Powder going bad


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Blakenzy
June 26, 2013, 11:11 AM
So I have somewhere over a pound of IMR4895. A little more than a month ago when I last pulled it out and took a look at it, this powder was just fine. Smelled OK, nothing noteworthy about appearance. This powder hasn't been actually loaded and shot for some time though. I believe origin of powder is demilled ammo... from a trustworthy source I have dealt with repeatedly.

Anyhow, yesterday I am tidying up the bench, and went through the powder stores. Checking caps, making sure they are well closed, etc. When I get to this container, I sniff it (just because) and I get a significantly stronger smell from it than what I remembered. Struck me as strong acetone/nail polish. OH NO.

I pour it and grey dust lifts off. I find grey dust residue on bottom of white cup I was using to inspect. Looks like graphite. After inspection, I notice that some granules are taking on a slight bronze-ish color. No clumping at all but when pouring down a funnel I notice that they clog and need constant tapping to fall through. I pour a small pile on a ceramic plate and burn it. Burned completely, left sticky residue behind. I load a light 30 grains under a 160gr lead gas check bullet in my .308 and try it out. Fired fine. Loaded a few more and take it out to a 50m target. No chronograph, but they "felt" just about right, all bullets on paper. Inspecting the bore I saw what could have been two unburned powder granules in the throat.

So my conclusion is that this powder is in the initial stages of decomposing. Just how bad? Storage was the same as all the other powders I have. What I would like to know is if there is any way of slowing down the deterioration so I can get the most out of it. I was thinking that storing it in a colder place might buy me some time. Any thoughts?

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rcmodel
June 26, 2013, 01:09 PM
Struck me as strong acetone/nail polish. OH NO.That's what it's supposed to smell like.
If it was breaking down, it would smell like acid fumes.

Graphite dust is normal too, as most all powder is tumbled in graphite when it is made.

Sounds fine to me.

rc

SlamFire1
June 26, 2013, 01:23 PM
Whether powder is good is not easily answered unless the powder has gross indications of going bad.

The gross indications are the bitter smell due to NOx, red powder granules, fuming gas emissions, others have said “red gas”. By the time you see this the powder went bad a long time before.

Half of all the surplus IMR 4895 I purchased went bad.

The first 16 lbs, I used up eight pounds quickly. For whatever reason, I pulled the bullets on some of that stuff and found green corrosion on the bases of the bullets.

Similar to these pull down bullets from old US ammunition. Not the horrible one, but the small green spots.

http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/DSCN1108CorrodedBullets.jpg

http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/DSCN1115corrodedbullets.jpg

(I don't remember what US ammunition these came off, I pulled them decades ago, might have been WWII ammunition that came back from China.)
The last eight pounds, it sat around. When I opened the bottle top, it smelled bitter. Red dust flew around.

I gave it to a machine gunner guy. He put it in the laundry room. Passing by the laundry room he tossed soiled shorts at the hamper, but missed. The short ended up on top of the powder bottle. Overnight, acid gas from the bottle ate holes in the shorts!! :what: This freaked my friend and he poured the stuff out over his lawn.

Since then I have had more surplus 4895 powder from a different vendor go bad in the case. Green corrosion on the bottom of the bullets and cracked case necks.

This powder never smelt bitter at all. I shot this powder in highpower matches and it shot exceptionally well, but case necks cracked after firing. I also received “funny” retorts and the occasional sticky extraction. The longer the ammunition sat around the more cases necks would split after firing. In time virtually all of the remaining 700 loaded cases experienced cracked case necks .

From what I had read on the internet, which is a repeat of what is said in gun magazines, powder has an “indefinite” shelf life. Remember reading statements to the effect that powder lost energy as it got old, making it essentially benign. This turned out to be totally bogus.

I found this out after encountering an real Insensitive Munitions expert. This IM expert explained that powder deteriorates from the day it leaves the factory.

Nitrocellulose decomposes through the reduction-oxidation process. Called Redox. The expert said “The molecular stability of the functional groups on the organic chain determine the life time of the nitrocellulose molecule.” All ionic compounds react with those bonds and accelerate the deterioration of the powder. Even though water is not ionic, it is polar, and it reacts with the double oxygen bonds.

The bottom line is that nitrocellulose is a high energy molecule that wants to become a low energy molecule.

Heat accelerates the deterioration/decomposition of powder and the rate is directly proportional to the Arrhenius equation. If you read in the Insensitive munitions literature, you will see that they use high temperature to accelerate aging of smokeless propellants.

ROLE OF DIPHENYLAMINE AS A STABILIZER IN PROPELLANTS;
ANALYTICAL CHEMISTRY OF DIPHENYLAMINE IN PROPELLANTS
Nitrocellulose-base propellants are essentially unstable materials
that decompose on aging with the evolution of oxides of nitrogen. The
decomposition is autocatalytic and can lead to failure of the ammunition or disastrous explosions.


http://www.dtic.mil/dtic/tr/fulltext/u2/783499.pdf

Heat, as you can see in the report, will age gunpowder

http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/Propellantaging.jpg


Combustion pressures will rise after high temperature storage. I am of the opinion that this high temperature experiment is an accelerated age test. So, it is reasonable to assume that gunpowder will increase combustion pressures as it gets older.

INVESTIGATION OF THE BALLISTIC AND CHEMICAL STABILITY OF 7.62MM AMMUNITION LOADED WITH BALL AND IMR PROPELLANT

Frankfort Arsenal 1962

3. Effects of Accelerated Storage Propellant and Primer Performance

To determine the effect of accelerated isothermal storage upon propellant and primer performance, sixty cartridges from each of lots E (WC 846) and G (R 1475) were removed from 150F storage after 26 and 42 weeks, respectively. The bullets were then removed from half the cartridges of each lot and from an equal number of each lot previously stored at 70F. The propellants were then interchanged, the bullets re-inserted, and the cases recrimped. Thus, four variations of stored components were obtained with each lot.

Chamber pressures yielded by ammunition incorporating these four variations were as follows. These values represent averages of 20 firings.


http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/Pressurevariationsduetostoragetempertures-1.jpg

Double based powders have a reduced lifetime compared with single base. Double based powders have nitroglycerin (NG) in the grain. Nitroglycerine remains a liquid and it migrates within the grain to react with the NO bonds on the nitrocellulose, increasing the rate of reduction-oxidation reaction. All ionic compounds react with those bonds and accelerate the deterioration of the powder. Rust is bad as ferric oxide is ionic. Water is polar covalent ion and is ever present in the air.

Because water reacts in a negative way with smokeless propellants, quality ammunition is manufactured in humidity controlled environments. Between 40% and 20% humidity. They don't go lower due to electro static discharge concerns.

The best storage condition for powders is arctic. Cold and dry.

Due to the migration of NG within double based powders, the surface of the grain will become rich in NG even though the total energy content of the propellant has decreased. This will cause changes in the burn rate, and can cause pressures to spike. The surface of nitrocellulose powders also change as the powder deteriorates, and it changes unevenly. This creates conditions for erratic burn rates. Burn rate instability is undesirable and can cause explosive conditions in firearms. In retrospect, this explains the “funny” retorts I experienced and the sticking cases. It is an extremely rare occurrence, but old ammunition has caused rifle Kabooms. When I discussed this with a machine gunner buddy, he said that explained the two top cover explosions he had with old Yugoslavian 8 MM ammo. I think it explains the Garand kaboom in the link below.




Section from the Propellant Management Guide:

Stabilizers are chemical ingredients added to propellant at time of manufacture to
decrease the rate of propellant degradation and reduce the probability of auto ignition during its expected useful life.

As nitrocellulose-based propellants decompose, they release nitrogen oxides. If the nitrogen oxides are left free to react in the propellant, they can react with the nitrate ester, causing further decomposition and additional release of nitrogen oxides. The reaction between the nitrate ester and the nitrogen oxides is exothermic (i.e., the reaction produces heat). Heat increases the rate of propellant decomposition. More importantly, the exothermic nature of the reaction creates a problem if sufficient heat is generated to initiate combustion. Chemical additives, referred to as stabilizers, are added to propellant formulations to react with free nitrogen oxides to prevent their attack on the nitrate esters in the propellant. The stabilizers are scavengers that act rather like sponges, and once they become “saturated” they are no longer able to remove nitrogen oxides from the propellant. Self-heating of the propellant can occur unabated at the “saturation” point without the ameliorating effect of the stabilizer. Once begun, the self-heating may become sufficient to cause auto ignition.

NOx gas is a mix of compounds all of which are reactive. http://en.wikipedia.org/wiki/NOx http://en.wikipedia.org/wiki/Nitrogen_oxide When smokeless propellants break down NOx gas is released. Nitric acid gas is only produced in the presence of water, because it requires a hydronimun ion, but there is plenty of water in air.

The Armed Forces have stockpile surveillance programs but each Service does theirs a little differently. If you want to see all the different tests the military uses to determine propellant characteristics, look at Mils Std 286 Propellants, Solid: Sampling, Examination and Testing to be found at https://assist.daps.dla.mil/quicksearch/.

If you look, you will find aging tests. One common test is for powder to be kept at 65 C (150 F) until it fumes. It if fumes within 30 days it is checked for stabilizer or scrapped.

The Navy expert told me a few ways the Navy samples its powders and propellants. If the powder is outgassing nitric gas (as determined by change of color of methly violet paper in contact with the powder (Methly Violet test, or Talliani test)), the stuff is tested to see how much stabilizer is left. If the amount is less than or equal to 20%, the lot is scrapped.

Scrapping powders and propellants with this percentage of stabilizer appears to be consistent across all services.

Pages 5-11 of the 2003 Army Logistics Propellant Management Guide provide the protocols for testing and subsequent actions for their Stockpile Propellant Program. Basically, all propellant lots are tracked. The trigger for investigation is: "When Master Sample Stability Failure Occurs"

The Navy expert provided 'rules of thumb' concerning when to expect problems with double based and single based propellants. The rules of thumb are: Double based powders and ammunition are scrapped at 20 years, single based 45 years. In his words “These 'rules of thumb' are particularly useful when the protocol fails. The protocol can easily fail when workmanship or good housekeeping measures are not followed during manufacture of propellant and/or rocket motor or during storage of the weapon system components, respectively.”

Early in the last century the storage lifetime of smokeless powders was considered to be 20 years or less:

Army Ordnance Magazine, June 1931, page 445 says:

“Smokeless powder constitutes one of the greatest hazards from a storage standpoint, due to the fact that it is subject to deterioration and at the best cannot be expected to have a life greater than about twenty years…….Master samples of all lots of smokeless powder are under constant observation in the laboratories at Picatinny Arsenal. Should any of these samples indicate rapid deterioration, notification is given at once, and steps are taken to use this deteriorating material within a very short period, if possible, or else withdraw it from service.”


For the home reloader, if the powder has turned red, or smells like acid, it is way beyond its safe limits.

I am of the opinion that the reason this is not discussed in the popular gun press is because if the shooting community knew that powders had a shelf life, it might effect sales. As we all know, gunwriters are shills for the industry and for decades the shills have been reassuring us that as powder gets old, it becomes benign. I cannot see a reason why industry wants you, the shooter, to be picky about old powders and old ammunition. You might not buy, you might have reservations about buying. It is all about profits you know.

The military does not talk about this, but bunkers and ammunition storage areas have gone Kaboom due to old powder. That nitric acid builds up, creates heat, and the stuff blows up. It blows up inside the case or the shell.

http://www.liveleak.com/view?i=13c_1205681217

This powder is from a FA 11-1898 30-40 Krag cartridge. Obviously it is bad.

http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/30-40FA11-1898Crackedcaseneck.jpg

http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/30-40FA11-1898RedpowderDSCN1095.jpg

I sent the IM expert the link with this Garand blowup, http://www.socnet.com/showthread.php?p=1344088
and the pictures of my corroded bullets and pulled Krag red powder, and this is what he wrote back:

Wow

The red color indicates that the stabilizer is depleted and the redox reaction is degrading the nitrate ester. (I assume this is a single base gun propellant, and the nitrate ester is NC.) Please dispose of this powder and ammo supply before it starts to get warm or self-heat (via autocatalytic exothermic reaction). This stuff can be a runaway reaction and spotaneously explode in storage.

The cracked case necks are proof that the outgassing of NOx is occurring. The pressure build-up is evidently enough to fatigue the metal at a high stress location in the cartridge case (@ the neck bend). You should also see a bulge in the cartridge base (where the firing pin would strike b/c there is a circular joint crimp there between the two metals). This ammo would explosively vent at the crack if you tried to fire it in a gun. Just like the Garand example you sent. Please discard this ammo.

The corroded ammo is the same as above (redox reaction gassing NOx) except this stuff actually got wet too. Water provides a medium for corrosive acid reactions to result. Please discard this ammo.

Lessons learned -
(1) Ammo has a finite shelf life
(2) Ammo can be dangerous

Blakenzy
June 26, 2013, 07:10 PM
Well the acetone smell was a lot stronger than what I remember it being. It definitely stood out. And with the graphite now clearly separating from the powder (when there was no indication of that before) there has to be something going on.

That was some very interesting info on degrading powder creating excess pressure. Thank you. I had a doubt about that.

I suppose my powder is still serviceable, but I think I better use it up before long.

herrwalther
June 26, 2013, 10:29 PM
The smell probably stood out because it hasn't been opened in awhile. I have never seen powder go bad but if it doesn't smell like acetone and is discolored. It has probably gone bad.

klausman
June 27, 2013, 01:03 AM
It is kind of shocking to see the powder pictured all red like that. The powder in the picture was made by Laflin & Rand specifically for the 30-40 Krag cartridge. It was originally kind of an ivory color and was not graphited. It was a double based powder called WA-30. I think that the shocking color is in large part because there was no graphite to cover it up. I also suspect that the cracked neck has more to do with the deterioration of the mercuric primer than the outgassing from the deteriorating powder. These cases were tinned inside and out most likely to minimize the effect of the mercury on the brass. The first stabilizers were introduced about 1910, so the powder pictured had none at all.

HOOfan_1
June 27, 2013, 09:43 AM
Wow

The red color indicates that the stabilizer is depleted and the redox reaction is degrading the nitrate ester. (I assume this is a single base gun propellant, and the nitrate ester is NC.) Please dispose of this powder and ammo supply before it starts to get warm or self-heat (via autocatalytic exothermic reaction). This stuff can be a runaway reaction and spotaneously explode in storage.

The cracked case necks are proof that the outgassing of NOx is occurring. The pressure build-up is evidently enough to fatigue the metal at a high stress location in the cartridge case (@ the neck bend). You should also see a bulge in the cartridge base (where the firing pin would strike b/c there is a circular joint crimp there between the two metals). This ammo would explosively vent at the crack if you tried to fire it in a gun. Just like the Garand example you sent. Please discard this ammo.

The corroded ammo is the same as above (redox reaction gassing NOx) except this stuff actually got wet too. Water provides a medium for corrosive acid reactions to result. Please discard this ammo.

Lessons learned -
(1) Ammo has a finite shelf life
(2) Ammo can be dangerous

Film used to have a nitrocellulose base and of course that was extremely flammable. They replaced it with "safety film" with a cellulose acetate base....but thise stuff degrades to acetic acid smells like vinegar...like North Carolina BBQ. It is also prone to redox which gives you rust like blemishes and even turns the entire film pinkish and gets really brittle. Now they make film with a polyester base.

Anyway...just seems neat that film and powder both suffer from redox. Storage is key though

Smokey Joe
June 27, 2013, 12:54 PM
Blakenzy--From your description in post #1, I am not certain that your powder is bad. However (there is always that darn "however"!) also from your description, YOU are not CERTAIN that the powder is GOOD, either.

Rather than experiment with the stuff, I would spread it on the lawn, just on suspicion. Life is too short to futz with finding the correct load for this perhaps half-strength powder--Once you find the correct load you will have used up a bunch of the powder in question, testing, and you'll only have a finite amount left to actually use for shooting. When you buy new 4895, you'll have to do the load development all over again.

You said it's only a bit over a pound. That's $25-30 worth of powder. How much is your time and aggravation and futzing around worth?

SlamFire1
June 27, 2013, 11:06 PM
It is kind of shocking to see the powder pictured all red like that. The powder in the picture was made by Laflin & Rand specifically for the 30-40 Krag cartridge. It was originally kind of an ivory color and was not graphited. It was a double based powder called WA-30. I think that the shocking color is in large part because there was no graphite to cover it up. I also suspect that the cracked neck has more to do with the deterioration of the mercuric primer than the outgassing from the deteriorating powder. These cases were tinned inside and out most likely to minimize the effect of the mercury on the brass. The first stabilizers were introduced about 1910, so the powder pictured had none at all.

I had about 30 rounds given to me, I passed all but a couple to a cartridge collector. Every single one of these 30-40 Krag rounds had a cracked case neck.

I attributed the cracked case necks to NOx outgassing and it is not unreasonable considering all the cracked case necks I got with surplus powder in 308 LC cases. But, it could be as you said, or it could be that the necks were not stress relieved.

Take a look at the cracked case necks on unfired factory ammunition and the fired examples.

Bad Bad 7.62x25 Ammo
http://www.ramanon.com/forum/showthread.php?57650-Bad-7-62x25-Ammo


I will say, I popped the bullets on several cases and poured out the powder in my unlighted garage, and the first powder I dumped out was glowing ruby red in the dusky conditions. It was actually beautiful and reminded me of hot charcoal briquettes.

I don’t know when stabilizers were first used in US ammunition. This DTIC report makes it sound as if stabilizers were universal by the time you get to 1910, but there could have been a phase in period.

ROLE OF DIPHENYLAMINE AS A STABILIZER IN PROPELLANTS; ANALYTICAL CHEMISTRY OF DIPHENYLAMINE IN PROPELLANTS

December 1973

The use of diphenylamine to suppress the autocatalytic decomposition
of nitrocellulose contained in propellants was apparently first proposed
by Nobel in a German patent in 1889 (). Shortly afterwards,
Germany in great secrecy adopted the use of diphenylamine for most
propellants. However, other countries soon were using diphenylamine
for this purpose and by about 1910 its use was fairly universal.

I would like to incorporate your comment that the original powder was ivory colored WA-30. I will double check my Lafin reference to see if it was in fact double based.

Film used to have a nitrocellulose base and of course that was extremely flammable. They replaced it with "safety film" with a cellulose acetate base....but thise stuff degrades to acetic acid smells like vinegar...like North Carolina BBQ. It is also prone to redox which gives you rust like blemishes and even turns the entire film pinkish and gets really brittle. Now they make film with a polyester base.

I have been told that this Queen knife has celluloid handles and the dark spot is just the beginning of uncontrolled and unstoppable acid decay.

http://img.photobucket.com/albums/v479/SlamFire/knives/DSCN1919Queen9jpg.jpg (http://smg.photobucket.com/user/SlamFire/media/knives/DSCN1919Queen9jpg.jpg.html)

243winxb
June 27, 2013, 11:31 PM
The metal can is the first problem you should eliminate. Find black plastic bottles with "HDPE" on the bottom. Frosted is ok, but keep out of sun. I had/have some Dupont IMR 4895 & 4198 get reddish dust in it. I am shooting the IMR 4198 now. The 4895 looked ok, but i got rid of it. http://i338.photobucket.com/albums/n420/joe1944usa/th_IMR4895_20090928_1.jpg (http://s338.photobucket.com/user/joe1944usa/media/IMR4895_20090928_1.jpg.html)

gamestalker
June 28, 2013, 03:21 AM
If it smells kind of like ether, it's not bad. I have IMR-4350 an old bench rest shooter gave me back in the mid 1980's that he had bought years earlier, and it still smells fresh, and shoots fine.

I apologize for hijacking your thread, but on a similar note, I either have the worst luck at finding old Longshot on the shelf than most, or Longshot simply doesn't resemble the smell of others. I can't remember ever buying LS that smelled like other powders do. It always smells bad, kind of like manure does. The first time I noticed it was with a rather half used up 1 lb. canister, which I tossed on the lawn, actually I burned it, much more fun doing that. But following that incident, I decided to just use it since it always smells the same when I buy it, and have been doing so with absolutely no issues in performance or evidence of pressure problems.

Maybe RC can clarify this for me since I seem to encounter this with every single purchase of it, including the 2 lbs. I bought a month or so ago.

GS

JSmith
June 28, 2013, 08:45 AM
Very interesting.

The best storage condition for powders is arctic. Cold and dry.

I use powder fairly slowly. I got a 4lb. jug of 231 I expect to last for a couple of years. What do you think about keeping it in the chest freeezer when I'm not using it?

USSR
June 28, 2013, 11:45 AM
I use powder fairly slowly. I got a 4lb. jug of 231 I expect to last for a couple of years. What do you think about keeping it in the chest freeezer when I'm not using it?

Not necessary at all. Basements which tend to have cool, year-round temperatures are near ideal for long-term powder storage. I have nearly 50 pounds of pulldown surplus IMR4895 of unknown vintage, and it looks as good as ever. I suspect previous storage conditions may have a lot to do with some surplus powder going bad.

Don

iiranger
June 28, 2013, 12:34 PM
O.K. Powder is made with solvents like alcohol and acetone and should smell like rubbing alcohol and nail polish remover (acetone). Obviously, having the can open lets some of the vapors get away. If it is going bad then it gives off acidic smell like vinegar and the rotten powder turns to red dust... No rust, no vinegar smell, probably o.k.

NRA finally dispelled the urband legend a few years back. During WW II Dupont was making powder for the government. TONS. (Oh surprise. There was a war on.) The bean counters determined that the process could be speeded up by leaving out a "washing step" and since it was supposed to be shot at the enemy SOON who cared how long it would keep... Orders given and followed AND war ended and some of this less washed product got into surplus channels... This was the stuff that would eat thru the side of a metal can and spill and while it remains great fertilizer... (dump it on the lawn lightly), shooting it should be very undependable...

Personally I have fired ammo from just after WW I. Spanish 7x57. Worked fine. Friend, gunsmith had a WW I revolver -.45 ACP. He handed it to me to examine. I noticed the gray cased ammo and looked... "18" Steel cased ammo made for WW I. I said, don't you have anything newer? He said, "I'm not worried."

As said, nature has a system for recycling. Everything deteriorates somehow. Iron rusts. Calcium reacts with Carbonic acid in rain (water and CO2) to form calcium carbonate, limestone, gravel ... Powder goes so slowly, you might lose 25 fps in a couple decades. Unless there is the red dust that forms and the acid/vinegar smell and maybe the can is weakened and... use it and enjoy unless you are in a top flight target match... that might warrent new supplies for you. Me? I won't be there, oh welllllll Luck Happy trails.

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