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Re: Water+steel=rust?

To: mgs@Autox.Team.Net
Subject: Re: Water+steel=rust?
From: Barney Gaylord <barneymg@MGAguru.com>
Date: Fri, 12 Nov 2004 01:09:33 -0600
At 11:11 AM 11/11/04 -0500, Dennis (BarrMark262@aol.com) wrote:
>....
>We all know when moisture and steel mix, the result on our cars is  rust.
>
>Question is, what causes this to happen?

I'm surprised there wasn't a rash of off the cuff responses to this 
one.  Brace yourself for more than you need to know, and I will try to 
condense a couple of chapters of RUST-101 into a single page.

Rusting is a chemical reaction of iron in the presence of oxygen.
Common sheet metal rusting in dry air works like this:
      4 Fe + 3 O2 --> 2 Fe2O3
This reaction is relatively slow and produces a thin coating of stable iron 
oxide Fe2O3, which is (technically) rust, but is a fairly benign form of rust.

However, .... if it happens in the presence of water, or even moisture in 
the air, a second step works like this:
      Fe2O3 + H2O --> Fe2O3 x H2O
This produces hydrated iron oxide, or RUST (the common kind the eats your 
sheet metal).  This reaction happens much faster and is much more 
destructive.  Add a little road salt to the mixture to ionize the process, 
and it goes even faster (please don't ask for that equation).  This form of 
ferric oxide is bulky and porous (mechanically much different than Fe2O3), 
so it allows more oxygen access to the iron below, causing additional 
rusting.  If allowed to continue, the oxygen and water will completely 
convert the remaining iron to ferric oxide (or solid rust), which is weak 
and flaky, hence big holes in metal (cancer).

For parts submerged in water, or filled with water (like the cooling jacket 
of an engine block), it works more like this:
      3 Fe + 4 H2O --> Fe3O4 + 4 H2
The resulting stable oxide Fe3O4 is magnetite (ferrous ferrite or magnetic 
iron oxide).
It can also work like this:
      3 Fe(OH)2 --> Fe3O4 + 2 H2O + H2
This is ferrous hydroxide producing the same magnetite.
Notice that both of these reactions release (small amounts of) hydrogen 
(into the water) when oxygen from the water is incorporated into the 
rust.  This does not require the presence of free air.  It also results in 
a thin and generally protective coating.  This coating will be constantly 
breaking down and re-sealing itself, so it can eventually lead to more 
extensive corrosion (and accumulation of caked up crud in the bottom of the 
engine block water jacket).  This is why you want to add corrosion 
inhibitors when running plain water for coolant.

Fe3O4 can also be formed into a MORE protective coating.  This is an 
industrial process.  Do not try this at home.  An iron or steel part is 
placed in a closed chamber and heated to 1600dF, after which it is blasted 
with superheated steam.  This results in rapid formation of both red oxide 
(Fe2O3) and magnetic oxide (Fe3O4).  Carbon monoxide is then introduced to 
reduce the red oxide material to magnetic oxide, like this:
      3 Fe2O3 + CO = 2 Fe3O4 + C
The whole process only takes about 20 minutes.  This leaves a bit of carbon 
in the surface, making it very black.  The resulting magnetic oxide is 
highly corrosion resistant.  This is also known as black magnetic oxide (or 
just black oxide).  You may recall that this was used extensively on hand 
tools before chrome plating was popular.  It is still used fairly 
extensively in industry to apply a cheap and relatively corrosion resistant 
surface to steel parts.

The glossy black coating on "Russian Iron" is produced by laying up sheets 
of iron with powdered charcoal in between, and the whole mass then being 
heated and hammered.  This is a lot of work and not very practical with 
high labor rates, but it does yield a nice appearance.  This is not 
actually rust at all, but I mention it because it is similar in appearance 
to black oxide.

Iron and steel may also be oxide coated by electrolytic means, with the 
object to be coated connected as the anode in an alkali solution.  This is 
primarily for appearance, as for black iron stove parts (hardly worth 
mentioning as rust).

Many rust neutralizing paint-on coatings work by chemically converting red 
oxide (RUST) into black oxide (if it's not too thick).  Then you can paint 
over the stable black oxide.  That may be one of the key points you like to 
know about restoration work.

Collect your diploma on the way out.

Barney Gaylord
1958 MGA with an attitude
http://MGAguru.com




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