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Stop using Ferric Chloride etchant! (A better etching solution.)

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Picture of Stop using Ferric Chloride etchant!  (A better etching solution.)
Ferric chloride is a traditional home-use circuit board etchant. It's easy enough to come by, and the Ferric by itself is no big environmental problem. However, once you've etched a board with it, you're left with a solution with a bunch of copper chloride in it. This dissolved copper is an environmental problem, and you can't just pour it down the drain (legally) -- you're supposed to take it to a hazardous waste facility. (For instance: How to Dispose of Ferric Chloride in this FAQ. )

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.

 
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Step 1: Ingredients: The Starter Etchant

For the starter etchant itself, you only need two ingredients: hydrochloric acid and hydrogen peroxide.

(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.)

Step 2: Put the Lime in the Coconut...

Measure out two quantities of hydrogen peroxide and pour it into your non-metalic container.

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.

Step 3: Add PCB and you're Etching.

Toss the PCB into the solution and it'll take off.

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.

Step 4: Chemistry Break

Picture of 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.

Step 5: Save the etchant for next round. You're done.

Once you're done etching, pour the etchant back into your storage bottle, rinse off the board, flux, drill, populate, and solder.

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.

Step 6: Alternative (overly-complex) Method: Make Cupric Chloride Faster.

When I originally started trying to make Cupric Chloride etchant, I hadn't thought of just using the regular procedure of etching to get there. So I deliberately dissolved a bunch of copper from a wire.

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.

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With all the positive comments below, I gotta try this solution.

jmsheehan8626 days ago
Question. First off I'm new to pcb etching. Always used perf boards. Tried this solution and love it! First few boards I etched took minutes with a fresh solution. I had to make another solution and dropped a board in it. It took nearly 20-30 minutes to etch a small board. Tried to mix another solution like instructable says and same thing. Slow etch. Why? Should the board be dry after rubbing paper off or could paper from the laser etcher still be on there slowing etch time down? Also, light? Could light really slow it down that fast? Heating? Can that speed it up? And I know about agitating it. Thanks!

I started using this combination to etch copper for jewelry components. i like it very much. It works fast and due to the size and amount you get of the pool acid, you can etch many things at a time in many containers. The etching is also very crisp.

WP_20141019_008.jpg
Victor8o5 made it!1 month ago

Thanks! I finally got a laser printer and now I can print my own circuits. Your instructable has been very useful, I probably couldn't had been able to find Ferric Chloride in my area.

I'm making a coupler for a savaged VFD so I can hook it to a breadboard for testing. I intend to make a retro alarm clock with it.

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mbarela821 month ago
I tried it today and it works perfectly!
temp_-1389446284.jpg

Works really good, significantly reduces waste.

Bartm12 months ago

HI, I made this solution as described and tested some boards with a little bit of the solution and it worked great, in fact the best! But however, I did not use any of the bulk solution as yet, so it was as it was mixed, but now a week and a half later I wanted to use the solution and it has depleted its etching properties. how can I re-generate this mixture back to what it was. I did use distilled water. Do you think or can I re-mix the proportions using the old solution from 1 part acid to 2 parts H2OO, i.o.w 33% H2OO with the old solution to make the 3 % to mix with the acid. maybe I need to just make a bubbler for it?

Thanks L

synthdood2 months ago

Hey cool! I never use ferric chloride anymore. I use the same technique in my Instructable check it out,

http://www.instructables.com/id/DIY-PCB-using-Liquid-Photoresist/

Newton5 months ago
Tried this method this morning and it worked like a charm. Messed up the mask a bit but nothing that cant be fixed.
temp_-644216103.jpg
The Real Elliot (author)  Newton4 months ago

Not bad! And awesome for a first run.

Are you using toner transfer? If so, I'd say your iron is running a little hot b/c of the smudged-out pin holes. Try using more pressure (lean into the iron with your full body weight) and less temperature and see if it's easier to get consistent results.

If you're feeling really experimental, you can run a bunch of practice prints reducing the temperature each time until you get a transfer that's not smudgy. No need to waste copper board by etching each trial either -- just wipe away with acetone and try again. You should get the proper temperature dialed in within half an hour.

Tanks for the feedback. Definitely giving this another try. I think I got the wrong transfer paper as it took forever to transfer to the copper. But time will tell, I'll post another pic when the next one is done.
JesusGeek Newton2 months ago

Also based on experience (and smell of burnt paper) don't use gloss paper for photos and such! Every time I tried this it burnt and left broken/smudged traces everywhere. I have seen online people using magazine paper with a sheet of aluminum foil on top (keeps the magazine paper from leaving residue on your iron). This seems to work better, so use magazine paper, not gloss photo paper.

Thanks for the hints! Will indeed try that myself! I always was afraid of pressure... Because of this smudging... But yeah: Maybe a higher pressure + Lower temperature may just do the trick!
Thanks!

Orngrimm3 months ago

I got a goob ammount of crystaline CuCl2 (i think). If pics are needed, please say so, Can make them in the weekend.

If i want to etch with this, i only need HCl and bubble it up during etching if i did my chemistry correctly, right?
Sorry... Electronician here not a chemist...

AKL3213 months ago

What is the best way to wash off the hydrochloric acid and hydrogen peroxide after the etching is done? Water? Would ammonia or baking soda cause a dangerous reaction?

dunnos3 months ago

Haha, I just got my hands on some 30% H2O2 and i thought it would be funny to make it really acidic. I mixed one part 30% H2O2 with three parts HCl.

Put in my board (about 10cm by 10cm). It made a hissing sound, I couldn't see my board through all the bubbles. Took 20 seconds for the entire etch. I was just standing there looking at the mixture like: what ಠ_ಠ

The Real Elliot (author)  dunnos3 months ago

Yeah. You _can_ push the concentrations up a lot, but eventually there are tradeoffs. Mainly:

1) Fuming. Highly concentrated HCl solutions end up in the atmosphere, rusting your kitchen knives and/or any other exposed metal nearby. (Guess how I know?) It's just a lot more convenient to handle lower (2-4M) concentrations. Keep the lid tight when you're storing the etchant regardless.

2) Etching too fast. There's a thin line between etching all the exposed copper away, and etching more than you wanted. If you think of the copper layer on the board in 3D, while the topmost surface may be protected, the sides are vulnerable once the etch is done. This kind of over-etching is called "undercutting". And all things equal, undercutting is easier to avoid (the timing is less critical) with a slower-moving etch.

I aim for a 10-minute (or so) etch with continuous agitation.

Next time it would probably be best to just get a plate and poor it on top while sitting outside.

Ares33x made it!3 months ago

Easy instructions and works pretty well. Thank you for this easy to follow and knowledgeable instructable. The comments were quite helpful and enlightening. Here is some quick boards I've done and the container for it. Does anyone know the pressure this solution can build up to in a container? or can I leave in a semi-sealed tank?

Swishing the board around really helps even with the bubbler now, I was thinking of heating the solution a little and somehow getting either a pump or something to keep the liquid moving over the boards. Without swishing it around it just wouldn't etch or etched really slowly and unevenly because the oxidized layer. With swishing it's taken around 20-30 mins depending on how much copper I am removing.

Also noted that the poor bubbler stone was nice and blue when I bought it, after sitting there for half a day it was very light and then a day late is just whitish now.

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The Real Elliot (author)  Ares33x3 months ago

Nice job, great results, well documented. Best comments evar! :)

Thanks for mentioning your experience with swirling / agitation. I absolutely should have highlighted that in the instructable. The etchant (any etchant) saturates pretty quickly in the immediate neighborhood of the part you're etching, and it'll slow down almost to a crawl unless you keep that layer mixing with the rest of the solution.

When you swirl it, you can sometimes even see little dark brown clouds of copper coming off the board and then dissolving into the rest of the solution.

The bubbler looks awesome. Let us know how that holds up in the long run. And be careful not to let the etchant back up into the pump!

A hint, if I may:

You etched away a _lot_ of copper. If you add a ground plane pour in your design, you can drastically reduce the amount of copper to remove, and you'll speed the time up a lot. Or heck, use up some of that free space on the board for art...

Anyway, like I said: awesome comment!

Yeah, I have done some ground plane boards but for these particular ones I was trying to do a single point ground as suggested in the datasheet for the fun of it, and to get the solution started. The large board however I would have take the approach but I have 12 gauge wire on a lot of the tracks (it's an adjustable current sink). But the art ideas is an interesting way save up some copper from being eaten away, never thought of that, thank you.

m-m-owen4 months ago

Followed directions using 200ml 3% hydrogen peroxide and 100ml 31.45% HCL (muriatic acid). Worked perfectly and exactly as described. Good stuff. Way cheaper than the ferric chloride I have been using and I dont have to heat it.

Victor8o56 months ago

Hi, I've noticed that the mix I've made releases small bubbles, resembling champagne ones, even thought there isn't any copper inside and the last reaction took time hours ago is this safe?

The amount of bubbles seems to be very low, but it keeps going for hours.

As a precaution measure the lid is a bit loose to avoid pressure to build up inside.

pelrun Victor8o55 months ago

Hydrogen Peroxide decomposes to water and oxygen spontaneously; that'll be what you're seeing. So it's pretty safe.

It happens faster when exposed to light, which is why it's sold in dark bottles.

JLDohm6 months ago

If you want more concentrated H2O2, is is available as "Clear Hair Developer" in the drug store with the hair dyes. 10 Volume is 3%, on up to 40 volume which is 12%.

rizoma made it!6 months ago

Hi, thanks for the tutorial, I successfully etched my first board today, before that I was using a cnc from a friend avoiding etching cause the concerns of disposing the acid etc, so the idea of the recycling etch was really amazing. Even thou seems that most people don't get it, and just like this recipe for the fast first etching...

I just did a little test, it was great, I got 15% hcl and 3% h2o2 I started mixing by 1:1, no etching so after 5 minutes I added another part of h202 and the etching started, took less then 5 minutes. Great.
I used a little glass bottle for the enchant, but after reading some comments now I'm afraid it could explode for the pressure, but I don't won't to leave it open cause I'm afraid it would loose it's effect... any advice for storage and for the next pcb? I would like to do the best I can for re-use everything the best possible way. I want to use a acquarium pump too...
ps. I think I got just 25ml of total for this little board picture attached.

my1stPCB.jpgnasty.jpg
mykiscool6 months ago

I found one that just uses vinegar and peroxide. That's as cheap and safe as you could get!

www.youtube.com/watch?v=D8M5BIo0a9Y

Ananse156 months ago

What metals will I be able to etch with this solution? I usually work with brass, copper and nickel silver blanks.
Thanks!

dkamegawa7 months ago

Reporting results after first use: this thing is sick, in the best way. Money for roughly 1.5 litres of this stuff set me back the same as a small (250ml) bottle of FeCl3. Roughly twice as fast on the first use, and if it can be reused almost indefinitely, this means I won't have to buy more chloride ever again. Piece of advice for everyone, this thing's quite friendly for toner and should be awesome for serigraphy (haven't tried) but it's very destructive on sharpie lines; try to make at least 3 layers of marker beforehand, because this tends to wash away the ink rather fast.

mkeen859 months ago

what is the minimum percentage HCL acid needed?

I can get 33% online, but is a bit pricey.

but i can get brick cleaner from local shop which is a lot cheaper but is only 10-15% HCL

The Real Elliot (author)  mkeen858 months ago

My recipe calls for 34ish% acid (10M) and 3% peroxide (97% water) mixed 1:2. This means the resulting acid is diluted by a third (one part in three total parts) and so is around 10%.

You're starting out with around 10% acid, so you can't really afford to add too much peroxide. If I were you, I'd experiment with straight 10% acid, and tossing in a few capfuls of peroxide at a time. Or maybe I'd go as far as a 1:1 mix of weaker acid and peroxide. Or maybe try to find some strong (10-15%) peroxide so that you don't have to water the mix down as much.

Either way, experiment. The worst that'll happen is that it doesn't work very quickly, but even with a weaker acid solution you should get etching. Post back with your results?

thanks i think i can get some 10% peroxide but would 30% hydrogen peroxide be over kill?

also once i have made the copper chloride could i boil it down then add more HCL to make it stronger?

If you do go down that road (attempting to concentrate the Peroxide) be *very* careful as it will become extremely caustic (chemical burns for you) and once past 80-90% concentration, it becomes explosive. I made a mess in a college chem lab by neglecting to watch some hydrogen peroxide I was boiling down. Thankfully, nobody was hurt.

The Real Elliot (author)  mkeen858 months ago

30% peroxide _is_ probably overkill. But then again, too much overkill is never enough!

On the other hand, boiling the acid is probably not a good idea. The stuff (at 3M) is nasty enough without being hot and spiiting.

If you need to increase the acid concentration, one way to go is to simply leave it sitting out in a shallow tray. The water evaporates. Done.

double_g mkeen859 months ago

I bought some 31% Muriatic acid at Home Depot which was $4 (or somewhere around there) for a quart. I think they had it for pool supplies.

I'm not a chemist, but I would think that 15% would work, but your etching would take longer. You'd probably want to double down on HCl in the recipe above so you'd be adding the same amount of HCl as you should.

mkeen85 double_g9 months ago

thanks I will try that.

fschonholz10 months ago
So ... I have been experimenting with your technique and it is cool. As a first time etcher ... this made it easy. I have been having an issue with the "mask" (not sure what it is called technically) to etch. I used shappies and nail polish. The shappies have been useless. The nail polish has been a hit and miss, as some of the nail polish stays, some gets eaten away and some half way.

I build guitars and wan tot do one with an aluminum front that is decorated. I want the decorations to be etched out.

The question is, what should I used to "draw" the decoration that I do not want the acid to act on? and what should I use to protect the back of the plate I want to etch so only the front is etched?

Thank you!

The easiest and cheapest way is to just get a letter-size magazine you no longer care about, torn apart a few pages and print the art over them with a laser printer (ink does not work). Then iron (yes, an actual iron) the printed page over whatever you want the art to stay on for like 25-30 minutes and remove gently with water.

Thank you for the assistance. I actually found the way to do it using nail polish ... just needed to find the right nail polish.

If I want to etched in the design, I paint the full surface with nail polish and then scrub out the design. If I want to etch out, then I draw the design with a market and then pain it with nail polish.

You can find the results here: http://fabianschonholz.com/

It is a bit rough for a first try; but just an excuse to do more :)

I have always used the toner transfer method, print what you want on photo paper. Lay the paper with the print upside down (toner facing the copper), use an old iron to melt the toner on it by putting it on the paper for a minute. Lay the board with the paper on it in a bowl of water (the paper should stick to the board, before you lay it in the water). Rub of the paper, and you have a very nice etch resist. Only works on laser printers.

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