Question about Pb and Redline

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This kind of relates to Al's latest UOA and his previous UOA of just RL. From what I understand, the GM guy said their is hardly any Pb being used in bearings. Whats the deal wit RL and the bearings? We've heard of the chemical layer reaction put forward by RL themselves (laying down the protective layer) and others on BITOG. Maybe Mark from Butler labes can chime in here....
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I don't think it's wear as we think of it, which if we could prove, would ease a lot of fear for potential RL users.
 
Hi Buster

I don't have any personal experience with Redline but we do see high lead levels where the cause is not obvious. Conditions in the oil can change and affect the solubility of lead so it will go up without being an indicator of wear. We frequently see this with degraded oil when the oxidation-sulfation-nitration numbers are high. In the case of Redline it is probably due to the oil's formulation and an additive reacting with the lead in the bearings or soldered parts in the engine. This isn't necessarily a bad thing and in fact it is usually harmless. Some additives can cause the same thing and some additives themselves contain very high levels of lead. Glycol in the oil can also drive up lead and copper due to chemical reactions and not necessarily wear. It would be interesting to see if the high lead is happening when conditions favor condensation since water hydrolyzes esters to form acids and certain acids can react with lead.

I can't speak for GM bearings but the engines we work with (heavy-duty diesels) the bearings have a lead and tin overlay with a very thin layer of copper and then aluminum (or vice versa) and finally the steel backing. We look for elevated levels of tin to help us decide it bearing wear is occurring or not. If tin is not up then most likely it isn't abnormal wear; this of course depends of the construction of the bearing.

I think some folks try to attach too much significance to slight changes of wear elements. There are many factors that can affect the levels reported on the report, things such as instrument limitations, interferences, the actual wear mechanism and particle size, etc. Most of the labs I am familiar with run with a +/- 10% check standard (some go even higher for certain elements) so this is the normal error you would expect to see. In our lab we run the check standard every 24 samples and if it doesn't pass the instrument recalibrates itself and starts all over again. Lead, tin, sodium, and antimony are soft metals and poor emitters so they are hard to read (the signal is weak and hard to pull out of the noise). These metals can have more error than the hard metals (strong emitters) like chrome, nickle, iron, etc. which give strong signals. When people start adding additives it is possible to have interferences that go undetected. Before anyone starts criticizing the labs for not getting absolute accuracy remember what you are paying for an analysis and then go to an environmental lab or some of the other labs on the Internet and ask them what they charge to run just one element (not 21). Don't be shocked if you see the price is well over $100! Fortunately the accuracy we get is sufficient for what oil analysis was intended.
 
Stinky, I hate to hijack this thread, but you said in a post a while back that Butler was going to start testing for antimony. When will that be?
 
Thanks for the info, "Stinky." I'm interested in this question also as an occasional RL user. I found the following comment interesting:
It would be interesting to see if the high lead is happening when conditions favor condensation since water hydrolyzes esters to form acids and certain acids can react with lead.

beacuse it is at odds with what Molekule has posted about esters and also fully-formulated oils. He has posted that once a "dry" ester is solved with an alcohol(?? do I have that right?), it is no longer susceptible to hydrolyzation by water. Perhaps I misunderstood?
 
quote:

Stinky, that was an excellent, honest post.

Thank you.

Sure was, thank you very much. Appreciate that.
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quote:

This isn't necessarily a bad thing and in fact it is usually harmless.

Roy Howell said the same thing. Your right, too much emphasis on small ppm wear differences.
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[ April 23, 2005, 10:49 PM: Message edited by: buster ]
 
Bulwnkl,

Well Molakule knows a lot more about oil chemistry than I do so if that is what he said then I would accept it as fact. I was thinking about some information I saw on phosphate esters and it's been a long time since I've studied some of this stuff so I've probably forgot a few things or never understood them completely to start with.
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G-Man, we started running Sb about a week ago.
 
quote:

Originally posted by Stinky Peterson:
I think some folks try to attach too much significance to slight changes of wear elements. There are many factors that can affect the levels reported on the report, things such as instrument limitations, interferences, the actual wear mechanism and particle size, etc.

Good post Stinky. I discovered the above 20 years ago when doing R&D on jet aircraft engines for the AF. To bad that isn't better understood here. Wear elements may be used by an expert analyzer to point to a potential problems, but you can't automatically gauge wear levels by it. Especially laymen.
 
Redline reacts quite aggressively towards the softer bearing overlay materials used by some manufacturers such as Honda. This effect normally dissipates with long term use of the product, so I'm not terribly concerned about it. Honda motorcycles don't exhibit this chemical reaction and I suspect they use a different type of metallurgy than the car engines....

The harder (Pb/Sn/Ni) bearings used by Toyota and most German manufacturers aren't affected by the RL chemistry. This is very obvious when looking at the UOA's that have been posted over the past several years.

TS
 
quote:

Originally posted by buster:
http://theoildrop.server101.com/cgi/ultimatebb.cgi?ubb=get_topic;f=3;t=002024

This kind of relates to Al's latest UOA and his previous UOA of just RL. From what I understand, the GM guy said their is hardly any Pb being used in bearings. Whats the deal wit RL and the bearings? We've heard of the chemical layer reaction put forward by RL themselves (laying down the protective layer) and others on BITOG. Maybe Mark from Butler labes can chime in here....
cheers.gif
I don't think it's wear as we think of it, which if we could prove, would ease a lot of fear for potential RL users.


Buster..I don't think that the RL has a whole lot to do with this high lead (in my case anyway) this vehicle has always had higher lead values. That may be to the way I drive it (lots of Low RPM driving..on the verge of lugging the engine.) This engine is getting better though.

I am planning on continuing to use the RL mainly bc of the cleaning effect of the Ester (since I am using dino oils now).
cheers.gif
 
web page

SAE Standards
Document Number: ARP5991
Date Published: December 2002


Title: Test Method for the Determination of Water Concentration in Polyol Ester and Diester Aerospace Lubricants By Coulometric Karl Fischer Titration

Issuing Committee:
E-34 Propulsion Lubricants

Scope:
The test method describes the procedure for the direct determination of water concentration in polyol ester and diester based aerospace lubricants by the commercially available automated coulometric Karl Fischer titration instrument. The method was validated to cover the water concentration range of 150 to 3500 \gmg/g. The method may also be suitable for the determination of water concentrations outside this range and for other classes of fluids, however, the precision statement shall not be applicable for such uses.

Knowledge of the water concentration in polyol and diester aerospace lubricants is required since the presence of excess amounts of water can lead to hydrolysis of the lubricant, resulting in corrosion and wear of the lubricated components and degradation of the lubricant. Significant variability observed in inter-laboratory Karl Fischer test results for these lubricants highlighted the need for a standardized Karl Fischer test procedure, specifically suited for these lubricants.
 
That's what I was thinking about Mamala! I guess I wasn't hallucinating after all
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I don't know what kind of esters are in use but I did encounter an aircraft oil that had a terrible smell and it hadn't been used. After doing some reading we came to the conclusion that it had absorbed water and hydrolyzed because it sat in an unsealed can (covered with a plastic bag) for a number of years. This was a phosphate ester if I remember correctly and the oil did have some 4 carbon compounds. We came to the conclusion that it had hydrolyzed since compounds with butane (4 carbon) groups are frequently very stinky. I can't remember the oil but the info was at the Mobil site.

For those not familiar with hydrolysis, water reacts with the ester and splits the molecule. The products of the hydrolysis are an alcohol and a carboxylic acid.
 
quote:

Originally posted by Stinky Peterson:
This was a phosphate ester if I remember correctly and the oil did have some 4 carbon compounds.

Phosphate esters are fire resistant hydraulic fluids. Skydrol is a big name in aviation.

Mobil Jet II is one of several polyol ester based jet turbine oils.

Either ring a bell?
 
I'd like to see how WW's 5w-20 UOA will next time around to see if that 10ppm of Pb will come down ever further.
 
I have to agree that most of the high pb levels we see with RL is on Honda's smaller high revving motors. Doesn't seem too prevalent on their larger truck motors, or motors of other manufacturers. There has to be some correlation to the materials used in Honda motors IMO, but I'm not chemist. When I run Redline in my turbo Dodge (with Al non pb bearings) there is no lead detection, so it doesn't seem that the pb is being created by a chemical process in this engine. One thing about Honda's smaller high revving engines, most use an oil cooler which might contain soldered or lead parts, whereas their larger motors do not use oil coolers. Just throwing out some ideas here.
 
Nice to hear from another chemhead, Stinky.
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I work in an analytical lab too, except we analyze soil and rocks instead of oil... looking for the next big gold mine. We charge about $20 for ICP multi-element analysis, but I'm not sure if that includes sample preparation costs. I've never had to worry about how the pricing works, I'm one of the gnomes working the machines in the background.
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And you're absolutely right about a certain amount of error being inevitable, and some elements being particularly difficult to get good results for. Being +/- 10% is not that big a deal in many cases. Gold actually can be more jumpy than that, but I don't think that's something you worry about often.
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Not many people have golden engines to wear off into their oil, even if the dealerships charge like it!
 
Good point Idrinkmotoroil. Dave did tell me that the Pb we see with RL is most likely Pb and not oxides as I've stated. The guy from Analystsinc who do their testing told me that it was oxides. No clue. I think it just depends on the metals used in the engine.
 
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