环氧树脂改性双环戊二烯型氰酸酯树脂固化反应性

采用凝胶试验、 FTIR和DSC等手段研究了环氧E-51与双环戊二烯型氰酸酯(DCPDCE)共聚体系的固化反应性以及阶梯固化过程中—OCN基、 三嗪环、 唑啉、 噁唑啉酮的变化情况。结果表明, 环氧树脂既能够催化氰酸酯本身三聚成环反应, 又对氰酸酯三聚成环反应有稀释作用。当环氧树脂含量(环氧占混合物总量的质量百分比)大于5wt％时, 催化效果增加不明显, 稀释作用加强; 当环氧树脂含量约为25wt%时, 以上两种作用效果基本平衡, 改性体系的固化反应活性和纯DCPDCE相当。阶梯固化时, 低温阶段(160~180℃)主要发生生成三嗪环和唑啉的反应, 高温阶段(200~220℃)主要发生三嗪环和唑啉向噁唑啉酮的转化反应。另外, —OCN基的低温转化率随着环氧树脂含量的增大而提高, 固化树脂的最终结构组成和环氧树脂的含量有关。      

Moisture absorption by cyanate ester modified epoxy resin matrices. Part V: effect of resin structure

A series of epoxy resins of varying functionality (in terms of the number of epoxide groups) were used to cure the cyanate ester resin, AroCy L10 (1,1-bis(4-cyanatophenyl) ethane). The effect of thermal spiking on moisture absorption and changes in glass transition temperature (T_g) were studied.With the tetra functional (MY720) epoxy a more polar crosslinked density matrix forms. However, after thermal spiking to 140 °C a second peak appeared in the DMTA spectrum which was attributed to partial hydrolysis. The other two systems were much more stable.All systems exhibited the enhancement of moisture absorption as a result of thermal spiking.The mechanism of this phenomenon has been discussed in detail and related to the distribution of unoccupied volume in the dry resin and the location of water molecules at hydrogen bonding sites. The redistribution of the water molecules throughout the sites during thermal cycling is considered responsible for the enhancement and the reduction in moisture contents at high thermal spike temperatures.     

氰酸酯/环氧树脂的固化反应历程

采用傅里叶红外光谱仪研究了4种不同比例的氰酸酯(CE)/环氧树脂(EP)混合体系在一系列固化温度下固化后的产物组成,结果证实了6步反应的存在。当EP含量高时,体系生成物主要是口恶唑烷酮和部分异氰酸脲,而三嗪环很不显著;EP含量低时,首先形成三嗪环,然后三嗪环与环氧生成口恶唑烷酮或异氰酸脲。反应温度较低时(≤160℃),CE首先生成三聚体,再同环氧反应生成口恶唑啉、口恶唑烷酮以及异氰酸脲;在较高温度下固化时(160℃～180℃),主要进行的是三聚氰酸酯重排生成异氰酸脲的反应以及异氰酸脲同环氧官能团生成口恶唑烷酮的反应。生成物组成的差异是影响固化物宏观性能,如耐热性的根本原因。     

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.     

Thermal,mechanical, and conductivity properties of cyanate ester composites

Cyanate ester resins have been widely proposed as replacements for epoxy resins in high temperature applications. One such application, semiconductor encapsulation, uses a large amount of inorganic filler, typically 65 wt%. The effect of filler incorporation, on the properties of cyanate ester composites, was assessed incrementally in this work.It was found that, as is the case with epoxy based encapsulants, silica filler increased cyanate ester composite thermal conductivity, Young's modulus, and dielectric constant (slightly), and decreased encapsulant thermal expansion. It was also found that silica addition resulted in a marginal decrease in strength. This indicated a high degree of interfacial adhesion between the untreated silica filler and the cyanate ester matrix, a conclusion supported by work by Possart et al. [1].     

Effect of clay and PEO-PPO-PEO block copolymer on the microstructure and properties of cyanate ester/epoxy composite

In this study, processing, morphology and properties of poly (ethylene oxide)-block-poly (propylene oxide)-block-poly (ethylene oxide) (PEO-PPO-PEO) triblock copolymer and clay modified cyanate ester/epoxy hybrid nanocomposites were investigated. The PEO-PPO-PEO triblock copolymer preferentially reaction-induced microphase separate into spherical micelles in the cyanate ester/epoxy matrix. PEO-PPO-PEO was used as both nanostructuring agent for cyanate ester/epoxy blended resin and thus the predominantly intercalated and few exfoliated platelets of were also observed with clay, which successfully reduced the brittleness of the cyanate ester/epoxy blended resin increasing the toughness of designed materials. The stiffness and heat resistance of the neat BCE/EP resin could be retained in the BCE/EP/F68/clay hybrid nanocomposites. The optimum property enhancement was observed in the hybrid nanocomposites containing 5 wt% PEO-PPO-PEO and 3 wt% clay. The thermo/mechanical properties of the hybrid nanocomposites depend on microstructure, dispersion state and the ratio between organic and inorganic modifiers content.     

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。     

国产T800碳纤维用氰酸酯树脂开发及其复合材料性能

基于飞行器减重对耐高温结构复合材料的应用背景,为了拓展国产T800碳纤维增强氰酸酯复合材料体系的应用,通过对国产T800碳纤维表面上浆剂的分析,开展适于国产T800碳纤维的氰酸酯树脂基体配方设计,研究国产T800碳纤维/氰酸酯复合材料的力学性能和耐热性能,分析树脂基体对复合材料界面性能的影响。结果表明:国产T800碳纤维表面上浆剂中含有环氧基团。配方优化后的氰酸酯树脂与国产T800碳纤维复合后,复合材料的室温-湿态力学性能保持率大于74.8%,200℃力学性能保持率大于57%,玻璃化转变温度为226℃,具有优异的热机械性能和界面性能。     

Adhesive repair of bismaleimide/carbon fiber composites with bisphenol E cyanate ester

The adhesive strength and repair efficiency of bisphenol E cyanate ester (BECy) is investigated for the injection repair of high temperature polymer-matrix composites (PMCs) by lap shear (LS), short beam shear bending (SBSB), and double-cantilever beam (DCB) tests. Bismaleimide/carbon fiber (BMI-cf) composites were chosen as a model substrate. The BECy resin showed similar strength at room temperature to a benchmark epoxy adhesive and outperformed the epoxy at high temperature (200 °C) in all mechanical tests performed. The influence of moisture content of the PMC substrate on the adhesive strength of BECy was systematically investigated. Drying of PMC before repair was necessary for excellent repair performance. Both the flexural strength of repaired SBSB specimens and the inter-laminar fracture toughness of repaired DCB specimens were significantly higher than that of the control composites and stable over a broad temperature range.     

石墨烯/氰酸酯-环氧树脂复合材料的制备和性能

为优化石墨烯/氰酸酯(CE)复合材料的制备工艺并提高其韧性,制备了对苯二胺(PPD)功能化的氧化石墨烯(GO-PPD),分别以GO和GO-PPD为添加物,以CE和环氧树脂(质量比为7:3)共混物为基体树脂制备了GO/CE-环氧树脂和GO-PPD/CE-环氧树脂复合材料。采用红外和拉曼光谱表征GO和GO-PPD的结构,并研究了二者在溶剂中的溶解性。GO-PPD在乙醇等低沸点和低毒性的有机溶剂中表现出稳定的溶解性,与GO相比,GO-PPD明显改善了复合材料制备的工艺性。性能研究表明,GO和GO-PPD的加入均会降低基体树脂的固化温度,明显提高其力学性能和热性能,使基体树脂的介电常数和介电损耗显著增大,但仍然基本保持良好的耐湿热性和耐腐蚀性。石墨烯表面的化学性质影响石墨烯/CE-环氧树脂复合材料的综合性能,与GO相比,GO-PPD的加入能更明显提高复合材料的力学性能和耐热性。     

环氧树脂与氰酸酯共固化产物性能的研究

用DSC,介电和动态力学等分析方法研究了组成对乙酰丙酮过渡金属络合物催化促进的环氧树脂与氰酸酯共固化反应体系反应动力学参数,固化产物力学、电气和耐热性能以及玻璃化转变温度的影响。结果表明,随着共固化反应体系中氰酸酯含量的增加,其表观反应活化能和频率熵因子均随之升高;在相同的固化条件下,共固化产物中三嗪环结构含量增加,聚醚结构减少,玻璃化转变温度升高,耐热性能、介电性能提高。      

用于RTM工艺的改性氰酸酯树脂的研究

用环氧树脂改性氰酸酯树脂得到了可用于RTM工艺的树脂体系,借助于红外光谱（IR）、差示扫描量热（DSC）、热失重（TGA）等分析手段,研究了改性树脂体系的粘度特性、储存稳定性、反应性以及固化树脂的力学性能、耐热性、耐湿热性等。     

氰酸酯/环氧树脂CE-40体系的固化反应

采用差示扫描量热(DSC)方法计算得到氰酸酯/环氧树脂CE-40体系反应动力学常数,分析了温度和浓度对反应速率的影响,同时结合红外光谱对各温度段发生的反应进行了推断。研究表明,CE-40体系有两个反应温度区——低温区(150℃-180℃)和高温区(200℃-250℃)。低温区是环氧与氰酸酯直接反应,产物为三聚氰酸酯和口恶唑啉,反应速率对浓度敏感,随反应物浓度下降而降低;高温区是低温区的生成物与环氧的进一步反应,主要产物为口恶唑烷酮和异氰酸脲,反应温度决定了反应速率。     

Effects of moisture and thermal cycling on in-plane shear properties of graphite fibre-reinforced cyanate ester resin composites

The weight change and retention of in-plane shear (±45°) strength of graphite fibre-reinforced cyanate ester resin matrix composites have been estimated on exposure to high humidity and thermal cycling, respectively. Cyanate ester resin matrix composites absorbed a remarkably small amount of moisture on exposure to high humidity. However, the degree of moisture absorption underwent a rather sudden increase to a new equilibrium level after prolonged exposure. A morphology study showed the occurrence of extensive cracking in the matrix/interface region in the form of delamination between plies as well as translaminar cracking within plies. The phenomenon is believed to be caused by weakening of the fibre-matrix interface, which was confirmed by microscopic analysis of fracture surfaces. A sudden moisture gain associated with extensive matrix/interface cracking was found to reduce the in-plane shear strength and fatigue lifetime at a given stress amplitude. The slope of the S-N curve was lower for wet specimens, implying a higher growth rate of local cracks as well as delamination. The rate of in-plane shear strength degradation was also measured on static exposure to dry heat as well as after thermal cycling to a peak temperature of 150 or 204°C. At a frequency of 10 min/cycle and for a relatively short duration, the effect of thermal cycling seems to be represented by the cumulative sum of thermal oxidation effects at the peak temperature.     

Investigation of the long term effects of moisture on carbon fibre and epoxy matrix composites

The aim of this work is to investigate the long term effects of moisture on the interface between a carbon fibre and an epoxy matrix. High modulus carbon fibres were used to prepare single fibre model composites based on an epoxy resin. The samples were immersed in the seawater and demineralised water and their moisture uptake behaviour was monitored. The equilibrium moisture content and diffusion coefficients for the samples were determined. DSC has been used to analyse the moisture effects on glass transition temperature and thermal stability of the pure epoxy specimens. These results showed a reduction in the glass transition temperature (T_g) after moisture absorption. Tensile tests were also carried out for the epoxy specimens and a general decrease in the mechanical properties of the epoxy matrix was observed. Raman spectroscopy was used to observe the effects of moisture on the axial strain of the carbon fibre within the composite and stress transfer at the interface as a function of exposure time. The results show that the decrease in the mechanical and interfacial properties of the model composites under the seawater immersion is more significant than under demineralised water immersion.     

Moisture absorption by epoxy/montmorillonite nanocomposite

The peculiarities of moisture absorption of epoxy–nanoclay composite are estimated in the paper. Second Fick’s law of diffusion was used to predict moisture diffusivity and equilibrium moisture content using accelerated analytical procedure. It was experimentally confirmed that sorption process in NC passes more slowly than in pure epoxy resin, for the highest filler content diffusivity reduces about half of diffusivity as for epoxy resin. The deviation from mixture rule was obtained for the equilibrium moisture content and the estimation of interphase content in composite was undertaken. It was determined that the higher content of interphase consistently leads to greater moisture absorption.     

与液氧相容聚合物基体材料

为改善环氧树脂与液氧的相容性,研究了环氧／溴环氧／氰酸酯树脂三元共固化体系,并探讨了2-乙基-4-甲基咪唑 ( 2E4MZ ) 对于共固化体系的促进作用。实验发现,2E4MZ可以显著降低共固化体系在不同温度下的凝胶时间。采用傅立叶红外光谱跟踪固化过程,结果表明,无论在环氧基团过量还是氰酸酯基团过量情况下,2E4MZ均能够明显加快固化反应速度,同时增大固化产物中共聚产物的比例,提高反应的选择性。热分析、闪点和氧指数以及液氧冲击试验结果表明,2E4MZ促进的较低氰酸酯含量的共固化体系具有较好的抗氧化和阻燃性能,与液氧的相容性也得到较大幅度改善。采用咪唑促进这种相对简单有效的改性途径,可得到与液氧相容性较好的、综合性能理想、成本合理的环氧树脂体系。      

硼酸铝晶须增强氰酸酯树脂的性能

采用硼酸铝(AlBw)晶须改性氰酸酯树脂制备出氰酸酯树脂/晶须复合材料,研究了表面处理和晶须用量对氰酸酯树脂体系的反应活性、复合材料力学性能以及耐湿热性的影响.结果表明,未经表面处理的AlBw晶须不能改善氰酸酯树脂体系的韧性,反而使树脂韧性下降,表面处理的晶须均可以改善树脂的力学性能,经硼酸酯偶联剂处理后的AlBw晶须使树脂体系冲击强度提高.采用硼酸酯偶联剂对AlBw晶须进行表面处理可明显改善晶须在树脂体系中的分散性.在晶须用量低于8%时,随着晶须加入量的增加,树脂体系的力学性能增大,氰酸酯树脂/晶须复合材料表现为韧性断裂并有明显的晶须拔出现象.晶须的加入使树脂体系耐热性和耐湿热性提高,加入8%的AlBw晶须使体系吸水率下降,冲击强度和弯曲强度保持率提高.     

CE改性及柔性膜性能

研究了催化剂、固化时间和温度对环氧树脂(EP)或丁腈橡胶(A)改性氰酸酯树脂(CE)固化反应的影响以及CE/A膜性能.不舍催化剂的CE/EP体系160℃不能有效固化,而含有二月桂酸二丁基锡(B)的CE/EP体系能有效固化,且固化反应速度随着B用量增加而提高.CE/A/B体系的固化程度随着固化时间延长和温度升高而提高.C...     

不同湿热条件下碳纤维/环氧复合材料湿热性能实验研究

对比研究了环氧5228A树脂及碳纤维/环氧5228A树脂复合材料层合板在3种湿热环境(水煮、70℃水浸,70℃85%相对湿度)下的湿热性能,考察了湿热条件对复合材料层间剪切性能的影响规律,并从吸湿特性、物理化学特性、树脂力学性能、湿应力等方面分析了不同湿热环境下复合材料性能衰减的机制。研究表明,碳纤维/高温固化环氧树脂复合材料层间剪切性能主要是由吸湿率决定,相同吸湿率不同湿热条件下性能的下降幅度基本相同;3种湿热条件下该树脂及其复合材料未发生化学反应、微裂纹等不可逆变化,复合材料层合板湿热老化机制主要是吸入水分后基体增塑和树脂、纤维湿应变不一致导致的湿应力对复合材料性能的负面作用。