Delayed Failure of Hi-Nicalon and Hi-Nicalon S Multifilament Tows and Single Filaments at Intermediate Temperatures (500°–800°C)

Previous results have shown that tows of SiC Nicalon fibers are sensitive to the phenomenon of delayed failure, at temperatures below 700°C. The present paper examines the static fatigue of Hi-Nicalon and Hi-Nicalon S when subjected to constant load, at temperatures between 500° and 800°C in air. Multifilament tows and single filaments were tested. Experimental data show that the rupture times of tows depend on the applied stress according to the conventional power law t σ ⁿ = A . In contrast, the stress-rupture time data obtained on single filaments exhibit significant scatter. A model based on slow crack growth in single filaments shows that the stress-rupture of fiber tows follows the conventional time power law. The dependence on temperature was introduced. The model allowed sound calculations of tow lifetimes and characteristics of the slow crack growth phenomenon to be extracted from the tow stress-rupture time data.     

Piezoresistivity of Hi-Nicalon Type-S Silicon Carbide-Based Fiber

Piezoresistivity effect of a silicon carbide-based ceramic fiber (Nicalon family) was evaluated when a single fiber was buried at the tensile plane in a plastic rectangular bar subjected to bending to apply a stable tensile strain. Electrical resistivity change during the bending was monitored by a digital high-resistance meter. From the fracture strain, Young's modulus, and the resistivity change, the piezoresistance coefficient is calculated to be 1.6 × 10⁻¹¹ m²/N, which is in agreement with the reported value for silicon carbide single crystals and our own reported value for polycrystalline silicon carbide ceramics.     

Effects of High Water-Vapor Pressure on Oxidation of Silicon Carbide at 1200°C

The oxidation of SiC at 1200°C in a slowly flowing gas mixture of either air or air + 15 vol% H₂O at 10 atm (1 MPa) was studied for extended times to examine the effects of elevated water-vapor pressure on oxidation rates and microstructural development. At a water-vapor pressure of 1.5 atm (150 kPa), distinct SiO₂ scale structures were observed on the SiC; thick, porous, nonprotective cristobalite scales formed above a thin, nearly dense vitreous SiO₂ layer, which remained constant in thickness with time as the crystalline SiO₂ continued to grow. The pore morphology of the cristobalite layer differed depending on the type of SiC on which it was grown. The crystallization and growth rates of the cristobalite layer were significantly accelerated in the presence of the high water-vapor pressure and resulted in rapid rates of SiC surface recession that were on the order of what is observed when SiO₂ volatility is rate controlling at high gas-flow velocities (30 m/s). The recession process can be described by a paralinear kinetic model controlled by the conversion of dense vitreous SiO₂ to porous, nonprotective SiO₂.     

Corrosion Behavior of Silicon Carbide in 290°C Water

The fundamental corrosion behavior of silicon carbide (SiC) ceramics was investigated after immersion in 290°C water solutions with different pH and dissolved-oxygen concentrations. The weight loss in the oxygenated solution was more than that in the deoxygenated solution and was accelerated by increasing pH. Preferential attack could be found at grain boundaries and around pores on the sample surface immersed in the oxygenated alkaline solution. The weight change, dW, followed the general rate law, (dW)^m= kt. The exponent, m, was 1.11 in the alkaline solution and 0.45 in the acidic solution. Based on the above results, the SiC was considered to be directly hydrolyzed to a silica sol, with its dissolution kinetics dependent on the sol stability. This corrosion behavior is quite different from those in high-temperature or vapor-phase hydrothermal oxidation, where the oxidation rate is controlled by oxidant diffusion through the protective silica surface layer.     

Reactions of Silicon Carbide and Silicon(IV) Oxide at Elevated Temperatures

The reaction between SiC and SiO₂ has been studied in the temperature range 1400–1600 K. A Knudsen cell in conjunction with a vacuum microbalance and a high-temperature mass spectrometer was used for this study. Two systems were studied—1:1 SiC (2 wt% excess carbon) and SiO₂; and 1:1:1 SiC, carbon, and SiO₂. In both cases the excess carbon forms additional SiC within the Knudsen cell and adjusts to the direct reaction of stoichiometric SiC and SiO₂ to form SiO( g ) and CO( g ) in approximately a 3:1 ratio. These results are interpreted in terms of the SiC-O stability diagram.     

Strength Distribution of Reinforcing Fibers in a Nicalon Fiber/Chemically Vapor Infiltrated Silicon Carbide Matrix Composite

The strength distribution of fibers within a two-dimensional laminate ceramic/ceramic composite consisting of an eight harness satin weave of Nicalon continuous fibers within a chemically vapor infiltrated SiC matrix was determined from analysis of the fracture mirrors of the fibers. Comparison of the fiber strengths and the Weibull moduli with those for Nicalon fibers prior to incorporation into composites suggests that possible fiber damage may occur either during the weaving or during another stage of the composite manufacture. Observations also indicate that it is the higher-strength fibers which experience the greatest extent of fiber pullout and thus make a larger contribution to the overall composite toughness than do the weaker fibers.     

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.     

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.     

Oxidation of Silicon Carbide-Reinforced Oxide-Matrix Composites at 1375° to 1575°C

Oxidation studies were conducted on Al₂O₃-SiC and mullite-SiC composites at 1375° to 1575°C in O₂ and in Ar-1% O₂. The composites were prepared by hot-pressing mixtures of Al₂O₃ or mullite and SiC powders. The reaction products contained alumina, mullite, an aluminosilicate liquid, and gas bubbles. The parabolic rate constants were about 3 orders of magnitude higher than those expected for the oxidation of SiC. Higher rates are caused by higher oxygen permeabilities through the reaction products than through pure silica. Our results suggest that oxygen permeabilities are comparable in the three condensed phases observed in the reaction products.     

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.     

Etching of Silicon Carbide Materials at Elevated Temperatures in a Nitrogen-Based Gas

Two sintered SiC-based materials were heat-treated for 150 h at 1300°C in a nitrogen-based gas (1.2% H₂, 0.6% CO) at a total pressure of 130 Pa. Sintered SiC samples were also preoxidized and then exposed to this gas under the same conditions to evaluate the protective nature of an SiO₂ scale. In this atmosphere, SiO gas and cyanogens are predicted to form, rather than SiO₂. Experimental studies confirmed that etching of sintered SiC occurs. Preoxidation does not provide protection from etching, because of the rapid removal of SiO₂ by H₂ as H₂O and SiO.     

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.     

Homogeneity Region of Strontium- and Magnesium-Containing LaGaO3 at Temperatures between 1100° and 1500°C in Air

Phase stability studies were performed within the quasi-ternary system LaGaO₃-SrGaO_2.5-"LaMgO_2.5". Emphasis was cast on the temperature dependence of the homogeneity region of La_{1− x} Sr _x Ga_{1− y} Mg _y O_3−δ perovskite solid solutions. Isothermal sections were determined at 1100°, 1250°, 1400°, and 1500°C in a static air atmosphere. The single-phase homogeneity region was found to considerably diminish with decreasing temperature, indicating a reduction of the solid solubility of Sr and Mg, and below 1100°C the doped perovskite becomes unstable. Consequently, the cubic perovskite phase was found to exist only at elevated temperatures and for high Sr and Mg amounts. Sample preparation was performed by the mixed-oxide process as well as by a modified combustion synthesis.     

Interactions in the Silicon Carbide–Polyacrylic Acid–Yttrium Ion System

Interactions in the SiC powder–polyacrylic acid (PAA, dispersant)–Y³⁺ ion (sintering additive) system were investigated in the pH range from 2 to 6. The amount of Y³⁺ ions adsorbed on SiC particles increased with an increase of pH because of the electrostatic attraction between the negatively charged SiC surface and Y³⁺ ions. On the other hand, the amount of PAA adsorbed on SiC particles decreased with increasing pH because of the electrostatic repulsion between the negatively charged SiC surface and dissociated PAA. The addition of PAA to the SiC suspension with Y³⁺ ions increased the amount of Y³⁺ ions fixed to SiC particles through the strong interaction between Y³⁺ ions and PAA adsorbed on SiC particles. The above-described interactions in the SiC–PAA–Y³⁺ ions system were closely related to the coagulation of SiC particles and the rheology of SiC suspensions. The coagulation of SiC particles through the adsorbed Y³⁺ ions decreased the specific surface area of SiC powder after calcination in an argon atmosphere. The addition of PAA to the SiC suspensions with Y³⁺ ions kept the SiC particles separate during calcination, i.e., the PAA addition contributed to enhancement of the driving force of sintering (no decrease of specific surface area) and to control of the amount of Y³⁺ ions uniformly fixed to the SiC surface.     

Cyclic Fatigue–Crack Propagation Behavior in Silicon Carbide: Long- and Small-Crack Behavior

Cyclic fatigue properties of high-toughness SiC with additives of Al₂O₃ and Y₂O₃ were examined, with a focus on differences between long- (>3 mm) and small-crack (<200 μm) behavior. Small cracks were initiated with Vickers indents placed on the tensile surfaces of beams, and crack extension was monitored optically under cyclic load. For small cracks, high growth rates which exhibited a negative dependence on the far-field driving force were observed. Such behavior was explained by both indent-induced residual stresses and the relative size of cracks compared with bridging zone lengths.     

Nanoscale Densification Creep in Polymer-Derived Silicon Carbonitrides at 1350°C

The measurement of axial and radial strains during uniaxial compression creep of SiCN shows the deformation to be entirely volumetric (as opposed to shear). Phenomenologically, the densification strain rate shows a good fit to an exponential stress dependence. This result is explained by the large volume of the diffusing molecular units in the oligomeric amorphous structure of SiCN, which causes the driving force to become nonlinear in stress. The size of the diffusing unit is estimated to be 1.2 nm.     

Active Corrosion of Sintered α-Silicon Carbide in Oxygen–Chlorine Gases at Elevated Temperatures

The active corrosion of sintered α-silicon carbide from heat exchanger tubes in the temperature range 900° to 1100°C in gas mixtures containing 2% Cl₂ by volume with additions of O₂ or H₂ has been investigated by thermogravimetric analysis and subsequent examination of the corrosion products. The presence of a small amount of oxygen accelerated rapid active corrosion in chlorine-containing gas mixtures, but the corrosion was suppressed by an active-to-passive transition when the concentration of oxygen in the gas mixture was too high. Low rates of attack were observed in the environments containing H₂ even when the chlorine potential was high. The concentration of oxygen necessary to produce the active-to-passive transition was found to vary from one material to another and may be related to the amount of excess carbon in the sintered silicon carbide.     

Poly(methylsilane)—A High Ceramic Yield Precursor to Silicon Carbide

Preceramic polymers offer exceptional potential for low-temperature processing of both oxide and non-oxide ceramics. In addition, shapes such as fibers, films, and membranes that are not commonly available using standard processing techniques are readity available using preceramic polymers. In non-oxide ceramics, the ceramic products generally available from preceramics do not exhibit all of the typical properties associated with the same materials produced by standard, high-temperature processing approaches. In part, this appears to be because there are very few preceramic polymers that lead to high-purity, single-phase materials. Poly(methylsilane), (–[MeHSi] _x –), produced from MeSiH₃, can be used to produce relatively pure, bulk SiC at temperatures below 1000°C. The transformation process from polymer to ceramic is followed by ²⁹Si NMR and diffuse reflectance IR. The polymer first undergoes a major rearrangement from poly(silane) to poly(carbosilane) at 400°C. Above 400°C, the resulting poly(carbosilane) decomposes to a hydrogenated form of SiC as shown by spectroscopic analysis of the 600°C material. Further heating, to 1000°C for 1 h, provides very narrow ²⁹Si peaks indicative of β-SiC mixed with small amounts of α-SiC polytypes. Chemical analysis, when coupled with the ²⁹Si and XRD results, suggests that poly(methylsilane) produces resonably pure, nanocrystalline SiC at temperatures much lower than previously observed for other SiC preceramic polymers.     

The nanogranular behavior of C-S-H at elevated temperatures (up to 700 °C)

Cement-based materials are non-combustible, but the complex chemo-physical mechanisms that drive at elevated temperatures the thermal degradation of the mechanical properties (stiffness, strength) are still an enigma that have deceived many decoding attempts. This paper presents, for the first time, results from a new experimental technique that allows one to rationally assess the evolution of the nano-mechanical behavior of cement paste at elevated temperatures. Specifically, the thermal degradation of the two distinct calcium-silicate hydrate (C-S-H) phases, Low Density (LD) C-S-H and High Density (HD) C-S-H, is assessed based on a statistical analysis of massive nanoindentation tests. From a combination of nanoindentation, thermogravimetry and micromechanical modeling, we identify a new mechanism, the thermally induced change of the packing density of the two C-S-H phases, as the dominant mechanism that drives the thermal degradation of cementitious materials. We argue that this loosening of the packing density results from the shrinkage of C-S-H nanoparticles that occurs at high temperatures, most probably due to the loss of chemically bound water.     

Effect of Dynamic Microstructural Change on Deformation Behavior in Liquid-Phase-Sintered Silicon Carbide with Al2O3–Y2O3–CaO Additions

Nanocrystalline β-SiC with additions of 7 wt% Al₂O₃, 2 wt% Y₂O₃, and 1 wt% CaO was subjected to tensile deformation to study its microstructural behavior under the dynamic process. The liquid-phase-sintered body had a relative density of >97% and an average grain size of 170 nm. Tension tests were conducted at initial strain rates ranging from 2 × 10⁻⁵ to 5 × 10⁻⁴ s⁻¹, in the temperature range 1973–2023 K, in both argon and N₂ atmospheres. Although grain-boundary liquids formed by the additions vaporized concurrently with the decomposition of SiC and extensive grain growth, the maximum tensile elongation of 48% was achieved in argon. Annealing experiments under the same conditions revealed that vaporization and grain growth were both dependent on experimental time. Therefore, high strain rates suffered less from the hardening effect when cavitation damage was more severe. Testing in an N₂ atmosphere brought about crystallization of the grain-boundary phase and prevented severe vaporization; however, fracture occurred at only 8% elongation. Grain-boundary sliding was still the dominant mechanism for deformation.