粗糙度对碳纤维/聚芳基乙炔复合材料界面性能的影响

采用二氧化碳超临界(scCO2)处理碳纤维(CF)表面的方法,研究了粗糙度对碳纤维/聚芳基乙炔(PAA)树脂复合材料界面性能的影响.处理前后的碳纤维通过XPS,AFM和表面能测量进行了表征.CF/PAA复合材料的界面力学性能通过层间剪切强度测试(ILSS)与断口形貌分析进行了评价.结果表明,scCO2处理前后碳纤维表面的化学组成基本上没有变化.随着碳纤维表面粗糙度的增加,CF/PAA复合材料的界面力学性能先增加后减小.其中粗糙度范围为30～45 nm的样品有最高的ILSS值,43.36MPa,比未处理的样品提高了44%.对复合材料的ILSS提高起主要作用的因素是碳纤维与PAA树脂的界面齿合作用.而齿合作用程度的不同主要是由于不同粗糙度而引起的碳纤维表面物理状态的不同.     

γ-射线辐照对碳纤维及其复合材料力学性能的影响

以60Coγ-射线为辐照源对碳纤维(CF)表面进行处理,利用扫描电子显微镜(SEM)观察经辐照处理后的碳纤维单丝表面及其与环氧树脂制备的复合材料试样的层间剪切断口;通过层间剪切强度比较了吸收剂量对其复合材料层间剪切强度(ILSS)的影响,并根据GB/T3362—1982标准比较了辐照前后碳纤维复丝拉伸强度的变化。结果表明:辐照处理后的碳纤维增强环氧树脂复合材料的界面明显得到改善,在一定的吸收剂量范围内能够有效地提高复合材料的ILSS,但是过大的辐照剂量和接枝率不利于复合材料的界面改性;当辐照剂量小于250kGy时,碳纤维的复丝拉伸强度有所提高。     

超临界CO2对碳纤维环氧树脂的界面性能的改善

为提高碳纤维/环氧树脂复合材料的界面结合性能,采用超临界CO2对碳纤维表面进行处理.结果表明:在处理后碳纤维的单丝拉伸强度下降2.81％,碳纤维/环氧树脂界面剪切强度和层间剪切强度在处理后分别提高25.19％和17.11％.通过对碳纤维原子力显微镜(AFM)观察,经过处理的碳纤维表面粗糙度增加明显,同时对复合材料层间剪切断口端面用扫描电子显微镜(SEM)观察,经过超临界CO2处理后的碳纤维与环氧树脂的复合性能得到改善.     

碳纤维的改性及其界面性能

采用化学接枝的方法对篮球鞋用碳纤维进行了表面改性处理,将柠檬酸接枝到碳纤维表面制备了碳纤维/环氧树脂复合材料,对比分析了改性前后碳纤维的表面形貌、界面剪切强度和层间剪切强度,并对断口形貌进行了观察。结果表明:经过柠檬酸改性后的碳纤维表面粗糙度明显增加,与树脂基体的结合力最强;碳纤维、氧化后的碳纤维、对苯二胺接枝的碳纤维、聚柠檬酸接枝的碳纤维和二次接枝对苯二胺的碳纤维的界面剪切强度分别为46.8,53.4,68.2,62.4,82.2 MPa,改性碳纤维的界面剪切强度都高于原始碳纤维,二次接枝对苯二胺的碳纤维的界面剪切强度最大;经过表面改性处理的碳纤维的层间剪切强度都有不同程度提高,且二次接枝对苯二胺的碳纤维的层间剪切强度最大。     

微脱黏法在碳纤维/环氧树脂界面性能评价中的应用

利用微脱黏法测定碳纤维/环氧树脂复合材料的界面剪切强度,并分析了造成测试结果分散的影响因素.结果表明:在脱黏过程中,最大脱黏力随碳纤维埋人环氧树脂内长度的增加而线性递增,当埋人长度超过一定值后最大脱黏力趋于稳定:碳纤维与环氧树脂间的接触角对复合材料界面剪切强度有一定影响,接触角越大,界面剪切强度越高;测试结果的分散性与树脂微球的半月板区域、钳口区等因素有关;未经表面处理的碳纤维增强环氧树脂复合材料的界面剪切强度仪为39.4 MPa,低于处理后的复合材料(60.6 MPa).     

γ-射线辐照碳纤维对其复合材料力学性能的影响

利用高能射线(60Coγ-射线)辐照接枝技术对碳纤维(CF)表面进行处理。对辐照处理前后的CF分别利用SEM观察其复合材料层间剪切断口;比较了吸收剂量对碳纤维增强环氧树脂复合材料层间剪切强度(ILSS)的影响。结果表明:辐照处理后的,碳纤维增强环氧树脂复合材料的界面明显得到改善,辐照接枝技术在一定的剂量范围内能够有效地提高复合材料的ILSS,但是过大的辐照剂量和接枝率不利于复合材料的界面改性。     

PAMAM接枝改性碳纤维表面及分子动力学模拟

采用化学法将聚酰胺-胺树枝状大分子(PAMAM)接枝在T700碳纤维(CFs)表面,对比了不同代数PAMAM分子接枝前后CFs表面的微观形貌,并对CFs/环氧微复合材料的界面剪切强度(IFSS)进行测试及材料拉脱断口处形貌观察。与未处理纤维相比,经过G1.0代PAMAM接枝处理后的复合材料IFSS值提高了30.37%。采用Materials Studio程序包,建立碳纤维、环氧树脂及两者间界面的结构模型并进行优化,通过分子动力学模拟并计算了界面相互作用能,结果表明,引入PAMAM分子会提高CFs与环氧树脂间的界面结合能,与实验结果一致。     

碳纤维表面处理对碳纤维/聚丙烯复合材料界面结合性能的影响

研究了电化学氧化、环氧上浆处理对碳纤维/聚丙烯(CF/PP)复合材料界面结合性能的影响,首先通过AFM、XPS等测试不同碳纤维的表面形貌和化学性质,然后借助微球脱粘实验考察对比不同CF/PP的界面剪切强度(IFSS)。结果显示高温碳化后的碳纤维表面呈惰性,复合材料IFSS仅有3.76 MPa;经过电化学氧化处理,表面粗糙度增大,羟基和羧基基团增多,IFSS增加到4.85 MPa;上浆处理后,表面引入活性的环氧基团,IFSS进一步增加到5.51 MPa,同时界面均匀性也有所改善。根据结果分析,碳纤维表面性质改变引起的界面区域机械锁合、范德华力以及分子链缠结作用增加是界面性能提升的主要原因。但与相容剂相比,传统碳纤维表面处理对CF/PP界面改善效果相对较弱,开发更加有效的改性方法十分必要。     

热解沉积结合PAMAM接枝改性碳纤维表面

采用热解沉积结合聚酰胺-胺型树枝状高分子(PAMAM)接枝的改性方式对碳纤维进行表面处理,对比了碳纤维原丝(CFs)、只经热解沉积处理碳纤维(PD-CFs)和沉积结合接枝处理碳纤维(PD-PG-CFs)的表面形貌、表面元素组成和质量分数、与极性液体和非极性液体的接触角、表面自由能的变化;制备了不同处理条件下碳纤维/环氧微复合材料,与未处理的碳纤维原丝相比,经热解沉积处理的碳纤维/环氧复合材料的界面剪切强度(IFSS)提高了26.87%,而经沉积结合PAMAM接枝处理碳纤维/环氧复合材料的IFSS则提高了38.81%。通过纳米压痕测试定量的表征了复合材料中碳纤维、热解碳层和树脂基体3者的模量,结果表明,热解碳层的模量介于碳纤维和树脂之间,它所起到的过渡层效应是复合材料界面性能得到改善的重要原因。     

臭氧处理对碳纤维表面及其复合材料性能的影响

利用X射线光电子能谱(XPS)研究了碳纤维经臭氧(O3)氧化处理后表面元素组成及表面官能团的变化，结果发现，O3表面处理主要增加了碳纤维表面上的羟基或醚基官能团；研究了表面O3氧化处理对复合材料力学性能的影响，结果表明，碳纤维经O3氧化处理后明显改善了碳纤维与环氧树脂间的界面粘结，其复合材料的层间剪切强度明显提高。     

氨气处理碳纤维 第I报 表面组成和反应机理

采用原位漫反射红外光谱(FT-IR)在线分析碳纤维表面谱图变化。结果发现,当温度升至500℃后,3260cm-1处吸收峰减弱,在3157cm-1、3048cm-1、2829cm-1和1405cm-1处新增吸收峰。用X-射线光电子能谱(XPS)对未处理与在氨气气氛中600℃处理30s后碳纤维的表面官能团组成进行分析对比发现,处理后的碳纤维表面氮元素显著增加,而氧含量降低。由FT-IR和XPS的谱图变化推测出在高温时,碳纤维表面的羟基和羧基与氨气发生反应,形成了氨基官能团。     

Effect of surface cold ablation on shear strength of CFRP adhesively bonded joint after UV laser treatment

Ultraviolet(UV) laser treatment on the surface of the carbon fiber reinforced polymer (CFRP) laminate becomes an effective method to benefit the bonding strength of adhesively bonded joint in aerospace industries. In the present research, homomorphic CFRP laminates with different resin distribution on the surface are bonded into single-lap joints. Their shear strengths are tested to evaluate the effect of surface resin distribution on bonding mechanical performance. The different resin distributions on the surface of CFRP laminate are obtained by UV pulse laser with different laser scanning speeds. The scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) are conducted to analyze the laser treated surfaces and fracture surfaces of tested joints. The experimental results indicate that the residual resin of CFRP surface increases with the increase of scanning speed. Compared with both the reference surface without laser pre-treatment and that with no-residual resin for bonding, the surface with partial residual resin results in an enhancement of the shear strength of bonded joint. Moreover, the shear strength of the reference sample is higher than that bonded by the surface with no-residual resin. The research lays foundation for understanding the relationship between surface resin distribution and bonding strength.     

碳纤维在不同电解质体系下的电化学表面改性

使用电化学氧化法对PAN基碳纤维进行表面改性,通过扫描电子显微镜（SEM）、Raman光谱和X射线光电子能谱仪（XPS）表征了碳纤维表面物理化学结构,同时结合力学性能分析,评价了碳酸氢铵、硫酸铵和复合铵盐溶液3种电解质体系的改性效果。实验结果表明,碳酸氢铵溶液下的电化学改性有利于界面粘结强度的提高,而硫酸铵溶液下的电化学改性有利于降低抗拉伸强度的损失,当采用复合溶液改性时,则可以同时提高碳纤维的抗拉伸强度和其复合材料的抗层间剪切强度。     

Nanoscale toughening of carbon fiber‐reinforced epoxy composites through different surface treatments

Interests in improving poor interfacial adhesion in carbon fiber‐reinforced polymer (CFRP) composites has always been a hotspot. In this work, four physicochemical surface treatments for enhancing fiber/matrix adhesion are conducted on carbon fibers (CFs) including acid oxidation, sizing coating, silane coupling, and graphene oxide (GO) deposition. The surface characteristics of CFs are investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, interfacial shear strength, and interlaminar shear strength. The results showed that GO deposition can remarkably promote fiber/matrix bonding due to improved surface reactivity and irregularity. In comparison, epoxy sizing and acid oxidation afford enhancement of IFSS owing to effective molecular chemical contact and interlocking forces between the fiber and the matrix. Besides, limited covalent bonds between silane coupling and epoxy matrix cannot make up for the negative effects of excessive smoothness of modified CFs, endowing them inferior mechanical properties. Based on these results, three micro‐strengthening mechanisms are proposed to broadly categorize the interphase micro‐configuration of CFRP composite, namely, “Etching” “Coating”, and “Grafting” modifications, demonstrating that proper treatments should be chosen for combining optimum interfacial properties in CFRP composites. POLYM. ENG. SCI., 59:625–632, 2019. © 2018 Society of Plastics Engineers     

Increasing the interfacial strength in carbon fiber/epoxy composites by controlling the orientation and length of carbon nanotubes grown on the fibers

Multi-walled carbon nanotubes (MWCNTs) were grafted onto carbon fibers (CFs) using an injection chemical vapor deposition method. The orientation and length (16.6–108.6 μm) of the MWCNTs were controlled by the surface treatment of the CFs and the growth time, respectively. The interface between the MWCNTs and the CFs indicated the grafted CNTs were immobilized by embedding catalyst on CFs. Two orders of magnitude increase in the specific surface areas of CFs was obtained by grafting the MWCNT. MWCNT–CF hybrids exhibited good wettability with the epoxy resin due to the surface roughness and capillary action. Single-fiber composite fragmentation tests revealed an remarkable improvement of interfacial shear strength (IFSS) controlled by the orientation and length of MWCNTs. MWCNTs with an perpendicular alignment and long length showed a high IFSS in epoxy composites due to better wettability and a large contact interface between the hybrids and the resin. Hybrids with an optimum length (47.2 μm) of aligned MWCNTs showed a dramatic improvement of IFSS up to 175% compared to that of pristine CFs.     

Improving the interfacial properties of carbon fiber–epoxy resin composites with a graphene-modified sizing agent

We successfully prepared a graphene-modified carbon fiber (CF) sizing agent with good dispersity and stability by dispersing reduced graphene oxide (RGO) into an emulsion-type sizing agent. RGO was obtained by the reduction of graphene oxide (GO) with the help of gallic acid. The influence of the graphene-modified sizing agent on the interfacial properties of the CF–epoxy resin composites was investigated with microbond testing and the three-point bending method. The results show that optimized interfacial properties were achieved when the size of the modified graphene was less than 1 μm, the content of RGO was 20 ppm, and the pH value of the sizing agent was 10.5. The interfacial shear strength of the composites reached 92.3 MPa, which was 29.6% higher than that of the composites with unmodified CFs. Compared with commercial-CF-fabric-reinforced composites, the interlaminar shear strength of the composites treated with the RGO-modified sizing agent increased by 21.5%. Both the interfacial and interlaminar failure morphologies of the composites were examined with scanning electron microscopy (SEM). The results show that a large amount of residual resin adhered to the surfaces of the CFs treated with the RGO-modified sizing agent; this indicated good interfacial properties between the CFs and the resin matrix. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47122.     

Relationship Between Some Mechanical Strengths of CFRP and Interfacial Properties

The relationships between microscopic properties such as interfacial shear strength (IFSS) and macroscopic properties such as flexural strength were investigated for CFRP prepared from carbon fiber and epoxy resin. Flexural, tensile and impact strengths all went through maximum values when plotted against the surface treatment time of the carbon fiber. The flexural strength of CFRP as a function of the treatment time of the carbon fiber behaved similarly to the adhesive strength of the resin and carbon fiber. Also, the results indicated that the bahavior of tensile and impact strengths varied with the treatment time in much the same way as the interfacial shear strength did. The occurrence of these two types of macroscopic and microscopic property effects can be understood by taking into account the chemical activity and roughness of the carbon fiber surface.     

Improved interfacial adhesion in carbon fiber/epoxy composites through a waterborne epoxy resin sizing agent

A series of self‐emulsified waterborne epoxy resin (WEP) emulsions were used as surface sizing for carbon fibers (CFs) to improve the interfacial adhesion between the CF and epoxy matrix. In this work, the hydrogenated bisphenol‐A epoxy resin (HBPAE) was modified by polyethylene glycol (PEG) with molecular weights of 400, 800, 1000, 1500, 2000, 4000, and 6000 g/mol. The properties of the WEP emulsion were examined by Fourier transform infrared spectroscopy, dynamic light scattering, and transmission electron microscopy. The surface characteristics of sized CFs were evaluated using scanning electron microscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy. Afterwards, CF/EP composites were prepared and their fracture surface and interlaminar shear strength (ILSS) were examined. The results indicated that PEG2000 modified HBPAE sizing had the optimum emulsion stability and film‐forming ability. Meanwhile, the results also demonstrated that a continuous and uniform sizing layer was formed on the surface of CFs and the surface sizing was excellent in improving the chemical activity of CFs. Compared with unsized CFs, the O1s/C1s composition ratio was observed to increase from 11.51% to 33.17% and the ILSS of CF/EP composites increased from 81.2 to 89.7 MPa, exhibiting better mechanical property than that of commercial Takemoto S64 sized CFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44757.     

Interface improvement of carbon fiber/methylphenylsilicone resin composites by fiber surface coating of polyhedral oligomeric silsesquioxanes

To enhance interfacial properties of carbon fibers (CFs)-reinforced methylphenylsilicone resin (MPSR) composites, we introduced an appropriate interface reinforced by trisilanolphenyl-polyhedral oligomeric silsesquioxanes (trisilanolphenyl-POSS) between CFs and MPSR with a liquid phase deposition strategy. Chemical bonds among silanol groups of trisilanolphenyl-POSS, hydroxyl-functionalized CF (CF–OH), and silanol end groups of MPSR in the coating were expected to be formed through condensation reaction during the prepared process. CFs with and without sizing treatment-reinforced MPSR composites were prepared by a compression molding method. X-ray photoelectron spectroscopy revealed that trisilanolphenyl-POSS particles enhanced the contents of fiber surface oxygen-containing groups and silicon-containing functional groups. Scanning electron microscopy and atomic force microscopy images showed that trisilanolphenyl-POSS nanoparticles have been introduced onto the fiber surface obviously and the surface roughness increased sharply. Dynamic contact angle analysis indicated that trisilanolphenyl-POSS-modified sizing agent could improve the fiber wettability and surface energy significantly. Short-beam bending test and impact toughness test results showed that the interlaminar shear strength and impact resistance of the sized CFs composites were enhanced greatly with increasing amplitudes of more than 35 and 27% in comparison with those of untreated CF composites, respectively. Cryo-fractured surface topographies of composites confirmed that interfacial adhesion between CFs and MPSR has been improved after sizing treatment. Meanwhile, the sizing treatment does not decrease single fiber tensile strength.     

空气氧化法对CFRP力学性能的影响

讨论了炭纤维经瞬时高温空气氧化法表面处理后，炭纤维增强树脂基复合材料的力学性能。特别是层间剪切强度的变化情况。结果表明瞬时高温空气氧化法表面处理能提高ＣＦＲＰ的界面粘结强度，其ＩＬＳＳ随空气氧化温度提高而提高。虽然ＩＬＳＳ也能提高到９０ＭＰａ以上，但同时增加了复合材料的脆性炭纤维抗位强度也会严重下降。