Petroleum Products and Black Powder

[Mako]

People have heard for so many years that petroleum products are bad with BP we simply repeat it not realizing there are differences in the products of base petroleum.  For instance most people don't realize that crude oil actually contains thousands of compounds.   But even with those thousands of compounds the hydrocarbons in crude can be divided into three main groups: paraffinic, naphthenic and aromatic.  To jump ahead, motor oil, machine oils and most modern firearms lubricants and greases are naphthenic and many modern lubricants also contain other aromatic compounds which make the lubricity better especially through different temperature ranges.

Crude oil after removing the lighter constituents and fuels like gasoline, diesel and kerosene is relatively high in paraffinics.  These are actually considered to be less desirable, the remaining oil is further refined to remove or separate most of them.  Mineral oil, paraffin and things like petroleum jelly are the byproducts of continued refining crude oil to get the more "desirable" (meaning worth more) naphthenic and aromatic based compounds.

Paraffinic oils are straight chain or simple branched aliphatic hydrocarbons.  One characteristic of these open chains is that they are capable of being emulsified without the addition of a secondary agent like a soap, etc.   Naphthenic or alicyclic oils have the characteristics of naphthenes, which are saturated hydrocarbons of which the molecules contain at least one closed ring of carbon atoms.  These closed rings make them extremely hydrophilic and you can't emulsify them without a secondary emulsifying agent.  In addition, paraffins are also saturated with respect to hydrogen, the rich hydrogen chains easily bond to oxygen if exposed to the heat of Black Powder ignition and form water and compounds incorporating water in the resulting residue.

The above paragraph in a nutshell is the difference between the petroleum oils and lubricants we warn people about and the "good" petroleum (this includes coal oil based products)  like Ballistol, paraffin and the petrolatum based toilet bowl rings that people like Noz , Dick Dastardly and many others use.

We all talk about soft fouling and moister fouling being created by certain types of powders (like Swiss) and some shooters will use blow tubes to pass moist air through a barrel to allow it to be infused and keep the fouling soft.  What we don't talk about is that naphthenic lubricants don't incorporate water or water based compounds because it has a closed ring.  The results are hard tarry deposits.  This is why when you submerge a gun part fouled in those hard tarry deposits it doesn't soften in water.

As weird as it sounds, the way to determine if you can or should use a lube in contact with burning Black Powder comes down to whether or not you can eat it, or I should say ingest it (not always a good idea, but it won't poison you).  If the product has a medicinal use like paraffin, petroleum Jelly, mineral oil, etc.  You can probably use it with BP.  The reason is that it is going to be low in naphthenic compounds.  The body will react to naphthenic compounds and they will basically poison you.  If Mineral oil was poisonous many of us would be dead and our mothers would still be in prison.

That's enough for a start, I'll talk about fatty acids next.  That's another key to what makes a superior BP lubricant.

Regards,
Mako

[August]

I'm somehow hungry after reading this post.

[Mako]

We can all thank Noz for this treatise.   A while back he was looking at Soy grease as a replacement for Mutton Tallow or other organic oils/greases.  So I've been investigating why animal or plant based oils don't have the problem with hard and tarry fouling that common naphthenic petroleum greases and oils do.  I want to point out this is still a work in progress so feel free to point out problems with it.

To make a decent Black powder lubricant for balls or bullets we need a lubricant, a stiffener and a residue "softener."   Paraffins, Beeswax, Toilet sealing rings, Carnuba wax, Soy wax and so on are the stiffeners for the lubricant. Oils or greases whether they are animal, vegetable, mineral based or synthetic are the primary "lubricant" and usually supply the portions of the mixture critical to keeping the BP fouling soft.  Materials like Petroleum Jelly, Cosmoline (which can be the lubricant or an extender) and Even Beeswax can act as extenders while helping with the lubricity.  Beeswax is one of those wonderful things that acts as a stiffener and still helps with lubricity.   

As a side note another wonderful thing about Beeswax is that it also contains things like ester myricyl palmitate which is a fatty acid which we will talk more about.  In many of the old traditional lubricants they used only beeswax and a fat, or some sort of oil.  When paraffin became readily available it became used more and more as the primary stiffener because it was so abundant and cheap.  But the lube gets brittle when the amount of paraffin gets above 40% or so.  With a lot of Paraffin mixes Beeswax is added to keep the paraffin ratios lower and Beeswax also acts as a stiffener.

At one time in the 19th century U.S. government arsenals used Japan Wax alone as a lubricant which confuses many people, but Japan wax is not a true wax, but a fat derived from berries of trees like sumacs that contains palmitin, stearin, olein and japanic acid.  Note all of those are fatty acids.

When comparing the "better" BP lubricants one thing begins to stand out.  They all contained abundant "fatty acids" in one form or another.  This is one of the things that all the petroleum based lubricants and oils whether Paraffinic or Naphthenic  lack in comparison to animal and vegetable oils.  When looking at petroleum greases it's not just the hydrocarbon rings in naphthenic oil but the lack of fatty acid groups that exacerbate the hard fouling and creates the hard "tar" looking residues.

In the case of saturated animal fats the fatty acids act as emulsifiers and give them their semi solid characteristics.  For instance the three primary acids in Mutton Tallow are Oleic acid, Palmitic acid and Stearic Acid, other tallows have similar characteristics.   An oil that looks a bit like an animal fat is Soy Oil.  Soy beans have more linolenic acid than anything else which is not surprising because it is plant based.  But they also contain oleic and palmitic saturated acids, it also has stearic acid.  Olive oil is another vegetable oil high in triacylglycerols, it has Oleic, Linoleic, Palmitic, Stearic and Linolenic (not Linoleic) acids in it.

Petroleum greases have "soaps" added to them as emulsifiers to make them thicker.  Organic emulsifiers would increase the affinity for water which is the chemical mechanism that keeps Black Powder fouling soft, but the petroleum in the forms we see as extreme pressure or high pressure greases is hydrophobic and the emulsifiers are usually sterates such as lithium, sodium or calcium sterates.  The sterates can increase water affinity  to some extent in the compounds liberated at ignition, but way below the levels of natural fatty acids.

Fatty acids are hydrophilic and bond with hydrogen during exposure to heat incorporating water into the compounds that are created.  Petroleum is hydrophobic by nature and has limited incorporation of water liberated or created by the combustion process.  Without the oxygen in the water or the water based compound the carbon is free to associate with other elements and creates the hard substance we see in both smokeless and Black Powder residues.  When water is present the carbon is almost always incorporated to a large extent.

The hard to clean carbon fouling is simply the product of pyrolysis.  It is simply the conversion of an organic substance through carbonization.  In any pyrolytic process oxygen is removed and you are left with a hard carbon or carbon compound unless there is an abundant source of oxygen that keeps the process from fully removing the oxygen.  Water supplies the oxygen to keep the pyrolysis to a minimum.  With hydrophilic additives or naturally occurring sources as you have with the fatty acids in non-petroleum oils or greases they keep the pyrolysis from being as complete. 

The fact that naphthenic oils also have closed hydrocarbon chains that I wrote about earlier adds to the problem with pyrolysis.   With no fatty acids and with hydrocarbon groups that don't create a lot of water or water compounds during the ignition reaction we get a hard and moisture resistant fouling as a primary residue.  This along with the fact Black Powder is so inefficient and leaves a large amount of residue means we get a harder tarry like residue which quickly fouls our bores and sometimes even the arbors if the gases get back in between the bore and the arbor bore on the cylinder.

So if you look at everyone's pet recipes that actually work they all have some common factors, high fatty acid content, the lack of hydrocarbon chains that are bound up in rings (note that fatty acids are merely carboxylic acids with long hydrocarbon chains with abundant hydrogen and free access to the hydrogen), and some sort of stiffener.

Sound about right?

Regards,
Mako

[Abilene]

Excellent information. 

You are making my head hurt.

[rickk]

Edible... explains why mice at the lube off my bullets and devoured another pound or so of it in the lube tray over the course of the last couple weeks.

[Cuts Crooked]

As weird as it sounds, the way to determine if you can or should use a lube in contact with burning Black Powder comes down to whether or not you can eat it, or I should say ingest it (not always a good idea, but it won't poison you).  If the product has a medicinal use like paraffin, petroleum Jelly, mineral oil, etc.  You can probably use it with BP.  The reason is that it is going to be low in naphthenic compounds.  The body will react to naphthenic compounds and they will basically poison you.  If Mineral oil was poisonous many of us would be dead and our mothers would still be in prison.

.......and that is essentially what The Mad Monk told me many years ago!

[Mako]

...it all comes down to whether or not you can eat it...
.......and that is essentially what The Mad Monk told me many years ago!

How do you think Bill went mad in the first place?

Yep, he's a treasure and has taught me a lot.  I'm constantly referring to his unpublished works he has provided.

I am just trying to compile some of the information and separate the facts from superstition.  Too many rituals of BP are almost voodoo instead of science or even pragmatic trial and error as they should be.  That doesn't mean we all won't have our favorite lubes, bullets, loads, etc., it just means we will understand why the "sky gets angry" when there is a thunderstorm...

Well for most of us...I'm still not sure about Noz.  Rumor has it he wears silk stockings and other unmentionables  under his shooting duds for luck.  I had discounted that rumor until the first time I saw the picture of him in blonde pigtails.

Regards,
Mako

[Dick Dastardly]

Thanks Mako,

That explains why I have to store my PL-II in metal containers.  The mice seem to thrive in it.  I haven't hung any our in our suet feeders, but I suspect our various wood peckers would eat it.

Perhaps made a mite thinner it would make good schmaltz. . . .

DD-DLoS

[Noz]

How do you think Bill went mad in the first place?

Yep, he's a treasure and has taught me a lot.  I'm constantly referring to his unpublished works he has provided.

I am just trying to compile some of the information and separate the facts from superstition.  Too many rituals of BP are almost voodoo instead of science or even pragmatic trial and error as they should be.  That doesn't mean we all won't have our favorite lubes, bullets, loads, etc., it just means we will understand why the "sky gets angry" when there is a thunderstorm...

Well for most of us...I'm still not sure about Noz.  Rumor has it he wears silk stockings and other unmentionables  under his shooting duds for luck.  I had discounted that rumor until the first time I saw the picture of him in blonde pigtails.

Regards,
Mako

I shall ignore the "silk stocking" reference but say that the information above is exactly what we who desire some experimentation require.  My candle wax, toilet bowl ring and vegetable shortening lube looks real good and is CHEAP. Ratio seems to be 1.5 # candles, 1# toilet bowl rings and 1# vegetable shortening.  As I said It came out a little stiffer than expected until I added the last 1/2# of vegetable shortening.
Since it is cheap to make, I can try other stuff as well. I have a local butcher that is looking for some lamb fat for me. Mutton is not real high on the list of desirable meats in the hills of Missouri.

[Norton Commando]

Now hold on there Noz - someone reported on this forum recently that the toilet bowl ring is comprised of petroleum products.

Now I happen to have some left-over toilet bowl ring material on my work bench that I've been itching to try as a lubricant. My plan was to squish (engineering term here) it into some felt wads and then place the waxy-felt-wad between ball and powder. But if my toilet bowl ring is actually petroleum based as some folks have alluded to and, thus, perhaps hydrophobic, then here comes the hard stuff, carbon presumably.

So, you may want to reconsider using that toilet bowl ring in your lube mixture, unless of course you eat spoon full or so and don't get the squirts afterwards!   

[Cuts Crooked]

Now hold on there Noz - someone reported on this forum recently that the toilet bowl ring is comprised of petroleum products.

Nort, that's what Mako has been saying............but not all petrol products are the same, some good, some bad! If that ring has a lot of mineral oil in it and is soft, it will probably work fine in a lube mixture

[Mako]

I shall ignore the "silk stocking" reference...

Noz,
Don't get your knickers in a wad... My sincerest apologies.

You may wear what you wish.  And obviously do based on pictorial evidence.

~Mako

[Professor Marvel]

Ah My Dear Mako -

You have expounded upon Dutch Bill and Noz's findings and are Blinding us With Science!
The explanation of the difference betwixt the "open chains" and the "closed rings", and identifying
for us which belongs to which is priceless data, and, even tho I am confounded by Carbon Rings and Esters,
for that you have my undying gratitude.

"if you can eat it, you can use it" - I will take that one to the bank.

your enlightened servant
prof marvel

[zymurgeist]

Would sufficient heat help drive off any remaining naphthenic or aromatic elements from otherwise usable materials? Outdoors of course, I've no desire to poison myself.

[Cuts Crooked]

Would sufficient heat help drive off any remaining naphthenic or aromatic elements from otherwise usable materials? Outdoors of course, I've no desire to poison myself.

Nah! I think adding heat would make asphalt!

[Noz]

Noz,
Don't get your knickers in a wad... My sincerest apologies.

You may wear what you wish.  And obviously do based on pictorial evidence.

~Mako

You misunderstood. I didn't say I didn't wear them, I merely stated I would ignore your reference. 
I don't, by the way. I find them too much of a barrier when urgent bathroom visits come up. 

[Steel Horse Bailey]

GOOD info, Mako.  I actually understood 34 words! 



Seriously, I've often marveled at the experts and their Voodoo "rules" about BP+oils, when I personally had no problems using Good quality gun lubes and BP without getting the dreaded "Hard tarry residue."  I always chalked it up to ignorance.  Mine.  Since I didn't KNOW (my ignorance) that the two didn't mix, I used what I wanted with no issues!

They say "Ignorance is Bliss."

If so, there must be some awfully happy, blissful people out there!

[Cuts Crooked]

You misunderstood. I didn't say I didn't wear them, I merely stated I would ignore your reference. 
I don't, by the way. I find them too much of a barrier when urgent bathroom visits come up. 

OMG!!!!!!!!!! I REALLY didn't need to know that!

[Mako]

You misunderstood. I didn't say I didn't wear them, I merely stated I would ignore your reference. 
I don't, by the way. I find them too much of a barrier when urgent bathroom visits come up. 

Oh, I didn't misunderstand at all, I never said you didn't wear them, I was just apologizing for upsetting you  and making you get your thong in a wad.

OMG!!!!!!!!!! I REALLY didn't need to know that!

Yeah... now you know how I feel.

Mako

[Mako]

Would sufficient heat help drive off any remaining naphthenic or aromatic elements from otherwise usable materials? Outdoors of course, I've no desire to poison myself.

The problem is that the naphthenics and aromatics are pretty much all that remain.  The paraffinics have been refined out of the "unfriendly" petroleum products.

Cuts is right if you heated it all you would do is drive off any volatiles and light constituents.  It wouldn't be Bitumen, but it would be a close approximation.  Nasty, dark and tarry.

Why would you do that anyway?  The refined oils are much more expensive than Mineral Oil, or the petrolatum byproducts.  Just buy them.  There is no advantage with BP to using a naphthenic compound, you already have all the lubricity you need with any lube, what you need is something that binds oxygen and isn't hydrophobic.

Regards,
Mako