Blackened and antiqued hardware!

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Blackened and antiqued hardware! How does this work?

Leif S
Posted 19 January 2004 - 10:31 AM

In the mineral world ferric minerals are normally rust colored,some darker than others (up to dark chocolate),
and ferrous minerals normally gray-green to gray-greenish black. Both can sometimes appear totally black.
Rust is ferric hydroxide, Fe(OH)3, a result of oxidicing massive iron. Ferrous iron is a result of reduction.
The reason this mix of yours reacts so fast is that the H-peroxide reacts with the vinegar to create a weak base
that oxidices the iron. This reaction also produces water, which speeds up the rusting process.
Now comes the tricky bit, why does it turns black? It could be as simple as that boiling reduces ferric iron into
ferrous iron. It could also be that the boiling turns the hydroxides into oxides with a little denser stucture which
make them appear black. It could even be both.
Tell me, if you don't coat with ren wax does your pieces rust?
"Damnation! I need a flagon of wine!"
-King Conan of Aquilonia
http://forge.leifern.com (http://forge.leifern.com)

Robert Hatcher
Posted 21 January 2004 - 08:07 AM

I dont have anything to add, but Im taking notes. this is good stuff thanks guys! [notworthy]

Brian Vanspeybroeck
Posted 22 January 2004 - 05:25 PM

And thanks for the chemists version of why it turns black....the whole rust thing fascinates me. :cool:
Thanks for your contribution.
Brian
"Imagination is more important than knowledge" - Albert Einstein
"The innovator is not an opponent of the old. He is a proponent of the new."
- Lyle E. Schaller
http://home.mchsi.co..._Edged_Art.html (http://home.mchsi.com/~hermits
/BrianRVanSpeybroeck_Edged_Art.html)

Brian Vanspeybroeck
Posted 18 January 2004 - 09:45 AM

I have been experimenting with a durable rust finish for sword hardware for some time now (years actually)
and have come up with a fast rust finish that is durable and *black* which was what I was after.
Posted Image
It's nothing new really, just a twist on the way guys used to blue/blacken firearms by rusting, carding, and then
boiling. I used hydrogen peroxide, salt, and vinegar to flash rust the surface for multiple cycles and then boiled

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the fittings in distilled water for 10 minutes. The fittings were covered in Ren. wax while still hot.
My question is: What chemically happens to the red rust when it's boiled to make such a deep black color? It
just amazes me how durable this finish seems to be (we all know how hard it is to get rust off of clean steel
surfaces!) but my wife asked me why does the red turn black and I simply don't know. [dunno]
Any chemists out there?
Brian
"Imagination is more important than knowledge" - Albert Einstein
"The innovator is not an opponent of the old. He is a proponent of the new."
- Lyle E. Schaller
http://home.mchsi.co..._Edged_Art.html (http://home.mchsi.com/~hermits
/BrianRVanSpeybroeck_Edged_Art.html)

Brian Vanspeybroeck
Posted 18 January 2004 - 06:07 PM

The mixture is simple. I use approx. 1/2 cup of regular Walmart hydrogen peroxide and warm it up in the
microwave....don't boil it, just steamy. Then put it in a glass container with a screw on lid (a mason jar) and add
table salt a bit at a time until it is saturated. Add a little, shake it up, add a little more til no more will dissolve.
Then add about a couple of capfulls of white vinegar...say maybe an ounce.
I warm it back up and put it in a little spray bottle. Use very clean steel and spray it all over the piece. It will
foam and steam and you will immediately see red rust in the foam. Spray it again and keep it wet for maybe 30
seconds. then just stand there and let it complete it's reaction...it will stop foaming. Rinse under hot tap water,
don't rub the piece just rinse it.
Then while it's still hot spray 'er again. Repeat the spray and rinse routine for about 6 or 7 cycles and the steel
will have a thick, uniform coating of fine red brown rust. Rinse it and then boil it in distilled water for 10
minutes until it turns jet black...Remove from the boiling and coat with Rennaisance Wax. It's done and
beautiful.
Posted Image
The texture on the tsuba (the tsuba and kashira in my first pix) was actually pre existing due to other botched
attempts at producing the right results. But I like the antique look so it stayed. The fuchi/collar was done with a
very clean and etched surface and it came out glossy and without any pitting or antiquing at all. It actually
shines in direct light. I will continue experimenting with textures but the finish is *very* tough...like rust. I love
it.
Like the pix above! See the shine?
soooo...
Why does the red rust turn black? And remember, don't hide how it's done if it works for you. Pass it along to
others who need the help or can use the process.
Brian
"Imagination is more important than knowledge" - Albert Einstein
"The innovator is not an opponent of the old. He is a proponent of the new."
- Lyle E. Schaller
http://home.mchsi.co..._Edged_Art.html (http://home.mchsi.com/~hermits
/BrianRVanSpeybroeck_Edged_Art.html)

R.H. Graham
Posted 19 January 2004 - 11:17 AM

Stuff that's browned or browned and blackened can develop rust occasionally, if not oiled and waxed, but it's like
a bleed-out effect... a little oil and light rub with steel wool and it blends right into the finish and dissapears.
Browning has been one of my favorite finishes since I was a kid... even do it on blades occasionally, takes care
of the "I hate stainless" issues :0)
I was using brownells "Plumb brown" for awhile but ended up going back to old-timey recipe's like Brians', they
make a deeper and nicer coloured finish in the end.

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To add to brian's routine, if you heat the piece being browned as well, 200f or so , while you are applying, not
only does it make an incredible mess in the workspace that never ever cleans up totally, but it gives you
intermediate shades between the tradtional reddish and the boiled black oxide... it's a deep chocolate brown
with hints of a purple undertone sometimes, similar to the colour you see on antique Japanese ironwork
occasionally.
Spray it on and keep spraying coats untill the piece is cooled and isn't steaming off the mix anymore, then
re-heat and re-apply.
After this, if you boil it, it'll turn black but still seems to have a different undertone of colour, at least to me.
1.618

Guy Thomas
Posted 19 January 2004 - 12:43 PM

This sounds like the perfect finish for a tsuba I'm close to finishing!
I've been fiddling a bit with rust finishes but I can't get them to turn black by boiling. [wtf]
Guy Thomas

Guy Thomas
Posted 19 January 2004 - 09:13 PM

Just to share a rather botched experiment, I found an ancient recipe that was supposed to yield a nice blue-black
finish on steel. You were supposed to mix sulphur into pure turpentine heated over an alcohol lamp and apply
this mixture to the steel and heat with the lamp. Well on my first attempt I flashed the turpentine sulphur
mixture wich made the most god awful stink and then couldn't get the sulphur (flowers of sulphur from the
drug store) to mix into the artists quality turpentine but tried to coat the steel with it anyway. Boy what a mess
that made! Needless to say I didn't get any kind of finish I'd want to show anyone! And I had to get several
showers before I got rid of the burning sulphur smell from my hair and skin! I will definitly be trying this quick
rust recipe soon!
Guy Thomas

Mike Blue
Posted 21 January 2004 - 10:50 AM

I like the quick and easy home brew nitrate formulae, but it sounds an awful lot like the low temperature gun
bluing solutions. The temperature is pretty much exactly what the commercial solutions recommend. The
nitrate gun blues would be a viable alternative. Some of those come out nearly black. The home recipe is good,
no hazmat shipping fee.
There has been some confusion over the term "hot blue." What I think of hot bluing is running low
temperature salts, sodium and potassium nitrates up to about 600-700 degrees F.
More commonly it seems that hot bluing refers to the chemical baths in the 290 degree F range.
Blacksmiths, respected but not necessarily respectable. H. Clark

Ken Burns
Posted 21 January 2004 - 09:08 PM

Robert , the book I got the formula out of says the solution is good for 35 - 50 blacking jobs. Apparently the
AN stays in the tank and only the lye and water boils out. It also says to add a pound of lye every 12 -15 jobs
(remember this is based on the full mixture) and water as necessary. I know from experence if you get the
temp too high the solution will boil away fairly quickly. Also as to Brain's concern about a durable finish this
finish is supposed to take a wire brush test without any damage (I don't know - ain't gona try it on my tsuba).
Ken

lwrhea
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Posted 18 January 2004 - 02:31 PM

I cant answer your question, but I have one for you. Do you kill the vinegar solution on the peice with baking
soda between dips? This is very new to me and I can see that I could use this technique. Is you hardware mild
steel or does it apply to carbon as well? Are you willing to give the mixing ratio of the parts? From the pictures ,
I see that it works great and would appreciate more info. Lin Rhea

DFogg
Posted 19 January 2004 - 04:53 AM

Great tip Brian, I am going to try that next time out. Good question on the color shift, I am sure someone out
there is up on their chemistry and will fill us in. Thanks. [applause]
Don Fogg
Don Fogg Custom Knives (http://www.dfoggknives.com)

Podmajersky
Posted 19 January 2004 - 04:28 PM

If I remember correctly Red Iron Oxide is Fe2O3 while Black Iron Oxide is Fe3O4. This info is from pottery
supply catalogs where both compounds are sold. I would imagine, (educated guess here) that the boiling
converts the Fe2o3 to Fe3o4.

Brian Vanspeybroeck
Posted 20 January 2004 - 06:50 AM

ksb, on Jan. 19 2004,8:55, said:

For a really nice deep black smooth finish try a nitrate finish. Some of the old German firearms used it.
Ken
Hey Ken, can you describe how the nitrate finish is done? What stuff do we need and how is it applied? I'm
always lookin' for another way.
Thanks!
Brian
"Imagination is more important than knowledge" - Albert Einstein
"The innovator is not an opponent of the old. He is a proponent of the new."
- Lyle E. Schaller
http://home.mchsi.co..._Edged_Art.html (http://home.mchsi.com/~hermits
/BrianRVanSpeybroeck_Edged_Art.html)

Phillip Jones
Posted 21 January 2004 - 11:11 AM

Cast iron skillets are nice and shiney to start and then, as they season for a while, turn black. It has to come
from the oil used on them to season it. Just like the oil used on that tsuba.
Phillip Jones
http://customknives.com/jonesbrothers/ (http://customknives.com/jonesbrothers/)

Podmajersky
Posted 21 January 2004 - 12:23 PM

I was doing some investigation into the chemistry involved and ran across a reference to the following chemical
equation:

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Fe + 4Fe2O3 = 3Fe3O4
So since Fe2O3 is hematite or red iron oxide and Fe3O4 is magnetite or black iron oxide it seems plausable that
the application of heat in the proper environment would allow the Fe2O3 to react with the Fe (iron) while
preventing the iron from reacting with any oxygen. Hence the red rust is converted to black. I'm not a chemist
and I don't currently have any chemist friends to verify this either but what I do remember of college chem
classes seems to support the above.

Geoff Keyes
Posted 21 January 2004 - 11:15 PM

I use a cold blue on my damascus. You apply and then buff the high spots down, leaving the blue in the
hollows. Do you suppose this process would work for that kind of application?
Geoff
"The worst day smithing is better than the best day working for someone else."
I said that.

Dan McDougall
Posted 18 January 2004 - 03:06 PM

I can't answer either, however I was also wondering if you were willing to give out the ratio of the mixture?
I have heard of people heating the piece up and rubbing it with linseed oil to get a black finish but it doesnt
look nearly as good as yours. Your process also creates a very unique texture. Very nice.
Daniel L. McDougall

Mike Blue
Posted 19 January 2004 - 08:22 AM

A bit of brief research hasn't produced anything in my books about colors changing. The gun folks have used
boiling water for years to change the gun barrel colors from brown to blue or black. I wonder if it isn't a
heat/oxygen change.
However, the last time I acquired iron (94% powder and 96% sintered nuggets) from the mine, it was black. The
powder was a dead black, the nuggets more black gray. Exposed to the atmosphere/humidity they both turn
red.
Both of those forms are listed as iron oxide. There are two molecular forms. Ferric oxide and Ferrous oxide
that would be simplified to plain iron oxide. I'm still checking on the colors of both types though. Chemistry
books aren't that complete.
Any artist types out there who work with iron as a pigment? They might have a better answer.
Blacksmiths, respected but not necessarily respectable. H. Clark

Brian Vanspeybroeck
Posted 19 January 2004 - 05:37 PM

Guy, this was the part that took me years to get right. I used to rust the stuff for days with all kinds of crazy
concoctions (like the peroxide and salt ain't a concoction ??? ) but it all just came together when I flash rusted
and boiled. The whole #### thing takes about 20 minutes if you do it the way I described above.
Thanks for the explainations from Mike and Leif...I guess if it works who really cares how or why. [dunno]
Still, I sometimes wish for more technical education.
Randal, the variations as you stated are also *very* nice. the purpleish browns are very classy as well...I ran into
those colors along the way. I hope to be able to produce multicolor fittings this way eventually but have a few
projects that will delay that experiment for a while yet.

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I have not seen any rust form after finishing....but it has not been that long and the wax is sure to stop that from
happening as it was applied while the steel was yet very warm. It is virtually encased in wax but I will do an
oiled version next.
Good stuff, Dudes. It's magic. Me like. [ylsuper]
Brian
"Imagination is more important than knowledge" - Albert Einstein
"The innovator is not an opponent of the old. He is a proponent of the new."
- Lyle E. Schaller
http://home.mchsi.co..._Edged_Art.html (http://home.mchsi.com/~hermits
/BrianRVanSpeybroeck_Edged_Art.html)

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