Prolongo M G, Martínez-Casado F J, Masegosa R M, Salom C
Dpt. Materiales y Produccidn Aeroespacial, Univ. Politicnica de Madrid, 28040 Madrid, Spain.
J Nanosci Nanotechnol. 2010 Apr;10(4):2870-9. doi: 10.1166/jnn.2010.1385.
Epoxy/Clay nanocomposites with two organically modified montmorillonites (Cloisite 30B and Cloisite 15A) have been prepared. Cloisite 15A has higher cation exchange capacity, interlayer spancing and hydrofobicity than Cloisite 30B. Different methods were carried out to disperse the clay in the epoxy monomer (diglycidyl ether of bisphenol A) with and without solvent, using stirring and ultrasound sonication. The epoxy hardeners used were 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylsulfone which generate high glass transition temperature epoxy thermosets. The content of clay in the nanocomposites ranged from 2 to 11 wt%. The effect of Cloisites on the curing reaction has been studied by differential scanning calorimetry, finding that the presence of Cloisite 30B accelerates the curing reaction. The glass transition temperature of the epoxy thermoset decreases when the clay content increases, due to the plasticizing effect of the alkylammonium cations. The dispersion of the layered silicates within the crosslinked epoxy matrix was studied by wide-angle X-ray diffraction. In all the cases, the nanocomposites show intercalated clay structures, being the interlayer clay spacing almost independent of the method of dispersion, of the clay content, and of hardener used. Moreover the d-spacing differences between C30B and C15A nanocomposites are insignificant. Epoxy molecules intercalate in a smaller proportion in C15A than in C30B, as it was deduced from the increase of the d-spacing. The dynamic mechanical thermal properties of these nanocomposites were also investigated. Nanocomposites with Cloisite 30B show higher values of storage modulus than neat epoxy, both in the glassy and in the rubbery states. However Cloisite 15A does not improve the epoxy storage modulus, and such divergent behavior agrees with the different intercalation of epoxy in the clays. The fracture surfaces of the nanocomposites analyzed by environmental scanning electron microscopy indicate an improvement of toughness.
制备了含有两种有机改性蒙脱土(Cloisite 30B和Cloisite 15A)的环氧/粘土纳米复合材料。Cloisite 15A比Cloisite 30B具有更高的阳离子交换容量、层间距和疏水性。采用搅拌和超声处理等不同方法,在有溶剂和无溶剂的情况下将粘土分散在环氧单体(双酚A二缩水甘油醚)中。使用的环氧固化剂是4,4'-二氨基二苯甲烷和4,4'-二氨基二苯砜,它们可生成高玻璃化转变温度的环氧热固性材料。纳米复合材料中粘土的含量范围为2至11 wt%。通过差示扫描量热法研究了Cloisites对固化反应的影响,发现Cloisite 30B的存在加速了固化反应。由于烷基铵阳离子的增塑作用,当粘土含量增加时,环氧热固性材料的玻璃化转变温度降低。通过广角X射线衍射研究了层状硅酸盐在交联环氧基体中的分散情况。在所有情况下,纳米复合材料均呈现插层粘土结构,层间粘土间距几乎与分散方法、粘土含量和所用固化剂无关。此外,C30B和C15A纳米复合材料之间的d间距差异不显著。从d间距的增加可以推断,环氧分子在C15A中的插层比例比在C30B中更小。还研究了这些纳米复合材料的动态机械热性能。含有Cloisite 30B的纳米复合材料在玻璃态和橡胶态下的储能模量值均高于纯环氧树脂。然而,Cloisite 15A并未提高环氧树脂的储能模量,这种不同的行为与环氧在粘土中的不同插层情况一致。通过环境扫描电子显微镜分析的纳米复合材料的断裂表面表明韧性有所提高。