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Sodium persulfate Etching

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uzzors2k
Thu Jun 18 2009, 06:26PM Print
uzzors2k Registered Member #95 Joined: Thu Feb 09 2006, 04:57PM
Location: Norway
Posts: 1308
I'm a about to make a PCB for the first-time (!) using the photoresist method. I've got everything I need but just want a few tips on the use of sodium persulfate for etching.

Question #1: How well does it keep in storage? On the bag it says a used but not exhausted solution can be stored and reheated later before use. I seem to remember reading that it decomposes in just a few weeks after being dissolved in water however. So should I mix it all up at once or just make little batches for each PCB I do?

Question #2: Reusabilty? I read here Link2 that some guy uses electrolysis to revitalize an exhausted sodium persulfate solution. Is it feasable, and/or are there other methods for recycling sodium persulfate?
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MinorityCarrier
Fri Jun 19 2009, 05:25AM
MinorityCarrier Registered Member #2123 Joined: Sat May 16 2009, 03:10AM
Location: Bend, Oregon
Posts: 312
You might want to check out the Material Safety Data Sheets (MSDS) for sodium persulfate. They will provide some information on decomposition.
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uzzors2k
Fri Jun 19 2009, 07:53AM
uzzors2k Registered Member #95 Joined: Thu Feb 09 2006, 04:57PM
Location: Norway
Posts: 1308
I did, but it just gives vague hints about it. Like:

Stability:
Unstable. Gradually decomposes losing oxygen. Decomposes more rapidly at higher temperatures. Stability decreases in the presence of moisture.
Which is great to know, but just how quickly does it decompose when dissolved in water?
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Proud Mary
Fri Jun 19 2009, 08:23AM
Proud Mary Registered Member #543 Joined: Tue Feb 20 2007, 04:26PM
Location: UK
Posts: 4992
Yes, how stable is 'unstable?" I'd make up a fresh solution for each occasion - so much work is involved before you get to etching that it would be a shame to spoil it by using spent chemicals.

But best to wait until find someone who has actually used the sodium salt. My own experience is only with ammonium persulphate, and, of course, ferric chloride.
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uzzors2k
Mon Mar 01 2010, 05:18PM
uzzors2k Registered Member #95 Joined: Thu Feb 09 2006, 04:57PM
Location: Norway
Posts: 1308
It's been 9 months and 7 or 8 PCBs later and my solution is starting to get weak. It's really blue, so I'm assuming it's nearly exhausted, and now the time has come for either a new solution or regenerating it. (For those interested, Sodium persulfate works great for ecthing.) Now can someone just check to see if this is feasible, or more importantly if it's completely retarded? If it's plausible I'll try it, but I don't want to go to all the trouble of acquiring platnium electrodes and what not, just to fail when someone here knew it was doomed from the start.

Mr. babui2008 claims:

I have got a way to recycle and reuse persulfate-type copper etchant infinitely. Its an electochemical setup that will cost you a lot when you set it up for the first time. But it does not require any kind of maintainence. You dont have to add any chemicals later. You can reuse the same solution forever.

THEORY : First, I will discuss the theoritical principles involved.

sodium/ammonium persulfate (Na2S2O8 / (NH3)2S2O8) etches copper in the following way :-

Na2S2O8(aq) + Cu(s) ----> Na2SO4(aq) + CuSO4(aq)

The electrochemical mechanism reverses this in the following way :-

CuSO4 ---> (Cu)2+ + (SO4)2-

At cathode (-ve electrode) :

(Cu)2+ + 2e ---> Cu (copper gets deposited on the electrode itself, thus removing copper ions from the solution)

At anode (+ve electrode) :

2 (SO4)2- ---> (S2O8)2- + 2e

Thus the persulfate ions ,ie. the primary oxidiser, is regenerated from the sulfate ions.

REQUIREMENTS : You will need the following components to set up your etching apparatus.

1) a platinum electrode (1 pcs) for the anode : This will be the most expensive component in the whole apparatus. Also note, there are two varieties of Pt electrodes. A) The platinized platium electrode , which is black or grey in colour because it is coated with Platinum Black (an allotrope of platinum), and, B) The shiny platinum electrode, without the coating, which has a shiny silver-like appearance. You are supposed to use the shiny-type Pt electrode. The black one won't work.
2) a copper electrode for the cathode : you may use a length of a copper wire (after striping off the insulation) or a spare bit of copperclad pcb. Make sure this electrode has a large surface area.
3) a glass/plastic container to hold the solution and act as your etching tray
4) sodium persulfate (Na2S2O8) : Alternatively, sodium sulfate (Na2SO4) may be used to begin with and sodium persulfate can be generated from that by electrolysis.
5) a little bit of conc. sulfuric acid (H2SO4) to lower the pH a bit : an acidified solution helps to speed up the etchant-regeneration process.
6) water : ordinary tap water would do but distilled water is better.
7) Power Supply - a mechanism to supply a lot of current (about 5-10 Amps) at controlled voltages to the electrodes : A simple 9-volt battery with a potentiometer might do. But a 9-volt battery can't supply sufficient amount of current. So the regeneration process may be too slow to be acceptable. A better way is to draw the power from the house-electric supply. Use a 12-volt DC wall transformer/adapter to get a 12V DC source of current. Then prepare a custom voltage-regulation circuit that uses the 12V DC output and can provide 5-10 Amps at a voltage that you can control precisely.
(Note : the required output voltages are typically between 0.5V to 4.5V DC with a control precision of atleast 0.1V)
8) You can also add an agitator mechanism (aquarium pump) and a heater mechanism (immersion heater / aquarium thermostat) to the apparatus to speed up the etching process.

SETUP THE APPARATUS :-

Prepare a sodium persulfate solution at a concentration of 230 gram/litre. If you are starting with sodium sulfate instead of sodium persulfate, mix at a concentration of 460 gram/litre. Add to it about 10 ml of conc. sulfuric acid per litre of the solution. Your etching solution is ready.

Now pour your etching solution in your etching tray and drop the electrodes in it. (the copper electrode is supposed to be the cathode (-ve) and the platinum electrode is to be anode(+ve). Make sure you connect them correctly.)

Now, if you mixed your solution with sodium persulfate, you are ready to go. But if you used sodium sulfate, you need to run a current through the solution so that sodium persulfate can be generated within the solution. Calibrate the voltage of the regulator and let the current run for some time (about one hour). (The voltage calibration process is being given below, as a part of the etching process.)

THE ETCHING PROCESS :-

Drop the pcb, which is to be etched, in the solution and start a current in the circuit.

Then you need to adjust the potentiometer or the v-reg to supply the correct voltage.
The goal would be to set the voltage as large as possible but just short of when a vigourous bubbling starts at the platinum anode.

(Note, if you are are using an aquarium air-pump to agitate the solution, you must turn it off during this voltage calibration process. Otherwise you wont be able to distinguish the bubbling at the anode. After calibration, you can turn on the pump and leave the apparatus to etch your pcb.)

Ideally, You must begin with a voltage as low as possible and increase the voltage until you can see a lot of bubbling at the anode. Once you find the threshold point, you must set the voltage to slightly less that.

POST-PROCESSING OF ETCHANT SOLUTION :-

After etching is completed, remove the pcb from the solution and let the current run for some more time. This will allow all copper ions dissolved in the solution to get deposited on the cathode and clean-up the solution. (It is easy to detect presence of copper ions in the solution. Copper ions impart a blue colour to the solution. So wait till the blue colour fades away)

After this process completes, you must remove both the electrodes from the solution before you remove power from the electrodes. If you remove power from the electrodes while they are in the solution, the cathode which is made of copper, turns into an ordinary copper rod, and the etchant immediately starts eating away copper from the electrode. So if you leave the cathode in the solution without power supply, the etchant will essentially get used up and you will need to regenerate it again before you can use it.
Note that, although the solution doesn't react with the platinum electrode, but if left in it for a long time, it can corrode the suface. And you don't want the most expensive part of your etching apparatus destroyed.

Best of Luck with your new etching system

Is his chemistry sound? Bored Chemist? Chris?
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Bored Chemist
Mon Mar 01 2010, 07:56PM
Bored Chemist Registered Member #193 Joined: Fri Feb 17 2006, 07:04AM
Location: sheffield
Posts: 1022
It might sort-of-work but the yield of persulphate from sulphate is poor. To get it to work well you need to keep the solution ice cold and run at a high current density.
The official method for making persulphate uses the potassium salt because potassium persulphate isn't very soluble. It falls out of solution. If it's not removed in this way it will diffuse to the cathode and be reduced back to sulphate again.
Frankly I'd not bother- the stuff isn't that expensive.
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ragnar
Tue Mar 02 2010, 01:30PM
ragnar Registered Member #63 Joined: Thu Feb 09 2006, 06:18AM
Location:
Posts: 1425
Uzzors wrote ...

Question #1: How well does it keep in storage? On the bag it says a used but not exhausted solution can be stored and reheated later before use. I seem to remember reading that it decomposes in just a few weeks after being dissolved in water however. So should I mix it all up at once or just make little batches for each PCB I do?
Make up little batches for each PCB. It decomposes slower than ammonium persulphate, but you should be more concerned about the rate at which it is consumed by the copper.

By making up minute quantities of solution, you circumvent any storage problems and you can quickly and completely exhaust each small batch of solution on the circuit board you're etching.

Uzzors wrote ...

Question #2: Reusabilty? I read here Link2 that some guy uses electrolysis to revitalize an exhausted sodium persulfate solution. Is it feasable, and/or are there other methods for recycling sodium persulfate?
In a word, don't. It might be feasible, but the quantities you're using should be small enough that you won't need a new jar very often at all. If it's anything like ammonium persulphate, one generously heaped teaspoon can dissolve about 8sqin of 0.5oz/sqft copper.

For best results I like to etch at 100C by heating water to boiling point in a nonreactive vessel, turning down the gas to a simmer, and then adding the persulphate. Flip the PCB after 30 seconds.

Choose a pot-plant you don't like for the expended solution and you can worry about proper disposal of the copper compounds when the soil is saturated and you have a whole batch.
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uzzors2k
Wed Mar 03 2010, 06:54PM
uzzors2k Registered Member #95 Joined: Thu Feb 09 2006, 04:57PM
Location: Norway
Posts: 1308
Thanks for the insight guys. I had forgotten how little the sodium persulphate cost, so I'll just buy a new batch, or maybe try cupric chloride. As for disposal our community provides red "hazmat" boxes for anything that shouldn't go in with the regular waste. Batteries, paint, electronics, spent fuel rods, etc. These are collected biannually IIRC. I'll just let the water evaporate off, mark the crystals, and hope the guys on the other end know how to dispose of it.
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Bored Chemist
Wed Mar 03 2010, 09:16PM
Bored Chemist Registered Member #193 Joined: Fri Feb 17 2006, 07:04AM
Location: sheffield
Posts: 1022
Just a thought, one way that persulphate decomposes is to give oxygen gas. You don't want that in a sealed container.
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uzzors2k
Fri Mar 05 2010, 03:46PM
uzzors2k Registered Member #95 Joined: Thu Feb 09 2006, 04:57PM
Location: Norway
Posts: 1308
I forgot about that during the summer holidays last year. Summer heat + sealed plastic motor oil bottle + 30 days. When I came home the bottle had puffed up like a balloon, but not leaked. Had I used glass things wound have been real ugly.
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