Petra Uhlmann

Wetting gradient induced separation of emulsions: A combined experimental and lattice Boltzmann computer simulation study

Guided motion of emulsions is studied via combined experimental and theoretical investigations. The focus of the work is on basic issues related to driving forces generated via a stepwise (abrupt) change in wetting properties of the substrate along a given spatial direction. Experiments on binary emulsions unambiguously show that selective wettability of one of the fluid components (water in our experiments) with respect to the two different parts of the substrate is sufficient in order to drive the separation process. These studies are accompanied by approximate analytic arguments as well as lattice Boltzmann computer simulations, focusing on effects of a wetting gradient on internal droplet dynamics as well as its relative strength compared to volumetric forces driving the fluid flow. These theoretical investigations show a qualitatively different dependence of wetting gradient induced forces on contact angle and liquid volume in the case of an open substrate as opposed to a planar channel. In particular, for the parameter range of our experiments, slit geometry is found to give rise to considerably higher separation forces as compared to open substrate.Guided motion of emulsions is studied via combined experimental and theoretical investigations. The focus of the work is on basic issues related to driving forces generated via a stepwise (abrupt) change in wetting properties of the substrate along a given spatial direction. Experiments on binary emulsions unambiguously show that selective wettability of one of the fluid components (water in our experiments) with respect to the two different parts of the substrate is sufficient in order to drive the separation process. These studies are accompanied by approximate analytic arguments as well as lattice Boltzmann computer simulations, focusing on effects of a wetting gradient on internal droplet dynamics as well as its relative strength compared to volumetric forces driving the fluid flow. These theoretical investigations show a qualitatively different dependence of wetting gradient induced forces on contact angle and liquid volume in the case of an open substrate as opposed to a planar channel. In particula...

Stability and dynamics of droplets on patterned substrates: insights from experiments and lattice Boltzmann simulations

The stability and dynamics of droplets on solid substrates are studied both theoretically and via experiments. Focusing on our recent achievements within the DFG-priority program 1164 (Nano- and Microfluidics), we first consider the case of (large) droplets on the so-called gradient substrates. Here the term gradient refers to both a change of wettability (chemical gradient) or topography (roughness gradient). While the motion of a droplet on a perfectly flat substrate upon the action of a chemical gradient appears to be a natural consequence of the considered situation, we show that the behavior of a droplet on a gradient of topography is less obvious. Nevertheless, if care is taken in the choice of the topographic patterns (in order to reduce hysteresis effects), a motion may be observed. Interestingly, in this case, simple scaling arguments adequately account for the dependence of the droplet velocity on the roughness gradient (Moradi et al 2010 Europhys. Lett. 89 26006). Another issue addressed in this paper is the behavior of droplets on hydrophobic substrates with a periodic arrangement of square shaped pillars. Here, it is possible to propose an analytically solvable model for the case where the droplet size becomes comparable to the roughness scale (Gross et al 2009 Europhys. Lett. 88 26002). Two important predictions of the model are highlighted here. (i) There exists a state with a finite penetration depth, distinct from the full wetting (Wenzel) and suspended (Cassie-Baxter, CB) states. (ii) Upon quasi-static evaporation, a droplet initially on the top of the pillars (CB state) undergoes a transition to this new state with a finite penetration depth but then (upon further evaporation) climbs up the pillars and goes back to the CB state again. These predictions are confirmed via independent numerical simulations. Moreover, we also address the fundamental issue of the internal droplet dynamics and the terminal center of mass velocity on a flat substrate.

Structure and flow of droplets on solid surfaces

The structure and flow of droplets on solid surfaces is investigated with imaging and scattering techniques and compared to simulations. To access nanostructures at the liquid-solid interface advanced scattering techniques such as grazing incidence small-angle x-ray scattering (GISAXS) with micro- and nanometer-sized beams, GISAXS and in situ imaging ellipsometry and GISAXS tomography are used. Using gold nanoparticle suspensions, structures observed in the wetting area due to deposition are probed in situ during the drying of the droplets. After drying, nanostructures in the wetting area and inside the dried droplets are monitored. In addition to drying, a macroscopic movement of droplets is caused by body forces acting on an inclined substrate. The complexity of the solid surfaces is increased from simple silicon substrates to binary polymer brushes, which undergo a switching due to the liquid in the droplet. Nanostructures introduced in the polymer brush due to the movement of droplets are observed.

Microfluidic emulsion separation—simultaneous separation and sensing by multilayer nanofilm structures

Emulsion separation is of high relevance for filtration applications, liquid-liquid-partitioning of biomolecules like proteins and recovery of products from droplet microreactors. Selective interaction of various components of an emulsion with substrates is used to design microfluidic flow chambers for efficient separation of emulsions into their individual components. Our lab-on-a-chip device consists of an emulsion separation cell with an integrated silicon sensor chip, the latter allowing the detection of liquid motion via the field-effect signal. Thus, within our lab-on-a-chip device, emulsions can be separated while the separation process is monitored simultaneously. For emulsion separation a surface energy step gradient, namely a sharp interface between the hydrophobic and hydrophilic parts of the separation chamber, is used. The key component of the lab-on-a-chip system is a multilayer and multifunctional nanofilm structure which not only provides the surface energy step gradient for emulsion separation but also constitutes the functional parts of the field-effect transistors. The proof-of-principle was performed using a model emulsion consisting of immiscible aqueous and organic solvent components. Droplet coalescence was identified as a key aspect influencing the separation process, with quite different effects during separation on open surfaces as compared to slit geometry. For a detailed description of this observation, an analytical model was derived and lattice Boltzmann computer simulations were performed. By use of grazing incidence small angle x-ray scattering (GISAXS) interfacial nanostructures during gold nanoparticle deposition in a flow field were probed to demonstrate the potential of GISAXS for in situ investigations during flow.

Polymer Brushes, Hydrogels, Polyelectrolyte Multilayers: Stimuli-Responsivity and Control of Protein Adsorption

The research field of smart polymer surfaces benefits from non-invasive ellipsometric investigations, especially in-situ measurements, monitoring the swelling of polymer films and protein adsorption processes thereon at varying ambient conditions. With ellipsometry in the VIS-range layer thickness and refractive index of the polymer layers can be evaluated. Appropriate models for in-situ measurements will be discussed and results of the influence of solution parameters summarized. In-situ IR-ellipsometry provides information about changes in the vibration band structure for swelling and adsorption processes, where optical modelling in the IR-range yields complementary information about layer thicknesses and structural properties.

In Situ Monitoring of Linear RGD-Peptide Bioconjugation with Nanoscale Polymer Brushes

Bioinspired materials mimicking the native extracellular matrix environment are promising for biotechnological applications. Particularly, modular biosurface engineering based on the functionalization of stimuli-responsive polymer brushes with peptide sequences can be used for the development of smart surfaces with biomimetic cues. The key aspect of this study is the in situ monitoring and analytical verification of the biofunctionalization process on the basis of three complementary analytical techniques. In situ spectroscopic ellipsometry was used to quantify the amount of chemisorbed GRGDS at both the homopolymer poly(acrylic acid) (PAA) brush and the binary poly(N-isopropylacrylamide) (PNIPAAm)–PAA brushes, which was finally confirmed by an acidic hydrolysis combined with a subsequent reverse-phase high-performance liquid chromatography analysis. In situ attenuated total reflection-Fourier transform infrared spectroscopy provided a step-by-step detection of the biofunctionalization process so that an optimized protocol for the bioconjugation of GRGDS could be identified. The optimized protocol was used to create a temperature-responsive binary brush with a high amount of chemisorbed GRGDS, which is a promising candidate for the temperature-sensitive control of GRGDS presentation in further cell-instructive studies.