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General discussion => Gun Building => Topic started by: pflyman on October 02, 2008, 07:29:31 PM

Title: Vinegar and Iron
Post by: pflyman on October 02, 2008, 07:29:31 PM: I am practicing techniques for an upcoming build of Don Stith's 1792 Contract Rifle. While I have Aqua Fortis (Wahkon Bay), I was intrigued with a past thread on the use of vinegar and iron. I created a batch with 5% cider vinegar and 0000 steel wool (I added heat to perhaps speed the action). It appears that some builders use and are pleased with this approach, but I would like to hear from those that have what techniques, secrets, successes or failures they may have encountered. Is heat necessary to react it? If necessary, is the heat applied after the solution has dried or is still wet?
Title: Re: Vinegar and Iron
Post by: Acer Saccharum on October 02, 2008, 07:39:25 PM: commercial steel wood has oil on it. It's good to wash it in detergent and hot water, then clear rinse several times before using.

Long John got me started using vinegar stain, and I am very fond of it. It's an acid which carries iron molecules into the wood. Same thing that aqua fortis does, but with no toxicity issues. I use it to stain maple, leather, pine, poplar, etc. Beautiful. Takes a while to brew, though.

I never had to heat the wood afterwards to bring out the color.

Acer

here's my photobucket album with colors: http://s12.photobucket.com/albums/a246/Tom45-70/Vinegar%20stains/
Title: Re: Vinegar and Iron
Post by: t.caster on October 02, 2008, 07:47:39 PM: Acer, do you use cider or white vinegar? Full strength or water diluted?
Title: Re: Vinegar and Iron
Post by: Long John on October 02, 2008, 07:56:36 PM: Pflyman,

You have already made it harder than it need be. Just drop some old barbed wire into a bottle of cider vinegar and come back in a week or two. No need to heat! As a matter of fact, since acetic acid has such a high vapor pressure heating drives acetic acid out of the solution so there is less to react with the iron.

If you have an excess of iron for the acetic acid in the vinegar you will get a solution that is mainly ferrous acetate which will yield brownish black color when applied to the wood. If you have excess acid for the iron in the solution you will get a solution that is predominately ferric acetate which will yield a reddish brown color when applied to the wood. With a weak acid for your acid/iron stain you get to choose.

When you put the iron into the vinegar you get a solution of ferrous acetate and ferric acetate. When this solution is applied to the wood and the water begins to evaporate the acetic acid evaporates right along with it. The evaporation of the acetate leaves the iron ions, ferrous and ferric, all alone and they snag onto oxygen from the air turning into either ferrrous oxide (brownish black) or a mixture of ferric oxide (reddish orange) and ferrosoferric oxide (reddish brown) in the wood. No heat is necessary! When the stock stops smelling like salad dressing the vinegar is gone and the reaction is complete. This is the only respect where acetic acid from vinegar differs from nitric acid. Nitric acid must be heated to get it to evaporate from the wood, acetic acid does not. The oxides of iron left in the wood are exactly the same, whether they were obtained using vinegar or nitric acid.

This rifle was stained with vinegar iron stain.
(http://i50.photobucket.com/albums/f349/jmcholin/DSC_0019.jpg)

I took a small quantity of my stain solution from the masonry crock I store it in and mixed it 50/50 with vinegar. That "pushed" the chemical equilibrium between ferrous and ferric acetate towards the ferric acetate end to give me a redder final color. If I had not added the vinegar the stock would have turned out much browner. I applied 3 coats of stain, allowing the stock to dry and then rubbing down with steel wool between coats. Essentially, I de-whiskered and stained at the same time. The final finish is tung oil.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Acer Saccharum on October 02, 2008, 08:05:54 PM: I used cider vinegar, straight from the supermarket.

Iron filings.

Time.

The stuff stinks when it's brewing, by the way. You might get some dirty looks if you brew it in your kitchen.
Title: Re: Vinegar and Iron
Post by: FG1 on October 02, 2008, 08:17:55 PM: I tried it using degreasd steel wool and white vinegar( that was in pantry) instead of cider vinegar and the results were a black and gray appearance on cm ? Any ideas why ?
Title: Re: Vinegar and Iron
Post by: BobT on October 02, 2008, 09:02:38 PM: I just mixed up my first batch of vinegar stain the other day using about a cup and a half of white vinegar and a handful of nails. I applied it to a white pine powder horn end cap I'm making. It turned out a "muddy" brown color, not bad but not exactly what I was after. I plan to experiment with more/less iron and different vinegar.

Not to steal the thread but what is the shelf life of this stuff?
Title: Re: Vinegar and Iron
Post by: Ephraim on October 02, 2008, 09:46:27 PM: I use it all the time cyder viniger and old cut nails or barbed wire work best it is a good old time stain .
Ephraim
Title: Re: Vinegar and Iron
Post by: Acer Saccharum on October 02, 2008, 09:52:17 PM: I have never had highly predictable results with the vinegar stain. the color you get is often a reaction between the wood and the stain. Put the same stain on maple from different trees is going to yield different results.

This stain really needs to sit on the shelf and cook for a long time. Get yourself a batch going, and then let six months go by. Age seems to improve it. Add vinegar when needed.

Acer

Notes from John Cholin, from the old ALR:
For those of you curious about cider vinegar/iron nails stain I have posted on the topic a couple of times. I don't know if those posts were saved or tossed.
About 20-some years ago I read, some where I wish I kept the article, that the old timers stained stocks with a mixture of cider vinegar and iron nails. I was building my first rifle at that time so I took a jug of apple cider that had gotten "randy" tossed in some nails and let it work. Ever since then that has been my stain.
When you make aqua fortis/iron stain what you are really doing is making iron nitrate with some excess acid. Nitric acid has a very low vapor pressure at room temperature so it does not evaporate from the wood very fast. Once in the stock the iron nitrate gives up the iron ion to oxygen in the air which becomes one of the 3 iron oxides (ferric oxide, FeO3, ferrous oxide, FeO or ferrosoferic oxide fe3O4iron oxide). Heating the stock accellerates these reactions. The nitrate ion bonds with a hydrogen in the wood and has to evaporate or be neutralized and washed away.
You can make the iron oxide with acetic acid too! Acetic acid is a weaker acid than nitric so you have to give it more time to combine with the iron and turn the iron into iron ions that are in solution as iron acetate. The nice thing about acetic acid is that you can drink it or sprinkle it on your salad with out much adeiu. It also has a much higher vapor pressure so it evaporates out of the wood quite quickly. If the stock does not smell like salad the acid is gone and all of the iron ions have become iron oxide. Thus there is no need to neutralize unless you can't wait another hour.
Ferrous oxide, FeO, is black to blackish brown. Ferric oxide, Fe2O3, is orange to red to readish brown. Ferrosferic oxide, Fe3O4, is brown. With the iron acetate (cider vinegar/iron nails) stain you can modify the color by changing the relative concentrations of the acid and the iron. Like blackish brown stain? Put in excess iron into the pot, wait a couple of weeks had use it just like any water based stain. Like a redder stain? Put in excess vinegar, wait a couple of weeks and use like any other water-based stain.
I use the stain to raise the grain on my rifles. Each rifle gets 3 or 4 applications of stain, followed by a good rub down with OOOO steel wood. On the carving I use a brush made from hemp rope to burnish the stock wood.
5 years ago I built my 54. On that rifle I had a pretty even balance and it came out reddish brown. On my nephew's rifle he wanted more of a walnut color so I added iron to the pot. By the time his rifle was ready for staining it was turning the wood a nice chocolate brown. On my brother's rifle he wanted a redder stain so I added vinegar to the pot and by the time his rifle stock was ready to stain the stain was turning maple wood a nice reddish brown. Paul's rifle was in there too. He liked a dark stain so he got extra iron. Now that I am building another one for my self I will add a little iron to brown it some from what I had for my brother's rifle.
Since modern nails are often made from manganese steel, these days I hve started getting my iron from old barbed wire that I find up on the farm.
I have been using the same pot of stain ever since I built my first rifle over 20 years ago. (I built a couple disasters quit for 15 years and have now gotten back into it.) A couple of the kids' guns were stained with commercial stain. I didn't like the way they came out but the kids don't care - it goes bang and makes lot's of smoke. But on the adult rifles, for family and friends, I use the cider vinegar and iron stain. Besides, all of the old time gunmakers had plenty of vinegar at their dispoal, they did not have to have it shipped in from England.
I hope this answers your questions. And yes, I was a chemistry major in college.
If your mixture has just turned a dull gray it could be because of alloying elements other than iron. I started with rusty nails from an old barn. Now i am using bits of old barbed wire for iron. It could also just need more acid (vinegar). My pot of stain has been brewing for over 20 years! I end up adding vinegar or hard, sour cider every so often to make up for evaporation. It looks like coffee. You could also add some hydrogen peroxide (H2O2) solution, obtained from the pharmacy. Hydrogen peroxide is know as a bleaching agent because it oxidizes pigments, changing their color. When iron is exposed to hydrogen peroxide solution the H2O2 breaks down to H2O and O, free oxygen. that free oxygen should combine with the iron to produce iron oxide. But iron oxide is not very soluble in water. The ferric ion needs a cation like the nitrate or the acetate to keep it in solution. When the solution of iron ions is applied to the wood and the solution dries, the positively charged ferric ions are left with out a negatively charged nitrate or acetate and combines with atmospheric oxygen during the drying process. The key is in finding a negative ion that keeps the iron in solution but leaves once the stain is aplied. the acetate works well because of its high vapor pressure at room temperature.
Yes there is a bit of a difference between white vinegar and cider vinegar in that white vinegar is distilled, I think over mineral oil but I'm not sure, to refine out the compounds responsible for the tan color. As long as the acetic acid contents are the same the chemical properties will be the same. when I have to add vinegar to my pot of stain I go into the kitchen and get what ever is in the cupboard. If you REALLY like a red color you could probably use wine vinegar but the wood might turn out purple!
Ferric nitrate mixed with dilute acetic acid (vinegar) would probably produce a similar solution but I have never tried it.
Over the next couple of days I will try my hand at posting some pictures at theat photobucket site so you can see what I get with an iron/vinegar stain.
Best Regards,
John Cholin
Title: Re: Vinegar and Iron
Post by: Roger Fisher on October 02, 2008, 10:11:49 PM: Well now, looks as if I have to cart the wire cutters along hunting or stay with my mix of Jimmy Chamber's stains.
Title: Re: Vinegar and Iron
Post by: cal.43 on October 03, 2008, 12:37:45 AM: (http://img150.imageshack.us/img150/3466/vinegarstainzo2.jpg)
Vinegarstain on cheap maple, the stain was made from concentrated vinegar and steelwool
Title: Re: Vinegar and Iron
Post by: pflyman on October 03, 2008, 12:50:55 AM: Great information! I even got a refresher on chemistry - most of which disappeared from my "hard drive" years ago. Acer is right. The mixture does stink. After I heated it last night, my wife brought that to my attention. I have an old pistol kit that has remained unfinished for perhaps 20 years or more. Initial prep of the maple suggests that it might have some nice figure. No harm in trying with this piece. I will report back with my results. Thank you all.
Title: Re: Vinegar and Iron
Post by: Dphariss on October 03, 2008, 03:46:57 AM: Quote from: pflyman on October 02, 2008, 07:29:31 PM
I am practicing techniques for an upcoming build of Don Stith's 1792 Contract Rifle. While I have Aqua Fortis (Wahkon Bay), I was intrigued with a past thread on the use of vinegar and iron. I created a batch with 5% cider vinegar and 0000 steel wool (I added heat to perhaps speed the action). It appears that some builders use and are pleased with this approach, but I would like to hear from those that have what techniques, secrets, successes or failures they may have encountered. Is heat necessary to react it? If necessary, is the heat applied after the solution has dried or is still wet?

Just be aware that vinegar and iron does not stain wood in the way that Nitrate of Iron (AF) does since vinegar will not dissolve as much iron. Thus it may require repeated applications to get the color desired. AF will stain maple in one coat, less "water" put on the stock is better.
I assume that if there is a sludge in the bottom of the container used to make the vinegar stain that this might give better color. But its not the same process as using nitric acid to dissolve the iron. Note also that wine vinegar is 8% cider is generally 4% acid. Compared to nitric cut 50% with water it is very very weak and will not "eat" as much iron. Thus the nitric acid will produce a stain with far more iron in solution and better color. I think the time required to make the stuff and the low iron content are probably why vinegar and iron was not used for gunstocks. It was apparently used as a tint in furniture building according to my source.
If the store bought AF you have is made to the old formula it has hydrochloric acid added and this tends to muddy the grain and produce a browner stock over the long term. At least for me.

I let the stain dry completely or nearly so. Wet wood is harder to heat. Use radiant heat.

I have never tried my home brewed AF on pine but it works great on oak.

Dan
Title: Re: Vinegar and Iron
Post by: Acer Saccharum on October 03, 2008, 04:42:16 AM: pflyman, give your stain mix plenty of time to dissolve and stop reacting before you put it to use on the real thing.

Acer
Title: Re: Vinegar and Iron
Post by: Blacktail on October 03, 2008, 05:36:17 PM: Vinegar stain again, awesome! I made some up with degreased steel wool and cider vinegar. The liquid is dark, reddish brown, but when I apply it to maple, it comes out a nasty bluish-gray color. Any ideas why?
Title: Re: Vinegar and Iron
Post by: Acer Saccharum on October 03, 2008, 06:47:20 PM: I suspect one of the following:
a) your batch hasn't spent enough time brewing
b) you need more applications of the solution( I found up to four apps works best)
c) there is not enough acetic acid in the batch(add more vinegar)

For additional color variation, try a wipe with DILUTE Hydrogen peroxide. This may turn a dark stain reddish, or even rusty orange.

This gun is vinegar stain, with a peroxide wash:
(http://i12.photobucket.com/albums/a246/Tom45-70/Moravian%20smooth%20rifle/patchbox.jpg)
Title: Re: Vinegar and Iron
Post by: pflyman on October 03, 2008, 08:27:54 PM: Well...I have made two applications of the vinegar/ steel wool brew. The concoction is a dark coffee color in the jar, but I must admit, I jumped the gun rather than give it the time to "brew" as has been recommended. It went on light brown but it turned grey. It is not what I had hoped for, but the gist of this thread has been not to expect a certain color. The good news is that, when rubbed down with steel wool, the result is surprising definition of the figure in the wood which was not evident in the untreated piece. I would have preferred red-brown, but the result when finished may be attractive. I am not deterred. My next try will probably include old barbed wire (there is plenty of that in S Dakota) and more patience.

Dave
Title: Re: Vinegar and Iron
Post by: Long John on October 04, 2008, 04:21:42 AM: pfly,

The gray color is ferrous oxide. If you have ferrous oxide that means that there is more iron in your solution than there is acidity so the iron has to compete for acetates. Under those conditions the iron only gives up 2 electrons and the resulting oxide is gray. Pour your stain solution ONLY into a clean jar. Add fresh vinegar to it until you have twice the volume of liquid. Put a lid on the jar and let it sit for a few days. NO HEATING! Then try the new stain on a fresh test block. And, yes, I usually apply several coats allowing the stain to dry between as mentioned above.

If you are really impatient rub the gray wood with a little dilute hydrogen peroxide. You will get the same effect but quicker.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Karl Kunkel on October 04, 2008, 05:08:56 AM: This thread is great. How much iron do you need to add to a bottle of vinegar (how many nails)? About how long are we talking for the stain mixture to brew? Sounds intriguing.
Title: Re: Vinegar and Iron
Post by: Woodbutcher on October 04, 2008, 05:13:06 AM: The colors that I see on those rifles are incredible!
OK, so I get a quart bottle of cheap white vineger. And some steel wool. I'll wash the steel wool and rinse it well, and then rinse it in alcohol, to degrease it.
(1) How or where does one get concentrated vinegar? Would it help?
(2) How long is enough time to brew? 2 weeks or more enough?
(3) Does rust matter, or should it be brushed off?
(4) It smells bad, so does that mean that you leave the lid off? If the lid is kept on tight would there be a problem when it's opened? H-mmmmmm!?!!
(5) Would it be good to pour the vinegar into a larger container, perhaps a quart poured into a glass gallon jug.
(6) With winter coming this will need to be kept from freezing, so outside won't work. This "smells bad" thing could be a problem, even in a cool basement! A fella could get shot and have the thing buried with him! Any suggestions about dealing with the "smells bad" would be helpful.
(7) I see mention of a dilute hydrogen peroxide wash. About how much water, maybe half and half?
Testing the finished brew on scrap wood and adding fresh vineger to get the desired color seems clear enough. It will be interesting to see the effect on other types of wood. Thank you. Woodbutcher
Title: Re: Vinegar and Iron
Post by: Seven on October 04, 2008, 12:42:44 PM: woodbutcher, I don't think it smells all that bad. It smells mostly like, well, vinegar. I used to keep a quart jar of it brewing on a shelf in my work room and the only time I really noticed it was when I was doing things right next to that shelf. I use cider vinegar as that is what was recommended on the first thread of vinegar stain making from the 'old board'. I haven't used white vinegar so I have no comparison. Once I got my stain to the point of looking good on wood I put the cap on the jar and now I don't smell it at all. I started with steel wool and then I made another batch with some old rusty nails. I let my original batch sit for six months. I've let other batchs since then sit for much shorter (a month or so).

I did use the hydrogen peroxide trick before I had gotten my stain figured out. For that I just used a cotton ball. Placed it on top of the bottle and tipped the bottle over wetting the cotton ball. Then squeezed out the cotton ball over the sink until I got as much out as I could. Then used that to wipe on to the wood. The result is immediate. Second and third wiping of Hydrogen peroxide didn't do anything, so I'd have to assume that the reaction from the first wiping was enough to make it complete.

I have not used this stain on a stock yet, but I have used it on a fair number of scraps around the shop. It really brings out the curl and in my opinion looks great. The part I love about this stain is that I made it and it is very easy. Don't over think the process. Listen to Long John's post (two or three above this one). And have some patience when brewing up a batch.
-Chad
Title: Re: Vinegar and Iron
Post by: Acer Saccharum on October 04, 2008, 03:52:50 PM: Bad smell: interpret as smells like @$#%. This only is very noticeable in the first few days of brewing. DON"T screw the cap on tight, as the gas buildup could conceivably blow up the jar. Then you have a real problem. To speed brewing, I screw the cap tight, shake the bottle, then back off on the cap to allow gas to escape. Always back the cap off. This stuff keeps outgassing for months.

In my experience:
A note on the hydrogen peroxide: if your stain is too dark, and you choose to use peroxide to change the color, go very cautiously into the application. The change in color is usually immediate and dramatic. Further applications of vinegar stain have very little effect on peroxide treated wood.

Acer
Title: Re: Vinegar and Iron
Post by: Woodbutcher on October 04, 2008, 11:11:22 PM: Thank you gentlemen, all of you. I'll be getting a bottle of apple cider vinegar this afternoon and starting my own brew. Woodbutcher
Title: Re: Vinegar and Iron
Post by: BobT on October 06, 2008, 12:10:36 AM: This would be a good thread for the tutorials!
Title: Re: Vinegar and Iron
Post by: Elnathan on October 06, 2008, 04:08:42 PM: Does the metal involved in making this stain have to be real iron or can one use steel? I think I recall reading on previous threads that it had to be iron, not steel, but that aspect doesn't seem to have been brought up thus far. I have never really had any access to wrought iron in significant quantities, so I have never tried to make vinager stain - if I can use mild steel, that makes it a lot more practical endeavor.
Title: Re: Vinegar and Iron
Post by: Long John on October 06, 2008, 04:36:33 PM: Wood,

What alloy is the steel in the steel wool? Common alloying elements are chromium, nickel and manganese. Aoll of these produce green or blue oxides. Consequently, I stay away form it for stock stain. I just go out for a walk and brning back a foot or two of old barbed wire. You can use cider vinegar or white vinegar. Or, since its apple time you can take the last quarter of the jug of fresh cider you got this weekend and let it "turn".

1. Concetrated acetic acid is called "glacial acetic acid" and it is available from the chemical supply you local high school uses for cehistry supplies. I have nver used it for stock staining. Why when a 39 cent bottle of cider vinegar works well?
2. 2 weeks should be enough. I have a masonry crock on the shelf that has been tere for about 15 years. It has a Saran Wrap and rubber band lid. When I notice that the liquid level has gone down I add a little randy apple cider or cider vinegar to it, depending upon the time of year.
3. Rust is a mixture of iron oxides. It doesn't matter. Iron oxides are slightly soluble in acids. But remember when you use the stain you want a clear liquid like tea. You don't want a a muddy brown liquid. If it looks muddy you have suspended iron oxide crystals in the stain which will tend to make the stock finish look muddy. That's why I pour the stain solution of the top of a settled crock of iren and vinegar and dilute my stain with fresh vinegar.
4. It doesn't smell any worse than salad dressing! Acetic acid has a high vapor pressure at room temperature. That means that it wants to evaporate. If you leave it uncovered you will end up with a pile of rust in the bottl of a gar of water. the acetic acid will leave by its own accord if you let it. Keep your jar of stain covered.
5. My stain crock is a 1/2 gallon masonry pot I bought at Colonial Williamsburg a bunch or years ago. Before that it was a larg mayonaise jar with a rusted-out top.
6. I don't think freezing will ruin the stain but it will stop the reaction that produces the iron acetates that do the staining. It will also proable crack the crock or jar it is stored in. Come spring you might have a mess.
7. I don't know how dilute to make the hydrogen peroxide especially since hydrogen peroxide spontaneously decomposes at room temperature. If you have a fresh bottle I suspect 25% or 50 % would be a reasonable start. If the bottle is old it is probably already at 25%.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Darrin McDonal on October 06, 2008, 05:35:27 PM: I just applied some vinegar stain / reagent that I mixed up and has been sitting for a good 6 mos. In interesting, very interesting. It turned out a beautiful vibrant silvery/gray on a scrap piece of curly maple. Not the color I would put on a gun stock but still a really cool color.
Anyone else get this color?
Darrin
Title: Re: Vinegar and Iron
Post by: bob in the woods on October 06, 2008, 08:13:28 PM: If gray, add more vineger.
Title: Re: Vinegar and Iron
Post by: FG1 on October 07, 2008, 01:04:58 AM: Thats what I got Darrin . Kind of like laminate camoflaged stocks that Richards Microfit sells ;D
Title: Re: Vinegar and Iron
Post by: Woodbutcher on October 07, 2008, 02:41:47 AM: Long John:
You've put a lot into these posts. All of you have. Thank you!
OK, I know of a couple of old barns and a couple of old buildings. I'll get some old nails and remove some rust. By weight you're only talking about a couple of ounces. The trick is to use iron, not steel.
Barbed wire is available, but it's probably only 20 years old or so, and I have no way of knowing the alloy.
Plastic for a lid and no bad smell, I'm in business.
This is going to be fun! Woodbutcher
Title: Re: Vinegar and Iron
Post by: pflyman on October 07, 2008, 04:22:55 AM: Ok...I finished the pistol stock with 3 applications of Tom's 1/3 Mix- a paste of equal proportions of beeswax, boiled linseed oil, and turpentine. I found it easy to apply and dries quickly to a soft, velvety finish. No tacky feel as I anticipated. We will see how it holds up, but it certainly goes on easily and provides an attractive finish. When initially applied, the stain went on light brown but turned a decided grey. After the beeswax, you be the judge: grey, green, brown, or a bit of all three? The light makes a decided difference. I am currently mixing a new batch of stain. Apple cider vinegar with rusty barb wire, no heat and more time. It appears to be brewing well. I hope the photo comes through.(http://i489.photobucket.com/albums/rr259/pflyman/IMG_0945.jpg)
Title: Re: Vinegar and Iron
Post by: Long John on October 08, 2008, 04:07:12 PM: Even though the stock wood is beech, the color you have sugggests that you had a very iron-rich solution. When you saw the stock turn gray that was your indication that you were getting ferrous oxide forming as the acetate left the stock. You could have applied straight vinegar to redden the color or used hydrogen peroxide. Either would have caused a shift towards ferric oxide and given you a redder color.

When you use a vinegar/iron stain you are in control of the color. Yuo can get anything from black to red by manipulating the chemistry a little. With a nitric acid/iron stain you have much less control; you get just reddish brown.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Seven on October 08, 2008, 07:33:09 PM: I'd also like to point something out that has been hinted around a little bit. I had a batch of the vinegar stain brewing from a while ago. It looked pretty gross when put on wood, dark and blotchy and not at all like I'd seen others accomplish. At first I thought it was in the state that Long John describes as iron saturated, so I put in more steel wool. Same results, yuck!! Then on a whim I threw in an old rusty nail. About two weeks later the stain is a whole different brew. I'm attributing my first result of this batch on using steel wool. And once I finally got some real iron in there it turned the stain right around into something usable. You guys can experiment some more if you want, but I'm sold on iron and not steel wool for future projects. -Chad
Title: Re: Vinegar and Iron
Post by: pflyman on October 09, 2008, 12:07:50 AM: I have to agree with you, Chad. My first batch which I used to stain the pistol, contained steel wool- the first batch heated and then eventually I added washed (degreased) steel wool. The degreased steel wool still looks shiny and does not appear to have oxidized. Perhaps the acid in the vinegar has attenuated. The batch I have brewing now used rusty barbed wire and it continues to react. Although I haven't tried it yet, this will be my formula for future trials and the steel wool is out.

Dave
Title: Re: Vinegar and Iron
Post by: rich pierce on October 09, 2008, 04:54:03 PM: I'm not 100% sure the type of steel or iron is the main variable. I know John uses old rusty barbed wire successfully. As far as I know (I built and repaired a lot of barbed wire fence in my youth) all barbed wire since WWII has been galvanized- coated with zinc. It may be rusted up now but unless you find old forms of barbed wire- like the type that is twisted spiky ribbon, not wire with barbs attached- it likely has lots of zinc still in there somewhere. Any barbed wire from before WWII is probably underground or dissolved unless it's found in a barn.

It is just as likely that something else (not zinc) in steel wool can cause a problem. Old mild square nails (not modern hardened masonry nails) would be my best bet for unalloyed iron. But of course ore from different areas has different composition, etc. So maybe it's not the source of iron used that is the primary variable.
Title: Re: Vinegar and Iron
Post by: Dphariss on October 10, 2008, 07:09:24 PM: Quote from: Long John on October 08, 2008, 04:07:12 PM
Even though the stock wood is beech, the color you have sugggests that you had a very iron-rich solution. When you saw the stock turn gray that was your indication that you were getting ferrous oxide forming as the acetate left the stock. You could have applied straight vinegar to redden the color or used hydrogen peroxide. Either would have caused a shift towards ferric oxide and given you a redder color.

When you use a vinegar/iron stain you are in control of the color. Yuo can get anything from black to red by manipulating the chemistry a little. With a nitric acid/iron stain you have much less control; you get just reddish brown.

Best Regards,

John Cholin

It is impossible to get "iron rich" vinegar stain with over the counter vinegar. At least as compared to AF/Nitrate of Iron. Its too weak to dissolve much iron. As a result it does not stain the wood in the same matter as AF will.
This is probably why nitrate of iron was used historically.
Vinegar/iron was used as a *tint* for cabinets and furniture. Its was not used as a stain historically or so I am told by good authority.
I would also point to the fact that hydrogen peroxide was pretty rare in the 18th century since it *did not exist* being a man made chemical first produced in 1818.

I am also told that the color of the iron oxide is determined by the water molecules attached to it. Black or grey has more water, redder has less to none.

I would also point out that the red is actually correct for Nitrate of Iron stained maple though some *may* be more honey colored.
I have no desire for a grey/brown or green/brown or other weird colored gunstock.

Unless you dye the wood it is very difficult to get "the color you want" in maple. I use AF/nitrate of iron stain and I know its right for a maple stocked longrifle. Some maple stocks were not stained at all and simply varnished with a dark, reddish oil based varnish perhaps made with leaded boiled oil and sandarac. This varnish looks like this. Sorta reddish even though put on circa 1850-60. This is a traditional finish, used on maple with no stain at all so far as I can tell.

(http://i72.photobucket.com/albums/i199/DPhariss/ML%20Guns/DSC03013.jpg)

This is a "Connestoga Rifle Works" (Leman) 54 caliber FS in unused condition. It is coated with a red varnish. It is dated on the lock 1840.
(http://i72.photobucket.com/albums/i199/DPhariss/ML%20Guns/capbox.jpg)

Nitrate of iron may look like this:
(http://i72.photobucket.com/albums/i199/DPhariss/ML%20Guns/Swivel2.jpg)

Or this:
(http://i72.photobucket.com/albums/i199/DPhariss/ML%20Guns/Pistol2_1.jpg)

Or this:
(http://i72.photobucket.com/albums/i199/DPhariss/ML%20Guns/DSC03572-1.jpg)

Depending on the wood and the batch of stain the range of colors above is typical.

The new rifles only have 2 coats of finish in these photos.
You will note in the photos of the 2 original rifles that the common undertone is red.

The red falls into the realm of AF stains or red/reddish varnishes made with an oil with reddish tones as a result of its formulation o the varnish was intentionally colored a translucent red as in the case of the Leman. Thus while there are rifles with stocks of other colors we can assume that the red/gold or red/brown stain produced with AF and/or shop made or purchased oil based vanishes are correct from the historical perspective for a wide range of rifles.

There ARE exceptions, but note the color of the wood UNDER the varnish on the late Hawken rifle. Its honey colored where the varnish has worn away (note its not chipped or flaked). So when you see a light honey colored rifle with traces of a reddish brown varnish in protected areas you can assume the rifle was probably varnished with a shop made varnish originally and that it was reddish brown when new.
Now if you dislike AF color or that produced by the vanishes such as those above by all means stain as you like.

But do not scoff at red/gold or reddish/brown. It is irrefutably historically correct for American rifles for at least 130+ year span from circa the F&I war to the end of serious ML production in the 1880s-90s.

Dan
Title: Re: Vinegar and Iron
Post by: Trkdriver99 on October 11, 2008, 12:00:11 AM: I really like the looks of the pistol. I like the way the curl shows up and just the looks in general. I have a box of old square nails ( I believe some are hand forged ) that I got in a junk store in Maine. I think they will work well in my wife's vinegar.. ;D :o

Ronnie
Title: Re: Vinegar and Iron
Post by: Ohioan on October 17, 2008, 09:04:01 PM: Alright, so this thread got me interested, and a bough some apple cider vinegar.

Into a clean half gallon milk jug I poured 4 cups of vinegar and about 3 oz of 0000 steel wool.

Is that enough vinegar:steel or should I pour in more vinegar?

I'm mostly worried about keeping the reaction going.

thanks
Title: Re: Vinegar and Iron
Post by: Paddlefoot on October 18, 2008, 07:58:59 AM: This brew makes a great black leather dye too.
Title: Re: Vinegar and Iron
Post by: Long John on October 21, 2008, 04:11:25 AM: Zach,

Vinegar/iron stain is easier than you are making it. No measuring is required. I do NOT recommend using steel wool as you have no idea of how much alloying is present in the steel wool. The only reason to use steel wool is that the fine texture of the steel wool allows for a faster reaction.

I would get a 1 quart mayonaise jar with a plastic lid and fill it with vinegar. Toss in a small hand full of nails, the older the better for the same reason that steel wool is not ideal, or old rusty barbed wire. (Rich I appreciate your observations but the barbed wire I have access to shows no evidence of zinc plating.) Or you can saw pieces of an old horseshoe. Just get the purest iron you can, toss in a hand full, put the lid on the jar and put it up on the shelf for a couple of weeks. That's all there is to it!

When you try your stain out it might turn the wood gray. If it does that means you got ferrous acetate rather than ferric acetate in the solution. Pour some of your stain solution into a clean plastic cup and add fresh vinegar. Stir gently for a few minutes. Now when you use the stain you should end up with a brownish orange color. That's how I got the color below.

(http://i50.photobucket.com/albums/f349/jmcholin/DSC_0003.jpg)

You might notice that it looks a lot like the color obtained by Dan with nitric acid/iron stain. That's because the reddish brown color comes from ferric oxide and ferrosoferric oxide. In the case of the vinegar iron stain the acetic acid in the vinegar ionizes the iron, dissolving it. When the stain is applied the acetic acid evaporates, leaving the iron ions behind which snag onto oxygen atoms from the air and form iron oxides. When nitric acid is used the acid ionizes the iron, dissolving it. When the stain is applied the nitric acid will very slowly evaporate away over the course of many weeks or you can speed it up by heating the stock. This drives the nitric acid off as a vapor, leaving the iron ions behind. The iron ions snag oxygen from the air forming iron oxides. The iron oxides don't know how the iron ions were formed. They don't care.

There are advantages to each staining system. I like the vinegar iron system. Others prefer the nitric acid system. When you add hydrochloric acid to the mix you complicate the chemistry because the hydrochloric acid has a much lower vapor pressure and must be heated longer and hotter to drive it off the stock.

Some others have made certain statements about the chemistry that I believe are incorrect, but this is a free country and they have the right to believe what they wish. Furthermore, I have no need to change their minds.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Paddlefoot on October 21, 2008, 04:24:42 AM: Hey John, I hit upon a source for cast iron. Brake drums or rotors. they get changed frequently enough you could probably get one for free at a local repair shop. Old Harley cylinders are also iron and the fins break off pretty easy if you want to put a small batch together. Not sure if these sources are pure iron, maybe someone else knows but brake rotors flash rust right now when you wash your car so I gotta figure they are relativly pure.
I haven't played around with the batch I made from letting the vinegar stand in the old rusty dutch oven so it will be interesting to see how that works. It's been sitting a good 18 months.
Title: Re: Vinegar and Iron
Post by: Acer Saccharum on October 21, 2008, 04:29:59 AM: John, you are hard to beat when it comes to vinegar and iron!

This is why you were elected as grand poobah of the Betheren of the Vinegar Stain. You rock.

The iron oxides don't know how the iron ions were formed. They don't care.

Something I did not know about Aqua Fortis: the color will change over time, heating just causes the change to come sooner. Do I have that right?

Thanks

by the way, Grrrreat color on a sweet rifle!
Title: Re: Vinegar and Iron
Post by: old guy on October 21, 2008, 05:07:59 AM: Shortly after this thread started I replaced a porch floor and I started a batch
using the old cut nails. Well she looks good and stout now (about like the coffee
they used to brew on the mountain farm).
My question is do I leave the nails in or remove them after a period of time
and can the be used a second time. Just courious.

Leo( old guy)
By the way, i;ll be 70 this winter and I was youngest one on crew for the church
porch floors.
Title: Re: Vinegar and Iron
Post by: Long John on October 21, 2008, 04:19:31 PM: Friends,

To answer a few of the questions, I have the following:

Paddlefoot, When I reconstrcuted the explosion at Jahn Foundry several years ago I learned that they were making bread drums and rotors for Chevrolet and Saturn vehicles at the time of the explosion. These components were "gray iron" with a veryhigh purity. I suspect that analogous parts of other cars are also gray iron. If I had a Harley I would ride it! If the cooling fins break off easily it is probably quite pure iron.

Acer, In theory the nitric acid will slowly evaporate by itself given enough time. As it does the iron ions will combine with atmospheric oxygen and produce the oxides we seek. However, strong acids will also attack the cellulose in the wood, producing a chemical char. That's right, a char, just like you get when you expose wood to temperatures above 425 F. This is why some stocks stained with strong acids like nitric or hydrochloric continue to get darker and darker until they are essentuially black. Residual acid in the wood chars the wood over time. The key to avoiding this is to use a diluted solution. Most of the recipes for nitric acid/iron stain call for some pretty healthy dilution for good reason. When you dilute the solution you are also diluting the concentration of iron ions. One advantage of vinegar is that it is not strong enough to cause a chemical char of the wood. A dissadvantage of vinegar is that it is marginally strong enough to produce a preponerance of ferric ions over the ferrous ions. When you dilute the nitric acid enough to avoid charring you essentially have an acid of similar strength to the acetic acid in vinegar. So there is some convergence here, the two methods end up yielding very similar results most of the time.

Leo, I have an old earthen-ware crock that i tossed some nails and old rusty barbed wire in about 20 years ago. I never took anything but clear stain out of the crock by gently pouring it off the top of the mix. If I stir the mix the thing is a muddy brown. If I leave it sit the liquid looks like tea. I don't know if your should remove the nails or not. I didn't. But, when I started using my stain for the rifle I pictured above it was too blackish-brown for what I wanted so I added fresh vinegar to some decanted stain mixed it and that reddened the color nicely. I suppose you could achieve the same result by removing the source of iron once the stain was giving the color you wanted but you will have to put a vapor-tight lid on the jar to keep the acetic acid from evaporating out of the solution. If it does youwill get rust (iron oxide) precipitating out of solution as a layer on the bottom of your jar.

There is also the assertion that vinegar/iron stain is not historically documented. I am NOT a historian. I do not while away the hours reading historical documents. So I don't know if there is any documentation to support the use of vinegar/iron stain. But I do know that every old homestead had apple trees as pickeling was a well-used method of preserving foods. Pickeling is essentially boiling in vinegar. So the early 18th century gunmakers had access to vinegar. It was ubiquitous in the settlements. I read somewhere that vinegar and iron stain was used to stain leather (it stains leather a deep black) since the middle ages. It is not too large a stretch to conclude that some one might have tried to stain maple with the stain they used for harnesses. Indeed, I remember a post on this board that refered to an add in the Philadelphia Gazette for a lost rifle that was "stained dark with aqua fortis". This language suggests that staining dark with aqua fortis was out-of-the-ordinary for the time. Otherwise, why include it as a distinguishing attribute for the rifle? The language in the add seems to imply that some other stain was more commonly used and resulted in a color that was not so dark.

Can I prove that vinegar and iron were used by colonial gunmakers? No. It was cheap and readily available in colonial America. It would do the job. Furthermore, I have a little difficulty believing that some one could successfully transport a glass ampule of nitric acid down the wagon road from Philadelphia to Lancaster, Reading or North Hampton in the back of a freight wagon in the decades preceding the American Revolution. But I use it because I like the results I get with it.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Mad Monk on October 21, 2008, 08:26:13 PM: John,

I suspect that both the vinegar and iron stain and the nitrate of iron stain were period correct.

"Furthermore, I have a little difficulty believing that some one could successfully transport a glass ampule of nitric acid down the wagon raod from Philadelphia to Lancaster, Reading or North Hampton in the back of a frieght wagon in the decades preceding the American Revolution."

James Whisker's writings show the sale of nitric acid to a gunsmith in the 1820's in Bedford County, PA.

Nitric acid was used extensively in fabric dyes. Look at Rev War officer's uniforms. The "buff" facing was dyed with nitrate of iron. This could be used on wool, lionen or cotton fabrics. When dyed with nitrate of iron and then dipped into a strong solution of tannic acid you got a dark brown. When dipped in a solution of gallic acid you got a jet-black color.
Production of mineral acids in Philadelphia was one of the early industries. The two document acid works could not begin to keep up with the demand so large amounts of the mineral acids had to be imported from England.

The question of availability away from Philadelphia probably centers on the completion of the Schuylkill River Canal and the Union Canal out of Reading.

I do know that prior to the building of the Schuylkill River Canal the iron products produced in Berks County went down to Philadelphia by horse drawn wagons. Hauling back supplies needed in the area.

The question begs. Why wouldn't vinegar have been used. Sour wine vinegar was used to manufacture cupric acetate and lead acetate way back in time. In 50 A.D. Pliny, the Elder, wrote on how to test the purity of cupric acetate to see if it had been adulterated with cheaper iron salts, ie., ferrous sulfate. Using a strip of reed soaked in gallic acid. He would take some of the sample to be tested. Dissolve it in water and then dip the gallic acid treated reed into the solution. If the reed turned black he knew it had iron salts added.

Lead or copper plates would be suspended in a crock. Sour wine vinegar would be poured into the crock. Not enough to touch the plates. The fumes from the vinegar being far more reactive (corrosive) than if you immersed the metal into the vinegar. Far faster to use the fumes that to submerge into the liquid.
This goes back to the ancient Greeks as Pliny, the Elder, simply rewrote a lot of older Greek information.

Cider vinegar runs about 4% acetic acid while sour wine vinegar runs around 8% acetic acid.

The acetate "acid metal salts" were also widely used in fabric dye work.

In terms of length of history and amounts used the vinegar metal salts were better known and more widely used.

You see in old writings the mention of "green hides" going into a tannery. When I worked on the copper acetate horn dye I had been dealing with the Museum Of The Fur Trade. When I told them what I had found and what I was doing they told me that I had solved a mystery that had puzzled them. They found very large amounts of cupric acetate had gone west in the trade system. Being very toxic it could not have been used to worm livestock. It was actually used to treat hides being shipped back east to the tanneries.
Cupric acetate was also used to treat cattle horns prior to shipment over long distances.
In both cases the cupric acetate acted as an bacterial killing agent and protected the goods from insect attack.

To sum all of this up. Here we have something in wide use all over the world at the time in question. Why would it not be used to color wood. Very large amounts then being used to color various fabrics.

The thing about the use of nitric acid is that you can get a lot more iron into the liquid compared to vinegar.

As long as you are using iron oxide as the colorant you will get darkening of the stock in varying degrees. Depends on how much iron oxide you get in and on the wood and how much tannic acid is in the wood. The tannic acid reacts with the iron oxide to give an iron tannate complex that is jet-black in color in the curl and a general overall darkening. I would point out that prior to the introduction of steel pen points during the Civil War the standard writing ink was a mixture of ferrous sulfate and tannic acid that you mixed with water.

Bill K.
Title: Re: Vinegar and Iron
Post by: Ohioan on October 21, 2008, 09:16:42 PM: John,

The reason I measured is because I would like to be able to easily reproduce the same outcome if I like the stain. It's my attempt to be scientific.

The gun you posted has a beautiful color to it.

I stained my first and only gun with Aqua Fortis that I made. It worked well, and I'm pleased with the color. The only issue I have is that Nitric Acid is hard to find and is relatively expensive.

I think I might mix up another batch of vinegar/iron stain. This time use a scrap brake rotor. There would only be a weeks worth of time difference between my first batch and this batch. Then compare.
Title: Re: Vinegar and Iron
Post by: Acer Saccharum on October 21, 2008, 09:31:47 PM: Zach, you have mentioned the very fly in the ointment...... quest for repeatable results.

Ah, Grasshopper! You wish consistency in a sea of change!

The only thing consistent I have gotten out of vinegar stain is that I usually like the color I get.

The most frustrating thing I have found is to have a certain color in mind, and then try to reproduce it in the flesh.

The color you get is a reaction between the stain and the wood. The color you get will be a collaboration between the chemicals/minerals in the wood, and the acid/iron ratio in the stain itself.
Title: Re: Vinegar and Iron
Post by: Paddlefoot on October 22, 2008, 07:47:29 AM: Just another Idea for iron sources. Quite a bit of old machinery was made of cast grey iron. For a few years I was a printer working on some fairly outdated equipment. A lot of pieces had to be handled with some caution because they were iron and would break if you dropped them or hit them just right. I'm sure there must be old abandoned pieces of equipment laying around at swap meets and junk yards that could give up a hunk of iron for a batch of stain.
Title: Re: Vinegar and Iron
Post by: Ionian on October 22, 2008, 04:05:02 PM: I am using stove pipe wire and it's working real well. I have noticed that when I put the wire in the vinegar it was heavily rusted and in a couple of days it removed all the rust off and the wire now looks clean. I assume the acid will keep working on the rest of it. My question is that when you use the stain, do you have to strain it first? I have a lot of rust in the bottom of the jar and I could see through the vinegar unless I stir it.
Title: Re: Vinegar and Iron
Post by: T*O*F on October 22, 2008, 05:44:14 PM: Go to your local brake shop. Ask them for a jarful of the turnings from their drum and rotor turning lathe. These turnings are iron. They are in a form that will give maximum reaction time whereas with nails or wire you have to wait. Saves waiting weeks.

They will contain a fair amount of dirt. Sock them first in a cotton sock or a a piece of flannel. Then pick up the remainder with a magnet to further remove any clunkers.
Title: Re: Vinegar and Iron
Post by: Clark Badgett on October 22, 2008, 08:58:37 PM: Quote
Ask them for a jarful of the turnings from their drum and rotor turning lathe

If they are under 10" I can do this at home. Wonder how much scrap rotors go for at the junkyard.
Title: Re: Vinegar and Iron
Post by: T*O*F on October 22, 2008, 10:09:46 PM: Quote
If they are under 10" I can do this at home. Wonder how much scrap rotors go for at the junkyard.
Why go thru the trouble of traveling to and from a junkyard, buying a scrap rotor, turning it yourself and ending up with something that is free for the asking at any shop?
Title: Re: Vinegar and Iron
Post by: billd on October 23, 2008, 12:32:58 AM: I don't know if it makes a difference, but most brake parts are made from ductile iron or pearlitic iron which is different from common grey iron. I used to know the difference, something about free ferrite in the metal. We machine lots of both and the chips are worth almost nothing. I don't think the cost of the scrap even pays for getting it hauled away. If anyone walked into my shop and ask for a couple pounds of scrap turnings, I'd give them for free. If anyone is using turnings from a machine shop, wash them first. They will have coolant on them from the machining process. Ours is water soluable.

Bill
Title: Re: Vinegar and Iron
Post by: Long John on October 23, 2008, 06:24:47 AM: Nick,

You should use ONLY the clear solution. That is a solution of ferrous and ferric acetate. The precipitate at teh bottom of the jar might be iron acetate or iron oxide. IWhat ever is not in solution it will make your stock finish look muddy and the wood will not have the clarity and depth you want in the finished appearance.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Ionian on October 23, 2008, 06:49:00 AM: Thank you John.
Title: Re: Vinegar and Iron
Post by: FL-Flintlock on October 23, 2008, 02:42:20 PM: Quote from: billd on October 23, 2008, 12:32:58 AM
I don't know if it makes a difference, but most brake parts are made from ductile iron or pearlitic iron which is different from common grey iron. I used to know the difference, something about free ferrite in the metal. We machine lots of both and the chips are worth almost nothing. I don't think the cost of the scrap even pays for getting it hauled away. If anyone walked into my shop and ask for a couple pounds of scrap turnings, I'd give them for free. If anyone is using turnings from a machine shop, wash them first. They will have coolant on them from the machining process. Ours is water soluable.

Bill

I've been following this thread closely and from the start I was wondering if the alloy makes a difference or not. The barbed wire and hard-cut nails often referenced have a lower Fe content than say common round nails - the harder the steel, the less actual Fe that's in it. Ductile or grey cast iron has higher Fe content than any of the steel items.

Also in relation to, Bill's question above, most brake parts are now made in China and seeing the results of their performance in brake systems - there is no alloy consistency to them at all. Root of the question is, what affect, if any, do the particular alloying elements have on the resultant mixture and or color?

Thanks,
Mark
Title: Re: Vinegar and Iron
Post by: bob in the woods on October 23, 2008, 02:55:31 PM: I use this for my rifles all the time, and have had the best performance with old fence wire from my property [ ie "really old" ] or filings from pure iron I use for making triggers etc. I was able to purchase some from Cabin Creek. I'm hoping to try and forge a barrel from it this winter.
Title: Re: Vinegar and Iron
Post by: Ohioan on October 26, 2008, 04:21:09 AM: Well, I just tried some of my vinegar stain. It turned the wood grey. So I need more vinegar. Now, if I make another batch, I know to start out with less iron! And since I measured my ingredients, I have an idea of what not to do next time. :)
Title: Re: Vinegar and Iron
Post by: Long John on October 26, 2008, 06:03:41 AM: Zach,

You can also just put some vinegar on the wood and it should turn the gray to reddish brown. Or you can just add some more vinegar to the stain you got and it should redden-up.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Trkdriver99 on October 26, 2008, 03:37:56 PM: I made a batch using some old square nails that I had and 5% white vinegar. It sat about a week or so. Turned the wood gray, wiped with peroxide came out really pretty, not quite to my taste dark enough but I think a couple of more coats and it will. I really like this thread. I saw some other kinds of vinegar that was higher % of acid (balsamic), would that help work better or quicker? I might try that.

Ronnie
Title: Re: Vinegar and Iron
Post by: Z. Buck on October 26, 2008, 05:40:13 PM: Ronnie, balsamic vinegar is just white wine vinegar that has been aged in casks and has picked up sugars and chems from the wood, some cheaper ones (not technically balsamic) are white wine vinegar that has caramel added to it, neither would be appropriate for making stain
Title: Re: Vinegar and Iron
Post by: Ohioan on October 26, 2008, 05:40:36 PM: John,
Thanks for the advice. I wiped some straight 5% apple vinegar on a section of grey, and it is still grey. Then I diluted my solution 4:1. It's still grey. I must have waaaaaaay to much iron.
Title: Re: Vinegar and Iron
Post by: Karl Kunkel on October 27, 2008, 04:11:37 AM: Okay, I'm taking the plunge. I started a batch this afternoon. Quart of 5 % Apple Cider Vinegar, and about 12 inches of old fence wire, cut into one inch pieces.

Too much iron, or not enough? About how long does this need to brew until it becomes a viable stain? I'm just going to play with some scrap maple. I don't have a project right now.
Title: Re: Vinegar and Iron
Post by: Paddlefoot on October 27, 2008, 04:15:56 AM: Take your time and play with it in a month or two. It won't look like anything is going on but it is. You'll know if too much or too little when you first start applying it. I would advise to add all the wire it will eat then adjust with more vinegar after you see what it does on scrap.
Title: Re: Vinegar and Iron
Post by: Long John on October 28, 2008, 04:37:51 PM: Zach,

The gray color of your wood is due to ferrous oxide. Sometimes you can get the ferrous oxide to convert to ferric oxide, it was worth a try.

I am not sure you have a case of too much iron as not enough time. The acid oxidation of iron is a step wise process. The acid combines with an iron molecule converting it to a ferrous (+2) ion. Then more acid attacks the ferrous ion and converts it to a ferric (+3) ion. What I would do in your situation is to take a cup of your current stain solution that is turning the wood gray and add to it 2 cups of cider vinegar. Put the mix in a jar, screw on the lid, label the jar and put it on a shelf somewhere. Try it again in a couple of weeks. You should now get a reddish brown color.

My crock of stain has been sitting on the shelf for almost 20 years. Each time I complete a rifle and it is ready to stain I take the lid off the crock and pour in some fresh vinegar, mix it up, let it sit for a few days and then pour the clear stain solution I am going to use off the top of the liquid into a plastic cup. Vinegar/iron stain is NOT a Polaroid product. It takes time! The nitric acid/iron stain is quick. Each stain technique has its advantages and disadvantages. I suspect (don't know for sure) that the old timers knew that they were going to stain a rifle long before they started making the parts. I suspect (don't know) that they had a crock of stock stain sitting up on a shelf somewhere.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Ohioan on October 28, 2008, 07:36:38 PM: You know, i noticed a difference in the color of the stain this morning.

There was a sludge on the bottom of the jar, and the rest was more of a dark vinegar color.
Title: Re: Vinegar and Iron
Post by: Trkdriver99 on November 01, 2008, 01:48:03 AM: Mine turned grey and I used a wipe with peroxide to clear it up. I have a question about the container. If I used a brass/copper(not tinned) container would it have any change on the mix and color?

Ronnie
Title: Re: Vinegar and Iron
Post by: Randy Hedden on November 01, 2008, 03:09:47 AM: Quote from: Trkdriver99 on November 01, 2008, 01:48:03 AM
Mine turned grey and I used a wipe with peroxide to clear it up. I have a question about the container. If I used a brass/copper(not tinned) container would it have any change on the mix and color?

Ronnie

If you put copper into nitric acid you get a green color dye. I would imagine that if you put copper into vinegar you would also get a green color dye. Therefore, if you put vinegar in to a copper container I would imagine that you will produce a green dye.

Randy Hedden

www.harddogrifles.com
Title: Re: Vinegar and Iron
Post by: Mad Monk on November 01, 2008, 03:46:36 AM: Randy,

No question there. Expose copper to vinegar and you get cupric acetate. Long used to dye horns, wool, leather and other protein-based goods.
Title: Re: Vinegar and Iron
Post by: Trkdriver99 on November 01, 2008, 04:24:52 AM: Thanks for the info.

Ronnie
Title: Re: Vinegar and Iron
Post by: Ohioan on November 11, 2008, 01:07:10 AM: I made some with steel wool and the results are grey. I've diluted it a lot, and still gray. I even tried wiping with peroxide.

I bought some more cider vinegar and found some old barbed wire fence. I a piece aobut 3 inches long in the 32 oz bottle of vinegar. It's sat for two weeks. It turned the wood a light brown. There is a lot of sludge at the bottom of the bottle.
Title: Re: Vinegar and Iron
Post by: LynnC on November 11, 2008, 04:53:17 AM: I started a new batch when this thread got going. Glass coffee jar about 1/2 full of plain white vinegar and one large square nail. Now it's coffee color liquid. Just stained an old beech kit stock and it came out a good dark walnut color. Put on three coats. Went on near clear and darkened as it dried. Did have a slight even gray cast to it but looked great when oil finished.

Great results! If I had been shooting for a redder brown color I should have used the stain about a week ago...........................Lynn
Title: Re: Vinegar and Iron
Post by: Karl Kunkel on November 11, 2008, 06:11:47 AM: I started a batch of apple vinegar with some fence wire Oct 26th. It's now taking a gray/green hue, with some sediment in the bottom. Still eating the wire.
Title: Re: Vinegar and Iron
Post by: Paddlefoot on November 23, 2008, 08:41:16 AM: It does appear that getting enough Iron in the stain is not the problem. I started several batches about 2 years ago when the saved posts went up on the old ALR forum. Been busy with stuff and got my building projects set aside. Tested those batches and found it still made a dark blue-grey stain. A couple weeks ago I put some of the old stain into a clean jar and added fresh white vineger to it 2parts vinegar to 1 part stain. Even though I was careful pouring the iron rich solution I ended up with some sediment in the bottom of that jar. Not sure if I just wasn't careful enough or maybe it was a reaction to the fresh vinegar...still staining Blue-grey after two weeks. Took some of the 2nd solution and a new jar and added vinegar roughly 1 to 1. It's only been sitting a couple days but when I wipe it on it goes on a nice nut brown but darkens to the blue-grey when dry....I do feel like I'm getting closer though. I will probably hit it with a shot of peroxide just to see what happens.
Title: Re: Vinegar and Iron
Post by: Ohioan on November 23, 2008, 04:19:41 PM: I wonder... What brand opf vinegar u all are using.

I'm using Kroger.
Title: Re: Vinegar and Iron
Post by: Paddlefoot on November 23, 2008, 08:00:47 PM: Some is Heinz and some is Albertson's or Von's store brand.
Title: Re: Vinegar and Iron
Post by: LynnC on November 23, 2008, 09:38:41 PM: I'm using cheap "Piggly Wiggly" brand white vinegar ;D - Works great!.........Lynn
Title: Re: Vinegar and Iron
Post by: Mike Krall on February 05, 2009, 04:42:04 AM: I've got a couple of questions...

Would pure, 99.7% acetic acid (16oz.) and iron filings (what amount???) be a good base for this stain or won't the same chemical reaction happen? Seems like a person could make a large amount of base stain this way.

The variation in color based on wood chemistry... If the stain used is "ferric", being red toned, what kinds of changes would a person see if the wood had a flood coat of concentrated tea applied (and dried) before hand?

Mike
Title: Re: Vinegar and Iron
Post by: Long John on February 05, 2009, 04:56:40 AM: Mike,

I doubt that 99% "pure" acetic acid is obtainable. "Glacial acetic acid" is the most concentrated form generally available and it runs around 40%.

In order for any acid to work it must have sufficient water to permit the formation of hydronium ions H₃O+. It is actually the hydronium ions that do the work. Consequently, don't think that by using a more concentrated form of acid that you will get a more vivid color. It doesn't work that way. If the acid is too concentrated it will just char and weaken the wood when it is applied.

In a 1/2 gallon jug of commercial, off-the-shelf white cider vinegar I would use a length of unplated, rusted barbed wire about 1 foot long. That should give you enough iron to get nice color. I suppose you could use wine vinegar if you wanted. I have never tried that. I usually use the stain to whisker my stock so I generally apply 3 coats, de-whiskering well between coats.

Best Regards,

John Cholin
Title: Re: Vinegar and Iron
Post by: Mike Krall on February 07, 2009, 07:58:04 AM: John,

OK, I get it... and I appreciate the effort. Teaching well is an art. Starts with knowing a thing correctly and sometimes is like driving nails in oak... requires concentration on the task and follow though. Thank you.

If a concentrated black tea solution were applied to maple and dried prior to applying vinegar/iron stain, what would you expect to see?

Mike

PS http://secure.sciencecompany.com/Acetic-Acid-Glacial-16oz-P16220C0.aspx (http://secure.sciencecompany.com/Acetic-Acid-Glacial-16oz-P16220C0.aspx)
Title: Re: Vinegar and Iron
Post by: Mike Krall on August 07, 2009, 05:03:38 AM: Well, I made up a batch of V/I with white vinegar and rusted barb wire. Put in more than one length of the wire and let it set 4 months. Filtered it through a paint filter and didn't get any residue to speak of. Let that set for a few days and took some off the top. It had a fair amount of black specks in it and looked muddy when applied to maple. Filtered the batch again, this time through a coffee filter. It is a lot clearer and is not as muddy looking.

I tested the stain this way:

1-4 applications on maple and maple washed with strong tea solution (6 bags per cup). The tea was left to dry before applying V/I stain. There were four concentrations of V/I... full strength, 3parts V/i & 1 part cider vinegar, 2 parts V/I & 2 parts cider vinegar, 1 part V/I & 3 parts cider vinegar. All applications were dried before additional applications.

I expected to see significant darkening with each application (1-4) but did not. I expected to see distinct differences between stain on bare wood and on tea stained wood but I didn't. I expected to see color change with various dilutions from full strength to 1 V/I & 3 vinegar and very barely did.

What is wrong with my expectations?

Mike

PS ~ I've got a batch of 1 V/I & 6 vinegar aging now but it will be days before I'll know if more dilution will get me red/brown or red/orange.