Comparison of Two Processes for Manufacturing Ceramic Matrix Composites from Organometallic Precursors

A commercial polysilazane is used as a silicon carbonitride matrix precursor for the manufacture of ceramic matrix composites using bi-directional SiC Nicalon fabrics as reinforcing material. The objective is to develop a simple and fast process leading to materials able to compete with SiC/C/SiC composites obtained by the Chemical Vapour Infiltration (CVI) route. Two processes are investigated: (1) a ‘conventional’ process using the densification of a SiC fibre preform by several cycles of impregnation of the preform with the polymer followed by pyrolysis and (2) a ‘modified’ process consisting in a powder filling of the fibre preform prior to the precursor impregnation and pyrolysis. This paper describes the different steps of both processes. The materials obtained are characterised in terms of their porosity, microstructure and mechanical properties. ©     

Additive manufacturing of silicon carbide by selective laser sintering of PA12 powders and polymer infiltration and pyrolysis

In this work, we propose a novel hybrid additive manufacturing technique, which combines selective laser sintering (SLS) of polyamide powders and subsequent preceramic polymer infiltration and pyrolysis to manufacture Silicon Carbide components for complex architectures. By controlling the porosity of the sintered polymeric preform we are able to control the shrinkage upon the first infiltration and pyrolysis. This enabled the manufacturing of smaller features than those achievable with other manufacturing techniques. The mechanical strength of the resulting ceramic increased with the number of reinfiltration cycles up to 24 MPa, inversely the residual porosity decreased to 10 vol%. The microstructure showed two distinct phases of SiOC and SiC. The first was attributed to the interaction between the porous polyamide and the ceramic precursor during the first infiltration. SiC derived from the pyrolysis of the preceramic precursor alone.     

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.     

用有机聚合物连接碳化硅陶瓷及陶瓷基复合材料

用陶瓷先驱体有机聚合物连接陶瓷及陶瓷基复合材料是一种成本低廉、工艺新颖、可满足特殊高温条件下连接件要求的新型连接技术。介绍了近年来采用先驱体有机聚合物连接SiC及其复合材料的研究现状，重点对影响连接强度的因素进行分析，并提出相应的改进措施。由于该技术具有连接温度较低、连接过程简单、接头热应力小，连接件的热稳定性高等特点，因此它是陶瓷及其复合材料最有前途的连接方法之一。     

Modeling the pyrolysis of preceramic polymers: A kinetic study of the polycarbosilane SMP-10

A material model was developed to predict changes in mass, density and thus volume of cured preceramic polymers for CMC matrices as they pyrolyze into ceramics. Because part warpage and delaminations are most likely to occur when matrix strain rates and strain rate gradients are the highest, the ability to accurately predict changes in a matrix material’s volume is essential to determining the processing conditions that will efficiently minimize composite scrap rates. Experimental and model analysis of the SiC forming polycarbosilane, SMP-10, revealed that volume shrinkage is initially driven by mass loss, is quickly dominated by density’s contribution, and has both temperature and time at temperature dependencies, where density is not a simple function of mass yield. While material density is rarely reported in the open literature, the ability to predict changes in density is essential to accurately predicting the volume yield of preceramic polymers used in ceramic matrix composites.     

Effects of CVI SiC amount and deposition rates on properties of SiCf/SiC composites fabricated by hybrid chemical vapor infiltration (CVI) and precursor infiltration and pyrolysis (PIP) routes

The SiC_f/SiC composites have been manufactured by a hybrid route combining chemical vapor infiltration (CVI) and precursor infiltration and pyrolysis (PIP) techniques. A relatively low deposition rate of CVI SiC matrix is favored ascribing to that its rapid deposition tends to cause a ‘surface sealing’ effect, which generates plenty of closed pores and severely damages the microstructural homogeneity of final composites. For a given fiber preform, there exists an optimized value of CVI SiC matrix to be introduced, at which the flexural strength of resultant composites reaches a peak value, which is almost twice of that for composites manufactured from the single PIP or CVI route. Further, this optimized CVI SiC amount is unveiled to be determined by a critical thickness t₀, which relates to the average fiber distance in fiber preforms. While the deposited SiC thickness on fibers exceeds t₀, closed pores will be generated, hence damaging the microstructural homogeneity of final composites. By applying an optimized CVI SiC deposition rate and amount, the prepared SiC_f/SiC composites exhibit increased densities, reduced porosity, superior mechanical properties, increased microstructural homogeneity and thus reduced mechanical property deviations, suggesting a hybrid CVI and PIP route is a promising technique to manufacture SiC_f/SiC composites for industrial applications.     

Optimized preceramic polymer for 3D structured ceramics via fused deposition modeling

3D structured ceramics stemmed from preceramic polymers via additive manufacturing have attracted much attention recently. However, these polymers with high ceramic yield are so brittle that extrusion-based additive manufacturing techniques are hardly able to be utilized for assembling 3D structures. Herein, we developed a strategy to prepare feedstocks for these manufacturing techniques, i.e., utilizing a small amount of thermal-plastic polymer to optimize the preceramic polymer while good compatibility is required between the two polymers to ensure a homogeneous mixture. Polycarbosilane and polypropylene were selected as the representative materials. Polypropylene occupied a small proportion (≤5wt.%) and significantly improved the formability of the precursor. Three-dimensional SiC were obtained via fused deposition modeling combined with crosslinking and pyrolysis. The SiC ceramic filaments showed a mean tensile strength of 471 MPa. The strategy is also applicable to a large field of ceramic systems with corresponding precursor, such as sialon ceramic and multicomponent Si-based ceramics.     

聚合物制备工程陶瓷的研究概况

随着聚碳硅烷、聚硅氮烷、聚硅氧烷以及聚硅硼烷等先进前驱体材料的开发,由含硅陶瓷预制体聚合物制备的工程陶瓷在Si-O-C-N-B体系中占有重要的地位。耐高温的SiC和SiN陶瓷纤维增强陶瓷基复合材料(CMC)已在航空、航天结构中获得应用,而耐中、低温的新型涂层、单向带,泡沫和复杂形状的构件在未来将在能源、环境、运输和通讯领域占有重要的地位。综述了陶瓷预制体聚合物的合成、聚合物制备陶瓷的性能、聚合物制备陶瓷的方法以及影响聚合物热解的主要因素。     

A polymer infiltration and pyrolysis (PIP) process model for ceramic matrix composites (CMCs)

This work describes a physics-based model to simulate the polymer infiltration and pyrolysis (PIP) manufacturing process for ceramic matrix composites (CMCs). Models have been developed to characterize volumetric distribution of constituents and track porosity inside the composite at different PIP stages utilizing test data from TGA and DSC characterization of a commercial preceramic polymer. Laboratory experiments were done using C/SiC CMC specimens manufactured with a variable number of PIP cycles in order to obtain inputs for the models, and the analytical results have been shown to agree with porosity determined from physical measurements.     

A Process for Cf/SiC Composites Using Liquid Polymer Infiltration

A continuous carbon fiber/silicon carbide matrix composite material has been produced by a low-cost process. In this process the space in a two-dimensional carbon fiber preform is filled with a SiC powder by a pressure infiltration method. High particle packing densities are achieved within the fiber preform in this way. The compact body is heat-treated at 400°C to form a porous framework, which is then infiltrated with a liquid preceramic polymer, Ceraset^TM SN. Subsequently the infiltrated polymer is pyrolyzed in argon at 1300°C. The microstructure of the final composite is characterized, and mechanical properties of these composites are discussed.     

Failure mechanism and tensile constitutive model of the unidirectional-laminated Cf/SiC–Al composites

The unidirectional-laminated C_f/SiC–Al composites were prepared by using precursor infiltration and pyrolysis (PIP) and vacuum pressure infiltration processes. Bulk density and open porosity of as-prepared C_f/SiC–Al composites were characterized which showed a large number of pores in the unidirectional-laminated carbon fiber preform were filled with SiC and Aluminum alloy matrix. The uniaxial tensile tests were conducted to study the mechanical properties. The fracture surface and cross-section of tensile specimens were characterized to clarify the failure mechanism. The results showed that under the action of load, the propagation of microcracks in matrix led to interface debonding, fiber fracture and pull-out. According to the stress-displacement behavior and analysis of damage process, the prediction formulas of the linear proportional limit stress value and the tensile strength value were proposed. A bilinear constitutive model was established based on the assumption of the damage process which well characterized constitutive response of the composites.     

Processing and properties of Nextel™ 720 fiber reinforced alumina-zirconia ceramic matrix composites

The continuous Nextel? 720 fiber-reinforced zirconia/alumina ceramic matrix composites (CMCs) were prepared by slurry infiltration process and precursor infiltration pyrolysis (PIP) process. The introduction of submicron zirconia powders into the aqueous slurry was optimized to offer comprehensively good sintering activity, high thermal resistance and good mechanical properties for the CMCs. Meanwhile, the zirconia and alumina preceramic polymers were used to strengthen the porous ceramic matrix through the PIP process. The final CMC sample achieved a high flexural strength of 200 MPa after one infiltration cycle of alumina preceramic polymer and thermal treatment at 1150 °C for 2 h. The flexural strength retention of the improved CMC sample was 104% and 89% respectively after thermal exposure at 1100 °C and 1200 °C for 24 h.     

Influence of precursor concentration on the densification efficiency and properties of SiC/SiC composites

The SiC/SiC composites were manufactured by polymer precursor impregnation pyrolysis process with near stoichiometric SiC fiber 2D preform as the reinforcing phase, the mixed solution of polycarbosilane (PCS), and xylene as impregnant. The effects of PCS concentration on the densification process, microstructure, and mechanical behavior of SiC/SiC composites were investigated using mechanical property testing, scanning electron microscopy, and other characterization techniques. Results showed the porosity and flexural strength of SiC/SiC composites increased first and then decreased with the increase of PCS concentration. When the concentration of PCS was 55% and 60%, the flexural strength of SiC/SiC composites reached 565.77 and 573.02 MPa, respectively. The mechanical behavior of SiC/SiC composites presented typical pseudoplastic characteristics such as fiber pulling-out, fiber bridging, and interface layer peeling, which would meet the dual requirements of optimizing the matrix and interface structure.     

Fabrication of dense SiSiC ceramics by a hybrid additive manufacturing process

In this work, we report the fabrication of Silicon infiltrated Silicon Carbide (SiSiC) components by a hybrid additive manufacturing process. Selective laser sintering of polyamide powders was used to 3D print a polymeric preform with controlled relative density, which allows manufacturing geometrically complex parts with small features. Preceramic polymer infiltration with a silicon carbide precursor followed by pyrolysis (PIP) was used to convert the preform into an amorphous SiC ceramic, and five PIP cycles were performed to increase the relative density of the part. The final densification was achieved via liquid silicon infiltration (LSI) at 1500°C, obtaining a SiSiC ceramic component without change of size and shape distortion. The crystallization of the previously generated SiC phase, with associated volume change, allowed to fully infiltrate the part leading to an almost fully dense material consisting of β-SiC and Si in the volume fraction of 45% and 55% respectively. The advantage of this approach is the possibility of manufacturing SiSiC ceramics directly from the preceramic precursor, without the need of adding ceramic powder to the infiltrating solution. This can be seen as an alternative AM approach to Binder jetting and direct ink writing for the production of templates to be further processed by silicon infiltration.     

Friction and wear properties of C/C–SiC braking composites

Two series of C/C–SiC composites were fabricated via precursor infiltration pyrolysis (PIP) and chemical vapor infiltration (CVI) using porous C/C composites with different original densities as preforms, respectively. The tribological characteristics of C/C–SiC braking composites were investigated by means of MM-1000 type of friction testing machine. The friction and wear behaviors of the two series of composites were compared and the factors that influence the friction and wear properties of C/C–SiC composites were discussed. Results show that the friction and wear properties relate close-knit to the content of SiC and porosity. As the original preform density increasing, the content of SiC and porosity decrease, and then the friction coefficient increases obviously, the braking time and the wear rate both decrease. Preparation techniques play an important role in the tribological properties of C/C–SiC composites. Compared with PIP process, the samples from CVI have a little higher friction coefficient, shorter braking time and higher wear rate.     

Fabrication of Porous SiC Ceramics with Special Morphologies by Sacrificing Template Method

Sacrificial template technique is widely used in producing porous materials with controlled morphologies and tailored properties. In this paper, unique templates such as filters, carbon nanotube, carbon fiber and silica were used to make porous SiC ceramic with special morphologies. Template derived porous ceramic plates, SiC nano-net, fiber-inverse and bead-inverse porous SiC ceramic were successfully prepared from the preceramic precursor, polymethylsilane (PMS). The synthesis procedures were involved with the infiltration of the templates with appropriate concentration of the preceramic polymer, their curing, pyrolysis and subsequent template removal. The synthesized porous SiC was characterized by SEM, TEM, XRD and BET methods.     

Tribological behavior and applications of carbon fiber reinforced ceramic composites as high-performance frictional materials

Due to the favorable tribological, mechanical, chemical, and thermal properties, carbon fiber reinforced ceramic composites, especially carbon fiber reinforced carbon and silicon carbide dual matrix composites (C/C–SiC), has been considered as high-performance frictional materials. In this paper, current applications and recent progress on tribological behavior of C/C–SiC composites are reviewed. The factors affecting the friction and wear properties, including the content of silicon carbide and carbon matrix, carbon fiber preform architecture, as well as the matrix modification by alloy additives and C/C–SiC composites under various test conditions are reviewed. Furthermore, based on the current status of researches, prospect of several technically available solutions for low-cost manufacturing C/C–SiC composites is also proposed.     

碳化锆陶瓷有机前驱体的热解过程

合成了碳化锆陶瓷有机前驱体,研究了其在热解过程中化学成分和物相组成变化,探讨了从有机高分子向无机陶瓷转化的机理,对碳热还原反应进行了热力学分析。结果表明,前驱体在600℃以下完成了有机结构的断裂、裂解碎片的重排与挥发,600℃以上裂解产物不再具备有机特征;随热解温度升高,无定型碳和单斜相ZrO2逐渐生成,大于1200℃时可检测到立方相ZrC,1400℃时单斜相ZrO2基本消失;1500℃时完成碳热还原反应,在远低于热力学反应温度的条件下生成了高度结晶的纳米尺寸的立方相碳化锆陶瓷。     

Stereolithography-based additive manufacturing of polymer-derived SiOC/SiC ceramic composites

In order to overcome challenges typically encountered during additive manufacturing of ceramics via the polymer precursor route, a novel polymer-derived SiOC/SiC composite system suitable for advanced geometric designs achievable by lithography-based ceramic manufacturing was established. The photoreactive resin system filled with 20 wt% SiC exhibits suitable viscosity characteristics, adequate stability against sedimentation, and a fast photocuring behavior. After printing and pyrolytic conversion, SiC particulates were well-dispersed within the polymer-derived SiOC matrix. A direct comparison with the unfilled polysiloxane-based resin system showed that the addition of particulate SiC increases handleability, reduces shrinkage, and significantly increases critical wall thicknesses up to 5 mm. The biaxial Ball-on-Three-Balls testing methodology yielded a characteristic strength of 325 MPa for SiOC/SiC composites. The results highlight the high potential of particle-filled preceramic polymer systems toward the fabrication of high-performance SiC-based materials by lithography-based additive manufacturing.     

Synchrotron X-ray tomographic characterization of CVI engineered 2D-woven and 3D-braided SiCf/SiC composites

The properties of ceramic matrix composites strongly depend upon their complex internal structures. To better understand and improve the properties of the silicon carbide fiber-reinforced silicon carbide matrix composites (SiC_f/SiC), we explored the microstructural properties of composites reinforced with either two-dimensional (2D) woven or three-dimensional (3D) braided preforms using synchrotron X-ray computed microtomography. Transects and volumetric images of the composites were reconstructed from objection images and the microstructures were investigated in three spatial directions. The network of void space in a composites was visualized in 3D and quantitative analysis of the porosity was performed to characterize the fiber-tissue structures. 2D-woven SiC_f/SiC composite exhibited important fluctuations of porosity in different directions and the stacking of plies had a significant effect on the porosity distribution. In contrast, 3D-braided SiC_f/SiC composites showed much less variation of porosity. We found the degree of densification of the composite also influenced the porosity distribution.