U.S. patent number 3,767,488 [Application Number 05/226,545] was granted by the patent office on 1973-10-23 for pressure sensitive explosive with organosilane coating.
This patent grant is currently assigned to The United States of America as represented by the Secretary of the Army. Invention is credited to William O. Seals.
United States Patent |
3,767,488 |
Seals |
October 23, 1973 |
PRESSURE SENSITIVE EXPLOSIVE WITH ORGANOSILANE COATING
Abstract
A pressure sensitive explosive composition is provided which is
rendered insensitive to water or water vapor by means of a coating
of an organofunctional silane capable of polymerization on contact
with water or water vapor. Additionally, a method is provided of
coating such a composition by the use of the above-mentioned silane
in a halocarbon solvent having a relatively low vapor pressure at
ambient conditions. The composition may be a mixture of an
inorganic oxidizer and fuel such as potassium chlorate, red
phosphorous and ground glass or a mixture of a primary explosive
such as lead azide and a secondary explosive such as RDX, either
mixture being coated with a silane such as .gamma. (.beta.
aminoethyl) aminopropyl trimethoxy silane applied from a volatile
halocarbon liquid such as 1,1,2 trichloro-1,2,2 trifluoro ethane.
The silane, after evaporation of the liquid, coats the composition
and polymerizes on contact with water or water vapor to form a
water impermeable film and this renders the composition insensitive
to water deactivation.
Inventors: |
Seals; William O. (Budd Lake,
NJ) |
Assignee: |
The United States of America as
represented by the Secretary of the Army (Washington,
DC)
|
Family
ID: |
22849347 |
Appl.
No.: |
05/226,545 |
Filed: |
February 15, 1972 |
Current U.S.
Class: |
149/7; 102/401;
149/11; 149/19.2; 149/29; 149/31; 149/35; 149/92; 149/93 |
Current CPC
Class: |
C06B
45/18 (20130101) |
Current International
Class: |
C06B
45/18 (20060101); C06B 45/00 (20060101); C06b
019/02 () |
Field of
Search: |
;149/11,35,92,93,105,19,7,29,85,31 ;102/8 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Rechel et al., S.N. 579,481, Abstract Thereof, published Nov. 1,
1949..
|
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Miller; E. A.
Claims
I claim:
1. A pressure sensitive, moisture insensitive, explosive
composition for use in pressure sensitive antipersonnel mines
comprising a particulate, pressure sensitive explosive composition
selected from the group consisting of a mixture of an inorganic
oxidizer, red phosphorus and ground glass and a mixture of a
primary explosive selected from the group consisting of lead azide
and lead styphnate and a secondary explosive selected from the
group consisting of cyclotrimethylenetrinitramine, pentaerythritol
tetranitrate and cyclotetromethylenatetranitramine, wherein the
particles are coated with an organo-functional silane monomer
capable of reacting with atmospheric moisture at atmospheric
temperatures to form a water impermeable polymer.
2. A composition as defined in claim 1 wherein said inorganic
oxidizer is selected from the group consisting of potassium
chlorate and potassium perchlorate.
3. A composition as defined in claim 1 wherein said
organo-functional silane monomer has the general formula
R.sub.(4.sub.-n) -- Si -- R'.sub.n
wherein R is a radical selected from the group consisting of
halogen, amino, alkoxy and arlyoxy, R' is a radical selected from
the group consisting of alkyl, aryl, aminoalkyl, aminoaryl,
alkylamino and arylamino, and n is an integer from 1 to 3
inclusive.
4. A composition as defined in claim 3 wherein said
organo-functional silane monomer is selected from the group
consisting of .gamma.(.beta. aminoethyl) aminopropyl trimethoxy
silane; .gamma. aminopropyl triethoxysilane, methyl
triethoxysilane, phenyltrichlorosilane, n butyl trichlorosilane,
dimethyl dichlorosilane and methyl phenyl dichlorosilane.
5. A composition as defined in claim 3, wherein the amount of said
monomer is between about 1 percent and 5 percent by weight of said
explosive composition.
Description
The invention described herein may be manufactured, used and
licensed by or for the Government for governmental purposes without
the payment to me of any royalty thereon.
BACKGROUND OF THE INVENTION
For certain battlefield applications, it is desirable to deploy a
large number of packaged explosives over a pre-selected area of the
battlefield. Aircraft dispersal is the most convenient method of
deployment. This type of dispersal requires maintenance of the
packages in a substantially insensitive state until after they hit
the ground. An effective, economical method for fabrication of
these packages is accomplished by placing the explosive in a vapor
permeable container and filling the container with a desensitizing
liquid, which will permeate the container. After the package is
deployed the liquid will evaporate through the container and leave
the enclosed explosive armed. One of the principal drawbacks of
this type of system is the possibility of premature desensitization
of the explosive by water or water vapor. For example, rainfall
will cause moisture permeation of the package and permanently
desensitize the explosive before it can effectively function.
Additionally, a very humid atmosphere has a strong tendency to
effect premature complete desensitization due to permeation of the
package by water vapor.
The difficulty thus encountered is of relatively recent origin and
although many organic compounds, including silanes and siloxanes
have been used for various purposes with energetic components (see
for example U. S. Pat. Nos. 3,551,222; 3,404,061; 3,058,858;
3,190,775; 3,190,776 and 3,110,638), these uses were neither
analogous to the instant problem nor indicative of a solution
thereto.
It is, therefore, an object of this invention to provide an
explosive composition which is insensitive to moisture.
Another object is to furnish a method of rendering an explosive
composition insensitive to moisture.
A further object is to provide a moisture insensitive, pressure
sensitive, explosive composition for use in antipersonnel
mines.
Other objects and many of the attendant advantages of this
invention will be readily appreciated as the same become better
understood by reference to the following description, wherein it is
shown that the above mentioned objects are attained and the prior
art deficiencies are overcome by the use of an organo-functional
silane monomer in a solvent solution to coat all of the components
of an explosive composition and thus render the composition
insensitive to water vapor, or water.
DESCRIPTION OF A PREFERRED EMBODIMENT
Certain types of mines have been used which are dispersed over a
preselected area of a battlefield by air drop. These mines must be
maintained in an insensitive condition until they hit the ground.
One advantageous method of accomplishing this is by using a
pressure sensitive explosive or pyrotechnic composition immersed in
a desensitizing liquid, the whole being enclosed in a container
which is permeable to the vapor of the desensitizing liquid. By the
use of this method the mines could be deployed while insensitive
and then become armed through the evaporation of the desensitizing
liquid. On standing in a humid atmosphere or in a rainstorm, the
contained explosive or pyrotechnic tended to become inert because
of sorption of water vapor or actual inundation by rain water. I
have found that by adding a soluble, organo-functional silane
monomer, which polymerizes on contact with water vapor, to the
desensitizing liquid and by intimately mixing the resultant
solution with the selected explosive or pyrotechnic composition, a
mixture is formed which will leave a coating of silane monomer on
the explosive composition when the desensitizing liquid volatilizes
on standing. Since the monomer polymerizes on contact with water
vapor and since the polymer thus formed is not permeable to water
or water vapor, this coating provides a means of making the
explosive or pyrotechnic composition insensitive to moisture. I
have also found that this polymer coating does not interfere with
the pressure sensitivity necessary to ultimately activate a
mine.
Indeed, my invention need not be used exclusively with a mine, it
may be used with any compatible explosive or pyrotechnic
composition which must be protected from moisture either vapor or
liquid.
The solvent liquid used with my invention must be capable of
dissolving the silane monomer and additionally possess the
properties of non-reactivity and non-solvation with the explosive,
non-reactivity with the organo-functional silane monomer and a
vapor pressure, such that the liquid will evaporate in a relatively
short time at ambient temperatures, thus in effect resulting in a
reversibly desensitized mine. Additionally, if my invention is to
be used with the type of mine described, the liquid solvent must be
capable of desensitizing the explosive or pyrotechnic while the
explosive is still thoroughly wetted by the liquid. Any liquid
which will meet these critera can be used.
It has been found that halocarbons of a chain length of one or two
carbon atoms containing at least one halogen substituent are
preferable, for example Freon 113 or perchloroethylene. These
halocarbons preferably have a boiling point between about
30.degree.C and about 120.degree.C. Other preferred halocarbons are
1,1,2 trichloro-1,2,2 trifluoroethane; 1,1,2,2 tetrachloro-1,2
difluoroethane; 1,1,2,2 tetrafluoro-1,2 dibromoethane; carbon
tetrachloride and tetrachloroethylene. Additionally, when the
organo-functional silane is a liquid of sufficiently low viscosity,
it can be readily mixed with the explosive and it will not be
necessary to use a desensitizing liquid. This procedure, although
effective is not preferred because of attendant hazardous mixing
conditions. My invention can be utilized for protection of any
solid explosive composition susceptible to desensitization by
moisture, for example: mixtures of red phosphorous, a strong
inorganic oxidizer such as potassium chlorate or perchlorate and
ground glass and pressure sensitive mixtures of primary explosives
such as lead azide or lead styphnate and secondary explosives such
as RDX, PETN or HMX.
My invention utilizes organo-functional silane monomers capable of
reacting with moisture at atmospheric temperatures to form
R.sub.water impermeable polymer. The monomer must be soluble in the
desensitization liquid and adhere strongly to the solid explosive
or pyrotechnic substrate. This is usually accomplished either
during the immersion of the substrate in the liquid or upon
substantial volatilization of the liquid thus leaving a monomeric
coating. Additionally, the monomer must be capable of forming a
moisture impervious coating of polymer upon contact with water or
water vapor. Further, the coating must not prevent initiation of
the explosive. The total amount of silane monomer used will depend
on the amount of surface area of explosive substrate because a
complete coating is desired. Additionally, the amount used must not
be enough to cause excessive desensitization. I have found that
between about 1% and 5% by weight of monomer, based on the amount
of explosive or pyrotechnic substrate, will give satisfactory
results. 2% by weight is preferred. Organo-functional silanes
capable of use with my invention are well known and can be
represented by the general formula, R.sub.(4.sub.-n) -- Si --
R'.sub.n
wherein Si represents a silicon atom, at least one of the R
substituents is selected from the group consisting of halogen,
amino, alkoxy and aryloxy and R' represents a substituent selected
from the group consisting of alkyl, aryl, aminoalkyl, aminoaryl,
alkylamino, arylamino, alkoxy and aryloxy and n is an integer from
1 to 3 inclusive. Generally, the reaction of such an
organo-functional silane to effect protection against moisture for
the composition of my invention is thought to be a hydrolytic
polycondensation which is believed to proceed largely as
follows:
1. R.sub.4.sub.-n SiR'.sub.n + nH.sub.2 O .fwdarw. R.sub.4.sub.-n
Si(OH).sub.n + nHR'
2. r.sub.4.sub.-n Si(OH).sub.n .fwdarw. Polymer + H.sub.2 O
wherein R, R' and n have the aforementioned definitions. The
silanol product of reaction (1) is unstable and reacts further to
form a polymeric silicon containing material. In some cases a
siloxane is formed, in other cases a cyclic polymer and in yet
others a polyorganosiloxane. The type of polymer formed depends
upon the type and number of the R and R' substituents. R is
selected for its ability to hydrolyze to form the necessary
intermediate silanol and R' is selected for its ability to lend
water impermeability to the formed polymer. Generally, where R is
alkoxy it will be a short chain i.e. from one to four carbon atoms.
Additionally, the polymerization rate also depends on the
substituents selected. Since the purpose of my invention is broadly
to provide protection against water and water vapor, the
polymerization rate should be relatively rapid upon contact with
water or water vapor.
Some examples of silanes that may be used with my invention,
follow: .gamma.(.beta. aminoethyl) aminopropyl trimethoxy silane;
.gamma. aminopropyl triethoxy silane; methyl triethoxysilane;
phenyltrichlorosilane; n butyltrichlorosilane; dimethyl
dichlorosilane and methyl phenyldichlorosilane.
In certain cases catalysts which are soluble in the liquid used as
a desensitizing solvent may be added to insure polymerization of
the monomer if they are compatible with the ultimate function of
the explosive or pyrotechnic composition.
The method and composition of this invention, which may be used to
produce a safe desensitized explosive item having the properties
desired, are set forth in the following examples. It is, of course,
understood that these examples are meant to be illustrative and not
restrictive of my invention.
EXAMPLE 1
A one percent solution of .gamma.(.beta. aminoethyl) aminopropyl
trimethoxy silane in 10 cc. of 1,1,2 trichloro-1,2,2 trifluoro
ethane was prepared under dry conditions. 0.2 gram of fumed silica
thickening agent and then 5 grams of potassium chlorate were added
to the solution with agitation. 2 grams of red phosphorous were
then added and the resulting desensitized slurry was agitated until
homogeneous. 1 gram of cut pyrex glass was added to a small
polyethylene cup under dry conditions and dampened with 1,1,2
trichloro-1,2,2 trifluoro ethane. 3 grams of the desensitized
slurry was added to the cup and then the cup was closed with a
rigid polyethylene disc and heat sealed. The cup was conditioned at
a specified temperature and relative humidity and subsequently
tested for effectiveness by standard tests. The polyethylene cup
and disc were made from Alathon A 3120 film (a registered trademark
of E. I. DuPont de Nemours Co.), this product, marketed by DuPont,
was found suitable for the present application.
EXAMPLE 2
Using the same procedure as in Example 1, but in place of the
potassium chlorate, red phosphorous and ground glass, enough RDX
and lead azide is introduced into the halocarbon, silane, silica
slurry to form a final mixture containing 60 parts by weight of RDX
to 40 parts by weight of lead azide.
RESULTS
Ten of the cups were prepared by the method of Example 1, and
allowed to stand at ambient temperature and humidity until the
solvent was removed by evaporation. After a predetermined time five
of the cups were detonated and the pressure required to cause
detonation was recorded. The pressure required to initiate the
detonation of the cups fell between 6 and 8 psi which compared
favorably with control cups identically prepared without the silane
additive. The remaining 5 cups were placed in a 95 percent relative
humidity chamber at room temperature for humidity testing. Two cups
were removed after 7 days and tested; one of the cups detonated at
6 psi, the other required 16 psi. Three cups were removed after 14
days in the chamber and tested; one of the cups detonated at 9 psi,
the other two required 38 psi and 40 psi respectively.
These results indicate that there is no apparent desensitization of
the explosive by the addition of silane as shown by the
comparability of the pressure required to detonate the test cups
and the pressure required to detonate control cups prepared without
silane. Additionally, with the 7 day test, since one of the samples
was in line with the necessary standard control pressure, the
indication is that the silane has provided water vapor protection.
The second result which was high may indicate poor coverage by the
silane due to inhomogeneity of the original mixture. The test after
14 days indicates the same water vapor protection evident in one of
the samples while the other two high results may again indicate
inhomogeneity.
Thus, it can be seen that the use of my invention, wherein an
explosive composition is coated with a water reactive
organo-functional silane monomer to prevent detrimental contact of
the explosive by moisture, forms the basis for an advance in the
art.
I wish it to be understood that I do not desire to be limited to
the exact details described, for obvious modifications will occur
to a person skilled in the art.
* * * * *