Super pickle

First, THANK YOU ALL for participating in this excellent forum - I
have learned so much, and I love to feel the connection with other
craftspersons and artists. Although I’ve been reading a while, this
is my first post (hope it goes where it’s supposed to.)

My teacher told me to make some “super pickle” to clean up some
intense oxidation - she said to use 1 T of Sparex to one cup hydrogen
peroxide. This resulted in a thick white layer on the sheet of
silver. When I showed it to her, she laughed and said, “no, 1 T of
PICKLE (already mixed) and 1 c. hydrogen peroxide.” So now I have
this super, super pickle - can I use it for anything, and HOW do I
get rid of it? It is a blue color - soaking silver and copper in it
results in lots of small magnetized filings - I think it’s the
silver breaking down. It also stripped the enamel off my kitchen
sink. Any ideas ? - (and yes, I CAN hear you laughing!) :slight_smile:

Thanks -
Sam Kaffine
Sterling Bliss

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It is a blue color - soaking silver and copper in it results in
lots of small magnetized filings - I think it's the silver breaking
down. It also stripped the enamel off my kitchen sink. Any ideas ?
- (and yes, I CAN hear you laughing!) :) 

Um, if all you put in is silver or copper there shouldn’t be
anything magnetic present as magnetics tend to be made from iron,
cobalt, and or variations on those with some rare earth metals thrown
in to up the strength of the magnets.

Yes well you have made a rather corrosive mix there, adding copper
should break down the peroxide (copper is a class 4 metal as far as
peroxide goes, i.e. it causes it to decompose into water and oxygen
on contact), and for the Sparex baking soda should help with that.
Don’t forget to dilute it, say 10:1 with water, add the supper pickle
to the water, this will make it somewhat less aggressive so when you
add the baking soda the reaction won’t be quite as violent…

Wear gloves and safety glasses when you do this, and don’t forget to
wash your hands well afterwards too.

Keep safe.

Cheers, Thomas.
Janstrom Designs.

A couple idea. First off, review some basic chemistry before
thinking any pickle would somehow break down silver or copper
(elements, after all) into MAGNETIZED particles, since neither is a
magnetic metal. That would require turning the silver into another
metal that is magnetic. A good trick indeed (alchemy went out of
style some centuries ago). In strong pickle (sulphuric acid salt)
copper will dissolve. Silver itself will only slightly be attacked,
but not much dissolved. However, you mention it stripped enamel off
your sink. Most enamel sinks are, under the enamel, made of steel.
Could that be the source of your magnetic particles? Seems more
likely to me. Other sources would be anything else made of iron or
nickle that got into the pickle (tweezers?). But silver and copper
simply won’t have broken down into magnetic material. The blue color
is normal for dissolved copper. Any normally made pickle solution,
especially if strong, will dissolve copper, eventually becoming blue
in color. With peroxide added, this happens a lot faster, so a
peroxide containing pickle will rather quickly dissolve copper. But
not silver. Only a light etch on silver, and then the attack stops
after a surface film forms.

As to the pickle itself, well, add water. Hydrogen peroxide is not
itself very stable. It will mostly break down within a few days,
especially when exposed to air and light, leaving merely water. Even
a little remaining peroxide would still make the stuff an aggressive
pickle, so fully breaking down might take longer. But what you’d then
have is very concentrated sparex. All you need do is add enough
water, roughly the amount you might originally have used to mix up
normal pickle solution from that volume of dry chemical, and what
you’d then have is roughly the same as normal, but rather used (since
you say it’s now blue in color) pickle. If it then still works, it’s
usable as such. If you then wish to dispose of it, the usual disposal
methods would also apply. In general, this simply means diluting it a
lot, so it’s only mildly acidic, and then flushing it down the toilet
(assuming a municipal waste water system that then gets treated
downstream). In this situation, the only real concern is the copper
salts, which are a polutant if introduced into a waste water stream
that won’t be treated. So dumping it down the toilet if you’ve got a
septic tank, isn’t such a good idea.

Note that you don’t need to worry about neutralizing the acid in
pickle before dumping it. Simple dilution with water is enough. The
concern is heavy metals, like copper, contained in it.

The final concern, of course, is how to explain the damaged sink to
the rest of your household… (good luck with that… :slight_smile: )

Peter

Um, if all you put in is silver or copper there shouldn't be
anything magnetic present as magnetics tend to be made from iron,
cobalt, and or variations on those with some rare earth metals
thrown in to up the strength of the magnets. 

If the sterling alloy contains any nickel then there would be
magnetic particles. In the UK sterling is 92.5% silver and 7.5%
copper but I’ve been told that in the States, the 7.5% isn’t always
pure copper. Any chance there could be some nickel in there?

Helen
UK

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Hi Helen,

If the sterling alloy contains any nickel then there would be
magnetic particles. In the UK sterling is 92.5% silver and 7.5%
copper but I've been told that in the States, the 7.5% isn't
always pure copper. Any chance there could be some nickel in there? 

I can’t really answer that, but it is a possibility, but to my
knowledge sterling silver (more or less regardless of where you are
in the world is 925:75 silver/copper alloy, other alloys are always
possible and do exist, but AFAIK they tend to go by proprietary names
(eg Argentium).

That said maybe he was pickling a nickel silver, some alloys have
rather high silver content and could be mistaken for sterling, which
might result in nickel grains being left in the pickle.

BTW I don’t know how nickel reacts to a Sparex based pickle, or if
the addition of peroxide will change this. From dim memory I seem to
remember nickel being rather corrosion resistant, so maybe this isn’t
a possibility after all. Oh well back to the chemistry books, maybe
I’ll learn something new!

Cheers, Thomas.
Janstrom Designs.

If the sterling alloy contains any nickel then there would be
magnetic particles. In the UK sterling is 92.5% silver and 7.5%
copper but I've been to ld that in the States, the 7.5% isn't
always pure copper. Any chance there could be some nickel in
there? 

Sterling has no nickle in it. At this point over the years on this
forum, this is the one persistent myth, rumor, mis-I
have seen. Ad naseum.

It would be such a relief if I never saw this again on this forum.
Have you ever tried to pick up a nickle with a magnet. Does your
pickle get contaminated by nickle pin findings. Hint, No.

Are the people who are self taught spreading this among themselves,
perhaps. You do not learn this by being taught in a class, workshop,
or from an instructor. Unless you are really unfortunate. This is not
personal toward anyone.

Nickle will not melt with silver in the U.K. or in the U.S., metal
behaves the same regardless of geography. Pretty amazing, huh? Not as
amazing as how this mishas the legs it does.

Richard Hart

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If the sterling alloy contains any nickel then there would be
magnetic particles. In the UK sterling is 92.5% silver and 7.5%
copper but I've been told that in the States, the 7.5% isn't
always pure copper. Any chance there could be some nickel in there? 

In a word, No. Sterling in the U.S. is generally the same as in the
U.K., except for the specialty versions like Argentium, or others,
formulated to be free of fire scale or tarnishing, etc. These don’t
generally rely on nickel as an additive.

Peter

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Well, I guess since I developed the formula around 1980 at KU I
should answer your questions. Ate your sink huh? Had never heard that
one. It was developed to remove pink oxides from brass. Other uses
have evolved and I do not keep track of them. H2O2 left out in the
light will convert to H2O, Sparex you can neutralize and dispose in
your normal fashion. “Magnetized parts” what can you mean? Nothing
magnetic in non-ferrous metals. The original paper is somewhere in
the Orchid archives.

Bill
Bill, Deborah & Michele
Reactive Metals Studio, Inc
928-634-3434, 800-876-3434, 928-634-6734fx

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Hi Sam,

The super pickle I have used is mixed very unscientifically by
adding a “bit” of hydrogen peroxide to my regular pickle solution.
(In my case, regular pickle is pH minus for swimming pools, sodium
bisulphate, I think, without going down to check.) I use it
warm/hot, specifically FOR the purpose of dissolving copper! If you
ever make the error of dropping some iron into your pickle solution
(although it’s rare, a pinstem is my usual culprit), you will copper
plate all the silver pickling in the solution. This super pickle
does a super job of dissolving this copper plating without bothering
the silver in any way. In an unintended experiment, I dropped a
piece made of silver and copper into cold super pickle, planning to
texture and etch the copper. (Yes, I know of other ways to do this,
such as ferric chloride). I forgot it when I closed up shop. When I
returned 1-2 days later, there was no copper left on the piece, the
silver was completely intact, and the pickle was a lovely shade of
opaque blue. Although I have not tried this with sparex, they are
sufficiently similar that it seems to me that some other contaminant
was at work in your pickle. It should NOT dissolve or damage silver,
or cause any filings of any kind. It WILL dissolve copper, and the
copper ions WILL turn your pickle blue. To neutralize, I would
personally dilute the heck out of it (you could add some to a pail
of cold water - always add acid to water, not the reverse), and add
baking soda bit by bit until it stops foaming. It’s sink safe at
that point. As already mentioned here, the peroxide will decompose
into water pretty quickly, even faster if heated, but the strong
pickle (acid) remains a problem, and I think it’s wise to neutralize
it. As for the copper ions (heavy metals), it’s nasty for the water
supply, but without setting up a lab, I don’t know any way to
recover the copper/clean up the water.

As for the sink - enamel paint, and a good bottle of wine to toast
the occassion? : ) Good luck!!

Lisa W

Richard,

Nickel will melt/alloy with silver, its call nickel silver, and
although the majority partner in the alloy is nickel the balance is
silver (IIRC~40%).

I do agree that there is no nickel in sterling silver and never was,
but there are some pretty weird proprietary alloys out there, so I
wouldn’t rule out a nickel bearing silver based jewellery alloy, even
if I haven’t actually seen any other alloys in common use than nickel
silver!

Having said that I did question whether nickel could contaminate
pickle and I thought it wasn’t possible, but that I was unsure. And
yes nickel is one of the “magnetic” metals along with iron, cobalt,
neodymium, yttrium and some others used in ceramic high strength
magnets. That it isn’t magnetic “out of the box” but has to be
magnetised/sensitised does make it unlikely that what was observed is
nickel. BTW liquide oxygen is also a “magnetic” element, specifically
it’s paramagnetic, and will be held by a strong magnetic field, funny
to see a liquid hovering between the poles of a partial loop magnet.
(Think of a horse shoe magnet bent all the way round so the poles are
only 3/4" apart.)

Ok so now this is getting rather off topic so I’ll let it go now.

Cheers, Thomas.
Janstrom Designs.

Nickel and silver are virtually insoluble in each other (think oil
and water) so if you try to alloy them they remain separate, so you
will have a mixture not an alloy. You can get a little more in
solution if you add copper to the mix but the copper and nickel are
what alloys not the silver and nickel so you still have separate
areas of nickel- copper and silver-copper. It is rare to find any
commercial alloys of sterling that contain nickel due to this.

James Binnion
@James_Binnion
James Binnion Metal Arts

360-756-6550

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Nickel will melt/alloy with silver, its call nickel silver, and
although the majority partner in the alloy is nickel the balance
is silver (IIRC~40%). 

I do not know where you got your Nickel silver is a
metal alloy of copper with nickel and often but not always zinc. It
is named for its silvery appearance, but contains no elemental silver
unless plated.

Other common names for this alloy are German silver, paktong, new
silver and alpacca (or alpaca)Many alloys fall within the general
term of “nickel silver”. All contain copper and nickel, while some
formulations may additionally include zinc, antimony, tin, lead or
cadmium. A representative industrial formulation, Alloy No. 752, is
65% copper, 18% nickel, and 17% zinc. In metallurgical science, such
alloys would be more properly termed nickel brass. The white alloy of
75% copper and 25% nickel used in coins, such as the United States
nickel, is better known as copper-nickel, cupro-nickel or
cupronickel.

Some nickel silver alloys, especially those containing high
proportions of zinc, are stainless (corrosion-resistant).

Nickel silver alloys are commonly named by listing their percentages
of copper and nickel, thus “nickel silver 55-18” would contain 55%
copper, 18% nickel, and 27% other elements, most probably entirely
zinc. A two-element alloy may be named for its nickel content alone,
thus NS-12 is 88% copper and 12% nickel.

Seeing any silver anywhere?

I showed you mine, now you show me yours.

Richard Hart

Nickel will melt/alloy with silver, its call nickel silver, and
although the majority partner in the alloy is nickel the balance
is silver (IIRC~40%). 

Nickel silvers are a group of copper-zinc-nickel alloys with no
silver content at all. See http://tinyurl.com/2nojvc

When molten silver can hold less than 0.7 % nickel and virtually
none at room temperature, they just don’t like each other.

James Binnion
@James_Binnion
James Binnion Metal Arts

360-756-6550

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Well, I guess since I developed the formula around 1980 at KU I
should answer your questions. 

I didn’t know you developed this, Bill! Around here, we call it
“bright dip”, and use it in the classroom, as you said, to remove
pink after heating/soldering brass. It works great! It is also the
solution of choice when somebody puts steel in the pickle and
copper-plates everyone’s work. Thanks!

Noel

Nickel will melt/alloy with silver, its call nickel silver, and
although the majority partner in the alloy is nickel the balance
is silver (IIRC~40%). 

The alloy usually called "nickel silver does NOT contain silver.
It’s essentially a white brass, containing copper (the majority
metal), zinc, and nickel. The term “nickel silver” is a bit of a
misnomer, since that alloy only looks somewhat like silver (well,
it’s white, but not at all as white as sterling), but does not
actually contain silver.

Silver and nickel might indeed form an alloy (I don’t really know),
but frankly, I’m not aware of any such alloys in common commercial
jewelry use…

Peter Rowe

It is rare to find any commercial alloys of sterling that contain
nickel due to this. 

So if it is “rare” then I wasn’t completely off the mark then? ie
such things do exist.

Helen
UK

Thanks Noel, At the time another graduate, Glenice Mathews, had a
paper describing a commercial pickling process for brass using
strong H2O2 and chromic acid (Very bad!). I somehow figured I could
reverse engineer it. It actually worked. It will even work with
vinegar as the catalyst. That was in 1979-80. It seems the word has
spread far and wide. Makes me smile. I should probably chronicle all
the ways it is used and write a new paper.

Bill
Bill, Deborah & Michele
Reactive Metals Studio, Inc
928-634-3434, 800-876-3434, 928-634-6734fx

Hello Orchidland,

Sterling has no nickle in it. At this point over the years on this
forum, this is the one persistent myth, rumor, mis-I
have seen.

I have even heard a dermatologist make the statement that sterling
should not be worn by those with nickle allergies, inferring that
the alloy contains nickle.

Judy in Kansas, who is shaking her head over such a statement from
someone who is regarded a an authority.

So if it is "rare" then I wasn't completely off the mark then? ie
such things do exist. 

I used rare rather than none just because I am not 100 percent
certain that some of these fancy no-low tarnish alloys might have
traces of nickel in them but I have not seen any. The only silver
alloy I know of that has nickel in it is a solder that is used for
silver brazing stainless steel and contains 2% nickel the balance
being silver 50%, copper 28% and zinc 20%. I do not know of any
sterling alloys that contain nickel. It is so hard to get any nickel
in the alloy as it just will not alloy with silver. At best you
would end up with a two phase alloy. For example if you used copper
to hold the nickel in the mix then you would end up with mostly
silver-copper matrix with random areas of copper-nickel not a uniform
distribution.

James Binnion
@James_Binnion
James Binnion Metal Arts

360-756-6550

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I have a nickel allergy and I have been wearing sterling my whole
life, and we won’t get into how long that is.

Megin
Megin Diamond Designs
www.megindiamond.com

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