改进 ICVI工艺制备 C/C复合材料的基体织构研究

利用偏振光显微镜(PLM)和高分辨透射电镜(HRTEM)从微米到纳米尺度研究了改进等温化学气相沉积(ICVI)技术制备的C/C复合材料基体热解炭织构和精细结构特征.结果表明:纤维周围有3层不同织构的热解炭,由纤维向外,分别为光滑层、粗糙层和暗层.基体与纤维之间以及不同织构基体间的界面结合较好,高织构热解炭内有微裂纹存在,并且裂纹在界面处终止扩展,或以桥连的形式扩展.不同织构热解炭在HRTEM下晶格条纹的近程和长程的择优取向度有明显区别.     

热解炭过渡层-中间相沥青基炭/炭复合材料的微观结构

借助偏光显微镜、扫描电镜、透射电镜对具有热解炭过渡层的中间相沥青基炭/炭复合材料的微观结构进行了研究。结果表明:材料的基体由热解炭和中间相沥青炭组成,在偏光显微镜下均呈现出光学各向异性。材料内部形成了多层次的界面结构,热解炭与纤维的界面连续,界面层内的石墨微晶择优取向度较高,晶格条纹排列规整;中间相沥青炭与热解炭界面不连续,为"裂纹型"界面,界面层内主要为非晶态碳。材料中炭纤维、热解炭、中间相沥青炭的石墨微晶大小逐渐增大,择优取向度逐渐增高,晶格条纹的排列逐渐规整。片层条带状结构的中间相沥青炭以及材料内的微裂纹平行于炭纤维轴向。     

2D C/C复合材料微观结构与力学性能的研究

采用等温化学气相渗透方法,通过调整沉积工艺,制备了具有不同微观组织结构的2D C/C复合材料.利用偏光显微镜(PLM)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)结合选区电子衍射(SAED),研究了热解炭基体微观组织结构,借助万能试验机测试了材料的三点弯曲性能.结果表明:层状高织构(HT)热解炭基体占优时C/C复合材料表现为假塑性断裂;扁平片状中织构(MT)热解炭与颗粒状各向同性层热解炭(ISO)有利于提高材料的弯曲强度;HT基体与炭纤维界面结合良好,界面处不存在非HT织构,但取向角(OA)略有增大.     

石墨化处理对不同高织构含量C/C复合材料微结构的影响

采用化学气相沉积工艺制备出炭毡增强炭/炭(C/C)复合材料和3K炭布叠层增强C/C复合材料,并对材料进行2500℃高温石墨化处理。利用X射线衍射仪;偏光显微镜及拉曼光谱仪对所制材料进行表征。结果表明,炭毡C/C复合材料基体是单一的高织构(HT)热解炭,3K炭布叠层C/C复合材料的基体是带状组织,从纤维表面向外依次为各向同性热解炭、HT和中织构(MT)热解炭,其中HT含量低于50%;沉积态和热处理后,两种C/C复合材料都具有相似的石墨化度,且热处理后的石墨化度超过80%,但Lc值差异明显,炭纤维、MT和HT热解炭的La值均升高,其中HT热解炭升幅明显大于炭纤维和MT热解炭。HT热解炭的含量是导致这两种C/C复合材料具有相似石墨化度而Lc值却显著差异的原因。     

C/C复合材料不同基体炭的微观结构

借助偏光显微镜、扫描电镜、透射电镜和X射线衍射仪对C/C复合材料不同基体炭的微观结构进行了研究。结果表明:不同基体炭在偏光显微镜下呈现出不同的光学活性度,其平均光学活性度依次由普通沥青炭、热解炭的光滑层、热解炭的粗糙层、中间相沥青炭逐渐增强;在SEM下,普通沥青以"葡萄状"结构为主,热解炭分为块状和"皱褶状"片层状结构,中间相沥青炭为形状各异的片层条带状结构;在HRTEM下,中间相沥青炭的晶格条纹排列规整,是一种长程有序的晶体结构,晶化程度很高。XRD分析表明,材料B(中间相沥青基C/C复合材料)的石墨化度最高,层间距最小,材料D(热解炭基C/C复合材料)次之。     

循环加载周期对二维C/C复合材料弯曲疲劳强度的影响

采用频率为10 Hz、 应力比为0.1的正弦波研究了室温下循环次数对二维炭毡C/C复合材料(2D炭毡C/C复合材料)的弯曲疲劳强度的影响, 并利用偏光显微镜和扫描电子显微镜对该材料的热解碳组织形貌以及疲劳前后的断口形貌和微观结构进行了观察。结果表明, 2D炭毡C/C复合材料的热解碳结构由光滑层和各向同性层组成, 其疲劳极限为76.5 MPa, 是静态弯曲强度的90%。在不同循环周次的疲劳载荷作用后, 材料的剩余弯曲强度和韧性都得到了提高。在疲劳加载过程中, 纤维/基体的界面结合强度发生弱化, 纤维的协同承载能力得到提高, 使C/C复合材料出现了疲劳强化现象。      

炭纤维热处理对C/C复合材料力学性能的影响

采用化学气相沉积工艺对未处理和2 500℃热处理的炭纤维预制体进行致密化,对致密化后的C/C复合材料进行弯曲力学性能测试,借助偏光显微镜和扫描电子显微镜观察热解炭的组织、纤维的表面和弯曲试样断口的形貌.结果显示:高温热处理后,纤维表面变的更加光滑,表面出现很多沿纤维轴向的沟槽;致密化后的两种C/C复合材料的基体消光角约为21°,均为高织构热解炭;与未处理纤维增强C/C复合材料相比,经高温热处理后纤维增强的C/C复合材料的弯曲强度和模量均大幅下降,断裂特征由脆性转变为典型的假塑性,断口处有大量纤维拔出,纤维表面未粘附热解炭,表明对纤维进行高温热处理显著降低了纤维和热解炭基体的界面结合强度,导致材料强度降低,断裂呈假塑性.     

沉积在核石墨IG-110基体上的热解炭涂层微观结构

采用化学气相沉积技术,以甲烷作为碳源,在核石墨IG-110基体上制备层状热解炭涂层。利用偏光显微镜、扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及同步辐射掠入射X射线衍射(GI-XRD)研究热解炭涂层的微观结构和生长特性。结果表明,热解炭涂层具有大锥体、小锥体和再生锥体三种生长锥微观结构,热解炭片层间结合紧密,生长锥间结合密实。热解炭涂层存在光滑层和再生层两种织构,每种织构都含有两种晶面间距不同的相结构,平滑层主要含有低石墨化度相,而再生层主要含有高石墨化度相。热解炭涂层致密的微观结构和仅存在的纳米级别的微孔使其可以作为气体阻隔涂层。     

C/C复合材料结构显微激光喇曼光谱研究

采用显微激光喇曼光谱,以增强体为薄毡叠层、基体分别为粗糙层及光滑层结构热解炭的两种C/C复合材料为研究对象,分析、表征了两种材料炭结构的微观分布特征及其在石墨化过程中的变化状况。结果表明,不仅复合材料中不同组元,而且同一组元不同部位石墨微晶的完整度不同。在石墨化过程中,各自的石墨化进程及可石墨化能力存在差异:炭纤维体积含量较高的炭布层中的热解炭,与网胎层中的热解炭相比,石墨微晶的完整度较好,石墨化进程较快;在炭纤维体积含量较低的网胎层中,炭纤维及热解炭在其界面部位的石墨化进程较快;粗糙层结构热解炭比光滑层结构热解炭容易石墨化。借助激光喇曼光谱微区分析手段,有可能实现对复合材料中石墨化程度微观分布状态的调整和控制。     

不同纤维体积分数CVI 炭/ 炭复合材料的石墨化度

为确定不同纤维体积分数的化学气相浸渗(CVI) C/ C 复合材料的最佳热处理工艺, 以40 %、30 %、25 %三种不同纤维体积分数的针刺整体毡为坯体, 经三次CVI 后制得C/ C 复合材料, 采用X射线衍射和拉曼光谱微区分析测试了三种不同纤维体积分数的CVI C/ C 复合材料试样未经热处理及经2200 ℃、2400 ℃热处理下宏观和微区石墨化度。结果表明: 三次CVI 热解炭均为光滑层结构, 且纤维体积分数越高, C/ C 复合材料的石墨化度也越高;纤维与光滑层热解炭界面及两种不同热解炭界面在高温热处理时会发生应力石墨化, 应力石墨化程度前者大于后者, 这是纤维体积分数高的C/ C 复合材料石墨化度高的原因; 热处理温度越高, 应力石墨化程度越大。      

Fabrication and characterization of highly crystalline and stable phase-pure rutile nanowires

A homogeneous thin layer of TiO2 has been successfully coated on the surface of multiwalled carbon nanotubes (MWCNTs), which were produced by catalytic chemical vapor decomposition method, via an in situ sol-gel method. The obtained MWCNT-TiO2 composite materials were heat treated in air at high temperatures, attempting to produce highly crystalline pure rutile nanowires. Through comprehensive characterization obtained by scanning electron microscopy (SEM), transmission electron microscope (TEM), energy dispersive X-ray (EDX), and X-ray powder diffraction (XRD), the effect of heat treatment on crystallization and phase transformation was discussed, and the effect of absence of MWCNTs on the morphology of pure rutile nanowires was analyzed. Both anatase and rutile phases exist after heat treatment in 700 degrees C while only rutile phase exists after heat treatment in 800 degrees C. The crystal size of rutile is formed to be significantly larger than that of anatase, and the hollow tubular structure is found to be destroyed which resulted in nanowire structure.     

热处理温度对中间相沥青基碳/碳复合材料力学性能的影响

通过三点弯曲实验,并借助XRD,SEM断口形貌分析,研究了最终热处理温度对中间相沥青基碳/碳复合材料微观结构与力学性能的影响,并对其断裂机制进行了探讨.结果表明:随着最终热处理温度的升高,材料的石墨化度增大,层间距d002减小,微晶尺寸Lc增大;材料未经热处理时,纤维与基体间界面结合较强,抗弯强度较高,弯曲断口较为平整,具有脆性断裂特征;随着热处理温度的升高,基体收缩,纤维与基体间界面结合减弱,抗弯强度减小,弯曲断口纤维拔出较长,材料具有韧性断裂特征.     

Microstructure and chemical analysis of C/Cu/Al interfacial zones

The fibre–matrix interface in carbon–aluminium composites has been examined. Composites were prepared using uncoated carbon preforms and carbon preforms coated with copper. Auger and transmission electron microprobe microscopy were used to study the interface. The role of the copper layer on the microstructural and chemical evolution of the system after a 96 h heat treatment at 600 °C is discussed.     

C/C复合材料石墨化度P1模型的表征及测定

C/C复合材料的石墨化度反映了材料中碳结构与理想石墨晶体结构的接近程度,并且是影响其性能的一个重要结构参数,石墨化度P1是一种能够比较准确地表示碳材料石墨程度结构的参数,本文利用P1的基本原理,编制了相应的计算程序,通过X光衍射（XRD）分析,计算了不同热处理温度C／C复合材料石墨化度P1,结果表明它可以较好的表征C／C复合材料的石墨化程度,并进一步讨论了热处理温度（HTT）与石墨化度的关系。     

Microstructure of ceramic coating on titanium surface as a result of hydrothermal treatment

Hydroxyapatite coating on commercially pure titanium has been produced by a biomimetic method in order to improve osteointegration for medical implant purposes. A specific chemical treatment by etching titanium substrate with different concentrations of NaOH aqueous solution at 130 °C in an autoclave, followed by heat treatment at 600 °C was selected to obtain an activated titanium substrate. The microporous surface obtained has allowed the nucleation and growth of a calcium phosphate layer by soaking the substrate in a simulated body fluid (SBF). Scanning electron microscopy (SEM) together with energy dispersive analyzer for X-ray (EDS), X-ray diffraction (XRD) as well as Fourier transform infrared spectroscopy (FT-IR) were employed to evaluate the hydroxyapatite coating. A homogeneous structure coating without cracks defined the chemical treatment condition of the substrate. © 2000 Kluwer Academic Publishers     

Sol–gel derived hydroxyapatite/titania biocoatings on titanium substrate

A simple sol–gel method was successfully developed for a hydroxyapatite (HA)/TiO₂ double layer deposition on a pure titanium substrate. Phase formation, surface morphology, and interfacial microstructure were investigated by differential scanning calorimetry analysis (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The TiO₂ layer was coated by a spin coating method at a speed of 1500 rpm for 15 s, followed by a heat treatment at 560 °C for 20 min. The HA film was subsequently spin coated on the outer surface at the same speed and then heat-treated at difference temperatures. Results indicated that the HA phase began to crystallize after a heat treatment at 580 °C; and the crystallinity increased obviously at a temperature of 780 °C. The HA film showed a porous structure and a thickness of 5–7 μm after the heat treatment at 780 °C. SEM observations revealed no delamination and crack at the interfaces of HA/TiO₂ and TiO₂/Ti. The HA film with a porous structure is expected to be more susceptible to the natural remodeling processes when it is implanted in a living body.     

The effect of heat treatment temperature on the interfacial shear strength of C/C composites

This paper investigates the effect of heat treatment temperature on the interfacial shear strength (IFSS) of carbon/carbon composites reinforced with polyacrylonitrile-based fibers. A series of single fiber push-out tests were performed on specimens heat treated at 1800, 2100, and 2400 °C, using a nanoindenter with a flat ended conical tip. The microstructure was characterized using polarized light and transmission electron microscopy and the debonded fiber/matrix interface was examined using scanning electron microscopy. Wavelet analysis of the load–displacement data was used as an additional tool to investigate the initiation and progression of debonding. Compared to 1800 °C, heat treatment at 2400 °C was associated with a decrease in IFSS, from 12 to 7 MPa. Transmission electron microscopy study showed that the microstructure of the fiber/matrix interphase remained amorphous even with heat treatment at 2400 °C. The decrease in the IFSS can be partly attributed to the reorganization of the graphene sheets in the matrix in the vicinity of fiber/matrix interphase. The thermal expansion mismatch between fiber and pyrocarbon matrix is another possible reason for the observed decrease in the IFSS.     

On the mechanism of mechanochemical synthesis of Ti2SC from Ti/FeS2/C mixture

In this study, the synthesis of Ti₂SC MAX phase by high energy ball milling, and the effects of heat treatment on ball milled powder was investigated. To this aim, a mixture of Ti, FeS₂ (as sulfur source), and C according to Ti₂SC stoichiometry, were ball milled by a planetary ball mill for different milling periods up to 10 h. The structural evolution, and the morphology of the products was studied by x-ray diffraction (XRD), and scanning electron microscopy (SEM) equipped with energy-dispersive spectroscopy (EDS), respectively. The results showed that after 10 h of ball milling, the raw materials reacted together and resulted in the formation of Ti₂SiC and TiC phases. The ball milled powder was then compacted and heat treated at 1000 and 1200 °C. Heat treatment caused the progressing of synthesis reactions, and led to increasing the purity of Ti₂SC phase. The heat-treated powder was leached in 1 M HCl for 2 h to remove iron from the product. The XRD results confirmed successful iron removal by leaching. SEM micrographs of the final product revealed the specific lamellar structure of MAX phases. Elemental mapping confirmed the homogeneous distribution of Ti, S and C elements.     

Thermal Treatment Optimization of Electrodeposited Hydroxyapatite Coatings on Ti6Al4V Substrate

Thermal behavior of electrodeposited hydroxyapatite (HAP) coating on a titanium alloy (Ti6Al4V) is investigated in order to optimize the heat treatment conditions for this prosthetic material. The synthesized coatings are annealed in air atmosphere at 400, 600, 800, and 1000 °C, and then characterized by X‐ray diffraction (XRD) and selected area electron diffraction (SAED) for structure and phases analysis. Scanning and transmission electron microscopy associated to energy dispersive X‐ray microanalysis (SEM‐EDXS and STEM) are used for morphology and composition analysis. The results show that when the electrodeposited coating is annealed at temperatures greater than 600 °C, a well‐crystallized HAP is obtained with a notable change of its morphology. However, at these temperatures the surface of Ti6Al4V alloy (uncoated zones of the implant) is deteriorated by the formation of a thick surface oxide layer. Therefore, we limit the heat treatment temperature for the electrodeposited coatings on a Ti6Al4V alloy at 550 °C. At this optimized temperature it is demonstrated that the link between the coating and the substrate is improved and the crystallinity of the coating is controlled which make it well bioactive.     

炭/炭复合材料表面C/SiC/Si-Mo-Cr多层复合防氧化涂层研究(英文)

为提高炭/炭(C/C)复合材料的高温抗氧化性能,采用料浆涂刷法首先在C/C复合材料表面制备了预炭层,然后以Si粉及石墨粉(Si粉与石墨粉的质量配比为:60～80:10～25)为原材料采用包埋法经高温热处理获得C/SiC内涂层,最后在涂有C/SiC内涂层的C/C复合材料表面采用包埋法制备Si-Mo-Cr外涂层。借助扫描电镜、X射线衍射、电子能谱等分析测试手段对涂层试样的微观结构进行了分析,研究了涂层C/C复合材料在1 873 K和1 973 K下的氧化行为。结果表明:由于涂层氧化过程中表面生成了SiO2和Cr2O3复合玻璃层,其在1 873 K温度下表现出优异的防氧化性能,可以有效保护C/C复合材料达135 h。当氧化温度提高至1 973 K并氧化30 h后,该复合涂层氧化过程玻璃层完整性被破坏,涂层失效。