Surfaces of a Wyoming SWy-2 sodium montmorillonite were modified using microwave radiation through intercalation with the cationic surfactants octadecyltrimethylammonium bromide, dimethyldioctaclecylammonium bromide, and methyltrioctadecylammonium bromide by an ion exchange mechanism. Changes in the surfaces and structure were characterized using X-ray diffraction (XRD), thermal analysis (TG) and infrared (IR) spectroscopy. Different configurations of surfactants within montmorillonite interlayer are proposed based on d(001) basal spacings. A range of surfactant molecular environments within the surface-modified montmorillonite are proposed based upon their thermal decomposition. IR spectroscopy using a smart endurance single bounce diamond attenuated total reflection (ATR) cell has been used to study the changes in the spectra of CH asymmetric and symmetric stretching modes of the surfactants to provide more information of the surfactant molecular configurations. (c) 2006 Elsevier Inc. All rights reserved.