Evaluation of Alkaline Compounds Used for Deacidification and Simultaneous Lining of Extremely Degraded Manuscripts
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Maria Sistach
M. Carme Sistach , born in 1953, graduated in biochemistry and organic chemistry at the University of Barcelona in 1979. She graduated in Escola Superior de Conservació i Restauració de Bens Culturals de Catalunya in 1990 and gained her degree in paper and cellulose chemistry at the Polytechnic University of Terrassa in Barcelona in 2002. Since 1986 she is the chemist of the Laboratory of Restoration at the Archive of the Crown of Aragon in Barcelona. She participates in the two EU projects: “Transition Metals in Paper - MIP” and “EnviArt -COST D42”.Eva Marín , born in 1980, received her Fine Arts degree at the University of Barcelona in 2004 in the specialization of Conservation of Cultural Heritage. She obtained her Ph.D. in analytical chemistry in 2015 at the University of Barcelona. Currently she is involved in several projects in collaboration with the University of Barcelona. Her research is focussed on the development and application of specific analytical techniques to the study of different artworks, especially paper-based documents.Dr. José F. García , born in 1959, obtained his Ph.D. in analytical chemistry in 1989 at the University of Barcelona. At present, he is a full professor at the Analytical Chemistry Department at the University of Barcelona. Since 1982, he has been working in radio-analytical chemistry; since 1997, he is involved in analytical chemistry applied to cultural heritage. His main interest is focused on the development and application of specific analytical techniques to the study of different sets of artworks. Contact: Departament de Química Analítica, Facultat de Químiques, Universitat de Barcelona, Diagonal Ave 645 (08028) Barcelona Spain. jfgarcia@ub.edu.
Abstract
Iron gall ink’s natural acidity promotes the degradation of manuscripts. This process mostly affects the areas containing ink, causing fragility of the paper carrier that limits its manipulation. The cellulosic material is modified by two chemical reactions, acidic hydrolysis and oxidation, both depending on the pH of the paper. This article explores the distribution of acidity in manuscripts and its link to iron gall ink corrosion and cellulose degradation. Subsequently, different treatment methods of deacidification, specifically designed for extremely degraded paper documents and sheets bound in volumes were tested. Documents were deacidified and at the same time mechanically supported, using an alkaline compound for deacidification that increases the pH to a range at which iron ion oxidation is decreased. Three alkaline compounds at different concentrations were evaluated: (1) calcium carbonate microparticles, (2) calcium hydroxide nanoparticles and (3) calcium propionate solution. The immediate and long-term effects after ten months of storage of these compounds on the increase of the pH of manuscripts are described in this study. All tested compounds were able to increase the pH and maintain it in the course of the observed period. Moreover, a lining with thin tissue and a mixture of 3 % gelatine dissolved in 60 % water and 40 % alcohol provides the consolidation required for manipulation of the manuscripts.
Zusammenfassung
Die Behandlung von tintenfraßgeschädigten Manuskripten mit einer Kombination von Entsäuerung und Kaschierung
Eisengallustinte schädigt durch ihren Säuregehalt Papier vor allem in den Bereichen, die Tinte enthalten. Das Blatt wird in der Folge brüchig und jede Handhabung kann weitere Schäden verursachen. Cellulose wird dabei durch zwei chemische Reaktionen abgebaut: saure Hydrolyse und Oxidation; beide Reaktionen verlaufen in Abhängigkeit vom pH Wert des Papiers. In der vorliegenden Studie wurde der Zusammenhang von der Verteilung des Säuregehalts im Papier und dem Abbau der Cellulose untersucht. In der Folge wurden verschiedene Entsäuerungsmethoden getestet, die speziell für stark tintenfraßgeschädigte Objekte und für Tintenfraßschäden in Büchern entwickelt worden waren. Dabei wurden alkalische Verbindungen eingesetzt, die den pH Wert des Papiers so weit erhöhen, dass die durch Eisenionen verursachten Oxidationsprozesse verlangsamt werden. Drei alkalische Verbindungen wurden dazu in verschiedenen Konzentrationen getestet: (1) Calciumcarbonat Mikropartikel, (2) Calciumhydroxid Nanopartikel und (3) eine Calciumpropionat Lösung. Die unmittelbare und längerfristige Wirkung dieser drei Verbindungen auf den pH Wert des Papiers wurde untersucht. Darüber hinaus wurden tintenfraßgeschädigte Papiere im selben Arbeitsschritt durch eine Kaschierung mit sehr dünnem Japanpapier und 3 %iger Gelatine in einer Mischung aus 60 % Wasser und 40 % Ethanol mechanisch gefestigt.
Résumé
Evaluation de composés alcalins utilisés pour la désacidification et le renfort simultané de manuscrits très endommagés.
La dégradation des manuscrits engendrée par l´encre métallo-gallique est accélérée par l´acidité. Cette corrosion affecte principalement les zones portant l´écriture, ce qui cause une fragilité du papier et ce qui rend sa manipulation difficile. Le matériau cellulosique est modifié par deux réactions chimiques l´hydrolyse acide et l´oxydation, toutes deux étant accélérées en milieu acide. Pour répondre à ce problème en restauration, nous avons testé différents traitements de désacidification et plus précisément ceux utilisés pour des manuscrits en papier très dégradés et pour des volumes reliés.
Cet article montre la distribution de l´acidité dans les manuscrits et son lien avec la corrosion et la dégradation. Une méthode permettant en même temps de désacidifier et de renforcer par une couche supplémentaire des manuscrits très fragiles a été développée et améliorée, en utilisant un composé alcalin pour la désacidification qui augmente le pH à un niveau auquel l´oxydation de l´ion fer est réduite.
Un fin papier de doublage (Nao K00 3gr/m2) a permis d´améliorer la manipulation et a été collé sur le manuscript avec un mélange GEOL, une solution de gélatine à 3 % diluée dans 60 % d´eau et 40 % d´alcool.
Trois composés alcalins à différentes concentrations dans le mélange GEOL ont été évalués: des microparticules de carbonate de calcium, des nanoparticules d´hydroxyde de calcium et une solution de propionate de calcium. Les effets immédiats et à long terme de ces composés sur le pH des manuscrits sont présentés dans cet article.
About the authors
M. Carme Sistach, born in 1953, graduated in biochemistry and organic chemistry at the University of Barcelona in 1979. She graduated in Escola Superior de Conservació i Restauració de Bens Culturals de Catalunya in 1990 and gained her degree in paper and cellulose chemistry at the Polytechnic University of Terrassa in Barcelona in 2002. Since 1986 she is the chemist of the Laboratory of Restoration at the Archive of the Crown of Aragon in Barcelona. She participates in the two EU projects: “Transition Metals in Paper - MIP” and “EnviArt -COST D42”.
Eva Marín, born in 1980, received her Fine Arts degree at the University of Barcelona in 2004 in the specialization of Conservation of Cultural Heritage. She obtained her Ph.D. in analytical chemistry in 2015 at the University of Barcelona. Currently she is involved in several projects in collaboration with the University of Barcelona. Her research is focussed on the development and application of specific analytical techniques to the study of different artworks, especially paper-based documents.
Dr. José F. García, born in 1959, obtained his Ph.D. in analytical chemistry in 1989 at the University of Barcelona. At present, he is a full professor at the Analytical Chemistry Department at the University of Barcelona. Since 1982, he has been working in radio-analytical chemistry; since 1997, he is involved in analytical chemistry applied to cultural heritage. His main interest is focused on the development and application of specific analytical techniques to the study of different sets of artworks. Contact: Departament de Química Analítica, Facultat de Químiques, Universitat de Barcelona, Diagonal Ave 645 (08028) Barcelona Spain. jfgarcia@ub.edu.
Acknowledgements
We would like to thank the Spanish Ministerio de Economía y Competitividad (HAR-2014-56526-R), whose support enabled us to undertake this research. We are also grateful to the CSGI, University of Florence, who provided the nanoparticles used in this study.
References
Amornkitbamrung, L., Mohan, T., Hribernik, S., Reichel, V., Faivre, D., Gregorova, A., Engel, P., Rupert, K., Ribitsch, V.: Polysaccharide for deacidification and strengthening of paper. RSC Advances 5 (2015): 32950–32961.10.1039/C4RA15153DSearch in Google Scholar
Baglioni, P., Chelazzi, D., Giorgi, R., Xing, H., Poggi, G.: Alkaline nanoparticles for the deacidification and pH control of books and manuscripts. In: Nanoscience and Cultural Heritage, Atlantis Press and the authors, P. Dillmann et al. (eds.), 2016: 253–281. DOI: 10.2991/978-94-6239-198-7_9.Search in Google Scholar
Baty, J. W., Maitland, C. L., Minter, W., Hubbe, M. A., Jordan-Mowery, S. K.: Deacidification for the conservation and preservation of paper-based Works: A review. Bioresources 5 (3) (2010): 1955–2013.10.15376/biores.5.3.1955-2023Search in Google Scholar
Belhadj, O., Phan Tan Luu, C., Jacobi, E., Meslet-Struyve, S., Vez, S., Reissland, B., Rouchon, V.: The Dutch Fe-migration Mending test. Journal of Paper Conservation 15 (1) (2014): 9–15.Search in Google Scholar
Brückle, I.: Remoistenable lining with methylcellulose adhesive preparation. The Book and Paper Group and Annual of the American Institute for Conservation of Historic and Artistic Works (AIC) 1 (15) (1995): 25–26.Search in Google Scholar
Budnar, M., Vodopivec, J., Mandò, P. A., Lucarelli, F., Casu, G., Signorini, O.: Distribution of chemical elements of iron gall ink writing studied by Pixe method. Restaurator 22 (4) (2001): 228–241.10.1515/REST.2001.228Search in Google Scholar
Calvini, P., Gorassini, A.: The degradation action of iron and copper on paper. A FTIR-deconvolution analysis. Restaurator 23 (4) (2002): 205–221.10.1515/REST.2002.205Search in Google Scholar
Csefalvayová, L. H., Čepan, M., Jakubíková, Z.: The influence of iron gall ink on paper ageing. Restaurator 28 (2) (2007): 129–139.10.1515/REST.2007.129Search in Google Scholar
Ferrer, N., Sistach, M. C.: Analysis of sediments on iron gall inks in manuscripts. Restaurator 34 (3) (2013): 175–193.10.1515/res-2013-0010Search in Google Scholar
Giorgi, R., Dei, L., Ceccato, M., Schettino, C., Baglioni, P.: Nanotechnologies for conservation of cultural heritage paper and canvas deacidification. Langmuir 18 (2002): 8198–8203.10.1021/la025964dSearch in Google Scholar
Hahn, O., Wilke, M., Wolf, T.: Influence of aqueous calcium phytate, calcium hydrogen carbonate treatment on the chemical composition of iron gall inks. Restaurator 29 (4) (2008): 235–250.10.1515/rest.2008.017Search in Google Scholar
Huhsmann, E., Hähner, U.: Work standard for the treatment of 18th and 19th century iron gall inks documents with calcium phytate and calcium hydrogen carbonate. Restaurator 29 (4) (2008): 274–319.10.1515/rest.2008.020Search in Google Scholar
ISO 6588-1: Paper, board and pulps - Determination of pH of aqueous extracts. International Standard Organization, Reference number ISO/6588-1. Vol. 4. (Refinement 2011).Search in Google Scholar
Jacobi, E., Reissland, B., Phan Tan Luu, C., Velzen, B.: Rendering the invisible visible. Journal of Paper Conservation 12 (2) (2011): 25–34.Search in Google Scholar
Kolar, J.: Mechanism of autoxidative degradation of cellulose. Restaurator 18 (4) (1997): 163–176.10.1515/rest.1997.18.4.163Search in Google Scholar
Kolar, J., Malešič, J., Kočar, D., Strlič, M., De Bruin, G., Koleša, D.: Characterisation of paper containing iron gall ink using size exclusion chromatography. Polymer Degradation and Stability 97 (2012): 2212–2216.10.1016/j.polymdegradstab.2012.08.005Search in Google Scholar
Kolar, J., Možir, A., Balažic, A., Strlič, M., Ceres, G., Conte, V., Miruzzo, V., Steemers, T., De Bruin, G.: New antioxidant for treatment of transition metal containing inks and pigments. Restaurator 29 (3) (2008): 184–198.10.1515/rest.2008.013Search in Google Scholar
Kolar, J., Možir, A., Strlič, M., De Bruin, G., Pihlar, B., Steemers, T.: Stabilisation of iron gall ink: Aqueous treatment with magnesium phytate. Preservation Science (4) (2007): 19–24.Search in Google Scholar
Kolar, J., Strlič, M., Budnar, M., Malešič, J., Šelih, V.S., Simčič, J.: Stabilisation of corrosive iron gall inks. Acta Chimica Slovenica (50) (2003): 763–770.Search in Google Scholar
Kolar, J., Sala, M., Strlič, M., Šelih, V.-S.: Stabilisation of paper containing iron-gall inks with current aqueous processes. Restaurator 26 (3) (2005): 181–189.10.1515/rest.2005.26.3.181Search in Google Scholar
Kolar, J., Strlič, M. (eds.): Ageing and stabilisation of paper containing iron gall inks. In: Iron Gall Inks: On Manufacture, Characterization, Degradation and Stabilization, National and University Library, Ljubljana, Slovenia, 2006: 181–194.Search in Google Scholar
Kolbe, G.: Gelatine in historical paper production as an inhibiting agent for iron gall ink corrosion on paper. Restaurator 25 (1) (2004): 26–39.10.1515/REST.2004.26Search in Google Scholar
Malešič, J., Kočar, D., Balžic, A.: Stabilisation of copper and iron containing papers in mildly alkaline environment. Polymer Degradation and Stability 97 (1) (2012): 118–123.10.1016/j.polymdegradstab.2011.09.025Search in Google Scholar
Malešič, J., Šala, M., Šelih, V.-S., Drago, K.: Evaluation of a method for treatment of iron gall ink corrosion on paper. Cellulose (2014). DOI: 10.1007/s10570-014-0311-6, online, last visited November 2016.Search in Google Scholar
Marín, E., Sistach, M. C., Jiménez, J., Clemente, M., García, G., García, J. F.: Distribution of acidity and alkalinity on degraded manuscripts containing iron gall ink. Restaurator 36 (3) (2015): 229–247.10.1515/res-2015-0002Search in Google Scholar
Martin, A., Rouchon, V., Aubry, T., Cauliez, N., Desroches, M., Margez, M.: Local strengthening of mould-damaged manuscripts. Journal of Paper Conservation 12 (1) (2011): 21–29.Search in Google Scholar
Mohan, T., Faivre, D., Kovalcik, A., Ribitsch, V.: Polysaccharide for deacidification and strengthening of paper. RSC Advances (5) (2015): 3290–3261.10.1039/C4RA15153DSearch in Google Scholar
Neevel, J. G.: Phytate a potential conservation agent for the treatment of ink corrosion caused by irongall inks. Restaurator 16 (3) (1995): 143–160.10.1515/rest.1995.16.3.143Search in Google Scholar
Neevel, J. G.: The behaviour of iron and sulphuric acid during iron-gall ink corrosion. Proceedings of ICOM- CC Meeting, 30 August-3 September, Lyon. (1999): 528–535.Search in Google Scholar
Pataki, A.: Remoistenable tissue preparation and its practical aspects. Restaurator 30 (1/2) (2009): 51–69.10.1515/rest.004Search in Google Scholar
Plossi-Zappalà, M.: Il propionato di calcio nella deacidificazzione e/o stabilizzazione della carta. [Calcium Propionate in the Deacidification and/ or Stabilisation of Paper] Cellulosa E Carta 45 (3) (1994): 55–58.Search in Google Scholar
Poggi, G., Baglioni, P., Giorgi, R.: Alkaline earth nanoparticles for the inhibition of metal gall ink corrosion. Restaurator 32 (4) (2011): 247–273.10.1515/rest.2011.012Search in Google Scholar
Poggi, G., Giorgi, R., Toccafondi, V. K., Baglioni, P.: Hydroxide nanoparticles and concomitant inhibition of iron-gall ink corrosion on paper. Langmuir 26 (24) (2010): 19084–19090.10.1021/la1030944Search in Google Scholar
Poggi, G., Sistach, M. C., Marín, E., Garcia, J. F., Giorgi, R., Baglioni, P.: Calcium hydroxide nanoparticles in hydroalcoholic gelatine solutions (Geolnan) for the deacidification and strengthening of papers containing iron gall ink. Journal of Cultural Heritage 18 (2015): 250–257.10.1016/j.culher.2015.10.005Search in Google Scholar
Poggi, G., Toccafondi, N., Melita, L. N., Knowles, J. C., Bozec, L., Giorgi, R., Baglioni, P.: Calcium hydroxide nanoparticles for the conservation of cultural heritage. New formulations for the deacidification of cellulose-based materials. Applied Physics A, Materials Science and Processing (114) (2014): 8172–8177. DOI: 10.1007/s00339-013-8172-7.Search in Google Scholar
Reissland, B.: Ink corrosion aqueous and non-aqueous treatment of paper objects-state of art. Restaurator 20 (3–4) (1999): 167–180.10.1515/rest.1999.20.3-4.167Search in Google Scholar
Rouchon, V., Desroches, M., Duplat, V., Letouzey, M., Stordiau-Pallat, J.: Methods of aqueous treatments. The last resort for badly damaged iron gall ink manuscripts. Journal of Paper Conservation 13 (3) (2012): 7–13.Search in Google Scholar
Rouchon, V., Duranton, M., Belhadj, O., Bastier-Deroches, M., Duplat, V., Walbert, C., Vinther-Hansen, B.: The use of halide charged interleaves for treatment of iron gall ink damaged papers. Polymer Degradation and Stability (89) (2013): 1339–1347.10.1016/j.polymdegradstab.2013.03.028Search in Google Scholar
Saverwyns, S., Sizaire, V., Wouters, J.: The acidity of paper. Evaluation of methods to measure the pH of paper samples. In: ICOM: 13th Triennial Meeting, Rio ICOM-CC (2002): 634–638.Search in Google Scholar
Schalkx, H., Iedema, P., Reissland, B., Velzen Van, B.: Aqueous treatment of water-sensitive paper objects. Journal of Paper Conservation 12 (1) (2011): 11–20.Search in Google Scholar
Sistach, M. C., Gibert, J. M., Areal, R.: Ageing of laboratory irongall inks studied by reflectance spectrometry. Restaurator 20 (3+4) (1999): 151–166.10.1515/rest.1999.20.3-4.151Search in Google Scholar
Strilč, M., Kolar, J., Kocar, D., Drnovsed, T., Selih, V.-S., Susic, R.: What is the pH of alkaline paper?. E- Preservation Science 1 (2004): 35–47.Search in Google Scholar
Strlič, M., Kolar, J., Šelih, V.-S., Kočar, D., Pihlar, B.: A comparative study of several transition metals in Fenton-like reaction system at circum-neutral pH. Acta Chimica Slovenica (50) (2003): 619–632.Search in Google Scholar
TAPPI T 529 om-99: Flat electrode measurement of pH in printing papers. Tappi 55 (3) (1975): 393–395.Search in Google Scholar
Wójciak, A.: Washing, spraying and brushing. A comparison of paper deacidification by Magnesium hydroxide nanoparticles. Restaurator 36 (1) (2015): 3–23.10.1515/res-2014-0010Search in Google Scholar
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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
