AW hydro oils run from 300-600 PPm ZDDP BUT remember there are ?? 5-10 different Types of ZDDP from Carbon chain lenght to alcohol type and tey ALL will perform differently as to AW and to oxidation protection.
bruce
ZDDP depletion issue
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bruce
TooSlick beat me to it...
Ray,
I saw it too. The key word is "some of the [...} by-products." I bet the hydrolysis products do not. One more reason short trips (with water condensation) is bad for oil.
Also, note how even the by-products diminish dramatically between 3-5000 miles (figure 6). Phosphate end product is not likely to have AW properties IMO.
I saw it too. The key word is "some of the [...} by-products." I bet the hydrolysis products do not. One more reason short trips (with water condensation) is bad for oil.
Also, note how even the by-products diminish dramatically between 3-5000 miles (figure 6). Phosphate end product is not likely to have AW properties IMO.
LOL, this is a joke, right?
I'm not versed in the complexities phosphate EP chemistry to authoritively dispute your speculation, but the placement and prominance in the article indicating the steady-state presence of phosphate (at nearly 74%, no less) well past 6,000 miles suggests to me that the authors consider phosphate is more than a free radical breakdown product with no further usefull function.
I'm not well versed either, but the figure 5 legend states: "The oil in this example has been used beyond its additive’s useful lifetime. As a result, significant increases in the wear metals were observed during the last few miles of the application."
The figure 6 shows that the only significant forms of P left after a long run on oil are phosphates.
If one combines these 2 statements, a common sense conclusion is that phosphates are useless.
However, this is my speculation only, so I could be totally off.
The figure 6 shows that the only significant forms of P left after a long run on oil are phosphates.
If one combines these 2 statements, a common sense conclusion is that phosphates are useless.
However, this is my speculation only, so I could be totally off.
So, does that mean add more CD-2 SLOB to gain more ZDDP as we head to 10K? Or, should we simnply go back to 3K OCI?
Not in the cooling system..
Three points - 1> the increase in wear metals may be related to factors other than ZDDP depletion, such as accumulated dirt, oxidation by-products, and inevitable wear metals sloshing around in the oil samples, 2> oxidation breakdown products in the oil sample, itself, would have a bearing on oil performance if we're considering a conventional blend, and, 3> Though I called your conclusion into question, I never intended to target you as "way off".
This from Wikipedia:
"The mechanism of function of ZDDP lies in chemical reaction with the surface of the metal gears under high pressure and temperature. Pressure concentrates on small unevennesses on the surfaces in contact; pressure and temperature at these points sharply rises. At such conditions, ZDDP decomposes and forms a layer of iron phosphate or iron sulfate, effectively chemically polishing the surfaces."
In short, the release of phosphate is the very avenue involved in ZDDP's achieving its protective properties. Presuming the roaming sulphate (the "thio" part...) and phosphate radicals are "activated" at the sites of maximum heat, sliding parts in contact such as bearings and piston rings, into protective iron compounds, I am mystified how the term "useless" can be applied.
I think it is important to realize that this study is really about analytical methods and how to interpret the results. The author is pointing out that most analytical methods used in oil analysis test for the elements, i.e., zinc, phosphate, etc. The author is saying that the ZDDP breaks down into different forms, and typical oil analysis does not tell you the form they are in. Very interesting article, as were some of the links on the page. Deep stuff, good info, imho.
I checked my old Physics 201 book and the numbers for the Planck constant, C and Avogadro constant are correct as stated. Now what do we do with them?
It seems that you argue for the sake of arguing:
Here are my counterpoints:
If the increased wear is indeed caused by the oxidation process like you claim, well, that is another argument for the ZDDP depletion theory as ZDDP is one of the antioxidants and active ZDDP would prevent oil base oxidation.
Besides you either misunderstood of twisted my words. I did not claim that intermediate breakdown products of ZDDP were “useless”.
I only claimed that the line labeled “phosphate” on the figure 6, also explained as “final decomposition product,” is likely useless for the AW purpose.
You are using the term phosphate to encompass all forms of ZDDP. This is incorrect as ZDDP itself is also a form of phosphate. Unfortunately the authors chose to use the term “phosphate” to designate end product of ZDDP decomposition, most likely inorganic (ionic) phosphates.
If the “final decomposition product” of ZDDP were indeed active as AW additive, ZDDP depletion issue would not exist; yet we know that ZDDP depletion is a fact, hey, GM oil monitor was built around this issue!
This related site (link below) has additional info and even claims that “Acid phosphate, (RO)2P(O)O-Salt and (RO)3P(O) (seen at 10 to -8 ppm), are the final oxidation products before phosphate production, and are potentially precipitated out of the oil as zinc or calcium phosphate.”
Now, we hear that some of the ZDDP degradation products can be potentially harmful:
http://www.noria.com/learning_center/category_article.asp?articleid=764&relatedbookgroup=OilAnalysis
And finaly, the below link supports my conclusions (from patent application):
“[0086] In addition to oxidation products, the presence of a ZDDP concentration in the fluid is characterized via FTIR peak area calculations at 645 cm.sup.-1 (indicative of P.dbd.S bond concentration) and 970 cm.sup.-1 (indicative of P--O--C bond concentration), as illustrated in FIG. 20. During decomposition of this additive, non-ionic intermediates are produced, which further decompose into ionic products. The final decomposition product is zinc phosphate or pyro-phosphate, which has poor solubility in the oil matrix. As the free radicals are formed, the ZDDP quenches them, and prevents the hydrocarbon oxidation. The calcium carbonate forms salts with the oxidized acids, yielding the carbonate concentration depletion (via FTIR data at 860 cm.sup.-1) as a function of ongoing fluid sampling, as shown in FIG. 21.”
http://www.freshpatents.com/Fluid-f...t20050908ptan20050194977.php?type=description
LN Engineering, a Porsche engine rebuilder is very vocal about the latest "Energy Starburst" oils including some Mobil 1 variants, and their depleted levels of ZDDP.
Check it out here:
http://www.lnengineering.com/oil.html
Excerpt:
Many Porsche repair shops have acknowledged that these newest SM and CJ-4 motor oils are not sufficient for protecting any Porsche engine. With longevity and the protection of vital engine components in mind, many shops are recommending non-approved motorcycle or racing oils, or the addition of oil supplements at every oil change, for their higher levels of protection.
Oil companies have been cutting back on the use of Zn and P as anti-wear additives and switching to alternative zinc-free (ZF) additives and ash-less dispersants in their new low SAPS oils since Zn, P, and sulfated ash have been found to be bad for catalytic converters. One such ZF dispersant/anti-wear additive is boron, which does not foul the catalysts in the particulate emissions filters or catalytic converters. For most owners, the reduction in longevity of a catalytic converter is a small price to pay considering the many thousands of dollars it costs to properly rebuild a Porsche engine. It is worth noting that most Porsches have lived the majority of their lives with high Zn and P oils as found in API SG-SJ oils as late as 2004, and we never hear of problems with their catalytic converters.
In addition to protecting emissions controls, there are many other design considerations in formulating engine lubricants, which include improving fuel economy and longer drain intervals. High friction can result in areas with boundary lubrication or where high viscous friction forces and drag may occur with hydrodynamic lubrication in bearings. The use of friction modifiers, such as moly (there are many different species of Mo-based friction modifiers, help to reduce friction in metal-to-metal contact with the formation of tribofilms characterized with their glassy, slippery surfaces. Lower viscosity motor oils are key to increasing fuel economy by their reduction in drag where high viscous friction occurs in hydrodynamic lubrication. While lower viscosities improve fuel economy greatly, they also reduce the hydrodynamic film strength and high temperature high shear viscosity of the motor oil, factors both of which are key to protecting high performance engines, especially aircooled ones.
However, it is worth noting that these new API guidelines do not need apply to “racing,” “severe duty,” or any motor oils that do not carry an API “starburst” seal or clearly state for off-road-use only. Motor oils meeting “Energy Conserving I or II” standards should be avoided as well as those with an API SM or ILSAC GF-4 classifications. The European ACEA A3/B3 classifications, which place a cap on P levels at 0.10-0.12% but allow for higher Zn levels, to be better in taking into consideration wear and engine longevity, setting much lower wear limits, while still limiting emissions and protecting emissions control devices. It is common to find API SJ rated oils, particularly those meeting Volkswagen's stringent 505.01 standard for PD TDI engines, to also meet ACEA A3/B3 requirements. The current ACEA A3/B3 classifications require higher high-temperature high-shear (HTHS) viscosities, stay in grade sheer stability, and tighter limits on evaporative loss (noack volatility), high temperature oxidation, and piston varnish. This makes oils meeting these ACEA standards that much better for your Porsche, especially since wear limits are much more stringent for valve train wear, 1/6th to 1/4th the wear allowed in the sequences for API's newest SM or CJ-4 standards. Of particular interest is the upcoming ACEA E9 standard to supersede the API CJ-4 standard in Europe, creating a classification for low ash oils that are low detergent and are very effective in controlling wear in legacy engines.
Failure to use the right oil, use proper filtration, or observe proper changing intervals can affect the performance of even the best motor oil. This also includes changing the oil too often (needlessly bad for the environment and your wallet) or not often enough. Against conventional wisdom, engine wear decreases as oil ages to a certain extent, which means that changing your oil more frequently actually causes engine wear; these findings were substantiated by studies conducted by the auto manufacturers and petroleum companies, leading to drain intervals increased from 3,000mi/3 months to 5,000-7,500mi/6 months in most domestic vehicles, using mostly non-synthetic oils. Based off of extremely long drain intervals recommended by most European manufacturers, some in excess of two years and 20,000 mi, some users have found it best to reduce those intervals by half or even a quarter. Porsche for the 2008MY has reduced their extended drain intervals significantly to one year/12,000 mi, which is actually less miles than Porsche recommended back in the 1990s with 964 and 993 based aircooled 911s. Based on UOAs provided to us by our customers, new Porsche owners should consider reducing their drain intervals further to no more than 9,000 mi or one year.
Vehicles with track time or sustained high oil temperatures or RPMs should have their oil changed after every event (or every other event). This translates to a total of about 10 hours max, with vehicles with 12 qt or higher oil capacities- engines with smaller capacities must be changed more often. Vehicles subjected to very short drives or sustained operation in heavy traffic should indeed be serviced more often. Likewise, vehicles not driven often but driven hard a few times a year can probably go a year between oil changes, but that doesn't mean you shouldn't use a good oil! Regular used oil analysis is the best way to determine ideal drain intervals for your driving habits - one good rule of thumb I have seen quoted is to change the oil with the TBN (total base number) is reduced by 50% of the original total (requiring you to also know your oil's virgin TBN). Another common recommendation is to change the oil once it's TAN (total acid number) equals the TBN. Other factors to consider are fuel dilution and shearing out of grade when determining your drain interval. With this knowledge in hand, using a quality motor oil with proper filtration and regular service is the best thing to do for your engine and to protect your investment.
Check it out here:
http://www.lnengineering.com/oil.html
Excerpt:
Many Porsche repair shops have acknowledged that these newest SM and CJ-4 motor oils are not sufficient for protecting any Porsche engine. With longevity and the protection of vital engine components in mind, many shops are recommending non-approved motorcycle or racing oils, or the addition of oil supplements at every oil change, for their higher levels of protection.
Oil companies have been cutting back on the use of Zn and P as anti-wear additives and switching to alternative zinc-free (ZF) additives and ash-less dispersants in their new low SAPS oils since Zn, P, and sulfated ash have been found to be bad for catalytic converters. One such ZF dispersant/anti-wear additive is boron, which does not foul the catalysts in the particulate emissions filters or catalytic converters. For most owners, the reduction in longevity of a catalytic converter is a small price to pay considering the many thousands of dollars it costs to properly rebuild a Porsche engine. It is worth noting that most Porsches have lived the majority of their lives with high Zn and P oils as found in API SG-SJ oils as late as 2004, and we never hear of problems with their catalytic converters.
In addition to protecting emissions controls, there are many other design considerations in formulating engine lubricants, which include improving fuel economy and longer drain intervals. High friction can result in areas with boundary lubrication or where high viscous friction forces and drag may occur with hydrodynamic lubrication in bearings. The use of friction modifiers, such as moly (there are many different species of Mo-based friction modifiers, help to reduce friction in metal-to-metal contact with the formation of tribofilms characterized with their glassy, slippery surfaces. Lower viscosity motor oils are key to increasing fuel economy by their reduction in drag where high viscous friction occurs in hydrodynamic lubrication. While lower viscosities improve fuel economy greatly, they also reduce the hydrodynamic film strength and high temperature high shear viscosity of the motor oil, factors both of which are key to protecting high performance engines, especially aircooled ones.
However, it is worth noting that these new API guidelines do not need apply to “racing,” “severe duty,” or any motor oils that do not carry an API “starburst” seal or clearly state for off-road-use only. Motor oils meeting “Energy Conserving I or II” standards should be avoided as well as those with an API SM or ILSAC GF-4 classifications. The European ACEA A3/B3 classifications, which place a cap on P levels at 0.10-0.12% but allow for higher Zn levels, to be better in taking into consideration wear and engine longevity, setting much lower wear limits, while still limiting emissions and protecting emissions control devices. It is common to find API SJ rated oils, particularly those meeting Volkswagen's stringent 505.01 standard for PD TDI engines, to also meet ACEA A3/B3 requirements. The current ACEA A3/B3 classifications require higher high-temperature high-shear (HTHS) viscosities, stay in grade sheer stability, and tighter limits on evaporative loss (noack volatility), high temperature oxidation, and piston varnish. This makes oils meeting these ACEA standards that much better for your Porsche, especially since wear limits are much more stringent for valve train wear, 1/6th to 1/4th the wear allowed in the sequences for API's newest SM or CJ-4 standards. Of particular interest is the upcoming ACEA E9 standard to supersede the API CJ-4 standard in Europe, creating a classification for low ash oils that are low detergent and are very effective in controlling wear in legacy engines.
Failure to use the right oil, use proper filtration, or observe proper changing intervals can affect the performance of even the best motor oil. This also includes changing the oil too often (needlessly bad for the environment and your wallet) or not often enough. Against conventional wisdom, engine wear decreases as oil ages to a certain extent, which means that changing your oil more frequently actually causes engine wear; these findings were substantiated by studies conducted by the auto manufacturers and petroleum companies, leading to drain intervals increased from 3,000mi/3 months to 5,000-7,500mi/6 months in most domestic vehicles, using mostly non-synthetic oils. Based off of extremely long drain intervals recommended by most European manufacturers, some in excess of two years and 20,000 mi, some users have found it best to reduce those intervals by half or even a quarter. Porsche for the 2008MY has reduced their extended drain intervals significantly to one year/12,000 mi, which is actually less miles than Porsche recommended back in the 1990s with 964 and 993 based aircooled 911s. Based on UOAs provided to us by our customers, new Porsche owners should consider reducing their drain intervals further to no more than 9,000 mi or one year.
Vehicles with track time or sustained high oil temperatures or RPMs should have their oil changed after every event (or every other event). This translates to a total of about 10 hours max, with vehicles with 12 qt or higher oil capacities- engines with smaller capacities must be changed more often. Vehicles subjected to very short drives or sustained operation in heavy traffic should indeed be serviced more often. Likewise, vehicles not driven often but driven hard a few times a year can probably go a year between oil changes, but that doesn't mean you shouldn't use a good oil! Regular used oil analysis is the best way to determine ideal drain intervals for your driving habits - one good rule of thumb I have seen quoted is to change the oil with the TBN (total base number) is reduced by 50% of the original total (requiring you to also know your oil's virgin TBN). Another common recommendation is to change the oil once it's TAN (total acid number) equals the TBN. Other factors to consider are fuel dilution and shearing out of grade when determining your drain interval. With this knowledge in hand, using a quality motor oil with proper filtration and regular service is the best thing to do for your engine and to protect your investment.
Very interesting stuff, M104-AMG.
I'm posting this short selection from that site in case I lose the bookmark in the future:
"You want to make sure the oil meets the ACEA A3/B3 requirements as well, as the ACEA is much more stringent in allowable tolerances for wear required for the much more severe driving conditions European cars sustain."
Question: Is there any potential problems with boosting the Zn and P in my API SM or CJ-4 oil or such a thing as too much ZDDP?
Answer: Beware of ZDDP boosters and concentrates being sold under various names. These products should truely only be used at time of break in. I haven't tested every one of these products, but one thing is very obvious to me. Every product previously sold to boost ZDDP, be it STP or EOS, always had roughly an equal amount of detergents to offset the affect of ZDDP in reducing the TBN of motor oil. Most of these ZDDP concentrates omit detergents altogether or have very little compared to EOS or STP! I'll have to go back through the various SAE journals to find exactly where it is, but it is in there that you have to have additional detergency because of the breakdown of ZDDP in peroxides and its interaction with combustion byproducts to form sulfuric acid. More acid, will increase the oils TAN, and will lead to corrosive wear of bearings. For once, I will have to say that more is not better, especially in this case. EOS and STP are decades old, and proven products that work synergistically with your existing motor oil and were never designed to boost the Zn and P more than 100-200ppm - unlike some recommendations to run double the ZDDP, in excess of 2000 ppm! It is not only the level of Zn and P that is important, but also starting with an oil that meets the ACEA A3/B3 standard would assure a starting TBN of 10 or higher and with similarly higher HTHS viscosities will also give you greater protection too. If you do choose to use these products, you must do used oil analysis to determine drain intervals and monitor overall TBN retention and ensure that the TAN increase does not lead to increased bearing wear! Too much ZDDP can also foul spark plugs and oxygen sensors, not to mention plug EGR valves and the catalytic converter.
========================
Question: How can I boost the level of Zn and P safely?
Answer: IF YOU MUST, PLEASE REMEMBER MORE IS NOT ALWAYS BETTER AND THAT USING THE RIGHT OIL IS ALWAYS BETTER THAN ADDING OIL SUPPLEMENTS TO INFERIOR OILS!
We're shooting for 1200-1400ppm Zn and P! Some may say that it is out of date to be recommending EOS (new part number for EOS is 88862586) or STP. Well, I am concerned about the various highly concentrated products being marketed, aiming at boosting Zn and P to 2000+ ppm. There is no published evidence to show that you need those levels of Zn and P and more importantly, you are drastically altering the chemistry of the lubricant by doing so. Remember, STP and EOS have been around for decades and are proven!
One way would be to use GM's Engine Oil Supplemental additive. By our calculations, between .5 and .66 oz of GM EOS has to be added to each quart of oil to raise the Zn and P by 100 ppm each. For a Porsche 911, I recommend using 1 bottle (pint) of GM EOS with every oil change if the oil you are using has less than the recommended 1200-1400 ppm (0.12-0.14%) Zn and P. If the oil you want to use has less than 1000 ppm (0.10%) Zn and P, choose a different oil, since you will need to add too much of the GM EOS to boost this. One pint of GM EOS is sufficient to boost the levels in the very popular SM rated Mobil 1 0w40 and Mobil 1 15w50 products in a 911. For a four cylinder Porsche, 1 bottle of STP 4-cyl treatment (red bottle) is the perfect amount for boosting the Zn and P in a ~4 quart fill. Alternatively, about 1/3 of the bottle of EOS will be more than enough.
If adding oil additives isn't for you, alternatively you can use Mobil 1 MX4T or V-Twin, as these oils have significantly more additives. If you were to blend 50/50 regular Mobil 1 and the Mobil 1 V-Twin, you will end up with Zn and P in the 1400-1500ppm range, which is basically like a SJ or CI-4.
Link: http://www.lnengineering.com/oil.html#Z12
.
I'm posting this short selection from that site in case I lose the bookmark in the future:
"You want to make sure the oil meets the ACEA A3/B3 requirements as well, as the ACEA is much more stringent in allowable tolerances for wear required for the much more severe driving conditions European cars sustain."
Question: Is there any potential problems with boosting the Zn and P in my API SM or CJ-4 oil or such a thing as too much ZDDP?
Answer: Beware of ZDDP boosters and concentrates being sold under various names. These products should truely only be used at time of break in. I haven't tested every one of these products, but one thing is very obvious to me. Every product previously sold to boost ZDDP, be it STP or EOS, always had roughly an equal amount of detergents to offset the affect of ZDDP in reducing the TBN of motor oil. Most of these ZDDP concentrates omit detergents altogether or have very little compared to EOS or STP! I'll have to go back through the various SAE journals to find exactly where it is, but it is in there that you have to have additional detergency because of the breakdown of ZDDP in peroxides and its interaction with combustion byproducts to form sulfuric acid. More acid, will increase the oils TAN, and will lead to corrosive wear of bearings. For once, I will have to say that more is not better, especially in this case. EOS and STP are decades old, and proven products that work synergistically with your existing motor oil and were never designed to boost the Zn and P more than 100-200ppm - unlike some recommendations to run double the ZDDP, in excess of 2000 ppm! It is not only the level of Zn and P that is important, but also starting with an oil that meets the ACEA A3/B3 standard would assure a starting TBN of 10 or higher and with similarly higher HTHS viscosities will also give you greater protection too. If you do choose to use these products, you must do used oil analysis to determine drain intervals and monitor overall TBN retention and ensure that the TAN increase does not lead to increased bearing wear! Too much ZDDP can also foul spark plugs and oxygen sensors, not to mention plug EGR valves and the catalytic converter.
========================
Question: How can I boost the level of Zn and P safely?
Answer: IF YOU MUST, PLEASE REMEMBER MORE IS NOT ALWAYS BETTER AND THAT USING THE RIGHT OIL IS ALWAYS BETTER THAN ADDING OIL SUPPLEMENTS TO INFERIOR OILS!
We're shooting for 1200-1400ppm Zn and P! Some may say that it is out of date to be recommending EOS (new part number for EOS is 88862586) or STP. Well, I am concerned about the various highly concentrated products being marketed, aiming at boosting Zn and P to 2000+ ppm. There is no published evidence to show that you need those levels of Zn and P and more importantly, you are drastically altering the chemistry of the lubricant by doing so. Remember, STP and EOS have been around for decades and are proven!
One way would be to use GM's Engine Oil Supplemental additive. By our calculations, between .5 and .66 oz of GM EOS has to be added to each quart of oil to raise the Zn and P by 100 ppm each. For a Porsche 911, I recommend using 1 bottle (pint) of GM EOS with every oil change if the oil you are using has less than the recommended 1200-1400 ppm (0.12-0.14%) Zn and P. If the oil you want to use has less than 1000 ppm (0.10%) Zn and P, choose a different oil, since you will need to add too much of the GM EOS to boost this. One pint of GM EOS is sufficient to boost the levels in the very popular SM rated Mobil 1 0w40 and Mobil 1 15w50 products in a 911. For a four cylinder Porsche, 1 bottle of STP 4-cyl treatment (red bottle) is the perfect amount for boosting the Zn and P in a ~4 quart fill. Alternatively, about 1/3 of the bottle of EOS will be more than enough.
If adding oil additives isn't for you, alternatively you can use Mobil 1 MX4T or V-Twin, as these oils have significantly more additives. If you were to blend 50/50 regular Mobil 1 and the Mobil 1 V-Twin, you will end up with Zn and P in the 1400-1500ppm range, which is basically like a SJ or CI-4.
Link: http://www.lnengineering.com/oil.html#Z12
.
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