Study of stability of brown-gray inks on paper support
- Milena Reháková1Email author,
- Michal Čeppan†1,
- Katarína Vizárová†1,
- András Peller†2,
- Danica Stojkovičová†3 and
- Monika Hricková†1
© Reháková et al.; licensee Springer. 2015
Received: 26 September 2014
Accepted: 10 February 2015
Published: 1 April 2015
Research into paper artworks and the identification of drawing techniques dating from the 15th to the 19th century from the collection of Slovak National Gallery revealed that the most frequently used means of writing was a set of brown-gray inks. This set includes bistre, sepia, and iron-gall inks (IGI). The light fastness of these organic compounds is not considered very high. Moreover, iron gall inks attack paper support by the processes commonly known as iron gall ink corrosion. In the experimental part of the research, the stability of three different brown-gray inks was studied. Model inks, i.e. bistre, sepia and IGI with two molar ratios Fe : gallic acid were prepared according to historical recipes. Whatman paper was used as a support material. Samples were submitted to accelerated aging in closed vessels at 100°C with and without the presence of NO2 in concentration of 100 ppm as well as to the light aging in a light chamber. Changes of mechanical, optical and chemical properties of the samples as well as spectra in the IR region were studied. The observed changes allowed an evaluation of the effect of particular inks on paper support and effect of various external factors of aging (temperature, light, pollutants) on the model systems. Simultaneous thermal analysis (DTA/TG) was carried out in order to study the thermo-oxidative stability of the materials. Sepia and bistre inks have been assessed as generally more stable than iron-gall inks.
Bistre is a brown dye obtained by extraction of soot in boiling water followed by evaporation and drying . Its aqueous suspensions may have a golden-brown, grayish or brown color, depending upon the thickness of the coating. Color is affected by the type of the wood used. The main part of a wood tar composition, which is similar to that of asphalt, is dehydroabietic acid with a lower portion of pyrolytic products . According to other sources , the main color components in the bistre ink are formed by substituted, water-soluble phenols. Historical sources refer to the bistre changes of its hue when exposed to light. After being exposed to a strong light source, the tar part oxidizes and the dye gains cooler hue and possibly bleaches .
Bistre as a writing material was already known in the Middle Ages . In the 15th century, it was widely used in Italy and subsequently in Northern Europe. In the 17th and 18th centuries, the use of bistre was popular among artists such as Rembrandt van Rijn, Claude Lorrain, Conez Alexander and Thomas Gainsborough. Bistre was often used in miniature drawings. Although the inks used by Rembrandt are described traditionally as bistre, analytical studies carried out on 22 Rembrandt drawings from the collection of the Metropolitan Museum of Art have confirmed that the majority of the 22 drawings were made using iron-gall ink .
Sepia ink is obtained by adding gum Arabic into the extracts derived from Sepia officinalis cuttlefish. Sepia’s main constituents are melanin giving a typical hue of ink and mucous compounds . Grayish brown eumelanin is a macromolecule consisting of 5,6-dihydroxyindol a 5,6-dihydroxyindol-2-karboxylic acid. Melanin significantly absorbs UV and the visible wavelength range and almost all absorbed light energy is converted into the heat [8-11]. Melanin may act as a light stabilizer and this fact could explain relatively high light fastness of this organic dye.
Long-term irradiation in the presence of oxygen and UV light, however, results in lightening – the fading of melanin [12,13] that is a result of oxidative degradation, in the process of which the benzene core ring opens .
J. Seydelmann was the first person to prepare sepia ink mixed with gum Arabic (as discussed in ref. ) as a method of watercolor painting technique in Dresden in 1780. During the 19th century, bistre was gradually substituted by sepia ink.
Main components of iron gall inks (IGI) are hydrolysable extracts from plant materials containing mainly gallotannins and ferrous sulfate . A freshly prepared water solution of ink is a colorless complex of Fe (II) with gallic acid. Writing means gain their typical color by oxidation of Fe (II) into Fe (III) supplying the deep black-blue complex with gallates. With the passage of time, a degradation process of paper support was taking place . This “iron gall inks corrosion” is considered to be directly caused by two particular mechanisms: acid hydrolysis of cellulose (in excess of acidic compound presented in IGI) and the oxidative degradation of paper support catalyzed by the transitional metals (Fe, Cu) . After the absorption of light, an excited state of deep-blue complex is created and its reaction with the other ingredients leads to a decomposition into the brown colored compounds . Visual signs of corrosion are brown rims in the ink areas and brown strike through patches of ink appearing on verso.
From the late antique period to the early years of the 20th century, iron gall inks were the most used means of manuscript writing. In 15th century, inks were widely spread and during the following centuries commonly used by the old masters in drawings. At present time, all renowned galleries and museums of the world house the greatest collections of drawings by Leonardo da Vinci, Rembrandt van Rijn, Giovanni Francesco Barbieri known as Guercino, Claude Lorrain, Vincent van Gogh, etc.
The objective of this research was to study the stability of three types of historical brownish gray inks, i.e. bistre, sepia, and iron gall ink on the paper substrate during accelerated thermal aging in dark as well as light aging. This work gives a summary of properties of brown-gray inks based on own survey results. The obtained information can help conservators with an understanding and a broadened knowledge useful in preventive preservation, specifically in determining appropriate storage conditions in depositories and chiefly in expositions. Research into paper artworks of drawing techniques dating from the 15th to the 19th century from the collection of Slovak National Gallery revealed that the using of more kinds of brown-gray inks on one drawing was very frequent . In these cases, the storage conditions must adapt to the most vulnerable ones.
Materials and methods
Three types of inks were studied: bistre ink 12100 (Kremer Pigmente GmbH & Co KG) – B, sepia ink 12401 (Kremer Pigmente GmbH & Co KG) – S, iron gall inks prepared from monohydrate of gallic acid (Sigma Aldrich) and ferrous sulfate heptahydrate (Lachema, Czech Republic). The molar ratios of Fe (II) ion: gallic acid were 1:1 and 1:2 – IGI 11, IGI 12. Solutions of inks were prepared according to Neevel . For their preparation an aqueous (deionized water) solution of gum Arabic (Fluka BioChemika, Sigma-Aldrich) with the mass concentration 7.852 g/100 ml was used. Whatman filter paper (Whatman Lab. Division, Maidstone, England), Cat. No 1001917, 87 g.m−2, pH 6.7 - purified cotton linter cellulose was used as a substrate – W. Paper samples were immersed into the ink solutions for 15 seconds. Excess liquid was removed using two filter papers and then left to dry at room temperature. Water solutions of iron gall inks were applied to the paper substrate after being kept in dark room for seven days and subsequent filtration.
Accelerated aging methods
Two methods of accelerated aging were employed. Light aging according to ISO 105-B02 : a laboratory device for simulating daylight consisting of a MeX-lamp OSRAM POWERSTAR HQI TS 400/D UV-reduced and two fluorescent lamps with the maximum of emission spectrum in UVA, power 2 × 15 W, temperature 45 ± 5°C, relative humidity 25 ± 5%, exposure dose 105 klx in VIS, 95 mW/cm2 in UVA were used. Exposure times were 20, 40, 80, 120 and 160 hours.
Accelerated thermal aging in air with/without pollutant according to ISO 5630–5 : samples were placed in Pyrex® bottles, conditioned for 24 hours at 23°C and 50% RH and closed with polyphenylsiloxane airtight seal with Viton® gasket. NO2 in a 100 ppm concentration was introduced into selected bottles. Ageing times were 0, 4, 16, 24, 48, 120 hours for pure paper, bistre and sepia and 1, 2, 4, 8 and 24 hours for iron-gall inks.
Degree of polymerization and the rate constant of depolymerization
where DP 0 and DP are degrees of polymerization at the beginning of aging and after time of aging t.
15 × 100 mm samples were air-conditioned (24 hours, 23°C, 50% RH) and folding endurance was measured by the MIT method according to . The device used was Tinius Olsen, tension of samples 3 N, average of 10 measurements, standard deviation 35 ± 5%.
Thermooxidation of both, non-aged and at most aged samples was studied. With regards to thermal ageing, the aging time for the samples W, B and S was 120 hours and for the sample IGI 11, IGI 12 24 hours. In the case of light-thermal aging, the aging time was 160 hours for all samples.
FT-IR spectra of samples on paper support were measured with FT-IR spectrophotometer EXCALIBUR series, FTS 3000 MX (Digilab) and FT-IR microscope Varian 610-3R Series by ATR method with diamond crystal. FT-IR spectra of powder dyes were measured in KBr pellets. Color measurements were done with the SpectroDens A 504009 Premium (Techkon GmbH) spectrophotometer, standard illumination D50, standard observer 2°.
Results and discussion
The evaluation of the optical properties
Evaluation of ink’s stability considering stability of blue wool standards (minimum 1, maximum 8)
Degree of stability at the maximal aging time of
Thermal aging with NO 2
The evaluation of the mechanical properties
Determination of depolymerisation rate constants
Values of the depolymerisation rate constants of model samples at the maximum time of light, thermal and thermal aging with NO 2
Depolymerisation rate constant [10 −6 s −1 ] at the maximal aging time of
Thermal ageing with NO 2
0.89 ± 0.10
2.25 ± 0.26
2.45 ± 0.23
1.25 ± 0.33
1.87 ± 0.31
2.89 ± 0.58
0.72 ± 0.19
0.81 ± 0.28
0.88 ± 0.26
3.09 ± 0.77
1080 ± 250
1550 ± 280
2.24 ± 0.53
490 ± 109
860 ± 150
Similar trends were observed for the light aging but the depolymerisation rate constant was of the same order (Table 2).
Degradation of paper pad depended on the ratio of Fe : gallate in the iron gall ink, the most noticeable was at Fe : GAL = 1 : 1. This piece of knowledge corresponds with results of optical stability as well (Figure 1, Table 1).
Evaluation of thermooxidation
Estimated residual stabilities (R) with their standard deviations and 95% reasonability ranges of R at the maximum time of light, thermal and thermal aging with NO 2
Residual stabilities (R) and 95 % reasonability ranges of R
Thermal ageing with NO 2
R 95 %
R 95 %
R 95 %
0.85 ± 0.49
1.8 ± 1.2
5.2 ± 3.4
1.7 ± 0.9
0.79 ± 0.19
0.79 ± 0.23
2.4 ± 2.1
4.8 ± 1.6
300 ± 124
0.49 ± 0.16
0.18 ± 0.07
0.36 ± 0.18
The values of R for the Whatman paper after aging can attain any value from the range <0;1 > so that no conclusion on the decrease of thermooxidation stability of the sample W during aging can be drawn. A considerable decrease of thermooxidation stability was indicated for the sample IGI 11 after all kinds of aging. The decrease of the thermooxidation stability for bistre does not seem high for all kinds of thermal aging; in the case of light aging, any value from the range <0;1 > can be obtained. A surprising result was obtained for the samples with sepia. Within the 95% confidence interval, the values of R > 1 for thermal aging and thermal aging with 100 ppm NO2 have been found. This finding can be accounted for in the only way – during thermal aging with and without NO2 a compound preventing thermooxidation was formed.
The results indicate that thermooxidation represents only a minor reaction path in the aging of paper/ brown-gray ink systems during the thermal methods of aging, except for iron-gall inks where the thermooxidation might become the prevailing degradation reaction path. Moreover, considering the results of rate constants of depolymerisation, the iron-gall inks accelerated both reaction paths, i.e. thermooxidation and depolymerisation. In the case of the light aging, depolymerisation was the prevailing degradation reaction way.
After assessing chemical, optical and mechanical properties of the historic brown-gray ink on the paper support, we concluded that the most stable appears to be the sepia ink, followed by bistre. Iron gall inks are the least stable of all. Degradation of paper pad depends on the ratio of Fe in the iron gall ink, the most noticeable is at Fe: GAL = 1: 1. The influence of light on stability of brown-gray inks on paper support is less significant than the influence of temperature and pollutants (in the studied time intervals); the most dangerous combination is high temperature with increased relative humidity and presence of air pollutants. Both degradation reaction paths – thermooxidation and depolymerisation in the aging of paper/gray-brown ink systems are noticeable and depend on the way of accelerated aging and the kind of applied ink. The acquired knowledge can be useful for conservators in securing optimum conditions of storage and accessibility of pieces of art.
This work was accomplished under the auspices of the Slovak Research and Development Agency under the contract No. APVV-0324-10.
- Watrous J. The craft of old-master drawings. Madison: The University of Wisconsin Press; 1957.Google Scholar
- Winter J, FitzHugh WE. Pigments based on carbon. In: Berrie HB, editor. Artists’ Pigments. London: Archetype; 2007. p. 1–37.Google Scholar
- Neevel JG. The develpoment of in-situ methods for identification of iron gall inks. In: Kolar J, Strlič M, editors. Iron gall inks: on manufacture, characterisation, degradation and stabilisation. Ljubljana, Slovenia: National and University Library; 2006. p. 147–72.Google Scholar
- Church AH. The chemistry of paints and painting. 4th ed. Seeley: Service & Co. Ltd., London; 1915.Google Scholar
- Le Bégue J. Experimenta de coloribus. In: Merrifield MP, editor. The original treatises. London 1847: Dover Publ. New York; 1966.Google Scholar
- Shelley M. Rembrandt’s inks. In: Jensen CW, editor. The Book and Paper Group Annual, The American Institute for Conservation. 2nd ed. 1983.Google Scholar
- Lopez-Montez A, Blanc R. Characterization of sepia ink in ancient graphic documents by capillary electrophoresis. Microchem J. 2009;93:121–6.View ArticleGoogle Scholar
- Meredith P, Sarna T. The physical and chemical properties of eumelanin. Pigment Cell Res. 2006;19:572–94.View ArticleGoogle Scholar
- Sarna T. Properties and function of the ocular melanin – a photophysical view. J Photochem Photobiol B. 1992;12:125–58.View ArticleGoogle Scholar
- Sarna T, Swartz HM. Interaction of melanin with oxygen (and related species). In: Scott G, editor. Atmosheric Oxidation and Antioxidants, vol. III. Amsterdam: Elsevier; 1993.Google Scholar
- Meredith P, Powell BJ, Riesz J, Nighswander-Rempel SP, Pederson MR, Moore EG. Towards structure–property-function relationship for eumelanin. Soft Mater. 2006;2:37–44.View ArticleGoogle Scholar
- Chedelek MR, Smith SK, Post PW, Pokora A, Vessell DL. Photodestruction of pheomelanin: role of oxygen. Proc Natl Acad Sci U S A. 1993;75:5395–9.View ArticleGoogle Scholar
- Zreba M, Sarna T. Effects of photodegradation on the physical and antioxidant properties of melanosomes isolated from retinal pigment epithelium. Photochem Photobiol. 2006;82:1024–9.View ArticleGoogle Scholar
- Hebenstreit W. Wissenschaftlich-literarische Enzyklopädie der Aesthetik. Strauss and Cramer GmbH (Ed.), Wien, Gerold; 1843. LXXXVII, 994 p.Google Scholar
- Mitchell CA, Hepworth TC. Inks – their composition and manufacture. 2nd ed. London: Ch. Griffin & Cy., Ltd.; 1916.Google Scholar
- Reissland B. Ink corrosion aqueous and non-aqueous treatment of paper objects – state of the art. Restaurator. 1999;20:167–80.View ArticleGoogle Scholar
- Kolar J, Strlič M. Evaluating the effects of treatments on iron gall ink corroded documents. A new analytical methodology. Restaurator. 2004;25:94–103.View ArticleGoogle Scholar
- Popoff T, Theander O. Formation of aromatic compounds from carbohydrates. IV. Chromones from reaction of hexuronic acids in slightly acidic aqueous solution. Acta Chem Scand. 1976;B30:705–10.View ArticleGoogle Scholar
- Gál L, Čeppan M, Reháková M, Dvonka V, Tarajčáková J, Hanus J. Chemometric tool for identification of iron–gall inks by use of visible–near infrared fibre optic reflection Spectroscopy. Anal Bioanal Chem. 2013;405:9085–91.View ArticleGoogle Scholar
- ISO. Textiles – tests for colour fastness – part B02. In: Colour fastness to artificial light: xenon arc fading lamp test. Geneva: International Organization for Standardization; 1988. ISO 105-B02.Google Scholar
- ISO. Paper and board – accelerated ageing – part 5. In: Exposure to elevated temperature at 100°C. Geneva: International Organization for Standardization; 2008. p. 5630–5. ISO.Google Scholar
- ISO. Cellulose in dilute solutions – determination of limiting viscosity number – Part 1. In: Method in cupriethylene-diamine (CED) solution. Geneva: International Organization for Standardization; 1981. p. 5351–1. ISO.Google Scholar
- Strlič M, Kolar J, Žigon M, Pihlar B. Evaluationof size-exclusion chromatography and viscometry for the determinationof molecular masses of oxidised cellulose. J Chrom A. 1998;805:93–9.View ArticleGoogle Scholar
- Emsley AM, Heywood RJ, Ali M, Eley CM. On the kinetics of degradation of cellulose. Cellulose. 1997;4:1–5.View ArticleGoogle Scholar
- Evans R, Wallis AFA. Comparison of cellulose molecular weight determined by HPSEC and viscometry. In: Proceedings of the 4th International symposium on wood, fibre and pulping chemistry. Paris, France: Eucepa; 1987. p. 201–5.Google Scholar
- Kolar J, Štolfa A, Strlič M, Pompe M, Pihlar B, Budnar M, et al. Historical iron gall ink containing documents – properties affecting their condition. Anal Chim Acta. 2006;555:167–74.View ArticleGoogle Scholar
- ASTM International. Standard test method for folding endurance of paper by the M.I.T. tester. Conshohocken, Pennsylvania 19428, USA: ASTM International; 2007. ASTM D2176-97a.Google Scholar
- Šimon P. Material stability predictions applying a new non-Arrhenian temperature function. J Therm Anal Cal. 2009;97:391–6.View ArticleGoogle Scholar
- Hynes MJ, Coinceanainn MO. The kinetics and mechanism of the reaction of iron (III) with gallic acid, gallic acid methyl ester and catechin. J Inorg Biochem. 2001;85:131–42.View ArticleGoogle Scholar
- Vizarova K, Rehakova M, Kirschnerova S, Peller A, Šimon P, Mikulašik R. Stability studies of materials applied in the restoration of a baroque oil painting. J Cult Her. 2011;12:190–5.View ArticleGoogle Scholar
- Peller A, Reháková M, Ciglanská M, Šimon P. Role of thermoxidation and depolymerization in the aging of systems paper/gum arabic/historical ink. Chem Pap. 2014;68:564–74.View ArticleGoogle Scholar
- Fratričová M, Šimon P, Schwarzer P, Wilde H-W. Residual stability of polyurethane automotive coatings measured by chemiluminescence and equivalence of Xenotest and Solisi ageing tests. Polym Degrad Stab. 2006;91:94–100.View ArticleGoogle Scholar
- Senvaitiene J, Beganskiene A, Kareiva A. Spectroscopic evaluation and characterization of different historical writing inks. Vibrational Spectroscopy. 2005;37:61–7.View ArticleGoogle Scholar
- Hamilton GA. Role of oxygen radicals in biological systems. In: Hayashi O, editor. Molecular mechanism of oxygen activation. New York: Academic Press; 1974. p. 405–51.View ArticleGoogle Scholar
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly credited. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated.