Multi-analytical study of techniques and palettes of wall paintings of the monastery of Žiča, Serbia

• Wall paintings were analysed by micro-Raman, FT-IR, SEM–EDS and ED-XRF spectroscopies.
• Fresco technique and natural earth pigments were identified.
• Composition and technique of gilding identifies golden tin deposit over yellow ochre.

The present multi-analytical study concentrates on establishing the painting techniques and the identity of the wall painting materials used by the artists from the 13th and 14th centuries to decorate the Žiča monastery, Serbia. For this purpose, we demonstrate that micro-Raman spectroscopy is an efficient, non-destructive method with high spatial resolution which gives molecular and crystal structural information of a wide variety of both inorganic and organic materials. It is shown that elementary composition revealed through scanning electron microscopy with energy dispersive X-ray spectroscopy and energy dispersive X-ray fluorescence spectroscopy is necessary in some cases to confirm the identity of pigments and binders identified by micro-Raman spectroscopy. It was found that a fresco technique, in combination with mainly natural earth pigments such as red ochre, yellow ochre and green earth, was used. Expensive natural pigment lapis lazuli was exclusively used for obtaining blue colour while pure vermilion was used by the artists from the first period of decorations at the beginning of the 13th century. A mixture of pigments was used for attaining different colour shades. For the gilding of saint's haloes, thin golden foil was deposited over the tin sheet. In order to get a desirable optical and aesthetical impression, the metallic leaves were deposited over the yellow ochre preparatory layer. Deposits of gypsum on wall paintings as well as traces of weddellite are degradation products formed as a result of exposing wall paintings to environmental conditions.

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