Separating Pd and Ag from Tungsten filaments

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bhaden57

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Joined
Jul 14, 2022
Messages
12
We have about 80+ lbs. of pure Tungsten filaments used to evaporate an 80( Ag )/20( Pd ) alloy.
The residue of Pd/Ag is about 3-4% by weight.

What is the best method to strip the Pd & Ag and preserving the Tungsten metal for separate recycling ?
Then , how best to separate the Pd and Ag into best purity for sale to a purchaser ?
 
We have about 80+ lbs. of pure Tungsten filaments used to evaporate an 80( Ag )/20( Pd ) alloy.
The residue of Pd/Ag is about 3-4% by weight.

What is the best method to strip the Pd & Ag and preserving the Tungsten metal for separate recycling ?
Then , how best to separate the Pd and Ag into best purity for sale to a purchaser ?
Maybe Nitric, Tungsten is quite inert in Nitric while both Pd and Ag dissolves in it.
The question is how filaments react in Nitric.
Then add some Chloride and the Silver will precipitate as Silver Chloride.
Then Cement the Pd with either Zinc or Copper.
 
Maybe Nitric, Tungsten is quite inert in Nitric while both Pd and Ag dissolves in it.
The question is how filaments react in Nitric.
Then add some Chloride and the Silver will precipitate as Silver Chloride.
Then Cement the Pd with either Zinc or Copper.
If you have a mixed solution of Silver Nitrate and Palladium Nitrate you'll get a much better separation using the Formic acid/Sodium Formate method.
 
If you have a mixed solution of Silver Nitrate and Palladium Nitrate you'll get a much better separation using the Formic acid/Sodium Formate method.
I would like to hear more about formate separating Pd and Ag during reduction. So far, I always got mixture, that is why I used AgCl drop and other variations of this approach - silver drop as halide.
It is close pH monitoring issue or there is some other factor that allows one to separate Ag and Pd ?
 
We have about 80+ lbs. of pure Tungsten filaments used to evaporate an 80( Ag )/20( Pd ) alloy.
The residue of Pd/Ag is about 3-4% by weight.

What is the best method to strip the Pd & Ag and preserving the Tungsten metal for separate recycling ?
Then , how best to separate the Pd and Ag into best purity for sale to a purchaser ?
I would try nitric acid first. Tungsten is relatively stable in nitric solution.

I used to have "scenario" where I refined mixed cut contacts from contactors/relays/switches etc... And some small portion of mixed lots was always sintered tungsten. It never dissolved (like dissolved into the solution), but after longer heating/simmering, they tend to crumble back to powder. I do not know if it was due to some binder metal just dissolving or due to tungsten itself... But it happened. I do not know how would solid tungsten behave as I never had any pure tungsten in my material - always some sintered stuff laced with Mg/Al/whatever other metal.
 
This old thread should get you started with formate reduction and the reaction will leave Palladium in solution for separate recovery.
Very informative thread, thanks a lot :)

I am quite familiar with formate reduction of Pd. I did it like myriad of times, as final method for producing 99+ Pd to be sold. Many batches over few hundred grams...

And as I am going through the lines, I now know why I always got Ag contamined Pd when some traces of Ag were present in solution... So it is the pH..

We all learn every day :) It can "imbalance" me a bit (said politely :D ) that I have done something for several years in my life and simply better pH adjustment could possibly save me several weeks of my life sitting around AgPd parting :D
 
Very informative thread, thanks a lot :)

I am quite familiar with formate reduction of Pd. I did it like myriad of times, as final method for producing 99+ Pd to be sold. Many batches over few hundred grams...

And as I am going through the lines, I now know why I always got Ag contamined Pd when some traces of Ag were present in solution... So it is the pH..

We all learn every day :) It can "imbalance" me a bit (said politely :D ) that I have done something for several years in my life and simply better pH adjustment could possibly save me several weeks of my life sitting around AgPd parting :D
You could use really tiny tweezers and an electron microscope to pick the Ag atoms out one by one... ;D
 
You could use really tiny tweezers and an electron microscope to pick the Ag atoms out one by one... ;D
I would gladly do something like this - for few minutes, then lose patience :D But I will very much like to see that under good electron microscope.
THere, it would be probably the one and only place, where having impure and contamined precipitate would be more interesting and preferable - just to observe the few atoms of silver, gold and other PGMs just sitting there :D alongside with sodium ions from tapwater.
 
I would like to hear more about formate separating Pd and Ag during reduction. So far, I always got mixture, that is why I used AgCl drop and other variations of this approach - silver drop as halide.
It is close pH monitoring issue or there is some other factor that allows one to separate Ag and Pd ?
There's a process I've used (thanks to Owltech) for taking out the Pd completely leaving pure Silver Nitrate in solution. I don't have time to find it today but I will happily find it for you. It works beautifully.
 
There's a process I've used (thanks to Owltech) for taking out the Pd completely leaving pure Silver Nitrate in solution. I don't have time to find it today but I will happily find it for you. It works beautifully.
That would be awesome :) I am not in hurry, I just want to know for the future. Since I processed significant amounts of AgPd in the past. And now, I realize, that I have done things quite wastefuly in terms of time spent around :)
 
I used to have "scenario" where I refined mixed cut contacts from contactors/relays/switches etc... And some small portion of mixed lots was always sintered tungsten. It never dissolved (like dissolved into the solution), but after longer heating/simmering, they tend to crumble back to powder. I do not know if it was due to some binder metal just dissolving or due to tungsten itself... But it happened. I do not know how would solid tungsten behave as I never had any pure tungsten in my material - always some sintered stuff laced with Mg/Al/whatever other metal.

Orvi - per the things I highlighted above - I have processed MANY kilos of the sintered tungsten type contact points - the "binder" metal in them that you are questioning should be nothing other then silver in them

So they are a "matrix" (not an alloy) of ultra fine tungsten & silver metal powders that as you say have been "sintered" (a processed of mixing the metal powders together & then applying HIGH heat & pressure to form the "sold" points)

They generally come in two types - 60/40 W/Ag or 70/30 W/Ag with the 60/40 being the more common

Having done MANY kilos of them the one & only place I have ever seen them is in "hand thrown" circuit breakers like in household electrical panels (which have very small points) as well as larger to VERY large industrial hand thrown circuit breakers (which of course have larger points in them)

They should always be processed separate from other types of points & that is because they are difficult the get "all' the silver leached out of them because as you pointed out (for the most part) the tungsten does not dissolve in nitric

Therefore - to get the nitric to leach the silver all the way out to the core (center) of the matrix you need to literally BOIL them in the nitric - the BOILING action of the nitric provides the kinetic energy needed for the nitric to "penetrate" the matrix for leaching the silver out all the way to the core of the point(s)

Depending on the size of the points &/or the size of the batch it can take anywhere form 24 hours to 48 hours of BOILING them in the nitric to insure all the silver is leached out to the core of the matrix

So because they should be processed separate from other points there are two ways to identify them

1) if they come out of hand thrown circuit breakers you can bet/count on them being the W/Ag type contact points

2) if they are de-soldered from the bus bar they are brazed to they will have some sort of "waffle" pattern on the bottom side of the point(s) - when I say "some sort" of waffle pattern I mean a rough/raised pattern on the bottom side surface of the point(s) - it can be straight lines - or raised dots - or actual squares that look like a waffle

And one more note - though for the most part tungsten will not dissolve in nitric because W/Ag points are made by sintering ultra fine metal powders & due to the BOILING in nitric "some" tungsten will actually dissolve - you will see it as a DARK blue/black ink if/when you dilute the solution - that is the result of colloidal tungsten precipitating out of solution upon dilution (somewhat like silver dissolved in AR precipitating out as silver chloride when you dilute the AR that has "some" silver dissolved in it)

For what it is worth

Kurt
 
Orvi - per the things I highlighted above - I have processed MANY kilos of the sintered tungsten type contact points - the "binder" metal in them that you are questioning should be nothing other then silver in them

So they are a "matrix" (not an alloy) of ultra fine tungsten & silver metal powders that as you say have been "sintered" (a processed of mixing the metal powders together & then applying HIGH heat & pressure to form the "sold" points)

They generally come in two types - 60/40 W/Ag or 70/30 W/Ag with the 60/40 being the more common

Having done MANY kilos of them the one & only place I have ever seen them is in "hand thrown" circuit breakers like in household electrical panels (which have very small points) as well as larger to VERY large industrial hand thrown circuit breakers (which of course have larger points in them)

They should always be processed separate from other types of points & that is because they are difficult the get "all' the silver leached out of them because as you pointed out (for the most part) the tungsten does not dissolve in nitric

Therefore - to get the nitric to leach the silver all the way out to the core (center) of the matrix you need to literally BOIL them in the nitric - the BOILING action of the nitric provides the kinetic energy needed for the nitric to "penetrate" the matrix for leaching the silver out all the way to the core of the point(s)

Depending on the size of the points &/or the size of the batch it can take anywhere form 24 hours to 48 hours of BOILING them in the nitric to insure all the silver is leached out to the core of the matrix

So because they should be processed separate from other points there are two ways to identify them

1) if they come out of hand thrown circuit breakers you can bet/count on them being the W/Ag type contact points

2) if they are de-soldered from the bus bar they are brazed to they will have some sort of "waffle" pattern on the bottom side of the point(s) - when I say "some sort" of waffle pattern I mean a rough/raised pattern on the bottom side surface of the point(s) - it can be straight lines - or raised dots - or actual squares that look like a waffle

And one more note - though for the most part tungsten will not dissolve in nitric because W/Ag points are made by sintering ultra fine metal powders & due to the BOILING in nitric "some" tungsten will actually dissolve - you will see it as a DARK blue/black ink if/when you dilute the solution - that is the result of colloidal tungsten precipitating out of solution upon dilution (somewhat like silver dissolved in AR precipitating out as silver chloride when you dilute the AR that has "some" silver dissolved in it)

For what it is worth

Kurt
Yup, I know what you are talking about.

And also that "waffle" pattern is very common. However I also encountered some sintered tungsten, which only shown W on XRF. There certainly wasn´t any silver in some, that is why I wrote about this experience.

There can be a significant difference in typical breaker materials compositions between US products and late-Soviet era or post-Soviet goods in former USSR countries :) Here, the material for practically 90% of all points for high current switching devices (breakers, switches, emergency switches, relays...) was AgC or AgCd. Later in time (90´s and later), sintered points started to be more common (mainly magnetic Ag ones, sintered with W/Ni/C whatever).

As older buildings were reconstructed or demolished, significant influx of this scrap came to the refiners - as many people were "instructed" by us and set this type of escrap aside in local scrapyards and such :) Also, many industrial premises and production facilities are refurbished with new electrical lines and equipment, resulting in quite a bit of this "breaker/switch" escrap to be available. Regular "Joe´s" are after copper wires and usually leave the breakers be :) Some dismantle the large ones, but usually only take copper from them, leaving silver+brass aside.

I know that tungsten holds relatively well in nitric, but it it etched in AR. Due to high silver content, iodine/iodide won´t be the best way to process these filaments - despite the fact that tungsten is virtually intact by this leaching mixture. Otherwise, this will be the first method I will recommend :)

So, we need somebody to take pure solid piece of tungsten and simmer it in 50 % nitric :D to tell us what happened.

But if I was him, I will take few hundred grams (if he supposedly have 80+ pounds) and leach in nitric. This should be straightforward and quick. And result should be obvious. Reduce everything down with ascorbic acid + base and you have metal powder ready to be melted within hour or two. Since there would be only metals of interest you can overshoot base quite a bit without any issues - it will just speed up the reduction.
 
We have about 80+ lbs. of pure Tungsten filaments used to evaporate an 80( Ag )/20( Pd ) alloy.
The residue of Pd/Ag is about 3-4% by weight.

What is the best method to strip the Pd & Ag and preserving the Tungsten metal for separate recycling ?

If the Ag/Pd is just a surface coating on the W then a nitric leach will remove the Ag/Pd without effecting the W
Then , how best to separate the Pd and Ag into best purity for sale to a purchaser ?

There are a number of ways to do this (from the Ag/Pd nitric dissolved solution)

1) drop the silver as silver chloride & then wash (very well) the dissolved Pd out of the silver chloride & then precipitate the Pd by any of the many different methods of Pd precipitation - my personal preference here would be to (1) cement the Pd with copper - or (2) drop the Pd with DMG & the reduce the DMG/Pd salt by ion exchange with HCl & zinc - (3) would be formic acid reduction - which is a bit of a pain in the butt as you need to get Ph control "just right" as well as time & temp just right for the reduction to take place - so a bit more learning curve here

The problem with this one is trying to wash all the dissolve Pd out of A LOT of silver chloride - which will likely result in a VERY dilute Pd solution that will likely need being evaporated down before going for Pd recovery - you will need DMG for testing to know when you have all the Pd washed out of the silver chloride

2) or you can drop the Pd first with DMG & then wash the silver nitrate out of the precipitated Pd/DMG salt - basically the same as above only going for the Pd first instead of the silver first

3) or as others have posted the sodium formic acid process - but this requires getting the chemistry (Ph/time/temp etc.) "just right"

For what it is worth - I have done all 3 of the above methods & as a personal preference I would likely go with option #2

Kurt
 
There can be a significant difference in typical breaker materials compositions between US products and late-Soviet era or post-Soviet goods in former USSR countries

I sometime forget that you are over there in one of the "old" Soviet block countries so forget that indeed you get to see some stuff that is quite different then what we see over here in the USA :D ;);)

Kurt
 
There's a process I've used (thanks to Owltech) for taking out the Pd completely leaving pure Silver Nitrate in solution. I don't have time to find it today but I will happily find it for you. It works beautifully.

Yes - Owltech has done a very good video on this - which is where I learned it - likewise I just don't have time to find it & post it right now

Kurt
 
This video is only to recover metallic Silver from silver nitrate solution. One could remove dissolved Palladium first using a Dimethylglyoxime process followed by either this process or others depending on how pure you want your Silver.
I did not take the time to watch it, just did a quick google search.
There were others from Owltech.
My point is that they should be easy to find.
 

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