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RESEARCH PRODUCT

Electrochemical Characterization of Archaeological Tin-Opacified Lead-Alkali Glazes and Their Corrosion Processes

subject

description

The electrochemical response of weathered and unweathered archaeological tin-opacified glazes attached to paraffin-impregnated graphite electrodes is described. Upon comparison with the square wave voltammetric response of SnO2, PbO and PbO2, Sn- and Pb-centered reduction processes can be characterized. Reduction of Sn(IV) involves the stepwise formation of solid Sn(II) and Sn metal, successively, at potentials of −0.08 and −0.55 V vs. AgCl/Ag. Reduction of network-modifier Pb(II) in glazes occurs at −0.5 V and is accompanied by the reduction of network-forming Pb(IV) at potentials ranging from +0.65 to +0.20 V, confirming the presence of such centers in glazes. Voltammetric data suggest the presence of small amounts of Sn(II) resulting from the reduction of cassiterite during the firing process. A series of correlations between the peak currents can be established, indicating that the weathering process obeys a kinetic process rather than a equilibrium-like situation.