Colloidal aggregates tested via nanoindentation and quasi-simultaneous 3D imaging.

The mechanical properties of aggregated colloids depend on the mutual interplay of inter-particle potentials, contact forces, aggregate structure and material properties of the bare particles. Owing to this variety of influences, experimental results from macroscopic mechanical testings were mostly compared to time-consuming, microscopic simulations rather than to analytical theories. The aim of the present paper was to relate both macroscopic and microscopic mechanical data with each other and simple analytical models. We investigated dense amorphous aggregates made from monodisperse poly-methyl methacrylate (PMMA) particles (diameter: 1.6 µm via nanoindentation in combination with confocal microscopy. The resulting macroscopic information was complemented by the three-dimensional aggregate structure as well as the microscopic strain field and strain tensor. The measured strain field and tensor were in reasonable agreement with the predictions from analytical continuum theories. Consequently, the measured force-depth curves could be analyzed within a theoretical framework that had been frequently used for nanoindentation of atomic matter such as metals, ceramics and polymers. The extracted values for hardness and effective Young's modulus represented average values characteristic of the aggregate. On the basis of of these parameters we discuss the influence of the strength of particle bonds by introducing polystyrene (PS) between the particles.

The softer the better: fast condensation on soft surfaces.

Condensation on soft elastic surfaces differs significantly from condensation on hard surfaces. On polymeric substrates with varying cross-linking density, we investigate the nucleation and the growth of condensing water drops. With increasing softness of the substrates, we find (1) increasing nucleation density, (2) longer relaxation times for drop shape equilibration after merging of two drops, and (3) prevention of merging on very soft surfaces. These effects lead to higher surface coverage and overall condensed volume on soft surfaces.

Versatile high-speed confocal microscopy using a single laser beam.

We present a new flexible high speed laser scanning confocal microscope and its extension by an astigmatism particle tracking velocimetry (APTV) device. Many standard confocal microscopes use either a single laser beam to scan the sample at a relatively low overall frame rate or many laser beams to simultaneously scan the sample and achieve a high overall frame rate. The single-laser-beam confocal microscope often uses a point detector to acquire the image. To achieve high overall frame rates, we use, next to the standard 2D probe scanning unit, a second 2D scan unit projecting the image directly onto a 2D CCD-sensor (re-scan configuration). Using only a single laser beam eliminates crosstalk and leads to an imaging quality that is independent of the frame rate with a lateral resolution of 0.235 µm. The design described here is suitable for a high frame rate, i.e., for frame rates well above the video rate (full frame) up to a line rate of 32 kHz. The dwell time of the laser focus on any spot in the sample (122 ns) is significantly shorter than those in standard confocal microscopes (in the order of milli- or microseconds). This short dwell time reduces phototoxicity and bleaching of fluorescent molecules. The new design opens up further flexibility and facilitates coupling to other optical methods. The setup can easily be extended by an APTV device to measure three dimensional dynamics while being able to show high resolution confocal structures. Thus, one can use the high resolution confocal information synchronized with an APTV dataset.

Adsorption and Diffusion Moderated by Polycationic Polymers during Electrodeposition of Zinc.

Electrodeposition of metals is relevant to much of materials research including catalysis, batteries, antifouling, and anticorrosion coatings. The sacrificial characteristics of zinc used as a protection for ferrous substrates is a central corrosion protection strategy used in automotive, aviation, and DIY industries. Zinc layers are often used for protection by application to a base metal in a hot dip galvanizing step; however, there is a significant interest in less energy and material intense electroplating strategies for zinc. At present, large-scale electroplating is mostly done from acidic zinc solutions, which contain potentially toxic and harmful additives. Alkaline electroplating of zinc offers a route to using environment-friendly green additives. Within the scope of this study an electrolyte containing soluble zinc hydroxide compound and a polyquarternium polymer as additive were studied during zinc deposition on gold model surfaces. Cyclic voltammetry experiments and in-situ electrochemical quartz crystal microbalance with dissipation (QCM-D) measurements were combined to provide a detailed understanding of fundamental steps that occur during polymer-mediated alkaline zinc electroplating. Data indicate that a zincate-loaded polymer can adsorb within the inner sphere of the electric double layer, which lowers the electrostatic penalty of the zincate approach to a negatively charged surface. X-ray photoelectron spectroscopy also supports the assertion that the zincate-loaded polymer is brought tightly to the surface. We also find an initial polymer depletion followed by an active deposition moderation via control of the zincate diffusion through the adsorbed polymer.

Superhydrophobic surfaces by hybrid raspberry-like particles.

Surface roughness on different length scales is favourable for superhydrophobic behaviour of surfaces. Here we report (i) an improved synthesis for hybrid raspberry-like particles and (ii) a novel method to obtain superhydrophobic films of good mechanical stability. Polystyrene spheres with a diameter of 400 nm-1 microm are decorated with silica colloids < 100 nm in size, thus introducing surface asperities on a second length scale. To improve mechanical resistance, we then coated the polystyrene core and attached silica colloids with a smooth silica shell of 10 nm to 40 nm thickness. All three steps of this synthesis procedure can be sensitively tuned so that the average size and number of the silica colloids as well as the morphology of the resulting raspberry particles can be predicted. As the particles disperse in water, either monolayers can be prepared by dip coating or multilayers by drop casting. Although mechanically stable, the shells are porous enough to allow for leakage of molten or dissolved polystyrene from the core. In tetrahydrofuran vapour polystyrene bridges form between the particles that render the multilayer-film stable. Leaked polystyrene that masks some asperities can be removed by plasma cleaning. Surface roughness on larger scales can be tuned by the drying procedure. The films are hydrophobized by silanization with a semi-fluorinate silane.