STUDY OF DEMULSIFICATION OF WATER-IN-CRUDE OIL EMULSION

Demulsification of water-in-crude oil emulsion was studied at two different salinities, 0.5% and 10% sodium chloride, using five different nonionic surfactants. Equilibrium crude oil-water interfacial tension was measured with drop volume method. Low molecular weight surfactants were found to be completely ineffective as demulsifiers. Three surfactants which were effective demulsifiers, exhibited good interfacial activity, surface adsorption and surface pressure. The performance of the demulsifiers changed with change in salinity of aqueous phase. Surfactants effective as demulsifiers reduced surface tension of water by more than 25 dynes-cm^-1. For a given crude oil-water system, the surfactant which developed surface pressure in excess of 15 dynes-cm^-1 was found to be good demulsifier for that system. Based upon these studies, a physical model of demulsification has been proposed     

Time-resolved and steady state spectroscopy of polydisperse colloidal silver nanoparticle samples

A signal due to coherently excited vibrational motion has been observed in polydisperse silver nanoparticle samples. The particles were synthesized via a wet chemistry seed mediated method, which yields different particle shapes, including spheres, rods, and irregular triangular-shaped particles. The measured vibrational periods were compared to the results from continuum mechanics calculations. This analysis shows that the observed signal arises from the triangular-shaped particles, rather than the rods or spheres. The period of vibration increases as the dimensions of the triangular-shaped particles increase; specifically, we find that the period is given by 2h/c(l), where h is the bisector of the triangle and c(l) is the longitudinal speed of sound in silver.     

Book Review

Summary Surface and Interfacial Tension Measurement, Theory and Applications Surfactant Science Series, Vol. 119; Edited by Stanley Hartland     

The effect of hydrodynamic coupling on the thinning of a film between a drop and its homophase

The rate of thinning of a film trapped between a drop approaching its homophase according to a model incorporating hydrodynamic coupling is dramatically different from earlier, uncoupled models. Implications for film thinning of microflows analyzed in the preceding paper are here investigated using similar analytical methods to derive a nonautonomous, nonlinear evolution equation for the film thickness which has been solved numerically under a variety of conditions after asymptotic analytical behavior has been extracted. The applied force squeezing the film, together with the initial motion in the three phases, determines the rate of film thinning in a complicated manner through the coupling parameter R = (ρ_Aμ_A/ρ_Bμ_B)^{$\text{1}\text{2}$}. Experimental observations that normal drop circulation enhances thinning, whereas reversed drop circulation can cause thickening, are predicted theoretically for the first time. Films much more viscous than their surroundings are found to thin faster than the converse case, a conclusion at odds with offhand intuition but substantiated experimentally; both classes of systems behave differently, often qualitatively so, from predictions of hydrodynamically decoupled systems, and in particular film thinning rates are generally faster because of less resistance to drainage, although the limit of vanishing R does recover the special case of Reynolds' model. For short times, films are shown analytically to thin more rapidly if there is initially outward film motion and normal drop circulation, but with decreasing effectiveness as R increases, in contrast to the effect of R for intermediate and longer times; if there is initially inward film motion, thickening tendencies are enhanced by reverse drop circulation but with decreasing effectiveness as R increases. These and other detailed conclusions, most predicted theoretically for the first time, are not only in qualitative agreement with experimental observations, they are in quantitative agreement with available data.     

Time-resolved spectroscopy of silver nanocubes: observation and assignment of coherently excited vibrational modes

The response of single crystal, cubic silver particles to ultrafast laser-induced heating has been examined experimentally and theoretically. The transient absorption traces display clear modulations due to coherently excited vibrational modes. Nanocube samples with edge lengths smaller than 50 nm show a single modulation, whereas samples larger than 50 nm show two vibrational modes. The results are compared to finite element calculations, where the cubes are modeled as having cubic crystal symmetry with the principal axes parallel to the sides of the particle. The action of the laser pulse is treated in two ways, first, as creating a uniform initial strain. In this case the predominant mode excited is the breathing mode. The period of this mode is in reasonable agreement with the vibrational periods measured for the smaller cubes and with the higher frequency modulation observed for the larger cubes. A nonuniform initial strain is also considered, which could arise from nonuniform heating for particles larger than the optical skin depth of the metal. In this case the predominant mode excited is a nontotally symmetric mode. The calculated periods from this analysis are in reasonable agreement with the lower frequency modulations observed for the larger samples. The results from this study show that, to within the accuracy of these measurements, the elastic constants of cubic silver nanoparticles are the same as bulk silver.     

Ultrafast laser studies of the photothermal properties of gold nanocages

Au nanocages were synthesized via a galvanic replacement reaction. The extinction peak of these hollow structured particles is shifted into the near-IR compared with the Ag nanocube templates. Energy transfer from the Au nanocages into the surrounding environment (water) as well as the coherently excited vibrational modes of the nanocages were studied by femtosecond pump-probe spectroscopy. The time scale for energy relaxation was found to increase with the size of the particles, with the relaxation time being independent of the laser intensity. The time scales for relaxation are comparable to those for solid spherical gold particles and are consistent with energy relaxation being controlled by heat dissipation in the solvent. The period of the coherently excited vibrational mode is proportional to the dimensions of the nanocages. Intensity-dependent measurements show that in solution the nanocages maintain their integrity up to lattice temperatures of 1100 +/- 100 K.     

Electronic dephasing in bimetallic gold-silver nanoparticles examined by single particle spectroscopy

The scattering spectra of single gold, silver, and bimetallic gold-silver particles (both core-shell and alloyed) have been examined using dark-field microscopy. The results show that the plasmon resonances for the bimetallic particles are broader than those of the pure silver or pure gold particles. However, plots of the width of the plasmon resonance vs resonance frequency for the core-shell and alloyed samples are very similar. This implies that the broadening is due to the frequency dependence of the dielectric constants of the particles. For the core-shell particles, scattering at the interface between the two metals does not seem to be a significant effect.