Publikationen

The nanoscale interactions of room temperature ionic liquids (RTILs) at uncharged (graphene) and charged (muscovite mica) solid surfaces were evaluated with high resolution X-ray interface scattering and fully atomistic molecular dynamics simulations. At uncharged graphene surfaces, the imidazolium-based RTIL ([bmim+][Tf2N-]) exhibits a mixed cation/anion layering with a strong interfacial densification of the first RTIL layer. The first layer density observed via experiment is larger than that predicted by simulation and the apparent discrepancy can be understood with the inclusion of, dominantly, image charge and π-stacking interactions between the RTIL and the graphene sheet. In contrast, the RTIL structure adjacent to the charged mica surface exhibits an alternating cation-anion layering extending 3.5 nm into the bulk fluid. The associated charge density profile demonstrates a pronounced charge overscreening (i.e., excess first-layer counterions with respect to the adjacent surface charge), highlighting the critical role of charge-induced nanoscale correlations of the RTIL. These observations confirm key aspects of a predicted electric double layer structure from an analytical Landau-Ginzburg-type continuum theory incorporating ion correlation effects, and provide a new baseline for understanding the fundamental nanoscale response of RTILs at charged interfaces.

While pressure sensitive adhesives in general consist of a layer of viscoelastic glue sandwiched between two adherents, we explore here the design of an adhesive embedded with microchannels which remain either open to atmosphere or pressurized to different positive and negative pressures. We subject these layers to indentation by a rigid cylinder such that in addition to adhesion between the indenter and the adhesive surface, the inner walls of the channels too self-adhere; during retraction of the indenter, these surfaces debond, but at a different load, thus resulting in hysteresis. When these channels are pressurized to different extents, the contact areas of various interfaces vary, so also the resultant hysteresis. For experiments with constant depth of indentation, the hysteresis increases and attains maxima at an intermediate value of the internal pressure inside the channels. The hysteresis increases also with the skin thickness of the adhesive over the channels. These results show that subsurface channels in an adhesive allow active manipulation of adhesion over a large range via coupled effect of geometry of channels, their surface characteristics, and the pressure inside.

In this work, the adhesion of biomimetic polydimethylsiloxane (PDMS) pillar arrays with mushroom-shaped tips was studied on nano- and micro-rough surfaces and compared to unpatterned controls. The adhesion strength on nano-rough surfaces invariably decreased with increasing roughness, but pillar arrays retained higher adhesion strengths than unpatterned controls in all cases. The results were analysed with a model that focuses on the effect on adhesion of depressions in a rough surface. The model fits the data very well suggesting that the pull-off strength for patterned PDMS is controlled by the deepest dimple-like feature on the rough surface. The lower pull-off strength for unpatterned PDMS may be explained by the initiation of the pull-off process at the edge of the probe, where significant stress concentrates. To micro-rough surfaces, pillar arrays showed a maximum in adhesion for a certain intermediate roughness, while unpatterned controls did not show any measurable adhesion. This effect can be explained by the inability of micropatterned surfaces to conform to very fine and very large surface asperities.

Flow of a liquid inside a helical tube is composed of axial and circumferential components, the latter arising because of its specific geometry. For a gas-liquid two-phase flow inside a helical tube, the coupled effect of these two flow components leads to a variety of flow patterns, for example, slug, bubble, and stratified flow. We present here a novel triple-helical microchannel, in which, the two-phase flow is found to engender several additional flow patterns not observed with the conventional geometries, for example, the parallel and oscillating annular flow and even simultaneous occurrence of several such patterns. We show that the transition between these patterns depends not only on the fluid rates of the two liquids but also on the helix angle. We have presented detailed phase diagrams to elaborate these effects. We have examined also the effect of channel geometry on the specific features of these flow patterns.

In their comment (M. Lagos et al., Scripta Mater. (2012), http://dx.doi.org/10.1016/j.scriptamat.2012.04.018), Lagos et al. propose a two-dimensional plasticity model based on grain boundary sliding to explain the deformation behavior of ultrathin Cu and Ta/Cu film systems on polyimide substrates. Here, we critically discuss their comments and include new results obtained by peak profile analysis of the original in situ diffraction data; they strongly suggest that the deformation behavior of the different film systems is very likely not self-similar as claimed by Lagos et al.

We report direct measurement of surface deformation in soft solids due to their surface tension. Gel replicas of poly(dimethysiloxane) masters with rippled surfaces are found to have amplitudes that decrease with decreasing gel modulus. Surface undulations of a thin elastomeric film are attenuated when it is oxidized by brief exposure to oxygen plasma. Surface deformation in both cases is modeled successfully as driven by surface tension and resisted by elasticity. Our results show that surface tension of soft solids drives significant deformation, and that the latter can be used to determine the former.

Adhesion tests were performed on single macroscopic pillars as model systems for artificial gecko surfaces. Polydimethylsiloxane macropillars with 400 μm diameter and aspect ratios ranging from 1 to 5 were fabricated. The tip geometries were modified to achieve spherical, flat and mushroom shaped tips. Unlike spherical tips, flat tip pillars exhibited a strong angle dependency of the pull-off force. For mushroom shaped tips the pull-off force was tilt angle dependent only for low preload, where no complete tip contact was formed. No clear influence of pillar aspect ratio on adhesion could be identified. Implications of the results for the adhesion performance of fibrillar arrays are addressed.

Current adhesion measurement setups designed for experiments on bioinspired fibrillar surfaces, either commercial or constructed in-house, do not allow adhesion measurements with in situ visualization, high resolution, high force range, and controlled alignment at the same time. In this paper a new adhesion tester is presented, which enables contact experiments with controlled tilt angle (accuracy of ±0.02°). This allows the use of flat probes and thus greatly simplifies the determination of experimental parameters such as pull-off strength or Young's modulus. The deflection of a double-clamped glass beam is measured by laser interferometry with an accuracy of ±60 nm, which yields a precise force measurement over three orders of magnitude force range without changing the glass beam. Contact formation and detachment events can be visualized in situ. The current adhesion tester is designed for force measurements in the range of 1 µN to 1 N and fills the gap between macroscopic tests and atomic force microscopy measurements.

Purpose: A powerful principle in nature is the presence of surface patterns to improve specific characteristics or to enable completely new functions. Here, we present two case studies where bioinspired surface patterns based on the adhesive system of geckos may be applied for biomedical applications: residue-free adhesion to skin and gecko-inspired suture threads for knot-free wound closure. Methods: Gecko-inspired skin adhesives were fabricated by soft lithography of polydimethylsiloxane with successive inking and dipping steps. Their adhesion was measured using a home built adhesion tester designed for patterned surfaces. Preliminary lap shear tests on the back of a human hand were also performed. Commercial suture threads from different materials were patterned in the group of A. del Campo at the Max-Planck-Institute for Polymer Research (Mainz, Germany) using oxygen plasma. The treated threads were pulled through artificial skin in both directions measuring the peak force and the pull through force. Results and Conclusions: Unpatterned reference samples of the skin adhesive did not stick to human skin, while the patterned samples all showed notable adhesion up to 1.2 Newton for a sample size of approximately 3 cm². First results with the patterned suture threads indicated that the surface patterning of the thread has only a minor effect on the pull-through forces. To achieve knot-free sewing the surface geometry of the suture threads needs to be optimized and more realistic testing procedures, e.g. testing on human skin, are necessary.

While directional effects in adhesion and locomotion have in general been generated by creating symmetry breaking topographic features on the surface of a soft bodied object, here we present a novel method for imparting this effect to thin adhesive layers by embedding liquid filled microchannels arranged in pairs with specific intra and inter pair distances. The adhesive exhibits uniform adhesion in classical peel tests when both the channels are filled with either air or a wetting liquid. But the asymmetric effect shows up when only one of the channels in the pair is filled with the liquid. The liquid alters the surface tension of the inner wall of the channel, which results in bulging deformation of the thin skin of the adhesive over the channel. The bulging however remains asymmetric, the extent of asymmetry depending on the intra-pair spacing between the channels. Besides the bulging effect, filling in one channel of a pair with liquid also leads to an asymmetric variation in its modulus. As a result, when an adherent is peeled off the adhesive from two opposite directions, significantly different adhesion strengths result. A similar directional effect also results when channels of two different diameters are used in the pair, thus opening up the possibility of generating several different adhesion strengths simply by altering the geometric features of the embedded microstructure and its filling status. We show also that for both channels in a pair filled with liquid, the adhesion strength increases significantly, by over 60 times of what is achieved for a smooth, featureless, adhesive layer.