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The adsorption of single colloidal microparticles (0.5--1 $\mu$m radius) at awater-oil interface has been recently studied experimentally using digitalholographic microscopy [Kaz \textit{et al., Nat. Mater.}, 2012, \textbf{11},138--142]. An initially fast adsorption dynamics driven by capillary forces isfollowed by an unexpectedly slow relaxation to equilibrium that is logarithmicin time and can span hours or days. The slow relaxation kinetics has beenattributed to the presence of surface "defects" with nanoscale dimensions(1--5\,nm) that induce multiple metastable configurations of the contact lineperimeter. A kinetic model considering thermally activated transitions betweensuch metastable configurations has been proposed [Colosqui \textit{et al.,Phys. Rev. Lett.}, 2013, \textbf{111}, 028302] to predict both the relaxationrate and the crossover point to the slow logarithmic regime. However, theadsorption dynamics observed experimentally before the crossover point hasremained unstudied. In this work, we propose a Langevin model that is able todescribe the entire adsorption process of single colloidal particles byconsidering metastable states produced by surface defects and thermal motion ofthe particle and liquid interface. Invoking the fluctuation dissipationtheorem, we introduce a drag term that considers significant dissipative forcesinduced by thermal fluctuations of the liquid interface. Langevin dynamicssimulations based on the proposed adsorption model yield close agreement withexperimental observations for different microparticles, capturing the crossoverfrom (fast) capillary driven dynamics to (slow) thermally activated kinetics.

Colloidal particle adsorption at liquid interfaces: Capillary driven dynamics and thermally activated kinetics