Ink Ingredients: Modern and Medieval

I try to keep my posts under 750 words so that they can be read in a shorter amount of time.  Posts that are going to be longer I try to break up in component parts like I did with the calligraphy analysis posts.  This post could be broken into pieces but I believe doing that would lose some informational value if I did..  Please enjoy this post and let me know what you think of it by giving it a star rating or making a comment at the end.

Ink is absolutely vital to having a robust and healthy understanding of history and so ink is very much like the blood history. There are many other things that we can use to see how things were in history, such as archeological discoveries, paintings, pottery and much more.  But reading what the people wrote about themselves makes the guesswork far easier.  Yes, I acknowledge that writing was not (and even today is not,) always done using ink, but very rare is the culture that never wrote with some kind of ink on some kind of surface.

But, what do we know about how they put ink together? What were the ingredients?  Where did they get those ingredients from?  In this blog I have answered the first two questions already, but what about that last one?

A quick review of the basic ingredients that go into ferro-gallic ink:

– Tannic Acid

– Iron

– Liquid Base

– Binder

– Extras

Tannic Acid:

Tannic acid has many names.  Among the most common names are Gallotannin; Glycerite; Gallotannic acid; Digallic acid and Tannin.  Tannic acid is not the same as the tannin in your tea.  “In scientific terminology, the formula for tannic acid (Acidum tannicum) is C4  H10  O9.   The formula for tea tannins is C20  H20  O9.  As you can see, tea tannins have a longer carbon chain than tannic acid.”

Tannic acid was derived mostly from oak galls.  We are interested in the so-called “Oak Apples.”  Some oak galls are largish and paper-like and very light weight. They vaguely resemble apples and so they came to be known as “Oak Apples,” though you would never want to eat one like an apple.  Other kinds of “oak apples,” are small, hard as a marble and have little spike-like protrusions coming off of them.  These are the aleppo oak galls and have the highest concentration of tannic acid among the oak galls.  All of these are good oak galls for our purposes.

We do see recipes that derived tannic acid from the bark of trees and bushes. Generally speaking this involved boiling and re-boiling the bark several times before it was able to be used.  It would be nice to be able to know where the original recipe writer was. This way we could determine more about the availability of various sources of oak galls.  Determining where a certain recipe began can be relatively difficult as plagiarism was rampant and recipes travelled.

This ingredient is simple enough and straight forward.  Find the requisite tree or bush and gather what you need from it.  Oak galls can be plucked from the tree or gathered off the ground.  I have done both.  Peeling the bark from the tree or bush is easy enough though one should be careful not to peel a circle of bark from the trunk as that can kill a tree.  You can also purchase oak galls online.  My go to resource for buying aleppo oak galls in John Neal Bookseller.

You can order tannic acid directly. Make sure you follow the Material Safety Data Sheet (MSDS) recommendations.  No, I have never done this.

Iron:

Iron was needed to interact with the tannic acid.  The reaction between these two chemicals is what makes the ink black.  Yes, Iron Gall ink is a chemical, and thus synthetic, ink.

Iron was introduced into the process in two main forms.  1 – A hunk of iron, often heated but not always. And 2 – Iron Sulfate.

A hunk of iron of some kind can be found in some recipes.  Often they say something along the lines of, “Put leftover nails into the ink to soak for three weeks and this will make a good ink.”  Sometimes though we see instructions that say, “Put a red hot iron into the ink and let it cool there.  When it is no longer hot, take out the iron and you will have a good black ink.”

I’ve seen the leaving iron chunks in it thing work.  It is a slow process but it is a definite one.  I’ve never tried or seen the heat up the iron to red glowing hot and drop it in method.  Yes, I do plan to try it someday.

Copperas and Green vitriol were medieval names for Iron Sulfate though it is properly called Ferrous Sulfate in modern chemistry terms.  It is chemically written as Fe(II) SO4 having one atom of Iron and one molecule of sulfate. Ferrous sulfate is a salt meaning it is two ions, one positively charged and one negatively charged and they are weakly bound to one another.  When put into a water based solution the ions separate out and look for something else to bind with.  In the case of the ink, the iron binds with the tannic acid, causing the iron to oxidize black.

Remember how In period it was called copperas and green vitriol.  This tells us that it was specifically Ferrous Sulfate Heptahydrate.  Or Fe(II) SO4 + 7 H20.  We know this because this form of ferrous sulfate is a blue green colored crystal.  Without the 7 H20 molecules it is a white powder.

So how did they acquire copperas in period?  Like needed chemicals of today, they manufacture it.  The Tankerton Copperas Works on the North Kent Coast in England is just one example of highly-capitalized large-scale production, in England.  The article in the link discusses the process.   In theory the process was as simple as finding some sulfurous dirt, pouring water over it to get the sulfur out.  Then pouring that solution over some iron and you could get copperas.  I doubt highly that was an efficient or reliable method, but it could work.

Modern making of ferrous sulfate is greatly varied.  The video in the link shows some methods.  And it can be manufactured in rather large amounts.  Yes in this video,that is a barge full of ferrous sulfate and they are using a bulldozer to move the ferrous sulfate.

How can you get ferrous sulfate?  Order it from a chemical supply shop.  In the USA you can also get it from greenhouse stores.

Liquid Base:

So what liquids did they use?  The list will surprise you.

– Rain Water

– Clean running water

– Pure wine

– Vinegar

– Strong Wine (Brandy)

– White wine

– Red wine

– Beer

– New beer

Most of these can be found, “A Book of Secrets” and in “ Der Win Arzt”

If we wish to have the discussion of “Did you use medieval period authentic materials?” the answer in this case is going to be, “Of course not.”  The water in rain varies from place to place and even more so from one time period to another time period.  We know that our atmosphere today is not the same as the atmosphere from the Middle Ages.  Therefore the composition of rainwater and anything that comes from rainwater or frankly any natural water source is not going to be the same either.  It simply can not be.

What we can do is look for what the medieval ink makers were trying to do.  Rain water and clean running water both indicate to use that they were looking for the purest water they could get. Well water often had minerals and such dissolved into it that made the water what we today call hard or soft water.  Hard and soft water means the chemical makeup of the water is very different.  The medieval ink maker wanted something as close to pure water they could get.

Today distilled water fits that bill pretty well   It isn’t the purest form of water you can get (especially the store bought stuff), but it is likely to be about as pure as the pure water they were after in the middle ages.   And where I live, a gallon will cost you about one dollar.

 Wine and the other alcohols including vinegar:

We can buy wine, vinegar, brandy and beer.  Buying these items doesn’t have to be expensive.  Keep in mind that people have strong opinions as to the proper uses of alcohol and making ink isn’t usually on that list.  As long as you don’t tell anyone you aren’t likely to be run out of town for ruining the alcohol by turning it into ink.

But there are a couple of problems for the medieval enthusiast, here.  First, all of these alcohols and vinegars are water based, so we have that same water problem. Secondly, modern alcohol production is not at all like period alcohol production.  So the modern alcoholic drinks are not going to resemble the period alcoholic drinks in chemical and microbial makeup.  After all it is microbes that produce the alcohol to begin with.  And the kinds of microbes that existed in the Middle Ages are not going to be the exact same mixture (and possibly kind,) of microbes we have today.

 So, the hard part is finding a person who makes these alcohols in a very medieval period way.  While there are lots of brewers in the SCA, finding one who uses period methods, tools and materials can be very difficult.  I’m willing to bet that some medieval period methods are deemed unsafe for human consumption.  In contrast some ancient recipes had antibiotics in the beer.

 Vinegar today is pasteurized fairly pure acetic acid mixed with water.  Vinegar in period was the continued breakdown of wines and/or fruit juices that were allowed to ferment in an oxygen rich environment. The major component of that kind of vinegar was acetic acid but there were many other compounds in the vinegar as well.

 I currently purchase my vinegar from a vender at the farmers market.  He makes jams and preserves.  He takes the waster fruit fluids and puts it in a bucket and then lets it turn into vinegar.  It hasn’t been pasteurized or in any way purified.  This is as close as I have been able to come to a medieval period vinegar.

Binder:

 The single most common binder for ink that I have run across is so-called Gum Arabic.  I use the term gum arabic without any problem, however, it is most correct to call it gum acacia.  Of course what is and what was gum arabic is a question that doesn’t have as straightforward an answer one might think.  In D.V. Thompson’s “The Materials and Techniques of Medieval Painting” he discusses gum arabic showing how the term was a general use term that could have meant the gum of several different trees and/or bushes.

Before Gum Arabic was easily obtained in europe they used different binder the most common I have seen being glair and fish glue.  Glair is the residue of what happens when you hyper-whip egg whites.  Fish glues come from various parts of the fish from bones to skins. The best fish glue comes from the air bladder of the fish.  Honey is sometimes mentioned but more of a way to increase the flexibility of the binder once it dries.  I used raw unpasteurized honey once by itself as a binder. This was a mistake.  Honey is hygroscopic and will pull moisture in out of the air.  This means your ink never really dries and frankly that is a disaster.

Extras:

There are all sorts of things that get added to inks  The list is very interesting and sometimes makes you wonder what the heck they were thinking.

Some instances:

– Dirt from a grindstone

– Rose Water

– Logwood

– Brazilwood

– Alum

– Copper Sulfate (Blue Vitriol, Roman Vitriol)

I have no idea why dirt from a grindstone would make good ink but somebody sure did.  Rose water?  Why?  Isn’t that better for making something to eat or drink?

Logwood and Brazilwood are both naturally occurring acid/base indicators.  They change colors depending on the pH of the solution they are in.  When they come in contact with iron they turn black.  So does the iron.  This you would think would be excellent for making ink.  However, even in the middle ages they seemed to discover that logwood was not stable enough for long term permanent inks.  This didn’t stop it from being in various ink recipes but it was apparently not allowed to be in any court records first in France and then in England.

Logwood and Brazilwood can be purchased from cloth dying resources.  I like to buy by logwood from outdoor stores as it is cheaper to buy there.

Alum is  KAl(SO4)2  or Potassium Aluminum Sulfate.  That sulfate thing again.  I haven’t discerned why sulfates keep popping up but there are three sulfates that you see in ink ingredients.  Iron Sulfate, Alum and Copper Sulfate.

Copper sulfate shows up with such regularity that it could almost be thought to be useful in making ink.  I have made ink recipes that included copper sulfate in the ingredient list.  I split one batch so that half the batch of ink had the appropriate amount of copper sulfate and the other half had no copper sulfate in it.  The half without the copper sulfate wrote much blacker.  So why include it at all?  I don’t know. But I think  they might have stumbled across one of the laws of chemistry.  There is a hierarchy of interactive metals.  The more reactive metals will replace the less active metals.  This video does a great job explaining it.  So if they were using a raw iron such as scrap iron and were using the copper sulfate they would have been making Iron Sulfate with the copper dropping out of solution.  This video shows that happening.

Ink making is a very creative process that changed depending on what you had around you to make the ink.  Over time the ink recipes changed becoming more refined but also more robust finding more ingredients that would, in theory, make better inks than the previous inks.  In the end the sheer variety of ingredients alone is a testament to the creativity that went into making ink. And this creativity allowed a very permanent chemical ink to be created in vastly disparate places and times.  And because of that ink we know about taxation, transactions, inventories, domesday, the Magna Carta, calendars, Archimedes, Plato and just about every aspect we know anything about in the middle ages.  We owe all that knowledge from the past we have to ink.