Strength-Degrading Mechanisms for Chemically-Vapor-Deposited SCS-6 Silicon Carbide Fibers in an Argon Environment

The room-temperature tensile strengths of chemically-vapor-deposited SCS-6 silicon carbide fibers were measured after 1 to 400 h heat treatments in 0.1 MPa of argon at temperatures up to 2100°C. The fibers heat-treated for 1 h above 1400°C and those heat-treated for 400 h above 1300°C showed strength degradation. Scanning and transmission electron microscopic examination of the degraded fibers showed formation of a recrystallization region within the outer zone of the SiC sheath and the growth of SiC particles in the carbon-rich surface coating. The activation energy for the growth of the recrystallization region was ∼370 kJ/mol. The tensile strength of the fibers was found to vary as an inverse function of the recrystallized zone thickness.     

Monazite Coatings on SiC Fibers I: Fiber Strength and Thermal Stability

Commercially available SiC fibers were coated with monazite (LaPO₄) using a continuous vertical coater at 1100°C. Coated fibers were heat treated in dry air, argon, and laboratory air at 1200°C for 1–20 h. The tensile strengths of uncoated and coated fibers were measured and evaluated before and after heat treatment. Fiber coating did not degrade SiC fiber strength, but heat treatment afterwards caused significant degradation that correlated with silica scale thickness. Possible strength degradation mechanisms for the coated fibers are discussed. Coating morphology, microstructure, and SiC oxidation were observed with scanning electron microscopy and transmission electron microscopy. Monazite reacted with SiC to form lanthanum silicate (La₂Si₂O₇) in argon, but was stable with SiC in air. Despite the large coefficient of thermal expansion difference between monazite and SiC, micron thick monazite coatings did not debond from most types of SiC fibers. Possible explanations for the thermomechanical stability of the monazite fiber coatings are discussed.     

Zirconia–Silica–Carbon Coatings on Ceramic Fibers

Precursors for zircon–carbon mixtures were made to coat fibers for ceramic-matrix composites. Precursors were characterized using XRD, TGA, and DTA. Zircon formed from vanadium- or lithium-doped precursors after heat treatments at ≥900°C in air, but it did not form at 1200°–1400°C in argon when large amounts of carbon were added. Some precursors were used to coat Nextel™ 720 and Hi-Nicalon™ fibers. The coatings were characterized using SEM and TEM, and coated-fiber tensile strengths were measured. Although zircon formed in powders, only tetragonal-zirconia–silica mixed phases formed in fiber coatings at 1200°C in air. Loss of vanadium oxide flux to the fibers may have caused the lack of conversion to zircon. The strengths of the coated fibers were severely degraded after heat treatment at ≥1000°C in air, but not in argon. The coated fibers were compared with zirconia–carbon-coated fibers made using similar methods. Mechanisms for fiber strength degradation are discussed.     

Stress-Oxidation Behavior of a Carbon/Silicon Carbide Composite in a High-Temperature Combustion Environment

A carbon/silicon carbide composite with a silicon carbide coating was prepared by chemical vapor infiltration. Stressed oxidation testing was performed on the composites in a self-built high-temperature combustion environment. The gas in this environment contained oxygen, steam, carbon dioxide, and some nitrogen. Test conditions were controlled at temperatures of 1300°, 1500°, and 1800°C, and the stress was sustained at 40, 80, 120, 160, and 200 MPa. The effect of combustion environment and applied load on stress-oxidation behavior was discussed by analyzing the residual strength and weight loss. The morphology of the fracture surface of the tested specimens was observed by scanning electron microscopy. The high-temperature combustion environment and the high sustained stress above 80 MPa enhanced the material failure and led to strength reduction by determining crack openings and thus oxidation of fibers. However, sustained stress below 80 MPa resulted in no strength degradation after exposure for 10 min at 1500°C.     

Transverse Strength of SCS-6 Silicon Carbide Fibers

A diametral compression test was used to measure the transverse strength of SCS-6 SiC fibers before and after heat treatment. Subjecting fibers to diametral compression successfully produced transverse tensile failure in the form of fiber cracking along the same diametral plane in which the compressive load was applied. An analysis of the hoop stress along the diametral plane, in which the effects of the C core were included, showed that there is a large tensile hoop stress concentration in the SiC sheath at the interface between the C core and the SiC sheath, where the stress is 6.3 times greater than the stress present in a solid SiC fiber under identical loading. This high tensile hoop stress concentration promotes crack initiation near the core and significantly limits the capability of these fibers to withstand transverse compressive loading. The maximum tensile hoop stresses, located at the interface between the C core and SiC sheath, at the measured failure loads were 850 MPa for the as-received SCS-6 fiber and 1210 MPa for fibers exposed to a 1-h heat treatment at 1850°C in 138 MPa of Ar.     

Tensile Creep Behavior and Thermal Stability of Orthogonal Three-Dimensional Woven TyrannoTM ZMI Fiber/Silicon-Titanium-Carbon-Oxygen Matrix Composites

This article presents experimental results for tensile creep behavior of orthogonal three-dimensional woven Tyranno™ ZMI fiber/Si-Ti-C-O ceramic matrix composites at 1300°–1450°C in air. The composite contained Tyranno ZMI (56% silicon, 1% zirconium, 34% carbon, and 9% oxygen) fibers with a BN coating layer to improve interface properties, and it exhibited excellent tensile properties at elevated temperature in air. For creep stresses between 60 and 140 MPa, the creep rate decreased continuously with time, with no apparent steady-state regime observed at 1300°–1450°C. Under the test conditions, the microstructure of the Tyranno ZMI fiber and Si-Ti-C-O matrix was unstable, resulting in weight loss and SiC grain growth. As a result, the viscosity of the fiber and matrix increased, because increased viscosity caused a creep rate that continuously decreased, which made steady-state creep impossible under these conditions.     

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.     

Influence of Precursor Densification on Strength Retention of Zirconia-Coated Nextel™ 610 Fibers

Strength degradation of Nextel^™ 610 fibers by continuous liquid phase coating was investigated for four different zirconia precursors. The precursors differed regarding their chemical composition (with or without yttrium), phase composition (amorphous or crystalline), and decomposition behavior. Phase transformation and densification of the films were characterized and found to depend on the kind of precursor. Single fiber Weibull's strength was measured for calcination temperatures between 250° and 1150°C for all precursors. Each precursor had an individual degradation behavior. For an annealing temperature of 1150°C highly damaged (∼1600 MPa) and undamaged (>3300 MPa) fibers were obtained depending on the kind of precursor. Fiber degradation could be correlated to mechanical stresses. Stress concentration due to inhomogeneous film thickness distribution is proposed as the cause of fiber strength degradation. Full strength could be retained for porous coatings or coatings where stresses were reduced by phase transformation.     

Combined Effects of Exposure to Salt (NaCl) Water and Oxidation on the Strength of Uncoated and BN-Coated Nicalon™ Fibers

The environmental stability of uncoated and boron nitride-coated (BN-coated) Nicalon fiber has been investigated by studying the effect of annealing in air at 1000°C (2 h) on the strength of the fibers. The results imply that uncoated and BN-coated fibers both degrade in strength, with the BN-coated fiber suffering a higher strength loss. The degradation is significantly enhanced if the fibers are exposed to salt (NaCl) water prior to the air anneal, if the concentration of salt is >0.5 wt%. The BN-coated Nicalon fibers also have been studied at 800° and 900°C; the degradation in strength due to salt water exposure is greater at 800°C than that at 900° or 1000°C.     

Monazite Coatings on Fibers: I, Effect of Temperature and Alumina Doping on Coated-Fiber Tensile Strength

Monazite was continuously coated onto Nextel 720 fibers, using an aqueous precursor and in-line heat treatment at 900°–1300°C. Some experiments were repeated with alumina-doped precursors. Coated fibers were heat-treated for 100 h at 1200°C. Coatings were characterized by optical microscopy, scanning electron microscopy, and analytical transmission electron microscopy. Coated-fiber tensile strengths were measured by single-filament tensile tests. The precursors were characterized by X-ray diffractometry, differential thermal analysis/thermogravimetric analysis, and mass spectrometry. Coated-fiber tensile strength was lower for fibers coated at higher deposition temperatures. Heat treatment for 100 h at 1200°C decreased tensile strength further. The coatings were slightly phosphate-rich and enhanced alumina grain growth at the fiber surface, but phosphorus was not detected along the alumina grain boundaries. Fibers with alumina-doped coatings had higher tensile strengths than those with undoped coatings after heat treatment for 100 h at 1200°C. Alumina added as α-alumina particles gave higher strengths than alumina added as colloidal boehmite. Alumina doping slowed monazite grain growth and formed rough fiber–coating interfaces after 100 h of heat treatment at 1200°C. Possible relationships among precursor characteristics, coating and fiber microstructure development, and strength-degradation mechanisms are discussed in this paper.     

Effect of high-pressure vapor on the microstructure and mechanical properties of TiO2 continuous fibers

During the preparation of TiO₂ continuous fibers, the organic ligands of the precursor fibers are severely decomposed and generated a large amount of gas, which can reduce the fiber matrix strength. Tt is necessary to choose a suitable treatment strategy to avoid this and obtain high-quality TiO₂ continuous fibers. In this study, flexible continuous TiO₂ fibers with a diameter of about 30 μm were prepared using a high-pressure vapor pretreatment method. The high-pressure vapor pretreatment caused precursor hydrolysis, which promoted the decomposition of the organic ligands in a mild way and prevented fiber fracture caused by the violent oxidative decomposition. The crystallization temperature decreased by 120 °C because of the synergistic effects of vapor and pressure. The hydrolysis of the precursor and the reduction in the crystallization temperature were conducive to the formation of compact fibers with high strength. However, the presence of water vapor caused the fibers to undergo the dissolution-precipitation process simultaneously, forming a large number of defects, which was harmful to its strength. The sample 1501 composed of anatase and rutile showed the highest average tensile strength of 385 MPa because it had fewer defects than the other samples. Although the highest average tensile strength is lower than the reported value of 800 MPa, the method is easy to implement and solves the problem of organics decomposition, which is helpful for industrial preparation.     

Porous Yttrium Aluminum Garnet Fiber Coatings for Oxide Composites

A porous oxide fiber coating was investigated for Nextel^™ 610 fibers in an alumina matrix. Polymeric-solution-derived yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) with a fugitive carbon phase was used to develop the porous fiber coating. Ultimate tensile strengths of tows and minicomposites following heat treatments in argon and/or air were used to evaluate the effect of the porous fiber coating. The porous YAG fiber coatings did not reduce the strength of the tows when heated in argon, and they degraded tow strength by only ∼20% after heating in air at 1200°C for 100 h. Minicomposites containing porous YAG-coated fibers were nearly twice as strong as those containing uncoated fibers. However, after heating at 1200°C for 100 h, the porous YAG coatings densified to >90%, at which point they were ineffective at protecting the fibers, resulting in identical strengths for minicomposites with and without a fiber coating.     

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.     

Heat treatment effects on microstructure and properties of CVI SiC/SiC composites with Sylramic™-iBN SiC fibers

Chemical-vapor-infiltrated (CVI) SiC/SiC composites with Sylramic?-iBN SiC fibers and CVI carbon, BN, and a combination of BN/C interface coating were heat treated in 0.1-MPa argon or 6.9-MPa N₂ at temperatures to 1800 °C for exposure times up to 100 hr. The effects of thermal treatment on constituent microstructures, in-plane tensile properties, in-plane and through-the-thickness thermal conductivities, and creep behavior of the composites were investigated. Results indicate that heat treatment affected stoichiometry of the CVI SiC matrix and interface coating microstructure, depending on the interface coating composition and heat treatment conditions. Heat treatment of the composites with CVI BN interface in argon caused some degradation of in-plane properties due to the decrease in interface shear strength, but it improved creep resistance significantly. In-plane tensile property loss in the composites can be avoided by modifying the interface composition and heat treatment conditions.     

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.     

Degradation Studies of Thermoplastics Composites of Jute Fiber–Reinforced LDPE/Polycaprolactone Blends

This article reports the fabrication, properties, and degradation studies of jute fiber–reinforced thermoplastic polymers. One of the non-traditional outlets of jute fiber is in the area of fiber-reinforced composites. However, the major drawback associated with the application of jute fiber for this purpose is its high moisture regain. To impart hydrophobicity to the fibers and to concomitantly increase interfacial bond strength, which is a critical factor for obtaining better mechanical properties of composites, jute fibers were treated with benzoylchloride, Y-glycidoxytrimethoxysilane, and neo-alkoxy-tri(N-ethylenediamino)ethyltitanate. Such a treatment resulted in an increase in the diameter and denier of the treated fibers, and deterioration in the mechanical properties was observed. SEM studies revealed an increase in surface roughness after titanate and alkali treatment, which in turn increases interfacial bond strength. A series of low-density polyethylene (LDPE) blends with 5–20% (w/w) of poly(e-caprolactone) (PCL) and with/without treated and untreated jute fibers were prepared by using a single-screw extruder. LDPE modified by blending with PCL (80:20, wt/wt) was used as a thermoplastic matrix. Composites were fabricated by using 1-cm-long jute fibers; the weight fraction of unmodified fibers, silane-treated fibers, and titanate-treated fibers was varied from 0.05 to 0.13. An increase in weight fraction of fibers resulted in an increase in tensile strength and modulus and decrease in elongation at break. Thin sheets and dumbbells were used for enzymatic degradation tests. The degradation of the material was monitored by weight change and loss of mechanical properties. The enzymatic degradation in the presence of Pseudomonas cepacia lipase gave appreciable weight loss in PCL and blended materials.     

Combined Effect of Salt Water and High-Temperature Exposure on the Strength Retention of Nextel™720 Fibers and Nextel™720-Aluminosilicate Composites

The relative contribution of fiber strength loss to reported degradation in the mechanical behavior of Nextel^™720-aluminosilicate composites after exposure to salt fog (ASTM B117) was explored. Single filament tension tests were performed on Nextel^™720 (3M, Inc., Minneapolis, MN) fibers after immersion in NaCl solutions followed by high-temperature exposure in air. The results were compared with the behavior of control specimens which received high-temperature exposure but were not immersed in NaCl solution. There was no degradation in fiber strengths for NaCl solutions below 1 wt%. However, significant degradation was observed at 5 wt% NaCl upon exposure to temperatures between 900° and 1150°C, while no degradation was observed upon an exposure to 1200°C. The relative contribution of fiber strength loss to composite degradation was estimated as nearly 50%, indicating that both fibers and matrix/interface degrade from exposure to salt water. X-ray diffraction and transmission electron microscopy of the exposed fibers and composites were conducted to help rationalize the observations. Microstructure of degraded fibers showed presence of Na at grain boundaries near the surface, without any evidence of a crystalline phase, indicating weakening from segregation or formation of an amorphous phase. The degraded composites showed that matrix and fiber/matrix interfaces had Na rich regions/phases.     

Effects of Heat Treatments in HCl on the Fiber Bundle Strength of a Two-Phase Polycrystalline Oxide Fiber

The effects of heat treatments in air and in an HCl gas atmosphere on the strength of Nextel 720 fibers were investigated. These fibers were polycrystalline oxide fibers containing two phases: mullite and alumina. The fibers were heat treated in air and in HCl at 1200° and 1300°C for 1 h to simulate possible processing conditions for all-oxide ceramic fiber composites. These fibers were tested as bundles containing approximately 400 fibers, as supplied by the manufacturer. Tests with fibers in the as-received condition were also conducted for comparison. The as-received fibers had a bundle strength of approximately 1 GPa. Most of the fiber heat treatments appear to cause modest reductions in the average strength, although there was scatter in the results. Fibers heat treated in HCl at 1300°C did not appear to show a statistically significant reduction in strength, and suggest the suitability of this process for strengthening an all-oxide ceramic fiber composite. Examination of the fracture surfaces indicated that weld lines (at locations where the fibers were touching when the fibers were made) were the source of the critical flaws that caused fiber fracture. The possible effects of the heat treatments on the weld lines and the bundle strengths were discussed.     

Effect of Environment on the Stress-Rupture Behavior of a Carbon-Fiber-Reinforced Silicon Carbide Ceramic Matrix Composite

Stress-rupture tests were conducted in air, under vacuum, and in steam-containing environments to identify the failure modes and degradation mechanisms of a carbon-fiber-reinforced silicon carbide (C/SiC) composite at two temperatures, 600° and 1200°C. Stress-rupture lives in air and steam-containing environments (50–80% steam with argon) are similar for a stress of 69 MPa at 1200°C. Lives of specimens tested in a 20% steam/argon environment were about twice as long. For tests conducted at 600°C, composite life in 20% steam/argon was 30 times longer than life in air. Thermogravimetric analysis of the carbon fibers was conducted under conditions similar to the stress-rupture tests. The oxidation rate of the fibers in the various environments correlated with the composite stress-rupture lives. Examination of the failed specimens indicated that oxidation of the carbon fibers was the primary damage mode for specimens tested in air and steam environments at both temperatures.     

Mechanical Behavior of SiC(f)/SiC Composites and Correlation to in situ Fiber Strength at Room and Elevated Temperatures

Mechanical properties of Nicalon-fiber-reinforced silicon carbide matrix composites were evaluated, in flexure, at various temperatures ranging from ambient to 1300°C. First matrix cracking stress ranged from 250 to 280 MPa and was relatively insensitive to test temperature. The measured ultimate strength showed a small increase from a room-temperature value of 370 to 460 MPa at 800°C. Beyond 800°C, however, strength dropped to as low as 280 MPa at 1300°C. This decrease in ultimate strength at elevated temperatures is believed to be partly due to degradation of in situ Nicalon fiber strength. Scanning electron microscopy was employed to evaluate the in situ Nicalon fiber strengths via fracture mirror size measurements. Degradation of Nicalon fiber strength is attributed to thermal damage and to structural changes to the fiber at elevated temperatures. Measured values of ultimate strength of the composites were compared with predictions made on the basis of in situ fiber strength characteristics and an available analytical model.