High-entropy environmental barrier coating for the ceramic matrix composites

A novel high-entropy material, (Yb_0.2Y_0.2Lu_0.2Sc_0.2Gd_0.2)₂Si₂O₇ ((5RE_0.2)₂Si₂O₇) was prepared by the sol-gel method and investigated as a promising environmental barrier coating (EBC) for SiC-based composites. The results of X-ray diffraction and transmission electron microscopy indicated that rare-earth elements were distributed homogeneously in the single monoclinic phase. Moreover, it was found that the new material (5RE_0.2)₂Si₂O₇ had good phase stability, well-matched coefficient of thermal expansion with SiC-based composite, and excellent resistance to water-vapor corrosion. The water-vapor corrosion test of (5RE_0.2)₂Si₂O₇ coated C_f/SiC composites further confirmed that (5RE_0.2)₂Si₂O₇ was suitable for application as EBC material and could provide effective protection to C_f/SiC composites from water-vapor damage.     

Additive manufacturing of polymer-derived ceramic matrix composites

This study presents a fabrication method and identifies processing bounds for additively manufacturing (AM) ceramic matrix composites (CMCs), comprising a silicon oxycarbide (SiOC) ceramic matrix. A digital light projection printer was used to photopolymerize a siloxane-based preceramic resin containing inert ceramic reinforcement. A subsequent pyrolysis converted the preceramic polymer to SiOC. Particle reinforcements of 0 to 40% by volume in the green state were uniformly dispersed in the printed samples to study their effects on pyrolysis mass loss and shrinkage, and CMC notch sensitivity and strength. Both particle and whisker reinforcements toughened the glassy SiOC matrix (1 MPa m^1/2), reaching values >3 MPa m^1/2. Bending strengths of >300 MPa (>150 MPa (g cm⁻³)⁻¹) and a Weibull modulus of 10 were measured on AM samples without surface finish. We identified two pore formation mechanisms that placed processing bounds on sample size and reinforcement volume fraction. Methods for increasing these bounds are discussed. With properties commensurate to traditionally processed technical ceramics, the presented process allows for free-form fabrication of high-performance AM CMC components.     

Crack opening behavior in ceramic matrix composites

The evolution of matrix cracks in a melt‐infiltrated SiC/SiC ceramic matrix composite (CMC) under uniaxial tension was examined using scanning electron microscopy (SEM) combined with digital image correlation (DIC) and manual crack opening displacement (COD) measurements. CMC modeling and life prediction strongly depend a thorough understanding of when matrix cracks occur, the extent of cracking for given conditions (time‐temperature‐environment‐stress), and the interactions of matrix cracks with fibers and interfaces. In this work, strain relaxation due to matrix cracking, the relationship between CODs and applied stress, and damage evolution at stresses below the proportional limit were assessed. Direct experimental observation of strain relaxation adjacent to regions of matrix cracking is presented and discussed. Additionally, crack openings were found to increase linearly with increasing applied stress, and no crack was found to pass fully through the gage cross‐section. This calls into question the modeling assumption of through‐cracks for all loading conditions and fiber architectures, which can obscure oxidation mechanisms that are active in realistic cracking conditions. Finally, the combination of SEM with DIC is demonstrated throughout to be a powerful means for damage identification and quantification in CMCs at stresses well below the proportional limit.     

Modeling creep behavior in ceramic matrix composites

In this work, a three-dimensional viscoplasticity formulation with progressive damage is developed and used to investigate the complex time-dependent constituent load transfer and progressive damage behavior in ceramic matrix composites (CMCs) subjected to creep. The viscoplasticity formulation is based on Hill's orthotropic plastic potential, an associative flow rule, and the Norton-Bailey creep power law with Arrhenius temperature dependence. A fracture mechanics-informed isotropic matrix damage model is used to account for CMC brittle matrix damage initiation and propagation, in which two scalar damage variables capture the effects of matrix porosity as well as matrix property degradation due to matrix crack initiation and propagation. The Curtin progressive fiber damage model is utilized to simulate progressive fiber failure. The creep-damage formulation is subsequently implemented as a constitutive model in the generalized method of cells (GMC) micromechanics formulation to simulate time-dependent deformation and material damage under creep loading conditions. The developed framework is used to simulate creep of single fiber SiC/SiC microcomposites. Simulation results are in excellent agreement with experimental and numerical data available in the literature.     

Novel ceramic matrix composites with tungsten and molybdenum fiber reinforcement

Ceramic matrix composites usually utilize carbon or ceramic fibers as reinforcements. However, such fibers often expose a low ductility during failure. In this work, we follow the idea of a reinforcement concept of a ceramic matrix reinforced by refractory metal fibers to reach pseudo ductile behavior during failure. Tungsten and molybdenum fibers were chosen as reinforcement in SiCN ceramic matrix composites manufactured by polymer infiltration and pyrolysis process. The composites were investigated with respect to microstructure, flexural- and tensile strength. The single fiber strengths for both tungsten and molybdenum were investigated and compared to the strength of the composites. Tensile strengths of 206 and 156 MPa as well as bending strengths of 427 and 312 MPa were achieved for W/SiCN and Mo/SiCN composites, respectively. The W fiber became brittle across the entire cross section, while the Mo fiber showed a superficial, brittle reaction zone but kept ductile on the inside.     

Temperature dependent fracture toughness model for whisker-reinforced ceramic matrix composites

A temperature dependent fracture toughness model for whisker-reinforced ceramic matrix composites was developed in this study, which considers the effects of matrix fracture toughness, residual thermal stress, crack bridging, crack deflection, and their temperature dependence. Its predicted results were compared with the fracture toughness of six types of whisker-reinforced ceramic matrix composites at different temperatures, and good agreement between predicted results and experimental results is obtained. Furthermore, based on this model, we systematically analyzed the effects of the volume fraction and aspect ratio of whisker, Young's modulus of matrix and whisker, thermal expansion coefficient difference, stress-free temperature, the ratio between the fracture energy of matrix and that of interface, on their temperature dependent fracture toughness for the first time. Finally, insights and suggestions which could help to optimize and improve the composite fracture toughness at different temperatures are provided.     

Three-dimensional preforming via wet-laid nonwoven technology for ceramic matrix composites

In this study, a new 3D preforming method was developed using wet-laid nonwoven technology, for application in manufacturing ceramic matrix composites (CMC). For this purpose, a process setup was developed and tested on an example geometry (radome). HTS 45 carbon fibers and Nextel610 alumina fibers were used for the preforming. The resulting C/C-SiC and OXIPOL materials were mechanically characterized and the microstructure was investigated. A radome was manufactured from each material and subjected to DLR's L2K and VMK wind tunnels. The tests have been successful with the C/C-SiC and OXIPOL radome. Overall the application-oriented tests show that load-bearing components can be produced with the newly developed preform method and that they also prove themselves in the application. The knowledge gained, demonstrates the potential of the 3D wet-laid nonwoven preforming method and represents a new possibility for CMC production with complex shapes.     

Unified tensile model for unidirectional ceramic matrix composites with degraded fibers and interface

In order to overcome the roughness of the previously proposed micromechanical model [Acta Mech. Sin. (2011) 382], an enhanced multiscale analytical model was thus developed based on the rule of mixture, shear-lag theory and statistical approach to forecast the load carrying capacity of the prestressed ceramic matrix composites (CMCs) subjected to high-temperature oxidation. For comprehensive characterization of the mechanical degradation mechanisms, the oxidation induced fiber necking (or embrittlement) and fiber-matrix interface weakening were both taken into account. The suggested model was then applied to 2D-C/SiC composites. The influences of interface friction resistance, interface recession length, fiber necking factor and oxidation duration upon the residual mechanical property were investigated. Parametric analysis demonstrates that the modified formulations are much more reasonable than the previous model. The predicted residual tensile modulus and strength for the 2D-C/SiC composite agree well with the experimental data and furthermore the microscopic damage mechanisms were correlated properly with the macroscopic fracture morphologies.     

以聚酯薄膜为载体制备超薄镍箔的工艺

以厚度为0.05 ～ 0.20 mm的耐高温、平整度好的PET薄膜作为载体,利用高真空磁控溅射技术使薄膜单面金属化,然后预镀光亮铜,接着浸涂羧基苯并三唑溶液形成一薄层有机物离析层,继而采用氨基磺酸盐镀镍工艺在其表面沉积规定厚度的镍层,最后将镍层从基材上剥离,即获得超薄镍箔材料.给出了各工序的操作条件,指出了预镀光亮铜、...     

碳纤维增强SiC陶瓷复合材料的研究进展

碳纤维增强SiC陶瓷基复合材料具有良好的高温力学性能，是航空航天和能源等领域新的高温结构材料研究的热点之一．本文回顾了增强体碳纤维的发展，对材料的成型制备工艺，材料的抗氧化涂层研究进展和现有的一些应用做了综述，并展望了碳纤维增强SiC陶瓷基复合材料以后的研究重点及发展前景．     

Joining oxide ceramic matrix composites by ionotropic gelation

The production of complex-shaped all-oxide ceramic matrix composites (Ox-CMC) is somewhat restricted by their current processing methods, as well as by the lack of applicable joining techniques. Thus, we present a new method for joining Ox-CMCs based on the gelation of slurries with the polysaccharide polymer alginate. For this investigation, Nextel 610/alumina-zirconia composites were produced using alginate as binder and aluminum acetate as gelling agent. The joining capabilities of this technique were investigated with microstructural analyses and single-lap compression shear tests. For that, a slurry-containing alginate was used to join two composite plates at different stages of the processing: gel state, dried green body and after sintering. Joining composites plates in their gel or green state was successful as the joints showed shear strength values similar to the interlaminar shear strength of the composites plates. The quality of the joints was attributed to the interactions between the alginate chains of the composite plates and the joint. We also show that even the joining of already sintered Ox-CMCs is feasible. However, densification cracks and lower shear strength are observed for such cases.     

Enhancing thermal stability of oxide ceramic matrix composites via matrix doping

To overcome the main limitation of oxide ceramic matrix composites (Ox-CMCs) regarding thermal degradation, the use of matrix doping is analyzed. Minicomposites containing Nextel 610 fibers and alumina matrices with and without MgO doping were produced. The thermal stability of the minicomposites was evaluated considering their microstructure and mechanical behavior before and after thermal exposures to 1300 °C and 1400 °C for 2 h. Before heat treatment, both composite types showed very similar microstructure and tensile strength. After heat treatment, densification, grain growth and strength loss are observed. Furthermore, the MgO dopant from the matrix diffuses into the fibers. As a result, abnormal fiber grain growth is partially suppressed and MgO-doped composites show smaller fiber grains than non-doped composites. This more refined microstructure leads to higher strength retention after the heat treatments. In summary, doping the matrix can increase the overall thermal stability without impairing the room-temperature properties of Ox-CMCs.     

Tribological and electrical properties of ceramic matrix composites with carbon nanotubes

Tribological behaviur of carbon fibrous phases (nanofibers and nanotubes) containing composites with Si₃N₄, ZrO₂ and Al₂O₃ matrices was studied by pin-on-disk technique in conditions of dry sliding. Coefficients of friction and wear rates were measured, wear damage mechanisms were observed and identified. The resulting tribological behaviur was related to microstructure and mechanical properties of respective materials. Electrical conductivity was measured in wide range of frequencies by two-point method and effect of volume fraction and distribution of CNTs and CNFs on percolation threshold was evaluated. Both coefficient of friction and electrical resistivity decreased with increasing amount of carbon phases, in both cases the nanofibers were more efficient than the nanotubes. The wear resistance in most cases decreased but for Si₃N₄–CNT composite a certain optimum (～5 wt.% CNT) was found.     

Evaluation of novel interphases for oxide/oxide ceramic matrix composites

Abstract

Stoichiometric MXO₄ type compounds, where M represents a rare earth or yttrium ion and X a pentavalent cation, have been prepared using mixed oxide and liquid precursor methods. Their stability in relation to Al₂O₃, mullite, and yttrium–aluminium garnet (YAG) has been determined by examining interfaces exposed in reaction couples after heating to 1400°C. Complex oxides of the phosphate and vanadate type are shown to possess the desired chemical stability with some of the candidate oxides and can be considered as suitable interphase materials. Close control over composition and homogeneity is shown to be important in determining their performance as potential interphases due to the possible formation of a liquid phase which can react readily with the oxide matrix or fibre. Selected MXO₄ compounds have also been successfully deposited on to oxide substrates and woven oxide fibres using liquid precursors and RF magnetron sputtering techniques, yielding controlled and uniform fibre coatings.     

Thermodynamic modelling of directed melt oxidation processing for ceramic matrix composites

Equilibrium thermodynamic modelling is used to predict the likely species that will form in the production of ceramic matrix composites using Li, Mg, Na and Zn as external dopants, with growth into an alumina preform. The modelling indicates strong similarities between all these systems. Interpretation of the results suggests that initiator dopants for the directed melt oxidation of aluminium should be volatile at the reaction temperature and should be capable of forming a mixed oxide phase with aluminium.     

陶瓷基复合材料疲劳损伤模拟与界面优化设计

本文从界面损伤模拟出发研究了陶瓷基复合材料(CMCs)的抗疲劳设计方法.以CMCs微观结构演变为切入点,在微观尺度建立复合材料各组分损伤机制的物理模型,然后集成到细观尺度的有限元分析之中,从而建立CMCs疲劳损伤的数值模拟方法,并对界面相组成、结构等因素影响疲劳性能的作用机制进行探究,以实现界面的抗疲劳设计.通过多尺度...     

Temperature-induced fibre/matrix interactions in porous alumino silicate ceramic matrix composites

The thermal stability of alumino-silicate fibre (Nextel 720)/porous mullite matrix composites was investigated in the temperature range between 1300 and 1600°C. In the as-prepared state the fibres consist of mullite plus α-Al₂O₃, while the porous mullite matrix includes minor amounts of a SiO₂-rich glass phase. Temperature-controlled reactions between the silica-rich glass phase of the matrix and α-Al₂O₃ at the rims of the fibres to form mullite have been observed. At the end of this process, virtually all glass phase of the matrix is consumed. Simultaneously, alumina-free layers about 1 μm thick are formed at the periphery of the fibres. The mullite forming process is initiated above about 1500°C under short time heat-treatment conditions (2 h) and at much lower temperature (1300°C) under long-term annealing (1000 h). Subsequent to annealing below the thermal threshold, the composite is damage tolerant and only minor strength degradation occurs. Higher annealing temperatures, however, drastically reduce damage tolerance of the composites, caused by reaction-induced gradually increasing fibre/matrix bonding. According to this study, the thermal stability of alumino silicate (Nextel 720) fibre/mullite matrix composites ranges between 1500°C in short-term and 1300°C in long-term heat-treatment conditions.     

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.     

In-plane thermal expansion behavior of dense ceramic matrix composites containing SiBC matrix

In order to reveal the effect of matrix cracks resulted from thermal residual stresses (TRS) on the thermal expansion behavior of ceramic matrix composites, SiBC matrix was introduced into C_f/SiC and SiC_f/SiC by liquid silicon infiltration. The TRS in both two composites were enlarged with incorporating SiBC matrix which has higher coefficients of thermal expansion (CTEs) than SiC matrix. Due to the relatively high TRS, matrix cracks and fiber/matrix (f/m) debonding exist in C_f/SiC-SiBC, which would provide the space for the expansion of matrix with higher CTEs. For SiC_f/SiC, no matrix cracking and f/m debonding took place due to the close CTEs between fiber and matrix. Accordingly, with the incorporation of SiBC matrix, the in-plane CTE of C_f/SiC between room temperature to 1100 °C decreases from 3.65 × 10⁻⁶ to 3.19 × 10⁻⁶ K^-1, while the in-plane CTE of SiC_f/SiC between room temperature to 1100 °C increases slightly from 4.97 × 10⁻⁶ to 5.03 × 10⁻⁶ K^-1.     

High temperature abradable sealing coating for SiCf/SiC ceramic matrix composites

A study of porous YSZ abradable sealing coating (ASC) plasma-sprayed onto SiC_f/SiC ceramic matrix composites (CMC) through the compatibility of intermediate layers is reported. The multilayer Si/Yb₂Si₂O₇/LaMgAl₁₁O₁₉ thermal-environmental barrier coating (T-EBC) is served as intermediate layers in consideration of its ability to protect the CMC from recession and ease the misfit of the thermal expansivity. Isothermal exposure and thermal shock tests were conducted at 1200°C and led to the decomposition of t'-ZrO₂ phase to t-ZrO₂ and c-ZrO₂ phases in YSZ topcoat, the formation of mud-cracks throughout the entire coating structure and thermally grown oxide (SiO₂), with following an Yb₂Si₂O₇ reaction layer. The measured bond strength of the coated samples was 5.47 ± 0.85 MPa, and the fracture position mainly happened inside the CMC substrate. The Superficial Rockwell Hardness (HR15Y) considered to be an important factor in abradability increased by only 1.34% after 1200°C isothermal exposure for 100 h, showing excellent high temperature hardness stability. The abradability of the ASC was investigated by a sliding wear test, the fatigue wear mainly occurred in worn scar when encountering Si₃N₄ ceramic ball with high hardness and low thermal conductivity, while adhesive wear occurred when GCr15 steel ball with low hardness and high thermal conductivity are encountered.