Stop Using Ferric Chloride Etchant! (A Better Etching Solution.)
by The Real Elliot in Workshop > Science
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Stop Using Ferric Chloride Etchant! (A Better Etching Solution.)
Wouldn't it be nice if there were an etchant that you could re-use indefinitely so that you don't have to worry about disposing of the copper, and that could be made in lifetime supply for like $10.00 with ingredients bought at hardware and drugstores? (And it's prettier too.)
I got seven words for you: Copper Chloride in Aqueous Hydrochloric Acid Solution! (Exclamation point!)
But how're you going to get CCiAHAS? Conveniently enough, by starting out with a simple two-ingredient starter etchant, and doing a bunch of etching.
Ingredients: the Starter Etchant
(OK, actually three. But the third one's copper. See the chemistry section for an explanation.)
Hydrochloric (muriatic acid, "pool acid", etc.) is available at a hardware store. The acid I got is 31.45% (or 10M) and should run around $5 per gallon. Which is more than you'll ever, ever need.
The peroxide is normal 3% for mouthwash or cleaning cuts, and can be bought at a drug store for $2-3 for a big bottle.
You'll also need a non-metallic container that fits your PCB and two standardized measuring cups.
As long as you're in the hardware store, pick up some acetone if you don't already have some. It's useful for removing the etch resist. (That's for another instructable.)
Put the Lime in the Coconut...
Measure out one quantity of hydrochloric acid and pour it in. ("Do like you oughta, add acid to water" to minimize the chance of an out-of-control exothermic reaction.)
Be careful with the acid. This stuff (at 10 molar) is strong. Mine fumed a bit when I took the cap off. Don't breathe it directly, and be sure you've opened the kitchen window.
The starter etchant you've just made, on the other hand, is not so bad -- around 3M HCl with a medium-strong oxidizer. I find it doesn't fume much at room temperature when I'm re-using a batch.
That said, you've got to be very careful to keep it away from metal -- especially your stainless-steel kitchen sink. It'll eat the stainless coating right off. Keep plenty of water flowing at all times when you've got any of this (even a drop) near the sink.
Add PCB and You're Etching.
If this is the first time you're using this batch of solution (and I presume it is), it'll etch super-fast. This small board took only 2 minutes. Yikes!
Since I use a deep container, I tend to swirl it around as it etches. This stuff is so active, though, that I'm not sure it's necessary.
Keep the window open for ventilation because the starter solution gives off a little chlorine gas. (The end-etchant gives off much, much less.)
Also, note how the etchant gets greener over time as it eats away the copper. This is good news.
What's happening is that you're dissolving the copper from the board and turning it into cupric chloride. In the long-run, the cupric chloride will be doing most of the etching (instead of requiring disposal). For now, just watch your solution turn light green. Next time you use it, the color will deepen.
Chemistry Break
(Note: I'm an economist, not a chemist. Please leave a comment if you've got any corrections and/or additions to this stuff!)
I stumbled on this idea when I saw this website: Etching with Air Regenerated Acid Cupric Chloride by Adam Sechelle. Cupric chloride can be re-used indefinately by topping up the acid levels and adding oxygen (bubbled in from the atmosphere). Sounds cheap and environmentally friendly to boot.
The website's got a lot of good chemistry info on cupric chloride etching. His data on etching speeds is great, and his simple titration procedure for maintaining the acidity of the solution is pretty nice.
To make the cupric chloride solution, he dissolves a bunch of copper wire in hydrochloric acid, and mentions maybe using hydrogen peroxide to speed up the oxidation, but doesn't go into detail.
Which got me thinking. You didn't have any cupric chloride yet, but you can make it by dissolving copper. Dissolving copper is the name of the etching game. So we can make one etchant that makes another etchant that's infinitely re-chargeable. Elegant.
Turns out that hydrochloric/peroxide is a common home-brew etchant (and I've re-re-invented the wheel, again) but I guess that people got so used to throwing away their "spent" etchant that they don't think about re-using it. The whole point of this instructable is that you don't throw it away, but use the dissolved copper forevermore as your long-run etchant.
Here's what's going on chemically:
Before there's much copper dissolved in the solution, Cu + 2 HCl + H2O2 -> CuCl2+ 2H2O is the dominant net reaction. That is, the extra oxygen in solution from the peroxide is oxidizing the copper metal, in presence of the acid, to make copper (II) chloride. That's our starter etchant. The resulting CuCl2 shoud be a nice emerald green color.
After you've dissolved a lot of copper into the solution, and used up all the peroxide, the copper chloride does most of the etching for you: CuCl2 + Cu -> 2 CuCl. That's the end etchant.
Eventually you etch so much that you convert all the CuCl2 into CuCl, which doesn't dissolve copper (and is a yucky brown color). As long as you've got enough acid in the solution, you can simply add more oxygen to re-oxidize the copper(I), making more copper(II) chloride and water: 2 CuCl + 2 HCl + O -> 2 CuCl2 + H2O. And then you can etch again.
Bottom Line:
Two things to maintain: CuCl2 levels and acid levels.
CuCl2: After all the peroxide is used up, and the solution starts turning brownish, you'll have to add oxygen to regenerate the solution again: toss in a few more capfuls of peroxide or bubble air through the solution or swirl it around vigorously, or just pour it into an open container and wait. It's easy to tell when you're ready to etch again, because the solution turns green.
It's also impossible to add too much oxygen by adding air, so bubble/swirl to your heart's content. If you're using peroxide to add oxygen, be sparing -- a little goes a long way, and it's mostly water so you're diluting your etchant by adding it.
Acid: Note that HCl is being consumed in the starter etchant and the regeneration reactions. So we're going to have to add a bit more acid as time goes by. If you notice that it's harder to re-green your brown etchant, it's probably time to start thinking acid.
I've tried the titration described on Adam's site a couple times, and it's pretty easy but requires an accurate scale and pure lye (back to the hardware store...). It's easier to just toss in a capful of acid every few batches of boards, which seems to do the trick for me.
Save the Etchant for Next Round. You're Done.
Some final notes here:
1) You can make quite a bit of this stuff very easily, and since you're re-using it, there's no real reason to skimp; put plenty of etchant in your "tank." When you use too little FeCl etchant, for instance, it can get saturated with copper and slow down which can result in long etching times and pitting or undercutting or worse. When I'm etching a board with copper chloride, I'll pour a couple extra inches of solution into the container. It's reusable anyway, and the extra exposure to oxygen just regenerates it. Live large.
2) Don't make too much. As you keep re-using the solution, you're going to need to add a little more acid and a little more peroxide every once in a while. If you've got a 750 milliliter container, start out with less than 500 milliliters of solution. Give yourself some room to grow over time. After all, the main point is to avoid having to dispose the copper in spent etchant.
3) If you've got too much volume of etchant (it will happen eventually) you can evaporate out the extra water by putting it in a shallow (non-metallic) pan or beaker or whatever and letting it sit for a while. This concentrates the copper in solution, giving you a stronger etchant. It'll also re-oxidize some of the copper for you, a bonus. Remember when you're adding the peroxide that you're actually adding 97% water.
4) The linked website suggests that the acid levels in the etchant are not critical as long as there's some acid in solution to do the CuCl2 regeneration. The amount of CuCl2 (vs CuCl) present is easy to diagnose by the color of the solution. Add oxygen to re-green, and add a bit of acid if that's not working. Worst case is that you may have to wait a few more minutes per etch with a sub-optimal bath. This isn't rocket surgery.
5) I do have an aquarium pump ($6 at fish store) that I've used to re-activate my solution. Sometimes I'd leave it on for a few hours while I'm at work if I've been etching a lot. But lately I've been lazy/impatient and tossed in a couple capfuls of peroxide. Both seem to work just fine.
6) The environmental benefit of etching with copper over ferric lies mostly in not having to dispose of the copper that comes off your boards every few times you etch. When and if you do end up with too much copper etchant, please treat it like the hazardous waste that it is -- look into your local hazardous chemical disposal options. There's no getting around the fact that copper salts are (for instance) poisonous to fish even in very dilute concentrations.
Alternative (overly-complex) Method: Make Cupric Chloride Faster.
I don't think it's a particularly good idea, but here's how I got to the end-stage etchant faster.
I mixed the acid/peroxide 1:1 instead of 1:2. The idea was to have a bunch of acid leftover for later regeneration. I don't think it's a good idea, and I wouldn't do it again. 1:2 is probably better, and results in more copper in solution faster with less fuming.
To control the fumes, I used the patent-pending (just kidding) Two-Pint-Glass Fume-Containment-Apparatus. Pour in the peroxide, add the copper, then put one glass on top of the other. Pour the acid down through a small gap between the two glasses and re-seal. Voila. No fumes. (See video. I think I did it with water as an example.)
I also kick-started the formation of cupric chloride by first making copper oxide, which turns to cupric chloride just in the presence of acid alone. This isn't necessary at all, but it was fun. Heat up a coil of copper wire on the stove to red-hot and you get a flakey coating of copper oxide.
Otherwise, it's basically the previous procedure, so just see the pics for notes. I wouldn't recommend it anyway. The less copper you dissolve, the less copper needs to be (eventually?) disposed of, and the acid/peroxide etchant is plenty easy to use.
The two-cup technique is cute. I still recommend it.