Growth of gold nanoparticle films driven by the coalescence of particle-stabilized emulsion drops.

We have investigated the mechanism of the spontaneous growth of a gold nanoparticle film on a container wall when an aqueous dispersion of gold nanoparticles is shaken with an oil phase containing octadecylamine, as first described by Mayya and Sastry (Mayya, K. S.; Sastry, M. Langmuir 1999, 15, 1902.). Experimental evidence is described, which shows that the film growth is driven by the coalescence of particle-coated emulsion drops with the flat oil-water interface separating the oil and water phases.

Optical microscope absorbance imaging of carbon black nanoparticle films at solid and liquid surfaces.

We have used an optical transmission microscope equipped with a digital camera and fitted with a narrow-band-pass filter to obtain absorbance images consisting of an array of pixel absorbance values. Absorbance images of films of carbon nanoparticles were used to derive spatially resolved images of the carbon film thicknesses with a resolution in the thickness dimension of a few nanometers. The technique was applied to the characterization of carbon nanoparticle films at cellulose-coated glass surfaces and at the oil-water interfaces of emulsion drops. For the emulsions, it was necessary to use oil and water phases of equal refractive index to avoid artifacts due to the drops acting as lenses.

Evaporation rates of water from concentrated oil-in-water emulsions.

We have investigated the rate of water evaporation from concentrated oil-in-water (o/w) emulsions containing an involatile oil. Evaporation of the water continuous phase causes compression of the emulsion with progressive distortion of the oil drops and thinning of the water films separating them. Theoretically, the vapor pressure of water is sensitive to the interdroplet interactions, which are a function of the film thickness. Three main possible situations are considered. First, under conditions when the evaporation rate is controlled by mass transfer across the stagnant vapor phase, model calculations show that evaporation can, in principle, be slowed by repulsive interdroplet interactions. However, significant retardation requires very strong repulsive forces acting over large separations for typical emulsion drop sizes. Second, water evaporation may be limited by diffusion in the network of water films within the emulsion. In this situation, water loss by evaporation from the emulsion surface leads to a gradient in the water concentration (and in the water film thickness). Third, compression of the drops may lead to coalescence of the emulsion drops and the formation of a macroscopic oil film at the emulsion surface, which serves to prevent further water evaporation. Water mass-loss curves have been measured for silicone o/w emulsions stabilized by the anionic surfactant SDS as a function of the water content, the thickness of the stagnant vapor-phase layer, and the concentration of electrolyte in the aqueous phase, and the results are discussed in terms of the three possible scenarios just described. In systems with added salt, water evaporation virtually ceases before all the water present is lost, probably as a result of oil-drop coalescence resulting in the formation of a water-impermeable oil film at the emulsion surface.

Measurement of long-range repulsive forces between charged particles at an oil-water interface.

Using a laser tweezers method, we have determined the long-range repulsive force as a function of separation between two charged, spherical polystyrene particles (2.7 microm diameter) present at a nonpolar oil-water interface. At large separations (6 to 12 microm between particle centers) the force is found to decay with distance to the power -4 and is insensitive to the ionic strength of the aqueous phase. The results are consistent with a model in which the repulsion arises primarily from the presence of a very small residual electric charge at the particle-oil interface. This charge corresponds to a fractional dissociation of the total ionizable (sulfate) groups present at the particle-oil surface of approximately 3 x 10(-4).