Home Made Ink (Mostly Ig) & **tips And Tricks**

[pharmacist]

In my surge for making different colours of iron gall inks, I started to make a standard solution without any dye in it. It is a clear ink with slight yellowish taint in it.

 

First I started to use malachite green to make a bright cyanish green ink, which is a pretty nice colour, by dissolving it in a about 10 ml's of destilled water and I added the standard iron gall ink solution to it. It formed a greenish sludge immediately, which was very difficult to remove from the in bottle and it looks like the dye is precipitated from the solution as the ink als seems to lost its nice colour. Despite the nice colour, this dye is incompatible to iron gall ink.

 

I will try crystal violet to make purple ink and see if this is compatible to the iron gall ink or not. The problem is that crystal violet is not a acid dye, so I am not sure it will precipitate or not.

 

So far only high quality anilin blue W.S. and Lamy Black fountain pen ink seems to be compatible to this ferro-gallotannate solution, without causing precipitation.

 

Just to confirm crystal violet is NOT compatible to iron gall ink. It too formed a sludgy precipipitation of the dye. I tried nigrosine and this seems to be OK, but I have to let the ink to rest and see how it behaves the next days.

Edited August 28, 2011 by pharmacist

[ville900]

Very interesting experiment pharmacist with colour iron gall inks... Keep us informed that'll be quite interesting to see which colours you manage to produce.

[pharmacist]

Just un update: both malachite green, eosin red are incompatible to IG ink and will form a sludge very rapidly. Nigrosine seems to be less tricky, but still not as good as good quality aniline blue W.S.

 

The almost colorless IG basic solution seems to write well in my fountain pen's: it writes almost invisible from the pen and it gradually darkens into an indelible black. I am not sure this colorless IG ink will be popular.

[ville900]

Thanks for the update. Not sure transparent ink is very easy to use even if it darkens to black when drying.

I guess finding the right pigment that doesn't transform or precipitate is a very subtle exercise, which is probably there is no offer for couloured ferrogallic inks on the market. I guess colour pigment inks such as the Japanese (Sailor or Platinum I can't remember) is a different chemical formulation.

[RGH]

In my surge for making different colours of iron gall inks, I started to make a standard solution without any dye in it. It is a clear ink with slight yellowish taint in it.

 

First I started to use malachite green to make a bright cyanish green ink, which is a pretty nice colour, by dissolving it in a about 10 ml's of destilled water and I added the standard iron gall ink solution to it. It formed a greenish sludge immediately, which was very difficult to remove from the in bottle and it looks like the dye is precipitated from the solution as the ink als seems to lost its nice colour. Despite the nice colour, this dye is incompatible to iron gall ink.

 

I will try crystal violet to make purple ink and see if this is compatible to the iron gall ink or not. The problem is that crystal violet is not a acid dye, so I am not sure it will precipitate or not.

 

So far only high quality anilin blue W.S. and Lamy Black fountain pen ink seems to be compatible to this ferro-gallotannate solution, without causing precipitation.

 

Just to confirm crystal violet is NOT compatible to iron gall ink. It too formed a sludgy precipipitation of the dye. I tried nigrosine and this seems to be OK, but I have to let the ink to rest and see how it behaves the next days.

 

I've just stumbled across this thread and as an ex-chemist (sort of, I switched to molecular biology for my Ph.D. - much easier!) I just wanted to ask you about your findings using both Gallic Acid and Tannic acid.

 

From the structure of Tannic Acid given by Wikipedia it appears to be a Gallic Acid oligo-ester (with glucose - I think - in the centre). Surely then, the addition of HCl would eventually break the Tannic Acid down into Gallic Acid. Although I must admit I don't know where the equilibrium or kinetics vs thermodynamics of this reaction would be. Have you really noticed a difference when adding Gallic acid to your recipe? Do you think this would be eliminated over time as the Gallic Acid/Tannic acid ratio reaches equilibrium?

 

I've found a source for Tannic Acid here in the US, but no luck on the W.S. Aniline dye as yet. I'd definitely be interested to know if you find another one that is suitable.

 

Incidentally I noticed when rereading this topic that pgar (who you indicated you knew) posted a long list of organic dyes he had found to be compatible with Iron Gallate inks. These include Fast Green and Tartrazine. You might want to look back at them. I have found that Kremer Pigments (which is a German Company with a branch in the US sells almost all of these. Unfortunately a lot of the dyes are restricted here in the US, but I am going to try your original recipe with indigocarmine (AKA Indigotin).

 

Thanks

 

Robert

 

In cell biology we use a number of water soluble dyes both to stain proteins (e.g. Coomassie blue) and to identify running postion on electrophoretic gels (e.g. Bromophenol Blue, Orange G etc). I wonder if any of these could be used. Since you're in Europe, Hoechst makes a huge number of different dyes that might be useful. Do you know what chemical properties might be required to prevent precipitation?

 

Anyway keep us all updated.

Edited October 3, 2011 by RGH

[pharmacist]

The have the tannic acid to be broken down into gallic acid will require a lot of effort and in normal ink this is none existing. You have to boil it in a strong acid for a long periode, therefore the most efficient way is to have it consumed by yeast enzymatically, which is the way it is done commercially.

 

Actually gallic acid gives you the most blackest ink and tannic acid a more brownish pigment. The type of dye to be used should be acid (having sulfonic groups), but even then you have to experience. I have tried several acid dyes with my ferro-gallotannate inks and most of them will give you precipitations. Pgary uses ferro-gallic inks, which are much easier to handle and compatible to much more dyes, BUT thiese types of inks are less archival.

 

So you can make all kinds of fancy colours using these types of dyes in ferro-gallic inks, but I rather prefer to make the much more archival ferro-gallotannic inks, so my choices of dye are therefore limited drastically.

[RGH]

Thanks for the reply. I've had a look at a couple of articles looking at acid and alkali hydrolysis of tannic acid, I didn't realise that it would be so resistant to acid hydrolysis.

Unfortunately Gallic acid is impossible to buy in the US since it can be used to make mescalin. Is tannic acid easy to ferment? Or would it be worth trying to do alkaline hydrolysis (which apparently is much much easier) followed by acid work up?

 

 

I don't know how I would get rid of the NaCl. According to Wiki Gallic acid solubility is 15g/L versus 2850g/L for Tannic Acid (I'm not entirely sure I believe these numbers), so perhaps I could preferentially precipitate the Gallic Acid over NaCl.

 

Do I need Gallic acid at all?

 

Any advice you can offer would be great.

 

With reference to the dyes, I see the issue. I wonder how the tannate moiety induces precipitation. I've noticed that most of the acid food dyes (which is what Pgary uses) are sulfonated, have you noticed whether the organic:ionic ratio affects precipitation? OR the general size of the entire molecule. I have to admit this whole discussion reminds me of why I went into chemistry in the first place! Thank you for rekindling my interest!

 

Robert

[pharmacist]

To be short: yes, gallic acid is necessary to make a good shading ink. If you use tannic acid only you will end with a brownish ink.

 

Not sure about the relation bethween the size of the molecule and the rate of precipitation. How does the other groups (alkyl, aryl,) interact with the tannic acid molecule. Does the Fe(II) ion complexes with the sulfonic or other acid groups (like propionic or acetic groups) to form a insoluble complex...So much speculation and the only way is to try it out and see how the ink behaves. Note: most dyes are triturated with salt and having the highest quality dye stuff is very difficult and extremely expensive. As a molecular biologist, you probably knows how much water blue W.S. costs.....

[RGH]

To be short: yes, gallic acid is necessary to make a good shading ink. If you use tannic acid only you will end with a brownish ink.

 

Not sure about the relation bethween the size of the molecule and the rate of precipitation. How does the other groups (alkyl, aryl,) interact with the tannic acid molecule. Does the Fe(II) ion complexes with the sulfonic or other acid groups (like propionic or acetic groups) to form a insoluble complex...So much speculation and the only way is to try it out and see how the ink behaves. Note: most dyes are triturated with salt and having the highest quality dye stuff is very difficult and extremely expensive. As a molecular biologist, you probably knows how much water blue W.S. costs.....

 

Yes I'm well aware of how much some of the dyes cost. It's one of the reasons I thought you might want to try Coomassie Blue (not sure what it would be called in Belgium (either Flemish or French), but it's VERY acid soluble.

http://en.wikipedia.org/wiki/Coomassie_Brilliant_Blue

 

The only possible problem is that it will seriously stain your hands if you get any on you!

 

I also want to look at Orange G which again is very soluble, and reasonably cheap. I think it might go towards a nice green when mixed with Blue. Unfortunately I don't know how pure these are.

 

Lots to try. Unfortunately the cheapest source of Tannic Acid I have found in the US - which is actually a German Company (kremerpigments.com) is out of stock for a couple of months. Interestingly they have a whole section devoted to chemicals required for ink gall inks (including a number of organic dyes), but they list aniline not W.S. Analine. I'm wondering if I should let them know there is a BIG difference!

 

thanks for the information

 

Robert

[stevenrs11]

Hey,

 

I have still been working on my inks on and off, and I got some pure gallic acid!! Now I dont have to worry about fermenting and unknown amounts and my makeshift titration setup (<- which was an epic failure).

 

Still though, I have some problems with the formula you posted second, Pharmacist. It doesn't quite flow well out of an older waterman I found (the pen is very nice, it seems) and adding detergents doesn't really help. I got some photo-flow from Kodak for this. In my pilot parallel, however, it flows like crazy and turns a perfect black, except for an odd metallic iridescence when it flows too much.

 

If I take a drop of the ink and smear it, where the ink is thickest, it forms the metallic strangeness, but everywhere else it is too light of a black (greyish). But if I rub the metallic part, it goes away and becomes the deep black I am going for. Have you encountered this at all?

 

By the way, photoflow is the most insane surfactant I have ever seen. Even in the greatest dilutions, it causes water to creep like acetone. One drop of 1:1000 photoflow:foodcoloring will spread on paper into a drop 5 inches across if I stop it from drying out by keeping it in a humid place.

 

By the way x2, I used my ink I made earlier all during my school semester at Dartmouth. Used a good 100ml of the stuff and even took tests in it. I am a fountain pen convert now.

[pharmacist]

@stevennrs11,

 

you might try to add some alcohol (start with about 3-5%) to modify the surface tension. Using detergents to modify flow is not a good idea, as you might have experienced. Did you use an apropriate acid dye to colour the ink ? The ink should be perfectly limpid, if not, the dye is not suited for IG or it is not pure enough. I have searched for a long time to get the purest form of anilin blue W.S. Most dye stuff are triturated with salts, and some of them cause a precipitation with the IG components.

[stevenrs11]

Hmm... Yea, I'll try some different alcohols and see if that helps. I never added any other dye, actually. My ink just starts a very pale shade of blue. It's pretty cool to see it change colors, too. It's not a simple darkening, either. The ink slowly turns around the edges of the letter to a golden color that rapidly becomes more and more brown, then adds in blue/purple shades until it becomes entirely black.

 

Also, is it normal that the shading is sorta purple-black, and not pure black like my ink I made from galls? Its not much of a difference, but I still notice it.

 

And what is a good, inexpensive fountain pen that has flow characteristics similar to more expensive pens? The pilot parallel is nice, but it uses a very different feed mechanism and I'm afraid it may treat inks differently than a more standard pen.

 

Thanks for all the help, by the way. So many questions, much to learn...

 

Edit- RGH, I found some Gallic acid for sale in the US. Pricey, but you never need much. From a pool chem supplier!!

 

http://www.jimswim.com/taylor-js-r-7046-j.html

Edited November 28, 2011 by stevenrs11

[ville900]

Hi,

 

The Pilot 78G is a good cheap fountain pen to try inks. It costs 10 US$ or less, shipped from Hong-Kong and is available in 3 different nibs: F, M, B

[brewerjeff]

I have not read every word here on mixing inks together, so beg pardon if I missed something.

 

Does anyone make ink from scratch, using pigments etc etc? Reason I ask is while looking for small empty glass bottles I came across some dyes that I used to use for staining biological specimens and wondered about using them to make ink. I have several reds and a blue.

 

Thanks in advance

[Sholom]

I have not read every word here on mixing inks together, so beg pardon if I missed something.

 

Does anyone make ink from scratch, using pigments etc etc? Reason I ask is while looking for small empty glass bottles I came across some dyes that I used to use for staining biological specimens and wondered about using them to make ink. I have several reds and a blue.

 

Thanks in advance

 

Yes, I have, but.... Pigments need to be colloidal, preferably nano-sized to not clog pens, and that requires dispersing equipment (a blender might work but is messy; things like rotor-stator homogenizers, colloid mills, sand mills, etc. would be better, and of course you will need a dispersant to keep the pigment particles from agglomerating). Dyes are a lot easier. Besides water and dye, you will minimally need a humectant (e.g. glycerol or a glycol) to keep the nib from drying out too fast, a wetting agent carefully adjusted to achieve the rate of paper penetration, ink flow from the pen, and ink spread, and a reasonably strong preservative. Actually, if you are not fussy about flow, lubrication, ink spread, or moldy ink all you need is water and a dye, but that mix's performance won't compare to a properly formulated ink. There have been previous discussions about using food colorings as inks. Also, filter the ink (I used a 0.45 micron syringe filter in my lab) before you use it.

 

The real problem with the microscopy stains is the purity (or lack thereof) and impermanence of many of them. For microscopy stains, the standards for some of those dyes permit less than 50% actual dye content, the balance being mostly salts and byproducts that may be corrosive to pens. Additionally, dyes like Crystal Violet, Malachite Green and some others fade amazingly rapidly if exposed to sunlight or even bright fluorescents. Some of the yellows (e.g. Tartrazine and Quinoline Yellow S) are better in that regard. And don't mix cationic (e.g. Methylene Blue) and anionic (e.g. Eosin Y) dyes as they will precipitate each other (as in Jenner Stain) and clog your pen. That said, I've made a passable (but hard to clean out of the pen) red from Amaranth dye, water, polyethylene glycol (I think, maybe it was diethylene glycol [toxic]), a Pluronic surfactant, and some isopropyl alcohol (c. 5-10%) as preservative. I could write with it but much prefer commercial inks.

 

But don't let that stop you from experimenting a bit with an inexpensive pen given the above.

[PersianPenName]

Hey hey folks! So, I have a question on the IG inks.

 

I got a bunch of galls from a texas live oak, crushed them up, boiled, fermented, added ferrous sulphate and HCL. The HCL took me a few days to source, so at first I had small experimental portions inside little glass nail polish jars that I had around. Black precipitate formed, as expected.

 

When I put the 25% HCL in, since I didn't know how much to put (gall strength unknown and all that), I tried it out with just a few drops into my 5mL bottle. Overnight, the liquid cleared to a brownish-yellow translucent color, but I also got a red-brown precipitate.

 

Does anyone know what that could be? As the ferrous sulphate, I used the iron pills I take as a suplement, which also contain calcium carbonate. I figured that would be good, since some folks would crush up eggshells in their ink.

 

I tried sucking off the brown liquid and trying it out, it does still change color but it's going to a medium grey instead of a black. I do plan to try future ink with actual gallic acid and ferrous sulphate crystals, but I would like to be able to make an ink out of the actual galls as well, as several friends have expressed interest in a jar of the more natural stuff. Does boiling down the fermented liquid concentrate it into a darker color at all?

[fiberdrunk]

Hey hey folks! So, I have a question on the IG inks.

 

I got a bunch of galls from a texas live oak, crushed them up, boiled, fermented, added ferrous sulphate and HCL. The HCL took me a few days to source, so at first I had small experimental portions inside little glass nail polish jars that I had around. Black precipitate formed, as expected.

 

When I put the 25% HCL in, since I didn't know how much to put (gall strength unknown and all that), I tried it out with just a few drops into my 5mL bottle. Overnight, the liquid cleared to a brownish-yellow translucent color, but I also got a red-brown precipitate.

 

Does anyone know what that could be? As the ferrous sulphate, I used the iron pills I take as a suplement, which also contain calcium carbonate. I figured that would be good, since some folks would crush up eggshells in their ink.

 

I tried sucking off the brown liquid and trying it out, it does still change color but it's going to a medium grey instead of a black. I do plan to try future ink with actual gallic acid and ferrous sulphate crystals, but I would like to be able to make an ink out of the actual galls as well, as several friends have expressed interest in a jar of the more natural stuff. Does boiling down the fermented liquid concentrate it into a darker color at all?

 

Hmmm... I've made homemade iron gall inks before (a few different recipes), but have never used hcl or calcium carbonate in them, and I use iron sulfate (from the fertilizer section of gardening stores) rather than iron pills. I do know that the best galls to use are the blue aleppo galls from the middle east. They have a very high level of tannic acid compared with what we have here in America... you need to use 3 1/2 to 4 times more of your Texas oak galls to equal what the aleppo galls have. The aleppo galls are also the only source of tannins that I've used that have given me a truly black ink. (I've used California oak apples in the Jane Austen ink recipe and it gave me a black with a brownish hues... and it's brown when I use a glass pen, but black with a metal dip nib, so I suspect the metal in the nib is reacting to something in the ink to get that blacker color. I've used pomegranate peels to make iron gall ink, too, and it gives me a gray with sometime brownish and even green tints.) You may not be able to coax a truly jet-black ink from your Texas oak galls. So just know that the aleppo gall is the superior gall to use for both ink color and ink permanence/stability. That doesn't mean you can't make a wonderful ink from your Texas galls. It'll still be pretty. I, for one, enjoy making inks from plants I can obtain locally.

 

One other point. Dr. Stark, a chemist in the 1800's, found the most stable inks came from using a ratio of 3 parts aleppo galls to 2 parts iron sulfate. Like I said earlier, with Texas galls, you'll need to increase the galls to 3 1/2 to 4 times more.

 

Also, sometimes an ink needs to age a few days before it ripens into a darker ink.

 

I also use a cold-process with my inks, preferring a longer fermenting period over cooking the galls down. From the research I've done, the cold-process way does a better job extracting the tannic acid. Maybe try fermenting your next batch for a month. The only cooking I do is to bring it to a boil for 5-10 minutes at the end to stop fermentation and kill the ink beasties (this is after straining). By fermenting, much of the tannic acid is converted into gallic acid, and this will help give you a blacker and richer ink.

 

Hope that helps you with your sleuth work. Good luck and have fun with your experiments! If you want to compare, here are my recipes on my Flickr account:

 

Dr. Stark aleppo iron gall ink

Jane Austen iron gall ink (using California oak apples as a substitute)

Pomegranate iron gall ink

Edited September 15, 2012 by fiberdrunk

[wallylynn]

What are some other sources of tannins? I've never seen any galls where I live (just acorns). Should I buy a box of cheapo tea bags?

 

How would I know it's fermenting properly? My pokeberries fermented and smelled like wine. My walnut husks molded over and I'm afraid to put my nose in it.

[fiberdrunk]

What are some other sources of tannins? I've never seen any galls where I live (just acorns). Should I buy a box of cheapo tea bags?

 

How would I know it's fermenting properly? My pokeberries fermented and smelled like wine. My walnut husks molded over and I'm afraid to put my nose in it.

 

Pomegranate peels have a lot of tannic acid and make a nice dark gray ink. The fermentation was obvious for this ink. You can see mold on top:

 

http://farm5.staticflickr.com/4074/5395538477_4f8610ec38_z.jpg

 

Black walnut is naturally anti-fungal so while the husks may mold over, after you strain them out, you will not see mold form on the liquid. I've made a cold-process black walnut ink this year, so rather than repeatedly cook the husks down in water, I simply soaked the husks for five months in water and then strained out the solids; and then I let it evaporate it down to strength (at which point I strained and boiled it again for 5-10 minutes to kill the ink beasties). Mold never formed on top. However, after several months of letting it evaporate in the summer heat, I could smell a strong yeast smell-- similar to rising bread dough. I made a very large quantity, though (a couple gallons worth). Someone making a smaller quantity this way might not have to take this long with it.

 

I let mine ferment covered. Whether mold happens or not, I just trust that it has occurred if the conditions are warm enough.

 

You can get tannic acid from a lot of different plants, but not all of them will produce an archival ink:

 

Tannic acid. Because tannic acid is used for so many treatments (burns, antihemorrhagics, antihelminthics, antiseptics, antidiarrheals, antifungals, bronchitis, skin inflammation, lice), a note as to its preparation is in order. All thready plants, especially trees, contain tannic acid. Hardwood trees generally contain more than softwood trees. Of the hardwoods, oak—especially red and chestnut—contain the highest amount. The warty looking knots in oak trees can contain as much as 28 percent tannic acid. This knot, the inner bark of trees, and pine needles (cut into 2-centimeter [1-inch] strips), can all be boiled down to extract tannic acid. Boiling can be done in as little as 15 minutes (very weak), to 2 hours (moderate), through 12 hours to 3 days (very strong). The stronger concoctions will have a dark color that will vary depending on the type of tree. All will have an increasingly vile taste in relation to their concentration.

 

--U.S. Army Field Manual FM 3-05.70 - Survival Use of Plants Ch. 9

 

This talks about boiling down plant matter to extract tannic acid. For ink-making, David Carvalho mentions in his ink book that a cold-process is actually better and more stable for inks. That means weeks or months of soaking. But know that any source you use other than the aleppo gall will force you to guess how much tannogallic acid you'll end up with. In your experiments, just take copious notes... write down amounts you used, make handwriting samples, test them in the sun, see how the color changes over time and how fast, and if you get a good stable result, save that recipe! A brownish black ink indicates a high tannic acid (and perhaps not enough gallic acid-- try a longer fermentation time); a greenish black is rather poor quality (this is what I ended up with when I tried leaf galls). You most likely will not be able to coax a truly jet-black ink out of these other sources of tannin. I compensate by adding at least 3 1/2 to 4 times more, say, California oak apples to a recipe that requires aleppo galls. But still, it won't be purely black. Still, you can make a nice ink that will be waterproof and pretty permanent, though probably not the kind that will last centuries without eating the paper.

Edited September 21, 2012 by fiberdrunk

[taharka]

I've just been turned on to the concept of making my own inks - fascinating! Thanks so much for sharing all of your work here.

While searching the literature for more information on iron gall ink, I found several references to this paper, whose author is cited as suggesting that an Iron-pyrogallol complex is partially responsible for the color. Elsewhere I read that pyrogallol does form deep-purple complexes with metals. My institution doesn't have access to this paper, but maybe it will enlighten someone else.

 

One thing though. It's been said more than once in this thread that the sale of gallic acid is restricted in the US. Why do you think this to be the case?

It's not on any of the DEA Lists and is not scheduled itself in any way. I do see some mentions of it being on a watched list.... on an archive web page, where it was quoted from a book that was published almost 15 years ago. Check the references cited on the wiki article, and you'll see that it was just ol' Strike's imagination. Gallic acid is not listed, watched, surveilled, or monitored.

 

All that aside, it is not illegal for you to purchase or possess DEA listed chemicals as long as you're not doing it with the intention to make controlled substances. You might find some companies hesitant to sell them to you, but as for gallic acid (which isn't on any of these lists), it's available all over the place. If you earnestly want to use gallic acid to tweak your IGs, if you're not hiding a clandestine drug laboratory in your basement, then you have no need to be nervous about buying small quantities of gallic acid.