In situ Raman observation of the crystallization in NaNO3-Na2SO4-H2O solution droplets

Several double salts have been detected in building materials and most of these salts are incongruently soluble compounds. In contrast to single salts, however, no systematic investigations of the crystallization behavior and deleterious effects of incongruently soluble double salts exist. To assess the damage potential of these salts, a systematic investigation of their highly complex behavior is desirable. This paper deals with the crystallization behavior of various solids in the ternary mixed NaNO3-Na2SO4 system including the formation of the double salt darapskite, Na3NO3SO4 center dot H2O. The crystallization sequence during droplet evaporation experiments at room conditions was determined using Raman and polarization microscopy. The basic idea of this research is to use deviations of the crystallization sequence of a salt or a mixed salt solution from the equilibrium pathway as an indicator to detect the degree of supersaturation. The observed crystallization pathway includes the formation of the metastable phases Na2SO4(III), Na2SO4(V) and darapskite. The experimental observations are discussed on the basis of the NaNO3-Na2SO4-H2O phase diagram and the results provide evidence for crystal growth from highly supersaturated solutions in both systems. If the crystals growing under these conditions are confined, these supersaturations result in substantial crystallization pressures.