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topic 4170

Tarnishing of brass and copper plating



A discussion started in 1999 & continuing through 2017

(1999)

Q. For brass and copper(cyanide based) plating, we are using normal tap water containing Ca, Mg,Fe, chloride. The plate becomes blackish and tarnished quickly. how can we overcome this problem?

DIPANKAR SEN
- CALCUTTA, INDIA


(1999)

? Is this tarnish taking place between processes or is the plating both brass & copper being sent as it is ?

Khozem Vahaanwala
Khozem Vahaanwala
Saify Ind supporting advertiser
Bangalore, Karnataka, India

saify logo


(2000)

? Do you apply any anti tarnish at post-treatment process?

Mad [last name deleted for privacy by Editor]
Malaysia


(2000)

A. As pointed out in the other replies do you have the problem during or after plating? If after plating one must first be sure that a thick enough plate has been deposited and it is as non porous and fine grained as possible. It should also be thoroughly rinsed. Then either treat with a proprietary anti tarnish (or 1 ounce/gal chromic acid) or lacquer.

Gene Packman
process supplier - Great Neck, New York


(2000)

Q. Tarnishing occurs both during and after plating both in case of copper plating and brass plating. We don't have any post treatment step for anti tarnishing.

DIPANKAR SEN [returning]
- CALCUTTA, INDIA


(2000)

A. Dear Mr Sen,

The best non proprietary anti tarnish I have used is 20 gms per litre of Sodium Dichromate in Dm Water .

regards

Khozem Vahaanwala Khozem Vahaanwala
Saify Ind 
Bangalore, Karnataka, India


(2000)

A. Benzotriazole and toltriazole are very good post treatment products for copper and brass to prevent tarnish without adversely effecting visual characteristics of the part.

Kurt Sammons
- Rocky Mount, North Carolina


(2000)

A. Thank you very much Mr. VAHANWALA for your information. I however observed blackish deposition when tap water (having hardness 700 ppm approx). The same process provides satisfactory deposition when soft water or D.M. water is used. Regarding post treatment did you observe any effect of little amount of sulfuric acid along with dichromate?

DIPANKAR SEN
- CALCUTTA, INDIA


(2000)

Dear Dr Sen,

Will try out the sulphuric acid as you suggest.

Regarding sourcing of the water, we use a little device which is a magnet covered in PP and is to be connected online. This is supposed to convert hard water into soft water by breaking down the crystals resulting in the formation of CaCo3 molecules, etc.

The difference between hard and soft water therefore we have not observed.

regards

Khozem Vahaanwala Khozem Vahaanwala
Saify Ind 
Bangalore, Karnataka, India


(2002)

A. Economical Post Treatment for preventing Tarnishing of copper & Brass parts produced using Copper / Brass Strips, produced by Stamping / Press operations.

Our company was having the problem of Brass Terminals getting tarnished over a period of time (3-4 months).

The problem was eliminated by applying a 5% solution of a chemical called ANTAR (manufactured by Prosol Chemicals, Hyderabad, India), mixed with a rust preventive-cum lubricant - CASTROL, when applied by dipping / spraying on the strip to be treated & allowing it to dry for a few minutes at room temperature , solved the problem, without affecting any electrical properties / showing any visual change in the appearance of the finished terminals.

Trials were conducted by subjecting the treated products to temperatures up to 75 °C at 95 % humidity for over 15 days. The untreated products showed clear tarnishing, while the treated ones remained as bright as the original brass strip. Now we have introduced this as a regular process prior to stamping operation and we have NOT had any customer complaints due to Tarnishing of our Terminals. Of course there was a very nominal increase in cost. The chemical did contain Benzotriazole -- the usual constituent of most Anti-Tarnish compounds for Brass & Copper. The process is in operation since the last one year.

R.Vishwanathan
- Delhi , India

----
Ed. note: We do not promote nor discourage specific proprietaries like Antar in this forum, but we know from Mr. Vishwanathan's several earlier postings on other threads that he was having a serious problem for a long time and are pleased that he found that a benzotriazole-based chemical plus a lubricant/rust preventative solved his problem. We thank him for his generosity in sharing his solution!thumbs up sign



July 27, 2016 -- this entry appended to this thread by editor in lieu of spawning a duplicative thread

Q. My question is regarding copper plating finish. After some time copper plated product has tarnish. What we do for this?
Do you have any permanent solution for this?

arpit agnihotri
- delhi india


July 2016

A. Hi Arpit. There is no permanent solution to tarnish, but a dip in benzotriazole will provide a major improvement, a dip in chromate is probably even better if the toxicity and color change is not a problem. And benzotriazole followed by lacquer or clearcoating, or a lacquer or clearcoat with benzotriazole is probably the 'most permanent'.

Please carefully detail your exact situation. Thanks!

Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"


September 26, 2016

A. Ted's answer is very good. I would just like to add that the trivalent chromates will also provide good shelf-life protection without the toxicity issues. Circuit board manufactures use an anti-tarnish coating based upon dilute organic acids that also would work, and are heavy metal-free. Entek is one of these.

Lyle Kirman
Consultant - Cleveland Heights



November 11, 2017

Q. A question following on from Ted's advice use of Benzotriazole.

Does anyone have any recommendations regards the following parameters for the Benzotriazole application bath?

concentration / pH / temperature / additional reagents - oxidisers etc / time of immersion

My particular interest is in treatment after acid copper plating but before a lacquer is applied; it is desirable that the copper has short term 'clean' dry air tarnish protection prior to lacquer application but thereafter enhanced protection above that afforded by only the lacquer.

I am currently using Benzotriazole but I am keen to know whether my use is optimal or for instance, whether a shift in pH would be beneficial - I am currently using a saturated solution, room temperature, pH neutral, half hour soak.

I have consulted the following literature - the latter two being academic whilst the first is perhaps recommended industrial practises but perhaps an older document.

It seems that a near saturated solution (25 g per litre) at a modest temperature of 20 °C is a good choice but I am not sure I see much conclusion regards pH.

Really I am asking what has been found to work best in practice?

Are the industrial recommendations given in the first reference still best practice (pH is not mentioned so I take this to indicate pH7).

Here are the references:

=========================

https://www.copper.org/publications/pub_list/pdf/a1349.pdf

see page 4 - note the improvement afforded by K3Fe(CN)6 - not a chemical I personally intend to get involved with - it appears to play the role of an oxidiser.
==============================

http://www.electrochemsci.org/papers/vol3/3010001.pdf
see page 8

"From this reaction it can be seen that increase of BTA concentration shifts the reaction towards
formation of larger amount of protective complex Cu(I)BTA, that is confirmed in numerous
experiments [12,18,22-24,27,29,30,35-38]. Also it can be observed that pH increase favours complex
formation. [12]"
===============================

http://iopscience.iop.org/article/10.7567/JJAP.56.07KH01
see concluding section
===============================

thanks Jon

jon light
- Wexford Ireland


November 2017

A. Hi Jon. You are certainly welcome to investigate the benzotriazole literature as deeply as you wish, and if other readers can help you with its application and implementation, great!

But speaking just for myself, a mechanical engineer who has acquired a little book knowledge of metal finishing chemistry, when I suggest 'benzotriazole' for a given situation, it's much like suggesting zinc plating for another situation. To me 'benzotriazole' doesn't mean chemically pure sodium benzotriazole, it means a proprietary formulation of benzotriazole-rich copper preservative operated in accord with the technical data sheet supplied by the process vendor :-)

I've seen it applied on copper electroformed recording masters and on copper plated grounding rods, and perhaps another application or two ... but always as a preservative solution purchased from a plating process supplier, complete with technical data sheet, material safety sheet, and technical assistance as required for its implementation :-)

Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"


November 14, 2017

Q. Many thanks Ted,

Actually I had never come across a proprietary product which is why I had gone the route of using the pure chemical.

I will start a Google serach, initial searching did not come up with anything so if any of the site sponsors have such a product and it does not contravene your site policies please post.

By the way I am assuming that we are talking here of some form of liquid dip or soak product prior to use with a proprietary lacquer and not the lacquer itself.

Personally I have no wish to avoid proprietary products - happy to pay up for the best solution - my route evolved simply because none of the literature or books that I consult mention anything other than the proprietary benzolate lacquer mentioned in the "copper org" link I indicated

Thanks Jon

Jon Light [returning]
- Wexford Ireland


November 2017

A. Hello again, Jon. The benzotriazole product I saw was offered by Atotech and was added to water in a dip tank and used in the fashion of a passivating final rinse. I believe it operated at room temperature and the immersion time was short, perhaps 20 seconds. I would expect that Macdermid Inc. [a finishing.com supporting advertiser] and Henkel and other major suppliers offer it as well.

Our purpose is not to get in the way of solving problems, so we have no objection to mentioning proprietary names. Problems arise only if people start offering testimonials for one brand over another. And again, if you can find the answer you need in technical articles or patents, or people can relate their experience for you, that's fine too.

Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"



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