When milsurp ammo goes bad.........

[Larry Gibson]

Have had a lot of 7.65 Argentine for several years; SF 80. I have shot about half of it but hadn't shot any for a couple years. Took some out this last summer and loaded 5 into the mag of my M1909, took up a good sitting position and set the sights at 600m for a sage brush on a hillside about that far away. Fired the first shot and smack into the sage, worked the bolt and fired the second shot and smacked the sage again. worked the bolt and the third shot wen high right and away.......dropped the but of the rifle out of the shoulder and immediately noticed smoke curling up out of the receiver........not good:(

Opened the bolt and the case came out minus the primer:( Checked the other 2 shots and they all had high pressure signs. Stopped shooting.

I finally got around to pulling the rest of the bullets and about 2/3 had severe corrosion inside the cases and on the bases of the bullets. Picture shows 2 of the fired cases including the blown primer. Middle case shows corrosion inside the cases. Bullet on right shows corrosion on the base. Other 2 bullets cleaned up nice with polishing. Powder looks good with no discoloration and smells good but will make good fertilizer anyway..........

Larry Gibson

96228

[MtGun44]

Larry,

Any idea why apparently good, undeteriorated powder was associated with the internal
corrosion? I could imaging that extremely high bullet pull forces (bullet corroded in
place) could be contributory or even primary in the pressure issues. What do you
think?

Bill

[CastingFool]

Never seen that happen before.

[bruce drake]

Had a same result with some Turk 8mm made in 49 and some Pakistani 303 Brit made in 63. Blew the extractor off a Turk 38 Mauser (easily repaired) and dropped primers in a No4 Enfield.

The Turk ammo was pulled and reloaded with fresh powder, the 303 Brit since it was cordite based got pulled and the cases were placed in a small fire that got big really fast ;) Only plus there was the +300 174gr FMJ-BT to be loaded in my other 31 caliber rifles.

[Larry Gibson]

Pure speculation on my part; the powder had to be breaking down quickly. Many of the cartridges had gas pressure in them. They actually "swooshed" when the bullet was pulled. Any chemical engineers out there?

Larry Gibson

[mikeym1a]

Last fall, I took some old Argentine surplus to the range with me. It had been sitting around for a LONG time. It was marked 'SF' 81 on the head. I fired off about 20 rounds in my '09, and was surprised that these good looking cases on the outside had lots of splits, and flattened primers. I did not have any evidence of any gas coming out the rear of the action, all the splits were in the forward case wall and the neck. There was only 7 that showed no evidence of splitting. Later review of these cases showed that only 4 survived without any splits, what so ever. Oh, 5" offhand group at 75yds. mikey

[BruceB]

Around 1990, I bought several thousand rounds of Portuguese 7.92x57, headstamp-dated as 1983 production. It was bright, shiny beautiful ammunition.

In my MG42, which hits primers with a tremendous impact, this ammo initially gave about two percent misfires. By 1995, it was unusual to fire a five-round burst successfully (i.e.: without without a misfire stopping the gun).

When I finally finished the blasted stuff in '97, it was up to over thirty percent misfires.

Obviously, this ammo was placed on the surplus market when Portuguese inspectors detected the early signs of trouble with the batch. Pulling a few bullets did not reveal any obvious reason for the failings, but I strongly suspect the Berdan primers... the misfired rounds had primers which had apparently not fired.

The MG42 fired normally with all other ammo types I tried in it, although that didn't amount to much variety.

[fguffey]

Not related: Old Ammo. A 30/40 Crag was involved in an inheritance, I was asked to ‘checke it out’. I thought I was being hustled, I was told what to think and believe.

The owner was not a reloader, but he had his ammo reloaded by the worlds greatest etc.. The rifle was the most accurate etc., etc..

I went to the range, before chambering a round I shook the cases to determine if I could feel loose powder, I did on the first round, I chambered the round, pulled the trigger and I got nothing but smoke. I held the rifle for at least 30 seconds and then finally bang. I then shook 40+ rounds for loose powder, some had loose powder, others did not.

I return home and began pulling the bullets, some of the case necks came off with the bullets, some of the cases required required a dowel to poke holes In the powder before pouring. Other cases had powder caked in the primer end of the case, the powder would burn slowly through the column then ignite the powder in the front of the case.

The cases with powder caked behind the bullet were disasters waiting to happen. The primers worked, the powder in the rear of the case was loose and would ignite but the powder caked behind the bullet would act like an obstruction. There was not one case out of the 40+ that was safe to use.

Impact and point of air, off at 100 years and could be measured in feet. The will did not list ‘Grandfather’s rifle’ as a Crag’, just rifle. I had the new owner promise he would not fire the rifle.

F. Guffey

[Larry Gibson]

Went back and checked my records; I pressure tested that SF 80 on 31 May, 2011. It averaged 2448 fps (10 shots) out of the test 24" barrel with an ES of 89 fps and an SD of 29 fps. Psi(M43) was 54,700 with and ES of 5,700 psi(M43). All quite normal for milsurp ammunition. Sure went south since then.......

Larry Gibson

[Tackleberry41]

I have seen that sort of thing in some 308 surplus I had gotten somewhere. Little bit of a hiss when you pulled a bullet. the base all green like in the pic, the powder starting to clump together.

What I have had the most problem with is that 40s era Turkish 8mm they used to sell dirt cheap in bandoliers. Not that it wont fire, but whatever brass they use gets brittle and the neck splits. Easy to find them the bullet is loose, sure enough the neck is split. I kept the bullets, put the powder in a can. Recently made a bunch of 8mm brass from free 270 range brass a friend gets me, weighed the charges out and put em back together.

[Larry Gibson]

Tackleberry41

Done a lot of that with the Turk ammo also, still have about 2K of it. Last bunch I pulled the bullets and those necks that did not split on bullet pull I NS'd and reloaded with the bullet and same powder but dropping the charge 5%. Only a very few split on sizing and seating the bullet. Those are shooting very well and bolt lift is normal as the hard brittle cases aren't quite expanded as much. Scharfshuetzer pulled a bunch too (we got the same lot at the Puyallup Gunshow) and reloaded the bullets and powder in boxer primed cases. He gave me a gob of the Turk primed cases. I salvaged about 95% of them and loaded them with the GB 190 gr cast bullet over 28 gr 4895 and a Dacron filler. Only got about a hundred left but they sure were good walk about loads and killed a lot of rocks.....wish he'd give some more:-D

Larry Gibson

[tomme boy]

I have seen pictures of ammo loaded recently with VIHTAVUORI powder. The rounds were loaded in the late 90's. Wondering if the nito is separating out would cause this?

[MtGun44]

Pretty amazing to have it go from that good to that bad in three years. The whoosh is probably
the gases that are generated in a hurry when it oxidizes quickly (burning) but just the same
reaction going in slo-mo at room temp.

Bill

[gew98]

About 30 years ago a buddy of mine had several dozens of tins of chinese surplus 7,92 S patronen. Many tins had bad corrsion to the exterior of the barass... and gobs of split case necks. Many tins looked flat new when opened , but a high percentage of split necks too. In all tins a percentage of the rounds had turned the powder charge to a green goo...much like the super low quality 30 caliber rifle ammo made for the US during WW1. The cleanest of the lot that had a good shake to the powder charge were all very hot loads...much hotter than the hottest turk surplus. They made an MG17 purr real fast short of a case failure !.
I pulled the vast majority of these of bullets that I bought ... copper clad steel jacketed hollow cone base 154 grain S bullets...great bullets by the way !. Still have several hundred left but ran out of WC852 long ago ( 52 gns of that powder really was accurate with those projos ).
I did have a 30 caliber can filled to the brim with 185 grain argie boat tailed bullets and most showed corrosion to their boat tailed bases. But they shot beautifuly in 303 british propelled by Accurate 2230. I only have a scant few handfulls of these excellent projos left...wish I had more !.

[W.R.Buchanan]

Larry: were the primers and bullets sealed in those rounds? Most American made Military ammo has both sealed primers and sealed bullets thus preventing any moisture whatsoever from intruding into the cases.

From the looks of the corrosion,,, IE: green,,, it appears that there may have been some moisture intrusion. A small amount of moisture would not harm the powder any significant amount but certainly would promote corrosion which would in turn glue everything together and ultimately cause the problems you experienced. A layer of corrosion on the inside of the case would also decrease the volume of the case and with the powder charges essentially staying the same would cause higher pressures. Similar to what happens when you load 5.56 cases with max .223 loads.

It all works this way in my head.

Randy

[Larry Gibson]

I believe the primers are sealed as they appear that way. I saw no sealant on the bullets but there was very tight neck tension. There was no chance they got water in them from when I tested them in 2011. However, I did move to Arizona and the ammo came with me. They were stored in a commercial storage for 9 months from July to the following January. Perhaps the heat caused the break down?

Larry Gibson

[Multigunner]

Heat is the worst enemy of stored ammo.
Also the preservative additives used for propellants don't last forever.
Carbamite lasts aprox 25 years before it beguns to lose its effectiness, other additive may last longer.
Ammo shpuld always be stored in a cool dry environment. Unfortunately few war zones of the late 20th century were both cool and dry, unusually it was one or the other.

[madsenshooter]

I once pulled down a SL43 50BMG round that my uncle had brought home from gunnery school, he was a B24 belly ball gunner. It had sat in my grandma's knick knack cabinet for near 60yrs. The powder was very dry. I believe the brass had sucked all the moisture out of the powder. Verdigris is the common name for a green pigment obtained through the application of acetic acid to copper plates. Acetic acid acid itself and acetone are used in the manufacture of smokeless powder.

[Pirate69]

Pure speculation on my part; the powder had to be breaking down quickly. Many of the cartridges had gas pressure in them. They actually "swooshed" when the bullet was pulled. Any chemical engineers out there?

Larry Gibson

You may find this interesting:

Nitrocellulose deteriorates with time, yielding acidic byproducts. Those byproducts catalyze the further deterioration, increasing its rate. The released heat, in case of bulk storage of the powder, or too large blocks of solid propellant, can cause self-ignition of the material. Single-base nitrocellulose propellants are hygroscopic and most susceptible to degradation; double-base and triple-base propellants tend to deteriorate more slowly. To neutralize the decomposition products, which could otherwise cause corrosion of metals of the cartridges and gun barrels, calcium carbonate is added to some formulations.

To prevent buildup of the deterioration products, stabilizers are added. Diphenylamine is one of the most common stabilizers used. Nitrated analogs of diphenylamine formed in the process of stabilizing decomposing powder are sometimes used as stabilizers themselves.[18][19] The stabilizers are added in the amount of 0.5–2% of the total amount of the formulation; higher amounts tend to degrade its ballistic properties. The amount of the stabilizer is depleted with time. Propellants in storage should be periodically tested for the amount of stabilizer remaining, as its depletion may lead to auto-ignition of the propellant.

[Larry Gibson]

Pirate69

That very well may be the answer. Thanks

Larry Gibson

[tygar]

[QUOTE=Larry Gibson;I finally got around to pulling the rest of the bullets and about 2/3 had severe corrosion inside the cases and on the bases of the bullets. Picture shows 2 of the fired cases including the blown primer. Middle case shows corrosion inside the cases. Bullet on right shows corrosion on the base. Other 2 bullets cleaned up nice with polishing. Powder looks good with no discoloration and smells good but will make good fertilizer anyway..........
Larry Gibson QUOTE]

Dam Larry

Now I'm worried. I have a number of GI spam cans of M1 ammo in M1 clips, that I've had for 20, 30 or even 40 yrs, sitting around waiting for the revolution.

I havn't opened one in years. I do have several 30 cal ammo cans full of lc surplus & NM that I use for standardization testing. I can't remember if they are the same.

Also have sealed in plastic in the wood cases 308 in Austrian, Argentine & British surplus at least 20yo.

Don't remember ever having a problem but I do remember some with external corrosion on the brass.

I'd hate to open airtight cans or sealed plastic to check.

What do you guys think?
Tom

[uscra112]

That green corrosion would indicate the presence of ammonia, would it not? As a breakdown product?

[Pirate69]

That green corrosion would indicate the presence of ammonia, would it not? As a breakdown product?

Could be since you do have a nitrogen based compound. But it could also be copper acetate. Will have to take a harder look at what is going on.

[Multigunner]

Some South American, and other, 7.62 NATO ammo was loaded using surplus powder formerly used to load Mauser ammunition. The powder was good at the time but might have been thirty years old then and nearing the end of its shelf life.

Some 7.62 NATO ammo I pulled down had powder so degraded it smelled like cat urine. Under the verdris on the outside I found tiny pinholes eaten through the case walls.
When I put the powder in a steel IMR powder can the can disintegrated into fine brown dust up to the level of the powder after a couple of months.

[UBER7MM]

Larry,

I once was given a box of commercial hunting cartridges that were about 30 years old. The retail tag stated $12.95 for the 20 rounds. I pulled the bullets. One of the bullets was stuck when I pulled it I tore the neck. The copper bullet was fused to the base case. I wonder what kind of pressure would have been if I'd fire that it.

[Larry Gibson]

Uber7mm

Yes some of those 7.65 bullets were very hard to pull which may very well have raised the pressure.

Tygar

Don't know what to tell you except I also have a "stash". I will be checking it now. However, your stuff that is U.S made, still in the sealed cans should still be good. But how do we know?

Larry Gibson

[Uncle Grinch]

After I had one of my 30-06 cases split during a vintage service rifle match, I pulled the balance of the ammo. Some was ball powder and others were stick, Quite a few had a wet look to the powder. It was clotted up and almost slimey. The outside looked good with no suspicious anomolies.

[Argentino]

Larry,

I understand that you had that issue with some argentinean milsurp ammo. If that´s the case, I´m afraid is not uncommon at all: a lot of similar situations are commonly seen over here as well, since we have a lot of milsurp ammo available for our 1891 and 1909 military Mauser rifles. I´ve seen for sale some 7,65 x 54 mm. milsurp ammo manufactured during the late 40´s! Some of those will shoot just fine, some others will experience the same issues you had.

As long as I understand, powder decomposition is the cause of that problem. When decomposing, it corrodes the cases and the FMJ bullets as well just the way they are in your pictures. Argentinean military powders are not particular uniform from batch to batch and not particularly stable as time goes by; they tend to decompose that way after several years. However, it will also depend on how those rounds were stored during the last 30, 40 or even 60+ years; we may have been taking good care of those rounds during the last few years but who knows how they were stored during the first 10, 20 or even 30 years since they were manfactured? I guess that ammo storage conditions also plays an important role regarding powder decomposition too.

In here, when buying a real old batch of 7.65 x 54mm. milsurp ammo, is a common practice among civilian gun owners to take apart each round in order to discard the powder and to save both the cases and the FMJ bullets. We hear very often of those issues with old milsurp ammo. Split cases, higher than expected pressures and bullets lodged in the barrel do not happen all the time but are not uncommon either.

p.s.
I remember a guy who once told me that he couldn´t sleep for a couple of nights because of some sizzling noise whose origin he could not identify. Turned out to be that the sizzling was gas escaping from the cases of several 7,65 x 54 milsurp ammo that he had bought some time ago. Of course, he took apart those rounds and he only saved the cases and the FMJ bullets since the powder was mostly rotten.

[tygar]

Uber7mm

Yes some of those 7.65 bullets were very hard to pull which may very well have raised the pressure.

Tygar

Don't know what to tell you except I also have a "stash". I will be checking it now. However, your stuff that is U.S made, still in the sealed cans should still be good. But how do we know?

Larry Gibson

Sh.......

[Pirate69]

May I suggest the following may be occurring.

The nitrocellulose is decomposing to generate the acetate radical. This may be the result of moisture entering the case.

C6H8(NO2)2O5 + H2O =3CH3COOH + 2NO2
The NO2 is a reddish-brown colored gas that has a sharp, biting odor. I have read where our members have opened powder cans and found the gas and the “bad” smell. If there is moisture present, the NO2 will react with the water and form nitric acid.

NO2 + H2O = 2HNO3 + NO (In your nose as well, the biting odor)

There is elemental copper present in the case. Dilute nitric acid will react with copper and oxidize it to the +2 valence state.

Cu0 = Cu+2 + 2e-
3Cu0 + 8HNO3 = 3Cu+2 + 2NO + 4H20 + 6NO-3
The copper will then react with the acetic acid to form Copper(II) Acetate. This is a greenish colored solid material that is seen on the brass and bullets. Copper Acetate is used as a catalyst and oxidizing agent. This may enhance further reactions.

Cu+2 + 2CH3COOH = Cu(CH3COO)2 + 4H2 (Slight gas pressure in the case from the hydrogen?)
Just my guess as to what may be occurring.

[tygar]

May I suggest the following may be occurring.

The nitrocellulose is decomposing to generate the acetate radical. This may be the result of moisture entering the case.

C6H8(NO2)2O5 + H2O =3CH3COOH + 2NO2
The NO2 is a reddish-brown colored gas that has a sharp, biting odor. I have read where our members have opened powder cans and found the gas and the “bad” smell. If there is moisture present, the NO2 will react with the water and form nitric acid.

NO2 + H2O = 2HNO3 + NO (In your nose as well, the biting odor)

There is elemental copper present in the case. Dilute nitric acid will react with copper and oxidize it to the +2 valence state.

Cu0 = Cu+2 + 2e-
3Cu0 + 8HNO3 = 3Cu+2 + 2NO + 4H20 + 6NO-3
The copper will then react with the acetic acid to form Copper(II) Acetate. This is a greenish colored solid material that is seen on the brass and bullets. Copper Acetate is used as a catalyst and oxidizing agent. This may enhance further reactions.

Cu+2 + 2CH3COOH = Cu(CH3COO)2 + 4H2 (Slight gas pressure in the case from the hydrogen?)
Just my guess as to what may be occurring.


You may suggest all you want but all of that is "Greek" to me! I'm just a guy with an "ology" degree who barely squeeked thru algebra & geometry.

[Pirate69]

Basically, I am saying that the powder is decomposing to generate two compounds of interest. One is conditioning the brass and the other is reacting with the brass, after conditioning, to generate the copper acetate. I have read about this before but had never considered what was really happening.

I have also read that a trick used by people pulling old military rounds was to seat them a few thousandths deeper to break any corrosion bond. This may help to eliminate any pressure concerns if the rounds are to be fired rather than disassembled.

[WallyM3]

May I suggest the following may be occurring.

The nitrocellulose is decomposing to generate the acetate radical. This may be the result of moisture entering the case.

C6H8(NO2)2O5 + H2O =3CH3COOH + 2NO2
The NO2 is a reddish-brown colored gas that has a sharp, biting odor. I have read where our members have opened powder cans and found the gas and the “bad” smell. If there is moisture present, the NO2 will react with the water and form nitric acid.

NO2 + H2O = 2HNO3 + NO (In your nose as well, the biting odor)

There is elemental copper present in the case. Dilute nitric acid will react with copper and oxidize it to the +2 valence state.

Cu0 = Cu+2 + 2e-
3Cu0 + 8HNO3 = 3Cu+2 + 2NO + 4H20 + 6NO-3
The copper will then react with the acetic acid to form Copper(II) Acetate. This is a greenish colored solid material that is seen on the brass and bullets. Copper Acetate is used as a catalyst and oxidizing agent. This may enhance further reactions.

Cu+2 + 2CH3COOH = Cu(CH3COO)2 + 4H2 (Slight gas pressure in the case from the hydrogen?)
Just my guess as to what may be occurring.

Now I got it!

Well, not really, but it looks like there's a chemically understandable reaction taking place.

Is there a way to prevent deterioration or perhaps identify likely occurrances?

[Larry Gibson]

Argentino

Thank you for the very good reply. That's what's great about this site; we have members everywhere:drinks:

Makes a lot of sense to me. I have a very nice M91 rifle and a very nice M1909 in original configuration. I also have 2 other M91s that were "sporterized" to sell here years ago. I call one "Evita" and the other "Juan" for obvious reasons. Evita is a real shooter in scout configuration and is a prized rifle of mine. I also have converted a M91 by rebarreling it to 35 Remington and it is an excellent cast bullet hunting rifle. The 7.65 is an excellent cartridge and I've been enjoying it for years. A pleasure to chat with you.

Larry Gibson

96585

[Larry Gibson]

May I suggest the following may be occurring.

The nitrocellulose is decomposing to generate the acetate radical. This may be the result of moisture entering the case.

C6H8(NO2)2O5 + H2O =3CH3COOH + 2NO2
The NO2 is a reddish-brown colored gas that has a sharp, biting odor. I have read where our members have opened powder cans and found the gas and the “bad” smell. If there is moisture present, the NO2 will react with the water and form nitric acid.

NO2 + H2O = 2HNO3 + NO (In your nose as well, the biting odor)

There is elemental copper present in the case. Dilute nitric acid will react with copper and oxidize it to the +2 valence state.

Cu0 = Cu+2 + 2e-
3Cu0 + 8HNO3 = 3Cu+2 + 2NO + 4H20 + 6NO-3
The copper will then react with the acetic acid to form Copper(II) Acetate. This is a greenish colored solid material that is seen on the brass and bullets. Copper Acetate is used as a catalyst and oxidizing agent. This may enhance further reactions.

Cu+2 + 2CH3COOH = Cu(CH3COO)2 + 4H2 (Slight gas pressure in the case from the hydrogen?)
Just my guess as to what may be occurring.

Got it.....probably a good guess.........:???:

I ask for it didn't I............:drinks:

Thanks for the technical explanation.

Larry Gibson

[Wolfer]

May I suggest the following may be occurring.

The nitrocellulose is decomposing to generate the acetate radical. This may be the result of moisture entering the case.

C6H8(NO2)2O5 + H2O =3CH3COOH + 2NO2
The NO2 is a reddish-brown colored gas that has a sharp, biting odor. I have read where our members have opened powder cans and found the gas and the “bad” smell. If there is moisture present, the NO2 will react with the water and form nitric acid.

NO2 + H2O = 2HNO3 + NO (In your nose as well, the biting odor)

There is elemental copper present in the case. Dilute nitric acid will react with copper and oxidize it to the +2 valence state.

Cu0 = Cu+2 + 2e-
3Cu0 + 8HNO3 = 3Cu+2 + 2NO + 4H20 + 6NO-3
The copper will then react with the acetic acid to form Copper(II) Acetate. This is a greenish colored solid material that is seen on the brass and bullets. Copper Acetate is used as a catalyst and oxidizing agent. This may enhance further reactions.

Cu+2 + 2CH3COOH = Cu(CH3COO)2 + 4H2 (Slight gas pressure in the case from the hydrogen?)
Just my guess as to what may be occurring.

I don't remember covering this in school but I got drafted before I finished the third grade.:roll:

[jonk]

I bought a whole can of this ammo knowing it had these issues, probably close to 900 rounds. I found in pulling it down that about half was perfectly fine, half looked just like what you have here.

I put the pull down powder in an empty powder can, works fine for cast loads... at least the pull down that wasn't nasty looking.

The bullets I tossed in the tumbler with some mineral spirits for an hour, they cleaned up fine and still shoot fine.

The brass is either going to be scrapped or reprimed if I want to bother with the berdans.

[390ish]

I have a tin of WWII era Soviet 7.62x54r ammo that gave it necks and very difficult extraction. Only fired about 4 rounds. I need to pull some rounds and see what the powder and bullets look like.

[Huffmanite]

FWIW, my commet about surplus 7.65 argentine ammo is based on some made in the 1940s, I'd bought back in the later 1960s to shoot in my 91 argentine sporterized rifle. Used Norma ammo back then for deer hunting. Maybe 6 years ago, opened up a storage box and came across some of this old surplus ammo, long forgotten about. Hmmmm, examined the ammo, seriously doubting it was any good. Noticed something about the neck of the brass on some of the rounds I didn't like. I could grip the bullet/neck of brass and break it off at the shoulder with my hands....brass had corroded thru from the inside. I supposerd it was the corrosive primers that caused the corrosion. I destroyed all the rounds.

[MT2DAY]

What is the best way to get rid of degraded power besides burning?

[WallyM3]

Saturating it with WD-40. ?

[willvabch]

Garbage disposal

[madsenshooter]

Send it to me to throw in the sulpher creek.

[Frank46]

I had about 800 rounds of British 303. It did not enjoy a good life in storage. Neck splits were common. Pulled the remaining bullets, burned off the powder a little at a time and scrapped the cases. Somewhere around here is a box with about 700 or so 303 bullets. Frank

[birddog1148]

I have a bandoleer of WW1 30-06 ammo I have had stored in the closet at my parents house for the last 25 years or so. Came out of an estate and I bought all the old Military stuff. Going to have to post some pics, but now I am wondering what I should do with it, some of the necks are cracked and corroded. Have just kind of held onto it because of it's age until now.
http://i287.photobucket.com/albums/ll124/birddog1148/GEDC0153_zpsfc202637.jpg (http://s287.photobucket.com/user/birddog1148/media/GEDC0153_zpsfc202637.jpg.html)
http://i287.photobucket.com/albums/ll124/birddog1148/GEDC0156_zps7047e428.jpg (http://s287.photobucket.com/user/birddog1148/media/GEDC0156_zps7047e428.jpg.html)
http://i287.photobucket.com/albums/ll124/birddog1148/GEDC0158_zpseae6a669.jpg (http://s287.photobucket.com/user/birddog1148/media/GEDC0158_zpseae6a669.jpg.html)
http://i287.photobucket.com/albums/ll124/birddog1148/GEDC0155_zps2b1f0c42.jpg (http://s287.photobucket.com/user/birddog1148/media/GEDC0155_zps2b1f0c42.jpg.html)
http://i287.photobucket.com/albums/ll124/birddog1148/GEDC0160_zps95753039.jpg (http://s287.photobucket.com/user/birddog1148/media/GEDC0160_zps95753039.jpg.html)
http://i287.photobucket.com/albums/ll124/birddog1148/GEDC0161_zps45a6f0cc.jpg (http://s287.photobucket.com/user/birddog1148/media/GEDC0161_zps45a6f0cc.jpg.html)

[Matt_G]

What is the best way to get rid of degraded power besides burning?

Spread it on your lawn.
Great fertilizer...

[dale2242]

Larry, I dismantled some 7.65 Arg milsurp ammo with exactly the same issues.
I pulled the apart with an impact bullet puller.
and the necks of the cases broke off at the top of the shoulder.
The corrosion had eaten into the base of some of the bullets very badly.
Nasty looking stuff.....dale

[Artful]

I had a sealed spam can of 7.62x54r that was junk when opened - nothing salvageable.
I now when buying spam cans open them within limits of complaint/warranty replacement for comm. surplus
I have much more faith in western surplus.

[TNsailorman]

Hence the warning on powder: "store in a cool, dry climate." I had some old WW II 30-06 ammo that had corrosion around the outside of the primers. I pulled the rounds down and checked the components. Powder smelled ok, bullets and cases showed no corrosion anywhere but on the outside edges of and inside primer cup itself. I cleaned the primer pockets with diluted a vinegar and water solution. I reamed the primer crimp out. I re-primed the cases with a Federal large rifle primer. I reloaded the rounds using the same components and took them to the range to fire. They shot and grouped just fine with no signs of pressure. The ammo came out of a can of surplus LC ammo I had bought back in the 60's. There were only a few rounds in the can that were showed this corrosion. They were is sealed boxes inside the case, not loose or on clips. I have seen fired cases from corrosive lots of 30-06 that showed the same corrosion inside the necks that Larry showed in his picture. These were cases that had been fired at the local range and left on the ground, which I picked up and went thru the same cleaning process I had used on the primer pocket corrosion. They are still going strong after several reloading. I don't know the chemistry involved but Pirate69's opinion might be spot on. I doubt if very many ammunition warehouses were air conditioned or humidity controlled, especially in the third world countries. my .02 anyway, james

[TNsailorman]

follow up: None of the ammo I mentioned looked anywhere near as bad as the pictures birddog shows. That is nasty looking stuff. james

[454PB]

I've been "pouring powder" for 45 years now, and have also disassembled many rounds of old ammunition. In all that time, the only powders I've ever seen deteriorate and/or cause corrosion like this are "IMR" or extruded. I've never seen it with ball powders.

I had a can of IMR 4064 that sat around unopened for 20 or more years, and when I broke the factory seal, it was full of red dust. The metal can was rusty inside and the smell was acrid enough to take my breath away.

[SlamFire1]

Gunpowder has a shelf life. This is a high energy compound that is breaking down, from day one, to a low energy compound. Our gunpowders are either nitrocellulose or nitrocellulose & nitroglycerine. The nitroglycerine is there basically for the energy boast. Because nitroglycerine attacks the double bonds on nitrocellulose the lifetime of double based powders is less than half that of single based. Stabilizers are mixed with the nitrocellulose/nitroglycerine as a sacrificial compound: stabilizers soak up the nitric acid gas that is created when nitrocellulose deteriorates. When the stabilizer gets low , gunpowder is extremely unstable and unsafe. In quantity it will auto combust and the burn rate is irregular. Burn rate instability has and will blow up firearms.

A good rule of thumb is that single base powders will last 45 years and double based 20 years. Like all rules of thumb this is wrong more often than it is right.

This thread has really excellent pictures:

Has anyone else had Vihtavuori N140 corrode in loaded ammo?

http://www.falfiles.com/forums/showthread.php?p=3745264 (http://www.falfiles.com/forums/showthread.php?p=3745264)

Notice that the gunpowder is only around 25 years old and yet people are experiencing nasty corrosion due to nitric acid gas release from the gunpowder. It was not that long ago that 20 years was considered the shelf life of gunpowder.

Army Ordnance Magazine, May 1931, Safety Hazards, Picatinny Arsenal

Smokeless powder constitutes one of the greatest hazards from a storage standpoint, due to the fact that is subject to deterioration and at the best cannot be expected to have a life greater than about twenty years

The worst enemy of gunpowder is heat. The lifetime of gunpowder is reduced exponentially with increases in temperature. This chart came from a UN manual on ammunition inspection. Section 7.3 is well worth reading

Surveillance and in-service proof - the United Nations
http://www.un.org/disarmament/convar...Proof(V.1).pdf (http://www.un.org/disarmament/convarms/Ammunition/IATG/docs/IATG07.20-Surveillance_and_In-Service%20Proof(V.1).pdf)

http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/Propellantdeteriorationyearsversustemperature_zps2 9357560.png (http://smg.photobucket.com/user/SlamFire/media/Reloading/Old%20Gunpowder/Propellantdeteriorationyearsversustemperature_zps2 9357560.png.html)

Exposure to water is bad, even though water is a polar covalent molecule, it acts ionic. All ionic compounds break gunpowder down faster. I think that may be a reason why gunpowder now comes in plastic cans, the tin cans released rust into the powder and that accelerated powder breakdown. Water is in air, so it is best to keep gunpowder cans sealed.


Federal says their ammunition has a ten year shelf life:
Federal Ammunition :

http://www.federalpremium.com/company/faq.aspx


What is the shelf life of ammo and storage?


Store reloading components and ammunition in a cool, dry place, protected from direct exposure to sunlight. If stored properly there is a 10-year shelf life on loaded ammunition.

There is very little information on the internet about gunpowder aging and causing pressure problems because all that was ever needed to be known was determined well before WW2. However ball powders did come out at the end of WW2 and I was able to find this data showing that gunpowder at the end of its lifetime will pressure spike. Heat is used to accelerate the age of gunpowder, so what you are seeing is in fact because of “age”, not heat, but it took heat to age the powder quickly. The IMR is a single based and the WC is a double based ball powder.

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 (http://smg.photobucket.com/user/SlamFire/media/Reloading/Old%20Gunpowder/Pressurevariationsduetostoragetempertures-1.jpg.html)
You can google “surplus ammunition Kaboom” or the equivalent and find a surprising number of reports of firearms that have blown up with old military ammunition. Now I am going to tell you the terrible truth about surplus ammunition. The stuff was surplused because it was at the end of its service life and the Army that owned it, determined that it was unsafe to store and unsafe to shoot. Some Ammunition Specialist went through that lot and found evidence that the gunpowder had deteriorated and the stuff was sold to eager Americans who do not know about the risks of old ammunition.



This section came from the Dec 2003 U.S Army 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.


There are only a few compounds used as stabilizers, and as the Propellant Management Guide tells us, stabilizers are consumed with age.

This is a good reference on stabilizers,

ROLE OF DIPHENYLAMINE AS A STABILIZER IN PROPELLANTS;ANALYTICAL CHEMISTRY OF IPHENYLAMINE 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 (http://www.dtic.mil/dtic/tr/fulltext/u2/783499.pdf)

They are using heat to age the powder and as the powder ages, the stabilizer content decreases.

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


The bitter smell and red color (probably nitric acid gas) we see and smell in very old gunpowder is a consequence of not enough stabilizer left to sop up all of the NOx. As NOx escapes it reacts with water to produce nitric acid gas. That nitric acid gas corrodes brass, bullets, weakens brass, is evidenced by cracked case necks, eats up the ammunition containers; nitric acid gas is nasty stuff. I am certain that a cloud of red fuming nitric acid gas is as toxic as any of the chemicals used in WW1 for chemical warfare.

Our Armed Services have stockpile surveillance programs (but each Service does theirs a little differently) and one of the easiest things to show that gunpowder is at the end of its service life is that red fuming nitric acid gas. Of course there are a lot of tests, if you want to see all the different tests the military uses look at Mils Std 286 Propellants, Solid: Sampling, Examination and Testing to be found at https://assist.daps.dla.mil/quicksearch/.

One common test for gunpowder age is placing the suspect powder in an oven at 65 C (150 F) until it fumes. If the sample fumes within 30 days the lot in the field is either chemically tested for the percentage of stabilizer or it is simply scrapped.

This is from a 1969 Symposium:


http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/1969Ammunitionsurveilliance_zps6bd27200.jpg (http://smg.photobucket.com/user/SlamFire/media/Reloading/Old%20Gunpowder/1969Ammunitionsurveilliance_zps6bd27200.jpg.html)

This is from a 1970 Symposium:
http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/1970ammunitionlotsdisposed_zps9776bafa.jpg (http://smg.photobucket.com/user/SlamFire/media/Reloading/Old%20Gunpowder/1970ammunitionlotsdisposed_zps9776bafa.jpg.html)


Each service has its own peculiarities, a Navy expert told me they keep master samples in test tubes. In the test tube is a methyl violet paper, if the paper changes color, they track down the powder lot and test to see how much stabilizer is left. If the amount is less than or equal to 20%, the lot is scrapped. I think this is called the Methly Violet test, or Talliani test in Mil Std 286.

The Army must do something similar because page 5-11 of the 2003 Army Logistics Propellant Management Guide provides the protocols for their Stockpile Propellant Program. The trigger for investigation is: "When Master Sample Stability Failure Occurs". The Navy and Army are consistent in that they scrap powders and propellants when the stabilizer is decreased from 100% to 20%.

If you don’t have a chemistry lab to check the percent of stabilizer all you have are the gross indications of seeing fuming nitric acid and smelling a horrible bitter smell. The smell will knock your socks off. If you see or smell fuming nitric acid the powder went bad long ago. The stuff is absolutely unsafe to shoot and unsafe to store.

Why some powder goes bad quickly and other lasts longer, heck if I know. The strangeness of this can be found in this thread at Post 61. This is Unclenick’s experience and it is worth looking at the picture:


http://thefiringline.com/forums/showthread.php?t=539440&highlight=old+gunpowder&page=3 (http://thefiringline.com/forums/showthread.php?t=539440&highlight=old+gunpowder&page=3)


Of particular interest to me was the link to the thread on N140. In the early 1990's, my dad got a 1/4 lb free sample container of N140 at Camp Perry, and gave half of it to me. That's about 20 rounds worth in .308; not enough to do serious load development with. I put it in a plastic bottle with a plated and painted steel cap with cardboard seal disc. I left it at the back of a high shelf in the basement where it was out of sight and soon out of mind. Some time later I bought a full pound of N140 to experiment with, but that original 1/4 lb continued to sit.

I finally re-encountered the bottle during some cleaning out activity. It looked like this:


The powder in it was not powder any longer. The grains were all stuck together. That was the result of the lid seal failing and letting humidity in. The acid fumes corroded the lid out. Rinse water put over it poured out yellow. At that point I cut the container open and buried the wet mass under the compost heap to let nature take its course.

Interestingly, the remaining 1/8 lb still at my father's place (also untouched)

http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/UnclenicksN140powder_zps3f235f13.jpg (http://smg.photobucket.com/user/SlamFire/media/Reloading/Old%20Gunpowder/UnclenicksN140powder_zps3f235f13.jpg.html)

Regardless of expectations that gunpowder and surplus ammunition will last forever, gunpowder does not get better with age, heat ages powder fast, and old gunpowder will blow up your firearm. There are irrational types out there, deniers, who don’t believe that ammunition deteriorates, that the pressure increases, and can blow up guns. You encounter deniers on all sorts of topics, such as those who don’t believe that single heat treat Springfield have brittle receivers. They will always create arguments that the blowups were due to “bore obstructions”, "over loads", anything but the most plausible cause: old deteriorated gunpowder. However anyone with a $100,000 dollar machine gun should seriously consider for themselves the risks of shooting cheap surplus military ammunition. Machine gunners shoot orders of magnitude more ammunition than most people, so as they are burning through a pallet of surplus ammunition, they are more likely to find that statistically improbable bad round. A machine gunner bud of mine told me he had “blown the top cover twice” with 50’s Yugo 8mm. After I told him about pressures and old ammunition, he said it all made sense. If however, that cheap surplus ammunition had wrecked the registered part of the machine gun, his machine gun would have been a total loss. The BATF is not your friend in this matter as the policy of the Federal Government is to reduce the number of machine guns in the hands of the public. You blow yours up, guess what, that is considered a good thing, and you have to find another to replace the one you destroyed.

[barnetmill]

I had something like the OP case to happen to me with 30-06 reloads based on WWII GI cases and 3031 powder. The powder was routinely stored up in my uncle's attic in Meeteetse, WY in about 1961 when I reloaded them. Reloaded rounds were stored for 6 yrs in the late 70's and early 80's in my brother;s attic somewhere else and about 1985 I was shooting them at a rifle range in Lafayette, LA. They were shooting very well in a 1917 Enfield and I noticed some smoke coming out of the breech. Foolish me I fired another one and had a partial case separation. I took out the round and noticed corrosion. I wanted to look at the powder and stuck the bullet of a loaded round in the muzzle to work the bullet loose. The case broke in half. What had happen apparently was that the nitrate (N03) had dissociated from the powder and attacked the brass case. Nitric acid dissolves copper. That brass had become extremely fragile. A lot of good lessons learn that day.

[tygar]

Since I have discovered dessicant, I have always put the small packs in any opened powder & larger packs in ammo cans.

Don't know how effective it is but havn't seen any problems.

[WallyM3]

Tygar, what dessicant do you use?

The last batch I got melted at the recommended regeneration temp.

[tygar]

I just use all the little packs I get in various items & change them about every year. No big plan, just thought it a good idea.

[WallyM3]

That's a pretty good plan, actually. Thanks.

[barnetmill]

Rice is a very good natural desiccant and is easily purchased as needed for very little.

[WallyM3]

(duh..oh!) Rice is one of the ingredients that I use in my brass tumblers.

[barnetmill]

(duh..oh!) Rice is one of the ingredients that I use in my brass tumblers.
Often used to keep salt from lumping during hot southern summers.

[nola jack]

Damn!

[desi23]

Smokeless powder certainly does deteriorate over time and storage conditions often play a large part in this. The quality and chemical makeup of the powder is also important. Certain types of powders seem to be more vulnerable to breakdown, single base extruded powders are the ones I have encountered the most. Historically, double base powders have a good record for durability, Hecules powder company manuals used to refer to test lots of their early powders that they had kept from the early 1900's that were still good. Ball powders were developed in the 1930's by Winchester/Western as a way to salvage deteriorated single base powder left over from WW I by re-blending it and adding nitroglycerin. It worked so well that they went on to develop more types of Ball powder.

Military forces have fairly strict standards for ammunition, largely because ammunition that fails to perform to the highest standard puts their troops and, indeed, the country at risk. Most dispose of ammo at a point where it I still quite useable, well before the projected lifetime of the loads. Some genuinely bad stuff does get out to the commercial market, victims of bad storage, overlooked old stock or was just questionable to start with. Deteriorating powder can corrode the bullet to the case neck, increasing bullet pull and sending pressures sky high. Inspecting ammo for case neck corrosion should be done with any old ammo you obtain, I routinely pull down a couple rounds to check with any lot of old stuff I pick up just to double check for internal corrosion. If it's bad I can still usually salvage the bullets for reloading.

Suplus ammo can be great, cheap shooting but like anything else there are risks. Inspect carefully before use, if in doubt tear it down and check further.

[SlamFire1]

I know Hercules has a canister of powder, that they have had under water, since 1900 or earlier. I have reviewed the Army Ordnance Magazine from the late 20’s to the 40’s and found articles on gunpowder stability. Exposure to water is bad for several reasons, one of which water dissolves chemicals out of the gunpowder gelatin. The paper I read showed micro cracks in the powder grain. Hercules did not conduct any lifetime tests outside of the water and I highly suspect that powder deterioration of their sample would accelerate once out of the water.

http://img.photobucket.com/albums/v479/SlamFire/Reloading/Old%20Gunpowder/1936ArmyOrdnanceBullseyelasting25years_zpsf46afb0c .jpg (http://smg.photobucket.com/user/SlamFire/media/Reloading/Old%20Gunpowder/1936ArmyOrdnanceBullseyelasting25years_zpsf46afb0c .jpg.html)

In 1936 Hercules was bragging about Bullseye lasting 25 years. It is obvious to me that if they were bragging about their double based powder lasting 25 years then the lifetime of powder was relatively short prior to WW2. Perhaps better controls in industrial processes have extended the shelf life of gunpowder, but in 1931, 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.”

A major consideration with old gunpowder is auto combustion. Misfire and malfunction rates are a real concern and I believe one criteria for flushing out ammunition out of inventory, but the greatest concern, because of the damage caused when an ammunition dump explodes, is auto combustion.

Ammunition Surveillance Procedures SB 742-1

https://acc.dau.mil/adl/en-US/238111/file/68728/SB%20742-1%20AIN47-13A.pdf

Chapter 13 Propellant and Propelling Charges

page 13-1

WARNING

Nitrocellulose-based propellant can become thermally unstable as the age. The normal aging process of the propellants involves deterioration of the nitrocellulose with an accompanying generation of heat. At some point, the propellant may reach a state where heat is generated faster than it can be dissipated. The accumulation of heat can lead to combustion (autoignition). Chemical stabilizers are added to propellants to slow the aging process. In time, the stabilizer levels will drop to a point where the remaining effective stabilizer (RES) is not sufficient to prevent an accelerating rate of decomposition. When this point is reached, the propellant may autoigniet, with possible catastrophic results to property and life. Monitoring the stability level of each propellant lot is essential for continued safe storage.

Page 13-5 , Table 13.2 Propellant Stability Codes.

Stability Category A 0.30 or more Percent Effective Stabilizer
Acceptable stabilizer loss: safe for continued storage

C 0.29-0.20 Percent Effective Stabilizer
Significant stabilizer loss. Lot does not represent an immediate hazard, but is approaching a potentially hazardous stability condition. Loss of stabilizer does adversely affect function in an uploaded configuration. Disposition instructions will be furnished by NAR. All stability category “C” assests on the installation must be reported in writing…
One year after becoming stability category “C” a sample of the bulk propellant lot or the bulk-packed component lot will be retested. If the lot has not deteriorated to category “D”, it will be retested each year until it has been expended, or it has deteriorated to category “D”, at which point it will be demilitarized within 60 days.

D Less than 0.20 Percent Effective Stabilizer
Unacceptable stabilizer loss. Lots identified as stability category “D” present a potential safety hazard and are unsafe for continued storage as bulk, bulk-packed components , or as separate loading propellant chargers. Bulk propellant, bulk –packed components and separate loading propelling charges will be demilitarized within 60 days after notification of category “D” status.

There were huge stockpiles of old ammunition in eastern Europe when Communism collapsed. There was no money to fund stockpile surveillance activities and within a couple of decades old ammo dumps started exploding.

Albanian Depot Explosion
http://www.youtube.com/watch?v=j8UK6b2y3kQ

http://www.youtube.com/watch?v=oYNZCwkKisc

[hendere]

I collect cartridges, mostly military. For what it's worth, I've torn down quite a few that were going bad. Sometimes quickly expanding holes with green slime coming out. But I don't think I've ever actually seen powder that looked bad. Maybe a few green flakes, but nothing that I would say was obviously not from the brass. I'm sure it's mostly always the powder deteriorating, but it just never looks bad. As far as hot and humid storage goes, it's very common to see German and Finnish stuff going bad. And I've had a fair amount of American stuff also. Powder just goes bad sometimes.....