EPA on Zn, S and P in Engine Oil

[LubeMaster77]

Steve over at RennSportSystem told me about a question posted on Rennlist concerning EPA mandated reductions of Zn, P, & S in all the oils. Here was my response. I wanted to make sure that any Pelican Pals were informed as well.

The EPA has stayed away from regulating the chemical and physical properties of motor oils. As such, there are no EPA standards regulating Zn, S and P in motor oils. The EPA prefers to regulate emission and fuel economy requirements for the OEMs, which requires them to modify their equipment and lubricants in order to meet the emission and CAFÉ requirements. The OEMs work thru ILSAC and API to address the technical concerns of the lubricants (with respect to the mechanical modifications that the OEMS are planning on implementing) and establish industry standards for maximum and minimum levels of P and S. The one exception to this is in the area of fuels, where the EPA is taking a two pronged approach setting standards for emissions, and certain chemical composition of the fuel with respect to sulfur and aromatics. But lets not go down the fuels path just now. The take away is that it is a cooperative effort of industry participants that set the chemical and physical standards, not the EPA. And these standards are set so that OEMs can make the necessary mechanical modifications to the vehicles so that they can meet emission and CAFÉ standards.

The OEMs would really like to see phosphorous levels of 0.05% wt in engine oils to address the issue of catalyst poisoning from any phosphorous that might be carried thru in exhaust gases. There is industry concern about the ability of 0.05% phosphorus levels being able to provide adequate antiwear protection (remembering that the P comes from the ZDDP antiwear/antioxidant chemistry), especially in older model vehicles. For the current SM category, ILSAC and API have agreed to P levels of no more than 0.08% wt. and no less than 0.06% wt. Sulfur limits have been set at 0.5%max for 0W and 5W multigrades and 0.7% max for 10W multigrades. There are no standards for Zn. Note that an oil has to meet these requirements if they seek API certification or claim they meet API performance categories. Since these elements are not regulated by the government (EPA), an oil can be made with levels exceeding the standards but they will not be able to get API certification or claim that they meet API standards. The OEMS will also not honor warranty issues with these oils.

Regarding the primary and secondary zinc issue. Mixed zincs are used because they decompose at different temperatures (ZDDPs must decompose to provide antiwear protection so that the polar ends of the decomposition products can interact with the metal surface to provide boundary lubrication). The primary zincs start to decompose around 184-186 degrees F while secondary zincs (made with branch alkyl groups) decompose at higher temperatures depending upon the degree of branching and chain length, thus providing antiwear protection across a broad temperature range. This is why you do not want to heat motor oil (to drive off water) after you have mixed/blended in the additive package as the ZDDP will start to decompose at temperatures high enough to drive off water.

[Steve@Rennsport]

Mike:

You're awesome,...

Thanks VERY much for the detailed information, Sir.

[LubeMaster77]

Steve,
Sorry, I forgot to add a bit about yellow metals.

The yellow metal issue is associated with the sulfurized olefin used in gear oil additive packages. This chemistry is separate and distinct from ZDDP. The issue with the sulfurized olefin is dependent on the supplier. Specifically, the Lubrizol additive starts coming apart at temperatures around 250F and becomes aggressive to yellow metals. Other suppliers, such as Afton, have chemistry that is more stable and this phenomena is not associated with their additives.

There was one issue, historically, about ZDDP that was raised by Dennison, when an old guy by the name of Ellis Borne was their head guru. In piston hydraulic pumps, there was some feeling at Denison that ZDDP somehow interfered with the frictional property of the hydraulic oil, giving rise to bronze transfer from the piston shoes to the swash plate. It was never proved conclusively that this was the case, and much time and effort was spent on it. But Dennison preferred R&O oils for their piston pumps. However, over time, the industry figured out how to make ZDDPs that were excellent performers with both steel on steel pumps and bronze on steel pumps so it really is not an issue in today’s world.

I sent you an e-mail containing this info, don't know if you got it or not. Because I sent it to you first and not posting it, I give you complete permission to post it on Rennlist with out fear or reprisal of any copyright infringement!

[LubeMaster77]

oh ya, your welcome - I just love this ***** .

[Steve@Rennsport]

Originally posted by LubeMaster77
oh ya, your welcome - I just love this ***** .

Me too!

Thanks VERY much.

The local PCA chapter does an annual National Tech Session every November called "Rainbonnet" and I'm going to see if I can get you invited (they pay all expenses) to give a presentation. Under today's circumstances, I think that it would be quite timely.

[mikez]

Now if we can just get the STATES to agree on a uniform gasoline blend....

[LubeMaster77]

I actually do type of thing all the time. It is one aspect of the job I really like.

I will be in Portland on August 15 to do an all day Lubrication Seminar at the Airport Holiday Inn in Portland.

As for November, I think I might be able to slid that in.

[LubeMaster77]

MikeZ - the History Channel had a great show about fuel. A Chevron Spokesperson was on and actually stated something that we had known for many years - all the gas is the same. Many states have different requirements but the refineries make to the tightest and ship it to everyone. Like the low sulfur diesel fuel vs the high sulfur - they have pretty much always made it low sulfur - they just dyed the off road stuff to indicate it was "high sulfur" for tax reasons when infact it was low sulfur all along.

[mikez]

Maybe so...but the oil companies use the excuse whn they have ample gas in AZ and CA gets tight supplies....

And the red dye diesel for off road use which typically means no taxes...not necessarily a different blend....

Ag and the construction bidness use red dye....they have a pretty goo lobby. But the bottom line is it's EASIER and CHEAPER to make one flavor...

[Steve@Rennsport]

Originally posted by LubeMaster77
I actually do type of thing all the time. It is one aspect of the job I really like.

I will be in Portland on August 15 to do an all day Lubrication Seminar at the Airport Holiday Inn in Portland.

As for November, I think I might be able to slid that in.

Sounds like fun,.........I'll call you when you're in town on the 15th.

[LubeMaster77]

We should see if some local Pelicans can stray from work to attend! If nothing else, I give out some really cool prizes during my seminars...

[cnavarro]

Mike, do you mind if I repost your post on my web site, giving due credit of course. It explains the reduction better than I did :-)

[movin]

What about molybdenum and boron, are they on the chopping block too? The current Kendall oils are woefully deficient of the boron they once had. Seems like everything is being so degraded!

[cnavarro]

It seems that many manufacturer specific formulations don't have moly. I know that the moly has a tendancy to build up on surfaces, but what is the real reason for their omission? Mike?

[Steve@Rennsport]

Originally posted by LubeMaster77
We should see if some local Pelicans can stray from work to attend! If nothing else, I give out some really cool prizes during my seminars...

Thats a fine idea since this will be the week following the Portland Parade,...

Send me the particulars about start times and such and I'll pass the word to some folks I know.

I'll be there!!!

[LubeMaster77]

Originally posted by cnavarro
Mike, do you mind if I repost your post on my web site, giving due credit of course. It explains the reduction better than I did :-)

Post away, use my name or steal it. I don't mind.

[LubeMaster77]

Originally posted by movin
What about molybdenum and boron, are they on the chopping block too? The current Kendall oils are woefully deficient of the boron they once had. Seems like everything is being so degraded!

The moly can come in two different forms - the particulate (aka Micronized molybdenum disulfide) and the oil soluble form of moly typically called moly complexes.

A lilttle cut-n-paste from my freinds at Climax:

" The naturally occurring form of molybdenum, MoS2 is an important solid lubricant. It is used primarily for reduction of wear and friction and maintains good lubricating performance in tough conditions.

Molysulfide® (Climax lubricant grade MoS2) is a black powder insoluble in most solvents. It is an excellent high temperature lubricant stable in air to 350°C and in vacuum or inert atmospheres to 1200°C. Molysulfide® is widely used in products such as greases, dispersions, friction materials and bonded coatings.

Molybdenum complexes, soluble in petroleum oils and other organic solvents, are finding increased use as antiwear and extreme pressure additives as well as friction modifiers in lubricating oils and greases.

Molybdenum disulfide, the most common natural form of molybdenum, is extracted from the ore and then purified for direct use in lubrication. Molybdenum disulfide because of its layered structure is an effective lubricant. When MoS2 particles are located between moving surfaces the MoS2 layers layers slide over each other, permitting the surfaces of steel and other metals to move fluidly, even under severe pressures, as bearing surfaces. Since molybdenum disulphide is of geothermal origin, it has the durability to withstand heat and pressure. This is particularly so if small amounts of sulphur are available to react with iron and provide a sulfide layer which is compatible with MoS2 in maintaining the lubricating film.

Molybdenum disulfide will perform as a lubricant in vacuo where graphite fails.

A number of unique properties distinguish molybdenum disulfide from other solid lubricants:

A low coefficient of friction (0.03-0.06) which, unlike graphite, is inherent and not a result of absorbed films or gases;
A strong affinity for metallic surfaces;
Film forming structure;
A yield strength as high as 3450 MPa (500 ksi);
Stability in the presence of most solvents;
Effective lubricating properties from cryogenic temperatures to about 350oC in air (1200oC in inert or vacuum conditions).
A combination of molybdate and water soluble sulfides can provide both lubrication and corrosion inhibition in cutting fluids and metal forming materials. Oil soluble molybdenum-sulfur compounds, such as thiophosphates and thiocarbamates, provide engine protection against wear, oxidation and corrosion. Several commercial manufactures supply these additives to the lubrication industry.

A layer of molybdenum atoms is sandwiched between two layers of sulfur atoms. When molybdenum disulfide is dispersed between two metal surfaces a layer binds to each metal surface through the sulfur atoms. Then the asperities (surface irregularities on the metals) are prevented from coming into contact. Sliding contact is between the outer layers of sulfur atoms which are only weakly interacting. The surfaces are therefore able to slide easily relative to one another.




A side view of the layer structure of molybdenum disulfide. The lighter spheres represent molybdenum atoms and the darker spheres sulfur. The outer layers of sulfur atoms bind to each metal surface. Contact between the metal surfaces is prevented.


Now, for homework...

[LubeMaster77]

Movin - to answer your question, Boron has some interesting properties which I will gladly go into if you want - but I think the Moly classhas a few heads spinning. It is not as good an antiwear agent as many would hope. We have been trying to come up with a formula that uses Boron compounds in engine oil yet have had limited success. I think they would be great in specific grease and metal working applications. They can br pricey as well.

Moly is really a great additive provided you know what you are doing. The mirconized version can clog oil gallies in engines if you are not careful with the % and prepartion. The oil soluble versions are good but do not plate on metal as well as the solids.

The solids are great in greases and open gear lubes but in engines I would be careful.

As for the EPA and API looking to ban them? Not heard that. The API doesn't allow them in engine oils (in the particulate form) just becuase they have not be approved.

Both are pretty safe compared to other things out there so I really don't know the EPA position on them. I will make a few calls to some people I know at the EPA and API and see what I can learn.

[LubeMaster77]

I placed a call to some insiders I know at the EPA and API, and they have no knowledge of the EPA issuing any guidelines on Moly and Boron in oil and I am pretty sure there aren’t any.

However, the physical state of the elements in question is the key. The OEMs (and therefore ILSAC and API) are very much against oils containing any suspended solids, such as molybdenum disulfide or boron hydride - sorta like what I said earlier.

The two issues are the stability of the solids in suspension and their accumulation behind piston rings, resulting in proudness of the rings. Boron, as an element has been around for some time in certain dispersants (boronated succinimides) used in motor oils and gear oils. However, it is elemental boron complexed in a dispersant molecule and not a solid. Initially there was an issue with stabilizing the boron chemistry, as when it encountered water, boric acid would ppt out, however this has been worked out in recent years. Since the OEMs feet are being held to the fire on emissions their approach is to want to eliminate any and all chemistries that have the potential to contribute deposits in any form in the engines.

The OEMs are very much against using oils containing suspended moly, graphite, boron, teflon or any other suspended chemistries. Since the main stream additive companies have stayed away from these types of chemistries, the industry (ILSAC/API) has not found a need to place limits on them but stay tuned as this area is ripe for being the next industry regulated type of chemistry!

[donstevens]

Originally posted by LubeMaster77
....Note that an oil has to meet these requirements if they seek API certification or claim they meet API performance categories. Since these elements are not regulated by the government (EPA), an oil can be made with levels exceeding the standards but they will not be able to get API certification or claim that they meet API standards. The OEMS will also not honor warranty issues with these oils.

Lube Master, I rarely disagree with you but on this issue I must. As you know I am an Amsoil fan and most of their oils have higher levels of Zn and P than API limits. They claim that the oil "Exceeds API SL and CI-4" specifications. They explain some myths here: http://www.amsoil.com/articlespr/articlemyths.aspx.

They do happen to have a couple of products that are API certified but most products are designed with slight higher levels of Zn and P .

Don