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#2447937 - 11/29/11 08:05 AM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: JD4440]
JAG Offline


Registered: 10/23/05
Posts: 4532
Loc: Fredericksburg, VA

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#2447938 - 11/29/11 08:09 AM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: JD4440]
dnewton3 Offline



Registered: 05/14/07
Posts: 5618
Loc: Indianapolis, IN
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.
_________________________
Conventionals vs. Synthetics isn't about which is "better"; it's about which lasts longer, while assuring safe operation, in relation to cost. Any product can be over or under utilized. The same applies to filters.
Make an informed decision; first consider your operating conditions, next determine your maintenance plan, and then pick your lube and filter. Don't do it the other way around ...

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#2448159 - 11/29/11 01:03 PM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: JD4440]
OVERKILL Offline


Registered: 04/28/08
Posts: 26417
Loc: Ontario, Canada
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 grin
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#2448247 - 11/29/11 02:44 PM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: JD4440]
ltslimjim Offline


Registered: 08/06/10
Posts: 5143
Loc: PL&F
^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...
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#2448345 - 11/29/11 04:02 PM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: dnewton3]
demarpaint Offline


Registered: 07/03/05
Posts: 21314
Loc: NY
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
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#2448357 - 11/29/11 04:14 PM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: JD4440]
ltslimjim Offline


Registered: 08/06/10
Posts: 5143
Loc: PL&F
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. grin2
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#2448566 - 11/29/11 07:10 PM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: dnewton3]
Pablo Offline


Registered: 10/28/02
Posts: 46685
Loc: Duvall WA - Pacific NW USA
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?

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#2448578 - 11/29/11 07:16 PM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: JAG]
Pablo Offline


Registered: 10/28/02
Posts: 46685
Loc: Duvall WA - Pacific NW USA
Originally Posted By: JAG


Wow - awesome article. One thing I missed - I called it perhaps oxidation, but sulfidation actually fits better. Same discussion we are having.

As I stated many times - we need to get some particle analysis.

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#2448933 - 11/30/11 04:38 AM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: JD4440]
dnewton3 Offline



Registered: 05/14/07
Posts: 5618
Loc: Indianapolis, IN
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?


Edited by dnewton3 (11/30/11 08:43 AM)
_________________________
Conventionals vs. Synthetics isn't about which is "better"; it's about which lasts longer, while assuring safe operation, in relation to cost. Any product can be over or under utilized. The same applies to filters.
Make an informed decision; first consider your operating conditions, next determine your maintenance plan, and then pick your lube and filter. Don't do it the other way around ...

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#2448943 - 11/30/11 06:00 AM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: JD4440]
dnewton3 Offline



Registered: 05/14/07
Posts: 5618
Loc: Indianapolis, IN
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.







Edited by dnewton3 (11/30/11 06:22 AM)
_________________________
Conventionals vs. Synthetics isn't about which is "better"; it's about which lasts longer, while assuring safe operation, in relation to cost. Any product can be over or under utilized. The same applies to filters.
Make an informed decision; first consider your operating conditions, next determine your maintenance plan, and then pick your lube and filter. Don't do it the other way around ...

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#2448944 - 11/30/11 06:16 AM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: dnewton3]
Pablo Offline


Registered: 10/28/02
Posts: 46685
Loc: Duvall WA - Pacific NW USA
There is a lot to agree on in that article, but still many open questions. As I have stated many times and has he so very clearly states, a simple spectrographic UOA doesn't tell us what we need to know.

Quote:
Copper from wear debris will rarely produce concentrations greater than 50 ppm....


If you said this, then I missed it. My apologies.

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#2449390 - 11/30/11 04:39 PM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: demarpaint]
Bayman Offline


Registered: 10/15/11
Posts: 173
Loc: Indiana
Originally Posted By: demarpaint
Originally Posted By: dnewton3
The "chemistry thing" also happens readily with 15w-40 products, and has been shown to happen with other brands as well such as RL, RP and I've even seen it with TDT/Delvac 1.


Wouldn't it be better to use an oil that shows less of a "chemistry thing" in your particular application?


Maybe the OP can try a different oil and then he can get a UOA and compare the COPPER NUMBERS against his last UOA with Amsoil 15/40.

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#2479083 - 01/01/12 10:27 AM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: Hermann]
law3500 Offline


Registered: 03/01/09
Posts: 150
Loc: Colorado springs CO, USA
Originally Posted By: Hermann
One of this board's main forums is the UOA forum. Having just posted a UOA about 10 days ago, the memory of not being to easily make a attachment, and ultimatly having to type it in,(a pain in it own right) it was probably the last that I will post. Surely there is a way this can be improved upon. It would surely spur me on to do more UOA's.



+1
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#2523150 - 02/02/12 02:59 PM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: JD4440]
LeakySeals Offline


Registered: 02/18/11
Posts: 5070
Loc: MA
So after reading all that the conclusion is....inconclusive?
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#2625920 - 05/13/12 08:18 PM Re: 10,255 miles on amsoil 15/40 = copper @364ppm [Re: Bayman]
JD4440 Offline


Registered: 04/24/10
Posts: 253
Loc: Orlinda, TN
Originally Posted By: Bayman
Maybe the OP can try a different oil and then he can get a UOA and compare the COPPER NUMBERS against his last UOA with Amsoil 15/40.

Not sure where I left off on this as it's been a while since I've been here seems like. I did in fact switch to Mobil Delvac and the analysis was good. I'm getting a little concerned now as It's been 9k miles and the OLM hasn't pinged me to change the oil yet.
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