Granulation & Germanium

Those of you who have been using copper carbonate to eutectic (or
chemical) solder fine silver granules to fine silver may be
interested to know that adding germanium instead of copper produces
the same (?) result.

Dissolve about a lentil-size amount of germanium powder into about
1/4 teaspoon of Battern’s flux, mix well, then added three drops of
Klyr-Fire (the brand name of organic glue used in enameling). Add to
this solution the number of fine silver granules you plan to use.
Apply granules to 24-gauge sheet fine silver and wait for the glue
to dry. Place the silver with granules on a wire rack that sits
flush with the floor of an Ultralite kiln (Rio Grande). Place the
rack on the lid of a pre-heated kiln for a few minutes to heat up
the rack. Then, place the rack in the kiln, cover, and heat for 5
minutes. (After about 2 minutes the organic glue (black color) burns
off. Remove from kiln and air cool.

That’s it, no torch or additional anything is needed. (In fact, when
I tried to torch-heat, I just melted all of the granules.) The
kiln-heated granules are firmly attached. The following photo shows
two example pieces just as they look straight out of the kiln. The
granules are 0.65 mm and, under 30x magnification, look exactly like
granulation made with copper. There are small bridges where granules
touch and a connection with the base. It really does look like they
are floating on the surface. (Sorry for the poor quality photo, all
of my photo lights burned out.) On other pieces, I have polished the
surface between the granules with 3M radial bristle discs and rubbed
the surface of the granules with a “sunshine cloth”.

My source of powdered germanium is special order from Whole Foods,
health food section (it is an anti-oxidant health food supplement.)
The one I have is Jarrow Formulas, bis-beta carboxyethyl germanium
sesquioxide. Or, " Ge-132 organic germanium sesquioxide."
(www.jarrow.com). There are other sources of germanium on the web
that probably cost less than $6.00 US per gram in the 5 gram bottle
I got from the store.

The whole idea started when I wondered if germanium applied to the
surface of regular Sterling silver would provide a tough coating
that would be better than lacquer or wax. When heated, the surface
of the sterling silver melts at a lower temperature (and doesn’t
look good) but that is when the idea came for use in granulation.
I’m still interested in finding some way to coat sterling silver
with germanium.

I hope some of you will try experimenting with germanium, especially
granulation because this is really easy to do.

Nancy

Dear Granulation Enthusiasts

I need to amend the earlier post in a big way. The granules are
firmly attached to each other and to the base unless subjected to
pickle. Then it all falls apart. Sorry about that. I was trying to
attach gold granules to sterling/gold bi-metal. Everything was fine
until I put it in the pickle. I hadn’t done this with the fine
silver because there was no discoloration to remove. But alas, it
too dissolved the connections.

Nancy

I need to amend the earlier post in a big way. The granules are
firmly attached to each other and to the base unless subjected to
pickle. Then it all falls apart.

Oh, man! I was afraid that was too good to be true! Too bad. I do it
the hard, old-fashioned way, so if anybody has any great tips or
shortcuts, especially for gold-to silver, I’d sure love to hear 'em.

–Noel

Nancy:

My metals instructor and I were thinking last night about your
germanium post and your amendment to it. We were curious about a
couple of things. Is there truly an eutectic bond between the
granules and the sheet, and what are you pickling with that would eat
that bond away?

Marya
Columbus OH US

Is there truly an eutectic bond between the granules and the
sheet...? 

Has a silver/germanium phase diagram been published?

If so, wouldn’t a “u-shaped” curve lying between the two melting
points of the two metals and showing that boundary between the
liquidus and the solidus of the various mixtures of the two metals
touching the boundary that denotes the alpha phase of the alloys be
sufficient to indicate a eutectic point?

Just a thought.

David

A browse on the Internet turned up a phase diagram for silver -
germanium (albeit under microgravity conditions) at

www.ingentaconnect.com/content/maney/mst/1999/00000015/00000011/art00008

This describes a well-defined eutectic at 17.6 wt% Germanium.

Marya,

I saw a bond between the germanium and the fine silver that looks
exactly like a eutectic bond, but it likely is the clear glassy
germanium forming a type of coating on the outside of the fine silver
granules. If it had worked as I originally and unrealistically
thought, the fine silver and germanium would have become a lower
melting alloy on the surface (like Argentium silver) and bonded that
way. Instead, the pickle dissolved the germanium and left perfectly
intact (but separated) fine silver granules. Sigh.

David, I honestly don’t have any background that helps me to
understand your comment

Nancy

Hi Nancy,

in response to your comment:

   David, I honestly don't have any background that helps me to
understand your comment 

If you have Time McCreight’s “The Complete Metalsmith”, revised
edition, then please turn to page 182 to see the Silver/Copper Phase
Diagram.

(If you don’t, may suggest that you buy one? Mine is well thumbed.
Might I also suggest Brepohl’s “The Theory & Practice of
Goldsmithing” too, if you do not have it? It’s like having personal
classroom instruction on why we do the things the way we do.)

Let’s return to our sheep.

Notice how the line is ACB is “u-shaped” with the lowest point of
the curve being 71.9% silver and the balance copper. One current
theory* states that you can fuse the granules of a
silver(>>71.9%)/copper alloy onto a sterling or fine silver sheet
without flux so long as it is done in a reducing atmosphere with
free copper because the surface of the granules will have lower
composition of silver (71.9%) and will start to melt before the
interior of granules or the sheet will, all else being equal.

My comment is about what the shape of this curve looks like for a
Silver/Germanium alloy. We know that the melting temperatures for
Silver and Germanium are 961.93deg C and 937.4deg C respectively,
not much room for a u-shaped curve that must drop down to the
solidus zone (light grey). Further, there is only approximately a
24deg C diff between the two elements. My first question is thus,
what is the shape of the liquidus curve and does that curve touch
the solidus boundary?

My next question is whether the above two criteria are both
necessary and sufficient for granulation to take place for any alloy
(reasoning from the specific to the general)?

*what I would like to see both a back-scattered electron micrgraph
and its associated energy dispersive micrograph of a cross section
of a granule fused to silver. If it is true that the copper
composition is higher on the surfaces than in the enteriors of the
granule and the substrate, both micrographs should confirm it. In
the first, the image will have a light surface and a dark interior
while the second should have many more “dots” on the surface than in
the interior when the analyzer is tuned to the Copper K alpha x-ray
fluorescence line.

No doubt that these images are around, I just don’t know where. Can
any metalurgist help?

David

ps. I used to do lots of energy dispersive x-ray fluorescence
analysis and electron microscopy in another life.

If the glue held the bead in place long enough bfor it to fuse, the
pickle would not take it off. Granulation not fused may be held on
by the flux until you out it in the pickle

Eve Welts

A browse on the Internet turned up a phase diagram for silver
germanium (albeit under microgravity conditions) at 
ingentaconnect.com/content/maney/mst/1999/00000015/00000011/art00008
This describes a well-defined eutectic at 17.6 wt%
Germanium.

Wow, and there is a whole 250deg C to play with.

So if current theory is accurate, then granulation with argentium
might be possible. I guess the task now is to find what is the best
salt or base of germanium that can be reduced to provide the
element.

David

David, I honestly don't have any background that helps me to
understand your comment

I second that! Thank goodness Nancy responded, because I was at a
loss. Thank you Nancy, for the input, I appreciate it M

PS: I spent the day in a tool making work shop—made my own
sinusoidal stakes, Great fun! Anybody know why we did not have to
retemper the Steel after bending it?.

Nancy,

I am wondering if the other materials in your germanium containing
compound along with the Batterns and Klyr-Fire just fused into a
thin glass like flux and that they then dissolved away in the pickle.
In looking at the phase diagram it would appear that you should be
able to granulate with germanium and silver. I also am wondering just
how much germanium was present in the compound you used. Most dietary
supplements don’t contain great amounts of metals as the amount of
metals needed by the body are tiny trace quantities and too much of
any of them is often poisonous. I did a quick search and found a
germanium compound, germanium dioxide that is available from
chemical suppliers. However it is quite expensive at $98 for 10
grams. You can also buy pure germanium powder but it is even more
expensive at $124 for 10 grams. However I would think you will have
greater luck in your experiments using these higher concentrations of
germanium.

James Binnion
@James_Binnion
James Binnion Metal Arts

360-756-6550

If the glue held the bead in place long enough bfor it to fuse,
the pickle would not take it off. Granulation not fused may be held
on by the flux until you out it in the pickle 

Eve,

I see your point, that is, that maybe flux was holding it together.
However, Battern’s flux doesn’t build up a glassy coat as does paste
flux, and I saw granulation type connections between the granules
with each other & the base. That’s why I thought it was a germanium
coat, but you may be right. My sister (a chemist) said I should have
tried pure germanium, not an organic compound, and that maybe that
would be a better test.

Another interesting thing to try is fine silver granules over
Argentium silver. The fine silver granules seem to fuse/alloy/solder
(?) with the Argentium base but not with each other. The bond is very
firm and does not come off in hot pickle. And, I have not been able
to poke or pry any granules off. Looks good too. Under 30x
magnification, I can see black spots on the Argentium surface under
the fine silver granules, but it doesn’t affect the overall
appearance under normal viewing. Some of the black pickles off, but
not all. Also works with sterling silver granules (but they tarnish,
so it’s not a good idea anyway), but doesn’t seem to work with gold
granules.

Nancy

    Another interesting thing to try is fine silver granules over
Argentium silver. The fine silver granules seem to
fuse/alloy/solder (?) with the Argentium base but not with each
other. Also works with sterling silver granules (but they tarnish,
so it's not a good idea anyway), but doesn't seem to work with gold
granules. 

Hi Nancy,

I’ve been watching this thread, and wondering why you are not trying
to fuse Argentium Sterling granules to Argentium Sterling sheet.
Since Argentium Sterling fuses to itself well, it seems to me that it
would likely work well for granulation.

Cynthia Eid

Since Argentium Sterling fuses to itself well, it seems to me that
it would likely work well for granulation. 

Cynthia,

At your suggestion, I tried granulation with Argentium granules on
Argentium sheet. I expected it to be the same as the exasperating
experience fusing of fine silver granules to a fine silver base.
That is, because the melting temp. is the same, I expected to have a
very small window of opportunity between not fusing and melting.
However, the Argentium granules worked very well and the window of
opportunity is quite wide in that I did not melt any granules even
when the sheet metal looked close to meltdown. I heated (torch) the
sheet until a small amount of surface melting occurs. It is not the
flash of fine silver but a slight liquid look. Also, I decided to add
more granules to already fused granules (in case one falls off can
another one be added later) and that worked very well. I also tried
granules with half sterling and half Argentium. It worked but didn’t
seem to be any different than Argentium granules (i.e., no benefit).

Less is better, in that a really good “granulation effect” is
achieved if they adhere just enough; if heated longer, metal begins
the fill in between the granules for more of a “cast look”. Even when
heated too long the result is passable but not the “floating on the
surface” look that is so beautiful in classic granulation.

Thanks for bringing this up. I hope others will try this because it
is much easier than with silver/copper granulation as well as fine
silver fusing.

Nancy