10,255 miles on amsoil 15/40 = copper @364ppm

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Originally Posted By: JAG
I'm using an IPhone to view and post so can't easily post quotes to everything that you thought I think. Literally everything that you thought that I think that you disagreed with are not things that I think. Ever feel like someone put words into your mouth? I got a super-sized sandwich from you.
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I just read something that I disagree with. I think that UOAs do detect sub-micron particle sizes. For example, even 100% elemental (free ions or atoms) particles would be detected and detected very accurately. The ionization that occurs before detection is used to break down the material to free ions. For example, if NaCl were completely dissolved in water, there are only Na+ and Cl- ions...no NaCl. Spectrographic analysis would detect the Na+ and Cl-.


My apologies for stuffing you full. I've been known to misinterpret people before.

OK in regard to um size - I'm not saying you're wrong, but it does contradict what I've read and experienced. Still - I'm open to that if you can point me to some sources that support your position. I'm not in a position to agree with you yet, but I'm always willing to learn something new. Has the technology changed that dramatically in the last several years?

Is it only the low end? IOW, only the "less than 1um" that we're in debate here? Is the upper end still 5um, give or take a little?
 
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Yes only the low end is what I'm in disagreement with. The 1 to 5 or 1 to 10 micron range mentioned refers to the upper end range of detection, not THE RANGE of detection, IMO. There are plenty of web site references if you Google something like: spectrographic analysis ICP particle size. Here is one:
http://www.cceco.net/CCECO/Spectrographic-Analysis.html

Somewhere on this site, a nice graph was posted showing the detection accuracy as a function of particle size. It drops off as particle size increases.
 
You wrote:

Originally Posted By: dnewton3


If it's that small, then it would not be showing up on a UOA.


This statement left me confused.

From JAG's ad:

Quote:
SPECTROMETERS MEASURE ONLY VERY SMALL PARTICLES AND DISSOLVED MATERIAL IN OIL


This is truth and what I go by. I'll need to read your new posts but it appears you are getting it now.
 
Remembering way back to my days at the Ford lab, I recall that the effective range was 1-5um. I'm sure it can pick up elements greater than that, but with lesser accuracy. And as that size increases, the accuracy diminishes on a parabolic rate, as I recall. That's why I've always believed that spectral analysis is reasonably reliable at 1-5um; above that it can get "iffy" or worse. Can it work below that? Ok - probably can. But how "small" of a particle can it pick up? I don't know that anyone really knows.

As for a "dissolved" metal, I'll accept that it's in solute. Nothing more or less by defition. However, that leads me to believe that not only would Cu from chelation be in solute, but so would Cu from wear. Not all Cu from wear, but the Cu that the spectral analysis can see.

I fully understand, and have for years, that UOAs have their limits as well as benefits. As long as we understand these, it is an excellent tool. I also concur that PC is a tool to help understand equipment and lube health, but PC cannot distinguish what elements are in play; it can only detect size and not composition, to the best of my understanding. Am I wrong here?

At it's core, I have fundemental questions, and simple answers are the best answers, IF the question is reasonably defined.
"Yes" or "No" answers are the best; if you think I've not clearly defined the question, then feel free to explain your viewpoint, but please avoid the "end-run" of the answer.

1) Can particles from "wear" and particles from "chelation" both exist in a UOA simultaneously?

2) Can spectral analysis differentiate between Cu that is from chelation and Cu that is from mechanical wear?

3) Can the "chemical" process that attacks (works upon, interacts with, etc) the Cu in a heat exchanger also have that same reaction with Cu from other sources, such as bearings?

4) Can we call the removal of metals "desirable", regardless of the method of which it is removed from its origin?

5) Can "wear" be accurately predicted by a UOA?

I have my predisposition of answers to these questions after my years of research and expereiences, but I'd like to hear from others.
 
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Originally Posted By: dnewton3
But how "small" of a particle can it pick up? I don't know that anyone really knows.


Funny you always catch me in rush mode. I got to get ready for work now. But I will answer the above. I think all people who run any type of spectral analysis know - there is no bottom. JAG and I have been trying to explain to you and it's frankly getting a bit frustrating. It will detect atoms. There is no lower limit. The 1-5um is just an upper LIMIT RANGE. Get it? It's not a size to be detected range.

Here's another way to think about it. Why do you think Terry and company speak of digested samples? Typically digestion means nitric acid - so all the metal in a sample will go into solution and be detected.
 
I realize we all have time constraints, Pablo. I don't find fault in your brevity for that; it happens to us all. You are due all the courtesey we'd all want when the clock is against us.

OK - so the upper end of the UOA is 1-5um, and the lower is is so deep that we cannot see it. Fine; I can accept that. It does not completely agree with my established understanding, but I'm willing to take on a new view for the sake of the debate.

So, when you get a chance as time permits, please answer my questions above.
 
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Following this thread is making me want to do a UOA on my Dmax & Ford. + I'm wondering how my recently aquired MB will do since this last oil chang I put in:
RTS T6 5-40 1qt
JD+ CI 15-40 3qts
RTS CJ 15-40 3qts
DeloLE 15-40 1qt
To clean up my left over oil supply. ( i wouldn't dare post that on an MB forum)
 
Originally Posted By: dnewton3
1) Can particles from "wear" and particles from "chelation" both exist in a UOA simultaneously?


YES. (but your use of the word chelation is strange, chelation is just a method of how a metal ion is held in solution, not a method of particle creation)

Originally Posted By: dnewton3
2) Can spectral analysis differentiate between Cu that is from chelation and Cu that is from mechanical wear?


No. "from chelation" makes no sense. Chelated ions and particles under about 1um-5um will be detected.


Originally Posted By: dnewton3
3) Can the "chemical" process that attacks (works upon, interacts with, etc) the Cu in a heat exchanger also have that same reaction with Cu from other sources, such as bearings?


No. Cu in a cooler or heat exchanger is typically near pure Cu, plus I suspect the Cu being removed is a copper oxide. Whereas bearings are some alloy that can contain some copper. Highly unlikely copper oxide is formed on the wear surfaces of the bearings.

Originally Posted By: dnewton3
4) Can we call the removal of metals "desirable", regardless of the method of which it is removed from its origin?


No. Typically not, but this is a loaded question. I wouldn't consider the removal of surface atoms in a cooler a huge deal. After 50 years, that cooler will be be there, the engine long dead
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Originally Posted By: dnewton3
5) Can "wear" be accurately predicted by a UOA?


Predicted? No. UOA's are looking in the rear view mirror. A UOA can tell you have an engine problem - a coolant leak? Yes. Can you take another engine's UOA with a certain oil and say it will perform in some manner like folks on BITOG think? In a VERY fuzzy gut feel way - maybe - but it's very squishy at best. Accurately? Never.
 
OK Pablo, substitute the word "chemistry" for Chelation if you like with regard to #2.
Restated: Can spectral analysis differentiate between Cu being removed from chemical esters versus Cu from wear? I suspect the answer you and I would agree on is "No."

In regard to #3, I disagree with you. I don't know of any "near pure" Cu in an engine. It's all some form of Cu alloy. And the Cu surface of bearings isn't grossly different from the Cu in the cooler. If the ester can attack the Cu in the cooler, it can attack the Cu in the bearing. Even if you believe it to be "copper oxide", does that not exist on a bearing as well? I would agree that it may not be in the same order of magnitude, but I completely disagree with you in regard to this topic. I currently work in the HVAC industry where I specifically oversee the manufacture of Cu-based heat exhanger systems. I have a very good knowledge of what Cu alloys exist in a heat exhanger. What I work on is VERY similar to those type heat exchangers in the auto industry; I know because I've been to lots of industry seminars and see the same people again and again. And I'm no novice to a bearing, either. Worked as a maintenace supervisor and engineer for too long to say otherwise.

As far as #5, I also disagree with you. Yes, a UOA is a look back. But it is a predictor of future performance within a sub-set of one engine, tranny, diff, etc. UOAs can say "based upon a ppm count of XXX metals over YYY miles, you should be able to continue safe use of the oil for ZZZ additional miles." I've seen you do this many times; I do it too. We all do it. Wear rates, when steady and within control limits, allow for the predicted wear for future mileage accumulation. And for you to state otherwise is completely in contradiction to many statements both you and I have made. If this were not possible to do, then why ever do a UOA to only know hisotry, and not predict future performance? If we cannot predict wear based upon statistical analysis, they why do we all comment on it daily? If we cannot predict wear, are we only able to predict clelated metals? What good is that? Your postion on this makes no sense to me. If you feel this is not true, that we cannot make reasonable predictions for future mileage accumulation based upon wear rates, then don't you dare ever make a comment on that topic in another UOA henceforth. I challenge you to put your $$$ where your mouth is in that regard.
 
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#3 - So tell me what Cu alloys are used in cooler tubing? What alloys are used in bearings? I tell you - my point is - they are different alloys. You tell me what the alloys are. I also say on an EP wear surface the chemistry will be different as well. My point - an oxide typically won't form on a "soft" wear surface.

#4 - I did say we do this on BITOG, but it's squishy and not accurate - remember your word choice - you used "wear" and "accurate". I suspect "wear" was very much on purpose.
 
Cu with traces of Zn, Tn, Ni, and others. That's common in heat exchangers. And in bearings.

Bearings also use those trace elements to "harden" the Cu, because it's too soft by itself to perform well in a bearing. Then, as you likely know, Pb and Tn are also used as "backers" to that Cu alloy, and finally the main backbone for support it steel (Fe and other components).

If I'm to accept that the Cu in "dissolved" chelated form is due to the ester chemistry working on the cooler at some molecular level (as I recall you stated down to the atoms in one post way above), then how can it be that the same process that can separate Cu out of the Cu alloy in the heat exchanger cannot find its way to also work on the Cu in a Cu-alloy bearing? Is there some form of Cu bigotry going on at a molecular level?

The Cu in a heat exchanger has Tn and Zn in it as well as some Ni and Pb. The Cu in a bearing is primarily dosed with the same elements to harden it, and then backed by Pb and then steel. Both heat exchangers and the bearings use Cu alloys with similar composition. I'd agree that the small percentage differences make a performance difference depending upon application (we alter our brazing material by tenths of a percent depending upon final goal) but in essence, spectral analysis is going to see all these elements as singular, and not in composition, and cannot detect the origin of their source.

It's not like the Cu in a heat exchanger is 99% Cu and 1% others, while a bearing is 99% "others" and 1% Cu. They are blended along lines to best fit their application.

Either the Cu is liberated from its source in all aspects, or none of them. Are you asking me to believe that a Cu alloy in a heat exchanger can be affected by esters, but the Cu alloy in a bearing cannot? I find that preposterous. You don't get to have it both ways.
 
Originally Posted By: dnewton3
Further, if the ONLY use for a UOA were to predict "chemical" Cu, and not wear, then why do the UOA, ever?


Why to monitor contaminant levels, check for coolant leaks and monitor/determine lube life of course
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^Yes.

UOA isn't to predict or determine absolute wear, one 'may' be able to make an 'educated guess' once trends for an engine have been established. Generally, it's to detect the contaminants/lube life etc, first. With the types of UOA we have posted here on BITOG anyway...
 
Originally Posted By: dnewton3


1) Can particles from "wear" and particles from "chelation" both exist in a UOA simultaneously?

2) Can spectral analysis differentiate between Cu that is from chelation and Cu that is from mechanical wear?

3) Can the "chemical" process that attacks (works upon, interacts with, etc) the Cu in a heat exchanger also have that same reaction with Cu from other sources, such as bearings?

4) Can we call the removal of metals "desirable", regardless of the method of which it is removed from its origin?

5) Can "wear" be accurately predicted by a UOA?

I have my predisposition of answers to these questions after my years of research and expereiences, but I'd like to hear from others.


I'll take a shot.

1. Yes
2. No, I doubt it although some people would like to believe otherwise.
3. Yes, I doubt the chemical knows the differences between what copper parts its attacking?
4. Yes
5. No
 
Is the use of 'chelate' backed with the idea of certain chemistry base oils(ester and/or PAO?) that 'clean up' some surface imperfections(metals that were 'ready to go') but conventional oil wasn't taking with it during use?

Is this the argument of 'how do we know' it isn't 'wear' vs. 'clean out'?

I mean, unless the oil was actually corroding the metal(the other base oils)??? Maybe 'shock' initially???

Okay, what about when a car gets on Red Line for the first time? Often there is that spike in metals.

How about the 3rd subsequent UOA of continuous Red Line use? To me, if the numbers fall back and trend right, it's not 'corrosive' to the health of your engine and it wasn't actual 'increased wear' according to the UOA alone.

If the 'chelation' posed doesn't relate to this, please disregard the point.
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Originally Posted By: dnewton3
Cu with traces of Zn, Tn, Ni, and others. That's common in heat exchangers. And in bearings.


Can you tell me what the alloys actually are - then I can tell you the percentages of Cu. I think you will find the tubing itself is 98-99% copper. Maybe a bit less. Whereas bearing materials range from 59-83% copper.

Originally Posted By: dnewton3
Bearings also use those trace elements to "harden" the Cu, because it's too soft by itself to perform well in a bearing. Then, as you likely know, Pb and Tn are also used as "backers" to that Cu alloy, and finally the main backbone for support it steel (Fe and other components).


True. The copper is an alloy usually a bronze - depending on the application, the loads, etc.

Originally Posted By: dnewton3
If I'm to accept that the Cu in "dissolved" chelated form is due to the ester chemistry working on the cooler at some molecular level (as I recall you stated down to the atoms in one post way above), then how can it be that the same process that can separate Cu out of the Cu alloy in the heat exchanger cannot find its way to also work on the Cu in a Cu-alloy bearing? Is there some form of Cu bigotry going on at a molecular level?


Actually the alloy does effect the copper retention. If it's a sulfide that is being stripped then it could easily be bound at the surface of a bronze bearing, but not in a tube that is a richer copper alloy. It may not take much. I'm sure you are familiar with Al alloys with even a very small amount of copper that have a raised corrosion resistance (just an example). Plus at the EP boundary, the complexes being formed may stay in place because of the alloy.

Originally Posted By: dnewton3
The Cu in a heat exchanger has Tn and Zn in it as well as some Ni and Pb. The Cu in a bearing is primarily dosed with the same elements to harden it, and then backed by Pb and then steel. Both heat exchangers and the bearings use Cu alloys with similar composition. I'd agree that the small percentage differences make a performance difference depending upon application (we alter our brazing material by tenths of a percent depending upon final goal) but in essence, spectral analysis is going to see all these elements as singular, and not in composition, and cannot detect the origin of their source.


See above. I do think alloy bearings have less copper than copper tubing.

Originally Posted By: dnewton3
It's not like the Cu in a heat exchanger is 99% Cu and 1% others, while a bearing is 99% "others" and 1% Cu. They are blended along lines to best fit their application.


As I stated, 59-85% in bearings. 97-99% in tubing.

Originally Posted By: dnewton3
Either the Cu is liberated from its source in all aspects, or none of them. Are you asking me to believe that a Cu alloy in a heat exchanger can be affected by esters, but the Cu alloy in a bearing cannot? I find that preposterous. You don't get to have it both ways.


It's not preposterous at all. Besides, why doesn't the high copper thing happen in gas (or diesel) engines with no oil coolers?
 
Lots of info; I'll have to take time to digest as soon as I get a chance. Been out of the office a lot.

One thing for everyone to note: there is no Cu "tubing" in a Dmax. The HX is integral to the oil filter mount. All the oil plumbing is internal; in fact, there really isn't much plumbing at all in the conventional sense. The cooler stack is inserted into the coolant flow on the driver side of the block. Here's a look at one. Notice how the stacked plates are small and IIRC the stack is only about an inch or so tall. In the picture, the stack is "under" the the filter mount. If you've seen the Dmax filter mount in person, you'll realize it's not large.
http://www.merchant-automotive.com/duramaxengineoilcoolerassembly.aspx

That is one reason I get so miffed about people talking about "Cu leaching from the cooler and lines". Folks, there isn't very much Cu present in the HX circut in the Dmax to begin with. They are stacked plate HXs; not tube and fin. There is not a lot of Cu to begin with in the stacked plate design, and very little brazing material used. BTW - if you take one apart, you're going to buy a new one, because they are non-servicable units. I know; I've seen one taken apart. Have you all?


Which goes back to my main point I'm trying to get across to everyone here ...

If the esters are acting on the HX in a Dmax, (which uses Cu that is a Cu-alloy and not high-Cu tubing), then it's VERY PROBABLE the esters are also acting upon the bearings, because there is prescious little differnce in construction materials between the bearings and the HX. I'll accept Pablo's numbers of Cu tubing being 95-99% Cu, and Cu-based bearing being around 60-85% Cu. BUT THERE IS NO Cu TUBING IN A DMAX. The Cu in the bearings is every bit as susceptible to esters as the HX because their construction materials are VERY similar!

I do understand that Cu ion bonds are different with different Cu alloys, and that will affect the nature of the Cu "shedding" (leaching, chelation, whatever you want to call it). I'm not a chemist, but I understand it a little. I'm not a metalurgist, but I've taken classes and understand the basics.

But people seem to think that 100% of the Cu in a Dmax/ester-oil UOA is all due to the HX cooler, and it's not.
What if we could assign a ratio of the Cu in these UOAs; would the numbers convince you? Let's be REALLY generous and say that 80% of the Cu in a Dmax/Red Line UOA (not picking on Amsoil here ...) is due to the cooler, and only 20% is the bearings. If the Cu count is 684ppm, that would mean that 137ppm is due to the bearings being acted upon by the esters! In a "normal" Dmax UOA at 6.6k miles, the "universal average" of Cu is 12ppm. Am I supposed to believe that 137ppm is not of significant consequence to the bearing????? Again, I just picked the ratio of 80/20. It could be more or less. But that is a very telling scenario, is it not? If there was not an ester-based oil present, and we were seeing 137ppm of Cu from a dino oil in 6.6k miles, we'd all freak out, and rightfully so. But for some reason, the niche markets have everyone convinced that the ester-based "reaction" is all HX and no bearings.

In fact, often we hear something along the lines of this as an explanation: "If no Pb or Tn is present with the Cu, then everything's OK".
Really? I suppose we could make a deduction from that statement. If we can ignore Cu and only use Pb and Tn for the bearing "markers", then why do we ever test for Cu at all? Frankly, that's preposterous and we all know it. Yes, we need to look for things together. But we cannot ignore massive Cu counts just because we are told that "chemistry" is attacking only the HX, as if it were capable of some type of Cu-alloy bigotry.


Does that make sense?
 
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In reviewing the article that JAG posted, I noted a few things the directly support my statements in many different threads, including this one:

(from the Cooler Core Leaching topic)
" ... it has been reported that copper sulfide, even in these high concentrations, is generally benign and as such may not be associated with (cause or effect) cooler failure, accelerated wear or lubricant oxidation. While I personally have not seen the data that support these claims, I also have no basis to refute them."
That is exactly what I've been saying as well. I cannot prove that this chemical interaction is damaging, but neither can we be assured it's not harmful. More studies need to be done. (note that I underlined the sentence above).
Pablo's position is that he can tell you for sure this is not harmful. My position is that there is no data to assure us of that. Not in my database, and not in the author's 30,000 UOAs! My position is that it might be harmful; "might" being a possilbility but not an assurance.


(from the Copper as a Wear Metal topic)
"Copper from wear debris will rarely produce concentrations greater than 50 ppm, in fact, 10 ppm to 20 ppm would be more typical. As such, higher concentrations of copper from cooler core leaching and coolant leaks may mask more serious sources of copper associated with wear."
(note that I underlined the "masking" sentence above)

Sound familiar to anyone? Do those quotes not echo the exact thoughts I've been touting for a few years now?

For the last time, and then I'll exit:
High Cu counts in UOAs from ester-based oil reactions may have the ability to increase and/or mask wear. And to state otherwise is wrong in my opinion, as verified by Mr. Fitch.
 
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