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Letter 9408
Electropolishing using perchloric acid
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Hi!
I "touch up" some stainless steel samples using the "brush
electropolishing"technique using a 900ml ethanol+20ml water and 80ml
perchloric acid solution. Is it safe using it as I am not using it
using the conventional "Vat technology" and do not immerse it in the
solution. Besides the stylii(SS) used are approx 4 sq.inches thru
which the electrolyte is pumped.
Solomon Mordecai
- INDIA
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Hi Solomon,
First off, I was never a plater ... and sure don't know if your
use of Perchloric is a standard in the plating industry.
My only thought is the concern of any spillage of the Perchloric
(onto wood, for example) and any ventilation. This is a super
oxidizer, more efficient than Sodium Chlorate ... so if, perchance,
you are venting it at all, you need to take some precautions!
Anyhow, your supplier would doubtless, I hope, have given you a
data sheet on it's properties and shortcomings! Hope so, anyhow!
Seems, too, that s.s. is A.OK for puming it around but PVC would
cost far less.
Cheers!

Freeman Newton
specialist in Perchloric ventilation systems - White Rock, B.C.
Canada ... just above the American border
+
Hey Mr.Newton!
Thanks for getting back to me about the potential hazard in
handling Perchloric acid. Adequate venting is provided and at any
given time only 5-15 ml of the soln. is pumped through the stylus .
Solomon
- INDIA
+
Perchlorate electropolishing. This is illegal in the US since the
Los Angeles detonation. I probably don't have the facts exact but in
general a 250 gallon tank denonated in the late 1950-early 1960.
Killed 18 people and leveled 4 blocks! Is your little stylus
dangerous? Probally not if kept in the "safe" window of
concentration; if not, probably not more dangerous than a hand
gernade without the pin in it.
Regards,
Jon Quirt
- Fridley, MN
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Hi Jon,
What you said was very interesting ... can you get a factual
update on that?
When I first got into Perchloric, all I knew was that the
Industry, the mining laboratory peope who are called Assayers, had
had problems and ducting blowing up and a few deaths.
It's so easy to be worldly-wise now but at that time, people just
didn't realize (by people I also mean the sellers of stainless
fumehood systems) that an Assayer will do all his digestions in one
hood & remove the organics... and then, at the end, will use
Perchloric because Perchloric and Organics go BANG.
Ah, but the predigestion acids these people use are BAD NEWS to
stainless, to stone, to fibreglass, even to the exotic alloys, even
to Titanium ...Aqua Regia, HCl, nitric, Sulphuric (which is boiled
off at around 320 degr.C) HF and Perchloric.
Ergo, if your ducting isn't suitable, those other nice acids will
make holes in it (especially on the underside of a 90 degree bend)
through which the Perchloric can drip down and, if it drips on wood,
ah, it has hit an organic and in time, POOF!
Maybe the plating industry was premature in banning Perchloric....
who knows. But to-day in the Assay field one really never, ever hears
of any problems, not in this continent... and I don't want to hear of
them either. So far I've been fortunate and call these systems
Perchloric Fail-Safe Systems ... which I sure wouldn't were they in
metal!
Freeman Newton
- White Rock, B.C. Canada
+
Ted,
A follow up on a subject of a couple months ago on electropolish
using Perchloric acid solutions. I believe I have the following
correct. The Los Angeles detonation was in 1947 it was the result of
a 200 gallon tank detonating. This solution was outside the "safe"
zone. It killed 15 people and leveled 4 city blocks. While I have not
read the article I believe more information on this and other such
mishaps can be found in an article written be Pierre Jacquet and
published in Metal Finishing 47 (11)
(1949) 62. Should you dig it out I would be most interested in
reading it.
Jon Quirt
- Fridley, MN
First of two simultaneous responses -- +
(sent via mail)
The perchloric acid explosion occurred in Los Angeles about 1953.
Jon Quirt had the details correctly. It was the O'Connor
Electroplating Company. I believe it was written up in Metal
Finishing at the time.
The cooling pipes in the electropolishing tank stopped
functioning. The staff did not live to report the conditions. Two
stories survived. One was that the chemist wasn't really a chemist.
The other is more romantic. The families of the chemist and the
assistant would not let them marry so they went together to
perchloric heaven.
I started my lab a few years later and no property owner would
rent to a plating company. I wouldn't recommend any, no matter how
small, usage of the perchloric electropolishing solution.
Milton "Dr. Eddy" Weiner
- CA, USA
Second of two simultaneous responses -- +
We thank Fred Freyer of Metal Finishing magazine for making the
article in question available. The following is an excerpt from
"The Safe Use of Perchloric-Acetic Electropolishing Baths" by
Dr. Pierre A. Jaquet, published in Metal Finishing, November
1949 --
Los Angeles Accident
This occurred on the twentieth of Feb. 1947 in an
electroplating factory which was studying the polishing of aluminum
on an industrial scale in 800 liters of an electrolyte containing 3
parts of 72% perchloric acid and one part of acetic anhydride. The
explosion, extremely violent, completely destroyed the factory of
brick construction, leaving in the place of the bath a crater 2.2.
meters deep and 6 to 7 meters in diameter; 116 houses in the
vicinity, some at fairly great distances, were more or less damaged.
This accident cost the lives of 17 people and injured about 150. The
destruction was evaluated at about 2 million dollars.
The investigating committees established the following
points:
A. The pretended inventor of the process was an adventurer
without technical knowledge but who did not appear, however, to
ignore the danger of his electrolyte.
B. The process had been studied since the first of September,
1946. A bath of 120 liters functioned for several months without
accident.
C. An automatic system of refrigeration was provided for, so
that the temperature would not rise above 27° C. A short time
before the accident this system stopped operation but the
electrolysis was nevertheless continued.
D. The day of the accident the racks for the work, formerly of
iron, were replaced by metallic pieces covered with a plastic
(cellulose aceto-butyrate).
The above results allow confirmation of the fact that the
explosion was a result of serious faults in the principles and
conduct of the process, faults which would have been evident to a
competent technician. At the moment of the accident there was in
effect, a combination of three dangerous conditions:
- Very high concentration of perchloric acid (75% of HCIO, of
density 1.72 when the normal electrolytes contain a maximum of 37%
HCIO, of density 1.61).
- Excessive heating of the mass of the bath, and still much
more in the neighborhood of the electrodes.
- Presence of organic matter in contact with a hot bath.
One of the chemists charged with the inquiry at Los Angeles had
obtained an explosion in the laboratory by adding 1cc. of this
plastic to 1cc. of a mixture of 2 parts of perchloric acid and 1 part
of acetic anhydride and heating progressively.
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Ted Mooney, P.E.
finishing.com
Brick, New Jersey
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VERY Interesting!
But one asks oneself, WHY didn't they go by the warning data on
Perchloric? Why blame Perchloric? Heck, for that matter, let's go and
totally ban nitric and sulphuric and glycerine ... which, ah,hah, if
mixed together in the right proportions gives you a mega super bang.
Commonly called Nitro Glycerine!
Perchloric isn't dangerous... by itself! It's the people who
misuse it who have caused the problems so that now the entire plating
industry is scared witless about using it yet it is safely used daily
all over the world by Assayers.
The mention of a plastic called, you said, Cellulose Aceto
Butyrate (which I've never heard of) sounds suspiciously like it
might have been of the cellulose nitrate family, which is commonly
known as, ah, gun cotton. Those were early days for plastics.
Cellulose nitrate was a really super plastic EXCEPT for an
enormous fire hazard potential. Mixed with camphor you get a good
hard bounce effect and it is absolutely totally ideal for ... Ping
Pong balls! ... and for the cognescenti, those balls are now not 38
but 40 mm in dia.
Freeman Newton
- White Rock, B.C. Canada
Ed. note: Courtesy of Dean Ward of Haward
Corporation we have also now obtained a copy of the earlier article
on the accident, written by Fred A. Herr and published in the March
1947 issue of Metal Finishing magazine, pages 72, 73, and 107. 15
people were killed, and an estimated 150 injured; it completely
wrecked a number of adjacent structures and damaged an estimated 300
buildings. I believe that I would agree with Milton Weiner that
perchloric acid should never be used in a metal finishing shop at
all.
++++++
I would like to know the detailed equations regarding
electropolishing of Aluminium foils using perchloric acid and ethanol
mixture.Is it safe?
Anuradha Bhattacharya
Student - India
+++++++
to John Quirt:
You seem to say electropolishing with Perchloric Acid electrolyte
solutions is ILLEGAL now. If that is what you truly mean, can you
point me to any official pronouncements so stating? I am currently
looking at literature from an electro-polisher company which suggests
a number of electrolyte solutions containing Perchloric acid.
Cautions which are included only raise more questions in my mind.
Richard Lareau
Forging - Cheshire, CT, U.S.
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