Properties of radiation stable, low viscosity impregnating resin for cryogenic insulation system

Impregnating resins in fusion magnet technology are required to be radiation stable, low viscosity, long usable life and high toughness. To meet these objectives, we developed a new epoxy based composite which consists of triglycidyl-p-aminophenol (TGPAP) epoxy resin and isopropylidenebisphenol bis[(2-glycidyloxy-3-n-butoxy)-1-propylether] (IPBE). The ratio of TGPAP to IPBE can be varied to achieve desired viscosity and working time. The boron-free glass fiber reinforced composites were prepared by vacuum pressure impregnation. The radiation resistance was evaluated by ⁶⁰Co γ-ray irradiation of 1 MGy at ambient temperature. The mechanical properties of the composites have been measured at room temperature and at 77 K.     

用核壳型聚合物粒子增韧改性环氧树脂

介绍了环氧树脂增韧改性的新方法,即用橡胶弹性体、热塑性树脂、刚性粒子和核壳型结构聚合物来增韧环氧树脂。采用种子乳液聚合法制备出了聚丙烯酸丁酯/聚甲基丙烯酸甲酯(PBA/PMMA)核壳型聚合物粒子,并对其表观形貌及结构进行了SEM和FTIR分析。将所制备的核壳型聚合物粒子增韧改性环氧树脂,当用量仅为环氧树脂用量2％时,冲击强度有明显提高。     

A novel method to prepare a microflower-like superhydrophobic epoxy resin surface

A novel microflower-like superhydrophobic epoxy resin surface was obtained using a novel method. The water contact angle and sliding angle of the superhydrophobic epoxy resin surface was 158 ± 1.7° and 3°, respectively. The as-prepared microflower-like superhydrophobic epoxy resin surface also showed superhydrophobic property in the pH range of 3–14. After being stored in ambient environment for one month, no decrease in water contact angle was observed.     

Characterization of carbon nanotube 3D-structures infused with low viscosity epoxy resin system

This work presents the use of carbon nanotube (CNT) skeletons and the resin infusion process as a path towards the production of polymer composites with high and well dispersed nanotube content. A general purpose low viscosity epoxy resin was used as matrix in the reported process assessment. Thin CNT papers, called skeletons, were initially produced to obtain CNT networks. The impregnation was made by infiltrating the non-diluted resin through the carbon nanotube structure. The results show the proposed processing approach as one capable of producing well dispersed nanocomposites with high CNT loading (more than 15 wt% CNT by composite weight), which are important for developing high performance structures based on carbon nanotubes with good thermal and electrical conductivity. The absolute mechanical performance was lower than expected, and discussed in light of manufacturing problems detected by microscopy observations under scanning electron microscopy (SEM).     

等离子体诱导接枝聚合修饰碳纳米管及其环氧树脂复合材料

以马来酸酐(MAH)为有机单体,通过等离子体诱导接枝聚合法修饰碳纳米管(CNTs),借助红外光谱、扫描电镜分析手段,对所得表面为聚合物膜修饰碳纳米管(p-CNTs)进行表征。将上述p-CNTs应用于环氧树脂(EP)固化体系,制备出p-CNT/EP纳米复合材料,研究了其对EP性能的影响。结果表明:等离子体可诱导马来酸酐在CNTs表面接枝聚合成膜。利用包覆于CNTs表面的聚马来酸酐(PMAH)薄膜功能化修饰CNTs。合适含量的p-CNTs可显著提高环氧树脂的强度和韧性,使其高度强韧化。     

环氧改性酚醛树脂的耐腐蚀性能研究

利用环氧树脂(PF)与酚醛树脂(EP)共混,再冷压-烧结成型得到改性酚醛树脂.通过在70%、50%、30%硫酸、50%盐酸、20%氢氧化钠溶液中改性酚醛树脂的腐蚀实验,证明环氧改性酚醛树脂的耐腐蚀性能优于纯酚醛,其中耐腐蚀性能最好配方是PF:EP=100:50.改性酚醛树脂耐酸性能优于耐碱性能,且在非氧化酸性(盐酸)环境中的耐腐蚀性能优于氧化性酸性(硫酸)环境下的耐腐蚀性能.热重分析(TGA)表明,环氧改性酚醛树脂的耐热性能较纯酚醛有所提高.     

一种新结构超支化环氧树脂的合成及其性能研究

以双酚A(BPA)作为A2单体,异氰尿酸三缩水甘油酯(TGIC)作为B3单体,采用质子转移法合成了一种结构新颖的超支化环氧树脂.采用FTIR、NMR、GPC对该环氧树脂的结构和分子量进行了表征.固化产物的极限氧指数达到26,热分解(5%)温度为266℃,具有较好的阻燃性与热稳定性.     

超低温介质对碳纤维增强树脂基复合材料力学性能的影响

针对超低温介质液氮和液氧对碳纤维增强树脂基复合材料(CFs/EP)力学性能的影响进行研究,将T700碳纤维和CFs/EP在液氮和液氧中处理120h,采用X射线光电子能谱(XPS)和SEM分析碳纤维表面元素和表面形貌的变化;并研究液氧和液氮处理后碳纤维和复合材料试样的力学性能。结果表明,在经液氮处理后的碳纤维表面,上浆剂有明显损伤产生,而经液氧处理后的碳纤维表面则没有损伤出现;两种超低温介质处理对碳纤维单丝拉伸强度、表面元素及其含量的影响几乎没有区别;经液氮和液氧超低温介质处理后,CFs/EP拉伸强度均有所下降,且两者下降率接近,分别约为15.26%和14.38%;弯曲强度均有大幅提高,且提高率接近,分别约为56.18%和57.81%。因此,液氧和液氮处理对CFs/EP力学性能的影响基本没有区别。     

环氧树脂与氰酸酯共固化物的结构与性能

研究了用乙酰丙酮过渡金属络合物等促进剂催化促进环氧树脂与氰酸酯(在氰酸酯欠量,适量和过量条件下)的共固化反应行为、固化反应的机理、固化物的结构特征以及结构与性能关系.结果表明,促进剂能明显地降低体系的固化反应温度,缩短固化反应时间,其促进效果与促进剂种类有关.在固化反应过程中,先是氰酸酯发生自聚反应形成二聚体或三聚体(三嗪环),然后二聚体进一步形成三嗪环,此过程伴随着环氧树脂的聚醚反应,最后是三嗪环与剩余的环氧基反应形成噁唑烷酮.在氰酸酯欠量的条件下,固化物的交联结构主要是聚醚网络结构和噁唑烷酮结构,三嗪结构很少.在氰酸酯适量和过量条件下,固化物交联结构主要是三嗪环和噁唑烷酮结构,聚醚结构很少.随着氰酸酯含量的增加,三嗪结构随之增加,聚醚结构减少,固化物的耐热性能和介电性能随之提高.     

Photoluminescence of epoxy resin modified by carbazole and its halogen derivative at 82 K

The spectra and relative quantum yield of fluorescence and phosphorescence were measured for 9-(2,3-epoxypropyl)carbazole (EPK) added to epoxy resin (R) (R₅EPK – 5% weight content of the carbazole group in a polymer) and its mono and dihalogen derivative (Cl and Br). The materials under study have excellent mechanical properties. At 82 K photoluminescence (PL) spectra of these materials are composed of fluorescence (FL) and phosphorescence (PH) components while at 280 K, PH component is not observed. The vibrational frequencies of fluorescence and phosphorescence for R₅EPK were determined using Gaussian deconvolution. A decrease in the fluorescence and an increase in the phosphorescence quantum efficiency were observed after chemical bonding of heavy atoms Cl and Br.     

Mean stress/strain effect on fatigue behavior of an epoxy resin

Mean stress/strain effect on the fatigue life of an Epon 826/Epi-Cure Curing Agent 9551 epoxy system has been investigated by carrying out series uniaxial fatigue tests with four different mean strain ratios under strain-range-controlled mode. Quantitative analysis of the mechanical properties, such as mean stress relaxation, evolution of stress range and strain energy density, have been performed based on the stress–strain data recorded by a non-contact real-time strain measurement and control system. Mean stress/strain functions have been introduced into the equivalent damage parameters to include the mean stress/strain effect on the fatigue life of the epoxy polymer material. The procedure to characterize the mean stress/strain functions has been demonstrated and material constants were calibrated in the case of either stress, strain or energy approach, respectively. Good agreement can be seen between the predictions and the test data.     

多壁碳纳米管的辐照处理及其对多壁碳纳米管/环氧树脂复合材料热性能的影响

在空气中用高频高压电子加速器辐照多壁碳纳米管(MWCNTs),采用红外光谱、能谱分析、拉曼光谱和透射电镜表征分析辐照处理对碳纳米管结构的影响;通过原位复合法制备MWCNT/环氧树脂(EP)复合材料.采用场发射扫描电镜、热失重分析和动态力学分析研究辐照处理MWCNTs对环氧树脂热稳定性的影响.结果表明:电子束辐照处理使MWCNTs表面接入了少量的含氧基团,同时破坏了MWCNTs的完整结构,当辐照剂量为170 kGy时,接枝含氧基团的量最多(约为4％),且结构破坏程度较小.与原始MWCNT/EP体系相比,经电子束辐照处理后的MWCNTs在EP中分散得更均匀,并能使材料的最大热分解温度和玻璃化转变温度较纯EP有所提高,在EP中加入质量分数0.5％的经170kGy辐照处理后的MWCNTs,能够使材料的最大热分解温度和玻璃化转变温度分别提高约14℃和8℃.     

固化阶段环氧树脂表面能及其极性变化的表征

采用座滴、吊片等间接表面能测试方法,表征分析了固化阶段2种典型环氧树脂体系的表面能变化规律,并对座滴法测得的总表面能极性、色散分量进行了深入研究。结果表明：2种方法测得的环氧618-咪唑体系和环氧5224体系的总表面能随固化时间延长均呈下降趋势,座滴法测得的树脂表面能高于吊片法;座滴法结果表明2种环氧树脂体系表面能极性分量均随时间延长而降低;红外分析表明,环氧618-咪唑体系表面能的极性分量的降低是由于羟基及环氧官能团的减少。     

接枝和非接枝聚氨酯/环氧树脂互穿网络聚合物的制备及其性能

采用分步法分别制备了接枝和非接枝聚氨酯(PU)/环氧树脂(EP)互穿网络聚合物(IPNs),研究了不同配比对材料力学性能和热性能的影响。红外结果显示接枝聚氨酯/环氧树脂互穿网络聚合物分子间形成了氨基甲酸酯的接枝结构;力学性能测试结果表明,聚氨酯的引入显著地提高了材料的力学性能,当m(PU)∶m(EP)=15∶85时,接枝聚氨酯/环氧树脂互穿网络聚合物的拉伸和冲击强度达到最大值(分别为36.7MPa和22.39kJ/m2),当m(PU)∶m(EP)=10∶90时,非接枝互穿网络聚合物拉伸和冲击强度达到最大值(分别为27.8MPa和19.34kJ/m2);TGA结果证实接枝互穿网络聚合物的热稳定性明显优于非接枝互穿网络聚合物。     

Investigation of the microwave curing of the PR500 epoxy resin system

Microwave heating has been used to cure a resin system, PR500 (3M). The same resin has been cured using a conventional oven. The cured resins have been compared using a number of techniques including modulated differential scanning calorimetry (MDSC), dynamic thermal analysis, infrared spectroscopy (IR) and solid-state NMR spectroscopy. The reaction path appears to be slightly different depending upon the nature of the heating. The epoxy-amine reaction occurs to a greater extent than the epoxy-hydroxyl reaction in the microwave cured resin compared to the thermally cured resin. The dielectric properties for the thermally and microwave cured materials were measured for degrees of cure greater than 75% and over this range are similar for materials cured by the two techniques and thus not sensitive to this change. Broadening of the glass transition for microwave-cured epoxy resins was observed. Since the IR and solid-state NMR results show small differences as does the DMA behaviour of materials cured using the two routes the broadening is attributed to a difference in network structure.     

氰酸酯／双马来酰亚胺／环氧树脂三元共聚物及性能研究

采用双马来酰亚胺和环氧树脂与氰酸酯共聚对氰酸酯树脂进行改性，用FTIR跟踪了其固化过程。性能测试表明，当BCE：BMI：EP为5：2：3时，其固化物的冲击强度达到了12．2kJ·cm^-2，韧性有较大的提高；改性树脂的耐热性随着EP含量的增加而下降，当EP含量为30％时，Tg为233．7℃；改性后的氰酸酯树脂在1MHz频率下的介电常数和介电损耗角正切都比纯CE的有所增加，但上涨的幅度较小，仍具有优异的介电性能；DMA分析表明，在瓦温度时，损耗因子和损耗模量达到最大值，其中，tanδmax为0．359。     

硫醇@三聚氰胺甲醛树脂/环氧树脂固化剂的制备及性能表征

采用三聚氰胺-甲醛树脂(PMF)为壁材,三羟甲基丙烷三(3-巯基丙酸酯)(TMPMP)作为芯材,原位乳液聚合法制备了硫醇@三聚氰胺甲醛树脂(TMPMP@PMF)微胶囊固化剂。研究了乳化剂种类及用量,囊壁质量比,反应温度,反应时间,pH值对合成TMPMP@PMF微胶囊粒径及稳定性等影响。结果表明:当反应乳液中芯材的质量分数达到2wt%,同时芯材与壁材的单体质量比达到2∶1时,能制备出粒径在大约100μm,粒径均匀的TMPMP@PMF微胶囊。TMPMP@PMF微胶囊的结构稳定,耐热性好,并且呈闭孔结构。采用TMPMP@PMF微胶囊为固化剂,与环氧树脂(EP)基体混合配制成压敏型TMPMP@PMF/EP固化剂,发现微胶囊结构在受到外力作用时能及时破裂,室温甚至低温下都能短时间使环氧树脂固化,并且能够很好地改善固化剂的抗冲击性能。     

聚氨酯和蒙脱土协同增韧增强环氧树脂

采用聚合物互穿技术与原位插层聚合相结合的方法制备了有机蒙脱土修饰的环氧树脂/聚氨酯互穿网络纳米复合材料.傅立叶红外光谱,X射线衍射及透射电镜分析表明剥离或插层的蒙脱土片层表面羟基能与环氧树脂/聚氨酯基体发生交联反应,并且均匀分散在环氧树脂/聚氨酯基体中.力学性能测试结果表明聚氨酯,蒙脱土的加入同时增加了环氧树脂的拉伸强度和断裂韧性.扫描电镜分析表明聚氨酯和蒙脱土协同增韧增强环氧树脂的主要原因为剪切屈服和微裂纹增韧.     

橡胶/环氧树脂复合补强胶片的制备及性能研究

以丁腈橡胶、天然橡胶及环氧树脂共混制备高分子合金,采用压延法与玻璃纤维布复合成汽车用补强胶片。通过扫描电镜、热分析对高分子合金进行表征,用弯曲强度表征补强胶片对钢板的增强作用,用剪切强度表征丁腈橡胶/天然橡胶/环氧树脂复合材料与钢板的粘接性能。     

Monitoring the curing process of epoxy resin nanocomposites based on organo-montmorillonite – a new application of resin curemeter

Curing of a resin system is the critical and productivity controlling step in the fabrication of thermosetting matrix composites including nanocomposites. In the past few years, in the case of polymer-layered silicate nanocomposites, too many interests were taken in the material structure and properties, while only a few researches were carried on the cure behavior of this type of nanocomposite. The goal of the present work pays mainly attention to the cure kinetics for epoxy resin/organo-montmorillonite (Org-MMT)/2-ethyl-4-methyl-imidazole (2,4-EMI) nanocomposites. The experiments of monitoring curing process of nanocomposite materials are successively made via the HLX-II Resin Curemeter. The results derived from the non-equilibrium thermodynamic fluctuation theory indicated that the theoretical prediction is in good agreement with the experimental cure curve. The apparent activation energies were evaluated based on the gel time, t_g and relaxation time, τ, respectively. The increasing of cure temperature accelerated the cross-linking reactions for either nanocomposites or pure epoxy system. The addition of Org-MMT reduces the gel time, t_g as well as the completed cure time, t_c, and increases the rate of cure.