FIREARM PROPELLANTS

Propellant (fills the interior of a cartridge casing for the expulsion of a bullet) materials are the evolutionary product of a basic tenet in weapon technology: energy must be stored for later use. The concept of a propellant is that energy can be stored in chemical form, possibly years before it is ultimately released. This demands a material that is reasonably stable, compact, and portable. There are a number of materials that can store chemical energy and convert it to heat and gas for propulsive purposes. Most early experiments focused on blends of charcoal, sulfur, and an oxidizing agent. One of the most abundant, naturally occurring oxidizers is potassium nitrate (KNO3), known to the ancients as saltpetre, nitre, and petral stone. Early propellants were used for entertainment and religious rites (fireworks), fire starting, and moving material (blasting) for a long time before the concept of a fixed, chemical-filled tube launching a projectile was conceived. Black Powder The term black powder first appeared only in about 1890. Before this time it was called gun powder or simply powder. The change of its name became necessary to distinguish it from the recently invented white powder, as nitrocellulose powder was called at first. It should be noted that gun powder actually was dark-gray to dark cafe-brown and not black. The deeply black color of todays black powder is caused by the graphite coating, used to improve its flow properties and damp resistance. In American English, the term gunpowder also refers broadly to any gun propellant. A mixture of potassium nitrate and charcoal, if confined into an enclosed space will explode violently if heated up to 400 degree centigrade. By adding sulphur to this mixture, the ignition temperature is reduced significantly. The mixture containing sulphur develops white smoke versus the sulfurless powder which burns nearly smokeless. The exact date and place of the invention of black powder, the first propellant, is unknown. It is possible that the development occurred independently at multiple locations over a period of two- to three-hundred-year time period. It is probable that, given the similarity of formulations, gunpowder was invented in a single location and the technology was exported and spread by early explorers and traders. The key ingredient is saltpeter (KNO3); the burning of any organic substance is accelerated by adding saltpeter. Ignition of the powder packed behind a bullet in a case must generate enough pressure to force it from the case to the muzzle at high speed, but not enough to rupture the gun barrel. Gunpowder is classified as a low explosive because of its relatively slow decomposition rate and consequently low brisance (the shattering capability of an explosive). Low explosives deflagrate at subsonic speeds, whereas high explosives detonate, producing a supersonic wave. Gunpowder is thus less suitable for shattering rock or fortifications. Gunpowder was widely used in small arms, to fill artillery shells and

in mining and civil engineering to blast rock roughly until the 2nd half of the 19th century, when the first high explosives (nitro-explosives) were discovered. Gunpowder is no longer used in modern explosive military warheads, nor is it used as main explosive in mining operations due to its cost relative to that of newer alternatives like ANFO [for ammonium nitrate/fuel oil; it is a widely used bulk industrial explosive mixture; it consists of 94% porous prilled ammonium nitrate (NH4NO3), that acts as the oxidizing agent and absorbent for the fuel and 6% Number 2 Fuel Oil, compositions that do not meet the 94% AN/6% FO formulation are not ANFOs]. Constituents The pervasive formula for early propellants was a simple mechanical mixture of charcoal, sulfur, and potassium nitrate. This technology did not arise in Europe until the thirteenth century A.D., although it is likely that the Chinese had launched projectiles with black powder two hundred to three hundred years earlier. Most old formulas called for charcoal made from the wood of certain tree species (Willow wood was highly prized as a source of charcoal). The quality of the charcoal affected many aspects of propellants, including ease of mixture, power, and cleanliness. Varying the ratio of the three components produced different black powders for different purposes. For example, the formula for blasting has traditionally differed from that for propellant use. Propellant-grade black powder is seventy-five parts potassium nitrate (KNO3), fifteen parts charcoal, and ten parts sulfur. Manufacturing Process Black powder makers relied on fine grinding of the components to ensure that they were mixed thoroughly. However, military use of propellant-grade black powder gave rise to a serious problem; dry components could separate during transport over rough roads. This caused a degradation of the propellants power. A short-term cure was to transport the components separately to the battlefield and mix them just before loading. The hazards of a propellant blending operation close to an active line of cannon are easily imagined. The solution for the separation of the components of this mechanical mixture proved to be the only significant improvement to black powder in its long history. Small amounts of water were added during the milling and grinding operations. Potassium nitrate is soluble in water; adding a small amount of water causes it to become slightly sticky. Then the potassium nitrate can act as a binder to hold the two insoluble components in close contact. The presence of moisture also reduces dust. This largely mitigates the major hazard of blending and grinding as long as an adequate moisture level is maintained. This wetting process is called corning, and the resulting product was called corned powder. The corned powder is pressed into cakes and allowed to dry. After drying, the cake is broken into granules. All granules contain uniform proportions of the components and maintain those proportions until consumed. Corned powders proved to be much more powerful than the dry mixture, largely due to the incorporation of ingredients. Some cannon that were suitable for the weaker dry-blended powders proved inadequate for corned powder. The improvement in propellant forced an

improvement in gun metallurgy. The granulation process serves another useful purpose; some control of the rate of energy release is afforded by sizing the granules. The granulated pieces are passed through sieves to sort them by size. Larger granules release energy at a slower rate than fine granules. This characteristic means the user can select from several grades to obtain the best velocity from a black powder firearm. Large-bore devices, such as cannon, use coarse granules (up to several millimeters average size). Small-bore devices, such as shoulder arms, use much finer material. Some have suggested that black powder propels a projectile by a weak but high-order detonation, unlike modern propellants that burn to push the bullet out of the barrel with a progressive increase in pressure. A research where black powder was loaded in a cartridge [.45-.70 government cartridge with a 500-grain (32.4 gram) bullet] and then test fired in a modern piezoelectric ballistic pressure system. The research showed the following: 1. Black powder produces time-pressure curves that are remarkably similar to modern propellants, indicating progressive burning and a measured release of energy over time. 2. Black powder in finer granulations produced higher pressures than equal quantities of coarser black powder, indicating the burning rate is controllable by granulation. 3. Black powder peak pressures were as high as 21,000 psi, and roughly equal to modern factory ammunition for this cartridge. Disadvantages With the improvements of corning and grading, black powder remained largely unchanged until military and sporting arms transitioned to modern propellants at the beginning of the twentieth century. Today, black powder is still a useful propellant for specialized purposes. For example, black powder is somewhat easier to ignite than modern propellants; it is commonly used as a booster charge in large-caliber military applications. In spite of the ability of black powder to allow the use of lethal force at a distance, it was not without problems. 1. Black powder has a limited amount of total energy per unit of volume. To gain greater velocity, a larger volume of propellant must be used, necessitating a larger cartridge case. With the trend to repeating firearms, large cartridges common to single-shot black powder firearms could not be accommodated. 2. In cartridge firearms, velocities seldom exceed 1400 ft/sec. (426 m/sec). This again is a limitation of energy content and cartridge size. 3. Black powder is volumetrically inefficient. Depending on the grade, granulation, and loading density, gas production is only 45 to 55 percent of the total output. The remaining inert solids, largely dense smoke and fouling, contribute nothing to propulsion. 4. Black powder produces a dense smoke cloud. As military tactics shifted from massed troops to individual riflemen, a smoke puff helped the enemy to spot the shooters position.

5. Black powder residue is corrosive to steel. Several by-products of black powder combustion are hygroscopic, releasing corrosive compounds when hydrolyzed. This accelerates wear to the firearm. Modern Propellants To avoid the shortcomings of black powder, researchers had to consider propellant chemicals that incorporated oxidizers rather than inorganic materials that contribute corrosive by-products. Eliminating sulfur from the material was important for the same reason. The quest for reduced smoke meant that higher combustion temperatures would be required. Most importantly, the new propellant had to be controllable and reproducible to be safe. 1. Nitrocellulose (Guncotton) In 1845, a substance was invented that showed promise. Nitrocellulose was the result of treating common cotton fibers (containing cellulose) with nitric acid. This reaction adds nitrogen and oxygen to cellulose molecules. The nitration process is performed in the presence of sulfuric acid to scavenge extra-water generated by the reaction and allows the attachment of the maximum number of nitrate radicals to permit better combustion. When burned, the added oxygen in the nitrate radicals allows full involvement of the fuels in cotton, releasing significantly more energy than untreated cellulose. This produces a large volume of gas and leaves minimal visible solid by-products. In contrast, black powder would produce smoke and fouling. Although this development gave chemists the selfcontained oxidizer and minimal residue, guncotton could not be predictably controlled in its native state. Its combustion could prove too violent for iron gun systems of that period; numerous accidents were attributed to the attempts to manufacture it for propellant use. The solubility of guncotton in a mixture of alcohol and ether was discovered a year after nitrocellulose was developed. Dissolved nitrocellulose (celluloid) is the initial critical step in the development of smokeless propellant. 2. Plasticizer French military commanders had been complaining for some time about the problems of giving orders on a battlefield that was swathed in thick smoke from the gunpowder used by the guns. In 1880, Paul Marie Eugne Vieille (2 September 1854 14 January 1934), a French chemist working for the French government, undertook to solve the problem of harnessing the powerful but unstable substance nitrocellulose as a propellant charge to replace black powder by experimenting with the alcohol/ether solubility of nitrocellulose. By 1884 Vieille invented modern nitrocellulose-based smokeless gunpowder called Poudre V. Made from gelatinized nitrocellulose mixed with ether and alcohol; it was passed through rollers to form flexible thin sheets, which were cut with a guillotine to flakes of the desired size. The residual alcohol/ether mixture acted as a plasticizer that helped prevent the granules from shattering. These small flakes burned inward from the surface. This property meant

that the volume of gas produced decreased as the burning granules became smaller, which is a useful characteristic in propellants. Changing the dimensions of the granules resulted in different rates of energy release. Vielles discovery opened the door to modern propellants. His work was so effective that cut-sheet propellants are in limited use today. A major disadvantage of Vielles method was dehydration. If the alcohol/ether plasticizer evaporates in storage, the rate of energy release increases. Dry granules could also break into smaller pieces, increasing surface area and thus the release rate. The French Army was the first to use Poudre V but it was not long before other European countries followed their example. It revolutionized the effectiveness of small guns and rifles. Firstly because practically no smoke and left virtually no residues of combustion was formed when firearms were fired and secondly because it was three times more powerful than gun powder for the same weight, giving an accurate rifle range of up to 1000 yards. 3. Nitroglycerin The discovery of dynamite in 1887 by Alfred Nobel allowed nitroglycerin to be used as a high explosive. He found that he could blend nitroglycerin with less-nitrated nitrocellulose to form a colloidal mass similar to that used to make Vielles nitrocellulose. Nitroglycerin served as the plasticizer and added significant energy to the mix. When well mixed with nitrocellulose, the usually unforgiving nitroglycerin was stable, allowing the formation of clean-burning grains without the use of any additional solvents. Smokeless powders Smokeless powders are a class of propellants that were developed in the late 19th century to replace black powder. The term smokeless refers to the minimal residue left in the gun barrel following the use of smokeless powder. In forensic analysis, smokeless powders are often encountered as organic gunshot residue or as the explosive charge in improvised explosive devices. All smokeless powders can be placed into one of three different classes according to the chemical composition of their primary energetic ingredients. A single-base powder contains nitrocellulose, whereas a double-base powder contains nitrocellulose and nitroglycerine. The energetic ingredients in triple-base powders are nitrocellulose, nitroglycerine, and nitroguanidine, but because triple-base powders are primarily used in large caliber munitions, they are difficult to obtain on the open market. Cordite In a race to develop a smokeless powder, the British government commissioned a research group. Their solution was to mix acetone, nitrocellulose, nitroglycerin, and petroleum jelly to form a colloid. After evaporating the acetone solvent, the material could be extruded into long, cylindrical cords. In 1889, the resulting end product was named Cordite. Vielles smokeless propellant, with nitrocellulose as the sole storehouse of energy, became known as single-base propellant. Nobels

invention (which he named Ballistite) and the British Cordite, with their dual energy sources, became known as double-base propellants. Both singlebase and double-base types are still in use today. Smokeless propellants still retain the base ingredients used in the 1880s. However, knowledge of granule control, deterrent coatings, and safe processing has produced ammunition suitable for a wide range of uses from the smallest rimfire cartridges to massive naval guns. Cordite is now obsolete, and it is no longer produced. Production ceased in the United Kingdom, around the end of the 20th century, with the closure of the last of the World War II cordite factories, ROF Bishopton. It has been replaced by other propellants, such as the DuPonts Improved Military Rifle (IMR) line of extruded powder or the Olins WC844 ball propellant currently in use in the 5.5645mm NATO. The smell of cordite is frequently referenced (erroneously) in fiction to indicate the recent firing of weapons. Cordite largely consisted of nitrocellulose (gun cotton), dissolved in acetone. It was acetone that gave cordite its characteristic, sweet smell. Cordite, like nail polish is typically made of nitrocellulose dissolved in an acetone-based solvent. Acetone is also found in nail polish remover and superglue. In other respects, cordite would smell similar to other explosives such as dynamite, which are also based on nitrogen compounds. When cordite is ignited, it releases nitrogen oxides (nitric oxide and nitrogen dioxide). These have a sharp, pungent odor, similar to bleach. Cordite MD, used in ammunition in both the First and Second World Wars, contained 65% gun cotton, 30% nitroglycerin and 5% petroleum jelly. A solvent-free form of Cordite, Cordite SC, was used in the Second World War. However, this was not used in ammunition for .303 rifles (by far the most common weapon used by soldiers). Cordite SC was mainly used for naval ammunition. Composition The major classes of compounds in smokeless propellants include energetics, stabilizers, plasticizers, flash suppressants, deterrents, opacifiers, and dyes. A particular propellant powder will contain one or more of these additives depending on its use. 1. Energetics are the explosive ingredients, facilitates the explosion. The base charge is nitrocellulose, a polymer that gives body to the powder and allows extrudability. The addition of nitroglycerine softens the propellant, raises the energy content, and reduces hygroscopicity. Adding nitroguanidine reduces flame temperature, embrittles the mixture at high concentration, and improves energy-flame temperature relationship. 2. Stabilizers prevent or slow down self-decomposition of nitrocellulose and nitroglycerine by neutralizing nitric and nitrous acids that are produced during decomposition. If the acids are not neutralized, they can catalyze further decomposition. Stabilizers are preservatives used to increase storage life of the energetics; some of the more common stabilizers used are diphenylamine, the centralites (methyl centralite and ethyl centralite) and resorcinol. Diphenylamine (DPA) is the most common stabilizer used in smokeless powders, especially in single base powders. In smokeless powders the diphenylamine content is usually about

1%. In addition to DPA, the main reaction products of nitric oxide (NO2) with DPA, 2nitrodiphenylamine, 4-nitrodiphenylamine, and N-nitrosodiphenylamine have also been reported to be frequently encountered. Another group of stabilizers used in smokeless powders are the centralites. The most common is ethyl centralite and is usually found in double base powders. 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 in storage and should be periodically tested for the amount of stabilizer remaining, as its depletion may lead to auto-ignition of the propellant. 3. Plasticizers are mixed with the powder components in the process of making powder grains to reduce the need for volatile solvents necessary to colloid nitrocellulose, to provide enhanced strength , and elasticity (flexibility) to the grains (soften the propellant), and reduce hygroscopicity. Examples of plasticizers include nitroglycerine, dimethyl phthalate, diethyl phthalate, and dibutyl phthalate, ethyl centralite, and glyceryl triacetate (riacetin). 4. Flash suppressants interrupt free-radical chain reaction in muzzle gases (to produce nitrogen gas to dilute the muzzle gases) and work against secondary flash. They are typically alkali or alkaline earth salts that either are contained in the formulation of the propellant or exist as separate granules. Dinitrotoluene is used as a flash suppressor in some smokeless powders; nitroguanidine fulfills the same role. 5. Deterrents (moderants), coat the exterior of the propellant granules to reduce the initial burning rate on the surface as well as to reduce initial flame temperature and ignitability. The coating also broadens the pressure peak and increases efficiency. Deterrents may be a penetrating type such as Herkote, dibutyl phthalate, dinitrotoluene, ethyl centralite, methyl centralite, or dioctyl phthalate; or an inhibitor type such as Vinsol resin. 6. Opacifiers enhance reproducibility primarily in large grains and keep radiant heat from penetrating the surface. They may also enhance the burning rate. The most common opacifier is carbon black. 7. Dyes are added mainly for identification purposes. 8. Other ingredients may be one of the following: A graphite glaze used to coat the powder to improve flow and packing density as well as to reduce static sensitivity and increase conductivity. Bore erosion coatings applied as a glaze to reduce heat transfer to the barrel, but uncommon in small-arms propellants. Ignition aid coatings that are most commonly used in ball powders to improve surface oxygen balance. Morphology Chemical composition is one important characteristic defining smokeless propellants; however, another important characteristic is its morphology. Shape and size have a profound effect on the burning rate and power generation of a powder. Unburned gunpowders can have recognizable shapes, colors, and sizes of grains. Common particle shapes of smokeless propellants include balls, discs, perforated discs, tubes, perforated tubes, and aggregates. A few common types of smokeless powder morphologies can be seen in Figure 1.

Figure 1 Morphology also lends clues to whether a powder is single- or double-base. Most tube and cylindrical powders are single-base, with the exception of the Hercules Reloaderseries. Disc powders, ball powders, and aggregates are double-base, with the exceptions being the PB and SR series powders manufactured by IMR Powder Company. Except for ball powder, smokeless powder is manufactured by one of two general methods, differing in whether organic solvents are used in the process. A single-base powder typically incorporates the use of organic solvents. Nitrocellulose of high- and low-nitrogen content are combined with volatile organic solvents, desired additives are blended with them, and the resulting mixture is shaped by extrusion and cut into specified lengths. The granules are screened to ensure consistency, and the solvents are removed. Various coatings, such as deterrents and graphite, are applied to the surface of the granules. The powder is dried and screened again, then blended to achieve homogeneity. Manufacture The manufacture of double-base powders requires the addition of nitroglycerine to the nitrocellulose. Two methods can be used. One method uses organic solvents, the other uses water. The organic solvent method mixes nitrocellulose and nitroglycerine with solvents and any desired additives to form a doughy mixture. The mixture is then pressed into blocks that can be fed into the extrusion press and cutting machine. The resulting granules are screened prior to solvent removal and the application of various coatings. The powder is dried, screened again, and then blended to achieve homogeneity. The water method adds the nitroglycerine to a nitrocellulose water suspension to form a paste. The water is removed by evaporation on hot rollers, then the dried powder is shaped by extrusion and cutting. Triple-base powders use a solvent-based process similar to the double-base powder process. Nitrocellulose and nitroglycerine are premixed with additives prior to the addition of a nitroguanidine

solvent mixture. The nitroguanidine is incorporated into the overall mass without dissolving in the other materials. The final mixture is then extruded, cut, and dried. The manufacture of smokeless ball powder requires a more specialized procedure. Nitrocellulose, stabilizers, and solvents are blended into a dough, then extruded through a pelletizing plate and formed into spheres. The solvent is removed from the granules, and nitroglycerine is impregnated into the granules. The spheres are then coated with deterrents and flattened with rollers. Finally, an additional coating with graphite and flash suppressants is applied, and the batch is mixed to ensure homogeneity. In the manufacturing process, smokeless powders are recycled and reworked. When a powder within a batch is found to be unsatisfactory, it is removed and returned to the process for use in another lot. Manufacturers save money by recycling returns by distributors or the return of surplus or obsolete military powders. Hence, reworking and recycling the material assures good quality control of the final product, reduces costs by reusing materials, and reduces pollution by avoiding destruction by burning. DuPonts Improved Military Rifle (IMR) Improved Military Rifle (IMR) describes a series of tubular nitrocellulose smokeless powders evolved from World War I through World War II for loading military and commercial ammunition and sold to private citizens for reloading rifle ammunition for hunting and target shooting. IMR powders are coated with dinitrotoluene (DNT) to slow initial burning and graphite to minimize static electricity during blending and loading. They contain 0.6% diphenylamine as a stabilizer and 1% potassium sulfate to reduce muzzle flash. Introduced in 1914, the IMR series was merely an improvement over DuPonts earlier Military Rifle (MR) series of powders such as Pyro DG. From the mid-20s until the mid-50s, IMR powders were the US militarys primary choice for loading cartridges. Olins Ball powder propellant During the same time frame, the only major US military use of Ball propellant in small arms ammunition was in .30 Carbine ammunitions. The tide began to shift toward Ball powders in the 50s; in April 1954, the Chief of Ordnance wanted every small arms cartridge to be loaded with it. Declared the greatest development in the field of explosives in nearly 100 years by W.H.B. Smith, Ball powders offered significant strategic advantages.

Dr. Fred Olsen (employed by Western Cartridge Company forerunner of the Olin Corporation) developed a process for manufacturing spherical smokeless powder by 1933. Reworked powder or washed pyrocellulose can be dissolved in ethyl acetate containing small quantities of desired stabilizers and other additives. The resultant syrup, combined with water and surfactants, can be heated and agitated in a pressurized container until the syrup forms an emulsion of small spherical globules of the desired size. Ethyl acetate distills off as pressure is slowly reduced to leave small spheres of nitrocellulose and additives. The spheres can be subsequently modified by adding nitroglycerine to increase energy, flattening between rollers to a uniform minimum dimension, coating with phthalate deterrents to retard ignition, and/or glazing with graphite to improve flow characteristics during blending. Its manufacture was significantly faster than other types. Before the Second World War, production of other types of gunpowder took nearly six months. During the war, DuPont was able to get the process for one IMR type down to two weeks. In contrast, Olin could complete a production lot of Ball powder in less than two days. More importantly, Ball powder could be stored longer than conventional smokeless powders. Excess acids left over from the manufacture of nitrocellulose cause gunpowder to deteriorate with age, and with age, even more acids are created during decomposition once stabilizing agents are overwhelmed. The manufacturing method for Ball powder was more efficient at eliminating the excess acids and preventing new acids from forming as the powder aged. In part due to this ability to remove and neutralize excess acids, the manufacture of Ball powder did not require virgin nitrocellulose, as did other gunpowders. Smokeless gunpowders of any type and most any age could be reused and recycled for their nitrocellulose. The manufacturing process for Ball powder was also safer as it took place almost entirely in water. If additional manufacturing plants were required for the expansion of gunpowder production or the replacement of powder mills lost due to accident, the manufacturing process for Ball powders required less specialized equipment. This would equate to faster construction and lowered costs for materiel and labor. Replica Black Powders Pyrodex (Hodgdon Powder Company), introduced in 1976, is the most successful black powder substitute on the market. Pyrodex products are safe, clean burning and produce 30% more shots per pound than common black powder. Pyrodex also makes it easier to clean the gun after shooting. It was developed to overcome the high transportation costs and storage limitations of black powder. Pyrodex is similar in composition to black powder, consisting primarily of charcoal, sulfur, and potassium nitrate, but it also contains graphite and potassium perchlorate, plus additional ingredients protected by trade secret. For such purposes, it falls in the same shipping class as modern propellants. Pyrodex is formulated to replace black powder on a volume, not weight basis. In keeping with its replica duties, added materials generate the satisfying puff of white smoke so characteristic of

original black powder. (Hodgdon also makes Triple Seven and Black Mag3; Western Powders Company introduced Blackhorn 209).