Degradation mechanisms of Prussian blue pigments in paint layers

Prussian blue is a modern synthetic pigment discovered in Berlin at the beginning of the eighteenth century. Prussian blue is a hydrated iron(III) hexacyanoferrate(II) complex and its color results from an intervalence charge transfer between the iron(II) and iron(III) ions when light is absorbed at ca. 700 nm. Because of both its highly intense color and its low cost, Prussian blue enjoyed immediate popularity among artists and was widely used as a pigment in paintings until the 1970's. However, the permanence of Prussian blue had already been questioned by the mid-eighteenth century, because it exhibits a tendency to fade in light and to turn green. The preparative methods were rapidly recognized as a contributory factor in the fading of the pigment. The main objective of this thesis is the identification of the degradation mechanisms of Prussian blue pigments in paint layers.

Prussian blue was synthesized according to both ancient and modern preparation methods. A thorough analysis of the pigments revealed a dependency upon the type of synthesis, the crystallite size, and vacancy content, all properties that influence the local electronic and structural configurations of the iron ions in Prussian blue. The presence of nanocrystalline ferrihydrite as an undesirable iron containing reaction product was identified in Prussian blue pigments prepared according to eighteenth-century recipes. Discoloration upon light exposure in Prussian blue paint layers was induced by accelerated ageing. Pure Prussian blue painted in a dark shade is extremely light fast but fades when either painted in a lighter shade or mixed with white pigments. The fading of Prussian blue was attributed to a reduction of the iron(III) ions at the surface of the paint layer. A partial oxidation of Prussian blue in the entire paint layer was also observed. The analysis of works of art containing Prussian blue confirmed the combined oxidation and reduction of Prussian blue iron ions upon ageing.

The study of alteration mechanisms in a painting pigment is essential both for conservation and historical studies in order to best preserve our cultural and artistic heritage with respect to an artist’s original intentions.