Revisiting Mechanism of NaOH Dechlorination Treatments for Bronze Conservation in Quantitative Study

Dechlorination is a crucial strategy for archeological bronze stabilization to resist corrosion induced by cuprous chloride (CuCl). Conventional samples, either archeological or simulated ones, have deficiencies in revealing dechlorination mechanisms for their complex rust layers and difficulties in quantifying chlorine content. In this work, samples with fixed chlorine amounts were prepared by compressing method to solve overcomplicated and unquantifiable problems. Then, patina profiles and desalinization solutions were analyzed to revisit the dechlorination mechanism across varying solution concentrations and current densities after dechlorination treatments. Results indicate that the sodium hydroxide (NaOH) desalinization method is achieved by converting CuCl to trihydroxychloride (Cu₂(OH)₃Cl). However, this transformation leads to an expansion of the CuCl layer, nearly doubling the CuCl layer thickness at the current density of 25 μA/cm². Dechlorination solution measurements provide information on quantifying chlorine removal and dechlorination progress. Theoretically, the endpoint (c₀) for the NaOH dechlorination method is supposed to be a chloride ion concentration of 358.2 ppm. As the NaOH solution concentrations vary from 10^-6 to 10^-2, CuCl dechlorination progress (E_t=24h) calculations are at about 3% to 6% at 24 h. Applying the current significantly improves the effectiveness of dechlorination at 2.5 μA/cm². However, the chloride ion concentration in the solution starts to decrease after reaching a current density of 12.5 μA/cm², even dropping to 12.07 ppm at 25 μA/cm². According to a theoretical analysis, chlorine evolution during electrolytic processes would be responsible for this phenomenon.