Easiest antique finish on silver

Jewelry Discussion
41

Jeffrey,

The easiest, dark gray-black patina is Tech-ox "P"

have you bought it recently, I searched their web site. Nowhere
could I find it. Not even the MSDS. Perhaps they’ve disconitinued it?

By the way, it’s very much like, at least from your descriptions,
another product that’s become hard to find. “Win-Ox”. Also with
teluric (?) acid etc. Also nasty stuff, and also an instant deep
black. From what I was told, the fellow who used to make it (in his
garage, no less) died. His daughter I think, either was, or is,
trying to revive the product, but at least for the moment, I’ve not
been able to find a source. Even if you do find it, it’s hazmat
shipping, so you end up paying more for shipping than the product.

Have you got a direct link to the product itself on the Technic web
site? Something they don’t let their search button find?

cheers
Peter Rowe

42

Leonid,

I have read Pliny the elder - in latin, and you’re right. It does
mention glass - but not as a cellar cup - just as the change over
from silver and gold to glass. This was a fashionable material to
use instead of metal because of its expense and rarity. Ostentatious
people rather enjoyed smashing them on purpose to demonstrate their
affluence.

Nothing here about poison, cellar cups or anything else you wanted
to insist on. I’m afraid you just took a reference off a website.
You’ll find the source in Book 31 I think, I can’t remember the
letter number.

I’ve done a really good search of my own library on the subject and
looked at the V & A catalogue of silver and failed to find any
reference to a cellar cup (the actual reference was to a cellerer’s
cup) before 1790. Not, I agree, Victorian, Georgian in fact but the
term “celler cup” came into use in about 1836 although the word
cellar (selar, callar) dates from the 14th century (The Greater
Oxford English Dictionary.)

William Young’s Latin Dictionary of 1768 does not contain the
word/phrase. Pliny just says “vinum vas.”

So I’m afraid it does pass a giggle test, and an academic one as
well.

Vincent La Chapelle (1690 or 1703 - 1745) was a chef, not a
viticulturist or an expert on wine. He’s frequently wrong, even
about food, and did not refer directly to the ancient sources as he
had no Latin or Greek. He’s what a librarian would call a “secondary
source” and a dubious one at that. We even have to take Pliny with a
pinch of salt sometimes as he was an aristocrat and reported what he
thought was right rather than what was actual practice. See the
Introduction to Pliny’s letters by H. Rackham (Pliny: Natural
History, Volume I, Books 1-2 (Loeb Classical Library No. 330.))

(Blowing own trumpet…I read Ancient Greek, Italiian, French (not
very well and my lips get tired) and I can get by in German.)

This is all a long way from your original claims that people got
poisoned by drinking wine that has somehow been contaminated with
cyanide.

Sarcasm is cheap and nasty. Try not to use it in phrases like
"Incidentally, any good librarian could have pointed you in the
right direction." I know how to use a library. I have the use of the
British Library in London and you don’t get that unless you have a
vetted ticket.

I’m not going to pull rank or claim that I have advantageous
academic credentials (oh alright, I have a bit…) here but your
original post was, not through your own fault, misleading and
contrary to the source materials and studies that have been done.

Tony Konrath

43

Perhaps we should refer Leonid’s musings on the cyanide content of
ancient wines to a winemaking forum. I’ve made wine for many years,
and never heard of any problem with it, and it seems unlikely that
older winemaking techniques would result in more crushing of the
seeds, but let’s leave that aside, along with the lima beans and
cassava roots. What’s really more on-topic here is his assertion that
minute quantites of cyanide in wine would instantly turn silver
black. I’ve heard of cyanide being used to clean silver and gold, but
I’ve never heard of its use as a blackening agent. Does this really
occur, or is it just part of this legend? It seems like something
that’s susceptible to proof or disproof with a simple experiment. I
don’t have any cyanide on hand, or I’d try it myself, but I’m sure
someone out there has some on the shelf - maybe they could try it on
some silver and get back to us?

Andrew Werby

44

Hello Peter,

Technic should still carry it, though, you may have to call them:
401/781-6100. And yes, it would be hazmat shipped, but Tech-ox “P”
has an unlimited shelf life. Here’s an MSDS:

http://apps.risd.edu/envirohealth_msds/techoxp.pdf

If anyone knows of a grey-black chemical that’s less hazardous, I’m
all ears.

Jeff Herman

45 
I've heard of cyanide being used to clean silver and gold, but I've
never heard of its use as a blackening agent.

Well, since you never heard of it, than it got to be false.

Leonid Surpin

46 
Vincent La Chapelle (1690 or 1703 - 1745) was a chef, not a
viticulturist or an expert on wine. He's frequently wrong, even
about food, and did not refer directly to the ancient sources as
he had no Latin or Greek.

Too many points to respond, so let me try it this way. There is a
difference between fact and perception. There was a perception and
people acted on it. It cannot be either proven or disproven because
they way we do things now are different, then they were done before.
So saying that something could not had been because it is not now is
a logical fallacy. It is what lawyers call assuming facts not in
evidence.

As far as Vincent Chapalle of course he was not viticulturist because
the science did not exist. A chef was a final authority on drinking
and eating.

Leonid Surpin

1 Like
47 
By the way, it's very much like, at least from your descriptions,
another product that's become hard to find. "Win-Ox". Also with
teluric (?) acid etc.

I have made some similar stuff. Tellurium metal powder and straight
HCl. I forget the actual mix, but a slight excess of tellurium seems
fine. Nasty evil stuff, instant black, even works on gold with a
steel applicator. (another use for all those broken saw blades) Don’t
ultrasonic it for long unless you like a mottled look.

Hazmat on the acid, and I’m not sure which watch list will add your
name for the tellurium. :slight_smile:

jeffD
Demand Designs
Analog/Digital Modelling & Goldsmithing
http://www.gmavt.net/~jdemand

48 
but I've never heard of its use as a blackening agent. Does this
really occur, or is it just part of this legend?

Well, Andrew, in a word, no. Or I should say that my friend who does
gold plating with cyanide solution just gold plates silver daily and
it doesn’t turn black, it plates gold. That is gold cyanide solution,
not straight sodium or potassium cyanide. Also most silver plating
solutions - the good ones, anyway - are cyanide based. No
experimentation needed, it’s being done every day, has been for a
long, long time.

And to further finish it off - apples, cherries, almonds, cassava and
peaches do NOT contain cyanide to begin with. They have substances
(cyanogenic glycosides) that metabolize to form free cyanide in the
presence of certain enzymes. A few also contain those enzymes, so
they DO have free cyanide - bitter almonds is one of those. Meaning
that putting mashed apple pips on silver isn’t cyanide at all, it’s
only cyanide when the enzymes come into play, as in the body. Eating
enough of those smashed apple pips could be very bad for you, to be
sure. Grapes, grape skins and grape seeds have none of those - zero,
zip, nada.

“The moment after a black cat ran across my path I tripped and broke
my leg.” “I took elemental silver (even though the body can’t process
it), and my rash went away. It couldn’t be that the weather cooled
off, it must be the silver.” “The father drank 25 year old homemade
wine and died, so the wine must be poisoned.” These are how
superstitions start, propogate, and endure.

49

about win-ox:

Hi Peter, I didn"t post this to the forum, It probably is not of
general interest, to most of the group.

The win-ox I knew was made by a fellow named Bob Winston. There was
an interesting interview with him at :

http://www.aaa.si.edu/collections/collection/winsto02.htm

for the archives of american art. It is quite long.

Bob was one of the American Modernist Jewelers, Sometimes one of his
pieces will come up for resale (goggle -Bob Winston jewelry)

At this time, one of his pieces is at:

http://www.aaa.si.edu/collections/collection/winsto02.htm

I would like to know how he achieved the green patina on this piece.

I knew Bob slightly, in the 60s. He was always experimenting with
chemicals and materials.There are probably people in the bay
area,who knew him much better. He was well known in that area in the
90s and early 2000s.

regards,
Andrew

50 
And to further finish it off - apples, cherries, almonds, cassava
and peaches do NOT contain cyanide to begin with. They have
substances (cyanogenic glycosides) that metabolize to form free
cyanide in the presence of certain enzymes. A few also contain
those enzymes, so they DO have free cyanide - bitter almonds is one
of those. Meaning that putting mashed apple pips on silver isn't
cyanide at all, it's only cyanide when the enzymes come into play,
as in the body. Eating enough of those smashed apple pips could be
very bad for you, to be sure. Grapes, grape skins and grape seeds
have none of those - zero, zip, nada.

This subject is way to complex to describe in several sentences. To
say that grapes do not contain cyanide is factually accurate, but in
the context of discussion is misleading, because while grapes on the
vine do not, fermented grapes quite another matter. So to assume
properties of resulting compound based on starting substances is not
good way of thinking.

The same applies to using cyanide for patination. What must be
realized that there are thousands of cyanide compounds with different
properties.

All I can say it that do research and do not limit yourself to
snippets available on the internet. For this subject one needs to hit
the books in serious way.

Leonid Surpin

51 
The easiest, dark gray-black patina is Tech-ox "P"

I spoke to the company, and it is still available. Win-Ox is still
available thru Indian Jewelers Supply. I’ve wondered about the
Tech-ox “P” before when Jeffrey mentioned it. The Technic rep
wouldn’t comment on their ingredients, but I wonder if Win-OX or
Black Max or Silver and Black might be essentially the same stuff?
Anyone know?

Allan

52

Many years ago, my first shop was heavily into silverware
restorations, holloware, flatware, sterling, plate, Sheffield,
Britannia, you name it we did it. We used cyanide solutions as a
bleach before a scratch brush and cut n color buff. Cyanide will
remove previous oxidations, whether purposely applied or just thru
accumulated age. The silver comes out of the cyanide a foggy whitish
color. Not at all black.

Silver will go black even if a trace of cyanide is present.

I don’t know what source you have for that erroneous info but it is
indeed…erroneous.

gold lining is always an indication of poor quality of an article
and traditionally is used to conceal the defects.

Plain wrong. The gold is there to reduce staining.

rolls eyes

53

Leonid,

Your original contention was not “People thought this was true”
(which I think us false) but “This is true.” (which we know to be
false.)

A viticulturist is not a scientist. It’s just a term for an wine
maker. Have you actually read la Chapelle? A chef of the period was
an expert on cooking and not on farming.

Just sent a relevant quote (with edition and page number) from a
contemporary of the the period that silver was turned black by
cyanide.

That’s all you have to do.

Tony Konrath

54 
I don't know what source you have for that erroneous info but it
is indeed...erroneous.

There is a relevant joke in it.

A professor conducts a lecture. There is a cadaver in front of him.
He shoves one of his fingers in cadaver rectum, licks finger and
proclaims that he can taste sugar and therefore the cause of death
was diabetes. He invites students to confirm.

A student repeats the process and says that he cannot taste
anything. Professor gives student A for bravery and D for
observation, because he probed with the middle finger, but licked the
ring finger.

How, does it apply to the comments?

We say silver, but we mean sterling silver, which is an alloy of
silver and copper. Cyanide is very general, so let’s say we have a
version of Scheele’s acid. Silver will be dissolved exposing copper
and the indicator reaction is between cyanide reagent and copper.

As far as gold plating, browse Christie’s or Sotheby’s catalogs of
antique silver and pay attention to prices. I guaranty that the
truth will be self-evident.

Leonid Surpin

1 Like
55 
Just sent a relevant quote (with edition and page number) from a
contemporary of the the period that silver was turned black by
cyanide.

This is getting quite entertaining. I will do so if you send a
relevant quote (with edition and page number) from a contemporary of
the period, that it did not

Leonid Surpin

1 Like
56

ok…this is my only comment on cassava In South America there are
2 types that are grown AND used…there may be more
sub-species…let’s leave that… There is the type you see in the
stores which is the edible kind. Never a problem to eat just
cook…steam, boil or fry till cooked. Tapioca is made from cassava.
The problem is with what is known as poison, bitter cassava. This is
the type that seems to be grown in Africa. In South America this type
is ground and the mash is put in a 1.5 metre tube made of woven reeds
and squeezed dry. The washing is done several times to remove the
poison or puric acid. The ground fiber is then cooked in circles til
dry to destroy the remaining poison. It is known as cassava bread. It
is toasted and buttered to eat.

The liquid is left to settle. The bottom will be starch used for
clothes and the water is boiled to reduction again to destroy the
poison. It becomes thick and spices are added to it. When done it
looks darker than molasses. This is used to make an Amerindian
(indigenous people in the Brazil, Surinam, Guyana area) dish called
cassareep. …and I know this does not really belong on Orchid…but
I would hate for people to think that the Cassava that we buy in the
store can kill you. Spring is finally here in Ottawa

Simone

57 
All I can say it that do research and do not limit yourself to
snippets available on the internet.

That’s good advise, Leonid, you should listen to it.

I’m 40 minutes drive from Napa/Sonoma valley - wine central in
America. I have a sister in law who’s a chemist at a winery. My
wife’s family had a vineyard, before it got lost in a divorce -
we’re talking 100 years, here. I’m personally aquainted with around a
half-dozen winemakers, I’ve taken the tours and seen it all. Been to
wine groups and clubs, discussed the various fermentation methods
and products - on, and on, and on, and on, and on. I’m not a wine
expert (a relative term) but I’m certainy very knowlegable on the
subject.

There is NO cyanide in grapes, grape wine, grape juice, grape seeds,
grape skins, grape products, raisins, nor will there ever be under
any circumstances unless they are tampered with. Any grapes, all
grapes. Children around the world just suck them down…

There is, in effect, only ONE cyanide - the cyanide ion. Whether that
is bonded to hydrogen, sodium or potassium is of little meaning in
the real world. Basic chemistry. Facts.

58

I’ve heard of cyanide being used to clean silver and gold, but
I’ve never heard of its use as a blackening agent.

Well, since you never heard of it, than it got to be false.

Not at all, Leonid; I’m sure there are plenty of things I’ve never
heard of that are true. Can you admit that there may be some things
you have heard of that might not be? I take it this isn’t something
you’ve personally experienced, but that somebody told you about it,
and you believed it enough to pass it along. I just thought it seems
odd that something used as a cleaning agent and plating bath would
also be a blackening agent. That’s why I was proposing a simple
experiment to sort this out. If I crushed up some peach-pit kernels
and soaked them in wine, then exposed the solution to some clean
silver, that should do it, right? According to you, the silver would
turn instantly black. If it didn’t, can we consider this myth
“busted”? Or is there some other factor I’m not considering which
you’d suggest be a part of this experiment?

Andrew Werby

59 
We say silver, but we mean sterling silver, which is an alloy of
silver and copper. Cyanide is very general, so let's say we have a
version of Scheele's acid. Silver will be dissolved exposing
copper and the indicator reaction is between cyanide reagent and
copper.

As I mentioned in another post days ago, I tested just this. A bit
of plain old sodium cyanide in water, on a bit of sterling silver. A
bit of a hazy spot, as the cyanide dissolved metal, but not obvious
darkening. Tried the same thing tonight on a bit of plain copper
sheet. Cleans it up as well as it cleans up silver.

So, what gives?

As John Donovan pointed out, the only chemically relevent ion in
cyanide per se is the CN ion, which is cyanide. You can pair it with
whatever you like for different preparations, but the cyanide is the
CN ion, which is the toxic part. It does not seem to cause, at least
not by itself, blackening on either sterling silver or copper. Can
you suggest some other componant to the solution that, in combination
with cyanide, might give a darkening effect? I’d normally expect such
a reaction to be something where a more reactive chemical might
cause a less reactive one to drop out of solution, some sort of
oxidation/reduction mechanism. But usually this would require
something more reactive being added to the mix, to drop something
else out on the silver. Such as happens when iron drops copper out
onto silver in the pickle. Or in this case, perhaps something
oxidized in the solution that the copper can reduce, itself then
becoming oxidized, which might be black. But as with that pickle
example, iron already in the solution doesn’t cause the effect,
limiting the number of potential remaining mechanisms. For the copper
to reduce it, becoming itself oxidized, your componant in the wine
would need to be less reactive than copper, I believe. What might be
in your bad wine, that combined with the relatively less reactive
silver, or even the copper therein as you suggest, might then give a
dark color? Nothing obvious occurs to me, but that doesn’t mean there
isn’t something. But if so, it’s not the cyanide doing it. It’s the
something else, perhaps in combination with the cyanide…

And again, this is why I, and others, might appreciate your
references. It is indeed an interesting subject if true…

Peter Rowe

60 
This is getting quite entertaining. I will do so if you send a
relevant quote (with edition and page number) from a contemporary
of the period, that it did not

Now you’re being silly, Leonid. The observation that nothing
happened when wine, with or without some contamination, is not likely
to have been made. If contaminated wine WERE indicated by a certain
type of metal cup, THAT would have been notable. But the lack of such
an observation? Why would anyone even think to make note of it? At
the point in time we’re talking about, I don’t think the word
“cyanide” was even invented yet, was it… Only if your contention
that silver was indeed used to detect poison is true, would there be
mention of the connection. But please. since you say you WILL provide
such a reference if you’re provided with the reference that it did
not, suggests that you do indeed have such a reference.

So please put your money (or reference) where your mouth (or
keyboard) is. Otherwise, we’ll know you’re bluffing. Show us, please,
that even if this is indeed an untrue “urban legend”, that you can at
least show some documentation or source of this (be it
truth or not) beyond your own memory and interpretation of it.

thanks.

And you’re right. It is getting a bit amusing. Some of us may be
amused by different aspects than you. Others may be getting
frustrated rather than amused. I myself might have gone a little
overboard in comments at the end of my post sent yesterday (on the
list today, thursday). If I offended, I apologize. It was a
fruestrating day for reasons having nothing to do with jewelry, and
that attitude bled over a little to my posting.

Peter Rowe