Applicability of classical Lifshitz-Slyozov theory of Ostwald ripening is analyzed and found limited by relatively large cluster sizes due to restrictions imposed by theoretical assumptions. An assumption about the steady state ripening regime poses
an upper limit, while another, implicit assumption of continuous description poses a cluster size-dependent lower limit on the supersaturation level. These two limits mismatch for the clusters under certain size in the nanometer scale making the theory inapplicable. We present a more generic, molecular theory of Ostwald ripening, which reproduces classical Lifshitz-Slyozov and Wagner theories in appropriate extreme cases. This theory has a wider applicability than classical theories, especially at lower supersaturation levels, and is more suitable for nanoscale systems.
The phenomenon of Ostwald Ripening is generally considered a limiting factor in the monodisperse production of nanoparticles. However, by analysing the free energy of a binary AB solution with precipitated A particles we show that there is a region i
n the parameter space of component concentrations and interaction energies where smaller particles are more stable than bigger ones. The strong binding of B species to surfaces of A particles significantly decreases the particle effective surface energy, making it negative. The global minimum of free energy in such a system is thus reached when mass is transferred from bigger particles to the smaller ones, such that all particles become identical in size. The process of mass transfer is opposite to Ostwald ripening, and can be used for generating monodisperse arrays of nanoparticles.
