Does a True Fatigue Limit Exist for Continuous Fiber-Reinforced Ceramic Matrix Composites?

The high-cycle high-frequency fatigue behavior of a Nicalon-fiber-reinforced calcium aluminosilicate ceramic composite was investigated. A key goal of the room-temperature fatigue experiments was to determine if a true fatigue limit or endurance limit existed for this ceramic matrix composite. Although no fatigue failures occurred beyond 10⁷ cycles, the stress–strain hysteresis modulus and frictional heating continued to change up to 10⁸ cycles, at which point the 200 Hz experiments were terminated. This suggests that fatigue damage continued to evolve and that a true fatigue limit may not exist in ceramic matrix composites that have undergone interfacial frictional sliding.     

Yttrium Silicate Coatings for Oxidation Protection of Carbon–Silicon Carbide Composites

Yttrium silicate (Y₂SiO₅) coatings complement SiC coatings for protecting ceramic multilayer composite materials based on carbon-fiber-reinforced SiC composites (C-SiC). Thick (100 μm), dense Y₂SiO₅ coatings were prepared by dip coating, using concentrated aqueous slips. The resulting phases were studied by taking into account the simultaneous presence of oxide and non-oxide materials, which affected the chemical stability of the coatings. Thick, mechanically stable coatings were obtained by sintering in carbon crucibles and a SiC bed in an argon-flow furnace. Pure Y₂SiO₅ coatings completely separated from the SiC substrates. A high percentage of Y₂Si₂O₇ was necessary to fit the thermal expansion coefficients and ensure the stability of the coatings. Oxidation resistance of the coated substrates was investigated by isothermal and stepwise oxidation tests.     

Intermediate Temperature Internal Oxidation of a SiC/SiCN Composite with a Polymer‐Derived Matrix

SiC‐based composites exhibit oxidative embrittlement at intermediate temperatures. Although the mechanisms of internal oxidation in composites with initially hermetic matrices have been studied extensively, comparable studies on composites with semipermeable matrices, such as those produced by polymer infiltration and pyrolysis, have not been reported. The present article focuses on the latter class of composites, specifically a SiC_f /SiCN_m with a dual BN/Si₃N₄ fiber coating. It describes detailed SEM and TEM analyses of the microstructure before and after oxidation in dry air or water vapor at 800°C. The results show that internal oxidation is more aggressive in water vapor and occurs appreciably even in the absence of an applied stress. The sequence of oxidation of the constituent phases appears to be consistent with the underlying thermodynamic hierarchy for the respective oxidation reactions. Notably, contrary to existing models based on preferential oxidation of BN coatings, oxidation occurs first on the SiC fiber surfaces and the Si₃N₄ overcoat; crystalline BN remains even after significant fiber and matrix oxidation has occurred. The results are discussed in terms of rate‐controlling kinetic processes, the effect of oxidant type, and applied stress.     

Intermediate temperature oxidative strength degradation of a SiC/SiNC composite with a polymer‐derived matrix

The article describes an experimental investigation of oxidative degradation in mechanical performance of a SiC fiber‐reinforced composite with a SiCN matrix produced by polymer infiltration and pyrolysis. Tensile stress rupture and retained strength tests were performed at 800°C in dry air and in water vapor. Fracture surfaces were examined to determine the degree of fiber pull‐out and constituent oxidation and to measure radii of representative fiber fracture mirrors. The results indicate that degradation in tows adjacent to cut surfaces occurs equally rapidly in water vapor with or without application of stress; regions in the composite interior and near as‐processed (uncut) surfaces appear far less affected. Similar effects are evident but less pronounced in dry air. Although oxidation of fiber coatings is observed in some cases, collectively the results suggest that fiber degradation is the main mechanism leading to reduced composite strength.     

Oxidation kinetics strength of Hi‐NicalonTM‐S SiC fiber after oxidation in dry and wet air

Hi‐Nicalon?‐S SiC fiber strengths and Weibull moduli were measured after oxidation for up to 100 hours between 700°C and 1400°C in wet and dry air. SiO₂ scale thickness and crystallization extent were measured by TEM. The effect of furnace environment on trace element levels in the SiO₂ scales was characterized by secondary ion mass spectroscopy. Crystallization kinetics and Deal‐Grove oxidation kinetics for glass and crystalline scale, and the transition between them, were modeled and determined. Crystallization retards oxidation kinetics, and scale that formed in the crystalline state was heavily deformed by the growth stress accompanying SiC oxidation volume expansion. Glass scales formed in dry air slightly increased fiber strength. Glass scales formed in wet air did not increase strength, and in some cases significantly decreased strength. Scales more than 200 nm thick were usually partially or completely crystallized, which degraded fiber strength. Contamination of scales by trace impurities such as Al and Ca during heat treatment inhibited crystallization. The oxidation kinetics and the strengths of oxidized Hi‐Nicalon?‐S fibers are compared with previous studies on SiC fibers, bulk SiC, and single‐crystal SiC. Empirical relationships between oxidation temperature, time, scale thickness, and strength are determined and discussed.     

Oxidation of Mullite-Zirconia-Alumina-Silicon Carbide Composites

The isothermal oxidation of mullite-alumina-zirconia-silicon carbide composites obtained by reaction sintering was studied in the temperature interval 800° to 1400°C. The kinetics of the oxidation process was related to the viscosity of the surface glassy layer as well as to the crystallization of the surface film. The oxidation kinetics was halted for T ≤ 1300°C, presumably because of crystallization.     

纳米碳颗粒/碳化硅陶瓷基复合材料的氧化行为

以微米硅(Si)和纳米碳黑(Cp)粉体为主要原料,采用经机械化学法合成的碳化硅(SiC)和15%和25%的纳米碳颗粒与碳化硅(Cp-SiC)的复合粉体,并经无压烧结得到了Cp/SiC陶瓷基复合材料,分析了在不同温度条件下Cp/SiC烧结体的氧化行为。结果表明:当温度小于700℃时,Cp/SiC复合陶瓷在空气中的氧化受C—O2反应控制,致使其为均匀氧化;700℃时,氧化后的复合材料显气孔率最大,弯曲强度达极小值;大于700℃,氧化过程受O2的气相扩散控制,呈非均匀氧化;700~900℃之间,O2通过微裂纹的扩散控制着Cp/SiC的氧化过程;900~1 100℃之间,O2通过SiC缺陷的扩散控制着Cp/SiC的氧化过程,并在1 000℃时的最初的2 h内,复合材料弯曲强度增大,且达到了极大值。同时表明,纳米碳含量是影响复合材料强度及氧化行为的关键因素,添加纳米碳质量分数为15%的Cp/SiC复合陶瓷可以作为一种抗氧化性能优良的玻璃夹具材料。     

Improvement in the Oxidation Resistance of Oxide-Matrix Silicon Carbide-Particulate Composites by Mullite Infiltration

A SiC–∼50 vol% mullite-particulate composite fabricated by melt infiltration was found to exhibit excellent oxidation resistance at temperatures >1500°C in air. Cristobalite was found on the surface of samples after 100 h oxidation at temperatures of 1515°, 1620°, and 1650°C. The oxidation rate constant at 1515°C was almost comparable to hot-pressed bulk SiC, and at least 1 order of magnitude lower than the lowest value for the oxide-matrix SiC-particulate composites made by conventional processes, as reported in the literature and made by melt infiltration in the present study.     

Oxidation Behavior of SiC-Whisker-Reinforced Alumina-Zirconia Composites

During high-temperature oxidation in air, SiC-whisker-reinforced Al₂O₃—ZrO₂ composites degrade by the formation of a whisker-depleted mullite-zirconia scale. The reaction kinetics have been studied as a function of time and temperature for composites with whiskers preoxidized for different times. The evolution of the microstructure has been investigated by optical, scanning and transmission electron microscopy. Possible reaction mechanisms have been discussed. A model compatible with our observations on Al₂O₃—ZrO₂—SiC and the results reported in the literature for Al₂O₃—SiC whisker composites is proposed: The oxidation occurs at an internal reaction front. Oxygen diffuses along dislocations and grain boundaries through the mullite scale to react at this front with silicon carbide, thereby forming amorphous silica and graphite. Silica penetrates grain boundaries and further reacts with alumina and zirconia to form mullite and zircon, while the second reaction product, graphite, is oxidized into carbon monoxide when the reaction front moves deeper into the sample.     

Fabrication of Continuous-SiC-Fiber-Reinforced SiAlON-Based Ceramic Composites by Reactive Melt Infiltration

A technique for fabrication of β'-SiAlON-based ceramics in three-dimensional woven fabrics of BN-coated SiC (Hi-Nicalon™) fibers was developed by reactive melt infiltration in a controlled N₂ atmosphere. β'-SiAlON was produced in situ by the reaction of β-Si₃N₄, AlN, and Y-Al-Si-O molten glass. The wettability of the fibers with the molten glass was improved by infiltration and pyrolysis of perhydropolysilazane, resulting in fully dense matrix composites. The reaction between the fiber and molten glass could be depressed by increasing the N₂ partial pressure during the melt infiltration. The inhibition of the interfacial reaction may be related to the formation of carbon and oxynitride on the SiC fiber, in agreement with thermodynamic calculations as a function of N₂ partial pressure. The fabricated composites had a high ultimate flexure strength and a large work of fracture at room temperature. Degradation of the mechanical performance of the composites was small, even at 1773 K in an argon atmosphere.     

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.     

Oxidation Behavior of Silicon-Infiltrated Carbon/Carbon Composites in High-Enthalpy Convective Environment

Thermal response and oxidation behavior of commercial metal-silicon-infiltrated carbon/carbon composites (MICMAT^TM; Si-CC) were evaluated in a high-enthalpy convective environment using an arc jet facility (an arc wind tunnel). Composite specimens were put into a supersonic plasma air stream having a gas enthalpy of 12.7–18.8 MJ/kg for 50–600 s. Cold-wall heat fluxes measured by a Gardon-type calorimeter ranged from 1.0 to 1.8 MW/m², and the maximum surface temperature reached 1300°–1660°C. After the arc jet testing, no surface recession was observed in the samples, and the mass loss rate of the composites was far less than that of graphite. The excellent oxidation resistance was caused by formation of a porous SiC layer at the surface of the composite. Oxidation behavior of the composites is discussed based on a simplified airflow blocking model of the porous SiC layer. The composites exhibited excellent oxidation resistance for short-term exposure in high-enthalpy airflow.     

Oxidation mechanisms of SiC-fiber–reinforced Si eutectic alloy matrix composites at elevated temperatures

SiC-fiber–reinforced binary Si eutectic alloy composites have been developed for aerospace applications using the melt infiltration method. In this study, the oxidation mechanisms of various binary Si eutectic alloys were evaluated at elevated temperatures. We suggest that the oxidation resistance of eutectic alloys could be predicted using the Gibbs energy change for the oxidation reaction. Based on these calculations, eutectic alloys of Si-16at%Ti, Si-17at%Cr, Si-22at%Co, Si-38at%Co, and Si-27at%Fe were prepared. These alloys produced uniform SiO₂ layers and showed the same oxidation resistance as Si at 1000°C under humid conditions. Therefore, SiC composites using Si alloys with excellent oxidation resistance can be predicted using thermodynamic calculations.     

Degradation of a SiC-SiC composite in water vapor environments

The article examines degradation of a SiC-based fiber composite containing Tyranno ZMI fibers in water vapor at elevated temperatures (800°C and 1100°C). Degradation is characterized through mechanical tests under cyclic and quasi-static tensile loading in the near-threshold regime, at stresses at or slightly above the matrix cracking limit. These tests are augmented by examinations of fracture surfaces and polished cross-sections, measurements of fracture mirror radii, and measurements of interfacial debond toughness and sliding resistance. Degradation involves highly localized consumption of fibers through reactions of water vapor with the fibers and the BN coatings in regions adjacent to the few matrix cracks present at low stresses; the global hysteresis response and the average interfacial properties are minimally affected. Boria formed by oxidation of BN appears to play a fluxing role; it combines with silica on the fibers to form a non-protective molten glass. Inhomogeneous fiber consumption leads to stress concentrations in the fibers and hence reduced fiber strength. Spatial variations in the degradation process occur at two length scales: at the macroscopic scale, because of cracking of the external CVI SiC overcoat and subsequent water ingress through the cracks, and at the tow-scale, because of cracking of the CVI SiC around the tows. Parsing the kinetic processes over the two length scales remains a significant challenge.     

Influence of Thermal Conductivity and Fracture Toughness on the Thermal Shock Resistance of Alumina—Silicon–Carbide–Whisker Composites

The thermal shock resistance (indentation–quench method), fracture toughness, and thermal conductivity of three alumina–silicon–carbide–whisker composites and alumina have been investigated. A new procedure for the evaluation of thermal conductivity data is suggested, and higher room-temperature thermal conductivity than that reported in the literature is determined for silicon carbide whiskers. The ranking of the materials according to thermal shock resistance is consistent with the ranking according to fracture toughness but disagrees with the ranking according to thermal conductivity. This finding supports the analytically obtained result that, in defining thermal shock resistance, fracture toughness is more important than thermal conductivity.     

High-temperature oxidation of BN-coated sylramic SiC fibers in dry and wet atmosphere

The oxidation behavior of SiC Sylramic fibers coated with chemically vapor deposited Si-doped boron nitride (BN) was investigated at temperatures between 800 and 1200°C in dry and wet O₂ atmospheres. Thermogravimetric analysis was used to study the oxidation kinetics of the fiber and the influence of the BN layer and the environment. The morphology and composition of the thermally grown oxide scale was determined posttest by scanning electron microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectrometry. This study gives new insights into the synergistic effects of BN and water vapor on the oxidation behavior SiC Sylramic fibers. The vulnerability of the BN fiber interphase and the behavior of the fiber under conditions relevant to high-temperature turbine applications are discussed.     

Bimodal Microstructure in Silicon Nitride–Barium Aluminum Silicate Ceramic-Matrix Composites by Pressureless Sintering

A distinct bimodal microstructure has been obtained in a Si₃N₄–BAS (barium aluminum silicate) ceramic-matrix composite by pressureless sintering. It is shown that the addition of coarse β-Si₃N₄ seeds causes abnormal grain growth in this composite, and hence encourages the formation of a bimodal microstructure. This abnormal grain growth is due to the nature of the heterogeneous nucleation mechanism in Si₃N₄α-to-β phase transformation, and is promoted by the transformation. After complete phase transformation, further abnormal grain growth is comparably slow and governed by the Ostwald ripening mechanism. Therefore, a stable bimodal microstructure can be easily achieved by pressureless sintering.     

The use of electric potential drop techniques to detect delamination in a melt-infiltrated SiC-based composite

For composite systems where the matrix is electrically conductive, the possibility that the nature of electrical current flow in the composite can be used to detect defects such as out-of-plane delamination. Melt-infiltrated SiC-based composites are an ideal candidate material for such to verify this since the Si content of the matrix is the primary current carrier in the system. Two different potential drop techniques utilizing the four-point probe method were developed on a composite panel that had a large preexisting delamination defect that occurred during processing. The first technique incorporated current leads to supply current in a through-thickness manner and determine the nature of current spreading (voltage drop) some distance away from the current source to assess the location of the delamination. The other technique incorporated current leads in a more conventional manner to produce axial current flow and assessed the nature of current flow in between the current leads on both surfaces of the composite. In this way, in the presence of a delamination, current flow was forced to primarily flow on the side of the current leads. Both techniques were quite effective at locating the preexisting delamination in a panel of 2D woven Tyranno ZMI slurry-derived melt-infiltrated SiC composite.     

Thermogravimetry, Differential Thermal Analysis, and Mass Spectrometry Study of the Silicon Nitride–Boron Carbide–Carbon Reaction System for the Synthesis of Silicon Carbide–Boron Nitride Composites

Thermogravimetry, differential thermal analysis, mass spectrometry, and X-ray diffractometry were used to study the reaction process of the in situ reaction between Si₃N₄, B₄C, and carbon for the synthesis of silicon carbide–boron nitride composites. Atmospheres with a low partial pressure of nitrogen (for example argon + 5%–10% nitrogen) seemed to inhibit denitrification and also maintain a high reaction rate. However, the reaction rate decreased significantly in a pure nitrogen atmosphere. The experimental mass spectrometry results also revealed that B₄C in the Si₃N₄–B₄C–C system inhibited the reaction between Si₃N₄ and carbon and, even, the decomposition of Si₃N₄. The present results indicate that boron could be a composition stabilizer for ceramic materials in the Si-N-C system used at high temperature.     

Inverse Problem for Composites with Imperfect Interface: Determination of Interfacial Thermal Resistance, Thermal Conductivity of Constituents, and Microstructural Parameters

An explicit method is introduced to solve inverse problems for composites with imperfect interfaces. We apply the method to determine the thermal conductivity of constituents and the interfacial thermal resistance in SiC-particulate-reinforced aluminum-matrix composites and to estimate the whisker thermal conductivity, the interfacial thermal resistance, and the whisker alignment distribution in two types of SiC-whisker-reinforced lithium aluminosilicate glass-ceramic composites from their measured effective thermal conductivity reported in the literature. Certain bounds for these three properties of both SiC-whisker-reinforced glass-ceramic composites are obtained, and reasonable estimates for their exact values from room temperature to 500°C are made. The inverse problem is quite sensitive to noise in the measurements. We also comment on existing estimates.