热处理温度对二维高导热炭/炭复合材料结构及热导率的影响（英文）

以高导热沥青基炭纤维布为增强体,中间相沥青为黏结剂,采用热模压成型及液相浸渍裂解工艺增密,并经高温石墨化处理制备二维高导热炭/炭复合材料。利用X射线衍射仪和透射电子显微镜对经不同温度处理后的沥青基炭纤维及二维高导热炭/炭复合材料的结构和形貌变化进行表征,并考察石墨化处理温度对复合材料热导率的影响。结果表明,随着热处理温度的升高,纤维及复合材料内部石墨微晶尺寸增大、取向度变好,纤维与基体间界面结合紧密、裂纹减少,而基体碳层间裂纹则呈扩大趋势。此外,二维高导热炭/炭复合材料的热导率随热处理温度的升高而线性增加,经3 000℃处理后,材料热导率高达443 W/m·K。     

高压浸渍-炭化制备炭/炭复合材料的组织结构

为研究高压浸渍-炭化制备的炭/炭复合材料的组织结构,以1 K PAN基高强度炭纤维为增强体,以调制中温煤沥青为基体前驱体,采用超高压浸渍-炭化工艺制备出2.5D沥青基炭/炭复合材料.采用偏光显微镜及SEM电镜对材料内部的组织形态进行了观察.研究表明:以中温沥青为基体前驱体所制备的炭/炭复合材料,在纤维束内,由于纤维之间的孔隙较小,形成的基体组织主要为镶嵌组织;而在纤维束之间,由于空间较大,出现的基体组织既有镶嵌型组织,也有域型组织.在沥青基炭基体中,有孔洞、裂纹、沟槽等缺陷.     

三维高导热炭/炭复合材料的制备、结构及性能（英文）

采用连续沥青基炭纤维与商业PAN基炭纤维的混编制备了三维炭/炭复合材料预制体,通过多次化学气相渗透(CVI)、液压浸渍(LPI)工艺对其进行增密处理和一系列的炭化和石墨化处理获得高导热三维炭/炭复合材料。在此典型结构中,沥青基炭纤维沿x,y方向水平正交排布,而商业PAN基炭纤维沿z方向双向贯通排布。研究了炭/炭复合材料的显微结构以及炭纤维和热解炭对炭/炭复合材料热导率和力学性能的相对贡献。CVI热解炭具有高结晶度并且沿纤维轴高度择优取向。通过3CVI和3CVI+4LPI工艺制备的炭/炭复合材料的密度分别达到了1.58和1.84 g/cm3。所制备的炭/炭复合材料沿x,y方向分别具有115.9 W/m·K (3CVI)和234.7 W/m·K (3CVI+4LPI)的高热导率,沿z方向的热导率分别只有18.6(3CVI)和41.5 W/m·K (3CVI+4LPI)。热扩散和热导率主要依赖于炭/炭复合材料中的连续性沥青基炭纤维。通过PAN基炭纤维的引入和后续增密过程,三维炭/炭复合材料的力学性能相对于一维炭/炭复合材料和二维炭/炭复合材料显著提高。     

具有中间相沥青过渡层的炭/炭复合材料的微观结构与力学性能

采用液相浸渍-炭化和CVI复合工艺, 制备出在炭纤维和热解炭之间具有中间相沥青过渡层的炭/炭复合材料, 借助偏光显微镜、扫描电镜、透射电镜以及力学性能测试研究了所制备的炭/炭复合材料的微观结构与力学性能. 结果表明: 在偏光显微镜下中间相沥青炭的光学活性高于热解炭的光学活性, 中间相沥青炭在SEM和TEM下均呈片层条带状结构, 热解炭在SEM下呈“皱褶状”片层结构, 在TEM下为粒状结构; 在HRTEM下, 中间相沥青炭、热解炭和炭纤维的晶化程度依次降低. 在加载过程中, 材料内部多层次的界面通过改变裂纹扩展路径而延缓其扩展速度, 在断口形貌上体现出锯齿状的断裂形式, 纤维拔出长度适中, 材料表现出韧性破坏的断裂特征. 材料具有较高的力学性能, 抗弯强度达到244MPa, 断裂韧性达到9.7MPa·m^1/2.     

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。     

纤维含量和热处理对炭/炭复合材料性能的影响

研究了炭纤维体积分数和预制体热处理温度对炭/炭复合材料力学性能的影响.结果表明,随着预制体中炭纤维体积分数的增加炭/炭复合材料的硬度逐渐增加,但当炭纤维的体积分数大于30%时,炭/炭复合材料硬度增加的幅度减小.炭纤维体积分数的增加对炭/炭复合材料硬度的影响有两个相反的作用,纤维的增强作用将使硬度增大,而孔隙率的增加将导致硬度的减小.炭/炭复合材料的抗弯强度随着纤维体积分数的增加而增加,但因纤维体积分数的增加会导致孔隙减小.致使热解炭不能充分地渗透填充到纤维间的孔隙内,抗弯强度下降,所以随着纤维体积分数的增加,材料的弯曲强度会出现拐点.随着预制体热处理温度的不同,炭/炭复合材料有脆性断裂、整束纤维拔出的假塑性断裂和部分炭纤维拔出的假塑性断裂三种断裂机制.     

短切炭纤维的表面处理对沥青基C/C复合材科性能的影响

采用模压半炭化成型工艺,在大气环境下制备了短切炭纤维增强的沥青基C/C炭复合材料.借助材料万能试验机和扫描电镜研究了短切炭纤维的表面处理对C/C复合材料体积密度和抗压强度的影响.结果表明:随着短切炭纤维表面处理强度的增大,C/C复合材料的抗压强度明显提高.用联合处理方法改性的短切炭纤维制备的C/C复合材料的抗压强度,比未处理的短切炭纤维增强的C/C复合材料的抗压强度,约提高了138.5%.     

反应温度对水热改性炭/炭复合材料抗氧化性能的影响

以磷酸、B₄C、SiC和Al₂O₃粉料为原料, 采用一种新颖的水热法对炭/炭(C/C)复合材料基体进行了抗氧化改性. 重点研究了水热反应温度对改性试样的物相组成、微观结构及抗氧化性能的影响. 采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能量色散谱仪(EDS)及X射线光电子能谱(XPS)对改性后试样进行了表征. 结果表明：经过水热改性处理, 炭/炭复合材料表面缺陷被玻璃相B₂O₃、HPO₃和微晶Al(PO₃)₃所组成的涂层所覆盖, 材料的抗氧化性能明显提高; 抗氧化性能在120～200℃范围内随着水热改性温度的升高而提高; 在200℃水热改性后的炭/炭复合材料在700℃的空气中氧化10h后的质量损失仅为2.31%.     

炭/炭复合材料用基体前驱体煤沥青的研究动态

综述了近年来炭／炭复合材料用基体前驱体煤沥青的研究动态，重点阐述了不同改性方法对煤沥青的残炭率及高温流变性能的影响，指出了开发综合性能优良的改性煤沥青是制备低成本高性能炭／炭复合材料的关键。     

γ射线辐照对高模量碳纤维及碳纤维/氰酸酯复合材料性能的影响

通过模拟空间γ射线辐照环境,采用⁶⁰Co-γ射线对高模量碳纤维及其增强的改性氰酸酯复合材料进行辐照,采用SEM和XRD对辐照前后的碳纤维及碳纤维/氰酸酯复合材料进行了分析和表征,研究了复合材料的质量损失率、拉伸性能及层间剪切强度随γ射线辐照剂量的变化规律。结果表明,γ射线辐照能增加碳纤维表面粗糙度;质量损失率随γ射线辐照剂量增大先增加后趋于平缓,但均小于1%;碳纤维/氰酸酯复合材料拉伸性能与层间剪切强度均随γ射线辐照剂量增大先提高后降低,在吸收剂量为5×10⁵ rad时出现最大值,拉伸强度为1 803 MPa,拉伸模量为243 GPa,层间剪切强度为72 MPa。     

沥青过渡层对C/C复合材料力学性能的影响

在2D碳／碳（C／C）复合材料的碳纤维与基体热解碳间引入中间相沥青做过渡层，研究了中间相沥青的引入对C／C复合材料力学性能的影响．结果表明，与没有过渡层，普通沥青做过渡层、中间相沥青做过渡层的三类C／C复合材料比较．采用沥青做过渡层可以提高复合材料的力学性能，采用中间相沥青做过渡层制备的C／C复合材料的弯曲强度比采用普通沥青做过渡层提高44％，剪切强度提高15％．中间相沥青的引入可以使碳纤维束间和束内的结合强度不同，从而使基体断裂产生的裂纹扩散时发生偏转，复合材料的强度和韧性同时得到提高．     

碳纤维改性对不饱和聚酯自修复复合材料性能的影响

采用H_2O_2和浓HNO_3对碳纤维(CF)表面分别进行氧化处理,得到氧化碳纤维(OCF1和OCF2),采用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)对OCF1进行接枝处理,得到接枝改性碳纤维(KCF),将改性前后CF应用于不饱和聚酯(UP)自修复复合材料中,分析比较了不同改性剂及改性方法对碳纤维/不饱和聚酯(CF/UP)自修复复合材料性能的影响。利用FTIR、XPS、SEM表征CF与CF/UP自修复复合材料的化学结构与形貌,通过TGA、万能拉力试验机、悬臂梁冲击仪、邵氏硬度计等对复合材料的热稳定性、力学性能及自修复效率进行测试。结果表明:氧化、接枝反应均可增加CF表面的粗糙度和活性官能团含量,从而改善CF与UP基体的界面相容性。其中OCF1/UP自修复复合材料的综合力学性能比OCF2/UP自修复复合材料好,KCF/UP自修复复合材料的力学性能在三者之中最佳,其自修复效率最高,可达67.03%。     

Microstructure and mechanical properties of carbon foams and fibers reinforced carbon composites densified by CLVI and pitch impregnation

Carbon foams and fibers reinforced carbon composites were prepared using chemical liquid-vaporized infiltration and pitch impregnation. The microstructure and mechanical properties of the composites were investigated. The results showed that the final density of these samples was in a range of 1.34–1.45 g/cm³. The pores in carbon foams were filled with pyrocarbon and pitch carbon. The flexural and tensile strength of the composites increased gradually with increasing the content of carbon fibers, whereas the compressive stress went up to a maximum value of 35.9 MPa at the fiber content of 7%.     

Effect of γ-ray irradiation grafting on the carbon fibers and interfacial adhesion of epoxy composites

A special technique using γ-ray irradiation-induced graft-polymerization was applied to carbon fibers. Epoxy resin and chloroepoxy propane reacted with carbon fibers by a co-irradiation grafting method and acrylic acid was graft-polymerized onto the fiber surface via a pre-irradiation grafting method. The roughness, amount of containing-oxygen functional groups and surface energy were all found to increase significantly after irradiation grafting. Gamma-ray irradiation grafting improved marginally the tensile strength of carbon fibers, which was evaluated by statistical analysis using the Weibull distribution. The interlaminar shear strength of treated carbon fiber/epoxy was enhanced by at least 17.5%, compared with that of untreated carbon fiber/epoxy. The mechanisms of irradiation grafting are proposed by radical reactions. The γ-ray co-irradiation grafting and pre-irradiation grafting are both an effective method for modifying the physicochemical properties of carbon fibers and improving the interfacial adhesion of composites.     

Mechanical properties improvement of carbon/carbon composites by two different matrixes

Carbon/carbon (C/C) composites with two different matrixes of pitch carbon and pyrolytic carbon were fabricated using 2-dimensional (2D) carbon felts preform. In order to study the effects of matrixes on mechanical properties, C/C composites with single matrix of pitch carbon were prepared. The mechanical properties were tested on CMT5304-30KN universal testing machine. Polarization microscope and scanning electron microscope were used to investigate the microstructures and fracture surface of C/C composites. It was resulted that the flexural strength of C/C composites with two matrixes was improved by 96% compared with that of C/C composites with single matrix. Meanwhile, better toughness was also obtained with two matrixes. For the composites, multilayer microstructures were generated after filling up of voids caused during carbonization of mesophase pitch by pyrolytic carbon. The multilayer microstructures were beneficial to the improvement of mechanical properties of C/C composites, especially the toughness. More energy could be dissipated during mechanical tests while cracks might extend along multiple paths, such as the interface between fiber and matrix or the interface between different matrixes.     

KH-570接枝改性碳纤维/乙烯-醋酸乙烯共聚物复合泡沫材料的制备及表征

采用浓H₂SO₄/浓HNO₃混合酸对碳纤维(CF)进行表面氧化处理得到氧化碳纤维(OCF),再利用γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)与OCF进一步反应得到KH-570接枝改性碳纤维(KCF),随后将其应用于乙烯-醋酸乙烯共聚物(EVA)复合泡沫材料中。利用FTIR、XPS、Raman、FESEM和电子万能试验机等考察了碳纤维的表面改性效果以及碳纤维/EVA复合材料的结构与性能。结果表明:氧化和接枝反应均可以增加碳纤维表面的活性官能团含量和粗糙度,从而改善碳纤维与EVA基体之间的相容性,使碳纤维/EVA复合泡沫材料的物理性能得到改善。相同条件下,KH-570接枝改性碳纤维/EVA复合泡沫材料的物理性能更优异。      

Comparison of chemical vapor deposition and chemical grafting for improving the mechanical properties of carbon fiber/epoxy composites with multi-wall carbon nanotubes

By engineering the fiber/matrix interface, the properties of the composite can be changed significantly. In this work, we increased the effective surface area of the fiber/matrix interface, to facilitate additional stress transfer between fibers and matrix, by grafting carbon nanotubes on to carbon fibers (in the form of carbon fabric) by two different methods: (1) chemical vapor deposition (CVD) method and (2) a purely chemical method. With the CVD process, carbon nanotubes (CNT) were directly grown on carbon fiber substrate using chemical vapors. For the chemical method, CNT with carboxyl groups were grafted on functionalized carbon fiber via a chemical reaction. The morphology of CNT/carbon fibers was examined by scanning electron microscope (SEM) which revealed uniform coverage of carbon fibers with CNT in both of CVD method and chemical grafting method. CNT-grafted woven carbon fibers were used to make carbon/epoxy composites, and their mechanical properties were measured using three-point bending and tension tests which showed that those with CNT-grafted carbon fiber reinforcements using the CVD process has 11 % higher tensile strength compared to those containing carbon fibers modified with the chemical method. Also, composites with CNT-grafted carbon fibers with chemical method showed 20 % higher tensile strength compared to composites with unmodified carbon fibers. The results of tensile test revealed that both CVD and chemical grafting could significantly improve the mechanical properties of the carbon fiber composites.     

Effect of surface treatment of carbon fibers with gamma-ray radiation on mechanical performance of their composites

Gamma-ray radiation was used to surface treat PAN carbon fibers. The efficiency of gamma-ray radiation was compared with air oxidation in terms of variations in the surface structure of carbon fibers and the mechanical performance of their composites. It was observed that the composites reinforced with the gamma-radiated carbon fibers showed higher interfacial adhesion strength and thus better flexural and shear properties than the composites reinforced with air-treated fibers. The observed higher content of carboxyl group on the surface of the gamma-radiated carbon fibers is likely to be responsible for the stronger fiber-matrix bonding. It is concluded that gamma-ray radiation is an effective approach of tailoring surface properties of carbon fibers.     

γ射线辐照对碳纤维表面接枝改性的影响

为提高碳纤维/环氧树脂复合材料的界面粘结性能, 采用γ射线共辐照接枝方法对碳纤维表面改性, 利用X光电子能谱仪(XPS)、 扫描电子显微镜(SEM)、 电子万能材料试验机, 研究了在缩乙二醇丙酮溶液和环氧氯丙烷丙酮溶液中经200 kGy剂量的γ射线辐照接枝后, 碳纤维的表面化学元素及官能团组成、 表面形貌、 复合材料剪切断面形貌及其层间剪切强度(ILSS)的变化。研究表明, 缩乙二醇类接枝液的接枝效果较理想, 碳纤维接枝率达7%; 辐照处理碳纤维表面O/C比值和含氧官能团含量增加, 以此制备的碳纤维/环氧复合材料的ILSS提高, 最大提高率达31.2%; 同时还发现辐照接枝后的碳纤维表面粗糙度增大。     

国产ZT7H碳纤维表面状态及其复合材料界面性能

目前我国在高性能碳纤维研发生产方面已取得了突破性的进展。本文选用不同批次和牌号的国产ZT7H碳纤维,对其进行去浆和上浆处理,并制备碳纤维增强环氧树脂基复合材料,探究国产H1型上浆剂对ZT7H碳纤维表面形貌和微观界面性能的影响及不同牌号碳纤维复合材料界面性能的差异。研究表明,H1上浆剂增加了碳纤维表面粗糙度和极性组分含量,增强了湿热老化前后复合材料的微观界面力学性能。同时,碳纤维织物的编织方式对其复合材料的静态力学性能和界面性能有很大影响。实验证明,国产ZT7H碳纤维的性能已超过东丽T700碳纤维,但其加工工艺性仍有待提升。