Revisiting the bleeding effect in historical cobalt porcelain pigments: Mechanism, influence and technical responses

Abstract

The bleeding phenomenon, a persistent and widespread issue in the application of cobalt-bearing pigment during porcelain decoration, has spurred different civilisations to develop various response strategies to alleviate this problem. In this study, we challenge the prevailing hypotheses concerning the role of composition and viscosity in determining the bleeding effect on blue-and-white wares, proposing a novel physical model framing it as a diffusion process that occurs within vitreous silicate, where the severity can be qualitatively expressed using the diffusion distance. Drawing upon the phenomenological Fick's law and microscopic diffusion mechanism, we quantitatively discuss the primary physical parameters that influence the diffusion behaviour for the first time, clarifying that the diffusion of cobalt ions is not related to the medium viscosity. Moreover, compared with the microstructural features of blue decors with and without the bleeding effect, we reveal that domestic cobalt particles are all encapsulated by anorthite crystals, acting as a passivation shell to hinder the dissolution of cobalt particles. Significantly, our reinterpretation has broader archaeological implications for the bleeding effect associated with cobalt pigment in ceramics, elucidating the historical trajectories of responsive practices and the multifaceted interplay between resource form, artistic expression and technological advancement across varying environmental and cultural contexts. Overall, these responses to the bleeding effect exemplify the complexities of technological evolution, highlighting that technology is not merely an extension of technical knowledge but also functions as a form of social construction deeply intertwined with its local context. This comprehensive understanding contributes to our understanding of historical narratives in ceramics and the diversity of human ingenuity in ancient societies, with potential implications for contemporary pigment manufacture.