Epoxy/Clay Nanocomposites: Effect of Clay and Resin Chemistry on Cure and Properties

Abstract

Polymer/clay nanocomposites consisting of an epoxy resin matrix filled with organoclays have been investigated. The main objective of this study was to determine which combination of components led to the greatest enhancement in

properties of the epoxy resin. Exfoliation of the clay was desired, as exfoliated nanocomposites are known to exhibit great improvements in mechanical properties [1].

The epoxy resins studied were di-functional DGEBA and tetra-functional TGDDM. The epoxy resin was cured with three different hardeners, these included: the high functionality amine hardener, TETA, and two anhydride hardeners, accelerated MTHPA and pure HHPA. The three organoclays used, contained alkylammonium

cations and were also compared to the unmodified clay.

Morphology was investigated by XRD and TEM, and the flexural properties of the resulting nanocomposites were studied. The effect that the addition of an organoclay has on the cure of the epoxy resin was investigated using MDSC. Both the

temperatures required to cure the resin with, and without, the clay, and any changes in the total heat flow that occurred were studied. The Tg++ of the cured nanocomposites was also measured using MDSC.

The heat flow results indicated that the clays added to the epoxy resins act as a physical barrier, which prevents the resin from reaching full cure. In the higher functional resin, the addition of clay resulted in a significant decrease in the total heat flow, suggesting that a large amount of epoxy remains uncured, and, as a result, there should be a reduction in the amount of cross-linking. The lower cross-link density led to a significantly lower Tg and the mechanical properties were also poorer.

The reactivity of the hardener towards the resin was found to have the greatest impact on the cured nanocomposite morphology. Intragallery polymerisation occurring at a faster rate than the extragallery polymerisation causes exfoliation. In order to achieve a balance that favours intragallery polymerisation, it was found that the curing reaction was required to be catalysed by the alkylammonium cation of the organoclay, and not catalysed by other means. The DGEBA cured with HHPA provided the largest layer expansion in the clay structure due to the alkylammonium cation catalysing the anhydride ring-opening reaction. The effect was not seen with TGDDM due to the tertiary amine in its structure. The accelerator within the MTHPA assisted extragallery polymerisation of the resin and the TETA cured readily without additional catalysis.