Emanation thermal analysis (ETA), DTA, SEM, and XRD were applied for the characterization of the effect of Na+ and NH
ions used for saturation of natural Mg-vermiculite on the microstructure during heating. The microstructure changes were characterized by ETA under in situ conditions of samples heating in air in the temperature range 20–1300°C. It was found that Na+ and NH
ions have a significant effect on the microstructure changes during heat treatment of the natural Mg-vermiculite sample saturated with these ions. For Mg-vermiculite and Na+ saturated vermiculite thet emperatures of the onset of the collapse of interlaminar space were determined by ETA. Differences in thermal stability of the microstructure of dehydrated vermiculite samples were observed by ETA: the microstructure of dehydrated Mg-vermiculite, and Na-vermiculite was found stable until 650 and 350°C, respectively. For dehydrated NH4-vermiculite the annealing of the microstructure started at 730°C. The onset temperatures of the formation of new crystalline phases were indicated by ETA as the increase of the radon release rate. The onset temperatures of the ordering of the vermiculite structure or sintering under presence of the glassy stage (for Na-vermiculite), respectively, were determined from the decrease of the radon release rate. The ETA results were confirmed by DTA, XRD and SEM.