阳极氧化及上浆过程中PAN基碳纤维表面形态结构的演变

采用阳极氧化法对PAN基碳纤维的表面进行改性,然后使用上浆剂对纤维表面进行上浆处理。使用扫描电镜、原子力显微镜、X射线光电子能谱仪等分析了处理过程中碳纤维表面形态结构的变化,研究了阳极氧化及上浆处理对碳纤维的拉伸强度及其与环氧树脂间界面剪切强度(IFSS)的影响。结果表明:阳极氧化处理后,碳纤维表面平均粗糙度从48.0 nm增大到90.5 nm,而上浆后碳纤维平均粗糙度下降到32.3nm;经阳极氧化处理后,碳纤维表面碳(C)元素含量降低,氧(O)、氮(N)元素含量增加,—OH基团含量由14.43%增加到39.32%,而上浆后纤维表面—OH基团含量变化不大;在阳极氧化过程中随着氧化程度的提高,碳纤维的拉伸强度逐渐降低,但其IFSS逐渐升高;上浆对碳纤维拉伸强度影响不大,但上浆剂中较高的活性基团使得其IFSS进一步提高。     

聚吡咯层对碳纤维/环氧树脂复合材料界面粘结性能的影响

以三氯化铁为氧化剂,采用吡咯液相沉积聚合方法制备聚吡咯-碳纤维(PPy-CF),然后与环氧树脂(EP)复合,制得PPy-CF/EP复合材料,并对其进行拉伸性能测试,研究了聚合温度对PPy-CF/EP复合材料界面剪切强度(IFSS)的影响。结果表明:在CF表面吡咯沉积聚合最佳工艺条件为聚合温度70℃,时间30min,经过吡咯沉积聚合改性后,得到的PPy-CF/EP复合材料的IFSS有所提高;最佳条件下制得的PPy-CF/EP复合材料的IFSS是CF/EP复合材料的1.24倍;在PPy-CF中,PPy与CF之间无化学键作用,PPy-CF/EP复合材料的IFSS与PPy-CF表面含氧基团和粗糙度有关;吡咯化学沉积聚合改性是一种提高纤维与树脂界面粘结性能的有效方法。     

碳纤维树脂基复合材料的制备及在景观设计中的应用

采用Hummers法制备氧化石墨烯，并通过上浆剂对碳纤维进行了表面修饰，制备不同处理方式的碳纤维增强环氧树脂基复合材料。结果表明：经过上浆处理后试样的后加工性能得到一定程度改善，而氧化石墨烯会在一定程度上增加碳纤维试样的粗糙度和硬挺度。经过不同处理后的碳纤维增强环氧树脂复合材料的层间剪切强度相对除浆碳纤维d-CF增强环氧树脂复合材料要大，且小尺寸氧化石墨烯上浆处理的碳纤维增强环氧树脂复合材料的层间剪切强度最大（47.50 MPa），其耐磨性为2 049次、毛丝量为4.9 mg、硬挺度为66 mm，适宜于在景观设计中应用。     

含碳纳米管上浆剂改性碳纤维及其复合材料的研究

利用上浆法和含多壁碳纳米管(MWCNT)的上浆剂对碳纤维(CF)进行表面改性,采用手糊成型和热压成型工艺制备CF复合材料,借助扫描电子显微镜(SEM)和电子万能试验机研究MWCNT对CF表面形貌及复合材料力学性能的影响。结果表明,MWCNT在上浆剂中的分散状态会直接影响MWCNT在CF表面分布的均匀性、对CF的改性效果及CF复合材料的力学性能。质量分数为0. 5%MWCNT上浆剂对CF的改性效果较好,经0. 5%MWCNT上浆剂改性CF复丝的拉伸强度与去浆CF相比提高了70. 8%,改性CF复合材料的弯曲强度和层间剪切强度与去浆CF复合材料相比分别提高了42. 8%和72. 9%。     

潜伏型上浆剂对CF与MAPP树脂界面作用的影响

本文制备了三种不同潜伏型交联剂含量的上浆剂,DH1.5%、DH3.0%和DH6.0%,通过处理上浆提高碳纤维(CF)与马来酸酐接枝聚丙烯(MAPP)树脂之间的界面作用。利用微脱粘实验表征复合材料的界面剪切强度(IFSS),并利用傅里叶变换红外光谱(FTIR)和扫描电子显微镜(SEM)表征界面增强作用。结果表明:随着上浆剂中潜伏型交联剂含量的增加,复合材料的IFSS值也随之增加,当使用DH6.0%处理CF时,IFSS值达到7.42 MPa,相较于不做处理的CF/MAPP复合材料提高了204.1%。从FTIR和SEM的结果可知界面性能的提高是由于潜伏型交联剂会在复合材料界面处与CF、MAPP发生化学键合作用。     

芳纶纤维的热氧化处理及对环氧树脂界面黏结的影响

采用红外光谱(FTIR)、热重(TG)、差示扫描量热(DSC)对芳纶纤维在N_2和空气气氛下的热行为进行了研究,并以透射电镜(TEM)、界面剪切强度(IFSS)研究了芳纶纤维的空气热氧化处理及对其环氧树脂界面黏结的影响。结果表明:芳纶纤维在空气条件下,150～200℃温度范围内,仅仅是纤维表层上浆剂的挥发。250℃以上会出现分子链的氧化,同时纤维表层分子链能够重排使得氢键增强。高温过程中芳纶纤维的分子链苯环C—H被氧化成—C—OH、—COOH,从而使纤维表面极性增强。极性的结构有利于与环氧树脂的界面反应,使纤维与环氧树脂间形成40～50 nm的界面层。热处理后,芳纶纤维与环氧树脂微滴间界面剪切强度值增至18.05 MPa,与原丝相比增加了11.9%。同时,高温氧化后的芳纶纤维/环氧树脂界面黏合增强,复合材料的层间剪切强度为76.2 MPa,与原丝相比提高16.16%。     

淀粉纳米晶对玻璃纤维的表面改性研究

采用自制的淀粉纳米晶(SNC)对玻璃纤维进行表面处理,增加其与环氧树脂基体的界面剪切强度(IFSS)。研究了处理方式、处理时间、SNC乙醇分散液浓度、热处理温度等工艺参数对SNC在玻璃纤维表面沉积情况的影响,以及对改性玻璃纤维与环氧树脂的界面性能的影响规律。采用扫描电子显微镜、单纤维强力仪对处理前后玻璃纤维进行表征,并采用微脱粘法测试玻璃纤维与环氧树脂的界面粘结情况。结果表明,当重力静置处理时间24 h,SNC乙醇分散液浓度为1 g/100 m L时,SNC在玻璃纤维表面均匀沉积,且能显著提高玻璃纤维与环氧树脂的IFSS,为27.29 MPa,较未处理的纤维增加29.3%。150℃热处理4 h后,X射线光电子能谱结果显示SNC与玻璃纤维形成化学键合,进一步增加纤维与环氧树脂的界面粘结,IFSS值达到32.30 MPa,较未处理的纤维增加53%,且纤维的拉伸强度得到较好的维持。     

氧气低温等离子体对PBO纤维的表面改性

采用氧气低温等离子体对聚对苯撑苯并双噁唑(PBO)纤维进行表面改性,讨论了处理时间、处理功率及气压对PBO纤维单丝强度、与环氧树脂基体的界面剪切强度(π_(IFSS))、形态结构、表面元素组成和亲水性的影响。结果表明:在处理时间为2.5 min,处理功率为30 W,处理气压为50 Pa的最佳工艺条件下,经氧气等离子处理后的PBO纤维与环氧树脂的π_(IFSS)比原丝提高60%,达9.38 MPa,与水的接触角也从105°下降到72°。     

含碳纳米管上浆剂上浆改性碳纤维及其界面研究

碳纤维(CF)是一种高强度、高模量的高性能纤维,被广泛应用于复合材料中,但是纤维表面的活性官能团含量低,与基体之间的界面结合性能较差。本文利用含氨基化碳纳米管(NH_2-CNTs)上浆剂对光威GQ4922/12K型碳纤维表面进行改性,改善碳纤维与环氧树脂之间的界面结合性能。通过傅里叶红外光谱、扫描电镜、X射线光电子能谱、接触角和微脱粘对改性后的纤维表面组成、表面形貌、表面自由能和界面剪切强度进行分析,发现NH_2-CNTs可成功接枝到碳纤维表面,改性后纤维表面的氧(氮)元素含量增加,与水接触角从67.1°降低到50.5°,表面自由能从32.2 mN/m增加到了41.1 mN/m;界面剪切强度在氨基化碳纳米管质量浓度为0.6%时达到最大,相比未改性纤维从62.3 MPa提高到76.8 MPa,提高了23.3%。结果表明通过在上浆剂中引入氨基化碳纳米管,可以增加碳纤维表面活性,提高碳纤维与基体树脂的界面结合性能。     

共辐照接枝处理芳纶纤维F3A表面

以环氧氯丙烷为接枝剂,通过高能射线共辐照法对国产芳纶纤维(AFs)进行表面处理,对比了辐照前后芳纶表面形貌、动态接触角、表面自由能及其本体结晶情况变化。用不同辐照剂量下处理的纤维(IAFs-200和IAFs-400)制备了芳纶/环氧(IAFs/ER)复合材料,与未处理纤维相比,共辐照处理的芳纶增强复合材料的界面剪切强度(IFSS)和层间剪切强度(ILSS)分别提高了51.56%和25.79%。辐照处理后纤维表面活性的稳定性良好。     

Interfacial shear strength and durability improvement by monomeric and polymeric silanes in basalt fiber/epoxy single-filament composite specimens

Silane coupling agent effects in basalt fiber-epoxy systems have been investigated through measurement of the interfacial shear strength (IFSS) in single-fiber composite (SFC) specimens. Three silane were studied: 3-aminopropyltriethoxysilane (APS) and two polymeric silanes in which dimethoxy- or trimethoxysilane groups are attached via side chains to a polyethyleneimine backbone. Optimal conditions for silane application were standardized. Crosslinking of the deposited silanes is shown to result in decreased interpenetration by the matrix epoxy resin and lower values of IFSS. The polymeric silane with trimethoxy groups was found, as expected, to be inferior to the other two. APS and the polymeric dimethoxysilane gave similar results in improvement of IFSS and its retention after 1 h boiling in water. Monitoring of acoustic emission (AE) during straining of SFC specimens established a one-to-one correspondence between the number of AE events and fiber breaks. Measurement of AE pulse energies provided evidence for the sizing effect of polymeric silane coatings, through healing of surface flaws, as well as for moisture attack at severe surface flaws on the fiber during silane treatment.     

Effect of Halloysite Nanotube Incorporation in Epoxy Resin and Carbon Fiber Ethylene/Ammonia Plasma Treatment on Their Interfacial Property

Abstract

Effects of halloysite nanotube (HNT) loading of up to 2% in epoxy resin on its mechanical properties were characterized. The interfacial property of the resin with carbon fiber nanocomposite was also studied. Single fiber composite (SFC) technique was used to characterize the carbon fiber/epoxy resin interfacial shear stress. Carbon fibers were also coated with ammonia/ethylene plasma polymer to obtain a thin coating of the polymer with amine groups that could react with the epoxy and thus improve the interfacial property. The results indicated that the Young’s modulus of HNT containing nanocomposites increased slightly up to a loading of 0.25% after which it started to decrease. The tensile strength, however, steadily decreased with increasing of HNT loading although the fracture strain did not change significantly. This might be related to the nanotube shape, size and clustering. The interfacial shear strength (IFSS) was also increased slightly with HNT loading. The ethylene/ammonia plasma polymer coated fibers exhibited significantly higher IFSS by over 150%, independent of the HNT loading. The highest IFSS obtained was almost 79 MPa for plasma treated fibers. The results suggest that the carbon fiber/epoxy interface is not affected by the incorporation of up to 1.5% of HNT. Furthermore, the fiber surface modification through plasma polymerization is an effective method to improve and control the IFSS.     

Effects of surface treatment of carbon fiber: Tensile property,surface characteristics,and bonding to epoxy

In this article, effects of electrochemical oxidation and sizing treatment of PAN‐based carbon fibers (CFs) on the tensile properties, surface characteristics, and bonding to epoxy were investigated. As found, the electrochemical oxidation improves the tensile strength of single CF by 16.0%, due to weakening the surface stress concentration and smoothing the surface structure. Further sizing treatment shows a negligible effect on the tensile strength. Both oxidation and sizing treatments significantly improve the wettability and surface energies of CFs by introducing oxygen‐containing functional groups. Microbond test was conducted to characterize the interfacial shear strength (IFSS) between a single fiber and an epoxy droplet. The oxidation treatment increases IFSS slightly, which is due to the contradictory effects of the formation of chemical bonds between the resin and CFs, and the reduced mechanical interlocking. Further sizing treatment significantly enhances IFSS from 73.6 to 81.0 MPa, due to the formation of vast chemical bonds. Furthermore, the oxidation and sizing treatment can effectively reduce the degradation of IFSS to the hygrothermal ageing for the CF/epoxy system. POLYM. COMPOS., 37:2921–2932, 2016. © 2015 Society of Plastics Engineers     

Mechanical properties of carbon fiber composites modified with nano-SiO2 in the interphase

The performance of carbon fibers-reinforced composites is dependent to a great extent on the properties of fiber–matrix interface. To improve the interfacial properties in carbon fibers/epoxy composites, nano-SiO₂ particles were introduced to the surface of carbon fibers by sizing treatment. Atomic force microscope (AFM) results showed that nano-SiO₂ particles had been introduced on the surface of carbon fibers and increase the surface roughness of carbon fibers. X-ray photoelectron spectroscopy (XPS) showed that nano-SiO₂ particles increased the content of oxygen-containing groups on carbon fibers surface. Single fiber pull-out test (IFSS) and short-beam bending test (ILSS) results showed that the IFSS and ILSS of carbon fibers/epoxy composites could obtain 30.8 and 10.6% improvement compared with the composites without nano-SiO₂, respectively, when the nano-SiO₂ content was 1 wt % in sizing agents. Impact test of carbon fibers/epoxy composites treated by nano-SiO₂ containing sizing showed higher absorption energy than that of carbon fibers/epoxy composites treated by sizing agent without nano-SiO₂. Scanning electron microscopy (SEM) of impact fracture surface showed that the interfacial adhesion between fibers and matrix was improved after nano-SiO₂-modified sizing treatment. Dynamic mechanical thermal analysis (DMTA) showed that the introduction of nano-SiO₂ to carbon fibers surface effectively improved the storage modulus of carbon fibers/epoxy.     

Effect of sizing on interfacial adhesion of commercial high strength carbon fiber‐reinforced resin composites

The influence of sizing agent on interfacial shear strength (IFSS) of carbon fiber/epoxy (CF/EP) and carbon fiber/bismaleimide (CF/BMI) was investigated. Since sizing agent can alter physicochemical properties of CF surface, possible affecting factors, including sizing reactivity, chemical reactions between sizing and resin, wettability of fiber with resin, fiber surface roughness, and chemical composition of fiber surface, were discussed. It is found that contact angle of fiber with resin and sufficient chemical reactions between sizing and resin reveal strong correlation with the interfacial adhesion of CF/EP and CF/BMI, while the effect of surface roughness and the amount of oxygen on the fiber surface are relatively weak. Due to EP type of the composition, the sizing agent tends to improve the wettability of CF with EP, while goes against for the fiber with BMI. POLYM. COMPOS., 254–261, 2016. © 2014 Society of Plastics Engineers     

石墨烯改性对环氧树脂/碳纤维复丝拉伸性能的影响

采用直接分散法和上浆剂法分别制备了环氧树脂/碳纤维复丝,通过红外光谱、分光光度法等分析方法对处理的石墨烯的表面官能团及表面形貌进行表征,借助扫描电子显微镜对碳纤维表面进行微观形貌观察,研究了石墨烯改性对环氧树脂/碳纤维复丝界面性能的影响。结果表明:石墨烯表面成功地接枝了硅烷偶联剂KH-560;接枝硅烷偶联剂KH-560的石墨烯的环氧树脂/碳纤维复丝的拉伸性能优于未经改性的石墨烯的复丝;上浆法制得的环氧树脂/碳纤维复丝的拉伸性能优于分散法制得的复丝的拉伸性能;上浆剂法制备的石墨烯改性的环氧树脂/碳纤维复丝的断裂强力比未经过改性的未上浆的复丝的提高了48.6%,拉伸强度提高了30.4%,断裂伸长率提高了90.9%。     

The effect of silica (SiO2) nanoparticles and ammonia/ethylene plasma treatment on the interfacial and mechanical properties of carbon-fiber-reinforced epoxy composites

A nanoparticle dispersion is known to enhance the mechanical properties of a variety of polymers and resins. In this work, the effects of silica (SiO₂) nanoparticle loading (0–2 wt%) and ammonia/ethylene plasma-treated fibers on the interfacial and mechanical properties of carbon fiber–epoxy composites were characterized. Single fiber composite (SFC) tests were performed to determine the fiber/resin interfacial shear strength (IFSS). Tensile tests on pure epoxy resin specimens were also performed to quantify mechanical property changes with silica content. The results indicated that up to 2% SiO₂ nanoparticle loading had only a little effect on the mechanical properties. For untreated fibers, the IFSS was comparable for all epoxy resins. With ethylene/ammonia plasma treated fibers, specimens exhibited a substantial increase in IFSS by 2 to 3 times, independent of SiO₂ loading. The highest IFSS value obtained was 146 MPa for plasma-treated fibers. Interaction between the fiber sizing and plasma treatment may be a critical factor in this IFSS increase. The results suggest that the fiber/epoxy interface is not affected by the incorporation of up to 2% SiO₂ nanoparticles. Furthermore, the fiber surface modification through plasma treatment is an effective method to improve and control adhesion between fiber and resin.     

Improvement of interfacial shear strengths of polybenzobisoxazole fiber/epoxy resin composite by n‐TiO2 coating

Smooth polybenzobisoxazole (PBO) fiber has limited interfacial interaction with resin matrix. In this article, nano‐TiO₂ coating on PBO fiber is applied to improve the interfacial adhesion between PBO fiber and epoxy resin. The test results suggest that the PBO fiber had good interaction with epoxy resin matrix after its treatment with n‐TiO₂ sol. Nano TiO₂ particle embedded onto PBO fiber surface, acting as a chock, which made fiber implanted into the resin better. This greatly improved the shear strengths (IFSS) of PBO fiber/epoxy resin composite. It has been found that a 56% increase in interfacial IFSS has achieved without sacrificing mechanical properties of fiber. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improvement of the interfacial shear strength of poly(p‐phenylene benzobisoxazole) fiber/epoxy resin composite via a novel surface coating agent

Poly(p‐phenylene benzobisoxazole) (PBO) fiber with a smooth surface exhibits limited interfacial interaction with resin matrix. One of the effective strategies to improve the adhesion between the fiber and resin matrix is through surface modification of the fiber. In this study, we have proposed a novel surface treatment agent based on phosphoester cross‐linked castor oil (PCCO) for effective surface treatment of PBO fibers. The surface treatment agent was prepared by a simple cross‐linking reaction between hydroxy phosphorylated castor oil (PCO) and epoxy resin, with alcohol as the solvent at 65°C. Once the PBO fiber was treated with this agent, the interfacial adhesion between the PBO fiber and the epoxy resin could then be improved. Systematic analyses suggest that the surface treatment with (PCO + epoxy)/alcohol solution improves the interaction of the PBO fiber with the epoxy resin matrix. The PCCO coated onto the surface of PBO fiber acts as a coupling agent, improving the interfacial shear strength (IFSS) of the PBO fiber/epoxy resin composite. Results indicate a 156% increase in IFSS without compromising the mechanical properties of the fiber. POLYM. COMPOS., 37:1198–1205, 2016. © 2014 Society of Plastics Engineers