A study of some illuminated Armenian manuscripts

Due to its early Christianization, Armenia has preserved a huge patrimony of religious figures in paintings, statues, icons and illuminated codices. Most of the latter are still conserved in Matenadaran Library in Yerevan and their chronology is widely represented from the Middle Ages to XIX century. Armenian manuscripts embrace also various humanities, such as history, philosophy, law, medicine and mathematics. A rich historiographic literature is also present. Therefore it was attractive to carry out an attempt to discover materials and techniques used in the past to prepare the manuscripts and to assemble the codices. Inks and gilding were also considered. Specific materials of Armenian culture will be emphasized. The samples were taken by some of us at the Matenadaran Library of Yerevan (Armenia) and some additional materials, such as Armenian bole and cochineal powder, were found in Yerevan too. The samples were taken with a lancet on deteriorated portions of some papers and parchments pertaining to Armenian codices. Only small fragments were used, since the spectroscopic techniques used need amount down to some micrograms. This is due to their high spatial resolution, enabling also the overlapping layers of pigments and preparation to be studied and their molecular identity to be ascertained in a non-destructive non –invasive way: the same samples could be subjected to other analyses with other techniques. The use of so small samples enabled the use of high performance instrumentation in the Centre of Great Instruments in Modena (CIGS) and to carry out additional experiments with silver nano-particles for Sers technique (surface enhanced Raman spectroscopy). Fourier-Transform infrared (FTIR) spectra were recorded using an Alpha FT-IR spectrometer (Bruker) equipped with the Diffuse Reflection Infrared Fourier Transform ( DRIFT) module in the spectral range 7500 – 375 cm-1 at a resolution of 2 cm-1 cumulating at least 200 scans. The use of SEM-EDX technique was important for characterization of papers and inks. Py/GS/MS was fundamental for organic binding media characterization. The methods of study were the application of atomic (XRF X-ray fluorescence spectroscopy), molecular (FT-IR and microRaman), SEM-EDX and pyrolisis GS/MS spectroscopic techniques to the samples in such a way to obtain the information useful for the understanding of the materials and art techniques applied. Particularly, the analysis of the different inks used in different times and the decoration with gilding on bole with a proper binder was taken into consideration. Experimental Results. Many materials were seen to be used through centuries in Armenian illumination. As already pointed out by Orna and co-workers [1, 2] many materials were identified and the execution techniques were clarified. According to recent investigation [3] other results on new materials and specific products coming from the territory have appeared based on Raman microscopy. A rich polychromy was often present and rare materials are shown to have been employed, such as the green antlerite, a basic copper sulfate mineral present in Caucasus and South of Iran. Lazurite, vermilion, azurite, orpiment, white lead, red lead, indigo, litharge, massicot, carbon were identified. Gilding was applied on an assisa. The Armenian bole is shown to be composed of white Kaolinite and Hematite. Forthcoming information is the application of Raman Sers technique for the identification of the materials and techniques used in Armenian illumination through times. The Armenian Cochineal (from Porphyrophora hamelii Brandt) is composed of carminic acid, that is highly fluorescent in Raman microscopy, unless Sers is used on a sample. With the application of simple atomic and molecular spectroscopy techniques available in many laboratories it was shown to be possible to obtain fundamental information on the specificity of Armenian illumination techniques. The palette of the pigments identified is rich and accompanied by the use of mixtures for preparing green, gray, orange and brown shades; gilding on a red bole with a gold leaf. The most shining red shades were obtained with porphyrophora hamelii, a cochineal proper from Armenia. Literature 1. M. V. Orna, T. F. Mathews, Uncovering the secrets of Medieval Artists, Anal. Chem. 60(1988) 47A-56A. 2. D.E. Cabelli, M.V. Orna, T.F. Mathews, Analysis of Medieval Pigments from Cilician Armenia, Archaeological Chemistry III. Chapt.12 (1984) 243-54. 3. Pietro Baraldi, Gayane Eliazian, Yeghis Keheyan, A study on the polychromy and technique of some Armenian illuminated manuscripts by Raman microscopy, 2nd International Congress of Chemistry for Cultural Heritage, Istanbul, July 9-12, 2012.