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Author: Subject: Selective Dissolution of Copper and Manganese metals
elementcollector1
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[*] posted on 22-11-2012 at 13:29
Selective Dissolution of Copper and Manganese metals


I have a copper PCB, plated on both sides with a tiny amount of manganese metal. Because copper is so much less reactive than manganese under almost any circumstances, I needed something that can selectively dissolve copper. I tried ammonium nitrate, hoping for the ammonia complex, and it works, however slowly. The manganese, however, seems to be oxidising as well.
Does anyone have thoughts on a better method of separating these two metals (with the goal of leaving the manganese metal untouched)?
Pics as soon as I can get them.




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elementcollector1
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[*] posted on 22-11-2012 at 14:59


Here are some pics (attached):
The first one is showing the copper electrode in the ammonium nitrate solution.
The second shows the manganese plating cell, with copper cathode, MnCl2 aqueous catholyte, vinegar/water/MnCl2 mix anolyte, and lead-tin solder anode (the last two are not visible).
Unfortunately, it seems as if most of the manganese had oxidized to useless MnO2, rendering a need for another plating.




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weiming1998
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[*] posted on 23-11-2012 at 05:11


Maybe immerse the PCB in ammonia solution, then bubble oxygen through? That's the only way I could think of without the manganese becoming oxidized.
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blogfast25
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[*] posted on 23-11-2012 at 06:01


Quote: Originally posted by weiming1998  
Maybe immerse the PCB in ammonia solution, then bubble oxygen through? That's the only way I could think of without the manganese becoming oxidized.


Freshly prepared manganese is apparently reactive enough to react with water (I've actually seen this happen). EC1 is trying to dissolve the less reactive metal (Cu) while leaving the very reactive one (Mn) untouched: that's a bit of a tall order...



[Edited on 23-11-2012 by blogfast25]




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AJKOER
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[*] posted on 23-11-2012 at 14:39


OK, try melting in an inert gas/vacuum.

Cu melts at 1,085 C.

Mn melts at 1,246 C.

May be workable, perhaps using a butane torch whose flame temperature is around 1,300 C in air (which can be lowered by increasing the nitrogen content of the air intake).


[Edited on 23-11-2012 by AJKOER]
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[*] posted on 23-11-2012 at 15:04


Are you sure you can't rather separate out the manganese from the copper once both are dissolved? I don't think you can pull this off without oxidising the manganese at least to some extent, no matter what method is used. If both the copper and manganese are dissolved, you can simply precipitate them according to their reduction potentials.



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watson.fawkes
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[*] posted on 23-11-2012 at 16:22


Quote: Originally posted by elementcollector1  
Does anyone have thoughts on a better method of separating these two metals (with the goal of leaving the manganese metal untouched)?
I can't tell what the real goal is. Are you trying to use the manganese metal as a kind of resist for removal of the non-masked copper? Or what?
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elementcollector1
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[*] posted on 23-11-2012 at 17:32


The real goal is the isolation of the thin manganese plate.



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blogfast25
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[*] posted on 24-11-2012 at 07:17


As per this source:

http://www.americanmanganeseinc.com/wp-content/uploads/2011/...

“Using typical commercial electrowinning conditions, a sheet of manganese metal was
plated over a 24 hour period at a current efficiency of up to 67%. This represents
typical commercial performance.”


A stainless steel 316 cathode was used (see p.68)




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watson.fawkes
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[*] posted on 24-11-2012 at 07:33


Quote: Originally posted by elementcollector1  
The real goal is the isolation of the thin manganese plate.
Given the dimensions, I'd call it a foil rather than a plate.

Given what you've said, I'm quite pessimistic about the prospects of recovering an intact foil from your current piece. If there were a solvent-reagent that had a very high differential etch rate for copper over manganese, you might have a hope, and even then, getting a liquid in and out of a thin film between the foil and the substrate seems hard. Getting a manganese foil seems realistic, though, just not with this method.

The biggest chemical problem you've got is that anything that will oxidize a metal plating substrate is likely to oxidize manganese. So you need a different conductive substrate, one that doesn't need to be oxidized for removal. What comes immediately to mind is a conductive lacquer. Take a solvent-based lacquer and load it with graphite. Apply it to your mechanical substrate and let it dry. Dissolve it out with lacquer thinner (or any other handy organic solvent) when you're done. For a substrate, I'd recommend mylar or polyethylene film, something that's unreactive in the plating bath, flexible, and inexpensive.
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blogfast25
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[*] posted on 24-11-2012 at 09:50


Or perhaps something much simpler: use a manganese sheet or film as cathode (substrate) in the manganese electrowinning process. That may present some problems too but from a development starting point it's quite promising, I think.



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[*] posted on 25-11-2012 at 13:34


You can't just peel it off? Try stainless or titanium instead, few things adhere to these readily.

Tim




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[*] posted on 26-11-2012 at 07:05


Myst32YT on Youtube posted a very interesting video some time ago about chemically removing the copper shell from a penny. He found a mixture that would react with the copper plating but not with the zinc core. A pretty impressive achievement in my opinion, because zinc is usually so much more reactive. Since Mn is very close to zinc on the activity series, you might consider giving this a try! Here's the link: http://www.youtube.com/watch?v=jRiBYMv6Tz4
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elementcollector1
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[*] posted on 26-11-2012 at 11:12


That might be something to try, as soon as I get my hands on powdered sulfur. Furthermore, if that works and I get a very thin Mn sheet as the product, I could follow up on blogfast's suggestion to use Mn itself as the cathode for the electrolytic cell.




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[*] posted on 27-11-2012 at 11:35


I rewatched the video, and frankly I'm a bit worried about his cleanup procedure. I would have to very carefully remove the manganese (because it's on the surface) from the plate, or figure out some other method of breaking such a potentially fragile item.



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