Green Slime

[kprinz]

I have a 45 slp that constantly builds up with green slime in the valve section and tuning slides. Especially the 3rd valve slide. I use Hetman valve oil and slide oil on the instrument. Could the synthetic oil be causing the slime build up? Any suggestions on how to prevent it?

[Ace]

It's probably the oil. I use Hetman's, and it leaves green slime deposits in the valve and slide areas.

Ace

[tbn.al]

Me too. I personally think it is the interaction of Hetman's and petroleum based lubricants. We'll see. Probably know in a few months of using nothing but Hetman's anywhere on my horn.

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[Rick Denney]

Me too. I personally think it is the interaction of Hetman's and petroleum based lubricants.

I don't think so. I've been using Hetmans for a while, with Hetmans products in all places.

It may be that Hetmans doesn't have the solvent characteristics of petroleum-based valve oil, and thus the crud we put into the instrument is not cleaned away as effectively.

But I never used to have a problem with green slime the way I have been for the last couple of years--since I've been using Hetmans exclusively. And I don't get the green slime in my rotary tubas, where I don't use much or any valve oil (with them, I lube the bearings with a heavier oil). I play my rotary F tuba enough to see at least to some degree the same thing I see with the Holton, if there was something to see. I'm going to change to something else after my next cleaning and see what happens.

Rick "about time for a chem clean anyway" Denney

[kprinz]

Me too. I personally think it is the interaction of Hetman's and petroleum based lubricants. We'll see. Probably know in a few months of using nothing but Hetman's anywhere on my horn.

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tnb.al: I've been using Hetman's exclusively for quite a while now, and I still get the slime...just letting you know.

[Ben]

Disclaimer. I am not affiliated with any oil company. I have used Hetmans on my piston horns in the past and found buildup to be a problem. I no longer use Hetmans, it was nice until it got gunky.

The chemist in me is begining to isolate variables.

Logic argument: The "literature" (first had reports) claim exclusive use causes the deposits, so I rule out combination arguments.

Unknowns
Hetman lubricant structure/composition of the oil, and it's reactivity towards:
a. Brass, other materials, and electrochemical interfaces
b. Oxygen over time
c. Resident microorganism flora of the instrument
d. Water over time in above environments
e. pH
f. Other elements of the users chemistry that may be in play


There are many variables, and I may not be even on the right path here, but Hetmans gets bad after extended time in the horn, and I hypothesize that b, c, and d may be in play, in conjunction with e based on the users chemistry and hygiene practices.

Ill look into the composition/structure of Hetmans, and may be able to postulate with more certainty.

[tbn.al]

Interestingly it is only the piston horn that has had buildup problems. I never had a problem with my 184 and I used Hetman's exclusively for 5 years. I have no problem with my Bass Trombone and I use Hetman's/Trombontine for for the slide and Hetmans rotor oil for the rotors. I use Hetman slide grease on all of them. If it were something chemical with my body fluids one would think it would affect the other horns as well. My King 2280 doesn't seem to be a problem, but it gets used so infrequently. If the green stuff comes back this time I'll just find something else to use.

[Ben]

There may still be other reasons for this:
Brass alloy compositions may interact differently, or maybe the alloy/alloy interactions (bimetalic dielectric constants) of the different horns have different effects.

Additionally I think the type of oiling on piston vs rotary horns may also be an issue. In a rotary, if you flush oil down the leadpipe, then it may drip out and every time you flush again, you help dissolve some of the built-up/oxidized/goopy gunk (may be paritially soluble in unreacted Hetman oil). This flush may "treat" the problem, and you are better for it. When pistons are oiled, it may well build up on the surfaces around the ports and at the end of the throw of the valves, but never get flushed out, as noone I know pours oil down a piston horn leadpipe... So yes, this very treatment issue may be more the cause than my previous hypotheses. I think it addresses your piston vs rotor issue. Do you "flush"? I am looking for the patent, if I find it, I will post later.

[pgym]

When pistons are oiled, it may well build up on the surfaces around the ports and at the end of the throw of the valves, but never get flushed out, as noone I know pours oil down a piston horn leadpipe.

It may not be common among tubists, but it's a fairly common practice in euph circles. (In fact, Dave Werden suggested it be taught to beginning euphers in a 2006 blog post, and there are several dozen posts in his forum by various posters mentioning/recommending it.) I've done it since the mid-'70s (learned it from my HS band director), and most euphers I've asked do it at least occasionally.

Last time I had my euph chem cleand, the repair tech applied Hetman's to my valves and slides afterward. When I went to oil the valves about a week later, I found a pale yellow waxy film--which I presume is the precursor to the green slime--coating the surface of the ports of all four valves. (I had not flushed oil down the leadpipe in the interim.) Same story a week later, so I went back to Blue Juice.

Switched over to Yamaha Synthetic shortly thereafter (stuck with Hetman 7 slide grease, though) and haven't had a recurrence of gunk.

[Ben]

Today I took my lubricants (Hetaman piston 1 & 2, and Yamaha piston as a control) to the work with me and did some initial testing in the lab.I have already set up a time dependent evaporation study to determine if the mass of the oil changes with time - this will demostrate evaporation rate, and possible mass increase if we see oxidation products form. I do not have access to a GCMS (http://en.wikipedia.org/wiki/Gas_chroma ... ectrometry" target="_blank) - this particular instrument would assist in determining number of components and help identify them. I have taken a sample of each oil and taken an NMR (http://en.wikipedia.org/wiki/Proton_NMR" target="_blank)- this technique also helps elucidate the structure of the material.

NMR is very diagnostic. Hetman piston 1 & 2 are CLEARLY from the following family: Polyolefin (http://en.wikipedia.org/wiki/Polyalphaolefin" target="_blank). In fact by NMR the lubricants apear nearly identical, which means they are most likely differeing polymers of the same sub-unit. I had suspected they may be flourinated or a silicon oil, but this does not seem to be the case. The Yamaha piston valve oil contains no olefin, it is plain old hydrocarbon of some undetermined length.

I suspect the issue with the oils is air oxidation. Olefins are known to slowly air oxidize:
Lineseed oil (varnish, linoleum manufacture) http://en.wikipedia.org/wiki/Linseed_oil" target="_blank
Wacker Process (Pd/Cu promoted): http://en.wikipedia.org/wiki/Wacker_process" target="_blank

Once the oil oxidizes, MANY things can happen, the green color may be due to copper being leached from the surface of the horn and incorporated into the new gamish of materials.

As I continue with the "evaporation" experiment, I will be observing the mass of the materials and eventially take another NMR to see if the olefinated materials have changed.

[tbn.al]

Do you "flush"?

No I don't flush. I always apply the oil directly to the surface of the valve. This is not very often with Hetman's, which is why I like it. You may have something with your hypothesis concerning the metals makeup. It is obviously differnt on the Olds vs. the King or the Hagmann valves on my bone. I am interested in what you find out, but regardless will make a change if this green stuff doesn't stop.

[Ben]

Science!

Warning link contains some language:
http://funny-pictures-blog.com/wp-conte ... ctures.jpg" target="_blank" target="_blank

Iterative questioning based on feedback is science. I happen to use some crazy tools, but it's pretty simple stuff. A film of olive oil would oxidize/polymerize if let set out on a plate for a few weeks... it too is an olefin... I am guessing that oxygen and oiling technique are the largest factors in the green goop.

tbn.al (appologies!!): Which Hetman oil do you use on the 184? I will be analizing my rotor oils (9 & 15?!? don't remember) some time next week when I have them on hand.

[tbn.al]

I'm not tuben, but I don't mind the comparison. He really plays well! I use #12 on my Hagmann valves and I'm pretty sure that is what I used on my 184 while I had one. If fact I know it is. It's the same bottle I've had for a while. Doesn't take much.

[Ben]

UPDATE!!!

tbn.al & others interested - I took a peek at Hetman 12 and Hetman 15 this morning. These oils are NOT terminal or unsubstituted-olefin containing molecules. Based on the NMR, these oils may be in a different category of lubricant, and may not have the same liabilities (oxidative polymerization) as Het1 & Het2. Honestly I was a little surprised that they differed that much. I will cannot speculate as to what Het 12 & 15 are, as the NMR experiement is limited by symmetry constraints, I do know they are heavy molecules that look like grease, similar yet different than the Yamaha valve oil. Unless anyone wants me to look at other oils, I will conclude this portion of my study - I do own a bottle of Het 3 & Bluejuice, but complex mixtures analize poorly (I suspect Bluejuice is a complex mixture of natural hydrocarbon and detergents), I think Het 3 will be fairly similar to 1 & 2. I am open to a quick analysis of other lubricants if you are willing to ship me a sample.

Update on the evaporation experiment. I weighed out a know amount of liquid in a vial with known mass, and have been re-massing these vials every 3 days or so. The vials have been left on my benchtop side by side, so the temperature and airflow effects should be identical. The three vials all have a small but identical cross-section (surface area is constant) therefore liquid/air interface is identical and the only variable in evaporation should be the difference in vapor pressure of the 3 liquids.

Results - all three vials have been loosing mass.

Mass Table
Yamaha: Initial=265.6mg, t-6hr= -1.9mg, t-3d= -4.4mg, t-6d= -4.0mg
Hetman1: Initial=146.0mg, t-6hr= -0.5mg, t-3d= -1.2mg, t-6d= -0.6mg
Hetman2:Initial=165.2mg, t-6hr= -0.4mg, t-3d= -0.8mg, t-6d= -0.4mg
Note: Mass loss is cumulative, t= time, hr = hour, d = days

The evaporative loss of the natural oil is significantly greater than the loss of the synthic oil. In a high surface area enviroment this trend may be even more striking.

I will update one more time in another week with an interpretation of the residue in the vessels to determine if they have markedly changed over time. The oils remain colorless and do not appear to visually be thickening, but these glass vials are a significantly different environment than the tuba (dark, wet, metallic, microbes...).

[tbn.al]

Thanks Ben! The fact that Het 1&2 are substanially different than Het 12&15 is really surprising. Maybe I should try my Het 12 in my piston horn. I suspect it would be too viscous, but I may try it. BTW, I checked the King Euph and the green stuff is there, just not a lot of it yet.

[Ben]

Jim - The chemistry of olefins allows for a process called expoxidation and then subsequent dihydroxylation... these types of molecules can then be further oxidized to acids similar to vinegar (read mild). Diol molecules and their more oxidized relatives can coordinate to metals promoting a "leaching" effect. I think the green color is from trace amounts of copper, and the effect may not be terribly significant - no more so than the bacteria chewing up your lunch/beer exhaust and making carboxylic acids... Short answer - I doubt much deterioration from the use of these oils.

tbn.al - let me know how 12 works in the piston horn. It is a good extension of the experiment.

[Ben]

I'm curious what they use. One problem: brass does not rust... Their corossion "inhibitor" may be present to inhibit the degredation of their own synthetic oil, if it is an olefin product. I don't own Yama synthetic, so I won't be able to answer the question.

Not buying it, I'll take plain old hydrocarbon anyday now.

[tbn.al]

That is interesting! Especially the plate test at the end. I didn't see any green slime, only red though.

[Rick F]

I've been using Yamaha Light (YAC-LVO) for about 2 or 3 years. Before that I used Hetman's light, but got tired of the yellow goop that built up after time (it was yellow goop - not green slime on my horn).

[euphomate]

I have similar problems as decribed in my Besson EEb Sovereign and Yamaha 642 euphonium. I use ULTRA PURE valve oil exclusively in both. It is a synthetic oil like Hetmans. Maybe it's something to do with synthetic valve oil and it's combination/reaction to water. I haven't done a comparison test by using a petrochemical oil only.