Gun Powder "substitutes"

[user 13289]

Bill Knight, often posting as "Mad Monk" is the man to whom I refer. He shared with me many of his writings and he might share them with any of you. Most folks won't hear what they don't want to hear, but I respect Bill's work and have enough real experience to accept it. Here's an except from one of his papers. Very few men understand powder better than Bill.

Hodgdon’s Triple Seven evolved out of Pyrodex after the 20 year patent on Pyrodex had
expired. Changes in the market also dictated that a replacement for Pyrodex was necessary to
retain sales volumes. Pyrodex will be addressed first.

Basic ingredients.
Sodium benzoate
Charcoal
Potassium nitrate
Potassium perchlorate
Sulfur
Dicyanamide

The basic concept in this is the use of potassium nitrate and sodium benzoate. As such
the combination would burn as a gas generating composition rather than fast enough for use as a low pressure propellant powder. The “reactivity” of the sodium benzoate alone is not suited to a fast burning propellant powder. The addition of a small amount of sulfur will act to speed up the burning of the potassium nitrate and sodium benzoate. But still not fast enough for use as a propellant powder. So the addition of potassium perchlorate, in place of a portion of potassium nitrate, acts to speed up the burn rate to a point where it will be acceptable as a propellant powder in a gun that would otherwise be loaded with black powder. The inclusion of potassium nitrate, charcoal and sulfur forms the basis for the claim that it is a modified black powder.

This composition does violate an old rule of thumb dated back to the chlorate/perchlorate
cartridge primers that replaced those primed with fulminate of mercury. That rule of thumb
being that one never combines a chlorate, or perchlorate, with elemental sulfur. Sulfur particles will form a one molecule thick coating of the oxide of sulfur on the surfaces of the particles.When combined with traces of moisture the resulting acid acts to attack the potassium chlorate or perchlorate. This sets up what is commonly called as self-accelerating decomposition reaction. Primers thus made have a limited shelf life. As this self-accelerating decomposition reaction proceeds the primer strength weakens. The primers then become erratic in their action. Eventually they simply go dead...

 

[user 13289]

Bill sent me a dozen or more PDF papers on various formulations and companies. I'll share in PM or email all or any.

Here's the pertinent part on cyanide according to Bill Knight:


The formulation includes a cyanide based chemical compound known as Dicyanamide.
This sees industrial use in the chemical industry. Used to “passivate” the surface of various
ferrous metals. In glass lined reaction vessels with bits of glass lining chipped away a
dicyanamide and water solution “flush” will help to protect the bare metal areas from forming
polymer build up deposits.

If the Pyrodex did not incorporate this dicyanamide into the mixture of ingredients a
charge resting in the breech of the gun would pit corrode the bore. In brass cartridge it would
simply leach copper from the brass making the cartridge cases brittle and then create holes in the cases.

Hodgdon will tell shooters that their Pyrodex contains an anti-rust additive. Left out of
their claim is the fact that during actual powder combustion this dicyanamide is heat
decomposed. Giving off cyanide gas. In effect. The powder does in fact contain an anti-rust
additive/agent but it is broken down/destroyed during powder combustion so there is nothing in
the post combustion bore residue to prevent electrolytic corrosion by the minute crystals of
potassium chloride scattered over the surfaces of the bore. During powder combustion the
particles of potassium perchlorate simply give up their oxygen to become potassium chloride.
Pyrodex residue, in the bore, is highly corrosive and noted for rapid micro-pitting of the surfaces of the bore. This becomes critical if used in brass cartridges. As soon as the fired cartridge cases are removed from the gun they should be placed in a jug of water to prevent rapid pitting and copper leaching in the fired cases.

Pyrodex should not be fired in any confined shooting area with poor ventilation. This
would be mainly indoor shooting ranges. But should also include outdoor covered ranges with
low roofs and little air movement.

 

[Okie Hog]

Yep, i know who the man is and i'm not disparaging him. He has more experience in the manufacturing of black powder than any other person on the planet. But the man stated that Triple Seven does not contain potassium perchlorate, that is not so. Potassium perchlorate as used in black powder substitutes don't cause serious corrosion.

http://ns.hodgdon.com/PDF/MSDS Files/Muzzleloading/Triple Seven SDS Sheet-2013.pdf

i question his statements about cyanide. i don't think he has extensive experience in the development of black powder substitutes.

 

[user 13289]

I sent Bill a note in case he cares to, or is able to contribute here. I think he had some health issues when we last spoke.

 

[user 13289]

Yep, i know who the man is and i'm not disparaging him. He has more experience in the manufacturing of black powder than any other person on the planet. But the man stated that Triple Seven does not contain potassium perchlorate, that is not so. Potassium perchlorate as used in black powder substitutes don't cause serious corrosion.

http://ns.hodgdon.com/PDF/MSDS Files/Muzzleloading/Triple Seven SDS Sheet-2013.pdf

i question his statements about cyanide. i don't think he has extensive experience in the development of black powder substitutes.

Yes, T7 is a different formulation and is not in any of what I quoted but is also in that PDF. I'll send you a copy if you like. I am only speaking about Pyrodex. T7 is not the same, Bill well knows that.

 

[Okie Hog]

T7 is not the same, Bill well knows that.

If Bill well knows that then why did he state on a forum that Triple Seven does not contain potassium perchlorate?

i don't need the PDF.

 

[Carbon 6]

If you have a pdf copy of black mz MSDS i'll take it. MSDS not SDS. SDS sheets are useless.

The MSDS for Dicyandiamde does list cyanide gas as a product of decomposition. However, it doesn't define decomposition as combustion. So it's "gray" but probable.

The part I don't yet understand is this;

If the Pyrodex did not incorporate this dicyanamide into the mixture of ingredients a
charge resting in the breech of the gun would pit corrode the bore. In brass cartridge it would
simply leach copper from the brass making the cartridge cases brittle and then create holes in the cases.

 

[Frontier's]

I'll believe there's cyanide when I see the first report of someone dying from the pyrodex smoke

 

[Zonie]

IMO, this cyanide scare tactic is just that. A scare tactic.
It is the same sort of displaced fear that caused people to over-react and cause Kasnit to become unavailable to the general public. (Kasenit contains cyanide in a harmless form.)

There are a lot of things that can be deadly if they are in one form and totally harmless when they are in another form or compound.
Chlorine for instance, can be deadly in one form but when it combines with sodium to form salt (NaCl), it is essential for human life.

 

[Dphar1950]

There is no cyanide in Pyrodex. If there was, it would have to be listed in the Material Data Safety Sheet.
The information below is a copy of the Hodgdon Pyrodex MSDS

"...
Section II. HAZARDOUS INGREDIENTS/IDENTITY INFORMATION
Hazardous Components
(Chemical Identity: Common Name(s) OSHA PEL ACGIH TLV Other Limits %(optional)
Charcoal NA NA NA
Sulfur NA NA NA
Potassium Nitrate NA NA NA
Potassium Perchlorate NA NA NA
Graphite NA 2.5 mg/m3 Respirable Dust
Other: Other ingredients are trade secrets, but can be disclosed per 29 CFR 1910.1200(i)
Section III. PHYSICAL/CHEMICAL CHARACTERISTICS
Boiling Point Not Applicable Specific Gravity (H2O =1): Bulk density is 0.75 (g/cc)
Vapor Pressure (mm HG): Not Applicable Melting Point: Not Applicable
Vapor Density (AIR = 1) Not Applicable Evaporation Rate: Not Applicable
Solubility in Water: Partially (Butyl Acetate = 1)
Appearance and Odor: Medium to dark pray granular solid. Slight odor when ignited.
Section IV. FIRE AND EXPLOSION HAZARD DATA
Auto-ignition Temperature: 740 (F) (Pellets: 500[f]) Flammable Limits: N/A LEL: N/A UEL: N/A
Extinguishing Media: For unattended fire prevention, water can be used to disburse burning Pyrodex. Pyrodex has its own oxygen supply, so flame
smothering techniques are ineffective. Water may be used on unburnt Pyrodex to retard further spread of fire.
Special Fire Fighting Procedures: Pyrodex is extremely flammable and may deflagrate. Get away and evacuate the area.
Unusual Fire and Explosion Hazards: As with any pyrotechnic, if under confinement or piled in moderate quantities, Pyrodex can explode
violently, toxic fumes such as sulfur dioxide are emitted while burning.
Section V. REACTIVITY DATA
Stability Unstable: Conditions to Avoid: Avoid storage at temperatures above 150[F],
Stable: X impact, hot embers, sparks and static discharges.
Page 1 of 3
file://C:\DOCUME~1\reeder\LOCALS~1\Temp\triGEHML.htm 7/8/2002
Incompatibility (Materials to Avoid) Metal powders and acids
Hazardous Decomposition or Byproducts: CO, CO2, SO2, non-metallic oxides, and suspended particulate matter from burning.
Hazardous May Occur: Conditions to Avoid: Not known to occur.
Polymerization: Will Not Occur: X
Section VI. HEALTH HAZARD DATA
Route(s) of Entry: Inhalation?: Yes Skin?: Yes Ingestion?: Yes
Health Hazards (acute and Chronic): TLV unknown for ingestion of dust, Acute oral LD50 in rats is calculated to be 4.0 [g/kg body weight].
Carcinogenicity: No NTP? No IARC? No OSHA regulated?: No
Signs and Symptoms of Exposure: Burning or itching of the eye, nose, or skin; shortness of breath.
Medical Conditions Generally Aggravated by Exposure: Some people may be unusually sensitive to the product.
Emergency and First Aid Procedures: Remove patient from exposure, and if skin contact, wash affected area with copious amounts of water.
Section VII. PRECAUTIONS FOR SAFE HANDLING AND USE
Steps to Be Taken in Case Material is Released of Spilled: Do not smoke in the area. Powder should be scooped or swept up using non-sparking,
conductive tools. This should be done in a manner so that no dusting occurs.
Waste Disposal Method: Wet thoroughly with water to dissolve the powder. Comply with all federal, state, and local laws.
Precautions to Be Taken in Handling and Storing: Pyrodex is a solid propellant which is designed to propell a mass. Thus appropriate care should
be taken to avoid heavy confinement and ignition sources such as, but not limited to, heat, static discharge, embers, friction, and impact. ..."

For the curious, here is what the two oxidizers used in Pyrodex consist of:

Potassium perchlorate consists of potassium, chlorine and oxygen.
Potassium nitrage consists of potassium, nitrogen and oxygen.

According the Bill Knight the chemical reaction of burning Pyrodex produces low levels of cyanide. I believe Bill. And remember there are things in the stuff that they don't list and I don't think anyone actually tests it to see if the MSDS is actually accurate.

 

[Dphar1950]

None of the "replica powders" are "new". All of them, in some form, were tried in the 19th c trying to get a non-fouling propellant. But some, like the sugar powders, tend to suck up water like a sponge. I.E. Some of the recent iterations would actually liquify if exposed to the air long enough. So far as I know none of them give low velocity spreads like BP will. BP is still the best choice. But since the gov't does not like its low ignition temp they list is as a class A explosive.

 

[Carbon 6]

According the Bill Knight the chemical reaction of burning Pyrodex produces low levels of cyanide. I believe Bill. And remember there are things in the stuff that they don't list and I don't think anyone actually tests it to see if the MSDS is actually accurate.

Combustion produces large volumes of C0 and Co2, ain't seen no one die from those yet.

 

[Frontier's]

IMO its just scare tactics to scare someone away from using pyrodex and stick to the real thing. How long ago were these articles written anyway?

 

[Griz44Mag]

My information comes from a man who was a chemist involved with multiple black powder manufacturing companies-and in the development of many various formulations for substitutes. He has written extensively on the subject.

Name please? Published document? Hazmat warnings?

 

[Carbon 6]

Anyone can write an article, on any subject without expertise. Most "articles" are written that way, written by Writers.

 

[Erwan]

Please excuse my facetious humor.

You're all excused, you couldn't have known...
At the moment, we are more or less ticklish on these subjects and by writing/reading, it is not always easy to grasp the joke.

 

[Walkingeagle]

There are a lot of things that can be deadly if they are in one form and totally harmless when they are in another form or compound.

I do believe that pure nitrogen is deadly when breathed, as is pure oxygen. When mixed they form a compound, that too when breathed is responsible for the deaths of thousands worldwide each year, yet without it life cannot exist as we know it.
Walk

 

[SDSmlf]

The primary ingredient in many of best known black powder solvents, cleaners and patch lubes is Dihydrogen Monoxide. This stuff is found in acid rain, in it’s gaseous state can severely burn exposed skin and it is typically found in cancerous tumors. Yet we continue to use it........

It is how you present or spin the facts, like when you are selling snake oil or maybe engaged in a political debate.

 

[Zonie]

According the Bill Knight the chemical reaction of burning Pyrodex produces low levels of cyanide. I believe Bill. And remember there are things in the stuff that they don't list and I don't think anyone actually tests it to see if the MSDS is actually accurate.

If burning Pyrodex created any form of cyanide in a form that was harmful or deadly, Hodgdon would have had to report it in the MSDS.
Failure to do that would result in the Federal Government imposing severe penalties on Hodgdon and prohibit them from making or selling Pyrodex in any form.

 

[Okie Hog]

Used Pyrodex for many years, still use the stuff for target shooting. It's a very good and consistent powder. One of my guns has fired over 3,500 rounds using Pyrodex. The still bore looks new.

"Doc" White of White rifles fame likes Pyrodex too:

http://whitemuzzleloading.com/black-powder-its-substitutes/

The patent:

https://patents.google.com/patent/US4128443A/en