The Gall Of That Person!

[Corona688]

So I've been trying to make an Iron Gall ink, and doing a pretty awful job at it. A list of my attempts, and mistakes not to make:

• Really dark tea plus Ferric Chloride. Turns black instantly, none of that "slowly darkening" bit. But only slightly black, and no blacker.
• Really dark tea plus steel wool left in vinegar. Very little happens.
• Really dark tea plus steel wool boiled in vinegar. Part success. Turns black instantly. But not very black.
• Really dark tea plus steel wool boiled in vinegar and filtered. Failure. All the ferrous turned ferric before I finished filtering.
• Really dark tea plus steel wool boiled in vinegar plus potassium ferrocyanide (to eat up the ferrites). Weird failure. Slowly turns blue until there's no iron left.

So I have learned a few things here.

• Iron gall uses Ferrous iron - not Ferric. Iron(III) reacts instantly with tannins, Iron(II) waits.
• Tea is not a great tannin source. It contains some but not a lot. Which makes sense. People don't drink tea for the tannins.
• Ferrous iron does not keep. The more time you spend trying to remove the ferrites, the more time it spends exposed to air, the more ferrous iron oxidizes to ferric.
• You will stain everything you own. Anything you boil ferrous compounds in will be crusty orange forever.

My last failure was kind of interesting. There was much less ferrites than I thought when I started, but the more I mixed and filtered, the more blue it got. I accidentally made ink which faded blue instead of black.

 

All in all, unless I find a cheap and easy source of ferrous iron at the garden store, I doubt I'll try making iron gall again.

[Corona688]

Looking through my grandfather's old chemicals I found a great number of things which were intended to be biological stains for microscopy. Particularly I found a jar of logwood. With visions of the ancient red-purple-violet which sustained the british empire filling my mind, I dunked a bit in water and got ... sawdust floating in water. It's not dye, it's sawdust.

 

Looking it up, I found the interesting note: "Hematoxylin is extracted by boiling chips or shavings of logwood in water. The presence of a considerable amount of tannin in the purplish-red dye bath allows the logwood extract to react with iron salts to give a permanent black color."

 

I also stumbled across the fact somewhere that it's easier to extract anything from logwood with alcohol than water. So, experiments six and seven:

5. Logwood sawdust in methyl alcohol: Yellow coloration escapes into the water. Hematoxilyn and presumably tannins. Presumably tannins (logwood coloration itself should need time and mordants to oxidize.)

6. Addition of ferrous sulfate to above. Instantly turns grey. Argh.

 

There's definitely tannins in it, but did I mention how old these chemicals are? That was ferrous sulfate was ferrous in 1934. It has not stood the test of time and a large amount must have become ferric, hence the instant reaction.

 

Still, this explains why some iron gall recipies call for logwood. It's just another tannin source, and might have been how it became stereotyped as a "purple black". This stuff, once dried, is definitely a purple black...

Edited April 3, 2018 by Corona688

[Corona688]

Remembering I hadn't actually tried this "ferrous" sulfate with tea yet, I gave it the college try.

 

7. Tannins from tea, plus (old, impure) ferrous sulfate. Instantly produces a grey precipitate.

8. Tannins from tea, some household ammonia (reducing agent), and impure ferrous sulfate. Acts like iron gall - for a while!

 

Ammonia is a reducing agent, so I hoped it'd slow down / reverse the oxidization of the iron somewhat. And it definitely helps. It'd write almost water-clear, then darken to the color of coffee.

 

Then all the ammonia boiled out and the unused ink curdled into unpleasant black chunks. Even given that, it still works, after a fashion. It doesn't darken anywhere near as much as the first writing I did, but it still darkens a bit.

 

My tannins are obviously still weak, but I can boil down that tea some more. The iron remains a problem.

Edited April 4, 2018 by Corona688

[Corona688]

I may have stumbled on something by accident. You don't get ordinary ferrogallate when you add ammonia, you get something else! Now please forgive my excessive linking and quoting but FPN had a previous thread on this subject, which is now shot full of holes from photobucket rot. Argh!

 

From this pdf:

 

Not until very recently did the work of the Section of Organic Chemistry of the National Bureau of Standards and the laboratory of the Government Printing Office make this possible in an ink first discovered in 1908 by Silberman and Ozorovitz of Rumania. This new ink is composed of iron, ammonia and gallic acid, and is technically known as diammonium hydroxyferrigallate. Details on a manufacturing procedure for this ink as developed by Morris S. Kantrowitz and Earl J. Gosnell may be found in Alkaline Writing Ink, Technical Bulletin No. 25, 1947, of the United States Government Printing Office.

Which led to here/

 

8. DIAMMONIUM HYDROXYFERRIGALLATE INK

 

An ink wliich is of no present commercial importance, yet which gained some prominence in the newspapers on account of its having been found to have so httle harmful action on paper in an accelerated-aging test (see section II, 13), is a solution of diammonium hydroxy-ferrigallate.^^ In 1908 two Rumanian chemists published the results of their studies on iron-gall inks, and among other things described the method for preparing this compound. They said that a 7- to 8 -percent solution of it in water made good suiting ink.

 

For those who may be interested, the method as taken from the abstract in the Chemisches Zentralblatt is given here. Dissolve 7.5 g of ferric cliloride (presumably FeCl 3 . 6 H 20 , though it is not so stated by the authors) and 7 g of gallic acid in 100 ml of water. Add 15 ml of concentrated ammonia water, and then 140 ml of strongthe usual 95-percentethyl alcohol. This precipitates the diammonium hydroxy-ferrigallate, winch is filtered off and washed, first with dilute alcohol and then vdth strong alcohol. The washing with dilute alcohol is intended to remove most of the ammonium chloride formed in the reaction. This salt is nearly insoluble in strong alcohol. At this Bureau, in the absence of definite instructions by the authors, the first washing was done with a mixture of 12 volumes of strong alcohol and 10 volumes of water; a second washing was with 20 volmnes of strong alcohol and 10 of water, while the final washing was with strong alcohol alone. The black mass that remains on the filter is dried in the air. It dissolves readily in cold water, with an intense blue-^dolet color. When this solution dries on paper, it becomes insoluble in water in less than an hour, and black in a few hours. The solution soon becomes turbid and deposits sediment in the bottle.

 

Unless some less wasteful method of preparation can be devised, it is unlikely that the compound will ever be used for making commercial ink. The liquid filtered from the original precipitate is intensely black and the wash-alcohol is strongly colored, so it is evident that a considerable proportion of the material is lost. In addition, the large volume of alcohol that is needed increases the cost. A few experiments made at the Bureau indicated the possibility of preparing the compound by dissolving ferric hydroxide in a solution of gallic acid, and adding ammonia water to this solution of ferric gallate. However, to make a large quantity of ferric hydroxide and to wash it free from salts is a difficult task.

Which led to here:

 

It is now learnt from an article contributed by William J. Barrow, Document Restorer, Virginia State Library, to the American Archivist (October 1947) that the Organic Section of the National Bureau of Standards, U.S.A. has succeeded in completely eliminating the drawbacks mentioned and in evolving a new process for making a non-acid permanent iron ink. The ink is composed of iron, ammonia and gallic acid. The addition of ammonia has made the ink soluble and slightly alkaline. It differs from the normal iron gall ink in that the latter contains sulphuric acid which is harmful to paper. This new ink on the other hand is not injurious to paper and does not clog pens. The characters written with it become in- soluble in water within a few hours. The ink is being furnished by the Government Printing OfiBce, U.S.A., to several Federal Departments.

...which doesn't seem to be anywhere anymore. "I have discovered a truly remarkable proof of this theorem which this margin is too small to contain." Argh!

 

American Archivist actually has the issue online but they skip straight over the one and only relevant page.

Edited April 4, 2018 by Corona688

[Corona688]

...and here it is, page 338. Which says that the ink exists, not what it is. Argh!

[Corona688]

The April 1959 issue of New Scientist strongly hints that this di-ammonium hydroxyferrigallate stuff is what they used in fountain pen galls for the next 40 years or so. It was water-soluble, could be made very quick-drying, and Parker certainly used it.

Edited April 4, 2018 by Corona688

[Corona688]

It pretty quickly became a trade secret, obviously. Everyone references it but nobody publishes it. There seems to be one copy in Stanford, and another in Australia, hidden offsite. Beyond that this government-published book has evaporated into trade secrecy.

Edited April 4, 2018 by Corona688

[Corona688]

9. Attempted to make diammonium hydroxyferrigallate ink using the recipe above.

 

It's as difficult and inefficient as they say. It just refuses to pass through a filter unless incredibly diluted, and so much is wasted in the process... I doubt I was able to wash it enough for it to work. It doesn't darken like normal iron gall, it kind of starts that way, but is supposed to change from soluble to insoluble.

 

The other idea they mention, "preparing the compound by dissolving ferric hydroxide in a solution of gallic acid", is probably a better way to go...

[Corona688]

(Herregud, FPN is super ultra laggy today. I'd report the ads, but with three per page I have no idea which are responsible!)

 

10. This is a complicated one. Mixing ferrocyanides with bases is not for the faint of heart, only attempt this somewhere with really good ventilation and don't eat it!

• Brew 600ml of really, really, really strong tea. Then leave it on a cupwarmer overnight to concentrate it double beyond that.
• Add perhaps 2g - 3g of powdered Prussian Blue and stir. This is plenty enough for the blue to overpower the brown.
• Add 300ml household ammonia and stir. This is where things get hairy.
  • The Prussian Blue will dissolve in the ammonia, producing Ferric Hydroxide, and either Ammonium Ferrocyanide or Ferrocyanic Acid, and a small amount of unknown gas.
  • The Ferric Hydroxide will react with the tea tannins and the ammonia to produce something soluble and black - presumably biammonium gallitannate.
• Since this isn't toxic enough yet, add a load of concentrated ethanol or methanol.

I am unhappy with this process since it may result in some cyanide which I'll have to bleach to make safe. It appears to work - both the tea and the prussian blue are completely gone - but haven't dried it enough to write with yet.

 

Next time I'll add ferric chloride to ammonia+tea+methanol and see if that accomplishes everything in one step.

Edited April 8, 2018 by Corona688

[amberleadavis]

Quite interesting. thank you for sharing your journey with us.

[Corona688]

Thanks for your interest. Here's writing with the result of #10. It did not fade into being like traditional iron gall. It's instead intended to start soluble but become indelible.

http://burningsmell.org/images/i/iron-gall-ammonia.jpg

 

I dripped water onto the words 'iron' and 'pen' with a paintbrush. It ran, but only a little, so I think I ended up with a mix of "iron gall" which became indelible and "random brown stuff". That'd be about right as I haven't precipitated it.

 

The random brown could be an unintended side-effect of steeping tannins in ammonia too long. That apparently can make "ellagic acid", which is yet another brown tree material in a long list of brown tree materials.

Edited April 11, 2018 by Corona688

[Corona688]

I've hit a bit of an impasse. I can make this ammonium ferrigallate ink, and alcohol does make it precipitate, but it clogs a paper filter instantly. I don't know if it'll become the soluble or insoluble form if I just let it dry in the filter. We'll see.

Edited April 24, 2018 by Corona688

[Corona688]

In the end there wasn't enough ferrogallate to be useful. Yesterday I tried a a completely different tack. I had logwood extract from some of my grandfather's old chemicals, and that's supposed to contain 10% tannin, and ammonia is supposed to be good at extracting tannins from any plant. So:

 

1. Mix 0.500 g of Logwood extract with 3g of household ammonia.

2. Profit.

 

This rapidly produces a chunky mixture of tannins, logwood dye, and wood pulp, which writes purple and dries tea-brown.

 

After leaving it in ammonia overnight, the logwood dye all disappeared, leaving only tannin. (at this point it ceased to be a logwood ink, hence me posting it in this thread instead.) Lots of tannin. Such much tannin that adding iron made blueblack paste. That's my first look at what iron gall is supposed to look like, and a better result than ten entire bags of tea!

 

Then again, I never tried steeping tea in ammonia. Maybe that will make a lot more tannin too?

 

And my iron still sucks.

Edited August 23, 2018 by Corona688

[inkstainedruth]

Interesting experiments.

Reminds me a bit of the times we went to get ferrous oxide (aka rust) for a completely different purpose -- smelting iron. Yeah, experimental archaeology -- we did a few runs of making iron in our back yard in a clay furnace (built of clay dug out of our back yard; we also built a clay oven a couple of the times).

We found a local-ish source of ferrous oxide, which is normally sold by the truckload to line smokestacks (as scrubbers to trap noxious chemicals from flooding the environment). The guy running the place thought we were nuts since we were ONLY buying a couple hundred pounds. And on another trip there (when my husband wasn't available and I couldn't call him because the place was in a cell phone tower dead zone) the guy -- somewhat suspiciously -- asked if we were making fireworks!

One of the runs did really well, and we ended up with a 50 pound "muck bar" (not sure where that ended up -- an artisan blacksmith friend might still have it, because he was supposed to pound it down to get all the impurities out). Another time, the same guy brought his dad (who I thought was a retired steelworker -- turned out nope, the dad was a lawyer but ALSO an artisan blacksmith; they both have decorations on the gates of the New Globe Theatre in London, BTW ; only one other American does). All afternoon, the dad kept saying "This can't work -- you need a crucible!" And then, at the end of the afternoon, he suddenly found himself saying "Wait! What? It *worked*!" [Yes, it's based on IIRC a medieval type II furnace found in places like Scandanavia and Poland.... and a lot of what they were working was actually from meteor strikes....]

Ruth Morrisson aka inkstainedruth

 

ETA: I may be misremembering the weight of the muck bar (it's been a few years) -- it might only have been about 25 pounds. Unfortunately our friend had a severe stroke a couple of years ago and hasn't recovered enough to do much.

Edited August 23, 2018 by inkstainedruth

[Corona688]

Fireworks!? Iron oxide is pretty inert! I suppose you could have been making thermite, but if you had that much aluminum powder you didn't need his help making havoc

 

Stumbled on this note explaining why iron gall inks used to contain acid:

Chemistry of Iron in Natural Water

 

Solutions of tannic (digallic) acid at concentrations of 5 or 50 parts per million reduce dissolved ferric iron to the ferrous state when the pH is less than 4.

 

So iron gall has something of a self-preserving effect when acidic enough. Which is interesting as otherwise, acid ought to make it worse! This explains a bit - such as how anyone managed to get plain ferrous sulfate to survive longer than minutes in a jar of ink.

Edited August 27, 2018 by Corona688

[Corona688]

Alright, so steeping teabags in ammonia makes a richly brown liquid -- which darkens only slightly when iron is added. And when the PH is neutralized, all the supposed "tannins" clump up into bits of sawdustlike stuff. So, just as bad as tea-tannin was before plus clumpy.

 

Next experiment, then, steeping logwood in hot water.

[amberleadavis]

Any photos?

[Corona688]

Nothing worth photographing, because nothing works.

[inkstainedruth]

Fireworks!? Iron oxide is pretty inert! I suppose you could have been making thermite, but if you had that much aluminum powder you didn't need his help making havoc

I suppose the look on my face when the guy asked me that was pretty much the same look as on my brother's face the time we came back from Canada when I was a kid and my brother got asked at the border if he'd *bought* any fireworks while in Quebec.... (We'd gone to see "Man and His World" outside of Montreal, which was what was left after the Montreal World Expo, and then drove west and crossed the border near Massena, NY where there is a lock on the Saint Lawrence Seaway and you could see boats go through the locks up close).

My parents very firmly told the Customs guy "No he most certainly does NOT have any fireworks!"

Actually, though, in catching up with this thread, it occurred to me that you might want to try and search for the thread from about 5-6 years ago when FPN member Pharmacist was experimenting with making iron gall inks and wrote extensively about his researches. Sadly, he has seemed to have dropped off the map -- but he was playing around with doing colors other than the "standard" blue-black a couple of years before KWZI inks were known about (outside of Poland, at least). It was just sort of a hobby of Pharmacist's, but I'd dearly love to be able to get a back-up bottle of his Turkish Night (a "cyan-black" that actually oxidized to a nice greenish teal -- and I say that as someone who normally doesn't like green-blues or teals for the most part). And sadly, much as I like a lot of the KWZI IG inks -- IG Turquoise just is NOT a substitute for Turkish Night.

Ruth Morrisson aka inkstainedruth

[Corona688]

The big problem now is finding any decent gallotannins. That oak works is no mystery -- oak bits have enough tannins to literally kill a horse. But hardwoods don't grow around here and my substitutes aren't.