Micro-Chemical and Spectroscopic Study of Component Materials in 18th and 19th Century Sacred Books
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Maja Kostadinovska
Maja Kostadinovska has a Bachelor of Science Degree in Chemical Engineering, received in 2007 at the University Ss Cyril and Methodius, Faculty of Natural Sciences and Mathematics in Skopje. She currently works as a Conservator on chemical analyses related to conservation research in the Conservation and Restoration Laboratory at the National Library in Skopje. She has research interests in the investigation of ancient artefacts and other works of art made of paper, but also in the analysis of inks and pigments on Rare Books and Manuscripts.
,
Orhideja Grupče
Orhideja Grupče is Professor of Analytical Chemistry at the Faculty of Natural Sciences and Mathematics in Skopje. Her field of interest is Molecular Spectroscopy (IR and Raman) and its application in the field of manuscripts, icons, and pottery.Zorica Jakovleska Spirovska has a Master of Science Degree in Biological Sciences, received in 2009 at the University Ss Cyril and Methodius, Faculty of Natural Sciences and Mathematics in Skopje. She worked as a Conservator in the Conservation and Restoration Laboratory at the National Library in Skopje from 1997–2004. Since 2005, she has been promoted to Head of the Department for Library funds, services and protection of library materials. In 2012 she has been awarded with the title of a Senior Conservator and since 2015 she is Head of the Library Funds and Services, protection of library materials.Biljana Minčeva-Šukarova is Professor emeritus at the Faculty of Natural Sciences and Mathematics, University Ss Cyril & Methodius in Skopje. She received PhD in Physics, Department of Physics, King’s College, London, UK in 1982. She was teaching Physical Chemistry, Radiochemistry, Spectroscopy, Material Science, Archaeometry and Forensic Chemistry. Her research interests are: Molecular Spectroscopy: IR and Raman spectroscopy of high pressure phases of ice, minerals, pigments, automotive paints, ceramics, glass, fibres, inks and dyes. She was a coordinator of FP6 project (2007–2009), coordinator for Chemistry in Tempus project (2008–2010) and participated at two COST projects (between 2006 and 2013).
Abstract
The Cyrillic books Menology for May (1705), The Bible (1822) and Mirror (1816) were consigned for conservation to the Conservation Laboratory at the National Library in Skopje. The first two books were printed in Moscow, while the third book was issued in Vienna, although it originates from the territory of the former Ottoman Empire, present-day Republic of Macedonia. In order to design a conservation protocol, papers and inks used in the books were characterized and their condition was assessed. Micro-chemical tests were used in order to identify the type of paper fibres and materials added to the paper pulp. FTIR was applied to confirm the findings for the sizing and fillers found in the paper support. Inorganic pigments were analysed by micro-Raman spectroscopy. The original paper in the Russian books was made of rags with less than 5 % lignin content present, whereas the paper in Mirror was made of raw and unbleached hardwood. Distinct types of sizing have been identified: gelatine/alum in Menology for May and Mirror and gelatine/rosin in The Bible. The pigments identified are lamp black, vermilion, Prussian blue and calcite. The study elucidates which internal and external factors could cause further decay of the books and will help in making informed decisions concerning the further preservation of the objects.
Zusammenfassung
Untersuchung der Materialzusammensetzung von drei Büchern aus dem 18. und 19. Jahrhundert mittels mikrochemischer Tests und instrumenteller Analysetechniken
Die drei kyrillischen Bücher Monatsbuch für Mai (1705), eine Bibel (1822) und Spiegel (1816) wurden zur Erhaltung an das Konservierungslabor in der Nationalbibliothek in Skopje übergeben. Die ersten beiden Bücher wurden in Moskau gedruckt, während das dritte Buch in Wien herausgegeben wurde, obwohl es aus dem Gebiet des ehemaligen Osmanischen Reiches, der heutigen Republik Mazedonien, stammt. Um ein Konservierungsprotokoll zu erstellen, wurden Papiere und Pigmente die in den Büchern verwendet wurden, charakterisiert und deren Zustand beurteilt. Es wurden mikrochemische Tests verwendet, um die Art der Papierfasern und der dem Zellstoff zugesetzten Materialien zu identifizieren. FTIR wurde angewendet, um die Ergebnisse der mikrochemischen Tests für die Leim- und Füllstoffe zu bestätigen. Anorganische Pigmente wurden durch Mikro-Raman-Spektroskopie analysiert. Das Originalpapier in den russischen Büchern wurde aus Lumpen mit weniger als 5 % Ligninanteil hergestellt, während das Papier im Spiegel aus ungebleichtem Laubholz bestand. Es wurden verschiedene Arten der Papierleimung identifiziert: Gelatine/Alaun im Monatsbuch für Mai und im Spiegel, sowie Gelatine/Kolophonium in der Bibel. Die Pigmente sind Lampenschwarz, Zinnoberrot, Preußischblau und Calcit (Calciumcarbonat). Die Studie erläutert, welche internen und externen Faktoren einen weiteren Verfall der Bücher verursachen könnten, und wird dazu beitragen, fundierte Entscheidungen über weitere Erhaltungsstrategien der Objekte zu treffen.
Résumé
Analyse de la composition des matériaux de trois livres du XVIIIe e et XIXe siècle au moyen de tests microchimiques et d’analyses instrumentales.
Les livres cyrilliques Le ménologe du mois de mai (1705), La bible (1822) et Miroir (1816) ont été confiés au laboratoire de restauration de la Bibliothèque Nationale de Skopje, afin d’être traités. Les deux premiers livres ont été imprimés à Moscou alors que le troisième, publié à Vienne est originaire du territoire de l’ancien empire ottoman, à l’heure actuelle la République de Macédoine. Afin de définir un protocole de restauration, le papier et les encres utilisés dans les livres ont été étudiés et leur état évalué. Des tests micro-chimiques ont permis d’identifier le type de fibres du papier et les matériaux ajoutés à la pâte à papier. La spectroscopie IRTF a confirmé les résultats concernant l’encollage et les charges trouvés dans le papier. Les pigments inorganiques ont été analysés par microspectroscopie Raman. Le papier d’origine des livres russes est de pâte chiffon avec moins de 5 % de lignine alors que le papier du Miroir est une pâte à bois non blanchie. Nous avons identifié différents types d’encollage du papier: gélatine/alun dans Le ménologe du mois de mai et Miroir et un mélange gélatine/colophane dans La bible. Les pigments identifiés sont le noir de lampe, le vermillon, le bleu de Prusse et la calcite.
L’étude explicite quels facteurs internes et externes pourraient causer des dommages supplémentaires aux livres et permettra de définir de manière avisée la préservation approfondie de ces objets.
About the authors
Maja Kostadinovska has a Bachelor of Science Degree in Chemical Engineering, received in 2007 at the University Ss Cyril and Methodius, Faculty of Natural Sciences and Mathematics in Skopje. She currently works as a Conservator on chemical analyses related to conservation research in the Conservation and Restoration Laboratory at the National Library in Skopje. She has research interests in the investigation of ancient artefacts and other works of art made of paper, but also in the analysis of inks and pigments on Rare Books and Manuscripts.
Orhideja Grupče is Professor of Analytical Chemistry at the Faculty of Natural Sciences and Mathematics in Skopje. Her field of interest is Molecular Spectroscopy (IR and Raman) and its application in the field of manuscripts, icons, and pottery.
Zorica Jakovleska Spirovska has a Master of Science Degree in Biological Sciences, received in 2009 at the University Ss Cyril and Methodius, Faculty of Natural Sciences and Mathematics in Skopje. She worked as a Conservator in the Conservation and Restoration Laboratory at the National Library in Skopje from 1997–2004. Since 2005, she has been promoted to Head of the Department for Library funds, services and protection of library materials. In 2012 she has been awarded with the title of a Senior Conservator and since 2015 she is Head of the Library Funds and Services, protection of library materials.
Biljana Minčeva-Šukarova is Professor emeritus at the Faculty of Natural Sciences and Mathematics, University Ss Cyril & Methodius in Skopje. She received PhD in Physics, Department of Physics, King’s College, London, UK in 1982. She was teaching Physical Chemistry, Radiochemistry, Spectroscopy, Material Science, Archaeometry and Forensic Chemistry. Her research interests are: Molecular Spectroscopy: IR and Raman spectroscopy of high pressure phases of ice, minerals, pigments, automotive paints, ceramics, glass, fibres, inks and dyes. She was a coordinator of FP6 project (2007–2009), coordinator for Chemistry in Tempus project (2008–2010) and participated at two COST projects (between 2006 and 2013).
Specific ATR bands, their assignments related to the components present in Old printed holy books (18–19th century).
| Wavenumber [cm‒1] | Assignment | Component | Menology for May | The Bible | Mirror | |||||
|---|---|---|---|---|---|---|---|---|---|---|
| (R_MM) | (R_BI) | (O_MI) | ||||||||
| Original paper | Restoration paper | Original paper | Original paper | |||||||
| ATR band | Aia/Atb | ATR band | Ai /At | ATR band | Ai /At | ATR band | Ai /At | |||
| 3500–3100 | H-bonded OH stretch | Cellulose, free H2O | 3336 | 0,4283 | 3332 | 0,3498 | 3329 | 0,4113 | 3341 | 0,3727 |
| ̴ 2918 | Asym. CH2 stretch in long alkyl chains | Waxes /Pectin | 2919 | 0,1901 | 2902 | 0,1462 | 2898 | 0,1508 | 2906 | 0,1721 |
| ̴ 2850 | Sym. CH2 stretch in long alkyl chains | 2852 | 0,1660 | 2851 | 0,1294 | 2857 | 0,1486 | |||
| ̴ 1735 | C=O vibration in C(O)OH groups | Non-conjugated carboxyl groups of cellulose | 1732 | 0,1039 | 1735 | 0,0765 | 1732 | 0,0860 | ||
| 1730 | C=O vibration | Oxidation of cellulose | 1730 | 0,0554 | ||||||
| ̴ 1710 | C=O vibration in C(O)OH groups | Non-conjugated carboxyl groups of Rosin | 1711 | 0,0571 | ||||||
| ̴ 1648 | Typical peptide C=O (Amide I band) | Animal glue or gelatine | 1648 | 0,3862 | 1648 | 0,3050 | 1648 | 0,1697 | 1647 | 0,2388 |
| ̴ 1635 | Absorbed H2O in cellulose | Intramolecular H2O, conjugated C=O | 1584 | 0,1309 | ||||||
| Unassigned | / | 1566 | 0,1303 | |||||||
| 1546–1559 | Typical peptide N–H (Amide II band) | Animal glue or gelatine | 1542 | 0,2025 | 1550 | 0,1011 | 1541 | 0,1492 | ||
| Unassigned | / | 1523 | 0,0840 | |||||||
| ̴ 1510 | C=C stretch in aromatic rings | Lignin | 1515 | 0,0285 | 1506 | 0,0762 | 1509 | 0,1272 | ||
| ̴ 1455 | OH in plane bending | Cellulose | 1453 | 0,2076 | 1456 | 0,1619 | 1456 | 0,2010 | ||
| ̴ 1425 | CH2 bending; asym. C-O stretch in CaCO3 | Cellulose; CaCO3 (Calcite) | 1429 | 0,2354 | 1427 | 0,1718 | 1428 | 0,1932 | 1427 | 0,2243 |
| ̴ 1370 | CH bending (deformation stretch) | Cellulose | 1370 | 0,2290 | 1369 | 0,1870 | 1369 | 0,1920 | 1365 | 0,2244 |
| ̴ 1335 | OH in-plane bending | Cellulose | 1334 | 0,2189 | ||||||
| 1315–1320 | OH and CH bending; Typical peptide N–H (Amide III band) | Cellulose; Animal glue or gelatine | 1317 | 0,3063 | 1320 | 0,2910 | 1315 | 0,2431 | 1316 | 0,2774 |
| ̴ 1280 | CH twisting (deformation stretch) | Cellulose | 1278 | 0,1752 | 1280 | 0,1367 | 1280 | 0,1447 | 1280 | 0,1693 |
| ̴ 1247 | OH out-of-plane bending | Cellulose | 1249 | 0,1455 | 1246 | 0,1069 | 1247 | 0,1126 | 1248 | 0,1406 |
| ̴ 1200 | OH in-plane bending | Cellulose | 1205 | 0,1257 | 1205 | 0,0957 | 1205 | 0,0933 | 1204 | 0,1286 |
| ̴ 1155 | Asym. ring breathing in β-glycoside (C1–O–C4) bond; Sulphates asym. valence vibration | Cellulose, Sulphates (SO42‒) | 1161 | 0,3077 | 1160 | 0,3110 | 1160 | 0,3000 | 1160 | 0,3170 |
| ̴ 1105 | Asym. in-plane ring stretch in β-glycoside (C1–O–C4) bond | Cellulose, Alum | 1107 | 0,5429 | 1109 | 0,5197 | 1110 | 0,5299 | 1106 | 0,5471 |
| ̴ 1055 | C–O stretch in 2° alcoholic groups of cellulose | Cellulose | 1053 | 0,9168 | 1054 | 0,9211 | 1054 | 0,9351 | 1054 | 0,9199 |
| ̴ 1030 | C–O stretch in 1° alcoholic groups of cellulose | Cellulose | 1030 | 1,0000 | 1030 | 1,0000 | 1030 | 1,0000 | 1030 | 1,0000 |
| ̴ 1000 | C–O, C-H stretch | Cellulose, Starch | 1000 | 0,8895 | 1000 | 0,8633 | 1000 | 0,8773 | 1001 | 0,8779 |
| ̴ 985 | C–O, C-H stretch | Cellulose | 985 | 0,8049 | 985 | 0,7798 | 985 | 0,7937 | 985 | 0,7886 |
| 895–900 | Asym. out-of-phase ring stretch in β-glycoside (C1–O–C4) bond | Cellulose | 901 | 0,2117 | 900 | 0,1682 | 900 | 0,1814 | 907 | 0,1931 |
| ̴ 875 | Sym. C-O stretch of CaCO3 | CaCO3 (Calcite) | ||||||||
| ̴ 712 | O-C-O bending (in-plane deformation) | CaCO3 (Calcite) | 703 | 0,0827 | 704 | 0,0839 | 702 | 0,0839 | 704 | 0,1686 |
| ̴ 670 | Sulphates bending vibration | Sulphates (SO42‒) | 663 | 0,1601 | 668 | 0,1481 | 663 | 0,1201 | 663 | 0,2095 |
a Ai – Internal absorbance – negative logarithm to the base of 10 of the internal transmittance of the medium itself and refers to energy loss by absorption.
b At – (Total) Absorbance – negative logarithm to the base of 10 of the ratio of radiant power transmitted by the sample to the radian power incident on the sample.
The incident radiant power is usually obtained as that transmitted by a non-absorbing reference material. (Applied Spectroscopy Vol.66, 1, 2012, pp. 132).
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Articles in the same Issue
- Frontmatter
- Ethanol as an Antifungal Treatment for Silver Gelatin Prints: Implementation Methods Evaluation
- Evaluation of Alkaline Compounds Used for Deacidification and Simultaneous Lining of Extremely Degraded Manuscripts
- Longevity of Optical Disc Media: Accelerated Ageing Predictions and Natural Ageing Data
- Micro-Chemical and Spectroscopic Study of Component Materials in 18th and 19th Century Sacred Books
Articles in the same Issue
- Frontmatter
- Ethanol as an Antifungal Treatment for Silver Gelatin Prints: Implementation Methods Evaluation
- Evaluation of Alkaline Compounds Used for Deacidification and Simultaneous Lining of Extremely Degraded Manuscripts
- Longevity of Optical Disc Media: Accelerated Ageing Predictions and Natural Ageing Data
- Micro-Chemical and Spectroscopic Study of Component Materials in 18th and 19th Century Sacred Books
