Identification and analytical examination of copper alloy pigments applied as golden illuminations on three persian manuscripts

Golden pigments are among the most common colourants used in Persian illuminated manuscripts. In this research, golden pigments were investigated in three eighteenth- to nineteenth-century manuscripts. Initially, scanning electron microscopy-energy dispersive spectrometry analyses showed that different kinds of metallic pigments were present and some of them were ternary alloys made up of copper, zinc and tin, hence copper-based alloys were ascertained as cheap alternatives to gold. Discolouration of the pigment was observable through alteration of the metallic pigments to greenish residues in the manuscripts. Subsequently, the greenish products in the golden pigments were studied by Raman spectroscopy. Copper carboxylates were recognized as degradation products. We inferred that the alteration is a consequence of the interaction between copper alloy pigments and carboxylic acids in conditions of high humidity. Moreover, more progressive degradation has caused the discolouration, brittleness and gradually crumbling of the paper in the painted areas. Signs of damages in the paper were comparable with decomposition of the paper by green copper pigments such as verdigris in historical documents and miniatures