Stop Using Ferric Chloride Etchant! (A Better Etching Solution.)

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Introduction: 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.

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

(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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801 Comments

0
plbenn
plbenn

8 days ago

I've just tried this making 100ml of the etchant but I must have something wrong. I used 2 parts 6% Hydrogen Peroxide and 1 part 320g/l Hydrochloric Acid. The mix instantly went a dark orange/red colour but the solution shown here is clear until it starts etching some copper. I put two copper strips in it, one connect to +ve of a 12v battery and the other connected to the -ve. The solution changed to a dark yellow/green as it etched the copper. Can anyone suggest why I have this initial colour?
I tried etching some stainless steel with the battery connected to the work piece and a cotton bud soaked in the solution and it worked.

0
elishabanana
elishabanana

Question 5 weeks ago

Hey guys, I need to know what percentage of nitric acid will work when etching PCBs...should it be 30% pure or higher? You see I used to used approx 98% pure but now I can only get 60% and the process is super slow and doesn't workout nicely. Please help guys.

0
Chrissi M
Chrissi M

Question 5 weeks ago on Step 3

Do you think this would be suitable for etching sterling silver ?

0
uniquecreator7
uniquecreator7

7 weeks ago

Just curious, but wouldn't a copper sulfate electrolytic etch system work the same without all the other chemicals? just salt water and current?

0
The Real Elliot
The Real Elliot

Reply 7 weeks ago

Yes, but all of the parts of the circuit board have to be electrically connected, which is almost never the case...

0
Howiesf
Howiesf

8 months ago on Introduction

I would not advise people to buy acetone and hydrogen peroxide at the same time. This could result in a vist from numerous law enforcement and federal agencies

0
SirNeeek
SirNeeek

Reply 8 months ago

Not is you are in South Africa ;) but yeah, I know were you are going with this.. that is one science experiment I will not ever be repeating (and yes I do have all my fingers)

0
Warsfamily
Warsfamily

Question 1 year ago

I am a bladesmith just getting into making Damascus and need an etching solution to show the pattern in the steel. I was looking for ferric chloride at a hardware store with no luck. I found this article thru Google and I bought the muratic acid peroxide and acetone although I don't get what I do with it yet. And put it all in a 5000ml erlynmeyer flask. It's green. Now is it ready? Lastly who the heck buys a computer and takes it apart to etch the microchips? With is that all about?

0
SirNeeek
SirNeeek

Answer 8 months ago

Warsfamily, not sure if you will see this or if you have your answer already, but please never mix those three together ever again.. granted the volumes of each were different, if left, you get a precipitate forming, that is nicknamed "Mother of Satan" by Jihadists.. also known as Peroxyacetone, Tricyclic Peroxyacetone, Acetone Peroxide.. its a rather power explosive

0
coffeeoutlaw
coffeeoutlaw

2 years ago

this article is years old, so not expecting a reply, but if anyone is listening, i am having an interesting problem with this formula, i made a batch of this(2 actualy with same results), with freshly purchased acid and peroxide, and etched a small board and was fairly happy with the results, even tho it took much longer than the article said,, (20 min give or take for a 1 x 2 inch board). but the real issue is, when i put the second board in just a hour or 2 later.. it sat for hours with no etching, even scrubing the board after would not remove any copper, its almost as if after one use the solution completely neutralized. i even left the board in overnight, with no progress, any idea why such strange behaviour?

0
sharkhamster
sharkhamster

Reply 8 months ago

Hey coffeeoutlaw! It's now been ages since you left this comment so I don't know if you're still interested... but I had exactly the same issue as you. I managed to solve it by using a different pen for the relief (see picture attached!), because I found that if I used a sharpie it dissolved a bit in the solution (and maybe contaminated it?). I also found that putting the etchant in a jar with a screw top made it last longer. Hope that helps!

etchpen.jpg
0
Warsfamily
Warsfamily

Reply 1 year ago

With is people doing with boards? What benefit is it to etch a compu to er board? Does it add speed to the computer? Lost. Me

1
danger0372
danger0372

Reply 1 year ago

why do people think computers are the only things that require or use circuit boards? This isn't for making a circuit board for a computer. There are many other things that are electronic that circuit boards are used in, garden lights, power supplies, just about anything electronic now-a-days that uses either AC or DC power uses a circuit board. Look up circuit board on YouTube, expand your knowledge a little.

2
AvielN1
AvielN1

Reply 1 year ago

i have the same problem, and i am using 50% preoxide. did you find any zolution?

1
HUNDFITZ
HUNDFITZ

Reply 1 year ago

Try 12 or 15% Hydrogen Peroxide from a Beauty supply house. (It's the stuff they use to make blonds.) :-)

1
PesonaF
PesonaF

Reply 2 years ago

hi, just wanted to share my experience after trying this method.

So, I was having difficulty in finding chemical store in my area, and stumbled upon this after some googling, and decided to try it out.

I grabbed myself two cleaning products from groceries store. one is cleaning products for toilets containing 20% HCL. and the other one is some form of liquid soap used to remove stain on your clothes, contain 5% of Hydrogen Peroxide (H2O2).

By mixing two parts of HCL and 1 part of Hydrogen Peroxide (I also added 1 part of water) its ( 120ml HCL+ 60ml H2O2 + 60ml water)

after mixing all the liquid in plastic container, I then put a piece of small PCB in it.

at first i did not see any visible reaction, and thought that i failed (because i add water :D). Then i let the thing do whatever it is doing, and come back a couple of hours later to only to find that all copper on the pcb already wiped out and the liquid solution turned green.

after that, i tried to put another pcb and I can see reaction, I let the pcb submerged in it for a few minutes without doing anything, not even touching anything. and it worked great, wiped all the copper on the pcb in a view minutes.

0
The Real Elliot
The Real Elliot

Reply 2 years ago

How are you agitating the solution? What temperature is it? How did you clean and/or prepare the board's surface beforehand?

20 min for a fresh acid/peroxide mix is _way_ long if you're constantly swirling stuff around, unless it's very cold.

Look at the board as it etches. If you swirl a bit and you see a thin cloud of darker stuff coming off the board -- dissolved copper -- then you're not agitating enough. Swirl more / continuously.

0
Imaybeslowbutmyworkspoor
Imaybeslowbutmyworkspoor

Tip 8 months ago

It's likely mentioned in the nearly 800 other comments, but "Rye" probably shouldn't be the label on a bottle of etchant, no matter what you might think of rye or its enthusiasts.
Thanks for the thorough, thoughtful, and helpful instructable.

1
AroAro
AroAro

10 months ago

The idea of replacing ferric chloride is good, very good, but it is much easier and cheaper.

1. Manufacture of cupfercloride:

Take iron chloride and etch with it until the solution is used up. An ugly brown film will form on the bottom of the container.
Then slowly and carefully pour 30 percent hydrochloric acid into the etching vessel. Stir again and again and until the brown topping has completely dissolved.
The cupfercloride produced in this way must first be regenerated so that it can be used!

That was the first step.

2. regenerate:
I've been blowing air into the solution for days - all nonsense.
It's much easier and cheaper. In cosmetics and for liquid detergents there are plastic bottles that are not round but flat.
Put only a little into such an empty bottle, close it and put it on its side. This gives you a large contact area between the solution and the air and the solution remains under control. If there is a lot of solution, use a larger bottle or several.
Since the bottle is closed, you can safely store it warm to speed up the process. Open the bottle 3 times a day and squeeze it to expel the used air and suck in more.
Etching can take place again after 1-2 days.

When a brown precipitate forms again in the vessels, it is time to add a little hydrochloric acid. So much until the covering disappears. A simple indicator.

I've been working like this for years and one liter of hydrochloric acid will last for many years. Many PCBs cost less than 50 cents a year!

0
DriesC2
DriesC2

4 years ago

Hi from sunny South Africa. Thanks for a great post. I tried this today with great results in 3 minutes. I sacrificed a pcb blank to test the different permanent markers and the best one was a "Artline 70" xylene free marker. The tip is thin and I managed lines less than a millimeter.