四脚氧化锌晶须/氢化环氧树脂形状记忆复合材料的制备与性能EI北大核心CSCD

采用不同比例的四脚氧化锌晶须(T-ZnOw)与氢化环氧树脂(H-EP)共混,在聚丙二醇二缩水甘油醚(PPGDGE)和异佛尔酮二胺用量不变的前提下,经完全固化制备出一种新型的复合材料。通过动态力学性能测试、力学测试、红外光谱、扫描电子显微镜和U型形状记忆测试系统地研究了该体系的力学性能和形状记忆性能。实验结果表明,该体系复合材料的玻璃化转变温度最高可达到61.5℃,其力学性能比纯环氧树脂提高了15.87%。该试样具有良好的形状记忆性能,变形的试样几乎可以完全回复。     

环氧树脂的增韧与形状记忆性能研究

以聚丙二醇二缩水甘油醚(PPGDGE)为增韧剂改性环氧树脂E-51/甲基四氢邻苯二甲酸酐固化体系,研究了PPGDGE用量对环氧树脂的力学性能和形状记忆性能的影响。结果表明:PPGDGE的加入提高了环氧树脂体系的力学性能,当含量为15%时,韧性提高了65%;同时较大幅度提高环氧树脂的形状记忆性能,当PPGDGE含量为10%时,最大形变量增加了约43%,形状回复速率提升了75%;当PPGDGE含量为15%时,固定率提高了2.2%,回复率提高了4.5%,且形状重复性也有较大提高。     

聚丁二烯环氧改性氰酸酯的形状记忆效应

选择环氧化烯烃类树脂聚丁二烯环氧树脂,以不同质量配比与双酚A型氰酸酯进行混合共聚,经适度交联固化后制备出嵌段聚合物,并对该聚合物的结构与交联程度、力学性能、动态力学性能和形状记忆性能进行了研究。结果表明,经适度交联固化的聚合物体系具有良好的形状记忆特性,随着聚丁二烯环氧树脂用量的增加,弯曲强度和储存模量降低,玻璃化温度(Tg)降低;形变恢复率均为100%,形变恢复速率随聚丁二烯环氧树脂用量的增加而增大,最大形变恢复速率为0.013 s-1。     

聚醚/双酚A环氧甲基丙烯酸酯复合光固化膜的性能

由聚醚型聚丙二醇二缩水甘油醚和甲基丙烯酸合成了可光固化的聚丙二醇二缩水甘油醚二甲基丙烯酸酯(DMA),再按不同质量配比将此合成物与双酚A型环氧甲基丙烯酸酯(BEMA)混合,经紫外光照射得到复合光固化膜,然后对所得固化膜的耐热性、柔韧性、硬度、光泽度、可见光透过率和微观形貌进行表征.研究结果表明,复合膜兼具DMA和BEM...     

环氧化合物上浆处理的MWCNTs对MWCNTs/环氧树脂复合材料性能的影响

利用氨基化多壁碳纳米管(MWCNTs-NH2)与环氧化合物苄基缩水甘油醚(EP 692)和十二-十四烷基缩水甘油醚(EP AGE)反应,通过球磨工艺制备了两种不同分子结构环氧化合物上浆处理的多壁碳纳米管(MWCNTs)MWCNTs-692和MWCNTs-AGE。将均为1wt%的MWCNTs-NH2,MWCNTs-692和MWCNTs-AGE分别添加到二氨基二苯甲烷(DDM)固化双酚A二缩水甘油醚(DGEBA)环氧树脂体系中,分析了三种MWCNTs对树脂体系黏温关系、固化动力学、热力学性能和弯曲性能的影响。FT-IR,TGA和XPS测试表明,EP 692和EP AGE通过共价键接枝到碳纳米管的表面。与MWCNTs-NH2相比,MWCNTs-692和MWCNTs-AGE可以有效提高碳纳米管在环氧树脂基体中的分散性和相容性,减少纳米粒子对树脂体系黏度和固化动力学的影响。此外,添加上述三种碳纳米管都可以改善纯环氧树脂体系的储能模量和弯曲性能,其中经过含有刚性分子结构上浆剂处理的MWCNTs-692增强效果最为显著。添加1wt%MWCNTs-692后,MWCNTs-692/环氧树脂复合材料的常温储能模量提高了30.6%,弯曲强度和模量分别提高了18.8%和22.5%。     

环氧树脂部分

一种水性环氧树脂涂料及其制备方法；吸油性快固化胶黏剂；防辐射型环氧树脂地坪涂料；环氧树脂、其制造方法、使用该环氧树脂的环氧树脂组合物以及固化物；耐高温双酚A二缩水甘油醚环氧树脂体系及其制备方法。     

环氧/酸酐体系网络结构对形状记忆性能的影响

以环氧/酸酐(双酚A型缩水甘油醚/甲基纳迪克酸酐,DGEBA/MNA)类形状记忆复合材料基体为研究对象,探讨了无定形树脂基体的网络结构与其形状记忆性能之间的关系.以2,4,6-三(二甲胺基甲基)苯酚(DMP-30)和异辛酸锌作为DGEBA/MNA体系的促进剂,调节基体配方获得具有不同网络结构的环氧体系.通过对固化物皂化前后的胶化量测定确定了三种网络结构,即酯网络、醚网络和酯-醚混合网络,并采用动态热机械分析(DMA)测量各体系的动态热力学性能.以形状回复率、形状回复时间和形状回复力为指标,对三种不同网络结构树脂基碳纤维复合材料进行形状记忆折叠-展开测试.结果表明,三种网络结构均具有较高的形状回复率,且反复的热力学循环对三种网络结构形状回复率的影响均很小;酯网络结构、醚网络结构和酯-醚混合网络结构的形状回复时间依次延长,而形状回复力逐渐降低.同时,在较低的回复程度下,三种网络结构的形状回复力均随折叠-展开次数的增加而下降,而随回复程度的增加,回复力的下降幅度逐渐降低.     

氰酸酯/环氧树脂共混物热分解动力学

利用动态TGA方法研究了双酚A二缩水甘油醚环氧树脂和酚醛环氧树脂与双酚A二氰酸酯的两类共混物的热稳定性。用Coats-Redfern研究了不同配比共混物的热分解动力学。结果表明,氰酸酯含量大的双酚A二缩水甘油醚环氧树脂/双酚A二氰酸酯共混物具有两阶段分解机理,而环氧含量大的双酚A二缩水甘油醚环氧树脂/双酚A二氰酸酯共混物具有均一的热分解活化能;相比较而言,酚醛环氧树脂/双酚A二氰酸酯共混物的分解活化能基本上不随温度和组成变化。从后期失重温度和活化能看,酚醛环氧树脂/双酚A二氰酸酯共混物具有比双酚A二缩水甘油醚环氧树脂/双酚A二氰酸酯共混物更高的热稳定性。     

环氧树脂新型有机硅改性剂

研究了含酚羟基有机烷氧基硅烷及3,3',3"-三羟基苯氧基硅烷三缩水甘油醚两种新型有机硅改性剂对双酚F环氧树脂力学性能及热性能的影响.研究结果表明,两种改性剂均可有效提高环氧树脂浇铸体的韧性,提高其抗开裂指数,降低线胀系数.3,3',3"-三羟基苯氧基硅烷三缩水甘油醚改性剂在提高环氧树脂的力学性能的同时,保持固化物较高的玻璃化温度, 并可降低双酚系环氧树脂基体的粘度.     

有机金属铬催化剂制备噁唑烷酮改性环氧树脂及其固化材料的性能

用有机金属铬催化剂催化4,4’-二苯甲烷二异氰酸酯(MDI)与双酚A二缩水甘油醚(DGEBA)的反应,合成了噁唑烷酮改性环氧树脂(OXEP),研究了投料比和反应时间等对合成OXEP的影响。利用OXEP、DGEBA与甲基四氢苯酐进行固化反应,制备了不同OXEP含量的固化材料。研究结果表明,随着OXEP含量即噁唑烷酮杂环含量的增加,固化材料的玻璃化转变温度、耐热性、拉伸强度、弯曲强度和冲击性能均得到大幅提高。     

Development and characterization of active nanocomposites with embedded shape memory alloy wires

Active nanocomposites of epoxy resin containing bentonite clay and shape memory alloy (SMA) were made to evaluate the thermomechanical behavior in the range of phase transformation of shape memory alloy during heating. The epoxy resin system studied was prepared using bifunctional diglycidyl ether of bisphenol A (DGEBA), crosslinking agent diaminodiphenylsulfone (DDS), purified bentonite organoclay (APOC) and thin Ni‐Ti shape memory alloy wires. The evaluated ratio DGEBA/DDS was 100:40, for the epoxy resin/clay system was 100:1 and the shape memory alloy volumetric fraction of Ni‐Ti wires were 1.55%; 2.56%; 3.57% and 4.54%. The formation of nanocomposite was confirmed by X‐ray diffraction analysis. Phase transformation of the shape memory alloy wires were determined by differential scanning calorimetry (DSC). Specimens of the active nanocomposites were characterized mainly by dynamic mechanical analysis (DMA). According to the DMA results was evidenced a significant increase in glass transition temperature and storage modulus when 1 parts per hundred resin of clay is added to epoxy resin. A recover of storage modulus was observed in the active nanocomposite during heating in the range of the phase transformation of Ni‐Ti shape memory alloy wires when the volumetric fraction is above 3.5%.     

Improvement of tensile properties and toughness of an epoxy resin by nanozirconium-dioxide reinforcement

Zirconium dioxide (ZrO₂) nanoparticles were systematically added as reinforcement to a diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin. A series of composites with varying amounts of nanoparticles was prepared and their morphology and mechanical properties were studied. The obtained nanocomposites were characterized by tensile tests, dynamic mechanical thermal analysis, and fracture toughness (K_IC) investigations; by standardized methods, to define the influence of the nanoparticle content on their mechanical and thermal properties. The morphological analysis of the composites shows that nanoparticles form small clusters, which are uniformly distributed into the matrix bulk. The tensile modulus (E) and the K_IC of the epoxy matrix increase at rising zirconia content. Improvements of more than 37% on modulus and 100% on K_IC were reached by the nanocomposite containing 10 vol.-% ZrO₂ with respect to the neat epoxy (E_o = 3.1 GPa, K_ICo = 0.74 MPam^0.5). The presence of nanoparticles produces also an increment on glass transition temperature (T _g). The epoxy resin added with 8 vol.-% ZrO₂ records a T _g approximately 8% higher than the unmodified matrix (T _go = 100.3 °C).     

Poly(ether ether ketone) with pendent methyl groups as a toughening agent for amine cured DGEBA epoxy resin

A diglycidyl ether of bisphenol-A (DGEBA) epoxy resin was modified with poly(ether ether ketone) with pendent methyl groups (PEEKM). PEEKM was synthesised from methyl hydroquinone and 4,4′-difluorobenzophenone and characterised. Blends of epoxy resin and PEEKM were prepared by melt blending. The blends were transparent in the uncured state and gave single composition dependent T _g. The T _g-composition behaviour of the uncured blends has been studied using Gordon–Taylor, Kelley–Bueche and Fox equations. The scanning electron micrographs of extracted fracture surfaces revealed that reaction induced phase separation occurred in the blends. Cocontinuous morphology was obtained in blends containing 15 phr PEEKM. Two glass transition peaks corresponding to epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum of the blends. The crosslink density of the blends calculated from dynamic mechanical analysis was less than that of unmodified epoxy resin. The tensile strength, flexural strength and modulus were comparable to that of the unmodified epoxy resin. It was found from fracture toughness measurements that PEEKM is an effective toughener for DDS cured epoxy resin. Fifteen phr PEEKM having cocontinuous morphology exhibited maximum increase in fracture toughness. The increase in fracture toughness was due to crack path deflection, crack pinning, crack bridging by dispersed PEEKM and local plastic deformation of the matrix. The exceptional increase in fracture toughness of 15 phr blend was attributed to the cocontinuous morphology of the blend. Finally it was observed that the thermal stability of epoxy resin was not affected by the addition of PEEKM.     

Morphology and thermal properties of organic–inorganic hybrid material involving monofunctional-anhydride POSS and epoxy resin

Monofunctional-anhydride polyhedral oligomeric silsesquioxane (i-C₄H₉)₇Si₈O₁₂OSi(CH₃)₂(C₈H₉O₃) (AH-POSS) was synthesized and characterized by FTIR, NMR, element analysis. Then AH-POSS was incorporated into epoxy system either pre-reacted or non-reacted using hexahydrophthalic anhydride (HHPA) as curing agent. Pre-reacted system hybrid materials were obtained by two-step preparation. First, AH-POSS reacted with part of diglycidyl ether of bisphenol A (DGEBA) to form AH-POSS-epoxy precursor in DGEBA, then cured with HHPA. Non-reacted POSS/epoxy hybrid materials were prepared by directly mixing AH-POSS, HHPA and DGEBA together and cured afterwards. The GPC and FTIR spectra suggested successful bonding of AH-POSS and epoxy resin. Morphologies of hybrid materials were characterized by SEM and TEM. Non-reacted system led to a dispersion of spherical particles with sizes in the range of micrometers. For pre-reacted system, polymerization-induced phase separation took place with POSS content lower than 30 wt% and also some “vesicle” structure was formed after curing. A typical macro-phase separation happened with POSS content up to 40 wt% before and after curing. The glass transition temperatures (T_g's) and the storage modulus were measured by dynamic mechanical analysis (DMA). T_g's and modulus displayed irregularly decrease. The initial thermal decomposition temperatures (T_d's) characterized by TGA were also irregularly decreasing for both systems. However, they were higher than those of epoxy composites when using amine as the curing agent.     

海因环氧树脂/DDS体系的制备与性能

合成了海因环氧树脂,采用红外光谱和核磁共振进行了表征,制备了海因环氧树脂/二氨基二苯砜(DDS)体系,研究了海因环氧树脂/DDS体系的固化反应特性及固化物的性能。结果表明,树脂体系在100℃~296℃有一放热峰,峰值温度为197℃,140℃的凝胶时间长于42 min,在180℃下仅8 min;树脂浇铸体的氧指数为26.6,弯曲强度为111MPa,弯曲模量为4.14 GPa,冲击强度为14.8 kJ/m2。     

海因环氧树脂/HHPA体系的制备与性能

合成了海因环氧树脂,采用红外光谱和核磁共振进行了表征,以六氢苯酐(HHPA)为固化剂,制备了海因环氧树脂/HHPA体系,研究了海因环氧树脂/HHPA体系的固化反应性及其固化物的性能。结果表明:树脂体系在升温速率为10℃/min的条件下,在90～210℃有一放热峰,峰值温度为152.5℃;100℃下的凝胶时间大于42min,在140℃下为8min;树脂浇铸体的氧指数为23,抗弯强度为122MPa,弯曲模量为2.7GPa,冲击强度为14.9kJ/m2。     

Ambient cure POSS–epoxy matrices for marine composites

A room-temperature cure epoxy consisting of diglycidyl ether of bisphenol-F (DGEBF) and diethylene triamine (DETA) was modified with 26.5 wt.% and 63.5 wt.% octaglycidyl polyhedral oligomeric silsesquioxane (POSS) to investigate elevated temperature thermomechanical performance. Composites fabricated using vacuum assist resin transfer molding (VARTM) were compared to vinylester and epoxy standards. POSS modified matrices were low viscosity of 0.25–0.40 Pa s. Although T_g was 20% lower than vinylester, we observed an increase of >300% in 150 °C storage modulus, >50% in tensile modulus, >35% in flexural modulus, and the complete elimination of a heat distortion temperature (HDT) up to 200 °C. The matrices demonstrated an excellent balance of flow, wetting, and pot-life behaviors making them attractive alternatives for ambient cure marine applications.     

Toughening mechanism for a rubber-toughened epoxy resin with rubber/matrix interfacial modification

For a rubber-toughened piperidine-DGEBA epoxy resin, the interface between the rubber particle and the epoxy resin matrix was modified by an epoxide end-capped carboxyl terminated butadiene and acrylonitrile random copolymer (CTBN). The end-capping epoxides used were a rigid diglycidyl ether of bisphenol-A (Epon 828), a short-chain flexible diglycidyl ether of propylene glycol (DER 736), and a long-chain flexible diglycidyl ether of propylene glycol (DER 732). The microstructures and the fracture behaviour of these rubber-modified epoxy resins were studied by transmission electron microscopy and scanning electron microscopy. Their thermal and mechanical properties were also investigated. In the rubber-modified epoxy resins, if the added CTBNs were end-capped by a flexible diglycidyl ether of propylene glycol (DER 732 or DER 736) before curing, the interfacial zone of the undeformed rubber particle, the degree of cavitation of the cavitated rubber particle on the fracture surface and the fracture energy of the toughened epoxy resin were all significantly increased. The toughening mechanism based on cavitation and localized shear yielding was considered and a mechanism for the interaction between cavitation and localized shear yielding that accounts for all the observed characteristics is proposed.