Determination of the Fe(II)/Fe(III) ratio in iron gall inks by potentiometry: A preliminary study

Burgaud, Cédric; Rouchon, Véronique; Wattiaux, Alain; Bleton, Jean; Sabot, R.; Refait, Philippe

doi:10.1016/j.jelechem.2010.09.015

Cited by 25 publications

(15 citation statements)

References 28 publications

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“…It attests to the persistence in the ink of Fe(II) species resulting from the low availability of oxygen within the ink pot as well as from the high capability of gallic acid to reduce Fe(III). 35 The incorporation of a high amount of gum Arabic in the solution makes it signicantly more viscous. A drop of "Fe + Ac + Gu" solution deposited on a bathophenanthroline impregnated paper therefore behaves differently (Fig.…”

Section: Visual Observationsmentioning

confidence: 99%

Mapping iron gall ink penetration within paper fibres using scanning transmission X-ray microscopy

Rouchon

Bernard

2015

J. Anal. At. Spectrom.

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International audienceIron gall inks have largely been used for writing in European western countries from the Middle Ages to the twentieth century. Yet, their use may significantly damage the paper through acid hydrolysis and iron catalysed oxidation. These phenomena are not only governed by the chemistry of the ink + cellulose system, but also by the penetration of the ink within the paper sheet. Here, we investigate ink penetration at the scale of a paper fibre using synchrotron-based STXM. This technique allows in situ mapping of the iron redox state and carbon speciation down to the sub-micrometre scale. Linen fibres have been impregnated by iron sulphate, gallic acid and gum Arabic; i.e. the three main ingredients of iron gall inks. Soft X-ray transparent ultrathin foils of impregnated fibres have been extracted using FIB milling. The data reported here evidence that ink components do not penetrate through the paper fibres the same way. In the absence of gum Arabic, gallic acid penetrates within the fibre but mostly remains in the outer part of the cell wall. A significant precipitation of Fe(III) gallate occurs during this migration whereas small amounts of iron (mostly Fe(II)) penetrate through the inner part of the fibre. The addition of gum Arabic as a binder makes the ink more viscous and significantly jeopardizes its ability to penetrate the fibre. The ink thus remains at the surface of the fibre. Low amounts of iron, essentially Fe(II), do still penetrate the fibre

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Section: Visual Observationsmentioning

confidence: 99%

Mapping iron gall ink penetration within paper fibres using scanning transmission X-ray microscopy

Rouchon

Bernard

2015

J. Anal. At. Spectrom.

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“…However, the chemistry of these inks still remains poorly understood, mainly because of the high reactivity of iron that allows many interactions with surrounding components: precipitation with gallic acid [2][3][4], chelation with polysaccharides [5], redox reactions with gallic acid [6], oxidation induced by atmospheric oxygen, etc. All these reactions may compete with each other.…”

Section: Introductionmentioning

confidence: 99%

Application of Arrhenius law to DP and zero-span tensile strength measurements taken on iron gall ink impregnated papers: relevance of artificial ageing protocols

et al. 2016

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Iron gall inks (IGI) were largely used for writing until the nineteenth century. Under certain circumstances, they provoke a substantial degradation of their cellulosic support. It was shown in a previous works that combination of oxygen and iron largely impacts cellulose chain breaking occurring in acidic conditions (pH 3-4). The present study aims to study the kinetic of this degradation. It assesses the validity of Arrhenius law between 20 and 90°C taking advantage of the fast depolymerization of IGI impregnated papers at room temperature and using two complementary tools: DP measurements and zero-span tensile strength. The first one is sensitive enough to measure degradation at its very beginning, while the second is more appropriate for advanced stage of degradation. Similar activation energies (97 ± 2 kJ mol -1 ) were found via DP and zero-span measurements, and reaction rates of IGI impregnated papers were 1-2 orders of magnitude above available data related to lignin-free acidic papers. These observations suggest a dominant hydrolytic mechanism that involves directly or indirectly oxygen and iron.

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“…This suggests that the oxidized cellulose reorganizes through chain scissions with a kinetic that is much faster than that of acidic hydrolysis. In addition, it was shown that gallic acid was favouring oxidation phenomena [6], probably because of its high ability to reduce iron III into iron II [8,9].…”

Section: Iron Gall Inks: a Major Threat For Western Archivesmentioning

confidence: 99%

The use of halide charged interleaves for treatment of iron gall ink damaged papers

Rouchon¹,

Duranton²,

Belhadj³

et al. 2013

Polymer Degradation and Stability

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International audienceIn certain conditions, iron gall inks induce substantial damages on cellulosic supports. Existing curative treatments necessitate the immersion of the documents in aqueous solutions. This implies several undesirable side effects: mechanical stress of the most damaged papers, substantial colour changes, and a drastic modification of the paper/ink composition. This work investigated an alternative treatment that consists in compressing the document between two interleaves that are charged with active compounds. When this operation is operated in moist conditions, active compounds may migrate from the interleaves to the document, and thus achieve the treatment of the paper. As high humidity conditions may additionally induce some migration of iron and acidic compounds out of the ink line, it first appeared necessary to research humidity conditions which minimize these undesirable migrations. This investigation was performed on a set of 53 original manuscripts and led us to consider that a relative humidity of 80% was quite reasonable. The second part of the paper deals with the evaluation of interleaving treatment efficiency. It was performed on laboratory samples, using several types of antioxidant halide salts (NaCl, NaBr, CaBr 2) (halides are known to act as radical scavengers). These compounds were tested separately or in combination with calcium carbonate as an alkaline buffer. The samples were made of Whatman paper that was preliminary impregnated with iron gall ink. It has shown that a charge of 2% calcium carbonate in the interleaves has no impact on the treatment efficiency, which mainly depends upon the concentration of salts, the contact pressure and the duration of the treatment. Elemental measurements show that the mobility of the salts is much higher than that of iron, suggesting the possibility to find optimum treatment conditions that minimize the iron migration risk while achieving an effective migration of halides

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Determination of the Fe(II)/Fe(III) ratio in iron gall inks by potentiometry: A preliminary study

Cited by 25 publications

References 28 publications

Mapping iron gall ink penetration within paper fibres using scanning transmission X-ray microscopy

Mapping iron gall ink penetration within paper fibres using scanning transmission X-ray microscopy

Application of Arrhenius law to DP and zero-span tensile strength measurements taken on iron gall ink impregnated papers: relevance of artificial ageing protocols

The use of halide charged interleaves for treatment of iron gall ink damaged papers

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