Theory of Nanoparticles Mechanosynthesis

A theoretical investigation of the solid-phase mechanochemical synthesis of nano-sized target product on the basis of dilution of the initial powdered reagent mixture by another product of an exchange reaction is presented. On the basis of the proposed 3-mode particle size distribution in mechanically activated mixture, optimal molar ratios of the components in mixture are calculated, providing the occurrence of impact-friction contacts of reagent particles and excluding aggregation of the nanosized particles of the target reaction product. Derivation of kinetic equations for mechanochemical synthesis of nanoscale particles by the final product dilution method in the systems of exchange reactions is submitted. On the basis of obtained equations the necessary times of mechanical activation for complete course of mechanochemical reactions are designed. Kinetics of solid phase mechanosynthesis of nano-TlCl by dilution of initial (2NaCl + $Tl_2SO_4$) mixture with the exchange reaction product (diluent, $zNa_2SO_4$, $z=z^*=11.25$) was studied experimentally. Some peculiar features of the reaction mechanism were found. Parameters of the kinetic curve of nano-TlCl obtained experimentally were compared with those for the model reaction KBr + TlCl + zKCl = (z + 1) KCl + TlBr ($z=z_l^*=13.5$), and for the first time the value of mass transfer coefficient in a mechanochemical reactor with mobile milling balls was evaluated. Dynamics of the size change was followed for nanoparticle reaction product as a function of mechanical activation time.