Archival Qualities Of Iron Gall Inks

[XiaoMG]

  pelahale said:

Very interesting! Seems risky to use on marriage documents? What's the point of that requirement? Why not require the use of say a Noodler's eternal line of inks instead?

 

I don't understand the need for iron-gall inks - is it all about the rapid drying or the supposed permanence?

I only like IG for shading and transformation while being waterproof. When they oxidize and go gray/black, I think the shading effects can be gorgeous.

 

I filled my TWSBI Vac700 with Urkundentinte and a few weeks later had to work quite hard to remove the stuff from the plunger rod and other internal surfaces. I only had rice vinegar and not white vinegar to clean with, so that could have been the problem...but it was very annoying. I put ESSRI in a Pilot 78G and it dried up on me pretty quickly and clogged the pen, and was hard to clean off the underside of the nib and the feed despite the nib and feed being easy to remove.

 

I have Pharmacist's Turkish Night in a Sailor Profit Standard MF, and it has worked pretty well, though I dread the day when I have to clean it, though its IG content should be much less than Urkundentinte or ESSRI. I also have Scabiosa in a Sailor HighAce Neo, and have not yet flushed it, so I do not know how much of a nightmare it'll be to clean.

 

I do use Sailor's Kiwaguro and Seiboku and have found them to be a little tricky to clean, but not nearly as stubborn as my IGs. I wonder if I should get white vinegar or something else to dissolve it more easily...rice vinegar seems pretty ineffective. It's too bad, because I loooove the way some of them look, and I like the water resistance a lot.

[Paddler]

  On 7/31/2012 at 8:48 PM, fiberdrunk said:

  On 7/31/2012 at 6:55 PM, Paddler said:

Properly made carbon ink does not just sit on the surface of paper. It will soak down among the paper fibers and be protected from abrasion and most water damage (I know. I have done the experiments.). Writing done with it will last longer than the paper it is written on. In my estimation, its selection is a no-brainer.

 

What brand of carbon ink have you found to work for you?

I have experimented with Pelikan Fount India, Higgins, and various sumi sticks (Yasutomo is an identifiable brand). There is a powdered variety sold by the Williamsburg printer that works also. The sumi sticks are most versatile; you can make the ink as dark and thick as you want. These are not completely waterproof. Running water will wash them out eventually. Standing water doesn't cause the carbon to migrate much. Keep the book closed in a flood and the writing will be relatively safe. Light doesn't affect the carbon. Air pollution will probably wreck the paper before it affects the writing.

[Paddler]

  On 7/31/2012 at 7:06 PM, Uncle Red said:

Paddler

Diamine, Ecclesiastical Stationery Supplies, Rohrer und Klingner and whoever makes for Akkerman do not start with oak galls; they use properly sourced chemicals with known concentrations. Nothing is left to chance.

That is good to know. However, as soon as you dissolve a sulfate (ferrous or ferric sulfate used in IG ink) in water, you have sulfate radicals from the chemical, plus a few hydrogen ions from the water. This is sulphuric acid. It may be a low concentration, but eventually it will corrode paper or animal skin. It is not used up in the reaction and it never sleeps. The way to slow it down is to keep it dry and cold.

 

Maybe this is a moot point. Maybe a thousand years is long enough for writing to last. I just don't like the idea of making something with the seeds of its destruction already put in place.

[MarkTrain]

  On 8/1/2012 at 1:35 PM, Paddler said:

 

That is good to know. However, as soon as you dissolve a sulfate (ferrous or ferric sulfate used in IG ink) in water, you have sulfate radicals from the chemical, plus a few hydrogen ions from the water. This is sulphuric acid. It may be a low concentration, but eventually it will corrode paper or animal skin. It is not used up in the reaction and it never sleeps. The way to slow it down is to keep it dry and cold.

 

 

This is nonsense. Dissolving a metal sulfate salt in water gives the very stable sulfate ion SO4^2-, not the sulfate radical which involves a completely different kind of chemistry. The solution is made acidic solely to increase the solubility of iron. Again as been mentioned in the literature it is excess free/uncomplexed iron that causes ink corrosion via the well known Fenton reaction. Once the iron is complexed with tannic/gallic acid the Fenton reaction is quenched.

[Uncle Red]

  On 8/1/2012 at 9:03 AM, XiaoMG said:

  pelahale said:

Very interesting! Seems risky to use on marriage documents? What's the point of that requirement? Why not require the use of say a Noodler's eternal line of inks instead?I don't understand the need for iron-gall inks - is it all about the rapid drying or the supposed permanence?

I only like IG for shading and transformation while being waterproof. When they oxidize and go gray/black, I think the shading effects can be gorgeous.I filled my TWSBI Vac700 with Urkundentinte and a few weeks later had to work quite hard to remove the stuff from the plunger rod and other internal surfaces. I only had rice vinegar and not white vinegar to clean with, so that could have been the problem...but it was very annoying. I put ESSRI in a Pilot 78G and it dried up on me pretty quickly and clogged the pen, and was hard to clean off the underside of the nib and the feed despite the nib and feed being easy to remove.I have Pharmacist's Turkish Night in a Sailor Profit Standard MF, and it has worked pretty well, though I dread the day when I have to clean it, though its IG content should be much less than Urkundentinte or ESSRI. I also have Scabiosa in a Sailor HighAce Neo, and have not yet flushed it, so I do not know how much of a nightmare it'll be to clean.I do use Sailor's Kiwaguro and Seiboku and have found them to be a little tricky to clean, but not nearly as stubborn as my IGs. I wonder if I should get white vinegar or something else to dissolve it more easily...rice vinegar seems pretty ineffective. It's too bad, because I loooove the way some of them look, and I like the water resistance a lot.

Xiao, I know what you mean. I let Registrar's ink dry out in a little Chinese pen and that was that. My Sheaffer No Nonsense is closing in on a year filled with RI though and it's been fine. Some times it sits for weeks unused.

[fiberdrunk]

  On 8/1/2012 at 6:38 AM, pelahale said:

 

 

I don't understand the need for iron-gall inks - is it all about the rapid drying or the supposed permanence?

 

 

Well, even though some iron gall recipes led manuscripts to their eventual self-destruction, even these manuscripts using unbalanced recipes lasted for centuries. So people use iron gall inks for the proven longevity. The Declaration of Independence was written in iron gall ink. Most governments have a standard iron gall ink recipe they use for important documents-- even the U.S. did, at least they did in the early 1900's. I don't think they use it any more, though. I seem to remember signing my kids' birth certificates with an ordinary ball point pen, for instance. But apparently in England they still use Registrars Ink for such documents.

[cellmatrix]

That's what Pharmacist's Urkundentinte Document Ink is based on, a standard government ink recipe.

[Paddler]

  On 8/1/2012 at 4:19 PM, MarkTrain said:

  On 8/1/2012 at 1:35 PM, Paddler said:

 

That is good to know. However, as soon as you dissolve a sulfate (ferrous or ferric sulfate used in IG ink) in water, you have sulfate radicals from the chemical, plus a few hydrogen ions from the water. This is sulphuric acid. It may be a low concentration, but eventually it will corrode paper or animal skin. It is not used up in the reaction and it never sleeps. The way to slow it down is to keep it dry and cold.

 

 

This is nonsense. Dissolving a metal sulfate salt in water gives the very stable sulfate ion SO4^2-, not the sulfate radical which involves a completely different kind of chemistry. The solution is made acidic solely to increase the solubility of iron. Again as been mentioned in the literature it is excess free/uncomplexed iron that causes ink corrosion via the well known Fenton reaction. Once the iron is complexed with tannic/gallic acid the Fenton reaction is quenched.

Have it your way. Me, I will use carbon, thank you very much.

[Chris]

Just a quick note to say that, sadly, the UK registry of births, deaths and marriages is moving to an electronic system and away from the use of hand-written registers. So, instead of a system that has worked very well for hundreds of years we move to digital media where constant updating of hardware and software seems to be the order of the day

 

Who remembers punched cards, computer tapes, 8" floppy discs, 3 1/4" diskettes? What about microfilm? Microfiche? All come and gone in decades, along with the means to retrieve the information stored on them.

 

Of course, not all records were made using a government approved ink. Parish and other church records from the past as well as the records kept of transactions in shipping, country houses and who knows where else would have been written using whatever ink was to hand. Many of these records have remained beautifully legible for several hundred years or more and are researched still by historians and the curious to this day. Try doing that to a punched card today, or a DVD/CD in twenty-five years .

 

Chris

[doc4]

  On 7/29/2012 at 9:10 PM, ElaineB said:

 

I worked for years in the Harvard University library system, in special collections (rare books and archives), and iron gall ink was notorious for eating away at the paper substrates. I could easily put my hands on manuscripts that had been written in iron gall inks, in which the ink ate through the paper and left mostly sheets of what looked like laser cut lace. The acidity of the ink destroyed the paper, even robust quality handmade rag papers from the 17th century and such. Similarly, I've seen reproductions of J.S. Bach manuscripts that are also nothing but paper and air now.

 

 

 

Given your experience and knowledge, perhaps you can tell me, curious as I am ... were there other types of ink in use "back then" as well as IG, or was it just the IG?

[CDKeth]

The domesday bookis in iron gall ink and it's creeping up on a millennium old.

[LucasT]

It all depends on which, "back then" you are talking about. If you are talking about 17th century, walnut inks were around, lampblack/carbon/charcoal based inks were around. (and still around, and have always been around). Iron Gall inks were made from a myriad of different sources. Everything from imported wood, oak galls (the tannin content of galls can vary from 3%-95% depending upon the oak tree and the wasp, so this can GREATLY change the stability and quality of your ink). In fact, in the United States one of the best sources for tannins is sumac leaves (not the poison kind, the regular kind). I ought to post how to do this at some point.

 

Anyway, those are your darker ones. Then you have a red/pink made from Brazilwood, a green and a yellow made from buckthorn, a miriad of other colors made from fruits, berries, etc.

 

Then you get egg tempera paints, which can be readily thinned and applied with a quill...These aren't technically inks, but behave similarly to a thick india ink.

 

Oh, yeah and I believe some Chinese stick inks were imported too.

 

The general theory seems to be is that if it was colored and liquid, somebody wrote with it at some point, but by the 17th century (honestly by the 13-14th centuries) everyone who wrote knew what didn't last in a book and what did. (Read some of Cennino de'Andrea Cennini, Il Libro dell’Arte)

 

Oh, yeah and then there are the invisible inks too...(very nifty article here)

[GeneralSynopsis]

  On 7/31/2012 at 2:15 PM, Paddler said:

I have done some reading on the subject. The best information I have found came from a paper written about "paper corrosion". It seems that iron gall inks generate sulphuric acid in the process of making the black pigment. The acid breaks down the paper in a kind of circular reaction where the acid is continuously regenerated, almost like a catalyst. So, no matter how carefully the ink is made, the iron sulfate component will make the acid and eventually eat through the paper. Vellum and parchment are attacked by the acid also.

 

For this reason, I gave up on the iron gall project for record permanence. I am using India ink for my journals. Carbon is forever.

 

Reality check; if true of modern IG (and in particular) registrar's inks they would not be mandaded in the UK for registrar's use.

 

.

Edited August 7, 2012 by GeneralSynopsis

[LucasT]

I believe modern IG ink uses hydrochloric acid, gallic acid/tannic acid/pyrogallic acid, and potentially Iron (II) chloride. You no longer have a sulphate to deal with and get a fully volatile acid. The issue would be the sulfate associating with the acid instead of the iron and forming FeCl2/FeCl3 instead of FeSO3/Fe2(SO3)3 complexes. Anyway I would suspect the reaction would drive towards the HCl side.

 

In "old" Iron gall inks your biggest issues with parchment and paper attack were excess iron sulfate and copper contamination. Iron sulfate was known as copperas and copper sulfate was known as blue copperas. They come from the same mines and have to be separated, thus contamination issues.

If you have all of your iron complexed by gallic/tannic acid it can't catalyze the oxidation of cellulose due to its ligand sites being ligandized (er, not a word but made sense to me).

 

 

Anyway, short version, you don't have to use Iron (II) Sulfate, you can use an Iron (II) Chloride, the acid evaporates as hydrogen chloride gas, the Iron oxidizes, and behold you get a nice dark black pigment that is insoluble in water, etc.

[doc4]

  On 8/7/2012 at 2:02 PM, LucasT said:

It all depends on which, "back then" you are talking about. If you are talking about 17th century, walnut inks were around, lampblack/carbon/charcoal based inks were around. (and still around, and have always been around). Iron Gall inks were made from a myriad of different sources. Everything from imported wood, oak galls (the tannin content of galls can vary from 3%-95% depending upon the oak tree and the wasp, so this can GREATLY change the stability and quality of your ink). In fact, in the United States one of the best sources for tannins is sumac leaves (not the poison kind, the regular kind). I ought to post how to do this at some point.

 

Anyway, those are your darker ones. Then you have a red/pink made from Brazilwood, a green and a yellow made from buckthorn, a miriad of other colors made from fruits, berries, etc.

 

Then you get egg tempera paints, which can be readily thinned and applied with a quill...These aren't technically inks, but behave similarly to a thick india ink.

 

Oh, yeah and I believe some Chinese stick inks were imported too.

 

The general theory seems to be is that if it was colored and liquid, somebody wrote with it at some point, but by the 17th century (honestly by the 13-14th centuries) everyone who wrote knew what didn't last in a book and what did. (Read some of Cennino de'Andrea Cennini, Il Libro dell’Arte)

 

Oh, yeah and then there are the invisible inks too...(very nifty article here)

 

Thanks for the info!

[Steven Avery]

  On 7/31/2012 at 4:44 PM, Mangrove said:

... Check Codex Sinaiticus and Codex Vercellensis for proof that proper iron gall ink will stand for thousands of years and does not completely deteriorate the medium at the same time. Notice that the ancient parchment is probably more acidic than modern paper due of the manufacturing process.

 

And I don't think Codex Sinaiticus can be relied upon for any such evaluation, it is an anomalous ms and may well be less than 200 years old. (Created c. 1840 as either a forgery or replica.) Using it as a base of comparison for anything physical is dicey.

 

And I would be interested in seeing the Codex Vercellensis comparison:

 

Seeing the Codex Vercellensis in a New Light: Multispectral Imaging and the Old Latin Bible

http://evangelicaltextualcriticism.blogspot.com/2015/03/seeing-codex-vercellensis-in-new-light.html

 

Dating to the first half of the 4th century, the Codex Vercellensis or Codex A is the earliest manuscript of the Gospels in Latin. As such, it is perhaps the closest witness to the text of the Christian Bible in the West in the age of Constantine and the Council of Nicaea. Housed in the Capitulary Library of Vercelli since the time of St. Eusebius of Vercelli under whose auspices it was written, the manuscript now contains 317 folios, many of which are badly damaged by mold and decay to the point of illegibility. In fact, the last edition of Codex A to be made from an original reading of the manuscript was in the mid 18th century when it was considerably more legible than it is today.... To stabilize the crumbling manuscript ...

 

So I don't see much there about the legibility of the ink. Do you have any pictures to view? (Not facsimile editions.)

 

Thanks!

 

Steven Avery

Dutchess County, NY

 

Edited February 24, 2016 by Steven Avery

[Steven Avery]

The Cambridge History of the Bible: Volume 2, The West from the Fathers to the Reformation (1975)
editor - Geoffrey William Hugo Lampe
https://books.google.com/books?id=jTWlhe7wlN8C&pg=PA61 ,

"Early Christian Book-Production: Papyri and Manuscripts" - Theodore Cressy Skeat

Practically all Greek papyri use carbon ink, but from the fourth century A.D., and perhaps earlier, Greek parchment manuscripts used metallic ink: notable examples of the use of metallic ink are the Codex Sinaiticus and the Codex Alexandrinus; the latter has sustained serious damage as a result of the ink eating through the parchment.

===================

Sinaiticus, however, was immune from such damage. Did have the special "Tishon" coating that prevented such damage?

(ie. The concocted story from Tischendorf that Sinaiticus was a 4th century ms.)

Caution: do not use Sinaiticus for 1500+ years ink science.

===================

 

Report on the different inks used in Codex Sinaiticus and assessment of their condition

Sara Mazzarino

http://codexsinaiticus.org/en/project/conservation_ink.aspx

"The Codex Sinaiticus inks have never been chemically characterized, and the type and proportions of ingredients mixed together have never been determined."

===================

Steven

Edited February 25, 2016 by Steven Avery

[Piper 987]

The Wikipedia article on iron gall ink has a few modern recipes including the one for the US Government 'standard ink' (1935).

 

• 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^[10]

 

I found a few suppliers on the net where you can still get this type of stuff (tannic acid, gallic acid etc.).

 

That said, I like the idea of brewing up a batch of the old school stuff the way fiberdrunk has done. And yes, you can even order aleppo oak (Quercus infectoria) galls over the net.

Edited February 26, 2016 by Piper 987

[Simulacrum]

Hi, I've been very interested in using Iron Gall Inks (permanent/waterproof) but have not yet taken the plunge. So far I've been using Platinum pigment inks which are awesome- esp. carbon black - love it -side note. I think I have been convinced that modern Iron Gall Inks have at least a similar chance of permanence as other 'permanent' inks. And a few hundred years is good enough for me either way. But I have been unable to find out how long before it all goes black. If it's all going to change to black then I'll just use black right away. Unless it will retain colour for 50-100 years or something then that is maybe good enough? If I make a drawing of something I am choosing colours on purpose - I generally want them to stay those colours. But I love the darkness of the IG inks (like the platinum classic inks) and I like the idea that there is some shifting and they look cool but I don't want them to go completely black and lose the colour. It seems there are some chemists posting on here and I am wondering if anyone can shed some light on this question of darkness. How long until the colour is gone ? Thanks.

[fiberdrunk]

  On 1/16/2018 at 7:00 PM, Simulacrum said:

Hi, I've been very interested in using Iron Gall Inks (permanent/waterproof) but have not yet taken the plunge. So far I've been using Platinum pigment inks which are awesome- esp. carbon black - love it -side note. I think I have been convinced that modern Iron Gall Inks have at least a similar chance of permanence as other 'permanent' inks. And a few hundred years is good enough for me either way. But I have been unable to find out how long before it all goes black. If it's all going to change to black then I'll just use black right away. Unless it will retain colour for 50-100 years or something then that is maybe good enough? If I make a drawing of something I am choosing colours on purpose - I generally want them to stay those colours. But I love the darkness of the IG inks (like the platinum classic inks) and I like the idea that there is some shifting and they look cool but I don't want them to go completely black and lose the colour. It seems there are some chemists posting on here and I am wondering if anyone can shed some light on this question of darkness. How long until the colour is gone ? Thanks.

 

 

Most modern day iron gall inks are of the gallo-ferric variety, lacking the tannic acid, and therefore aren't very permanent. The most permanent iron gall inks will have both the gallic and tannic acid in them, and to my knowledge, nobody is producing this kind for fountain pens commercially (for one thing, most fountain pens don't handle this combo very well and are better suited for dip pens. See my thread for which fountain pens have worked for me). Also, when you add any colored dye to any type of iron gall ink, its permanence/stability is even further diminished, as per the work of chemist Dr. James Stark (he lived in the 1800's... he tested many iron gall ink recipes for 20 years and developed a very permanent recipe. But all those iron gall inks that had any dyes added, including the blue sulfate of indigo (i.e. indigotine), browned and became less stable in a shorter amount of time. I have made his recipe and left out the dye, and those writing samples are still black after 7 years, whereas other recipes I have made are browning after a few years, including the one with indigotine, just as Stark said (this will also depend on the type of nib you use and the paper you write on, too, and how the sample is stored-- all these things affect iron gall inks, which are reactive little buggers). Even after these inks brown, they will likely remain on the page for many years, probably even centuries. But if the ink is improperly balanced, it could be destructive to the paper eventually (such as what we're seeing on Bach's manuscripts today). So, you want an ink that resists browning for as long as possible as that shows a more stable recipe. I know this is disappointing... those colorful iron gall inks are just lovely! You can try conducting your own "sunshine tests" on these inks to see for yourself how well they hold up. There are a few of us here who have done just that, myself included. But it's better if you test these things with the pens and paper you, yourself, are using. Know also that metal nibs are rarely good with acidic inks like iron gall... it's really better to use a quill or glass pen for ultimate permanence.

 

If you really want a colored permanent ink, look to the Noodler's bulletproof and eternal inks, or the pigmented ones by Platinum. These should last. Otherwise, you can make Dr. Stark's recipe and just leave out the indigotine, if you don't mind a black ink. Another alternative are acrylic inks (such as Magic Color)... but these require careful handling and not all fountain pens can handle them (Rotring ArtPen and Platinum Parallel Pens can handle them, but don't neglect the pen and let the ink dry out in them). Any permanent ink will tend to be fussier and require more pen maintenance, but it's a small price to pay if what you seek is permanence on the page.

 

See one of my older light-fastness tests to see which inks survived and which ones faded away.

Edited January 16, 2018 by fiberdrunk