Damage From Leather Reel Case?

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wrong99
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Damage From Leather Reel Case?

Post by wrong99 »

Is this damage to the reel's plating the result of the chemical reaction when storing these in a leather reel case? I know we had an earlier discussion of this problem.
https://www.ebay.com/itm/Rare-1903-Amer ... 1438.l2649
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RonG
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Re: Damage From Leather Reel Case?

Post by RonG »

I have seen many cases were German silver reels turn green in local areas where they are in contact with a leather case.
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john elder
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Re: Damage From Leather Reel Case?

Post by john elder »

As Ron said, i have seen some awful vertigris caused by leather and i never leave my reels in cases for that reason. However, the problem with the American reel appears different. Would livecto see if that would clean up!
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Ron Mc
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Re: Damage From Leather Reel Case?

Post by Ron Mc »

vertigris is a misnomer - Most copper corrosion salts are green. Nickel sulfate is also green.
Vertigris is the protective copper carbonate that forms from rain on copper roofing and bronze statues in weathering exposure.
When you see green on reels, especially salt reels, it's paratacamite, copper oxide chloride hydrate (that said, chloride exists in most water).
When you see the dark red on reels like Mark linked, that's dealloying corrosion (dezincification, denickelification) of the brass (or nickel silver).
Long-term storage of reels in dank, biological leather cases produces exactly the result Mark linked.
Long-term storage with decaying line on the spool also produces this result.

Here's a cross section of dezincification in brass - while the surface of the metal looks full-thickness, the dealloying is corrosion pits filled with a porous mat of replated, structurally unsound metallic copper
Image
the copper, zinc and nickel dissolve, the copper atoms re-plate as metallic copper, and the zinc and nickel salt out as white and green deposits.
Image Image
You can see all the salts on the native Leonard fly reel. On the cleaned reel, the pink spots on the spool is dealloying.
Last edited by Ron Mc on Thu Jan 11, 2018 8:55 am, edited 2 times in total.
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john elder
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Re: Damage From Leather Reel Case?

Post by john elder »

Thanks, Ron, for your learned editions to the subject.
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Specializing in saltwater reels...and fly reels...and oh, yeah, kentucky style reels.....and those tiny little RP reels.....oh, heck...i collect fishing reels!...and fly rods....and lures
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Re: Damage From Leather Reel Case?

Post by oc1 »

Thank you for that Ron. If you soak a corroded old reel part in vinegar or other acid to get the green and white salts off, it leaves a pinkish layer that looks like polished copper. From what you say, that is re-plated copper (?). Was the re-plated copper already there before the green and white salts were removed, or does the re-plating happen in the process of dissolving them? Thanks,
-steve
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Ron Mc
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Re: Damage From Leather Reel Case?

Post by Ron Mc »

Hi Steve, the replated copper has been there since the process began, and is not a result of chemically cleaning the surface deposits. This is why you can't see surface roughness/thickness changes occurring with the corrosion, as you would see with pitting of steel or aluminum. Electrochemically, the redeposited metallic copper is the cathode, and the corrosion interface of the base metal is the anode. The dissolving copper ions plate out within the corrosion pit. The surface deposits are part of the conditions required for dealloying to occur, essentially preventing oxygen from reaching the metal interface to form a protective patina. Also, the electrochemical reduction forming the zinc and nickel surface salts is the driving force for the copper plating reaction. The bulk effect is the alloying elements are "leached" from the brass alloy.
The reactions are very specific to brass/ nickel silver. The thick dark red deposits on the outer surface is where the replated copper layer is "seeing oxygen" and forming red copper oxide, essentially the copper equivalent to red rust on steel.

The answer to stopping the process is removing the deposits to remove the causing environment, allowing the base metal interface to "see" the air and reform a protective patina. Thick porous deposits such as red rust on steel create the environment for localized corrosion to occur by trapping corrosive chemical solutions. and forming a localized battery.

The generic use of the word patina means anything that accumulates on stuff over time - including the slime on a cork rod grip.
From a metallurgy/corrosion science standpoint, a patina is different - it is a thin, protective (oxide) layer that is in crystallographic phase with the grains of the base metal, forming a dense, tight barrier. You can look at it as natural anodizing. In fact, anodizing is a chemical process to give reactive aluminum the same weathering advantages that steel and copper possess naturally.
Last edited by Ron Mc on Wed Jan 10, 2018 8:13 am, edited 1 time in total.
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Re: Damage From Leather Reel Case?

Post by oc1 »

Thank you very much for that Ron. One more question and I'll leave you alone....

If you have a newly-shined brass or nickel silver reel it is going to start to oxidize and darken in a few days with a humid environment. If you take a newly-shined brass or nickel silver reel fishing in seawater it is going to start to form the green and white corrosion in a few days.

If the metal is exposed to atmospheric oxygen and darkens for a period of time prior to being exposed to the chlorides in seawater, will the formation of the green and white corrosion be delayed or reduced?

A bit of cold bluing (selenium dioxide) seems to produce the same effect as prolonged exposure to atmospheric oxygen but the darkening happens immediately. Again, the same question (oops, maybe it is two questions now). Would the patina produced by cold bluing reduce or delay the formation of green and white corrosion salts after exposure to seawater? Gunsmiths say that cold bluing provides very little corrosion protection. But maybe a little protection is better than none.

Thanks again.
-steve
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Ron Mc
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Re: Damage From Leather Reel Case?

Post by Ron Mc »

Steve, the patina on nickel silver is gold to slightly pink. It forms instantly in the air, but is only a few atomic layers thick, which prevents it from changing perceptibly over long times. It's so thin, it appears as a tint rather than a color. The best place to see it would be the reel collections of Bill M. and Ron G.
And I have a few nice ones in my cabinet, too.
Image
(and yes, the nickel silver hardware on this 1914 Thomas Mahogany grade bait rod has been phosphoric-acid-blued, possibly a second time by the rod restorer)
I wish you could see how the appointments on my Floyd Burkett cane fly rod have aged. Floyd makes everything 100%, machining ferrules, cap-and-band reel seat, and winding checks from nickel silver bar.
Image
But all the hardware has the most beautiful golden tint after years of fishing and dipping in the river.

As far as chemical patination using oxidizing acids, it's a process to increase the thickness of the patina and make the color of oxide show. I have a 1957 Raleigh Lenton Grand Prix that was gun-metal blued beneath the paint, and the frame is rust-free, though interestingly, the orginal silver paint has also taken on the gun-metal hue. While the bike or a firearm was never intended to be left in the weather, the process certainly improves the short-term weathering resistance of the steel - it's not going to rust after a day in the rain.
Jamming it in the mud and leaving the mud, or getting a spot of blood on it and leaving it, would eventually break the patina and allow it to rust there. Maybe gunsmiths don't know.
Image
this is patina on a 60-y-o bicycle frame (as opposed to rust)
Image

To answer your middle question, fishing a nickel silver reel in salt water is not going to change the patina as long as you clean the reel. If you were fishing it with a braided line, you should wind your line onto a line drier (rinse it down for the salt) and let it dry.
Image
Naval brass also upgraded nickel content over time, making higher-nickel alloys, Muntz metal (60% Ni) and Monel (65% Ni), that could weather salt spray with little-to-no attention. A few Monel reels were also made for salt fishing. (Nickel silver is essentially naval brass with 18% nickel added.)

What produces dealloying corrosion/pitting is destruction of the patina by wet line, storage of the reel in wet leather, or surface deposits, and that process takes time. The products of biological activity can also be present - ammonia, hydrogen sulfide, decomposing lubricants, add water, and the salts that form over time from this exposure. You eventually reach a point that everything deposited on the surface of the reel is thick enough to be detrimental and to retain bad-acting chemicals - the surface of nickel silver should never be red.

Stainless steel is another good example. The chromium-rich patina on stainless steel is impervious until it's broken. If you see red deposits on stainless steel, those sites are active corrosion pits.

A specific point about chloride salts, e.g. green paratacamite. This salt contains copper ion, oxide, chloride, and water of hydration. The salt itself can oxidize to red copper oxide, freeing up hydrochloric acid (a reducing acid) to invade deeper into the metal. Hopefully you can understand from this mechanism how the salts contained in thick surface deposits release the bad chemicals to attack fresh metal deeper in the interface.
(fwiw, I've spent my career using electron microscopes to analyze deposits and corrosion interfaces, from household plumbing to ethylene production)

Hope this helps.

If you have old leather reel cases, don't store your reels in them.
Ok to use them for a prop in your display.
Image
Last edited by Ron Mc on Fri Jan 12, 2018 9:45 am, edited 1 time in total.
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Mike N
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Re: Damage From Leather Reel Case?

Post by Mike N »

I sent a link to this thread to a friend who is a P.E./metallurgist.

He doesn’t think the felt-lined(?) leather case likely had anything to do with whatever is going on with that reel. I don’t know enough about that type of damage to say if that opinion is right or wrong, but I’m relaying it nonetheless.

On the other hand, that case stamped “America” is pretty incredible and the first one I’ve seen.

The auction ends soon and I’ll be interested to see how it does, as a high price (over $200) would indicate to me someone thinks that reel is saveable (or a collector really wanted that stamped case).

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Ron Mc
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Re: Damage From Leather Reel Case?

Post by Ron Mc »

Metallurgists have a way of calling each other out - it's a hand waving science. Licensed PE's are required to stick to opinions within the bailiwick of our direct experience. I've been doing this 35 years and am a metallurgist, corrosion engineer, active on NACE committees, and licensed P.E.
I've analyzed copper alloy corrosion and deposits from chillers, seawater condensers, industrial tidewaters - you name it - including microbial-influenced corrosion - using electron microscopy, X-ray microanalysis, and X-ray diffraction. For my first 10 years, I ran these labs for the premiere industrial insurance company, and researched deposits and corrosion. In the course of my career, have investigated over 5000 case histories. I spend about 5% of my time working litigation cases. If you want more information from my resume, I will provide it.
The leather is not the problem, but the water and what grows in the leather over decades - mildew, bacteria, their products - and decades of storage in that closed environment (same with rotting line). I suspect your friend may have never put his nose inside a 100-y-o leather reel case. If you do, you can smell the mildew. Publishing a professional opinion without direct experience would be in violation of PE license requirements.
TX No. 75665

Old leather reel cases are really cool, but virtually every one of them is a biohazard. Keep your quality reels outside of them. If someone buys that reel, removes it from the case and cleans the reel, they can mitigate the corrosion damage to its current condition. I took the OP's call as a request to contribute to the topic. Relaying this information falls within the ethics of my PE license.

Image Image
I don't own either of these valuable 19th century reels, but was hired by their owners to clean and preserve them, among many others. In addition to being an investment in history, $4000 reels are a significant monetary investment, making a committed and informed opinion more valuable than a casual one.

If you want to search antique firearms forums, you can find similar examples of otherwise valuable firearms corroding inside their closed gun cases. Firearms collectors don't store their valuable guns inside their cases, either - and firearms don't contain wet line.
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Re: Damage From Leather Reel Case?

Post by big hoss »

This is an excellent thread that all collectors should read - it explains so many things I have come across when cleaning up reels. Brilliant information - my thanks to the contributors.
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Re: Damage From Leather Reel Case?

Post by Ron Mc »

Whether it's fabric in a gun case, a leather reel case or braided line, once a biological process begins, there's virtually no stopping it.
Even if you can desiccate it completely, there are still spores waiting for the next round of humidity.
Fungus, algae, aerobic and anaerobic bacteria feed on each other's waste and decay.
(um, denying this is Dark Ages - though if you've ever had a sour Belgian ale, it's produced by a second fermentation of bacteria feeding on the decaying yeast.)
Last edited by Ron Mc on Thu Jan 11, 2018 9:11 am, edited 2 times in total.
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kyreels
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Re: Damage From Leather Reel Case?

Post by kyreels »

Great information, thanks for posting all of this. It is a great service to our association.

I had heard the same thing for guns, and it reminded me that one of my gun cases is leather (suede) and I need to remove it. I was warned years ago.

One more question for clarification. I have at least one good reel with a little bit of green paratacamite on the spool, I never worried too much about removing it, because it doesn't seem to have pitted anything and it is in a dry environment now. If I understand your comments, it could in fact still cause a future reaction and it should be removed. Is that correct?
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Re: Damage From Leather Reel Case?

Post by john elder »

Corrosion never sleeps
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Re: Damage From Leather Reel Case?

Post by Mike N »

The reel sold for a strong $360 on 16 bids. I think the lot strength was due to the rare stamped case.
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wrong99
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Re: Damage From Leather Reel Case?

Post by wrong99 »

I agree. The case could easily have been worth that to the right guy. Now, the seller is selling an original America-marked bag.
Mark
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Re: Damage From Leather Reel Case?

Post by Mike N »

wrong99 wrote:I agree. The case could easily have been worth that to the right guy. Now, the seller is selling an original America-marked bag.
Mark
Here is the eBay link to that bag:

https://www.ebay.com/itm/Rare-1903-Amer ... SwXtNaVkvb
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Re: Damage From Leather Reel Case?

Post by Ron Mc »

kyreels wrote:Great information, thanks for posting all of this. It is a great service to our association.

I had heard the same thing for guns, and it reminded me that one of my gun cases is leather (suede) and I need to remove it. I was warned years ago.

One more question for clarification. I have at least one good reel with a little bit of green paratacamite on the spool, I never worried too much about removing it, because it doesn't seem to have pitted anything and it is in a dry environment now. If I understand your comments, it could in fact still cause a future reaction and it should be removed. Is that correct?
Hi Matt, crazy busy day - no words for it.

The little bit of green is not helpful because it's a storehouse for chloride - when given moisture and air, will gradually oxidize to red, and release HCl to go just a little bit deeper into the base metal. Again, a slow process, but can be Completely Stopped by cleaning to bright metal. You can also feel confident about lining the clean reel with new line.
I'm sure we have threads between this and several other forums that give cleaning steps such as the vinegar bath.
Regards

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Last edited by Ron Mc on Thu Jan 11, 2018 8:41 am, edited 3 times in total.
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Re: Damage From Leather Reel Case?

Post by Ron Mc »

Matt, adding these before and after spindle shots on the Leonard bimetal.
I'm also not advocating mechanical polishing, but cleaning to remove deposits.
Though I occasionally do a little light polishing on pink spots on nickel silver, especially if the light polishing result shows the plated copper layer is thin. (Also use light polishing on oxidized ebonite.)

Image Image
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