Flexural Creep of Coated SiC-Fiber-Reinforced Glass-Ceramic Composites

This study reports the flexural creep behavior of a fiber-reinforced glass-ceramic and associated changes in micro-structure. SiC fibers were coated with a dual layer of SiC/BN to provide a weak interface that was stable at high temperatures. Flexural creep, creep-rupture, and creep-strain recovery experiments were conducted on composite material and barium-magnesium aluminosilicate matrix from 1000° to 1200°C. Below 1130°C, creep rates were extremely low (∼10⁻⁹ S⁻¹), preventing accurate measurement of the stress dependence. Above 1130°C, creep rates were in the 10⁻⁸ s⁻¹ range. The creep-rupture strength of the composite at 1100°C was about 75–80% of the fast fracture strength. Creep-strain recovery experiments showed recovery of up to 90% under prolonged unloading. Experimental creep results from the composite and the matrix were compared, and microstructural observations by TEM were employed to assess the effectiveness of the fiber coatings and to determine the mechanism(s) of creep deformation and damage.     

Influence of Stress Ratio on the Elevated-Temperature Fatigue of a Silicon Carbide Fiber-Reinforced Silicon Nitride Composite

The influence of stress ratio on the tensile fatigue behavior of a unidirectional SiC-fiber/Si₃N₄-matrix composite was investigated at 1200°C. Tensile stress ratios of 0.1, 0.3, and 0.5 were examined. Fatigue testing was conducted in air, at a sinusoidal loading frequency of 10 Hz. For peak fatigue stresses below the proportional limit of the composite (approximately 195 MPa at 1200°C) specimens survived 5 × 10⁶ cycles, independent of stress ratio. At peak stresses above the proportional limit, fatigue failures were observed; fatigue life decreased significantly as the stress ratio was lowered from 0.5 to 0.1. Creep appears to be the predominant damage mechanism which occurs during fatigue below the proportional limit. Both mechanical cycle-by-cycle fatigue damage and creep contribute to specimen failure at peak stresses above the proportional limit.     

Crack-Healing Behavior of Si3N4/SiC Ceramics under Cyclic Stress and Resultant Fatigue Strength at the Healing Temperature

Si₃N₄/SiC composite ceramics were sintered and subjected to three-point bending. A semi-elliptical surface crack of 100 μm surface length was made on each specimen. The crack-healing behavior under cyclic stress of 5 Hz, and resultant cyclic fatigue strengths at healing temperatures of 1100° and 1200°C, were systematically investigated. The main conclusions are as follows: (1) Si₃N₄/SiC composite ceramics have an excellent ability to heal a crack at 1100° and 1200°C. (2) This sample could heal a crack even under cyclic stress at a frequency of 5 Hz. (3) The crack-healed sample exhibited quite high cyclic fatigue strength at each crack-healing temperature, 1100° and 1200°C.     

Thermomechanical Fatigue Behavior of a Silicon Carbide Fiber-Reinforced Calcium Aluminosilicate Composite

Isothermal fatigue and in-phase thermomechanical fatigue (TMF) tests were performed on a unidirectional, continuous-fiber, Nicalon®-reinforced calcium aluminosilicate glass-ceramic composite ([O]_16, SiC/CAS-II). Monotonic tensile tests were performed at 1100°C (2012°F) and 100 MPa/s (14.5 ksi/s) to determine the material's ultimate strength (σ_ult) and proportional limit (σ_pl). Isothermal fatigue tests at 1100°C employed two loading profiles, a triangular waveform with ramp times of 60 s and a similar profile with a superimposed 60-s hold time at σ_max. All fatigue tests used a σ_max of 100 MPa (40% of σ_pl), R = 0.1. TMF loading profiles were identical to the isothermal loading profiles, but the temperature was cycled between 500° and 1100°C (932° and 2012°F). All fatigued specimens reached run-out (1000 cycles) and were tested in tension at 1100°C immediately following the fatigue tests. Residual modulus, residual strength, cyclic stress-strain modulus, and strain accumulation were all examined as possible damage indicators. Strain accumulation allowed for the greatest distinction to be made among the types of tests performed. Fiber and matrix stress analyses and creep data for this material suggest that matrix creep is the primary source of damage for the fatigue loading histories investigated.     

Elevated-Temperature-Delayed Failure of Alumina Reinforced with 20 vol% Silicon Carbide Whiskers

Alumina composites reinforced with 20 vol% SiC whiskers were exposed to applied stresses in four-point flexure at temperatures of 1000°, 1100°, and 1200°C in air for periods of up to 14 weeks. At 1000° and 1100°C, an "apparent" fatigue limit was established at stresses of ∼ 75% of the fast fracture strength. However, after long-term (>6 weeks) tests at 1100°C, some evidence of crack generation as a result of creep cavitation was detected. At 1200°C applied stresses as low as 38% of the 1200°C fracture strength were sufficient to promote creep deformation and accompanying cavitation and crack generation and growth resulting in failures in times of <250 h.     

Mechanical Behavior at 20° and 1200°C of Nicalon-Silicon-Carbide-Fiber-Reinforced Alumina-Matrix Composites

Tensile and fracture tests were conducted at 20° and 1200°C on a ceramic-matrix composite that was composed of an alumina (Al₂O₃) matrix that was bidirectionally reinforced with 37 vol% silicon carbide (SiC) Nicalon fibers. The composite presented nonlinear behavior at both temperatures; however, the strength and toughness were significantly reduced at 1200°C. In accordance with this behavior, matrix cracks were usually stopped or deflected at the fiber/matrix interface, and fiber pullout was observed on the fracture surfaces at 20° and 1200°C. The interfacial sliding resistance at ambient and elevated temperatures was estimated from quantitative microscopy analyses of the saturation crack spacing in the matrix. The in situ fiber strength was determined both from the defect morphology on the fibers and from the size of the mirror region on the fiber fracture surfaces. It was shown that composite degradation at elevated temperature was due to the growth of defects on the fiber surface during high-temperature exposure.     

Creep Deformation in an Alumina–Silicon Carbide Composite Produced via a Directed Metal Oxidation Process

Flexural creep studies were conducted in a commercially available alumina matrix composite reinforced with SiC particulates (SiC_p) and aluminum metal at temperatures from 1200° to 1300°C under selected stress levels in air. The alumina composite (5 to 10 μm alumina grain size) containing 48 vol% SiC particulates and 13 vol% aluminum alloy was fabricated via a directed metal oxidation process (DIMOX(tm))† and had an external 15 μm oxide coating. Creep results indicated that the DIMOX Al₂O₃–SiC_p composite exhibited creep rates that were comparable to alumina composites reinforced with 10 vol% (8 (μm grain size) and 50 vol% (1.5 μm grain size) SiC whiskers under the employed test conditions. The DIMOX Al₂O₃–SiC_p composite exhibited a stress exponent of 2 at 1200°C and a higher exponent value (2.6) at ≥ 1260°C, which is associated with the enhanced creep cavitation. The creep mechanism in the DIMOX alumina composite was attributed to grain boundary sliding accommodated by diffusional processes. Creep damage observed in the DIMOX Al₂O₃-SiC_p composite resulted from the cavitation at alumina two-grain facets and multiple-grain junctions where aluminum alloy was present.     

Mechanical Behavior and High-Temperature Performance of a Woven Nicalon™/Si-N-C Ceramic-Matrix Composite

A modern ceramic-matrix composite (CMC) has been extensively characterized for a high-temperature aerospace turbine-engine application. The CMC system has a silicon-nitrogen-carbon (Si-N-C) matrix reinforced with Nicalon fibers woven in a balanced eight-harness satin weave fabric. Tensile tests have demonstrated that this CMC exhibits excellent strength retention up to 1100°C. The room-temperature fatigue limit was 160 MPa, ∼80% of the room-temperature tensile strength. The composite reached run-out conditions under cyclic (10⁵ cycles at 1 Hz) and sustained tension (100 h) conditions at a stress of 110 MPa, which was ∼35 MPa above the proportional limits at temperatures up to 1100°C in air. At stress levels >110 MPa, cyclic loading at 1000°C caused a more severe reduction in life, based on time, compared with sustained tension. Further life degradation was observed in the 1000°C fatigue specimens that were exposed to a salt-fog environment. This degradation decreased the fatigue life ∼85% at the stress levels that were tested.     

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.     

Cyclic-Fatigue Behavior of SiC/SiC Composites at Room and High Temperatures

Tension-tension cyclic-fatigue tests of a two-dimensional-woven-SiC-fiber-SiC-matrix composite (SiC/SiC) prepared by chemical vapor infiltration (CVI) were conducted in air at room temperature and in argon at 1000°C. The cyclic-fatigue limit (10⁷ cycles) at room temperature was ∼160 MPa, which was ∼80% of the monotonic tensile strength of the composite. However, the fatigue limit at 1000°C was only 75 MPa, which was 30% of the tensile strength of the composite. No difference was observed in cyclic-fatigue life at room temperature and at 1000°C at stresses >180 MPa; however, cyclic-fatigue life decreased at 1000°C at stresses < 180 MPa. The fracture mode changed from fracture in 0° and 90° bundles at high stresses to fracture mainly in 0° bundles at low stresses. Fiber-pullout length at 1000°C was longer than that at room temperature, and, in cyclic fatigue, it was longer than that in monotonic tension. The decrease in the fatigue limit at 1000°C was concluded to be possibly attributed to creep of fibers and the reduction of the sliding resistance of the interface between the matrix and the fibers.     

Tensile Creep and Creep-Strain Recovery Behavior of Silicon Carbide Fiber/Calcium Aluminosilicate Matrix Ceramic Composites

The tensile creep and creep strain recovery behavior of 0° and 0°/90° Nicalon-fiber/calcium aluminosilicate matrix composites was investigated at 1200°C in high-purity argon. For the 0° composite, the 100-h creep rate ranged from approximately 4.6 × 10⁻⁹ s⁻¹ at 60 MPa to 2.2 × 10⁻⁸ s⁻¹ at 200 MPa. At 60 MPa, the creep rate of the 0°/90° composite was approximately the same as that found for the 0° composite, even though the 0°/90° composite had only one-half the number of fibers in the loading direction. Upon unloading, the composites exhibited viscous strain recovery. For a loading history involving 100 h of creep at 60 MPa, followed by 100 h of recovery at 2 MPa, approximately 27% of the prior creep strain was recovered for the 0° composite and 49% for the 0°/90° composite. At low stresses (60 and 120 MPa), cavities formed in the matrix, but there was no significant fiber or matrix damage. For moderate stresses (200 MPa), periodic fiber rupture occurred. At high stresses (250 MPa), matrix fracture and rupture of the highly stressed bridging fibers limited the creep life to under 70 min.     

Thermal Degradation of Fiber Coatings in Mullite-Fiber-Reinforced Mullite Composites

The thermal degradation behavior of single-layer BN and of double-layer BN/SiC chemically vapor-deposited fiber coatings in mullite-fiber-reinforced mullite composites was investigated by means of transmission electron microscopy after processing and heat treatment of the composites at 1000°, 1200°, and 1300°C for 6 h in air. The single-layer BN coatings were ˜0.7 mu m thick and consisted of turbostratic BN with (0001) basal planes lying parallel to the surfaces of the fibers plus nanosized areas that had no preferential orientation. This microstructure remained unchanged up to 1000°C; however, distinct coarsening of the randomly oriented BN crystallites occurred in the temperature range of 1000°-1200°C. The single-layer BN coatings were stable against oxidation, up to 1200°C. At higher temperatures, degradation of the coatings via oxidation occurred. Double-layer BN/SiC coating systems consisted of BN that was 0.08 mu m thick and SiC layers that were 0.16 mu m thick and deposited onto the mullite fibers. The turbostratic BN was highly anisotropic and did not undergo any microstructural change, up to 1300°C. The outer SiC layer of the double-layer coating system improved the oxidation resistance of BN in the 1200°-1300°C temperature range, despite a partial oxidation of SiC to SiO₂.     

Influence of Dopant Concentration on Creep Properties of Nd2O3-Doped Alumina

The microstructural features and tensile creep behavior of Al₂O₃ doped with Nd₂O₃ at levels ranging from 100 to 1000 ppm (Nd:Al atomic ratio) were systematically investigated. Compositional mapping, using both high-resolution scanning transmission electron microscopy and secondary ion mass spectroscopy revealed that, for all of the compositions studied, the Nd³⁺ ions were strongly segregated to the Al₂O₃ grain boundaries. Microstructural observations revealed that the solubility of Nd₂O₃ was between 100 and 350 ppm. Tensile creep tests were conducted over a range of temperatures (1200°–1350°C) and stresses (20–75 MPa). Both the stress and grain-size exponents were analyzed. In selected experiments, controlled grain-growth anneals were used to enable creep testing of samples of the same average grain size but different neodymium concentrations. Independent of dopant level, the neodymium additions decreased the creep rate by 2–3 orders of magnitude, compared with that of undoped Al₂O₃. The value of the apparent creep activation energy increased with increased dopant concentration and then saturated at dopant levels exceeding the solubility limit. Overall, the results of the present study were consistent with a creep-inhibition mechanism whereby oversized segregant ions reduce grain-boundary diffusivity by a site-blocking mechanism.     

Intermediate-Temperature Environmental Effects on Boron Nitride-Coated Silicon Carbide-Fiber-Reinforced Glass-Ceramic Composites

The environmental effects on the mechanical properties of fiber-reinforced composites at intermediate temperatures were investigated by conducting flexural static-fatigue experiments in air at 600° and 950°C. The material that was studied was a silicon carbide/boron nitride (SiC/BN) dual-coated Nicalon-fiber-reinforced barium magnesium aluminosilicate glass-ceramic. Comparable time-dependent failure responses were found at 600° and 950°C when the maximum tensile stress applied in the bend bar was 60% of the room-temperature ultimate flexural strength of as-received materials. At both temperatures, the materials survived 500 h fatigue tests at lower stress levels. Among the samples that survived the 500 h fatigue tests, a 20% degradation in the room-temperature flexural strength was measured in samples tested at 600°C, whereas no degradation was observed for the samples tested at 950°C. Microstructure and chemistry studies revealed interfacial oxidation in the samples that were fatigued at 600°C. The growth rate of the Si-C-O fiber oxidation product at 600°C was not sufficient to seal the stress-induced cracks, so that the interior of the material was oxidized and resulted in a strength degradation and less fibrous fracture. In contrast, the interior of the material remained intact at 950°C because of crack sealing by rapid silicate formation, and strength/toughness of the composite was maintained. Also, at 600°C, BN oxidized via volatilization, because no borosilicate was formed.     

Preparation of Dispersed Phase Ceramic Boron Nitride and Aluminum Nitride Composite Coatings by Chemical Vapor Deposition

Dispersed phase ceramic composite coatings containing BN and AIN were prepared by chemical vapor deposition. The BN + AIN coatings were deposited on Al₂O₃ from the BCI₃–AICI₃-NH₃ reagent system in the temperature range of 700° to 1200°C. Also, single-phase BN and AIN coatings were prepared for comparison purposes. The composite coatings consisted of very small BN and AIN regions which were either crystalline or amorphous, depending on deposition temperature and reagent concentrations. For example, a composite containing AlN whiskers of less than 100-nm diameter in a matrix of turbostratic BN of 2-nm grain size was deposited at 1100°C and 20 kPa.     

Static Fatigue Limit for Sintered Silicon Carbide at Elevated Temperatures

The modified static loading technique for estimating static fatigue limits was used to study the effects of oxidation and temperature on the static fatigue limit, K ₁₀ for crack growth in sintered silicon carbide. For as-machined, unoxidized sintered silicon carbide with a static load time of 4 h, K ₁₀× 2.25 MPa * m^1/2 at 1200° and ∼1.75 at 1400°C. On oxidation for 10 h at 1200°C, K ₁₀ drops to ∼1.75 MPam^1/2 at 1200° and ∼1.25 at 1400°C when tested in a nonoxidizing ambient. Similar results were obtained at 1200°C for tests performed in air. A tendency for strengthening below the static fatigue limit appears to result from plastic relaxation of stress in the crack-tip region by viscous deformation involving an oxide grain-boundary phase for oxidized material and, possibly, diffusive creep deformation in the case of unoxidized material.     

Flexural Creep Deformation of ZrB2/SiC Ceramics in Oxidizing Atmosphere

Flexural creep of ZrB₂/0–50 vol% SiC ceramics was characterized in oxidizing atmosphere as a function of temperature (1200°–1500°C), stress (30–180 MPa), and SiC particle size (2 and 10 μm). Creep behavior showed strong dependence on SiC content and particle size, temperature and stress. The rate of creep increased with increasing SiC content, temperature, and stress and with decreasing SiC particle size, especially, at temperatures above 1300°C. The activation energy of creep showed linear dependence on the SiC content increasing from about 130 to 511 kJ/mol for ceramics containing 0 and 50 vol% 2-μm SiC, respectively. The stress exponent was about 2 for ZrB₂ containing 50 vol% SiC regardless of SiC particle size, which is an indication that the leading mechanism of creep for this composition is sliding of grain boundaries. Compared with that, the stress exponent is about 1 for ZrB₂ containing 0–25vol% SiC, which is an indication that diffusional creep has a significant contribution to the mechanism of creep for these compositions. Cracking and grain shifting were observed on the tensile side of the samples containing 25 and 50 vol% SiC. Cracks propagate through the SiC phase confirming the assumption that grain-boundary sliding of the SiC grains is the controlling creep mechanism in the ceramics containing 50 vol% SiC. The presence of stress, both compressive and tensile, in the samples enhanced oxidation.     

Thermal stability of CVI and MI SiC/SiC composites with Hi-Nicalon™-S fibers

The influence of high-temperature argon heat-treatment on the microstructure and room- temperature in-plane tensile properties of 2D woven CVI and 2D unidirectional MI SiC/SiC composites with Hi-Nicalon?-S SiC fibers was investigated. The 2D woven CVI SiC/SiC composites were heat-treated between 1200 and 1600 °C for 1- and 100-hr, and the 2D unidirectional MI SiC/SiC composites between 1315 and 1400 °C for up to 2000 hr. In addition, the influence of temperature on fast fracture tensile strengths of these composites was also measured in air. Both composites exhibited different degradation behaviors. In 2D woven CVI SiC/SiC composites, the CVI BN interface coating reacted with Hi-Nicalon?-S SiC fibers causing a loss in fast fracture ultimate tensile strengths between 1200 and 1600 °C as well as after 100-hr isothermal heat treatment at temperatures > 1100 °C. In contrast, 2D unidirectional MI SiC/SiC composites showed no significant loss in in-plane tensile properties after the fast fracture tensile tests at 1315 °C. However, after isothermal exposure conditions from 1315° to 1400°C, the in-plane proportional limit stress decreased, and the ultimate tensile fracture strain increased with an increase in exposure time. The mechanisms of strength degradation in both composites are discussed.     

Stress Rupture in Tension and Flexure of a SiC-Whisker-Reinforced Silicon Nitride Composite at Elevated Temperatures

Stress rupture of a 20 vol% SiC whisker-reinforced Si₃N₄ composite processed by gas pressure sintering was investigated by both tension and flexure methods. The stress exponents for the stress rupture decrease with increasing temperature. The fracture surfaces of both tensile and flexural stress rupture at 1000°C consist of mirror, mist, and hackle regions. The size of the mirror region increases with decreasing stress. Crack propagation is a mixture of intergranular and transgranular modes at 1000°C. Both tensile and flexural fracture surfaces under constant stress at 1200°C were characterized by a rough zone and a mirror zone; the size of the rough zone increased with decreasing stress. Creep crack growth occurred at 1200°C, which is a process of cavity nucleation, growth, and interlinkage in front of a crack. The transition of fracture mechanisms with temperature is discussed.     

Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy Study of Nonstoichiometric Silicon-Carbon-Oxygen Glasses

Crystallization behavior of Si-C-O glasses in the temperature range of 1000°–1400°C was investigated using transmission electron microscopy (TEM) in conjunction with electron energy-loss spectroscopy (EELS). Si-C-O glasses were prepared by pyrolysis of polysiloxane networks obtained from homogeneous mixtures of triethoxysilane, T^H, and methyldiethoxysilane, D^H. Si-C-O glass composition depended on the molar ratio of the precursors utilized. At a ratio of T^H/D^H= 1, the formation of a carbon-rich glass was observed, whereas a ratio of T^H/D^H= 9 yielded a Si-C-O glass with excess free silicon. Both materials were amorphous at 1000°C, but showed a distinct difference in crystallization behavior on annealing at high temperature. Although T^H/D^H= 1 revealed a small volume fraction of SiC precipitates in addition to a very small amount of residual free carbon at 1400°C, T^H/D^H= 9 showed, in addition to SiC crystallites, numerous larger silicon precipitates (20–50 nm), even at 1200°C. Both materials underwent a phase separation process, SiC _x O_2(1-x)→ x SiC + (1 - x )SiO₂, when annealed at temperatures exceeding 1200°C.