Degradation and dissolution of transparent semiconducting oxides is central to various areas, including design of catalysts and catalysis conditions, as well as passivation of metal surfaces. In particular, photocorrosion can be significant and plays a central role during photoelectrochemical activity of transparent semiconducting oxides. Here, we utilize an electrochemical flow cell combined with an inductively coupled plasma mass spectrometer (ICP-MS) to enable the in situ study of the time-resolved release of zinc into solution under simultaneous radiation of UV-light. With this system we study the dissolution of zinc oxide single crystals with (0001) and (101̅0) orientations. At acidic and alkaline pH, we characterized potential dependent dissolution rates into both the oxygen and the hydrogen evolving conditions. A significant influence of the UV radiation and the pH of the electrolyte was observed. The observed dissolution behavior agrees well with the surface chemistry and stabilization mechanism of ZnO surfaces. In particular, polar ZnO(0001) shows ideal stability at low potentials and under hydrogen evolution conditions. Whereas ZnO(101̅0) sustains higher dissolution rates, while it is inactive for water splitting. Our data demonstrates that surface design and fundamental understanding of surface chemistry provides an effective path to rendering electroactive surfaces stable under operating conditions.

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.

Ionic liquids (ILs) have been used effectively in many applications for reducing problems related to friction and wear. In this work, the potential of ILs as an anti-wear and extreme pressure lubricant additive for high load-carrying gearbox applications such as helicopter transmissions has been studied. Two halide-free ILs: $${{\rm{P}}_{8881}}{\left({{\rm{BuO}}} \right)_2}{\rm{PO}}_2^ - $$ P 8881 ( BuO ) 2 PO 2 − (1) and $${{\rm{P}}_{8881}}{\left({{\rm{MeO}}} \right)_2}{\rm{PO}}_2^ - $$ P 8881 ( MeO ) 2 PO 2 − (2), which are blended at 5 wt% each into a standard non-additivated FVA2 base oil (BO) are examined. Their solid—liquid interface, friction and load-carrying capacity, and wear (scuffing) behavior are studied on the nano-, lab-, and component-scale, respectively, at a different range of temperature and loading conditions by using the atomic force microscopy (AFM), Schwing—Reib—Verschleiß (SRV) friction tests, and Brugger tests, as well as forschungsstelle für zahnräder und getriebebau (FZG) back-to-back gear test rig. The AFM analysis shows nearly no change of adhesion over the full range of studied temperature for the IL blends compared to the BO. Similarly, IL blends demonstrate a very stable coefficient of friction (COF) of around 0.16, which even decreases with increasing test temperatures ranging from 40 to 120 °C. A clear reduction in COF up to 25% is achieved by adding only 5 wt% of the investigated ILs in the BO, and the Brugger tests also show a pronounced enhancement of load-carrying capacity. Finally, on the component-scale, a significant improvement in gear scuffing performance has been observed for both used IL blends. A detailed characterization of the wear tracks from the SRV friction tests via the transmission electron microscopy (TEM) revealed the formation of a phosphate (P—O)-based amorphous tribo-chemical layer of about 20 nm thickness. Therefore, this work may present an approach for ILs to be used as an additive in conventional lubricants due to their ability to enhance the lubrication properties, making them an alternative lubricant solution for high load-carrying gearbox applications.

No abstract

Localized surface reactions in confinement are inherently difficult to visualize in real‐time. Herein multiple‐beam‐interferometry (MBI) is extended as a real‐time monitoring tool for corrosion of nanometer confined bulk metallic surfaces. The capabilities of MBI are demonstrated, and the initial crevice corrosion mechanism on confined nickel and a Ni75Cr16Fe9 model material is compared. The initiation of crevice corrosion is visualized in real time during linear sweep polarization in a 1 × 10−3 m NaCl solution. Pre‐ and post‐experiment analysis is performed to complementarily characterize the degraded area with atomic force microscopy (AFM), optical microscopy, nano‐Laue diffraction (nano‐LD), scanning electron microscopy (SEM)/electron backscatter diffraction (EBSD), and X‐ray photoelectron spectroscopy (XPS). Overall, Ni75Cr16Fe9 displays a better corrosion resistance; however, MBI imaging reveals 200 nm deep severe localized corrosion of the alloy in the crevice opening. Chromium rich passive films formed on the alloy contribute to accelerated corrosion of the confined alloy by a strongly acidifying dissolution of the passive film in the crevice opening. Nano‐LD further reveals preferential crystallographic defect and corrosion migration planes during corrosion. MBI provides nanometer accurate characterization of topologies and degradation in confined spaces. The technique enables the understanding of the initial crevice corrosion mechanism and testing modeling approaches and machine‐learning algorithms.