Glass-Induced Lead Corrosion of Heritage Objects: Structural Characterization of K(OH)·2PbCO3

Inorg Chem. 2017 May 15;56(10):5762-5770. doi: 10.1021/acs.inorgchem.7b00391. Epub 2017 May 1.

Abstract

The investigation of the corrosion of a lid made from a tin-lead alloy of a 200 years old beer jug induced by the degradation of the potash based glass revealed SnO, Cerussite (PbCO3) and K(OH)·2PbCO3 as main corrosion product. A model experiment, simulating the corrosion of lead at room temperature confirmed the formation of K(OH)·2PbCO3 as a corrosion product in alkaline, potassium containing medium. For detailed characterization K(OH)·2PbCO3 was prepared by hydrothermal synthesis, as well. K(OH)·2PbCO3 crystallizes in space group P63/mmc with lattice parameters of a = 5.3389(1) Å and c = 13.9295(5) Å. The structure consists of Pb(OH)1/2(CO3)6/9[CO3]3/91/2- layers and intercalated K+ and exhibits a close relationship to the crystal structure of hydrocerussite (Pb(OH)2·2PbCO3), also known as "lead white". A novel structure family, Mn+(OH)n·2PbCO3 (with n = 1,2), was identified by structure solution of K(OH)·2PbCO3, which can be assigned to a 2H-type subspecies and detailed comparison to Pb(OH)2·2PbCO3, which represents a 3R-type subspecies.