Application of micro-Raman and infrared spectroscopy for the study of medieval manuscript

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This paper is a survey conducted on very rare medieval manuscript (XVI - XVII century) with the use of micro-Raman and infrared spectroscopy with the intent to characterize the inks and pigments in the written text and ornaments. The manuscript is
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  Application of micro-Raman and infrared spectroscopy for the study of medieval manuscript Maja Kostadinovska a , Zorica Jakovleska-Spirovska a  and Biljana Minceva-Sukarova b а    National and University Library “ St. Clement of Ohrid ”, Bul. Goce Delcev No.6, P.O. Box 566 1000 Skopje, Republic of Macedonia b Institute for Chemistry, Faculty for Natural Sciences and Mathematics, Ss. Cyril and Methodius University, Arhimedova 5, 1000 Skopje, Republic of Macedonia Abstract This paper is a survey conducted on very rare medieval manuscript (XVI - XVII century) with the use of micro-Raman and infrared spectroscopy with the intent to characterize the inks and pigments in the written text and ornaments. The manuscript is written in ancient religious language with Cyrillic letters in three different time periods. Eight pigments/inks were identified: lime white (calcite), lead white, red lead (minium), red ochre, vermilion, indigo, carbon and iron gall ink and their Raman spectra are presented. Most of the pigments were found in the manuscript of the first period (end of XVI century), although other two manuscripts of late XVII century are significantly richer in ornamentation. Examination of sections of the paper with and without text of red or black ink by infrared spectroscopy showed insignificant differences in spectra which gave no information on the type or degeneration of inks. An exception was the presence of calcite which was detected in comparison with the spectrum of modern paper. Additional analyzes were made on two types of kozo  paper (a paper used in the process of conservation). In modern paper clearly observed are bands at 875 and 1420 cm -1  due to the present calcite, and also noted are characteristic bands of cellulose. The infrared spectra of manuscript paper is partially different from the reference IR spectrum of modern paper and also kozo paper. Infrared spectra of inks (black and red) were compared with the spectra of the manuscript paper. Obtained infrared spectra of inks were very similar to those of clean paper and have no additional bands recognized as indication to the presence of ink or some damage of the inks. The tests were performed in the phase of restoration of the book in order to provide guidance for further action in conservation process. Micro-Raman spectroscopy proved to be a very effective technique for identification of inorganic pigments on manuscripts and is much more reliable method compared to infrared spectroscopy for their detection and identification. On the other hand, infrared spectroscopy proved to be a potential method for examining different composition of paper. Keywords: micro-Raman, infrared, spectroscopy, inks, paper
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