Raman analysis of complex pigment mixtures in 20th century metal knight shields of the Order of the Elephant

Abstract

The pigment composition of six painted metal knight shields of the Order of the Elephant dating from the second half of the 20th century belonging to the Danish royal collection were studied using Raman microscopy. By focusing a 785nm laser with a 50× objective on particles in paint cross sections, it was possible to identify the following 20 compounds: hematite, goethite, chrome red/orange, chrome yellow, zinc chrome yellow, carbon black, toluidine red PR3, chlorinated para red PR4, dinitroaniline orange PO5, phthalocyanine blue PB15, indanthrone blue PB60, ultramarine, Prussian blue, lead white, anatase, rutile, calcium carbonate, barium sulphate, gypsum and dolomite. The components were frequently present in complex pigment mixtures. Additional information was obtained by elemental analysis with scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDX) to identify cobalt blue, zinc white and cadmium red, as well as to indicate the presence of zinc white in some pigment mixtures. The study allowed a comparison between the industrially applied preparation layers and the artistic paint layers applied by the heraldic painter. Differences in the choice of paint and pigment types were observed on the earliest knight shields, demonstrating a general delay of industrial materials into artist paints.