Journal articles and book contributions

As a direct consequence of the restrictions on the use of hexavalent chromium compounds, the demand for a suitable replacement has arisen. In this work the electrodeposition of thick chromium layers (>1µm) from a trivalent electrolyte is investigated with the aim to identify an electrolyte composition for the deposition of hard functional coatings. These layers can be used to surface finish tribological components experiencing high wear rates or mechanical stress in applications such as coating printing cylinders, feed rollers or piston rods. The influence of different carboxylic acids (malonic acid, malic acid, glycolic acid) on the deposition has been studied. The effect of current density on the current efficiency was investigated using in-situ microgravimetry. For a technical application the electrolyte containing malonic acid was the most promising one and was further investigated regarding the properties of the deposits, such as surface morphology, crack formation, composition, thickness and hardness, aiming at properties as close as possible to those of hexavalent chromium. In comparison to hexavalent chromium, the layer of trivalent chromium showed the same properties in terms of crack formation, hardness and layer thickness (> 1 µm).

It is demonstrated that, besides classical nanocolumnar arrays, the oblique angle geometry induces the growth of singular structures in the nanoscale when using wisely designed patterned substrates. Well-ordered array of crosses, cylindrical nanorods or hole structures arranged in square or hexagonal regular geometries are reported as examples, among others. The fundamental framework connecting substrate topography and film growth at oblique angles is presented, allowing the use of substrate patterning as a feasible thin film nanostructuring technique. A systematic analysis of the growth of TiO2 thin films on 4 different lithographic patterned substrates in 4 different scale lengths is also presented. A first conclusion is the existence of a height-based selective growth in the initial stages of the deposition, by which the film preferentially develops on top of the tallest substrate features. This behavior is maintained until the film reaches a critical thickness, the so-called Oblivion Thickness, above which the film topography becomes gradually independent of the substrate features. A general formula relating the spatial features of the pattern, the coarsening exponent and the Oblivion Thickness has been deduced.

Photoelectrochemical (PEC) water splitting is one of the most promising sustainable methods for feasible solar hydrogen production. However, this method is still impractical due to the lack of suitable photoanode materials that are efficient, stable, and cost-effective. Here, we present a surprisingly simple fabrication method for efficient, stable, and cost-effective nanometer-thick hematite films utilizing a rapid, ambient annealing approach. In the oxygen evolution reaction, the fabricated hematite films exhibit a Faradaic efficiency of 99.8% already at 1 V versus the reversible hydrogen electrode (RHE), a real photocurrent density of 2.35 mA cm-2 at 1.23 V versus RHE, and a superior photo-oxidation stability recorded for over 1000 h. Considering the active surface area, the measured photocurrent density is higher than any value achieved so far by hematite and other single-material thin-film photoanodes. Hence, we show for the first time that undoped hematite thin films can compete with doped hematite and other semiconductor materials.

Experimental results are presented of a test of the theory of local turbulent heat transfer measurements proposed by Mocikat and Herwig in 2007. A miniaturized multi-layer heat transfer sensor was developed and employed in this study. The new heat transfer sensor was designed to work in air and liquids, and this capability enabled the simultaneous investigation of different Prandtl numbers. Two basic configurations, namely the flow past a blunt plate and the flow past an inclined square cylinder, were investigated in test sections of wind and water tunnels. Convective heat transfer coefficients were obtained through conventional testing (i.e., employing thoroughly heated test objects) and using the new miniaturized sensor approach (i.e., utilizing cold test objects without heating). The main prediction of the Mocikat-Herwig theory that a specific thermal adjustment coefficient of the employed actual miniaturized heat transfer sensor should exist in the fully turbulent flow regime was proven for developed two-dimensional flow. The observed effect of the Prandtl number on this coefficient was in good agreement with the prediction of the asymptotic expansion method. The square cylinder results indicated the inherent limits of the local turbulent heat transfer measurement approach, as suggested by Mocikat and Herwig.

Hematite, a low-cost, nontoxic, and earth-abundant n-type semiconductor, is still an intriguing photoanode material for photoelectrochemical (PEC) water splitting. Nevertheless, the PEC performance of hematite is still hindered by ultrafast recombination rates or short diffusion lengths of charge carriers. Therefore, nanostructure implementation has been proposed in this and other cases to overcome this limitation, while simultaneously improving the photon harvesting efficiency. However, this approach must be critically reviewed. We show that both, hematite nanowire- and nanoflake-decorated photoelectrodes, show a low PEC performance in a NaOH (1 M) electrolyte. Reproducible nanostructure synthesis was achieved by the thermal oxidation of low-cost steel foils using only ambient air. Full absolute-energy reconstruction under ambient conditions of the electronic surface band structure of these nanostructured surfaces showed distinct Fermi-level pinning, resulting in high recombination rates. Based on our results, we can conclude that unmodified nanostructures hardly improve the performance but suffer from the lack of internal electrical splitting fields, which suppresses the electron-hole pair separation and can thus actually decrease the performance of PEC electrodes.