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March 3, 2026Journal of Applied Electrochemistry0 citationsOpen Access

Reaction mechanisms of high-rate copper electrochemical machining in chloride and sulfate electrolytes

LJLeonie JakobLRLasse RieckJBJonas Bartsch

Key Points

  • The reaction mechanism for copper dissolution differs in chloride versus sulfate electrolytes, affecting surface film properties.
  • Key metrics include limiting current densities of 15–35 V in NaCl and 35 V in Na2SO4, both linked to dissolution behavior.
  • Assessment through polarization studies suggests unique solvo-chlorination and solvo-sulfatization mechanisms for each electrolyte.
  • Understanding these mechanisms may improve efficiency and application of electrochemical machining in various contexts.

Abstract

The electrochemical dissolution behavior of copper in sodium chloride and sodium sulfate electrolytes is analyzed mainly by measuring polarization curves. The nature and the influence of the surface film formed at the limiting current density plateau, on the reaction mechanism and etching behavior were examined. For high current densities, novel complexation mechanisms for the dissolution were assumed. These “Solvo-Chlorination” and “Solvo-Sulfatization” mechanisms were similar to the “Solvo-Nitration” mechanism that has recently been postulated for nitrate electrolytes. Differences in the limiting current density and the re-rise voltage (15–35 V in NaCl, 35 V in Na2SO4) were strongly connected to the properties of the surface film and the valence of dissolution. The dissolution mechanism of copper during high-rate electrochemical machining in chloride and sulfate electrolytes is investigated mainly by polarization studies. A similar change in reaction mechanism as postulated for nitrate electrolytes including the formed surface films can be assumed. However, the nature of the surface films differs. Institute Twitter/X account: @Fraunhofer ISE.

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Cite This Study

Jakob et al. (2026) studied this question.

synapsesocial.com/papers/69a76586badf0bb9e87d9676https://doi.org/10.1007/s10800-025-02398-8
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