Chlorinated paraffins... Again!

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I know this topic is done to death, but has anyone got a UOA done after using such an additive? The reason I ask is because probably about 10 years ago I had a kdx200 and used either zx1 or activ8 in the 2 stroke oil. On the first lap of the race the radiators got clogged with mud and I lost all coolant. I ran the whole race (3hrs) and at points I stopped and the kill switch wouldn't stop the engine, it was that hot! Anyway when I got the bike home I ripped the top end apart and there was no damage to bore and piston, so I have some belief that these products work, and after all their use in the metals industry (cold drawing lubricants) and drill tips etc is well founded. Everybody mentions about acids being produced but these products claim to contain buffers that neutralise them, so is the next biggest worry is environmental? Anyway, I'd love to see a UOA if anyone has one, I've searched for a couple days now and not had any luck outside of anecdotal evidence of which I am partially adding to with my experience..
 
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I think he is asking if these things are as bad as people say, or if they actually are good to use, if even in only certain circumstances, since he seems to have had good luck with them.
 

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I know this topic is done to death, but has anyone got a UOA done after using such an additive? The reason I ask is because probably about 10 years ago I had a kdx200 and used either zx1 or activ8 in the 2 stroke oil. On the first lap of the race the radiators got clogged with mud and I lost all coolant. I ran the whole race (3hrs) and at points I stopped and the kill switch wouldn't stop the engine, it was that hot! Anyway when I got the bike home I ripped the top end apart and there was no damage to bore and piston, so I have some belief that these products work, and after all their use in the metals industry (cold drawing lubricants) and drill tips etc is well founded. Everybody mentions about acids being produced but these products claim to contain buffers that neutralise them, so is the next biggest worry is environmental? Anyway, I'd love to see a UOA if anyone has one, I've searched for a couple days now and not had any luck outside of anecdotal evidence of which I am partially adding to with my experience..
What did the parts from the bottom end look like? Simply because you were able to finish a race with this stuff doesn't mean there was no damage done.

You didn't say how much of the CP you used.

As far as the supposed buffers, what are they referring to? 2-cycle oils already have metal inihibitor and anti-corrsion chemistry in them which is probably what saved your engine.

CP's have no place in any combustion engines for many reasons.
 

Motopsycho87

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What did the parts from the bottom end look like? Simply because you were able to finish a race with this stuff doesn't mean there was no damage done.

You didn't say how much of the CP you used.

As far as the supposed buffers, what are they referring to? 2-cycle oils already have metal inihibitor and anti-corrsion chemistry in them which is probably what saved your engine.

CP's have no place in any combustion engines for many reasons.
The question I'm asking is that there is no real evidence in either direction. There is anecdotal evidence that they are good, and anecdotal evidence that they are bad. I've only experienced good (I continued running the bike for 2 years on same piston and crank).

Hence why I'd like to know of anyone has a UOA or a scientific paper proving either way? We know they produce acids, so does combustion, we know they attack copper, but not with acidity buffers. So if we can treat the metal with a chemical that makes the outer surface harder wearing a smoother, what are the cons? Of it lasts "up to 25,000 miles" what's wrong with using it and then changing the oil soon after to remove any residual material that may cause issue? It just surprises me that nobody on either side of the argument provides this information...
 

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Not pertaining to engine oils, rather metalworking applications and the phasing out of Chlorinated Parafins, but it's a good read:


STLE member Dr. Paul Bonner, lubricant applications team leader for Croda Inc. in Snaith, U.K., believes that two different approaches can be used to achieve equivalent or superior performance to chlorinated paraffins in standard cutting and grinding applications. He says, "The first approach is the use of an organic-based lubricity package that optimizes the friction reduction in the metal-cutting process. This low-friction package reduces the temperature of the operation, lowers wear and eliminates the need for chlorinated parafffins."

Microtap testing shows modified natural esters exhibit comparable and in some cases superior cutting efficiencies to chlorinated paraffin. Evaluation in real-world applications has confirmed these test results.

STLE member Larisa Marmerstein of The Elco Corp. comments that higher disposal costs due to new regulatory restrictions increase the cost of working with chlorinated paraffins. She says, "The new, alternative EP additive chemistries have no regulatory restrictions, can be used at a third to a fifth the treat rate of chlorinated paraffins and still get equal or better performance in bench testing and real-world applications. These chemistries may cost more per pound than chlorinated paraffin, but it may be the same or less when the net treat cost is taken into account."

Another consideration is the possibility for residual chlorinated paraffin left on metal parts to interfere with coating or cause corrosion. Marmerstein continues, "Chlorinated paraffins form a tenacious film that, if left on the parts, may interfere with coatings or cause steel corrosion. In contrast, amine-phosphite chemistries are easy to clean and may have additional corrosion inhibiting benefits."

Anderson agrees about the possibility of residual chlorinated paraffin presenting corrosion issues and maintains that the main benefit of replacing chlorinated paraffins is environmental. He adds, "One other benefit of alternative EP additives is found in water-containing fluids where the intrinsic stability of phosphate esters and sulfurized additives is somewhat higher than chlorinated paraffins."
 

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It is beyond me how people are convinced that engine oils need Extreme Pressure (EP) additives, except they are simply misinformed. Engine oils primarily need anti-wear (AW) and anti-friction (AF) additives. The application for EP additives are in highly loaded differentials and other highly loaded gear trains. Halogen-based (Chlorinated paraffins, Chlorinated Esters) EP additives have been mostly phased out. New EP additives based on different chemistry are now used in those applications.

"...Hydrogen chloride formed in the presence of larger quantities of moisture can cause severe corrosion of the metal surfaces. As the corrosion hazards increase along with the EP properties with increasing reactivity of the chlorine atoms..."

Reference: Rudnick L., Editor, Lubricant Additives Chemistry and Applications, P. 235, Second Edition.

An AMSOIL Technical Service bulletin TSB: MO-2010-04-01 from back in 2010 made the following observation of a failed Cummins engine in which someone had added an aftermarket chlorine additive:

"...A recent AMSOIL Technical Services investigation on a Cummins OTR ISX-485 engine failure revealed a high amount of chlorine in the engine oil.

The Cummins parts analysis determined the engine failure was the result of a corrosive attack to the cam follower pins, causing valve and injector camshaft lobe failures. Five injector lobes and four valve lobes were significantly spalled, meaning the metal flaked off the surface of the lobes. Analysis of the injector pin and valve pin showed corrosive attack in both the wear and non-wear areas of the pins, while severe galling was observed on the cams and cam follower pins. Galling is the transference of material when moving parts are no longer fully separated and protected. Furthermore, surface analysis showed peaks of chlorine in the actual metal surface, which is not normally present on a cam follower pin under normal operating conditions.

The chemical data on the lubricant and surface analysis of the failed engine parts revealed the root cause of the failure was corrosive wear. Acidic components in lubricants directly lead to corrosive wear. In this case, an abnormal amount of chlorine was found in the engine oil. Chlorine, when combined with hydrogen and water in the engine, can create hydrochloric acid. This, in turn, can cause severe TBN depletion, which was the case with this Cummins engine. It was determined that a chlorine-containing additive was used when an oil sample from the engine tested at 11,000 ppm of chlorine. The result was an extreme corrosive environment which was responsible for the upper end engine failure within 195,000 original miles...."


So someone destroyed an expensive Cummins engine by playing backyard/shadetree chemist.
 
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MolaKule

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The question I'm asking is that there is no real evidence in either direction. There is anecdotal evidence that they are good, and anecdotal evidence that they are bad. I've only experienced good (I continued running the bike for 2 years on same piston and crank).

I'd say you were lucky. See the references in the above post which give actual scientific evidence of corrosive attacks on metal surfaces. Again, how much CP did you add? Was a microscopic analysis done on the piston, rings, bearings, crank, piston pin, etc. to determine corrosive effects? You have yet to respond to these questions.
Hence why I'd like to know of anyone has a UOA or a scientific paper proving either way?

See the references in the above post which give actual scientific evidence of corrosive attacks on metal surfaces.
We know they produce acids, so does combustion, we know they attack copper, but not with acidity buffers.

What evidence do you have that acids produced in normal combustion without CP's are comparable to those acids produced with the inclusion of CP's?
So if we can treat the metal with a chemical that makes the outer surface harder wearing a smoother, what are the cons?

Please clarify, "surface harder and wearing smoother." What does this mean?
Of it lasts "up to 25,000 miles" what's wrong with using it and then changing the oil soon after to remove any residual material that may cause issue?
Who or what is making the claim, "lasts 'up to 25,000 miles'," and what actual testing by ASTM procedures proves this to be the case?

It just surprises me that nobody on either side of the argument provides this information...
See the references in the above post which give actual scientific evidence of corrosive attacks on metal surfaces.
 
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Motopsycho87

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I'd say you were lucky. See the references in the above post which give actual scientific evidence of corrosive attacks on metal surfaces. Again, how much CP did you add? Was a microscopic analysis done on the piston, rings, bearings, crank, piston pin, etc. to determine corrosive effects? You have yet to respond to these questions.


See the references in the above post which give actual scientific evidence of corrosive attacks on metal surfaces.


What evidence do you have that acids produced in normal combustion without CP's are comparable to those acids produced with the inclusion of CP's?


Please clarify, "surface harder and wearing smoother." What does this mean?

Who or what is making the claim, "lasts 'up to 25,000 miles'," and what actual testing by ASTM procedures proves this to be the case?


See the references in the above post which give actual scientific evidence of corrosive attacks on metal surfaces.
You're asking the same questions I'm asking. I just want evidence, not the rubbish put out by manufacturers warning people off. There are plenty of scientific journals citing their use in heavy industry, and having previously worked in the metals industry I have first hand use of their effectiveness in cold metal forming processes. What I'm asking is are there any internal combustion engine specific articles? Even going through the "citations" (quote marks because the 2 legitimate papers didn't actually mention anything about their usage, just maximum quantities).

Again, I'm not fighting for or against, I'm just asking does anybody have any EVIDENCE (UOA, or study specifically on performance / wear)? As I am personally very interested.
 
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There is anecdotal evidence that they are good, and anecdotal evidence that they are bad. I've only experienced good (I continued running the bike for 2 years on same piston and crank).

A single, even a few, anecdotal experiences doesn't negate scientific data. Just because someone smokes a pack of a cigarettes a day for 50 years and doesn't get lung cancer doesn't mean the risk of lung cancer isn't exponentially increased.

The problem with chlorinated paraffins is that they decompose rather quickly in high heat such as you would see on cylinder walls and valve stems. When they breakdown, they form hydrogen chloride which dissolves in water to form hydrochloric acid which is very corrosive.

Take this scenario. You dump in Motorkote at their recommended 2 oz per quart treat rate which is 6.25% of the sump. Motorkote is 27% chlorinated paraffin which comes out to 1.69% of the sump at that treat rate. Depending on exactly which CP is used, the chlorine content is between 0.8-1.2% (8,000 to 12,000 ppm) of the sump capacity. To give you a comparison and prelude for what's to come, the total amount of detergents (combined from all sources) is typically between 1500-3000 ppm which is just 0.15-0.3% or <1/3 the amount of chlorine and <1/5th the amount of CP. In this form, by itself and not exposed to heat or moisture yet, isn't really corrosive. This is how supplements advertising CPs are able to get away with saying... "Does not cause corrosion..." by conveniently leaving out the very important end to that statement... "...if you don't get it hot."

You start up the engine and go for a nice 30 minute drive on the highway. The oil is at 210-230°F in the sump, 240-275°F at bearing exit, and upwards of 450°F on the cylinder walls. In the presence of high temperatures, the CP decomposes into hydrogen chloride which you can actually smell quite distinctly. Your engine produces a lot of water as a result of the combustion of hydrocarbons. Burning 1 gallon of gasoline produces 1.03 gallons of water. Most of the water exits through the exhaust as a vapor, but some of it inevitably ends up in the crankcase. The contrast in temperature between the crankcase and ambient air allows for condensation in the crankcase which settles into the oil after the engine is shut off and oil temperature falls, adding more water to the mix. The hydrogen chloride dissolves in this water and forms hydrochloric acid. Your detergents, in the form of calcium carbonate and magensium carbonate, will jump into action to neutralize the HCl as best it can, but against so much of it, it's like Beglium vs Nazi Germany in WWII. They don't stand a chance. It reacts with iron to form ferric chloride which is also very corrosive and breaks down more iron to form more ferric chloride which can also react with oxidizing catalysts at those same high temperatures to form ferrous oxychloride which hydrolyses in that same moisture to... you get the idea. It's a snowball chain reaction of hell.

With these strong acids depleting the detergents, other weaker acids begin to spread as well. Think of the oil in this case like a human respiratory system. Covid-19 (hydrochloric acid) has tied up the immune system and reduced breathing capacity significantly making it very easy for something like pneumonia (other acids) to kill rather quickly. The oil starts a process of rather rapid oxidation and decomposition, and sludge isn't far away.

Yet, you do a UOA and see no significant increase in iron wear. You figure everything is fine. However, the corrosion is running away under a barrier of iron oxides which eventually get bad enough that the surface of the metal breaks down and begins to chip off in a process known as spalling. By the time you start to notice the damage, it's too far gone.

Also, CPs aren't even that great of a friction reducer compared to what we have out there. Moly and titanium based additives are superior to CPs in this regard in much, much lower concentrations, while also providing an anti-oxidant benefit, and already in modern engine oils.
 
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A single, even a few, anecdotal experiences doesn't negate scientific data. Just because someone smokes a pack of a cigarettes a day for 50 years and doesn't get lung cancer doesn't mean the risk of lung cancer isn't exponentially increased.

The problem with chlorinated paraffins is that they decompose rather quickly in high heat such as you would see on cylinder walls and valve stems. When they breakdown, they form hydrogen chloride which dissolves in water to form hydrochloric acid which is very corrosive.

Take this scenario. You dump in Motorkote at their recommended 2 oz per quart treat rate which is 6.25% of the sump. Motorkote is 27% chlorinated paraffin which comes out to 1.69% of the sump at that treat rate. Depending on exactly which CP is used, the chlorine content is between 0.8-1.2% (8,000 to 12,000 ppm) of the sump capacity. To give you a comparison and prelude for what's to come, the total amount of detergents (combined from all sources) is typically between 1500-3000 ppm which is just 0.15-0.3% or <1/3 the amount of chlorine and <1/5th the amount of CP. In this form, by itself and not exposed to heat or moisture yet, isn't really corrosive. This is how supplements advertising CPs are able to get away with saying... "Does not cause corrosion..." by conveniently leaving out the very important end to that statement... "...if you don't get it hot."

You start up the engine and go for a nice 30 minute drive on the highway. The oil is at 210-230°F in the sump, 240-275°F at bearing exit, and upwards of 450°F on the cylinder walls. In the presence of high temperatures, the CP decomposes into hydrogen chloride which you can actually smell quite distinctly. Your engine produces a lot of water as a result of the combustion of hydrocarbons. Burning 1 gallon of gasoline produces 1.03 gallons of water. Most of the water exits through the exhaust as a vapor, but some of it inevitably ends up in the crankcase. The contrast in temperature between the crankcase and ambient air allows for condensation in the crankcase which settles into the oil after the engine is shut off and oil temperature falls, adding more water to the mix. The hydrogen chloride dissolves in this water and forms hydrochloric acid. Your detergents, in the form of calcium carbonate and magensium carbonate, will jump into action to neutralize the HCl as best it can, but against so much of it, it's like Beglium vs Nazi Germany in WWII. They don't stand a chance. It reacts with iron to form ferric chloride which is also very corrosive and breaks down more iron to form more ferric chloride which can also react with oxidizing catalysts at those same high temperatures to form ferrous oxychloride which hydrolyses in that same moisture to... you get the idea. It's a snowball chain reaction of hell.

With these strong acids depleting the detergents, other weaker acids begin to spread as well. Think of the oil in this case like a human respiratory system. Covid-19 (hydrochloric acid) has tied up the immune system and reduced breathing capacity significantly making it very easy for something like pneumonia (other acids) to kill rather quickly. The oil starts a process of rather rapid oxidation and decomposition, and sludge isn't far away.

Yet, you do a UOA and see no significant increase in iron wear. You figure everything is fine. However, the corrosion is running away under a barrier of iron oxides which eventually get bad enough that the surface of the metal breaks down and begins to chip off in a process known as spalling. By the time you start to notice the damage, it's too far gone.

Also, CPs aren't even that great of a friction reducer compared to what we have out there. Moly and titanium based additives are superior to CPs in this regard in much, much lower concentrations, while also providing an anti-oxidant benefit, and already in modern engine oils.
Fantastic explanation! Thanks!
 

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You never have answered the legitimate questions posed to you in post #9 and elsewhere. Why is that?

You're asking the same questions I'm asking.

No, not asking questions. I gave solid scientific evidence of their corrosive effects. You gave some anecdotal conjectures that prove nothing.
I just want evidence, not the rubbish put out by manufacturers warning people off.

The Scientific data presented was from a known expert in the field of EP chemistry. What background or education do you have to refute this data?
There are plenty of scientific journals citing their use in heavy industry, and having previously worked in the metals industry I have first hand use of their effectiveness in cold metal forming processes.
The use of CP's in metal machining and metal forming processing has been displaced by water soluble esters and other chemistry. You seem to be behind the technology curve here.

What you do not seem to comprehend is that the use of one chemistry in one specific industry does not mean that chemistry is viable for other applications.

What I'm asking is are there any internal combustion engine specific articles? Even going through the "citations" (quote marks because the 2 legitimate papers didn't actually mention anything about their usage, just maximum quantities).

Again, I'm not fighting for or against, I'm just asking does anybody have any EVIDENCE (UOA, or study specifically on performance / wear)? As I am personally very interested.

The Amsoil article I linked presented ample scientific evidence that chlorinated additives can destroy an engine.

Your arguments thus far show some faulty logic:
1. Faulty Analogy - assuming one type of chemistry for one application is suitable for another application. This is definitely not the case.
2. Affirming the Consequent - this is similar to the following: When it's cold outside it snows. Since it's cold outside, it has to be snowing. You: Since I used CP's and my engine didn't explode, CP's can be used in engines. There could also be other reasons why it didn't explode such as the additives in the two-cycle oil saved it from serious damage.
3. Begging the Question - this is the fallacy of assuming the very thing you are trying to prove. Student: "I believe in Alien Spaceships." When asked why? "How else could aliens get here?" The student is falsely assuming a mechanism in which he is trying to prove. You: I am making the arbitrary assumption (without proof and similar to 1.) that since I used or observed CP's in metal working I can use CP's in engines without damage. You give some anecdotal conjectures that "begs" the question.

RDY4WAR took the time to make some calculations to show that the HCl acid concentrations are commensurate with those found in the Amsoil study. So it doesn't matter what brand of CP was used, the corrosive effects of CP's and their resulting HCl concentrations destroy engines.

Your logical fallacies here show that you continue to believe your own misinformed presuppositions in spite of valid scientific evidence to the contrary.
 
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The Scientific data presented was from a known expert in the field of EP chemistry. What background or education do you have to refute this data?

Les Rudnick, who is arguably to the oil and chemical field what Gordon Ramsey is to cooking. With numerous patents, white papers, and technical books he's written, anything stated by him you can take to the bank. It seems the OP only seeks confirmation, not information.
 

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The use of CP's in metal machining and metal forming processing has been displaced by water soluble esters and other chemistry. You seem to be behind the technology curve here.

Yep, that was well detailed in the link I provided. Even in that field, where CP's have been dominant, they have been displaced by more modern products that don't have the same drawbacks.
 
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There have been multiple posters over the years using the same MO as in this thread, asking (over and over) for technical proof of why CP is a bad idea. Most eventually circle around to one specific product and it's likely most are the same individual making the posts.

What was that one dude that used to aggressively promote Motorkote from time to time?
 
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What did the parts from the bottom end look like? Simply because you were able to finish a race with this stuff doesn't mean there was no damage done.

You didn't say how much of the CP you used.

As far as the supposed buffers, what are they referring to? 2-cycle oils already have metal inihibitor and anti-corrsion chemistry in them which is probably what saved your engine.

CP's have no place in any combustion engines for many reasons.
How hot does the bottom end of a 2 stroke get?
 

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How hot does the bottom end of a 2 stroke get?
From the combustion temperature profiles of pistons from the crown to the bottom skirt, the piston wrist pin location is at about 320F. So that thermal energy will Conduct down from the Gudgeon Pin (wrist pin), down the connecting rod, and then to the crank, bearing, and pin bearings. at that approximate same temperature.

We have to keep the big picture in mind: This is a "once-through" lubrication system. No oil sump, no oil cooling, only a thin film of lubricant passing through with approximately the same viscosity as gasoline, about 0.6 [email protected]
 
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A single, even a few, anecdotal experiences doesn't negate scientific data.

<<<mega mic-drop>>>

You never have answered the legitimate questions posed to you in post #9 and elsewhere. Why is that?

You're asking the same questions I'm asking.

No, not asking questions. I gave solid scientific evidence of their corrosive effects.
<<<double-mega-anvil-drop>>>

Any oil chemistry or additive that relies on chlorinated parrifins has no application in ICE applications.

Just like particulate TPFE (Teflon) products. In the latter, NASA rejected it on the basis that it can collect in areas that ultimately restrict oil circulation and clog things up which at least proved that straight oil of superior quality beat an oil that was boosted with additives.

You're twisting the throttle on 2-cycle OPE? Don't do anything more than mix 89~93 Octane gas with 50:1 of Echo Red Armor 2-cycle lube.

Leave the chlorinated parrifins out of the equation.
 
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