Oliver Bäumchen

Slip effects in polymer thin films

Probing the fluid dynamics of thin films is an excellent tool for studying the solid/liquid boundary condition. There is no need for external stimulation or pumping of the liquid, due to the fact that the dewetting process, an internal mechanism, acts as a driving force for liquid flow. Viscous dissipation, within the liquid, and slippage balance interfacial forces. Thus, friction at the solid/liquid interface plays a key role towards the flow dynamics of the liquid. Probing the temporal and spatial evolution of growing holes or retracting straight fronts gives, in combination with theoretical models, information on the liquid flow field and, especially, the boundary condition at the interface. We review the basic models and experimental results obtained during the last several years with exclusive regard to polymers as ideal model liquids for fluid flow. Moreover, concepts that aim to explain slippage on the molecular scale are summarized and discussed.

Solid capillarity: when and how does surface tension deform soft solids?

Soft solids differ from stiff solids in an important way: their surface stresses can drive large deformations. Based on a topical workshop held in the Lorentz Center in Leiden, this Opinion highlights some recent advances in the growing field of solid capillarity and poses key questions for its advancement.

Self-similarity and energy dissipation in stepped polymer films.

The surface of a thin liquid film with a nonconstant curvature is unstable, as the Laplace pressure drives a flow mediated by viscosity. We present the results of experiments on one of the simplest variable curvature surfaces: a thin polymer film with a step. Height profiles are measured as a function of time for a variety of molecular weights. The evolution of the profiles is shown to be self-similar. This self-similarity offers a precise measurement of the capillary velocity by comparison with numerical solutions of the thin film equation. We also derive a master expression for the time dependence of the excess free energy as a function of the material properties and film geometry. The experiment and theory are in excellent agreement and indicate the effectiveness of stepped polymer films to elucidate nanoscale rheological properties.

Influence of slip on the Plateau-Rayleigh instability on a fibre

The Plateau–Rayleigh instability of a liquid column underlies a variety of fascinating phenomena that can be observed in everyday life. In contrast to the case of a free liquid cylinder, describing the evolution of a liquid layer on a solid fibre requires consideration of the solid–liquid interface. Here we revisit the Plateau–Rayleigh instability of a liquid coating a fibre by varying the hydrodynamic boundary condition at the fibre–liquid interface, from no slip to slip. Although the wavelength is not sensitive to the solid–liquid interface, we find that the growth rate of the undulations strongly depends on the hydrodynamic boundary condition. The experiments are in excellent agreement with a new thin-film theory incorporating slip, thus providing an original, quantitative and robust tool to measure slip lengths.

Numerical solutions of thin-film equations for polymer flows

We report on the numerical implementation of thin-film equations that describe the capillary-driven evolution of viscous films, in two-dimensional configurations. After recalling the general forms and features of these equations, we focus on two particular cases inspired by experiments: the leveling of a step at the free surface of a polymer film, and the leveling of a polymer droplet over an identical film. In each case, we first discuss the long-term self-similar regime reached by the numerical solution before comparing it to the experimental profile. The agreement between theory and experiment is excellent, thus providing a versatile probe for nanorheology of viscous liquids in thin-film geometries.Graphical abstract

Capillary-driven flow induced by a stepped perturbation atop a viscous film

Thin viscous liquid films driven by capillarity are well described in the lubrication theory through the thin film equation. In this article, we present an analytical solution of this equation for a particular initial profile: a stepped perturbation. This initial condition allows a linearization of the problem making it amenable to Fourier analysis. The solution is obtained and characterized. As for a temperature step in the heat equation, self-similarity of the first kind of the full evolution is demonstrated and a long-term expression for the excess free energy is derived. In addition, hydrodynamical fields are described. The solution is then compared to experimental profiles from a model system: a polystyrene nanostep above the glass transition temperature which flows due to capillarity. The excellent agreement enables a precise measurement of the capillary velocity for this polymeric liquid, without involving any numerical simulation. More generally, as these results hold for any viscous system driven...

Solid surface structure affects liquid order at the polystyrene-self-assembled-monolayer interface.

We present a combined x-ray and neutron reflectivity study characterizing the interface between polystyrene (PS) and silanized surfaces. Motivated by the large difference in slip velocity of PS on top of dodecyl-trichlorosilane (DTS) and octadecyl-trichlorosilane (OTS) found in previous studies, these two systems were chosen for the present investigation. The results reveal the molecular conformation of PS on silanized silicon. Differences in the molecular tilt of OTS and DTS are replicated by the adjacent phenyl rings of the PS. We discuss our findings in terms of a potential link between the microscopic interfacial structure and dynamic properties of polymeric liquids at interfaces.

Vesicles-on-a-chip: A universal microfluidic platform for the assembly of liposomes and polymersomes

Abstract.In this study, we present a PDMS-based microfluidic platform for the fabrication of both liposomes and polymersomes. Based on a double-emulsion template formed in flow-focusing configuration, monodisperse liposomes and polymersomes are produced in a controlled manner after solvent extraction. Both types of vesicles can be formed from the exact same combination of fluids and are stable for at least three months under ambient storage conditions. By tuning the flow rates of the different fluid phases in the flow-focusing microfluidic design, the size of the liposomes and polymersomes can be varied over at least one order of magnitude. This method offers a versatile tool for future studies, e.g., involving the encapsulation of biological agents and the functionalization of artificial cell membranes, and might also be applicable for the controlled fabrication of hybrid vesicles.Graphical abstract

Nanofluidics of thin polymer films: Linking the slip boundary condition at solid–liquid interfaces to macroscopic pattern formation and microscopic interfacial properties

If a thin liquid film is not stable, different rupture mechanisms can be observed causing characteristic film morphologies: spinodal dewetting and dewetting by nucleation of holes. This rupturing entails liquid flow and opens new possibilities to study microscopic phenomena. Here we use this process of dewetting to gain insight on the slip boundary condition at the solid-liquid interface. Having established hydrodynamic models that allow for the determination of the slip length in a dewetting experiment based on nucleation, we move on to the quantification and molecular description of slip effects in various systems. For the late stage of the dewetting process involving the Rayleigh-Plateau instability, several distinct droplet patterns can be observed. We describe the importance of slip in determining what pattern may be found. In order to control the slip length, we use polymeric liquids on different hydrophobic coatings of silicon wafers. We find that subtle changes in the coating can lead to large changes in the slip length. Thus, we gain insight into the question of how the structure of the substrate affects the slip length.

Can liquids slide? Linking stability and dynamics of thin liquid films to microscopic material properties

Whether a lubricant or a coating wets a surface or not is of great technical importance. Theoretically, it is possible to predict the stability of a thin liquid film on a surface, since it is governed by the effective interface potential. In practice, however, a prediction can be quite cumbersome, since liquids as well as surfaces often consist of numerous components which all influence the effective interface potential. A molecular layer on a substrates surface like a self-assembled monolayer mainly changes the short-range potential whereas the composition of the substrate below the surface determines the long-range interactions such as the van der Waals potential. The interplay of short- and long-range interactions, including the dielectric properties of all layers in the case of van der Waals interactions, governs the stability of a liquid film. If the film is not stable, distinct rupture mechanisms can be observed causing characteristic film morphologies: spinodal dewetting and dewetting by nucleation of holes, which both entail liquid flow and reveal new routes to study microscopic parameters such as the hydrodynamic boundary condition at the solid/liquid interface. A rather old question turns out to become very important again: Can liquids slide? The article links stability and dynamics of thin liquid films to microscopic material properties and, moreover, describes their experimental access.