Andrew J. Urban

Development of Inert Anode Materials for Electrowinning in Calcium Chloride Melts

The electroreduction of solid titanium dioxide in a calcium chloride melt is an attractive method for the production of titanium metal. Several groups have proposed versions of this route, but no commercial process yet exists. In laboratory studies, consumable carbon anodes are used that can give rise to a number of cell design and operational issues. The replacement of the carbon anode with an inert anode offers numerous benefits that include: elimination of carbon dioxide emissions; more efficient cell operation and reduced electrode costs. We studied the chemical stabilities and cell voltages in laboratory-scale, constant current electrolyses, of a wide range of candidate inert anode materials, including metals, alloys and conductive ceramics, in calcium chloride-based melts. All metals and alloys tested either dissolved in the melt and/or formed a thick, highly resistive crust. A conductive ceramic, chromium titanate, exhibited the best performance, with an acceptable cell voltage during electrolysis for 24 hours.

A furnace and environmental cell for the in situ investigation of molten salt electrolysis using high-energy X-ray diffraction

This paper describes the design, construction and implementation of a relatively large controlled-atmosphere cell and furnace arrangement. The purpose of this equipment is to facilitate the in situ characterization of materials used in molten salt electrowinning cells, using high-energy X-ray scattering techniques such as synchrotron-based energy-dispersive X-ray diffraction. The applicability of this equipment is demonstrated by quantitative measurements of the phase composition of a model inert anode material, which were taken during an in situ study of an operational Fray-Farthing-Chen Cambridge electrowinning cell, featuring molten CaCl(2) as the electrolyte. The feasibility of adapting the cell design to investigate materials in other high-temperature environments is also discussed.

Quantification of passivation layer growth in inert anodes for molten salt electrochemistry by in situ energy-dispersive diffraction

An in situ energy-dispersive X-ray diffraction experiment was undertaken on operational titanium electrowinning cells to observe the formation of rutile (TiO2) passivation layers on Magneli-phase (TinO2n−1; n = 4–6) anodes and thus determine the relationship between passivation layer formation and electrolysis time. Quantitative phase analysis of the energy-dispersive data was undertaken using a crystal-structure-based Rietveld refinement. Layer formation was successfully observed and it was found that the rate of increase in layer thickness decreased with time, rather than remaining constant as observed in previous studies. The limiting step in rutile formation is thought to be the rate of solid-state diffusion of oxygen within the anode structure.