Iron gall ink
Iron gall ink (also known as iron gall nut ink, oak gall ink, and common ink) is a purple-black or brown-black ink made from iron salts and tannic acids from vegetable sources. It was the standard writing and drawing ink in Europe, from about the 5th century to the 19th century, and remained in use well into the 20th century.
Preparation and useEdit
The ink was traditionally prepared by adding some iron(II) sulphate (FeSO4) to a solution of tannic acid (C76H52O46), but any iron ion donor can be used. The gallotannic acid (= tannic acid) was usually extracted from oak galls or galls of other trees; hence the name. Fermentation or hydrolysis of the extract releases glucose and gallic acid (C6H2(OH)3COOH),[clarification needed] which yields a darker purple-black ink, due to the formation of iron gallate.
The fermented extract was combined with the ferrous iron(II) sulphate. After filtering, the resulting pale-grey solution had a binder added to it, (most commonly gum arabic) and was used to write on paper or parchment. A well-prepared ink would gradually darken to an intense purplish black. The resulting marks would adhere firmly to the parchment or vellum, and (unlike india ink or other formulas) could not be erased by rubbing or washing. The marks could only be erased by actually scraping a thin layer off the writing surface.
By mixing tannin with iron sulphate, a water-soluble ferrous tannate complex is formed. Because of its solubility, the ink is able to penetrate the paper surface, making it difficult to erase. When exposed to oxygen a ferric tannate pigment is formed. This complex is not water-soluble, contributing to its permanence as a writing ink.
The gradual darkening of the ink is due to the oxidation of the iron ions from ferrous (Fe2+) to ferric (Fe3+) state by atmospheric oxygen. (For that reason, the liquid ink had to be stored in a well-stoppered bottle, and often became unusable after a time.) The ferric ions react with the tannic acid or some derived compound (possibly gallic acid or pyrogallol) to form a polymeric organometallic compound.
While a very effective ink, the formula was less than ideal. Iron gall ink is acidic ranging from roughly equivalent to a lemon (pH ≈ 2) to that of a cup of black coffee (pH ≈ 5). In chemistry, pH is a measure of the activity of the (solvated) hydrogen ion, where a lower pH level indicates a more acidic solution. For this reason some makers of iron gall ink used crushed egg shells (which contain calcium carbonate (CaCO3)) to temper the ink solution acidity, bringing it closer to a neutral pH (pH = 7) value. Depending on the writing surface being used iron gall ink can have unsightly "ghost writing" on the obverse face of the writing surface (most commonly parchment or paper). Also any excess of ferrous ions remaining in the ink over years, decades, and centuries, could create a rusty halo around the marks and ultimately it might eat holes through the surface it was on.
Paper has its own special problems with iron gall ink. The iron-tannic pigment does not make chemical bonds with the cellulose fibres. The ink sticks firmly to the paper, but largely by mechanical bonding; essentially, the dried ink penetrates the spaces between the fibres and, after drying, becomes entangled in them. The process of decaying the writing surface is accelerated on paper when compared to parchment, doing the damage in decades or years that could take more than a millennium on parchment.
The acidity of iron gall ink is well known, but may also be somewhat overstated; while there certainly are instances of damage to historical documents, there are thousands of manuscripts, some of them well over 1,000 years old, written with iron gall ink which remain intact and legible.
The earliest recipes for oak gall ink come from Pliny the Elder, and are vague at best. Many famous and important manuscripts have been written using ferrous oak gall ink, including the Codex Sinaiticus, the oldest, most complete Bible currently known to exist, thought to be written in the middle of the fourth century. Due to the ease of making iron gall ink and its quality of permanence and water resistance this ink became the favored one for scribes in the European corridor as well as around the Mediterranean Sea. Surviving manuscripts from the Middle Ages as well as the Renaissance bear this out as the vast majority are written using iron gall ink, the balance being written using lamp black or carbon black inks. Many drawings by Leonardo da Vinci were made with iron gall ink. Laws were enacted in Great Britain and France specifying the content of iron gall ink for all royal and legal records to ensure permanence in this time period as well.
The popularity of iron gall ink traveled around the world during the colonization period and beyond. The United States Postal Service had its own official recipe that was to be used in all post office branches for the use of their customers. It was not until the invention of chemically-produced inks and writing fluids in the latter half of the 20th century that iron gall ink fell from common use.
The permanence and water-resistance of the iron and gall-nut formula made it the standard writing ink in Europe for over 1,400 years, and in America after European colonisation. Its use and production started to decline only in the 20th century, when other waterproof formulas (better suited for writing on paper) became available. Today, iron gall ink is manufactured by a small number of companies and used by fountain pen enthusiasts and artists, but has fewer administrative applications.
Traditional iron gall inks intended for dip pens are not suitable for fountain pens which operate on the principle of capillary action. Ferro-gallic deposit accumulation in the feed system can clog the small ink passages in fountain pen feeds. Further, very acidic traditional iron gall inks intended for dip pens can corrode metal pen parts (a phenomenon known as redox reaction/flash corrosion). These phenomena can destroy the functionality of fountain pens.
Instead, modern surrogate iron gall formulas such as blue-black bottled inks by Lamy (discontinued in 2012), Montblanc (discontinued in 2012), Chesterfield Archival Vault, Diamine Registrar's Ink, Ecclesiastical Stationery Supplies Registrars Ink, Gutenberg Urkundentinte G10 Schwarz (certificate ink G10 black), Hero 232, KWZ Iron Gall ink, Organics Studios Aristotle Iron Gall or Rohrer & Klingner "Salix" and (purplish grey) "Scabiosa" inks are offered for fountain pens. Platinum also now make six coloured iron gall inks as part of their 'Classic' range.
These modern iron gall inks contain a small amount of ferro-gallic compounds and are also more likely to have a formulation which is stoichiometrically optimised. Historical inks often contained excess acid which was not consumed in the oxidation of the ferro-gallic compounds. Modern formulations also tend to use hydrochloric acid whereas many historical inks used sulphuric acid. Hydrochloric acid is a gas in solution, which will evaporate. As a result, modern fountain pen iron gall inks are less likely to damage paper than historical inks and are gentler for the inside of a fountain pen, but can still cause problems if left in a pen for a long period. Manufacturers or retailers of modern iron gall inks intended for fountain pens sometimes advise a more thorough than usual cleaning regimen – which requires the ink to be flushed out regularly with water – to avoid clogging or corrosion on delicate pen parts. For more thoroughly cleaning iron gall ink out of a fountain pen, sequential flushes of the pen with water, diluted vinegar or citric acid (to flush out residual iron gall compounds), water, diluted ammonia (if needed to flush out residual colour dye stains), then finally water are often recommended.
The colour dye in these modern iron gall formulas functions as a temporary colourant to make these inks clearly visible whilst writing. The ferro-gallic compounds through a gradual oxidation process cause an observable gradual colour change to grey/black whilst these inks completely dry and makes the writing waterproof. The colour-changing property of the ink also depends on the properties of the used paper. In general, the darkening process will progress more quickly and visibly on papers containing relatively high bleaching agent residues.
Though not in mainstream 21st-century use like dye-based fountain pen inks, modern iron gall inks are still used in fountain pens where permanence is required.
In the United Kingdom the use of special blue-black archival quality Registrars' Ink containing ferro-gallic compounds is required in register offices for official documents such as birth certificates, marriage certificates, death certificates and on clergy rolls and ships' logbooks.
In Germany the use of special blue or black urkunden- oder dokumentenechte Tinte or documentary use permanent inks is required in notariellen Urkunden (Civil law notary legal instruments).
German regulation for Urkundentinte inks (1933)Edit
- In a litre of ink there has to be at least 27 g of tannic acid and gallic acid, and at least 4 g of iron content. The maximum iron content is not allowed to surpass 6 g / l.
- After 14 days' storage in a glass container the ink is not allowed to have stained the glass or show sedimentation.
- Eight-day-old writings after washing with water and alcohol must remain very dark.
- The ink has to flow easily from the pen, and may not be sticky even immediately after drying.
U.S. government "standard ink" formula (1935)Edit
- 11.7 g tannic acid
- 3.8 g gallic acid C6H2(OH)3COOH
- 15 g iron(II) sulfate
- 3 cm3 hydrochloric acid (used to prevent sediment forming)
- 1 g carbolic acid (phenol) C6H5OH (biocide)
- 3.5 g china-blue aniline dye (water-soluble)
- 1000 cm3 distilled water
The Popular Science iron gall writing ink article also mentions methyl violet dye could be used to make a violet iron gall ink without revealing the amount and soluble nigrosine dye for an immediate black iron gall ink. To avoid the toxic carbolic acid biocide used as a preservative in the U.S. government "standard ink" formula, 2 g salicylic acid C6H4(OH)COOH can be used as a safer biocide alternative to prevent mold in the ink bottle. Both preservatives are enhanced by lowering the pH-value (acidifying the ink by adding hydrochloric acid).
Indian Standard 220 (1988)Edit
In India, the IS 220 (1988): Fountain Pen Ink – Ferro-gallo Tannate (0.1 percent iron content) Third Revision standard, which was reaffirmed in 2010, is in use. This Indian Standard was adopted by the Bureau of Indian Standards on 21 November 1988, after the draft finalized by the Inks and Allied Products Sectional Committee had been approved by the Chemical Division Council. IS 220 prescribes the requirements and the methods of sampling and tests for ferrogallo tannate fountain pen inks containing not less than 0.1 percent of iron.
Annex M stipulates that the IS 220 reference ink shall be prepared according to the following formula:
- 4.0 g tannic acid
- 1.5 g gallic acid
- 5.5 g ferrous sulphate crystals FeSO4·7H2O
- 5.0 g concentrated hydrochloric acid
- 5.0 g dye, ink blue (see IS 8642 : 1977)
- provisional dye (for inks other than blue black) As advised by supplier.
- phenol (see IS 538 : 1968)
- distilled water (to make the total volume one litre).
The IS 220 reference ink shall not be used for more than one month after the date of preparation and shall be stored in amber-coloured reagent bottles (see IS 1388 : 1959).
- Eusman, Elmer (1998). "Iron gall ink – Chemistry". The Iron Gall Ink Website.
- Fruen, Lois (2002). "Iron Gall Ink". The Real World of Chemistry. Kendall/Hunt Publishing. ISBN 0-7872-9677-5. Archived from the original on 30 April 2016.
- Mazzarino, Sara. "Report on the different inks used in Codex Sinaiticus and assessment of their condition". Retrieved 16 March 2013.
- White, Susan D. (2006). Draw Like Da Vinci. London: Cassell Illustrated, pp.18-19, ISBN 9781844034444.
- Registrars' Ink
- Henry 'Inky' Stephens – the inventor of blue-black ink (Stephens Blue-Black Registrar's Ink) at BBC Radio 4
- A Guide for Authorised Persons, HM Passport Office, General Register Office, Issued: 2012, Last Updated: February 2015, Registration stock, 1.18, Page 5
- Guidebook for The Clergy, HM Passport Office, General Register Office, Issued: 2011, Last Updated: February 2015, Ink, 1.9, Page 7
- Dienstordnung für Notarinnen und Notare (DONot), Abschnitt Herstellung der notariellen Urkunden § 29 (in German)
- Buchheister-Ottersbach: Vorschriften für Drogisten. 11. Auflage von Georg Ottersbach (Volksdorf/Hamburg). Verlag Julius Springer, Berlin 1933 (in German)
- Wailes, Raymond B. (January 1935). "Things to make in your home laboratory". Popular Science Monthly. 126 (1): 54–55.
- "IS 220 (1988): Fountain Pen Ink – Ferro-gallo Tannate (0.1 percent iron content) Third Revision" (PDF). Bureau of Indian Standards.
|Wikimedia Commons has media related to Iron gall ink.|
- Iron Gall Ink – Traveling Scriptorium – A Teaching Kit by the Yale University Library 21 March 2013
- The Iron Gall Ink Website
- Forty Centuries of Ink by David Carvalho (Project Gutenberg)
- IRON GALLATE INKS-LIQUID AND POWDER by Elmer W. Zimmerman, U.S. DEPARTMENT OF COMMERCE NATIONAL BUREAU OF STANDARDS RESEARCH PAPER RP807 Part of Journal of Research of the National Bureau of Standards, Volume 15, July 1935