Vinegar nickel plating chemistry gone stale?

[Tim9]

All great stuff. Thanks Graham and Homebrew. I have been reading up on this and was wondering about that micro crack layered nickel. You explanation makes perfect sense Graham. When I first read “cracked Nickel electroplating “ I actually thought it was some silly decorative coating. Finding out it’s micro cracks which aren’t visible makes total sense now.

FWIW, I spent half the day cleaning my dial and filling the pits with tin / silver ( 95/5 ) solder. Soaked it in Evapo-Rust and then I even did a quick acid dip to get the rust out of the pits. The filling of the pits came out great. But, I totally screwed the pup when I mounted it on the lathe and went to turn it down. My goal was to turn just back to the surface and then I was going to use a manual graver to clean the tin out of the lines and numbers.
It was going well but I ran into a problem because I just rushed it. I should have mounted the dial in my Tru-chuck. The problem is when I got to the surface on half of the dial…. I still had a lot of solder on the other side.

I might have to make a new one but it just the dial on the compound and I only need it for threads. And for threads which don’t have to mic to specs I can still wing it by “try and fit “ the thread depths.
It’s just that I don’t feel like spending all day for a dial with 200 graduations plus the numbers….especially 110 to 190. Just for the numbering means I have to spend the better part of another day building a jig set up to stamp the numbers.
Anyway, here’s a few of the pics.

in the end….I just cut too deep and removed all the numbers and graduations because I got distracted and I think I took too deep of a cut. The depth of the original graduations are really shallow on these dials. It’s almost like if I tried to make a new one, I’ll have to be super careful not to cut the lines deep and then the lines would just all mesh together.

 

[graham-xrf]

@homebrewed :
Hi Mark - I think the lid of the jar is a distinct possibility.
Here we have to start some logic, guessing, and detective work. The first is the brown stuff does seem to be a solution. You can see light through it. It may be brown, but it is not cloudy. Therefore, however that colour came about, it is the colour of some ionic radical, or mixture of some ionic radical with the (nickel 2+) and (acetate 2-). There will be H3O+ and OH- ions, which have no colourless. I am thinking the vinegar (acid) might have chewed up some lid iron. Iron(II)acetate ? Iron(III) acetate? Hmm.

Iron(II) acetate is white, though can get slightly discoloured. It also has a light green type.
Iron(III) actate is a red-brown complex once uses as a test for ferric, meaning iron(III), ions

Then I found --> https://en.wikipedia.org/wiki/Iron(II)_acetate
Particularly "Reaction of scrap iron with acetic acid affords a brown mixture of various iron(II) and iron(III) acetates that are used in dyeing".
I think that is likely what we have!

I know a certain weight of nickel went into that liquid, and it is still all in there, and it is not as bits of solid metal (I will check if it is not laying about on the bottom of the jar.

1. The next batch of fresh green nickel acetate I make will have a small amount sealed up in a test tube, and it can be kept long enough to see what happens to it.

2. I can plate away with the brown solution regardless, but I am not sure I should. Can one electroplate iron out onto steel?? I don't really want any ex-jar lid stuff becoming part of my counter-shaft! Logically, a negative electrode will donate two electrons to make the iron come out as iron (plating??). I would prefer it gets oxidized into rust, and drops out.

3. I might try some 36% hydrogen peroxide, or some other trick to precipitate the iron. It might make the solution go green again. These games will likely happen in a test tube. Sure, I will try out the brown for plating, and if it works, then great, I will use it some more. I just don't like the look of it, even if it can continue working indefinitely as a plating solution. I agree that contaminants might affect the plating quality.

4. My collection of nickel plating chemicals is becoming embarrassing. I do have nickel sulfate. I also have nickel ammonium sulfate which unexpectedly arrived when nickel sulfate was ordered. I don't know what to do with it, but I know I do not like ammonia. Maybe I can react it with something, and get the nickel sulfate out.

5. All future solution storage will be in glass jars with plastic lids. It's quite hard to get glass stoppers. Ground glass fit stoppers can get stuck forever, especially if you have something alkaline in the bottle.

When I was a child, I loved experimenting with chemistry stuff, but we could not afford a decent chemistry set, and my Mum did not approve anyway. So my chemistry was done somewhat in secret. Now, it seems things are still somewhat like that. The lady of the house knows I have tubs of various chemicals, and that I use electrolysis, but she thinks it's just more machinery restoration rust removal. (Citric acid, sodium carbonate, etc.)

 

[graham-xrf]

All great stuff. Thanks Graham and Homebrew. I have been reading up on this and was wondering about that micro crack layered nickel. You explanation makes perfect sense Graham. When I first read “cracked Nickel electroplating “ I actually thought it was some silly decorative coating. Finding out it’s micro cracks which aren’t visible makes total sense now.

FWIW, I spent half the day cleaning my dial and filling the pits with tin / silver ( 95/5 ) solder. Soaked it in Evapo-Rust and then I even did a quick acid dip to get the rust out of the pits. The filling of the pits came out great. But, I totally screwed the pup when I mounted it on the lathe and went to turn it down. My goal was to turn just back to the surface and then I was going to use a manual graver to clean the tin out of the lines and numbers.
It was going well but I ran into a problem because I just rushed it. I should have mounted the dial in my Tru-chuck. The problem is when I got to the surface on half of the dial…. I still had a lot of solder on the other side.

I might have to make a new one but it just the dial on the compound and I only need it for threads. And for threads which don’t have to mic to specs I can still wing it by “try and fit “ the thread depths.
It’s just that I don’t feel like spending all day for a dial with 200 graduations plus the numbers….especially 110 to 190. Just for the numbering means I have to spend the better part of another day building a jig set up to stamp the numbers.
Anyway, here’s a few of the pics.

in the end….I just cut too deep and removed all the numbers and graduations because I got distracted and I think I took too deep of a cut. The depth of the original graduations are really shallow on these dials. It’s almost like if I tried to make a new one, I’ll have to be super careful not to cut the lines deep and then the lines would just all mesh together.

Ouch! I do sympathize.
I suggest don't have too many regrets. If you "roll your own", you will have given something of you into the machine design, and even if it ends up as a bit of a quick fix, it can make you proud!

I get it that hard cut graduations can be a tedious path that might have several re-starts while one learns the pitfalls. Indexing using the clicks from a 100 or 200 tooth saw blade still involves making all those cuts, and still no numbers stamped in. You can make your own index disc just by printing a divided circle image on paper, and sticking it down on an old CDROM disc, or something out of plywood..

OR ..
You can dodge the cutting graduations altogether. You need to drive a drawing or imaging software, or use CAD, but the plan is to print the image what you need on a strip that is π x diameter of your dial. Now you have several routes to the final product.

1.. You can print it on photographic (good) shiny paper, wrap it around the dial glued on, and sealed with (careful) gentle coats of clear spray lacquer, so to avoid the paper going "transparent".

2. You can have the printed image protected under a layer of clear film, or under a clear plastic cover "drum".

3. You can print the image onto that clear film. Coat the dial with that resist stuff used for making PCBs, wrap the "image" around the dial, leave in the sunlight for a few minutes, then dunk in caustic soda (develop), and then into ferric chloride (which is also PCB etchant). It will etch the graduations into the iron. There are variations to this method, and low cost ingredients on eBay. There are also YouTube videos on how to etch anything on steel. I am considering something like this to put numbers on a tailstock quill.

4. You can keep an eye out on eBay for 200 division dials, and make a project to adapt one to your compound. I have to go this route. My compound dial, only 3/4" diameter to start with (ridiculous!) has graduations hardly visible any more! I already sawed through the Acme nut, and made my own from bronze powder in epoxy, and I will be welding the hell out of the T-slot, so having a go at the dial as well somehow seems OK.

I say that. I hope to get back to playing with the stuff I like soon.

For edification and amusement, see the knowledge of 1869. You will quickly see that those days, folk handled stuff OK in the full knowledge of how toxic the stuff was. I won't be using anything that involves cyanide, even though it is (industrially) very common. There is lots of great stuff about what will or won't plate onto various metals, and what stuff will mess you up. The language is quaint, and good Lord - I do have to figure out what is "one or two Smee cells" for an electric power source.

BUT.. the bottom of the last page taught me that the inadvertently incorrect supply of nickel ammonium sulfate instead of nickel sulfate is not to be a waste. It seems Isaac Adams used it to plate nickel - in 1869!

 

[Tim9]

My apologies for not directly addressing your question..
I do believe you can plate nickel onto just about anything. There is a reason nickel is the go-to first substance as "nickel strike" in so many plating operations. For example, when you get something chrome plated, if it's an awkward metal, then electroless nickel goes on first, to then allow a substantial thickness ductile copper coat. That coat is mechanically polished up to the shiny finish required. Then cleaned and degreased, and nickel is plated on. This coating is also relatively ductile. Then finally, the (thin) outer layer of chrome. Chrome plating is hard, and highly stressed, and can peel off. Versions of final plate are "micro-cracked" relieving stress, and having high adhesion. Oxygen and moisture may well penetrate the cracking, only to be stopped by the nickel undercoat. This "cracking" is not directly visible.

The lesson here is - nickel plates onto copper. Copper has a more positive electrode potential than nickel.

Zincate process
This is part of the tricks one has to get up to to plate onto aluminium. They use sodium hydroxide and zinc oxide. The caustic soda cuts through the surface oxide that is on aluminium, and lets the zinc deposit on (all by itself), without the help of any outside electricity. This thin layer of zinc adheres stronglgy, and is the base for copper or brass, and subsequent nickel.

Then they get clever, and add in some nickel solution to the zincate, along with other stuff to keep it all together, and plate away with the nickel.

There is the discovery of the "double zincate" preparation, which just means "do it twice". The first time it prepares the surface. Then they strip it off with nitric acid, and start again. It seems the surface reactions first time are different to second time. It bonds into the sponge-like matrix.

The lesson here is - you can plate onto zinc (which is what you asked).
On the way - we learn that is the route to plating aluminium.

Plating nickel onto tin
This question arises when folk want to nickel plate an item that has been brazed (95% tin + 5% Ag), silver soldered.
I don't have the immediate answer, but there is a lot of traffic on the subject. Without going too far into exotic chemicals, you can try it with the vinegar. Regular lead-free solder (for electronics) and maybe also for heating plumbing joints, is likely 99.3% tin and 0.7% copper.
If I get a chance, I might try a chunk in my nickel solution (I have a reel of "lead free" solder).

Your dial.
Re-finishing your dial from it's corroded state has me wonder .. what metal is it made of?
The pitting does not look like rust.

If aluminium, you might consider aome anodizing. This is very easy to do provided you keep it all clean, and follow the methods. The basic stuff you need is battery acid, or diluted battery acid. If it was aluminium, I would consider spinning it, and have a careful removal of surface corrosion, not aggressive enough to go through the graduations cuts. Shiny up. Then anodize. At the right stage, add in the dye to get the colour you want. You might consider black anodizing before the polish-up, leaving the graduations in strong black contrast, then follow with either clear anodizing (to protect it), or some paler colour you like.

Look on YouTube for anodizing electrolysis. The main trick is to "seal" the final dye surface, I think by using boiling hot water. Again - I don't really know much about this yet. From my little play with it, I ended up with a beautiful wine-coloured ring-pull torn from a beer can
.. and battery acid on my shirt!

Graham. I totally agree that it’s an odd metal. Originally it appears to have a zinc plating or maybe it’s a matted nickel plating. The pitted areas are obviously also the areas where the plating first degraded. At first I thought it maybe was a cast iron.
I thought I didn’t take a picture of my dial before I started but just found one. It really was unreadable.

It’s definitely not aluminum. The machined finish of it now is a mirror finish and that’s just from turning on the lathe.
Anyway Graham, after much thought… I think I’m just going to make an aluminum sleeve for it and engrave the graduations on the aluminum sleeve. Then anodize the aluminum graduated sleeve …and then Loctite the sleeve on the original dial. I just can’t justify 50.00 for another rusted dial in which I can’t set it to Zero because zero is all pitted.
Thanks for all of the info Graham. FWIW, I have made a couple of dials and gears over the years and even built an Arduino driven indexer in which I can set the ER-32 chucked arbor to spin at any number of graduations I set it to. It’s been about 2 years since I last used it. And I still will have to either engrave the numbers or stamp them. I’ll cross that bridge when I get to it. Just have to get off my butt and start doing it. I was just trying to snake it.
Oh well…it is what it is.

 

[graham-xrf]

Graham. I totally agree that it’s an odd metal. Originally it appears to have a zinc plating or maybe it’s a matted nickel plating. The pitted areas are obviously also the areas where the plating first degraded. At first I thought it maybe was a cast iron.
I didn’t take pictures of it before I started but it was 10 times worse than this one I found on EBay.(below picture)
It’s definitely not aluminum. The machined finish of it now is a mirror finish and that’s just from turning on the lathe.
Anyway Graham, after much thought… I think I’m just going to make an aluminum sleeve for it and engrave the graduations on the aluminum sleeve. Then anodize the aluminum graduated sleeve …and then Loctite the sleeve on the original dial. I just can’t justify 50.00 for another rusted dial in which I can’t set it to Zero because zero is all pitted.
Thanks for all of the info Graham. FWIW, I have made a couple of dials and gears over the years and even built an Arduino driven indexer in which I can set the ER-32 chucked arbor to spin at any number of graduations I set it to. It’s been about 2 years since I last used it. And I still will have to either engrave the numbers or stamp them. I’ll cross that bridge when I get to it. Just have to get off my butt and start doing it. I was just trying to snake it.
Oh well…it is what it is.

OK, so it seems you are well experienced in making up dials. I may be picking your brains soon!
Sorry that you blew $50 bucks on an eBay thing. The two I found were 200 graduations, and "new old stock", and will still need adapting. Also, they are "somewhere" mislaid, and will have to surface before I can play with them.

I think the silvery finish on them is nickel - the "satin finish" nickel variety. It may even be satin finish chrome over nickel. These kind are quite durable on cast parts, but once the pitting has started, it can travel sideways, and flake off more and more. This finish is most often seen on micrometer barrels, and indeed, some old micrometers show the same kind of corrosion. I have to look up the satin nickel recipe.
On the grim side, are we sure it is not some kind of paint?

There is a chemical method which can strip off nickel without hurting the iron. I know if you reverse polarity, you might etch the iron, but if the part is a dead loss anyway, it might be worth a try. If you can make the plating (assuming it is nickel) disappear into the vinegar, then you can pickle it, and start again. Even consider laying on just a thin starter strike, then some copper (from copper sulfate with a little dilute battery acid added). At that stage rub it up, and make it look like the finish you want. Then go for a nickel over it, and blacken in the graduations with paint.

For "starting over", I like your anodized aluminium sleeve idea. I should take care. On my machine, it might have a bit of "too much wrong lipstick on the old gal" aspect. I already risk a situation similar to new tyre and powder coat paint refurb - on only one wheel!

 

[homebrewed]

The redox potentials for Ni and Fe are -.49 and -.44 volts respectively, so if you have Fe ions in solution you probably can't prevent some from trying to plate out along with the Ni. Not enough selectivity there. But different metals "want" different plating conditions, Ph, temperature, additives, etc., with some being pickier than others in order to get a smooth coating. It's possible that the observed color difference in the contaminated plating bath is mostly a surface texture related phenomenon. Metallic iron should be silver-colored, too, right?

The presence of iron in your electroplated film may reduce its rust-protective properties so I'd suggest an experiment to test its effectiveness before you commit to plating stuff you really care about.

 

[graham-xrf]

The redox potentials for Ni and Fe are -.49 and -.44 volts respectively, so if you have Fe ions in solution you probably can't prevent some from trying to plate out along with the Ni. Not enough selectivity there. But different metals "want" different plating conditions, Ph, temperature, additives, etc., with some being pickier than others in order to get a smooth coating. It's possible that the observed color difference in the contaminated plating bath is mostly a surface texture related phenomenon. Metallic iron should be silver-colored, too, right?

The presence of iron in your electroplated film may reduce its rust-protective properties so I'd suggest an experiment to test its effectiveness before you commit to plating stuff you really care about.

I will be plating fresh - possibly from nickel sulfate. The counter-shaft and spindle MT3 taper is definitely stuff I care about!
The brown will experimented on. It gets to plate up some old bolts maybe. When it comes to stuff that's keepers, I think just like you do.

 

[Tim9]

Thanks for the input Graham. I have to make a note that you are the guy to ask when I have plating and finishing questions. Anyway I think I’m going to make a new one. I haven’t figured out yet what metal I’m going to use. Probably 4140 ?

Anyway I just got it working for now. The pits are filled and I mounted it in my Asian B & S Dividing Head and engraved the 200 divisions. It’s on the compound so it’s not like I really need numbers on it since the only time I need it is for threads and I’ll just ink in some numbers with permanent marker when I need it.

It was good practice for when I make a new one. And…FWIW, I think I’m going to make the replacement about 1/4” bigger diameter so I can get the graduations/numbers on it. You can see the original almost looks etched. And I think you’re right Graham… maybe the original was a Satin Nickel electro less finish.
(By the way… I apologize for a little bit of hijacking your thread. )

 

[graham-xrf]

Thanks for the input Graham. I have to make a note that you are the guy to ask when I have plating and finishing questions. Anyway I think I’m going to make a new one. I haven’t figured out yet what metal I’m going to use. Probably 4140 ?

Anyway I just got it working for now. The pits are filled and I mounted it in my Asian B & S Dividing Head and engraved the 200 divisions. It’s on the compound so it’s not like I really need numbers on it since the only time I need it is for threads and I’ll just ink in some numbers with permanent marker when I need it.

It was good practice for when I make a new one. And…FWIW, I think I’m going to make the replacement about 1/4” bigger diameter so I can get the graduations/numbers on it. You can see the original almost looks etched. And I think you’re right Graham… maybe the original was a Satin Nickel electro less finish.
(By the way… I apologize for a little bit of hijacking your thread. )

I just have to be impressed! Only a few hours have gone by, and you have a new one. B & S is Brown & Sharpe, right? The engraved graduations look like they were made with a fast-spinning round section D-Bit, or a very tiny round shape end-mill. One day, when my shop is a reality, I might try and acquire a dividing head

 

[Tim9]

Yes Graham. It’s the Asian copy of a Brown Sharp model 0 ( model # zero )

They go for about 220.00 on EBay. I have had it for a couple of years now and only use it occasionally. But they are decently made and for 220.00 delivered to your door it’s hard to beat. Came with a small chuck, inner and outer jaws, tailstock rest, and a few other accessories. Plus the spindle nut size is 1-1/2 8tpi so it matches my South Bend lathe accessories.
I made a dial with 100 graduations and used a rotary table for that. But the rotary table really was a slow go. Made a few screw ups and butchered a few of the numbers.
This is the first time using an Indexing head for a dial.
Once one gets a focused plan of action, dials aren’t hard. But they still are tedious but a lot easier and precise with the indexing head imo. And yes, the engraving was done using a mill spinning at about 2000 rpm and just a pointed carbide 1/8” bit. I blunted the tip a little by grinding it because otherwise the tips immediately broke if I wasn’t super slow on the feed.
these are the bits I used - https://www.amazon.com/dp/B07P99F3L1/ref=cm_sw_em_r_mt_dp_T0EAQ6NTQGSKP4017F32

I looked and looked for used indexing heads on EBay but they are both expensive and heavy so the shipping gets you. And just not enough used ones in my market. So the Asian one was it.
Here’s a review of it when I purchased it. It’s really a well made copy and others seem to agree. There’s a more recent review of a Precision Mathews sold unit. In my opinion they are all identical quality but some sellers do offer other options like different spindle threads or with a face plate instead of a chuck. My SB face plate fits the B S so I’ve got that.

Import EBay B & S #0 Indexing head.

Just want to comment how impressed I am with this import indexing head I just got from EBay retailer. Brown Sharpe design copy of model 0 index head I was expecting a decent set up because I read a few threads poo pooing the Indian imports. So far I really haven’t figured out where it’s made...

www.hobby-machinist.com

Anyway, I can now use my lathe. I found an unknown chunk of 3” diameter steel so I’m going to make a bigger and better dial. I’ll see how it acts when turning it.
And then back on subject of this thread… I will try to plate said new dial. I’m going to try nickel but might end up with zinc or tin. I say this because I’m not sure of the base metal I’m using. It may be leaded and I think that can cause issues with plating ?