Canadian
Intellectual Property
Office
‘An Agency of
Industry Canada
Office de la Propriété
Intellectuelle
du Canada
Un organisme
dindustrie Canada
CA 539080 (13) A
02.04.1957
(12)
(21) Application number. 6380800
(2) Date of ling
(51) Int. ct
(71) Applicant:
‘OLIN MATHIESON.
(72) Inventor:
HOLMES RAYMOND S ()
BALDRIDGE BYRON C ()
O'NEILL JOHN J JR (.
SILK CHARLES E ().
(64) SMOKELESS POWDER HAVING A SPECIFIC SURFACE
AREA
(57) Abstract:
(54) POUDRE SANS FUMEE AYANT UNE SURFACE
‘SPECIFIQUE
This First Page has been artificially created and is not part of the CIPO Official Publication10°
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This invention relates generally to explosives and
more particularly to a propollant.
‘The present invention provides a propellant charge
essentially of propelient grains whose cut surfaces are so spaced
that the surface area of the grains is from about 75 to about Bh
square centimeters per gram thereof, the web is from about 0.015
to about 0,025 inch, and having dispersed throughout the region of
tho grain which extends from cach surface about one-sixth of the
web of the grain a deterrent having a heat of explosion of less
than about ~200 calories per gram,
‘The present invention also provides a method for making
propellants which comprises extruding nitrocellulose powder base
through a die, subdividing the powder base into vropellent grains
having a surface area of from about 75 to about 8l, square cenbi~
meters per gram and a web of about 0,015 inch to about 0,025 inch
and thereafter treating with a deterrent having a heat of explosion
constant of less than about -200 calories per gram only the region
of the grain which extends from the surface thereof about one-sixth
of the web of the grain.
Propellent grains having various shapes and chemical
composition have been proposed, heretofore, for caliber .30 and
similar caliber cartridges but none of them have been found
entirely suitable in practice, Of these various types of propel-
lents, tubular propellent grains having dinitrotoluene coating
on the grain have the least number of disadvantages and, con~
sequently, grains of this type have boon utilized almost exclu
sively in such cartridges. These grains aro eminently suitable
for the purpose except for the fact that the accuracy and effi~
ciency of the projectile is no longer acceptable after a relative=
ly small number of cartridges have boon fired in a machine gun
or other repid firing guns, This decrease in accuracy has been10
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found to be due to the inner wall of the barrel substantially
adjacent the breech being eroded or otherwise damaged by the gases
developed by tho explosion of the propellent, Heretofore, the
only remedy for this condition has been to cease firing and change
the gun barrel, which is of disadvantage to the operator and has
not alleviated the disadvantage of short barrel life.
It is therefore an object of this invention to
provide @ novel propellent charge for rapid fire guns, An-
other object of the invention is to provide a propellant
which hae improved ballistic properties, Still another ob=
ject of the invention is to provide a propellant of caliber
«30 and simialr sized cartridges having improved barrel ero-
sion characteristics. A further object is to provide
a method for malcing an extruded propellant suitable for utiliza-
tion in machine guns and other rapid fire guns of caliber .30,
In accordance with this invention, the foregoing
objects, as well as others which will become apparent from the
following description are achieved by providing a propellent
charge composed essentially of propellent grains formed by
extrusion and having a surface area within the range of from
about 75 square centimeters to about Bl, square centimeters per
grem thereof ond having localized adjacent the surface of each
grain not less than about 3 per cont of a deterrent based on
the weight of the powder grain and having a heat of explosion
constant of about ~200 calories or less per gram thereof,
Ordinarily not more than about 12 per cent deterrent will be
required, ‘The web of the propellent grains mist be within the
range of about 0,015 inch to about 0,025 inch and the deterrent
must be dispersed only in that region of the grain extending from
the surface of the grain not more than about one-sixth of the web
of the grain, The invention thus contemplates shaping a nitro~
cellulose powder base by an extrusion process, subdividing the
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extruded powder base into propellent grains having a surface
area of from about 75 to about 8 square centimeters per gram
thereof and a web of from about 0,015 inch to about 0,025
inch, and thereafter dispersing a deterrent having a heat
of explosion of less than ~200 throughout that region of
the grain extending from each surface thereof inwardly not more
than one-sixth of the grain's web, The grain is preferably ex-
truded through a die adapted to impart the desired web to the
nitrocellulose but the grain can be formed by an extrusion pro-
cess, cut to length and theroafter rolled to the required web,
For most practical purposes, deterrents having a heat of explo~
sion as low as about ~1000 to -2500 are preferred although, as
stated hereinbefore, deterrents having a heat of explosion of
as high as about -200 can be utilized, but obviously are not as
effective,
The deterrent must be nonsmigratory at all tempera=
tures to which propellants are ordinarily exposed in order that
the deterrent will remain substantially uniformly dispersed with-
in the specified region of the grain and no significant amount
thereof will penetrate into the grain's core, Any non-migratory
deterrent having a heat of explosion constant of less than ~200
calories per gram can be utilized such as, for example, the
diakyl phthalates like dibutyl phthalate and diamyl phthalate,
the diaryl phthalates like diphenylphthalate, triphenyl phos-
phate, butyl stearate, diaryl dialiylureas euch as diethyl
@iphenyl urea, methyl ethyl diphenyl urea and dimethyl urea,
glycerol sebacate, tricresyl pholphate and the like, The pro~
cess disclosed by McBride in U, S. 1,955,927 has been found
to be particularly advantagoous for properly locating the deter=
rent in the prover region of the propellent grain,
‘The "heat of explosion" constant of the constituents
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of powder grains is a well known term in the, industry and has
been determined from the heat of combustion of the material
utilizing calculations involving the formulae published by dePauw
in articles in "Zeitschrift fur das gosamte Schiess-und Spreng~
stoffwesen" volume 32, pp. 11, 36 and 60 (1937), Actually the
value assigned as: the heat of explosion of deterrents is a con=
stant which represents the effect of the material on the heat
emitted upon firing of the explosive constituents of the grain.
This constant can also be determined experimentally.
In such a method, a dried sample of a propellent powder not hav-
ing any deterrent in its composition is burned in an adiabatic
calorimeter bomb having a nitrogen atmosphere therein and the
heat of combustion is measured by conventional procedures.
Another dried sample of propellant substantially identical
with the one utilized in the foregoing with the exception that a
known amount of deterrent is incorporated in the grain is then
burned in the bomb and the heat of combustion determined, The
difference between the heat of combustion of the untreated pro~
pellant and the treated propellant divided by the weight of the
deterrent is designated the heat of explosion of the deterrent.
Thus the heat of explosion constant of a deterrent is a measure~
mont of the effect of the deterrent on the explosion temperature
of a propellent base material, For example, to determine the
heat of explosion of dibutylphthalate, a dried sample of a pro-
pellant composed essentially of about 90 per cent. nitrocellulose
and about 10 per-cent nitroglycerine was burned in 4 calorimeter
bomb heving a nitrogen atmosphere, Then another sample of this
propellant treated in accordance with this invention to contain
about 7 per cent dibutylphthalate was burned under similar con
ditions, The heat of explosion of the propellant without deter~
vent was found to be 1070 calories per gram of propellant burned,10
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while the heat of explosion of the propellant which contained
the deterrent was found to be 840 calories per gram of propellant
burned, Inasmuch as 93 per cont of the grain was nitrocellulose
and nitroglycerine base material the heat due to the burning of
this explosive portion of ths, charge af propellant having a
deterrent should ave boon (93 x 1070) or 994 calories, Sub-
tracting 840 calories which was actually obtainod in the test
from 99h, calories leaves 154 calories difference per gram bo~
tween the heat of explosion between the two propellants, This
decrease is due to the deterrent since it was the only variable,
There was only .07 grams of dibutylphthalate per gram of propel~
lant so 154 mst be divided by .07 to determine the effect of the
deterrent on propellants in terms of grams of deterrent. In
other words each gram of dibutylphthalate will reduce the heat
of explosion of a propellant about 2200 calories, In order to
Indicate that it reduced the heat of explosion of the propellant
the number is referréd to as a negative number, Hence the heat
of explosion of dibutylphthalate is about -2200 calories per
gram,
The propellent grains are shaped into tubular or rod
form by extruding partially or completely colloided nitrocellu-
lgse through a die and thereafter subdividing the rod or tube
Into graine of suitable longth, The grains may or may not have
one or more perforations therein provided the specific surface
is within the range of about 75 square centimeters to about Ol,
square centimeters per gram of propellant, If the grain is
perforated, the walls of the perforation must be deterrent treat~
ed along with the other surfaces of the grain and, for that
reason, solid grains or perforated grains wherein the dimensions
of the perforation are such as to facilitate coating the walls
thereof aro preferred, Best results are obtained if the length
of tho grain is substantially equal to the thickness thereof,
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In accordance with the well known methods for utilizing
deterrents and enorgizers or energizing modifiers to obtain the
desired ballistic effects with nitrocellulose propellants, the
deterrent may be adjusted within the 3 per cent to 12 per cent
limit specified hereinbefore to obtain the ballistics essential
for the particular caliber .30 and, if necessary or desired to
produce particular ballistic effects, an energizing modifier, for
example a polyhydric alcohol, such as nitroglycerine, may also be
incorporated in the propellent grain, Ordinarily, powder grains
having a specific gravity of about 1,5 are utilized, but the
powder grains of this invention having a lower specific gravity
are also less erosive to the gun barrel, The amount of energizing
modifier required for double base propellant is usually within
the range of about 10 to 20 per cent by weight of the propellent
grain,
By "web" as utilized herein and in the appended claims
is meant the minimum thickness between any two surfaces of solid
or perforated grains, Hence, tho web of a tubular grain may be
the minimum distance between the wall bounding a perforation and
another surface of the grain or it may be the distance between two
external surfaces of the grain depending upon which distance is
the smaller and the word web is used here in its usual sense in
the art.
No definite exolanation has been resolved as to why
the propellant of this invention is less erosive to the breech
end of a gun barrel than the heretofore conventional propellants
having a heat of explosion greater than ~200 calories per gram
and having a surface area of only one-half or less of that of
the propellant of this invention, However, it has been found that
cartridges loaded with the propellant of the type provided by
this invention exhibit a phenomenal improvement over similar cart~
pidges loaded with a powder charge composed of perforated grains
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made in accordance with the process disclosed in Tochnical Manual
No, 9-2900 entitled "wilitary Explosives" published August 29,
1940 by the War Department of the United States Government, In
this test the barrel is considered no longer suitable when the
flight of the projectile indicates a yaw of at least ten degrees
or when the muzzle velocity of the projectile has decreased more
than 200 feet per second,
In order to further clarify the Invention, the follow
ing is a detail description of an embodiment thereof:
A Powder base having an average nitrogen content of
about 13.2 per cent is obtained by mixing about 3 parts by
weight nitrocellulose having a nitrogen. content of about 13.1
per cent with about one part nitrocellulose having a nitrogen
content of about 12.6 per cent, About 100 parts by weight of
the resulting nitrocellulose is dehydrated with about 125 parts
of ethyl alcohol in a conventional dehydrating press. Tho re~
sulting block of about 100 parts nitrocellulose and about 33
parts alcohol is broken up and 66 parts diethyl ether is added
thoreto to partially colloid the mass, During the agitation to
completely mix the solvent with the nitrocellulose, about one
part dephenylamine is added, Tho colloid 1s next pressed into
a block, forced through an extrusion die and again blocked in
conventional equipment and finally grained by oxtruding through
a die adapted to produce a solid rod, the die having an internal
diameter of about 0,042 inch, The solid rod is cut to lengths
substantially equal to its diameter to form propellent grains,
Phe ether-alcohol and othor volatiles are removed by air drying
in trays stored in a room having an average temperature of about
30°C, the first 2h hours, about 40°C, the next 2h hours and
about 45°C. for about one week,
About 100 parts of the resulting propellent grains y.re
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= 96
suspended in about 330 parts water, About 22 parts of an enul-
sion of about 11 parts nitroglycerine, about l parts ethyl acetate
and about 7 parts toluene and about 0,1 part gum arable in about
75 parts water are added and the temperature of the slurry is
raised to about 65°C, and further increased to about 70°C. in a
period of about four hours, The ethyl acetate and toluene are
than removed by passing air through the slurry while continuing
the agitation thereof, About 13 hours are required for substan-
tially complete renoval of the solvent after which the tempera-
ture is raised to about 72°C, and about 1} parts gum arabic are
added,
An emulsion of about 72 parts dibutylphthalate and about
0.05 parts emmisifying agent such as gum arabic in about 20 parts
water is added and the resulting slurry agitated for about 5 hours
after which the propellent grains are separated from the liguid.
About 1000 parts of the resulting grains are coated with about
5,0 parts potassium nitrate, about 2.5 parts diphenylphthalate
and about one-half part dinitrotoluene by tumbling the grains
therewith in a sweetie barrel for about 30 minutes at 55°C, after
which about 0, parts graphite are added and tumbling is continued
for an additional 30 minutes, The resulting grains have a surface
area of about 77 square centimeters per gram of propellant, have
& web of about 0,016 Inch and contain about 6.5 per cent by weight
of dibutylphthalate dispersed in that region of the grain extend
ing from each surface thereof about 0.003 inch.
While the foregoing embodiment has been described in
detail with respect to caliber .30 propellants, propellent charges
for other guns in this range of calibers such as caliber .303,
7.92 millimeter, 7 millimeter and the similar calibers are
contemplated by the invention,
The invention has been described in detail in the fore-
going for the purpose of illustration and variations therein
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will occur to those skilled in the art and can be made without
departing from the scope or spirit of the invention, For ex=
ample, other suitable methods can be utilized for treating the
propellent grains with the deterrent, Likewise, if a double base
propellent is desired, any suitable method for incorporating the
energizer in the grain can be utilized, As pointed out herein=
before, however, single base nitrocellulose propellents are
suitable for the purpose, Furthermore, for some purposes, it
might be desirable to include certain ballistics modifiers such
as carbon black or the likes
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The embodiments of the invention in which an
exclusive property or privilege is claimed are defined
as follows:
1. A propellent charge essentially of propellent
grains whose cut surfaces are so spaced that the surface
area of the grains is from about 75 to about 84 square
centimeters per gram thereof, the web is from about 0.015
to about 0.025 inch, and having dispersed throughout the
xegion of the grain which extends from each surface about
one-sixth of the web of the grain a deterrent having a
heat of explosion of less than about -200 calories per
gram.
2. A propellent charge composed essentially of
extruded propellent grains having a surface area of from
about 75 to about 84 square centimeters per gram thereof,
a web of about from 0,015 to about 0.025 inch, and having
a deterrent substantially uniformly dispersed throughout
the region of the grain which extends from each surface in-
wardly a distance equivalent to about one-sixth of the web
of the grain, said charge having a heat of explosion of not
more than 900 calories per gram thereof.
A propellent charge composed essentially of
extruded propellent grains having a surface area of be~
tween about 77 square centimeters per gram thereof, a web
of about 0.016 inch and having dispersed throughout the
region of the grain which extends from each surface about
one-sixth of the web of the grain a deterrent having a heat
of explosion of less than about -200 calories per gram.
4. A propellent charge composed essentially of ex-
truded propellent grains having a surface area of about 77536080
square centimeters per gram thereof, a web of about 0.016
inch and having dispersed throughout the region of the
grain which extends from each surface about one-sixth of
the web of the grain about 6.5 per cent of a non-migratory
deterrent having a heat of explosion of less than about
-200 calories per gram,
5. A propellent charge composed essentially of
extruded propellent grains having a surface area of about
77 square centimeters per gram thereof, a web of about
0.016 inch and having dispersed throughout the region of
the grain which extends from each surface about 0.003 inch
about 6.5 per cent dibutylphthalate.
6. A propellent charge composed essentially of
solid substantially cylindrical propellent grains having a
surface area of from about 75 to about 84 square centimeters
per gram thereof and a web of from about 0,015 to about
0.025 inch, and having dispersed throughout the region of
the grain which extends from each surface about one-sixth
of the web of the grain a substantially non-migratory
deterrent having a heat of explosion of less than about
-200 calories per gram.
7. A propellent charge composed essentially of
extruded nitrocellulose propellent grains impregnated with
about 10 per cent energizer and having a surface area of
about 77 square centimeters, a web of about 0.016 inch and
having dispersed throughout the region of the grain ex-
tending not more than about 0.003 inch £rom each surface about
6.5 per cent dibutylphthalate.
8. A propellent charge composed essentially of
extruded propellent grains having a surface area of from/ 2 539080
about 77 to about 84 square centimeters per gram thereof,
a web of from about 0.015 inch to about 0.025 inch, and
having dispersed throughout the region of the grain which
extends from each surface about one-sixth of the web a
non-migratory deterrent having a heat of explosion of less
than about -1000 calories per gram.SUBSTITUTE
REMPLACEMENT
SECTION is not Present
Cette Section est Absente