Evaluation of Treatments for Stabilization of Verdigris and Malachite Containing Paper Documents
-
Dr. Jasna Malešič received a degree in chemistry from the University of Ljubljana, Slovenia, in 1999. From 2001 until 2004 she worked at the NUL as a conservation scientist on two EU 5th framework projects (InkCor and Papylum). She obtained her Ph.D. in organic chemistry in 2005 with the thesis »The effect of various antioxidants on the stability of cellulose«. From 2004 she has been working as a conservator responsible for preservation of library materials and since 2005 she has been head of Preservation and Conservation Department.
,
Dr. Jana Kolar is founder of Morana RTD, a research intensive microcompany. She has published more than 50 papers in international peer-reviewed journals, 13 chapters in books and co-edited two books (Ageing and Stabilisation of Paper and Iron Gall Inks: On Manufacture, Characterisation, Degradation and Stabilisation): She is editor of e-Preservation Science journal.Dr. Manfred Anders is managing director and head of Research and Development at ZFB Zentrum für Bucherhaltung GmbH. He is a specialist in Cellulose-, Paper- and Textile-Chemistry. (PhD-Thesis at the University of “Stuttgart: “Analysis of paper ageing and preservation of damaged papers by deacidification and consolidation.”)
Abstract
Copper ions and acids lead to enhanced degradation of the paper carrier. Stabilization treatment of documents with pigments such as verdigris and malachite should therefore include addition of alkalis to combat acid hydrolysis of cellulose and antioxidants to retard oxidative degradation catalysed by copper ions. The paper reviews present approaches for stabilisation of green copper pigments. Furthermore, two recently proposed treatments containing tetraalkylammonium bromide antioxidants and alkali are evaluated. The first treatment is based on interleaving of paper samples containing malachite or verdigris pigments with papers, impregnated with alkaline buffer and antioxidant at elevated relative humidity and applied pressure. The second one is based on the use of non-aqueous suspensions of nano calcium carbonate and/or magnesium oxide particles and tetrabutylammonium or tetrapropylammonium bromide. Size exclusion chromatography is used to monitor the extent of degradation of samples during accelerated ageing, while colour changes of pigments are determined using colourimetry. Results demonstrate that effective stabilization of paper samples can be achieved with tetrabutylammonium bromide and calcium carbonate containing interleaves at 90% RH. When non-aqueous immersion treatment is applied, tetrabutylammonium bromide at a concentration 0.09 M in combination with calcium carbonate nano particles had the most beneficial effect on the paper as well as on the colour of the copper based pigments.
Résumé
Évaluation des traitements de stabilisation de documents papier contenant du vert de gris et de la malachite
Les ions et les acides de cuivre conduisent à une dégradation accrue du support papier. Le traitement de stabilisation des documents comprenant des pigments tels que le vert de gris et de la malachite devrait donc inclure plus de substances alcalines pour lutter contre l’hydrolyse acide de la cellulose et contre les antioxydants pour retarder la dégradation oxydative catalysée par des ions de cuivre. Cet article passe en revue les approches actuelles de stabilisation de pigments de cuivre vert. En outre, deux traitements récemment proposés contenant du bromure tétraalkylammonium antioxydant et alcalin sont évalués. Le premier traitement est basé sur l’empilement successif d’échantillons de papier contenant des pigments de malachite ou vert de gris alternés avec des papiers imprégnés de solution tampon alcaline et d’un antioxydant à une humidité relative élevée et sous pression. Le deuxième est basé sur l’utilisation de suspensions non aqueuses de nanoparticules de carbonate de calcium et/ou de particules d’oxyde de magnésium et de bromure de tétrapropylammonium ou tétrabutylammonium. La chromatographie d’exclusion de taille est utilisée pour mesurer l’étendue de la dégradation des échantillons au cours du vieillissement accéléré, tandis que les changements de couleur des pigments sont déterminés par colorimétrie. Les résultats montrent qu’une stabilisation efficace des échantillons de papier peut être obtenue avec l’insertion de papiers intercalaires contenant du bromure de tétrabutylammonium et du carbonate de calcium à 90% d’humidité relative. Lorsque le traitement d’immersion non aqueuse est appliqué, le bromure de tétrabutylammonium à une concentration de 0,09 M en combinaison avec des nanoparticules de carbonate de calcium a l’effet le plus bénéfique sur le papier ainsi que sur la couleur des pigments à base de cuivre.
Zusammenfassung
Kupferionen und Säure führen zu einem beschleunigten Abbau des Trägermaterials Papier. Aus diesem Grund sollten Stabilisierungsbehandlungen von Dokumenten mit kupferhaltigen Pigmenten den Zusatz von Alkalien zur Bekämpfung der sauren Hydrolyse und Antioxidantien zur Verlangsamung des oxidativen Abbaus der Cellulose, der durch Kupferionen verursacht wird, enthalten. Dieser Beitrag fasst die bestehenden Ansätze zur Stabilisierung von Papieren mit grünen Kupferpigmenten zusammen. Außerdem werden zwei neue Ansätze, die auf der Behandlung mit Antioxidantien auf der Basis von Tetraalkylammoniumbromiden beruhen, bewertet. Die erste Behandlung basiert auf dem Einsatz von mit einer alkalischen Reserve und Antioxidantien versehenen Zwischenlagepapieren, mit denen die Papiere, die Malachit oder Verdigris enthalten, bei erhöhter relativer Luftfeuchte und mit Druck in Kontakt gebracht werden. Bei dem zweiten Behandlungsvorschlag werden nicht-wässrige Suspensionen von Nano-Calciumcarbonat und/oder Magnesiumoxidpartikeln und Tetrabutylammonium- oder Tetrapropylammoniumbromid eingetragen. Größenausschlusschromatografie wurde eingesetzt, um das Ausmaß des Abbaus an den Proben im Verlauf der beschleunigten Alterung zu dokumentieren, wohingegen die Farbveränderungen der Pigmente mittels Farbmessungen bestimmt wurden. Die Ergebnisse der Analysen zeigen, dass eine effektive Stabilisierung der Papierproben mit Zwischenlageblättern, die mit Tetrabutylammoniumbromid und Calciumcarbonat versehen wurden und bei 90% rF behandelt werden, erreicht werden konnte. Bei der Anwendung einer nicht-wässrigen Behandlung konnten die besten Resultate sowohl auf dem Papier als auch bei der Farbstabilität mit Tetrabutylammoniumbromid bei einer Konzentration von 0,09 M in Kombination mit Calciumcarbonat Nanopartikeln erzielt werden.
Funding statement: Funding: Ministry of Higher Education, Science and Technology of the Republic of Slovenia (Grant/Award Number: 3211-10-000057) 7th framework project Nanoforart (Grant/Award Number: 282816).
About the authors
Dr. Jasna Malešič received a degree in chemistry from the University of Ljubljana, Slovenia, in 1999. From 2001 until 2004 she worked at the NUL as a conservation scientist on two EU 5th framework projects (InkCor and Papylum). She obtained her Ph.D. in organic chemistry in 2005 with the thesis »The effect of various antioxidants on the stability of cellulose«. From 2004 she has been working as a conservator responsible for preservation of library materials and since 2005 she has been head of Preservation and Conservation Department.
Dr. Jana Kolar is founder of Morana RTD, a research intensive microcompany. She has published more than 50 papers in international peer-reviewed journals, 13 chapters in books and co-edited two books (Ageing and Stabilisation of Paper and Iron Gall Inks: On Manufacture, Characterisation, Degradation and Stabilisation): She is editor of e-Preservation Science journal.
Dr. Manfred Anders is managing director and head of Research and Development at ZFB Zentrum für Bucherhaltung GmbH. He is a specialist in Cellulose-, Paper- and Textile-Chemistry. (PhD-Thesis at the University of “Stuttgart: “Analysis of paper ageing and preservation of damaged papers by deacidification and consolidation.”)
Acknowledgements
The authors acknowledge the financial support from the Ministry of Higher Education, Science and Technology of the Republic of Slovenia through the contract No. 3211-10-000057 (Center of Excellence for Polymer Materials and Technologies) and 7th framework project Nanoforart, project reference 282816. Vesna Zorko is thanked for technical assistance.
References
Ahn, K., Hartl, A., Hofmann, C., Henniges, U., Potthast, A.: Investigation of the stabilization of verdigris-containing rag paper by wet chemical treatments. Heritage Science 2 (2014) 12–26.10.1186/2050-7445-2-12Suche in Google Scholar
Banik, G.: Discoloration of green copper pigments in manuscripts and works of graphic art. Restaurator 10 (2009) 61–73.10.1515/rest.1989.10.2.61Suche in Google Scholar
Banik, G., Ponahlo, J.: Some aspects of degradation phenomena of paper caused by green copper-containing pigments. The Paper Conservator 7 (1982) 3–7.10.1080/03094227.1982.9638442Suche in Google Scholar
Banik, G., Stachelberger, H., Wächter, O.: Investigation of the destructive action of copper pigments on paper and consequences for conservation. In: Science and Technology in the Service of Conservation: Preprints of the Contributions to the Washington Congress, N. S. Brommelle, G. Thomson (eds.), London: IIC, 1982: 75–78.Suche in Google Scholar
Daniels, V., Leese, M.: The degradation of silk by verdigris. Restaurator 16 (1995) 45–63.10.1515/rest.1995.16.1.45Suche in Google Scholar
De la Roja, J. M., San Andres, M., Sancho Cubino, N., Santos-Gomez, S.: Variations in the colorimetric characteristics of verdigris pictorial films depending on the process used to produce the pigment and the type of binding agent used in applying it. Color Research and Application 32 (2007) 414–423.10.1002/col.20311Suche in Google Scholar
Ekenstam, A.: Behavior of cellulose in solutions of mineral acids. Part II: A kinetic study of cellulose degradation in acid solutions. Berichte Der Deutschen Chemischen Gesellschaft (A and B Series) 69 (1936) 553–559.Suche in Google Scholar
Faerber, I.: Kupferfraß auf papier. Benzotriazol zur behandlung korrodierter vergoldungsimitationen in einer osmanischen handschrift. PapierRestaurierung 8 (2007) 21–29.Suche in Google Scholar
Henniges, U., Banik, G., Potthast, A.: Comparison of aqueous and non-aqueous treatments of cellulose to reduce copper-catalyzed oxidation processes. Macromolecular Symposia 232 (2006a) 129–136.10.1002/masy.200551415Suche in Google Scholar
Henniges, U., Prohaska, T., Banik, G., Potthast, A.: A fluorescence labelling approach to assess the deterioration state of aged papers. Cellulose 13 (2006b) 421–428.10.1007/s10570-005-9030-3Suche 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.2012.08.005Suche in Google Scholar
Kolar, J., Možir, A., Balažic, A., Strlič, M., Ceres, C., Conte, V., Miruzzo, V., Steemers, T., de Bruin, G.: New antioxidants for treatment of transition metal containing inks and pigments. Restaurator 29 (2008) 84–198.10.1515/rest.2008.013Suche in Google Scholar
Kolar, J., Strlič, M.: Iron gall inks: On manufacture, characterisation, degradation and stabilisation. Ljubljana: National and University Library, 2006.Suche in Google Scholar
Mairinger, F., Banik, G., Stachelberger, H., Vendl, A., Ponahlo, J.: The destruction of paper by green copper pigments, demonstrated by a sample of Chinese wallpaper. In: Conservation within Historic Buildings. Preprints of the Contributions to the Vienna Congress, Vienna, 1980, N. S. Brommelle, G. Thomson, P. Smith (eds.), London: IIC, 1980: 180–185.Suche in Google Scholar
Maitland, C.: Where archival and fine art conservation meet: Applying iron gall ink antioxidant and deacidification treatments to corrosive copper watercolours. The Book and Paper Group Annual 28 (2009) 37–46.Suche in Google Scholar
Malešič, J., Kočar, D., Balažic, A.: Stabilization of copper and iron containing papers in mildly alkaline environment. Polymer Degradation and Stability 97 (2012) 118–123.10.1016/j.polymdegradstab.2011.09.025Suche in Google Scholar
Malešič, J., Strlič, M., Kolar, J., Polanc, S.: The influence of halide and pseudo-halide antioxidants in Fenton-like reaction systems containing copper(II) ions. Journal of Molecular Catalysis A: Chemical 241 (2005a) 126–132.10.1016/j.molcata.2005.06.047Suche in Google Scholar
Malešič, K. J., Strlič, M., Polanc, S.: The use of halides for stabilisation of iron gall ink containing paper-the pronounced effect of cation. E-Preservation Science 2 (2005b) 13–18.Suche in Google Scholar
Malešič, J., Šala, M., Šelih, V. S., Kočar, D.: Evaluation of a new method for treatment of iron gall ink corrosion on paper. Cellulose 21 (2014) 2925–2936.10.1007/s10570-014-0311-6Suche in Google Scholar
Meyer, F., Neumann, A.: Recombinant proteins: A new materials for the chemical stabilization of copper pigment corrosion on paper? Restaurator 30 (2009) 96–130.10.1515/rest.007Suche in Google Scholar
Michael, D.: Pigments through the Ages. http://www.webexhibits.org/pigments (accessed 3.2.2014).Suche in Google Scholar
Mortensen, K.: The changing nature of verdigris. Copper in the Arts 8 (2007) http://www.copper.org/consumers/arts/2007/december/Verdigris.html (accessed 10.2.2014).Suche in Google Scholar
Pigments: Historical, Chemical and Artistic Importance of Coloring agents. http://www.jcsparks.com/painted/pigment-chem.html#Top (accessed: 3.2.2014).Suche in Google Scholar
Poggi, G., Baglioni, P., Giorgi, R.: Alkaline hydroxide nanoparticles for the inhibition of metal gall ink corrosion. Restaurator 32 (2011) 247–273.10.1515/rest.2011.012Suche in Google Scholar
Porck, H. J., Castelijns, W.: A Study of the effects of Iron and Copper on the Degradation of paper and Evaluation of Different Conservation Treatment. In Preprints, IADA, 7th International Congress of Restorers of Graphic Art, Uppsala, K.J. Palm, M.S. Koch (eds.), Uppsala: IADA, 1991: 1–7.Suche in Google Scholar
Ricciardi, P., Pallipurath, A., Rose, K.: It’s not easy being green’: A spectroscopic study of green pigments used in illuminated manuscripts. Analytical Methods 5 (2013) 3819–3824.10.1039/c3ay40530cSuche in Google Scholar
Robert, A., Rerolle, P., Viallet, A., Borret, C. M.: Verwendung von sauerstoff zur zellstoffbleiche. Teil 1: Anwendung eines katalysators. Optimalbedingungen für die sauerstoffbehandlung. A.T.I.P. Bulletin 18 (1964) 151–176.Suche 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 98 (2013) 1339–1347.10.1016/j.polymdegradstab.2013.03.028Suche in Google Scholar
Saunders, D., Kirby, Jo.: The effect of relative humidity on artist iron-gall. In: National Gallery Technical Bulletin, vol. 25, A.Roy (ed.), London: National Gallery Company limited, 2004: 63–72.Suche in Google Scholar
Šelih, V. S., Strlič, M., Kolar, J., Pihlar, B.: The role of transition metals in oxidative degradation of cellulose. Polymer Degradation and Stability 92 (2007) 1476–1481.10.1016/j.polymdegradstab.2007.05.006Suche in Google Scholar
Shahani, C. J., Hengemihle, F. H.: Effect of Some Deacidification Agents on Copper-Catalyzed Degradation of Paper. Preservation Research and Testing Series No. 9501, Preservation Directorate, Library of Congress, Washington, DC, 1995, 1–13. http://www.loc.gov/preservation/resources/rt/copper.pdf (accessed 23.6.2015).Suche in Google Scholar
Stefanis, E., Panayiotou, C.: Deacidification of documents containing iron gall ink with dispersions of ca(OH)2 and mg(OH)2 nanoparticles. Restaurator 31 (2010) 19–40.10.1515/rest.2010.002Suche in Google Scholar
Stol, R., Pedersoli, J. L. Jr, Poppe, H., Kok, W. Th.: Application of size exclusion electrochromatography to the microanalytical determination of the molecular mass from objects of cultural and historical value. Analytical Chemistry 74 (2002) 2314–2320.10.1021/ac0111309Suche in Google Scholar
Strlič, M., Kolar, J.: Ageing and Stabilisation of Paper. Ljubljana: National and university library, 2005.Suche in Google Scholar
Strlič, M., Kolar, J., Kočar, D., Drnovšek, T., Šelih, V. S., Susič, R., Pihlar, B.: What is the pH of alkaline paper? E-Preservation Science 1 (2004) 35–47.Suche 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 systems at circum-neutral pH. Acta Chimica Slovenica 50 (2003) 619–632.Suche in Google Scholar
Tse, S., Trojan-Bedynski, M., St-Jacques, D.: Treatment considerations for the Haggadah prayer book: Evaluation of two antioxidants for treatment of copper-containing inks and colorants. The Book and Paper Group Annual 31 (2012) 87–97.Suche in Google Scholar
Vinther Hansen, B.: Improving ageing properties of paper with iron-gall ink by interleaving with papers impregnated with alkaline buffer and antioxidant. Restaurator 26 (2005) 190–202.10.1515/rest.2005.26.3.190Suche in Google Scholar
Williams, J. C., Fowler, C. S., Lyon, M. S., Merrill, T. L.: Metallic catalysts in the oxidative degradation of paper. In: Preservation of Paper and Textiles of Historic and Artistic Value, J. C. Williams (ed.), Washington: American Chemical Society, 1977: 37–61.Suche in Google Scholar
Appendix 1
The relative average molar masses were determined using a Hewlett Packard series 1100 chromatographic system. The column thermostat was set to 35°C and a UV detector was used. The polystyrene standards were determined at 210 nm and cellulose carbanilates at 235 nm. The injected volume was 50 μL. The columns used were a 5 cm Guard GPC mixed bed and two GPC mixed bed linear columns, both by Jordi F L P (Mw range 100–10,000,000 gmol−1). The mobile phase tetrahydrofuran (THF) was pumped into the system at a rate of 1mLmin−1. The chromatographic data were processed with HP G2182AA data analysis software. The polystyrene standards (PS, Polymer Standards Service) were prepared as mixed standards in three separate solutions containing in total 0.1 gL−1 of standards in THF. The first standard solution contained PS of the following peak molecular weights (Mp): 1,090,000 gmol−1, 130,000 gmol−1, 17,800 gmol−1and 1620 gmol−1, the second standard solution contained 2,570,000 gmol−1, 246,000 gmol−1, 34,800 gmol−1 and the third 579,000 gmol−1, 67,000 gmol−1 and 8400 gmol−1.
To calculate weight-average degree of polymerization (DPw) (Kolar et al. 2012), weight-average molar masses determined by SEC were divided by molar mass of carbanilated glucosidic monomer unit. DPw was then used to calculate the degradation rate constant of cellulose according to the Ekenstam equation (Ekenstam 1936):
where DP=degree of polymerization after ageing, DP0=degree of polymerization before ageing, k=rate constant of degradation, [h−1] and t=time of ageing [h]. Higher values of k represent higher rate of degradation of samples. The standard deviation (SD) of the determination of the degradation rate constant (k) is calculated according to the Ekenstam equation using linear regression, where k is the regression slope and SD is the error of the regression slope.
©2015 by De Gruyter
Artikel in diesem Heft
- Frontmatter
- Editorial
- The Effect of Iron Ions from Prussian Blue Pigment on the Deterioration of Japanese Paper
- Electron Paramagnetic Resonance as a Probe for Metal Ions and Radicals in Paper
- Evaluation of Treatments for Stabilization of Verdigris and Malachite Containing Paper Documents
- Aqueous Washing Treatment Aids: How to Remove Ionic Fixatives from Paper
- Cellulose Acetate Lamination: A Literature Review and Survey of Paper-Based Collections in the United States
Artikel in diesem Heft
- Frontmatter
- Editorial
- The Effect of Iron Ions from Prussian Blue Pigment on the Deterioration of Japanese Paper
- Electron Paramagnetic Resonance as a Probe for Metal Ions and Radicals in Paper
- Evaluation of Treatments for Stabilization of Verdigris and Malachite Containing Paper Documents
- Aqueous Washing Treatment Aids: How to Remove Ionic Fixatives from Paper
- Cellulose Acetate Lamination: A Literature Review and Survey of Paper-Based Collections in the United States
