Impact of fluid memory on wetting approaching the air entrainment limit.

The high shear rates innate to the flow fields near a moving contact line suggest that non-Newtonian behavior in a fluid should impact its dynamic wetting behavior. We compare the dynamic wetting behavior of an elastic Boger fluid with its Newtonian base fluid to probe the impact of slow (on the order of seconds) relaxation modes on dynamic wetting as the air entrainment limit is approached and the Weissenberg number is of order one.

Dynamic wetting with viscous Newtonian and non-Newtonian fluids.

We examine various aspects of dynamic wetting with viscous Newtonian and non-Newtonian fluids. Rather than concentrating on the mechanisms that relieve the classic contact line stress singularity, we focus on the behavior in the wedge flow near the contact line which has the dominant influence on wetting with these fluids. Our experiments show that a Newtonian polymer melt composed of highly flexible molecules exhibits dynamic wetting behavior described very well by hydrodynamic models that capture the critical properties of the Newtonian wedge flow near the contact line. We find that shear thinning has a strong impact on dynamic wetting, by reducing the drag of the solid on the fluid near the contact line, while the elasticity of a Boger fluid has a weaker impact on dynamic wetting. Finally, we find that other polymeric fluids, nominally Newtonian in rheometric measurements, exhibit deviations from Newtonian dynamic wetting behavior.

Dynamic wetting of Boger fluids.

The impact of fluid elasticity on the dynamic wetting of polymer solutions is important because many polymer solutions in technological use exhibit non-Newtonian behaviors in the high shear environment of the wedge-like flow near a moving contact line. Our former study [G.K. Seevaratnam, Y. Suo, E. Ramé, L.M. Walker, Phys. Fluids 19 (2007) Art. No. 012103] showed that shear thinning induced by a semi-flexible high molecular weight polymer reduces the viscous bending near a moving contact line as compared to a Newtonian fluid having the same zero-shear viscosity. This results in a dramatic reduction of the dependence of the effective dynamic contact angle on contact line speed. In this paper, we discuss dynamic wetting of Boger fluids which exhibit elasticity-dominated rheology with minimal shear thinning. These fluids are prepared by dissolving a dilute concentration of high molecular weight polymer in a "solvent" of the oligomer of the polymer. We demonstrate that elasticity in these fluids increases curvature near the contact line but that the enhancement arises mostly from the weakly non-Newtonian behavior already present in the oligomeric solvent. We present evidence of instabilities on the liquid/vapor interface near the moving contact line.

Unsteady motion of receding contact lines of surfactant solutions: the role of surfactant re-self-assembly.

Re-self-assembly of surfactant molecules must occur at moving contact lines of soluble surfactant solutions. Molecules are transported into and out of the contact line region from four sources: the three interfaces meeting at the contact line and the fluid confined between the solid-liquid and liquid-vapor interfaces. As molecules move among these sources at the contact line, they must rearrange. The dynamics of this re-self-assembly has been shown to have a dominating effect on the structure of advancing contact lines, causing unsteady motion and complex structure of the contact line. It might be assumed that the re-self-assembly for receding contact lines leads to more steady contact line movement. However, in this article we show that for a wide variety of systems this is not true. Quasi-static distortions of the contact line occur as it retreats because of the inability of the surfactant to completely re-self-assemble at localized positions along the contact line.

Wetting by simple room-temperature polymer melts: deviations from Newtonian behavior.

The hydrodynamics near moving contact lines of two room-temperature polymer melts, polyisobutylene (PIB) and polystyrene (PS), are different from those of a third polymer melt, polydimethylsiloxane (PDMS). While all three fluids exhibit Newtonian behavior in rotational rheological measurements, a model of the hydrodynamics near moving contact lines which assumes Newtonian behavior of the fluid accurately describes the interface shape of a variety of PDMS fluids but fails to describe the interface deformation by viscous forces in PIB and PS. The magnitude of the deviations from the model and the distance along the liquid-vapor interface over which they are seen increase with increasing capillary number. We conclude that the wetting behaviors of PIB and PS are influenced by weak elasticity in these low molecular weight melts and that dynamic wetting is more sensitive to this elasticity than standard rheometric techniques.

Characterizing the microscopic physics near moving contact lines using dynamic contact angle data.

Directly probing the fluid flow and liquid-vapor interface shape in the microscopic immediate vicinity of the moving contact line can only be accomplished in very specific and isolated cases. Yet this physics is critical to macroscopic dynamic wetting. Here we examine the microscopic (or inner) physics of spreading silicone fluids using data of macroscopic dynamic contact angle versus Capillary number Ca=U mu/sigma. This dynamic contact angle is precisely defined so that it can be related back to the microscopic behavior through detailed theory. Our results indicate that the parameters describing the inner region have a detectable dependence on spreading velocity when this velocity exceeds a critical value. This dependence is not scaled (i.e., the data are not collapsed) by Ca, which suggests that an additional time scale must be present in the model of the inner region.

Using x-ray reflectivity to determine the structure of surfactant monolayers

Interactions among the multiple degrees of freedom of surfactant molecules cause fascinating richness in the structure of their monolayers. Beyond this scientific motivation for studying surfactant monolayers, the technological use of monolayers for interfacial control and molecular assembly demands a clear understanding of monolayer structure. X-ray and neutron reflectivity have become prime techniques for determining this structure. We present x-ray reflectivity data for a representative surfactant monolayer system and outline an objective procedure for obtaining the maximum amount of structural information possible. Our approach combines tight control of instrumental parameters, dynamically optimized Monte Carlo and simulated annealing to probe the chi(2) hypersurface, and a set of statistical criteria for accepting and rejecting fits. We justify our procedure through tests using simulated data. Results indicate that an ensemble of fits must be performed for each set of reflectivity data in order to survey the chi(2) hypersurface adequately. A single good fit may yield structural parameters which are quite misleading, yet physically plausible. Thus, one must never be satisfied with performing just a single fit. In cases for which multiple, statistically equivalent fits are obtained, the apparent ambiguity is substantially mitigated by averaging the parameters over the ensemble of good fits. We also introduce a method of dealing with cases for which a good fit may be extremely difficult to find. Our analysis procedures can be generalized to other monolayer or multilayer systems and are also applicable to neutron reflectivity.

Reconstruction of bowing point friction force in a bowed string

A method is presented for reconstructing the friction force and the velocity at the bowing point of a string excited by a rosined bow sliding transverse to the string. Two versions of the method of reconstruction are presented, each approximate in different ways, but both capable of sufficient accuracy to allow useful application to problems of understanding frictional interactions in this dynamical system. The method is illustrated with simulated data to verify its accuracy, and results are shown for two contrasting cases of observed stick-slip string motion. As has been found in other investigations, the friction force during sliding is not determined by the instantaneous sliding speed. The results seem to be compatible with a thermally based model of rosin friction.

Elongation of confined ferrofluid droplets under applied fields.

Ferrofluids are strongly paramagnetic liquids. We study the behavior of ferrofluid droplets confined between two parallel plates with a weak applied field parallel to the plates. The droplets elongate under the applied field to reduce their demagnetizing energy and reach an equilibrium shape where the magnetic forces balance against the surface tension. This elongation varies logarithmically with aspect ratio of droplet thickness to its original radius, in contrast to the behavior of unconfined droplets. Experimental studies of a ferrofluid-water-surfactant emulsion confirm this prediction.

Microscopic and Macroscopic Dynamic Interface Shapes and the Interpretation of Dynamic Contact Angles.

We have studied shapes of dynamic fluid interfaces at distances 0.01. Our measured dynamic contact angle parameter extracted by fitting the analysis with viscous deformation to the shape near the moving contact line coincides with the contact angle of the static-like shape far from the contact line. We measure and explain the discrepancy between this dynamic contact angle parameter and the apparent contact angles based on meniscus or apex heights. Our observations of viscous effects at large distances from the contact line have implications for dynamic contact angle measurements in capillary tubes.

Fluorescent lifetimes of molecules on silver-island films.

The fluorescence of molecules on silver-island films exhibits nonexponential decay and is several orders of magnitude more rapid than on a silica surface, while the total emission intensity is slightly increased. This behavior results from the electromagnetic coupling between the fluorescing molecules and the plasmon resonances of the silver islands. We obtain good agreement with a model that uses the same theory for the electromagnetic coupling as has been used to account for surface-enhanced Raman scattering.

Excitation spectra of surface-enhanced Raman scattering on silver-island films.

Both the spectral dependence and the magnitude of the excitation spectra of surface-enhanced Raman scattering are found to be quantitatively related to the absorption spectra for silver-island films. This relationship is maintained even when the local electromagnetic enhancement at the islands is varied by coating the film with a layer of absorbing dye molecules. The results illustrate a simple experimental way to determine independently the role of the electronic plasma resonances in the enhancement process on these films and shed new insights into the details of the electromagnetic interactions responsible for surface-enhanced Raman scattering.

Optical absorption resonances of dye-coated silver-island films.

We have used Mie theory to account for the features of the transmission spectra of dye-coated silver-island films. The unusual behavior of the spectra arises from the effect of the dispersion and damping of the optical response of the absorbing coating on the structural resonances of the silver islands. Our modeling indicates that the power dissipation in the dye coating is enhanced compared with the dissipation of dye deposited on a nonresonant structure. These results help elucidate the excitation mechanisms of Raman and fluorescent emission of adsorbates at rough silver interfaces.

Optical characterization of powders: the use of Mie theory and composite media models.

The measurement of the optical response of materials occurring as finely divided powders is difficult due to the complex interaction of the optical wave with the material. Guided by methods used to study the optical properties of composite media, we have developed experimental and theoretical techniques for characterizing the optical properties of powders. We have applied these techniques to two supported catalysts and have observed several optical effects arising from the very small particle size of these materials.