C/C复合材料SiC-MoSi2-WSi2抗氧化涂层的制备及性能研究

为提高C/C复合材料的高温抗氧化性能,以聚碳硅烷(PCS)浸渍裂解法和Si,Mo,W粉浆料刷涂反应法在C/C复合材料表面制备SiC-MoSi2-WSi2复合涂层,借助X射线衍射仪、扫描电镜等分析手段,对涂层的微观形貌、组织结构及物相进行分析研究,优化涂层制备工艺,考察了涂层的高温抗氧化性能,分析了抗氧化机理.制备的SiC-MoSi2-WSi2复合涂层厚度200 μm左右,主要由SiC,MoSi2,WSi2构成.1500℃氧化试验结果表明复合涂层的静态氧化失重率较SiC单层涂层降低50％以上,较大地改善了C/C复合材料的抗氧化性能.     

C/C复合材料抗氧化耐高温SiC陶瓷涂层的研究

采用高温反应法和PVD法在SiC工业合成炉内制备了C/C复合材料耐高温抗氧化SiC陶瓷涂层.用XRD、SEM对其物相组成和显微结构进行了表征与分析,讨论了涂层的形成机理,并研究了其高温氧化性能.研究结果表明,所制备的陶瓷涂层主要由α-SiCβ-SiC组成,晶粒发育完整,涂层表面致密、无裂纹,且与碳基体结合紧密,涂层厚度约600μm,涂层抗氧化性良好,在1500℃空气中氧化10h失重约为0.3%.     

水热温度对SiC–C/C复合材料表面水热电泳沉积SiCn–MoSi2复合抗氧化涂层的影响

采用水热电泳沉积法在SiC–C/C复合材料表面制备了纳米碳化硅和二硅化钼的复相(SiCn–MoSi2)抗氧化涂层。采用X射线衍射和扫描电子显微镜等对制备涂层的晶相组成、表面及断面微观结构进行了表征。研究了水热温度对制备涂层的结构及高温抗氧化性能的影响,分析了涂层在1 600℃静态氧化行为及失效机理。结果表明:外涂层主要由MoSi2和β-SiC晶相组成。复相外涂层的致密程度、厚度及抗氧化性能随着水热温度的升高而提高。SiCn–MoSi2/SiC复合涂层具有较好的抗氧化和抗热震能力,在1 600℃氧化80 h后氧化质量损失为3.6×10–3 g/cm2。复合涂层在1 600℃的氧化失效主要是由于经过长时间氧化后SiO2玻璃膜层不能及时有效填补涂层中的缺陷,涂层中出现贯穿性的裂纹和孔洞导致的。     

ZrC改性C/C复合材料的抗氧化涂层研究

为了提高C/C复合材料的高温抗氧化性能，采用含锆有机溶剂实现了对C/C复合材料的ZrC改性，通过粉末包埋法在其表面制备了SiC过渡层，通过溶胶凝胶法制备了外部的复合陶瓷氧阻挡层。设计三因素三水平的正交试验，研究了ZrC改性增重、过渡层厚度和氧阻挡层厚度三个主要因素对C/C复合材料高温抗氧化性能的影响。9个样品在1600℃马弗炉中进行了30 min的静态氧化测试，结果表明，ZrC改性增重5%、过渡层厚度为60μm和氧阻挡层厚度为80μm的样品抗氧化性能最好，质量损失率仅约5.51%。     

水热温度对SiC-C/C复合材料表面水热电泳沉积SiCn-MoSi2复合抗氧化涂层的影响

采用水热电泳沉积法在SiC–C/C复合材料表面制备了纳米碳化硅和二硅化钼的复相(SiCn–MoSi2)抗氧化涂层。采用X射线衍射和扫描电子显微镜等对制备涂层的晶相组成、表面及断面微观结构进行了表征。研究了水热温度对制备涂层的结构及高温抗氧化性能的影响,分析了涂层在1 600℃静态氧化行为及失效机理。结果表明:外涂层主要由MoSi2和β-SiC晶相组成。复相外涂层的致密程度、厚度及抗氧化性能随着水热温度的升高而提高。SiCn–MoSi2/SiC复合涂层具有较好的抗氧化和抗热震能力,在1 600℃氧化80 h后氧化质量损失为3.6×10–3 g/cm2。复合涂层在1 600℃的氧化失效主要是由于经过长时间氧化后SiO2玻璃膜层不能及时有效填补涂层中的缺陷,涂层中出现贯穿性的裂纹和孔洞导致的。     

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。     

Cf/SiC 复合材料的 ZrB2-SiC/SiC 超高温陶瓷涂层研究

采用两步包埋法在Cf/SiC复合材料表面制备了Zr B_2-SiC/SiC超高温陶瓷涂层。借助SEM、XRD对涂层的微观结构及物相组成进行了分析研究,并进行了高温静态氧化和热震测试。研究表明,1500°C氧化5 h后,涂层表面覆盖有平整的玻璃相氧化层,氧化失重率为6.4%;热震测试10次后涂层的氧化失重率为14%。Zr B_2-SiC/SiC涂层能有效提高Cf/SiC复合材料的高温抗氧化性能。     

C/C复合材料SiC-Mo(Si,Al)_2涂层结构和抗氧化性能研究

采用高温原位反应法在C/C复合材料表面制备了SiC-Mo(Si, Al)_2防氧化复合涂层,用XRD、SEM测试表征了其物相组成和显微结构,对制备粉料中铝硅含量对涂层微观结构和抗氧化能力的影响进行了研究,分析了涂层失效原因。研究结果表明:添加Al粉使涂层制备过程粉料浸渗能力增强;Al、Si原子比为1∶10时所得到的复合涂层主要有Mo(Si, Al)_2、MoSi_2、SiC和游离Si等物相,具有较大的厚度和致密的结构,体现出良好的抗氧化性能。随着氧化的进行,SiO_2玻璃层出现的孔洞加速了涂层材料损耗,导致涂层中出现贯穿性裂纹,是涂层失效的主要原因。     

制备温度对ZrC-SiC复合涂层高温耐烧蚀性能影响北大核心

为提高C/C复合材料在超高温环境中的高温耐烧蚀性能,不同包埋温度1450,1550,1650,1750℃下在C/C复合材料表面制备了ZrC-SiC复合涂层。利用XRD、SEM和EDS等分析测试手段,对比研究了涂层的物相组成和微观结构,并借助等离子烧蚀设备进行烧蚀实验,分析讨论涂层的高温耐烧蚀性能和烧蚀机理。结果表明:1650℃包埋温度下的ZrC-SiC涂层与基体结合良好,其质量烧蚀率和线烧蚀率分别为0.129 mg/s和1.867μm/s,烧蚀性能最好。烧蚀后,ZrC-SiC涂层表面形成了ZrO2和SiO2熔融相,其中ZrO2分布在SiO2熔融物中,提高了氧化层的黏度和抗冲刷能力,使得ZrC-SiC涂层具有良好的高温耐烧蚀能力。     

C/C坯体结构对RMI制备C/SiC复合材料的影响

采用无涂层、SiC涂层、C和SiC复合涂层处理的炭布/网胎预制体,经过CVD和树脂浸渍/炭化混合致密,制备了4种C/C坯体,随后熔融渗硅获得C/SiC复合材料;研究了不同纤维涂层、基体炭类型对C/SiC复合材料弯曲强度和断裂方式的影响,并对复合涂层状态的C/SiC材料的摩擦磨损性能进行测试。结果表明:混合基体炭与纯热解炭的C/C坯体相比,制备的RMI-C/SiC材料弯曲强度更高,且经过涂层处理的C/SiC材料弯曲强度最高;复合涂层、混合基体炭均使材料表现出良好的"假塑性"。复合涂层处理的试样在制动压力0.6～0.8 MPa、惯量0.3～0.4 kg·m~2、转速为6000～7500 r/min的条件下,平均摩擦系数为0.348～0.454,且材料磨损量较小,最大为2.188μm/(面·次)。     

Structural design and ablation performance of ZrB2/MoSi2 laminated coating for SiC coated carbon/carbon composites

A protective coating alternated with ZrB₂ and MoSi₂ laminated layers was designed and prepared on carbon/carbon (C/C) composites with SiC inner layer by supersonic atmosphere plasma spraying. After ablated at a heat flux of 2.4 MW/m² for 30s, ZrB₂/MoSi₂ laminated coating was in good condition with a linear growth rate and mass gain rate of 1.67 μm/s and 0.44 mg/s, respectively. From the central region to the border region, the calculated residual thermal stress of ZrB₂/MoSi₂ laminated coating decreased at first and then increased rapidly, illustrating the size change of the generated laminated cracks. The alternate design of ZrB₂ layers for erosion and MoSi₂ layers for oxidation resulted in the laminated stress distribution and improved ablation resistance.     

High temperature oxidation resistance of Y2O3 modified ZrB2-SiC coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites from oxidation at high temperature, Y₂O₃ modified ZrB₂-SiC coating was fabricated on C/C composites by atmospheric plasma spraying. The microstructure and chemical composition of the coatings were characterized by SEM, EDS, and XRD. Experiment results showed that the coating with 10 wt% Y₂O₃ presented a relatively compact surface without evident holes and cracks. No peeling off occurred on the interface between the coating and substrate. The ZSY10 coating underwent oxidation at 1450 °C for 10 h with a mass loss of 5.77%, while that of ZS coating was as high as 16.79%. The existence of Y₂O₃ played an important role in inhibiting the phase transition of ZrO₂, thus avoiding the cracks caused by the volume expansion of the coating. Meanwhile, Y₂SiO₅ and ZrSiO₄ had a similar coefficient of thermal expansion (CTE), which could relieve the thermal stress inside the coating. The ceramic phases Y₂SiO₅, Y₂Si₂O₇ and ZrSiO₄ with high thermal stability and low oxygen permeability reduced the volatilization of SiO₂.     

Bimodal microstructure ZrB2-MoSi2 coating prepared by atmospheric plasma spraying for carbon/carbon composites against long-term ablation

To protect carbon/carbon composites against long-term ablation, a bimodal microstructure ZrB₂-MoSi₂ coating, consisting of an outer ZrB₂-MoSi₂ layer modified by Y₂O₃ and an inner basal ZrB₂-MoSi₂ layer, was prepared by atmospheric plasma spraying. The microstructure, phase composition and ablation resistance of the proposed coating were investigated in detail. Results showed that the bimodal coating maintained integrity in structure except for phase composition. There was no visible interlayer between the inner ZrB₂-MiSi₂ layer and the outer modified one. Mass ablation rate of the bimodal microstructure ZrB₂-MoSi₂ coated C/C composites was −2.02 × 10⁻³ g/s under an oxyacetylene flame ablation at 1873 K for 600 s, which exhibited better ablation resistance than a single ZrB₂-MoSi₂ coating. The excellent ablation resistance was ascribed to the positive effect of Y₂O₃, which not only pined in the glassy phase and alleviated the volatilization of SiO₂ glass phase by reacting with SiO₂ to form high viscosity of Y₂SiO₅, but also stabilized ZrO₂ and promoted its recrystallization and growth.     

碳/碳复合材料力学性能的研究进展

本文综述了碳/碳复合材料力学性能的研究进展,包括碳纤维、基体炭、界面性能、制备工艺及工艺参数等对碳/碳复合材料力学性能的影响。同时简单介绍了当今单向碳/碳复合材料力学性能的表征手段。希望对碳/碳复合材料力学性能的研究及应用提供帮助。     

The mechanical and repair behavior of damaged carbon/carbon composites

With the aim of understanding the effect of defect types on the mechanical performance of carbon/carbon (C/C) composites, three kinds of defects such as circle arc, square, and triangle shapes were prefabricated on their surfaces. The results show that the prefabricated defects damage the flexural strength of C/C composites compared to the pristine sample (101 ± 6 MPa). The flexural strength of C/C decreased by 30.84%, 45.84%, and 42.58% corresponding to the circle arc, square, and triangle type defects respectively. The defect-repair method with Ni-based solder as the additive was employed to repair the damaged C/C composites. After repair, the stress concentration of C/C composites decreases, and there is a good connection between carbon fiber and the repaired solder so that the load can be transferred continuously, therefore the flexural strength of C/C composites can be improved by 20–28%.     

Mechanical and thermophysical properties of carbon/carbon composites with hafnium carbide

Carbon/carbon (C/C) composites with addition of hafnium carbide (HfC) were prepared by immersing the carbon felt in a hafnium oxychloride aqueous solution, followed by densification and graphitization. Mechanical properties, coefficients of thermal expansion (CTE), and thermal conductivity of the composites were investigated. Results show that mechanical properties of the composites decrease dramatically when the HfC content is greater than 6.5 wt%. CTE of the composites increases with the increase of HfC contents. The composites with addition of 6.5 wt% HfC show the highest thermal conductivity. The high thermal conductivity results from the thermal motion of CO in the gaps and pores, which can improve phonon–defect interaction of the C/C composites. Thermal conductivities of the composites decrease when the HfC content is greater than 6.5 wt%, which is due to formation of a large number of cracks in the composites. Cracks increase the phonon scattering and hence restrain heat transport, which results in the decrease of thermal conductivity of the composites.     

国产碳纤维编织碳/碳喉衬烧蚀分析

采用国产T300级碳纤维进行轴棒法编织结构碳/碳(C/C)复合材料制备,并对C/C复合材料喉衬进行固体火箭发动机(SRM)地面点火试验,结合扫描电子显微镜(SEM),分别对烧蚀后喉衬入口部位、喉部和出口部位的烧蚀形貌进行分析。结果表明,在7.432 MPa压力下,国产T300级碳纤维轴棒法编织结构C/C喉衬的烧蚀性能较为稳定,烧蚀均匀,烧蚀后型面光滑,烧蚀率较低,平均线烧蚀率为0.159 6 mm/s,国产T300级碳纤维的性能满足发动机的工作要求。     

Enhanced bonding strength and thermal cycling performance of MoSi2–CrSi2–SiC–Si coating for carbon/carbon composites by surface modification via blasting treatment

Before the preparation of MoSi₂–CrSi₂–SiC–Si coating, blasting treatment of carbon/carbon (C/C) composites, as a surface modification method, was conducted under oxyacetylene torch. MoSi₂–CrSi₂–SiC–Si coating was prepared on the treated C/C composites by pack cementation, where an interlock interface was formed between the coating and the C/C substrate. After blasting treatment, the thermal expansion coefficient mismatch between the coating and C/C substrate was alleviated efficiently, and the bonding strength of the coating was increased by 45.6% and reached 26.2 MPa. To simulate the real working condition, thermal cycling test was conducted under oxyacetylene torch from 1600 °C to room temperature to construct an environment of combustion gas erosion. Due to the improvement of bonding strength and the alleviation of thermal expansion coefficient mismatch between the coating and the C/C substrate, thermal cycling performance of MoSi₂–CrSi₂–SiC–Si coating was enhanced. After 25 thermal cycles, the mass loss of the coated C/C composites without blasting treatment was up to 2.4%, and the C/C substrate was partially exposed. In contrast, the mass loss of the coated C/C composites with blasting treatment was only 1.1%.     

Ablation resistance of HfC-TaC/HfC-SiC alternate coating for SiC-coated carbon/carbon composites under cyclic ablation

HfC-TaC/HfC-SiC alternate coatings with different sublayer thicknesses were fabricated on SiC-coated carbon/carbon composites by supersonic atmosphere plasma spraying. Their ablation resistance was studied under oxyacetylene torch and compared with monolayered HfC-TaC coating. The alternate coating with 6 spray cycles of HfC-TaC and 3 spray cycles of HfC-SiC sublayers exhibited the best ablation performance as confirmed by the integral coating morphology and the lowest ablation rates. A dense oxide layer acting as an oxygen insulator and the release of thermal stress induced by the formation of dendritic cracks are thought to be responsible for its great ablation resistance. For the alternate coating with 4 spray cycles of HfC-TaC and 2 spray cycles of HfC-SiC sublayers, exfoliation occurred at the interface of two adjacent sublayers, leading to violent evaporation of exposed HfC-SiC sublayer.