U.S. patent number 3,731,625 [Application Number 05/143,328] was granted by the patent office on 1973-05-08 for packaged explosive.
This patent grant is currently assigned to ICI America Inc.. Invention is credited to Frank E. Slawinski.
United States Patent |
3,731,625 |
Slawinski |
May 8, 1973 |
PACKAGED EXPLOSIVE
Abstract
A skin-tight explosive not having an air space or sag, and a
method of making it. An explosive containing a
plasticizer-extractor is placed in a flexible polyvinyl chloride
bag which has been plasticized with an extractable plasticizer. The
air space or sagging bag which would normally form is eliminated
due to the shrinkage of the bag.
Inventors: |
Slawinski; Frank E. (Tamaqua,
PA) |
Assignee: |
ICI America Inc. (N/A)
|
Family
ID: |
22503591 |
Appl.
No.: |
05/143,328 |
Filed: |
May 14, 1971 |
Current U.S.
Class: |
102/324 |
Current CPC
Class: |
F42B
3/087 (20130101) |
Current International
Class: |
F42B
3/00 (20060101); F42B 3/087 (20060101); F42b
003/00 () |
Field of
Search: |
;102/24R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Materials Handbook, George S. Brady, Ninth Ed. 1963, McGraw-Hill
TA403 B75 1963 C.2 page 709.
|
Primary Examiner: Pendegrass; Verlin R.
Claims
What is claimed is:
1. A skin-tight packaged explosive composition free of air spaces
and sags contained in a sealed, flexible, plasticized polyvinyl
chloride film container, said container characterized in that a
portion of the plasticizer in said polyvinyl chloride film
container is extracted by said explosive composition, said
explosive composition characterized in that it contains an
extractor for said plasticizer in contact with said container.
2. A packaged explosive according to claim 1 wherein said
plasticizer is selected from the group consisting of dioctyl
phthalate, diisooctyl phthalate, diisodecyl phthalate,
trichloroethyl phosphate, trioctyl phosphate, tri-2-ethylhexyl
phosphate, octyl-diphenyl phosphate, decyl-diphenyl phosphate,
cresyl-diphenyl phosphate, tricresyl phosphate, dioctyl adipate,
polyethylene glycol di-2-ethyl-hexoate, and mixtures thereof.
3. A packaged explosive composition according to claim 1 wherein
said explosive is a dynamite.
4. A packaged explosive composition according to claim 1 wherein
said explosive composition is AN-FO.
5. A packaged explosive composition according to claim 1 wherein
said explosive composition is a slurry.
6. A packaged explosive composition according to claim 1 wherein
said explosive composition is a water-in-oil emulsion.
7. A packaged explosive composition according to claim 1 wherein
said polyvinyl chloride film contains about 20 to about 60 percent
plasticizer.
8. A packaged explosive composition according to claim 1 wherein
said container is a lap side sealed bag.
9. A packaged explosive composition according to claim 1 wherein
said extractor is a solvent for said plasticizer.
10. A packaged explosive composition according to claim 9 wherein
said extractor is an oil.
11. A packaged explosive composition according to claim 9 wherein
said solvent is selected from the group consisting of fuel oil,
mineral oil, lubricating oil, kerosene, nitroalkanes from C.sub.1
to C.sub.3, and nitroglycerine.
12. A packaged explosive composition according to claim 1 wherein
said polyvinyl chloride film is at least 4 mils and less than 50
mils thick.
13. A packaged explosive composition according to claim 11 wherein
said polyvinyl chloride film is about 6 to about 20 mils thick.
14. A packaged explosive composition according to claim 1 wherein
said explosive composition contains about 0.1 to about 80 percent
extractor.
15. A packaged explosive composition according to claim 14 wherein
said explosive composition contains about 1 to about 10 percent
extractor.
Description
Many explosives must be heated during their manufacture. They are
usually immediately placed in a package and sealed. This procedure
frequently causes the bag to wrinkle and sag or causes an air space
to form at the top of the package due to contraction of the
explosive as it cools. An air space or sag may also result due to
the rearrangement of particles to mate better as they settle. This
frequently happens when AN-FO (ammonium mitrate - fuel oil) is
packaged, which is done at ambient temperatures. The air space or
sag may also be caused by the coalescence of gases dissolved in the
explosive or the absorption of gases into solid particles and this,
too, may occur at ambient temperatures.
The presence of an air space or sag in the package is unattractive,
which makes the product less salable, and an air space may prevent
the propagation of the explosion from one container to the next
when they are stacked in a borehole.
I have discovered a skin-tight explosive package and a method of
making it. Due to an interaction between the container and the
explosive, the container shrinks with the explosive forming a
skin-tight package with no air space or sag. A flexible polyvinyl
chloride (PVC) film is plasticized with an extractable plasticizer
and formed into a bag. An explosive which contains a
plasticizer-extractor; preferably a solvent for the plasticizer
such as most oils, is placed in the bag and the bag is sealed.
Gradually, the bag shrinks as the plasticizer in the bag is allowed
to be extracted into the plasticizer-extractor in the explosive
which may migrate through the plastic to form a light film on the
bag.
In addition to the elimination of the air space and sag, the
packaged explosive of this invention has superior elasticity,
toughness, and memory which enable it to be dropped into boreholes
containing water without rupturing. The shrinkage of the polyvinyl
chloride bag also puts pressure on the explosive which may cause
the particles in an explosive such as AN-FO to rearrange themselves
to give the explosive a higher density. This may be desirable as it
will enable the explosive to sink better in a water-filled
borehole.
The accompanying drawing is a side view of a certain presently
preferred embodiment of this invention.
In the drawing, a sheet of flexible polyvinyl chloride which has
been plasticized with an extractable plasticizer is formed into a
tube 1 by making a side lap seal 2. One end of the tube is tied
with a cord 3 to form a bag and the bag is filled with an explosive
4 containing a plasticizer-extractor. The other end of the bag is
then sealed by tying it with a second cord 5 to form the packaged
explosive.
While the packaged explosive of FIG. 1 is preferred because of its
strength, low cost, and ease of manufacture, other types of bags
may also be used. Examples include blow-molded shells, seamless
tubing, vacuum-drawn containers, and spiral-wound shells. The bag
preferably is cylindrical and has a diameter of about 1 to 12
inches and a length of about 6 to 45 inches.
Although the polyvinyl chloride may be of any flexible thickness, a
thickness of at least about 4 mils and up to about 50 mils is
generally suitable. Preferably, for the best explosive packages,
the thickness should be between about 6 and about 20 mils.
The polyvinyl chloride bag is plasticized with a sufficient amount
of an extractable plasticizer to (1) obtain the desired degree of
shrinkage when the plasticizer is in part extracted and (2) leave
enough plasticizer unextracted to keep the bag flexible. I have
found that the amount of plasticizer in the polyvinyl chloride
should be about 20 to about 60 percent (all percentages herein are
by weight) of the polyvinyl chloride to obtain the best
results.
The plasticizer must be extractable. Examples of plasticizers which
are extractable in mineral oil and most other oils and are
therefore preferred include dioctyl phthalate, diisooctyl
phthalate, diisodecyl phthalate, trichloroethyl phosphate, trioctyl
phosphate, tri-2-ethylhexyl phosphate, octyl-diphenyl phosphate,
decyl-diphenyl phosphate, cresyldiphenyl phosphate, tricresyl
phosphate, dioctyl adipate, polyethylene glycol di-2-ethyl-hexoate,
and mixtures thereof. Certain alkyl aryl phosphates may also be
used. Table 1 gives the percent that various plasticizers were
extracted from a film after the film was soaked in S.A.E. 20 oil
for 10 days at 23.degree.C.
TABLE 1
Plasticizer % Extracted Dioctyl phthalate 17.3 Tri-2-ethylhexyl
phosphate ([C.sub.4 H.sub.9 CH(C.sub.2 H.sub.5) CH.sub.2 O].sub.3 P
= 0) sold under the trademark "Flexol TOF" by Carbide and Carbon
Chemicals Co. 29.1 Octyl-diphenyl phosphate sold under the
trademark "Santicizer 141" by Monsanto Chemical Co. 14.1 Tricresyl
phosphate 6.3 Dioctyl adipate 20.6 Polyethylene glycol
di-2-ethyl-hexoate (C.sub.7 H.sub.15 COOCH.sub.2 (CH.sub.2
OCH.sub.2).sub. 3 CH.sub.2 OCOC.sub.7 H.sub.15) sold under the
trademark "Flexol 4GO" by 25.2 ide and Carbon Chemicals Co. A
high-boiling liquid, sp. gr. 0.9564, boiling point 255.degree.C. (5
mm. Hg), flash point 420.degree.F., practically insoluble in water,
sold under the trademark "Flexol 8N8" by Carbide and Carbon
Chemicals Co. 12.8
The above table was in part obtained from "The Stabilization of
Polyvinyl Chloride" by Chevassus Broutilles, page 263.
Table 2 gives the percent extractability in mineral oil of various
phthalate plasticizers. The plasticizer concentrations are at 50
parts per hundred of resin.
TABLE 2
Phthalate % Extractable Dioctyl 1.0 Diisooctyl 1.3 Diisodecyl 2.4
Various linear phthalates made from Conoco, Ethyl, and Monsanto
alcohols 3.4 to 5.1
The above table was obtained from the November, 1970 issue of
"Modern Plastics," page 78.
Table 3 gives the percent extraction of various plasticizers in
kerosene. A 40 mil PVC film was used with a plasticizer
concentration of 67 p.h.r. (parts per hundred of resin).
TABLE 3
Plasticizer % Extraction Dioctyl phthalate 34 Trichlorethyl
phosphate 6.7 Trioctyl phosphate 74 Octyl-diphenyl phosphate.sup.1
7.3 Decyl-diphenyl phosphate.sup.2 6.7 Cresyl-diphenyl phosphate
2.1 Tricresyl phosphate 1.3 1. Sold by Monsanto Chemical Co. under
the trademark "Santicizer 141." 2. Sold by Monsanto Chemical Co.
under the trademark "Santicizer 148."
The above table was obtained from the Jan. 29, 1971 issue of
"Chemscope," page 18. The differences in extractability of dioctyl
phthalate between Tables 1, 2, and 3 may be due to experimental
differences such as the amount of plasticizer originally in the
film.
At least about 0.1 percent of the plasticizer should be extracted
to obtain a noticeable amount of shrinkage. Preferably, about 3
percent to about 40 percent of the plasticizer is extracted to
obtain a significant amount of shrinkage without leaving the
polyvinyl chloride bag inflexible and brittle.
Table 4 gives the percent contraction of 7" MD (machine-direction)
by 5" CD (cross-direction) sheets of PVC film after 1 week and 1
month of immersion in various solvents, primarily oils. "KDA-2076"
is a product designation of Union Carbide for a 12 mil PVC film
plasticized with 33.5 percent dioctyl phthalate and having a
density of 1.225 gms./cc. "KDA-2109" is a Union Carbide product
designation for a 20 mil PVC film having a density of 1.215
gms./cc. plasticized with 33.8 percent "Flexol 10--10" (a Carbide
and Carbon Chemicals Co. trademark for diisodecyl phthalate).
TABLE 4
"KDA-2076" "KDA-2109" 1 Week 1 Month 1 Week 1 Month Solvent MD CD
MD CD MD CD MD CD
__________________________________________________________________________
Alcaid Oil.sup.1 1.3% 1.2% 2.7% 2.6% 0.9% .2% 1.3% 1.8% Atreol
34.sup.2 2.3 2.6 3.6 3.8 1.9 1.8 2.3 2.6 Klearol.sub.3 2.3 2.6 4.0
4.4 1.3 2.6 2.3 3.2 Castor Oil 2.3 2.6 3.6 3.8 1.9 2.6 3.6 3.8 Cod
Liver Oil 1.9 3.8 2.7 5.6 3.6 4.4 5.4 5.0 Corn Oil 4.4 3.8 5.4 5.0
3.6 3.8 5.4 6.2 Corvus.sup.4 1.3 1.2 2.3 2.6 0.9 0.6 2.3 2.6
Compression Oil 1.9 1.8 3.1 3.2 1.9 1.8 2.7 3.2 DFO No. 2 3.6 3.8
5.4 5.6 2.7 3.8 4.4 5.0 Ebony B.sup.5 0.0 0.6 0.4 1.2 0.4 0.6 0.4
0.6 Gasoline 9.0 8.8 9.0 8.8 8.0 9.4 9.0 10.0 Glycerine 0.0 0.0 0.0
0.0 0.4 0.0 0.0 0.0 Glycol 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Kerosene
4.4 5.0 6.3 7.6 5.4 5.6 7.1 7.6 Linseed Oil 3.6 3.8 5.4 6.2 3.6 5.0
4.4 5.6 Mineral Spirits 6.3 6.2 8.0 8.8 6.3 6.8 7.1 7.6 Motor Oil
No. 10 0.9 1.2 1.9 2.6 0.9 1.2 2.7 2.6 Motor Oil 10-30 1.9 1.2 2.7
2.6 1.3 1.8 1.9 2.6 Nitromethane 9.0 7.6 10.1 6.2 7.8 5.0 7.1 5.0
NG (PGD -- 90% glycol -- 10% (glycerine) 6.7 6.9 10.0 10.9 7.0 50
8.8 9.3 Olive Oil 2.7 3.2 4.4 5.0 2.7 3.8 4.0 5.0 Paraffin Oil 1.3
1.8 3.1 3.8 1.3 1.8 1.8 2.6 Peanut Oil 3.1 3.2 4.4 5.0 3.1 4.4 4.4
5.0 Rustoleum Thinner.sup.6 6.3 6.2 7.1 7.6 5.4 7.6 7.1 7.6
Rabtex.sup.7 0.4 0.6 1.9 1.2 0.0 0.6 0.8 0.6 Safflower Oil 3.6 3.8
5.4 5.0 2.7 3.8 4.4 5.6 Soybean Oil 3.1 3.2 4.4 5.0 2.7 3.8 4.4 5.6
Actinol.sup.8 3.6 4.4 4.4 5.0 4.0 3.8 4.4 5.0 Turpentine 5.4 6.2
6.3 6.8 5.4 6.2 7.1 7.6
__________________________________________________________________________
1. Texaco, Inc., trademark for lubricating oil. 2. Atlantic
Richfield Co. trademark for mineral oil. 3. Witco Chemical Co.
trademark for mineral oil. 4. Texaco, Inc., trademark for
lubricating oil. 5. Atlantic Richfield Co. trademark for
lubricating oil 6. Rustoleum Corp. trademark for fish oil. 7.
Texaco, Inc., trademark for lubricating oil. 8. Arizona Chemical
Co. trademark for a fatty acid fraction of tall oil.
Fuel oil, mineral oil, lubricating oil, kerosene, nitroalkanes from
C.sub.1 to C.sub.3, and nitroglycerins are preferred as they are
the most useful in formulating explosives.
Table 5 shows the percent contraction of 5" CD by 7" MD sheets of
PVC film immersed for various periods of time at 70.degree.F. and
90.degree.F. in a mineral oil sold under the trademark "Atreol 34"
by the Atlantic Richfield Co. "KDA-2030" is Union Carbide's product
designation for 8 mil PVC plasticized with 33.7 percent dioctyl
phthalate and having a density of 1.237 gms./cc. "KDA-2078" is
Union Carbide's product designated for 12 mil PVC plasticized with
30 percent dioctyl phthalate and having a density of 1.251 gms./cc.
"Toywrap" is Transilwrap Co.'s product designation for 2-mil
plasticized PVC.
TABLE
.ident. 1 Day 3 Days 1 Week 1 Month Film 70.degree.F 94.degree.F
70.degree.F 94.degree.F 70.degree.F 94.degree.F 70.degree.F
94.degree.F
__________________________________________________________________________
KDA-2076 MD 1.4% 1.7% 1.7% 3.6% 3.6% 3.6% 4.4% 5.3% CD 2.0% 2.0%
1.2% 2.4% 2.4% 2.4% 5.0% 6.2% KDA-2030 MD 1.4% 1.7% 1.7% 2.7% 1.7%
3.6% 3.6% 4.4% CD 2.0% 2.0% 2.4% 2.4% 2.4% 4.0% 5.0% 6.2% KDA-2078
MD 1.4% 1.7% .86% 1.7% 1.7% 1.7% 2.7% 3.6% CD 2.0% 2.0% 1.2% 2.4%
1.2% 2.4% 2.4% 2.4% Toywrap MD 3.6% 2.9% 3.6% 3.6% 4.4% 3.6% 5.3%
4.4% CD 1.2% 2.0% 1.2% 2.5% 1.2% 2.4% 2.4% 3.8%
__________________________________________________________________________
table 6 shows the percent contraction of 5" by 7" sheets of PVC
film after immersion at 70.degree.F. and 104.degree.F. for various
periods in "Atreol 34" mineral oil. "Regalite" is the product
designation of Tenneco Chemical Co. for a plasticized PVC about 10
mils thick. ##SPC1##
Virtually any explosive containing about 0.1 to about 80 percent
extractor for the plasticizer may be used in this invention.
Preferably the explosive should contain about 1 percent to about 10
percent plasticizer-extractor in order to extract the plasticizer
in amounts previously described. Dynamite, AN-FO, slurries, and
water-in-oil emulsions are four common, suitable explosives which
may contain a plasticizer-extractor, usually an oil. Of the four,
water-in-oil emulsions are preferred because they exhibit the
greatest amount of noticeable product shrinkage and they cause the
greatest amount of bag expansion in the polyolefin and copolymer
bags commonly used.
A dynamite composition may comprise, for example, 1 pbw (part by
weight) inorganic oxidizer salt, about 0.3 to 8 pbw nitroglycerin,
nitroglycol, or mixtures thereof, and up to about 0.6 pbw
gelatinizing agent such as nitrocotton. Various fuels may also be
included.
AN-FO compositions contain ammonium nitrate prills and liquid
hydrocarbon fuel, for example, about 78 to 97 percent ammonium
nitrate and about 2 to 12 percent liquid hydrocarbon fuel, such as
fuel oil which is inexpensive. The compositions may also contain
surfactants, metals, additional fuels, sensitizers, and other
substances.
An oil-containing slurry explosive may comprise, for example, about
10 to about 70 percent inorganic oxidizer salt, about 10 to about
30 percent water, about 1 to 30 percent oil, and sufficient oil
thickener to keep the oil from separating. Other fuels, metals,
sensitizers, etc., may also be used.
A water-in-oil emulsion explosive may comprise, for example, about
1 to about 10 percent carbonaceous fuel (e.g., an oil), about 55 to
about 87 percent oxidizer, about 0.1 to about 15 percent
sensitizer, about 10 to about 25 percent water, about 1/2 to about
2 percent emulsifier, and sufficient gas to give the explosive a
density of about 0.9 to about 1.40 gms./cc. (See Bluhm U. S. Pat.
No. 3,447,978).
Table 7 shows the shrinkage and effectiveness of AN-FO explosives
in PVC bags after various intervals. The PVC bag used was a side
lap sealed bag as shown in the accompanying drawing made from
"KDA-2076" PVC. Product A is 90 percent whole and ground AN prills,
4 percent No. 2 diesel fuel oil, and 6% al. granules. Product B is
94.25 percent whole Al ground AN prills and 5.75 percent No. 2
diesel fuel oil. The samples were shot with 4" high-velocity
gelatin in 5" .times. 12" cartridges. ##SPC2##
The above table shows that the cartridge not only shrank but also
increased in density.
Table 8 gives the density and velocity when shot of various samples
of two water-in-oil emulsion explosives prepared according to Bluhm
U.S. Pat. No. 3,447,978 after various periods of storage at
90.degree.F. and ambient temperatures. All samples had a density of
1.15 gms./cc. when prepared. Emulsion A contained 2.5 percent
mineral oil. Emulsion B contained 0.5 percent mineral oil. The
samples were shot with 3" high-velocity gelatin primer in 3"
.times. 15" cartridges of "KDA-2076" PVC.
TABLE 8
Age of Emulsion A Emulsion B Sample Ambient 90.degree.F. Ambient
90.degree.F . 1 Week Velocity (fps) 18520 19050 16670 17090 Density
(gms./cc.) 1.203 1.203 1.207 1.203 3 Months Velocity (fps) 18520
18520 16025 14425 Density (gms./cc.) 1.223 1.197 1.260 1.267 5
Months Velocity (fps) 18820 18520 16305 10560 Density (gms./cc.)
1.213 1.217 1.220 1.270 6 Months Velocity (fps) 19050 19230 14960
failed Density (gms./cc.) 1.210 1.210 1.257 1.287
The above table shows the increase in density of each sample from
its original 1.15 gms./cc.
* * * * *