Abstract
Degradation of cellulose in historic paper by iron gall ink is a synergistic process of both, acid hydrolysis caused by acidic ink ingredients and oxidation catalyzed by free iron and/or copper ions. The interplay of both reactions was studied according to the CCOA method on historic paper samples. Only minute amounts (few mg) of the samples were required to obtain profiles of naturally present and oxidatively introduced carbonyl groups, which was done by group-selective fluorescence labeling in combination with determination of the molecular weight distribution by GPC-MALLS. In the present study naturally occurring degradation pathways in historic sample papers have been investigated. Different extents of oxidatitive degradation were shown for paper with and without ink. A typical pattern of the molecular weight distribution in naturally aged papers was identified, the peculiar feature being a distinctive shoulder in the region of low molecular weight, roughly between 25,000 and 5,000 g/mol corresponding to a DP between 150 and 30. This pattern was a typical attribute of degraded natural samples: any artificial aging procedures aimed at modeling natural aging processes must thus attempt to reproduce this feature. Although the historic samples had been more severely oxidized than model papers, the inhibition of further oxidation and hydrolysis by the calcium phytate/hydrogen carbonate treatment was evident and could be proven for the first time on the molecular level. Also on plain paper without ink application the oxidation was suppressed and the molecular weight was stabilized on a high level.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Banik G (1997) Decay caused by iron-gall inks. In: van der Windt E (ed) Iron-gall ink corrosion. Proceedings of European workshop on iron-gall ink corrosion, Amsterdam. pp 21–26
Banik G (1999) Phänomene und Ursachen von Tintenfraß auf Papier—eine Einführung. In: Banik G, Weber H (eds) Tintenfraßschäden und ihre Behandlung. Kohlhammer, Stuttgart, pp 11–24
Banik G, Stachelberger H (1984) Phänomene und Ursachen von Farb- und Tintenfraß. In: Vendl A, Pichler B (eds) Wiener Berichte über Naturwissenschaft in der Kunst, Wien. pp 188–213
Banik G, Stachelberger H, Messner K (1988) Untersuchung der destruktiven Wirkung von Tinten auf Schriftträgermaterialien. Restauro 94:302
Banik G, Kolbe G, Wouters J (2002) Analytical procedures to evaluate conservation treatments of iron gall ink corrosion. In: la conservation à l’ère du numérique, Paris. pp 205–217
Brown DG, Abbot J (1995) Effects of metal ions and stabilisers on peroxide decomposition during bleaching. J Wood Chem Technol 15:85. doi:10.1080/02773819508009501
Kolar J, Strlič M, Budnar M, Malešič J, Šelih VS, Simčič J (2003) Stabilisation of corrosive iron gall inks. Acta Chim Slov 50:763
Kolar J, Sala M, Strlič M, Šelih VS (2005) Stabilisation of paper containing iron-gall ink with current aqueous processes. Restaurator 26:181
Neevel J (1995) Phytate: a potential conservation agent for the treatment of ink corrosion caused by irongall inks. Restaurator 16:143
Potthast A, Röhrling J, Rosenau T, Borgards A, Sixta H, Kosma P (2003) A novel method for the determination of carbonyl groups in cellulosics by fluorescence labeling. Part III: monitoring oxidative processes. Biomacromolecules 4:743. doi:10.1021/bm025759c
Potthast A, Henniges U, Banik G (2008) Irongall ink-induced corrosion of cellulose: aging, degradation and stabilization. Part 1: model paper studies. Cellulose. doi:10.1007/s10570-008-9238-0
Reißland B (1999) Ink corrosion: aqueous and non-aqueous treatment of paper objects—state of the art. Restaurator 20:167
Restaurierung der durch Tintenfraß geschädigten Handschriften des Savigny-Nachlasses. Anwendung der Calciumphytat-Calciumhydrogencarbonat-Behandlung und der partiellen Stabilisierung in der Praxis. http://www.uni-marburg.de/bis/ueber_uns/projekte/dfgtinte/Bericht
Röhrling J, Potthast A, Rosenau T, Lange T, Borgards A, Sixta H et al (2002a) A novel method for the determination of carbonyl groups in cellulosics by fluorescence labeling. Part II: validation and applications. Biomacromolecules 3:369
Röhrling J, Potthast A, Rosenau T, Lange T, Ebner G, Sixta H et al (2002b) A novel method for the determination of carbonyl groups in cellulosics by fluorescence labeling. Part I: method development. Biomacromolecules 3:359
Šelih VS, Strlič M, Kolar J, Pihlar B (2007) The role of transition metals in oxidative degradation of cellulose. Polym Degrad Stabil 92:1476. doi:10.1016/j.polymdegradstab.2007.05.006
Shahani C, Hengemihle F (1986) The influence of copper and iron on the permanence of paper. American Chemical Society, Washington
Shirton LJ (1987) Winterthur water screen bathing. Paper Conservation News 42:3
Williams JC, Fowler CS, Lyon MS, Merrill TI (1977) Metallic catalysts in the oxidative degradation of paper. Adv Chem Ser 164:37
Zerdoun Bat-Yehouda M (1983) Les Encres Noires au Moyen Âge. Édition du Centre National de la Recherche Scientifique, Paris
Acknowledgments
We would like to thank Dr. Sonja Schiehser for practical assistance. We are grateful for the financial support by PAL GmbH, Leipzig, Germany and the Austrian Science Foundation (FWF Grant L188-N11 and FWF START 267-N11 for LA-ICP-MS analysis).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Henniges, U., Reibke, R., Banik, G. et al. Iron gall ink-induced corrosion of cellulose: aging, degradation and stabilization. Part 2: application on historic sample material. Cellulose 15, 861–870 (2008). https://doi.org/10.1007/s10570-008-9238-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-008-9238-0