Is an electric field always a promoter of wetting? Electro-dewetting of metals by electrolytes probed by in situ X-ray nanotomography.

We developed a special electrochemical cell enabling quantitative analysis and in situ X-ray nanotomography of metal/electrolyte interfaces subject to corrosion. Using this cell and applying the nodoid model to describe menisci formed on tungsten wires during anodization, the evolution of the electrolyte surface tension, the concentration of reaction products, and the meniscus contact angle were studied. In contrast to the electrowetting effect, where the applied electric field decreases the contact angle of electrolytes, anodization of the tungsten wires increases the contact angle of the meniscus. Hence, an electric field favors dewetting rather than wetting of the newly formed surface. The discovered effect opens up new opportunities for the control of wetting phenomena and calls for the revision of existing theories of electrowetting.

In situ X-ray nanotomography of metal surfaces during electropolishing.

A low voltage electropolishing of metal wires is attractive for nanotechnology because it provides centimeter long and micrometer thick probes with the tip radius of tens of nanometers. Using X-ray nanotomography we studied morphological transformations of the surface of tungsten wires in a specially designed electrochemical cell where the wire is vertically submersed into the KOH electrolyte. It is shown that stability and uniformity of the probe span is supported by a porous shell growing at the surface of tungsten oxide and shielding the wire surface from flowing electrolyte. It is discovered that the kinetics of shell growth at the triple line, where meniscus meets the wire, is very different from that of the bulk of electrolyte. Many metals follow similar electrochemical transformations hence the discovered morphological transformations of metal surfaces are expected to play significant role in many natural and technological applications.

Precipitation and surface adsorption of metal complexes during electropolishing. Theory and characterization with X-ray nanotomography and surface tension isotherms.

Electropolishing of metals often leads to supersaturation conditions resulting in precipitation of complex compounds. The solubility diagrams and Gibbs adsorption isotherms of the electropolishing products are thus very important to understand the thermodynamic mechanism of precipitation of reaction products. Electropolishing of tungsten wires in aqueous solutions of potassium hydroxide is used as an example illustrating the different thermodynamic scenarios of electropolishing. Electropolishing products are able to form highly viscous films immiscible with the surrounding electrolyte or porous shells adhered to the wire surface. Using X-ray nanotomography, we discovered a gel-like phase formed at the tungsten surface during electropolishing. The results of these studies suggest that the electropolishing products can form a rich library of compounds. The surface tension of the electrolyte depends on the metal oxide ions and alkali-metal complexes.