Nucleation of melt: From fundamentals to dispersed systems

Abstract

The most evident aspects of a first order transition of a system from an old to a new phase, are the presence of a discontinuity at the interface between both phases and the thermal effects related to the latent heat exchanged with the surrounding environment. These effects are the result of a sequence of events promoted by thermodynamic conditions persisting over the equilibrium in a metastable state. The breakdown of metastability is promoted by infinitesimal energy fluctuations resulting in the germination of clusters of the new phase that can grow to a critical size (nucleus) and then develop or vanish. Examples of these sequences are common in various technological fields such as combustion, food processing, pharmaceutical manufacturing, condensation, and phase change heat transfer, etc. This work aims to highlight a logical path that leads the readers from the fundamental phenomenology to the most intricated aspects of the nucleation within dispersed systems such as oil-in-water emulsions. Differences between the homogeneous and heterogeneous mechanisms are, under the light of the Classical Nucleation Theory (CNT), presented in bulk and confined systems until defining a minimum confinement size. By collecting insights coming from a rich scientific literature mostly focused on the stability of emulsified systems, the discussion is then on the aspects related to the surface related mechanisms. Two main aspects are then considered: a) the wettability of the nucleating cluster by the surrounding melt; b) the affinity between the adsorbed layer, where a surfactant is located, and the oil melt phase (mainly n-alkanes and triacylglycerols with different moieties). In cases where nucleation is dominating over the dewetting of the nucleus, the contact angle can be considered as a constant value. The affinity in terms of molecular features between the surfactant and the oil phase can promote the template effect. Several factors seem to play a role in this interaction such as the thermal characteristics of the surfactant and comparable dimensions between the molecule (or fractions) of the dispersed compound and the tail of the surfactant.

Keywords: Classical nucleation theory; Emulsion; Heterogeneous nucleation; Surfactants; Template; Wetting.