Characterization of silicon nitride ceramics by transmission electron microscopy (TEM) provides structural and compositional information on intergranular phases necessary to elucidate the factors that can influence the presence and thickness of grain-boundary films. Different TEM techniques can be used for the detection and determination of intergranular-film thickness, however, the most accurate results are obtained by high-resolution electron microscopy (HREM). HREM studies were applied, in conjunction with analytical electron microscopy, to investigate the correlation between intergranular-phase composition and film thickness. Statistical analyses of a number of grain-boundary films provided experimental verification of a theoretical equilibrium film thickness. Model experiments on a high-purity Si3N4 material, doped with low amounts of Ca, suggest the presence of two repulsive forces, a steric force and a force produced by an electrical double layer, that may act to balance the attractive van der Waals force necessary to establish an equilibrium film thickness.