Enchanced high-temperature performances of SiC/SiC composites by high densification and crystalline structure

We report the enchanced in situ performances of tensile strength and thermal conductivity at elevated temperatures of the PCS-free SiC/SiC composite with a high fiber volume fraction above 50% fabricated by NITE process for nuclear applications. The composite was fabricated by the optimized combination of the fiber coating, the matrix slurry and the pressure-sintering conditions, based on our previous composites’ study history. The composite showed the excellent tensile strength up to 1500 °C, that it retained approximately 88% of the room-temperature strength. Also, the thermal conductivity of the composites represented over 20 W/m K up to 1500 °C, which was enough high to take the advantage of the assumed design value for nuclear applications. Microstructural observation indicated that the excellent high-temperature performances regarding tensile strength and thermal conductivity up to 1500 °C were the contribution to the high densification and crystalline structure in matrix.     

C/C刹车盘快速致密化工艺及其性能

为了缩短C/C刹车盘制备周期并提高其性能,介绍了一种制备C/C飞机刹车盘的快速致密化工艺,即采用天然气与丙烷气的混合气体为炭源气体的等温压差CVI法。与常规致密化工艺（丙烯气为炭源气体的等温压差CVI法）相比,C/C刹车盘的CVI(Chemical vapor infiltration) 时间缩短了一半,其导热性能提高5%以上,拉伸、压缩、弯曲与剪切性能提高10%以上,摩擦磨损性能提高20%以上。      

Fabrication of Tia SiC2 modified C/C - SiC composites by liquid silicon infiltration

采用浆料浸渗结合液硅渗透法原位生成高韧性Ti3SiC2基体,制备Ti3SiC2改性C／C—SiC复合材料。研究了TiC颗粒的引入对熔融Si浸渗效果的影响,分析了Ti3SiC2改性C／C-SiC复合材料的微结构和力学性能。实验结果表明：TiC与熔融si反应生成Ti3SiC2是可行的,而且c的存在更有利于生成Ti3SiC2;在含TiC颗粒的C／C预制体孔隙（平均孔径22．3μm）内,熔融si的渗透深度1min内可达10．8cm;Ti3SiC2取代残余Si后提高了C／C-SiC复合材料的力学性能,C／C-SiC-Ti3SiC2复合材料的弯曲强度达203MPa,断裂韧性达到8．8MPa·m^[1/2];对于厚度为20rllm的试样,不同渗透深度处材料均具有相近的相成分、密度和力学性能,无明显微结构梯度存在,表明所采用的浆料浸渗结合液硅渗透工艺适用于制备厚壁Ti3SiC2改性C／C-SiC复合材料构件。     

多元耦合场CVI法快速致密化炭/炭复合材料研究

以液化石油气为碳源气体,采用多元耦合场CVI工艺方法快速制备了炭/炭复合材料.在自制冷壁CVI炉中,使用普通炭毡作为炭纤维预制体,设置特殊的导电发热层,沉积温度为650～1050℃,系统的气氛压力为0.1～30kPa,流量为0.1～0.5m3/h,沉积时间12h的条件下可将预制体一次性快速增密至1.75g/cm3.XRD分析表明:该材料经过2300℃,2h高温石墨化处理,其石墨化度(g)可达到61.3%,晶粒尺寸达到16.1nm.PLM分析表明所得材料偏光形貌表现为光滑层(SL)结构,SEM形貌照片测算可知热解炭沉积速率在6.6μm/h以上.分析了炭/炭致密化的过程和热解炭的沉积机理,说明多元耦合场加速了热解炭的沉积,缩短了致密化时间,降低了成本.     

多孔C/SiC复合材料的制备及其性能

以W丝作为成孔剂,采用孔隙预置技术制备了发汗多孔C/SiC复合材料,对其孔隙结构进行表征,研究了材料的力学性能和渗透行为.结果表明:采用孔隙预置技术能够有效的控制多孔C/SiC材料开孔率和孔隙结构,其孔隙主要由W丝去除后形成的直通孔组成,开孔率决定于W丝的体积含量,所制备的材料具有良好的力学性能和渗透性能.其弯曲强度达到358 MPa、弯曲模量达到124 GPa,断裂韧性达到16.7 MPa·m1/2,空隙率为23.5%,渗透率为1.02×10-3mm2,材料表现为韧性断裂模式,其孔隙的存在并没有对材料的力学性能产生明显的影响.     

炭/炭复合材料SiC/SiC+mullite/mullite涂层制备及其高温性能

为提高炭/炭复合材料的防氧化性能,采用包埋法与超音速等离子喷涂法相结合,在其表面制备了SiC/SiC+mullite/mullite多层防氧化涂层.外涂层主要组成是莫来石(mullite)相.对涂层试样进行了1 500℃恒温氧化和1 500℃～室温热震测试.实验结果表明,涂层试样经1 500℃恒温氧化150 h后,失重率仅为0.26%;经1 500℃～室温15次热震后,失重率仅为0.25%,显示出较优异的防氧化、抗热震性能.莫来石(mullite)具有良好的耐高温性能、低的氧扩散率,且SiC涂层氧化生成的SiO2在高温下能够愈合裂纹等缺陷,这是SiC/SiC+mullite/mullite涂层较好防氧化能力的主要原因.     

3D C/SiC复合材料的热辐射性能

利用稳态量热计法和傅里叶红外光谱仪分别测定了3D C/SiC复合材料在90℃时的半球向总发射率和室温法向光谱反射率,研究了表面形貌、涂层厚度及高温氧化对3D C/SiC热辐射性能的影响。结果表明:3D C/SiC具有优异的热辐射性能,其总发射率可达0.83;随着SiC涂层厚度的增加,3D C/SiC总发射率先降低后上升;高温氧化后,3D C/SiC的热辐射性能有所提高。      

致密化工艺对厚壁针刺C/C复合材料性能的影响

采用化学气相渗透(CVI)+树脂浸渍碳化法(PIC)、CVI+沥青高压浸渍碳化法(HPIC)及HPIC工艺分别制备了IR-C/C、IP-C/C以及P-C/C三种厚壁针刺C/C复合材料,研究了三种材料的热力学性能及材料内部密度均匀性。结果表明,IP-C/C材料轴向拉伸强度为24.7 MPa,IR-C/C材料轴向压缩强度达到200 MPa,而P-C/C材料轴向拉伸强度仅为7.4 MPa,相比IR-C/C材料降低了53%,相比IP-C/C材料降低了70%。复合致密化工艺制备的材料具有较低的热膨胀系数,而P-C/C材料1000℃热膨胀系数达到了3.566×10-6℃-1,是IPC/C材料的2.5倍。IP-C/C材料和P-C/C材料采用高压碳化工艺增密,材料的致密度高,密度分布均匀,导热系数高。IR-C/C材料内部密度降为14.5%,密度分布为外高内低。以CVI+HPIC复合制备的材料综合性能优异,且内部密度分布均匀,适合于制备厚壁材料。     

An approach to the mechanical behaviour of SiC/SiC and C/SiC ceramic matrix composites

The mechanical behaviour of two woven composites C/SiC and SiC/SiC was investigated at room temperature. The non-linear load-displacement curves and the damaging process were closely related to the specific structure of the composites, consisting of a network of impregnated bundles of fibres. The damage in the bundles proceeded by multiple cracking in the matrix before fibre failure, and dictated the response to the applied load. Other mechanisms, consisting mainly of distortions in bundles and their framework, induced a residual deformation and an energy dissipation. The behaviour was characterized according to the damaging process. Stress-electric strain curves revealed a mechanical response similar to those observed in unidirectional composites, although some effect of the specimen geometry on the curves was observed. Residual strains were similar in tensile and bending conditions. The work of fracture was consistently described by a volumetric rate of energy absorption, related to the applied strain, but the respective contributions of different damage mechanisms could not be determined.     

SiC/Mo-Si复合涂层C/SiC复合材料的氧化性能

采用化学气相沉积法(CVD)和刷涂法在C/SiC复合材料表面制备抗氧化涂层。该涂层由致密的CVDSiC层和多孔的Mo-Si层交替组成,其结构从里到外为:CVDSiC层→Mo-Si层→CVDSiC层→Mo-Si层→CVDSiC层。涂层试样于1400℃的氧化实验和1400℃100℃的热震实验结果表明:在氧化和热震过程中,涂层均保持完整,没有出现脱落和掉块等失效现象。经1400℃、150h氧化后,涂层试样的失重率仅为0.25%,失重速率为6.61×10-6g.cm-.2h-1。在热震过程中,涂层试样基本保持氧化增重。经25次和50次热震后,涂层试样的弯曲强度保持率分别为95.73%和81.61%。SiC/Mo-Si复合涂层具有优异的抗氧化和抗热震性能,可对C/SiC复合材料提供1400℃、长时间的氧化防护。     

Oxidation behaviour of three-dimensional woven C/SiC composites

Abstract

The oxidation behaviour of a three-dimensional woven C/SiC composite protected with an SiC seal coating and with an SiC coating combined with an SiO₂–B₂O₃ glassy coating have been respectively investigated through an experimental approach based on mass and flexural strength changes. Three main temperature domains exist for C/SiC composites protected with an SiC seal coating. At low temperatures (<700°C), the mechanisms of reaction between carbon and oxygen control the oxidation kinetics. At an intermediate temperatures (between 700 and 1100°C), the oxidation kinetics are controlled by gas phase diffusion through a network of microcracks in the SiC matrix and coating. At high temperatures (>1100°C), the oxidation kinetics are controlled by oxygen diffusion through the SiO₂ scale formed on the SiC coating. Composites of C/SiC with an SiC/(SiO₂–B₂O₃) coating exhibit better oxidation resistance. The filling of the pores and the microcracks and the flow of the glassy coating at higher temperatures result in a global decrease of mass loss in the composites. By researching the relationship between the residual flexural strength and the mass variation in different temperature ranges, it is shown that the change in the residual flexural strength is dominated by the degradation of carbon phase.     

BN/SiC复合界面层对SiC纤维和PIP-Mini复合材料力学性能的影响

采用化学气相渗透(CVI)工艺,在SiC纤维表面沉积BN和BN/SiC复合界面层,对沉积界面层前后纤维的力学性能进行了评价。采用聚合物浸渍裂解(PIP)工艺进行致密化,制得以原纤维、BN界面层和BN/SiC界面层纤维增强的三种Mini-SiCf/SiC复合材料,研究其微观结构和拉伸性能。结果表明:采用CVI工艺制得的界面层厚度均匀、结构致密,其中BN界面层中存在六方相,晶体尺寸为1.76 nm; SiC界面层结晶性较好,晶粒尺寸为18.73 nm;沉积界面层后SiC纤维的弹性模量基本保持不变,拉伸强度降低。与SiCf/SiC相比, PIP工艺制备的SiCf/BN/SiC和SiCf/(BN/SiC)/SiC-Mini复合材料所能承受的最大拉伸载荷和断裂应变明显提升, BN界面层起主要作用。由断面形貌分析可以看出, SiCf/BN/SiC和SiCf/(BN/SiC)/SiC复合材料的纤维拔出明显,说明在断裂时消耗的能量增加,可承受的最大载荷增大。     

等离子喷涂法制备炭/炭复合材料硅酸钇涂层研究

采用等离子喷涂(Atmospheric plasma spraying,APS)法在炭/炭复合材料碳化硅(SiC)内涂层表面制备了硅酸钇涂层。分别采用XRD和SEM分析了所得涂层的微观结构,并测试了带有SiC/硅酸钇复合涂层的炭/炭复合材料试样在1500℃静态空气中的抗氧化性能。结果表明:通过调节喷涂粉料中的SiO2和Y2O3的摩尔比,可制得Y2SiO5、Y2Si2O7、Y2Si2O7/Y2SiO5和Y4Si3O12/Y2Si2O7/Y2SiO5四种不同结构的硅酸钇涂层;1500℃氧化73h后,SiC/Y4Si3O12/Y2Si2O7/Y2SiO5涂层试样的氧化失重速率相对较低,仅为1.01×10-4g.cm-.2h-1。     

Laser ablation behaviors of C/SiC composites in air简

Ablation behaviors of silicon carbide (SiC) coated 2D carbon fiber reinforced silicon carbide matrix (designated as 2D C/SiC) composites prepared by chemical vapor infiltration (CVI) were investigated by a continuous wave CO₂ laser. The 2D C/SiC specimens were exposed under laser for 0.5 s in ambient air, and the laser powers varied from 500 W to 1500 W. A 3D finite element model was established to calculate the temperature distribution in the laser ablation process. The ablation depth, width and profile were measured by Laser Confocal Microscope (LCM). The results indicate that the increase of ablation depth follows a linear relation with the increase of laser power, and the increase of ablation width follows a similar trend with the increase of the isotherm diameter of 1712 ℃. The ablated surface can be distinguished into three different regions by scanning electron microscope (SEM) observation, including ablation center, transition zone and ablation fringe. The ablation behaviors of carbon fibers and SiC matrices in different regions were presented and discussed in the study.     

三维针刺C/SiC复合材料显微结构演变分析

以三维针刺碳毡作为预制体,采用树脂浸渍-热解工艺制备C/C多孔体,然后采用反应熔体浸渍法(Reactive melt infiltration,RMI)对C/C多孔体分别浸渗Si和Si-Mo合金制备C/SiC复合材料。首先研究了C/C多孔体制备过程中的显微结构演变。结果表明,浸渍过程中树脂主要填充在纤维束内小孔隙中,热解后裂纹增多,生成网格状C/C亚结构单元;高温热处理使C/C复合材料裂纹进一步扩展,石墨化度提高,束内闭气孔打开,从而为RMI渗Si提供通道。然后对C/C多孔体分别渗Si和Si-Mo合金所得材料的物相组成和显微结构进行对比分析。发现纯Si浸渗得到的复合材料残余Si较多,束内纤维受损严重;而浸渗Si-Mo合金可以减少残余Si含量,束内纤维受损轻微,仍保持着完整的C/C亚结构单元。     

C/SiC复合材料空气耦合超声检测数值模拟

针对高孔隙率C/SiC复合材料空气耦合超声检测,引入考虑孔隙形貌的随机孔隙模型开展数值模拟研究。结合力学和声学性能测试计算材料弹性刚度矩阵,借助组织分析建立考虑孔隙微观形貌、孔隙率分别为5%、10%、15%的随机孔隙有限元模型,研究了空气耦合超声透射法检测过程中超声波传播特征及典型缺陷的响应规律。结果表明:材料纵波声速约2830 m/s,横观各向同性五个独立弹性常数分别为158.149、88.589、34.141、15.288和13.793 GPa。孔隙呈长条状,随孔隙率增加,超声衰减逐渐增大;孔隙尺寸与波长的比值约在0.05~0.22范围,主要为瑞利散射机制。高孔隙率、复杂孔隙形貌显著影响超声波的传播过程,导致个别条件下声场指向性发生偏转,影响缺陷检测。当分层缺陷长度由0增加到25 mm时,接收信号幅值衰减增大,与无分层模型相比最大衰减增加33.9 dB。随着复合材料层板厚度的增加,超声衰减进一步增强,声场也将产生一定偏转,主要体现孔隙和分层的共同作用。计算结果与实验吻合较好,为高孔隙率C/SiC复合材料的高质量无损检测提供支撑。      

涂敷含硼硅玻璃SiC涂层的C/SiC复合材料空气氧化行为

以2D C/SiC复合材料为基底, 采用聚合物裂解工艺(Polymer plyen)制备了含硼硅玻璃SiC自愈合涂层。利用扫描电镜对含硼硅玻璃SiC涂层的2D C/SiC复合材料氧化前后的微结构形貌进行了分析。研究了含硼硅玻璃SiC涂层的C/SiC复合材料在静态空气中700℃、 1000℃和1200℃下的氧化行为, 并分析了涂层层数对C/SiC复合材料氧化行为的影响。结果表明: 含硼硅玻璃SiC涂层在该温度下形成的玻璃相可以较好地封填表面缺陷(裂纹和孔洞); 并且随温度升高及涂层层数增加, 试样在氧化过程中质量减少率降低, 氧化后的强度保持率提高。      

C/SiC材料表面Si/SiC涂层及其对基底结构的影响

采用泥浆预涂层反应法在C/ SiC 复合材料表面制备Si/ SiC 涂层。通过理论计算和实验确定了制备致密不开裂涂层的泥浆配比; 研究了埋粉烧结和气相硅真空反应烧结2 种不同烧结气氛对Si/ SiC 涂层微观形貌和成分的影响; 比较了单涂层和双涂层2 种不同涂层制备方法对C/ SiC 复合材料基底结构的影响; 用SEM 观察涂层形貌, 用XRD 分析涂层成分与晶体结构。结果表明: 泥浆中C∶Si (质量比) 在1∶1. 25 左右制备的涂层不开裂; 埋粉烧结制备的涂层成粉, 而气相硅真空反应烧结制备的涂层致密且与基底结合好; 单涂层法制备涂层后基底材料致密度高, 而双涂层法制备涂层后基底仍然保持多孔结构。      

Simultaneous synthesis and densification of TiC/Ni-Al composites

The process of combustion synthesis was used to produce ceramic-metal composite materials consisting of titanium carbide (TiC) and an intermetallic alloy of the Ni-Al system. The samples were produced by rapidly heating a mixture of elemental Ti, C, Ni, and Al powders in a graphite die up to the ignition temperature. By applying mechanical pressure during or immediately following the combustion reaction, products of greater than 99% theoretical density were obtained. The residual porosity and microstructural development were characterized using optical microscopy, and X-ray diffraction methods. The nature and composition of the product phases can be controlled by variations in the ratios of the starting reagents, level of mechanical pressure, addition of diluents, and the inclusion of dopants. By varying the combustion synthesis parameters, the properties of the product can be tailored to meet specific application needs. Apparent applications of such composites include cutting tools, wear parts, structural components, armour, etc.     

New technology for fabrication of C/SiC composites reinforced by continuous carbon tows

Abstract

Carbon/silicon carbide composites were fabricated using the continuous synchronous composite (CSC) process, which is an improved technology based on conventional chemical vapour infiltration principles to fabricate ceramic matrix composites reinforced with carbon cloth or continuous tows which are not braided to a preform. In the CSC process, a gradient temperature field on the surface of the graphitic substrate, consisting of high (1000–1200°C), intermediate (900–1000°C), and low (700–900°C) temperature regions, was obtained by a bottom heating element. Since the rotation of the substrate accompanied simultaneously the preparation of the reinforcement phase and the deposition of the SiC matrix, micropores were well infiltrated in the intermediate temperature regions by diffusion transport, and macropores were well infiltrated in the high temperature regions with flow transport, respectively. Using methyltrichlorosilane (MTS) as a precursor, with hydrogen as a carrying gas and argon gas as a diluent, in the present studies, densification of C/SiC composites was uniform, and the highest deposition rate obtained was 0.168 mg cm^-2 min^-1), and the conversion efficiency of MTS varied from 31% to a maximum of 47%.