Timing Chain Wear, LL-01, and moly as remedy

[1JZ_E46]

I found this report by Vanderbilt Chemicals in a separate thread and thought it was very interesting regarding GDI engines, timing chain wear, and the impacts of Mo, Zn, P, and B.

Essentially, they show that Zn and P actually increase timing chain wear in GDI engines (in a high-soot environment), and that Mo has the most significant impact in reducing timing chain wear.

Long story short, we just purchased a relatively new (20k miles) T-GDI Mini Countryman. It uses the "Prince" engine (Peugot/BMW joint venture) that has been plagued by worn-out timing chains in high instances; often in as little as 60k miles. What is interesting, is that the engine specifies BMW Longlife-01 oil (or its thinner variant, LL-01 FE)... which is an A3/B4-based oil with high-ZDDP, high-Calcium, and no Mo or Mg (commonly referred to as a "stout" oil here). The Longlife-01 oil specification, while incredibly stringent, largely pre-dates BMW GDI engines.

It got me thinking, perhaps Longlife-01 is not sufficient for the type of timing chain in the Prince engine, and perhaps using an oil with Moly (like the new d1g2 formulations) would help address the inherent timing chain issues with the Prince engine. HOWEVER, the car is under warranty, so I am stuck using LL-01 oil.

I am considering adding Moly via an additive to aid in timing chain protection, and I think getting the treat to be about 100ppm would be roughly inline with d1g2 formulations... This would require about a half-bottle of Liqui-Moly MoS2 (are there any other Moly additives?). Please let me know your thoughts and/or insights. (p.s. I don't want to get into a warranty debate... absent a UOA, there would be no way to know the moly is present). Thanks all!

 

[racin4ds]

I'd certainly run the MoS2, its great stuff and its cheap. What do you have to lose?

With a timing chain, shearing is also an issue. I wouldn't dare run a thin oil in a high revving small Displacement engine with a timing chain. Stick with 5W30 at a minimum.

 

[BMWTurboDzl]

Based upon their history of engine problems I'm convinced that a majority of these issues are simply the result of poor engineering/design rather than choice of oil formulation. For example BMW had among other things timing chain issues back in the 1990's.

I would say this to the VW TDI guys who were trying all sorts of oil formulations to address the flat tappet issue. Choice of oil won't prevent problems associated resulting from bad engineering/design.

 

[Brigadier]

If you are concerned with timing chain wear in a GDI engine, change your oil according to the severe service schedule. GDI engines produce a unique kind of soot that is abrasive to timing chains and is too small for oil filters to catch.

 

[1JZ_E46]

Originally Posted by BMWTurboDzl
Based upon their history of engine problems I'm convinced that a majority of these issues are simply the result of poor engineering/design rather than choice of oil formulation.


While I tend to agree, that has never stopped manufacturers from leveraging lubrication to address design problems.

 

[StevieC]

Originally Posted by Brigadier
If you are concerned with timing chain wear in a GDI engine, change your oil according to the severe service schedule. GDI engines produce a unique kind of soot that is abrasive to timing chains and is too small for oil filters to catch.


What micron is the soot, do you know by chance? Wonder if Bypass filtration as a supplement would help this.

 

[drtyler]

The BMW LL-01 5W-30 produced by Castrol had quite a bit of moly (~ 150 ppm), and the Shell produced LL-01 oils (TPT 5W30 and PP Euro 5W40) contain it as well, although not as much (~50 ppm). To say that all LL-01 oils do not contain moly is not accurate.



Originally Posted by 1JZ_E46
I found this report by Vanderbilt Chemicals in a separate thread and thought it was very interesting regarding GDI engines, timing chain wear, and the impacts of Mo, Zn, P, and B.

Essentially, they show that Zn and P actually increase timing chain wear in GDI engines (in a high-soot environment), and that Mo has the most significant impact in reducing timing chain wear.

Long story short, we just purchased a relatively new (20k miles) T-GDI Mini Countryman. It uses the "Prince" engine (Peugot/BMW joint venture) that has been plagued by worn-out timing chains in high instances; often in as little as 60k miles. What is interesting, is that the engine specifies BMW Longlife-01 oil (or its thinner variant, LL-01 FE)... which is an A3/B4-based oil with high-ZDDP, high-Calcium, and no Mo or Mg (commonly referred to as a "stout" oil here). The Longlife-01 oil specification, while incredibly stringent, largely pre-dates BMW GDI engines.

It got me thinking, perhaps Longlife-01 is not sufficient for the type of timing chain in the Prince engine, and perhaps using an oil with Moly (like the new d1g2 formulations) would help address the inherent timing chain issues with the Prince engine. HOWEVER, the car is under warranty, so I am stuck using LL-01 oil.

I am considering adding Moly via an additive to aid in timing chain protection, and I think getting the treat to be about 100ppm would be roughly inline with d1g2 formulations... This would require about a half-bottle of Liqui-Moly MoS2 (are there any other Moly additives?). Please let me know your thoughts and/or insights. (p.s. I don't want to get into a warranty debate... absent a UOA, there would be no way to know the moly is present). Thanks all!

 

[1JZ_E46]

Originally Posted by drtyler
The BMW LL-01 5W-30 produced by Castrol had quite a bit of moly (~ 150 ppm), and the Shell produced LL-01 oils (TPT 5W30 and PP Euro 5W40) contain it as well, although not as much (~50 ppm). To say that all LL-01 oils do not contain moly is not accurate.


Both of those oils are discontinued (the BMW ones).

 

[StevieC]

I would rather run a high moly oil than add moly to an oil and upset its carefully balanced additive package which can have unintended consequences.

 

[drtyler]

Agree 100%.

Besides, if you add MOS2 to an LL-01, the result is likely no longer LL-01 approved. What does Mini say about oil additives in the owner's manual and their effect on warranty? If you are concerned with using LL-01 only, then that has to be considered as well.

I'd go with PP Euro 5W40.


Originally Posted by StevieC
I would rather run a high moly oil than add moly to an oil and upset its carefully balanced additive package which can have unintended consequences.

 

[1JZ_E46]

Originally Posted by drtyler
Agree 100%.

Besides, if you add MOS2 to an LL-01, the result is likely no longer LL-01 approved. What does Mini say about oil additives in the owner's manual and their effect on warranty? If you are concerned with using LL-01 only, then that has to be considered as well.


Originally Posted by StevieC
I would rather run a high moly oil than add moly to an oil and upset its carefully balanced additive package which can have unintended consequences.



I can't find a single oil analysis of PP Euro 5W-40 (how do you know there's moly in it?). I want to stick with LL-01 for warranty reasons. And adding MoS2 to an LL-01 is a non-issue, warranty-wise, as there would be no record or ability to "see" moly in the oil. Again - I stated in my OP that I do not want this to spiral into a warranty debate, please.

 

[StevieC]

I would do a UOA without the MoS2 added and then add it and do another one and see how it affects your engine. You could be doing more harm than good by upsetting the chemistry in the oil you are using.

 

[1JZ_E46]

Originally Posted by StevieC
I would do a UOA without the MoS2 added and then add it and do another one and see how it affects your engine. You could be doing more harm than good by upsetting the chemistry in the oil you are using.


Thanks, and I agree there is the risk of upsetting the additive balance. Currently running Castrol Edge 0W-30 without MoS2. So the next OCI would be Edge 0W-30 with a half-bottle of MoS2. Castrols d1g2 formulations have both titanium and molybdenum.

 

[drtyler]

I've used PP 5W40 in an N52 application for years. I've done a few UOA's, and each comes back with approximately 50 ppm of moly and 40-50 ppm of magnesium. Most recent was done a few months ago.


Originally Posted by 1JZ_E46
Originally Posted by drtyler
Agree 100%.

Besides, if you add MOS2 to an LL-01, the result is likely no longer LL-01 approved. What does Mini say about oil additives in the owner's manual and their effect on warranty? If you are concerned with using LL-01 only, then that has to be considered as well.


Originally Posted by StevieC
I would rather run a high moly oil than add moly to an oil and upset its carefully balanced additive package which can have unintended consequences.



I can't find a single oil analysis of PP Euro 5W-40 (how do you know there's moly in it?). I want to stick with LL-01 for warranty reasons. And adding MoS2 to an LL-01 is a non-issue, warranty-wise, as there would be no record or ability to "see" moly in the oil. Again - I stated in my OP that I do not want this to spiral into a warranty debate, please.

 

[Brigadier]

Originally Posted by StevieC
Originally Posted by Brigadier
If you are concerned with timing chain wear in a GDI engine, change your oil according to the severe service schedule. GDI engines produce a unique kind of soot that is abrasive to timing chains and is too small for oil filters to catch.


What micron is the soot, do you know by chance? Wonder if Bypass filtration as a supplement would help this.



https://www.sciencedirect.com/science/article/pii/S0301679X15000432

Quote
Highlights
•
Soot-in-oil particles extracted from used lubricating oil of GDI engines.

•
Soot in oil shows modest branching with average length of 153 nm and 59 nm in width.

•
Soot spherical primary particles of 10-90 nm form the agglomerates.

•
Primary particles exhibit an amorphous shell structure of 5 nm.

•
Volatile structures were found to be deposited onto the surface of primary particles.

 

[StevieC]

I'll just be changing my oil early.

 

[oil_film_movies]

Originally Posted by 1JZ_E46
I am considering adding Moly via an additive to aid in timing chain protection, and I think getting the treat to be about 100ppm would be roughly inline with d1g2 formulations... This would require about a half-bottle of Liqui-Moly MoS2 (are there any other Moly additives?). Please let me know your thoughts and/or insights.


Use Ceratec (another LiquiMoly company product) as its got the same concentration of moly as LM MOS2, and the Ceratec uses ammonium molibdate (MSDS says).

Originally Posted by Izb
VOA of Ceratec: http://bmwservice.livejournal.com/38285.html Mo:5419(!) ppm Bo: 359 ppm


You don't need much to get to the 100 ppm moly goal. You only need a 2% sump of Ceratec to get 100 ppm. So, for example, 5 quarts x 0.02 = 3.2 oz Ceratec. There is some boron (HBN) in Ceratec, but really not that much at all.

Don't use LiquiMoly MOS2, and here is why:

Originally Posted by Edward Kollin
MoS2 forms it's slick surface from the non-interactive exposed sulfur groups. It is NOT reactive towards dispersants/detergents, as it is not acidic. It is difficult to disperse in an oil as the sulfur/sulfur Van der Waal forces cause agglomeration (as well as its low coefficient of friction). I have tested it quite thoroughly at Exxon, as many have done before me, and found it essentially useless in motor oil. It settles out in a similar manner to sub-micron lead chloride particles (when burning leaded fuel). It works very well in grease.



Originally Posted by MolaKule
I think what Ed said was very telling.

Originally Posted by Edward Kollin
We tried size distributions of less than 100nm to 1 micron. The larger particles settled out in low flow areas of the engines and the very small particles seemed to agglomerate into larger particles which settled out in low flow areas of the engines. We worked quite a bit on the dispersing of the primary particles with a wide variety of base oils and a great number of surfactants. Even at high loadings solid MoS2 did little. However, this work should be included as part of the prelude to the development of the oil soluble moly trimer (incredible additive) that we developed at Exxon and I got the opportunity to perform the initial engine testing.--Ed


The suspended or colloidal versions of powdered moly additives do settle out and conglomerate.

The soluble versions stay in solution, as would be expected.


So when you add a Moly additive, how do you know what are you getting, the colloidal version (suspended particles of powder) or the soluble version?

And how do you know how much should be added unless you have done extensive and expensive tests?

 

[1JZ_E46]

Thanks OFM. How do you know that Ceratec contains the soluble version?

 

[oil_film_movies]

Originally Posted by 1JZ_E46
Thanks OFM. How do you know that Ceratec contains the soluble version?
MSDS had it as ammonium molybdate, is all I saw. I do wonder if its OK to use that instead of molyDTC or trimer moly types, yet the MOS2 seems to be a problem. LiquiMoly likes Ceratec's form anyway, FWIW.

 

[oil_film_movies]

If ammonium molybdate in Ceratec is not soluble, unknown to me, then another alternative is Berryman Engine Oil Extender (EOE) with MSDS:

Petroleum Oil... 64742-65-0... 45-55% (Group II neutral oil)
Polybutylene Succinimide confidential... 9-12% (VII and dispersant)
Dialkylated Diphenylamine... 68411-46-1... 6-10% (Antioxidant)
Zinc Dialkyl Dithiophosphate proprietary... 2-5% (ZDDP - Anti-Wear)
Organomolybdenum Complex proprietary... 1-2% )(MoDTC, friction Modifier)

If you assume the MSDS's lower number, 1% MoDTC or 10,000 ppm, is about twice what's really in the product, due to the ambiguity of MSDS's in general, then you have the same concentration, 5,000 ppm, as what LM Ceratec has.
The other chemicals in Berryman EOE should be fine to use in small amounts. Like the discussion above with Ceratec, use about 3.2 oz Berryman to get boosted MoDTC.