• Gagliardi, Luca

Abstract

This thesis discusses the modeling of growth and dissolution of confined crystals. We focus on the dynamics within lubricated (or hydrophilic) contacts and derive a thin film continuum model accounting for diffusion, surface kinetics, hydrodynamics, surface tension and interactions with the substrate (disjoinining pressure). First, we study dissolution induced by an external load (pressure solution). We find the functional form of the disjoining pressure -finite or diverging at contact- to be crucial in determining steady state dissolution rates and morphologies. These forms respectively lead to load-dependent or load-independent dissolution rates, and to flat or pointy surface profiles.Second, we considered crystal growth in the vicinity of a flat wall. We found that a cavity appears on the confined crystal surface. We obtain a non-equilibrium morphology diagram in agreement with experimental observations. When crossing the transition line, a cavity can appear continuously or discontinuously depending on the form of the disjoining pressure (repulsive or attractive). For nanometric film thicknesses, viscosity can hinder the formation of the cavity.Finally, we study the force of crystallization exerted by a crystal growing between two flat walls. We point out the importance of a precise definition of the contact area to define the thermodynamic equilibrium pressure. During growth, the triple-line undergoes a kinetic pinning transition depending solely on the ratio between the diffusion constant and the product of the surface kinetic constant and distance between the walls. After this transition, the crystallization force decreases to zero, and a macroscopic film forms

Topics

• surface
• thin film
• viscosity
• crystallization