Materials Engineering Aspects of Intermetallic Anode for Aluminium Electro-Winning

"Successful use of inert anodes should reduce the CO2 footprint in aluminum production. The search for a “holy grail” inert anode for metal electro-winning from constituent oxides using molten salt bath as an electrolytic medium is continuing. In this article we demonstrate the engineering approaches for the fabrication of intermetallic anodes, based on a quaternary Al-Ti-Cu-M (M:Ni, Fe) system for primary aluminium production. In particular, we examine the microstructural and electrochemical properties of alloys, based on the quaternary compositions. We explain the aspects of phase stability under anodic potential, which leads to the loss of anodic materials in the temperature range of 850-1050oC. The results are analysed in the context of oxidation reaction and formation of oxide layers which readily dissolve in the cryolite melt and prevent passivation. The paper also describes the conditions under which the reduction of aluminium at the graphite cathode occurs which also strongly depends on the molten salt chemistry for the nucleation of molten aluminium at the cathode.1. IntroductionOxygen-evolving inert anodes are an alternative to the conventional consumable carbon anodes for the production of primary aluminium. In this paper the materials selection criteria chosen for the engineering of anode is based on the understanding of the thermodynamic stabilities of aluminide intermetallic phases, some of which are formed and remained stable in fluoride melts. For example, the formation Al3Ti dispersed in aluminium metal via molten-fluoride flux reaction is well known in the context of aluminium casting and grain refining [1-3]. It is for this reason in our research we concentrated on the engineering of stable intermetallic phase mixture in the Al-Ti-Cu ternary system, shown in Figure 1 [4]. In this figure two compositions in the Al3-0.5zTi1-0.5zCuz family are shown with the substitution of 7 atomic % and 11 atomic % copper. However initial investigations showed that these two compositions were unsuitable due to the formation of low-temperature liquid (~540oC) and intermetallic phase, Al2Cu along the Al-Cu binary edge during solidification. The Al2Cu phase segregated along the boundaries of Al3Ti and Al5Ti2Cu, and dissolved away when electrolysis was carried out using these anodes above 800oC. The presence of consequential porosity in the anode material increased the corrosion of the alloy through local heating due to high current density at 0.8 A cm-2. The early tests were carried out with cryolite melts, shown in Figure 2, having 3 weight percent of Al2O3 in the bath at 850oC."