Fabrication and characterization of carbon fiber reinforced SiC ceramic matrix composites based on 3D printing technology

A novel method has been developed to fabricate carbon fiber reinforced SiC (C_f/SiC) composites by combining 3D printing and liquid silicon infiltration process. Green parts are firstly fabricated through 3D printing from a starting phenolic resin coated carbon fiber composite powder; then the green parts are subjected to vacuum resin infiltration and pyrolysis successively to generate carbon fiber/carbon (C_f/C) preforms; finally, the C_f/C preforms are infiltrated with liquid silicon to obtain C_f/SiC composites. The 3D printing processing parameters show significant effects on the physical properties of the green parts and also the resultant C_f/C preforms, consequently greatly affecting the microstructures and mechanical performances of the final C_f/SiC composites. The overall linear shrinkage of the C_f/SiC composites is less than 3%, and the maximum density, flexural strength and fracture toughness are 2.83?±?0.03?g/cm³, 249?±?17.0?MPa and 3.48?±?0.24?MPa m^1/2, respectively. It demonstrates the capability of making near net-shape C_f/SiC composite parts with complex structures.     

A novel strategy for rapid fabrication of continuous carbon fiber reinforced (TiZrHfNbTa)C high-entropy ceramic composites: High-entropy alloy in-situ reactive melt infiltration

For the first time, dense continuous carbon fiber (C_f) reinforced (TiZrHfNbTa)C high-entropy ceramic (C_f/HEC) composites were rapidly prepared via in-situ reactive melt infiltration (RMI). A TiZrHfNbTa high-entropy alloy served as the cation source and carbon in C_f reinforced carbon matrix (C_f/C) preforms served as the anion source, and a (TiZrHfNbTa)C high-entropy ceramic phase with a near equimolar ratio was successfully formed. The results revealed that most of the TiZrHfNbTa high-entropy alloy reacted with the carbon matrix, and the harvested C_f/HEC composites exhibited an excellent bending strength (612.6 MPa) and low ablation rates. High reaction rates caused by ultra-high temperature and homogeneous distribution of elements in the high-entropy TiZrHfNbTa alloy significantly reduced the difference in reactivity with C among Ti, Zr, Hf, Nb, and Ta are considered to be the reasons for successful formation of (TiZrHfNbTa)C high-entropy ceramic with a near equimolar ratio in C_f/HEC composites.     

ZrO2f-coated Cf hybrid fibrous reinforcements and properties of their reinforced ceramicizable phenolic resin matrix composites

Carbon fiber-reinforced ceramicizable phenolic resin matrix composites have been widely used in the field of thermal protection materials. In this paper, the ZrO_2f-coated C_f (ZrO_2f/C_f) hybrid fibrous reinforcements were designed to improve oxidation resistance of carbon fiber and ceramicizable composites reinforced by ZrO_2f/C_f hybrid fibrous reinforcements were prepared to investigated oxidation resistance and mechanical properties of the composites at high temperature. The results show that ZrO_2f/C_f hybrid fibrous reinforcements have good thermal stability and high oxidation resistance, and its ceramicizable composites have good bending strength at high temperature. Weight loss rate of the composites is only 21 %, and bending strength can be as high as 39 MPa when ablation time was 12 min at 1400 °C.     

Mechanical property and microstructure evolutions of Cf/SiOC composites with increasing annealing temperature in reduced pressure environment

Three-dimensional (3D) carbon fiber reinforced silicon oxycarbide (C_f/SiOC) composites were fabricated through precursor impregnation and pyrolysis process using siloxane resin as precursor. These composites were further annealed at various temperatures to follow their mechanical properties and microstructure evolutions in reduced pressure environment. The decrease in strength of those composites could be attributed mainly to the decomposition of matrixes. When the annealing temperature increased from 1000 to 1250 °C, the mechanical properties of composites did not change too much, despite the matrixes underwent a redistribution of Si-O bonds and Si-C bonds. At temperature above 1300 °C, due to the weight loss and volume shrinkage of matrixes caused by carbothermal reduction, both the flexural strength and elastic modulus of C_f/SiOC composites decreased rapidly.     

Reactive melt infiltrated Cf/SiC composites with robust matrix derived from novel engineered pyrolytic carbon structure

Needle-punched C_f/SiC composites were fabricated by a novel pore tuned reactive melt infiltration (RMI) process. The novel hierarchically porous carbon structure in the fiber preform with the porosity well open to liquid silicon was engineered by impregnation of phenolic resin with addition of a pore former. Neither residual bulk carbon nor residual bulk silicon is detected in the matrix of the C_f/SiC composites prepared by the pore tuned RMI, indicating that a robust matrix with homogenous SiC can be formed. The composite prepared by the pore tuned RMI exhibits a tensile strength of 159±5 MPa, which is 46% higher than that without addition of pore former.     

Processing and mechanical performance of 3D Cf/SiCN composites prepared by polymer impregnation and pyrolysis

The processing of 3D carbon fiber reinforced SiCN ceramic matrix composites prepared by polymer impregnation and pyrolysis (PIP) route was improved, and factors that determined the mechanical performance of the resulting composites were discussed. 3D C_f/SiCN composites with a relative density of ∼81% and uniform microstructure were obtained after 6 PIP cycles. The optimum bending strength, Young's modulus and fracture toughness of the composites were 75.2 MPa, 66.3 GPa and 1.65 MPa m^1/2, respectively. The residual strength retention rate of the as-pyrolyzed composites was 93.3% after thermal shock test at ΔT = 780 °C. It further degraded to 14.6% when the thermal shock temperature difference reached to 1180 °C. The bending strength of the composites was 35.6 MPa after annealing at 1000 °C in static air. The deterioration of the bending strength should be attributed to the strength degradation of carbon fibers and decomposition of interfacial structure.     

Direct ink writing of chopped carbon fibers reinforced polymer-derived SiC composites with low shrinkage and high strength

The chopped carbon fiber reinforced SiC (C_f/SiC) composite has been regarded as one of the excellent high-temperature structural materials for applications in aerospace and military fields. This paper presented a novel printing strategy using direct ink writing (DIW) of chopped fibers reinforced polymer-derived ceramics (PDCs) with polymer infiltration and pyrolysis (PIP) process for the fabrication of C_f/SiC composites with high strength and low shrinkage. Five types of PDCs printing inks with different C_f contents were prepared, their rheological properties and alignment of carbon fiber in the printing filament were studied. The 3D scaffold structures and bending test samples of C_f/SiC composites were fabricated with different C_f contents. The results found that the C_f/SiC composite with 30 wt% C_f content has high bending strength (～ 7.09 MPa) and negligible linear shrinkage (～ 0.48%). After the PIP process, the defects on the C_f/SiC composite structures were sufficiently filled, and the bending strength of C_f/SiC composite can reach up to about 100 MPa, which was about 30 times greater than that of the pure SiC matrix without C_f. This work demonstrated that the printed C_f/SiC composites by using this method is beneficial to the development of the precision and complex high-temperature structural members.     

Ring compression properties of SiCf/SiC composites prepared by chemical vapor infiltration

SiC fiber reinforced SiC matrix (SiC_f/SiC) composites prepared by chemical vapor infiltration are one of promising materials for nuclear fuel cladding tube due to pronounced low radioactivity and excellent corrosion resistance. As a structure component, mechanical properties of the composites tubes are extremely important. In this study, three kinds of SiC_f preform with 2D fiber wound structure, 2D plain weave structure and 2.5D shallow bend-joint structure were deposited with PyC interlayer of about 150–200?nm, and then densified with SiC matrix by chemical vapor infiltration at 1050?°C or 1100?°C. The influence of preform structure and deposition temperature of SiC matrix on microstructure and ring compression properties of SiC_f/SiC composites tubes were evaluated, and the results showed that these factors have a significant influence on ring compression strength. The compressive strength of SiC_f/SiC composites with 2D plain weave structure and 2.5D shallow bend-joint structure are 377.75?MPa and 482.96?MPa respectively, which are significantly higher than that of the composites with 2D fiber wound structure (92.84?MPa). SiC_f/SiC composites deposited at 1100?°C looks like a more porous structure with SiC whiskers appeared when compared with the composites deposited at 1050?°C. Correspondingly, the ring compression strength of the composites deposited at 1100?°C (566.44?MPa) is higher than that of the composites deposited at 1050?°C (482.96?MPa), with a better fracture behavior. Finally, the fracture mechanism of SiC_f/SiC composites with O-ring shape was discussed in detail.     

Fabrication and properties of Cf/ZrC‐SiC‐based composites by an improved reactive melt infiltration

C_f/ZrC‐SiC composites with a density of 2.52 g/cm³ and a porosity of 1.68% were fabricated via reactive melt infiltration (RMI) of Si into nano‐porous C_f/ZrC‐C preforms. The nano‐porous C_f/ZrC‐C preforms were prepared through a colloid process, with a ZrC “protective coating” formed surrounding the carbon fibers. Consequently, highly dense C_f/ZrC‐SiC composites without evident fiber/interphase degradation were obtained. Moreover, abundant needle‐shaped ZrSi₂ grains were formed in the composites. Benefiting from this unique microstructure, flexural strength, and elastic modulus of the composites are as high as 380 MPa and 61 GPa, respectively, which are much higher than C_f/ZrC‐SiC composites prepared by conventional RMI.     

Fabrication of C/SiC composites by siliconizing carbon fiber reinforced nanoporous carbon matrix preforms and their properties

Reactive melt infiltration (RMI) has been proved to be one of the most promising technologies for fabrication of C/SiC composites because of its low cost and short processing cycle. However, the poor mechanical and anti-ablation properties of the RMI-C/SiC composites severely limit their practical use due to an imperfect siliconization of carbon matrixes with thick walls and micron-sized pores. Here, we report a high-performance RMI-C/SiC composite fabricated using a carbon fiber reinforced nanoporous carbon (NC) matrix preform composed of overlapping nanoparticles and abundant nanopores. For comparison, the C/C performs with conventional pyrocarbon (PyC) or resin carbon (ReC) matrixes were also used to explore the effect of carbon matrix on the composition and property of the obtained C/SiC composites. The C/SiC derived from C/NC with a high density of 2.50 g cm^?3 has dense and pure SiC matrix and intact carbon fibers due to the complete ceramization of original carbon matrix and the almost full consumption of inspersed silicon. In contrast, the counterparts based on C/PyC or C/ReC with a low density have a little SiC, much residual silicon and carbon, and many corroded fibers. As a result, the C/SiC from C/NC shows the highest flexural strength of 218.1 MPa and the lowest ablation rate of 0.168 µm s^?1 in an oxyacetylene flame of ～ 2200 °C with a duration time of 500 s. This work opens up a new way for the development of high-performance ceramic matrix composites by siliconizing the C/C preforms with nanoporous carbon matrix.     

C/C多孔体对C/C-SiC复合材料微观结构和弯曲性能的影响

以4种纤维含量相同(32%,体积分数,下同),用化学气相渗透(chemical vapor infiltration,CVI)法制备了4种密度的碳纤维增强碳(carbon fiber reinforced carbon,C/C)多孔体,基体炭含量约20%～50%.利用液相渗硅法(liquid silicon infiltration,LSI)制备了C/C-SiC复合材料,研究了C/C多孔体对所制备的C/C-SiC复合材料微观结构和弯曲性能的影响.结果表明:不同密度的C/C多孔体反应渗硅后,复合材料的物相组成均为SiC,C及单质Si;随着C/C多孔体中基体炭含量的增加,C/C-SiC复合材料中SiC含量逐渐减少而热解炭含量逐渐增加.C/C-SiC复合材料弯曲强度随着材料中残留热解炭含量增加而逐渐增加,热解炭含量为约42%的C/C多孔体所制备的C/C-SiC复合材料的弯曲强度最大,达到320 MPa.     

Microstructures and mechanical properties of Cf/LAS composite and Ti60 alloy joints brazed with TiZrNiCu + Cf mixed powders

In this paper, carbon fiber reinforced lithium aluminosilicate (LAS) glass-ceramics matrix composites (C_f/LAS composites) are joined to Ti60 alloy using TiZrNiCu + C_f mixed powders by proper process parameters. The carbon fibers distribute uniformly in the brazing interlayer and react with Ti, Zr elements in the brazing alloy to form (Ti, Zr)C thin reactive layers, which are between the carbon fibers and the Ti, Zr elements. The effect of C_f content on the mechanical properties and microstructure of brazed joints are investigated. The microstructure of brazed joints varied obviously with the increasing of C_f content. The thickness of reactive layer between interlayer and C_f/LAS composites and Ti solid solution (Ti (s.s)) decrease gradually, and the volume of eutectic structure (Ti(s,s) + (Ti,Zr)₂(Ni,Cu)) decrease gradually. The obtained brazed joints exhibit a maximum shear strength of 73.5 MPa at room temperature using TiZrNiCu + 0.3 wt% C_f mixed powders. The enhanced shear strength can be attributed to the reduction in thermal stress and the reinforcing effect originated from the carbon fiber addition.     

Processing of Cf/SiC composites by hot pressing using polymer binders followed by polymer impregnation and pyrolysis

Continuous carbon fiber (C_f) reinforced silicon carbide (SiC) matrix composite (C_f/SiC) was processed through hot pressing (HP) using polycarbosilane (PCS) in matrix and polysilazane in interphase regions as polymer binders. HP experiments were conducted at 4 MPa, 1200 °C and 1 h; followed by PCS polymer impregnation and pyrolysis (PIP) at 1200 °C under vacuum. The BN/SiC-Si₃N₄ interphase formed on the C_f cloth during BN dispersed polysilazane polymer coating and pyrolysis. The influence of PCS quantity during HP experiments on C_f/SiC composites was studied. Results suggest that sintering of SiC matrix in C_f/SiC composite improves by increasing PCS content during HP; however, high PCS content increases the liquidity of SiC-PCS mixture to flow out of the composite structure. The C_f/SiC composites with relative density ranging from 79 to 83% and flexural strength from 67 to 138 MPa was achieved.     

Additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites via paper laminating,direct slurry writing,and precursor infiltration and pyrolysis

In this study, continuous carbon reinforced C_f/(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C–SiC high entropy ceramic matrix composites were additively manufactured through paper laminating (PL), direct slurry writing (DSW), and precursor infiltration and pyrolysis (PIP). (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C high entropy ceramic (HEC) powders were synthesized by pressureless sintering and ball milling. A certain proportion of HEC powder, SiC powder, water, binder, and dispersant were mixed to prepare the HEC-SiC slurry. Meanwhile, BN coating was prepared on the 2D fiber cloth surface by the boric acid-urea method and then the cloth was cut into required shape. Additive manufacturing were conducted subsequently. Firstly, one piece of the as-treated carbon fiber cloth was auto-placed on the workbench by paper laminating (PL). Then, the HEC-SiC slurry was extruded onto the surface of the cloth by direct slurry writing (DSW). PL and DSW process were repeated, and a C_f/HEC-SiC preform was obtained after 3 cycles. At last, the preform was densified by precursor infiltration and pyrolysis (PIP) and the final C_f/HEC-SiC composite was prepared. The open porosity of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 7.7, 10.6, and 11.3%, respectively. And the density of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 2.9, 2.7 and 2.3 g/cm³, respectively. The mechanical properties of the C_f/HEC-SiC composites increased firstly and then decreased with the HEC content increase, reaching the maximum value when the HEC volume fraction was 30%. The mechanical properties of the C_f/HEC-SiC composites containing 45, 30 and 15% HEC were as follows: flexural strength (180.4 ± 14 MPa, 183.7 ± 4 MPa, and 173.9 ± 4 MPa), fracture toughness (11.9 ± 0.17 MPa m^1/2, 14.6 ± 2.89 MPa m^1/2, and 11.3 ± 1.88 MPa m^1/2), and tensile strength (71.5 ± 4.9 MPa, 98.4 ± 12.2 MPa, and 73.4 ± 8.5 MPa). From this study, the additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites was achieved, opening a new insight into the manufacturing of ceramic matrix composites.     

Effect of interphase on mechanical properties and microstructures of 3D Cf/SiBCN composites at elevated temperatures

Interphase between the fibers and matrix plays a key role on the properties of fiber reinforced composites. In this work, the effect of interphase on mechanical properties and microstructures of 3D C_f/SiBCN composites at elevated temperatures was investigated. When PyC interphase is used, flexural strength and elastic modulus of the C_f/SiBCN composites decrease seriously at 1600°C (92 ± 15 MPa, 12 ± 2 GPa), compared with the properties at room temperature (371 ± 31 MPa, 31 ± 2 GPa). While, the flexural strength and elastic modulus of C_f/SiBCN composites with PyC/SiC multilayered interphase at 1600°C are as high as 330 ± 7 MPa and 30 ± 2 GPa, respectively, which are 97% and 73% of the values at room temperature (341 ± 20 MPa, 41 ± 2 GPa). To clarify the effect mechanism of the interphase on mechanical properties of the C_f/SiBCN composites at elevated temperature, interfacial bonding strength (IFBS) and microstructures of the composites were investigated in detail. It reveals that the PyC/SiC multilayered interphase can retard the SiBCN matrix degradation at elevated temperature, leading to the high strength retention of the composites at 1600°C.     

新型炭纤维/泡沫炭预制体的制备及致密化研究

由炭纤维/酚醛树脂经过发泡、固化和炭化制备出4种不同炭纤维含量(3%,7%,10%和15%)的泡沫炭作为制备炭/炭复合材料新型预制体,通过等温化学气相沉积对预制体进行致密化处理。研究了炭纤维含量对预制体微观结构、致密化过程及力学性能的影响。结果表明:炭纤维含量增加,使预制体产生更多的微裂纹,并有更多的炭纤维裸露在泡沫炭韧带外,有助于提高化学气相沉积的沉积速率。炭纤维/泡沫炭预制体炭/炭复合材料压缩强度随着预制体中炭纤维含量的增加而增加,当炭纤维体积分数为10%时,压缩强度达到峰值,为43MPa。     

Cyclic thermal shock behaviors of carbon fibers reinforced SiCN ceramics with bio-inspired Bouligand-like architectures

Ceramic matrix composites (CMCs) are commonly used for high temperature components in aircrafts. However, thermal shock, as a typical loading case, will cause high thermal stresses in CMCs resulting in brittle fracture failure, and material cracking caused by thermal shock can further reduce the effectiveness of thermal protection function. In the present paper, we propose a bionic hierarchical fiber preform design method to improve the thermal shock resistance of ceramics. The effect of architectures of fiber preforms of continuous carbon fiber-reinforced CMCs on the thermal shock resistance was investigated to understand its importance and the related mechanical mechanisms. Thermal shock (cycling) tests were performed with continuous carbon fibers reinforced SiCN ceramic matrix composites (C_f/SiCN) prepared by PIP. 3D micro-CT scan and three-point bending tests were also conducted to evaluated the resultant damage. The results showed that smaller internal damage and higher thermal shock resistance can be obtained in comparison to pure SiCN ceramics, and the underlying mechanism can be explained by the fact that smaller pitch angle can resist the through-thickness crack propagation via promoting diffused in-plane damage. The present study offers a possibility in developing biomimetic C_f/SiCN ceramics with excellent thermal shock behavior.     

Microstructures and tribological behaviors of Cf/C-SiC composites tailored by Cu and Fe-Si matrices

Ternary Cu-Fe-Si alloy were applied to modify tribological behavior of carbon fiber/carbon-silicon carbide (C_f/C-SiC) composites by reactive melt infiltration. Microstructures, physical properties and tribological properties on a full-scale train brake test rig of the modified composites were studied. Results indicate that both Cu and Fe-Si alloy as matrices lead to significantly enhanced thermal conductivity and compressive strength for C_f/C-SiC composites. Moreover, the average friction coefficient of the modified composites is between 0.25 and 0.55, which is higher than that of copper metal matrix composites. In addition, the average volume wear rate of the modified composites is only 0.168 cm³/MJ. The C_f/C-SiC composites modified by Cu and Fe-Si alloy with improved physical properties and tribological properties meet the technical requirement and show high application potential in express train brake systems.     

Microstructure and mechanical properties of quasi-isotropic chopped fiber-reinforced PyC–SiC matrix composite prepared by novel nondamaging method

In this work, quasi-isotropic chopped carbon fiber-reinforced pyrolytic carbon and silicon carbide matrix (C_f/C–SiC) composites and chopped silicon carbide fiber-reinforced silicon carbide matrix (SiC_f/SiC) composites were prepared via novel nondamaging method, namely airlaid process combined with chemical vapor infiltration. Both composites exhibit random fiber distribution and homogeneous pore size. Young's modulus of highly textured pyrolytic carbon (PyC) matrix is 23.01 ± 1.43 GPa, and that of SiC matrix composed of columnar crystals is 305.8 ± 9.49 GPa in C_f/C–SiC composites. Tensile strength and interlaminar shear strength of C_f/C–SiC composites are 52.56 ± 4.81 and 98.16 ± 24.62 MPa, respectively, which are both higher than those of SiC_f/SiC composites because of appropriate interfacial shear strength and introduction of low-modulus and highly textured PyC matrix. Excellent mechanical properties of C_f/C–SiC composites, particularly regarding interlaminar shear strength, are due to their quasi-isotropic structure, interfacial debonding, interfacial sliding, and crack deflection. In addition to the occurrence of crack deflection at the fiber/matrix interface, crack deflection in C_f/C–SiC composites takes also place at the interface between PyC–SiC composite matrix and the interlamination of multilayered PyC matrix. Outstanding mechanical properties of as-prepared C_f/C–SiC composites render them potential candidates for application as thermal structure materials under complex stress conditions.     

针刺炭纤维预制体结构单元对C/C复合材料性能的影响

采用6K炭纤维无纬布/网胎交替叠层及12K炭纤维无纬布/网胎交替叠层,在针刺工艺,致密化、热处理工艺完全相同的情况下,制备了密度为1.8g/cm3的热解炭/树脂炭双元基体的两种C/C复合材料产品,考察了针刺预制体结构单元对C/C复合材料性能的影响.结果表明,两种C/C复合材料的热学（垂直方向导热系数）、电学性能及石墨化度基本相当;而针刺6K炭纤维无纬布/网胎预制体C/C复合材料的拉伸、弯曲、压缩、层间剪切强度分别为127MPa,189MPa,263MPa,24.6MPa;其平行方向导热系数为54.6W/m＆#183;K,比常规针刺12K炭纤维无纬布/网胎预制体C/C复合材料相应提高了38％,32.2％,32.8％,38.9％,21％,彰显了细化针刺预制体结构单元对C/C复合材料力学性能的显著影响.