ABSTRACT
Hard-core/soft shell (HCSS) particles have been shown to self-assemble into a remarkably rich variety of structures under compression due to the simple interplay between the hard-core and soft-shoulder length scales in their interactions. Most studies in this area model the soft shell interaction as a square shoulder potential. Although appealing from a theoretical point of view, the potential is physically unrealistic because there is no repulsive force in the soft shell regime, unlike in experimental HCSS systems. To make the model more realistic, here we consider HCSS particles with a range of soft shell potential profiles beyond the standard square shoulder form and study the model using both minimum energy calculations and Monte Carlo simulations. We find that by tuning density and the soft shell profile, HCSS particles in the thin shell regime (i.e., shell to core ratio ) can form a large range of structures, including hexagons, chains, squares, rhomboids and two distinct zig-zag structures. Furthermore, by tuning the density and r1/r0, we find that HCSS particles with experimentally realistic linear ramp soft shoulder repulsions can form honeycombs and quasicrystals with 10-fold and 12-fold symmetry. Our study therefore suggests the exciting possibility of fabricating these exotic 2D structures experimentally through colloidal self-assembly.
ABSTRACT
The adsorption of colloidal particles to fluid interfaces is a phenomenon that is of interest to multiple disciplines across the physical and biological sciences. In this review we provide an entry level discussion of our current understanding on the physical principles involved and experimental observations of the adsorption of a single isolated particle to a liquid-liquid interface. We explore the effects that a variation of the morphology and surface chemistry of a particle can have on its ability to adhere to a liquid interface, from a thermodynamic as well as a kinetic perspective, and the impact of adsorption behaviour on potential applications. Finally, we discuss recent developments in the measurement of the interfacial behaviour of nanoparticles and highlight open questions for future research.
ABSTRACT
Spherical colloidal particles generally self-assemble into hexagonal lattices in two dimensions. However, more complex, non-hexagonal phases have been predicted theoretically for isotropic particles with a soft repulsive shoulder but have not been experimentally realized. We study the phase behavior of microspheres in the presence of poly(N-isopropylacrylamide) (PNiPAm) microgels at the air/water interface. We observe a complex phase diagram, including phases with chain and square arrangements, which exclusively form in the presence of the microgels. Our experimental data suggests that the microgels form a corona around the microspheres and induce a soft repulsive shoulder that governs the self-assembly in this system. The observed structures are fully reproduced by both minimum energy calculations and finite temperature Monte Carlo simulations of hard core-soft shoulder particles with experimentally realistic interaction parameters. Our results demonstrate how complex, anisotropic assembly patterns can be realized from entirely isotropic building blocks by control of the interaction potential.
ABSTRACT
The interaction between micron-sized charged colloidal particles at polar/non-polar liquid interfaces remains surprisingly poorly understood for a relatively simple physical chemistry system. By measuring the pair correlation function g(r) for different densities of polystyrene particles at the decane-water interface, and using a powerful predictor-corrector inversion scheme, effective pair-interaction potentials can be obtained up to fairly high densities, and these reproduce the experimental g(r) in forward simulations, so are self consistent. While at low densities these potentials agree with published dipole-dipole repulsion, measured by various methods, an apparent density dependence and long range attraction are obtained when the density is higher. This condition is thus explored in an alternative fashion, measuring the local mobility of colloids when confined by their neighbors. This method of extracting interaction potentials gives results that are consistent with dipolar repulsion throughout the concentration range, with the same magnitude as in the dilute limit. We are unable to rule out the density dependence based on the experimental accuracy of our data, but we show that incomplete equilibration of the experimental system, which would be possible despite long waiting times due to the very strong repulsions, is a possible cause of artefacts in the inverted potentials. We conclude that to within the precision of these measurements, the dilute pair potential remains valid at high density in this system.
ABSTRACT
We study the structure of binary monolayers of large (3 µm diameter) very hydrophobic (A) and large (3 µm diameter) hydrophilic (B) or small (1 µm diameter) hydrophilic (C) silica particles at an octane-water interface. By tuning the composition and packing geometry of the mixed monolayer, we find that a rich variety of two-dimensional hexagonal superlattices of mixed A/B or A/C clusters are formed, stabilized by short-ranged electrostatic induced dipole interactions. The cluster structures obtained are in excellent agreement with zero temperature calculations, indicating that the self-assembly process can be effectively controlled.
ABSTRACT
We study the structure of mixed monolayers of large (3 µm diameter) and small (1 µm diameter) very hydrophobic silica particles at an octane-water interface as a function of the number fraction of small particles ξ. We find that a rich variety of two-dimensional hexagonal super-lattices of large (A) and small (B) particles can be obtained in this system due to strong and long-range electrostatic repulsions through the nonpolar octane phase. The structures obtained for the different compositions are in good agreement with zero temperature calculations and finite temperature computer simulations.
