Journal of Materials Science

, Volume 47, Issue 3, pp 1262–1267 | Cite as

An XPS study of the fluorination of carbon anodes in molten NaF–AlF3–CaF2

  • Richard G. Haverkamp
Materials in New Zealand


In the Hall–Héroult process for aluminum production electrolysis takes place in molten cryolite (NaF–AlF3–CaF2) with carbon electrodes. Dewetting of the anode leads to operational instability. A surface energy change due to surface fluorocarbon formation during electrolysis is suggested as a contributing factor to diminishing the wettability of the anode. In this work the surface composition of graphite anodes after electrolysis in molten NaF–AlF3–CaF2 is investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) for evidence of fluorination. Fluorocarbon is identified on an electropolished region of an anode surface resulting from anode effect. The discovery of surface fluorination provides an insight into high temperature electrochemical reactions of carbon with molten fluoride salts and informs aluminum smelter cell operation.


Fluorocarbon Cryolite Anode Surface AlF3 Carbon Anode 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This research was undertaken on the Soft X-ray beamline at the Australian Synchrotron, Victoria, Australia. The NZ Synchrotron Group Ltd provided travel funding. Melissa Basil-Jones and Isabel Beattie assisted with XPS data collection and Doug Hopcroft, Manawatu Microscopy Centre, collected the SEM images.


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© Springer Science+Business Media, LLC 2011

Authors and Affiliations

  1. 1.School of Engineering and Advanced TechnologyMassey UniversityPalmerston NorthNew Zealand

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