Olga I. Vinogradova

Slippage of Water over Hydrophobic Surfaces

When water is confined between hydrophobic surfaces, its flow properties are significantly different from those in bulk, or between hydrophilic surfaces. These changes (that are usually ignored) may be interpreted in terms of hydrophobic slippage. This chapter reviews recent developments in the hydrodynamics of water confined between solid hydrophobic surfaces, emphasizing the main experimental facts, theoretical models suggested, and different aspects of thin film drainage. The relevance of slippage in hydrophobic surface force measurements and on the coagulation rate of hydrophobic particles is discussed.

Wetting, roughness and flow boundary conditions

We discuss how the wettability and roughness of a solid impacts its hydrodynamic properties. We see in particular that hydrophobic slippage can be dramatically affected by the presence of roughness. Owing to the development of refined methods for setting very well controlled micro- or nanotextures on a solid, these effects are being exploited to induce novel hydrodynamic properties, such as giant interfacial slip, superfluidity, mixing and low hydrodynamic drag, that could not be achieved without roughness.

Tensorial hydrodynamic slip

We describe a tensorial generalization of the Navier slip boundary condition and illustrate its use in solving for flows around anisotropic textured surfaces. Tensorial slip can be derived from molecular or microstructural theories or simply postulated as a constitutive relation, subject to certain general constraints on the interfacial mobility. The power of the tensor formalism is to capture complicated effects of surface anisotropy, while preserving a simple fluid domain. This is demonstrated by exact solutions for laminar shear flow and pressure-driven flow between parallel plates of arbitrary and different textures. From such solutions, the effects of rotating a texture follow from simple matrix algebra. Our results may be useful for extracting local slip tensors from global measurements, such as the permeability of a textured channel or the force required to move a patterned surface, in experiments or simulations.

Elasticity of polyelectrolyte multilayer microcapsules

We present a novel approach to probe elastic properties of polyelectrolyte multilayer microcapsules. The method is based on measurements of the capsule load-deformation curves with the atomic force microscope. The experiment suggests that at low applied load deformations of the capsule shell are elastic. Using elastic theory of membranes we relate force, deformation, elastic moduli, and characteristic sizes of the capsule. Fitting to the prediction of the model yields the lower limit for Youngs modulus of the polyelectrolyte multilayers of the order of 1-100 MPa, depending on the template and solvent used for its dissolution. These values correspond to Youngs modulus of an elastomer.

Surface roughness and hydrodynamic boundary conditions

We report results of investigations of a high-speed drainage of thin aqueous films squeezed between randomly nanorough surfaces. A significant decrease in the hydrodynamic resistance force as compared with that predicted by Taylors equation is observed. However, this reduction in force does not represent the slippage. The measured force is exactly the same as that between equivalent smooth surfaces obeying no-slip boundary conditions, but located at the intermediate position between peaks and valleys of asperities. The shift in hydrodynamic thickness is shown to be independent of the separation and/or shear rate. Our results disagree with previous literature data reporting very large and shear-dependent boundary slip for similar systems.

Effective slip over superhydrophobic surfaces in thin channels.

Superhydrophobic surfaces reduce drag by combining hydrophobicity and roughness to trap gas bubbles in a microscopic texture. Recent work has focused on specific cases, such as arrays of pillars or grooves, with limited theoretical guidance. Here, we consider the experimentally relevant limit of thin channels and obtain rigorous bounds on the effective slip length for any two-component (e.g., low-slip and high-slip) texture with given area fractions. Among all anisotropic textures, parallel stripes attain the largest (or smallest) possible slip in a straight, thin channel for parallel (or perpendicular) orientation with respect to the mean flow. Tighter bounds for isotropic textures further constrain the effective slip. These results provide a framework for the rational design of superhydrophobic surfaces.

Mechanical properties of polyelectrolyte multilayer microcapsules

Polyelectrolyte multilayer microcapsules were recently suggested as a new type of nanoengineered microstructures and are potentially important in many areas of science and technology. The present review focuses on the mechanics of these microstructures, emphasizing novel experimental approaches and the main experimental observations. Methods based on confocal and atomic force microscopy—osmotic buckling, osmotic swelling, and compression experiments—are detailed. Also covered is the preparation of multilayer microcapsules and various encapsulation techniques. A discussion of the theoretical models suggested is given. Special emphasis is given to the analysis of experimental data. This covers regimes of deformations, the roles of elasticity and permeability in determining the capsule stiffness, the effects of ageing, molecular weight, pH, salt concentration, and organic solvent on the multilayer shell properties, a contribution from encapsulated (charged and neutral) polymers, and more.

Hydrodynamic slippage inferred from thin film drainage measurements in a solution of nonadsorbing polymer

Thin film drainage measurements are presented for submicron films of an “ideal elastic” or Boger fluid, which is a high molecular weight polymer solution in a high viscosity solvent. The measurements are made in a surface force apparatus, with the fluid being squeezed between two mica surfaces in a crossed cylinder geometry and the film thickness measured as a function of time to study its drainage behavior. No equilibrium surface forces are detected in this system, indicating that the polymer is nonadsorbing. The effect of fluid elasticity is predicted to make drainage more rapid in a Boger fluid than for the equivalent Newtonian fluid. Qualitatively this is what is observed for films less than 600 nm thick, but the drainage is even more rapid than predicted for the elastic fluid. To account for this, it is suggested that slippage is occurring at the fluid–solid interfaces, and the data is analyzed in terms of a simple slip model. The slip length required to fit the data is in the range 30–50 nm.

Effective slip in pressure-driven flow past super-hydrophobic stripes

A super-hydrophobic array of grooves containing trapped gas (stripes) has the potential to greatly reduce drag and enhance mixing phenomena in microfluidic devices. Recent work has focused on idealized cases of stick-perfect slip stripes. Here, we analyse the experimentally more relevant situation of a pressure-driven flow past striped slip-stick surfaces with arbitrary local slip at the gas sectors. We derive approximate formulas for maximal (longitudinal) and minimal (transverse) directional effective slip lengths that are in a good agreement with the exact numerical solution for any surface slip fraction. By representing eigenvalues of the slip length tensor, we obtain the effective slip for any orientation of stripes with respect to the mean flow. Our results imply that flow past stripes is controlled by the ratio of the local slip length to texture size. In the case of a large (compared to the texture period) slip at the gas areas, surface anisotropy leads to a tensorial effective slip, by attaining the values predicted earlier for a perfect local slip. Both effective slip lengths and anisotropy of the flow decrease when local slip becomes of the order of texture period. In the case of a small slip, we predict simple surface-averaged isotropic flows (independent of orientation).

Direct measurements of hydrophobic slippage using double-focus fluorescence cross-correlation.

We report the results of direct measurements of velocity profiles in a microchannel with hydrophobic and hydrophilic walls, using a new high-precision method of double-focus spatial fluorescence cross correlation under a confocal microscope. In the vicinity of both walls the measured velocity profiles do not go to zero by supplying a plateau of constant velocity. This apparent slip is proven to be due to a Taylor dispersion, an augmentation by shear diffusion of nanotracers in the direction of flow. Comparing the velocity profiles near the hydrophobic and hydrophilic walls for various conditions shows that there is a true slip length due to hydrophobicity. This length, of the order of several tens of nanometers, is independent of the electrolyte concentration and shear rate.