X-ray fluorescence investigation of gilded and enamelled silver: The case study of four medieval processional crosses from central Italy

The presence of multilayered structures is common in such cultural artefacts as paintings, corroded metals, objects that underwent a whatever form of surface qualification. One of the most usual and complete ways to investigate such structures is observing a cross section, which requires sampling. There are however situations where at least part of the stratigraphic information can be derived non-destructively: the literature shows that X-ray fluorescence (XRF) has frequently been used, in recent years, for this purpose, with special regard to paintings and gilded metals. Aim of this paper is to further explore the suitability of XRF-based techniques to characterise multilayered structures. This is achieved by introducing improvements, with respect to previous works, in both equipment and data processing.The method, that has been developed for gilded and enamelled silver artefacts, relies on optimum excitation conditions provided for silver and on the relationship existing between the ratio AgKα/AgKβ of its fluorescence lines and the gilding thickness itself. The coating (gilding or enamel) thickness is derived by verifying the condition CKα,Ag = CKβ,Ag, where CKα,Ag and CKβ,Ag are the mass fractions of silver calculated on the lines AgKα and AgKβ, respectively. The calculations are carried out by PyMCA, a Fundamental Parameters code that implements the analysis of multilayered samples.As a case study we investigated in situ the four processional crosses of Borbona, Sant'Elpidio, Rosciolo and Forcella, made of a wood core with attached gilt and embossed silver sheets and enamelled silver plates. The analyses allowed to distinguish ancient restorations from original parts, to characterise the enamels and find their composition consistent with the dates of manufacturing and, as regards the cross of Rosciolo, to hypothesize the contribution of different “hands” in its manufacturing.

► We discuss a non-destructive XRF method for the analysis of multilayered materials.
► The coating thickness is measured through the attenuation of the substrate X-rays.
► The method uses a Fundamental Parameters approach.
► Four medieval processional crosses from Central Italy are investigated.
► Different “hands” have been recognised in the manufacturing of the same object.