高温处理对3D C/SiC复合材料热膨胀性能的影响

研究了不同高温处理前后3D C/SiC复合材料热膨胀系数(CTE)的变化规律,从材料内部热应力变化及结构改变的角度定性地分析了其变化机理。研究发现,3D C/SiC复合材料的热膨胀系数受界面热应力的影响,其变化规律是纤维和基体相互限制、相互竞争的结果;高温处理可提高材料的热稳定性,并通过改变界面热应力及材料内部结构,来影响材料热膨胀系数的变化规律;通过增加基体裂纹来降低复合材料的低温热膨胀,但不影响其变化规律;通过改变材料内部结构,使热应力发生变化并重新分布,对复合材料的高温热膨胀产生显著影响。但高温处理没有改变3D C/SiC复合材料的基体裂纹愈合温度(900℃)。      

3D C/C复合材料的热膨胀性能

通过测定热膨胀系数(CTE),分析了不同密度以及高温处理前后热解炭基三维编织炭/炭复合材料(3DC/C复合材料)的热膨胀行为,并与PAN基炭纤维以及热解炭的热膨胀性能作了比较。结果表明:PAN基炭纤维在1200℃以后,出现明显的负膨胀。从室温到100℃,C/C复合材料呈负膨胀状态,CTE与密度成正比;从100℃到1000℃,C/C复合材料的CTE-温度曲线基本遵循热解炭基体的热膨胀规律变化;超过1000℃以后,CTE-温度曲线出现峰值,表明热解炭的膨胀受纤维的限制。复合材料的热膨胀行为由纤维和基体二者决定。     

热处理对含CSiCTaCC界面C/C复合材料力学性能的影响

以准三维针刺炭纤维毡为预制体, 采用化学气相渗透工艺在预制体中炭纤维/基体炭之间制备C-SiC-TaC-C复合界面, 利用树脂浸渍-炭化工艺对材料进一步增密, 获得含C-SiC-TaC-C界面的C/C复合材料。研究了1400～2500℃不同温度热处理前后复合材料的微观结构和力学性能。结果表明: 热处理前, SiC-TaC界面为管状结构, 复合材料的抗弯强度为241.6 MPa, 以脆性断裂为主; 经1400～1800℃热处理后, TaC界面破坏呈颗粒状, 复合材料的平均抗弯强度下降到238.9～226.1 MPa, 其断裂方式不变, 但断裂位移由0.7 mm增至1.0 mm; 经2000～2500℃热处理后, SiC、 TaC界面均受到破坏, 复合材料平均抗弯强度急剧下降至158.7～131.8 MPa, 断裂方式由脆性断裂转变为假塑性断裂。      

具有莫来石界面的C/Si-C-N复合材料热物理性能

以PIP方法制备界面层、CVI工艺制备基体,制备以Si-C-N陶瓷为基体、以莫来石为界面的碳纤维增强陶瓷基复合材料(C/mullite/Si-C-N).采用热膨胀仪和激光导热仪分别测试C/mullite/Si-C-N的热膨胀性能和热扩散性能,采用SEM和XRD分析材料的组织和形貌,采用DSC/TG同步分析仪分析基体材料的结构变化.结果表明:在25～1200℃范围内,C/mullite/Si-C-N复合材料的平均热膨胀率为1.58×10-6℃-1,线膨胀率为0.18％.复合材料的热扩散率与温度呈指数下降关系,这种指数关系是由基体的非晶结构造成的.热处理后的C/mullite/Si-C-N相对于未热处理的试样室温下的热扩散率显著下降,300℃以上的高温区段则略有升高,其在1000℃以下结构稳定,能满足工程应用需求.     

料浆浸渗法结合CVI制备3D C/SiC-TaC复合材料及其烧蚀性能研究

采用含1μmTaC微粉4%(体积分数)的料浆向10mm厚的3D碳纤维预制体中引入TaC,得到微粉含量高、中、低的三种预制体, CVI沉积SiC致密化后制得3D C/SiC-TaC多元基复合材料.氧-乙炔烧蚀试验后采用XRD和SEM对烧蚀产物和显微结构进行分析.结果表明:料浆法结合CVI可制备出C/SiC-TaC复合材料,高含量的TaC微粉烧蚀后形成的TaC和Ta2O5的固液混合物,能对烧蚀面进行有效包覆,有助于提高烧蚀性能.     

SiC/SiC复合材料在高温空气中的氧化行为

连续碳化硅纤维增强碳化硅复合材料(SiC/SiC)是先进航空发动机热端部件的重要候选材料.在高温燃气环境中,SiC/SiC会发生氧化腐蚀,导致材料性能迅速恶化.为了揭示国产SiC/SiC复合材料在高温燃气环境中的氧化腐蚀行为,本工作测试了SiC/SiC复合材料的1100～1300℃空气氧化性能,获得了材料的氧化动力学曲线,利用SEM,XPS和XRD分析了材料的形貌、成分和物相演变规律,以阐明其氧化行为.结果表明:SiC/SiC复合材料在1100～1300℃的氧化动力学均遵循抛物线规律;其氧化物为SiO2.SiC/SiC在1100℃时仅发生轻微氧化,温度高于1200℃时复合材料的氧化程度随温度升高而加剧.在BN界面相和基体孔隙附近的氧化现象更为明显.SiC/SiC复合材料的弯曲强度随氧化程度增加而降低.     

先驱体浸渍裂解C/SiCN复合材料的拉伸行为与基体开裂机制

采用先驱体浸渍裂解法制备陶瓷基复合材料过程中会形成基体裂纹和孔隙, 基体开裂和裂纹演化机制是工艺设计和性能优化的依据。本研究采用真空旋转浸渍-裂解法制备了无界面相的纤维束C/SiCN复合材料, 分析了该材料的拉伸性能和基体裂纹增殖现象, 讨论了浸渍裂解次数和热处理温度对基体裂纹的影响规律。研究结果表明: 当热处理温度为1000~1400 ℃时, 该复合材料的化学组成变化较小; 热处理温度达到1600 ℃时, 先驱体转化的SiCN基体分解, C含量降低, SiC含量升高。随浸渍裂解次数由1次增加到4次, 该复合材料的平均拉伸强度分别提升14.19%、38.83%和63.47%, 同时基体裂纹间距和裂纹开口距离均逐渐减小, 基体纤维结合增强, 断口纤维拔出减少。热处理温度从1000 ℃升高到1400 ℃, C/SiCN拉伸强度缓慢增大; 热处理温度为1600 ℃时, SiCN基体由无定形的SiC_xN_4-x四面体向SiC晶体转变, 基体与纤维脱粘, 二者结合强度降低, 同时基体体积收缩使C纤维损伤, 导致该复合材料拉伸强度陡然下降30.0%。     

炭纤维增强TaC基复合材料的力学性能和氧化行为

用化学气相渗透(CVI)方法在准三维针刺炭毡中沉积连续分布的TaC基体,制备出炭纤维增强TaC陶瓷基体C_f/TaC复合材料,研究了材料的力学性能和在1200-1600℃的氧化行为。结果表明,用CVI法可制备密度为5.12 g/cm~3的C_f/TaC复合材料,TaC陶瓷基体由相互平行的细纤维状晶体组成;与C/C材料相比,该复合材料的抗弯强度略低,但表现出较好的延展性断裂行为;在高温氧化过程中,C_f/TaC复合材料主要受气体在氧化层连通孔隙网络结构中的扩散和TaC/Ta_2O_5界面处的反应所控制。     

国内C/C复合材料基体改性研究进展

碳/碳(C/C)复合材料在高温含氧气氛下的氧化烧蚀问题严重制约该材料在航空航天领域的推广应用,基体改性技术是提高该材料高温抗氧化抗烧蚀能力的有效手段。介绍了目前发展的化学气相渗透、先驱体转化、反应熔体浸渗、化学气相反应等基体改性技术的主要方法,综述了SiC,ZrC,TaC,HfC,ZrB2,WC,Cu等抗氧化和抗烧蚀组元改性C/C复合材料的研究现状。指出难熔金属碳化物和硼化物,如HfC,ZrC,TaC,HfB2,ZrB2等,具有熔点高、高温性能稳定、抗烧蚀性能优良等特点,是提高C/C复合材料高温抗氧化抗烧蚀的理想基体改性材料,并提出了C/C复合材料基体改性研究中存在的问题和今后潜在的发展方向。     

1800℃热处理对PIP法C/SiC复合材料结构和性能的影响

采用扫描电镜(SEM)和透射电镜(TEM),研究氩气中1800℃热处理对先驱体浸渍-裂解(PIP)工艺制备三维编织C/SiC复合材料结构和性能的影响。结果表明:在1800℃热处理过程中,C/SiC复合材料的界面处发生了碳热还原反应和硅扩散,导致基体和纤维之间产生化学结合,纤维受到损伤;1800℃热处理后,PIP法C/SiC复合材料出现8%的失重率,力学性能急剧下降80%以上,断裂行为由韧性转变为脆性断裂。     

三维针刺C/SiC刹车材料的热物理性能

通过化学气相渗透(CVI)法结合反应熔体浸渗(RMI)法制备了三维针刺C/SiC刹车材料, 系统研究了三维针刺C/SiC刹车材料的热物理性能。结果表明: C/SiC刹车材料的热膨胀系数随温度升高总体呈增大趋势, 但呈规律性波动; 在相同温度下, 垂直于摩擦面方向的热膨胀系数远大于平行方向的。从室温至1300 ℃, 平行和垂直于摩擦面方向的平均热膨胀系数分别为1.75×10-6K-1和4.41×10-6K-1; C/SiC刹车材料的比定压热容随温度的升高而增大, 但增大速率逐渐减小。温度从100 ℃升到1400 ℃, 其比定压热容从1.41 J/(g·K) 增大到1.92 J/(g·K); C/SiC刹车材料的热扩散率随温度的升高而降低, 并趋于常量。平行于摩擦面方向的热扩散率明显大于垂直于摩擦面方向的热扩散率。      

Thermal expansion responses of pressure infiltrated SiC/Al metal-matrix composites

Aluminium-matrix composites containing thermally oxidized and unoxidized SiC particles featuring four average particle diameters ranging from 3 to 40 μm were produced by vacuum assisted high pressure infiltration. Their thermal expansion coefficient (CTE) was measured between 25 and 500°C. Oxidation of the SiC particles in air produces the formation at their surface of silicon oxide in quantities sufficient to bond the particles together, and confer strength to preforms. After infiltration with pure aluminium, the composites produced showed no sign of significant interfacial reaction. The CTE of the composite reinforced with unoxidized SiC particles featured an abrupt upward deviation upon heat-up near 200°C, and a second abrupt decrease near 400°C. The first transition is attributed to an inversion of stress across particle contact points. When composites are produced with oxidized SiC particles, these two transitions were removed, their CTE varying smoothly and gradually from the lower elastic bound to the upper elastic bound as temperature increases. With both composite types, the CTE decreased as the average particle size decreased. This work illustrates the benefits of three-dimensional reinforcement continuity for the production of low-CTE metal matrix composites, and shows a simple method for producing such composites. This revised version was published online in November 2006 with corrections to the Cover Date.     

Internal friction and dynamic modulus of three-dimensional silicon carbide-matrix composites

The internal friction and dynamic modulus of 3D C/SiC and SiC/SiC composites were investigated by means of forced vibration at elevated temperatures from room temperature to 600 °C, and the relationship between the microstructural defects in the composites and the internal friction mechanism was also discussed. It was found that the microstructural defects, which are produced by the mismatch of the coefficient of thermal expansion (CTE) between the fiber and matrix, have an important effect on the internal friction behavior and dynamic modulus of 3D C/SiC and SiC/SiC composites. C/SiC composites have a higher internal friction and lower dynamic modulus than SiC/SiC composites in the same testing conditions because of the damage.     

Study on the thermal expansion properties of C/C composites

Two different woven (2D and 3D) carbon/carbon composites (C/C) and a block carbon have been prepared by chemical vapor infiltration (CVI). The effects of the density and porosity of composites, preform architectures and heat treatment on the thermal expansion properties of the C/C composites were investigated. It is revealed that the coefficient of thermal expansion (CTE) of C/C composites is negative below 100 °C, and the CTE values are inversely proportion to its porosity. Comparing with 2D C/C composites, 3D C/C composites have a better thermal stability. Heat treatment can increase the thermal stability of composites by changing interfacial thermal stress. The thermal expansion behavior of C/C composites is considered as the result of interaction between fibers and matrix.     

Thermal expansion behaviour of plasma sprayed Al–SiCp composites

Abstract

Al with 55 and 75 vol.-%SiC powders were free mechanically mixed or ball milled as feedstock. The powder feedstock was deposited onto a graphite substrate to form near net shape of Al/SiC composites by air plasma spraying. The pores and the gaps at the Al/SiC interface as well as at the boundary of Al grains exist extensively in the as sprayed composites. Coefficient of thermal expansion (CTE) of the sprayed composites was measured in the temperature range of 25–300°C. The composites plasma sprayed with Al–75SiC powder feedstock can reach a low CTE value of 8 × 10^?6 °C^?1. The effect of pore on the CTE of the composites has been discussed. The gap at Al/SiC interface has an influence on thermal expansion behaviour only at lower test temperatures. Reduction and elimination of the gap with temperature can offset the thermal expansion of the as sprayed composites, resulting in lower CTE at the beginning of the CTE test. Roughly quantitative consideration of the effect of the interfacial gaps between Al and SiC on CET was given. Linear rule of mixture (ROM), Turner and Kerner's models were used to estimate the CTE of the sprayed composites. It was found that ROM and Kerner's model give closer CTE prediction for the present composites.     

高温氧化及热震对SiC/ZrB2-SiC/SiC涂层炭/炭复合材料力学行为的影响

为提高炭/炭(C/C)复合材料的高温抗氧化性能,同时分析涂层制备及高温氧化对涂层材料力学行为的影响,在C/C复合材料表面采用反应熔渗、料浆涂刷结合化学气相沉积工艺制备了SiC/ZrB2-SiC/SiC三层高温抗氧化涂层。利用SEM和XRD分析复合涂层的微观结构和相组成,考察涂层复合材料1500℃高温抗氧化和1500℃-室温的抗热震性能,研究高温氧化及热震对涂层C/C复合材料力学行为的影响。结果表明,复合涂层试样1500℃静态空气环境下具有优异的抗氧化及抗热震性能:1500℃氧化20 h后试样保持增重,1500℃至室温热震50次后增重为0.69%。因涂层制备过程中粉料的渗入反应,复合材料弯曲强度增长了7.08%。在经历1500℃氧化20 h和1500℃至室温50次热震后,涂层复合材料弯曲强度有所下降,且因材料界面结合力的减弱使得纤维拔出特征明显,材料塑性断裂特征增强。     

AlPO4环境障碍涂层材料水氧腐蚀性能研究

采用溶胶凝胶法合成了一种AlPO₄环境障碍涂层材料,测定了其热膨胀系数,在1350℃、50vol% H₂O/50vol%O₂、1.013×10⁵ Pa、气体流速0.085cm/s的水氧耦合环境中研究了其抗水氧腐蚀性能,并利用X射线衍射仪、能谱分析仪和扫描电子显微镜分析了材料组成和微观结构.结果表明,AlPO₄与C/SiC复合材料热膨胀基本匹配,抗水氧腐蚀性能良好.主要存在的问题是AlPO₄分解引起的失重,二氧化硅会加速其分解.