Would opening thr powder to check introduce oxygen, making the problem worse. Or more often??
Opening the bottle will introduce new water molecules to the container, call it humidity. Not that new water molecules are good, and neither is rust or anything ionic. Ionic materials will break the double bonded nitrates. Water is polar covalent, so it acts ionic. Heat is bad, very bad, heat exponentially reduces the lifetime of gunpowder. It is best to keep the stuff room temperature. I think freezing the stuff has risks too, read stuff about chemical changes at low temperatures. I do think heat is a primary problem but so also is something you can't do anything about: the acids that were not removed when the gunpowder was being made.
Green corrision on the inside of loaded ammo
https://www.thehighroad.org/index.p...de-of-loaded-ammo.898092/page-2#post-12128069
@brickeyee
30 Nov 2021
Green is usually copper corrosion.
Bullet jackets (AKA 'gilding metal') are NOT the exact same materiel as brass cases. There is significantly more copper in the bullet jackets. The slightest moisture (or other corrosive material) will create a primitive battery with tiny amounts of current flowing between the different alloys.
The acids used to make nitrocellulose (nitric and sulfuric) are never completely removed.The tiny amounts remaining are one of the things that determines the lifetime of the nitrocellulose. Wartime production often is left 'dirtier' than ammunition intended for long term storage. Why waste expensive solvents when the stuff is very likely to be consumed within a shorter period.
Long term storage of nitrocellulose powder is done under water. Radford Army Ammunition Plant was a primary nitrocellulose facility built in the 1940s to support the war effort. Way back in the early 1980s you could still see the outlines of the wooden buildings used for long term storage of nitrocellulose. Each was a lightly built 'log cabin' style of constriction with a basement 'swimming pool' to hold water. The partially completed powder was placed in the basement room, and then submerged in water.*
It was dangerous work..
Occasional explosions occurred all the way into the early 1988s from reprocessing. The old stuff was around 25% nitrocellulose.It was reprocessed to far higher level (closer to the mid 90%) to make solid rocket motors. Ejection seats used those rocket motors. As an EE I had a few contract jobs to try and measure, and minimize, the explosion hazard. A 'cake' of 90+% nitrocellulose was about 16 inches in diameter and 8 inches thick. I do not remember the exact weight, but it was pushing near 100 pounds. We developed some measurement techniques that allowed for easier monitoring of the purity and relative danger.
There was not a lot left of the truck or driver when one went off accidentally during transport from one part of the factory to another You could hear the occasional boom in Blacksburg at Virginia Tech, a couple mountain ridges away. Is sounded like remote thunder. My pager would go off a few minutes later. Time to go and figure out what the H happened.
my comment on *. Storage of old gunpowder in water is done to dissolve the NOx coming out of the powder and to keep it cool so I won't autocombust prior to demilling or repurposing.
This might be of interest, nitrocellulose was a very early plastic. Used on lots of things, gunpowder is more highly nitrated than commercial nitrocellulose, but they all have the same problem: unpredictable shelf lives.
This might show some of the issues:
The Use of Cellulose Nitrate in Art Conservation
Dr. Charles Selwitz Getty Museum
https://www.getty.edu/conservation/publications_resources/pdf_publications/pdf/nitrate.pdf
Cellulose nitrate is the polynitrate ester of the natural polysaccharide, cellulose, and for a polymer averaging 2.3 nitrate groups per glucose unit has the structure shown in Figure 1. The molecular weight for most commercial products ranges between 20,000 and 250,000. This semi synthetic polymer was first produced more than 150 years ago and is the most important and only commercially available inorganic ester of cellulose. Due to its unique physical properties and low cost it has been an important factor in many advances in the industrial arts and sciences over the years. Cellulose nitrate was initially used in the manufacture of military explosives where it came to be known as "gun cotton," the first major development in explosives since the introduction of black powder. When it was discovered that cellulose nitrate could be stabilized with camphor (in the ratio of 4:1), the resultant product, celluloid, inaugurated the advent of engineering plastics
In the years following World War I, cellulose nitrate lacquers and coatings were developed. While these have since been superseded by better materials, the largest industrial use today of cellulose nitrate (now also referred to as nitrocellulose) continues to be in its capacity as a lacquer, although substantial quantities are still used in explosives and propellants, printing inks, and plastics. Currently, the total commercial production of cellulose nitrate in the United States approaches 100 million pounds a year
in terms of stability, however, cellulose nitrate is a very suspect material. It does not have the resistance to degradation possessed by most other polymers used in conservation. Only when stability is defined as "the maintenance of solubility and reversibility" can cellulose nitrate, which degrades, but generally does not crosslink, be said to have stability
Chapter 3 Causes of Instability
Most of the literature on cellulose nitrate instability describes three primary modes of decomposition: hydrolytic, thermal, and photochemical. These modes are examined in this paper with concern for rates and mechanisms most likely to prevail under ambient conditions. Recent research can be interpreted to show that these three modes can be redefined into more fundamental mechanisms for primary decomposition, a finding that may provide additional insight into the properties of the polymer as well as the optimum conditions for its use. Primary decomposition processes slowly lead to breakdown products. If these are not swept away they can lead, catalytically, to a faster and more extensive degradation than that caused by the primary processes that engender them. Conclusions on the chemistry of decomposition caused by these breakdown products, i.e., secondary processes, are integrated with our analyses of the primary modes in the next section-a discussion on the overall stability of cellulose nitrate at ambient conditions.
Hydrolytic Decomposition via Acid Catalyzed Ester Cleavage
The earliest manufacturing processes of cellulose nitrate in the 19th century were concerned almost totally with the production of explosives. After a number of disastrous detonations took place, the search for their causes revealed in 1865 that the retention of small amounts of sulfuric acid from the nitrating mixture was responsible for the instability (Worden 1921:1604 et seq.), and, further, that this instability was roughly proportional to the amount of sulfuric acid left in the polymer (Wiggam 1931:536). It was also recognized that sulfate esters of partially nitrated cellulose were also formed (Hake 1909:457). In no case did the nitration of cellulose with mixed acid ever proceed to a completely nitrated product, i.e., to a D.S. of 3.0 and nitrogen content of 14.1%. The best that could be achieved was a product with 13.8% nitrogen in which only 29 out of 30 hydroxyl groups bore nitrate functionality because the 30th was converted to a sulfate ester. In cases where exhaustive nitration was done without using sulfuric acid, e.g., with nitrogen oxides (Bouchonnet et al. 1938:308) or with nitric acid and phosphorus pentoxide (Lenz et al. 1931:4) or acetic anhydride, a completely nitrated product 15 Instability with 14.1% nitrogen was obtained. These products were invariably of better stability than high nitrate product made with mixed acid (Barsha 1954:724-30).
How to Spot and Handle Dangerous Nitrate Film: Protecting Your Life and Legacy
https://everpresent.com/cellulose-nitrate-film/
The stories are true – the oldest film can burst into flames under the right conditions. Nitrate film sparked the 1937 Fox vault fire and fueled the MGM vault blaze of 1967. These fires were fatal, destructive, and erased huge chunks of U.S. film history in the process.
Although nitrate film was discontinued in the 1950s, it could destroy your whole family legacy if it’s left in your collection. This old film is an extreme fire hazard and gives off harmful gas that can damage other home movies and photos. We’re sharing this post to help you identify nitrate film in your archive and explain the best course of action if you find any.
How Dangerous is Nitrate Film?
Nitrate film is made from cellulose nitrate, a chemical used for military-grade explosives in the late 19th century. It’s so flammable that it even burns underwater, and improper storage makes the fire risk even worse.
Cellulose nitrate releases toxic gas that quickly eats away at any film stored without proper ventilation. Decayed nitrate film is even more volatile, and can self-ignite at temperatures over 100 degrees Fahrenheit. Even if the film doesn’t catch fire, its rapid decay can ruin the images it stores.
The bottom line is, periodically inspect your powders by sight and smell. It is unfortunate the average reloader cannot afford the $250,000 gas chromatography machines used by Government ammunition specialists to determine percentage of stablizer left in the gunpowder. The military standard is to get the stuff out of inventory when 20% of the stabilizer is left. The assumption is, 20% stabilizer gives the Government five years to dispose and demill before it catches on fire! When we smell bitter gases and see red fumes, there is almost no stabilizer left in the gunpowder and the stuff ain't fit for no purpose except burning your house down and blowing up your firearm.
Gunpowders are not nice and predictable as bamboo. When bamboo flowers in America, the same strand of bamboo in Asia also flowers. And when the bamboo in the USA dies, so does the same strand everywhere. Gunpowder lifetime is so variable that all first world countries pay people to go through their munition inventories, inspect and cull out the stuff that is going bad. Second and third world militaries were so broke they just let the stuff go bad, and many Munitions Depots went kaboom decades after Communism collapsed. I remember reading of the hundreds of millions of dollars the US and Western European countries spent cleaning up old Communist Ammunition Depots.
There are reasons the shooting community does not know about this, and one is the vocal deniers who have chased this information out of the shooting community. I think it is all based on human biases. People want control, want predictability, want invulnerability, want invincibility. Some so strongly that they also think they are immortal. Given that they are going to live forever, it only makes sense that their stash of ammunition and gunpowder also has to last forever. And they get angry if their immortality delusion is pricked. After all, if their ammunition is not immortal, then maybe perhaps, neither are they! In essence, popping their immortality delusion is an act of murder! Grrrr......
Another reason is, Industry has absolutely no reason to educate shooters on anything that might cause them not to spend money. Knowledgeable reloaders might demand best buy dates, (UNREASONABLE!) and be picky about paying top price on old ammunition and gunpowder. (HORRORS!) It is not their business to educate you, their business is to get you to buy, buy, buy. Don't worry, be happy!
Hope that's the last time you see it.
