Characterization of Carbon Dust on the Anode Surface in the Hall–Héroult Process

This study provides a comprehensive characterization of carbon dust adhesion on the anode surface induced by the anode effect (AE) in the Hall–Héroult process. The primary objective was to verify the hypothesis of electrophoretic carbon particle transport and its subsequent stabilization on the electrode substrate. Unlike previous studies conducted in horizontal configurations where gravitational sedimentation could interfere with observations, this research employs a unique vertical electrode setup to provide direct physical evidence of purely electrophoretic transport. Authentic industrial carbon dust was used as a tracer material, its presence on the high-purity graphite surface being definitively confirmed through the detection of trace markers (Mg, Ca) via SEM-EDS. The multiscale structural analysis revealed that spike initiation occurs through a dynamic arc-induced nucleation mechanism. Morphological observations suggest that micro-arc discharges during the AE provide the extreme localized energy for direct carbon-to-carbon “welding,” creating a conductive, porous scaffold on the vertical anode wall. XRD analysis identified crystalline cryolite (Na3AlF6) and chiolite (Na5Al3F14) within this structure. It was demonstrated that these fluoride phases represent the solidified product of molten, acidic electrolyte infiltration into the carbonaceous matrix via capillary action, rather than acting as binders that crystallize during the process. Raman spectroscopy confirmed the disordered, amorphous nature of the captured dust (high D-band intensity), distinguishing it from the highly ordered graphite substrate. Confocal microscopy visualized the topographical evolution from isolated clusters to interconnected three-dimensional “islands” as a function of AE duration. The results demonstrate that the anode effect serves as a critical flashpoint where synergistic electrophoretic forces and localized thermal anomalies initiate the growth of stable, conductive carbon–matrix composite spikes, providing new insights for mitigating current efficiency losses in industrial smelters.