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.     

Effect of activation on boron nitride coating on carbon fiber

Boron nitride (BN) thin coating has been formed on the surface of chemically activated polyacrylonitrile (PAN) carbon fibers by dip coating method. The chemical activation of PAN fibers was carried out by two different chemicals, i.e. nitric acid (HNO₃) and silver nitrate (AgNO₃) solution. The chemical activation changes the surface properties, e.g. surface area and surface microstructure of the carbon fibers. These surface modifications ultimately influence properties of boron nitride coating on carbon fibers. The boron nitride coating on carbon fibers showed better crystallinity, strength and oxidation resistance when carbon fibers were activated by HNO₃. This improvement in strength and oxidation resistance is attributed to better crystallinity of boron nitride coating on HNO₃ activated PAN fibers.     

Influence of boron nitride nanotubes on the damage evolution of SiCf/SiC composites

As-grown and BN-coated boron nitride nanotubes (BNNTs) were incorporated into SiC_f/SiC composites to produce nanotube-based hierarchical composites. In-depth studies on damage evolution reveal that early damage development are delayed owing to the restriction effects on crack propagations from as-grown and BN-coated BNNTs. Moreover, this delay effect is more pronounced from BN-coated BNNTs because BN-coated BNNTs/matrix interfacial bonding strength is low. Final failure of composites with as-grown BNNTs still comes much earlier compared with virgin composite due to strong fibers/matrix bonding enhanced by as-grown BNNTs. This premature final failure is remedied in large part in composites with BN-coated BNNTs because fibers/matrix bonding enhanced by as-grown BNNTs is weaken after the deposition of an interphase on nanotube surface. Additionally, the type, the number and the released energy level of damage mechanisms during the whole damage evolution after the incorporation of as-grown and BN-coated BNNTs were also discussed elaborately compared with virgin composite.     

Microstructural Stability of Nicalon at 1000deg;C in Air after Exposure to Salt (NaCl) Water

When either uncoated or BN-coated Nicalon fibers are exposed to water saturated with NaCl before being annealed in air at 1000^deg;C, accelerated degradation of the structure of the fiber occurs. The fiber surface oxidizes to tridymite instead of vitreous silica, and the crystallites of SiC in Nicalon begin to grow. These findings suggest that prior exposure to salt water may cause appreciable debit in the mechanical strength of Nicalon fibers with time at 1000^deg;C in air .     

Carbothermal synthesis of boron nitride coating on PAN carbon fiber

Boron nitride (BN) thin coating has been formed on the surface of chemically activated polyacrylonitrile (PAN) carbon fiber by dip coating method. Dip coating was carried out in saturated boric acid solution followed by nitridation at a temperature of 1200 °C in nitrogen at atmospheric pressure to produce BN coating. Chemical activation improved surface area of PAN fiber which favours in situ carbothermal reduction of boric acid. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) have shown the formation of boron nitride. The X-ray photoelectron spectroscopy reveals that the coating forms a composite layer of carbon, BN/BO_xN_y and some graphite like BCN with local structure of B–N–C and B(N–C)₃. The oxidation resistance of the coated fiber was significantly higher than uncoated carbon fiber. Tensile strength measurement reveals that the BN coated fiber maintained 90% of its original strength. As compared to chemical vapor deposition (CVD), this process is simple, non-hazardous and is expected to be cost effective.     

Fatigue of three advanced SiC/SiC ceramic matrix composites at 1200°C in air and in steam

High‐temperature mechanical properties and tension‐tension fatigue behavior of three advanced SiC/SiC composites are discussed. The effects of steam on high‐temperature fatigue performance of the ceramic‐matrix composites are evaluated. The three composites consist of a SiC matrix reinforced with laminated, woven SiC (Hi‐Nicalon?) fibers. Composite 1 was processed by chemical vapor infiltration (CVI) of SiC into the Hi‐Nicalon? fiber preforms coated with boron nitride (BN) fiber coating. Composite 2 had an oxidation inhibited matrix consisting of alternating layers of silicon carbide and boron carbide and was also processed by CVI. Fiber preforms had pyrolytic carbon fiber coating with boron carbon overlay applied. Composite 3 had a melt‐infiltrated (MI) matrix consolidated by combining CVI‐SiC with SiC particulate slurry and molten silicon infiltration. Fiber preforms had a CVI BN fiber coating applied. Tensile stress‐strain behavior of the three composites was investigated and the tensile properties measured at 1200°C. Tension‐tension fatigue behavior was studied for fatigue stresses ranging from 80 to 160 MPa in air and from 60 to 140 MPa in steam. Fatigue run‐out was defined as 2 × 10⁵ cycles. Presence of steam significantly degraded the fatigue performance of the CVI SiC/SiC composite 1 and of the MI SiC/SiC composite 3, but had little influence on the fatigue performance of the SiC/SiC composite 2 with the oxidation inhibited matrix. The retained tensile properties of all specimens that achieved fatigue run‐out were characterized. Composite microstructure, as well as damage and failure mechanisms were investigated.     

Effect of Microstructure on the Mechanical Behavior of Continuous-Fiber-Reinforced Ceramic-Matrix Composites

The mechanical behavior of a unidirectional continuous-fiber ceramic-matrix composite (CFCMC) was correlated with matrix-rich channels in the microstructure. A large population of CFCMCs was prepared via alkoxide infiltration, which incorporated either uncoated Nicalon fibers (64 samples) or BN-coated fibers (118 samples). No structure/property correlation was observed for the uncoated composites, because of the uniformity of the microstructure. For the BN-coated composites, both the flexure strength and work of fracture (WOF) were correlated with oriented matrix-rich channels. The channels were <90 μm wide and were distributed throughout the cross section. The BN-coated CFCMCs exhibited laminate-like behavior: the strength was statistically higher when the channels were aligned parallel with the applied load and the WOF was statistically higher when the channels were perpendicular to the load. Grouping the specimens on the basis of channel orientation, relative to applied load, reduced the variance in strength and WOF. This categorization also resulted in consistent, predictable failure behavior. This observation implies that prior CFCMC data that do not consider microstructure orientation may show wider scatter in mechanical behavior than is warranted.     

Fabrication and Properties of Ceramic Composites with a Boron Nitride Matrix

Boron nitride (BN) matrix composites reinforced by a number of different ceramic fibers have been prepared using a low-viscosity, borazine oligomer which converts in very high yield to a stable BN matrix when heated to 1200°C. Fibers including Nicalon (SiC), FP (A1₂O₃), Sumica and Nextel 440 (Al₂O₃-SiO₂) were evaluated. The Nicalon/BN and Sumica/BN composites displayed good flexural strengths of 380 and 420 MPa, respectively, and modulus values in both cases of 80 GPa. On the other hand, FP/BN and Nextel/BN composites exhibited very brittle behavior. Nicalon fiber with a carbon coating as a buffer barrier improved the strength by 30%, with a large amount of fiber pullout from the BN matrix. In all cases except for Nicalon, the composites showed low dielectric constant and loss.     

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.     

Effect of Bridged Boron Nitride Coatings on the Flexure Behavior of a Unidirectional Ceramic-Fiber Ceramic-Matrix Composite

A series of 50 vol/% unidirectional Nicalon™ fiber/zirconium titanate matrix composites were fabricated by alkoxide infiltration of the fiber tows. The fibers had a thin, amorphous boron nitride coating that was either heavily or lightly bridged. The bridged coatings were a result of localized excess boron nitride deposits and had the effect of binding adjacent fibers at boron nitride nodules during the immersion process. The resultant composites contained matrix-rich ribbons, which exhibited laminate-like mechanical behavior reported previously. Highest strength was obtained when the composites were loaded parallel to the ribbon orientation, and highest toughness (WOF) was obtained when the composites were loaded perpendicular to the ribbons. The ribbon orientation had a more pronounced effect on composite behavior than the presence or lack of bridging boron nitride nodules. However, the bridging nodules altered the relative orientation of the matrix-rich ribbons during fabrication and, thus, the direction of optimal strength or toughness.     

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.     

Stress Rupture of an Enhanced Nicalon/Silicon Carbide Composite at Intermediate Temperatures

The stress rupture characteristics of an enhanced Nicalon/SiC composite at 900°C have been examined. This temperature has been identified as being in the regime wherein oxidation embrittlement is operative. The enhancement of the composite involves the use of a coating around the fiber tows, comprising a C-rich matrix and B-containing particulates. The efficacy of this oxidation protection scheme has been evaluated by comparing the stress rupture characteristics with those of both Nicalon/SiC composites without the enhancement and the fibers alone. Such comparisons indicate that a substantial portion of the strength loss is attributable to a degradation of the fibers, and that the performance of the enhanced material is marginally better than that of the reference (nonenhanced) composite. Moreover, at stress levels greater than the matrix cracking limit, oxidation embrittlement occurs rapidly and the rupture times (several hours) are short in relation to the targeted service lives of most ceramic composite components. The mechanisms associated with the embrittlement have been identified using scanning electron microscopy and Auger spectroscopy.     

Lifetime-Applied Stress Response in Air of a SiC-Based Nicalon-Fiber-Reinforced Composite with a Carbon Interfacial Layer: Effects of Temperature (300° to 1150°C)

The lifetimes in air as a function of applied flexure stress and temperature (300–1150°C) are described for a Si–O–C based (Nicalon) fiber plain-weave cloth reinforced SiC-matrix composite (∼7% closed porosity) with an ∼0.3 µm thick carbon interfacial layer. The measured lifetimes of both samples with and without an external SiC seal coating were similar and decreased with applied flexural stress (for stresses greater than ∼90 MPa) and with temperature. At temperatures of ≥600°C, the external CVD SiC coating had negligible effect on the lifetimes; however, at 425°C, a detectable improvement in the lifetime was observed with an external SiC coating. When the applied stress was decreased below an apparent "threshold stress" (e.g., ∼90 MPa) for tests conducted at temperatures ≤950°C, no failures were observed for times of ≥1000 h. Electron microscopy observations show that the interfacial carbon layer is progressively removed during tests at 425° and 600°C. In these cases, failure is associated with fiber failure and pullout. At 950° and 1150°C, the carbon interface layer is eliminated and replaced by a thick silica layer due to the oxidation of the Nicalon fiber and the SiC matrix. This results in embrittling the composite.     

High-Temperature Chemical Stability of Plasma-Sprayed Ca05Sr05Zr4P6O24 Coatings on Nicalon/SiC Ceramic Matrix Composite and Ni-Based Superalloy Substrates

The potential application of Ca05Sr05Zr4P6O24 (CS50) as a corrosion-resistant coating material for Si-based ceramics and as a thermal barrier coating material for Ni-based superalloys was explored. A ∼200 (xm thick CS50 coating was prepared by air plasma spray with commercially available powder. A Nicalon/SiC ceramic matrix composite and a Ni-based superalloy coated with a ∼200 (xm thick metallic bond coat layer were used as substrate materials. Both the powder and coating contained ZrP2O7 as an impurity phase, and the coating was highly porous as-deposited. The coating deposited on the Nicalon/SiC substrate was chemically stable upon exposure to air and Na2SO4/O2 atmospheres at 1000°C for 100 h. In contrast, the coating sprayed onto the superalloy substrate significantly reacted with the bond coat surface after similar oxidation in air.     

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).     

陶瓷基复合材料的界面相容性研究

有关陶瓷基复合材料（CMC）的界面问题已经得到广泛的重视。为了使材料达到一个很好的刚性，在纤维与基体之间保持尽量小的界面作用力对于陶瓷纤维增强Si-C-O复合材料是非常重要的。在纤维界面上涂层有利于减小它们之间相互作用，涂层处理后的Si-C-O复合材料的弯曲强度比一般无涂层的复合材料高5倍。在介质涂层、基体、以及涂层与纤维间的三相物质中避免化学反应的发生。目前，可利用化学相容性的原理对涂层纤维进行选择。     

Oxidation Behavior of Si-C-O Fibers (Nicalon) under Oxygen Partial Pressures from 102 to 105 Pa at 1773 k

Polycarbosilane-derived SiC fibers (Nicalon) were oxidized at 1773 K under oxygen partial pressures from 10² to 10⁵ Pa. The effect of oxygen partial pressure on the oxidation behavior of the Nicalon fibers was investigated by examining mass change, surface composition, crystal phase, morphology, and tensile strength. The Nicalon fibers were passively oxidized under oxygen partial pressures of >2.5 ×10² Pa and actively oxidized under an oxygen partial pressure of 10² Pa. Under oxygen partial pressures from 2.5 × 10² to 10³ Pa, active oxidation occurred at the earliest stage of oxidation, resulting in the formation of both a silica film and a carbon intermediate layer. Although the unoxidized core retained considerable levels of strength under the passive-oxidation condition, fiber strength was lost under the active-oxidation condition.     

Synthesis of Boron Nitride Coating on Carbon Nanotubes

A method to synthesize boron nitride coating on the surface of carbon nanotubes (nanofibers) without damaging the tube walls has been developed. A reaction between boric acid and ammonia was performed at moderate temperatures on the surface of carbon nanotubes to form boron nitride (BN) coatings. The surface structure of the carbon nanotubes significantly influences the morphology of the boron nitride coating. If the surface of the tubes is free of defects, highly crystallized insulating BN nanotubes can encapsulate carbon nanotubes. On the surface of carbon nanotubes with disordered wall structure, a polycrystalline BN sheath was produced.     

Carbothermal Synthesis of Al-O-N Coatings Increasing Strength of SiC Fibers

Non-bridging Al-O-N coatings have been synthesized on the surface of Tyranno ZMI SiC fibers by a low-cost carbothermal nitridation method. First, a nanoporous carbide-derived carbon (CDC) layer is produced on the surface of SiC fiber by the extraction of Si with chlorine; the CDC layer on the fiber is then infiltrated by AlCl₃ solution, and finally nitrided in ammonia at atmospheric pressure to produce the coating. The intermediate carbon layer acts as a template for the coating, facilitates the formation of aluminum oxynitride, and helps to build a strong bonding between the fiber and coating. Optimization of the process parameters led to a more than 65% improvement in the tensile strength (up to ∼5.1 GPa) and a three-time increase in the Weibull modulus for the fiber with 200 nm coating compared to the as-received fibers. The coated fiber exceeds the strength of all other small-diameter SiC fibers reported in the literature. Al-O-N coating may also provide oxidation protection for the fibers in high-temperature applications.     

Study on Tribological Properties of Carbon/Aramid Fabric Coatings Modified by Boron Nitride of Single Layer

Carbon/aramid fabric composite coatings modified with boron nitride of single layer were fabricated through a dip-coating method. The composite coatings were cured with successive heating processes in an oven. The friction and wear properties of those as-prepared coatings were studied on a block-on-ring tester. The obtained results showed that the wear life of the coatings increased obviously after inclusion of boron nitride of single layer; however, the values of friction coefficients of the coatings almost remained constant. The optimal loadings of boron nitride of single layer in our experiments was 5 wt.%, and the wear life of the modified coating increased by ca. 360% compared with that of pristine fabric composite coating. The worn morphology of the sliding surface for both pristine fabric coating and the composite coatings filled with boron nitride of single layer was discussed, and the wear mechanisms were illuminated.