SiCf/SiC复合材料高温抗氧化研究进展

连续SiC纤维增韧SiC陶瓷基复合材料(SiCf/SiC CMCs)具有低密度、优异的高温力学性能和抗氧化性能,在航空发动机热端部件上具有广阔的应用前景,具备提高发动机推重比和使用温度、减轻无效重量、简化系统结构等显著优势.延长SiCf/SiC复合材料在航空发动机高温氧化环境下的服役寿命是当前需要解决的难题.本文从纤维、界面相、基体、表面涂层四个方面综述了SiCf/SiC复合材料高温抗氧化研究进展.采用多元多层自愈合界面相、对基体进行改性以及采用表面自愈合整体涂层都可以有效提高SiCf/SiC复合材料在高温氧化环境中的使用稳定性和寿命.     

基体改性对SiC/SiC复合材料高温抗氧化性能的影响

采用先驱体浸渍-裂解工艺结合三种基体改性方式制备了SiC/SiC复合材料,通过形貌分析和力学性能测试,分析了基体改性对Si C/SiC复合材料高温抗氧化性能的影响。研究表明,经1200℃静态空气氧化100h后,三种基体改性的复合材料弯曲强度几乎没有下降,氧化200h后,弯曲强度保留率均可达到80%;氧化300h后,复合材料内部结构没有氧化现象,表面区域界面层的氧化程度降低。改性基体中的B元素氧化生成液相封填SiC涂层表面,延缓了SiC涂层的氧化进程,并阻止氧化介质进入复合材料内部,保护纤维和界面层,从而使SiC/SiC复合材料的长时静态高温抗氧化性能明显提高。     

连续SiC纤维增韧SiC基体复合材料研究进展

近年来,SiC纤维增韧SiC基体复合材料(SiC<,f>/SiC)由于具有良好的高温力学、抗化学腐蚀、高的韧性与抗中子辐照等优异性能而受到广泛关注.本文主要从纤维、界面层、基体与应用四方面评述了近年来国内外的研究进展.SiC纤维的性能直接影响了界面层材料与基体制备技术的选择.电泳沉积有望成为一种低成本、节能及对环境无污染的界向层及基体制备技术.在应用方面,作为热结构材料,SiC<,f>/SiC复合材料已经得到了实际应用.核反应堆用SiC<,f>/SiC结构材料的研究到了实际考核验证阶段.高性能SiC纤维的大规模生产是SiC<,f>/SiC广泛应用的前提条件.     

SiC陶瓷基体及抗氧化涂层

介绍了5种主要SiC基体的成型方法,分别是化学气相渗透(CVI)、聚合物先驱体浸渍-裂解法(PIP)、液相硅渗透法(LSI)、反应烧结法、化学气相反应法(CVR)。阐述了各种基体的组织结构、致密效率及陶瓷基复合材料的性能,其中CVI+PIP/LSI的复合成型技术可达到优化的制备过程,提高基体的组织结构和致密化效率;C/C及C/SiC复合材料表面化学气相转换法SiC涂层及多层涂层技术是提高CMC抗氧化性能的有效途径,并已得到工程实际验证。     

SiC纤维及其增强SiCf/SiC复合材料的研究进展

SiC_f/SiC复合材料的低密度、耐高温、抗环境腐蚀及抗氧化等突出性能,使其在航天及空天飞行器的热端部件、热防护结构、发动机热端部件及核工业等领域取得了重大应用,是新一代最佳的高温结构材料。SiC纤维作为增强相,自身抗拉强度高、抗蠕变性能好、兼具耐高温、抗氧化等优点,且与陶瓷基体有着优异的相容性,可使陶瓷复合材料克服脆性,具有韧性,极大地推动了陶瓷复合材料的应用。文章以碳化硅纤维研发技术的三个重要发展阶段为例,详细阐述了碳化硅纤维的制备方法及性能特点,同时对碳化硅纤维增强陶瓷基复合材料的不同制备工艺进行了介绍,并分析了该复合材料当前国内外的应用现状,文章简述了SiC_f/SiC复合材料的发展及推广前景。     

采用在SiC毡上CVD—SiC涂层提高C／C复合材料抗氧化性能

最近发展起来的SiC纤维复合涂层，也就是SiC/SiC层与化学气相沉积（CVD）SiC结合形成复合涂层，已能够在高温下提高C／C复合材料的抗氧化性。形成的SiC纤维复合涂层约300μm厚，生产时先将SiC毡覆盖在3D－C／C基体材料上，然后浸渍一种碳粉与硅粉均匀分散的料浆进行化学气要沉积。通过化学气相沉积（CVD）过程，在复合材料上形成致密的涂层。在CO2－H2O－N2组成的混合气体（CO2 9％、N273％、H2O18％），1700℃下进行5h氧化实验，结果发现有SiC毡增强复合涂层比没有SiC毡增强复合材料失重率低。SiC纤维毡复合涂层由双层结构组成，里层是多气孔的SiC/SiC纤维层，外层为致密的SiC涂层。由于SiC/SiC纤维层热膨胀系数介于C／C复合基体材料与CVD－SiC涂层之间，因此，SiC/SiC中间层在复合材料中起了重要作用，从而由于热膨胀系数不同产生的热应力致使涂层开裂降低到最低程度。涂层试样氧化后，采用缓冲冲床（MSP）测试其残余强度。MSP测试结果表明氧化后C／C复合材料强度值呈发散性，从纤维折断面看有z轴方向分布纤维存在。然而，这种方法仅适用于测试小尺寸试样。从这篇论文中，可看出涂层后的C／C复合材料有高的抗氧化性，其氧化后仍能保持高的残余强度。     

Ni包裹SiC对SiC(Ni)/Fe复合材料性能的影响

分别以SiC粉体和Ni包裹的SiC复合粉体为硬质相,采用热压工艺(1000°C,20°C/min,40 MPa和45 min)制备了SiC含量为1 wt%~9 wt%的SiC/Fe复合材料。采用扫描电镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)等研究了复合材料的界面反应物。研究结果表明:Ni过渡层的存在有效避免了SiC颗粒与Fe基体之间的化学反应。随着Ni包裹SiC粉体含量的增加,复合材料的相对密度和抗弯强度先增加后减小,当SiC(Ni)粉体含量为5 wt%时达到最大值。     

电泳沉积-烧结两步法制备C/SiC复合材料

采用电泳沉积法在石墨基体上制备厚度可控的Si涂层,考察了电泳沉积参数(电压、沉积时间、固含量及添加剂量)对涂层沉积量的影响。所制备的Si涂层通过烧结与石墨基体发生在位反应形成SiC涂层。涂层成分的XRD分析表明烧结后生成β-SiC。用SEM观察涂层烧结前后的形貌,烧结后Si渗入基体内部。孔径分布数据表明所形成的SiC涂层导致石墨孔径变小。1200℃的抗氧化实验表明涂层起到了良好的防护作用。实验提供了一种制备C/SiC复合材料的新方法。     

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。     

连续碳化硅纤维增强碳化硅陶瓷基复合材料研究进展

碳化硅纤维增强碳化硅陶瓷基(SiC/SiC)复合材料具有轻质、耐高温、抗氧化的优异特性,在航空领域,如航空发动机的热端构件、高温结构功能一体化构件,航天及空天飞行器热防护结构部件、动力系统热端部件等领域具有广泛的应用前景,受到美国、欧洲、日本等国研究人员的广泛关注。本文从组成、制备工艺、加工工艺和考核应用等方面,综述了SiC/SiC复合材料的国内外研究进展,并指出了目前面临的问题和机遇。     

Tensile creep behavior of three-dimensional four-step braided SiC/SiC composite at elevated temperature

This article presents experimental results for tensile creep deformation and rupture behavior of three-dimensional four-step braided SiC/SiC composites at 1100 °C and 1300 °C in air. The creep behavior at 1300 °C exhibited a long transient creep regime and the creep rate decreased continuously with time. The creep behavior at 1100 °C exhibited an apparent steady-rate regime and the creep deformation was smaller than that at 1300 °C. However, the creep rupture time at both temperatures showed little difference. The mechanisms controlling creep deformation and rupture behavior were analyzed.     

基于核应用下碳化硅陶瓷及其复合材料的连接研究进展

SiC陶瓷及其复合材料凭借其自身固有的核辐射下的稳定性而有望成为新一代核裂变以及未来核聚变反应堆中重要的结构材料.能否满足核应用环境下各种苛刻条件而实现完美连接是其能够得到最终应用的关键.本文综述了目前国际上基于核应用上SiC陶瓷及其复合材料的几种连接工艺的发展情况.     

A chemo-mechanical coupled constitutive model applied to the oxidation simulation of SiC/SiC composite

Herein, a chemo-mechanical coupled constitutive and failure model is proposed to predict the tensile behavior of SiC/SiC composites under oxidizing environments. The diffusion of O₂ through the oxide scale and the oxidation reaction of SiC/O₂ are modeled and implemented in finite element software, through a user-defined element. Numerical validation studies and tests are conducted on a domestic SiC fiber. An orthotropic constitutive model for reinforcements, which considers modulus reduction due to oxidation damage, and a continuum damage model associated with O₂ diffusion along the micro-cracks in the SiC matrix are subsequently presented. The developed framework is used to simulate the mechanical behavior and oxidation process of a single fiber SiC/SiC composite.     

Wear behavior of SiC nanowire-reinforced SiC coating for C/C composites at elevated temperatures

To improve the wear resistance of SiC coating on carbon/carbon (C/C) composites, SiC nanowires (SiCNWs) were introduced into the SiC wear resistant coating. The dense SiC nanowire-reinforced SiC coating (SiCNW-SiC coating) was prepared on C/C composites using a two-step method consisting of chemical vapor deposition and pack cementation. The incorporation of SiCNWs improved the fracture toughness of SiC coating, which is an advantage in wear resistance. Wear behavior of the as-prepared coatings was investigated at elevated temperatures. The results show that the wear resistance of SiCNW-SiC coating was improved significantly by introducing SiC nanowires. It is worth noting that the wear rate of SiCNW-SiC coating was an order of magnitude lower than that of the SiC coating without SiCNWs at 800 °C. The wear mechanisms of SiCNW-SiC coating at 800 °C were abrasive wear and delamination. Pullout and breakage of SiC grains resulted in failure of SiC coating without SiCNWs at 800 °C.     

Improved thermal conductivity and mechanical properties of SiC/SiC composites using pitch-based carbon fibers

Pitch-based carbon fibers were assembled in horizontal and thickness directions of SiC/SiC composites to form three-dimensional heat conduction networks. The effects of heat conduction networks on microstructures, mechanics, and thermal conductivities were investigated. The results revealed the benefit of introducing heat conduction networks in the densification of composites. The maximum bending strength and interlaminar shear strength of the modified composites reached 568.67 MPa and 68.48 MPa, respectively. These values were equivalent to 18.6% and 69.4% increase compared to those of composites without channels. However, channels in thickness direction destroyed the continuity of fibers and matrix, creating numerous defects. As the volume fraction of heat conduction channels rose, the pinning strengthening effect of channels and influence of defects competed with each other to result in first enhanced mechanical properties followed by a decline. The in-plane thermal conductivity was found anisotropic with a maximum value reaching 86.20 W/(m·K) after introducing pitch-based carbon unidirectional tapes. The thermal conductivity in thickness direction increased with volume fraction of pitch-based carbon fibers and reached 19.13 W/(m·K) at 3.87 vol% pitch-based carbon fibers in the thickness direction. This value was 90.75% higher than that of composites without channels.     

Removal mechanism of SiC/SiC composites by underwater femtosecond laser ablation

Silicon carbide Ceramic matrix composites (SiC matrix with SiC fibers, abbreviated as SiC/SiC composites) are widely used in aerospace and energy applications due to their excellent resistance to high temperatures, corrosion, wear, and low density. However, the difficult machinability and surface oxidation of SiC/SiC composites are the main factors restricting their further application. To address these issues, this paper explores a novel method for underwater femtosecond laser ablation of SiC/SiC composites to obtain high cleanliness, low-oxidation microporous surfaces. This paper systematically analyses the changes in hole depth, material removal rate (MRR), surface morphology, and material components during underwater femtosecond laser ablation of SiC/SiC composites, and explains the formation of typical features such as induced cones, small banded pits, fiber debonding and shedding. Our work provides new research ideas for understanding the removal mechanism and surface oxidation resistance of SiC/SiC composites.     

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.     

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.     

Pore and microstructure change induced by SiC whiskers and particles in porous TiB2–TiC–Ti3SiC2 composites

TiB₂–TiC–Ti₃SiC₂ porous composites were prepared through a plasma heating reaction using powder mixtures of Ti, B₄C SiC whiskers (SiC_w) and SiC particles (SiC_p). The effects of the SiC_w and SiC_p content on pore structures, phase constituents, microstructure, and crystal morphology of TiC were studied. The results show that TiC, TiB, Ti₃B₄ phases are formed within the 5Ti+B₄C system. With the addition of SiC_w and SiC_p, the TiB and Ti₃B₄ phases are reduced, sometimes even disappeared. Interestingly, the content of TiB₂ and TiC increased, resulting in Ti₃SiC₂ and TiSi₂ being formed. The porosity of composites increases notably with the addition of SiC_w. However, with the increase of SiC_p, the porosity of the composites first decreases, followed by an increase. After adding the specified amount of SiC_w/SiC_p, the compressive strength of composites are improved significantly. Additionally, the pore size of the composites are decreased significantly with the addition of SiC_w/SiC_p. During the plasma heating process, some Si atoms will diffuse into the TiC lattice, which in turn made the cubic TiC grains into hexagonal lamellar TiC or Ti₃SiC₂ grains.