Degradation Mechanism of a Sauce-Glazed Ware of the Song Dynasty Salvaged out of the Water at Dalian Island Wharf: Part I—The Effect of the Surface-Attached Composite Coagula

Abstract

Dalian Island is located in the sea area near Pingtan County, Fujian, Southeast China. The sea area used to be the junction of the eastern and western ship routes on the Maritime Silk Road, and is also an important region for underwater archaeology in China. This study focused on a sauce-glazed ware of the Song Dynasty, with serious degradation, which was salvaged out of the water at the Dalian Island Wharf. Optical microscopy, scanning electron microscopy, X-ray diffraction analysis, and micro-Raman spectroscopy were used to comprehensively analyze the composition, phase attributes and microstructure of the ware and the surface-attached coagula. The findings revealed that the sea wave-borne debris scoured the surface of the ware, causing mechanical damage to varying degrees and a significant decrease in its degradation resistance. This was the primary factor accounting for the poor preservation state of the salvaged ceramic ware, and the precondition for the subsequent attachment of marine organisms and the deposition of inorganic pollutants. The calcareous skeletons formed on the surface induced by the bio-mineralization of coralline algae (a type of marine plant) could resist the mechanical action caused by the motion of sea waves, thereby slowing down the ware’s degradation process. In other words, the calcareous skeletons played a ‘bio-protective’ role to a certain degree. In addition, inorganic pollutants represented by iron rusts also participated in the corrosion of the glaze. Some pollutants were directly deposited on the pits and cracks on the surface of the ware, which brought stress to the glaze and glaze/body interface, causing the glaze to further crack and spall. Moreover, iron rusts reacted with the glaze, leading to chemical alteration, accompanied by the formation of iron silicate as the alteration product. Anorthite crystals in the interlayer did not participate in the reaction but remained at the original position. The alteration product gradually replaced the original glass phase of the glaze and entered into the body via pores and cracks. In conclusion, the complex degradation morphology of the salvaged sauce-glazed ware could be attributed to the combined action of mechanical damage, marine bio-fouling, and chemical alteration.