CF 表面低聚倍半硅氧烷涂层对复合材料界面性能影响

采用不同倍半硅氧烷(SSO) ( YGO-SSO 和Methacryl isobutyl-POSS) 涂层对碳纤维(CF) 改性, 有效地提高了碳纤维/ 聚芳基乙炔(CF/ PAA) 的层间剪切强度( ILSS) 。采用原子力显微镜(AFM) 以力调制模式对CF/ PAA复合材料横截面进行表面形貌和硬度分布研究, 通过对硬度图像进行统计学分析得到纤维、界面相、基体相硬度分布直方图和线分布图, 对不同涂层、同种涂层不同浓度改性后的复合材料界面相特性进行了比较和研究。结果表明, 不同结构、不同浓度SSO 涂层处理对界面的改性效果不同, 含大有机官能团的笼型倍半硅氧烷(MethacrylisobutylPOSS) 的改性效果好。AFM 分析直观地表明, 经不同结构SSO 涂层处理后CF/ PAA 复合材料中出现不同形貌结构、不同硬度的界面过渡层,该界面层提高纤维/ 树脂的粘接。      

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。     

碳纤维表面处理对脉冲电磁场作用下碳纤维增强聚乳酸基复合材料降解行为的影响

采用HNO₃氧化对碳纤维进行表面处理,并制备了碳纤维增强聚乳酸基（CF/PLA）复合材料。研究了脉冲电磁场（PEF）对该条件下CF/PLA复合材料降解特性的影响。结果表明,碳纤维的表面处理对PEF作用下CF/PLA复合材料的吸水率、质量保持率、弯曲强度和剪切强度等均有不同程度的影响。分析表明,碳纤维表面处理形成的酯键在受到PEF作用后存在某种改变,进而导致CF/PLA复合材料界面降解行为的特异性。本研究有望提供一种从材料本身和外部条件协同控制的可降解CF/PLA骨折内固定装置解决方案。     

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%。     

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%。      

氧化石墨烯改性玄武岩纤维及其增强环氧树脂复合材料性能

为了改善玄武岩纤维/环氧树脂复合材料的界面性能,通过偶联剂对氧化石墨烯进行改性,并将改性后的氧化石墨烯引入到上浆剂中对玄武岩纤维进行表面涂覆改性,同时制备了氧化石墨烯-玄武岩纤维/环氧树脂复合材料.采用FTIR表征了氧化石墨烯的改性效果;运用SEM分析了改性上浆剂处理对玄武岩纤维表面及复合材料断口形貌的影响和作用机制.结果表明:偶联剂成功接枝到氧化石墨烯表面;玄武岩纤维经氧化石墨烯改性的上浆剂处理后,表面粗糙度及活性官能团含量增加,氧化石墨烯-玄武岩纤维/环氧树脂界面处的机械齿合作用及化学键合作用增强,界面黏结强度得到改善,玄武岩纤维的断裂强力提高了30.8%,氧化石墨烯-玄武岩纤维/环氧树脂复合材料的层间剪切强度提高了10.6%.     

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。      

高强高模碳纤维表面电化学氮化机制

高温石墨化使高强高模碳纤维(CF)表面光滑,反应活性低,导致其复合材料界面粘接性能差。杂原子改性是改善CF表面反应活性的有效手段之一。采用循环伏安(CV)方法在有机复合电解液中对高强高模CF进行了表面氧化和氮化改性,采用CV优选的复合电解液进行恒流电化学氧化处理,研究了CV扫描次数和电解液中含氮有机物对CF表面化学组成的影响。电化学处理前后CF表面化学元素组成和微观形态变化通过XPS、SEM及拉曼光谱表征。基于实验数据探讨了CF表面含氮官能团的生成及转变机制。研究结果显示,有机溶剂、有机氮源和含硫铵盐的协同作用使CF表面N含量从0.28at%增至4.77at%。适量的水存在,可以使CF表面O含量显著提高。CF表面的含氧官能团可以与CO(NH₂)₂中的-NH₂及电解液中的NH₄⁺反应形成酰胺基团,随着反应时间延长,CF表面的酰胺N会先转变成氧化氮,随后转变成吡啶和吡咯N,并最终转换成石墨N。恒流电化学处理后CF/环氧树脂复合材料的层间剪切强度(ILSS)较未处理的提高了132%,...     

表面处理对碳纤维/聚醚醚酮复合材料相容性及其力学性能的影响研究

通过KMnO_4、(NH_4)_2HPO_4和浓HNO_3对PAN基碳纤维(T300)进行表面改性,以聚醚醚酮(PEEK)为基体,制备碳纤维(CF)/聚醚醚酮复合材料。利用红外光谱和拉曼光谱对改性后的CF表面结构进行了研究。通过扫描电镜观察了CF和PEEK之间的界面粘结情况,用拉伸实验机对复合材料进行力学测试。结果表明,KMnO_4、(NH_4)_2HPO_4和浓HNO_3处理后CF表面无序度和活性碳原子增多,提高了CF表面活性,其中浓HNO3处理后CF表面含无序度最大,表面活性更强,制备的CF/PEEK复合材料相容性及其力学性能最好。     

硅烷偶联剂及氧化石墨烯二次改性对芳纶纤维界面性能的影响EI北大核心CSCD

为改善芳纶纤维(PPTA)与丁腈橡胶(NBR)复合材料之间的界面强度,采用硅烷偶联剂A172和氧化石墨烯(GO)对芳纶纤维表面进行接枝改性处理,并对处理前后的芳纶纤维进行化学结构、表面形貌及H抽出力分析。利用SEM对抽出纤维表面和橡胶基芳纶纤维复合材料截面进行微观结构分析。结果表明:硅烷偶联剂和氧化石墨烯对芳纶纤维进行二次表面改性后,纤维表面含氧基团增加,化学活性提高,处理后表面存在明显的表层附着物,纤维结构未发生明显损伤且表面粗糙度得到明显改善。每个处理阶段后H抽出力均有提高,且氧化石墨烯二次改性后的芳纶纤维H抽出力提高效果最佳,从18.192 MPa提高到48.748 MPa,芳纶纤维与丁腈橡胶的界面结合力得到了显著提升,从而证实了硅烷偶联剂和氧化石墨烯二次改性芳纶纤维的有效性,为橡胶基芳纶纤维复合材料性能的研究提供了参考。     

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]     

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。      

树脂基复合材料界面及界面表征

在树脂基体和成型工艺一定的条件下，碳纤维表面及表面涂层的性质在很大程度上决定了复合材料界面的性质，通过对ＣＦ表面进行性改及改变ＣＦ表面涂层的性质，可优化界面，最大限度发挥界面的特性，有用了界面微脱粘仪及透射电镜照片伪彩色处理对界面进行直观表征。     

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.     

复合处理碳纤维增强聚酰亚胺复合材料力学性能

采用浓硝酸氧化和聚酰亚胺(PI)包覆复合方法对短切碳纤维(CF)进行表面改性,提高CF增强热塑性聚酰亚胺复合材料(CF/TPI)力学性能。采用比表面积及孔容分析、原子力显微镜、扫描电子显微镜、热重分析仪研究了CF表面处理前后结构和形貌的变化。结果表明：CF经浓HNO₃处理后比表面积增加144.2%,CF表面沟壑加深;复合处理后有PI层包覆在 CF表面;包覆处理后CF耐热性能提高。力学性能测试表明,经过包覆处理后CF/TPI复合材料的拉伸强度比未处理的提高11.34%,弹性模量提高109.2%,弯曲强度提高18.78%,冲击强度提高74.15%。     

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.     

Anisotropic oxidation and weight loss in PMR-15 composites

Durability and degradation mechanisms in composites are fundamentally influenced by the fiber, matrix, and interphase regions that constitute the composite domain. The thermo-oxidative behavior of the composite is significantly different from that of the fiber and matrix constituents as the composite microstructure, including the fiber–matrix interphases/interfaces, introduces anisotropy in the diffusion behavior. In this work, unidirectional G30-500/PMR-15 composite specimens were aged at elevated temperatures in air resulting in oxidation propagation parallel and perpendicular to the fibers. Four different specimen geometries were chosen such that different surface area ratios (i.e., ratios of surface area perpendicular to the fibers to surface area parallel to the fibers) were obtained. Weight loss and volumetric changes were monitored as a function of aging time to study the high-temperature anisotropic oxidation process. Optical micrographs were taken on polished internal sections and viewed in the dark-field mode to measure the degree, depth and distribution of thermal oxidation development from surfaces perpendicular and parallel to the fibers. An empirically based weight loss model is investigated and used to predict weight loss in unidirectional and woven composites.     

碳纤维形貌结构对其电化学氧化行为及其复合材料界面性能的影响

通过调控原丝工艺,制备得到形貌结构不同、力学性能相近的PAN基碳纤维(CF),用以模拟碳纤维表面光滑与沟槽结构对其电化学氧化行为的影响。研究表明:原始形貌光滑碳纤维在电化学过程中保持形貌能力较强,相同的电化学氧化强度下,其表面氧碳比高于原始表面粗糙的碳纤维,表明其氧化程度高。X射线光电子能谱(XPS)分峰结果表明,二者表面氧含量差别来自于表面羰基含量的差异。力学性能测试结果表明具有沟槽形貌的碳纤维拉伸强度及拉伸模量提高的幅度较大,其中拉伸强度提高最大值为17.3%。将氧化前后的碳纤维制备成碳纤维增强树脂基复合材料,探讨碳纤维形貌结构对其复合材料界面性能的影响。结果表明:由具有沟槽形貌的碳纤维制备得到的复合材料层间剪切强度(ILSS)较高,表明碳纤维表面物理形貌也是影响复合材料界面的重要因素。