Redline base oils

[emod]

Hi JAG and Tom,
Discussion is really great. Thank you both! Tom’s answers help me to have better understanding of the complexity of the analysis of motor oil.
And now I hope that I have more good news. I think that I have found what we needed – a GC of Toyota 0w20 oil. As I already mentioned in my previous post, I have found the entire document (case study), from which I have taken the examples of Pyrolysis – GC of the Toyota 0w20 oil. Today I had time to read it more carefully and I have found this:



The study suggests that the oil contains organic Molybdenum-Sulphur complex (not sure about the term), PAO, n-paraffins and isoparaffins. Esters are not mentioned.
On the other hand - the commonplace interpretation of the FTIR suggests that the base oil is only VHVI + small amount of esters (absorbance at 722.1 (VHVI) and 1735 cm-1 (esters)). The VOA of the oil also shows slightly higher oxidation value than the usual (22 IR Units) - which is also regarded as an indication of esters (although small amounts) in the oil. Please see the VOA data and FTIR in my previous posts.

Bearing the above in mind – is it possible to conclude that:
1. The oil contains not only VHVI but also PAO base oil?
2. The oil doesn’t contain esters and the peak at 1735 cm-1 on FTIR is coming from something else (Tom suggested earlier that the absorbance at 1735 cm-1 FTIR of the Red Line oil can come from multiple sources)?

I want to emphasize that I'm not trying to judge the quality of the Toyota 0w20 oil. I’m not interested how good or bad is this oil. Because this is a rare situation - VOA + FTIR + GC of the same oil, my only goal is to have a correct interpretation of the GC and differences that it shows to FTIR commonplace interpretation (Tom has already mentioned that his is not an expert on FTIR) in order to clarify (if possible) that:
1. The peak at 1735 cm-1 on FTIR doesn’t always indicate esters (as base oil; Tom’s suggestions about absorbance at 1735 cm-1 on FTIR of the Red Line oil).
2. The peak at 722.10 cm-1 is not fully informative about the nature of the base oil.

Tom, please excuse me for having bothered you with so many questions!

 

[Tom NJ]

Originally Posted By: JAG
Thanks Tom. MP Thirty-K motor oil MSDS from 9/11/2011 shows
Polyalphaolefin (CAS 68649-12-7): 20-55%
Polyester Polyol (CAS Proprietary): 21-55%
Ditridecyl Adipate, Diester (CAS 16958-92-2): 10-24%
http://mptindustries.com/msds/MSDSThirty-KMotorOil.pdf

Do you have any thoughts on those choices and proportions? Seeing that was one of the reasons I asked why a formulator would choose both diester and POE. As an aside...oddly, the company states that separation can occur when the oil sits for an extended period. I find that surprising.


They don't name the POE so I can't say why they chose it. Other than cost there is no technical reason to include this diester along with a typical POE base oil, unless it is a high viscosity POE oligomer and they want to balance it's low temperature properties.

 

[Tom NJ]

Originally Posted By: emod

Bearing the above in mind – is it possible to conclude that:
1. The oil contains not only VHVI but also PAO base oil?
2. The oil doesn’t contain esters and the peak at 1735 cm-1 on FTIR is coming from something else (Tom suggested earlier that the absorbance at 1735 cm-1 FTIR of the Red Line oil can come from multiple sources)?


This is a proper GC graph. I do not see any PAO or ester, only a petroleum distillate and perhaps a couple of anti-oxidants on the front slope. Keep in mind that GC only sees the volatile components which includes most base oils. If they state that it contains PAO it is likely a high viscosity PAO, i.e KV100 of 100+ which would not elute. I consider small doses of such high viscosity PAOs to be additives rather than a base oils.

Group III base oils do not normally need an ester for additives solubility and seal compatibility because they have more polarity than PAO.

Absorbance at 1735 cm-1 reflects C=O bond stretching, which includes esters but also some additives. If it is a very strong absorbance it is likely an ester base oil. Low absorbance levels can be ester or additives.

 

[JAG]

Great info., Tom. Thanks again. What do you think of the following ester? Trimethylolpropane tricaprylate/tricaprate with CAS 11138-60-6, comprising 65-75% of Maxima K2: http://www.maximausa.com/msds/2stroke/Formula K2 SDS.pdf

I believe it’s a TMP POE that was made using capric acid.

 

[Tom NJ]

Originally Posted By: JAG
Great info., Tom. Thanks again. What do you think of the following ester? Trimethylolpropane tricaprylate/tricaprate with CAS 11138-60-6, comprising 65-75% of Maxima K2: http://www.maximausa.com/msds/2stroke/Formula K2 SDS.pdf

I believe it’s a TMP POE that was made using capric acid.


This is TMP C8C10, probably the most common POE used in motor oils, including Mobil 1 for many years. I could see that dosage for a racing oil, exploiting the ester's high lubricity, high VI (140), and very low Noack (3%). When used in commercial brands for passenger cars the dose is usually 5-20%. I have used it up to 40% in personal blends for my car, balanced with an equal amount of PAO.

 

[emod]

THANK YOU, Tom!
For the first time I have an opportunity to look at all these data – VOA, FTIR and GC, gathered together and related to particular engine oil.
It seems that we have a “very good clue” (I intendedly don't use “confirmation”) that the FTIR absorbance at 722.10 cm-1 gives adequate information about the nature of the base oil. In our case the generally accepted interpretation of FTIR (value around 1) and GC both correspond to conclusion that base oil is most likely Group III VHVI oil (having in mind specifications of the oil). The other very important thing (from my point of view) is that your assumption that the low absorbance levels at 1735 cm-1 of the FTIR can be ester or additives has received strong data support.
Once again – Thank you! I greatly appreciate your comments.

 

[OVERKILL]

Originally Posted By: emod
THANK YOU, Tom!
For the first time I have an opportunity to look at all these data – VOA, FTIR and GC, gathered together and related to particular engine oil.
It seems that we have a “very good clue” (I intendedly don't use “confirmation”) that the FTIR absorbance at 722.10 cm-1 gives adequate information about the nature of the base oil. In our case the generally accepted interpretation of FTIR (value around 1) and GC both correspond to conclusion that base oil is most likely Group III VHVI oil (having in mind specifications of the oil). The other very important thing (from my point of view) is that your assumption that the low absorbance levels at 1735 cm-1 of the FTIR can be ester or additives has received strong data support.
Once again – Thank you! I greatly appreciate your comments.


With respect to TGMO that's consistent with the MSDS, which indicated it being entirely Group III based.

 

[JAG]

Thanks Tom! That Maxima K2 with the TMP ester is a 2-stroke oil. Maxima says the oil contains 2000 cSt esters, which I assume must be represented under the “synthetic base oils” category in the MSDS, because no way is it approximately 70% 2000 cSt oil. The finished product viscosity is around 14 cSt.

 

[BrocLuno]

And, now back to Redline

 

[OVERKILL]

Originally Posted By: BrocLuno
And, now back to Redline

Yup! Would love to see a GC graph interpreted by Tom of say AMSOIL 0w-40 or Redline's 0w-40....

 

[Tom NJ]

Originally Posted By: OVERKILL
Originally Posted By: BrocLuno
And, now back to Redline

Yup! Would love to see a GC graph interpreted by Tom of say AMSOIL 0w-40 or Redline's 0w-40....

If anyone chooses to post GC graphs, please remember to exclude the brand of the oil. I prefer to not know what brand I am commenting on at the time of comment as I still consult in this industry.

 

[OVERKILL]

Originally Posted By: Tom NJ
Originally Posted By: OVERKILL
Originally Posted By: BrocLuno
And, now back to Redline

Yup! Would love to see a GC graph interpreted by Tom of say AMSOIL 0w-40 or Redline's 0w-40....

If anyone chooses to post GC graphs, please remember to exclude the brand of the oil. I prefer to not know what brand I am commenting on at the time of comment as I still consult in this industry.


For sure, you made that clear earlier

 

[330indy]

 

[JAG]

I found an interesting paper, PAPER, from 2015 that has some GC graphs. Oils were “Fully synthetic (Shell Advance Ultra, 10W-40) and semi-synthetic (Shell Advance AX7, 10W-40) engine oils”. The researchers tested virgin/fresh oils and oils that were aged at 120, 149, and 200 °C. They identified some of the molecules in the GC graphs. The oils contain an amazingly complex variety of molecules, most of which are not noted in the graphs, but are stated in the text of the paper. Aging the oils altered their chemistry, of course, and the two oils responded differently to the aging.

 

[emod]

Great info. JAG! And I have found the following info. about the Red Line oil:

"Redline is not a Gp V oil. By gas chromatography it's only 15-18% polyol based. The rest is a crude Gp III and at one time was furnished to them by BP Houston."

You can find it here: http://www.city-data.com/forum/automotive/2212328-motor-oils-9.html#ixzz5HWaNfzKH (TrapperL's post; the third one from the top). However, we must keep in mind that the information is from 2014 and that the GC is missing.

 

[JAG]

Interesting find, emod. 15-18% is consistent with several recommended ester treat rates in motor oil that I have come across. I read all of TrapperL’s posts in all 12 pages of that thread to see if he is knowledgeable about oils and trustworthy. Some of what he said seems consistent with him stating that he is a retired tribologist, but he said some things that gave me significant doubt. One example of that are him stating that a purpose of ZDDP is as a detergent. Another example is that he said that in comparison to API and ILSAC motor oil specifications, ACEA specifications allow “boatloads” of ZDDP and “a gross overload of additives”.

Do I believe his statement of 15-18% polyolester in Red Line? I neither believe nor disbelieve it. It’s plausible, so I’ll put it in my mind as a claimed datapoint. Hopefully one day, new totally trustworthy data will become available to us.

 

[PeterPolyol]

Me either, but he said one thing that I'm sure is 100% true: "I have no idea where they source their base oils"

Guess who's got very serious doubts about TrapperL's credibility and sincerity?
He then goes into this "Pennzoil spends more money on R&D than any other...and by a lot. They are THE leader of the newest technologies available in the industry."
If I had a dollar for every big oil company that's been proclaimed as "THE leader of the newest technologies available in the industry", I'd have about 5 or 6 bucks...........

 

[JAG]

 

[bulwnkl]

Suppose someone had a GC machine 'just sitting around.' Where would such a person find a detailed protocol for running a motor oil GC scan correctly?

 

[Tom NJ]

Originally Posted By: bulwnkl
Suppose someone had a GC machine 'just sitting around.' Where would such a person find a detailed protocol for running a motor oil GC scan correctly?


Generally speaking, a high temperature column ramped from 100°C to 300°C @ 5°C/min should work. The column should be capable of 330°C and the injection port and FID detector at about 310°C. Injection size of about 0.1 ul should work but can be varied to give a good signal to noise ratio.

If you can get a copy of ASTM D2887 it will give more details, but there are many variations that would give acceptable chromatograms.