Calcium Concentration Dependence of the Intergranular Film Thickness in Silicon Nitride

High-resolution electron microscopy and nano-beam analytical electron microscopy have been used to characterize both the intergranular silicate film thickness and its local composition in a series of high-purity Si3N4 ceramics doped with 0–450 at. ppm Ca. Calcium was detected at both two-grain junctions and triple junctions, even in the 80-ppm-Ca-doped specimen. The thickness of the intergranular film at two-grain junctions was found to depend sensitively on Ca content. In undoped material, the thickness was 1.0 ± 0.1 nm. With increasing Ca content, the thickness decreased in the dilute region (80 ppm Ca), but then increased. The variation in film thickness can be qualitatively understood in terms of the balance of three long-range forces acting normal to the film, namely the van der Waals dispersion force, a structural “steric” force, and an electrical-double-layer force. By comparing the measured thicknesses to those predicted, estimates for the structural correlation length and the inverse Debye length can be made. These estimates have values of ∼ 0.22 nm and approximately 0.3–0.5 nm, respectively, for the calcia-free and 80 ppm calcia materials.