Is the Best PCB Etchant in Every Kitchen ?

Intro: Is the Best PCB Etchant in Every Kitchen ?

After a lot of reading and inspiring from Instructables for two years now I decided to step ahead and do my first Instructable on two subjects I particularly like : PCB making & The scientific method.
Feel free to comment and criticize my work, I think scientific method is also about improving and discussing the best way to experiment :) !
English is not my native language so please excuse my hesitating grammar.
5/30 Edit : I would like to thank you all for supporting this Instructables in the Scientific Method contest =D See you for other experiments !

Most of us Instructables users etch PCBs occasionally if not on a daily basis. This process is not anodyne as it may have a great impact on the quality of the future circuit, the environment and, last but not least, on your wallet !

Ferric chloride is commonly used to etch PCBs as it is both reliable and efficient. However, it's a dangerous product which requires special care in handling. Recently, some alternatives have been found to accomplish the same task. Among them is an astonishing hydrogen peroxide, salt and vinegar mix which seems to be a “Mac Gyverish” way to print a circuit board.

Let's assess the “Mac Gyverish” hydrogen peroxide/vinegar/salt mix using the “tried and tested” ferric chloride solution as a control !

To etch a PCB one can either immerse the board into a bath of etchant (most common technique) or rub it with an impregnated sponge. I have tested both ways with each etchant so that makes a total of 4 experiments.

The techniques and etchants will be compared according to four criteria :

• Time/Handling
• Quality of resulting circuit
• Cost
• Environmental impact

STEP 1: The Theory Behind Pcb Etching

A copper board is made of an epoxy resin board covered with a thin layer of copper. The etchant reacts with the layer of copper and dissolves it, except where a mask protects the copper. The epoxy is left intact as it does not interact.

Here are the two chemical reactions taking place : (1) is ferric chloride’s (aka Iron (III) chloride) and (2) is vinegar/hydrogen peroxide/salt mixture’s.

(1) FeCl3 + Cu --> FeCl2 + CuCl 

(2) H2O2 + 2(CH3COOH) + Cu  --> 2(CH3COO-) + Cu2+ + 2(H20)

The reactant is the result of the combination of acetic acid (which represents 80 grams per liter of white vinegar according to the bottle [which says 8° acidity]) and hydrogen peroxide (which is at 3% mass concentration).

We can calculate the optimal ratio of each component in order to get a maximum amount of it.

Hydrogen peroxide is 34 grams per mole and acetic acid is 60 grams per mole.

So, in a liter of vinegar there are 80 grams of acetic acid which represents 80/60 or 4/3 moles of acetic acid. In a liter of hydrogen peroxide, which approximately weighs a kilogram, we have 3% x 1000 grams = 30 grams, nearly a mole, of pure hydrogen peroxide.

Because the reaction uses twice the number of hydrogen peroxide molecules of acetic acid molecules we can say that we need to put roughly a 2/3 ratio of hydrogen peroxide/vinegar in volume to get things optimal.

Now you may be asking yourself “Why do we want to add salt to that ?”.

Well, one possible explanation (I'm not actually sure it is the right one) is that the reaction brings neutral Cu atoms of the board to Cu2+ ions in solution that would form copper acetate (it is the combination of one Cu2+ ion and two CH3COO- "acetate" ions). And, at one point the bath would reach an equilibrium (because there is as much Cu2+ forming from Cu than Cu2+ getting back at a solid Cu form).

Generally this happens before your board gets its beautiful tracks, which is quite sad. Table salt, or NaCl, brings chloride ions Cl- to which Cu2+ ions will bond to form cupric chloride or CuCl2 instead of being left in solution (those ions would endlessly come back and forth from Cu to Cu2+). You can see this during the reaction (if you leave the reaction with no salt it will turn blue which is the color of copper acetate and stop, whereas if you put salt it will turn green, the color of cupric chloride, and carry on).

2Cl- + Cu2+ --> CuCl2

By doing so, the equilibrium point is pushed forward and more copper can be dissolved, so that, if you are generous on salt (if you introduce table salt in excess) you may get your PCB in the end ! One tablespoon of salt on the board is generally sufficient.

Hypothesis : Given the concentrations of hydrogen peroxide and acetic acid in our "recipe" ferric chloride should be way more efficient. However the Salt/Vinegar/Hydrogen peroxide seems to be both less expensive and safer.

Now comes the fun part, let's put up the lab coat and etch PCBs !

STEP 2: Setup & Experiment

The experiment aims at comparing, in a "normal" situation, what etching method is the most efficient (immersed or rubbed ? Ferric chloride or Hydrogen peroxide/Vinegar/Salt mix ?)

I printed and ironed a toner "barcode" with strips of decreasing width (5/4/3/2/1.7/1.4/1.1/0.7/0.4 millimeters) on four identical boards, those will show the resolution achieved by each method (I chose resolution as quality indicator).

In my lab (aka shed), each board is then immersed in a small bath (approx. 200mL at room temperature : 70°F) of etchant or rubbed with an impregnated sponge up to the point where I can’t see any unmasked copper left. The board is then rinsed and the circuit is wiped with acetone to remove the mask.

In this experiment :

• Control variables (aka variables that do not change throughout the experiment) are lab temperature, size of copper board, masking technique, quantity of etchant in the bath/sponge.
• Dependent variables (aka variables that may vary because of tested factors) are achieved resolution, duration of etching process, cost and environmental impact.
• Independent variables (aka tested factors) are nature of etchant (Ferric chloride or Salt/Vinegar/Hydrogen peroxide) and etching technique (rubbed or immersed).

STEP 3: The Results

The experiment went very well even if got a little bit frustrated by my copper boards' poor quality and persistent toner ! ^^

Maximal resolution (0.4 millimeter) was obtained for each experiment which shows that the etchant/technique itself does not change the final quality of a regular PCB. I got some scratches on the rubbed PCBs because of the sponge (not very soft).

However the duration of etching process was not even : the shortest method is Ferric chloride rubbed (3 minutes) followed by Ferric chloride bath (10 minutes), Salt/Vinegar/Hydrogen Peroxide has the longest etching duration (11 minutes when rubbed and 20 when PCB is immersed).

STEP 4: Cost and Environmental Impact

Salt/Vinegar/Hydrogen peroxide mix is, by far, the cheapest etchant (Hydrogen peroxide 3% is 2$ for 16 oz, Vinegar is 2$ for a liter and salt is almost negligeable) with a price of less than 4$ per liter.

Ferric chloride costs around 10$ for 16 oz which is arround 20$ per liter, five times more than the first !

In terms of environmental impact "sponge technique" is, by far, the less dangerous for both etchants (and the most economic with only 10mL of etchant used). You only need to rinse your sponge once finished, a tablespoon of etchant is not harmful (I've asked local authorities).

Ferric chloride bath needs to be stored and brought where it can be treated. I'm not sure for Salt/Vinegar/Hydrogen peroxide mix as copper precipitates (the solution gets a pale blue tint only).

In terms of handling Salt/Vinegar/Hydrogen peroxide requires a small preparation before each etching session (the solution does not stay efficient very long) but it is safe whereas Ferric chloride is corrosive (wear gloves ;)).

STEP 5: And the Winner Is...

Salt/Vinegar/Hydrogen peroxide (immersed) and Ferric chloride (rubbed) are 1st ex-aequo. The first has the advantage of being both readily available in the kitchen and quite safe whereas the second is both cheap and quick =D !

Then comes Salt/Vinegar/Hydrogen peroxide (rubbed) which has all the advantages above plus the fact of being extremely cheap and green, however you need to rub the sponge for 11 minutes which is not that funny (with all the risks of destroying your tracks if you rub too hard) !

Finally "old fashioned" Ferric chloride (immersed) comes last as it is relatively both expensive and difficult to dispose of (if you are responsible).

STEP 6: Conclusion and Possible Improvements

The experiment in itself did not separate the two etchants which are almost as efficient for a regular hobbyist use. However factors such as cost, handling or environmental impact played a key role in putting the vinegar/salt/hydrogen peroxide mix forward. The setup and experiment are easy to make which is good for reproducibility. Don’t hesitate to cross check my results ;).

Though, as all experiments this one has limits. In fact I tested only two etchants whereas dozens exist and may be a middle ground such as Hydrochlorhydric acid + Hydrogen peroxide (which is more powerful than the Vinegar/Salt/Hydrogen peroxide mix) or Cupric chloride (whose effectiveness is comparable to the one of ferric chloride).

However Ferric chloride had the advantage of being the most common method for etching PCB so I thought it was the reference to which I had to compare other methods and Vinegar/Salt/Hydrogen peroxide was amazingly inoffensive and available at minimal cost. I was also skeptical about this “Mac Gyver” method : this experiment helped me to figure out that it is reliable =D !

One could also say that I only tested one temperature (21°C). Although this is true those chemicals’ reaction rate have the same dependence upon temperature. This means that if one method is relatively more efficient at 5°C, it will also be relatively more efficient at 40°C (but the reactions will take less time). The same goes about reaction rate in a bubbling tank or other setup improvements.

Please feel free to comment and help me improve this experiment with new factors and/or new methods ! =D

I had a great moment creating this first 'ible, I hope you liked it too ;)

Those great pages helped me making this 'ible :

Etch PCBs in One Minute !

Stephen Hobley's blog

Comments

[HairyBear2]

Warning! Copper Acetate is reported to be TOXIC. I doubt that the sewage people will approve of this being dumped in the sink.

[clancy1066]

Hmmm. I did the 1:2.4 ratio because of the 5% vinegar to get 200ml (the H202 was 3%). I then added MUCH salt(3 or 4 tablespoons at least.) but it stays blue with Cu2 I assume. I added more salt enough for a statue of Lot’s wife but still aqua blue. Room temp. Should I be heating it?

[mikeganz]

I wanted some clarity about
amounts, since most vinegar sold here in the states is 5%, not 8% as you used
(3% hydrogen peroxide is pretty standard, though).

Keep in mind – I’d never
heard “mole” referred to in math before this article, and I’m a little rusty
with equations, hehe.

Based on your final amount of
200mL for etching, you’d be using 80mL of 3% hydrogen peroxide, and 120mL of 8%
vinegar (aka, the 1:1.5 ratio, or 80:120).

If 8% equates to 80
grams/liter, and we’re using 120mL of vinegar, I perform the following
equation: (120/1000) x 80 = 9.6

Using 9.6 as my answer, if I
have 5% vinegar (50 grams/liter), solving for x, I get 192. E.g. (192/1000) x
50 = 9.6

So the new ratio would be 80:192,
or 1:2.4.

Also, using 1tbsp salt per
200mL, I get to just over a teaspoon of salt per ounce of peroxide/vinegar mix.

Can anyone tell me if this is
completely off-base here?

As always, thank you in advance!!!

[JohnZ57]

It is a pretty common unit in chemistry. For me it has been a while I used it, 26 years or so ;) didn't even know it was recently changed to a new standard.

The mole is the unit of measurement for amount of substance in the International System of Units (SI). Effective 20 May 2019, the mole is defined as the amount of a chemical substance that contains exactly 6.02214076×1023 (Avogadro's constant) constitutive particles, e.g., atoms, molecules, ions or electrons. This definition was adopted in November of 2018, revising its old definition based on the number of atoms in 12 grams of carbon-12 (12C) (the isotope of carbon with standard atomic weight 12 by definition). The mole is an SI base unit, with the unit symbol mol.

[mpopovic1]

Wish I knew where he gets 8% vinegar from too - bet it tastes great on fish n chips! It's usually 5% in the UK too. But seriously I'm not sure what your math was trying to prove other than that you've ended up at the wrong ratio which is kind of obvious if you use 5% rather than 8%. I think there's an easier answer: if you're using 5% vinegar it's 0.833 moles. If at the same time you're using hydrogen peroxide @ 3% it's 0.882 moles (almost parity). But you want quote 'twice the number of hydrogen peroxide molecules of acetic acid molecules' unquote. How about just using 6% peroxide? Then you simply use the same quantities of each. Contrary to previous scare-mongering 6% peroxide is widely available even in the EU. Ebay UK, for instance, has tons, I means thousands of litres, of the stuff.

[Michaela545]

My experience has been that the longer the dwell time the more likely that the resist will degrade. The best way I have found to make circuit boards is to make or obtain a plastic tank. Back when I did this, plastic fish tanks were not readily available,so I made mine out of acrylic scraps. These days plastic fish tanks are readily available at any walmart for fairly cheap. I made the tank very thin and used a small submersible aquarium heater to heat the etchant. (Warm etchant etches faster. Filling the entire tank with etchant would have been wasteful, instead I made a sprayer which used less etchant and massivly reduced the dwell time. I used an aquarium power head connected to some ridged pvc tubes to circulate the etchant. The spray nozzles were simply small plastic spray nozzles that are sold in the garden department. The nozzles from those misters for misting water to reduce temperatures outside in the summer might work well too. With warm ammonium persulfate (the common chemicals used for etching are ammonium persulfate, sodium persulfate and ferric chloride) I was able to etch a board in about a minute. You could literally see the copper dissolving off the board. The fast dwell time leads to sharper traces with less degradation of the resist and less undercutting. (if part of the board is etched but part is not,then the edges of the copper traces are exposed on the etched parts and because you have to leave it in the etchant the will undercut the resist in those areas, potentially damaging traces.The faster and more evenly you can etch the board the less problem this is)

On the subject of alternative etchants, this article demonstrates a variation of the acid peroxide etchant system that is sometimes used. Usually however its used with HCl + hydrogen peroxide +NaCl. HCl however, while commonly available as "Pool Acid" or "Muriatic Acid", is HIGHLY hazardous. I can cause severe damage to eyes and skin and if placed in a metal container can evolve explosive levels of hydrogen. (There was a case of a few thousand gallons of concentrated HCl stored in a steel tank some years ago. When an employee opened the tank, he generated a spark from static electricity and the tank exploded.) From a safety perspective HCl is probably the worst choice for an etchant. Vinegar however sounds pretty good. There are "cleaning vinegar" products available that have a higher concentration than the stuff intended for food as well.

[Tomkyde]

Reading your comment I would highly appreciate to get some photos of your construct. Is it possible that you post some pictures of it?

[cburg]

The source I found for 30% Hydrogen Peroxide was the local Beauty Shop supplier. I live in the USA so at least for now it is easy to buy.

I do have a question: What would the proper ratio be for h2o2 to vinegar?

In the past I have used 30% h2o2 and Muriatic Acid (HCl). 3 to 1. This worked well and if I put the tray in a hot water bath it worked even better. I never knew if this was the proper ratio or not but it did work.

I would like to try the vinegar instead of the muriatic acid and try adding the salt.

Thanks You for this Write up. Good Job!

[Michaela545]

30% hydrogen peroxide defeats the "safe" aspect. Might as well buy a bottle of ferric chloride or ammonium persulfate.

[phoulihan]

Does anyone know if there's an alternative to hydrogen peroxide? It's heavily restricted in the EU because some idiots were using concentrated solutions to whiten their teeth.

[gomibakou]

Is that the reason?! I found it was being restricted in some countries and I'm really pissed off with the fact i cannot find hydrogen peroxide 110vol (33% concentration or so), but i couldn't know the reason about such restriction.I read the restrictions were due to the possible use of high concentrated hydrogen peroxide to make fuel.

Anyway if you look on the Internet, you can find some sites where it's explained the process to get high concentrates from common use 3% h.peroxide, basicly baking it in a kitchen oven in low temperature. And it works (it's said).

Honestly bleach is also dangerous and you can buy easily so I don't think the reason to restrict the hperoxide is by bleaching teeth. Surely something related to the paranoid about terrorists (and actually the terrorists dress smart and use ties).

[Michaela545]

Yes, you never get acetone or any other ketone around peroxides. You should also avoid distilling organic solvents as some form highly unstable and dangerous organic peroxides.

[Nyxius]

Its restricted in the EU because it is an ingredient in diacetyl peroxide which is a form of explosive that is difficult to detect. I suspect that this is in reaction to the bombings.

[Nyxius]

I also encourage you to never try making diacetyl peroxide. It is very dangerous, very illegal, and very unstable. Think nitroglycerin and you'll have the right idea.

[jimmie.c.boswell]

how to make tri-nitro glycerol. VERY CAREFULLY!

[jimmie.c.boswell]

i do not think i would recommend, having hydrogen peroxide over 19 volume.

hydrogen peroxide over 29%, can explode on contact with any combustibles. and contact with flammables, would be even more disastrous.

this stuff over 30% can, self ignite explosively with any combustible material. even working with it, on a wood table is dangerous.

it can also form, metallic and organic peroxide salts that are highly explosive and highly sensitive.

this is the kind of stuff, you do not want to keep in storage. if you must use it, only order enough for immediate use.

and this concentration will do more, than bleach hair or teeth. hydrogen peroxide, at this concentration is highly toxic.

it kills living tissue, on contact. and internally it, will kill you. this is what does the killing, in radio-active contamination. the radio-ionization of water, produces toxic hydrogen peroxide in the body besides cooking you from the inside.

[RubenP51]

Whiten teeth? I assumed it was restricted to keep people from making aceton peroxide and blowing things up.

[aequanimitas]

You can get 3% hydrogen peroxide from amazon in Germany. So I assume, in EU it is not a big deal.

[Red.Dwarf]

You can buy up to 12% in the EU and anything over that is restricted. I purchased 30% a while back but when I returned for more I found that only up to 12% was available to the general population in the UK. I now get 9% so I do not have to mess around watering down with distilled water.

[jimmie.c.boswell]

maybe try something like sodium peroxide Na2O2? i, would suggest trying a very small test batch first. or if it, would remove the protective coating on copper clad board.

it is some pretty strong stuff, in pure or technical form. this and vinegar, may not go too well together. but it is a very strong oxidizer, so much caution is needed as with concentrated hydrogen peroxide. organic peroxides, may pose even a greater danger.

and i do not think i would recommend sodium perborate, since borates can form some pretty nasty super-catalytic toxins.