Electrical Properties in Plasma-Activation-Sintered Silicon Carbide with Rare-Earth-Oxide Additives

This study investigates the thermal and electrical properties of SiC ceramics with a combination of Y₂O₃ and rare-earth-oxide additions as sintering additives, by comparing four types of SiC starting powders varying in particle size and chemical composition. The powder mixtures were plasma-activation sintered to full densities and then annealed at high temperatures for grain growth. The thermal conductivity and electrical resistivity of the SiC ceramics were measured at room temperature by a laser-flash technique and a current–voltage method, respectively. The results indicate that the thermal conductivity and electrical resistivity of the SiC ceramics are dependent on the chemical composition and particle size of the starting powders. The thermal conductivities observed for all of the annealed materials with a rare-earth La₂O₃ sintering additive were >160 W·(m·K)⁻¹, although low electrical resistivity was observed for all materials, in the range 3.4–450 Ω·cm. High thermal conductivity, up to 242 W·(m·K)⁻¹, was achieved in an annealed material using a commercial 270 nm SiC starting powder.     

Mirror Constant for Tyranno® Silicon-Titanium-Carbon-Oxygen Fibers Measured in Situ in a Three-Dimensional Woven Silicon Carbide/Silicon Carbide Composite

The strength, S , of ceramic and glass fibers often can be estimated from fractographic investigation using the fracture mirror radius, r _m, and the relationship S = A _m/( r _m)^1/2, where A _mis the "mirror constant." The present work estimates the value of A _mfor Tyranno^® Si-Ti-C-O fibers in situ in a three-dimensional woven SiC/SiC-based composite to be 2.50 ± 0.09 MPa·m^1/2. This value is within the range of 2–2.51 MPa·m^1/2 previously obtained for nominally similar Nicalon^® Si-C-O fibers.     

Effect of Grain Boundaries on Thermal Conductivity of Silicon Carbide Ceramic at 5 to 1300 K

The thermal conductivity of a SiC ceramic was measured as 270 W·m⁻¹·K⁻¹ at room temperature. At low temperatures ( T < 25 K), the decrease in the conductivity was proportional to T ³ on a logarithmic scale, which indicated that the conductivity was controlled by boundaries. The calculated phonon mean free path in the ceramic increased with decreased temperature, but was limited to ∼4 μm, a length almost equal to the grain size, at temperatures below 30 K. We concluded that the thermal conductivity of the ceramic below 30 K was influenced significantly by grain boundaries and grain junctions.     

Effects of Grain-Boundary Structure on the Strength, Toughness, and Cyclic-Fatigue Properties of a Monolithic Silicon Carbide

An in situ -toughened silicon carbide (ABC-SiC) has been examined in the as-processed condition, where the grain-boundary films are predominantly amorphous, and following thermal exposure at a temperature of 1300°C, where the films become fully crystalline. Previous work has shown that, at elevated temperatures (up to 1300°C), after the grain-boundary films crystallize in situ , only a marginal reduction in strength, fracture toughness, and cyclic-fatigue crack-growth properties is observed, in comparison with those of the as-processed microstructure at 25°C. In the present study, the effect of such crystallization on the subsequent strength, toughness, and fatigue properties at 25°C is examined. Little or no degradation is observed in the room-temperature properties with the crystallized grain-boundary films/phase; in fact, although the strength shows a small reduction (∼3%), the fracture toughness and fatigue-crack-growth threshold both increase by ∼20%, compared with that of the as-processed structure with amorphous grain-boundary films.     

Strength of Nicalon Silicon Carbide Fibers Exposed to High-Temperature Gaseous Environments

The effects of exposures to high-temperature gaseous atmospheres on the strength of Nicalon SiC fibers were investigated. The exposure conditions were as follows: (1) H₂ with various P _H2O for 10 h at 1000° and 1200°C, and (2) air for 2 to 100 h at 800° to 1400°C. Individual fibers were tested in tension following each exposure. The strengths of the fibers were strongly influenced by the exposure atmosphere and temperature, but less affected by time at temperature. When exposed in air, a SiO₂ layer was formed on the surface, minimizing the degradation of strength. However, this beneficial effect was negated under conditions in which the SiO₂ layer became too thick. The most severe degradation resulted from exposure to a reducing atmosphere, presumably due to the reduction of SiO₂ inherent in the fibers.     

Oxidation of Low-Oxygen Silicon Carbide Fibers (Hi-Nicalon) in Carbon Dioxide

Polycarbosilane-derived low-oxygen SiC fibers, Hi-Nicalon, were heat-treated for 36 ks at temperatures from 1273 to 1773 K in CO₂ gas. The oxidation of the fibers was investigated through the examination of mass change, crystal phase, resistivity, morphology, and tensile strength. The mass gain, growth of β-SiC crystallites, reduction of resistivity of the fiber core, and formation of protective SiO₂ film were observed for the fibers after heat treatment in CO₂ gas. SiO₂ film crystallized into cristobalite above 1573 K. Despite the low oxygen potential of CO₂ gas ( p _O2= 1.22 Pa at 1273 K − 1.78 × 10² Pa at 1773 K), Hi-Nicalon fibers were passively oxidized at a high rate. There was a large loss of tensile strength in the as-oxidized state at higher temperatures because of imperfections in the SiO₂ film. On the other hand, the fiber cores showed better strength retention even after oxidation at 1773 K.     

碳化硅材料热导率计算研究进展

从声子散射机制出发,介绍了Si C热导率的温度特性和微观导热机理。综述了Si C单晶热导率的2种主要计算方法。Boltzmann-弛豫时间近似(RTA)适用于各个温度段的热导率计算,而分子动力学方法更适用于高温热导率计算。分子动力学方法相比于Boltzmann-RTA方法的优点在于它可以考虑所有高次项的非谐作用。介绍了3种Si C陶瓷热导率近似计算模型,包括界面热阻模型、Debye-Callaway模型及多相系统热导率模型。下一步研究的主要方向仍然是优化计算模型及减少拟合参数。     

Mechanical Properties, Thermal Shock Resistance, and Thermal Stability of Zirconia-Toughened Alumina-10 vol% Silicon Carbide Whisker Ceramic Matrix Composite

Zirconia-toughened alumina (Al₂O₃–15 vol% Y-PSZ (3 mol% Y₂O₃)) reinforced with 10 vol% silicon carbide whiskers (ZTA-10SiC _w ) ceramic matrix composite has been characterized with respect to its room-temperature mechanical properties, thermal shock resistance, and thermal stability at temperatures above 1073 K. The current ceramic composite has a flexural strength of ∽550 to 610 MPa and a fracture toughness, K _IC , of ∽5.6 to 5.9 MPa·m^1/2 at room temperature. Increases in surface fracture toughness, ∽30%, of thermally shocked samples were observed because of thermal-stress-induced tetragonal-to-monoclinic phase transformation of tetragonal ZrO₂ grains dispersed in the matrix. The residual flexural strength of ZTA–10 SiC _w ceramic composite, after single thermal shock quenches from 1373–1573 to 373 K, was ∽10% higher than that of the unshocked material. The composite retained ∽80% of its original flexural strength after 10 thermal shock quenches from 1373–1573 to 373K. Surface degradation was observed after thermal shock and isothermal heat treatments as a result of SiC whisker oxidation and surface blistering and swelling due to the release of CO gas bubbles. The oxidation rate of SiC whiskers in ZTA-10SiC _w composite was found to increase with temperature, with calculated rates of ∽8.3×10⁻⁸ and ∽3.3×10⁻⁷ kg/(m²·s) at 1373 and 1573 K, respectively. It is concluded that this ZTA-10SiC _w composite is not suitable for high-temperature applications above 1300 K in oxidizing atmosphere because of severe surface degradation.     

Thermal Expansion of Laminated, Woven, Continuous Ceramic Fiber/Chemical-Vapor-Infiltrated Silicon Carbide Matrix Composites

Thermal expansions of three two-dimensional laminate, continuous fiber/chemical-vapor-infiltrated silicon carbide matrix composites reinforced with either FP-Alumina (alumina), Nextel (mullite), or Nicalon (Si-C-O-N) fibers are reported. Experimental thermal expansion coefficients parallel to a primary fiber orientation were comparable to values calculated by the conventional rule-of-mixtures formula, except for the alumina fiber composite. Hysteriesis effects were also observed during repeated thermal cycling of that composite. Those features were attributed to reoccurring fiber/matrix separation related to the micromechanical stresses generated during temperature changes and caused by the large thermal expansion mismatch between the alumina fibers and the silicon carbide matrix.     

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.     

Thermal Shock Behavior of Porous Silicon Carbide Ceramics

Using the water-quenching technique, the thermal shock behavior of porous silicon carbide (SiC) ceramics was evaluated as a function of quenching temperature, quenching cycles, and specimen thickness. It is shown that the residual strength of the quenched specimens decreases gradually with increases in the quenching temperature and specimen thickness. Moreover, it was found that the fracture strength of the quenched specimens was not affected by the increase of quenching cycles. This suggests a potential advantage of porous SiC ceramics for cyclic thermal-shock applications.     

Models Proposed to Explain the Electrical Conductivity of Polymer‐Derived Silicon Carbide Fibers

Two types of silicon carbide fibers (SiC_f) were prepared employing different pyrolysis techniques. The relationship between the microstructure and the electrical resistivity of the fibers was investigated. The results indicated that the carbon layer present on the fiber surface acted as the main conductive phase in the SiC_f obtained by direct pyrolysis, whereas a free carbon phase determined the conductivity of the SiC_f prepared by the preheated pyrolysis method. A core‐shell model and a general effective media (GEM) theory were proposed to explain the conductivity of different types of SiC_f. Quantitative analysis based on these models indicated an electrical resistivity of ~10^?2 Ω·cm for the carbon layer on the surface of SiC_f obtained by direct pyrolysis. The electrical resistivity and the percolation threshold of the free carbon in SiC_f prepared by the preheated pyrolysis method were 10^?1 Ω·cm and 11.3% respectively.     

Multiscale Genome Modeling for Predicting the Thermal Conductivity of Silicon Carbide Ceramics

Silicon carbide (SiC) ceramics have been widely used in industry due to its high thermal conductivity. Understanding the relations between the microstructure and the thermal conductivity of SiC ceramics is critical for improving the efficiency of heat removal in heat sink applications. In this paper, a multiscale model is proposed to predict the thermal conductivity of SiC ceramics by bridging atomistic simulations and continuum model via a materials genome model. Interatomic potentials are developed using ab initio calculations to achieve more accurate molecular dynamics (MD) simulations. Interfacial thermal conductivities with various additive compositions are predicted by nonequilibrium MD simulations. A homogenized materials genome model with the calculated interfacial thermal properties is used in a continuum model to predict the effective thermal conductivity of SiC ceramics. The effects of grain size, additive compositions, and temperature are also studied. The good agreement found between prediction results and experimental measurements validates the capabilities of the proposed multiscale genome model in understanding and improving the thermal transport characteristics of SiC ceramics.     

Silicon Carbide Monofilament-Reinforced Silicon Nitride or Silicon Carbide Matrix Composites

SiC-monofilament-reinforced SiC or Si₃N₄ matrix composites were fabricated by hot-pressing, and their mechanical properties and effects of filaments and filament coating layers were studied. Relationships between frictional stress of filament/matrix interface and fracture toughness of SiC monofilament/Si₃N₄ matrix composites were also investigated. As a result, it was confirmed experimentally that in the case of composites fractured with filament pullout, the fracture toughness increased as the frictional stress increased. On the other hand, when frictional stress was too large (>about 80 MPa) for the filament to be pulled out, fracture toughnesses of the composites were almost the same and not so much improved over that of Si₃N₄ monolithic ceramics. The filament coating layers were found to have a significant effect on the frictional stress of the SiC monofilament/Si₃N₄ matrix interface and consequently the fracture toughness of the composites. Also the crack propagation behavior in the SiC monofilament/Si₃N₄ matrix composites was observed during flexural loading and cyclic loading tests by an in situ observation apparatus consisting of an SEM and a bending machine. The filament effect which obstructed crack propagation was clearly observed. Fatigue crack growth was not detected after 300 cyclic load applications.     

Silicon Carbide-Coated Boron Fibers

A study of a silicon carbide-coated boron fiber showed that it retained its room-temperature strength after being heated to 1000°C for 24 h in air. This fiber was consolidated successfully in a titanium matrix at 930°C without degradation, although previous results with another silicon carbide-coated boron fiber indicated that there might be a reaction problem at this temperature.     

Thermal Diffusivity/Conductivity of Alumina—Silicon Carbide Composites

Thermal diffusivity and conductivity values for several Al₂O₃-SiC whisker composites were determined. The thermal diffusivity values spanned the range from 373 to 1473 K, and thermal conductivity data wre obtained between 305 and 365 K. The thermal diffusivity decreased with increasing temperature and increased with SiC-whisker content. An estimate of the thermal conductivity of the whiskers was obtained from the direct thermal conductivity measurements, but attempts to derive whisker conductivity values from the thermal diffusivity data were not successful because the laser flash method lacks the required accuracy and precision. Specimens were subjected to two different thermal quench experiments to investigate the effect of thermal history on diffusivity. In the most severe case, multiple 1073- to 373-K quenches, radial cracks were observed in the test specimens; however, there was no change in diffusivity. The lack of sensitivity to thermal cycling appears to be related to the sample size.