Cobalt and Associated Impurities in Blue (and Green) Glass, Glaze and Enamel: Relationships between Raw Materials, Processing, Composition, Phases and International Trade

Abstract

Minerals able to colour in blue (and green in combination with yellow pigments) are limited in number and geologically. After presenting a short history of the use of cobalt as a colouring agent of glass, glaze and enamel in the Western/Mediterranean, Islamic and Asian worlds since Antiquity, we will present the different forms (dissolved ions, natural and synthetic crystalline phases/pigments) of cobalt and associated elements regarding primary (transition metals) and secondary geological deposits (transition metals and/or arsenic, bismuth, silver). Attempts to identify the origin of cobalt have been made by many authors considering the associated elements but without considering the important modifications due to different processing of the raw materials (extraction/purification/formulation). We review the information available in the ancient reports and present literature on the use of cobalt, its extraction and production from the ores, the different geological sources and their relationship with associated elements (transition metals, bismuth, arsenic, and silver) and with technological/aesthetic requirements. (Partial) substitution of cobalt with lapis lazuli is also addressed. The relative application of non-invasive mobile Raman and pXRF analytical instruments, to detect mineral phases and elements associated with/replacing cobalt is addressed, with emphasis on Mamluk, Ottoman, Chinese, Vietnamese and Japanese productions. The efficiency of Ni-Zn-As diagram proposed by Gratuze et al. as a classification tool is confirmed but additionally, CoO-Fe2O3−MnO and CoO-NiO-Cr2O3 diagrams are also found as very efficient tools in this research. The relationship between the compositional data obtained from the artefacts and historical questions on the origin and date of their production are discussed in order to obtain a global historical view. The need of a better knowledge of (ancient) deposits of cobalt ores and the evolution of cobalt ore processing with time and place is obvious.