Electroplating ABS prints from Prusa i3 - Problems

You're working with chemicals, you need to work with SI units.
Don't convert units, unless an expert says it's safe to do so.

International System of Units
[en.wikipedia.org]

Mole (unit)
[en.wikipedia.org])

Thanks for mentioning safety but I'm old enough and wise enough to be cautious and prudent...

Molar Mass Calculator

"The concentration of a solution is commonly expressed by its molarity, defined as the number of moles of the dissolved substance per litre of solution."
Mole (unit)

-Molar mass of H2O is 18.01532 -- I then take this to mean 1 litre of distilled water.

-Molar mass of H3PO4 is 97.99532 -- I then take this to mean 98 grams in 1 litre. Is this 98 grams + 1 litre of H2O or add 98 grams to water and bring the total volume up to 1 litre? That's the question to find out. But my interpretation of the above definition suggests I'd use 98 grams to create 1 litre total volume (moles of the dissolved substance per litre).

-Molar mass of H2SO4 is 98.0791 -- (Same question here but, this ratio is 2.5. So then do I use 245 g (98 x 2.5) to make 1 litre? Not sure, will ask chemist.)

-Molar mass of MnO2 is 86.93691 -- This is a powder so if I mix it at 60g/L then...

... I mix with the above and have 4 litres or about 1 gallon of etchant.

Still waiting to hear from a real chemist.

Edit: Gotta love the web and forums. I joined a Chemistry Forum and posted my mixing and volume questions. I hope to get some clarification.

Edited 2 time(s). Last edit at 02/03/2014 04:41PM by RobH2.

As a graduate chemist my take on this recipe is:-

based on volumes take
1 litre of water (use distilled water for this)
1 litre of Phosphoric acid (pure concentrated acid)
2.5 litres of concentrated Sulphuric acid (the molarity given around 18M or 18 moles per litre is that of concentrated acid)
Then for every litre add 60g of Manganese dioxide (MnO2) so for the full 4.5 litres use 270g of the dioxide.
You can use smaller quantities as long as you keep it to the same ratio 1:1:2.5 for the liquids and the equivalent quantity of MnO2.

Now for the safety aspects. Do not under any circumstances add the water to the conc sulphuric acid. Always wear good eye protection and if you can a rubber or PVC apron while mixing these chemicals.
I would recommend that you measure out your water then slowly add the sulphuric acid preferably while using a stirrer. Allow this to cool down as the mixing will produce a lot of heat. Once cool slowly add the phosphoric acid while stirring, again allow to cool then you can add the MnO2 while stirring. I am not sure just how much will dissolve as MnO2 is classed as insoluble, you may just get the powder suspended in the liquid.

The resulting mixture will be very corrosive so great care must be taken while using it wear good splash proof eye protection and PVC gloves to protect your hands, a PVC apron to protect clothing against splashes would also be a good idea.

Hope this is of some use to you.

Jim

Jim, that is exactly what I was looking for. I will corroborate your "take" on it with another chemist (don't know who that is yet) and if you two have the same result I'll assume that it is sound. I feel confident that you nailed it though.

I am familiar with the safety precautions when handling sulphuric acid. I do appreciate your reminding me of them. And I do know to never pour water into acid. I also have all the protective gear so I'm safe in that reguard. I only need about a 500ml of total liquid so I'll be dividing everything to arrive at a smaller total volume.

Great help. Thanks...

Quote
JimG
As a graduate chemist my take on this recipe is:-

based on volumes take
1 litre of water (use distilled water for this)
1 litre of Phosphoric acid (pure concentrated acid)
2.5 litres of concentrated Sulphuric acid (the molarity given around 18M or 18 moles per litre is that of concentrated acid)
Then for every litre add 60g of Manganese dioxide (MnO2) so for the full 4.5 litres use 270g of the dioxide.
You can use smaller quantities as long as you keep it to the same ratio 1:1:2.5 for the liquids and the equivalent quantity of MnO2.

Now for the safety aspects. Do not under any circumstances add the water to the conc sulphuric acid. Always wear good eye protection and if you can a rubber or PVC apron while mixing these chemicals.
I would recommend that you measure out your water then slowly add the sulphuric acid preferably while using a stirrer. Allow this to cool down as the mixing will produce a lot of heat. Once cool slowly add the phosphoric acid while stirring, again allow to cool then you can add the MnO2 while stirring. I am not sure just how much will dissolve as MnO2 is classed as insoluble, you may just get the powder suspended in the liquid.

The resulting mixture will be very corrosive so great care must be taken while using it wear good splash proof eye protection and PVC gloves to protect your hands, a PVC apron to protect clothing against splashes would also be a good idea.

Hope this is of some use to you.

Jim

@JimG:


Thank you!

Hi,

A2 asked for an update. I got side tracked with a project. 3d Animation is my primary business and plating these parts is an avocation at this point so it gets sidelined easily. I've designed something that I think I can market to some of my 3d clients and built a 3d printer. I've successfully learned the 3d printer and printed a number of the parts. The final stage is the plating. Once I get back to it I'm going to read through this thread again and meticulously follow all of the good suggestions. I'll report back then and let you know how it goes.

Where I left off however was here: I printed the ABS part with the filament I have (most likely not plating grade). I used a proper degreaser on it, painted it with copper conductive paint, tinned it and plated it with copper. My goal is to finally have a top nickel plate. I was hoping a thick copper plate would create a stable base layer. However, the copper was bubbly and was not sticking (I posted a photo showing the issue). It was shiny so I think that tank is performing well but just not sticking. That stopped me in my tracks. Then I got a large 3d project. I think that I'm having a moisture issue and that maybe some water is getting into the hollow ABS part. It seems to have a sealed continuous skin but maybe there is a micro leak between two layers of ABS. Then my 3d project hit and the whole thing abruptly stopped.

I'll get back to is soon. I'm sure if I carefully adhere to all of you guys excellent suggestions I'll solve it. I will report in.

Thanks again guys...

Tks for the update.
Copper looks steam punkish

Every thing is important, but the etching, and activation is really important to get the metal to adhere to the base material.
I've read that the copper conductive paint does not adhere very well.
Maybe if you etch the ABS before painting it will help.
You should de-grease it too, because any oils in the resin will rise to the surface.
I've experienced this with a different material that was extruded, wax came to the surface.

De-greasing removes oils from surfaces,
acid cleaning removes scaling,
etching (10 to 15 percent chromic-sulfuric acid, dissolves the butadiene), duration?
activation (dipped into a colloidal solution of palladium and tin), duration?

I also like the environmental friendly etching from the link that you found.
Environmentally friendly etching system:
Manganese dioxide (MnO2), (concentration was 60 grams/Litre ) + Sulfuric acid (H2SO4), (2.5 litre) or (concentration was 11.8∼12.7 M).
H3PO4 was added as a complexing agent into the MnO2-H2SO4 etching system.
[www.ncbi.nlm.nih.gov]
[www.researchgate.net]

Thanks again A2. I'll make up your etchant and I look forward to attacking this again. I'll report back in a few weeks. Adhesion is my big problem so I'll be a good boy and heed your warnings and suggestions...

JimG, thanks for the recipe as a chemist. And now that A2 feels like it's a good one also I'm going to try it. Not to initially doubt you but online you don't know anyone. So all I wanted was someone else to give a thumbs up. I hope you understand.

I'm trying to pull the necessary etchant components together. I can order H3PO4 easy enough, well, 85% pure food grade from Amazon. I can get Sulfuric Acid from the Autoparts store, in fact, I have that already. The problem is Manganese dioxide. Whether I order 0.1 grams or 500 grams, it costs $50 to ship (on top of the standard shipping fee) due to being a hazardous chemical. What is Manganese dioxide and does it have a street name that I can find locally?

Edit: Just found this on Ebay. Would it work? Manganese Dioxide

Edited 1 time(s). Last edit at 03/17/2014 05:24PM by RobH2.

Quote
JimG
I am not sure just how much will dissolve as MnO2 is classed as insoluble, you may just get the powder suspended in the liquid.

I think for your one-off creations that if you can etch it with the chemicals that you already have then save your money.

Try sourcing it from a ceramics store.

Manganese Dioxide [MnO2] with a mesh size of 300.
Uses include – ceramic glazes, pigment, dry cell batteries, matches, catalysts, laboratory reagents, scavengers and decolorizers, and textile dyeing.

Ok, good advice to try a ceramics store. Thanks. I did order the power. It only cost $9. We'll see but I bet you are right, it will just float around. I didn't read that it was insoluble.

Edit:

Just reporting back. I tried every ceramics supplier, chemical supplier, electroplating service and laboratory supplier in a 50-mile radius of Baltimore and no one uses or sells Manganese Dioxide liquid. So, I guess if my etchant does not work well without it, I'll have to bite the bullet and pay the $50 hazardous shipping addon to get some delivered.

I appreciate the "thinking outside the box" suggestion.

Edited 1 time(s). Last edit at 03/18/2014 12:22PM by RobH2.

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Prusa i3 8" (Makerfarm) / Dual Hexagon 0.4 extruder

I re-read the abstract, and looked up a few things.
If you can source the Manganese(IV) dioxide (MnO2) powder you should be fine, I think...

I think that the Phosphoric acid (H3PO4) creates a Manganese(IV) dioxide (MnO2) colloid via chelation.
You might need to filter the solution after chelation.

If Phosphoric acid (H3PO4) doesn't create a colloid (you'll know after you try it the first time),
then I think you might need a ball mill to reduce the particle size of the Manganese(IV) dioxide (MnO2) to 1 nm and 1 μm, (1 and 1000 nanometers).
Note (ball mill): You don't want any plastic resin, or any other type of particle mixed with the Manganese(IV) dioxide (MnO2), as it will kill, or hinder the plating process.

From your ebay link:
Manganese Dioxide [MnO2] with a mesh size of 300.
I don't know what scale the mesh size is referencing.



Mesh (scale)
[en.wikipedia.org])

MESH TO MICRON CONVERSION CHART
[www.showmegold.org]

Ball mill
[en.wikipedia.org]

Improvement in the etching performance of the acrylonitrile-butadiene-styrene resin by MnO2-H3PO4-H2SO4 colloid.
The present study aimed to evaluate the surface etching of the acrylonitrile-butadiene-styrene (ABS) resin in the MnO2-H3PO4-H2SO4 colloid.

To enhance the soluble Mn(IV) ion concentration and improve the etching performance of ABS resin,
Phosphoric acid (H3PO4) was added as a complexing agent into the Manganese(IV) dioxide (MnO2)-Sulfuric acid (H2SO4) etching system.
[www.ncbi.nlm.nih.gov]

Chelation = complexing agent.
Chelation describes a particular way that ions and molecules bind metal ions.
[en.wikipedia.org]

Colloid
particles dispersed in a medium have at least one dimension between approximately 1 nm and 1 μm, (1 and 1000 nanometers).
The dispersed-phase particles or droplets are affected largely by the surface chemistry present in the colloid.
[en.wikipedia.org]

Suspension
Usually they must be larger than 1 micrometer.
Unlike colloids, suspensions will eventually settle.
[en.wikipedia.org])

Manganese(IV) dioxide (MnO2).
Sulfuric acid (H2SO4).
Phosphoric acid (H3PO4).

Interesting factoid about Manganese(IV) dioxide (MnO2):
Manganese dioxide was one of the earliest natural substances used by human ancestors.
It was used as a pigment at least from the middle paleolithic (300,000 to 30,000 years ago).
It was possibly used first for body painting, and later for cave painting.
Some of the most famous early cave paintings in Europe were executed by means of manganese dioxide.
[en.wikipedia.org]

Edited 2 time(s). Last edit at 03/18/2014 12:58PM by A2.

A2, it's incredible the amount of info you provide on a regular basis. Makes me feel guilty sometimes. Don't you have other work that needs to get done...lol...?

Here's the mesh table I've been using for reference: Mesh Table

I'll read your reference info and as I mentioned, I did order some powder. We'll see what it does. It will be interesting and I'll certainly report back. It will be few weeks before I can tackle it as I've gotten interrupted with a paying project.

Great info. Let me go read it and it's much appreciated. Once I solve this I think we'll have a good thread for anyone who wants to plate their ABS printed parts.

Edit: I'm wondering if a rock tumbler and stainless steel ball bearings could function as a crude ball mill. Will have to investigate:
Ball Mill / Tumbler : Amazon?

Edited 2 time(s). Last edit at 03/18/2014 01:40PM by RobH2.

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Prusa i3 8" (Makerfarm) / Dual Hexagon 0.4 extruder

Quote

[plating 3d printed parts exhibited a] 10 fold increase in stiffness.

The coated models closely replicate traditional carbon fibre parts.

[www.3ddc.eu]

I designed zinc die cast parts that were chrome plated.
I melted out the zinc to measure the thickness of the plating, and explored the strength of the hollow metal shell.
The thin metal shell was very strong and ridged.

Edited 1 time(s). Last edit at 04/13/2014 04:17PM by A2.

I've been away from this project for a month or so as I've gotten very busy with my normal work. I hope to get back here soon with reports of success.

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Prusa i3 8" (Makerfarm) / Dual Hexagon 0.4 extruder

Video of FDM or DLP/SLA part copper/nickel electroplated.

Metal Plating 3d Printed Plastics by RePliForm Inc.:
[www.youtube.com]

Thanks for that. It's encouraging. I've still not been able to get back to my plating experiments but this will motivate me to carve out some time. Where I left off was collecting the chemicals to do a good etching stage. I see in the video that he mentions that. I think it might be the magic bullet for me. I was starting to get some good plating but no adhesion.

Good to see that, thanks again. I'll report back when I get rolling again.

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Prusa i3 8" (Makerfarm) / Dual Hexagon 0.4 extruder

You can get copper paint silver bit more expensive but I would look into spectra chrome that can give you a silver base coat I have done a lot of brush plating

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Check my rubbish blog for my prusa i3

up and running
[3dimetech.blogspot.co.uk]

chris33, what is the "copper paint silver" that you mention? I've investigated spectra chrome. I don't have a shop and spraying it without a proper booth and collection facilities is problematic. I wish I could use spectra chrome. I'm in a tiny home basement that has little ventilation. I just don't have the facilities to use it. I'm having to electroplate in 2gal buckets. I have room for that.

I need to look more at brush plating. Do you have good results with it?

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Prusa i3 8" (Makerfarm) / Dual Hexagon 0.4 extruder

Im at work at mo ill post you links where you can get conductive copper paint from when I get home

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Check my rubbish blog for my prusa i3

up and running
[3dimetech.blogspot.co.uk]

Thanks Chris. Here is what I have already. I just haven't had the chance to use it yet. I tried some "water based" copper conductive paint and it did not work well at all. So I ordered this. I just need to find time to test it.

[www.caswellplating.com]

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Prusa i3 8" (Makerfarm) / Dual Hexagon 0.4 extruder

ok thats what i was going show you

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Check my rubbish blog for my prusa i3

up and running
[3dimetech.blogspot.co.uk]

I like your blog. You are a busy guy... Thanks for the help.

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Prusa i3 8" (Makerfarm) / Dual Hexagon 0.4 extruder

Even more busy my printer is still in calibration as im going refit a new extruder soon so at mo im just playing around with it at mo

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Check my rubbish blog for my prusa i3

up and running
[3dimetech.blogspot.co.uk]

Just found this video of Adam Savage talking about his T-800 and how he electroplated it. He starts talking about it around 2:50.

Hi Sheldon, very cool. Besides the snippets of electroplating insights, the T-800 is amazing looking. I liked the weathering technique with oil paint. I'll definitely use that one day.

I've had adhesion issues with my plating. I think I'll try one thing he said. He mentioned spraying with auto primer. I think I'll try that and then use my copper conductive paint and see what happens.

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Prusa i3 8" (Makerfarm) / Dual Hexagon 0.4 extruder

Interesting electro-3d-plating radio wave lens.

MIT produces new metamaterial that acts as a lens for radio waves
[www.gizmag.com]
[newsoffice.mit.edu]
[www.thingiverse.com]

My method NFI if it works but it should.

Purchase a few things
home brew/wine making shop and purchase sodium bisulfite as neutraliser.
[www.goldn.co.uk] & [www.goldn.co.uk] from UK.
The two links point to white palladium plating solution & tin plating solution
extra fine pumice powder
copper pipe
plastic tubs
caswell triple and hard chrome plating kits



Couple of methods to etch the surface.
physical or chemical

Physical
Either Sand paper if parts large enough
or use suspension of 12% (w/w) of pumice fine powder in water.. Pumice in Water using one small hobby air brush kit would suffice.

or chemical etch. Get caswell triple and hard chrome kits. grab the chromic/sulfuric acid.

In a plastic tube, use chromic/sulfuric acid solution without connecting batteries and leave 6 minutes @60'C (or 12 - 15 mins. @ RT) to etch surface.
Then rinse in tap water,
Rinse in distilled water,
Dry in warm air (hair dryer)

Bath part in sodium bisulfite as neutraliser.

Then rinse in tap water,
Rinse in distilled water,
Dry in warm air (hair dryer)

(Might try a pen at this stage) or brush plate/activate with mix/combination of [www.goldn.co.uk] & [www.goldn.co.uk] from UK.
white palladium plating solution & tin plating solution

Then rinse in tap water,
Rinse in distilled water,
Dry in warm air (hair dryer)

Push it all through the nickel,copper, nickel, hard chrome baths following rest of directions from caswell and all should be dandy.

Edited 2 time(s). Last edit at 03/26/2015 02:14AM by printa3d.

I'll give this workflow a try. Thanks for posting it.

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Prusa i3 8" (Makerfarm) / Dual Hexagon 0.4 extruder

This may be germane to the discussion: Electroplating ABS 3D prints using graphite and acetone
With a little care, this looks like a great way to start the process.