Nanoscale colloidal particles display fascinating electronic, optical and reinforcement properties as a consequence of their dimensions. Stable dispersions of nanoscale colloids find applications in drug delivery, biodiagnostics, photonic and electronic devices, and polymer nanocomposites. Most nanoparticles are unstable in dispersions and polymeric surfactants are added generally to improve dispersability and control self-assembly. However, the effect of polymeric modifiers on nanocolloid properties is poorly understood and design of modifiers is guided usually by empirical approaches. Monte Carlo simulations are used to gain a fundamental molecular-level understanding of the effect of modifiers properties on the thermodynamics and interaction forces of nanoscale colloidal particles. A novel method based on the expanded ensemble Monte Carlo technique has been developed for calculation of the chemical potential of colloidal particles in colloid-polymer mixtures (CPM). Using this method, the effect of molecular parameters like colloid diameter, polymer chain length, colloid-polymer interaction strength, and colloid and polymer concentrations, on the colloid chemical potential is investigated for both hard-sphere and attractive Lennard-Jones CPM. The presence of short-chain polymeric modifiers reduces the colloid chemical potential in attractive as well as athermal systems. In attractive CPM, there is a strong correlation between polymer adsorption and colloid chemical potential, as both show a similar dependence on the polymer molecular weight. Based on the simulation results, simple scaling relationships are proposed that capture the functional dependence of the thermodynamic properties on the molecular parameters. The polymer-induced interaction forces between the nanoparticles have been calculated as a function of the above parameters for freely-adsorbing and end-grafted homopolymer modifiers. The polymer-induced force profiles are used to identify design criteria for effective modifiers. Adsorbing modifiers give rise to attractive interactions between the nanoparticles over the whole parameter range explored in this study. Grafted surface modifiers lead to attraction or repulsion based on the polymer chain length and grafting density. The polymer-induced attraction in both adsorbing and grafted modifiers is attributed primarily to polymer intersegmental interactions and bridging. The location of the thermodynamic minimum corresponding to the equilibrium particle spacing in nanoparticle-polymer mixtures can be controlled by tuning the modifier properties.

Interfacial instabilities and wetting phenomena of phase separated colloid-polymer mixtures are addressed in this study. Colloidal particles offer certain advantages over molecular systems, due to their larger lengthscales and slower timescales. Moreover, the phenomena can be directly visualised using laser scanning confocal microscopy, and a perfect match with soft-lithography fabrication techniques can be exploited. In particular, we study the viscous fingering instability in three dimensions, focusing on the role of wetting conditions and of thermal fluctuations. Combined with results obtained by lattice Boltzmann simulations, we reveal that the cross-over of the meniscus in the direction across the channel thickness is controlled by the capillary and Peclet numbers, and viscosity contrast of the system. The curvature of the meniscus has a pronounced effect on the onset of the Saffman-Taylor instability, in which the formation of the viscous fingers is suppressed up to a certain threshold. Furthermore, we investigate a related contact line instability, which leads to entrainment and subsequent droplet pinch-off. A theoretical prediction for the onset of the instability is developed, which shows a good agreement with the experimental observations and yields a method to directly measure the slip length of the interface. The large thermal fluctuations of our interface play an important role in pinch-off events, leading to periodic emission of droplets of similar sizes. Finally, we study wetting phenomena at geometrically sculpted walls. We focus on the shape, the thickness and the radius of curvature of the adsorbed liquid film, and find good agreement with theory. Changing the curvature of the wedge from a flat surface to a capil- lary slit furthermore smoothly connects wetting behaviour and capillary condensation, again in qualitative agreement with theory. Non-equilibrium effects may interfere with the data and are difficult to rule out. We end with recommendations for future work.