Effective interaction between large colloidal particles immersed in a bidisperse suspension of short-ranged attractive colloids.

The effective force between two large hard spheres mimicking lyophobic colloids (solute) immersed in an asymmetric two-component mixture of smaller particles (solvents), interacting via Baxter's sticky hard sphere (SHS) potential, was studied using integral equation theory and Monte Carlo simulation. The theoretical predictions were calculated from the analytic solution of the Percus-Yevick/Ornstein-Zernike integral equation for spatial correlations in a three-component mixture at vanishing solute concentration, while the simulation results were obtained by applying a special simulation technique developed for sampling the hard-sphere collision force. Due to layering of the solvent molecules, the effective force between the particles of the solute oscillates with periods equal to the molecular diameters of both solvent components. The attractive force between the solute particles in the SHS mixture comprising strongly attractive molecules of either component decays slower than that in the mixture with weaker interparticle attraction. Similar features are also observed when inspecting the separate contributions of individual components to the total solute-solute force. At sufficient strength of the interparticle stickiness, these oscillations disappear, the force becoming long ranged and attractive at all separations.

Depletion effects in a mixture of hard and attractive colloids.

Monte Carlo simulation and theory were used to study the potential of mean force (PMF) between a pair of big colloidal (solute) particles suspended in a sea of smaller particles (solvent) interacting via Baxter's sticky hard sphere (SHS) potential. Simulation results were obtained by applying a special simulation technique developed for sampling the hard sphere collision force, while the theoretical predictions were calculated from the analytic solution of the Percus-Yevick/Ornstein-Zernike integral equation for spatial correlations in a two-component mixture at vanishing solute concentration. Both theory and simulation revealed oscillations of the solute-solute PMF with a period equal to the diameter of the solvent molecules. Further, the attractive PMF between solute particles in the SHS fluid decays slower than in a hard sphere solvent. Upon increasing the strength of attraction (stickiness) between the molecules of solvent, these oscillations gradually disappear, the PMF becoming long ranged and attractive at all separations.

Local structures of fluid with discrete spherical potential: Theory and grand canonical ensemble Monte Carlo simulation.

Grand canonical Monte Carlo simulation and theoretical calculations based on Ornstein-Zernike (OZ) integral equation and third order+second order perturbation density functional theory (DFT) are performed to study a system of spherical particles interacting through a core-softened (CS) potential combining a repulsive square soft core and an attractive square well. Both theoretical predictions and simulation results reveal peculiar homogeneous and inhomogeneous local structures originating from the discontinuous nature of the CS potential. The bulk radial distribution function displays discontinuities at the distances coinciding with the ranges of the successive repulsive and attractive parts in the CS potential function. The density profiles of confined CS fluid show the shapes arising from the complex interplay among the steric effects and the competition between the repulsive and attractive parts of the CS potential. Satisfactory agreement between the theoretical results and simulation data leads to the following conclusions: (i) a modified hypernetted chain approximation combined with a hard sphere bridge function, which has been recently proposed by one of the authors of this study, is sufficiently reliable for the structural studies of CS fluid, and (ii) the third order+second order perturbation DFT, which has proven successful for the study of inhomogeneous structure of model fluids with continuous intermolecular potential function, posses a high adaptability to be applied for various types of interaction potentials and performs well also in the case of discontinuous CS model.

Simulating asymmetric colloidal mixture with adhesive hard sphere model.

Monte Carlo simulation and Percus-Yevick (PY) theory are used to investigate the structural properties of a two-component system of the Baxter adhesive fluids with the size asymmetry of the particles of both components mimicking an asymmetric binary colloidal mixture. The radial distribution functions for all possible species pairs, g(11)(r), g(22)(r), and g(12)(r), exhibit discontinuities at the interparticle distances corresponding to certain combinations of n and m values (n and m being integers) in the sum nsigma(1)+msigma(2) (sigma(1) and sigma(2) being the hard-core diameters of individual components) as a consequence of the impulse character of 1-1, 2-2, and 1-2 attractive interactions. In contrast to the PY theory, which predicts the delta function peaks in the shape of g(ij)(r) only at the distances which are the multiple of the molecular sizes corresponding to different linear structures of successively connected particles, the simulation results reveal additional peaks at intermediate distances originating from the formation of rigid clusters of various geometries.

Structural characterisation of water-Tween 40/Imwitor 308-isopropyl myristate microemulsions using different experimental methods.

Pharmaceutically usable microemulsion systems were prepared from water and isopropyl myristate with a constant amount of Tween 40 and Imwitor 308 at a mass ratio of 1. Their type and structure were examined by measuring density and surface tension, and by viscometry, electric conductivity, differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS), and the degree of agreement between the techniques was assessed. A model based on monodisperse hard spheres adequately fits the SAXS data in W/O microemulsions predicting, depending on composition, elongated or spherical droplets. It also suggests the involvement of strong attractive interactions in O/W systems. Results of conductivity, viscosity, density and surface tension measurements confirm the prediction of a percolation transition to a bicontinuous structure. DSC detects the degree of water interaction with surfactants thus identifying the type of microemulsion. The conclusions from all the techniques agree well and indicate that such studies could also be carried out on more complex systems. In future, the ability to determine type and structure of such microemulsion systems could enable partitioning and release rates of drugs from microemulsions to be predicted.