Corrosion of glaze in the marine environment: study on the green-glazed pottery from the Southern Song “Nanhai I” shipwreck (1127–1279 A.D.)

Abstract

The “Nanhai I” shipwreck is an important discovery in the underwater archaeology of China, and many ceramics have been unearthed. These ceramics are important material artifacts of China’s “Maritime Silk Road” and have considerable significance for the study of foreign trade in the Southern Song Dynasty (1127–1279 A.D.). However, these ceramics have been buried in a marine environment for approximately 800 years and have all been corroded to varying degrees, with green-glazed pottery being the most severely corroded. In this study, the chemical compositions of five samples of green-glazed pottery and the corrosion morphology and mechanism of a representative sample were analyzed by optical microscopy, scanning electron microscopy-energy dispersive X‐ray spectrometry (SEM–EDS), Raman spectroscopy, and X-ray diffraction (XRD). Results: The green glaze is a low-temperature silica-aluminum oxide-lead oxide (SiO2-Al2O3-PbO) glaze with copper ions (Cu2+) as the main colorant. The corrosion morphology is characterized by alternating silicon (Si)- and lead (Pb)-rich layers, a sharp reaction interface between the Si-rich layer and the pristine glaze, and a relatively high porosity of the Si-rich gel layer, which is formed by the accumulation of spherical hydrated silica colloidal particles. These features suggest that the glaze was corroded through an interface-coupled dissolution–precipitation mechanism and that the properties of the gel pores controlled the reaction kinetics. Fluctuations in the solution properties at the reaction interface produced the complex morphology of the gel layer, whereas changes in the dryness and humidity of the environment are not essential factors. The samples have been corroding in the marine environment for nearly a thousand years, and explorations of the corrosion morphology and mechanism could provide reference information on the corrosion of various ancient ceramics and glasses and a basis for scientific conservation of these objects.