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 Oxidized hard rubber
Author: EuGeneSee 
Date:   2006-08-12 19:58

I still have my old beginners horn from the mid 1950s, a hard rubber Boosey & Hawkes Edgeware which I would like to fix up, not because it is worth much, but for sentimental reasons.

The first problem I need to address is some sort of oxidation or aging process that has turned the body somewhat of a rusty reddish color. I am planning on disassembling it and cleaning it up, but don't know what to use to clean and/or polish it back to the original black color.

Although virtually everyone on here has wooden horns, I figured that many of you may have experienced similar discolorization issues with hard rubber mouthpieces (esp. vintage ones) and corrected them. In June Brad Behn had a thread (now in Keepers) on the discolorization of hard rubber mouthpieces that discussed many things about its effect on mpc performance and endurance, UV damage prevention, and the aesthetics of leaving the patina alone, but didn't get into the proper cleaning to remove the patina. That patina might actually be nice to keep on a mouthpiece, but maybe not so on the whole clarinet body.

Any advice on how to restore the finish will be appreciated.



Post Edited (2006-08-12 21:51)

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 Re: Oxidized hard rubber
Author: L. Omar Henderson 
Date:   2006-08-13 21:30

I have been able to turn many hard rubber mouthpieces back to black from various green and browns and remove the nasty odor at the same time. The issue is not oxidation but formation of sulphur compounds by various chemistries to sulfates and sulphites of various colors with compounds in the air. The process is speeded up by sunlight and various accelerators. The process that I use is not a DIY proceedure because it requires exact timing and various toxic chemicals. This is just my approach which involves changing the sulphur compound into black sulphur compounds which retards the formation of further colored sulphur compound formation. Perhaps others will chime in with a process that I have not thought of which is easier.
L. Omar Henderson

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 Re: Oxidized hard rubber
Author: bwilber 
Date:   2006-08-13 21:55

I got a plastic clarinet off of Ebay a while ago and it played great but it looked terrible because the plastic has turned an ugly greenish brown. It didn't cost much to begin with and I thought what have I got to lose so starting with the barrel, I took a medium steel wool and going straight up and down as if I were sanding with the grain, I rubbed the surface until it took off the top layer. The layer underneath was black. I then washed it and dried it and the surface looked whitish and like plastic that had been scratched so then I rubbed some bore oil over it and wiped it with a dry towel and low and behold, it looked just like grenadilla wood so I did that to the whole clarinet and now it looks black and like grenadilla wood. Even when I wash it, it still looks like black grenadilla wood. I don't think anyone would be able to tell the difference unless they look very closely. If you want to try this, I would start in a spot that isn't easy to see, maybe underneath the keys and just do a small spot and see what happens. Bonnie

Bonnie Wilber

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 Re: Oxidized hard rubber cleaning !
Author: Don Berger 
Date:   2006-08-13 23:19

Congrats, Bonnie, you may have found a "reclamation" method that has eluded our "resident chemistry prof." L O H , and our other "experimenters" including myself [ a chem. eng]. I presume you are sure it was NOT grenadilla to start with ? Can't wait to try it. Don

Thanx, Mark, Don

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 Re: Oxidized hard rubber
Author: EuGeneSee 
Date:   2006-08-13 23:48

Thanks for the responses. Doc, I can see where the chemical treatment route would not be a DIY project, as an amateur like me would do more harm than good. I really wouldn't be willing to play around with caustic or volatile chemicals, noxious fumes, etc. Also, since you mentioned that various sulfate and sulfites can cause the reactions leading to the discoloration, I suspect it would take considerable chemical knowledge just to determine which sulfur compound has been involved, what chemical compoung is present on the hard rubber, then decide which chemicals you need to use to restore the black color. All way over my head!

Now, Bonnie has something more along the lines of what I was thinking. I had been given an idea off-line to use some sort of auto polishing compound to remove the patina down to fresher, black rubber. Then I came up with the wild idea of smoothing it out that way, then with a soft cloth (old T-shirt?) rubbing into the body either india ink or lamp black, and doing a final polishing with about #0000 steel wool.

Of course while I had the horn stripped down for the above process, I could polish all the keys and repad/recork/respring it.

Doc, is there any evil sulfur or other mean & nasty stuff in india ink that would defeat the whole purpose of this exercise?

EuGene

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 Re: Oxidized hard rubber
Author: Gordon (NZ) 
Date:   2006-08-14 01:20

Soaking in dilute bleach seems to work for SOME of them. However I have no idea what invisible chemical damage this might do.

Removing the outer green layer by abrasive means is fine as long as the critical faces are not damaged in the process. However in my experience, the underlying blacker layers quickly turn green too, as if they were already most of the way to turning green, and a little exposure to atmosphere, saliva and UV was just what they needed to complete the process.

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 Re: Oxidized hard rubber
Author: bwilber 
Date:   2006-08-14 01:29

No, it was plastic and I can assure you that to an untrained eye, it is almost impossible to tell the difference unless you look very closely. I have taken clarinets that have terrible finishes and turned them into works of art, at least I think so. To my family, they all look like "clarinets" but to me they are all beautiful.

Years ago I bought some paint remover called Mister Chem because I saw it being demonstrated at a mall and a person didn't need rubber gloves when using it and it was supposed to remove paint and varnish It didn't work very well on removing paint but does take off varnish really well. I have gotten wood clarinets really cheap that have been varnished and the varnish is in terrible condition and using the Mister Chem and very fine steel wool turned them into beautiful clarinets again. I refinished a wood clarinet last week where somebody had sanded it across the grain in several places and it was a real mess and using the fine steel wool and some elbow grease, you can't tell the difference from that and a new one. After I take the varnish off and "sand" it with the steel wool, I wash them, dry them well, oil them, wipe the oil off and then buff, buff, buff with a dry cotton cloth. It's amazing what you can do with something that most people would look at and think is worthless. I fall in love with every one of them and I have over 20. Am I sick or do other people love clarinets as much as I do? Bonnie

Bonnie Wilber

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 Re: Oxidized hard rubber
Author: L. Omar Henderson 
Date:   2006-08-14 02:24

Unfortunately rubber formulations over 20-30 years ago were not very well standardized and sulfur concentrations (used as a catalyst) in vulcanization as well as curing regimes were also variable. I have seen old mouthpieces and clarinets from the same maker that have not turned colors while others appear in many shades of brown, green, yellow, etc. The colorant in all cases that I have tested is sulfur compounds. The coloration is usually less than 03 mm deep and abrasion to remove the colored compounds is one answer but the specimen will eventually again turn color (depending on environmental conditions) because of the excess sulfur in the material and its ability to migrate to the surface. Analysis of the polymerization patterns in these colored items also indicates a less crosslinked pattern than those that have not turned colors. Environmental conditions no doubt contribute to the speed and severity of coloration.

All vulcanized rubber will deteriorate - meaning loosing the original number and degree of crosslinking bridges - over time. If excess sulfur was present as a catalyst it can migrate to areas of less crosslinking more easily - usually the surface. The formation of colored sulphur compounds is complex and they are relatively stable. Reversing the chemistry to form different compounds - i.e. black - is also complex and takes strong reagents, heat, and proper timing. A good professional epoxy black paint job may be a reasonable alternative if you do not like the colored patina.
L. Omar Henderson

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 Re: Oxidized hard rubber
Author: Vytas 
Date:   2006-08-14 03:06

> *** Soaking in dilute bleach seems to work for SOME of them. However I have no idea what invisible chemical damage this might do. *** <

Bleach should not be used on any hard-rubber clarinet or mouthpiece. Bleach removes substantial amount of material altering the size of the bore and the facing (on mouthpieces). Bleach has instant chemical reaction with blued springs and will destroy them even faster than it turns the hard-rubber back to black. Maybe Doctor Henderson has some formula in the form of thick gel/grease? In this case it would work.

A mouthpiece re-facer might find soaking an affected mouthpiece in dilute bleach useful just before the work on facing and chamber is actually performed but I personally use faster and more effective ways to deal with this issue.

Vytas Krass
Professional clarinet technician
Custom clarinet mouthpiece maker
Former professional clarinet player




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 Re: Oxidized hard rubber
Author: EuGeneSee 
Date:   2006-08-14 12:17

L O H & Don: What if I just dye the clarinet black with india ink, lamp black, or some other black stuff like I suggested earlier?. Just before dying it I could smooth the instrument surface, leaving a layer of the "oxidized" discolorization to more or less seal the rubber from further sulfur reactions. Then I would blacken it and polish it with the #0000 steel wool. Do you chemists think this a viable plan?

Bonnie, I'm gonna try your Mister Chem restoration regimen on a couple of old wood clarinets to learn it and build up my confidence lavel, the when I'm sure I know what to do, I will refinish my bassoon!!

EuGene

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 Re: Oxidized hard rubber
Author: L. Omar Henderson 
Date:   2006-08-14 12:23

It would be tough to dye the hard rubber- it is relatively impervious to coloration. Lamp black or other colorants are added to the rubber mixture to make it balck.
L. Omar Henderson

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 Re: Oxidized hard rubber
Author: EuGeneSee 
Date:   2006-08-14 12:33

Rats! I though I was onto something there, then get slapped down by reality. Guess my choices have narrowed down to learn to love a rust colored horn or go the epoxy paint route. Anyhoo, it was worth the effort to try to find a way . . . Meanwhile, I gotta find out where to get some of that Mister Chem stuff here in the bowels of the Ozarks.

Eu

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 Re: Oxidised hard rubber
Author: Gordon (NZ) 
Date:   2006-08-14 12:47

Vytas wrote:
"Bleach should not be used on any hard-rubber clarinet or mouthpiece. Bleach removes substantial amount of material altering the size of the bore and the facing (on mouthpieces)."

Vytas, I have used dilute bleach only a few times, mostly with my own old mouthpieces, after reading about this treatment in a forum.

I did not notice any difference to the dimensions. If bleach attacked hard rubber to that degree I think I would have noticed rounding of the edges of the rails.

However your claim intrigued me, so I did a couple of experiments:

I measured the bore at the open end of an old, green, hard rubber mouthpiece, and left it soaking in "FULL STRENGTH" household bleach (actually only 3% sodium hypochlorite), for 40 minutes. I left the last 15 mm at the tip untreated, so that any alteration to the submerged part of the rails would hopefully be more visible. Then I scrubbed it well, and dried it.

The submerged part of the mouthpiece turned black. Under a 12x magnifier, I could see no change to the surface of the rails, nor the edges. I could find no measurable change in the bore where I had measured it.

Go figure. Perhaps different formulations of hard rubber behave differently. Perhaps the surface of the mouthpiece will vanish overnight.

Vytas wrote,
"Bleach has instant chemical reaction with blued springs and will destroy them even faster than it turns the hard-rubber back to black."

So for my next experiment

Next, for a really strong solution, to accelerate any reaction, I scraped about 2 cc of powder from a sodium hypochlorite tablet designed for swimming pool use, and mixed this with about a 20 ml of water. The solution was a pale yellow/green, indicating a high chlorine content. I solvent cleaned the outside of a blued steel needle spring, and soaked it in the powerful solution for 15 minutes, periodically stirring.

The diameter of the spring both before and after the treatment was 0.71 mm. The blued appearance was unchanged.

I acknowledge that my experiments are not definitive. If an entire clarinet body, including posts and springs, were submerged in bleach, there may be other chemical reactions between the different materials involved. An example would be galvanic action between the dissimilar metals of the springs and the posts, although their electrode potential is fairly similar, indicating little activity.

So I do wonder about the severity of the claims made. I would be interested in a report of the details of your own experiments.

"A mouthpiece re-facer might find soaking an affected mouthpiece in dilute bleach useful just before the work on facing and chamber is actually performed but I personally use faster and more effective ways to deal with this issue. "

I look forward to hearing about your own, more effective method.



Post Edited (2014-06-01 09:34)

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 Re: Oxidized hard rubber
Author: Don Berger 
Date:   2006-08-14 13:28

What an excellent experimentation-discussion we have going here, Dr. Goodyear should be proud of this extension of his [many-years-ago] research, and not "jump", only turn a bit. There should have been some early/ier] patent activity in this field, I'll try some searching, and if anyone has names/suggestions etc [like Brad et al] for search terminology, I'll be happy to try. Research is our best activity. Regards, Don

Thanx, Mark, Don

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 Re: Oxidized hard rubber
Author: Vytas 
Date:   2006-08-14 19:39

Gordon,

I was talking about "Clorox" or "ShopRight" brand you can buy in the US in the household section at the supermarket. This ready to use solutions was further diluted to about 75%-80% strength. Reaction on the blued springs was immediate and visible with your eyes. A slimy, dark colored substance formed around the springs in no time. This slimy stuff was eating springs in the way the rust would just many, many times faster. I did not take a chance and removed the clarinet (old HR Conn) after several minutes in the solution. The thinner springs were almost gone and I had to replace them.

On the HR mouthpieces the same solution attacked only affected area. When the affected area was 0.03mm deep it removed 0.03 mm of the affected material. If the colored compounds went deeper - more material was removed. I got the impression that this bleach solution was attacking only discolored HR and left alone the rest. I had two old Prohashka mouthpieces. One of them had bad case of discoloration, more than 0.05mm deep. After the treatment even the deeply engraved logo on the bottom completely disappeared. Good facing before the treatment was unusable afterwards. The perfectly smooth body surface before the treatment looked rough and terrible (with microscopic holes in it) after the treatment. The mouthpiece required a lot of work and polishing to make it presentable. The worst part was the logo. It was gone! And the no name mouthpiece is basically worthless if you tried to sell it. I did this many times on many mouthpieces until I got disgusted with all this messy and not very effective process.

I do understand that the strength of the solution and the timing is critical but I leave it to chemists. In my case it was not worthy of effort. There's a better way to do it.

What's your agenda and why you're trying to discredit my experience with bleach?


Vytas Krass
Professional clarinet technician
Custom clarinet mouthpiece maker
Former professional clarinet player




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 Re: Oxidized hard rubber
Author: Mark Charette 2017
Date:   2006-08-14 19:48

Vytas wrote:

> What's your agenda and why you're trying to discredit my
> experience with bleach?

Geez Vytas, someone comes up with different results than you and you think there's an "agenda"? He didn't experience what you did using essentially the same ingredients (full-strength over-the-counter bleach), so there's something else afoot here. Why the same things didn't affect what he did is interesting news.

When people post here they have to expect that someone will follow up with an experiment or a counter-argument. That's the way these kinds of BBoards work - there's no captive audience, but a bunch of independent thinkers who might not agree with your assessment.

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 Re: Oxidized hard rubber
Author: Vytas 
Date:   2006-08-14 21:58

> *** Geez Vytas, someone comes up with different results than you and you think there's an "agenda"? *** <

Mark,

If SOMEONE came up with different results than me I wouldn't think there's an agenda but when it comes to Gordon, I'm not sure.....

This is not an opinion, a theory, an experiment or a black magic. These are the facts that I've experienced MANY times with Clorox bleach on the HR

Vytas Krass
Professional clarinet technician
Custom clarinet mouthpiece maker
Former professional clarinet player




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 Re: Oxidised hard rubber
Author: Gordon (NZ) 
Date:   2006-08-14 22:50

Vytas,

"If SOMEONE came up with different results than me I wouldn't think there's an agenda but when it comes to Gordon, I'm not sure....."

The only thing I think I can take from that is that you think I was lying about my experiments. Not true! I don't appreciate the aspersion cast.

"This is not an opinion, a theory, an experiment or a black magic. These are the facts that I've experienced MANY times with Clorox bleach on the HR"

Likewise, there was no black magic or anything sinister in my experiments. BTW, are you saying that after discovering that bleach wrecks hard rubber and dissolves steel springs, you continued doing this, "MANY times"? I don't quite follow.

Re my "agenda". my agenda is science. Science consists of constant testing of any claims made, in as many ways as possible. I hope you have nothing against that.

I know almost nothing about the chemistry of hard rubber, other than that sulphur is used as a polymerising agent. Your post suggested that there was something I didn't know that I could learn about, so being the keen learner that I am, I carried out the experiment I described. What I learnt was that my results, which were more or less what I expected differed from yours. This simply suggests further experimentation, as I hinted at when I wrote that different formulations of hard rubber may have different chemical behaviour.

Regarding the springs:

I don't have much knowledge left from my somewhat elementary chemistry study a long time ago. But what little I do have, suggested that OXIDISING agents attack steel, not REDUCING agents... And that bleach is a reducing agent. Furthermore, when I was in charge of doctoring a school swimming pool, I bought and used 50 lb drums of sodium hypochorite - the powder form, VERY concentrated... 70% chlorine if I remember correctly. The containers were made from galvanised steel drums. If chlorine attacks steel, one would expect it to attack the much more reactive zinc galvanising even more. These drums lasted for months with no vanishing metal.

Putting this limited experience and knowledge of mine together, I acknowledge, I simply did not believe you. So I experimented to see if there was some factor I was not aware of. In my passion for the location and presentation of 'truth', I reported my findings. Yes, I had an agenda - to test what you wrote about the disappearing springs, because to me, with my limited chemistry background, it did not have a 'ring of truth'. Of course, in science, no single experiment is a conclusive proof, but the more experimenting is done, the closer we can get to truth.

Vytas, it does mystify me as to why our findings are so very, very different. An important part of science is the repeating of experiments. I invite others to carry out similar experiments. Be cautioned, however, that mixing VERY strong chlorine with combustible materials, can result in explosions.

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 Re: Oxidized hard rubber
Author: Vytas 
Date:   2006-08-14 23:54

Sorry Gordon but you're wasting my time. I stopped talking to you from now on. Bye!

Vytas Krass
Professional clarinet technician
Custom clarinet mouthpiece maker
Former professional clarinet player




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 Re: Oxidized hard rubber
Author: Vytas 
Date:   2006-08-15 00:42

Dear Doc,

Why are you so quiet? Is all of this just my imagination? LOL. You certainly know the answer. Please share your knowledge to the board. Thanks

Vytas Krass
Professional clarinet technician
Custom clarinet mouthpiece maker
Former professional clarinet player




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 Re: Oxidized hard rubber
Author: Mark Charette 2017
Date:   2006-08-15 01:13

Vytas wrote:

> Sorry Gordon but you're wasting my time. I stopped talking to
> you from now on. Bye!

Hmmm ... I don't have any old hard rubber mouthpieces to try, but I did just throw two blue steel springs in household Chlorox for the last hour. Nothing visibly different under a x10 lens comparing a control against the one in Chlorox ... but perhaps it's the alloy in these particular springs.

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 Re: Oxidized hard rubber
Author: Mark Charette 2017
Date:   2006-08-15 01:25

I wrote:

> Hmmm ... I don't have any old hard rubber mouthpieces to try,
> but I did just throw two blue steel springs in household
> Chlorox for the last hour. Nothing visibly different under a
> x10 lens comparing a control against the one in Chlorox ... but
> perhaps it's the alloy in these particular springs.

And ... a little research later points out that chlorine gas dissolved in an aqueous solution (Chlorox) is death to stainless steel but carbon steel (blue steel) is almost completely unaffected.

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 Re: Oxidized hard rubber
Author: Vytas 
Date:   2006-08-15 02:37

> *** And ... a little research later points out that chlorine gas dissolved in an aqueous solution (Chlorox) is death to stainless steel but carbon steel (blue steel) is almost completely unaffected". *** <

It was old and discolored Conn hard rubber clarinet. I removed the keys and placed parts in Clorox 75%-80% solution. I had no idea that the springs might react to the bleach so fast and violently. It was about five yeas ago so maybe the springs were stainless steel and not blue steel after all. I don't remember I guess. I've described what I experienced. It was the first and the last time I tried to treat a Hard-Rubber clarinet this way.

I used 75%-80% Clorox solution in the past on MANY HR mouthpieces just before the actual work on the facing and chamber was done. (I've described the results in my previous posts.) There's no such thing as a single HR formulation. Different brands had slightly different reaction to the treatment. The fact is: if you have an affected area on the facing the bleach will remove it from there. Period!... be it 0.03 mm or deeper it doesn't matter. The facing will be ruined!

I abandoned this method after I discovered better and faster ways to treat discoloration on HR mouthpieces.

Vytas Krass
Professional clarinet technician
Custom clarinet mouthpiece maker
Former professional clarinet player




Post Edited (2006-08-15 02:47)

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 Re: Oxidised hard rubber
Author: Gordon (NZ) 
Date:   2006-08-15 12:24

Well it just seems that on the particular mouthpieces I have used bleach on, especially the one I cite in my experiment, seem to have had no adverse effects. Perhaps if I were one of the world's top clarinetists I may have noticed an effect when I played on them. I think that for my experimental one, where I treated only part of the rails so I had a control area, I would have noticed damage as small as 0.03 mm.

So all that can be concluded, is that our experiences have simply been different, which makes it all the more interesting, what others experiences have been or will be, if/when they succumb to their curiosity in this matter. :-)

It is good to see that in our search for truth, our focus is now on stainless steel, rather than steel..

> *** And ... a little research later points out that chlorine gas dissolved in an aqueous solution (Clorox) is death to stainless steel but carbon steel (blue steel) is almost completely unaffected". *** <

I did some Googling on this, and found quite a bit of good information. For example, the process by which stainless steel can be attacked by chlorine is well described at http://www.mcnallyinstitute.com/04-html/4-1.html

So my curiosity got the better of me, and I made up another powerful chlorine solution using a swimming pool tablet. It certainly did a good job of bleaching my dish cloth!

I dropped in two stainless steel needle springs, one from Kraus, and one from Ferrees. In the light of this new information from Mark and the Web, I looked forward to a dramatic happening.

I was sadly disappointed. Two hours later I removed the springs and could detect no change, neither in appearance, diameter, or function.

So this adds further to the mystery. I did not research the net thoroughly enough on this topic to find whether there are some grades of stainless steel which resist chlorine attack. Perhaps this is the case.

My "Clorox" is "Bathroom Cleaner" and according to the MSDS, does not contain sodium hypochlorite, which is why I did not use this in my experiments. I note that Clorox make dozens of cleaning and bleaching products. I assume that Vytas and Mark are referring to a product containing perhaps 3% chlorine, as per the MSDS sheets for Clorox bleach.

I look forward to other forum members reporting on their own experiments.

Certainly, I would be wary about soaking an entire clarinet body with stainless steel springs in light of the information found. And I reiterate, that with SEVERAL different materials involved, soaking a clarinet body may introduce all manner of other reactions, including galvanic action (also well described in the link provided above.)

To me, the jury is out on chlorine's action on both hard rubber and stainless steel, with just a tiny bit of doubt remaining on its action on steel.



Post Edited (2006-08-15 12:27)

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 Re: Oxidized hard rubber
Author: BobD 
Date:   2006-08-15 14:04

Be careful about drawing conclusions about "stainless steel". Just as there are many formulations of HR there are different families and varieties of stainless steel within those families. And...the so-called "non-magnetic" stainless steels may become slightly magnetic when cold worked as for instance when making wire for springs.

Bob Draznik

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 Re: Oxidized hard rubber
Author: EuGeneSee 
Date:   2006-08-15 14:45

. . . and when you flatten the end of the spring so it will lock tightly in place when you put it through the post on the instrument.

In the meantime, it appears we have pretty much completed discussion on the subject of this thread.

EuGene

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 Re: Oxidized hard rubber
Author: Mark Charette 2017
Date:   2006-08-15 14:59

EuGeneSee wrote:

> In the meantime, it appears we have pretty much completed
> discussion on the subject of this thread.

I doubt that very much ...

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 Re: Oxidized hard rubber
Author: Anonymous666 
Date:   2010-09-13 11:45

I think it is worthwhile to note that bleach (sodium hypochlorite) is classified by the National Fire Protection Association as an oxidant.
http://en.wikipedia.org/wiki/Sodium_hypochlorite
Although, solutions under 5-12.5% are not counted as oxidizers for the purposes of storage. This is according to a PDF "FI430.pdf" dated 2004 posted by the NFPA found via a google search for Sodium Hypochlorite NFPA. Nonetheless, whether weak solutions are liable to cause problems when stored, the compound sodium hypochlorite still possesses similar, if not the same properties when concentrated or dilute. In particular, it is relatively unstable (note that it has a limited shelf life) when compared to sodium chloride, so the hypochlorite readily gives up its oxygen and therefore acts as an oxidizing agent.

Sodium hypochlorite shelf life
http://www.cdc.gov/safewater/publications_pages/pubs_disinfectant.htm

I am also puzzled by the characterization of sulfur as a catalyst. My understanding of a catalyst is that it is a material that speeds up a reaction and is not changed by it. Sulfur in the case of vulcanization cross-links carbon chains (isoprenoids) of latex. So, it is participating in the reaction and changing, in the sense that it goes from, what I assume is an unreacted, elemental or diatomic form to a form that is bonded to carbon or itself.

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 Re: Oxidized hard rubber
Author: L. Omar Henderson 
Date:   2010-09-13 13:02

In the strict sense you are correct that sulfur participates and becomes part (the disulfide linkages) of the vulcanized rubber. Latex by itself will only slowly and not completely crosslink the monomer chains even when subjected to heat and pressure used to make hard rubber. As much as 20-30% of hard rubber is sulfur.

Excess sulfur is added to be sure that as much crosslinking as possible with sulfur atoms takes place but this means that there is unreacted sulfur in the finished product which can react with atmospheric chemicals usually forming brown, tan, green, etc. very stable sulfur compounds which are hard to chemically remove.

The amount and types of crosslinking patterns in hard rubber are controlled by a number of factors including the purity (actually the type and amount of impurities in the natural latex e.g. plant proteins, particulates and dirt), temperature and pressure, curing cycles, and other factors. Modern hard rubber contains less free sulfur (unreacted) because of the addition of accelerators (including metals - steel is not one of them so "steel ebonite" is a misnomer and only marketing hype) and better control of vulcanization parameters. Additives including anti-oxidation chemicals and UV blocking chemicals are also used in many forms of modern hard rubber.

The rubber industry has also established standards for hardness, flexibility, and other physical properties of rubber as well as instrumentation that can detail the crosslinking patterns among batches of hard rubber for quality control purposes. Acoustic properties of hard rubber depend on a myriad of factors.

L. Omar Henderson
www.doctorsprod.com

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 Re: Oxidized hard rubber
Author: Lelia Loban 2017
Date:   2010-09-13 13:35

Another approach with plastic or rubber that turns brownish or greenish is: just leave it that way. If the clarinet is antique or old, that's what I do. I consider the discoloration "fair wear." It doesn't affect whether or not I buy a used instrument, unless the color change is severe and on only one side of a hard rubber clarinet.

If I see discoloration only on the upper side that's exposed with the case open, I take it as a sign that a flea market vendor has left the clarinet exposed to the hot sun for hours on end. In the Washington, D. C. area, where daytime temperatures can stay in the 90s for more than 50 days per year (as happened this summer), this type of discoloration means the rubber may have been heated enough to cause warping. Sometimes heat warping is grossly obvious (banana-shaped clarinet: bad), but sometimes it's subtle and the drastic color change on only one side is the only telltale. Since the flea market clarinet is almost never in playable condition, I can't check to see whether there's damage that will affect intonation, so I pass up that instrument.

Lelia
http://www.scoreexchange.com/profiles/Lelia_Loban
To hear the audio, click on the "Scorch Plug-In" box above the score.

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 Re: Oxidized hard rubber
Author: Jack Kissinger 
Date:   2010-09-13 16:31

"Modern hard rubber contains less free sulfur ... because of the addition of accelerators ... and better control of vulcanization parameters."

Does that mean it should take longer for Lyrique clarinets to turn green?

Best regards,
jnk

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 Re: Oxidized hard rubber
Author: L. Omar Henderson 
Date:   2010-09-13 17:51

Jack,
I have not analyzed the rubber in the Lyrique clarinet and do not know if less sulfur, accelerators, UV inhibitors, etc. have been used. From my own experience it is necessary to maintain tight quality control of off shore manufacturing to maintain a quality end product and also to set stringent materials and process specifications which are consistently monitored on site.

L. Omar Henderson
www.doctorsprod.com

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 Re: Oxidized hard rubber
Author: Anonymous666 
Date:   2010-09-17 06:34

...unless a previous experimenting owner left the hard rubber clarinet lying half submerged in vinegar too long, causing such discoloration.

Banana shaped clarinets with keys that won't close may be bad, but this sure looks cool. I wonder if it is playable and how the bore was formed in such an oddly shaped piece of wood.

http://www.oup.com/us/companion.websites/9780195343281/photo19/?view=usa

Nicola Papalini, Chiravalle, 5 key bass clarinet (B-Bruxelles, 940, ca. 1825), front view. Reproduced with permission of Musée des instruments de musique, Bruxelles.

This is from the front cover of:
From the clarinet d'amour to the contra bass. A history of large size clarinets. 1740-1860 Albert R. Rice Oxford University Press USA 2009.
I found it on http://www.vcisinc.com/clarinet.htm#C1394, but a google search for clarinet d'amour then image search did just as well the first time I tried finding it; (seems there are fewer hits just now when I retried, but I'm not sure what is up with that.)

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 Re: Oxidized hard rubber
Author: LaBelleEpoque 
Date:   2014-05-30 18:58

Hello. I work with hard rubber quite often. I was wondering if you could let me know what process you were using to change the sulphur compound into black sulphur compounds. It has been my experience that though some of the processes do work that they are often permanent and that they material will no longer achieve the same shine.

Sincerely,
Mark

lbepens1@gmail.com

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 Re: Oxidized hard rubber
Author: Tom Ridenour 
Date:   2014-05-30 20:39

Below is the solution we've given the small number of customers who have reported fading or discoloring.

*Disclaimer......While their may not be a problem doing so I wouldn't recommend this for mouthpieces, feel free to explore the issue yourself, as toxicity could be an issue.

If a hard rubber clarinet fades (Typically caused by excessive exposure to sunlight) it is very easy to reverse by simply buffing the faded areas with this....

http://www.tandyleatherfactory.com/en-usd/product/fiebings-dye-4-oz-usmc-black-2100-01.aspx

I say faded rather than green because in the small handful of instances this has occurred with our customers the description we've been given is that the clarinet started fading to white, I can't recall anyone ever mentioning it turning green. Latex is naturally white but is dyed black when made into clarinets for cosmetic reasons.

I've walked several individuals through the process below......no repair tech was required.

1. Remove the keys
2. Clean the body of the clarinet of any dirt, dust, debris, etc.
3. Using small amounts of leather dye, less is more....you can always add more but it's very difficult to take it off, buff the faded or discolored areas.
4. Let dry as per the instructions on the leather dye. While not 100%, this is something we very rarely deal with, I believe your supposed to wait 3 hours. However i've also heard people recommend letting it sit overnight.

We've had several customers, honestly not sure how many.....four? Five?, use this process successfully.

Ted Ridenour

Ridenour Clarinet Products, www.ridenourclarinetproducts.com, sales@ridenourclarinetproducts.com

Post Edited (2014-05-30 20:42)

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 Re: Oxidized hard rubber
Author: The Doctor 2017
Date:   2014-05-30 21:48

I respect Tom's great knowledge and experience with clarinets in general and with his hard rubber clarinets.

I have never heard of the process that he outlines but it sounds like it works for his clarinets. When we say "hard rubber" it is a family not a single species. The hard rubber produced in the last 70 years has constantly evolved with different amounts and types of accelerators and stabilizers in the vulcanization process. In this evolution the amount of sulfur used has been greatly reduced and the qualities of the rubber enhanced in durability, and oxidation reduction.

I have not seen an old mouthpiece turn white or fade so much in the depth of color but I have seen dozens of tan, brown, and olive green mouthpieces and even older hard rubber clarinets. I have a fine "A" clarinet in olive green myself.

The types of oxidation that cause the browns and greens comes from excess sulfur used as catalyst in making the older rubber migrates to the surface as the surface rubber begins to oxidize, break bonding patterns, or from exposure to sunlight or heat. This sulfur combines with chemicals in the air to produce very stable colored sulfur compounds. These compounds are very tough to remove or change back to a stable black sulfur compound and requires some toxic chemicals and experience to make it work.

I have gotten a number of requests to work on mouthpieces, clarinets, rubber fountain pen barrels (some of the best ones are made of hard rubber for its tactile feel), and even old bowling balls. I have done some but it is an expensive and not a DIY process and most customers opt to keep their products in hues of brown and green. Function wins out over beauty!

The brown and green sulfur compounds can be buffed off but this removes some material. I have never tried staining as Tom suggests, I will but, I would suspect that it would not be as successful on the old types of rubber from the 30's - 50's as on newer forms of hard rubber. In the older examples you have actual oxidation of the rubber in addition to forming colored sulfur compounds but as a scientist I would never say never to trying a new technique.

L. Omar Henderson
www.doctorsprod.com
www.chedevillemp.com

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 Re: Oxidized hard rubber
Author: Ken Shaw 2017
Date:   2014-05-30 23:51

Anonymous666 -

Papalini bass clarinets were made like cornettos. Two blocks of wood were carved to the outer shape, the serpentine bore was chiseled for each half and the halves were glued together and covered tightly with leather. You can see a bunch of them at http://anticwindbooks.chez-alice.fr/clarinet/clarbas12/clarbas12.html.

I've looked carefully at the example in the Metropolitan Museum. It's quite small -- the bottom rests in your lap. The fingering requires you to cover holes with the knuckles of both index fingers.

Al Rice's book has a section on them, and he has also written about them on the Early Clarinet board https://groups.yahoo.com/neo/groups/EarlyClarinet/conversations/messages.

I've never heard of a modern replica and know of no recording of one. The place to ask is on the Early Clarinet board, which is quite inactive but is monitored by Mr. Rice.

Ken Shaw

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 Re: Oxidized hard rubber
Author: Tony F 
Date:   2014-05-31 06:08

I've used the process described by Tom Ridenour on several badly discoloured hard rubber instruments with great success. A greeny yellow hard rubber ex-military Boosey and Hawkes Imperial became once again a shiny satin-finish black and has stayed that way for several years. Another ex-military B & H Emperor in similar condition now looks much like it did the day it was made. I'm not sure I'd try it on a mouthpiece, but I've used fine steel wool on discoloured hard rubber mouthpieces with great success. Done carefully it does not affect their playability.

Tony F.

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 Re: Oxidized hard rubber
Author: Paul Aviles 
Date:   2014-05-31 14:04

Of course you mean you used the fine steel wool on everything BUT the rails, table and tip!





.........Paul Aviles



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 Re: Oxidized hard rubber
Author: Tony F 
Date:   2014-05-31 14:16

"Of course you mean you used the fine steel wool on everything BUT the rails, table and tip!"
.........Paul Aviles

Absolutely correct!

Tony F.

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 Re: Oxidized hard rubber
Author: Ursa 
Date:   2014-05-31 18:20

Extra Virgin olive oil can be used as a cleaner and polish for discoloured hard rubber. The old mouthpieces I've treated with EVOO went from mottled green/yellow/tan to a rich chocolate brown.

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 Re: Oxidized hard rubber
Author: NoradBob 
Date:   2018-09-07 21:24

My comment is a little late for this discussion, but this problem is recent for me. I came across a fifty-year old (or more) Woodwind Co. New York Steel Ebonite clarinet mouthpiece with a G7 facing that I found extremely responsive with a fluid, centered sound -- but was so damaged by time and sun the only shiny part was where a ligature used to sit. I played Frank Wells mouthpieces for years that I dearly loved, then switched to Bob Borbeck's #11 when my Wells warped and Frank was gone. I liked Bob's piece for some time, but it just didn't blow as freely for me as my Wells -- so I started shopping again. I really like the WW G7 but couldn't put it in my mouth day after day as bad as it looked. After a few days searching for solutions on the web, I decided to try using Flitz metal polish, mentioned in earlier postings. It is also non abrasive and good for plastic, so as long as I kept away from the table, tip and rails, I didn't think I had much to lose.
Using a soft cotton cloth, I worked the Flitz polish in with slow strokes it worked like a charm but took 15 or 20 minutes to achieve visible results. So for the WW Steel Ebonite G7 mouthpiece, it looks like new. Anyone willing to give up a G6 or G6*?

RJH

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 Re: Oxidized hard rubber
Author: Dan Shusta 
Date:   2018-09-07 22:20

Hi NoradBob,

I immediately became concerned about toxicity and whether putting a Flitz polished mouthpiece into my mouth could possibly cause health problems.

After doing some research, the answer is "NO".

From https://www.flitz.com/faqs/:

"...Flitz Polish is completely non-toxic. It has USDA approval to use on surfaces in a food preparation area. Flitz can be safely used on serving pieces, such as silverware, without any danger. After polishing, just wash the piece in warm soapy water and dry off as usual. The Flitz will not leave any flavor or smell behind."

Sounds like you found a good product!



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 Re: Oxidized hard rubber
Author: shmuelyosef 
Date:   2018-09-11 03:12

Any silver polish designed for food serving/eating hardware is safe. I use Hagerty’s for restoring oxidized mouthpieces. Easy and safe

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 Re: Oxidized hard rubber
Author: LaBelleEpoque 
Date:   2018-09-11 05:01

While I agree that you can remove oxidation by sanding it is not something that I would personally recommend. I find that one ends up removing material that should not be removed. Also, you will loose your imprints doing it this way. It is better to do this chemically. One of the issues though is that most of the chemicals out there tend to damage the rubber as well. I have made something that will remove this top layer of oxidation without harming the rubber underneath. Once the oxidation is gone I polish. The polishes I make are made to break down very quickly. Again, this is done so as to not remove to much material. I finish by using a balm that is made with various anti-oxidants that shine and protect the rubber from further damage.

lbepens1@gmail.com

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 Re: Oxidized hard rubber
Author: LaBelleEpoque 
Date:   2018-09-11 05:02

Bleach is simply not good for the rubber. It damages it even more.

lbepens1@gmail.com

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 Re: Oxidized hard rubber
Author: LaBelleEpoque 
Date:   2018-09-11 05:06

I agree with you. It is impossible to dye black rubber. I have even tried to use a vacuum chamber with dye in it. While this worked a bit better then just dyeing it and letting it dry it was still not very effective.

lbepens1@gmail.com

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 Re: Oxidized hard rubber
Author: LaBelleEpoque 
Date:   2018-09-11 05:44

I am not really sure what point is being made to be honest. Bleach is simply not good for hard rubber. There is more then enough information on the internet to support this. Bleach is a very strong oxidizing agent that will in fact make the rubber more brittle and prone to cracking. It does not just remove the top layer of oxidation but attacks the rest of the hard rubber as well causing it to break down that much more quickly.

lbepens1@gmail.com

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 Re: Oxidized hard rubber
Author: Tony F 
Date:   2018-09-11 09:33

"I agree with you. It is impossible to dye black rubber. I have even tried to use a vacuum chamber with dye in it. While this worked a bit better then just dyeing it and letting it dry it was still not very effective."


If you follow the process described by Tom Ridenour, detailed earlier in the thread, you can successfully dye hard rubber. I have returned several greeny/grey hard rubber instruments, clarinets and flutes, to an even shiny black. On my personal instruments the process has lasted for perhaps 5 years without any deterioration. If they do show any signs of patchiness I'll just do it again, it only takes a few minutes after removing the keywork.

It doesn't work on plastic instruments, only on hard rubber. I haven't used the process on mouthpieces and I'm not sure that I'd want to. I've had good results on greenish rubber mouthpieces using very fine wire wool as used by cabinet makers followed with a light rub with almond oil. It hasn't affected the playing characteristics of the mouthpieces.

Tony F.

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 Re: Oxidized hard rubber
Author: NBeaty 
Date:   2018-09-14 22:06

I'm curious why this seems to be such a high concern for clarinet players. This is a purely cosmetic issue, not a functional one. As noted above, some of these solutions can be bad for the mouthpiece and/or bad for the player.

Short of buffing away the oxidized layer (not something that anyone and everyone should do, as it's easy to have the wheel hit the facing), I don't think most of the solutions are more than a temporary solution or optical illusion (olive oil for example).

There's not any reason to be concerned if a mouthpiece has dulled/turned light brown. Too many times I've been asked if I can remove the dullness of a mouthpiece body only to turn the mouthpiece around and notice unbalanced rail widths, chips/nicks, gouges, etc. that seem to be less concerning for the player.

If you're favorite mouthpiece is discolored, it should still be your favorite mouthpiece. If the facing, rails, baffle, and table are all in good order then there shouldn't be a worry about a purely cosmetic issue.

Hard rubber will fade to one degree or another over time and it really shouldn't be a major concern. Some of the best mouthpieces I've ever tried were light brown in color. It never has occurred to me to say, "This is a fantastic mouthpiece, if only the color of the body were darker".

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 Re: Oxidized hard rubber
Author: clarimad 
Date:   2018-09-15 01:50

My solution to this issue is to use a hot air gun.

I have here in the UK a Black & Decker (other manufacturers are available!!) hot air gun and if used slowly over any mouthpiece or "greened" clarinet body will restore it to its original state.

Here in the UK I use this method to restore my sun bleached garden furniture back to its bought colour.

A simple chemical process.

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 Re: Oxidized hard rubber
Author: donald 
Date:   2018-09-15 02:25

Mike Lomax restored two mouthpieces for me about 4 years ago, they came back with a perfect shiny black appearance (and haven't deteriorated since, they've been protected from UV). I'll ask Mike what process he uses.
These two mouthpieces had personal significance for me (passed on after the death of a colleague) so I wanted them preserved- but also, sometimes if I am preparing a mouthpiece for re-sale I want it to look good (as students here in NZ are very picky about 2nd hand goods and really don't like the "green look").
Really, the re-sale thing is my main motivation for wanting a mouthpiece to look new.



Post Edited (2018-09-16 08:34)

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