Reduced Zinc and its Implications

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MolaKule

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There is much interest in reduced phosphorus due to the latest GF-4 sepcs. This was posted in a "zinc" thread but since we have wide interest in this topic, I thought I would also post it here:

Phoshorus is one of the antiwear/antioxidant elements in the Phosphorus/Sulfur/zinc molecule of ZDDP. The sulfur atom of ZDDP is the activation atom for metal bonding, and provides a slight FM effect.

ZDDP's have been used since about 1950 as the primary antioxidant/antiwear agent in engine oils, and are the main source of phosphorus in lubricants. The Sequence IIIC test in the '70's led to the development of oils containing high levels of phosphorus (0.14 mass %). High phosphorus oils can lead to deposits of phosphate on the surface of rare earth element catalysts in the catalytic converters. It has also been discovered that the interaction of metal
detergents with ZDDP and their decomposition products can affect catalyst efficiency. However, the effects depends on the type and relative concentrations of metal and ZDDP in the oil.

In addition, ZDDP's contribute 15-20% of the sulfated ash content of a fresh oil. Reducing the ZDDP should also result in lower piston/ring deposits.

What you're going to see are new ashless antioxidants and AW/EP adds come into play now, such as alkylated diphenylamines (antioxidants), hindered phenols (antioxidants), and new AW adds such as boron esters, concentrated calcium and synthetic AW/EP adds (such as new esters). A newer type of zinc antioxidant/AW additive is ZDTC, or Zinc dialkyldithiocarbamate, which is similar to Moly DTC and Antimony DTC, and only varies as to the metallic element.
 
My HMO is that it will be good for engine deposit control IF (IF) the formulators pay attention to the supplementation of ZDDP with the Calcium and Borate Esters, Moly DTC, Antimony DTC, and the Cerium TDC supplemental AW/EP/Anitoxidant adds.

I don't think they will drop ZDDP entirely in the near future. So many other adds are synergistically dependant on ZDDP.

BTW, if anyone is interested in further technical aspects of this topic, there are two excellent papers on the subject from Lubrication Engineering of 1997:

1. "Effects of Ashless Antiwear agents on Valve Train and Sludge Formation in Gasoline Engines," March 13 1997.
2. "Low ZDDP High Performance Automotive Engine Oils using Polymer Esters as an Antiwear Booster," January 7 1997.

From the reading of paper No. 1, I believe the ILSAC and API groups used this author's results to create the 0.06% to 0.08% limits for phosphorous, because the author showed that this % range was the minimum phosphorus amount that could be used without supplemental AW/EOP/Antioxidant additives. Anything less and the result was accelerated cam lobe wear.
 
"Is there any more information a little fresher than 6 1/2 years old? "

What exactly are you looking for? An older reference does not necessarily mean the information is out of date.

I did post another 'Intersting Articles" tech brief on ZDDP and Detergents during breaking-in, from a paper written in 2003.

http://theoildrop.server101.com/ubb/ultimatebb.php?ubb=get_topic;f=4;t=000200

[ August 08, 2003, 11:38 AM: Message edited by: MolaKule ]
 
MolaKule, do you have any opinion on what the new lower limits for phosphorous will mean to motorcyclists that lubricate their transmissions with engine oil? Are the new supplimental organo-metallic esters up to the job of lubricating a gearbox?
 
Jay,

Yes, especially the Borates. I have proven this in proprietary diffy lubes for racers. If you use some ZDDP, moly, antimony, and borates, you will get the protection you need.


wlkjr,

I have two nephews who are GOCB's attending Georgia Tech. Know where Alfaretta (spelling?) is? One of the nephews is a Physics major; poor boy, he could have done better. Beautiful country, wedged bewteen the mountains and the flatlands of Atlanta cotton country.

That's my problem too, bodies usually fail before the engine does.

[ August 08, 2003, 04:01 PM: Message edited by: MolaKule ]
 
"I also want the Farmer to produce the same products that are cold pressed and blended onsite in local CO-OP's that balance the petroleum stranglehold on our economy."

Amen bro. Get people back to the farm and have the farm produce both fuel crops and vegetable (ester) oils.

Gotta have a few minerals; I mean, isn't there Iron in your blood, or do Texans have a different kind of FLUID trickling through their veins?
grin.gif
 
"Gotta have a few minerals; I mean, isn't there Iron in your blood, or do Texans have a different kind of FLUID trickling through their veins? "


I am so embarrassed to say this publicly but I am a Texas transplant, forgive me for that !!!!!

I'm a fake TEXAN !!!!!!!

Born in Kansas raised in Indiana, family from Northern Mississippi, I'm confused regionally and culturally and "like sands through the hour glass so are the days of our lives".
spaz.gif
 
Wulimaster,

"Good for the converter. Good for the animals?"

The new ashless additives will be good for both the engines and living organisms. Most of the ashless additives have much higher biodegradeabilities and thus leave less residual stuff in the biosphere.

Chemisty has played a huge part in mankind's lives for centuries (wine, bread, salt for preservation, etc). We just have to use it wisely.

[ August 08, 2003, 04:50 PM: Message edited by: MolaKule ]
 
Hey we forgot animal sourced oils and building blocks, thats good for some animals and not for the ones that must sacrifice for the greater good. It is a renewable source of lubricants though .
cheers.gif
 
Mola, I don't want ANY organo metallic additives in my veggie/animal based oils.
Combinations and GMO's may be the key. My Uncle Dyson the Physicist thinks this is possible too.
worshippy.gif


I also want the Farmer to produce the same products that are cold pressed and blended onsite in local CO-OP's that balance the petroleum stranglehold on our economy.

This is my lubricant and agricultural dream.
 
What exactly are you looking for? An older reference does not necessarily mean the information is out of date.

Actually, I'm just an ole country boy looking for a good motor oil that won't let me down for 5k mile change intervals. I use Delo400 in my diesels and Havoline in my gassers. Pretty good luck with both.
But I'm glad someone is continuing research and making oils better. Now if I could just get the rest of the vehicles to last as long as the motors, I'd be doing ok.
 
Jay;
I don't think those borate gear lubes are all that proprietary.
The role of ZDDP in motorcycle transmissions is overplayed in my opinion.
To improve shifting quality in motorcycles, gear and shifter traction needs to be reduced.
 
User,

"Yes, especially the Borates. I have proven this in proprietary diffy lubes for racers.'

They are proprietary if I develop them and don't tell anyone what's in them.
 
Userfriendly, I've used gas/diesel motor oil in my bike for years and haven't had any transmission problems, but the gearbox does put special EP demands on the oil. The ZDDP additives seemed to handle the job well, and handle it without causing any wet clutch problems.
 
When all else fails, praise the lord and pass the zink.
Property of the devoloper, inventer: proprietary.
Secerets are not kept long if they are talked about.
Non metalic EP lubricant tech devoloped for industrial use can be transferred to other household applications. Like race cars and motorcycles.
 
"I have proven this in proprietary diffy lubes for racers. If you use some ZDDP, moly, antimony, and borates, you will get the protection you need."

What I meant here was that while boron was one of the ingredients of the proprietary gear lube, the ratio of boron to other adds (and the TYPES of adds), and the make-up of the base oil and other adds, is not known to the general public or in patents.

[ August 20, 2003, 03:50 PM: Message edited by: MolaKule ]
 
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