United States Patent (19) ll 3,725,516

Kaufman 45 Apr. 3, 1973

54 MIXING PROCESS AND EXTRUSION (56) References Cited
OF SOLD PROPELLANTS" . .
75 Inventor: Martin H. Kaufman, China Lake, UNITED STATES PATENTS
Calif. 3,155,749 1 1/1964 Rossen et al.............................264/3
73 Assignee: The United States of America as 3,351,505 1 1/1967 Shapiro et al.......................... 14.9144
represented by the Secretary of the 3,431,154 3/1969 Kelly et al........................... 14.9144 X
Navy
Primary Examiner-Stephen J. Lechert, Jr.
22 Filed: June 11, 1968 Attorney-George J. Rubens and Roy Miller
21) Appl. No.: 738,721
57 ABSTRACT
Related U.S. Application Data An improved extrudable, high energy solid propellant
63 Continuation of Ser. No. 361,612, April 17, 1964. composition consisting essentially of the copolymer of
vinylidene fluoride and perfluoropropylene (Viton),
52 U.S. Cl........................ 264/3 B, 149/22, 149/40, an inorganic oxidizer such as ammonium perchlorate,
14914 1, 149142, 149/43, 14.9144 potassium perchlorate or ammonium nitrate, and a
51 Int. Cl......................................... .....C06b 21/02 metal powder such as aluminum, beryllium, magnesi
58 Field of Search..........264/3; 149/22, 60, 40, 42, um or zirconium. This composition is extrudable into
149/43, 44, 41, 76, 85, 19, 20 any suitable shape and has a very high percentage
theoretical maximum density so as to be practical for
utilization in rocket motors for propulsion.
4 Claims, No Drawings
 3,725,516 2
MIXENGPROCESS AND EXTRUSION OF SOLD and metal powder thereby forming a suspension. The
PROPELLANTS suspension is then washed with a quantity of a precipi
tant for the fluorocarbon, in this instance hexane. The
REFERENCE TO RELATED APPLICATION solid is permitted to settle and the liquid is decanted
This invention is a continuation of U.S. Pat. applica 5 off. The solid is washed again with hexane after which
tion Ser. No. 361,612, filed in the U. S. Patent Office the liquid is decanted off, the solid filtered and air dried
on 17 April 1964. or oven dried. The powder resulting is compression
molded or extruded into the desired shape. The object
BACKGROUND OF THE INVENTION of this method to produce an extrudable, high density
O solid propellant material which will have greater boost
The present invention relates to an improved ex velocity than existing propellants. A product which is
trudable, high energy, high density solid propellant and relatively safe to handle is formed and the process is
to the method of preparation thereof. amenable to large scale production of propellants,
Those concerned with the development of solid pyrotechnics, and explosive materials such as high
propellants have long known and recognized the need 15
energy, high density molding powders which can be
for a propellant with a high delivered density-impulse, molded or extruded.
high temperature stability and good safety charac Other objects and many attendant advantages of this
teristics. A propellant of this kind finds greatest use in invention will be readily appreciated as the same
the system where the propellant burnout mass is very become better understood by reference to the follow
large compared to the propellant volume. As variations 20 ing detailed description when considered in connection
in the properties are required for a specific application, with the accompanying graphs.
variations in the formulation are needed. Propellants
presently available have density specific impulse values BRIEF DESCRIPTION OF THE DRAWINGS
on the order of 430 - 470 g-sec/cc. The achievement of 25 FIG. 1 is a graph showing the theoretical impulse as a
high density in a composite propellant is controlled by
the density and generally the particle size of the in function
FIG. 2
of the basic composition;
is a graph showing the theoretical impulse as a
gredients and ultimately the method of fabrication function of a zirconium modified basic composition;
which is limited often by safety features of the FIG. 3 is another graph showing the theoretical im
processing system. Harsh working of the material may 30 pulse as a function of a beryllium modified composi
cause ignition.
The present invention attains a very high theoretical tion;FIG. 4 is yet another graph showing the theoretical
density impulse of a value between 490 and 622 g impulse
sec/cc which is a considerable increase over prior position;asanda function of another modified basic com
propellant compositions. Physical properties are 35 FIG. 5 is a graphic comparison of the boost velocities
changed; for instance, tensile strength is increased. of fluorocarbon bound propellants with propellants
Burning rate modifiers can be added to a basic com containing conventional binders.
position in order to improve ballistic properties of the
composition. The general purpose of this invention, DESCRIPTION OF THE INVENTION
therefore, is to produce a basic family of dense propel 40 In the present invention many compositions were
lants which are extrudable or can be compression
molded and which have suitable impulses that in studied, extruded, or pressed and fired. This invention
creased range results from their use in volume limited iscomposition
illustrated, but not limited, by the following basic
consisting essentially of a fluorocarbon
boost type application.
45 binder, such as a copolymer of vinylidene fluoride and
SUMMARY OF THE INVENTION perfluoropropene (Viton) and a copolymer of viny
The present invention is for an extrudable, high den lidene fluoride and trifluorochloroethylene (Kel-F
sity solid propellant composition and its method of elastomer), in the range of from 10 to 35 percent; ele
preparation. The composition consists essentially of a mental fuels and their hydrides or mixtures thereof,
fluorocarbon binder, such as a copolymer of vinylidene 50 such as aluminum, boron, zirconium, beryllium, titani
um, magnesium, and their hydrides, in the range of
fluoride and perfluoropropene (Viton) or a copolymer from about 5 to 70 percent; and an oxidizer, generally
of vinylidene fluoride and trifluorochloroethylene an inorganic oxidizer such as ammonium or alkali
(Kel-F elastomer), in the range of from 10 to 35 per metal perchlorate in the range of from about 25 to 75
cent; elemental fuels and their hydrides or mixtures 55 percent.
thereof, selected from the group consisting of alu In the use of very dense metals, less binder is
minum, boron, zirconium, beryllium, titanium, mag required on a weight basis as the fuel volumes get
nesium, and their hydrides, in the range of from about 5 smaller. For example, the density of boron is 2.34 g/cc,
to 70 percent; and an oxidizer, generally an inorganic but the density of lead is 11.4 g/cc, and that of tungsten
oxidizer selected from the group consisting of ammoni is 19.32 g/cc.
um or alkali metal perchlorate in the range of from Oxidizers such as ammonium or alkali perchlorates
about 25 to 75 percent. The tradename designations and nitrates are interchangeable as far as processing is
given for the fluorine containing polymers useful herein concerned. Calculations indicate that oxidizers such as
are “Viton", a duPont de Nemours and Company hydrazine nitroformate will theoretically provide even
polymer and "Kel-F Elastomer" available from the 65
better performance.
Minnesota Mining and Manufacturing Company. The The following basic composition was modified as
composition is prepared by dissolving the fluorocarbon hereinafter described.
in a solvent such as acetone, then adding the oxidizer
 3,725,516
Basic Composition Modified Composition B
Constituents Percent by weight Constituents Percent by weight
Ammonium perchlorate 59 Viton 25
Aluminum 2. Magnesium 20
Viton A 20 Ammonium perchlorate 55
The addition of various fuel mixtures to the above
extrudable basic composition provided changes in Burn rate results of the extruded propellant were as
follows:
burning rates which are shown in the following table. 0.54 in/sec at 1000 psi
For example, the addition of copper, iron, boron, O 1.07 in/sec at 4000 psi
chromium, zirconium, or their derivatives at the 5 per The process by which the present invention is made
cent level in the basic composition showed significant uses a resin kettle with a fast propeller stirrer and a stiff
burning rate changes:
rubber baffling device to prevent vortex formation. A
TABLE I
15
stainless steel drum may be used to make larger
batches. The required quantity of binder is placed in a
Burning Rate (in/sec.) container and dissolved in acetone or other suitable
1000 psi 4000 psi solvents such as methylethyl ketone and ethyl acetate.
Basic formulation
Extruded basic formulation
0.47 1.07 Approximately 25 cc of acetone per gram of Viton or
modified by addition of 20 Kel-F elastomer is used. Into this solution at room tem
Ferrocene
Copper
0.70
0.54
1.5
1.1
perature are stirred the dry solid ingredients, the metal
Boron 0.72 1.65 powder and oxidizer. After about 5 minutes of stirring
Chromium
Copper Chromite
0.5
0.64
1.
.5
the suspension a quantity of a precipitant for the
Copper Stearate 0.56 1.2 fluorocarbon, about two and one-halftimes by volume
Copper Oxide 0.56 1.2 25 that offluorocarbonsolventis added with stirring. Hex
Lead Salicylate 0.52 1.0
Lead Resorcylate 1.10 ane was used in this instance. Other hydrocarbons such
Titanium dioxide
Zirconium Boride
0.58
0.53
1.37
1.35
as petroleum ether may be used. After an additional 5
Lead Carbonate 0.52 35 minutes of stirring, the solid is permitted to settle and
the liquid is decanted off. Care must be taken at this
Mixtures of aluminum and zirconium as high energy, 30 point to prevent complete decantation, especially prior
high density ingredients also produced significant to the first washing. Residual solvent will permit easy
changes in the burning rate of the extruded basic com agglomeration of the powder at this stage if most of the
position as shown in the following table: hydrocarbon evaporates off. The latter is detrimental
to the preparation of a free-flowing molding powder
TABLE II 35
which is suitable for extrusion. The remaining wet solid
receives a second hexane wash after which it is de
Burning Rate (in/sec.) canted off, filtered and air dried or oven dried at 90 C.
Composition
(Percent by Weight)
Burning Rate
(psi)
In this manner agglomeration is avoided. If a finer
Viton AN Al KP ZT Tef 1000AP 4000 40 powder is desired, the second hexane wash may be de
5
5
45
45
20
20
15
20
s 0.60
0.77
1.35
1.95
canted off and the wet solid screened. The powder after
30 20 50 0.47 1.22 air drying and vacuum drying is compression molded or
20
25
80
75
0.40
0.40
0.82
0.84
extruded into the desired shapes. The propellant sur
5 85 0.06 0.15 faces not to be burned are inhibited prior to motor fir
15 75 10 0.45 0.92 45 ling.
16
18.5 45
50 20
16.5
10
16.5
4
3.5
0.63
0.53
.35
1.25
Referring now to the drawings, FIG. 1 is a graphic
view of the theoretical specific impulse as a function of
AP = ammonium perchlorate the basic formulation, as above set out, consisting es
AN = ammonium nitrate sentially of Viton, aluminum, and ammonium
Al Faluminum 50 perchlorate. FIG. 2 illustrates the theoretical specific
KP = potassium perchlorate impulse as a function of the composition wherein the
Zre zirconium basic formulation was modified by using zirconium as
Tef=Teflon the elemental fuel in place of aluminum. In FIG. 3 the
Other modifications of the basic composition which 55 theoretical specific impulse as a function of the com
showed significant changes in the burning are as fol position is shown in which beryllium was the elemental
lows: fuel used. FIG. 4 illustrates the theoretical impulse as a
function of the composition wherein hydrazine
Modified Composition A nitroformate is the oxidizer with a fluorocarbon binder
Constituents Percent by weight and the fuel, beryllium. FIG. 5 compares the boost
Viton
Sodium azide
18.5
9.1 velocities of fluorocarbon bound propellants with
Ammonium perchlorate 54.6 propellants bound with conventional binders such as
Aluminum 18.5 polyurethanes and polyhydrocarbons. These conven
tional binders are designated by the symbol -CH-.
The sodium azide acts as a catalyst. Burn rate results 65 The performance of an ideal rocket, i.e., no pressure
of the extruded strands were as follows: thrust, drag or gravitation or what may be termed "a
0.37 in/sec at 1000 psi gravitationless vacuum' is given by
0.78 in/sec at 4000 psi Veo-Caln (m/(m-m);) Cat-g
 3,725,516
S 6
The logarithmic relation makes Vo very dependent on AP = Ammonium perchlorate (100); V - Viton
a mass ratio. If the rocket were all propellant the Vo Al F Aluminum
would theoretically be infinite. Now if Zr FZirconium
mbo (mass of rocket at burnout) = m, -m.
and since, The invention described herein may be manufac
m = density of propellant, p. x volume of propellant, tured and used by or for the Government of the United
W States of America for governmental purposes without
the payment of any royalties thereon or therefor.
mu? (m m) = (mbo m)/mpo; 1 m/mao F 1 - Ip What is claimed is:
/(mbo/VBill 10 1. The process for preparing an extrudable, high
so that energy solid propellant comprising the steps of
VboF Ig ln(1 + (p/mol. V) 1. dissolving a copolymer of vinylidene fluoride and
wherein perfluoropropylene in acetone to form a solution;
Vao FVelocity of rocket at propellant burnout 2. adding while stirring weighed quantities of a dry
Cat-Time average exhaust velocity (cm/sec) = 1 15 oxidizer selected from the group consisting of am
m = Total rocket mass at time zero monium perchlorate, ammonium nitrate, potassi
m=Total propellant mass at time zero um perchlorate and mixtures thereof and a fuel
t = Time selected from the group consisting of aluminum,
IF Specific impulse boron, beryllium, magnesium, and zirconium to
g =Gravity form a homogeneous mixture;
Since the mass of a rocket without propellant, and 3. adding to said mixture while stirring a volume of
hexane about three times the volume of said
the volume to be occupied by the propellant generally acetone.
are both fixed by design, the ratio mo/ V (very often 4. permitting said acetone and mixture to stand
called the mass to volume ratio) is independent of 25 without stirring until all the solids settle;
propellant characteristics and actually characterizes 5. decanting off substantially all the liquid leaving a
the rocket or missile. residue,
In FIG. 5 it is shown that the boost velocity (V) of 6. washing the residue with hexane of about three
fluorocarbon bound propellant is considerably better times the volume of acetone;
than the conventional binders. 30 7. filtering out said residue;
The following table shows test results of several 8. air drying the residue, and
batches of propellants prepared in accordance with the 9. extruding said residue.
present invention.
2. The process as defined in claim 1 wherein the ox
TABLE III idizer is ammonium perchlorate and the fuel is alu
35 minum.
Composition (percent Meas- Percent
by weight) Composition ured theoretical Meas
Witon AP Al Zr
by analysis,
WIAPFAl/Zr
den-
sity
maximum
density
ured
Isp 3. The process as defined in claim 1 wherein the ox
idizer is ammonium perchlorate and the fuel is zirconi
20 65 15 -----22.08/63.39/14.53 1.987 99, 35 238 un.
20 59 21 ----------------------- 1984 99,20 228 40
20 62 18----- 2.98/60.48/17. 54 2.027 99.36 239
20 25 ----- 5519. 19/25. 04/55.06.
20 30 ----- 50 20.68/29. 55/49.77
2.994
2.824
96.89
96.7
149
162 4. The process as defined in claim 1 wherein the ox
20 35 - 45 19.65/35, 05/45. 32
20 40 ----- 4.0 9.90/39.63/40. 11
2.754
2.62
99.01
97.80
75
194
idizer is ammonium perchlorate and the fuel is berylli
20 45 ----- 3519.85/44.88/35. 37 2.510 99.21 96 1.
20 50 ----- 30 20.05/49.89/30.09 2.397 99.05 200
25 35 ----- 40 24, 37/34.86/40.77 2.607 98.75 185 45

50

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60

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