环氧树脂/蒙脱土/咪唑纳米复合材料固化行为的研究

运用非平衡态热力学涨落理论预估了环氧树脂 有机蒙脱土 咪唑插层型纳米复合体系在不同温度及不同有机蒙脱土用量时的固化行为 ,理论曲线与动态扭振的实验有良好的符合 .实验表明 ,有机蒙脱土的加入 ,使凝胶化时间tg 缩短 ,固化速率加快 ,但对凝胶点后的固化反活化能ΔH影响不大     

环氧树脂/蒙脱土/咪唑纳米复合材料固化行为的研究

运用非平衡态热力学涨落理论预估了环氧树脂/有机蒙脱土/咪唑插层型纳米复合体系在不同温度及不同有机蒙脱土用量时的固化行为,理论曲线与动态扭振的实验有良好的符合.实验表明,有机蒙脱土的加入,使凝胶化时间tg缩短,固化速率加快,但对凝胶点后的固化反活化能ΔH影响不大.     

动态扭振法研究聚甲基丙烯酸甲酯/蒙脱土纳米复合材料的本体插层聚合

用动态扭振法研究热塑性塑料聚甲基丙烯酸甲酯(PMMA)/蒙脱土(MMT)复合体系的本体插层聚合.并试用处理交联体系固化的Flory理论、非平衡态热力学涨落理论和Avrami方程研究PMMA/MMT复合体系的本体插层聚合,求取表观活化能Ea.实验发现,PMMA/MMT插层聚合转化率曲线中后期与热固性树脂的固化曲线极为类似,表明剥离后的蒙脱土片层在复合材料中起到交联点的作用.     

动态扭振法研究聚甲基丙烯酸甲酸／蒙脱土纳米复合材料的本体插层聚合

用动态扭振法研究塑性塑料聚甲基丙烯酸甲酸（PMMA）／蒙脱土（MMT）复合体系的本体插层聚合，并试用处理交联体系固化的Folry理论，非平衡态热力学涨落理论和Avrami方程研究PMMA／MMT复合体系的本体插层聚合，求取表观活化能Ea.实验发现，PMMA／MMT插层聚合转化率曲线中后期与热固性树脂的固化曲线极为类似，表明剥离后的蒙脱土片层在复合材料中起到交联点的作用。     

酚醛树脂/蒙脱土纳米复合材料的制备及固化反应动力学研究

利用自制的有机蒙脱土 ,采用浇模固化成型法制备酚醛树脂 /六次甲基四胺 /蒙脱土纳米复合材料 ,并用XRD观察有机蒙脱土分别在热塑性和热固性酚醛树脂中复合行为 .研究发现 ,由于两种树脂的固化反应机理不同 ,热固性酚醛树脂与蒙脱土复合 ,可得插层型纳米复合材料 ;而采用热塑性酚醛树脂进行固化 ,则得到部分剥离的纳米复合材料 .通过DSC进一步研究热塑性酚醛树脂 /蒙脱土复合体系的固化反应动力学 .运用Kissinger ,Flynn Wall Ozawa ,Crane方法求出活化能和反应级数等动力学参数 .结果发现 ,加入蒙脱土使固化反应活化能下降 ,反应级数减小 ,从而有利于固化工艺的实现 ,便于纳米复合材料实际应用 .     

酸酐固化环氧树脂/蒙脱土复合材料的等温固化动力学

用等温差示扫描量热法(DSC)研究了酸酐固化环氧树脂/蒙脱土复合材料的等温固化过程，考察了未处理的蒙脱土(MMT)和有机蒙脱土(OMMT)对环氧树脂固化动力学的影响. 实验表明， 环氧树脂的固化过程包含自催化机理，加入蒙脱土没有改变固化反应机理. 用Kamal方程对该体系的固化过程进行拟合，得到反应级数m、n，反应速率常数k1、k2，总反应级数(m + n)在2.4～3.0之间. MMT的加入使环氧树脂体系的k1、k2有所降低，而OMMT的加入对体系的k1、k2影响较为复杂，加入蒙脱土对环氧树脂固化体系的活化能影响较小.     

Avrami法研究环氧树脂/蒙脱土/咪唑纳米复合材料的固化动力学

运用Flory凝胶化理论和Avrami法研究环氧树脂／有机蒙脱土／咪唑插层型纳米复合体系在不同温度及不同有机蒙脱土用量时的固化动力学。实验表明,随固化温度的提高,Avrami速率常数k值增大,凝胶化时间tg缩短,凝胶点后的t1/2降低,固化速率加快,当固化温度低于90℃时,Avrami指数n值为3左右,而固化温度高于90℃时,n值为2左右。有机蒙脱土的加入,使固化速率加快,但并不改变固化反应的机理,Avrami方程可以很好地描述凝胶点后的固化动力学。     

4,4'-二氨基二苯醚二苯酮固化环氧树脂/粘土纳米复合材料的研究

采用离子交换法, 用十六烷基三甲基溴化铵处理钙基蒙脱土(MMT), 使蒙脱土的层间距由1.49 nm扩大到2.21 nm, 制备了环氧树脂/ BADK/MMT纳米复合材料, 并用XRD等手段研究了有机蒙脱土在环氧树脂中的插层及剥离行为. 研究结果表明, 蒙脱土含量及环氧树脂与有机土的混合温度和时间均对固化后复合材料的剥离产生影响, 只有在特定条件下才能得到剥离型纳米复合材料.     

环氧树脂/PAMAM体系的固化动力学研究

用动态扭振法研究以聚酰胺-胺(PAMAM)为固化剂的环氧树脂／PAMAM体系的固化动力学行为。结果表明,该实验体系能够很好地用Flory理论和Avami方程进行拟合。     

丙烯酸树脂／蒙脱土纳米复合材料的制备研究

采用离子交换法,用十六烷基三甲基溴化铵对钠基蒙脱土(Na-MMT)进行改性制备了有机蒙脱土(OMMT).用丙烯酸(AA)、硫酸化蓖麻油、乳化剂OP-10、过硫酸钾为原料进行水溶液聚合制得丙烯酸树脂.将丙烯酸树脂与改性蒙脱土通过聚合插层制备了丙烯酸树脂/ 蒙脱土纳米复合材料.通过傅立叶变换红外(FTIR)和X-射线衍射 (XRD)等手段对复合材料的结构进行了表征,结果表明:丙烯酸树脂插层进入有机蒙脱土内可形成插层型或剥离型的纳米复合材料.蒙脱土含量及蒙脱土与丙烯酸树脂的反应温度、反应时间均对复合材料的剥离行为产生影响,在蒙脱土含量为树脂固含量的7%、温度为70℃、反应4h的条件下可得到完全剥离的纳米复合材料.     

Cure behavior of epoxy resin/montmorillonite/imidazole nanocomposite by dynamic torsional vibration method

Flory’s gelation theory, the non-equilibrium thermodynamic fluctuation theory and the Avrami equation have been used to predict the cure behavior of epoxy resin/organo-montmorillonite (Org-MMT)/imidazole intercalated nanocomposites at various temperatures and Org-MMT loadings. The theoretical prediction is in good agreement with the experimental results obtained by a dynamic torsional vibration method. The results show that the addition of Org-MMT reduces the gelation time t_g and increases the rate of the curing reaction, the value of the kinetic constant k. The half-time t_1/2 of cure after the gel point decreases with increasing of cure temperature, and the value of n is around 3 at lower temperature (<90 °C) and decreases to ∼2 as the temperature increases. The addition of Org-MMT has no obvious effect on the apparent activation energy of the cure reaction. There is no special curing process required for the formation of an epoxy resin/Org-MMT/imidazole intercalated nanocomposite.     

Cure behavior of epoxy resin/MMT/DETA nanocomposite

The Flory's gelation theory, non-equilibrium thermodynamic fluctuation theory and Avrami equation have been used to predict the gel time t _g and the cure behavior of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposites at various temperatures and organo-montmorillonite loadings. The theoretical prediction is in good agreement with the experimental results obtained by dynamic torsional vibration method, and the results show that the addition of organo-montmorillonite reduces the gelation time t _gand increases the rate of curing reaction, the value of k, and half-time of cure after gelation point t_1/2 decreases with the increasing of cure temperature, and the value of n is ~2 at the lower temperatures (<60°C) and decreases to ~1.5 as the temperature increases, and the addition of organo-montmorillonite decreases the apparent activation energy of the cure reaction before gelation point, but has no apparent effect on the apparent activation energy of the cure reaction after gelation point. There is no special curing process required for the formation of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposite. This revised version was published online in July 2006 with corrections to the Cover Date.     

A New Method to Study the Sol-gel Transition Process of Organic/Inorganic Hybrid Materials

The sol-gel transition process of PMMA/SiO2 hybrid materials was first studied by means of the dynamic torsional vibration method. The different stages of the transition can be described by the change of torque. The temperature-dependent measurement of the gel time（ tg ） gives the possibility to determine the apparent activation energy.（ Ea ） of this transition according to Flory＇s gelation theory. The non-equilibrium thermodynamic fluctuation theory was used to predict the transition behavior. The isothermal transition experiments on hybrid sols with different TEOS（tetraethyl orthosilicate） contents were carried out. The results show that the Ea of a hybrid sol is higher than that of a non- hybrid sol of a TEOS-water-ethanol system. The increasing of TEOS content in a hybrid sol has no obvious effect on the Ea value, but it can enhance the sol-gel .reaction rate.     

Preparation and characterization of PE and PE-g-MAH/montmorillonite nanocomposites

Polyethylene (PE) was chemically modified with grafting maleic anhydride (MAH) monomer on its backbone at first. Then the melt-direct intercalation method was employed to prepare two kinds of nanocomposites, polyethylene (PE)/organic montmorillonite (Org-MMT) and maleic anhydride grafted polyethylene (PE-g-MAH)/Org-MMT nanocomposites. X-ray diffractometery (XRD) was used to investigate the intercalation effect and transmission electron microscopy (TEM) to observe the dispersion of Org-MMT interlayers in matrixes. The results show that an intercalated structure would be acquired on mixing the PE and Org-MMT; and an almost exfoliated system would be obtained by mixing the PE-g-MAH and Org-MMT. Moreover, further measurements via thermogravimetric (TGA) and differential scanning calorimetry (DSC) showed that both of the nanocomposites had a higher thermal decomposition temperature and a higher crystallization temperature when compared to the original matrix. At the same time, the thermal and crystal properties for the PE-g-MAH prepared in this experiment are also discussed.     

PE/Org-MMT nanocomposites

The non-isothermal crystallization kinetics of polyethylene (PE), PE/organic-montmorillonite (Org-MMT) composites were investigated by differential scanning calorimetry (DSC) with various cooling rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the non-isothermal crystallization process of these samples very well. The difference in the exponent n between PE and PE/Org-MMT nanocomposites, indicated that non-isothermal kinetic crystallization corresponded to tridimensional growth with heterogeneous nucleation. The values of half-time, Z_c and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PE and PE/Org-MMT composites, but the crystallization rate of PE/Org-MMT composite was faster than that of PE at a given cooling rate. The method developed by Ozawa did not describe the non-isothermal crystallization process of PE very well. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The results showed that the activation energy of PE/Org-MMT was greatly larger than that of PE. This revised version was published online in July 2006 with corrections to the Cover Date.     

动态扭振法及其在环氧树脂固化过程研究中的应用

本文改进了动态扭振的橡胶硫化仪.通过测定不同温度下环氧树脂E51-咪唑体系的等温固化曲线上的凝胶化时间推算该体系的固化反应表观活化能为12.9千卡/摩尔.测定了E51-三乙醇胺体系在100℃下的等温固化曲线,推得反应是一级反应,在凝胶点时的反应程度为48.2％,与理论值50％相当接近.     

环氧树脂-三乙醇胺体系固化行为的预估

应用Flory凝胶化理论和非平衡态热力学涨落理论对环氧树脂-三乙醇胺体系不同温度下的凝胶化时间t_g和t_g以后树脂体系的固化行为进行了预估。动态扭振的实验表明,理论预估与实验有良好的相符。