Instabilities in Drying Colloidal Films: Role of Surface Charge and Substrate Wettability

Abstract

The drying of colloidal suspensions leads to complex deposition patterns, accompanied by instabilities such as cracking and delamination. In this study, we experimentally investigate the coupled influence of particle surface charge and substrate wettability on the evaporation dynamics, final deposition morphology, and crack patterns of sessile droplets containing silica nanoparticles. We examine the dynamics of two types of colloids, namely the negatively charged colloidal silica nanoparticles (Ludox TM50) and the positively charged silica nanoparticle (Ludox CL30), at concentrations ranging from 0.1 to 5.0 weight percentages, deposited on glass, polystyrene, and polytetrafluoroethylene (PTFE) substrates with distinct wettability. Side and top-view imaging techniques are employed to capture the evaporation process and analyze the resulting cracks. Our results reveal that the nature of the particle charge and substrate wettability significantly affect the evaporation mode, with transitions observed between constant contact radius (CCR), constant contact angle (CCA), and mixed modes. TM50-laden droplets consistently exhibit radial cracks, whereas CL30 droplets display more randomly oriented and irregular cracks. At higher particle concentrations, TM50 suspensions form thicker deposits that undergo delamination, particularly on highly wettable substrates like glass. Quantitative analysis reveals that crack spacing and length follow power-law relationships with particle concentration. Additionally, the delamination behavior is strongly influenced by both the particle concentration and the type of substrate. We propose a mechanistic framework to explain the role of particle-substrate interactions in governing the observed cracking and delamination behaviors.