The cure reaction kinetics of epoxy resin, with organically modified montmorillonite loadings of up to 20 wt % and with stoichiometric conditions, has been studied by differential scanning calorimetry with a view to understanding further the fabrication of epoxy-based polymer layered silicate nanocomposites. The kinetic analysis of isothermal and nonisothermal cure shows that the autocatalytic model is the more appropriate to describe the kinetics of these reactions, and it is observed that a dominant effect of the montmorillonite is to catalyze the curing reaction. However, it was not possible to model the reactions over the whole range of degrees of conversion, in particular for nonisothermal cure. This attributed to the complexity of the reactions, and especially to the occurrence of etherification by cationic homopolymerization catalyzed by the onium ion of the organically modified montmorillonite. The homopolymerization reaction results in an excess of diamine in. the system, and hence in practice the reaction is off stoichiometric, which leads to a reduction in both the heat of cure and the glass transition temperature as the montmorillonite content increases. Small angle X-ray scattering of the cured nanocomposites shows that an exfoliated nanostructure is obtained in nonisothermal cure at slow heating rates, whereas for nonisothermal cure at faster heating rates, as well as for isothermal cure at 70 degrees C and 100 degrees C, a certain amount of exfoliation is accompanied by the growth of d-spacings of 1.4 mn and 1.8 nm for dynamic and isothermal cure, respectively, smaller than the d-spacings of the modified clay before intercalation of the resin. A similar nanostructure, consisting of extensive exfoliation accompanied by a strong scattering at distances less than the d-spacings of the modified clay, is also found for resin/clay mixtures, before the addition of any crosslinking agent, which have been preconditioned by storage for long times at room temperature. The development of these nanostructures is attributed to the presence of clay agglomerations in the original resin/clay mixtures and highlights the importance of the quality of the dispersion of the clay in the resin in respect of achieving a homogeneous exfoliated nanostructure in the cured nanocomposite. (c) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 108: 923-938, 2008.