For centuries, manuscripts were written in iron gall ink, an ink made from iron sulfate or copperas, the galls from oak trees knotty growths where wasps have laid their eggs under the bark, gum arabic, and water. Phytate treatment birgit reissland, karin scheper and sabine fleischer 2007 the calcium phytate calcium bicarbonate treatment requires to carry out several treatment steps in the right sequence. Conservation of the south carolina constitutions nedcc. Conserving a moulddamaged iron gall ink manuscript. Of all solutions investigated to delay iron gall ink corrosion, the calcium phytate treatment proposed in the 1990s neevel 1995. Upcoming and past events staff website u of i library. Papers presented at the book and paper group session, aic 38th annual meeting, may 1114, 2010, milwaukee, wisconsin. We examined photographs of famous texas documents written with iron gall ink, including the travis letter and. Aiccm book, paper and photographic materials symposium, 2008, 8189. Overall summary of research results and implications on treatment decisions abstract the effectiveness of calcium phytate in protecting works on paper containing iron gall ink has consistently been demonstrated since its. Most of the book was classified as in poor condition, due to extensive lacing, pages splitting, and high acidity and the discoloration of the paper below you can see some of the damage the ink had done to the paper. It was often homemade and there is a huge variation in recipe, but its principal ingredients are tannins usually extracted from oak galls, iron sulphate also known as vitriol, and water.
Library of congress, book and paper group annual, vol. To stabilize the free iron ions, pages are immersed in a calcium phytate solution. In this work, a combination of complementary analytical methods was used for the first time in order to study the phytate process which is used in conservation studios to stabilize damaged manuscrip. The darker the pink color on the test strips, the more deteriorated the iron gall ink. Iron gall ink under covers the university of chicago library.
Chelating soluble ironii from iron gall ink using calcium. The effectiveness of ethanol modified calcium phytate treatments in protecting paper with iron gall inks was laboratory tested at the canadian conservation institute. The binding of the book was in excellent condition, but the paper had been heavily damaged from the use of iron gall ink. It was the standard ink formulation used in europe for the fourteenhundred year period between the 5th and 19th centuries, remained in widespread use well. Calcium phytate treatmentoptimization of existing protocols. Mounting papers from the late eighteenth century offered the chance to test and evaluate conservation methods on naturally aged inks and papers. Kinetic study of nonreactive iron removal from irongall inks. During the immersion treatment, calcium phytate exchanges calcium ions for free iron ii and iron iii ions and forms ironphytate complexes. Oct 16, 2016 it will be a fullday, handson workshop focusing on testing iron gall ink stability, creating phytate solutions and performing phytate treatment. Co, and will appear in the postprints, the book and paper group annual.
Iron gall ink, widely used in the past, is a significant factor in the deterioration of documents and books conserved in libraries and archives. The objects are transferred on the rigid support into the calcium phytate solution. The documents were tested for the presence of free iron ions in addition to standard solubility tests to see if a calcium phytate treatment needed to be performed rather than a standard aqueous treatment. An initial treatment was carried out on the basis of the recipe and instructions from a workshop iron gall ink treatment held at the netherlands institute for cultural heritage icn, amsterdam in 1998. Birgit reissland, karin scheper and sabine fleischer 2007. Iron gall ink dates from antiquity and was the primary writing ink used throughout the western world from the 12th century until the beginning of the 20th century. Unfortunately, the ink ingredients contain corrosive transition metal ions and acids that cause severe damage to the paper carrier. Haloing is when a light brown halo spreads out from the inked area.
Calcium phytate in the treatment of corrosion caused by iron gall. Treatment options for irongall ink corrosion on paper, including the phytate treatment, were compared and evaluated in a joint research project. The canadian conservation institute is pleased to host the iron gall ink. Evaluation of a method for treatment of iron gall ink corrosion on paper article pdf available in cellulose 214 august 2014 with 1,594 reads how we measure reads. Work standard for the treatment of 18th and 19thcentury. Calcium phytate in the treatment of corrosion caused by iron. This chapter provides paper conservators with the description of an optimized immersion procedure. While participants made iron gall ink a few feet away, tslac conservation discussed the prevalence and challenges of iron gall ink in archives. As irongall ink seems to be unstable above ph 9, we can not recommend aqueous magnesiumbicarbonate solutions for deacidification. Therefore a combined calciumphytate calciumbicarbonate treatment was chosen to inactivate detrimental compounds and to prevent ink corrosion.
Its only made from a few relatively inexpensive ingredients but if made in the wrong proportions it can cause a lot of damage to paper or parchment substrates. Iron gall inks became prominent in the early 12th century. After an optional washing treatment, it consists of immersing the manuscript in a calcium phytate solution for chelating, followed by immersion in calcium bicarbonate solution for neutralization. Effects of aqueous treatments on nineteenthcentury irongall. Last week the graduate book students learned how to make iron gall ink, a common writing ink from the middle ages through the 20th century.
History of treating irongall ink at the library of congress. Calcium phytate treatment on 19th century iron gall ink. Preconditioned strips of blotter are used to test the iron gall ink for free iron ions both before and during treatment. At the iron gall ink workshop, participants will discuss the properties of iron gall ink, techniques for assessment and. This project investigates the use of the phytate treatment in agar gels to treat iron gall ink degradation insitu in an attempt to find a simple, practical, inexpensive solution to chelate soluble iron in bound volumes.
Ink corrosion conference thicc 24 th 25 october 2019. Discussing and treating iron gall ink tslac conservation. Items containing this ink can become brittle and the writing fades to brown. Reissland, birgit, ineke joosten, eva eis, anja schubert blotting sand on writing inks an underestimated source of information, summary, final european thematic framework meeting for transitional metals in paper mip, northumbria university, newcastle upon tyne, jan 2006 2006. Bpg iron gall ink this page is an attempt to coalesce the information on iron gall ink that is scattered throughout several pages of the wiki, and also to provide an annotated bibliography on the topic.
Kinetic study of nonreactive iron removal from irongall. Nondestructive study of iron gall inks in manuscripts. Reissland, birgit, ineke joosten, eva eis, anja schubert blotting sand on writing inks an underestimated source of information, summary, final european thematic framework meeting for transitional metals in paper mip, northumbria university, newcastle upon. May 04, 2010 most are written in iron gall ink, most on paper but some on parchment. Papers presented at the book and paper group session, aic 38th. Iron gall ink was the primary ink used in europe from the middleages right into the 19th and even 20th centuries. They should be surrounded by the treatment solution. A potential conservation agent for the treatment of ink corrosion caused by iron gall inks, restaurator 16 1995. At the iron gall ink workshop, participants will discuss the properties of iron gall ink, techniques for assessment and analysis, and options for conservation treatment. Bear in mind that cooking reduces a foods phytic acid content to some degree, as does soaking whole grains prior for use in baking. Pdf evaluation of a method for treatment of iron gall ink. Effects of aqueous treatments on nineteenthcentury iron. The use of an aqueous treatment for iron gall ink will have side effects, either.
Iron gall ink nonaqueous treatment titus, sonja, regina schneller, enke huhsmann, ulrike hahner and gerhard banik. Overall summary of research results and implications on treatment decisions by season tse, sherry guild, doug goltz, valeria. Many of the letters and documents feature wax seals and inscriptions or stamps in various inks, so solubility during aqueous treatment is an issue. Technical note on treatment options for iron gall ink on. In many cases, the iron gall ink exhibits ghosting, haloing and in some cases has corroded through the paper where it sits. Treatment of ink degradation in bound books has generally concentrated on not exacerbating the problem. Igi was in wide use from the 9th century until the 19th century, and there are innumerable objects that display the signs of iron gall ink deterioration. Applying this relatively new treatment involves certain risks.
Evaluation of the effectiveness of stabilization methods. A unified approach to the preservation of iron gall ink artifacts in lc collections was developed, to insure consistent practices in treatment and documentation. Many historical documents written with iron gall inks are endangered by the corrosive effects of these inks. Carme sistach, eva marin, hector bagan combined antioxidant treatments for iron gall ink corroded manuscripts spaine greta keraite investigation of the effect of interleaves with potassium bromide on ageing stability of paper with iron gall ink lithuania. A second internal protocols for iron gall ink treatment pit group subsequently developed examination and treatment guidelines for staff to use on iron gall ink inscribed artifacts. From the 15th century onward it gained in popularity as an artistic medium. These ions are present in degraded iron gall ink and are usually more prevalent in very acidic conditions. Pdf corrosive iron ions and acids in iron gall inks lead toenhanced degradation of paper. Effect of aqueous treatments on nineteenthcentury irongallink documents. Aug 31, 2015 the evening, titled inkery, offered talks and demonstrations about ink and printing. The last resort for badly damaged iron gall ink manuscripts. Marine letouzey completed a master degree in book and paper. The most tested and widely accepted conservation treatment for damaged iron gall ink manuscripts is the calcium phytate calcium bicarbonate treatment. Therefore, the treatment with aqueous calcium phytate always has to be followed by a subsequent deacidification.
This 15th century parchment manuscript exhibits severe burnthrough, haloing and lacing. The moisture introduced by the adhesive bears the risk to transport corrosive ions and acids, worsening the condition of the paper. Iron gall ink was the most widely used writing ink for paper from the middle ages to the twentieth century. Mar 22, 2005 summaries samples of pure cellulose paper watman no. State of knowledge in iron gall ink research and treatment techniques workshop day 1 dutch femigration mending test, remoistenable tissue and the spongeblotter system workshop day 2 phytate treatmenttraditional and controlled moisture workshop day 3 case studies, risks and benefits of treatments and treatment planning learning objectives. The results showed that ethanol modified calcium phytate is a beneficial treatment for works on paper inscribed with soluble iron gall ink. Evaluation of a method for treatment of iron gall ink. Iron gall ink also known as common ink, standard ink, oak gall ink or iron gall nut ink is a purpleblack or brownblack ink made from iron salts and tannic acids from vegetable sources. It will be a fullday, handson workshop focusing on testing iron gall ink stability, creating phytate solutions and performing phytate treatment. Calcium phytate treatment on 19th century iron gall ink documents. Several 19thcentury books made from cotton fibres and. The calcium phytate reacts with the iron to form iron phytate compounds, which progressively slows down the iron corrosion. This project uses nine original iron gall ink documents and compares various treatments with the combination of calcium phytate and calcium bicarbonate. Phytateassociated deficiencies of iron and zinc do occur in some thirdworld countries where people mostly eat grains.
Reissland and ligterink 2011 has been the most extensively tested. Numerous studies have been conducted in the past to determine the mechanism of the formation of the ink and its corrosive action on paper, however it has only been recently that it has been possible to. The solution is made by mixing with demineralised water. Ccaha illustrated guide to book terminology part two. However, iron gall ink is corrosive and damages paper over time waters 1940. Oct 16, 2018 to stabilise the iron gall ink, the pages were placed into four different water baths for 10 minutes each. In parallel, the nonreactive iron removal kinetics was investigated using the pseudo firstorder and secondorder kinetic models. This advanced professional development apd workshop will incorporate 20 years of international research in the chemistry, degradation and treatment of metallogallic inks and use this research as the basis for informed treatment decisions and risk evaluation. Building on the pioneering research initiated by the netherlands cultural heritage agency, which demonstrated the efficacy of calcium phytate and calcium bicarbonate to significantly slow the deteriorative mechanisms of iron gall ink, a team of conservators and scientists at the library of congress sought the identify effective cocktails, or.
Development and analysis of the conservation treatment with phytate. The conservation of manuscripts damaged by iron gall inks re. Technical note on treatment options for iron gall ink on paper with. Low moisture mending will be explored using remoistenable tissue and moisture levels will be monitored by using dutch iron migration test kits. Combining xanes, icpaes, and semeds for the study of. Iron gall ink has been used for the last several centuries, and some formulations can be. The aim of this study was to identify visual changes, determine immediate side effects, and assess the effectiveness of delaying ink corrosion. The ink produces sulfuric acid, and if the ink recipe is not properly balanced, it also contains excess.
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