Publikationen

Inspired by recent experiments on hierarchically structured adhesives, we analyze here the effect of spatial variation in surface topography and shear modulus of an elastomeric adhesive on its ability to adhere strongly to a flexible contactor. The undulation of surface and modulus both were assumed to be periodic with periodicity, which is either identical or different for the two parameters; for identical periodicity, the phase lag between the respective undulations is also systematically varied. Calculations show that during continuous lifting of the flexible contactor from complete initial contact, the interfacial crack between the two adherents does not propagate continuously but intermittently, with crack arrest and initiation at the vicinity of minimum thickness and modulus of the layer; the torque required to initiate an arrested crack increases significantly over that required to propagate it on a smooth adhesive surface. The adhesion strength estimated from the corresponding force vs displacement plot is calculated to be higher than that achieved on a smooth and featureless adhesive surface. For in-phase variation in topography and shear modulus of the layer, the adhesive strength is found to be higher than for nonzero phase lag between the two parameters. The adhesion strength is found to diminish also for nonidentical periodicity between modulus and surface undulation. We have derived a scaling law for relating adhesion strength to several of these parameters.

The efficient sunlight-induced crosslinking of 1,2-polybutadienes to generate fluorescent patterns with spatial resolution is reported. The employed photochemical conjugation method is based on a nitrile imine-mediated tetrazole-ene cycloaddition (NITEC), which proceeds under UV-light irradiation ([small lambda]max = 312 nm) at ambient temperature in the absence of any catalyst. The NITEC reaction between 1-pentene and a newly designed di-linker consisting of two photosensitive diaryl-substituted tetrazoles joined by a tetraethylene glycol spacer was investigated in an initial study. Detailed characterization of the small molecule model study was performed by size exclusion chromatography (SEC), UV-Vis and fluorescence spectroscopy, as well as electrospray-ionization mass spectrometry (ESI-MS), which is also employed for monitoring the reaction kinetics (100 % conversion in 20 min). Finally, light-triggered crosslinking is accomplished with two 1,2-polybutadienes of different molar masses. The crosslinking reaction parameters, such as concentration, di-linker fraction and reaction time were optimized via a SEC analysis and gravimetric determination of gel fractions. The applicability of the novel crosslinking technology for generating spatially controlled highly fluorescent gel patterns is demonstrated in a solvent-free reaction in 2 h in sunlight. The current study, in summary, thus introduces an efficient light-triggered technology platform for crosslinking polymers carrying non-activated double bonds.

We measured the shape change of periodic ridge surface profiles in gelatin organogels resulting from deformation driven by their solid-vapor surface stress. A gelatin organogel was molded onto poly-dimethylsiloxane (PDMS) masters having ridge heights of 1.7 and 2.7 [small mu ]m and several periodicities. Gel replicas were found to have a shape deformed significantly compared to their PDMS master. Systematically larger deformations in gels were measured for lower elastic moduli. Measuring the elastic modulus independently, we estimate a surface stress of 107 +/- 7 mN m-1 for the organogels in solvent composed of 70 wt% glycerol and 30 wt% water. Shape changes are in agreement with a small strain linear elastic theory. We also measured the deformation of deeper ridges (with height 13 [small mu ]m), and analysed the resulting large surface strains using finite element analysis.

Dynamic attachment is the key to moving safely and fast in a three-dimensional environment. Among lizards, hexapods and arachnids, several lineages have evolved hairy foot pads that can generate strong friction and adhesion on both smooth and rough surfaces. A strongly expressed directionality of attachment structures results in an anisotropy of frictional properties, which might be crucial for attachment control. In a natural situation, more than one leg is usually in contact with the substrate. In order to understand the collective effect of hairy foot pads in the hunting spider Cupiennius salei (Arachnida, Ctenidae), we performed vertical pulling experiments combined with stepwise disabling of the pads. We found the attachment force of the spider to be not simply the sum of single leg forces because with leg pair deactivation a much greater decrease in attachment forces was found than was predicted by just the loss of available adhesive pad area. This indicates that overall adhesion ability of the spider is strongly dependent on the antagonistic work of opposing legs, and the apparent contact area plays only a minor role. It is concluded that the coordinated action of the legs is crucial for adhesion control and for fast and easy detachment. The cumulative effect of anisotropic fibrillar adhesive structures could be potentially interesting for biomimetic applications, such as novel gripping devices.

Waterproof and self-cleaning surfaces continue to attract much attention as they can be instrumental in various different technologies. Such surfaces are typically rough, allowing liquids to contact only the outermost tops of their asperities, with air being entrapped underneath. The formed solid-liquid-air interface is metastable and, hence, can be forced into a completely wetted solid surface. A detailed understanding of the wetting barrier and the dynamics of this transition is critically important for the practical use of the related surfaces. Toward this aim, wetting transitions were studied in situ at a set of patterned perfluoropolyether dimethacrylate (PFPEdma) polymer surfaces exhibiting surface features with different types of sidewall profiles. PFPEdma is intrinsically hydrophobic and exhibits a refractive index very similar to water. Upon immersion of the patterned surfaces into water, incident light was differently scattered at the solid-liquid-air and solid-liquid interface, which allows for distinguishing between both wetting states by dark-field microscopy. The wetting transition observed with this methodology was found to be determined by the sidewall profiles of the patterned structures. Partial recovery of the wetting was demonstrated to be induced by abrupt and continuous pressure reductions. A theoretical model based on Laplace's law was developed and applied, allowing for the analytical calculation of the transition barrier and the potential to revert the wetting upon pressure reduction.

The mechanical properties of Al-7 wt.% Si can be enhanced by structural modifications of its eutectic phase. Addition of low concentrations of certain elements, in this case 150 wt-ppm Sr, is enough to cause a transition from a coarse plate-like Si structure to a finer coralline one. To fully understand the operating mechanism of this modification, the composition of the eutectic Si phase in unmodified and Sr-modified alloys was analysed and compared by atom probe tomography and (scanning) transmission electron microscopy. The unmodified alloy showed nanometre sized Al-segregations decorating defects, while the Sr-modified sample presented three types of Al–Sr segregations: (1) rod-like segregations that promote smoothening of the Al–Si boundaries in the eutectic phase, (2) particle-like segregations comparable to the ones seen in the unmodified alloy, and (3) planar segregations favouring the formation of twin boundaries. Al and Sr solubilities in Si after solidification were determined to be 430 ± 160 at-ppm and 40 ± 10 at-ppm, respectively. Sr predominantly segregates to the Si phase confirming its importance in the modification of the eutectic growth.

In this study, a combined tilt- and focal series is proposed as a new recording scheme for high-angle annular dark-field scanning transmission electron microscopy (STEM) tomography. Three-dimensional (3D) data were acquired by mechanically tilting the specimen, and recording a through-focal series at each tilt direction. The sample was a whole-mount macrophage cell with embedded gold nanoparticles. The tilt-focal algebraic reconstruction technique (TF-ART) is introduced as a new algorithm to reconstruct tomograms from such combined tilt- and focal series. The feasibility of TF-ART was demonstrated by 3D reconstruction of the experimental 3D data. The results were compared with a conventional STEM tilt series of a similar sample. The combined tilt- and focal series led to smaller "missing wedge" artifacts, and a higher axial resolution than obtained for the STEM tilt series, thus improving on one of the main issues of tilt series-based electron tomography.

Scanning transmission electron microscopy (STEM) of specimens in liquid, so-called Liquid STEM, is capable of imaging the individual subunits of macromolecular complexes in whole eukaryotic cells in liquid. This paper discusses this new microscopy modality within the context of state-of-the-art microscopy of cells. The principle of operation and equations for the resolution are described. The obtained images are different from those acquired with standard transmission electron microscopy showing the cellular ultrastructure. Instead, contrast is obtained on specific labels. Images can be recorded in two ways, either via STEM at 200 keV electron beam energy using a microfluidic chamber enclosing the cells, or via environmental scanning electron microscopy at 30 keV of cells in a wet environment. The first series of experiments involved the epidermal growth factor receptor labeled with gold nanoparticles. The labels were imaged in whole fixed cells with nanometer resolution. Since the cells can be kept alive in the microfluidic chamber, it is also feasible to detect the labels in unfixed, live cells. The rapid sample preparation and imaging allows studies of multiple whole cells.