纤维表面处理对CF/PAA复合材料界面性能的影响

采用多结构形态倍半硅氧烷（VMS—SSO）涂层结合等离子活化纤维表面的方法对碳纤维（CF）改性，研究了纤维表面处理对碳纤维／聚芳基乙炔复合材料界面性能的影响．结果表明，等离子活化前后纤维表面涂层处理使材料的ILSS分别提高25％和45％，在碳纤维与树脂之间引入了过渡层．等离子活化纤维在碳纤维与涂层间通过VMS-SSO引入了化学键连接．含活性官能团的多形态倍半硅氧烷涂层在等离子活化纤维前后处理碳纤维，都能提高复合材料的界面性能．但是效果不同．其原因是，碳纤维与树脂间相互作用的不同，前者主要是过渡层效应，后者在碳纤维与树脂间引入了化学键．     

碳纤维/聚芳基乙炔复合材料界面特性的原子力显微镜研究

为深入研究复合材料界面特性,分析复合材料界面改性机理,采用原子力显微镜以力调制模式研究了单向碳纤维/聚芳基乙炔 (CF/PAA) 复合材料横截面的表面形貌和硬度,得到了材料中各相的形态、分布和相对硬度等信息。通过对硬度图像进行统计学分析得到材料表面硬度分布直方图,对不同方法改性后的复合材料界面相特性进行了分析和比较。研究表明,CF未经表面改性处理时,复合材料中无明显的界面相出现,氧化处理后界面上出现硬度变化区域,界面相结构变得复杂,氧化结合高碳酚醛涂层处理后可以获得更为完善的界面相,在纤维与基体间形成一个模量适中的过渡区域,使材料的界面力学性能显著提高。      

甲基丙烯酰氧基倍半硅氧烷改性碳纤维/聚芳基乙炔复合材料界面性能

利用微脱粘法、三点弯曲法、扫描电镜（SEM）、力调制模式原子力显微镜（AFM）和动态力学热分析（DMTA）研究了甲基丙烯酰氧基倍半硅氧烷（Methacryl-POSS）涂层改性前后的碳纤维增强的聚芳基乙炔（PAA）复合材料的界面性能。用Wilhelmy法研究了处理前后的碳纤维与PAA树脂的浸润性。结果表明: POSS涂层处理后的碳纤维表面粗糙度增大,与PAA树脂的浸润性提高;复合材料的界面剪切强度提高了36%,层间剪切强度提高了50%。DMTA图谱表明, POSS涂层改性后,复合材料的玻璃化转变温度提高了12℃,损耗因子降低了53%,表明复合材料的界面粘接性能得到大幅度的改善。      

纤维热氧-接枝处理与基体改性对CF/VE复合材料力学性能的影响

针对碳纤维增强乙烯基酯树脂(CF/VE)复合材料界面性能薄弱的问题,通过热氧-接枝的方法对碳纤维表面进行改性,通过添加偶联剂改性树脂,并采用真空辅助成型工艺制备了CF/VE复合材料。通过纤维扫描电镜(SEM)表征和CF/VE复合材料力学性能测试、动态力学测试、界面粘结参数计算以及界面的微观表征验证改性方法的效果。SEM测试表明改性后纤维比表面积和粗糙度提高;TGA测试表明碳纤维氧化温度大于210℃,且氧化温度在600℃时,CF/VE复合材料综合性能最佳;CF/VE复合材料界面性能随隅联剂质量浓度的增大先提高后降低,且在其质量浓度为1%时,层间剪切强度最大,相对于未改性CF/VE复合材料的提高了74.3%;动态力学性能测试(DMA)表明改性CF/VE复合材料的玻璃化转变温度Tg较未改性的提高了约10℃;界面粘结参数A和α的定量计算表明改性CF/VE复合材料界面性能得到较大改善。     

聚多巴胺改性碳纤维增强尼龙6复合材料的界面性能

在碳纤维表面自聚合沉积多巴胺对其改性,制备出碳纤维增强尼龙6复合材料(CF/PA6)。使用扫描电镜(SEM)、原子力显微镜(AFM)、接触角测量仪、傅里叶红外光谱(FTIR)以及X射线光电子能谱仪(XPS)等手段表征碳纤维的表面形貌、粗糙度、润湿性和化学结构,研究聚多巴胺(PDA)沉积时间对复合材料界面力学性能的影响。结果表明：经过改性处理的碳纤维表面被一层均匀的PDA薄膜覆盖,显著提高碳纤维的表面活性、表面粗糙度和化学键能,也极大地提高碳纤维与尼龙6树脂基体之间的界面相容性。PDA沉积16 h的复合材料其界面结合强度最高,层间剪切强度达到31.7 MPa比改性前提高72.3%,弯曲强度达到308.2 MPa比改性前提高56.9%。     

电泳沉积氧化石墨烯的碳纤维表面改性及其增强环氧树脂复合材料界面性能

采用超声辅助电泳沉积法,以异丙醇作为溶剂,在连续碳纤维(CF)表面沉积一层氧化石墨烯(GO),对CF表面进行改性。再经200℃高温处理来增强(GO)与CF之间的黏合性,从而增加CF/环氧树脂(EP)复合材料的界面结合强度。利用SEM和AFM对改性前后CF的表面形貌及微观结构变化进行了表征,通过XPS对改性前后CF表面官能团的变化进行了检测。结果表明,在CF表面沉积GO并经200℃处理后,有效地部分还原了GO(RGO),填补或桥联了CF表面缺陷,使改性后CF的拉伸强度提高了34.58%。同时,高温处理使RGO与CF之间生成牢固的化学键,从而提高了RGO与CF之间的结合强度,最终使RGO-CF/EP复合材料的界面剪切强度(IFSS)提高了69.9%。      

氧化石墨烯改性不同表面性质的碳纤维/环氧树脂复合材料的微观形貌与动态热力学性能

通过模压成型，采用氧化石墨烯(GO)对四种碳纤维(CCF300、T700、CCF800、CCM40J)织物/环氧树脂(CF/EP)复合材料进行改性，通过复合材料的微观形貌、动态热力学性能等研究了GO对四种不同表面性质的CF/EP复合材料的改性效果。研究表明，添加GO后，GO/EP对四种CF的浸润性均比EP明显提高，纤维与GO/EP间的界面黏接比与EP基体间的黏接明显改善；CF/EP复合材料的破坏主要发生在CF与EP的界面，而GO的存在使GO-CF/EP复合材料的破坏由CF与EP基体的界面向GO/EP区域过渡。CF表面的氧碳比和沟槽均显著影响复合材料的玻璃化转变温度(T_g)，具有最高表面氧碳比的GO-CCF300/EP复合材料表现出最高的T_g，但沟槽更丰富的CCM40J和CCF300碳纤维对CF/EP复合材料的T_g表现出更好的GO改性效果。      

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%。     

基于微波等离子体方法生长的纳米碳对碳纤维/环氧树脂复合材料界面性能的影响

为了提高复合材料的界面性能,采用微波等离子体（MPECVD）方法,通过控制工艺参数,在碳纤维（CF）表面生长结构形貌各异的纳米碳,将其引入CF/环氧树脂（EP）复合材料界面微区。采用FESEM研究了不同MPECVD工艺参数对沉积纳米碳结构形貌的影响,采用单纤维破碎实验研究了纳米碳形貌对CF/EP复合材料的界面性能影响,探讨了纳米碳-CF/EP复合材料界面微观结构与其界面性能之间的关系。结果表明：随着MPECVD沉积功率的变化,沉积的纳米碳结构形貌变化较大。当沉积功率为700 W时,制备得到的多尺度纳米碳-CF/EP复合材料界面性能最高,界面剪切强度（IFSS）达到112.38 MPa,提高了118.85%。     

聚吡咯修饰碳纤维/环氧树脂复合材料的界面剪切强度

应用等离子体技术对碳纤维(CF)表面进行预处理,然后进行液相沉积聚吡咯处理。使用X射线光电子能谱仪、原子力显微镜(AFM)、扫描电子显微镜(SEM)和傅立叶红外光谱仪等手段对碳纤维表面形态和结构进行分析与表征,并进行单纤维界面剪切强度试验和SEM观测,研究了碳纤维复合材料的界面粘结性能。结果表明,等离子体预处理碳纤维沉积聚吡咯(PPy)使单纤维界面剪切强度提高了259.3%。分析结果表明,界面剪切强度的提高与纤维/树脂间的机械铆合和界面的作用力有关。等离子体预处理使碳纤维表面的羧基基团增多,在羧基和PPy之间形成氢键,从而提高了碳纤维复合材料的界面性能。     

Influence of oligomeric silsesquioxane coating treatment on interfacial properties of CF/PAA composites

Carbon fibres (CF) were modified with different oligomeric silsesquioxane (SSO) coatings to improve the interfacial property of carbon fibres/polyarylacetylene (CF/PAA). The interlaminar shear strength (ILSS) of CF/PAA was tested to determine the effect of the treatment. Atomic force microscopy (AFM) in force modulation mode was adopted to study the cross-section surface of unidirectional CF/PAA composites and the relative stiffness of various phases, including CF, interphase and resin. The probability histogram and line distribution of CF/PAA cross-section surface relative stiffness, obtained from the statistical analysis of relative stiffness image, were used to compare and study the interface characterizations of composites. The results show that the ILSS increases effectively and the effects on interfacial characterizations are distinguished from each other in accordance with the CF surface modified with different SSO coatings owing to the various structures. Cage oligomeric silsesquioxane, including large organic groups (methacryl isobutyl-POSS), has better treatment result. AFM observations lead to the conclusion that an interfacial transition layer with different morphology and stiffness appears in CF/PAA composites after being treated by the SSO coatings of different structures. It can be inferred that the appearance of the transition layer may contribute to the improvement of fibre/matrix adhesion. Translated from Acta Materiae Compositae Sinica, 2006, 23(1): 105–111 [译自: 复合材料学报]     

Influence of fibre surface oxidation–reduction followed by silsesquioxane coating treatment on interfacial mechanical properties of carbon fibre/polyarylacetylene composites

Carbon fibre was treated with oxidation–reduction followed by silsesquioxane coating method to improve the interfacial properties of carbon fibre/polyarylacetylene (CF/PAA) composites. The treatment method was divided into three phases, i.e., oxidation with oxygen plasma, reduction with LiAlH₄, and coating treatment with vinyl silsesquioxane (VMS–SSO). The fibre surface composition and functional group were analyzed using X-ray photoelectron spectroscopy (XPS). The polar functional groups, especially C–OH which could react with Si–OH on silsesquioxanes, were increased after redox reaction. VMS–SSO coating treatment imported vinyl groups which could react with PAA resin during PAA cure process. The surface morphology of carbon fibre was observed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The mechanical interfacial properties of the CF/PAA composites were characterized by short-beam bending testing method. Interlaminar shear strength (ILSS) of the CF/PAA composites in different treatment phases were increased by 31.7%, 28.8%, and 59.3%, respectively. The conclusion that oxidation–reduction followed by silsesquioxane coating treatment is an effective method to improve the interfacial properties of the CF/PAA composites can be drawn. This method can be used in other resin systems if the functional groups on silsesquioxane are changed according to those in resins.     

Effects of silsesquioxane coating structure on mechanical interfacial properties of carbon fibre/polyarylacetylene composites

Carbon fibres (CF) were treated with different coatings, including [3-(methacryloxy)propyl]trimethoxylsilane (MPMS), [3-(methacryloxy)propyl]silsesquioxane (MPMS-SSO), and (methacryloxy)propyl polyhedral oligomeric silsesquioxane (Methacryl-POSS), to improve the interfacial properties of carbon fibre reinforced polyarylacetylene (PAA) matrix composites. MPMS-SSO was obtained from the hydrolytic condensation of MPMS. The complicated structure, including cage and ladder one, of MPMS-SSO may be assigned by Fourier transforms infrared (FT-IR) spectra, ¹H, ¹³C and ²⁹Si nuclear magnetic resonance (NMR) and ultraviolet matrix-assisted laser desorption ionization time-of-flight mass spectrometry (UV-MALDI-TOF MS). Interlaminar shear strength (ILSS) was tested to investigate the effect of coating structure on the interfacial bonding. The values of ILSS of untreated and treated CF/PAA composites with different coatings (MPMS, MPMS-SSO and Methacryl-POSS) show that the treatment effect of Methacryl-POSS coating is the best one and the MPMS-SSO coating is better than that of MPMS coating. SEM micrographs of shear fracture of CF/PAA composites also suggested the different coating treatment effects. The differences of increasing degrees of ILSS indicate that the structure of coating is important when silsesquioxanes are used as coatings to treat fibre surface for building up the adhesion and improving interfacial properties of fibre reinforced polymer matrix composites.     

Interfacial properties and impact toughness of methylphenylsilicone resin composites by chemically grafting POSS and tetraethylenepentamine onto carbon fibers

Octaglycidyl polyhedral oligomeric silsesquioxane (gly-POSS) was successfully grafted on carbon fibers (CFs) surface to enhance interfacial properties and impact toughness of CFs reinforced methylphenylsilicone resin (MPSR) composites. After gly-POSS modification, POSS grafted CF (CF-POSS) with many epoxy functional groups was modified with tetraethylenepentamine (TEPA) to further enhance the interfacial strength. Atomic force microscopy (AFM) images showed that POSS and TEPA were grafted onto CFs surface uniformly and the surface roughness enhanced obviously. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed the chemical bonding nature between CFs and POSS, as well as between POSS and TEPA. POSS and TEPA modification could increase the fiber polarity, wettability and surface energy significantly. The interlaminar shear strength (ILSS) and impact toughness of composites showed a dramatic improvement, especially for grafting with POSS and further with TEPA (CF-POSS-TEPA). Additionally, the reinforcing and toughening mechanisms were also analyzed. Meanwhile, single fiber tensile strength (TS) had no decrease after modification.     

Influence of fibre surface oxidation treatment on mechanical interfacial properties of carbon fibre/ polyarylacetylene composites

Abstract

In the present work, the mechanical interfacial properties of carbon fibre (CF) reinforced polyarylacetylene (PAA) resin composites were modified through the surface oxidation treatment of carbon fibres by ozone. Both X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy showed that oxidation treatment could increase the amount of elemental oxygen on the fibre surface markedly by introducing more oxygen groups. Atomic force microscopy (AFM) images indicated that weak surface regions of fibres had been etched and removed, and the degree of fibre surface roughness was increased. The interlaminar shear strength (ILSS) and the interfacial shear strength (IFSS) of CF/PAA composites were both improved notably (no less than 50%). It could be concluded that an improvement of fibre surface chemical activity, better wettability of resin on the carbon fibre surface, and stronger mechanical joining between fibres and resin all resulted in the modification of interfacial properties of carbon fibre reinforced PAA composites. The influences of temperature, ozone concentration, and treatment time on the oxidation results were studied, and optimal treatment parameters determined.     

Enhanced mechanical properties of multiscale carbon fiber/epoxy composites by fiber surface treatment with graphene oxide/polyhedral oligomeric silsesquioxane

Graphene oxide (GO) and polyhedral oligomeric silsesquioxane (POSS) grafted carbon fiber (CF) was demonstrated to reinforce the mechanical properties of fiber composites. Such a fiber composite was prepared by grafting POSS onto the CF surface using GO as the linkage. The presence of GO linkage and POSS could significantly enhance both the area and wettability of fiber surface, leading to an increase in the interfacial strength between fibers and resin. Compared with the desized CF composites, the grafted CF composites fabricated by compression molding method exhibited 53.05% enhancement in the interlaminar shear strength. The changed surface morphology, surface composition and surface energy were supposed to be related with the interfacial performance of unidirectional composites, as revealed by scanning electron microscopy, atomic force microscope, dynamic contact angle test and X-ray photoelectron microscopy charaterizations.     

Effect of new epoxy matrix for T800 carbon fiber/epoxy filament wound composites

A new epoxy resin matrix with good adherence to T800 carbon fibers (T800 CFs) in filament winding was developed by addition of hardener and resin diluter. Interfacial behavior of the T800 CF/epoxy composites was analyzed according to the Naval Ordnance laboratory (NOL) ring test, short-beam-shear test and fracture surface observation. Meanwhile, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used in analysis of the interfacial behavior. The interfacial properties of the T800 CF/epoxy filament wound composites were improved by optimizing the matrices through increasing the toughness and reducing the viscosity, which is an important factor in influencing the wettability of T800 CFs. The Interlaminar shear strength (ILSS) of the unidirectional T800 CF/epoxy composites and the tensile strength of NOL-ring in this work reached to 123 and 2570 MPa, respectively. Also, the interfacial adhesion was much improved by the chemical reactions between the new matrix and the sizing on the T800 CFs.     

酚醛树脂表面处理剂对炭纤维增强环氧树脂复合材料界面强度的影响

采用酚醛树脂作为炭纤维表面处理剂, 可以显著提高多种炭纤维和环氧树脂界面强度。通过XPS、AFM、SEM和层间剪切强度等方法, 研究了不同浓度的酚醛树脂表面处理剂对炭纤维增强环氧树脂复合材料层间剪切强度、炭纤维表面元素和化学键组成的影响, 以及炭纤维增强环氧树脂复合材料断面微观形貌的变化。XPS和AFM分析结果表明酚醛树脂和炭纤维表面发生了化学反应, 而且酚醛树脂处理剂浓度越高, 和炭纤维表面发生反应的基团也越多, 表面越光滑平整, SEM和层间剪切强度研究表明酚醛树脂处理后的复合材料界面粘结性能得到很大的改善, 而且界面粘结性能强烈依靠处理剂浓度。