Microstructure and tensile behavior of (BN/SiC)n coated SiC fibers and SiC/SiC minicomposites

Interphase plays an important role in the mechanical behavior of SiC/SiC ceramic-matrix composites (CMCs). In this paper, the microstructure and tensile behavior of multilayered (BN/SiC)_n coated SiC fiber and SiC/SiC minicomposites were investigated. The surface roughness of the original SiC fiber and SiC fiber deposited with multilayered (BN/SiC), (BN/SiC)₂, and (BN/SiC)₄ (BN/SiC)₈ interphase was analyzed through the scanning electronic microscope (SEM) and atomic force microscope (AFM) and X-ray diffraction (XRD) analysis. Monotonic tensile experiments were conducted for original SiC fiber, SiC fiber with different multilayered (BN/SiC)_n interfaces, and SiC/SiC minicomposites. Considering multiple damage mechanisms, e.g., matrix cracking, interface debonding, and fibers failure, a damage-based micromechanical constitutive model was developed to predict the tensile stress-strain response curves. Multiple damage parameters (e.g., matrix cracking stress, saturation matrix crack stress, tensile strength and failure strain, and composite’s tangent modulus) were used to characterize the tensile damage behavior in SiC/SiC minicomposites. Effects of multilayered interphase on the interface shear stress, fiber characteristic strength, tensile damage and fracture behavior, and strength distribution in SiC/SiC minicomposites were analyzed. The deposited multilayered (BN/SiC)_n interphase protected the SiC fiber and increased the interface shear stress, fiber characteristic strength, leading to the higher matrix cracking stress, saturation matrix cracking stress, tensile strength and fracture strain.     

Oxidation of SiC/BN/SiC ceramic matrix composites in dry and wet oxygen at intermediate temperatures

The oxidation behavior of SiC/BN/SiC ceramic matrix composites (CMCs) was evaluated from 400° to 800 °C in 100% O₂ and 50% H₂O/50% O₂ gas mixtures. Thermogravimetric analysis (TGA) was utilized to measure weight change during controlled environment exposures at elevated temperatures for 1 and 50 hours. Oxidized CMCs and their oxides were studied post-exposure with scanning electron microscopy and energy dispersive spectroscopy. The oxidation onset and composition transition temperatures were evaluated. Key observations include oxide composition, oxide wetting, oxygen solubility in Hi-Nicalon SiC fibers and BN fiber coating oxidation and volatility behavior as a function of temperature. Degradation in wet environments at 600 °C was most extensive due to the formation of a non-wetting, non-protective surface oxide, allowing oxidant access to the BN fiber coatings followed by oxidation and volatilization. Implications of the CMC oxidation behavior are discussed for CMCs in service.     

2D-SiC/SiC陶瓷基复合材料的拉伸本构模型研究

通过单向拉伸试验,研究了2D-SiC/SiC复合材料的应力-应变行为.结果表明,材料单向拉伸应力-应变曲线表现出明显的双线性特征,且线弹性段较长.通过试件断口照片,分析了2D-SiC/SiC复合材料单向拉伸破坏机理和损伤模式.基于对损伤过程的假设,建立了二维连续纤维增强陶瓷基复合材料的双线性本构模型,并将其应用于2D-SiC/SiC复合材料的应力-应变曲线模拟,模拟结果与试验值吻合很好.同时,分析计算表明,2D-SiC/SiC复合材料的单轴拉伸行为主要由纵向纤维柬决定,横向纤维对材料的整体模量和强度贡献很小.     

Microstructure and strengthening behavior in high content SiC nanowires reinforced SiC composites

In this study, the high-content SiC_nw reinforced SiC ceramic matrix composites (SiC_nw/SiC CMC) were successfully fabricated by hot pressing β-SiC and sintering additive (Al₂O₃-Y₂O₃) with boron nitride interphase modification SiC_nw. The effects of sintering additive content and mass fraction (5–25 wt%) of SiC_nw on the density, microstructure, and mechanical properties of the composites were investigated. The results showed that with the increase of sintering additives from 10 wt% to 12 wt%, the relative density of the SiC_nw/SiC CMC increased from 97.3% to 98.9%, attributed to the generated Y₃Al₅O₁₂ (YAG) liquid phase from the Al₂O₃-Y₂O₃ that promotes the rearrangement and migration of SiC grains. The comprehensive performance of the obtained composite with 15 wt% SiC_nw possessed the optimal flexural strength and fracture toughness of 524 ± 30.24 MPa and 12.39 ± 0.49 MPa·m^1/2, respectively. Besides, the fracture mode of the composites with 25 wt% SiC_nw content revealed a pseudo-plastic fracture behavior. It concludes that the 25 wt% SiC_nw/SiC CMC was toughened by the fiber pull-outs, debonding, bridging, and crack deflection that can consume plenty of fracture energy. The strategy of SiC nanowires worked as a main bearing phase for the fabrication of SiC/SiC CMC providing critical information for understanding the mechanical behavior of high toughness and high strength SiC nanoceramic matrix composites.     

Interaction of fiber matrix bonding in SiC/SiC ceramic matrix composites

Non-oxide ceramic matrix composites (CMC) based on SiC fibers with SiC matrix were fabricated by polymer infiltration and pyrolysis (PIP) and characterized regarding their microstructural features and their mechanical properties. The fiber preform was made using winding technology. During the winding process, the SiC fiber roving was impregnated by a slurry containing SiC powder and sintering additives (Y₂O_3, Al₂O₃ and SiO₂). This already helped to achieve a partial matrix formation during the preform fabrication. In this way, the number of PIP cycles to achieve composites with less than 10% open porosity could be reduced significantly. Additionally, damage-tolerant properties of the composites were obtained by an optimal design of the matrix properties although only uncoated fibers were used. Finally, composites with a strength level of about 500 MPa and a damage-tolerant fracture behavior with about 0.4% strain to failure were obtained.     

Significant improvement of resistance to dry/water oxygen corrosion at medium and high temperatures of SiC/SiC composites upon matrix modification by Ca-Y-Al-Si-O microcrystalline glass

Matrix modification is of great significance for the densification of CVI-SiC/SiC, as well as the improvement of self-healing and oxidation resistance. A eutectic component of Y₂O₃-Al₂O₃-SiO₂ system modified with CaO (CYAS) was used in this study to modify SiC/SiC at 1400 °C. The oxidation behaviour of the composites was investigated under dry/water oxygen atmosphere at 900 °C and 1300 ℃. Compared to the relatively dense SiC/SiC, the modified SiC/SiC showed a slight increase in flexural strength and fracture toughness at room temperature, as well as a significant increase in oxidation resistance and densification. Our work provides a low-cost, simple-to-operate, short-cycle densification method for CVI-SiC/SiC composites that increases their oxidation resistance without compromising their mechanical properties at room temperature.     

Effect of oxidation treatment on KD–II SiC fiber–reinforced SiC composites

Continuous silicon carbide fiber–reinforced silicon carbide matrix (SiC_f/SiC) composites have developed into a promising candidate for structural materials for high–temperature applications in aerospace engine systems. This is due to their advantageous properties, such as low density, high hardness and strength, and excellent high temperature and oxidation resistance. In this study, SiC_f/SiC composites were fabricated via polymer infiltration and pyrolysis (PIP) with the lower–oxygen–content KD–II SiC fiber as the reinforcement; a mixture of 2,4,6,8–tetravinyl–2,4,6,8–tetramethylcyclotetrasiloxane (V4) and liquid polycarbosilane (LPCS), known as LPVCS, was used as the precursor; while pyrolytic carbon (PyC) was used as the interface. The effects of oxidation treatment at different temperatures on morphology, structure, composition, and mechanical properties of the KD–II SiC fibers, SiC matrix from LPVCS precursor conversion, and SiC_f/SiC composites were comprehensively investigated. The results revealed that the oxidation treatment greatly impacted the mechanical properties of the SiC fiber, thereby significantly influencing the mechanical properties of the SiC_f/SiC composite. After oxidation at 1300 °C for 1 h, the strength retention rates of the fiber and composite were 41% and 49%, respectively. In terms of the phase structure, oxidation treatment had little effect on the SiC fiber, while greatly influencing the SiC matrix. A weak peak corresponding to silica (SiO₂) appeared after high–temperature treatment of the fiber; however, oxidation treatment of the matrix led to the appearance of a very strong diffraction peak that corresponds to SiO₂. The analysis of the morphology and composition indicated cracking of the fiber surface after oxidation treatment, which was increasingly obvious with the increase in the oxidation treatment temperature. The elemental composition of the fiber surface changed significantly, with drastically decreased carbon element content and sharply increased oxygen element content.     

SiC/SiC mini-composites with yttrium disilicate fiber coatings: Oxidation in steam

Solutions of YPO₄ were used to precipitate YPO₄ on pre-oxidized Hi-Nicalon-S SiC fibers. Tows of the coated fibers were then infiltrated with a preceramic polymer loaded with SiC particles to form mini-composites. During pyrolysis of the matrix, SiO₂ and YPO₄ on the fibers reacted and formed a Y₂Si₂O₇ fiber matrix interphase. Mini-composites were exposed to steam at 1000 °C for 10, 50, and 100 h, tensile tested, and the effect of oxidation in steam on the functionality of the Y₂Si₂O₇ fiber coating was investigated. The minicomposites oxidized at 1000 °C for 10 h retained 100 % of their unoxidized strength, and those oxidized for 50 and 100 h retained 92 % and 90 % of unoxidized strength, respectively. Strength retention and fiber pullout in both unoxidized and oxidized minicomposites suggests that the Y₂Si₂O₇ interphase was effective in maintaining a weak fiber-matrix interface.     

Microstructure and corrosion behavior of in-situ grown Y3Si2C2 coated SiC fibers exposed to air and wet-oxygen at 1400 ℃

Y₃Si₂C₂ ternary ceramics were in-situ grown on the third-generation Chinese commercial SiC fiber (KD-SA SiC fiber) surface via molten salt method. Microstructures and oxidation/corrosion behavior of in-situ grown Y₃Si₂C₂ coated SiC fibers exposed to air and wet-oxygen at 1400 ℃ were investigated. Results indicated that the layered Y₃Si₂C₂ slices with thickness of approximately 15 nm can be successfully in-situ grown on SiC fibers. The product on the fibers surface after oxidation/corrosion at 1400 ℃ for 1 h in both ambient air and wet-oxygen are Y₂Si₂O₇ and SiO₂. Moreover, microstructural characterization indicates that the immigration and expansion of gaseous bubbles induced by oxidation product, mainly CO, result in microstructural differences of SiC fiber specimens, and finally oxidation mechanism based on the microstructural difference were proposed.     

Mechanical properties and microstructural evolution of Cansas-III SiC fibers after thermal exposure in different atmospheres

Cansas-III SiC fibers were exposed in argon, air and wet oxygen (12%H₂O+8%O₂+80%Ar) atmospheres for 1 h at 1000–1500 °C. The pristine fiber consisted of β-SiC, free carbon and SiC_xO_y phases. After exposure in air and wet oxygen, an amorphous SiO₂ layer with embedding α-cristobalite crystals formed, while stacking faults were generated in the SiC core to release the residual stress. With the increasing oxidation temperature, lots of pores formed in the oxide layer, accompanied with the thickening, cracking and spallation of oxide layer. The average tensile strength decreased with the exposure temperature increasing and the exposure atmosphere deteriorating (argon→air→wet oxygen). After exposure at 1400 °C in argon and air, the fiber strength retention rates were 84% and 70%, respectively. However, after exposure at 1300 °C in wet oxygen, the strength retention rate was only 51%, indicating the accelerating oxidation and severe strength degradation of fibers.     

Anomalous oxidation behaviour of pressureless liquid-phase-sintered SiC

The oxidation behaviour of pressureless liquid-phase-sintered (PLPS) SiC, an important non-oxide engineering ceramic, was investigated, and was found to be universally anomalous. Thermogravimetry oxidation tests performed in oxygen in the temperature range 1000-1225 °C on three PLPS SiC ceramics fabricated with different combinations of Al₂O₃-RE₂O₃ (RE = Gd, Sc, or Sm) as sintering aids indicated that the oxidation is in all cases passive and protective, but unexpectedly anomalous in the sense that the oxidation resistance does not scale inversely with temperature. In particular, in all cases it was observed that there is less oxidation above 1100 °C than below, in clear contradiction to the expectation for a diffusional process. Exhaustive characterization of the oxide scales by scanning electron microscopy, X-ray energy dispersive spectrometry, and X-ray diffractometry, together with detailed modeling of the oxidation curves, showed that the origin of this universal anomalous oxidation behaviour lies in the marked crystallization within the oxide scale of rare-earth silicates that act as effective barriers against the inward diffusion of oxygen thus improving notably the oxidation resistance. A strategy is proposed to provide PLPS SiC, and probably other SiO₂-scale-forming ceramics that are sintered using rare-earth oxides, with the superior oxidation resistance at moderate temperatures (i.e., <1100 °C) that they do not currently have.     

Modeling environmentally induced property degradation of SiC/BN/SiC ceramic matrix composites

The degradation of SiC‐based ceramic matrix composites (CMCs) in conditions typical of gas turbine engine operation proceeds via the stress rupture of fiber bundles. The degradation is accelerated when oxygen and water invade the composite through matrix microcracks and react with fiber coatings and the fibers themselves. We review micromechanical models of the main rate‐determining phenomena involved, including the diffusion of gases and reaction products through matrix microcracks, oxidation of SiC (in both matrix and fibers) leading to the loss of stiffness and strength in exposed fibers, the formation of oxide scale on SiC fiber and along matrix crack surfaces that cause the partial closure of microcracks, and the concomitant and synergistic loss of BN fiber coatings. The micromechanical models could be formulated as time‐dependent coupled differential equations in time, which must be solved dynamically, e.g., as an iterated user‐defined material element, within a finite element simulation. A paradigm is thus established for incorporating the time‐dependent evolution of local material properties according to the local environmental and stress conditions that exist within a material, in a simulation of the damage evolution of a composite component. We exemplify the calibration of typical micromechanical degradation models using thermodynamic data for the oxidation and/or volatilization of BN and SiC by oxygen and water, mechanical test data for the rate of stress rupture of SiC fibers, and kinetic data for the processes involved in gas permeation through microcracks. We discuss approaches for validating computational simulations that include the micromechanical models of environmental degradation. A special challenge is achieving validated predictions of trends with temperature, which are expected to vary in a complex manner during use.     

Surface oxidation behavior in air and O2-H2O-Ar atmospheres of continuous freestanding SiC films derived from polycarbosilane

In this contribution, thermodynamic computational calculations firstly carried out on Ar-Si-C-O/Ar-Si-C-O-H database demonstrate that passive oxidation is main reaction of continuous freestanding SiC films in both air and 14%H₂O/8%O₂/78%Ar atmospheres. SiC films were subsequently annealed at 1300?°C, 1400?°C and 1500?°C for 1?h in air and O₂-H₂O-Ar atmospheres. Results suggest that modulus, hardness and resistivity decrease whereas crystallite size of β-SiC and α-cristobalite increase with elevated annealing temperature. In particular, hardness of wet oxidized samples is lower than that of air oxidized ones. Additionally, their oxidation kinetics models were also established and verified by annealing at 1200?°C in air and wet oxygen for different time from 1?h to 100?h. Oxidation of continuous freestanding SiC films is identified to follow parabolic oxidation kinetics, and water could effectively enhance the oxidation rates. It is revealed that SiO₂ layer can protect SiC films from further oxidation, and their thickness increases with prolonged annealing time. In this study, a dense and uniform SiO₂ layer with a thickness of 1.1–1.6?µm was produced for sacrificial and passivation layer based on suitable thermal oxidation process (annealing at 1000?°C for 5?h in O₂-H₂O-Ar environment). Interestingly, fast diffusion paths in this oxide layer could effectively accelerate oxidation process of SiC films. These obtained achievements would promote further applications of SiC films on microelectromechanical systems (MEMS) devices in harsh environments.     

Effect of interface types on the heat-resistance of Cansas-II SiCf /SiC composites

The heat-resistance of the Cansas-II SiC/CVI-SiC mini-composites with a PyC and BN interface was studied in detail. The interfacial shear strength of the SiC/PyC/SiC mini-composites decreased from 15 MPa to 3 MPa after the heat treatment at 1500 °C for 50 h, while that of the SiC/BN/SiC mini-composites decreased from 248 MPa to 1 MPa, which could be mainly attributed to the improvement of the crystallization degree of the interface and the decomposition of the matrix. Aside from the above reasons, the larger declined fraction of the interfacial shear strength of the SiC/BN/SiC mini-composites might also be related to the gaps in the BN interface induced by the volatilization of B₂O₃·SiO₂ phase, leading to a significant larger declined fraction of the tensile strength of the SiC/BN/SiC mini-composites due to the obvious expansion of the critical flaws on the fiber surface. Therefore, compared with the CVI BN interface, the CVI PyC interface has better heat-resistance at high temperatures up to 1500 °C due to the fewer impurities in PyC.     

Oxidation behavior of medium-entropy (Y1/3Yb1/3Lu1/3)2O3 modified SiC ceramic at 1700 °C: Experimental and theoretical study

The medium-entropy oxide (Y_1/3Yb_1/3Lu_1/3)₂O₃ with a body-centered cubic structure was successfully synthesized by solid-state reaction process, and then it was introduced into SiC ceramic to study its effect on the oxidation behavior of SiC ceramic at 1700 °C. The (Y_1/3Yb_1/3Lu_1/3)₂O₃-modified SiC ceramic exhibited better oxidation resistance than its individual oxides (Y₂O₃, Yb₂O₃, and Lu₂O₃) modified SiC ceramic. The experimental and calculated results all indicate that the rare-earth atoms had the tendency to diffuse into the SiO₂ structure and occupy the interstitial positions within SiO₂ structure. The introduction of medium-entropy oxide (Y_1/3Yb_1/3Lu_1/3)₂O₃ reduced the initial oxidation rate of the ceramic samples (1?3 h), and enhanced the stability of SiO₂ structure, thus resulting in a better oxidation resistance at 1700 °C.     

High-temperature oxidation behavior of the SiC layer of TRISO particles in low-pressure oxygen

Surrogate tristructural-isotropic (TRISO)-coated fuel particles were oxidized in 0.2 kPa O₂ at 1200–1600°C to examine the behavior of the SiC layer and understand the mechanisms. The thickness and microstructure of the resultant SiO₂ layers were analyzed using scanning electron microscopy, focused ion beam, and transmission electron microscopy. The majority of the surface comprised smooth, amorphous SiO₂ with a constant thickness indicative of passive oxidation. The apparent activation energy for oxide growth was 188 ± 8 kJ/mol and consistent across all temperatures in 0.2 kPa O₂. The relationship between activation energy and oxidation mechanism is discussed. Raised nodules of porous, crystalline SiO₂ were dispersed across the surface, suggesting that active oxidation and redeposition occurred in those locations. These nodules were correlated with clusters of nanocrystalline SiC grains, which may facilitate active oxidation. These findings suggest that microstructural inhomogeneities such as irregular grain size influence the oxidation response of the SiC layer of TRISO particles and may influence their accident tolerance.     

Preparation of SiC/SiC composites with high toughness by reaction of the SiCP+C double-cladding layer with liquid silicon

SiC/SiC composites prepared by liquid silicon infiltration (LSI) have the advantages of high densification, matrix cracking stress and ultimate tensile strength, but the toughness is usually insufficient. Relieving the residual microstress in fiber and interphase, dissipating crack propagation energy, and improving the crystallization degree of interphase can effectively increase the toughness of the composites. In this work, a special SiC particles and C (SiC_P +C) double-cladding layer is designed and prepared via the infiltration of SiC_P slurry and chemical vapor infiltration (CVI) of C in the porous SiC/SiC composites prepared by CVI. After LSI, the SiC generated by the reaction of C with molten Si combines with the SiC_P to form a layered structure matrix, which can effectually relieve residual microstress in fiber and interphase and dissipate crack propagation energy. The crystallization degree of BN interphase is increased under the effects of C-Si reaction exotherm. The as-received SiC/SiC composites possess a density of 2.64 g/cm³ and a porosity of 6.1%. The flexural strength of the SiC/SiC composites with layered structure matrix and highly crystalline BN interphase is 577 MPa, and the fracture toughness reaches up to 37 MPa·m^1/2. The microstructure and properties of four groups of SiC/SiC composites prepared by different processes are also investigated and compared to demonstrate the effectiveness of the SiC_P +C double-cladding layer design, which offers a strategy for developing the SiC/SiC composites with high performance.     

Oxidation behavior of SiC nanowires: A nanowire radius-dependent growth of oxide scale thickness

SiC nanowires (SiC NWs) possess both high thermal stability of SiC ceramic and one-dimensional nanoscale features, which makes them highly attractive as reinforcements in ceramics or building units in resilient ceramic nanowires aerogels (NWAs) as well as blocks for electronic nanodevices. Understanding the oxidation behavior of SiC NWs at high temperatures is essential for their practical applications. Herein, we investigated the oxidation behavior of SiC NWs at 900–1200°C in air. Two oxidation stages were found, including an initial stage controlled by the reaction between oxygen and SiC at the SiO₂/SiC interface and a subsequent oxygen diffusion–dependent stage. The oxide scale thickness was strongly influenced by the radius of the SiC NWs. With the increase of the NW radius from 40 to 120 nm, the oxidation activation energy of the oxidation process increases from 84.05 to 98.32 kJ/mol. The thermal insulation performances of SiC NWA, which is composed of SiC NWs, have been improved after oxidation. The evolution of the thermal insulation performance of SiC NWA during oxidation is consistent with the trends of the growth of the amorphous oxide layer, which indicates that exploring the oxidation kinetics is of great significance in understanding the high-temperature behavior of SiC NW-based materials. The present work provides insight into exploring the size effects on oxidation of SiC NWs, which may be helpful to further understanding the high-temperature applications of SiC NWA.     

SiC/SiO2 interface properties formed by low-temperature ozone re-oxidation annealing

We propose an ECR ozone plasma re-oxidation annealing (ROA) method that can introduce high-concentration and high-reactivity O atoms to eliminate defects near the SiC/SiO₂ interface with low temperature (400 °C). This method can more effectively improve the electrical performance of SiC MOS capacitors compared with other ROA methods, including O₂, O₃ and O₂ plasma ROA methods. Secondary ion mass spectroscopy (SIMS), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS) are performed. Results indicate that the O3P-ROA can evidently re-oxidize near-interface defects, which optimize near-interface properties, including the elemental distribution of the near-interface region and the morphology of the SiC/SiO₂ interface. In addition, the effects of temperature and oxygen element on near-interface properties of SiC MOS capacitors are discussed in this paper.     

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.