Influence of Strong Fiber/Coating Interfaces on the Mechanical Behavior and Lifetime of Hi-Nicalon/(PyC/SiC)n/SiC Minicomposites

Hi-Nicalon fiber-reinforced silicon carbide matrix minicomposites (Hi-Nicalon/SiC) with nanoscale multilayered (PyC/SiC) _n fiber coatings (also referred to as interphases) have been manufactured via pressure pulse chemical vapor infiltration (P-CVI). Fiber/coating interfaces were strengthened by using treated fibers. The microstructures of the interphases as well as the propagation and deflection of cracks in the interfacial region were investigated by SEM and TEM. Interfacial shear stress was estimated using various methods based on either the width of hysteresis loops on unloading–reloading, crack spacing, or fitting of the force–deformation curve using a micromechanics-based model. Tensile behavior at room temperature and lifetime in static fatigue in air at 700°C were related to the interphase/interface characteristics.     

SiC/SiC minicomposites with structure-graded BN interphases

BN interphases in SiC/SiC minicomposites were produced by infiltration of fibre tows from BF₃–NH₃–H₂ gaseous system. During interphase one-step processing, the tow travels through a reactor containing a succession of different hot areas. By TEM characterization, the BN interphases were found to be made of a structural gradient: from isotropic to highly anisotropic. The very first coating is poorly organised and allows to protect the fibre from a further chemical attack by the reactant mixture. The minicomposites were tensile tested at room temperature with unloading-reloading cycles. The BN interphases act as mechanical fuses; the fibre/matrix bonding intensity ranges from weak to rather strong depending on the tow travelling rate during interphase infiltration. The specimen lifetimes at 700°C under a constant tensile loading were measured in dry and moist air. Compared to a pyrocarbon reference interphase, the BN interphases significantly improve the oxidation resistance of the SiC/SiC minicomposites.     

High-Temperature Oxidation of Boron Nitride: II, Boron Nitride Layers in Composites

The oxidation of BN composite interphases was examined with a series of model materials. Oxidation was examined in both low-water-vapor (∼20 ppm H₂O/O₂) environments at 900°C and high-water-vapor (1% and 10% H₂O/O₂) environments at 700° and 800°C. The low-water-vapor case was explored with layered BN/SiC materials. This case was dominated by borosilicate glass formation, and the 20 ppm water vapor gradually removed the boron from the glass, leaving a larger amount of SiO₂ than would be expected from simple SiC oxidation. Layered SiC/BN/SiC materials were also used to study low-water-vapor oxidation effects within the composite. The high-water-vapor case was explored with SiC/BN/SiC minicomposites, and it was dominated by volatilization of BN as HBO₂( g ), H₃BO₃( g ), and H₃B₃O₆( g ). A model for recession of the BN fiber coating was developed based on the gas-phase diffusion of these species out of the annular region around the SiC fiber and concurrent sealing of this annular region by oxidation.     

裂解碳包覆对SiC纳米纤维增强SiC陶瓷基复合材料性能的影响

以SiC纳米纤维(SiC_nf)为增强体,通过化学气相沉积在SiC纳米纤维表面沉积裂解碳(PyC)包覆层,并与SiC粉体、Al₂O₃-Y₂O₃烧结助剂共混制备陶瓷素坯,采用热压烧结工艺制备质量分数为10%的SiC纳米纤维增强SiC陶瓷基(SiC_nf/SiC)复合材料。研究了PyC包覆层沉积时间对SiC_nf/SiC陶瓷基复合材料的致密度、断裂面微观形貌和力学性能的影响。结果表明:在1 100 ℃下沉积60 min制备的PyC包覆层厚度为10 nm,且为结晶度较好的层状石墨结构;相比于纤维表面无包覆层的复合材料,复合材料的断裂韧性提高了35%,达到最大值(19.35±1.17) MPa·m^1/2,抗弯强度为(375.5±8.5) MPa,致密度为96.68%。复合材料的断裂截面可见部分纳米纤维拔出现象,但SiC_nf/SiC陶瓷基复合材料界面结合仍较强,纳米纤维拔出短,表现为脆性断裂。     

PyC interphase growth mechanism and control models of C/SiC composites

To better understand the pyrocarbon (PyC) interphase growth mechanism, a series of experiments was conducted on the PyC deposited on T-300™ and T-700™ carbon fibers by the chemical vapor infiltration (CVI) method. Nine groups of fabrication parameters were used to analyze the effects of deposition temperature, pressure, and residence time on the PyC interphase growth mechanism. Atomic force microscopy (AFM), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), Raman spectroscopy, and nanoindentation tests were performed to characterize the microstructures of carbon fibers and PyC interphase. The PyC interphase growth mechanism was discussed, and the relationships between the fabrication parameters, R (C₂/C₆) value, texture type, and interphase thickness were established through numerical simulations. The hardness and modulus of PyC for T-300™ and T-700™ carbon fibers were measured. The tensile behaviors of C/SiC minicomposites with medium and high textures PyC interphases were analyzed. The C/SiC composite with the medium texture PyC interphase possessed the higher fracture strength and failure strain with a longer fiber pullout length at the fracture surface.     

Al2O3─SiC Composites from Aluminosilicate Precursors

Al₂O₃ and SiC composite materials have been produced from mixtures of aluminosilicates (both natural minerals and synthetic) and carbon as precursor materials. These composites are produced by heating a mixture of kaolinite (or synthetic aluminosilicates) and carbon in stoichiometric proportion above 1550°C, so that only Al₂O₃ and SiC remain as the major phases. A similar process has also been used for synthesizing other composite powders having mixtures of Al₂O₃, SiC, TiC, and ZrO₂ in different proportions (all compounds together or selective mixtures of some of them), as desired. The microstructure of hot-pressed dense compacts, produced from these powders, revealed that the SiC phase is distributed very homogeneously, even occasionally within Al₂O₃ grains on a nanosize scale. The homogeneous distribution of SiC particles within the system produced high fracture toughness of the hot-pressed material (K_IC∼ 7.0 MPa · m^1/2) and having Vicker's hardness values greater than 2000 kgf/mm².     

Single- and Multilayered Interphases in SiC/SiC Composites Exposed to Severe Environmental Conditions: An Overview

Pyrocarbon (PyC), the common interphase for SiC/SiC, is not stable under severe environmental conditions. It could be replaced by boron nitride more resistant to oxidation but poorly compatible with nuclear applications. Other materials, such as ternary carbides seem promising but their use in SiC/SiC has not been demonstrated. The most efficient way to improve the behavior of PyC interphase in severe environments is to replace part of PyC by a material displaying a better compatibility, such as SiC itself. Issues related to the design and behavior of layered interphases are reviewed with a view to demonstrate their interest in high-temperature nuclear reactors.     

Evidence for Bulk Residual Stress Strengthening in Al2O3/SiC Nanocomposites

The fracture behavior of Al₂O₃/SiC nanocomposites has been studied as a function of the SiC volume fraction and compared to that of the pure Al₂O₃ matrix. A pronounced strengthening effect was only observed for materials with low SiC content (i.e., ≤10 vol%) although no evidence of concurrent toughening was found. Assessment of near-tip crack opening displacement (COD) could not experimentally substantiate significant occurrence of an elastic crack-bridging mechanism, in contrast with a recently proposed literature model. Quantitative fractography analysis indicated that transgranular crack propagation in Al₂O₃/SiC nanocomposites depends on the location of the SiC dispersoids within the matrix texture; the higher the fraction of transgranularly located dispersoids, the more transgranular the fracture mode. Experimental evidence of remarkably high residual stresses arising from thermal dilatation mismatch (upon cooling) between Al₂O₃ and SiC phases were obtained by fluorescence and Raman spectroscopy. A strengthening mechanism is invoked which merely arises from residual stress through strengthening of Al₂O₃ grain boundaries.     

Carbothermic Synthesis of Monodispersed Spherical Si3N4/SiC Nanocomposite Powder

The synthesis and structure of a monodispersed spherical Si₃N₄/SiC nanocomposite powder have been studied. The Si₃N₄/SiC nanocomposite powder was synthesized by heating under argon a spherical Si₃N₄/C powder. The spherical Si₃N₄/C powder was prepared by heating a spherical organosilica powder in a nitrogen atmosphere and was composed of a mixture of nanosized Si₃N₄ and free carbon particles. During the heat treatment at 1450°C, the Si₃N₄/C powder became a Si₃N₄/SiC composite powder and finally a SiC powder after 8 h, while retaining its spherical shape. The composition of the Si₃N₄/SiC composite powder changed with the duration of the heat treatment. The results of TEM, SEM, and selected area electron diffraction showed that the Si₃N₄/SiC composite powder was composed of homogeneously distributed nanosized Si₃N₄ and SiC particles.     

Carbon Interfacial Layers Formed by Oxidation of SiC in SiC/Ba-Stuffed Cordierite Glass-Ceramic Reaction Couples

Reaction couples between α-SiC and cordierite (2MgO·2Al₂O₃·5SiO₂═ Mg₂Al₄Si₅O₁₈) were prepared by sandwiching (and enclosing) SiC single crystals between plates of Ba-stuffed magnesium aluminosilicate (Ba-MAS) glass and hot-pressing; the Ba-MAS was subsequently crystallized at 1000° to 1200°C in argon or air. No reaction occurred at the SiC/Ba-MAS interfaces during hot-pressing, but crystallization heat treatments caused formation of amorphous carbon reaction layers at the SiC/cordierite interfaces, due to concurrent oxidation via the reaction SiC + O₂→ SiO₂+ C. The thickness of the carbon of the carbon layer was variable. These results suggest that formation of C layers at SiC/silicate interfaces in other composites (containing Nicalon fibers, for example) depends more on thermochemistry and less on the details of SiC nonstoichiometry than has heretofore been supposed.     

Oxidation of ZrB2–SiC: Influence of SiC Content on Solid and Liquid Oxide Phase Formation

The effect of SiC concentration on the liquid and solid oxide phases formed during oxidation of ZrB₂–SiC composites is investigated. Oxide-scale features called convection cells are formed from liquid and solid oxide reaction products upon oxidation of the ZrB₂–SiC composites. These convection cells form in the outermost borosilicate oxide film of the oxide scale formed on the ZrB₂–SiC during oxidation at high temperatures (≥1500°C). In this study, three ZrB₂–SiC composites with different amounts of SiC were tested at 1550°C for various durations of time to study the effect of the SiC concentration particularly on the formation of the convection cell features. A calculated ternary phase diagram of a ZrO₂–SiO₂–B₂O₃ (BSZ) system was used for interpretation of the results. The convection cells formed during oxidation were fewer and less uniformly distributed for composites with a higher SiC concentration. This is because the convection cells are formed from ZrO₂ precipitates from a BSZ oxide liquid that forms upon oxidation of the composite at 1550°C. Higher SiC-containing composites will have less dissolved ZrO₂ because they have less B₂O₃, which results in a smaller amount of precipitated ZrO₂ and consequently fewer convection cells.     

Influence of Interface Characteristics on the Mechanical Properties of Hi-Nicalon type-S or Tyranno-SA3 Fiber-Reinforced SiC/SiC Minicomposites

The tensile behavior of CVI SiC/SiC composites with Hi-Nicalon type-S (Hi-NicalonS) or Tyranno-SA3 (SA3) fibers was investigated using minicomposite test specimens. Minicomposites contain a single tow. The mechanical behavior was correlated with microstructural features including tow failure strength and interface characteristics. The Hi-NicalonS fiber-reinforced minicomposites exhibited a conventional damage-tolerant response, comparable to that observed on composites reinforced by untreated Nicalon or Hi-Nicalon fibers and possessing weak fiber/matrix interfaces. The SA3 fiber-reinforced minicomposites exhibited larger interfacial shear stresses and erratic behavior depending on the fiber PyC coating thickness. Differences in the mechanical behavior were related to differences in the fiber surface roughness.     

XPS Investigation of Si3N4/SiC Nanocomposites Prepared Using a Commercial Polymer

We have synthesized Si₃N₄/SiC nanocomposites using a commercial polymer. Formation behavior of SiC nanoparticles has been studied using X-ray photoelectron spectroscopy (XPS). Based on the XPS results, we concluded that SiC nanoparticles were formed by a chemical reaction of Si provided from Si₃N₄ with free carbon obtained by pyrolysis of a polymer around 1300°C. The presence of CN _x compounds in samples processed in an Ar atmosphere supported our explanation.     

Alumina Sol-Assisted Sintering of SiC—Al2O3 Composites

The composite sol—gel (CSG) technology has been utilized to process SiC—Al₂O₃ ceramic/ceramic particulate reinforced composites with a high content of SiC (up to 50 vol%). Alumina sol, resulting from hydrolysis of aluminum isopropoxide, has been utilized as a dispersant and sintering additive. Microstructures of the composites (investigated using TEM) show the sol-originating phase present at grain boundaries, in particular at triple junctions, irrespective of the type of grain (i.e., SiC or Al₂O₃). It is hypothesized that the alumina film originating from the alumina sol reacts with SiO₂ film on the surface of SiC grains to form mullite or alumina-rich mullite-glass mixed phase. Effectively, SiC particles interconnect through this phase, facilitating formation of a dense body even at very high SiC content. Comparative sinterability studies were performed on similar SiC—Al₂O₃ compositions free of alumina sol. It appears that in these systems the large fraction of directly contacting SiC—SiC grains prevents full densification of the composite. The microhardness of SiC—Al₂O₃ sol—gel composites has been measured as a function of the content of SiC and sintering temperature. The highest microhardness of 22.9 GPa has been obtained for the composition 50 vol% SiC—50 vol% Al₂O₃, sintered at 1850°C.     

Effects of the single layer CVD SiC interphases on the mechanical properties of the SiCf/SiC composites fabricated by PIP process

Owing to the degradation of the mechanical properties of the SiC fiber reinforced SiC matrix (SiCf/SiC) composites with the pyrocarbon (PyC) and BN interphases under oxidation environment and neutron irradiation, single layer SiC interphases prepared by chemical vapor deposition (CVD) process were employed to substitute for them. Effects of the CVD SiC interphases on the mechanical properties and interfacial characteristics of the SiCf/SiC composites fabricated by precursor infiltration and pyrolysis (PIP) process were investigated. Compared with the as-received SiCf/SiC composites, the SiCf/SiC composites with the single layer CVD SiC interphases exhibit an obvious toughened fracture behavior, the flexural strength of which is about 4 times that of the as-received SiCf/SiC composites. From the microstructural analysis, it can be confirmed that the SiC interphases play a key part in protecting the fibers from damage during composite preparation and weakening interfacial bonding, which can provide high in situ fiber strength and appropriate interfacial bonding strength for the SiCf/SiC composites.     

In-situ tensile damage and fracture behavior of PIP SiC/SiC minicomposites at room temperature

In-situ tensile damage and fracture behavior of original SiC fiber bundles, processed and uncoated SiC fiber bundles, SiC fiber bundle with PyC interphase, SiC/SiC minicomposites without/with PyC interphase are analyzed. Relationships between load-displacement curves, stress-strain curves, and micro damage mechanisms are established. A micromechanical approach is developed to predict the stress-strain curves of SiC/SiC minicomposites for different damage stages. Experimental tensile stress-strain curves of two different SiC fiber reinforced SiC matrix without/with interphase are predicted. Evolution of composite’s tangent modulus, interface debonding fraction, and broken fiber fraction with increasing applied stress is analyzed. For the BX™ and Cansas-3303™ SiC/SiC minicomposite with interphase, the composite’s tangent modulus decreased with applied stress especially approaching tensile fracture; the interface debonding fraction increased with applied stress, and the composite’s tensile fracture occurred with partial interface debonding; and the broken fiber fraction increased with applied stress, and most of fiber’s failure occurred approaching final tensile fracture.     

In Situ Processing and Properties of SiC/MoSi2 Nanocomposites

A novel concept for in situ processing of SiC/MoSi₂ nanocomposites has been developed that combines the pyrolysis of MoSi₂ particles coated with polycarbosilane and subsequent densification by hot pressing. After densification, a uniform dispersion of SiC particles is obtained in the MoSi₂ matrix. The strength at both room and elevated temperature is dramatically improved by the processing protocol employed. The average room-temperature flexural strength measured for the SiC/MoSi₂ nanocomposite was 760 versus 150 MPa for unreinforced MoSi₂. The average 1250°C flexural strength measured for the SiC/MoSi₂ nanocomposite was 606 versus 77 MPa for unreinforced MoSi₂.     

电泳沉积时间对SiC_f/SiC复合材料性能的影响

针对电泳沉积结合先驱体浸渍裂解的方法制备SiC_f/SiC复合材料过程,探讨沉积时间对SiC纤维及SiC_f/SiC复合材料性能的影响规律。实验结果得出:随电泳沉积时间的延长,SiC纤维逐渐被腐蚀,致使其单丝强度下降;而在SiC纤维表面覆盖PyC涂层可以有效地保护SiC纤维,由于悬浮液中的通电作用,Py C涂层与SiC纤维的界面结合强度略有降低,纤维单丝强度随电泳时间的延长先增大后减小。5 min的电泳沉积结合9个周期的PIP得到了SiC_f/SiC复合材料最大的弯曲强度为731 MPa,随后其力学性能随着沉积时间的延长先降低后略微回升;SiC_f/SiC复合材料的热导率随沉积时间的延长先增大后减小,10 min电泳沉积得到了常温下SiC_f/SiC复合材料的最大热导率为4.658 W/(m·K)(25℃)。     

Intragranular Particle Residual Stress Strengthening of Al2O3–SiC Nanocomposites

Al₂O₃/SiC ceramic nanocomposites were fabricated from nanocrystalline Al₂O₃ (10 nm in diameter) and SiC (15 nm in diameter) powders, and a theoretical model of intragranular particle residual stress strengthening was investigated. The SiC nanoparticles in the Al₂O₃ grains create a normal compressive stress at the grain boundaries and a tangential tensile stress in the Al₂O₃ grains, resulting in the "strengthening" of the grain boundaries and "weakening" of the grains. The model gives a good explanation of the experimental results of the authors and others which are difficult to be explained by the existing strengthening models, i.e. the maximum strength is normally achieved at about 5 vol% of SiC particles in the Al₂O₃–SiC ceramic nanocomposites. According to the model, there exists an optimum amount of SiC for strengthening, below which the grain boundaries are not fully "strengthened" and the fracture is mainly intergranular, above which the grains are "weakened" too much and the fracture is mainly transgranular, and at which the fracture is a mixture of intergranular and transgranular.     

Fabrication of Si3N4/SiC Composite by Reaction-Bonding and Gas-Pressure Sintering

Si₃N₄/SiC composite materials have been fabricated by reaction-sintering and postsintering steps. The green body containing Si metal and SiC particles was reaction-sintered at 1370°C in a flowing N₂/H₂ gas mixture. The initial reaction product was dominated by alpha-Si₃N₄. However, as the reaction processed there was a gradual increase in the proportion of β-Si₃N₄. The reaction-bonded composite consisting of alpha-Si₃N₄, β-Si₃N₄, and SiC was heat-treated again at 2000°C for 150 min under 7-MPa N₂ gas pressure. The addition of SiC enhanced the reaction-sintering process and resulted in a fine microstructure, which in turn improved fracture strength to as high as 1220 MPa. The high value in flexural strength is attributed to the formation of uniformly elongated β-Si₃N₄ grains as well as small size of the grains (length = 2 μm, thickness = 0.5 μm). The reaction mechanism of the reaction sintering and the mechanical properties of the composite are discussed in terms of the development of microstructures.