改性环氧树脂光固化速粘胶的粘接应用研究

采用玻璃纤维布/光固化胶粘剂复合材料补片,实现对铝合金片的快速粘接与固化。考察了国产UV胶粘剂预聚物和进口UV胶的粘接性能、耐温性能以及粘接强度随胶粘剂相对分子质量及其分布的变化规律。结果表明:进口光固化胶/玻璃纤维布复合材料补片与铝合金片的剪切强度在14.5～23.1MPa之间,国产光固化胶体系剪切强度在11.3～16.6MPa之间,两者均高于铆接强度(10.3MPa);作为胶粘剂基体树脂,相对分子质量分布越宽越有利于粘接强度的提高;此外,-40℃低温与100℃高温对体系粘接强度的影响很小(不超过10%)。     

后处理温度对EP/CF复合材料拉伸性能影响

采用模压成型工艺和拉挤工艺制备了加捻碳纤维增强环氧树脂(EP/CF)复合材料,利用微机控制电液伺服万能试验机和扫描电子显微镜研究了不同后处理温度对EP/CF复合材料的拉伸性能和断面微观形貌的影响。研究表明,相对于高温后处理下的EP/CF复合材料,室温后处理下的EP/CF复合材料的拉伸强度较优,其拉伸强度接近890 MPa;而随着后处理温度的升高,EP/CF复合材料的截面和表面显微硬度值呈先上升后下降趋势,当后处理温度为150℃时,其硬度值最优。随着后处理温度的上升,样品的断面形态由撕拉态变为剪切状态,整个断面转变为脆性断面,EP与CF之间的界面变差。较优后处理工艺为低温后处理;同时,常温固化剂下的EP和CF体系选择后处理工艺优化时,后固化温度应接近固化体系温度进行优化处理。     

光固化ES/CEP共混物及其复合材料力学性能研究

设计了不同质量比的有机硅环氧树脂/脂环族环氧树脂(ES/CEP)共混物,采用光固化技术,分别制备了ES/CEP共混物试样(EP)、玻璃纤维增强复合材料(GF/ES-CEP)以及GF/ES-CEP复合材料为补片的粘接修理铝合金试样,重点研究了有机硅环氧树脂(ES)的质量分数对试样拉伸力学性能的影响。结果表明:CEP添加ES、EP的抗拉强度有逐渐降低的趋势,延伸率则先增加后下降,EP的力学性能在加入15%的ES时达到最佳;GF/ES-CEP复合材料抗拉强度和延伸率则随ES比例的增加先上升后下降。以GF/ES-CEP复合材料为补片的复合材料粘接修理铝合金试样主要发生胶层与损伤结构界面的剥离破坏,表明复合材料力学性能优于界面力学性能。水浴处理后,GF/ES-CEP复合材料修理铝合金试样的力学性能有明显下降,加入适量有机硅树脂可以提高修复试样的耐湿热性能。     

一种低温固化的环氧树脂/碳纤维的制备及其性能研究

选用三乙烯四胺(TETA)、甲基六氢苯酐(MHHPA)、间苯二甲胺(MXDA)作为环氧树脂(EP)的固化剂,制备了一种固化温度为80℃的EP.研究表明,温度为80℃时,MHHPA不能单独固化该EP.少量的TETA或MXDA能够促进MHHPA对EP的固化,研究证明MHHPA和TETA或MXDA间生成了酰胺,TETA或MX...     

无卤阻燃PF/EP/GF布复合材料的固化性能和阻燃性能

采用环氧树脂(EP)作固化剂,2,4,6-三(二甲胺基甲基)-苯酚(DMP30)作固化促进剂改善酚醛树脂(PF)的固化性能,以氢氧化铝和有机磷阻燃剂协同改性其阻燃性能,将其涂覆于玻璃纤维(GF)布上,压制成无卤阻燃PF/EP/GF布复合材料.用傅立叶变换红外光谱(FTIR)仪和差示扫描量热(DSC)仪对无卤阻燃PF/EP/GF布复合材料的固化反应机理、固化反应动力学进行了分析研究,并测试了该复合材料的阻燃性能.结果表明,无卤阻燃PF/EP/GF布复合材料的固化反应表观活化能Ea=75.7 kJ/mol、反应级数n=0.91,起始固化温度、固化峰顶温度、固化终止温度分别为108.6、133.2、152.9℃;当氢氧化铝质量分数为14%、DMP30质量分数为1%、有机磷阻燃剂质量分数为4.8%时,无卤阻燃PF/EP/GF布复合材料的固化性能、阻燃性能均达到较佳状态.     

聚丙烯/马来酸酐接枝聚丙烯/环氧树脂/玻璃纤维复合材料的制备及其性能研究

通过双螺杆挤出机制备了聚丙烯/马来酸酐接枝聚丙烯/环氧树脂/玻璃纤维（PP/PP-g-MAH/EP/GF）复合材料,并研究了PP-g-MAH含量、EP含量及固化剂对复合材料力学性能的影响。结果表明,PP-g-MAH含量为10份,含有固化剂EP的含量为3份时,复合材料的综合力学性能最佳;与不加EP的复合材料相比,其拉伸强度、弯曲强度、冲击强度分别提高了41 %、47 %、86 %。扫描电子显微镜分析表明,EP的加入明显改善了GF和PP基体的黏结强度。     

Low-temperature fast curable behavior and properties of bio-based carbon fiber composites based on resveratrol

Environmentally friendly materials are an integral part of sustainable chemistry, and bio-based polymer composites are an important class of materials. The manufacture of composites is expected to reduce or even eliminate the use of adjuvants, considering the importance of reducing energy consumption and avoiding health and environmental risks. In this study, a phenyl-containing, polyfunctional, bio-based epoxy resin (TGER) was synthesized, and carbon fiber-reinforced, bio-based epoxy resin composites were fabricated by vacuum-assisted resin infusion using two aromatic amine curing agents, 4,4′-diaminodiphenylmethane (DDM) and 3,3′-diethyl-4,4′-diaminodiphenylmethane (DEDDM). Curing reactions and rheological behavior studies showed that TGER had higher curing reactivity toward DDM and DEDDM than to diglycidyl ether of bisphenol A (DGEBA) and possessed good processability. The results indicated that the resveratrol-based epoxy resin displayed low-temperature fast curing properties. The evaluation of the mechanical properties of the carbon fiber composites showed that the flexural strengths of CF/TGER/DDM and CF/TGER/DEDDM were 520 and 628 MPa, respectively. The initial decomposition temperature of CF/TGER composites is above 200°C. Furthermore, the carbon fiber–reinforced biopolymers possess excellent heat resistance. Therefore, carbon fiber-reinforced, resveratrol-based epoxy resin composites are promising candidates as alternatives to petroleum-based high-performance carbon fiber composites.     

快速固化环氧树脂/碳纤维复合材料的性能

利用差示扫描量热分析仪研究了一种快速固化环氧树脂体系的固化工艺参数,确定了以真空辅助树脂灌注工艺制备快速固化环氧树脂/碳纤维复合材料的成型方法,并与常规固化环氧树脂体系制备的碳纤维复合材料进行对比,采用傅里叶变换红外光谱仪对两种材料的树脂基体进行了分析,考察了两种复合材料的纤维含量、孔隙率及力学性能,最后通过扫描电子显微镜观察了快速固化树脂基体与碳纤维的界面结合性。结果表明,快速固化树脂在99℃下固化6 min后固化度可达96%,能够大幅缩减碳纤维复合材料的成型时间,以其制备的碳纤维复合材料拉伸强度比常规固化环氧树脂复合材料高11.20%,弯曲强度高16.92%,纵横剪切强度高7.44%,快速固化树脂与碳纤维界面结合性良好。     

环氧树脂室温固化体系的研制及性能研究

以兼具引发剂和稀释剂功能的自制BH-1为固化剂,通过引入低黏度活性稀释剂,制备室温固化EP(环氧树脂)胶粘剂;然后以EP/BH-1/活性稀释剂为基体、单向玻璃纤维为增强材料,制备相应的复合材料。研究结果表明:当w(BH-1)=4%时,EP浇铸体的室温(25℃)凝胶时间约为8.5 h和玻璃化转变温度(Tg)为130.9℃,并具有优异的力学性能,其冲击强度为50.0 kJ/m2、拉伸强度和模量分别为0.075 GPa和2.80 GPa、弯曲强度和模量分别为0.136 GPa和3.02 GPa;当m(EP)∶m(BH-1)∶m(活性稀释剂)=100∶4∶10时,复合材料的弯曲强度(0.984 GPa)和层间剪切强度(56.1 MPa)分别提高了26.4%和15.2%。     

一种回转体类构件用中低温固化环氧树脂体系研究

采用等温黏度实验和浇铸体力学性能测试来优选自制改性固化剂CUR–1的配比,通过不同升温速率下的固化过程差示扫描量热并对固化物进行傅立叶变换红外光谱分析,确定了体系的固化制度,研制出一种适用于发动机壳体或结构复杂的回转体类结构件的碳纤维湿法缠绕树脂基复合材料的中低温固化环氧树脂体系,用湿法缠绕工艺制作单向纤维缠绕成型复合材料环(NOL环)并进行了性能测试。结果表明:当CUR–1的含量为15份时,树脂体系具有适于湿法缠绕工艺的黏度和使用期,树脂可在80℃完全固化,同时浇铸体拉伸强度为84 MPa,拉伸弹性模量为3.8 GPa,断裂伸长率为5.4%,热变形温度为131℃。该树脂体系与纤维粘结性好,NOL环力学性能高,NOL环拉伸强度为2 451 MPa,拉伸弹性模量为146 GPa,层剪切强度为55 MPa。     

Influences of processing conditions on mechanical properties of recycled epoxy-anhydride vitrimers

The chemically crosslinked network structures make epoxies, the most common thermosets, unable or hard to be recycled, causing environmental problems and economic losses. Epoxy-based vitrimers, polymer networks deriving from epoxy resins, can be thermally malleable according to bond exchange reactions (BERs), opening the door to recycle epoxy thermosets. Here a series of experiments were carried out to study the effects of processing conditions (such as particle size distributions, temperature, time, and pressure) on recycling of an epoxy-anhydride vitrimer. Polymer powders from the epoxy-anhydride vitrimer with different size distributions were prepared and characterized, and the influence of particle size on the mechanical performance of recycled epoxy-anhydride vitrimers was investigated by dynamic mechanical analysis and uniaxial tensile test. Experimental results demonstrated that finer polymer powders can increase the contacting surfaces of recycled materials and thus result in high quality of recycled materials. In addition, the influences of other treating parameters, such as temperature, time, and pressure, were also discussed in this study. Adjusting these treating parameters can help the design of an optimized reprocessing procedure to meet practical engineering applications.     

Study on the mechanical properties and microstructure of high-performance carbon fiber/epoxy composites

A high-toughness epoxy has been prepared using carboxyl-terminated butadiene acrylonitrile (CTBN) as a toughening agent to modify the AG-80 epoxy resin. High-performance carbon fiber/epoxy (CF/EP) composites are fabricated using the CTBN-toughened epoxy resin as the matrix and two types of CF, namely, T800SC and T800HB, as reinforcement. The mechanical properties of the matrix, surface properties of the CFs, tensile properties, and fracture morphologies of the composites are systematically investigated to elucidate the key factors influencing interfacial bonding in high-performance CF/EP composites. The results reveal that the most significant improvement in toughness is achieved when the CTBN content is 6.90 wt.% in the epoxy resin. Owing to the high content of polar functional groups and excellent surface wettability of T800SC, the T800SC/EP composite exhibits superior mechanical properties compared with the T800HB/EP composite.     

CE/EP/CF复合材料的湿热性能研究

采用溶液预浸渍法分别制备了两种碳纤维(CF)增强环氧树脂(EP)改性氰酸酯树脂(CE)(CE/EP/CF)复合材料,研究了该复合材料的吸湿行为及湿热环境对其力学性能和微观结构的影响。结果表明,CE/EP基体具有比EP更小的吸湿能力;湿热环境对CE/EP/CF复合材料的纵向拉伸强度影响不大,但对其层间剪切强度的影响较为显著。     

碳纤维/单分子环氧树脂基复合材料的研究

以流动性优异的单分子环氧树脂4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯为基体树脂,甲基六氢邻苯二甲酸酐为固化剂,苄基二甲胺为促进剂,初步研究了其固化反应的化学流变特性,获得了基本的固化工艺。然后以T700S碳纤维平纹织物为增强材料,制备了2mm厚度的环氧/碳纤维复合材料层压板材。试验结果表明,通过稀释剂浸渍,复合材料中的CF质量分数可以达到70%以上。在完全无稀释剂时,CF的质量分数可以达到64%。复合材料的最高拉伸强度和弯曲强度分别为916MPa和1031MPa,其玻璃化转变温度为177℃。     

腰果酚接枝黄麻纤维不饱和聚酯复合材料的力学性能及界面调控

用甲苯二异氰酸酯与腰果酚(CNSL)合成大分子偶联剂接枝黄麻纤维。以接枝的黄麻纤维为增强体,通用的不饱和聚酯树脂为基体,采用热压方式制备复合材料。比较了纯饱和聚酯树脂、5 %CNSL增韧的不饱和聚酯树脂、25 %碱处理的黄麻纤维不饱和聚酯树脂复合材料和25 %的CNSL接枝黄麻纤维不饱和聚酯树脂复合材料的拉伸强度和冲击强度。结果表明,CNSL接枝于黄麻纤维上;CNSL的加入能提高材料的韧性,黄麻纤维能提高材料的拉伸强度而不能提高材料韧性;25 %CNSL接枝的黄麻纤维不饱和聚酯树脂能提高材料的拉伸强度和韧性,25 %CNSL接枝的黄麻纤维增强含5 %CNSL的不饱和聚酯复合材料,其冲击强度为12.10 kJ/m^2。     

短纤维层间增强碳纤维复合材料层板的力学研究

以斜纹3k T300碳纤维布、环氧树脂和0.3～0.5 mm短切碳纤维为主要实验原料,使用短切纤维铺放装置将短切碳纤维定量铺放在碳纤维布表面,并铺层得到5块层间短切纤维增强的预制体,每块预制体含8层碳纤维布且每块预制体层间短切碳纤维铺放面密度分别为5,10,20,30,40 g/m²,并增设一块层数为8层、层间不含短切纤维增强的预制体作为对照组。采用真空辅助树脂灌注成型方式浸渍预制体后高温固化,得到层间含不同面密度短切纤维的碳纤维复合材料层合板,研究了不同面密度短切纤维含量对碳纤维复合材料层合板拉伸、弯曲以及层间剪切强度的影响。研究结果表明,当短切碳纤维铺放面密度为5 g/m²时,复合材料层板的拉伸、弯曲强度最好,在5～40 g/m²范围内,复合材料层板的层间剪切强度随短切碳纤维铺放面密度的增大而增大。     

Reprocessable and Recyclable Crosslinked Polyethylene with Triple Shape Memory Effect

Thermosetting polymers, such as epoxy resins, have found widespread applications because of their excellent thermomechanical and solvent resistance properties. However, the recycling of thermosets remains a challenge, due to the irreversible covalent crosslinking bonds in the network. The exchangeable covalent bonds in vitrimers open opportunities in the way that materials can be dynamically repaired. However, in the case of polyolefins, the strategy of exchangeable vitrimers is still underexplored. Herein, a simple way is reported to prepare a high‐density polyethylene (HDPE) vitrimer with a triple shape memory effect, where exchangeable esters are introduced into the network of covalently crosslinked HDPE. With the incorporation of polyethers or polyesters into the crosslinked network, the two obtained vitrimers show outstanding recyclability and a good triple shape memory effect. This new strategy of preparing an HDPE vitrimer might allow the high‐value utilization of crosslinked polyolefins.     

适用于低温固化的低黏度高强度环氧树脂结构胶

以碳酸丙烯酯(PC)为活性稀释剂、自制增韧型421固化剂/快固型DETA(二乙烯三胺)固化剂作为复合固化剂,制备环氧树脂(EP)结构胶。研究结果表明:当m(EP)∶m(PC)∶m(421)∶m(DETA)=100∶20∶24∶6.0时,EP结构胶的初始黏度(60 mPa.s)相对较低,其强度和韧性俱佳(拉伸强度为45 MPa、压缩强度为70 MPa和钢/钢剪切强度为12.0 MPa);该EP结构胶可低温固化(5℃或常温固化7 d后的拉伸强度基本一致),也是一款适用于冬季施工的低黏度高强度EP结构胶。     

Curing and thermal degradation behavior of epoxy-based vitrimers

Epoxy with associative covalent adaptable networks (CANs), called vitrimer, is reported to be promising to realize the recyclable utilization. The typical epoxy vitrimers are synthesized from diglycidyl ether of bisphenol A and dicarboxylic catalyzed by triazabicyclodecene (TBD). The study on the curing and thermal degradation behavior facilitates in-depth understanding of the associative CANs. In this work, the effect of TBD on the curing and thermal degradation behavior is investigated via curing kinetics and thermal degradation performance analysis. The results reveal that the activation energy of curing reaction is increased as the amount of TBD is increased. EST-5 has an average activation energy of 70.1 kJ/mol, while EST-15 reaches as high as 75.1 kJ/mol. Especially, when the conversion is up to 50%, the activation energy shows an obvious increment. In addition, it has been demonstrated that TBD accelerates the thermal degradation of cured networks at lower temperature and increases the amount of volatiles during thermal decomposition.     

High-performance thermosets with tailored properties derived from multi-arm stared vanillin and carbon fiber composites

Vanillin, a rigid compound can be separated from lignin, is a promising sustainable candidate for industrial and high performance polymers, while synthesis of hexa-epoxies is challenging. Meanwhile, carbon fiber reinforced bio-based polymers combining high performance are more difficult to be achieved because of the contradictions of liquidity and high rigidity in the polymer structure and performance. In this paper, a novel hexa-epoxy functionalized bio-based epoxy resin (HPVIGEP) with a multi-arm star structure, which simultaneously reduced the viscosity and improved thermo-mechanical properties. The rheological behavior analysis results of HPVIGEP indicated that the viscosity was 3406.9 mPa·s at 25°C, which dramatically decreased by 75.8% compared to DGEBA (14,096 mPa·s), leading to excellent processability and adaptability. At the same time, the study on mechanical properties revealed that the cured HPVIGEP manifested 30.6%, 33.7% and 49.0% in higher tensile strength, tensile modulus and storage modulus (30°C) than of cured commercial epoxy, respectively. The tensile strength and flexural strength of carbon fiber composites which were applied HPVIGEP were increased by 9.3% and 10.9%, respectively. In a word, this work provides the promise for the application of environmentally friendly bio-based composite materials.