The second group of powders with a dissolved Ba content of ≥0.09 mol% exhibits a total relative shrinkage L/L0 of about 14%, and the shrinkage rate maxima at 1280 and 1332 ◦C are larger than in the first group. This is a consequence of the higher TiO2 excess located at the surface of the grains which favors the sliding processes and increases the amount of melting phase. In case of powders with a dissolved Ba content of >1.5 mol% the peritectic temperatures in the system BaTiO3–TiO2 at 1350 and 1365 ◦C [6] are unambiguously detectable as further local shrinkage ratemaxima.