U.S. patent number 3,833,432 [Application Number 05/014,827] was granted by the patent office on 1974-09-03 for sodium azide gas generating solid propellant with fluorocarbon binder.
This patent grant is currently assigned to The United States of America as represented by the Secretary of the Navy. Invention is credited to Marguerite S. Chang, Gerald L. MacKenzie, Bertram K. Moy.
United States Patent |
3,833,432 |
Moy , et al. |
September 3, 1974 |
SODIUM AZIDE GAS GENERATING SOLID PROPELLANT WITH FLUOROCARBON
BINDER
Abstract
Gas generating solid propellant compositions which utilize
sodium azide as nitrogen source and are further comprised of a
fluorocarbon binder material and a combustion catalyst of finely
divided colloidal silicon dioxide and/or finely divided carbon
black.
Inventors: |
Moy; Bertram K. (White Plains,
MD), MacKenzie; Gerald L. (Port Tobacco, MD), Chang;
Marguerite S. (Forest Heights, MD) |
Assignee: |
The United States of America as
represented by the Secretary of the Navy (Washington,
DC)
|
Family
ID: |
21767971 |
Appl.
No.: |
05/014,827 |
Filed: |
February 11, 1970 |
Current U.S.
Class: |
149/19.3;
149/35 |
Current CPC
Class: |
C06B
45/10 (20130101); C06B 35/00 (20130101); C06D
5/06 (20130101) |
Current International
Class: |
C06D
5/00 (20060101); C06D 5/06 (20060101); C06B
35/00 (20060101); C06B 45/10 (20060101); C06B
45/00 (20060101); C06d 005/06 () |
Field of
Search: |
;149/19,35,19.3 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Miller; E. A.
Attorney, Agent or Firm: Sciascia; R. S. Cooke; J. A.
Claims
What is claimed as new and desired to be secured by Letters Patent
of the United States is:
1. A gas generating solid propellant composition comprising sodium
azide, a fluorocarbon binder material, and a combustion catalyst
selected from the group consisting of a finely divided colloidal
silicon dioxide, a finely divided carbon black, and mixtures
thereof.
2. The gas generating solid propellant composition of claim 1
wherein said finely divided colloidal silicon dioxide is further
characterized by having a minimum surface area of about 175 square
meters per gram.
3. The gas generating solid propellant composition of claim 1
wherein said fluorocarbon binder material is a polymeric fully
fluorinated fluorocarbon.
4. The gas generating solid propellant composition of claim 1
wherein said fluorocarbon binder material is a polymeric partially
fluorinated fluorocarbon.
5. The gas generating solid propellant composition of claim 1 which
further includes a metal selected from the group consisting of
magnesium and aluminum.
6. The gas generating solid propellant composition of claim 1
wherein said sodium azide is present in an amount within the range
of from about 50 to about 75 weight percent, said fluorocarbon
binder material is present in an amount within the range of from
about 25 to about 40 percent by weight and said combustion catalyst
is present in an amount up to about 10 percent by weight.
7. The gas generating solid propellant composition of claim 1
wherein said sodium azide and said fluorocarbon binder material are
present in about stoichiometric quantities.
8. The gas generating solid propellant composition of claim 1
wherein said fluorocarbon material is selected from the group
consisting of polytetrafluoroethylene, and a copolymer of
vinylidene fluoride and perfluoropropylene.
9. The gas generating solid propellant composition of claim 3
wherein said polymeric fully fluorinated fluorocarbon is
polytetrafluoroethylene.
10. The gas generating solid propellant composition of claim 4
wherein said polymeric partially fluorinated fluorocarbon is a
copolymer of vinylidene fluoride and hexafluoropropylene.
11. The gas generating solid propellant composition of claim 4
wherein said polymeric partially fluorinated fluorocarbon is a
homopolymer of chlorotrifluoroethylene.
12. The gas generating solid propellant composition of claim 4
wherein said polymeric partially fluorinated fluorocarbon is a
copolymer of vinylidene fluoride and chlorotrifluoroethylene.
Description
BACKGROUND OF THE INVENTION
This invention relates generally to solid propellants and more
particularly to solid propellants especially useful as a self
generating gas pressurization systems.
Liquid propellant rocket engines can be classified generally as
either pump fed or pressure fed. The pump fed engine extracts the
liquid propellants from the tanks and pumps the propellants at high
pressure into the combustion chamber. The pressure fed systems
admit gas from a high pressure source into the propellant tanks,
thus driving the propellants directly into the combustion chamber.
The pump fed system requires some pressure in the tanks to push the
propellant through the inlet lines and to prevent cavitation in the
pump. The requirements for propellant pressurization are generally
similar for either type of liquid engine, but the pressures are
higher for the pressure fed system.
A self-generating gas system generates pressurized gas from a solid
propellant, as contrasted with a stored gas system, to replace the
propellant leaving the main tanks and thereby driving the liquid
oxidizer and fuel components into the combustion chamber. Thus a
self-generating gas pressurization system which generates inert or
neutral gas, such as nitrogen, and is compatible with all fuels and
oxidizers, is obviously desirable.
Heretofore however, the self-generating gaseous nitrogen
pressurization systems have not been completely adequate. Among the
primary disadvantages of these prior art systems is that complete
combustion is not always accomplished and furthermore deleterious
metals are customarily part of the combustion end products which
necessitates elaborate filtering means for their removal. Moreover,
other problems in the areas of formulation and storage of these
heretofore employed systems have also been unfortunately
encountered.
SUMMARY OF THE INVENTION
Accordingly, one object of this invention is to provide a gas
generating solid propellant.
Another object of this invention is to provide a gas generating
solid propellant especially useful as a self-generating gas
pressurization system.
Still another object of this invention is to provide a gas
generating solid propellant especially useful as a self-generating
gas pressurization system of which combustion gas is essentially
nitrogen.
A further object of this invention is to provide a gas generating
solid propellant particularly useful as a self-generating gas
pressuirzation system which does not produce deleterious combustion
end product materials.
A still further object of this invention is to provide a gas
generating solid propellant especially useful as a self-generating
gas pressurization system which has improved formulation and
storage characteristics.
These and other objects are accomplished by providing a solid
propellant composition comprised of sodium azide, a polymeric
fluorocarbon binder and finely divided colloidal silicon dioxide,
finely divided carbon black and mixtures thereof as a combustion
catalyst.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The gas generating solid propellant compositions of this invention
are based upon the reaction of sodium azide and a fluorocarbon
polymer matrix in the presence of finely divided silicon dioxide as
illustrated, e.g., by the following general reactions:
(I) 4NaN.sub.3 + (CF.sub.2).sub.n .sub..gtoreq. 2 .sup.SiO or C
4NaF + 6N.sub.2 + 2C
(ii) 8naN.sub.3 + (C.sub.5 F.sub.8 H.sub.2).sub. n .sub..gtoreq. 1
.sup.SiO or C 8NaF + 12N.sub.2 + H.sub.2 + 5C
(iii) 2naN.sub.3 + (CF.sub.2).sub.n .sub..gtoreq. 2 + Mg .sup.SiO
or C 2NaF + MgF.sub.2 + 2C + 3N.sub.2
(IV) 6NaN.sub.3 + (C.sub.5 F.sub.8 H.sub.2 ).sub.n .sub..gtoreq. 1
+ Mg .sup. SiO or C 6NaF + MgF.sub.2 +H.sub.2 + 9N.sub.2 + 5C
Thus, the solid propellants of the present invention, as
exemplified by general reactions I-IV employ NaN.sub.3 as the
source of nitrogen gas. Although other inorganic azides, such as
LiN.sub.3, which also is characterized by a relatively high
nitrogen content, will perform similarly to the NaN.sub.3 in the
propellants of this invention, it is rendered somewhat unsuitable
because of its high degree of instability and lack of commercial
availability.
With regard to the fluorocarbon binder materials considered to be
within the scope of this invention, general reactions I-IV above
indicate that such polymeric fluorocarbons as Teflon
(polytetrafluoroethylene) and Viton A (a rubbery copolymers of
vinylidene fluoride and hexafluoropropylene) may be employed in the
practice of this invention. For the purposes of this invention a
fluorocarbon is defined as being either a fully fluorinated
fluorocarbon consisting of carbon and fluorine or a partially
fluorinated fluorocarbon containing some other element or elements
besides carbon and fluorine, such as hydrogen, oxygen, nitrogen,
halogen, etc. Obviously, in cases where hydrogen gas cannot be
tolerated as one of the combustion gases (such as in the case where
either the oxidizer or fuel or both of a liquid propellant may not
be compatible with hydrogen as part of the pressurized gas) fully
fluorinated polymeric fluorocarbons such as e.g. Teflon are
preferred since nitrogen is the sole gaseous product. Otherwise
partially fluorinated fluorocarbons, such as e.g., Viton A, are
acceptable. Although it has been suggested that the solid
propellants of this invention are especially useful as
self-generating gas pressurization units it will be obvious to one
skilled in the art that they are also useful for driving trubines,
actuating valves and for all the other purposes for which
conventional gas-generating propellants are employed. For these
purposes the nature of the gaseous end products, i.e. whether a
mixture of hydrogen and nitrogen or essentially all nitrogen, does
not play a significant role. Among other polymeric fluorocarbons
that may be employed in the practice of this invention are for
example, partially fluorinated fluorocarbons containing functional
groups. One such material is L-2344 which is a hydroxyterminated
fluorocarbon made by Minnesota Mining and Manufacturing Company and
has an empirical formula of C.sub.73 F.sub.108 H.sub.42 O.sub.2. In
this case a curing agent, such as an isocyonate, is incorporated in
the binder for improved physical and mechanical properties. Other
polymeric fluorocarbons that are operable as binders herein are for
example the polynitrofluoroacrylates, Kel-F wax, which is a
homopolymer of chlorotrifluoroethylene, Kel-F elastomer which is a
copolymer of chlorotrifluoroethylene and vinylidene fluoride and
Teflon - 100 which is a copolymer of tetrafluoroethylene and
perfluoropropylene.
It has been surprisingly found that unless the propellant
compositions of the present invention incorporate a combustion
catalyst selected from the group consisting of a finely divided
colloidal silicon dioxide possessing a large surface area and
finely divided carbon black possessing a large surface area and
mixtures thereof, complete combustion of the reactants is not
attainable even at stoichiometric quantities. Therefore, in the
presence of these aforeidentified catalysts the propellants of this
invention fully combust without yielding any deleterious sodium
metal. Specifically, a silicon dioxide within the scope of this
invention is Cab-O-Sil, a finely divided colloidal silicon dioxide
with a minimum surface area of 175 square meters per gram made by
Cabot Inc., Boston, Mass. and a specific carbon black operable
herein is known as Graphite -5530 which is described as a finely
divided carbon black made by the Asbury Graphite Mill, New
Jersey.
Other materials may be added to the gas generating propellant
compositions of this invention to attain various other desirable
ballistic modifying results. For example, if metals such as
magnesium or aluminum are added, (see general reactions III and IV)
changes in the burning rates are attained, while coolants, such as
ammonium oxalate, oxamide and guanidine nitrate, lower the flame
temperatures of the propellants.
For operable results, the amounts materials incorporated in the
present gas generators are the following: sodium azide, from about
50 to about 75 percent by weight, fluorocarbon binder, from about
25 to about 40 percent by weight and catalyst up to about 10
percent by weight. Any ballistic modifiers, such as hereinabove
identified, which may be employed should not comprise more than
about 10 percent by weight (for each modifier) of the total
composition. For optimum results the reactive ingredients of the
propellants of this invention should be present in about
stoichiometric quantities.
The general nature of the invention having been set forth, the
following examples are presented as specific illustrations thereof
and also so that invention be better understood. Furthermore, it
will be understood that the invention is not limited to these
examples but is susceptible to various modifications that will be
recognized by one of ordinary skill in the art.
EXAMPLE I ______________________________________ Percent by weight
sodium azide 69.7 Teflon (powder) 26.8 Graphite - 5530 (a finely
divided carbon 3.5 black made by Asbury Graphite Mill, New Jersey)
______________________________________
EXAMPLE II ______________________________________ Percent by weight
sodium azide 50.2 Teflon (powder) 38.6 Graphite -5530 1.9 magnesium
9.3 ______________________________________
EXAMPLE III ______________________________________ Percent by
weight sodium azide 68.0 Teflon (powder) 26.0 Cab-O-Sil (a finely
divided colloidal 6.0 silicon dioxide made by Cabot Inc., Boston
Mass.) ______________________________________
EXAMPLE IV ______________________________________ Percent by weight
sodium azide 48.9 Teflon (powder) 37.4 Cab-O-Sil 4.5 magnesium 9.2
______________________________________
EXAMPLE V ______________________________________ Percent by weight
sodium azide 64.0 hydroxyterminated fluorocarbon (L-2344) 31.8
graphite - 5530 1.0 Isonate 390-P (an isocyanate curing agent 3.2
made by Upjohn Chemical Comp.)
______________________________________
EXAMPLE VI ______________________________________ Percent by weight
sodium azide 69.44 Viton A 28.56 Cab-O-Sil 2.0
______________________________________
EXAMPLE VII ______________________________________ Percent by
weight sodium azide 68.06 Viton A 27.94 Cab-O-Sil 4.0
______________________________________
EXAMPLE VIII ______________________________________ Percent by
weight sodium azide 66.65 Viton A 27.35 Cab-O-Sil 6.0
______________________________________
EXAMPLE IX ______________________________________ Percent by weight
sodium azide 68.68 Viton A 28.99 Cab-O-Sil 2.0 magnesium 0.33
______________________________________
The propellant compositions of this invention are easily formulated
employing conventional techniques. For example, when Teflon powder
is utilized as the binder all the propellant ingredients are simply
mixed homogenously in a V blender and then either extruded or
compression molded. When the binder employed is of the Viton A
type, i.e., a rubbery texture, a slurry mixing process is used.
This process involves mixing the binder in a solvent such as
acetone, followed by the addition of the remaining ingredients and
then stripping off the acetone. The formulation is then either
extruded or compression molded. When a thick liquid binder such as
L-2343 is used a slurry mix process may be employed or a standard
solventless mixing procedure is applicable. Again the mixture may
be either extruded or compression molded.
Obviously many modifications and variations of the present
invention are possible in the light of the above teachings. It is
therefore to be understood that within the scope of the appended
claims the invention may be practiced otherwise than as
specifically described.
* * * * *