碳纤维增强苯并噁嗪树脂基复合材料的研究进展

苯并噁嗪是近年来发展起来的一种新型的高性能复合材料基体树脂。本文较系统地综述了国内外碳纤维增强苯并噁嗪复合材料的研究进展,介绍了苯并噁嗪树脂及其复合材料的性能特点,指出了进一步的发展趋势。     

苯并噁嗪树脂基芳砜纶纤维及玻璃纤维复合材料性能的研究

本文对苯并噁嗪、苯并噁嗪/芳砜纶纤维、苯并噁嗪/玻璃纤维树脂基复合材料的结构和性能进行了研究,并考察了该树脂的力学性能及耐热性,测试了苯并噁嗪/芳砜纶纤维、苯并噁嗪/玻璃纤维树脂基复合材料的力学性能及介电性能,并对芳砜纶纤维表面进行了电镜扫描。结果表明,树脂的耐热指数为199℃,其耐热性能和稳定性好,芳砜纶纤维与树脂之间形成了一个互溶体系,导致了芳砜纶纤维/苯并噁嗪复合材料的力学性能比玻璃纤维/苯并噁嗪复合材料的低,与树脂浇铸体的力学性能接近。     

苯并噁嗪树脂改性环氧树脂胶黏剂的阻燃性能

以双酚A型环氧树脂E51为基体,苯并噁嗪树脂为改性剂,4,4-二氨基二苯甲烷为固化剂,并加入少量无机填料,制备了苯并噁嗪树脂改性环氧树脂胶黏剂,研究了其耐热性能与阻燃性能。结果表明：苯并噁嗪树脂改性的环氧树脂胶黏剂耐热性能和阻燃性能较好,在氮气气氛下质量损失10%时的温度由390.75℃提高到401.12℃,800℃时的残炭率为21.988%(w),175℃的拉伸剪切强度达到19.4 MPa,极限氧指数达到31.6%。     

苯并噁嗪树脂基复合材料的制备及性能表征

本文采用氧等离子体对碳纤维表面进行活化,后用偶联剂接枝的方法对碳纤维表面进行处理。按照GB3357-82和GB3356-82,对复合材料层间剪切强度和弯曲强度进行测试并研究等离子体处理及偶联剂接枝对碳纤维/苯并噁嗪(Polybenzoxazine,PBOZ)复合材料界面粘接性的影响。通过XPS,SEM对碳纤维表面及复合材料断裂面形貌进行测试,分析界面粘接机制。研究表明,氧等离子体处理使碳纤维表面粗糙度和活性含氧基团含量增加,增加了纤维与树脂之间的粘接性;氧等离子体处理后再进行偶联剂接枝,碳纤维表面的含氧官能团增加,浸润性得到改善,提高了碳纤维/PBOZ复合材料界面粘接性能。     

高性能苯并噁嗪模压复合材料的研究

利用不同苯并噁嗪树脂体系胶液浸渍短切玻璃纤维,制得苯并噁嗪模塑料,并热压成型.通过对各树脂体系升温黏度变化、DSC固化行为以及凝胶化时间的研究,表明胺类催化剂或环氧-胺类催化剂的加入明显降低了苯并嗯嗪的热固化温度,提高了体系反应活性.对模压制品弯曲性能和耐热性能进行表征,得出加入环氧-胺类催化剂的苯并噁嗪体系,弯曲强度和弯曲模量分别达到565 MPa和22.7 GPa,明显高于普通酚醛、聚酯模压材料,玻璃化转变温度达到195℃,具有较好耐热性.模压制品的弯曲断面观察结果显示玻纤被树脂良好浸渍,纤维树脂间显示了良好的黏结性.     

聚苯并噁嗪树脂合成及其高性能化改性研究进展

首先介绍了聚苯并噁嗪树脂(PBZ)的性能和应用,概述了合成PBZ树脂的反应机理以及溶液法、熔融法及悬浮法合成PBZ工艺的优缺点,简述了PBZ树脂固化机理和工艺,回顾了PBZ树脂的高性能化改性手段和PBZ纳米复合材料的国内外研究进展,分析了具有不同分子结构、通过不同加工手段以及含有不同纳米填料改性的PBZ树脂性能改善情况。得出了目前针对PBZ树脂改性研究的重点,并对PBZ树脂的研究与应用做出展望。     

SW280玻璃布/苯并噁嗪热熔法预浸料的性能研究

本文采用热熔法制备SW280玻璃布/苯并噁嗪预浸料,并对苯并噁嗪树脂工艺性、热失重性能,及复合材料动态热机械性能、高温力学性能保持率、阻燃性能等进行工艺试验和性能评价.结果表明,苯并噁嗪树脂软化点在41～42℃,最低黏度点为1835mPa·s,满足热熔法预浸料的制备要求;氮气氛围下起始分解温度280℃左右,800℃时残碳率可达61.3％.SW280玻璃布/苯并噁嗪复合材料力学性能优异,界面粘接良好,玻璃化转变温度为200℃,其200℃高温下的压缩强度、弯曲强度、弯曲模量和层剪强度保持率分别为90.6％、59.4％、83.2％和62.7％.SW280玻璃布/苯并噁嗪复合材料阻燃性能优异,无焰和有焰模式下最大烟密度均为0,氧指数＞58％,燃烧等级为V-1.     

新型聚苯并噁嗪树脂及其防腐复合材料的研究进展

本文首先对聚苯并噁嗪树脂(PBZ)的合成路线和反应机理进行了概述,并对比了溶剂法、无溶剂法和悬浮法制备PBZ的优缺点。然后介绍了金属防腐的必要性和紧迫性以及PBZ的性能及在耐腐防腐领域的应用,并指出存在的不足。最后对PBZ及耐腐蚀PBZ复合材料的国内外研究进展进行了详细概述,从不同的分子结构设计、共混共聚改性以及添加功能纳米填料等策略分析了PBZ树脂及其复合材料的耐腐蚀性能及机理,以期对PBZ树脂及其耐腐蚀复合材料的发展与应用前景作出展望。本文能为从事高性能聚苯并噁嗪树脂及其复合材料的研究和开发提供有价值的借鉴。     

苯并(噁)嗪/环氧树脂共聚固化过程研究

采用FT-IR、DSC研究苯并(噁)嗪与环氧树脂通过熔融搅拌混合均匀后,固化过程中2种树脂发生开环共聚合的可能性.结果表明:苯并(噁)嗪与环氧树脂熔融混合后,在高温区(180 ℃,200 ℃)发生了共聚反应,苯并(噁)嗪开环过程形成的中间体可以作为环氧树脂的固化剂使用.玻璃化转变温度随着共聚体系中环氧树脂含量的增加先升高,环氧树脂含量超堵塞30%降低,当苯并(噁)嗪与环氧树脂的质量比为70/30时,Tg达到最高(218 ℃),熔融共混在一起程度上提高了共聚体的玻璃化转变温度.     

短切玻璃纤维增强苯并噁嗪复合材料研究

通过在苯并噁嗪树脂中加入丙酮处理前后的不同长度,不同掺入量的短玻纤,制备了短切玻璃纤维增强苯并噁嗪复合材料。研究了玻璃纤维上浆剂、短切玻璃纤维的长度以及掺入量对复合材料力学和热性能的影响,对复合材料的弯曲断裂面进行了微观分析。     

Improvement of interfacial interactions in CF/PEEK composites by an s-PSF/graphene oxide compound sizing agent

The interfacial interactions of carbon fiber (CF)-reinforced polymer composites is a key factor affecting the overall performance of the material. In this work, we prepared a sulfonated poly(ether sulfone)–graphene oxide mixed sizing agent to modify the interface of CF/PEEK composites and improve the interfacial properties between the PEEK matrix and CF. Results showed that the mechanical and interfacial properties of CF/PEEK composites are improved by the sizing agent. Specifically, the flexural strength, flexural modulus and interlaminar shear strength of the materials reached 847.29 MPa, 63.77 GPa, and 73.17 MPa, respectively. Scanning electron microscopy confirmed markedly improved adhesion between the resin matrix and fibers. This work provides a simple and effective method for the preparation of high-performance CF/PEEK composites, which can improve the performance of composites without degrading the mechanical property of pristine CF.     

High improvement of interfacial and mechanical properties in reinforced PP composite by grafting polyethyleneimine modified carboxylic multi-walled carbon nanotubes on short carbon fiber

The properties of carbon fiber reinforced polymer composites (CFRPs) will benefit greatly from improving interfacial performance. In this study, the interfacial properties of the PEI-CNT-CF/PP composite was improved by coating polyethyleneimine (PEI) modified carboxylic multi-walled carbon nanotubes (CNTs) in aqueous solution (PEI-CNT) onto the surface of the CF (PEI-CNT-CF) to form a network structure. The network formation changed the chemical characteristics and compatibility of CF surface by introducing amine (imine) groups, and could induce transcrystallization (TC) at interface of composite. These positive factors led to a 24.6% increasement in the interfacial shear strength (IFSS) of PEI-CNT-CF/PP, and further resulted in 16.2% and 5.3% improvement in tensile and flexural strength, respectively. SEM images of the fracture surface demonstrated a significant improvement in the interfacial adhesion between PEI-CNT-CF and PP resin. These results indicated that the PEI-CNT was a great choice to strengthen the interface of CF/PP system.     

Interfacial improvement of carbon fiber-reinforced methylphenylsilicone resin composites with sizing agent containing functionalized carbon nanotubes

A liquid sizing agent containing multiwall carbon nanotubes (MWCNTs) was prepared for carbon fiber (CF) reinforced methylphenylsilicone resin (MPSR) composite applications. In order to improve the dispersion of MWCNTs in the sizing agent and interfacial adhesion between CF and MPSR, MWCNTs and CF were functioned by the chemical modification with tetraethylenepentamine (TEPA) used as a MPSR curing agents. The CF before and after the sizing treatment-reinforced MPSR composites were prepared by a compression molding method. The microstructures, interfacial properties, and impact toughness of CF were systematically investigated. Experimental results revealed that a thin layer of MPSR coating containing functionalized MWCNTs (MWCNT-TEPA) was uniformly grafted onto the surface of CF. The sized CF-reinforced MPSR composite showed simultaneously remarkable enhancement in the interlaminar shear strength and impact toughness. Meanwhile, the tensile strength of CF had no obvious decrease after sizing treatment. In addition, the interfacial reinforcing and toughening mechanisms were also discussed. We believe that the facile and effective method in preparing multifunctional fibers provides a novel interface design strategy of carbon fiber composites for different applications.     

Interfacial improvement of carbon fiber/epoxy composites using a simple process for depositing commercially functionalized carbon nanotubes on the fibers

An aqueous suspension deposition method was used to coat the sized carbon fibers T700SC and T300B with commercially carboxylic acid-functionalized and hydroxyl-functionalized carbon nanotubes (CNTs). The CNTs on the fiber surfaces were expected to improve the interfacial strength between the fibers and the epoxy. The factors affecting the deposition, especially the fiber sizing, were studied. According to single fiber-composite fragmentation tests, the deposition process results in improved fiber/matrix interfacial adhesion. Using carboxylic acid-functionalized CNTs, the interfacial shear strength was increased 43% for the T700SC composite and 12% for the T300B composite. The relationship between surface functional groups of the CNTs and the interfacial improvement was discussed. The interfacial reinforcing mechanism was explored by analyzing the surface morphology of the carbon fibers, the wettability between the carbon fibers and the epoxy resin, the chemical bonding between the fiber sizing and the CNTs, and fractographic observation of cross-sections of the composites. Results indicate that interfacial friction, chemical bonding and resin toughening are responsible for the interfacial improvement of nanostructured carbon fiber/epoxy composites. The mechanical properties of the CNT-deposited composite laminate were further measured to confirm the effectiveness of this strategy.     

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.     

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.     

基于NOL环的高性能纤维与环氧树脂的匹配性研究

纤维与树脂的界面对复合材料的整体力学性能有着显著的影响。基于NOL环的宏观力学测试一般被用来反映复合材料的界面粘结性能,因此适用于评价纤维与树脂之间的宏观力学性能匹配性。为了探究高性能碳纤维T700SC、T800HB及高强玻璃纤维与环氧树脂的宏观力学性能匹配性,本研究首先根据GB/T 1458—2008国家标准制备NOL环试样,再借助NOL环的拉伸和层间剪切强度测试分析了高性能纤维与环氧树脂不同匹配组合宏观力学性能差异的原因,并寻找出最佳匹配组合。结果表明:玻璃纤维与环氧树脂的界面存在最佳的粘结强度,而且不同粘结强度导致拉伸强度和破坏机理不同,而碳纤维复合材料界面性能较差,容易分层破坏;T800HB与环氧树脂的宏观力学匹配性优于T700SC,环氧树脂力学性能、碳纤维的表面微观结构与性质以及环氧树脂与碳纤维之间的相互作用关系是影响界面粘结性能的根本原因。该研究在高性能纤维单向复合材料的材料选择与设计方面具有现实意义。     

碳纤维布/玻纤布增强聚氨酯复合材料的研究

以聚氨酯为基体树脂,分别以碳纤维布、玻璃纤维布和这两种纤维布交替铺叠作为增强材料,采用真空辅助灌注成型工艺制备了4种复合材料.考察了纤维布的铺层结构对复合材料的弯曲、拉伸和冲击性能的影响.结果显示,复合材料的拉伸模量和弯曲模量随碳纤维含量增加而增加,冲击强度则降低.分别采用TGA、DMA和SEM对复合材料的热性能、界面...     

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     

Mechanical behavior of two-dimensional carbon/carbon composites with interfacial carbon layers

Effect of interfacial carbon layers on the mechanical properties and fracture behavior of two-dimensional carbon fiber fabrics reinforced carbon matrix composites were investigated. Phenolic resin reinforced with two-dimensional plain woven carbon fiber fabrics was used as starting materials for carbon/carbon composites and was prepared using vacuum bag hot pressing technique. In order to study the effect of interfacial bonding, a carbon layer was applied to the carbon fabrics in advance. The carbon layers were prepared using petroleum pitch with different concentrations as precursors. The experimental results indicate that the carbon/carbon composites with interfacial carbon layers possess higher fracture energy than that without carbon layers after carbonization at 1000°C. For a pitch concentration of 0.15 g/ml, the carbon/carbon composites have both higher flexural strength and fracture energy than composites without carbon layers. Both flexural strength and fracture energy increased for composites with and without carbon layers after graphitization. The amount of increase in fracture energy was more significant for composites with interfacial carbon layers. Results indicate that a suitable pitch concentration should be used in order to tailor the mechanical behavior of carbon/carbon composites with interfacial carbon layers.