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fiberdrunk
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[*] posted on 2-7-2014 at 07:01
iron gall ink


This is my first post. I was referred here by a Fountain Pen Network member. I'm not a chemist per se, but I am a hobbyist ink-maker (I've made: iron gall ink from oak galls and pomegranates; black walnut ink; pokeberry ink). I mostly make inks from plant materials. I've always wanted to make the U.S. Standard Ink (also an iron gall) recipe found in an old Popular Science issue (January 1935, pg. 54-55). I've never been able to find a place to get small amounts of the necessary chemicals. Can someone point me in the right direction? This is the recipe from the article:

U. S. Government Standard Ink
Recipe in Popular Science (January 1935, p. 54)

11.7 g tannic acid
3.8 g gallic acid
15 g iron sulfate
3 cc hydrochloric acid (or muriatic acid, or 2 cc sulphuric acid) – used to prevent sediment forming
1 g carbolic acid-- a preservative to prevent mold*
3.5 g china-blue aniline dye (water-soluble)
1000 cc distilled water

*Have corner drug store make up a solution containing 5 or 10 cc of water, the entire amount being substituted for the 1 gram called for in the formula

1. First dissolve the tannic and gallic acid crystals in about 400 cc water.

2. In another beaker, containing 200 cc water, place the ferrous sulphate and the hydrochloric or sulphuric acid.

3. The dye then should be dissolved in 200 cc of water placed in a third container.

4. When all three solutions are ready, mix them together and add the carbolic acid solution and enough additional water to bring the total solution up to about 1000 cc in volume. A part of this water can be used to rinse out the containers.

5. Pour the resulting ink into a bottle, leaving practically no air space at the top, and stopper it tightly. The ink is then ready for aging, a process that may vary from 12 hours to several weeks. The longer the ink ages, the freer it will be of suspended particles. A good ink will show no sediment after standing for 24 hours.

Skin-tight cappings may be placed on bottles by dipping the corked necks into a hot mixture of cooking gelatin, glycerin, and water.

Note: the article also mentions using methyl violet dye for a violet ink (quantity not given) or nigrosine dye for a blacker ink. However, a fellow ink-maker mentioned trying methyl violet dye and he had disastrous results with it.
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[*] posted on 2-7-2014 at 07:12


Sulfuric acid is sold as Rooto drain cleaner at Ace hardware stores. Hydrochloric acid can be bought at Home Depot (sold as muriatic acid). Iron(ii) sulfate is relatively easy to make by reaction of iron and sulfuric acid.

The other chemicals are harder to get. Carbolic acid, more commonly known as phenol, is easiest (although still not very easy) to buy, although it is possible to make from salicylic acid by decarboxylation. You might be able to get tannic and gallic acids from plant matter, or you could buy them. You'll have to buy the blue dye.




As below, so above.
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[*] posted on 2-7-2014 at 07:37


Traditionally, as the name suggests, iron gall ink was made solely from fermented wasp galls and iron sulfate, the wasp galls providing the crude tannic and gallic acids. The other ingredients improve the ink quality, and using the pure tannic and gallic acids would most definitely produce a better quality ink, but it would be more traditional to make it with wasp galls. Since I have a lot around my house, I was actually considering trying it myself.



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[*] posted on 2-7-2014 at 07:42


Quote: Originally posted by Cheddite Cheese  
Sulfuric acid is sold as Rooto drain cleaner at Ace hardware stores. Hydrochloric acid can be bought at Home Depot (sold as muriatic acid). Iron(ii) sulfate is relatively easy to make by reaction of iron and sulfuric acid.

The other chemicals are harder to get. Carbolic acid, more commonly known as phenol, is easiest (although still not very easy) to buy, although it is possible to make from salicylic acid by decarboxylation. You might be able to get tannic and gallic acids from plant matter, or you could buy them. You'll have to buy the blue dye.


Thank you! This helps a lot already! I didn't realize carbolic acid was the same as phenol-- I've always used whole cloves in my traditional inks as a preservative, which contain some phenol. I've already got the iron sulfate from the fertilizer section (Hi-Yield brand). I'm on my way to Ace and Home Depot for the others. Great tips, thanks!

I guess what I need to find now is a mail order place for the powdered tannic and gallic acid and blue dye. Do you know of any that sell small quantities?
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[*] posted on 2-7-2014 at 07:49


Quote: Originally posted by zts16  
Traditionally, as the name suggests, iron gall ink was made solely from fermented wasp galls and iron sulfate, the wasp galls providing the crude tannic and gallic acids. The other ingredients improve the ink quality, and using the pure tannic and gallic acids would most definitely produce a better quality ink, but it would be more traditional to make it with wasp galls. Since I have a lot around my house, I was actually considering trying it myself.


Yes, this is the way I've always made iron gall ink, from plants. See my efforts here (these are my recipes that I've worked out over the past few years):

Pomegranate (iron gall) Ink -- uses the tannin from the pomegranate; fermenting it produces the gallotannic acid

California Live Oak Iron Gall

Black Walnut Ink

Pokeberry Ink



I'd like to try making ink from powdered chemicals next. I tend to ferment my iron gall ink for 1 to 2 months, so it'd be nice to have a more instant ink to try out.
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[*] posted on 2-7-2014 at 08:05


Ok, cool, that's great! And the links are very helpful too. I guess I'll see how well Texas live oak galls work for ink. (I'm no expert on ink and pens though, I just find the general process of making the ink rather interesting)



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[*] posted on 2-7-2014 at 08:31


Quote: Originally posted by zts16  
Ok, cool, that's great! And the links are very helpful too. I guess I'll see how well Texas live oak galls work for ink. (I'm no expert on ink and pens though, I just find the general process of making the ink rather interesting)


Because of the acidic nature of the ink, you'll want to use stainless steel or gold-plated nibs if you're going to use a metal nib at all. Better, use a feather quill, glass pen or reed pen to avoid further chemical reactions between the nib and ink. Other helpful links:

Iron Gall Ink Website (formerly the Ink Corrosion Website)

Forty Centuries of Ink by David Carvalho

[Edited on 2-7-2014 by fiberdrunk]
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[*] posted on 2-7-2014 at 22:47


Fiberdrunk, all those chemicals can be ordered at ElementalScientific.net. Maybe not the China Blue, but you could ask them, I think some aniline dyes are used as biological specimen stains.

P.S., you can learn more about all these chemicals by using Wikipedia.


[Edited on 3-7-2014 by Artemus Gordon]
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[*] posted on 3-7-2014 at 05:18


Quote: Originally posted by Artemus Gordon  
Fiberdrunk, all those chemicals can be ordered at ElementalScientific.net. Maybe not the China Blue, but you could ask them, I think some aniline dyes are used as biological specimen stains.

P.S., you can learn more about all these chemicals by using Wikipedia.


[Edited on 3-7-2014 by Artemus Gordon]


Thank you!!!
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[*] posted on 3-7-2014 at 12:15


Quote: Originally posted by fiberdrunk  
Quote: Originally posted by Artemus Gordon  
Fiberdrunk, all those chemicals can be ordered at ElementalScientific.net. Maybe not the China Blue, but you could ask them, I think some aniline dyes are used as biological specimen stains.

P.S., you can learn more about all these chemicals by using Wikipedia.


[Edited on 3-7-2014 by Artemus Gordon]


Thank you!!!


My pleasure, and please do post any experimental results you get with your inks. I've dabbled in calligraphy with a dip pen, but I never heard that acid inks could destroy pen nibs before. Is it not possible to add alkalis to neutralize the acidity?
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[*] posted on 3-7-2014 at 12:41


Quote: Originally posted by Artemus Gordon  


My pleasure, and please do post any experimental results you get with your inks. I've dabbled in calligraphy with a dip pen, but I never heard that acid inks could destroy pen nibs before. Is it not possible to add alkalis to neutralize the acidity?


Will do! Iron gall ink actually relies on the acidity to create the pigment and to help keep it in suspension, so there's no getting around that one. That's the chemistry part that creates the magic.

My Speedball nibs have tarnishing and began to tarnish with the very first writing session. It isn't long before you notice flow problems with metal nibs when using these acid inks. But there are plenty of other kinds of nibs to use so it's not too much of a problem. In the Carvalho book I linked to earlier in the thread, he mentions a chemist from the 1800's named Dr. Stark who warned about using any kind of metal with iron gall inks (he was on a quest to discover what made the most permanent and stable iron gall ink, and he experimented for 20 years). He said using metal shortens the life of the nibs, the ink itself (it will precipitate out sooner due to a chemical reaction between the metal and acid), and even the writing on the page will suffer in time (it will brown prematurely and render it less stable over time). If I use a metal nib, even a gold-plated one, I make it a practice to set aside a small amount to dip from, that way I don't age the entire bottle. I also use a non-metal inkwell. There's evidence that using gelatin-coated papers (like what is found in good watercolor papers) helps coat and protect the fibers from the acidity of the ink, too. You're less likely to end up with holes in the paper a couple hundred years from now. Calligraphers often like permanence for their work, so those are a few tips you can use.

[Edited on 3-7-2014 by fiberdrunk]
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[*] posted on 3-7-2014 at 15:24


I found this in the Wikipedia entry for Iron Gall Ink:

"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."

They also mention that in the "Standard Ink" formula, salicylic acid can replace the more toxic carbolic acid as a biocide.
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[*] posted on 3-7-2014 at 19:40


Recently for a history project I synthesized two inks; Iron gall by both traditional and synthetic methods, and Prussian blue dye.
For the traditional iron gall ink I boiled three gallons of acorns for two day and then added 10 grams of iron sulfate. The thick black goop was then filtered through cheese cloth and mixed with honey and one gram of methylene blue.
Here are my results;


<img width="800" src="http://i.imgur.com/FoM1Eyp.jpg"></img>

Edit: don't link giant pictures at full size!

[Edited on 7-6-2014 by Polverone]




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[*] posted on 4-7-2014 at 04:44


Quote: Originally posted by Artemus Gordon  
I found this in the Wikipedia entry for Iron Gall Ink:

"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."

They also mention that in the "Standard Ink" formula, salicylic acid can replace the more toxic carbolic acid as a biocide.


I wonder if the ink precipitated out when they added the egg shells? The calligraphy website IAMPETH has a .pdf article for "freshening" an iron gall once it's separated out, by adding vinegar. The acidity keeps the iron from dropping out.

I'm going to try the salicylic acid instead of carbolic acid. As I placed my order for chemicals yesterday, I noticed the carbolic acid had added shipping fees on account of its more hazardous nature. Too cost prohibitive for me. I'll go the safer route.
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[*] posted on 4-7-2014 at 04:52


If you're already going to have some hydrochloric acid on hand for making, the ink, salicylic acid is easily prepared by refluxing aspirin(you'd have to purify it first) in hydrochloric acid. It's very cost effective for me to make it myself at home.



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[*] posted on 4-7-2014 at 05:30


Quote: Originally posted by Pinkhippo11  
Recently for a history project I synthesized two inks; Iron gall by both traditional and synthetic methods, and Prussian blue dye.
For the traditional iron gall ink I boiled three gallons of acorns for two day and then added 10 grams of iron sulfate. The thick black goop was then filtered through cheese cloth and mixed with honey and one gram of methylene blue.
Here are my results;



<img src="http://i.imgur.com/FoM1Eyp.jpg" width="800"></img>



So cool! How does it write? I made some acorn ink once but I did it the cold-process way and fermented it. But it didn't make a very good ink. Too little tannin. I think cooking it down is definitely the way to go.

[Edited on 7-6-2014 by Polverone]
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[*] posted on 4-7-2014 at 13:36


Quote: Originally posted by No Tears Only Dreams Now  
If you're already going to have some hydrochloric acid on hand for making, the ink, salicylic acid is easily prepared by refluxing aspirin(you'd have to purify it first) in hydrochloric acid. It's very cost effective for me to make it myself at home.


How does one reflux the aspirin and purify it? Sounds intriguing.
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[*] posted on 4-7-2014 at 13:44


Boil 3 gallons of acorns for 2 days ?

Propane and Insanity have their uses i guess.

Any chance of seeing some photos of your work using the ink ?

It is great to see an end result.

Quote: Originally posted by fiberdrunk  
How does one reflux the aspirin and purify it? Sounds intriguing.

Reflux is basically keeping all the bits in the Jar.
E.g. if the solvent in the Jar goes to a vapour or gas, you cool it, and force it back into the jar.

This is as complex as a liquid cooled jacketed Alhin condenser on top of your RBF, or as simple as a bowl of ice water on top of the jam jar you have as the 'reaction vessel'.

Basically if any of the bits escape when Hot, cool them so they fall back in the pot.

How refluxing Aspirin with HCl purifies it is unknown to me.
My guess would be that it removes the chalk.

[Edited on 4-7-2014 by aga]




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[*] posted on 4-7-2014 at 16:00


Quote: Originally posted by fiberdrunk  

So cool! How does it write? I made some acorn ink once but I did it the cold-process way and fermented it. But it didn't make a very good ink. Too little tannin. I think cooking it down is definitely the way to go.


The final ink was thin, and had to be boiled down until it reached a syrupy consistency. The naturally produced ink was initially more brown than black, but once the ink has dried it resembles normal ink, and I am very happy with the overall result. As it was for a history project, I used a traditional medieval quill. If a quill is used with iron gall ink, you must be very careful to clean it after every use, I used acetone.




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[*] posted on 4-7-2014 at 20:36


Haha, "Propane and Insanity." That could be a great band name!



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[*] posted on 5-7-2014 at 17:59


One thing about this forum I don't understand is that some people feel it's OK to criticize others' methodology when no one asked them to. As long as you are working safely and not harming the environment, there is no bad way to do an experiment. If one of us tries an experiment that is counter to the laws of Chemistry, well, then we will learn something. If we spend more money or time on an experiment than others do, hey, it's a hobby, ALL of us are spending more time and money on this than most of the world does.
Each one of us has our own ideas of what is fun and worthwhile, and denigrating someone else's projects isn't being helpful or nice.
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[*] posted on 5-7-2014 at 20:31


Quote: Originally posted by aga  
Boil 3 gallons of acorns for 2 days ?

Propane and Insanity have their uses i guess.


Are you insulting my procedure? Boiling large quantities of acorns in water (in case this was not clear from my first 2 posts) may not be the not efficient, but is the historical way of preparing iron gall ink. I think you criticism of is out of place and unnecessary and as Artemus Gordon pointed out, no one asked for your opinion or suggestions, especially since the point of this experiment was to recreate traditional processes, not to maximize yield (although tannic acid can be extracted from oak galls via soxhlet extraction).

Quote: Originally posted by aga  

Any chance of seeing some photos of your work using the ink ?

[Edited on 4-7-2014 by aga]


In regard to you more constructive comment;



[Edited on 7-6-2014 by Pinkhippo11]




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thumbup.gif posted on 6-7-2014 at 12:58


Your ink turned out really nice!
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[*] posted on 6-7-2014 at 13:21


Quote: Originally posted by Pinkhippo11  
Are you insulting my procedure?

Whoa dude ! No Insult meant, implied or otherwise.
Apologies for the unintended offence.

Just seemed Mad (to me) to be boiling gallons of acorns for two days.
Which Utterly Insane person first did that, and were they burned at the stake for doing so ?
When it was first done, it is HIGHLY unlikely that it was seen as a sane thing to be doing.

Anyway, it works, so Result=Good.

Nice calligraphy, and thanks for posting the photo of the end result.

@Artemus : that wasn't intended as a critical or negative comment.
Your assessment is correct.
As in all walks of life, there are arses that randomly say things we don't immediately like or agree with, such as me.

Unfortunately media such as this are Narrow Bandwidth media - there is much missing, and we tend to fill in all the Background, Meaning, Emotional State etc ourselves, which often leads to error.

[Edited on 6-7-2014 by aga]
Nice: http://www.scienceinschool.org/print/363

[Edited on 6-7-2014 by aga]




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[*] posted on 6-7-2014 at 16:01


This reminded me of the great poetry made by a great philosopher.
Portuguese (Original) Version: http://www.releituras.com/jregio_cantico.asp
Translatd to English version: http://writings.nunojob.com/2011/01/cantico-negro-black-chan...

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