Whats the crud on bottom of AP bucket?

Here's a pic of the bottom crud in my AP bucket.
I'm trying to run the bucket reaction for as long as it keeps working. Several pounds boards and fingers have run through it.

Now running air pump this crud is showing up more, last 2 clean/rinse outs.
Couple questions would be:
Is this stuff something to do with the copper chloride 1 and 2?
Is the copper content becoming saturated?
What about the nickel plate over copper, where does that go?
Does it matter, meaning does this effect my balance ability of the etch solution?

Checking the cards closely I have sprayed this crud off both sides of card surfaces, somehow it chooses to build on cards with less circulation in the bucket.
Also interesting is it appears to build-up right on top of the gold plate, is that normal?

Also some of the thicker foil traces still look like they have copper attached to them.
This is causing a longer time HCl prewash, of the foils.
Guess it doesn't matter because the foils need to be real clean anyways from copper.
Still the way I'm doing this, not that its time consuming but its taking a long time. I'm acid soaking and allowing 24hrs inbetween rinses.
The pile in the large glass measuring cup is growing considerably as I keep adding foil to it when I rinse more out of the bucket.

As long as I'm pulling green color out from the foils I guess its okay to keep rinsing in HCl?

Adam meet copper I chloride.

Just joking of course, that is copper I chloride and is a very good indication that your solution is saturated and does not contain any dissolved gold. It is easily converted to good copper II chloride with HCl and oxygen. First wash it out of the foils with HCl, then allow to absorb O2 from the air or via a bubbler and you have a fresh AP solution ready to digest more copper.

All of the other details that you mention are perfectly normal.

Steve

Well there it is, instant copper chloride 1 into HCl.
Thanks Steve, I would have been messing with this wasting rinse and filters.
Now I can pour/drip this out and throw it back in the AP bucket.

lazersteve said:

Adam meet copper I chloride.

Just joking of course, that is copper I chloride and is a very good indication that your solution is saturated and does not contain any dissolved gold. It is easily converted to good copper II chloride with HCl and oxygen. First wash it out of the foils with HCl, then allow to absorb O2 from the air or via a bubbler and you have a fresh AP solution ready to digest more copper.

All of the other details that you mention are perfectly normal.

Steve

Click to expand...

Wow did I sort of goof somewhere?

Cleaned out the bucket and added the little bit foils to my foil container.
The foil container sits with HCl in it slowly trying to absorb remainder copper in it.
After the last add and pour some fresh HCl was put in.

Checking and looking at foils I had a bothersome couple foils I've been looking at. I say that because I look at the bottom of the foil and see a off color. Not shiny gold but more tan like.
Been saying to myself that it was still copper maybe attached to that foil, but through many acid baths I could not touch it. (strange).

So here is the goof, but not a bad one.
Lets say maybe a full cup of acid is in the foil container, because of the very few pieces of odd tan color on some foil I decide to add a pinch of hydrogen peroxide to simulate AP. Sounded good to me.
Did it last night, maybe 1oz or less H2O2 was added to HCl.
Looked at it this morning and I was looking at maybe 1/2 of my foils and about 6 small places on the surface that were creating a tiny bubble reaction.
In with the stannous and wow! I'm taking gold into the AP I thought I was simulating.
So finished up the rest of the foils in chlorox.
Funny, just a splash of clorox and instantaneous poof. Auric chloride. No messing around with this batch.

Why did this slight AP react on my foils?
I know the foils were very clean from copper, but I was still working on this cleaning.

These are very normal observations you are having. Muriatic acid and hydrogen peroxide will dissolve gold, especially well when there are no base Metals present (like copper).

Here's a chart you may have seen before :



This is one reason why you need to be careful when using peroxide to rejuvenate your acid peroxide. The acid peroxide reaction with copper chloride should really be called the copper II chloride process, not the acid peroxide process. This is because the active etchant for the copper is the copper II chloirde, the acid and peroxide is an initiator for the reaction.

Steve

I did the same thing awhile back, thinking since they have been sitting in a/p anyway what would it hurt?
I was wrong but as it is said here "the gold is still there" so I was told to drop with copper in the solution and it worked.
I have learned to just follow steve's directions.

Wow Steve, if I could only understand chemistry better it would help a little.
Okay I see what you said about no base metals present then the A&P can disolve the gold.
Yes my buckets full of copper I&II so a little peroxide in there won't pull an effect on the gold foil.

Really hope you don't mind answering these trivial questions I ask, but your input is very helpfull.
I'm hoping after a while of looking at the chemical formula's that I eventually pick-up some understanding of the process.
Also its good for me to move along very slowly playing with this stuff so I can see the reactions its having.

Here's a wash cycle I do:
The cards and fingers I'm processing. Notice the one card at top. I'm wiping the cards off because that card at top was full of copper I all over its surface.
The reaction has slowed a bit, this batch ran near 2 days before the wash-out to gather foils.
I have noticed there was probably a excellent balance in my bucket a few days ago when it was etching real well for a couple wash/rinse outs.
It seems the reaction has slightly slowed and its making me wonder more about taking measurements of the specific gravity of the etch.
Something I have to get into.
Bucket on lower left is simple surface rinse of cards and hole/bucket.
Bucket on right is hand rub rinse of card material.

Why the color change?

lazersteve said:

These are very normal observations you are having. Muriatic acid and hydrogen peroxide will dissolve gold, especially well when there are no base Metals present (like copper).

Here's a chart you may have seen before :

This is one reason why you need to be careful when using peroxide to rejuvenate your acid peroxide. The acid peroxide reaction with copper chloride should really be called the copper II chloride process, not the acid peroxide process. This is because the active etchant for the copper is the copper II chloirde, the acid and peroxide is an initiator for the reaction.

Steve

Click to expand...

Copper I chloride is not soluble in water and makes a white cloud (left bucket).

Bucket on the the right contains some iron (red-brown color).


Don't add any peroxide to solid copper I chloride and gold foils, only peroxide to solutions containing copper chlorides.

Check my posts in these threads:

Acid Peroxide Help

and details of the chart abbreviations for the chemically challenged (just kidding):

Chart Abbreviations

Steve

Thank you much plenty Steve, your awesome! :mrgreen:

Now I was kind of wondering why Pins give a nice yellow/tan color powder and foils give a rich yellow/coffee color?

Don't worry chemically challenged is an understatement, taken all with humor. :lol:

lazersteve said:

Adam meet copper I chloride.

Just joking of course, that is copper I chloride and is a very good indication that your solution is saturated and does not contain any dissolved gold. It is easily converted to good copper II chloride with HCl and oxygen. First wash it out of the foils with HCl, then allow to absorb O2 from the air or via a bubbler and you have a fresh AP solution ready to digest more copper.

All of the other details that you mention are perfectly normal.

Steve

Click to expand...

lol... EVERY time I run a batch of fingers I deal with this crap, which always begins to appear as soon as I introduce water into the coffee filter to rinse the foils. Next thing I know my foils are engulfed in a rich layer of this powdery cloud in water, which once I've siphoned off the water will force me to pour off as much of this milky cloud as I can without losing any of the gold (which I've determined isn't possible, as micro fine particles of gold saturate the entire cloud layer), then save that in one container, while transporting the remainder of the cloudy water containing the foils in another container that's sealed so that the water won't evaporate and trap the foils in a white gelatin that's hard to free the foils from.

So... what I gather here Steve is all that I have to do to rid my foils of this substance is take my foils and the wash, add hcl and insert the bubbler, and the copper chloride 1 will disappear, leaving my gold free from this mess and sitting in clear water?

As for my acid peroxide solution itself, while evidently is over saturated with copper and thus the cause of this mess, just add a bit of hcl and the bubbler to it by itself as well, and this will balance out the over saturation issue?

My storage container used to store the solution has developed a white film on it as well... I'm to assume it's the same CuCl as well? So I should use the actual storage container to perform the above solution purge and the film should disappear too?

As always you've provided valuable information to things that have directly affected my operations Steve... and for that I once again thank you!

Slightly different procedure. This is just solution decanted after cycles of washing gold precipitate. I've got one dry batch of decent brown powder and one batch of brown powder with gold looking flakes.

Keep in mind this is two complete cycles of h2o hcl h2o ammonia h2o hcl and h2o...

My gold starts off as black black powder. I was going to make stannous chloride this evening but ran out of daylight.

Should I try to refine this gunk I it's own batch of hcl CL? I thought about dropping a 1982 penny in it to see if it was cemented AG. I started keeping all the decanted solution because I thought it had accumulated floating black gold... But I'm pretty sure all the good gold settles to the bottom quite nicely. The only reason I think it might be AG is because it doesn't appear until after the ammonia washes and I'm sure that it's highly contaminated with copper.

I could figure this stannous chloride but figured I'd bug ya'll and learn something from a conversation.

Hi there. I'm sorry I don't have any direct input on your post at the moment, but I would like to encourage you to pay more attention to the chemical symbols you are using - these details are more important than you may think. Capital and lowercase letters and subscripts have very specific meanings. They are not a matter of convention or convenience. I've included the correct use of a few examples below.

H2O
Ag
HCl
And if you want to abbreviate this one: HCl-Cl or HCl/Cl

Good luck,
Matt H

I have only put Peroxide in my AP once. To get the reaction started and that was only a little bit, maybe 2 table spoons.

When the white/ green appeared, I added a little more HCL. Now I just save a little of my AP when I start another batch.
This way, I don't dissolve any gold.

When I extract foils, I pour off as much liquid as possible. Then put the remains into a tall beer glass. Has a cone shape on the bottom.
I let settle with more HCL which also dissolves any more copper. Pour off and add more HCL and let settle. I do twice which seems enough to get clear solution. Then fill glass with water,(H2O), Settle and repeat maybe 3x. This will remove all acid and/or color.

After this, I swirl water with stirrer and let the larger flakes settle and then pout off as much as I can. 2-3x doing this gets larger flakes nice and clean to go in my "show" bottle. Looks pretty.

Then I will do washes on the sentiment several times as described here somewhere. What is left from the rinses will go into HCL+ Bleach I use to dissolve gold trim from glassware. When the solution stops dissolve from glassware, I let said material soak in it overnight. This helps to ready HCL+ bleach for dropping gold.

I'm not too concerned with yields so I'm dissolving gold from 2 sources.

Now every "spent" solution I get goes into a settling Glass. Artsy stores sell cylindrical glass vases which are great to let solutions sit for settling of material. I don't filter much at all this way as any PM will settle with time.

Then solutions are poured off into my Stock pot waste system. PMs removed if present, then copper, then on to dropping and rendering, and neutralizing of liquids for safe disposal as described in waste management section.

Hope something here helps someone.

B.S.

Clneal2003 said:

Should I try to refine this gunk I it's own batch of hcl CL?

Click to expand...

Yes.

Clneal2003 said:

I thought about dropping a 1982 penny in it to see if it was cemented AG.

Click to expand...

No need to check for Ag dissolved in AP solutions as the chlorides in the acid would have already converted it into a solid which would end up in your filter paper. An exception is if your solution is relatively free of base metals (eg: second refining) and highly acidic with muriatic acid, you will have a very slight amount (mg) of dissolved AgCl in solution. This can be removed with proper cooling with ice cubes before proper filtration.

Clneal2003 said:

... The only reason I think it might be AG is because it doesn't appear until after the ammonia washes and I'm sure that it's highly contaminated with copper.

Click to expand...

Copper compounds should dissolve in ammonia hydroxide (blue solution). AgCl dissolves in ammonia, but not to rapidly, a little heat helps it along. It's is not advisable to add ammonia to your processes if at all possible. The compounds formed with metals and ammonia tend to be explosive, especially in basic medium after sitting for a day or so. Additionally, the waste liquid is much more difficult to deal with. Two refining cycles with proper cooling and filtration between will effectively remove your trace AgCl.

Copper compounds are soluble in HCl as mentioned above. This is the best way (in my humble opinion) to remove copper compounds. Copper metal would require fresh AP to be formed, or to be removed in the second (or third if very heavily contaminated) refining with proper cooling and filtration.

Steve

Pantherlikher said:

I have only put Peroxide in my AP once. To get the reaction started and that was only a little bit, maybe 2 table spoons.

When the white/ green appeared, I added a little more HCL. Now I just save a little of my AP when I start another batch.
This way, I don't dissolve any gold.
...
Hope something here helps someone.

B.S.

Click to expand...

Tip of the week! In a yeast / breadmaking analogy, this is like keeping "mother" AP for new batches.