碳/碳复合材料氧化的研究进展

碳/碳(C/C)复合材料因比重轻、导电导热快等优异性能,成为航空航天领域应用的理想材料,但在643K以上温度的含氧环境中,碳/碳(C/C)复合材料易发生氧化而导致失效,因此,研究C/C复合材料的抗氧化性能非常必要。本文对C/C复合材料的氧化过程进行了总结,氧化过程主要是低温段的碳氧化学反应控制和高温段的氧气经边界层与碳反应的扩散控制。目前,针对C/C复合材料的抗氧化性弱的问题,有研究者提出,基体改性和涂层防护是提高材料抗氧化能力的主要方法。本文综述了静态氧化和高温氧化烧蚀的最新研究进展,从相关的研究进展可知,该材料的应用环境较为单一,为此本文基于海洋腐蚀环境,分析了C/C复合材料的氧化过程。     

SiC/SiC复合材料及其应用

日本开发的Nicalon和Tyranno两种品牌的SiC纤维占有世界上绝对性的市场份额。SiC/SiC复合材料典型的界面层是500 nm厚的单层热解碳(PyC)涂层或多层(PyC-SiC)n涂层,在湿度燃烧环境及中高温条件下界面层的稳定性是应用研究的重点。SiC/SiC复合材料,包括CVI-SiC基体和日本开发的Tyranno hex和NITE-SiC基体等,具有耐高温、耐氧化性和耐辐射性的特点,在航空涡轮发动机部件、航天热结构部件及核聚变反应堆炉第一壁材料等方面正开展工程研制应用。     

C/C复合材料SiC-SiO_2/ZrO_2-SiC复合抗氧化涂层

为了提高C/C复合材料在高温有氧环境的抗氧化性,在SiC抗氧化涂层防护的基础上,采用气相沉积法及溶胶凝胶吸附冷凝热蒸汽法在C/C复合材料表面制备出了SiC-SiO2/ZrO2-SiC复合涂层。利用扫描电镜、能谱质谱测试及X射线衍射等检测方法对涂层各层进行了分析。结果表明,溶胶吸附ZrCl4蒸汽法制备ZrO2涂层,不仅能够在高温自动修复单层SiC涂层的裂纹缺陷,还起到了在制备外层SiC涂层过程中缓冲应力的作用。这种多层复合涂层在高温下具有良好的抗氧化性,在1 800℃等离子焰动态空气氧化120 s后,计算得出该涂层失重速率仅为0.4 g/(m2·s),表明该涂层具有卓越的抗氧化性。     

热障涂层材料研究进展

热障涂层材料广泛应用于发动机热端部件的热防护,能有效提高航空发动机热端 部件的工作温度和使用寿命。目前商用的热障涂层材料为氧化钇部分稳定氧化锆,但其在服役 温度高于 1200?C 时会发生相变而失效,难以满足新一代航空发动机对热障涂层的性能要求。因 此,寻找新型热障涂层材料及其服役性能研究一直是近年来的热点。本文综述了近年来氧化钇 稳定氧化锆、钙钛矿氧化物、烧绿石氧化物以及稀土硅酸盐材料的研究进展,并展望了热障涂 层材料的未来发展趋势。     

碳石墨材料高温氧化防护的研究

用硅化物、硼化物、碳化物、锆粉以及镍粉等做涂层,碳石墨材料在1400℃下200h不被氧化,在1450℃下50h不被氧化。阐述了硅化物、硼化物、碳化物、锆粉以及镍粉等做涂层(简称SBZN涂层)防护碳石墨材料被氧化的机理,研究了SBZN涂层的结构,成分分布对碳石墨材料防护情况的影响,从理论和实践在解决碳石墨材料的高温抗氧化上有了突破。     

碳纤维增强碳复合材料高温抗氧化硅基陶瓷涂层的研究进展(英文)

碳纤维增强碳(carbon fiber reinforced carbon,C/C)复合材料抗氧化问题一直是国际材料界研究的热点。硅基陶瓷作为C/C复合材料抗氧化涂层,是目前研究最深入的涂层体系。综述了国内外近几年C/C复合材料高温抗氧化硅基陶瓷涂层的研究进展,总结了C/C复合材料高温抗氧化硅基陶瓷涂层的制备工艺和对已有工艺的改进方法,分析了硅基陶瓷涂层在高温空气中、燃烧环境中的氧化失效机理。结合硅基非氧化物陶瓷(SiC,Si3N4等)环境障碍涂层的发展,展望了C/C复合材料在复杂环境中抗氧化涂层的研究方向。     

喷涂聚脲应用于悬索桥主缆防护涂层的耐腐蚀性能研究

应用电化学阻抗谱技术(EIS)研究了处于模拟海洋环境中的镀锌涂层钢绞线、镀环氧涂层钢绞线、热挤高密度聚乙烯(HDPE)套防护钢绞线和喷涂聚脲涂层钢绞线在干湿交替环境中涂层的腐蚀程度。研究结果表明:镀锌涂层和镀环氧涂层的涂膜阻抗值均在涂层失效阻抗106Ω·cm2之下,涂层已经处于腐蚀后期;HDPE防护层的涂膜阻抗值的数量级为106,涂层即将进入腐蚀后期;喷涂聚脲防护层仍具有较大阻抗,防护性能良好。     

弥补愈合C/SiC-ZrC复合材料表面缺损的技术研究北大核心

热防护涂层可有效提高C/SiC-ZrC复合材料构件在极端热环境下的服役稳定性,然而材料表面一旦缺损,将不能使用,对具有表面缺损的C/SiC-ZrC复合材料进行有效修复,提高材料利用率及使用频次,是亟需解决的关键问题。本研究以短切炭纤维、硅溶胶、磷酸铝、超高温陶瓷混合粉为主要原料,利用喷涂工艺对C/SiC-ZrC复合材料表面缺损进行弥补愈合。研究发现,使用以磷酸铝为黏结剂,ZrB_(2)粉、SiC、Al_(2)O_(3)、SiO_(2)、硼硅玻璃粉等为主要成分的弥补料愈合效果优异。经过静态氧化和氧乙炔试验,复合材料接近零失重,保持了优异的抗氧化性能。     

模拟危化液体储罐复合热控涂层的开发与应用

设计了液体储罐用热控涂层结构:环氧云铁底涂(50~60μm)+聚氨酯硬泡隔热层+网格加强层+过渡层(0.5 cm)+热反射面层(50~60μm)。研究了聚氨酯隔热层厚度对20 L保温桶保温效果的影响,确定了适宜的厚度为5 cm,实现了腐蚀与防护、热阻隔、热反射等技术集成。对样板涂层各层间附着力、抗压强度、耐高低温交变、耐盐雾性能进行了测试,以13 m3和40 m3的储罐模拟化工储罐,分别涂覆复合热控涂层,与储罐旁的消防棚进行比较,进行热控性能测试。结果表明:钢板与底涂之间及过渡层与热反射层之间的附着力均为1级,底涂与保温层之间及保温层与过渡层之间的附着力分别为6.3 MPa和5.2 MPa;耐盐水及盐雾测试中,复合涂层表面无起泡、脱落现象;涂层的抗压强度约为0.35 N/mm2;高低温交变10个循环后,表面光滑平整,无裂纹。其性能满足储罐工作环境的需要。在涂层热控性能测试中,当消防棚内的温度在20~42°C之间波动时,13 m3和40 m3的储罐内水温波动在4°C以内,表明该复合涂层结构保温效果良好。     

碳/碳复合材料SiC-HfSi_2抗烧蚀复合涂层(英文)

为改善碳/碳(C/C)复合材料的抗烧蚀性能,采用包埋技术在C/C复合材料表面制备了碳化硅-硅化铪(SiC-HfSi2)抗烧蚀复合涂层。采用氧乙炔火焰烧蚀试验评价了C/C复合材料样品的抗烧蚀性能。通过扫描电镜观察、能谱分析及X射线衍射分析研究了烧蚀前后C/C复合材料抗烧蚀涂层的表面和断面形貌、元素分布和相组成。结果表明:涂层C/C复合材料在烧蚀后其表面出现了丛生的氧化硅纳米线。同时,与未涂层C/C复合材料相比,SiC-HfSi2涂层使C/C复合材料的质量烧蚀率下降了85.6%。     

Carbon fiber reinforced ultra-high temperature ceramic matrix composites: A review

Recent studies on carbon fiber-reinforced ultra-high temperature ceramic matrix (C/UHTC) composites fabricated by hot-pressing, chemical vapor infiltration, polymer impregnation and pyrolysis, and melt infiltration (MI) are reviewed. Various efforts have been made to improve these preparation processes and to combine two or more of these because they have both the advantages and disadvantages in terms of the processing time, operating temperature, and the porosity of the resulting C/UHTC composites. In addition, the parameters governing the fracture toughness, thermal conductivity, and recession behavior (in oxidizing environments) of these composites have been discussed. This review demonstrates that C/UHTC composites with Zr- or Hf-based UHTC matrices fabricated via MI are potential candidates for advanced heat-resistant structural materials.     

Aero-thermo-chemical characterization of ultra-high-temperature ceramics for aerospace applications

Ultra-High-Temperature Ceramic (UHTC) materials, because of their high temperature resistance, are suitable as thermal protection systems for re-entry vehicles or components for space propulsion. Massive UHTC materials are characterized by poor thermal shock resistance, which may be overcome using C or SiC fibers in a UHTC matrix (UHTCMC).The University of Naples “Federico II” has a proven experience in the field of material characterization in high-enthalpy environments. A hypersonic arc-jet facility allows performing tests in simulated atmospheric re-entry conditions. The Aerospace Propulsion Laboratory is employed for testing rocket components in a representative combustion environment. Ad-hoc computational models are developed to characterize the flow field in both facilities and perform thermal analysis of solid samples.Current research programs are related to a new-class of UHTCMC materials, for rocket nozzles and thermal protection systems. The activities include design of the prototypes for the test campaign, numerical simulations and materials characterizations.     

改性碳纳米管增强热塑性聚氨酯复合材料的性能研究

以碳纳米管（CNTs）和热塑性聚氨酯（TPU）为原料,通过硫酸（H₂SO₄）/硝酸（HNO₃）混合溶液处理碳纳米管颗粒表面以达到改性的效果,使用改性过后的碳纳米管熔融共混制备出TPU/CNTs复合材料。研究了不同含量的CNTs对TPU基体的流变、力学、耐磨性以及热性能的影响。结果表明, 改性过后的CNTs在TPU基体中形成了良好的分散性和相容性;TPU/CNTs复合材料在高频剪切下保留了复合材料的加工流动性,并且复合材料的拉伸强度以及耐磨性相较于TPU有明显的增强,其中在改性碳纳米管含量较低时,复合材料的力学性能改善较为明显;改性CNTs的加入提高了TPU基体的熔融温度和结晶度;改性CNTs的加入提高了复合材料的热降解温度,提高了TPU基体的热稳定性。     

Carbon foam matrices saturated with PCM for thermal protection purposes

In the present work, numerical and experimental studies are proposed to predict and investigate the thermal characteristics of a thermal protection system consists of carbon foam matrix saturated with phase change material, PCM. Several types of carbon foam matrices with different porosities and thermal properties were introduced for the sake of a parametric study. The composite (carbon foam matrix saturated with PCM) was introduced into a cylindrical enclosure while it experiences its heat from a heat source setting on the top of the enclosure. The numerical simulation was performed using the volume averaging technique and a finite volume technique was used to discretize the heat diffusion equation while the phase change process was modeled using the enthalpy porosity method. The results are portrayed in terms of temperature and heat absorption time history and the numerical and experimental results showed good agreement. The results illustrated that the higher the porosity the more stability of the thermal performance of the matrix composite. On the other hand, the thermal conductivity of the composite matrix acts sharply to increase or decrease its heat absorption rate.     

双隔离结构聚乙烯/石墨烯导热复合材料的研究

采用聚二烯丙基二甲基氯化铵改性石墨烯纳米片、聚苯乙烯磺酸钠改性聚乙烯颗粒,通过静电诱导自组装和热压成型工艺制备了具有蜂窝状石墨烯框架的聚乙烯复合材料(N?PE?HD/P?GNPs).利用红外光谱仪、扫描电子显微镜、导热系数测试仪、电子拉力试验机对复合材料的改性状态、微观形貌、导热性能和力学性能等进行分析表征.结果表明,...     

烧结温度对防氧化涂层性能影响研究

研制了一种以磷酸盐涂层和陶瓷涂层相结合的新型复合防氧化涂层,针对不同的烧结温度研究了这种复合涂层的防氧化性能。结果表明：在700℃静态氧化30h后,800℃烧结的复合涂层试样的氧化失重率最小,为0．99％,经过900℃、3min←→室温、2min30次和1100℃、3min←→室温、2min10次连续热震后,其氧化失重率仅为0．31％,氧化速率为1．34×10^-7g·cm^-2·s^-1。SEM观察结果显示不同烧结温度制备的涂层表面微观形貌明显不同,800℃烧结的涂层表面完整致密,氧化后涂层仍然保持完好,没有脱落,说明该涂层与炭基体的结合性能以及热稳定性能良好,适合作为飞机炭刹车副的防氧化涂料。     

Effect of additives on the thermal conductivity of zirconium diboride based composites – A review

Re-entry space vehicle necessities sharp leading edges for better aerodynamic performance and, hence, require advanced thermal protection materials with improved safety for crew members. Material possessing high thermal conductivity and oxidation resistance are desirable at nose cap and wings leading edge of spacecraft. Consequently, the thermal shock resistance improves due to reduced thermal gradient and stresses. ZrB₂ has drawn strong impetus for futuristic space vehicles as thermal protection materials under extreme thermal environments. This study reviews the effect of the incorporation of non-carbonaceous and carbon additives on the thermal conductivity of ZrB₂ ceramics and based composites. Several factors such as the purity of starting powder, initial particle size, amount of sintering aids, processing route, porosity, the grain size of ZrB₂ matrix, distribution of secondary phases in the matrix and sinter density of the final composite, controls the overall thermal conductivity of ZrB₂ based composites.     

轴棒法C／C复合材料微观结构及性能分析

采用轴棒法4D预制体、煤沥青为前驱体,经过常压、高压相结合的液相浸渍一炭化的致密工艺,制备出高密度轴棒法C／C复合材料。研究了轴棒法C／C复合材料的微观结构及其对轴向室温、高温（2800℃）拉伸破坏形式的影响。结果表明：轴棒法C／C复合材料轴向增强体采用炭棒,出现了一个特殊的界面,即炭棒与基体的“间隙”,主要原因是炭棒内部结合较强和纤维、基体的热膨胀系数不匹配而引起的;间隙的存在,使得轴棒法C／C复合材料的轴向室温、高温拉伸破坏形式出现较大差异,室温拉伸由于界面结合强度弱而引起的炭棒完整的拔出,未起到纤维应有的增强作用;高温拉伸却由于受热膨胀,间隙愈合,界面结合变强,试样从有效部位断裂,纤维增强作用明显提高。     

Development and characterization of a contoured passive thermal protection system

Present work deals with process refinement, fabrication, and testing of a novel contoured passive thermal protection system (TPS), based on aluminosilicate fiber reinforced silica matrix composite. Taguchi method-based statistical approach was employed to understand the effect of process parameters such as thickness, layer density, stacking sequence and firing temperature on dielectric properties, flexural strength, and bulk density of composites. Analysis of variance was performed to ensure the statistical significance. The developed TPS was characterized for thermal insulation properties by testing under infrared heating conditions. The science behind the insulation characteristics of the TPS was analyzed using FTIR, XRD, and SEM to understand the associated high-temperature phase transitions. Present study has shown that, the back-face temperature exponentially decays with TPS thickness. For TPS having 9 mm thickness, the back-face temperature was found to be below 100°C when the front face was exposed to 1000°C. The insulation index was found to be increasing with increase in temperature and TPS thickness. Improved thermal insulation characteristics of TPS are due to energy consuming processes such as crystalline changes and micro cracks formation.     

碳纤维的表面改性对导热顺丁橡胶性能的影响

研究了碳纤维的表面改性方法对碳纤维/顺丁橡胶(BR)复合材料的硫化特性、门尼粘度、导热性能和力学性能的影响.实验结果表明,碳纤维/顺丁橡胶复合材料与顺丁橡胶空白样相比,其硫化速度、导热系数与力学性能都有明显的提高.而碳纤维的表面改性对碳纤维/顺丁橡胶复合材料的硫化特性数据、门尼粘度和导热系数影响并不明显,加入碳纤维后的未改性的碳纤维/顺丁橡胶复合材料的导热性能最佳,其导热系数为0.527 W/(m·K),为顺丁橡胶空白样的1.7倍;经过高温氧化后碳纤维填充复合材料力学性能有所提高,其拉伸强度为2.39 MPa.