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Bronze Disease on Ancient Coins - Comments
Subject:
[Moneta-L] Re: Benzotriazole (was NEW COLLECTOR QUESTION)
Date: Sun, 1 Apr 2001 11:35:47 -0400
From: "Charlie Karukstis"
To: "Moneta"
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Hello all:
I'm sorry I haven't been participating for some time. Let me see if I
can catch up on some of the conservation threads that have been ongoing.
I've always been rather circumspect regarding benzotriazole and its effectiveness
on coins. Of course, I've only been working with benzotriazole since 1990,
and perhaps Hannes' enthusiasm for it is a result of longer experience
with it? It is true that a number of museum conservators have used it
when conserving large copper-alloy statuary, but as I've mentioned before,
what works for statuary doesn't always work on coins (like electrolytic
reduction).
Benzotriazole is controversial within the museum conservation crowd because
of its possible long-term ineffectiveness. The ineffectiveness doesn't
seem to result, however, from where the benzotriazole is, but from where
it ain't. Its permeation rate into a copper alloy flan is not going to
be as effective as other wet-based processes, and while it will form a
fairly effective chelate where it is present, if there are significant
parts of the flan (containing chlorides) that it doesn't reach, then its
long-term effectiveness is compromised. There are other assertions by
some conservators that there are more problems with the treatment, but
of course there are others that swear by it, and so the debate goes on.
This is one
of the reasons why I don't like benzotriazole as a first treatment, and
most assuredly not like Hannes suggests it, simply rubbed on the surface
for a few minutes. Longer impregnation times would seem to be important
(i.e. weeks), and of course you could then have possible complications
from the ethanol vehicle as Hannes correctly points out. Besides there
being better treatments available for coins, I've never recommended benzotrizole
to the list because it is simply not a safe substance to handle (maybe
Hannes has better lawyers than I do!) Carcinogenic qualities aside, it's
a dangerous chemical for people to handle on a casual basis.
Now, I have
used benzotriazole in cases where a flan has had a significant amount
of chlorides present, but only as a secondary process. After removal of
chlorides by an initial process, I have sealed coins with Incralac (a
lacquer containing benzotriazole). This has appeared to be useful in several
instances. The mechanics of applying Incralac to a coin, so that it doesn't
end up looking like a cough drop, are a considerable challenge. I usually
use an air-brush specifically adapted for the Incralac, but please understand
that there is airborne benzotriazole as a result (i.e. kids don't try
this at home).
I'm
going to stick with my original recommendation that people will still
do best by using a sesquicarbonate treatment for treating chlorides. With
regards to patina loss, the least-popular answer is, as usual, the correct
one. The possibility of loss of oxidation/other layers from a flan from
any treatment depends on the composition of those layers. That means a
5% sesquicarbonate solution might do nothing to the visual appearance
of one coin, and a 1% solution might strip three-quarters of the layers
of another.
If you have access to "Studies in Conservation", please look at Ian MacLeod's
seminal article "Conservation of corroded copper alloys":
A comparison of new and traditional methods for removing chloride ions"
(vol. 32 - 1987, pp. 25-40). This is the article that prompted me to pursue
this particular line of insanity, and to me remains (along with Plenderleith's
volume) the two best introductions to the subject. There's much that has
been published more recently, but they are a good start. As I mentioned
before to this frustrated list, there is never a single answer or approach
to all conservation issues, and sometimes we just have to be patient and
think things through.
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Subject:
Re: [Moneta-L] Re: Benzotriazole (was NEW COLLECTOR QUESTION)
Date: Sun, 1 Apr 2001 12:55:53 -0400
From: "Charlie Karukstis"
To: "Moneta"
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I have two
main areas of information that led me to my comments. The first is a study
group of coins I put together around 1991 or so specifically to test out
the various methods in MacLeod's article. The big weakness in my test
group, as I now painfully understand, is that the alloy composition is
not consistent throughout the group, rendering results of mixed value
(of course, who has twenty or so identical flans all with bronze disease,
anyway? Well, aside from Turkish museums...)
All coins had chlorides removed with sodium dithionite, and tested negative
for chlorides (well, below the detection limit I could measure)
One of the
coins in the group then received only a cursory coating of benzotriazole
- sort of as a surface sealant.
In testing the coin for chlorides every two years or so subsequently (
I haven't done it lately), I noticed by 1998 or so that I got a chloride
reading above my detection limit (~25ppm or so). Now, does that mean the
benzotriazole failed or did I do a poor job of removing the chlorides
in the first place? Also, other coins with other surface treatments didn't
do well either, so all my test really shows is that benzotriazole failure
is simply one possible cause.
The second
piece of information I had was a portion of a working paper testing benzotriazole
on shipwreck items ( I don't have the paper, I think it was from somewhere
within the Texas A&M facility, sorry for no information), which raised
questions similar to MacLeod's comments. I don't think I ever saw it published,
though, so take it for what it's worth.
Clearly, a treatment process like benzotriazole is head and shoulders
above most of what's currently practised out there, so I shouldn't sound
too negative about it.
I tend to be rather cautious about this sort of thing, and don't want
to lead people to think any one treatment is some sort of panacea for
everything. If it were less dangerous to handle, I might suggest people
try it on some coins as well.
Oh yes, the effect of sesquicarbonate on "patina". I agree that a 5% solution
will, if not completely remove the oxidation layers, will certainly change
the aethetics of a coin! The problem is that 1% solutions are in most
cases ineffective, being functionally almost no different from simply
using distilled water (for three to five years!) There's never a simple
answer to these things, and I think that is what fascinates (and frustrates)
so many of us - sort of a metallurical version of golf.
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Subject:
Re: [Moneta-L] Re: Benzotriazole (was NEW COLLECTOR QUESTION)
Date: Sun, 1 Apr 2001 13:16:06 -0400
From: "Charlie Karukstis"
To: "Moneta"
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Ah, the scourge of declining mental capacity. I mispoke
in my reply to Hannes when I said all coins were treated with sodium dithionite
first. Not quite half of the test coins were for the purpose of testing
sealants after treatment, with Incralac, benzotriazole alone, various
microcrystalline waxes and some sort of polymer I forget the name of (doesn't
matter, it was definitely cough-drop material). The rest of the group
were unconserved coins to test out the treatment processes; if you didn't
mind losing the "patina", the sodium dithionite was the most effective,
with various forms of sesquicarbonate coming in second in my highly subjective
evaluation.
I never have
had good success with citric acid (MacLeod sort of liked it), and please
don't ever handle acetonitrile if you don't know what it is. Interesting
experiment.
Of course, around the same time (1991 or so) I coated several identical
copper alloy blanks with "Deller's Darkener"; if you remember the thread
on it, it's basically some sort of sulfide compound in a petrolatum base.
At last examination, the solid black, soft, absolutely disgusting surfaces
are continuing to profilerate, and I suspect that any year now they will
grow arms and legs and take their leave of me.
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