CCL Blue vs Ferric Chloride Etchant

[Mechatrommer]

i've been using CCL Blue Etchant to etch PCB due to eco friendly feature and not as corrosive as ferric chloride. the white salt like appearance, becomes blue when etching copper. few weeks ago i bought the 2nd pack after the 1st pack expired after years of storage and very little use. by expired i mean it will not etch no matter how much i put the salt in the water. the 1st pack i thought i stored it poorly in not 100% air tight plastic container, the container got broken during years of storage i guess the reaction with the etchant.

but this 2nd pack only few weeks in storage, i put in glass container with better air tight plastic cover. the cover is red initially now is dissolved to white plastic i guess from etchant fume, what is suck is now the etchant exhibit the same "expired" behaviour. is it something wrong with my storage method? or simply this type of blue eco friendly etchant is totally not recommended by hobbiest community? anyone with some advice?

now i saw ferric chloride etchant is sold to international in ebay, this is good news. but is shelf life of ferric chloride exhibit the same behaviour as the blue etchant? if yes the how to store it properly? if no, is it unlimited lifetime? i think i'm going to buy the crystal (dry salt) form, not the liquid form as i dont want it to mess during shipping. the seller claims in the ads as indefinite shelf life, but will become liquid if not stored in air tight container.

advice guys please. thanks.

[MagicSmoker]

I have no idea what "CCL Blue" is, but the etchant I use at home - for the one time a year I might make a board myself - is a solution of 1 part "muriatic acid" (aka hydrochloric acid, sold here at 31.45% concentration) to 3 parts 3% hydrogen peroxide solution. Etches very fast without heating, is transparent, so it's easy to see when its done, and it is just about as cheap as dirt.

[Zero999]

i've been using CCL Blue Etchant to etch PCB due to eco friendly feature and not as corrosive as ferric chloride. the white salt like appearance, becomes blue when etching copper. few weeks ago i bought the 2nd pack after the 1st pack expired after years of storage and very little use. by expired i mean it will not etch no matter how much i put the salt in the water. the 1st pack i thought i stored it poorly in not 100% air tight plastic container, the container got broken during years of storage i guess the reaction with the etchant.

but this 2nd pack only few weeks in storage, i put in glass container with better air tight plastic cover. the cover is red initially now is dissolved to white plastic i guess from etchant fume, what is suck is now the etchant exhibit the same "expired" behaviour. is it something wrong with my storage method? or simply this type of blue eco friendly etchant is totally not recommended by hobbiest community? anyone with some advice?

now i saw ferric chloride etchant is sold to international in ebay, this is good news. but is shelf life of ferric chloride exhibit the same behaviour as the blue etchant? if yes the how to store it properly? if no, is it unlimited lifetime? i think i'm going to buy the crystal (dry salt) form, not the liquid form as i dont want it to mess during shipping. the seller claims in the ads as indefinite shelf life, but will become liquid if not stored in air tight container.

advice guys please. thanks.

It could be a number of things. I have some PnP etching powder which is a mixture of sodium persulphate and sodium bisulphate.

You might have ammonium persulphate or a similar solution to mine.

I avoid buying pre-diluted etching solution. I only buy powder which keeps almost indefinitely.

[jpanhalt]

Ditto.  What is CCL Blue?

You should know that all copper etching processes rely on oxidation of copper to a Cu(I), which is readily converted to Cu(II).

Can you explain in scientific terms (not advertisement) why you think CCL Blue is "more" environmentally friendly?  I consider ferric chloride as pretty environmentally friendly.   One of its major uses is in sewage treatment.  Yes it stains, and yes, it will etch stainless steel.   But, lots of stuff in the environment also stain.  And stainless steel is man made.

John

[janoc]

My guess is that it is just another marketing name for potassium persulfate or ammonium persulfate. The white powder/crystals that are being sold under this name on eBay would match it.

Don't believe marketing crap, this stuff is pretty much the same "ecologically friendly" as ferric chloride is. The "unecological" part are the copper ions - which are there regardless of the type of etchant.

However, persulfate decomposes over time, as the OP discovered. So if you are doing one board in a blue moon, it is not good to keep it - make a fresh batch every time. It also cannot be kept in an airtight bottle, because it decomposes and releases oxygen. The bottle could burst (or at least eject the stopper). About the only advantage persulfate has over ferric chloride is that it doesn't stain everything it touches.

[Mechatrommer]

I have no idea what "CCL Blue" is,

Ditto.  What is CCL Blue?

opps i thought the name CCL is common... here what i meant, sold in ebay china...
http://www.ebay.com.my/itm/1Pc-200g-Copper-Clad-Palte-CCL-Blue-Environmental-Protection-PCB-Etchant-/322198509937?hash=item4b04871971:g:4pEAAOSwo4pYbKVi
http://www.ebay.com.my/itm/2-Process-Reagent-for-Etchant-Environmentally-Friendly-/131867669459?hash=item1eb3ecf3d3:m:mT87mjaYS6kdWjpecJDB1-w
something in my lab got absorbed by this salt making it disfunctioned in a matter of days...

but the etchant I use at home - for the one time a year I might make a board myself - is a solution of 1 part "muriatic acid" (aka hydrochloric acid, sold here at 31.45% concentration) to 3 parts 3% hydrogen peroxide solution. Etches very fast without heating, is transparent, so it's easy to see when its done, and it is just about as cheap as dirt.

yeah i wish i have that supply shippable to my place. i just saw last night the ferric chloride also constructed from these ingredients. so i dont understand why the hassle of making ferric chloride all the way if hydrochloric acid + hydrogen peroxide can do the same job... here the video..

https://www.youtube.com/watch?v=43Xsh9J7S-g&feature=youtu.be

http://www.instructables.com/id/Stop-using-Ferric-Chloride-etchant!--A-better-etc/

I avoid buying pre-diluted etching solution. I only buy powder which keeps almost indefinitely.

thats what i did. buy powder. but my powder is not same as yours, my powder died in days of storage.

Can you explain in scientific terms (not advertisement) why you think CCL Blue is "more" environmentally friendly?  I consider ferric chloride as pretty environmentally friendly.

because this "CCL" produces oxygen during etching, can be disposed safely etc, so the sellers claim. as FeCl, lots of warning in the net saying not to disposed anywhere, even on land due to its corrosive nature, how true? i dont know. but from the appearance itself (in youtube), that brownish liquid looks a bit nasty compared to crystal clear liquid.

My guess is that it is just another marketing name for potassium persulfate or ammonium persulfate. The white powder/crystals that are being sold under this name on eBay would match it.

Don't believe marketing crap, this stuff is pretty much the same "ecologically friendly" as ferric chloride is. The "unecological" part are the copper ions - which are there regardless of the type of etchant.

However, persulfate decomposes over time, as the OP discovered. So if you are doing one board in a blue moon, it is not good to keep it - make a fresh batch every time. It also cannot be kept in an airtight bottle, because it decomposes and releases oxygen. The bottle could burst (or at least eject the stopper). About the only advantage persulfate has over ferric chloride is that it doesn't stain everything it touches.

thanks for the info. but does FeCl powder decompose as well with time? or we can store it indefinitely?

[Monkeh]

Yes, let's use mystery powder in a bag from China. That'll be safe and environmentally friendly.

Judging from the temperature requirements, it's ammonium persulfate. This produces ammonia, along with oxygen and a few other things. Don't breathe this.

Also don't bottle it without a pressure relief valve, don't pour it down drains, because copper salts are what cause problems and that's what you produce with any etchant. Don't get it on your skin, in your eyes, up your nose, certainly not down your throat or you'll get the epic shits, do not allow it near high temperatures or flame, especially in the presence of anything remotely combustible. It's an oxidant: EVERYTHING WANTS TO BURN MORE. LOTS MORE.

And yes, it decomposes if exposed to moisture. Atmospheric moisture is all it takes, you should open and use it all in one go. If the bags are too big for that, you have a storage problem. Silica gel is probably safe around it to absorb moisture, but don't quote me on that.

Use FeCl₃. It's cheaper, it stores pretty much indefinitely, it works quickly and can be reused numerous times, toxic and corrosive gasses are produced but only in small quantities and only while actively etching.

[IanB]

Use FeCl₃. It's cheaper, it stores pretty much indefinitely, it works quickly and can be reused numerous times, toxic and corrosive gasses are produced but only in small quantities and only while actively etching.

I don't think ferric chloride produces any gases when etching. It has never bubbled when I have used it. It just produces dark clouds in the solution where the copper is being dissolved.

But to echo what others have said, if you store it in a proper airtight container it will last forever.

[Ian.M]

Anhydrous ferric chloride reacts with moist air to produce hydrogen chloride fumes.
IIRC, excessively concentrated hot ferric chloride solution can produce hydrogen chloride fumes in trace quantities

[BrianHG]

Could the OP be talking about using using ammonium persulphate or sodium persulphate crystals?
Yes, this stuff is much less harsh to the environment than ferric chloride.

When I once used ammonium persulphate crystals, for best life and performance, you should only mix with steam distilled water and when etching, keep the mixture at 70-80 degrees C, with circulation during the entire etch.  Initially it etches really fast, but, looses strength quick as the water saturates with copper turning blue.  Tap water and lower temperatures gives you random results each time you use it.  Storage of unused crystals should be in an air tight plastic or glass jar.  If stored in a non humid cool environment, they should last years.

Ferric chloride at 70-80 deg C will etch more copper, faster (like a few minutes), with more consistent speed.  However, at this temp, there are fumes and they will damage/corrode exposed metals in you work-shop if you don't have good ventilation.

[Mechatrommer]

is it wise to buy 1Kg dry FeCl3?
http://www.ebay.com.my/itm/Ferric-Chloride-etching-copper-zinc-steel-brass-pcb-etchant-1-Kg-FeCl3-/261341838888?hash=item3cd92ffe28:g:f8AAAOSw-CpYB3oE

or should i buy smaller quantity? the point is i dont want to keep ordering and waiting weeks before i can etch current project board. i know i'll have etchant supply forever without worry. but the drawback is... if dry FeCl3 interacts with moisture in time and diminish its etching strength, then there is no point buying large quantity anyway.

[Monkeh]

You must keep it absolutely dry. Or.. mix it up and keep it liquid. It stores practically indefinitely in liquid form so long as it's sealed.

[Mechatrommer]

You must keep it absolutely dry.

or else?

It stores practically indefinitely in liquid form so long as it's sealed.

or else?

sometime i think a plastic bottle with screw cap is a "sealed" container, but apparently not for some containee.

[IanB]

Ferric chloride at 70-80 deg C will etch more copper, faster (like a few minutes), with more consistent speed.  However, at this temp, there are fumes and they will damage/corrode exposed metals in you work-shop if you don't have good ventilation.

Oh my. I've never used ferric chloride hot like that. Always at room temperature, or slightly warmed to 30 C or so. I fear to think how it would behave if you make it as hot as that.

[Ian.M]

The EBAY ad isn't anhydrous ferric chloride, its the hydrated ferric chloride crystals so although it will absorb atmospheric moisture, it wont give off HCl fumes if kept cool.

You *SHOULD* keep ferric chloride double-tubbed - if any leaks its is a real PITA and incredibly destructive.   Rather than opening your bulk tub frequently, I'd suggest making a stock solution.  I believe 50ml water to 100g of ferric chloride hexahydrate crystals is the correct ratio for an approximately 40% solution comparable to the concentrated commercial ones.  If any of the crystals have liquefied, it gets more difficult as that's a saturated solution. but if you drain that off, add water according to the remaining weight of crystals then add back what you drained off, it won't be far off.   *DON'T* use any metal containers (or lids) or utensils, or anything that you care if it gets stained.  Again, keep your 40% ferric chloride solution stock bottle tightly closed, upright inside a sealed non-metallic outer container, and for %DEITY%'s sake properly labelled!

[Mechatrommer]

thanks Ian.M for the advice. in fact double insulation is what i did to my ammonia or whatever persuphate etchant here. etchant in glass container with airtight plastic cover and then enclosed in clear plastic bag closed with cloth clip not so airtight but double insulation. but but... its not stopping moisture from coming in, or the inside etchant from interacting with the atmosphere. fwiw, attached picture is how i store my eco-etchant (right) the left container (liquid sweetener) is for reference only just how red the right cover was few weeks ago. you should see it inside the plastic bag. removing the glass container, the inside of plastic bag smell just like a cat's piss brewed for a week (and my hand is stained with that smell too) maybe thats how ammonia smells. not yet a good storage skill i guess.

[yada]

I found you can by most of these chemicals for cheap in bulk at pool supply stores. They sell 5 gallon buckets of the stuff.

[MrAl]

Hi,

I had some bottles of FC for years and years, like 10 or 15 years, and it still worked when needed.  The bottle i used was the one that came with it with one purchase, maybe from Radio Shack.  It's a plastic bottle but dont know what kind of plastic.  I've since gotten the dry form of FC and mixed my own (with water) and put that in the bottle, that lasts a very long time too.
I think all it does is dry out if exposed to air, so it becomes more and more concentrated.  In a closed bottle that is sealed well though it cant dry out.

[MagicSmoker]

but the etchant I use at home - for the one time a year I might make a board myself - is a solution of 1 part "muriatic acid" (aka hydrochloric acid, sold here at 31.45% concentration) to 3 parts 3% hydrogen peroxide solution. Etches very fast without heating, is transparent, so it's easy to see when its done, and it is just about as cheap as dirt.

yeah i wish i have that supply shippable to my place. i just saw last night the ferric chloride also constructed from these ingredients. so i dont understand why the hassle of making ferric chloride all the way if hydrochloric acid + hydrogen peroxide can do the same job... here the video..

I buy both chemicals locally: 3% hydrogen peroxide solution can be found at pretty much every pharmacy, grocery, etc. as it's used as a disinfectant and for cleaning small wounds and scrapes, while muriatic acid is used for lowering the pH of swimming pools so can be found at most hardware and pool supply stores.

Ferric chloride can be made from iron, hydrochloric acid and hydrogen peroxide (however, I know you can't make it by simply adding iron to hydrochloric acid), but since that requires one more ingredient than my formula, and makes a worse etchant to boot, I don't see the point. Also, iron powder reacts vigorously with oxygen in humid air, which at best leads to a rusty puddle; at worst leads to a fire (that is to say, if the powder is ground fine enough it will spontaneously catch on fire when exposed to air).

I'm still no closer to knowing what your mystery white powder called "CCL Blue" is after looking at that hilarious ebay link, but most likely it is a persulphate salt of either ammonia or sodium or potassium.

All three persulphate salts are better etchants than ferric chloride in that they work faster, are less dependent on heating/bubbling and are transparent, but the formula I gave before has all the advantages of the persulphate etchants as well as being easily made from locally available chemicals that are downright cheap. Just remember to Always Add Acid and don't leave the jug of muriatic acid open too long as the fumes are corrosive.

[janoc]

thanks Ian.M for the advice. in fact double insulation is what i did to my ammonia or whatever persuphate etchant here. etchant in glass container with airtight plastic cover and then enclosed in clear plastic bag closed with cloth clip not so airtight but double insulation. but but... its not stopping moisture from coming in, or the inside etchant from interacting with the atmosphere. fwiw, attached picture is how i store my eco-etchant (right) the left container (liquid sweetener) is for reference only just how red the right cover was few weeks ago. you should see it inside the plastic bag. removing the glass container, the inside of plastic bag smell just like a cat's piss brewed for a week (and my hand is stained with that smell too) maybe thats how ammonia smells. not yet a good storage skill i guess.

Oh yikes! Don't store ammonium persulfate in an airtight bottle! That thing decomposes and releases oxygen and ammonia - that could burst the bottle open! (and explains the "cat piss" smell). In fact, a solution of persulfate shouldn't be stored at all - mix as much as you need to etch the board and then  dispose of it. Make a fresh solution each time. The old one will likely not etch well/at all because it is decomposed already.

Ferric chloride can be reused and regenerated, persulfate not really because of its short useful life and complicated storage. That's why it is only mostly used in the industry where large amounts of boards are made in one go. It is not a very economic etchant for a hobbyist.

[janoc]

All three persulphate salts are better etchants than ferric chloride in that they work faster, are less dependent on heating/bubbling and are transparent, but the formula I gave before has all the advantages of the persulphate etchants as well as being easily made from locally available chemicals that are downright cheap. Just remember to Always Add Acid and don't leave the jug of muriatic acid open too long as the fumes are corrosive.

Actually, that's the opposite  - persulfate etches pretty poorly unless warm. Ferric chloride should not be heated at all (or only very little) because you will get corrosive fumes otherwise. Agitation/bubbling is important to any etchant.

Nobody should be forced to make their own ferric chloride. It is possible but why? Both crystals and pre-made etchant can be fairly easily bought online.

And if the OP is concerned about ecology/storage, hydrochloric acid + peroxide combo likely isn't a very good suggestion. Yes, it is very cheap, is available almost everywhere and etches quickly. But that's about the only thing going for it. The uber corrosive fumes from the acid will eat every metal you have nearby the (even properly closed - it is never 100% artight) bottle and it is a lot more dangerous to handle. It is also very easy to over-etch the boards with it because it literally eats the copper away in front of your eyes. Proper disposal of it after every etching (it cannot be reused) is also fun.

[DTJ]

Oh yikes! Don't store ammonium persulfate in an airtight bottle! That thing decomposes and releases oxygen and ammonia - that could burst the bottle open! (and explains the "cat piss" smell). In fact, a solution of persulfate shouldn't be stored at all - mix as much as you need to etch the board and then  dispose of it. Make a fresh solution each time. The old one will likely not etch well/at all because it is decomposed already.

Ferric chloride can be reused and regenerated, persulfate not really because of its short useful life and complicated storage. That's why it is only mostly used in the industry where large amounts of boards are made in one go. It is not a very economic etchant for a hobbyist.

Maybe that's a good idea, however I've stored ammonium persulphate powder and aqueous solution in plain old sealed plastic bottles under the sink in my workshop for years without any issue.

It might try to gas off a bit but I've never had so much as a bulging bottle on a 40C day.

Lately I've moved to just mixing a very small amount and etching the board in a stainless tray sat in an electric frypan. I just tip the leftover etchant down the sink (water authority said this is fine for small volumes).

[MagicSmoker]

For an interesting discussion on the relative merits of various etchants on electronics stackexchange:

https://electronics.stackexchange.com/questions/5540/ferric-chloride-or-muriatic-acid-hydrogen-peroxide-for-etching

EDIT - fixed url tag

[Ian.M]

Part of the storage problems may be the purity or lack there of of the mysterious chemicals sold on EBAY.   Ferric Chloride is cheap, and not too sensitive to purity, so in that case you are likely to get what you pay for, but %DEITY% knows what's in 'CCL Blue Etchant' powder.  We only know it contains a high proportion of Ammonium Persulfate, from its decomposition products.  The other part of the storage problem is probably Malaysia's climate. (Assuming O.P's location flag is correct) Its neither arid nor cool, both of which are requirements for long-term storage of solid Ammonium Persulfate.  Its recommended to store it below 25 deg C, and in bulk industrial quantities, properly stored, it has a shelf life of only three years with noticeable caking in as little as a year.  Its storage container needs to keep water vapour out but vent over-pressure without popping its lid off or bursting.  Solutions are not stable, especially when contaminated, to the point that all the major laboratory chemical suppliers advocate preparing them fresh.

I have edited my previous post to clarify that I am talking about hydrated ferric chloride, NOT ANYTHING ELSE. 

Although you cant store mixed Hydrochloric Acid + Hydrogen Peroxide etchant, its the starter for the air regenerated acid Copper(II) Chloride etchant system, so just tip in an excess of finely divided copper (e.g. scrap un-tinned stranded wire, stripped of its insulation and untwisted and crumpled) into your used etchant, to convert it to stable, storable Copper chlorides (however don't do this before disposal - you don't want to increase the copper concentration).

[Mechatrommer]

Ferric chloride can be made from iron, hydrochloric acid and hydrogen peroxide (however, I know you can't make it by simply adding iron to hydrochloric acid), but since that requires one more ingredient than my formula, and makes a worse etchant to boot, I don't see the point.

yup i've provided links to what you said. i'm not going to diy FeCl3 since i already ordered small quantity (560g FeCl3 dilute to 2L liquid) from our local online seller (i just found out we now have this locally, and it also affordable cheaper). we also have 3% hydrogen peroxide sold, but hydrochloric acid is still nowhere to be found unless from usa, german or romania at premium price + shipping. i'm not going to buy that corrosive and risk a leakage in an airplane.

I'm still no closer to knowing what your mystery white powder called "CCL Blue" is after looking at that hilarious ebay link, but most likely it is a persulphate salt of either ammonia or sodium or potassium.

well now it is revealed it some sort of ammonia and persulphate... since you havent used it, my advice is, dont buy it. its useless for making a board in a blue moon, only in mass production as people have mentioned here.

And if the OP is concerned about ecology/storage, hydrochloric acid + peroxide combo likely isn't a very good suggestion.

hell no. i dont care i just want to etch some pcb. i dont even know and care what components of that "CCL blue" white salt comprises until now. people adviced using glove i'm not going to, i just wash my hand afterward. i've experiment with many corrosive liquid with my hand nothing will peel off my skin at an instant, the worst chemical i've work with is car paint remover, but that i only experience a nasty itch in small quantity. so i know its a big no no if touching skin in big quantity. this ammonia sulphate is nothing near that hazard. i'll throw it anywhere at worst some giant lizard will die, well good for us giant lizard is a big harassment to the neighboorhood.

(Assuming O.P's location flag is correct) Its neither arid nor cool, both of which are requirements for long-term storage of solid Ammonium Persulfate.

we are known for 90% RH, the good part is we dont experience much semiconductor damage due to electrostatics here.

anyway, i've ordered my 1st pack of FeCl3, cant wait for it to arrive for me to learn some chemistry lesson.