oxidation – Hackaday https://hackaday.com Fresh hacks every day Fri, 01 Sep 2023 16:52:33 +0000 en-US hourly 1 https://wordpress.org/?v=6.9.4 156670177 Copper Be Gone: The Chemistry Behind PCB Etching https://hackaday.com/2023/08/31/copper-be-gone-the-chemistry-behind-pcb-etching/ https://hackaday.com/2023/08/31/copper-be-gone-the-chemistry-behind-pcb-etching/#comments Thu, 31 Aug 2023 14:00:32 +0000 https://hackaday.com/?p=610202 For a lot of reasons, home etching of PCBs is somewhat of a dying art. The main reason is the rise of quick-turn PCB fabrication services, of course; when you …read more]]>

For a lot of reasons, home etching of PCBs is somewhat of a dying art. The main reason is the rise of quick-turn PCB fabrication services, of course; when you can send your Gerbers off and receive back a box with a dozen or so professionally made PCBs for a couple of bucks, why would you want to mess with etching your own?

Convenience and cost aside, there are a ton of valid reasons to spin up your own boards, ranging from not having to wait for shipping to just wanting to control the process yourself. Whichever camp you’re in, though, it pays to know what’s going on when your plain copper-clad board, adorned with your precious artwork, slips into the etching tank and becomes a printed circuit board. What exactly is going on in there to remove the copper? And how does the etching method affect the final product? Let’s take a look at a few of the more popular etching methods to understand the chemistry behind your boards.

Wet, Dry, or In Between?

At the end of the day, PCB etching is all about removing copper from a board in as controlled a fashion as possible. PCB etching methods generally fall into one of two broad categories: wet and dry processes. For the home gamer, dry processes would include methods like milling out traces with a CNC router, or even the tried and true method of scratching out traces using a razor blade. On a commercial level, dry etching generally refers to methods like laser etching, where a high-power laser is used to ablate copper from the underlying substrate to create traces, or plasma etching, which uses RF energy to generate a reactive plasma from an etching gas.

Isotropic vs. anisotropic etching. Most wet etching methods are isotropic to some degree, which can lead to problems like undercutting.

With the notable exception of scratching out traces with an X-Acto, these dry etching methods all have the disadvantage of needing specialized machines of some sort. What they lack in simplicity, though, they make up for in the direction of etching and the fine control they achieve in copper removal. Dry etching methods are all anisotropic processes; that is, they direct copper removal in a single direction and avoid the risk of undercutting. Wet methods, all of which rely on chemical reactions to get metallic copper into an aqueous solution, are isotropic processes, meaning that they proceed more or less evenly in all directions. This can become a problem; if the process is not tightly controlled, the etching reactions can extend underneath the resist layer masking off areas of the future traces of the PCB, potentially creating high-resistance narrowing of traces or even open circuits.

Ferric Chloride

If you’ve done any PCB etching at home, chances are pretty good that you’ve at least tried the old standby, ferric chloride. It’s cheap and easy, and has a lot of advantages over other wet etching chemistries, not least of which is that you can make an almost unlimited supply of the stuff using nothing but a handful of nails and some chemicals you can easily source at a pool store and a pharmacy:

Also known as iron (III) chloride (FeCl3), ferric chloride quickly and effectively dissolves metallic copper, but what does the reaction look like? The overall reaction is pretty straightforward:

\bf 2 FeCl_{3} + Cu \rightarrow 2 FeCl_{2} + CuCl_{2}

When ferric chloride comes in contact with metallic copper, one of its chlorine atoms is transferred to a copper atom, making copper (II) chloride, or cupric chloride, which is soluble in water. This allows the copper that was once bonded to the PCB substrate to be rinsed away. It seems simple enough, but that overall reaction hides a lot of chemical complexity, and the details are worth digging into a bit.

First, a bit about nomenclature. Compounds with metal cations (positively charged species) have traditionally used different suffixes to denote their oxidation state, or the charge of the atom. The “-ic” suffix denotes the higher oxidation state, while “-ous” refers to the lower oxidation state. The suffix is tacked onto the Latin prefix for the metal, yielding names such as “ferric”, referring to iron with a 3+ oxidation state, or “ferrous”, which is a 2+ state. This convention stretches back almost to the days of alchemy, and while it’s still in common use, the standard nomenclature is now to indicate the oxidation state with parenthetical Roman numerals in compound names, iron (III) chloride (FeCl3) and iron (II) chloride (FeCl2).

The nomenclature sets the stage for understanding the underlying reactions that make ferric chloride good at etching copper. In solution, ferric chloride rapidly dissociates into iron (III) and chloride ions:

\bf FeCl_{3} \rightleftharpoons Fe^{3+} + 3 Cl^{-}    (eq. 1)

Likewise, water dissociates into hydrogen and hydroxyl ions:

\bf H_{2}O \rightleftharpoons H^{+} + OH^{-}    (eq. 2)

This results in an abundance of iron (III) ions with a strong positive charge in an environment with a lot of negatively charged hydroxyl ions. They get together and form iron (III) hydroxide, which is an insoluble compound that precipitates out of solution:

\bf Fe^{3+} + 3 OH^{-} \rightleftharpoons Fe(OH)_{3}    (eq. 3)

Pulling all those hydroxyl ions out of solution leaves behind a bunch of hydrogen ions, which has the effect of making the solution more acidic (decreasing its pH). This creates an environment where the iron (III) ions from equation 1 gain an electron (reduction) from the solid copper cladding on the PCB, resulting in oxidation of the copper to copper (II) ions in solution:

\bf 2 Fe^{3+} + Cu_{(solid)} \rightleftharpoons 2 Fe^{2+} + Cu^{2+}    (eq. 4)

The copper (II) and iron (II) ions in solution are then free to glom onto all those highly electronegative chloride ions from equation 1, forming the copper (II) chloride and iron (II) chloride products on the right side of the overall equation, and leaving behind copper-free areas on the newborn PCB. The etching solution eventually becomes saturated with copper (II) oxide, which starts precipitating out of the solution as a blue-green solid. It takes a while to get there, though; depending on the strength of the etchant when fresh, you can expect it to hold up to 50 grams per liter of copper metal before it can hold no more.

Persulfates

Ammonium persulfate. The persulfate bit on the right is what matters; the counterion on the left could just as easily be sodium or potassium. Source: [Kemikungen], own work (public domain).
Another wet etching method often used by hobbyists is the persulfate method. In general, persulfates are strong oxidizers, thanks to the oxygen-to-oxygen bond between the two sulfate groups. This makes persulfate a peroxide, like the more familiar hydrogen peroxide, where the double oxygen presents a good acceptor site for electrons.

Persulfates are usually available as salts of either sodium or ammonium, or sometimes even potassium. These positively charged species are known as counterions; when dissolved in water, persulfate salts rapidly dissociate into free persulfate ions and their counterions:

\bf \left[NH_{4}\right]^{+}_{2}\left[S_{2}O_{8}\right]^{2-} \rightleftharpoons 2 \left[NH_{4}\right]^{+} + \left[S_{2}O_{8}\right]^{2-}

The counterions just sort of float off and don’t participate in the following etching reaction in any serious way; they just busy themselves loosely binding to the persulfate ions and falling back off in a constant dance of equilibrium. The real action is with the persulfates, which are ready to get to work on metallic copper.

Unlike with ferric chloride, the overall reaction between persulfates and copper is pretty much the whole story:

\bf Cu_{(solid)} + \left[S_{2}O_{8}\right]^{2-} \rightarrow Cu^{2+} + 2 \left[SO_{4}\right]^{2-}

When the persulfate ions come in contact with solid copper, the metal eagerly donates electrons to the peroxide bond, reducing the bond and splitting the persulfate into two sulfate ions while solubilizing the copper. The dissolved copper then binds to one of the sulfate ions to make copper (II) sulfate, which lends the persulfate etchant solution a familiar blue-green tinge as etching proceeds.

Cupric Chloride

Another etchant popular with homebrewers and commercial manufacturers alike is cupric chloride, or using the currently accepted nomenclature, copper (II) chloride. It might seem a little weird that an etchant for copper would contain copper itself, but cupric chloride etches quickly and cheaply, and has the benefit of regeneration.

While it’s possible to just buy (or make) a cupric chloride solution by treating scrap copper with hydrochloric acid, it’s easier to just throw all the ingredients together with the PCB to be etched and let the copper on the board stand in for the scrap copper. The overall reaction is pretty simple, but again, it hides some interesting chemical complexity:

\bf CuCl_{2} + Cu_{(solid)} \rightarrow 2 CuCl

Cupric chloride attacks the metallic copper on the PCB, producing two molecules of soluble cuprous chloride in the process. Pretty simple, but where does the cupric chloride come from in the first place? We need a way to dissolve a little bit of copper from the board and get it to react with some chloride ions. This is commonly done with a mixture of hydrochloric acid and hydrogen peroxide. First, the hydrogen peroxide decomposes into water and an oxygen radical, while the hydrochloric acid dissociates into hydrogen and chloride ions:

\bf H_{2}O_{2} \rightarrow H_{2}O + O\cdot

\bf HCl \rightleftharpoons H^{+} + Cl^{-}

This is a pretty potent mix, with the oxygen radical and the chloride ions attacking the solid copper metal and forming a complex known as tetrachlorocuprate:

\bf O\cdot + 2 H^{+} + Cu_{(solid)} + 4 Cl^{-}\rightarrow H_{2}O + \left[CuCl_{4}\right]^{2-}

The chlorine-copper complex is capable of directly oxidizing copper, which creates the cupric chloride that will then go on and do the bulk of the etching:

\bf \left[CuCl_{4}\right]^{2-} + Cu_{(solid)} \rightarrow 2CuCl_{2}

The key advantage of cupric chloride etching is regeneration, which can be accomplished in a number of ways. Industrially, chlorine gas is often bubbled through the etchant; this changes the cuprous chloride back into cupric chloride without diluting the etchant, but is obviously not something that you’d want to do in the home lab. Sodium perchlorate, another strong oxidizing agent, is sometimes used industrially, but has the disadvantage of generating a sodium chloride precipitate to the etchant which needs to be removed. There are also electrolytic and electroosmotic methods that restore the cupric chloride while also recovering the metallic copper, but those are obviously complicated.

Luckily, the home gamer has a simple regeneration method available, one that uses chemicals that we’ve already added to get the reaction started: hydrochloric acid and peroxide:

\bf 2CuCl + 2 HCl + H_{2}O_{2} \rightarrow 2 CuCl_{2} + 2 H_{2}O

Oxidizing cuprous chloride with hydrogen peroxide in the presence of chloride ions from hydrochloric acid effectively resets the etching solution, restoring the cupric chloride and making the solution ready for another go at the solid copper metal. This does produce water molecules, though, so dilution is a problem, but that can be compensated for to some degree by adding more acid. Still, it’s a pretty neat system, a nearly closed-loop process that’s cheap and simple.

There are obviously a lot of details missing from this quick tour, and there are a ton of other etching methods I haven’t covered. But whichever one you choose to use, make sure you take the proper precautions, wear your PPE, and have a plan for what you’re going to do with the waste.

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Low-Tech Fix Saves Expensive, High-Tech TV From Junk Pile https://hackaday.com/2020/10/27/low-tech-fix-saves-expensive-high-tech-tv-from-junk-pile/ https://hackaday.com/2020/10/27/low-tech-fix-saves-expensive-high-tech-tv-from-junk-pile/#comments Tue, 27 Oct 2020 08:00:00 +0000 https://hackaday.com/?p=443771 [Tweepy]’s TV stopped working, and the experience is a brief reminder that if a modern appliance fails, it is worth taking a look inside because the failure might be something …read more]]>
Wiggling this connector caused the backlight to turn off and on.

[Tweepy]’s TV stopped working, and the experience is a brief reminder that if a modern appliance fails, it is worth taking a look inside because the failure might be something simple. In this case, the dead TV was actually a dead LED backlight, and the fix was so embarrassingly simple that [Tweepy] is tempted to chalk it up to negligently poor DFM (design for manufacture) at best, or even some kind of effort at planned obsolescence at worst.

What happened is this: the TV appeared to stop working, but one could still make out screen content while shining a bright light on the screen. Seeing this, [Tweepy] deduced that the backlight had failed, and opened up the device to see if it could be repaired. However, the reason for the backlight failure was a surprise. It was not the power supply, nor even any of the LEDs themselves; the whole backlight wouldn’t turn on because of a cheap little PCB-to-PCB connector, and the two small spring contacts inside that had failed.

The failed connector, once cut open, showed contacts in poor condition (click to enlarge). It was ditched for a soldered connection, and the TV lived again.

From the outside things looked okay, but wiggling the connector made the backlight turn on and off, so the connection was clearly bad. Investigating further, [Tweepy] saw that the contact points of the PCBs and the two little conductors inside the connector showed clear signs of arcing and oxidation, leading to a poor connection that eventually failed, resulting in a useless TV. The fix wasn’t to clean the contacts; the correct fix was to replace the connector with a soldered connection.

Using that cheap little connector doubtlessly saved some assembly time at the factory, but it also led to failure within a fairly short amount of time. Had [Tweepy] not been handy with a screwdriver (or not bothered to investigate) the otherwise working TV would doubtlessly have ended up in a landfill.

It serves as a good reminder to make some time to investigate failures of appliances, even if one’s repair skills are limited, because the problem might be a simple one. Planned obsolescence is a tempting doorstep upon which to dump failures like this, but a good case can be made that planned obsolescence isn’t really a thing, even if manufacturers compromising products in one way or another certainly is.

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Cheap PSoC Enables Electrochemistry Research https://hackaday.com/2018/08/04/cheap-psoc-enables-electrochemistry-research/ https://hackaday.com/2018/08/04/cheap-psoc-enables-electrochemistry-research/#comments Sun, 05 Aug 2018 05:00:52 +0000 http://hackaday.com/?p=318581 You may think electrochemistry sounds like an esoteric field where lab-coated scientists labor away over sophisticated instruments and publish papers that only other electrochemists could love. And you’d be right, …read more]]>

You may think electrochemistry sounds like an esoteric field where lab-coated scientists labor away over sophisticated instruments and publish papers that only other electrochemists could love. And you’d be right, but only partially, because electrochemistry touches almost everything in modern life. For proof of that look no further than your nearest pocket, assuming that’s where you keep your smartphone and the electrochemical cell that powers it.

Electrochemistry is the study of the electrical properties of chemical reactions and does indeed need sophisticated instrumentation. That doesn’t mean the instruments have to break the grant budget, though, as [Kyle Lopin] shows with this dead-simple potentiostat built with one chip and one capacitor. A potentiostat controls the voltage on an electrode in an electrochemical cell. Such cells have three electrodes — a working electrode, a reference electrode, and a counter electrode. The flow of electrons between these electrodes and through the solutions under study reveal important properties about the reduction and oxidation states of the reaction. Rather than connect his cell to an expensive potentiostat, [Kyle] used a Cypress programmable system-on-chip development board to do everything. All that’s needed is to plug the PSoC into a USB port for programming, connect the electrodes to GPIO pins, and optionally add a 100 nF capacitor to improve the onboard DAC’s accuracy. The video below covers the whole process, albeit with a barely audible voiceover.

Still not sure about electrochemistry? Check out this 2018 Hackaday Prize entry that uses the electrochemistry of life to bring cell phones back to life.

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Liquid Metal Changes Shape to Tune Antenna https://hackaday.com/2015/08/31/liquid-metal-changes-shape-to-tune-antenna/ https://hackaday.com/2015/08/31/liquid-metal-changes-shape-to-tune-antenna/#comments Mon, 31 Aug 2015 20:00:44 +0000 http://hackaday.com/?p=168212 Antennas can range from a few squiggles on a PCB to a gigantic Yagi on a tower. The basic laws of physics must be obeyed, though, and whatever form the …read more]]>

Antennas can range from a few squiggles on a PCB to a gigantic Yagi on a tower. The basic laws of physics must be obeyed, though, and whatever form the antenna takes it all boils down to a conductor whose length resonates at a specific frequency. What works at one frequency is suboptimal at another, so an adjustable antenna would be a key component of a multi-band device. And a shape-shifting liquid metal antenna is just plain cool.

The first thing that pops into our head when we think of liquid metal is a silvery blob of mercury skittering inside the glass vial salvaged out of an old thermostat. The second image is a stern talking-to by the local HazMat team, so it’s probably best that North Carolina State University researchers [Michael Dickey] and [Jacob Adams] opted for gallium alloys for their experiments. Liquid at room temperature, these alloys have the useful property of oxidizing on contact with air and forming a skin. This allows the researchers to essentially extrude a conductor of any shape. What’s more, they can electrically manipulate the oxidative state of the metal and thereby the surface tension, allowing the conductor to change length on command. Bingo – an adjustable length antenna.

Radio frequency circuits aren’t the only application for gallium alloys. We’ve already seen liquid metal 3D printing with them. But we need to be careful, since controlling the surface tension of liquid metals might also bring us one step closer to this.

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