Controlling the aqueous growth of urea crystals with different growth inhibitors: a molecular-scale study. Issue 21 (6th April 2021) - Singh, M. K.
Abstract : Effect of different growth additives on the aqueous growth of crystalline urea is investigated computationally at the different levels of supersaturation and additive concentration. Abstract : Molecular scale understanding of the mechanism of solution-mediated nucleation and the growth of crystalline materials in the presence of growth inhibitors together with the process parameters continues to attract the interest of the scientific community though much headway has been made in recent years. Growth inhibitors can be added to solution of a crystallizing parent molecule to alter the rate of growth of different crystal faces, size and shape of the crystalline materials. In this work, we investigated the effects of a number of shape-controlling inhibitors, such as acetone, biuret and biurea, on the growth kinetics of the various faces of aqueous-grown urea crystals as a means to predictably control the crystal growth morphology. We combined the adsorption energy landscape of various auxiliaries with the kinetics of the molecular growth processes to develop an analytical model to compute the rate of growth as a function of supersaturation and the additive concentration. The model relates the kinetic and thermodynamic aspects of the adsorption of the solute, solvent and additive to provide a quantitative description of the crystal growth. Ab initio periodic dispersion-corrected density functional theory using the hybrid exchange–correlation functional was employed to determine the interfacial structure of the adsorption of various auxiliaries at crystalline surfaces. The calculated adsorption energies of different auxiliaries were employed to examine the role played by these auxiliaries during the aqueous crystallization of urea crystals containing small amounts of additives. Our results showed that the growth of (110), (111) and (1̄1̄1̄) faces were nearly unaltered by the addition of moderate amounts of acetone as it has lower adsorption energies with the surfaces of these faces. Nevertheless, the presence of acetone in the solution reasonably impeded the growth of the (001) face. The addition of biuret or biurea in the solution led to a higher adsorption energy at (001) and (111) faces. Consequently, the low concentration of these additives severely obstructed the growth of (001) and (111) faces as most of the adsorption sites were occupied by these additives. On the other hand, these additives were weakly adsorbed at the (110) face and, hence, the growth of the (110) face largely remained unaltered. Moreover, unlike biuret, biurea considerably inhibited the growth of the (1̄1̄1̄) face. Our results are in agreement with the experimental and computational results reported in the literature.