摘要
环氧树脂固化物因具有优良的机械性能、电气性能、耐热性、耐化学药品性能而广泛应用于航空、航天、机械、电子等领域。然而,环氧树脂和固化剂分开存储的“两相体系”存在的弊端以及环氧固化物脆性大影响了其性能的发挥。本文研究了固化剂和增强相对环氧树脂性能的影响,从材料的制备、树脂固化物的力学性能、电学性能、固化动力学等方面进行了试验研究及理论分析。主要的研究工作分为两个部分:
1)环氧树脂/微胶囊固化剂的研究
针对环氧树脂两相固化体系的弊端,以2-乙基-4-甲基咪唑(EMI-2,4)固化剂为对象,研究了一种新型潜伏性固化剂——微胶囊固化剂,用以提高树脂体系的适用期。本文系统研究了固化剂的合成制备与优化、固化体系动力学和树脂固化物的力学性能。主要内容包括:
为了提高咪唑固化剂的适用期、并降低其水溶性来满足它作为微胶囊芯材的条件,本文首先对EMI-2,4固化剂进行改性,以大分子丁基缩水甘油醚(BGE)为改性剂合成了咪唑改性物EMI-g-BGE,用FTIR、1HNMR、元素分析对合成产物进行了表征和分析。
以热塑性聚醚酰亚胺(PEI)为壁材、采用乳液溶剂蒸发法将EMI-g-BGE包囊,研究表征了不同工艺条件与微胶囊的表面形貌、微胶囊的粒径及分布和微胶囊的芯材含量等的关联,获得了该体系的微胶囊最佳制备工艺:芯材壁材比为1:1、分散剂聚乙烯醇的浓度为8%、搅拌速度700rpm、溶剂蒸发温度36℃。
用非等温DSC法研究了EMI-g-BGE和微胶囊固化剂的固化动力学,通过Kissinger微分法和Ozawa积分法得到了固化动力学参数。结果表明,两种固化体系都属于同一复杂反应、动力学模型均为自催化反应,包囊前后的反应动力学机理是一致的;表观活化能从72.61kJ/mol提高到89.55kJ/mol,说明微胶囊固化剂的反应活性降低。研究证实:将所制备的微胶囊固化剂与环氧树脂按芯材化学计量比混合均匀,该树脂体系可室温稳定存储10个月而粘度几乎不变。
新固化体系固化物的性能研究表明:与EMI-2,4固化环氧树脂的性能相比,微胶囊固化树脂的冲击强度提高了一倍多,而弯曲强度和拉伸强度没有降低;热失重测试表明微胶囊的加入没有影响树脂固化物的热稳定性。
2)碳纳米管/环氧树脂复合材料的研究
针对环氧树脂固化物脆性大的缺点,本文将多壁碳纳米管(MWNT)引入到环氧树脂中,利用碳纳米管自身优异的力学、电学性能来提高复合材料的性能。论文对MWNT进行表面改性,首先用混酸超声氧化MWNT使其表面带有-COOH官能团,进一步酰氯化反应为-COOCl后用环氧树脂固化剂TETA进行胺化反应,得到表面带有胺基等极性基团的TETA-MWNT。FTIR、Raman图谱表明MWNT胺化反应成功并且没有改变其自身的石墨结构,“反滴定”法测试了酸化MWNT表面的羧基含量,元素分析法测试了TETA-MWNT表面N元素含量,由此计算了MWNT表面羧基的转化率为46.55%。
将碳纳米管及其改性物应用到环氧树脂中,用超声分散法制备碳纳米管/环氧树脂复合材料。改性前后MWNT的复合材料的力学性能及其对比实验结果表明:胺化碳纳米管/环氧树脂复合材料(记为TETA-MWNT/EP)的力学性能远优于碳纳米管/环氧树脂(记为MWNT/EP)、酸化碳纳米管/环氧树脂(记为a-MWNT/EP)复合材料。其机理在于:1)TETA-MWNT在环氧树脂中的分散性提高,碳纳米管之间的缠结团聚现象大大降低, FESEM结果表明胺化后MWNT与树脂的界面结合性及相容性得到了提高;2)TETA-MWNT/EP固化物的红外光谱表明碳纳米管表面-NH2与环氧基发生了开环固化反应,导致TETA-MWNT/EP复合材料的性能大幅度提高。不同含量的碳纳米管的力学性能曲线表明:当TETA-MWNT添加量为0.75wt%时,复合材料的冲击强度和拉伸强度均达到最大值。
应用“逾渗理论”研究了不同含量碳纳米管/环氧树脂复合材料的介电性能。当TETA-MWNT的体积含量小于4.14%时,材料的介电常数增加缓慢;而当TETA-MWNT含量大于4.14%时,介电常数增加迅速,呈现出突变,此时的含量在逾渗阈值附近。利用逾渗理论模型拟合,得到TETA-MWNT/EP复合材料的逾渗值fc为4.20%,与实验结果相符。在1kHz时,当碳纳米管含量为4.14%时,TETA-MWNT/EP复合材料的介电常数高达421,几乎是树脂基体的60倍,介电损耗为0.80,而MWNT/EP、a-MWNT/EP的介电常数为391、120,介电损耗为2.15、0.88。说明TETA-MWNT/EP的介电性能比较好。
复合材料的热失重测试表明TETA-MWNT/EP的热稳定性较未改性树脂有所提高,其中初始分解温度提高了20℃,最大热分解温度提高了30℃。用非等温DSC研究了TETA-MWNT/EP的固化动力学。结果表明:胺化碳纳米管与环氧树脂反应出现了一个放热肩峰,表明碳纳米管表面胺基参与了固化反应,用Kissinger微分法和Ozawa积分法求得了固化动力学参数,表观活化能为64.82kJ/mol,反应级数结果表明反应动力学模型也属自催化反应。
Epoxy resin is one of the most important thermosetting polymers, widely used in the fields of aeronautics, astronautics, machine and electronics due to its excellent mechanical and electrical properties, high heat distortion temperature and good chemical resistance. However, there are some shotcomings of the“two-pot”resin composites with curing agent as well as the cured epoxy is brittle, which affect the properties of epoxy resin. The effect of curing agent and reinforcement on the properties of epoxy resin were investigated in this paper.In order to accomplish this work, firstly, the curing agents and the resin composites were prepared, and then the mechanics properties and the dielectric properties of the composites along with the cure kinetic of the resin systems were studied by experimental and theoretical methods. There are mainly two parts in the research as following.
1) The research on epoxy resin/microcapsule mold-curing agent system.
To obtain a“one-pot”latent curing agent of epoxy resin, 2-ethyl-4-methyl imidazole (EMI-2,4) was imployed to prepare the microcapsule curing agent, which can improve the storage stability of resin system.The contents in our research include the preparation and optimization of the microcapsule agent, as well as curing kinetic and the mechanics of the resin composites.
The EMI-2,4 was modified by an epoxide ring opening from the second-type ring nitrogen of EMI with the large molecule of butyl glycidyl ether (BGE). The product EMI-g-BGE can be an effective latent curing agent of epoxy resin and can reduce the hydrophilicity of the products. Elemental analysis, FTIR spectroscopy, and 1HNMR spectroscopy have been used to characterize EMI-g-BGE.
EMI-g-BGE was encapsulated by evaporation emulsion method and with Polyether Imide thermoplastic resin (PEI) as the shell material. The surface morphology of microcapsules with the SEM photograph and particle size distribution along with the encapsulation efficiency has been investigated. The experimental results showed that the optimal microcapsules can be obtained with the ratio of core to shell being 1:1, the concentration of the dispersion agent 8%, the stirring speed 700rpm and the temperature 36℃.
There are more than 10 months of storage time in room temperature of epoxy resin composites with microcapsule curing agent. The curing kinetic of epoxy resin with EMI-g-BGE or microcapsule curing agent as curing agent was studied by non-isothermal DSC technique at different heating rates. The Kissinger and Ozawa methods were adopted to calculate the kinetic parameters of the two systems, with which results showed that they were both the same complex reaction and the kinetic model was a two-parameter (m, n) autocatalytic model. The apparent activation energy Ea had increased from 72.61kJ/mol to 89.55kJ/mol, which indicated the shell material of the microcapsule curing agent prevented the activation of the curing reaction.
The impact strength of the epoxy cured with microcapsule increased over one time more than that with EMI-2,4 curing agent, and the tensile strength and the flexural strength have not decreased. Thermogravimetic analysis (TGA) showed that the heat stability of the epoxy cured with microcapsules had not been affected.
2) The research on epoxy resin/carbon nanotubes composites
The mulltiwalled carbon nanotubes (MWNT) were introduced to improve the mechanical and electrical properties of epoxy resin. In our study, MWNT was modified with a mixture of H_2SO_4/HNO_3, and then the carboxylated MWNT (a-MWNT)was stirred using chloride. The obtained acyl chlorination MWNT was reacted with epoxy curing agent triethylene-tetramine (TETA). Finally, TETA-MWNT was obtained. The modified MWNT was testified by FTIR、Ramon analysis, and the titration test and the elemental analysis showed the reaction ratio from–COOH to–NH2 was 46.55%.
MWNT/EP composites were prepared by ultrasonicated dispersion method. The mechanical test showed that the composites of TETA-MWNT/EP had excellent properties than MWNT/EP and a-MWNT/EP composites. TEM graphs showed the dispersion of TETA-MWNT in epoxy matrix had been better than MWNT or a-MWNT, meanwhile, the morphology of fractured compositions showed the compatibility of TETA-MWNT in epoxy matrix improved greatly. IR analysis showed the reaction of amido group in TETA-MWNT with epoxy, which explained the good property of TETA-MWNT/EP composites.Mechanical test with different contents of TETA-MWNT showed that the best content was about 0.75 percent.
The dielectric properties of epoxy resin with different contents MWNT were researched according to the scaling law, with the theoretical percolation threshold of epoxy resin composites filled with TETA-MWNTs was 4.20%. The value of the relative dielectric constant of resin composites was as high as 421 with the TETA-MWNT content of 4.14vol% at 1kHz, which was almost 60 times higher than that of epoxy matrix and the dielectric loss was 0.80. The relative dielectric constant of MWNT/EP and a-MWNT/EP were 391 and 120, while the dielectric loss was 2.51 and 0.88 with the same MWNT contents as TETA-MWNT/EP. The results showed that the dielectric properties of TETA-MWNT/EP were well.
TGA tests of the composites indicated that the TETA-MWNT/EP composites had more heat stability than the pure resin. Comparing with the pure epoxy resin, the starting decomponded temperature of the composites increased 20℃, and the maximal decomponded temperature increased 30℃. The curing kinetic of TETA-MWNT/EP/EMI-2,4 system was studied with non-isothermal DSC technique at different heating rates. The results showed that there was a small peak in the DSC curve due to the reaction of TETA-MWNT with epoxy group. The kinetic parameters were obtained by Kissinger and Ozawa method, with the apparent activation energy Ea was 64.82kJ/mol and a two-parameter (m, n) autocatalytic model was found with the resin system.
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