Hyperlubrication!

[kilou]

My gearbox speciffically calls for a 75W80 GL5 oil. Even with this low viscosity, I still have some problems when cold. I cannot put 75W90 inside since although they are both 75W rated, 75W90 oils always have a higher viscosity when cold compared to 75W80 oils. Even Redline did not advise me to use their 75W90 GL5 because the viscosity at 40°C (cold) is twice the one of my actual oil (mine is 47 cSt at 40°C).

Further digging on the Mecacyl website and I found that this product contains no "active chlorine"! What does it mean? Is it the same as inactive sulfur for GL5 oils?

 

[kilou]

Volvo only use their own 75W80 GL5 oil. I do not know who is manufacturing this oil for them as they do not reply to the numerous mails I sent them. However I know that despite they claim it's a synthetic oil, I believe it is a poor synthetic blend one because the pour point is only -31°C! My actual oil is also a synthetic blend and its pour point is -40°C and good full synthetic oils can go down to -50 or even -60°C. Definitely the key point for my application is cold viscosity. My oil is 47 cSt at 40°C and I have found only one other gearoil with same specification that did better: it is Gearube RPC 75W80 GL5 from Kroon-oil but this oil is not available in Switzerland.

Well concerning Mecacyl and active chlorine, if I understand well, this would be the same process as the one used in inactive GL5 oils. These oils are safe to be used with yellow metals but as you said when the S- or P compounds brake down, these oils would also become corrosive! So Mecacyl would just act similary to EP additives in GL5 oils with respect to corrosion no? If yes, this shouldn't be a big problem if I do oil changes every 50'000km or so. Ok we still don't know about stability of these compounds. Mecacyl just state they are extremely stable but I doubt they would have said the opposite

Well I'll continue to dig further in that topic because if the corrosive effects are found to be very limited, this additive is really a good solution for me since I'm satisfied with the results. But I definitely take care of all your comments because they are very interesting and make things go further on in the very complicated topic of oil additives.

Another point is that if there is a corrosive effect, this should be even more pronouced with heat so be sure that I won't try this stuff in my engine (I wanted to do so at the beginning but this corrosive potential really annoy me). However temeprature are fairly low in a manual transmission so I suppose corrosion may be neglectable in this application no?

 

[MolaKule]

quote:

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...may inhibit potential corrosive reaction from Sulfur-phosphorus EP additive

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EP gear Lube additives today are supplied not just as some sulfur and phosphorus, but as a complete package, utulizing sulfurized isobutylenes, phoshorus esters, metal deactivators, antioxidants, and rust inhibitors.

Unless you take the tranny or diffy through water, I don't think you'll see any significant TAN increases until past 80,000 miles.

So I reject the above statement as misinformation.

"Chlorinated trioleyl phosphate, condensation products of fatty oils with alkali salts of dithiophosphoric acid diesters, and reaction products of glycols with PCl3 are examples of chlorine phosphorus additive used in earlier years."

Now, I have searched the literature for these Militec-type additives and found zilch.

So my conclusion at this time, and until I can find new data, is that these chlorinated "Whatevers" are simply re-births of the old discarded chlorinated gear lubricant formulas that contained chlorinated EP additives.

[ June 11, 2004, 03:26 PM: Message edited by: MolaKule ]

 

[kilou]

As far as I've understood, this is what George C. Fenell say too. It seems that chlorinated compounds are known for a long time and today hyperlubricants seem to use the same chlorinated molecules that were used previously. However hyperlubricants just as standard oils are also not only chlorinated compounds! What may have drastically changed between the past and the present is the efficiency of anti acid and anti corrosion techniques that would maybe now allow the use of these chlorinated compounds without the drawbacks of corrosion. Each hyperlubricant contains these anti-acid, anti-oxydant and rust inhibitors too if we trust their claims. For this reason it would be a good idea to know more about what is oxirane acid scavenging or organo-metallic substitution.

But you're right to say that there is almost no information about these products and personally I find this a bit suspicious too. On the other hand, it is very difficult to get information about standard oils too unless we are working in the domain. Maybe the same works for hyperlubricants.

Anyway, this discussion is very interesting for me and I hope that you find it pleasant too. I must say that I'm glad to have found such a specific forum because people here seem to know much more things than what I could learn on other forums and this is very useful for people like me who do not know anything in lubricant or additive chemistry

[ June 11, 2004, 05:21 PM: Message edited by: kilou ]

 

[MolaKule]

quote:

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What may have drastically changed between the past and the present is the efficiency of anti acid and anti corrosion techniques that would maybe now allow the use of these chlorinated compounds without the drawbacks of corrosion. For this reason it would be a good idea to know more about what is oxirane acid scavenging or organo-metallic substitution.

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My take on this chlorinated ester is that what they have done recently is to "encapsulate" or esterify the chlorine into a larger molecule with 'mitigating' components.

What is left to explain is at what temperature or under what conditions does the chlorine ester decompose and release "free" chlorine which could "potentially" be very corrosive.

Having lived in Missouri, I say "show me" before I'll include this stuff in any of my formulations or put it in any engine or transmission.

Indeed this has been an intersting discussion.

 

[kilou]

I hope this IS and not has been an interesting discussion

I contacted Mecacyl via email and fax and I hope to receive some answer about this chlorine content etc next week. However do you know what precise question I may ask them in order to clarify some points? What information should I ask for to know at which temperature these chlorinated compounds breakdown? Does it have something to do with the flash point of the substance?

 

[MolaKule]

Questions for vendor:

1. Percentage of chlorine by weight,
2. decomposition by-products,
3. At what temperature do these chlorinated compounds (CP's) decompose,
4. how hygroscopic are these esters/paraffins
5. What ASTM metal and corrosion tests have these CP's been subjected to, what were the testing parameters, and what were the results/findings.
6. useful life in lubricating fluids.

 

[Pablo]

I understand on the reluctance to use a 75W-90. What does the dealer use?

No active (free) Cl means it's chemically bonded in some carbon chain...but that's basically what we are talking about...if these compounds break down, then free Cl....

 

[kilou]

Thanks for the list of questios Molakule. I'll ask Mecacyl about them as soon as I get a reply for my first message.

Digging further in the topic of oil additives, I found that there are the following categories:

- PTFE: slick50...
- Petroleum distillate (containing chlorine): Duralube, Prolong....
- Molybdenum Disulfide: Moly-slip
- PP Formula 7

The last group seems interesting

"PP Formula 7. Discovered and patented in 1979 by a Boeing aircraft engineer, it is a process where different formulations of petroleum additives are re-synthezised and tiny, dense, round molecules of about 0.1 microns in size are created. The only product I personally know that uses PP Formula 7 is Petron Plus. However, it is very well possible that Militec uses the same formula. But I don't know that for a fact.

Formula 7 is the most promising oil additive as of today. However, it is beyond my knowledge in how far independent tests have been made to support the manufacturers claims, but there is one test known as load test that at least Petron Plus has passed with flying colors.

The re-synthesized petroleum molecules of PP Formula 7 are specifically designed to be used in combustion engines. They have undergone a significant molecular transformation. Their size is too small to be filtered out.
These magnetic molecules are very dense, so they have a high load factor wear. Their spherical shape gives them the highest shear factor in the industry for reducing friction.

Other than most engine conditioners that contain mostly a single-grade motor oil as a carrier of the solid particles, Formula 7 does not use any motor oil. Therefore, it is compatible with any kind of motor oil you use in your engine. It has been approved by OSHA, EPA, and COSHH regulations."

source: http://brickboard.com/ARCHIVES/1998NOV/20017664.shtml

Well, this is again and again not something that will tell us if these additives are good or bad but it's interesting because it seems there are 2 types of chlorinated additives:

- Petroleum distillates (chlorinated paraffin etc) such as Duralube and Prolong
- PP Formula 7 as the guy who wrote this article believes (without proof) that Militec-1 belongs to this group.

The main difference I could understand between these 2 groups is that PP Formula 7 are REACTED products. They are not a mix of different things "only". This is quite important because either Mecacyl, Mecarun and Militec claims that their product is reacted and becomes a PURE and UNIFORM ORGANICALLY BOUNDED SUBSTANCE!

What I want to say is that maybe the conclusion that chlorinated compounds can be corrosive is true but is based on the Petroleum distillate group additives. Maybe if Mecacyl, Mecarun and Militec really belongs to the PP Formula 7 and thus are REACTED products, they may behave differently.

Is this absurd? Do you have more information about what are these PP Formula 7 additives?

 

[mojo]

I have one basic question -
"The re-synthesized petroleum molecules of PP Formula 7 are specifically designed to be used in combustion engines. They have undergone a significant molecular transformation. Their size is too small to be filtered out.
These magnetic molecules are very dense, so they have a high load factor wear"
How can you re-synthesize petroleum molecules to have them become magnetic? Petroleum hydrocarbons typically have little polarity.

 

[rugerman1]

quote:

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Originally posted by mojo:
How can you re-synthesize petroleum molecules to have them become magnetic? Petroleum hydrocarbons typically have little polarity.

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Send them to the marketing department.The'll fix 'em up for 'ya.

Mark

 

[kilou]

quote:

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Originally posted by mojo:
How can you re-synthesize petroleum molecules to have them become magnetic? Petroleum hydrocarbons typically have little polarity.

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I think if they put esters in the stuff, this may become "magnetic". Castrol in their Magnatec series engine oils use this technique but as fas as I've heard, this "magnetic" abilities exists for any synthetic ester based oil. Now I do not know if this is the case for these additives. All I know is that Militec and Mecarun state they use chlorate esters...............but what does this become after they react everything together, I don't know.

 

[mojo]

Granted, that synthetic ester/diester/triester/polyol oils do have a greater degree of polarity than do conventional petroleum hydrocarbons. But I think it is a bit of a stretch to state that this re-synthesizing of whatever is present makes them magnetic.

 

[labman]

quote:

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Originally posted by rugerman1:

quote:

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Originally posted by mojo:
How can you re-synthesize petroleum molecules to have them become magnetic? Petroleum hydrocarbons typically have little polarity.

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Send them to the marketing department.The'll fix 'em up for 'ya.

Mark

---

--

Get the biggest, strongest magnet you can find, maybe one of those ones out of a hard drive. Hold it as close to the surface of the wonder drops as you can without touching. See if the magnet attracts the resynthesized to become magnetic material. Turn the other pole, and see if it repels it. Dip a piece of plain steel in the stuff and pull it out noticing how much clings. Then put it on the magnet and dip it in again and see if any more clings.

Adding oxygen, chlorine, metals, etc. makes hydrocarbons more polar, better solvents for polar materials, and wet or cling to metals better. It will not make them magnetic.

Most hydrocarbons have a straight chain structure. Adding branches changes both the physical and chemical properties compared to the unbranched ones. Isooctane is branched causing it to ignite easier leading to more controlled burning than normal octane. Here I am using the chemical sense of normal meaning straight chain. Branched hydrocarbons have a lower viscosity at a given molecular weight than the normal ones. This is part of the properties of PAO's. They are highly branched unlike dino. Even more highly branched, ball shaped, might have even better properties, but still would not be magnetic until passing through the marketing department.

 

[kilou]

This is what I found on a test of MT-10 again by George C. Fenell.

"As noted by Swift (38), halogenated organic compounds must be selected with care as many fail to fulfill one or more of the following criteria.

a) The appropriate degree of thermal stability

b) No corrosive or metal staining effect

c) Low volatility for the majority of applications

d) Neither toxic hazard nor objectionable odor

e) Available in sufficient quantities at an economic price

The materials most commonly used are halogenated paraffins and alpha olefins; heavily halogenated products which contain up to 70 wt% halides.(2, 7) Ideally, an EP additive must have a sufficient degree of instability to decompose as needed at the relatively high temperatures generated during severe sliding. On the other hand, the additive must demonstrate good hydrolytic stability and severe corrosion of lead has been reported at high temperatures.(7, 49) As a result, some halogen based additives require use of a rust inhibitor, such as an amine or alkaline sulphonate salt.(4) However, effective noncorrosive halogenated dicarboxylic acid additives have been available for many years and typically contain halide concentrations in the range 25 to 35 wt%.(7)

The halogenated hydrocarbon used in MT-10 was developed to provide the optimum balance between wear resistance and stability/corrosion resistance. The relatively stable nature of the molecule eliminated the need for stabilizers or corrosion inhibitors and no evidence of corrosion has been observed in exhaustive field tests. Careful formulation of the halogenated additive with other proprietary compounds produced a synergistic effect, which results in the MT-10 package being more effective than even unusually high concentrations of individual pure lubricant additives. As a result, MT-10 provided superior performance to the other additive packages evaluated."


Obviously the latter statements are publicity as George C. Fenell works for MPC, the manufacturer of MT-10. But here are the points I would consider for further investigation providing that NOW we have some "objective" sources of informations as references are available for statements in this article:

- it seems that different halogenated organic compounds exists and some may have no corrosive effects [1]

- the additive must demonstrate good hydrolytic stability and severe corrosion of lead has been reported at high temperatures.[2]

- halogenated organic compounds that are corrosive require the use of rust inhibitor, such as an amine or alkaline sulphonate salt [3]

- effective noncorrosive halogenated dicarboxylic acid additives have been available for many years and typically contain halide concentrations in the range 25 to 35 wt% [4]

References:

[1] Swift, G., “The Effect of Chlorinated Additives on Lubricated Systems,” Symposium on the Effects of Temperature on Lubricated Systems, Paisley College of Technology, Scotland, October 1969.
[2] Cusano, C.M., “Corrosion of Copper and Lead Containing Materials by Diesel Lubricants,” Lubrication Engineering, Vol. 51, 1, pp. 89-95, 1994.
Latos, E.J., Rosenwald, R.H., “Non-Corrosive Chlorine Containing EP Additives,” Lubrication Engineering, Vol. 25, No 10., pp. 401-411, 1969.
[3] Xue, Q., Liu, W., “Tribochemistry and the Development of AW and EP Oil Additives-a Review,” lubrication Science, &, 1, pp. 81-92, 1994.
[4] Latos, E.J., Rosenwald, R.H., “Non-Corrosive Chlorine Containing EP Additives,” Lubrication Engineering, Vol. 25, No 10., pp. 401-411, 1969.

Although it's dated 1969, the most interesting reference is [4]!!!!!!!!! If anybody knows how to get this paper, it would be very nice.

 

[mojo]

Your posting says - "This is what I found on a test of MT-10"

I saw no mention of any testing. As they say, where is the beef?

Past issues of Lubrication Engineering can more than likely be obtained from the Society of Tribologists and Lubrication Engineers (STLE) and their website is http://www.stle.org

 

[mojo]

Organo-chlorine compounds tend to be those that have strong adsorption (i.e., adhere to) qualities which is why they are so widelly used in the manufacturing industry. The chlorine component has a high degree of electronegativity which is the basis for this adsorption. Removing it may take a few flushes but you may want to initially use a strong polar solvent.

 

[kilou]

Pfff why did I put this stuff in my gearbox

But if I only drain out the gearbox and pour in new fresh oil, will the amount of chlorinated compound left in the gearbox still be enough to cause problem or may I consider it as negligible?

 

[unDummy]

Would it be easy enough to do a UOA on oil treated with whatever and see if the TBN took a drop?

If these chlorinated oil additives have issues, it would show up in the UOA, right?

Until then, all the pro/con arguments are just hearsay.

 

[kilou]

It is more a comparison than a real test. It can be found here: http://www.mpc-home.com/htmls/Aftermarket Comparisons MT-10.htm

Anyway, despite this topic is very interesting and I hope to get more information about it, I think you all definitely convinced me to get this crap out of my gearbox! I think it's better like this than to risk any excessive corrosion.

So what would be the best method to remove as much of the product as possible? Would only a simple drain of the oil/replacement with new fresh oil be sufficient or is there any better way to remove enough of this product so that I won't have problem with it? Does these chlorinated products stink to the metal in the gearbox?

Thanks in advance