Vinegaroon

[katsass]

I have read a number of forum entries re: vinegaroon, and none I have read mentioned the fact that vinegar comes in differing strengths of acetic acid. I found that a generic house brand of vinegar comes in a 4% strength, while a name brand (Heinz) comes in 5% strength. It seemed to me that the higher strength would combine chemically a bit better with iron oxide than a lower strength and could make a better solution.

I began with a gallon of Heinz (5% acetic acid) vinegar. I took two pads of 0000 steel wool and, using a propane torch, burned them well. This to remove any oils or wax. I cut the steel wool into strips narrow enough to slip into the narrow top of the vinegar jug and dropped them in. The stuff sat for about ten days with a piece of old t-shirt covering the open top to keep bugs and etc. out, but allowed air in. It was kept in an area that reached over 90 degrees during the warmth of the day.

After the ten day period, all that was left of the steel wool was a very fine black residue, similar to the black sand found when panning for gold....but as fine as flour. I filtered the stuff through a piece of old t-shirt (it had to be cleaned fairly frequently) and ended up with a gallon of a light amber colored liquid.

I wandered out to my shop and scrounged up every bit of different scrap veg-tanned leather I could find. I dumped a bunch of my concoction into a glass bowl and then each piece of leather in turn went in to it for 10 to 15 seconds. I quickly flushed each piece of leather with clear water and set them out to dry. Each piece was DEAD BLACK except one which was BLUE BLACK. There were no dirty grey pieces; no brown-black pieces like US Marine Corp recruits got (way back) when they first had to shine their issued brown dress shoes with a tin of black Lincoln shoe polish. Everything was just BLACK!!! If I were going to make holsters, etc. using this stuff the pieces would get a drenching in warm water with baking soda dissolved in it, then a rinse with cool water.

I feel (right or wrong) that the acetic acid must be high enough concentration to chemically work it's magic on enough iron oxide to make a good jug of vinegaroon. It seems to me that I hit it on the head. JMHO Mike

[MADMAX22]

Yeah great stuff aint it. My vinegaroon is pretty much black liquid but works really good.

The baking soda rinse will help turn it a darker black in some cases where it doesnt turn out as well. Also I have found that HO leather really does good, WandC does pretty good as well. Tandy is hit and miss with it. Same as alot of the import leather, these are either really good or do the blue thing.

Forgot I wanted to add that I am pretty spoiled with this stuff. I am currently working on a belt that I wanted to add some color to so had to dye the background black and color the tooling. I like just dipping, rinsing, then oiling and being done with it. No buffing and all the other fun that goes with dying things black.

Edited May 17, 2010 by MADMAX22

[katsass]

Yeah great stuff aint it. My vinegaroon is pretty much black liquid but works really good.

The baking soda rinse will help turn it a darker black in some cases where it doesnt turn out as well. Also I have found that HO leather really does good, WandC does pretty good as well. Tandy is hit and miss with it. Same as alot of the import leather, these are either really good or do the blue thing.

Forgot I wanted to add that I am pretty spoiled with this stuff. I am currently working on a belt that I wanted to add some color to so had to dye the background black and color the tooling. I like just dipping, rinsing, then oiling and being done with it. No buffing and all the other fun that goes with dying things black.

Another point that has come up is that it is said that the vinegaroon treatment will deteriorate the leather sooner than dyed leather. During my reading I found that in museums the experts find vinegarooned leather from as far back as the 17Th century..........it has deteriorated to a greater degree than other tanned leather from the period, but it still has it's shape and is easily seen for what it is. I think that the life of the holster etc. that I build will probably exceed the life of the customer. Mike

[ChuckBurrows]

Another point that has come up is that it is said that the vinegaroon treatment will deteriorate the leather sooner than dyed leather. During my reading I found that in museums the experts find vinegarooned leather from as far back as the 17Th century..........it has deteriorated to a greater degree than other tanned leather from the period, but it still has it's shape and is easily seen for what it is. I think that the life of the holster etc. that I build will probably exceed the life of the customer. Mike

FWIW - regarding the old pieces - that is old info and at times still touted even by some experts, but in fact the major reason for the red rot (which is irreversible) seen on old pieces is mostly from sulphuric acid - a major component of smog. Some old blackened goods in fact used ferrous sulfate rather than ferric nitrate (aka vinegar black/vinegaroon) and that increase the chance of red rot. Sulphuric acid is also one reason I no loner use the import hides, because many tanneries use sulphuric acid rather than other chemicals in the the bating process, which is an important part of the tanning process - in the past bating was also called dunging since it used animal dung, mostly chicken.

As for age, vinegar black has in fact been used at least as far back as the ancient Greeks - oldest reference I know of is 50 AD by Pliny the Elder in his writings, but the process is more than likely older.

As for the acetic acid content - yes a higher content will speed things as does the heat, but 4% and even lower will work - it just takes longer and the vinegar may need to be refreshed if all of the iron has not been dissolved in a certain period of time. Stirring the mix to aerate it also helps - the added oxygen helps break down the iron and make the process more complete. And again adding tannins (strong tea, high tannins bark solutions, etc.) to the leather either just before or just after the vinegar black will increase the likelihood of a good black.

And FWIW the iron isn't chemically bonding with the acid, but rather being dissolved by the acid. Leather crafter's in the 18th Century even used ferric nitrate (iron dissolved in nitric acid), but I've found it to be a bit too strong and it takes more time to off gas any residual acid even after "neutralizing" since nitric has a lower VOC than does acetic acid. Just be sure not to over neutralize because bark tan leather is normally somewhat acidic (about 4.5-5 on the PH scale where 7 is neutral) and too much/too long in the neutralizer will be detrimental in a couple of ways.

[katsass]

FWIW - regarding the old pieces - that is old info and at times still touted even by some experts, but in fact the major reason for the red rot (which is irreversible) seen on old pieces is mostly from sulphuric acid - a major component of smog. Some old blackened goods in fact used ferrous sulfate rather than ferric nitrate (aka vinegar black/vinegaroon) and that increase the chance of red rot. Sulphuric acid is also one reason I no loner use the import hides, because many tanneries use sulphuric acid rather than other chemicals in the the bating process, which is an important part of the tanning process - in the past bating was also called dunging since it used animal dung, mostly chicken.

As for age, vinegar black has in fact been used at least as far back as the ancient Greeks - oldest reference I know of is 50 AD by Pliny the Elder in his writings, but the process is more than likely older.

As for the acetic acid content - yes a higher content will speed things as does the heat, but 4% and even lower will work - it just takes longer and the vinegar may need to be refreshed if all of the iron has not been dissolved in a certain period of time. Stirring the mix to aerate it also helps - the added oxygen helps break down the iron and make the process more complete. And again adding tannins (strong tea, high tannins bark solutions, etc.) to the leather either just before or just after the vinegar black will increase the likelihood of a good black.

And FWIW the iron isn't chemically bonding with the acid, but rather being dissolved by the acid. Leather crafter's in the 18th Century even used ferric nitrate (iron dissolved in nitric acid), but I've found it to be a bit too strong and it takes more time to off gas any residual acid even after "neutralizing" since nitric has a lower VOC than does acetic acid. Just be sure not to over neutralize because bark tan leather is normally somewhat acidic (about 4.5-5 on the PH scale where 7 is neutral) and too much/too long in the neutralizer will be detrimental in a couple of ways.

Thanks for the information. History of this sort of things are of interest to me, as a matter of fact, I'll be attempting to make some walnut dye later this year....when I can get the walnut hulls. The one thing that has me wondering is that I thought I was making ferrous acetate and not ferric nitrate. ? Mike

[ChuckBurrows]

The one thing that has me wondering is that I thought I was making ferrous acetate and not ferric nitrate. ? Mike

With iron and vinegar (which generally contains 4-8% acetic acid) you are making ferrous acetate when dissolving unrusted iron with the acetic acid in the vinegar and ferric acetate when dissolving rusted iron with the vinegar/acetic acid - The way I understand it and I'm not a chemist is the difference has to do with the oxide state of the iron - that determines whether is ferrous acetate Fe(C2H3O2)2 or ferric nitrate Fe2(C2H3O2)3.

Ferric or ferrous nitrate on the other hand is made by dissolving one of the oxide forms of iron in nitric acid not vinegar so you are not making that.

With walnut dye it's best to use the green ones when possible and make a syrup thick mixture by boiling and re-boiling as needed. Even then it is not a wipe on dye - the leather will need to soaked for varying amounts of time dependent on how dark one wishes. Some folks will say you need to add iron as a mordant and that is true for some cloths, but is not necessary with leather and if added will give you more of dirty gray brown rather than a brown brown.

Some other original/natural dyes:

Other period dyes:

Logwood - various browns to black - you can get it from trapper's or some historical suppliers

Cochineal - reds - mix with walnut or logwood fro reddish browns

Walnut hulls - in general you need to make it strong and thick and leave the leather soak in it for a fair amount of time to get any real coloring

Turmeric - yellows

Madder root - reds

Coffee - dark roast biled strong makes nice browns (may not be "period" but it works pretty good)

Various barks (mostly inner) give good colors: i.e. willow gives reds to browns, oak bark gives browns

See more here - all of the materials are available on line from various suppliers

http://chestofbooks.com/reference/Henley-s-20th-Century-Formulas-Recipes-Processes-Vol2/Dyeing-Leather.html

http://www.museum.state.il.us/muslink/pdfs/dye_plants.pdf

Edited May 18, 2010 by ChuckBurrows

[katsass]

With walnut dye it's best to use the green ones when possible and make a syrup thick mixture by boiling and re-boiling as needed. Even then it is not a wipe on dye - the leather will need to soaked for varying amounts of time dependent on how dark one wishes. Some folks will say you need to add iron as a mordant and that is true for some cloths, but is not necessary with leather and if added will give you more of dirty gray brown rather than a brown brown.

Some other original/natural dyes:

Other period dyes:

Logwood - various browns to black - you can get it from trapper's or some historical suppliers

Cochineal - reds - mix with walnut or logwood fro reddish browns

Walnut hulls - in general you need to make it strong and thick and leave the leather soak in it for a fair amount of time to get any real coloring

Turmeric - yellows

Madder root - reds

Coffee - dark roast biled strong makes nice browns (may not be "period" but it works pretty good)

Various barks (mostly inner) give good colors: i.e. willow gives reds to browns, oak bark gives browns

See more here - all of the materials are available on line from various suppliers

http://chestofbooks....ng-Leather.html

http://www.museum.st.../dye_plants.pdf

Thanks Chuck, for the info......I just started searching through the "Foxfire" books for info on early leather working, don't know what I'll find. I became interested in the way leather was worked and colored in the past a little while ago. About July or maybe August a supply of walnut hulls will be available out here in the desert. I realize that it will take a lot of boiling plus a good quantity of hulls to make the stuff. I have used coffee and different teas for color back when I was doing a lot of tooling. Either of those can add shades not too easily obtained with commercial dyes IMHO. I enjoyed working with them back then, but nowadays I do very little tooling.......almost all of my stuff is unadorned (except for dye) working holsters with a shotgun or rifle case or scabbard thrown in now and again. Much of the call for holsters is for items either not readily available locally or by those that want one made specifically to their requirements. Many like the final rigidity of my holsters as I use two thicknesses of leather in almost all holsters (other than historically accurate ones), with a saddle stitch all around the edges, some (I think) just like the saddle stitching. A few just want something with my maker's mark on it......like their dad has. (My maker's mark is my avatar) For thirty years or more I hand drew it on all my work with a ball stylus 'till Ma Kat got me a stamp of my mark for a present a few years ago. I just use a mini monogram of my initials on my scrimshaw. Not too much call for hand scrim right now....to easy to get laser etched stuff at much less cost. Here's a pic of a bit of a unique holster I built a little while ago. Mike