April 2002 - Volume 4 - Number 2

Research and Technology

The Manufacture of Smokeless Powders and their Forensic Analysis: A Brief Review
Robert M. Heramb
Graduate Student
Bruce R. McCord
Associate Professor of Analytical and Forensic Chemistry
Department of Chemistry
Ohio University
Athens, Ohio
Introduction | Composition and Manufacturing | Distribution | Improvised Explosive
Devices | Analysis |Conclusions | References
Introduction
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.
Composition and Manufacturing
The major classes of compounds in smokeless propellants include energetics, stabilizers, plasticizers, flash
suppressants, deterrents, opacifiers, and dyes (Bender 1998; Radford Army Ammunition Plant 1987).

Energetics facilitate 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 energyflame temperature relationship.

Stabilizers prevent the nitrocellulose and nitroglycerine from decomposing by neutralizing

nitric and nitrous acids that are produced during decomposition. If the acids are not neutralized,
they can catalyze further decomposition. Some of the more common stabilizers used to extend
the safe life of the energetics are diphenylamine, methyl centralite, and ethyl centralite.

Plasticizers reduce the need for volatile solvents necessary to colloid nitrocellulose, soften
the propellant, and reduce hygroscopicity. Examples of plasticizers include nitroglycerine,
dibutyl phthalate, dinitrotoluene, ethyl centralite, and triacetin.

Flash suppressants interrupt free-radical chain reaction in 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.

Deterrents 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.
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.

Dyes are added mainly for identification purposes.

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

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 (Meyer 1987). Common particle

shapes of smokeless propellants include balls, discs, perforated discs,

Figure
1 Common smokeless
tubes, perforated tubes, and aggregates (Bureau of Alcohol, Tobacco
powder morphologies Click to
and Firearms 1994; Selavka et al. 1989). A few common types of
enlarge image.
smokeless powder morphologies can be seen in Figure 1 (Bender 1998).
Morphology also lends clues to whether a powder is single- or double-base (Bender 1998). 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 of Plattsburg, New York.
Except for ball powder, smokeless powder is manufactured by one of two general methods, differing in whether
organic solvents are used in the process (Meyer 1987; Radford Army Ammunition Plant 1987). 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.
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 (Meyer
1987; National Research Council 1998; Radford Army Ammunition Plant 1987). 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, then blended to
achieve homogeneity. The water method adds the nitroglycerine to a nitrocellulose water suspension to form a
paste (Meyer 1987; Radford Army Ammunition Plant 1987). 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 (Meyer 1987;
Radford Army Ammunition Plant 1987). 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 (National Research Council
1998). 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 (National Research Council 1998).
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.
Distribution
The production of smokeless powders is big business in the United States, where approximately 10 million
pounds of commercial smokeless powders are produced each year. Most of the powder is sold to the originalequipment manufacturers to be used for manufacturing ammunition. A large amount is sold to domestic and
foreign militaries (National Research Council 1998). The rest is sold in individual canisters (ranging from -pound
cans to 12- or 20-pound kegs) to gun stores or hunting and shooting clubs for hunters and target shooters who
prefer to hand load their own ammunition.
There are several ways smokeless powders are distributed within the United States (National Research Council
1998). Some manufacturers, foreign or domestic, produce, package, and sell their own powders commercially.
They may also sell in bulk to resellers and to original-equipment manufacturers that repackage and sell it under
their own labels. The powder manufacturers and repackagers may disburse large quantities of canister powders
to distributors who later sell to smaller distributors and wholesalers, who in turn, supply cans to dealers, gun
shops, shooting clubs, and other retailers. At this point, consumers can purchase a 1-pound canister of powder for
approximately $15 to $20 from a retailer, though the cost per pound can be cheaper if bought by the keg or
acquired through a gun club (National Research Council 1998).
Manufacturers who produce smokeless powders for the U.S. military can distribute it either by selling the powder
directly to the military or by selling them the preloaded ammunition. Powders can also be shipped to U.S. military
subcontractors, foreign governments, or foreign loading companies for loading into military ammunition (National
Research Council 1998).
Improvised Explosive Devices
An explosion is the result of energy-releasing reactions, generally accompanied by the creation of heat and gases
(a notable exception is thermites). A distinguishing characteristic of an explosion is the rate at which the reaction
proceeds. There are low-order and high-order explosives, based on the speed at which the explosives
decompose. In low-order explosives, the process of decomposition, called the speed of deflagration or burning,
produces heat, light, and a subsonic pressure wave. (The reaction speed of the deflagrating material is less than
the speed of sound.) In high-order explosives, decomposition occurs at the speed of detonation, creating a
supersonic shock wave that causes a virtually instantaneous buildup of heat and gases. Table 1 shows some
differences in low-order and high-order explosives (Bureau of Alcohol, Tobacco and Firearms 1994; National
Research Council 1998; Saferstein 1998).
For low-order explosives, rapid deflagration causes the production of large volumes of expanding gases at the
origin of the explosion. The heat energy from the explosion also causes the gases to expand. When the explosive
charge is confined in a closed container, the sudden buildup of expanding pressure exerts high pressure on the
container walls causing the container to stretch, balloon, then burst, releasing fragments of debris to nearby
surroundings. It is this fragmented debris that produces the fatal result following the deflagration of an improvised
explosive device (Saferstein 1998).

The safest and most powerful low-order explosive is smokeless powder. These powders decompose at rates up
to 1,000 meters per second and produce a propelling action that makes them suitable for use in ammunition.
However, the slower burning rate of smokeless powder should not be underestimated. The explosive power of
smokeless powder is extremely dangerous when confined to a small container. In addition, certain smokeless
powders with a high-nitroglycerine concentration can be induced to detonate. On the other hand, high-order
explosives do not need containment to demonstrate their explosive effects (Saferstein 1998). These materials
detonate at rates from 1,000 to 8,500 meters per second, producing a shock wave with an outward rush of gases
at supersonic speeds. This effect proves to be more destructive than the fragmented debris.
The typical smokeless powder improvised explosive device, a pipe bomb, is roughly 10 inches long and 1 inch
wide and contains approximately pound of powder. The materials used for these devices are cheap and readily
obtainable at commercial establishments. Smokeless powder is attractive for use in improvised explosive devices,
because it is readily available and has the potential for a powerful explosion when the powder is placed in a
closed container (National Research Council 1998). Larger explosive devices usually use bulk materials such as
ammonium nitrate and fuel oil, typically purchased in greater quantity at an even cheaper price.
Many types of containers are used in the construction of smokeless powder bombs (National Research Council
1998). Whereas metal pipes are most common, plastic pipes, cans,
CO2 cartridges, and glass or plastic bottles have been used. These
containers are often placed within larger packages for ease of transport
and concealment.
Another important part of the powder bomb is the initiation system, which
provides the impetus to start the powder burning within its container
(National Research Council 1998). A few examples include cigarettes,
matches, and safety fuses (Scott 1994; Stoffel 1972). Improvised
explosive devices utilizing smokeless powders within a robust container Figure 2 Pipe Bomb Click to
often include an initiation system, as shown in Figure 2 (Scott 1994).
enlarge image.
Using data from the National Research Council on reported actual and
attempted bombings using propellants during the five-year period from 1992-1996, Table 2 illustrates an average
of 653 incidents per year involving the use of black and smokeless powders. Bombs containing black or
smokeless powders were responsible for an average yearly count of about 10 deaths, 83 injuries, and almost $1
million in property damage for each of the five years. Using the National Research Councils data involving
devices filled with black and smokeless powders, Table 3 illustrates the number of actual bombings that caused
at least one death, one injury, or a minimum of $1,000 in property
damage, as well as attempted bombings aimed at significant targets
(National Research Council 1998).
Analysis
Many methods for the analysis of smokeless powders have appeared
over the years. These procedures have been extensively reviewed in a
number of recent texts (Beveridge 1998; National Research Council
1998; Yinon and Zitrin 1993). The initial characterization of the powders is Figure 3 Gradient HPLC
assessed using powder morphology and spot tests. Various instrumental analysis of an IMR 700X
smokeless powder. Conditions
analytical techniques allow organic additives such as nitroglycerine,
diphenylamine, ethyl centralite, dinitrotoluene, and various phthalates to Restek C-8 Column, 36-80%
methanol/water gradient, 1
be detected and quantitated. These materials are usually analyzed using
ml/min, UV detection at 230
gas chromatography-mass spectrometry (Martz and Lasswell 1983) and nm. Figure courtesy of Chad
liquid chromatography (Bender 1983; McCord and Bender 1998). Figure Wissinger, Ohio
3 illustrates the analysis of an IMR 700X powder using gradient high
University Click to enlarge
image.
performance liquid
chromatography (Wissinger and
McCord 2002). More recently,
methods involving capillary
electrophoresis have also been
shown to be effective (Northrop et al.
1991; Smith et al. 1999). Fourier
transform infrared microscopy can be
used for the identification of
nitrocellulose (Zitrin 1998).
The process of manufacturing
smokeless powders provides sources of
Figure 4 IC Analysis of H414
inorganic ions that are present in smokeless powder by
postblast residue. These can be
Hodgdon. Conditions
Nucleosil Anion IIColumn,
1mM DCTA pH 5.2, 1.5 ml/min,
UV detection at 205 nm.Click
to enlarge image.

analyzed by ion chromatography. Although not unique to propellants, the presence of these ions can be used in
forensic analysis to aid in the identification of the unknown powder. Potassium sulfate, sodium sulfate, potassium
nitrate, barium nitrate, and other salts may be added during the processing of the powder. Nitrate, sulfate,
hydrogen sulfide, chloride, and nitrite may appear as a result of the reactions for treating
the cellulose to obtain nitrocellulose (Radford Army Ammunition Plant 1987). Figure 4 illustrates the analysis of
H414 smokeless powder using ion chromatography. Also documented has been the presence of various cations
found in the residue of smokeless powders after deflagration (Hall and McCord 1993; Miyauchi et al. 1998).

Conclusions
The wide variety of chemical components and the different morphologies of smokeless powders present a
challenge for the forensic investigator. Physical characteristics of partially burned and unburned powder as well as
the organic and inorganic materials that remain must be considered in the analysis of postblast residue. Although
there are many techniques available for the determination of components in smokeless powder residue, the
various formulations of powders make it necessary to continue the advancement of existing analyses and to
develop new methods for testing the full range of available smokeless powders.

References
Bender, E. C. Analysis of low explosives. In: Forensic Investigation of Explosives. A. Beveridge, ed. Taylor and
Francis, London, 1998, pp. 343-388.
Bender, E. C. Analysis of smokeless powders using UV/TEA detection. In: Proceedings of the International
Symposium on the Analysis and Detection of Explosives. U.S. Government Printing Office, Washington, DC,
1983, pp. 309-320.
Beveridge, A., ed. Forensic Investigation of Explosives. Taylor and Francis, London, 1998.
Bureau of Alcohol, Tobacco and Firearms, Arson and Explosives Incidents Report (1994). ATF P3320.4,
Department of the Treasury, Washington, DC, 1994.
Hall, K. E. and McCord, B. R. The analysis of mono- and divalent cations present in explosive residues using ion
chromatography with conductivity detection, Journal of Forensic Sciences (1993) 38:928-934.
Martz, R. M. and Lasswell, L. D. Identification of smokeless powders and their residues by capillary column gas
chromatography/mass spectrometry. In: Proceedings of the International Symposium on the Analysis and
Detection of Explosives. U.S. Government Printing Office, Washington, DC, 1983, pp. 245-254.
McCord, B. and Bender, E. C. Chromatography of explosives. In: Forensic Investigation of Explosives. A.
Beveridge, ed. Taylor and Francis, London, 1998, pp. 231-265.
Meyer, R. Explosives. 3rd rev., Weinheim, New York, 1987.
Miyauchi, H., Kumihashi, M., and Shibayama, T. The contribution of trace elements from smokeless powder to
post-firing residues, Journal of Forensic Sciences (1998) 43:90-96.
National Research Council, Committee on Smokeless and Black Powder. Black and Smokeless Powders:
Technologies for Finding Bombs and the Bomb Makers. National Academy Press, Washington, DC, 1998.
Northrop, D. M., Martire, D. E., and MacCrehan, W. A. Separation and identification of organic gunshot and
explosive constituents by micellar electrokinetic capillary electrophoresis, Analytical Chemistry (1991) 63: 10381042.
Radford Army Ammunition Plant. Processing Manual. Radford, Virginia, 1987.
Saferstein, R. Criminalistics: An Introduction to Forensic Science. 6th ed., Prentice Hall, Upper Saddle River, New
Jersey, 1998.
Scott, L. Pipe and Fire Bomb Designs: A Guide for Police Bomb Technicians. Paladin Press, Boulder, Colorado,
1994.
Selavka, C. M., Strobel, R. A., and Tontarski, R. E. Systematic identification of smokeless powders, an update.
In: Proceedings of the Third Symposium on the Analysis and Detection of Explosives. Berghausen, Fraunhofer
Institute fur Chemische Technologie, 1989, Chapter 3, pp. 1-27.
Smith, K. D., McCord, B. R., MacCrehan, W. A., Mount, K., and Rowe, W. F. Detection of smokeless powder
residue on pipe bombs by micellar electrokinetic chromatography, Journal of Forensic Sciences (1999) 44:789794.
Stoffel, J. Explosives and Homemade Bombs. Charles C. Thomas, Springfield, Illinois, 1972.
Wissinger, C. and McCord, B. R. A reversed phase HPLC procedure for smokeless powder comparison,Journal of
Forensic Sciences (2002) 47:168-174.
Yinon, J. and Zitrin, S. Modern Methods and Applications in Analysis of Explosives. John Wiley, Chichester,
United Kingdom, 1993.
Zitrin, S. Analysis of explosives by infrared spectrometry and mass spectrometry. In: Forensic Investigation of
Explosives. A. Beveridge, ed. Taylor and Francis, London, 1998, pp. 267-314.