Effects of solvent,supersaturation ratio and silica template on morphology and polymorph evolution of vanillin during swift cooling crystallization

Swift cooling crystallization of vanillin was investigated in water,ethanol,isopropanol and ethyl acetate.Morphology and polymorph evolution of vanillin were discussed in terms of solvent,supersaturation ratio and silica template.PXRD,DSC,FTIR and microscope were used to identify polymorphs of vanillin.Results showed that the nucleated polymorphs of vanillin depended largely on the solvent,supersaturation ratio and silica template.Low supersaturation ratios favor the nucleation of stable form I in water,and high supersaturation ratio exceeds 7 generating 100%metastable form II.However,if the supersaturation ratio is too high(S>8),liquid-liquid phase separation will occur,and no crystals could be obtained.In other solvents such as ethanol,isopropanol and ethyl acetate,only form I was obtained.However,it should be noted that the morphology of form I prepared in ethanol,isopropanol and ethyl acetate is distinct from that obtained in water,the former is flake-like and the latter is rod-like.The nucleation of vanillin from different solution was also studied with the presence of SiO_(2),SiO_(2)-NH_(2)and SiO_(2)−COOH templates,which did not change the nucleated polymorph of vanillin,but changed the nucleation and growth rate of stable form I.

An experimental study of salt expansion in sodium saline soils under transient conditions

Salt expansion in sulfate saline soils that are widely distributed in northwestern China causes serious infrastructural damages under low-temperature conditions. However, the mechanism of salt expansion under low temperatures is not clear. In this study, we conducted a series of cooling experiments combined with salt crystallization to study this mechanism, and employed an ionic model to calculate the supersaturation ratio of the solution. During the experiments, the strength and the process of salt expansion were examined under different cooling rates and various crystal morphologies. The relationship between temperature and supersaturation ratio under transient conditions was also considered. Results indicate that the initial supersaturation ratio of a sodium sulfate solution is closely related to environmental conditions, and that this ratio decreases with slowing the cooling rates and stabilizing the crystal forms. Higher initial supersaturation ratios lead to an increased non-steady-state zone, resulting in less salt expansion. On the other hand, chloride ion content has a distinct influence on the crystallization supersaturation ratio of the sodium sulfate solution, and higher chloride ion content can inhibit salt expansion in sodium saline soils. These findings help explain salt expansion mechanisms in complex conditions such as seasonally frozen soils, and thus help search for improved methods of preventing salt expansion in sulfate saline soils.