Engineering Explained discusses ZDDP

Higher ZDDP can lead to catalyst poisoning if a lot of it ends up in the exhaust system. While less is required with roller followers and roller lifters, this does not mean that other areas may not benefit from slightly higher concentrations.

Depends on the non-roller application here. An old broomstick cam'd SBF or SBC doesn't require a whole heck of a lot of ZDDP to keep the parts separated. A cam-over-bucket application doesn't either, generally, unless it's design is such that it produces high pressure on a small contact patch (VW PD engines for example).

Mobil 1 15W-50 was broadly spec'd for GM roller applications in Corvette and Camaro.

Ultimately, my view on it is that phosphorous levels, unconstrained, generally land at around 900-1,000ppm for ideal protection in most passenger car applications, as evidenced by the full-SAPS Euro oils. Even the C3 oils typically have phosphorous approaching the 900ppm limit.

Where we see considerably lower levels of phosphorous is in the API/ILSAC oils, which can be blended very inexpensively, and typically have a higher volatility ceiling. These are also lighter. You combine those things, and odds are much higher that the oil is going to end up in the exhaust system, so catalyst protection becomes a bigger focal point, so we see phosphorous not only more restricted by regulation, but we see less of it used.

I concur, that the ZDDP will only poison cats if the car is burning the oil, and the ZDDP is actually making it into the exhaust stream.

I was specifically talking about Mobil 1 5w50 Supercar designed for DLC finger followers in the Corvette Z06 not 15w50 Mobil 1. The finger follower as the name implies directly touches the cam. To help with wear resistance they oil was specifically forumulated with higher ZDDP, Viscocity, lower deteregents. It perfomed better in testing for cam / finger follower wear than Mobil 1 0w40 Euro, 5W40, 5w50 FS x2 et al.

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I concur, that the ZDDP will only poison cats if the car is burning the oil, and the ZDDP is actually making it into the exhaust stream.

I was specifically talking about Mobil 1 5w50 Supercar designed for DLC finger followers in the Corvette Z06 not 15w50 Mobil 1. The finger follower as the name implies directly touches the cam. To help with wear resistance they oil was specifically forumulated with higher ZDDP, Viscocity, lower deteregents. It perfomed better in testing for cam / finger follower wear than Mobil 1 0w40 Euro, 5W40, 5w50 FS x2 et al.

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Right, I wasn't saying you were talking about the 15W-50, just pointing out that the 15W-50, which has 1,200ppm of Phosphorous and 1,320ppm of Zinc, was spec'd for numerous GM roller motors. This is even higher than the 1,100ppm/1,200ppm found in the Supercar 5W-50.
 
Phosphorus can disappear from the oil over time due to its volatility. The API standards even require oils to be tested for this, requiring a minimum phosphorus retention of 81% in the Sequence IIIHB engine test. The concern with this is keeping the phosphorus out of the catalytic converter.

The breakdown/depletion of ZDDP is a separate issue. When the ZDDP is sufficiently depleted, friction and wear will increase. This can happen even if there's no noticeable loss of phosphorus, and so it won't be obvious on a UOA. The same thing happens to friction modifier and other additives. Studies on additive depletion use different types of spectroscopy to measure additive depletion.

SAE 952543 is a good study on this. In this case, ZDDP depletion occurred within 6,700 km of commuting, and the MoDTC was 70% depleted. The oil's friction performance essentially dropped to that of the base oil. They didn't measure engine wear, but I expect it would have increased as well.

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That study is from 1995. Modern oils should perform better since the API standards have more stringent aged-oil fuel economy tests. Though, the modern tests still allow fuel economy to drop by several percent over a typical OCI due to additive depletion.

Here's an example of additive depletion from another study:

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I tried to tell them the same 15 year old common knowledge in laymans terms and was jumped on by the peanut gallery. They told me if I kept posting nonsense that I would not last long. Thank you for posting what they should already know.
 
I tried to tell them the same 15 year old common knowledge in laymans terms and was jumped on by the peanut gallery. They told me if I kept posting nonsense that I would not last long. Thank you for posting what they should already know.
I mean, 1995 (the date of that study) isn't 15 years ago, it's 30. But anyway, what you said was:
Stumalump said:
The trick is this: Oil is full of addatives that do not last as long as the oil. The good news is that you can tell exactly when additives fail. The level drops fast over about 500 miles. Might be a 1/4 quart or a half. That is when the additives break down and turn to vapor.
And:
Stumpalump said:
When you see the small drop it’s a great indication that the oil in that particular application needs to be changed and that is usually about the same time the ZDDP, molly or other addative you may be specifically concerned about is gone as well. Find the drop zone or milage and that is when you change it. Ones I know and remember are mitsubishy V6 only lasting 3000 miles, newer dodge V6 last 4500-5500 Miles. V10 in Ford truck is at 4000 when you see the drop in level. New company car Pacifica runs 8 or 9000 before it drops. The fleet manager lets me change it at 10,000. Best is change it at that drop level or if you want to hack the life longer because you are on the run then it’s the only OK time to add STP, lucus oil stabilizer or other snake oil additive because they are loaded with the additives that burned off.

I actually agreed with you that phosphorous will deplete over time, as I'm sure you recall. Where you ran into some issues were the claims that:
- The additives turn to vapor
- A drop in oil level signalled that this had happened
- A drop in oil level indicates the oil needs to be changed
- Lucas or STP replenishes additives because they are "loaded with them"

There are many different types of ZDDP, which @RDY4WAR I'm sure can expand on. There are several types of moly, as well as other FM compounds. Phosphorous retention (81% minimum), as noted, is covered in Sequence IIIHB, the details for which can be found here:
https://cdn.standards.iteh.ai/samples/106209/d8d3c805ead7450087a0c639db5a4268/ASTM-D8111-20.pdf

This is a 90hr test performed at high RPM and high load on a 3.6L Chrysler Pentastar engine. What 90hrs translates into in miles/km in your application will of course depend on the average speed of the vehicle. On my wife's truck, that's about 31km/h (lots of in-town driving) which in turn means ~2,800km.

Assuming (and the charts in the post you are quoting support this) a rather linear rate of decline, even if you had an oil that was crap and was right on the 81% threshold, that's 0.21% per hr, so to get to say 50% depletion, we are looking at ~240hrs, which, in the same application is ~7,400km.

Engines can consume oil for a wide variety of reasons. My old 5.4L drank 3L of AMSOIL SS 0W-30 between changes, but zero Mobil 1 AFE 0W-30 🤷‍♂️ Do I think that's because the engine consumed 3L worth of additives with the AMSOIL? No, of course not.

Oils, and OE approvals, developed for extended drains, are going to have better phosphorous retention, AW and FM performance.

And then of course there's the fact that oil doesn't age in miles. This is why industrial applications use hours. This is why IOLM's use engine hours, load, temperature and many other parameters to determine OCI length. Mileage counters are dumb, because they don't in any way account for factors like the rate at which the vehicle was driven and the conditions under which it was operated.
 
Additive compounds dissociate because of heat, oxidation, and intermixing with other additive compounds.

Once they dissociate, the individual atoms are free to roam around the oil mix and some atoms may be carried off when the oil volatizes. These "free" atoms will not have the same effects as when they are a recognizable compound.

ZDDP for example will eventually dissociate or break up into phosphorus, sulfur, and zinc atoms. While the phosphorus atom won't have the same affinity to ferrous surfaces, because of the loss of sulfur bonding, it will still attempt to form the ferrous phosphate glass-type structure at the surface whenever it comes in contact with the steel.
 
I feel as though an oil with 600-800 ppm P and 12% Noack is more detrimental to emissions systems (and the rings) than one with 1000-1200 ppm P and 5% Noack, especially if the second one also does far better in RPVOT and PDSC.
That statement, I believe, has an embedded assumption that the Zn and P volitalizes with the base stock. I’m not sure that’s absolutely true if the engine is not burning oil. In a non burning case, the higher back oil effectively distills itself as the lighter ends flash off.

Some may get swept off, but I’m not convinced it’s a primary mechanism, nor is it safe to convolute back with additive flash-off the way one would reasonably do when oil is actually burned.
 
That statement, I believe, has an embedded assumption that the Zn and P volitalizes with the base stock. I’m not sure that’s absolutely true if the engine is not burning oil. In a non burning case, the higher back oil effectively distills itself as the lighter ends flash off.

Some may get swept off, but I’m not convinced it’s a primary mechanism, nor is it safe to convolute back with additive flash-off the way one would reasonably do when oil is actually burned.

I have 3 thoughts about this. One process would be through volatility promoting ring coking which will promote the transport of oil (and thus additive) into the combustion chamber over time. Another one revolves around ZDDP's good anti-oxidant properties. Anti-oxidants make oil (and any liquid) difficult to burn. (or at least slow the burn rate) This could slow the rate at which the oil "burns" off the cylinder walls. The 3rd thought is that volatility is a reflection of stability which would effect misting. An oil that's more volatile (less stable) would also likely "mist" easier in the crankcase and valve cover(s). (from windage) This could result in more oil "mist" exiting the crankcase via the PCV system. These fine droplets could still carry Zn, S, and P with them.

I don't have any white papers to support this and not searching at the moment. This is just me putting thoughts down.
 
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Surprisingly, this study showed that when looking at a large set of different motor oils, the amount of phosphorus volatized:
1. Did not correlate well with the volatility of the motor oil
2. Did not correlate well with the phosphorus concentration in the motor oil.
https://www.savantgroup.com/media/ASTMJournal-Selby-Noack-PEI-2005.pdf

There were other conclusions as well. I just wanted to point out those in particular that I found most interesting.

2002 thread on phosphorus volatility: https://bobistheoilguy.com/forums/threads/phosphorus-volatility-and-catalytic-converters.18571/
 
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