U.S. patent application number 11/348616 was filed with the patent office on 2007-05-17 for gas-generating compositions, fracturing system and method of fracturing material.
Invention is credited to Roy Ault, Christopher Schmidt, Sean Weaver.
Application Number | 20070107820 11/348616 |
Document ID | / |
Family ID | 38345773 |
Filed Date | 2007-05-17 |
United States Patent
Application |
20070107820 |
Kind Code |
A1 |
Schmidt; Christopher ; et
al. |
May 17, 2007 |
Gas-generating compositions, fracturing system and method of
fracturing material
Abstract
Compositions and systems for use in breaking or fracturing hard
material are described. In particular, gas-generating compositions
exhibiting at least a dual burn rate, including compositions
comprising lactose, potassium perchlorate and ferrosilicon are
described.
Inventors: |
Schmidt; Christopher; (Palo
Alto, CA) ; Ault; Roy; (Lancashire, GB) ;
Weaver; Sean; (US) |
Correspondence
Address: |
MORRISON & FOERSTER LLP
755 PAGE MILL RD
PALO ALTO
CA
94304-1018
US
|
Family ID: |
38345773 |
Appl. No.: |
11/348616 |
Filed: |
February 6, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60649992 |
Feb 4, 2005 |
|
|
|
Current U.S.
Class: |
149/38 |
Current CPC
Class: |
C06B 33/00 20130101;
F42B 3/04 20130101; F42D 3/04 20130101; C06D 5/06 20130101; F42B
3/087 20130101; F42B 3/00 20130101; F42B 3/28 20130101 |
Class at
Publication: |
149/038 |
International
Class: |
C06B 33/08 20060101
C06B033/08 |
Claims
1. A composition comprising at least one of compositions (A), (B1),
(C1) and (D) wherein: composition (A) comprises (a) at least one
carbohydrate fuel; (b) at least one compound selected from the
group consisting of potassium perchlorate, potassium nitrate,
potassium chlorate, potassium sulfate and a perchlorate salt; (c)
at least one substance selected from the group consisting of
ferrosilicon, magnalium, aluminum metal and magnesium metal; and
(d) less than 5 weight percent ammonium oxalate; composition (B1)
comprises (a) at least one carbohydrate fuel; (b) at least one
compound selected from the group consisting of potassium
perchlorate, potassium nitrate, potassium chlorate, potassium
sulfate and a perchlorate salt; (c) at least one substance selected
from the group consisting of ferrosilicon, magnalium, aluminum
metal and magnesium metal; and (d) X weight percent ammonium
oxalate, wherein X is less than 12 weight percent ammonium oxalate,
and composition (B1) has a powder factor that is less than the
powder factor of composition (B2), wherein composition (B2) is
identical to composition (B1) with the exceptions: composition (B2)
comprises 12% ammonium oxalate and the sum of weight percentages of
components (a), (b) and (c) in composition (B2) is reduced in total
by 12-X; composition (C1) comprises (a) at least one carbohydrate
fuel; (b) at least one compound selected from the group consisting
of potassium perchlorate, potassium nitrate, potassium chlorate,
potassium sulfate and a perchlorate salt; (c) at least one
substance selected from the group consisting of ferrosilicon,
magnalium, aluminum metal and magnesium metal; and (d) X weight
percent ammonium oxalate, wherein X is less than 12 weight percent
ammonium oxalate, and composition (C1) has a powder factor that is
less than the powder factor of composition (C2), wherein
composition (C2) comprises 12 weight percent ammonium oxalate,
about 37 weight percent potassium perchlorate, about 24 weight
percent salicylic acid, about 26 weight percent ferrosilicon and
about 1 weight percent borax; composition (D) comprises (a) at
least one carbohydrate fuel; (b) at least one compound selected
from the group consisting of potassium perchlorate, potassium
nitrate, potassium chlorate, potassium sulfate and a perchlorate
salt; (c) at least one substance selected from the group consisting
of ferrosilicon, magnalium, aluminum metal and magnesium metal,
wherein the ignited composition exhibits a first change in burn
rate with change in ln(p) to a first pressure and a second change
in burn rate with change in ln(p) at pressures greater than the
first pressure, and wherein the second change in burn rate with
change in ln(p) is greater than the first change in burn rate with
change in ln(p).
2. The composition of claim 1, wherein the carbohydrate fuel
comprises a sugar.
3. The composition of claim 2, wherein the composition within the
cartridge contains no ammonium oxalate.
4. The composition of claim 2, wherein the sugar comprises a
disaccharide or a hydrate thereof.
5. The composition of claim 4, wherein the carbohydrate fuel
comprises lactose or a hydrate thereof.
6. The composition of claim 5, wherein said substance comprises
ferrosilicon.
7. The composition of claim 6, wherein said substance consists
essentially of ferrosilicon.
8. The composition of claim 7, wherein the composition contains no
ammonium oxalate.
9. The composition of claim 5, wherein said composition comprises
at least two members of the substance group.
10. The composition of claim 9, wherein said members of the
substance group comprise ferrosilicon and magnalium.
11. The composition of claim 10, wherein said members consist
essentially of ferrosilicon and magnalium.
12. The composition of claim 11, wherein the composition contains
no ammonium oxalate.
13. The composition of claim 10, wherein said members of the
substance group comprise magnesium and aluminum.
14. The composition of claim 13, wherein the composition contains
no ammonium oxalate.
15. The composition of claim 2, wherein said substance comprises
ferrosilicon.
16. The composition of claim 15, wherein said substance consists
essentially of ferrosilicon.
17. The composition of claim 16, wherein the composition contains
no ammonium oxalate.
18. The composition of claim 2, wherein said composition comprises
at least two members of the substance group.
19. The composition of claim 18, wherein said members of the
substance group comprise ferrosilicon and magnalium.
20. The composition of claim 19, wherein said members consist
essentially of ferrosilicon and magnalium.
21. The composition of claim 20, wherein the composition contains
no ammonium oxalate.
22. The composition of claim 2, wherein said members of the
substance group comprise magnesium and aluminum.
23. The composition of claim 22, wherein the composition contains
no ammonium oxalate.
24. The composition of claim 1, wherein said composition comprises
potassium perchlorate.
25. The composition of claim 24, wherein the composition within the
cartridge contains no ammonium oxalate.
26. The composition of claim 24, wherein the carbohydrate fuel
comprises a disaccharide or a hydrate thereof.
27. The composition of claim 26, wherein the disaccharide comprises
lactose or a hydrate thereof.
28. The composition of claim 27, wherein said substance comprises
ferrosilicon.
29. The composition of claim 28, wherein said substance consists
essentially of ferrosilicon.
30. The composition of claim 29, wherein the composition contains
no ammonium oxalate.
31. The composition of claim 30, wherein said substance consists
essentially of lactose or its hydrate.
32. The composition of claim 27, wherein said composition comprises
at least two members of the substance group.
33. The composition of claim 32, wherein said members of the
substance group comprise ferrosilicon and magnalium.
34. The composition of claim 33, wherein said members consist
essentially of ferrosilicon and magnalium.
35. The composition of claim 34, wherein the composition contains
no ammonium oxalate.
36. The composition of claim 35, wherein said substance consists
essentially of lactose or its hydrate.
37. The composition of claim 32, wherein said members of the
substance group comprise magnesium and aluminum.
38. The composition of claim 37, wherein the composition contains
no ammonium oxalate.
39. The composition of claim 38, wherein said substance consists
essentially of lactose or its hydrate.
40. The composition of claim 24, wherein said substance comprises
ferrosilicon.
41. The composition of claim 40, wherein said substance consists
essentially of ferrosilicon.
42. The composition of claim 41, wherein the composition contains
no ammonium oxalate.
43. The composition of claim 24, wherein said composition comprises
at least two members of the substance group.
44. The composition of claim 43, wherein said members of the
substance group comprise ferrosilicon and magnalium.
45. The composition of claim 44, wherein said members consist
essentially of ferrosilicon and magnalium.
46. The composition of claim 45, wherein the composition contains
no ammonium oxalate.
47. The composition of claim 43, wherein said members of the
substance group comprise magnesium and aluminum.
48. The composition of claim 47, wherein the composition contains
no ammonium oxalate.
49. The composition of claim 1, wherein the composition contains no
ammonium oxalate.
50. The composition of claim 1, wherein said substance comprises
ferrosilicon.
51. The composition of claim 50, wherein said substance consists
essentially of ferrosilicon.
52. The composition of claim 51, wherein the composition contains
no ammonium oxalate.
53. The composition of claim 1, wherein said composition comprises
at least two members of the substance group.
54. The composition of claim 53, wherein said members of the
substance group comprise ferrosilicon and magnalium.
55. The composition of claim 54, wherein said members consist
essentially of ferrosilicon and magnalium.
56. The composition of claim 55, wherein the composition contains
no ammonium oxalate.
57. The composition of claim 53, wherein said members of the
substance group comprise magnesium and aluminum.
58. The composition of claim 57, wherein the composition contains
no ammonium oxalate.
59. The composition of any of the claims above, wherein the ignited
composition exhibits said first change in burn rate with change in
ln(p) to said first pressure and said second change in burn rate
with change in ln(p) at said pressures greater than the first
pressure, and wherein the second change in burn rate with change in
ln(p) is greater than the first change in burn rate with change in
ln(p).
60. The composition of claim 1 wherein the composition is
composition (A).
61. The composition of claim 1 wherein the composition is
composition (B1).
62. The composition of claim 1 wherein the composition is
composition (C1).
63. The composition of claim 1 wherein the composition is
composition (D).
64. The composition of claim 60, claim 61, claim 62 or claim 63
wherein the composition contains ferrosilicon and magnalium.
65. The composition of claim 64, wherein the carbohydrate fuel is
lactose or a hydrate thereof.
66. The composition of claim 64, wherein the composition comprises
about 15 weight % ferrosilicon and about 10 weight % magnalium.
67. The composition of claim 65, wherein the composition comprises
about 15 weight % ferrosilicon and about 10 weight % magnalium.
68. The composition of claim 64, wherein the composition comprises
about 40 to about 50 weight % potassium perchlorate, about 25 to
about 35 weight % lactose or a hydrate thereof, about 10 to about
15 weight % ferrosilicon and about 5 to about 15 weight %
magnalium.
69. The composition of claim 64, wherein the composition comprises
about 50 to about 60 weight % potassium perchlorate, about 15 to
about 25 weight % lactose or a hydrate thereof, about 15 to about
25 weight % ferrosilicon and about 1 weight % of a flow agent.
70. The composition of any claim above, wherein the composition has
a tap density between about 0.8 g/cc and about 1.5 g/cc.
71. A system comprising: a material to be fractured; a cartridge
within a hole in the material to be fractured; a composition
according to any of claim 1-claim 70 within the cartridge, and a
stemming material above the cartridge.
72. A method for fracturing material comprising creating a hole in
the material, inserting a cartridge containing a composition
according to any of claim 1-claim 70 into the hole, at least
partially filling the hole with a stemming material, and igniting
the composition.
73. A method of making a composition comprising: (a) providing at
least one carbohydrate fuel; (b) providing at least one compound
selected from the group consisting of potassium perchlorate,
potassium nitrate, potassium chlorate, potassium sulfate and a
perchlorate salt; (c) providing at least one compound selected from
the group consisting of ferrosilicon, magnalium, aluminum metal or
magnesium metal; (d) combining the compounds provided in steps
(a)-(c) in amounts and under conditions sufficient to produce a
composition having a tap density of about 0.8 g/cc to about 1.5
g/cc.
74. A method of fracturing a material to be fractured comprising:
oxidizing a compound at a first change in burn rate as a function
of pressure within a hole in the material to produce a gas;
containing the gas generated in the oxidizing step to attain a
sufficient pressure within the hole such that a second change in
burn rate as a function of pressure occurs; producing an additional
amount of gas such that the pressure increases and the material
fractures.
75. A composition comprising (a) at least one carbohydrate fuel;
(b) at least one compound selected from the group consisting of
potassium perchlorate, potassium nitrate, potassium chlorate,
potassium sulfate and a perchlorate salt; (c) at least one compound
selected from the group consisting of sodium benzoate, sodium
nitrobenzoate or sodium gluconate.
76. The composition according to claim 75, wherein the carbohydrate
fuel is lactose or a hydrate thereof.
77. The composition according to claim 75 or claim 76, wherein the
composition comprises sodium benzoate and sodium nitrobenzoate.
78. The composition according to claim 75 or claim 76, wherein the
composition comprises sodium gluconate.
79. The composition according to claim 75 or claim 78, wherein the
composition comprises about 3 to about 5 times as much component
(b) by weight percent compared to the weight percent of component
(a).
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 60/649,992, filed Feb. 4, 2005, which is
incorporated by reference in its entirety.
STATEMENT OF RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED
RESEARCH
[0002] Not applicable.
TECHNICAL FIELD
[0003] This invention relates to material breaking or fracturing
methods and compositions and systems useful therein. More
specifically, it relates to gas-generating compositions, fracturing
systems, and methods of using and making the foregoing.
BACKGROUND OF THE INVENTION
[0004] Excavation of hard materials, such as rock and concrete, is
a primary activity in underground mining, surface mining, open pits
and quarries, earth moving and allied construction works, and in
civil demolition projects. Explosive blasting has historically been
used to break hard materials during excavation, but this technique
is not suitable for all applications due to handling and safety
concerns that accompany the use of high explosive materials. For
instance, explosive blasting is known to produce noise, vibration
and flyrock, and explosive materials are subject to strict handling
and transportation restrictions. Alternative methods for fracturing
or breaking hard material have become increasingly important in
recent years for several reasons. For instance, in civil
engineering and quarry operations, there is a growing need to
reduce insurance costs, increase worker safety, lower the cost of
safety, and achieve a lower total cost of fracturing the desired
materials.
[0005] Mechanical impact breakers and other rock breaking and
excavation tools, such as tunnel boring machines and roadheader
machines, are alternatives to explosive blasting. However, these
techniques require expensive and highly specialized tools.
Moreover, repetitive breaking can result in wear and dulling of the
machinery over time which can require sharpening or replacing
expensive machine parts.
[0006] Additional breaking methods have been developed that employ
a military-type cannon system. A propellant-based cartridge is
fired into the cannon to discharge high-pressure gasses into a hole
drilled into the material to initiate fracture. This is a
relatively safe method, but also relies on sophisticated and
expensive equipment that has a limited lifetime due to the
degradation accompanying repeated firings.
[0007] In some applications, high explosives cannot be used due to
regulatory restrictions and mechanical breaking means are
impractical due to the material's location and/or high compressive
strength. To this end, a variety of small charge breaking methods
have been developed.
[0008] In U.S. Pat. No. 6,679,175, Gavrilovic teaches a propellant
based small charge breaking system, including double-base
propellants combined with ammonium nitrate that intend to solve the
problems of fly-rock, noise, vibration, and the regulatory
restrictions associated with high explosives. While this method
offers a potential alternative to conventional means, it is not
without drawbacks. The propellant formulas disclosed are known to
be hygroscopic and have a high tendency to misfire, which is both
costly and dangerous. In addition, the fracturing efficiencies
disclosed, commonly expressed as the powder factor by those skilled
in the art of the propellants, are relatively low, leading to
higher drilling, boring, and cartridge costs.
[0009] In U.S. Pat. No. 6,145,933, Watson et al., describes the
combined use of small high explosive charges and mechanical
breaking means. This combined method provides improved efficiency
over either method when used alone, but does not overcome the
problems of regulatory restrictions and the high cost of transport
and safety when using a high explosive material.
[0010] In GB 2,341,917 and GB 2,395,714, non-explosive compositions
are disclosed for use in breaking systems, such as for breaking
rock.
[0011] Deflagrating compositions used in small charge breaking
applications are safer than high explosives, but can provide
insufficient results due to the time required to produce enough gas
to fracture the material. This delay in generating large quantities
of gas inside a hole drilled into the material provides more
opportunity for the gas that has been generated to escape by
rifling and ejecting the stemming material instead of building up
inside the hole. Thus, there continues to be a need for new safe
and/or cost efficient and/or effective methods for breaking hard
materials.
[0012] The present invention provides novel methods and
compositions for breaking or fracturing hard materials that address
one or more of the drawbacks present in alternate breaking systems
and/or provides additional alternatives to conventional breaking
methods. In particular, gas-generating compositions, fracturing
systems and methods of using the foregoing are described.
SUMMARY OF THE INVENTION
[0013] Provided are compositions useful in fracturing a material
such as rock or concrete and associated systems. The compositions
when ignited have a burn rate that is less than the speed of sound
in air at standard conditions. Systems typically include a
composition within a cartridge which may have an igniter suitable
to ignite the composition.
[0014] The composition typically exhibits at least two distinct
values of change in burn rate with change in natural log of
pressure. The composition typically burns at a lower rate when
first ignited, and then burns at a much faster rate once combustion
has proceeded and the combustion products produce a certain
pressure in a hole in the material to be fractured.
[0015] The composition may comprise one or more of the following
compositions (A), (B1), (C1), and/or D:
[0016] composition (A) comprises (a) at least one carbohydrate
fuel; (b) at least one compound selected from the group consisting
of potassium perchlorate, potassium nitrate, potassium chlorate,
potassium sulfate and a perchlorate salt; (c) at least one
substance selected from the group consisting of ferrosilicon,
magnalium, aluminum metal and magnesium metal; and (d) less than 5
weight percent ammonium oxalate;
[0017] composition (B1) comprises (a) at least one carbohydrate
fuel; (b) at least one compound selected from the group consisting
of potassium perchlorate, potassium nitrate, potassium chlorate,
potassium sulfate and a perchlorate salt; (c) at least one
substance selected from the group consisting of ferrosilicon,
magnalium, aluminum metal and magnesium metal; and (d) X weight
percent ammonium oxalate, wherein X is less than 12 weight percent
ammonium oxalate, and composition (B1) has a powder factor that is
less than the powder factor of composition (B2), wherein
composition (B2) is identical to composition (B1) with the
exceptions composition (B2) comprises 12% ammonium oxalate and the
sum of weight percentages of components (a), (b) and (c) in
composition (B2) is reduced in total by 12-X;
[0018] composition (C1) comprises (a) at least one carbohydrate
fuel; (b) at least one compound selected from the group consisting
of potassium perchlorate, potassium nitrate, potassium chlorate,
potassium sulfate and a perchlorate salt; (c) at least one
substance selected from the group consisting of ferrosilicon,
magnalium, aluminum metal and magnesium metal; and (d) X weight
percent ammonium oxalate, wherein X is less than 12 weight percent
ammonium oxalate, and composition (C1) has a powder factor that is
less than the powder factor of composition (C2), wherein
composition (C2) comprises 12 weight percent ammonium oxalate,
about 37 weight percent potassium perchlorate, about 24 weight
percent salicylic acid, about 26 weight percent ferrosilicon and
about 1 weight percent borax; and
[0019] composition (D) comprises (a) at least one carbohydrate
fuel; (b) at least one compound selected from the group consisting
of potassium perchlorate, potassium nitrate, potassium chlorate,
potassium sulfate and a perchlorate salt; (c) at least one
substance selected from the group consisting of ferrosilicon,
magnalium, aluminum metal and magnesium metal, wherein the ignited
composition exhibits a first change in burn rate with change in
ln(p) to a first pressure and a second change in burn rate with
change in ln(p) at pressures greater than the first pressure, and
wherein the second change in burn rate with change in ln(p) is
greater than the first change in burn rate with change in
ln(p).
[0020] Also disclosed is a method of fracturing a hard material
such as rock or concrete, in which a composition as disclosed
herein is inserted into a hole in the material, stemming material
is placed over the composition, and the composition is ignited to
produce gas, thus producing sufficient pressure to fracture the
material.
[0021] Also disclosed is a method of fracturing a material, in
which the method involves oxidizing a compound at a first change in
burn rate with change in ln pressure within a hole in the material
to produce a gas; containing the gas generated in the oxidizing
step to attain a sufficient pressure within the hole such that a
second change in burn rate with change in ln pressure occurs; and
producing an additional amount of gas such that the pressure
increases and the material fractures.
[0022] Also disclosed herein is a method of making a composition
comprising:
(a) providing at least one carbohydrate fuel;
(b) providing at least one compound selected from the group
consisting of potassium perchlorate, potassium nitrate, potassium
chlorate, potassium sulfate and a perchlorate salt;
(c) providing at least one compound selected from the group
consisting of ferrosilicon, magnalium, aluminum metal or magnesium
metal;
(d) combining the compounds provided in steps (a)-(c) in amounts
and under conditions sufficient to produce a composition having a
tap density of about 0.8 g/cc to about 1.5 g/cc.
[0023] A number of variations of the compositions, systems, and
methods above are discussed herein, including in the appended
claims which form a part of this specification.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is a view of a disassembled cartridge.
[0025] FIG. 2 is view of an assembled cartridge.
[0026] FIG. 3 is a view of a cartridge inside a hole.
[0027] FIG. 4 is a plot of burn rate as a function of the natural
log of pressure (ln(p)) for the gas-generating composition of
Example 1.
[0028] FIG. 5 is a plot of burn rate as a function of ln(p) for the
pyrotechnic mixture of Example 1.
DETAILED DESCRIPTION
[0029] Breaking hard material such as rock and concrete is
accomplished by the methods, systems and compositions disclosed
herein. The methods, systems and compositions can be used in a wide
variety of applications, including demolition and excavation
applications, and are particularly beneficial as alternatives to
high explosive blasting and/or mechanical fracturing or when
commercial propellant charges provide insufficient breaking
results.
[0030] The gas-generating compositions disclosed herein comprise
oxidizer and fuel components that upon ignition deflagrate and burn
sub-sonically even at elevated pressures, including but not limited
to pressures up to about 4,000 psig. In contrast, highly explosive
materials detonate, producing supersonic shock waves at atmospheric
pressure.
[0031] Various gas-generating compositions disclosed herein differ
from commercial propellants known to the inventors in that they do
not have a tendency to rifle or expel stemming material when used
in material breaking. While not wishing to be bound by theory, it
is believed that various compositions disclosed herein, when
ignited, may exhibit two (dual) or more distinct changes in burn
rate as a function of the natural log of pressure (ln(p)) over the
compositions' burn lifetime. That is, the compositions are believed
to exhibit a first change in burn rate as a function of ln(p) to a
first pressure and a second change in burn rate as a function of
ln(p) at pressures greater than the first pressure, wherein the
second change in burn rate as a function of ln(p) is greater than
the first change in burn rate as a function of ln(p). As will be
understood to those of skill in the art, a composition exhibits a
dual burn rate if, over the burn life of the composition or at
least between pressures ranging from about 100 psig to about 4,000
or from about 100 psig to about 2,000 psig or from about 500 psig
to about 4,000 psig or from about 500 psig to about 2,000 psig or
from about 600 psig to about 1,000 psig, the composition exhibits a
first change in burn rate as a function of ln(p) to a first
pressure and a second change in burn rate as a function of ln(p) at
pressures greater than the first pressure, wherein the second
change in burn rate as a function of ln(p) is greater than the
first change in burn rate as a function of ln(p). Except for the
inflection point indicating the identity of the first pressure
beyond which the second change in burn rate as a function of ln(p)
begins, positive or negative undulations in burn rate as a function
of ln(p) over small pressure ranges, for example over a pressure
range of 50 psig or under, are not considered distinct burn rates
for the purposes of establishing a dual or more burn rate. An
example of a composition exhibiting a dual burn rate is found in
Example 1 and a plot of the composition's burn rate as a function
of ln(p) is shown in FIG. 4. A plot of a propellant lacking a dual
change in burn rate as a function of ln(p) over the tested
pressures is shown in FIG. 5.
[0032] In one variation, the gas-generating compositions exhibit
dual changes in burn rate as a function of ln(p) where the second
change in burn rate as a function of ln(p) is at least about twice
as great as the first change in burn rate as a function of ln(p).
In other variations, the gas-generating composition exhibits dual
changes in burn rate as a function of ln(p) where the second change
in burn rate as a function of ln(p) is at least about 2 or 3 or 4
or 5 or 6 or 7 or 8 or 9 or 10 or 20 or 25 or 30 or 40 or 50 or
greater than about 10 or greater than about 25 or between about 10
and 15 or between about 10 and 45 or between about 20 and 45 or
between about 25 and 35 times greater than the first change in burn
rate as a function of ln(p). In another variation, the compositions
disclosed herein burn sub-sonically at pressures of about 5,000
psig or at pressures of about 10,000 psig or at pressures of about
15,000 psig or at pressures of about 20,000 psig and the
compositions exhibit a first change in burn rate as a function of
ln(p) to a first pressure and a second change in burn rate as a
function of ln(p) at pressures greater than the first pressure and
the second change in burn rate as a function of ln(p) is at least
about 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 20 or 25 or 30
or 40 or 50 or greater than about 10 or greater than about 25 or
between about 10 and 15 or between about 10 and 45 or between about
20 and 45 or between about 25 and 35 times greater than the first
change in burn rate as a function of ln(p). In one variation, the
gas-generating compositions burns sub-sonically at pressures of
about 5,000 psig or at pressures of about 10,000 psig or at
pressures of about 15,000 psig or at pressures of about 20,000 psig
and exhibits more than two changes in burn rate as a function of
ln(p). In compositions exhibiting more than two changes in burn
rate as a function of ln(p), a plot of burn rate as a function of
ln(p) will have more than one inflection point and will thus
identify at least two or three or more than three pressure ranges
at which the composition undergoes a change in burn rate as a
function of ln(p).
[0033] Any of the compositions disclosed herein may exhibit at
least a dual burn rate where the second or greater changes in burn
rates as a function of ln(p) can be any of the values specified
herein above, such as 30 times as great or more than the first
change in burn rate as a function of ln(p).
[0034] The compositions' dual or more change in burn rate as a
function of ln(p) is believed to result in greater volumes of gas
production over the same period of time when compared to
propellants that do not exhibit a dual change in burn rate as a
function of ln(p) or exhibit a lesser burn rate as a function of
ln(p) when compared to a first and/or a second change in burn rate
as a function of ln(p) exhibited by the compositions disclosed
herein. Because the gas-generating compositions and propellants for
use in fracturing material are generally ignited under confined
conditions, such as in a hole in the material to be fractured and
covered with stemming material, the gas-generating compositions
having a dual burn rate are believed to build up more pressure in
the form of gas during the same amount of time as compared to
propellants lacking the dual burn rate mechanism burning under
identical conditions. The present compositions' faster build-up of
pressure with time is believed to be at least partly responsible
for their decreased incidence of rifling and/or seepage of the gas
through the stemming material, and in their ability to provide
faster, more efficient breaking.
[0035] Various compositions disclosed herein generate a large
volume of gas in a short time period as compared to compositions
not exhibiting a dual or more burn rate. The compositions'
generation of a large volume of gas over a small time period is
believed to prevent the stemming material from rifling because the
stemming material does not have the time or power to be displaced
or ejected from the hole. Because the present compositions are not
high explosives, the benefits of fast, efficient breaking are
obtained without compromising safety and its associated costs.
[0036] In one variation, the compositions for use in the systems
and methods described herein comprise a fuel, an oxidizer and a
metal or alloy, provided that the composition comprises less than
about 10 weight percent or less than about 8 weight percent or less
than about 6 weight percent or less than about 5 weight percent or
less than about 4 weigh percent or less than about 3 weight percent
or less than about 2 weight percent or less than about 1 weight
percent or is substantially free of or is essentially free of or is
completely free of ammonium oxalate or other low-energy nitrogen
containing fuel such as oxamide or guanadine nitrate. In another
variation, the compositions for use in the systems and methods
described herein generally comprise a fuel, an oxidizer and a metal
or alloy, provided that the composition comprises less than 12
weight percent ammonium oxalate or other low-energy nitrogen
containing fuel such as oxamide or guanadine nitrate and the
ignited composition generates gas sufficient to fracture hard
material. In another variation, the compositions for use in the
systems and methods described herein generally comprise a fuel, an
oxidizer and a metal or alloy, provided that the ignited
composition exhibits a first change in burn rate as a function of
ln(p) to a first pressure and a second change in burn rate as a
function of ln(p) at pressures greater than the first pressure, and
wherein the second change in burn rate as a function of ln(p) is
greater than the first change in burn rate as a function of ln(p).
In another variation, the compositions for use in the systems and
methods described herein exhibit at least a dual burn rate when
ignited and generally comprise a fuel, an oxidizer and a metal or
alloy, provided that the composition comprises less than about 10
weight percent or less than about 8 weight percent or less than
about 6 weight percent or less than about 5 weight percent or less
than about 4 weigh percent or less than about 3 weight percent or
less than about 2 weight percent or less than about 1 weight
percent or is substantially free of or is completely free of
ammonium oxalate or other low-energy nitrogen containing fuel such
as oxamide or guanadine nitrate. In another variation, the
compositions for use in the systems and methods described herein
exhibit at least a dual burn rate when ignited and generally
comprise a fuel, an oxidizer and a metal or alloy, provided that
the composition comprises less than 12 weight percent ammonium
oxalate or other low-energy nitrogen containing fuel such as
oxamide or guanadine nitrate and the ignited composition generates
gas sufficient to fracture hard material.
[0037] Optional additional components may be added to the
gas-generating compositions, including substances known to modify
the burn rate of a gas-generating composition, such as substances
known to increase the burn rate. The gas-generating composition may
comprise oxidizer and fuel components selected for their low cost
and/or low hygroscopicity and/or long shelf life and/or favorable
burn rate and/or gas generation properties. In one variation, the
gas-generating composition comprises oxidizer and fuel components
that are selected for their low cost and low hygroscopicity and
long shelf life and favorable burn rate and gas generation
properties. By selecting materials having a low hygroscopicity, the
misfires common in certain existing compositions are reduced.
Misfires are often costly due to the loss of cartridges, and
dangerous due to the risks associated with live cartridge
extraction.
[0038] Oxidizers and/or fuels and/or additional components having a
hygroscopicity point greater than 90% are known to have lower
chances of absorbing water during manufacture and storage. Water
and moisture in a gas-generating composition can cause a reduction
in burn rate and a greater chance of misfires. In addition, low
hygroscopicity is believed to contribute to the long shelf life of
the gas-generating compositions, which can be stored for at least
up to several years. This stability over time is beneficial,
especially when compared to alternative formulations for fracturing
material, such as those consisting of ammonium nitrate and
nitrocellulose, which are known to be hygroscopic and exhibit a
relatively short shelf-life.
Oxidizer
[0039] An oxidizer having one or more or all of the following
properties may be used in the gas-generating composition: high
oxygen content and/or high reactivity and/or low hygroscopicity
which leads to a long shelf life. Such oxidizers include, but are
not limited to, inorganic perchlorate, chlorate, nitrate and
sulfate salts. For instance, potassium perchlorate, potassium
chlorate, potassium nitrate, and potassium sulfate may be used in
the gas-generating compositions. Salts composed of sodium ions and
ammonium ions are known to be hygroscopic and are not preferred,
though if the gas-generating composition is contained in a
cartridge that is suitably sealed against water ingress and/or
egress, they can be made to perform suitably and may be used in the
gas-generating composition. Other oxidizers known to those of skill
in the art can be used, provided that the resulting gas-generating
composition exhibits the gas-generating properties disclosed
herein, such as a dual burn rate. In one variation, an oxidizer
such as potassium perchlorate is used as the oxidizer due to its
high oxygen content and high reactivity and low hygroscopicity
which leads to a long shelf life.
Fuel
[0040] The gas-generating composition will generally employ a fuel
having one or more or all of the following properties: low
hygroscopicity and/or low cost and/or suitable reactivity with the
selected oxidizer components. In one variation, a fuel such as
lactose is used as the fuel component due to its low hygroscopicity
and low cost, and suitable reactivity with the selected oxidizer
components. Fuels that may be used in the gas-generating
compositions include, but are not limited to, carbohydrate fuels,
including monosaccharides, oligosaccharides and polysaccharides as
well as substances derived from monosaccharides by reduction of the
carbonyl group (alditols), by oxidation of one or more terminal
groups to carboxylic acids, or by replacement of one or more
hydroxy group(s) by a hydrogen atom, an amino group, a thiol group
or similar heteroatomic groups or any hydrate of any of the
foregoing or listed anywhere herein, such as a monohydrate or
dehydrate thereof. The carbohydrate fuel can be a sugar, such as a
monosaccharide or oligosaccharide, including an aldose, dialdose,
aldoketose, ketose and diketose, as well as deoxy sugars and amino
sugars, and their derivatives. The carbohydrate fuel can be an
oligosaccharide, including a trisaccharide, tetrasaccharide,
pentasaccharide, or a polysacharide including homopolysaccharide or
heteropolysaccharide, including any hydrate thereof, such as a
monohydrate. Other suitable fuels include carbohydrates and
starches such as lactose, sucrose, glucose, fructose, ascorbic and
erythroscorbic acids, and wheat and potato starches. Carbohydrate
fuels also include derivatives of any of the forgoing compounds,
meaning compounds that are derivable from carbohydrate starting
materials.
[0041] In one variation, the carbohydrate fuel is used with a
perchlorate oxidizer, such as potassium perchlorate. The
carbohydrate fuel and perchlorate oxidizer can be any of the fuels
and perchlorates disclosed herein, such as a composition including
a saccharide fuel and perchlorate oxidizer, a monosaccharide fuel
and perchlorate oxidizer or a lactose, sucrose, glucose or fructose
fuel and a perchlorate oxidizer. In one variation, lactose or a
hydrate thereof, such as lactose monohydrate, is used with the
oxidizer potassium perchlorate.
[0042] Various other components described in the section below
entitled `Additional Components` may also act as fuels and will be
readily recognizable as such by those of skill in the art.
Additional Components
[0043] Additional components may optionally be added to the
gas-generating composition, for example, to increase the burn rate
or to act as oxidizers in certain instances, which may improve the
fracturing efficiency of the proposed system. Other additional
components may act as catalysts which tend to increase the rate of
gas generation. Such catalysts include but are not limited to metal
oxides such as iron oxide and copper oxide, and organometalics such
as ferrocene. A composition with a high fracturing efficiency will
tend to reach a greater peak pressure within the drill hole before
initiating fracture. By more rapidly building up pressure, the
stemming material is less likely to be ejected, and the available
energy in the form of pressure that can be used to fracture and
move the material is greater
[0044] Additional components that may be added to the
gas-generating composition may be components known to increase the
rate of gas generation. Such additional components include, but are
not limited to, metal benzoate, nitrobenzoate, and gluconate salts,
including sodium benzoate, sodium nitrobenzoate, sodium gluconate,
and the analogous salts of potassium ions. Such additional
components have been found to increase the burn rate while at the
same time serving as fuel components that are able to contribute to
the total volume of gas generated.
[0045] Additional components that may be added to the
gas-generating composition may be components that are not known to
increase the gas generation but may, for instance, burn
exothermically and increase the heat of the reaction when the
composition is ignited. Such additional components have been found
to function suitably as burn rate enhancers, but add only heat to
the reaction and do not increase the volume of gas generated. By
adding heat to the reaction, the burn rate and therefore gas
generation rate is increased. Additionally, the heat functions to
expand the available gas, thereby increasing the pressure and
improving the fracturing efficiency.
[0046] Such additional components include, but are not limited to,
alkali metals or salts thereof, alkaline earth metals or salts
thereof, transition metals or salts thereof, other metals or salts
thereof or mixtures or alloys of the same that are known by those
of skill in the art to be relatively safe to handle. For instance,
ferrosilicon, magnalium, aluminum, and magnesium and the like are
relatively safe to handle whereas lithium metal is known to be
highly flammable and explosive when exposed to air.
[0047] Ferrosilicon is believed to act as a reducing agent in the
gas-generating compositions. Ferrosilicon, in the presence of an
oxidizer such as perchlorate, is believed to receive an oxygen from
the perchlorate oxidizer, resulting in an exothermic reaction which
gives off a great quantity of heat that increases the burn rate of
the composition.
[0048] Metal alloys for use in the gas-generating compositions as
additional components include any alloys having the properties
discussed above. Alloys comprising elements or metals selected from
iron, silicon, aluminum, magnesium, titanium and zirconium are
intended as additional components, such as components that achieve
the desired burn rate characteristics disclosed herein. Metal
alloys include single alloys or composites or two or more alloys.
Examples of suitable metal alloys include magnalium and alloys
created from iron, silicon, aluminum, magnesium, titanium and
zirconium. Ferroalloys, including but not limited to ferrosilicon,
ferromanganese, magnesium ferrosilicon, ferrochromium,
ferromagnesium, ferrotitanium, ferroboron and ferrophosphorous are
also metal alloys acceptable for use as additional components.
Metal alloys may be present in the gas-generating composition as
any alloy composition. For instance, ferrosilicon can be used in
the gas-generating composition as an alloy of 50/50 iron/silicon or
as other ratios such as 15, 45, 75 or 90% silicon. In one
variation, the gas-generating composition comprises ferrosilicon as
about a 50/50 iron/silicon alloy.
[0049] A single gas-generating composition may comprise more than
one additional component described herein. For instance, the
gas-generating composition may comprise at least two metal alloys
or at least one metal salt and at least one metal alloy. For
instance, a gas-generating composition may comprise both an
alkaline earth metal or other metal alloy, such as magnalium, and a
transition metal alloy, including a ferroalloy, such as
ferrosilicon. In one variation, the gas-generating composition may
comprise both an alkaline earth metal or other metal alloy and a
transition metal alloy, such as a gas generating composition
comprising both ferrosilicon and magnalium.
[0050] Because of the high temperatures and pressures achieved
within the drill hole, which is discussed in more detail under the
heading `hole` below, ferrosilicon and magnalium have been found to
be a useful combination in the gas-generating composition. While
not wishing to be bound by any theory, it is believed that
magnalium is reduced in the presence of ferrosilicon at high
temperature and pressure, thus acting as an oxidizing agent, and
then later oxidized again to liberate heat when the thermodynamic
conditions permit. Theory aside, the inventors have found this
combination to have a high fracturing efficiency in the
gas-generation composition and fracturing system.
[0051] Gas generating compositions comprising at least one metal
powder have been found to be powerful gas-generating compositions.
The more powerful gas generating compositions, including
compositions comprising at least one metal powder such as
compositions comprising aluminum and/or magnesium powder, are
suitable for applications where the material to be fractured is
difficult to break. Such materials include embedded material or
material having only one free face. These materials can require
significantly more power, such as about five times or more power,
to effect fracturing. Therefore, compositions with increasing
amounts of metals, including high energy metals like aluminum and
magnesium, find use in breaking or fracturing hard materials such
as embedded rock for mass excavation applications.
[0052] In general, a gas-generating composition can be prepared by
selecting at least one fuel, at least one oxidizer and at least one
additional component disclosed herein. By selecting the disclosed
fuel, oxidizer and additional components for the gas-generating
composition, an improvement over existing gas-generating
compositions can be achieved. In particular, the gas-generating
compositions disclosed herein may have improved fracturing
efficiencies and/or longer shelf life and/or a reduced tendency to
misfire. In one variation, the gas generating composition exhibits
improved fracturing efficiency and a longer shelf life and a
reduced tendency to misfire.
[0053] Gas-generating composition components can be present in the
gas-generating composition in any amount, so long as the
composition retains its ability to act as a gas-generator with a
sufficient burn rate, such as any of the particular burn rates and
mechanisms disclosed herein.
[0054] A fuel component may be present in the gas-generating
composition in an amount ranging from 5% to 45%, from 5% to 40%,
from 5% to 35%, from 5% to 30%, from 5% to 25%, from 5% to 20%,
from 5% to 15%, from 5% to 10%, from 10% to 45%, from 15% to 45%,
from 20% to 45%, from 25% to 45%, from 30% to 45%, from 35% to 45%,
from 40% to 45%, from 10% to 45%, from 10% to 40%, from 10% to 35%,
from 10% to 30%, from 10% to 25%, from 10% to 20%, from 10% to 15%,
from 15% to 45%, from 15% to 35%, from 15% to 30%, from 15% to 25%,
from 15% to 20%, from 20% to 45%, from 20% to 30%, from 25% to 35%,
and from 20% to 25% by weight.
[0055] An oxidizer may be present in the gas-generating composition
in an amount ranging from 30% to 85%, from 30% to 80%, from 30% to
75%, from 30% to 65%, from 30% to 60%, from 30% to 55%, from 30% to
50%, from 30% to 45%, from 30% to 40%, from 30% to 35%, from 35% to
80%, from 35% to 75%, from 35% to 70%, from 35% to 65%, from 35% to
60%, from 35% to 55%, from 35% to 50%, from 35% to 45%, from 35% to
40%, from 35% to 35%, from 40% to 80%, from 40% to 75%, from 40% to
70%, from 40% to 65%, from 40% to 60%, from 40% to 55%, from 40% to
50%, from 40% to 45%, from 45% to 80%, from 45% to 75%, from 45% to
70%, from 45% to 65%, from 45% to 60%, from 45% to 55%, from 45% to
50%, from 50% to 80%, from 50% to 75%, from 50% to 70%, from 50% to
65%, from 50% to 60%, from 50% to 55%, from 55% to 80%, from 55% to
75%, from 55% to 65%, from 55% to 60%, from 60% to 80%, from 60% to
75%, from 60% to 70%, from 60% to 65%, from 65% to 80%, from 65% to
75%, from 65% to 70%, from 70%-80%, and from 70% to 75% by
weight.
[0056] An additional component, such as a component that adds heat
to the ensuing reaction of the gas-generating composition or acts
as an oxidizer, may be present in the gas-generating composition in
a range from 0% to 30%, from 0% to 25%, from 0% to 20%, from 0% to
15%, from 0% to 10%, from 0% to 5%, from 5% to 30%, from 5% to 25%,
from 5% to 20%, from 5% to 15%, from 5% to 10%, from 10% to 30%,
from 10% to 25%, from 10% to 20%, from 10% to 15%, from 15% to 30%,
from 15% to 25%, from 15% to 20%, from 20% to 30%, and from 20% to
25% by weight.
[0057] In general, when the fuel, oxidizer and additional
component(s) chosen for a given composition are combined, the total
weight percentages of the fuel, oxidizer and additional
component(s) will be a value of about 100 total weight percent. As
known to those of skill in the art, additional components may be
added to the composition, including but not limited to flow agents
or binders, such as a flow agent or binder in an amount that is
less than about 5 weight % or less than about 3 weight % or about 1
weight % of the total weight of the composition.
[0058] In one variation, the oxidizer and fuel combination is
potassium perchlorate and lactose, respectively. Alternative
oxidizer and fuel combinations may be employed in the
gas-generating composition in order to achieve similar, though
sometimes slightly less effective, results.
[0059] The following Table 1 lists gas-generating compositions. The
compositions below may optionally comprise a second or more
additional component. For instance, it is intended that every
composition listed in Table 1 can further comprise at least one of
ferrosilicon, magnalium, aluminum, magnesium, sodium benzoate,
sodium nitrobenzoate, sodium gluconate, potassium benzoate,
potassium nitrobenzoate, potassium gluconate or iron oxide, the
same as if each combination were individually and separately
listed. By way of example, the compositions may comprise two
additional components, such as a composition comprising both
ferrosilicon and magnalium, or any other combination of more than
one additional component. In addition, the compositions below may
optionally comprise other components, such as a flow agent, for
example, Neosil. All such additional gas-generating compositions
are described herein to the same extent as if each and every
possible combination is individually and separately listed.
TABLE-US-00001 TABLE 1 Examples of gas-generating composition by
composition. FUEL COMPONENT OXIDIZER COMPONENT ADDITIONAL COMPONENT
Lactose Potassium Perchlorate None Lactose Potassium Chlorate None
Lactose Potassium Nitrate None Lactose Potassium Sulfate None
Lactose Sodium Perchlorate None Lactose Sodium Chlorate None
Lactose Sodium Nitrate None Lactose Sodium Sulfate None Lactose
Ammonium Perchlorate None Lactose Ammonium Nitrate None Lactose
Other Alternative Oxidizer None Lactose Potassium Perchlorate
Ferrosilicon Lactose Potassium Chlorate Ferrosilicon Lactose
Potassium Nitrate Ferrosilicon Lactose Potassium Sulfate
Ferrosilicon Lactose Sodium Perchlorate Ferrosilicon Lactose Sodium
Chlorate Ferrosilicon Lactose Sodium Nitrate Ferrosilicon Lactose
Sodium Sulfate Ferrosilicon Lactose Ammonium Perchlorate
Ferrosilicon Lactose Ammonium Nitrate Ferrosilicon Lactose Other
Alternative Oxidizer Ferrosilicon Lactose Potassium Perchlorate
Magnalium Lactose Potassium Chlorate Magnalium Lactose Potassium
Nitrate Magnalium Lactose Potassium Sulfate Magnalium Lactose
Sodium Perchlorate Magnalium Lactose Sodium Chlorate Magnalium
Lactose Sodium Nitrate Magnalium Lactose Sodium Sulfate Magnalium
Lactose Ammonium Perchlorate Magnalium Lactose Ammonium Nitrate
Magnalium Lactose Other Alternative Oxidizer Magnalium Lactose
Potassium Perchlorate Aluminum Lactose Potassium Chlorate Aluminum
Lactose Potassium Nitrate Aluminum Lactose Potassium Sulfate
Aluminum Lactose Sodium Perchlorate Aluminum Lactose Sodium
Chlorate Aluminum Lactose Sodium Nitrate Aluminum Lactose Sodium
Sulfate Aluminum Lactose Ammonium Perchlorate Aluminum Lactose
Ammonium Nitrate Aluminum Lactose Other Alternative Oxidizer
Aluminum Lactose Potassium Perchlorate Magnesium Lactose Potassium
Chlorate Magnesium Lactose Potassium Nitrate Magnesium Lactose
Potassium Sulfate Magnesium Lactose Sodium Perchlorate Magnesium
Lactose Sodium Chlorate Magnesium Lactose Sodium Nitrate Magnesium
Lactose Sodium Sulfate Magnesium Lactose Ammonium Perchlorate
Magnesium Lactose Ammonium Nitrate Magnesium Lactose Other
Alternative Oxidizer Magnesium Lactose Potassium Perchlorate Sodium
Benzoate Lactose Potassium Chlorate Sodium Benzoate Lactose
Potassium Nitrate Sodium Benzoate Lactose Potassium Sulfate Sodium
Benzoate Lactose Sodium Perchlorate Sodium Benzoate Lactose Sodium
Chlorate Sodium Benzoate Lactose Sodium Nitrate Sodium Benzoate
Lactose Sodium Sulfate Sodium Benzoate Lactose Ammonium Perchlorate
Sodium Benzoate Lactose Ammonium Nitrate Sodium Benzoate Lactose
Other Alternative Oxidizer Sodium Benzoate Lactose Potassium
Perchlorate Sodium Nitrobenzoate Lactose Potassium Chlorate Sodium
Nitrobenzoate Lactose Potassium Nitrate Sodium Nitrobenzoate
Lactose Potassium Sulfate Sodium Nitrobenzoate Lactose Sodium
Perchlorate Sodium Nitrobenzoate Lactose Sodium Chlorate Sodium
Nitrobenzoate Lactose Sodium Nitrate Sodium Nitrobenzoate Lactose
Sodium Sulfate Sodium Nitrobenzoate Lactose Ammonium Perchlorate
Sodium Nitrobenzoate Lactose Ammonium Nitrate Sodium Nitrobenzoate
Lactose Other Alternative Oxidizer Sodium Nitrobenzoate Lactose
Potassium Perchlorate Sodium Gluconate Lactose Potassium Chlorate
Sodium Gluconate Lactose Potassium Nitrate Sodium Gluconate Lactose
Potassium Sulfate Sodium Gluconate Lactose Sodium Perchlorate
Sodium Gluconate Lactose Sodium Chlorate Sodium Gluconate Lactose
Sodium Nitrate Sodium Gluconate Lactose Sodium Sulfate Sodium
Gluconate Lactose Ammonium Perchlorate Sodium Gluconate Lactose
Ammonium Nitrate Sodium Gluconate Lactose Other Alternative
Oxidizer Sodium Gluconate Lactose Potassium Perchlorate Potassium
Benzoate Lactose Potassium Chlorate Potassium Benzoate Lactose
Potassium Nitrate Potassium Benzoate Lactose Potassium Sulfate
Potassium Benzoate Lactose Sodium Perchlorate Potassium Benzoate
Lactose Sodium Chlorate Potassium Benzoate Lactose Sodium Nitrate
Potassium Benzoate Lactose Sodium Sulfate Potassium Benzoate
Lactose Ammonium Perchlorate Potassium Benzoate Lactose Ammonium
Nitrate Potassium Benzoate Lactose Other Alternative Oxidizer
Potassium Benzoate Lactose Potassium Perchlorate Potassium
Nitrobenzoate Lactose Potassium Chlorate Potassium Nitrobenzoate
Lactose Potassium Nitrate Potassium Nitrobenzoate Lactose Potassium
Sulfate Potassium Nitrobenzoate Lactose Sodium Perchlorate
Potassium Nitrobenzoate Lactose Sodium Chlorate Potassium
Nitrobenzoate Lactose Sodium Nitrate Potassium Nitrobenzoate
Lactose Sodium Sulfate Potassium Nitrobenzoate Lactose Ammonium
Perchlorate Potassium Nitrobenzoate Lactose Ammonium Nitrate
Potassium Nitrobenzoate Lactose Other Alternative Oxidizer
Potassium Nitrobenzoate Lactose Potassium Perchlorate Potassium
Gluconate Lactose Potassium Chlorate Potassium Gluconate Lactose
Potassium Nitrate Potassium Gluconate Lactose Potassium Sulfate
Potassium Gluconate Lactose Sodium Perchlorate Potassium Gluconate
Lactose Sodium Chlorate Potassium Gluconate Lactose Sodium Nitrate
Potassium Gluconate Lactose Sodium Sulfate Potassium Gluconate
Lactose Ammonium Perchlorate Potassium Gluconate Lactose Ammonium
Nitrate Potassium Gluconate Lactose Other Alternative Oxidizer
Potassium Gluconate Lactose Potassium Perchlorate Iron oxide
Lactose Potassium Chlorate Iron oxide Lactose Potassium Nitrate
Iron oxide Lactose Potassium Sulfate Iron oxide Lactose Sodium
Perchlorate Iron oxide Lactose Sodium Chlorate Iron oxide Lactose
Sodium Nitrate Iron oxide Lactose Sodium Sulfate Iron oxide Lactose
Ammonium Perchlorate Iron oxide Lactose Ammonium Nitrate Iron oxide
Lactose Other Alternative Oxidizer Iron oxide Sucrose Potassium
Perchlorate None Sucrose Potassium Chlorate None Sucrose Potassium
Nitrate None Sucrose Potassium Sulfate None Sucrose Sodium
Perchlorate None Sucrose Sodium Chlorate None Sucrose Sodium
Nitrate None Sucrose Sodium Sulfate None Sucrose Ammonium
Perchlorate None Sucrose Ammonium Nitrate None Sucrose Other
Alternative Oxidizer None Sucrose Potassium Perchlorate
Ferrosilicon Sucrose Potassium Chlorate Ferrosilicon Sucrose
Potassium Nitrate Ferrosilicon Sucrose Potassium Sulfate
Ferrosilicon Sucrose Sodium Perchlorate Ferrosilicon Sucrose Sodium
Chlorate Ferrosilicon Sucrose Sodium Nitrate Ferrosilicon Sucrose
Sodium Sulfate Ferrosilicon Sucrose Ammonium Perchlorate
Ferrosilicon Sucrose Ammonium Nitrate Ferrosilicon Sucrose Other
Alternative Oxidizer Ferrosilicon Sucrose Potassium Perchlorate
Magnalium Sucrose Potassium Chlorate Magnalium Sucrose Potassium
Nitrate Magnalium Sucrose Potassium Sulfate Magnalium Sucrose
Sodium Perchlorate Magnalium Sucrose Sodium Chlorate Magnalium
Sucrose Sodium Nitrate Magnalium Sucrose Sodium Sulfate Magnalium
Sucrose Ammonium Perchlorate Magnalium Sucrose Ammonium Nitrate
Magnalium Sucrose Other Alternative Oxidizer Magnalium Sucrose
Potassium Perchlorate Aluminum Sucrose Potassium Chlorate Aluminum
Sucrose Potassium Nitrate Aluminum Sucrose Potassium Sulfate
Aluminum Sucrose Sodium Perchlorate Aluminum Sucrose Sodium
Chlorate Aluminum Sucrose Sodium Nitrate Aluminum Sucrose Sodium
Sulfate Aluminum Sucrose Ammonium Perchlorate Aluminum Sucrose
Ammonium Nitrate Aluminum Sucrose Other Alternative Oxidizer
Aluminum Sucrose Potassium Perchlorate Magnesium Sucrose Potassium
Chlorate Magnesium Sucrose Potassium Nitrate Magnesium Sucrose
Potassium Sulfate Magnesium Sucrose Sodium Perchlorate Magnesium
Sucrose Sodium Chlorate Magnesium Sucrose Sodium Nitrate Magnesium
Sucrose Sodium Sulfate Magnesium Sucrose Ammonium Perchlorate
Magnesium Sucrose Ammonium Nitrate Magnesium Sucrose Other
Alternative Oxidizer Magnesium Sucrose Potassium Perchlorate Sodium
Benzoate Sucrose Potassium Chlorate Sodium Benzoate Sucrose
Potassium Nitrate Sodium Benzoate Sucrose Potassium Sulfate Sodium
Benzoate Sucrose Sodium Perchlorate Sodium Benzoate Sucrose Sodium
Chlorate Sodium Benzoate Sucrose Sodium Nitrate Sodium Benzoate
Sucrose Sodium Sulfate Sodium Benzoate Sucrose Ammonium Perchlorate
Sodium Benzoate Sucrose Ammonium Nitrate Sodium Benzoate Sucrose
Other Alternative Oxidizer Sodium Benzoate Sucrose Potassium
Perchlorate Sodium Nitrobenzoate Sucrose Potassium Chlorate Sodium
Nitrobenzoate Sucrose Potassium Nitrate Sodium Nitrobenzoate
Sucrose Potassium Sulfate Sodium Nitrobenzoate Sucrose Sodium
Perchlorate Sodium Nitrobenzoate Sucrose Sodium Chlorate Sodium
Nitrobenzoate Sucrose Sodium Nitrate Sodium Nitrobenzoate Sucrose
Sodium Sulfate Sodium Nitrobenzoate Sucrose Ammonium Perchlorate
Sodium Nitrobenzoate Sucrose Ammonium Nitrate Sodium Nitrobenzoate
Sucrose Other Alternative Oxidizer Sodium Nitrobenzoate Sucrose
Potassium Perchlorate Sodium Gluconate Sucrose Potassium Chlorate
Sodium Gluconate Sucrose Potassium Nitrate Sodium Gluconate Sucrose
Potassium Sulfate Sodium Gluconate Sucrose Sodium Perchlorate
Sodium Gluconate Sucrose Sodium Chlorate Sodium Gluconate Sucrose
Sodium Nitrate Sodium Gluconate Sucrose Sodium Sulfate Sodium
Gluconate Sucrose Ammonium Perchlorate Sodium Gluconate Sucrose
Ammonium Nitrate Sodium Gluconate Sucrose Other Alternative
Oxidizer Sodium Gluconate Sucrose Potassium Perchlorate Potassium
Benzoate Sucrose Potassium Chlorate Potassium Benzoate Sucrose
Potassium Nitrate Potassium Benzoate Sucrose Potassium Sulfate
Potassium Benzoate Sucrose Sodium Perchlorate Potassium Benzoate
Sucrose Sodium Chlorate Potassium Benzoate Sucrose Sodium Nitrate
Potassium Benzoate Sucrose Sodium Sulfate Potassium Benzoate
Sucrose Ammonium Perchlorate Potassium Benzoate Sucrose Ammonium
Nitrate Potassium Benzoate
Sucrose Other Alternative Oxidizer Potassium Benzoate Sucrose
Potassium Perchlorate Potassium Nitrobenzoate Sucrose Potassium
Chlorate Potassium Nitrobenzoate Sucrose Potassium Nitrate
Potassium Nitrobenzoate Sucrose Potassium Sulfate Potassium
Nitrobenzoate Sucrose Sodium Perchlorate Potassium Nitrobenzoate
Sucrose Sodium Chlorate Potassium Nitrobenzoate Sucrose Sodium
Nitrate Potassium Nitrobenzoate Sucrose Sodium Sulfate Potassium
Nitrobenzoate Sucrose Ammonium Perchlorate Potassium Nitrobenzoate
Sucrose Ammonium Nitrate Potassium Nitrobenzoate Sucrose Other
Alternative Oxidizer Potassium Nitrobenzoate Sucrose Potassium
Perchlorate Potassium Gluconate Sucrose Potassium Chlorate
Potassium Gluconate Sucrose Potassium Nitrate Potassium Gluconate
Sucrose Potassium Sulfate Potassium Gluconate Sucrose Sodium
Perchlorate Potassium Gluconate Sucrose Sodium Chlorate Potassium
Gluconate Sucrose Sodium Nitrate Potassium Gluconate Sucrose Sodium
Sulfate Potassium Gluconate Sucrose Ammonium Perchlorate Potassium
Gluconate Sucrose Ammonium Nitrate Potassium Gluconate Sucrose
Other Alternative Oxidizer Potassium Gluconate Sucrose Potassium
Perchlorate Iron oxide Sucrose Potassium Chlorate Iron oxide
Sucrose Potassium Nitrate Iron oxide Sucrose Potassium Sulfate Iron
oxide Sucrose Sodium Perchlorate Iron oxide Sucrose Sodium Chlorate
Iron oxide Sucrose Sodium Nitrate Iron oxide Sucrose Sodium Sulfate
Iron oxide Sucrose Ammonium Perchlorate Iron oxide Sucrose Ammonium
Nitrate Iron oxide Sucrose Other Alternative Oxidizer Iron oxide
Glucose Potassium Perchlorate None Glucose Potassium Chlorate None
Glucose Potassium Nitrate None Glucose Potassium Sulfate None
Glucose Sodium Perchlorate None Glucose Sodium Chlorate None
Glucose Sodium Nitrate None Glucose Sodium Sulfate None Glucose
Ammonium Perchlorate None Glucose Ammonium Nitrate None Glucose
Other Alternative Oxidizer None Glucose Potassium Perchlorate
Ferrosilicon Glucose Potassium Chlorate Ferrosilicon Glucose
Potassium Nitrate Ferrosilicon Glucose Potassium Sulfate
Ferrosilicon Glucose Sodium Perchlorate Ferrosilicon Glucose Sodium
Chlorate Ferrosilicon Glucose Sodium Nitrate Ferrosilicon Glucose
Sodium Sulfate Ferrosilicon Glucose Ammonium Perchlorate
Ferrosilicon Glucose Ammonium Nitrate Ferrosilicon Glucose Other
Alternative Oxidizer Ferrosilicon Glucose Potassium Perchlorate
Magnalium Glucose Potassium Chlorate Magnalium Glucose Potassium
Nitrate Magnalium Glucose Potassium Sulfate Magnalium Glucose
Sodium Perchlorate Magnalium Glucose Sodium Chlorate Magnalium
Glucose Sodium Nitrate Magnalium Glucose Sodium Sulfate Magnalium
Glucose Ammonium Perchlorate Magnalium Glucose Ammonium Nitrate
Magnalium Glucose Other Alternative Oxidizer Magnalium Glucose
Potassium Perchlorate Aluminum Glucose Potassium Chlorate Aluminum
Glucose Potassium Nitrate Aluminum Glucose Potassium Sulfate
Aluminum Glucose Sodium Perchlorate Aluminum Glucose Sodium
Chlorate Aluminum Glucose Sodium Nitrate Aluminum Glucose Sodium
Sulfate Aluminum Glucose Ammonium Perchlorate Aluminum Glucose
Ammonium Nitrate Aluminum Glucose Other Alternative Oxidizer
Aluminum Glucose Potassium Perchlorate Magnesium Glucose Potassium
Chlorate Magnesium Glucose Potassium Nitrate Magnesium Glucose
Potassium Sulfate Magnesium Glucose Sodium Perchlorate Magnesium
Glucose Sodium Chlorate Magnesium Glucose Sodium Nitrate Magnesium
Glucose Sodium Sulfate Magnesium Glucose Ammonium Perchlorate
Magnesium Glucose Ammonium Nitrate Magnesium Glucose Other
Alternative Oxidizer Magnesium Glucose Potassium Perchlorate Sodium
Benzoate Glucose Potassium Chlorate Sodium Benzoate Glucose
Potassium Nitrate Sodium Benzoate Glucose Potassium Sulfate Sodium
Benzoate Glucose Sodium Perchlorate Sodium Benzoate Glucose Sodium
Chlorate Sodium Benzoate Glucose Sodium Nitrate Sodium Benzoate
Glucose Sodium Sulfate Sodium Benzoate Glucose Ammonium Perchlorate
Sodium Benzoate Glucose Ammonium Nitrate Sodium Benzoate Glucose
Other Alternative Oxidizer Sodium Benzoate Glucose Potassium
Perchlorate Sodium Nitrobenzoate Glucose Potassium Chlorate Sodium
Nitrobenzoate Glucose Potassium Nitrate Sodium Nitrobenzoate
Glucose Potassium Sulfate Sodium Nitrobenzoate Glucose Sodium
Perchlorate Sodium Nitrobenzoate Glucose Sodium Chlorate Sodium
Nitrobenzoate Glucose Sodium Nitrate Sodium Nitrobenzoate Glucose
Sodium Sulfate Sodium Nitrobenzoate Glucose Ammonium Perchlorate
Sodium Nitrobenzoate Glucose Ammonium Nitrate Sodium Nitrobenzoate
Glucose Other Alternative Oxidizer Sodium Nitrobenzoate Glucose
Potassium Perchlorate Sodium Gluconate Glucose Potassium Chlorate
Sodium Gluconate Glucose Potassium Nitrate Sodium Gluconate Glucose
Potassium Sulfate Sodium Gluconate Glucose Sodium Perchlorate
Sodium Gluconate Glucose Sodium Chlorate Sodium Gluconate Glucose
Sodium Nitrate Sodium Gluconate Glucose Sodium Sulfate Sodium
Gluconate Glucose Ammonium Perchlorate Sodium Gluconate Glucose
Ammonium Nitrate Sodium Gluconate Glucose Other Alternative
Oxidizer Sodium Gluconate Glucose Potassium Perchlorate Potassium
Benzoate Glucose Potassium Chlorate Potassium Benzoate Glucose
Potassium Nitrate Potassium Benzoate Glucose Potassium Sulfate
Potassium Benzoate Glucose Sodium Perchlorate Potassium Benzoate
Glucose Sodium Chlorate Potassium Benzoate Glucose Sodium Nitrate
Potassium Benzoate Glucose Sodium Sulfate Potassium Benzoate
Glucose Ammonium Perchlorate Potassium Benzoate Glucose Ammonium
Nitrate Potassium Benzoate Glucose Other Alternative Oxidizer
Potassium Benzoate Glucose Potassium Perchlorate Potassium
Nitrobenzoate Glucose Potassium Chlorate Potassium Nitrobenzoate
Glucose Potassium Nitrate Potassium Nitrobenzoate Glucose Potassium
Sulfate Potassium Nitrobenzoate Glucose Sodium Perchlorate
Potassium Nitrobenzoate Glucose Sodium Chlorate Potassium
Nitrobenzoate Glucose Sodium Nitrate Potassium Nitrobenzoate
Glucose Sodium Sulfate Potassium Nitrobenzoate Glucose Ammonium
Perchlorate Potassium Nitrobenzoate Glucose Ammonium Nitrate
Potassium Nitrobenzoate Glucose Other Alternative Oxidizer
Potassium Nitrobenzoate Glucose Potassium Perchlorate Potassium
Gluconate Glucose Potassium Chlorate Potassium Gluconate Glucose
Potassium Nitrate Potassium Gluconate Glucose Potassium Sulfate
Potassium Gluconate Glucose Sodium Perchlorate Potassium Gluconate
Glucose Sodium Chlorate Potassium Gluconate Glucose Sodium Nitrate
Potassium Gluconate Glucose Sodium Sulfate Potassium Gluconate
Glucose Ammonium Perchlorate Potassium Gluconate Glucose Ammonium
Nitrate Potassium Gluconate Glucose Other Alternative Oxidizer
Potassium Gluconate Glucose Potassium Perchlorate Iron oxide
Glucose Potassium Chlorate Iron oxide Glucose Potassium Nitrate
Iron oxide Glucose Potassium Sulfate Iron oxide Glucose Sodium
Perchlorate Iron oxide Glucose Sodium Chlorate Iron oxide Glucose
Sodium Nitrate Iron oxide Glucose Sodium Sulfate Iron oxide Glucose
Ammonium Perchlorate Iron oxide Glucose Ammonium Nitrate Iron oxide
Glucose Other Alternative Oxidizer Iron oxide Wheat Starch
Potassium Perchlorate None Wheat Starch Potassium Chlorate None
Wheat Starch Potassium Nitrate None Wheat Starch Potassium Sulfate
None Wheat Starch Sodium Perchlorate None Wheat Starch Sodium
Chlorate None Wheat Starch Sodium Nitrate None Wheat Starch Sodium
Sulfate None Wheat Starch Ammonium Perchlorate None Wheat Starch
Ammonium Nitrate None Wheat Starch Other Alternative Oxidizer None
Wheat Starch Potassium Perchlorate Ferrosilicon Wheat Starch
Potassium Chlorate Ferrosilicon Wheat Starch Potassium Nitrate
Ferrosilicon Wheat Starch Potassium Sulfate Ferrosilicon Wheat
Starch Sodium Perchlorate Ferrosilicon Wheat Starch Sodium Chlorate
Ferrosilicon Wheat Starch Sodium Nitrate Ferrosilicon Wheat Starch
Sodium Sulfate Ferrosilicon Wheat Starch Ammonium Perchlorate
Ferrosilicon Wheat Starch Ammonium Nitrate Ferrosilicon Wheat
Starch Other Alternative Oxidizer Ferrosilicon Wheat Starch
Potassium Perchlorate Magnalium Wheat Starch Potassium Chlorate
Magnalium Wheat Starch Potassium Nitrate Magnalium Wheat Starch
Potassium Sulfate Magnalium Wheat Starch Sodium Perchlorate
Magnalium Wheat Starch Sodium Chlorate Magnalium Wheat Starch
Sodium Nitrate Magnalium Wheat Starch Sodium Sulfate Magnalium
Wheat Starch Ammonium Perchlorate Magnalium Wheat Starch Ammonium
Nitrate Magnalium Wheat Starch Other Alternative Oxidizer Magnalium
Wheat Starch Potassium Perchlorate Aluminum Wheat Starch Potassium
Chlorate Aluminum Wheat Starch Potassium Nitrate Aluminum Wheat
Starch Potassium Sulfate Aluminum Wheat Starch Sodium Perchlorate
Aluminum Wheat Starch Sodium Chlorate Aluminum Wheat Starch Sodium
Nitrate Aluminum Wheat Starch Sodium Sulfate Aluminum Wheat Starch
Ammonium Perchlorate Aluminum Wheat Starch Ammonium Nitrate
Aluminum Wheat Starch Other Alternative Oxidizer Aluminum Wheat
Starch Potassium Perchlorate Magnesium Wheat Starch Potassium
Chlorate Magnesium Wheat Starch Potassium Nitrate Magnesium Wheat
Starch Potassium Sulfate Magnesium Wheat Starch Sodium Perchlorate
Magnesium Wheat Starch Sodium Chlorate Magnesium Wheat Starch
Sodium Nitrate Magnesium Wheat Starch Sodium Sulfate Magnesium
Wheat Starch Ammonium Perchlorate Magnesium Wheat Starch Ammonium
Nitrate Magnesium Wheat Starch Other Alternative Oxidizer Magnesium
Wheat Starch Potassium Perchlorate Sodium Benzoate Wheat Starch
Potassium Chlorate Sodium Benzoate Wheat Starch Potassium Nitrate
Sodium Benzoate Wheat Starch Potassium Sulfate Sodium Benzoate
Wheat Starch Sodium Perchlorate Sodium Benzoate Wheat Starch Sodium
Chlorate Sodium Benzoate Wheat Starch Sodium Nitrate Sodium
Benzoate Wheat Starch Sodium Sulfate Sodium Benzoate Wheat Starch
Ammonium Perchlorate Sodium Benzoate Wheat Starch Ammonium Nitrate
Sodium Benzoate Wheat Starch Other Alternative Oxidizer Sodium
Benzoate Wheat Starch Potassium Perchlorate Sodium Nitrobenzoate
Wheat Starch Potassium Chlorate Sodium Nitrobenzoate Wheat Starch
Potassium Nitrate Sodium Nitrobenzoate Wheat Starch Potassium
Sulfate Sodium Nitrobenzoate Wheat Starch Sodium Perchlorate Sodium
Nitrobenzoate Wheat Starch Sodium Chlorate Sodium Nitrobenzoate
Wheat Starch Sodium Nitrate Sodium Nitrobenzoate Wheat Starch
Sodium Sulfate Sodium Nitrobenzoate Wheat Starch Ammonium
Perchlorate Sodium Nitrobenzoate Wheat Starch Ammonium Nitrate
Sodium Nitrobenzoate Wheat Starch Other Alternative Oxidizer Sodium
Nitrobenzoate Wheat Starch Potassium Perchlorate Sodium Gluconate
Wheat Starch Potassium Chlorate Sodium Gluconate Wheat Starch
Potassium Nitrate Sodium Gluconate Wheat Starch Potassium Sulfate
Sodium Gluconate Wheat Starch Sodium Perchlorate Sodium Gluconate
Wheat Starch Sodium Chlorate Sodium Gluconate Wheat Starch Sodium
Nitrate Sodium Gluconate Wheat Starch Sodium Sulfate Sodium
Gluconate
Wheat Starch Ammonium Perchlorate Sodium Gluconate Wheat Starch
Ammonium Nitrate Sodium Gluconate Wheat Starch Other Alternative
Oxidizer Sodium Gluconate Wheat Starch Potassium Perchlorate
Potassium Benzoate Wheat Starch Potassium Chlorate Potassium
Benzoate Wheat Starch Potassium Nitrate Potassium Benzoate Wheat
Starch Potassium Sulfate Potassium Benzoate Wheat Starch Sodium
Perchlorate Potassium Benzoate Wheat Starch Sodium Chlorate
Potassium Benzoate Wheat Starch Sodium Nitrate Potassium Benzoate
Wheat Starch Sodium Sulfate Potassium Benzoate Wheat Starch
Ammonium Perchlorate Potassium Benzoate Wheat Starch Ammonium
Nitrate Potassium Benzoate Wheat Starch Other Alternative Oxidizer
Potassium Benzoate Wheat Starch Potassium Perchlorate Potassium
Nitrobenzoate Wheat Starch Potassium Chlorate Potassium
Nitrobenzoate Wheat Starch Potassium Nitrate Potassium
Nitrobenzoate Wheat Starch Potassium Sulfate Potassium
Nitrobenzoate Wheat Starch Sodium Perchlorate Potassium
Nitrobenzoate Wheat Starch Sodium Chlorate Potassium Nitrobenzoate
Wheat Starch Sodium Nitrate Potassium Nitrobenzoate Wheat Starch
Sodium Sulfate Potassium Nitrobenzoate Wheat Starch Ammonium
Perchlorate Potassium Nitrobenzoate Wheat Starch Ammonium Nitrate
Potassium Nitrobenzoate Wheat Starch Other Alternative Oxidizer
Potassium Nitrobenzoate Wheat Starch Potassium Perchlorate
Potassium Gluconate Wheat Starch Potassium Chlorate Potassium
Gluconate Wheat Starch Potassium Nitrate Potassium Gluconate Wheat
Starch Potassium Sulfate Potassium Gluconate Wheat Starch Sodium
Perchlorate Potassium Gluconate Wheat Starch Sodium Chlorate
Potassium Gluconate Wheat Starch Sodium Nitrate Potassium Gluconate
Wheat Starch Sodium Sulfate Potassium Gluconate Wheat Starch
Ammonium Perchlorate Potassium Gluconate Wheat Starch Ammonium
Nitrate Potassium Gluconate Wheat Starch Other Alternative Oxidizer
Potassium Gluconate Wheat Starch Potassium Perchlorate Iron oxide
Wheat Starch Potassium Chlorate Iron oxide Wheat Starch Potassium
Nitrate Iron oxide Wheat Starch Potassium Sulfate Iron oxide Wheat
Starch Sodium Perchlorate Iron oxide Wheat Starch Sodium Chlorate
Iron oxide Wheat Starch Sodium Nitrate Iron oxide Wheat Starch
Sodium Sulfate Iron oxide Wheat Starch Ammonium Perchlorate Iron
oxide Wheat Starch Ammonium Nitrate Iron oxide Wheat Starch Other
Alternative Oxidizer Iron oxide Potato Starch Potassium Perchlorate
None Potato Starch Potassium Chlorate None Potato Starch Potassium
Nitrate None Potato Starch Potassium Sulfate None Potato Starch
Sodium Perchlorate None Potato Starch Sodium Chlorate None Potato
Starch Sodium Nitrate None Potato Starch Sodium Sulfate None Potato
Starch Ammonium Perchlorate None Potato Starch Ammonium Nitrate
None Potato Starch Other Alternative Oxidizer None Potato Starch
Potassium Perchlorate Ferrosilicon Potato Starch Potassium Chlorate
Ferrosilicon Potato Starch Potassium Nitrate Ferrosilicon Potato
Starch Potassium Sulfate Ferrosilicon Potato Starch Sodium
Perchlorate Ferrosilicon Potato Starch Sodium Chlorate Ferrosilicon
Potato Starch Sodium Nitrate Ferrosilicon Potato Starch Sodium
Sulfate Ferrosilicon Potato Starch Ammonium Perchlorate
Ferrosilicon Potato Starch Ammonium Nitrate Ferrosilicon Potato
Starch Other Alternative Oxidizer Ferrosilicon Potato Starch
Potassium Perchlorate Magnalium Potato Starch Potassium Chlorate
Magnalium Potato Starch Potassium Nitrate Magnalium Potato Starch
Potassium Sulfate Magnalium Potato Starch Sodium Perchlorate
Magnalium Potato Starch Sodium Chlorate Magnalium Potato Starch
Sodium Nitrate Magnalium Potato Starch Sodium Sulfate Magnalium
Potato Starch Ammonium Perchlorate Magnalium Potato Starch Ammonium
Nitrate Magnalium Potato Starch Other Alternative Oxidizer
Magnalium Potato Starch Potassium Perchlorate Aluminum Potato
Starch Potassium Chlorate Aluminum Potato Starch Potassium Nitrate
Aluminum Potato Starch Potassium Sulfate Aluminum Potato Starch
Sodium Perchlorate Aluminum Potato Starch Sodium Chlorate Aluminum
Potato Starch Sodium Nitrate Aluminum Potato Starch Sodium Sulfate
Aluminum Potato Starch Ammonium Perchlorate Aluminum Potato Starch
Ammonium Nitrate Aluminum Potato Starch Other Alternative Oxidizer
Aluminum Potato Starch Potassium Perchlorate Magnesium Potato
Starch Potassium Chlorate Magnesium Potato Starch Potassium Nitrate
Magnesium Potato Starch Potassium Sulfate Magnesium Potato Starch
Sodium Perchlorate Magnesium Potato Starch Sodium Chlorate
Magnesium Potato Starch Sodium Nitrate Magnesium Potato Starch
Sodium Sulfate Magnesium Potato Starch Ammonium Perchlorate
Magnesium Potato Starch Ammonium Nitrate Magnesium Potato Starch
Other Alternative Oxidizer Magnesium Potato Starch Potassium
Perchlorate Sodium Benzoate Potato Starch Potassium Chlorate Sodium
Benzoate Potato Starch Potassium Nitrate Sodium Benzoate Potato
Starch Potassium Sulfate Sodium Benzoate Potato Starch Sodium
Perchlorate Sodium Benzoate Potato Starch Sodium Chlorate Sodium
Benzoate Potato Starch Sodium Nitrate Sodium Benzoate Potato Starch
Sodium Sulfate Sodium Benzoate Potato Starch Ammonium Perchlorate
Sodium Benzoate Potato Starch Ammonium Nitrate Sodium Benzoate
Potato Starch Other Alternative Oxidizer Sodium Benzoate Potato
Starch Potassium Perchlorate Sodium Nitrobenzoate Potato Starch
Potassium Chlorate Sodium Nitrobenzoate Potato Starch Potassium
Nitrate Sodium Nitrobenzoate Potato Starch Potassium Sulfate Sodium
Nitrobenzoate Potato Starch Sodium Perchlorate Sodium Nitrobenzoate
Potato Starch Sodium Chlorate Sodium Nitrobenzoate Potato Starch
Sodium Nitrate Sodium Nitrobenzoate Potato Starch Sodium Sulfate
Sodium Nitrobenzoate Potato Starch Ammonium Perchlorate Sodium
Nitrobenzoate Potato Starch Ammonium Nitrate Sodium Nitrobenzoate
Potato Starch Other Alternative Oxidizer Sodium Nitrobenzoate
Potato Starch Potassium Perchlorate Sodium Gluconate Potato Starch
Potassium Chlorate Sodium Gluconate Potato Starch Potassium Nitrate
Sodium Gluconate Potato Starch Potassium Sulfate Sodium Gluconate
Potato Starch Sodium Perchlorate Sodium Gluconate Potato Starch
Sodium Chlorate Sodium Gluconate Potato Starch Sodium Nitrate
Sodium Gluconate Potato Starch Sodium Sulfate Sodium Gluconate
Potato Starch Ammonium Perchlorate Sodium Gluconate Potato Starch
Ammonium Nitrate Sodium Gluconate Potato Starch Other Alternative
Oxidizer Sodium Gluconate Potato Starch Potassium Perchlorate
Potassium Benzoate Potato Starch Potassium Chlorate Potassium
Benzoate Potato Starch Potassium Nitrate Potassium Benzoate Potato
Starch Potassium Sulfate Potassium Benzoate Potato Starch Sodium
Perchlorate Potassium Benzoate Potato Starch Sodium Chlorate
Potassium Benzoate Potato Starch Sodium Nitrate Potassium Benzoate
Potato Starch Sodium Sulfate Potassium Benzoate Potato Starch
Ammonium Perchlorate Potassium Benzoate Potato Starch Ammonium
Nitrate Potassium Benzoate Potato Starch Other Alternative Oxidizer
Potassium Benzoate Potato Starch Potassium Perchlorate Potassium
Nitrobenzoate Potato Starch Potassium Chlorate Potassium
Nitrobenzoate Potato Starch Potassium Nitrate Potassium
Nitrobenzoate Potato Starch Potassium Sulfate Potassium
Nitrobenzoate Potato Starch Sodium Perchlorate Potassium
Nitrobenzoate Potato Starch Sodium Chlorate Potassium Nitrobenzoate
Potato Starch Sodium Nitrate Potassium Nitrobenzoate Potato Starch
Sodium Sulfate Potassium Nitrobenzoate Potato Starch Ammonium
Perchlorate Potassium Nitrobenzoate Potato Starch Ammonium Nitrate
Potassium Nitrobenzoate Potato Starch Other Alternative Oxidizer
Potassium Nitrobenzoate Potato Starch Potassium Perchlorate
Potassium Gluconate Potato Starch Potassium Chlorate Potassium
Gluconate Potato Starch Potassium Nitrate Potassium Gluconate
Potato Starch Potassium Sulfate Potassium Gluconate Potato Starch
Sodium Perchlorate Potassium Gluconate Potato Starch Sodium
Chlorate Potassium Gluconate Potato Starch Sodium Nitrate Potassium
Gluconate Potato Starch Sodium Sulfate Potassium Gluconate Potato
Starch Ammonium Perchlorate Potassium Gluconate Potato Starch
Ammonium Nitrate Potassium Gluconate Potato Starch Other
Alternative Oxidizer Potassium Gluconate Potato Starch Potassium
Perchlorate Iron oxide Potato Starch Potassium Chlorate Iron oxide
Potato Starch Potassium Nitrate Iron oxide Potato Starch Potassium
Sulfate Iron oxide Potato Starch Sodium Perchlorate Iron oxide
Potato Starch Sodium Chlorate Iron oxide Potato Starch Sodium
Nitrate Iron oxide Potato Starch Sodium Sulfate Iron oxide Potato
Starch Ammonium Perchlorate Iron oxide Potato Starch Ammonium
Nitrate Iron oxide Potato Starch Other Alternative Oxidizer Iron
oxide Fructose Potassium Perchlorate None Fructose Potassium
Chlorate None Fructose Potassium Nitrate None Fructose Potassium
Sulfate None Fructose Sodium Perchlorate None Fructose Sodium
Chlorate None Fructose Sodium Nitrate None Fructose Sodium Sulfate
None Fructose Ammonium Perchlorate None Fructose Ammonium Nitrate
None Fructose Other Alternative Oxidizer None Fructose Potassium
Perchlorate Ferrosilicon Fructose Potassium Chlorate Ferrosilicon
Fructose Potassium Nitrate Ferrosilicon Fructose Potassium Sulfate
Ferrosilicon Fructose Sodium Perchlorate Ferrosilicon Fructose
Sodium Chlorate Ferrosilicon Fructose Sodium Nitrate Ferrosilicon
Fructose Sodium Sulfate Ferrosilicon Fructose Ammonium Perchlorate
Ferrosilicon Fructose Ammonium Nitrate Ferrosilicon Fructose Other
Alternative Oxidizer Ferrosilicon Fructose Potassium Perchlorate
Magnalium Fructose Potassium Chlorate Magnalium Fructose Potassium
Nitrate Magnalium Fructose Potassium Sulfate Magnalium Fructose
Sodium Perchlorate Magnalium Fructose Sodium Chlorate Magnalium
Fructose Sodium Nitrate Magnalium Fructose Sodium Sulfate Magnalium
Fructose Ammonium Perchlorate Magnalium Fructose Ammonium Nitrate
Magnalium Fructose Other Alternative Oxidizer Magnalium Fructose
Potassium Perchlorate Aluminum Fructose Potassium Chlorate Aluminum
Fructose Potassium Nitrate Aluminum Fructose Potassium Sulfate
Aluminum Fructose Sodium Perchlorate Aluminum Fructose Sodium
Chlorate Aluminum Fructose Sodium Nitrate Aluminum Fructose Sodium
Sulfate Aluminum Fructose Ammonium Perchlorate Aluminum Fructose
Ammonium Nitrate Aluminum Fructose Other Alternative Oxidizer
Aluminum Fructose Potassium Perchlorate Magnesium Fructose
Potassium Chlorate Magnesium Fructose Potassium Nitrate Magnesium
Fructose Potassium Sulfate Magnesium Fructose Sodium Perchlorate
Magnesium Fructose Sodium Chlorate Magnesium Fructose Sodium
Nitrate Magnesium Fructose Sodium Sulfate Magnesium Fructose
Ammonium Perchlorate Magnesium Fructose Ammonium Nitrate Magnesium
Fructose Other Alternative Oxidizer Magnesium Fructose Potassium
Perchlorate Sodium Benzoate Fructose Potassium Chlorate Sodium
Benzoate Fructose Potassium Nitrate Sodium Benzoate Fructose
Potassium Sulfate Sodium Benzoate Fructose Sodium Perchlorate
Sodium Benzoate Fructose Sodium Chlorate Sodium Benzoate Fructose
Sodium Nitrate Sodium Benzoate Fructose Sodium Sulfate Sodium
Benzoate Fructose Ammonium Perchlorate Sodium Benzoate Fructose
Ammonium Nitrate Sodium Benzoate Fructose Other Alternative
Oxidizer Sodium Benzoate Fructose Potassium Perchlorate Sodium
Nitrobenzoate Fructose Potassium Chlorate Sodium Nitrobenzoate
Fructose Potassium Nitrate Sodium Nitrobenzoate Fructose Potassium
Sulfate Sodium Nitrobenzoate Fructose Sodium Perchlorate Sodium
Nitrobenzoate Fructose Sodium Chlorate Sodium Nitrobenzoate
Fructose Sodium Nitrate Sodium Nitrobenzoate Fructose Sodium
Sulfate Sodium Nitrobenzoate Fructose Ammonium Perchlorate Sodium
Nitrobenzoate Fructose Ammonium Nitrate Sodium Nitrobenzoate
Fructose Other Alternative Oxidizer Sodium Nitrobenzoate Fructose
Potassium Perchlorate Sodium Gluconate Fructose Potassium Chlorate
Sodium Gluconate Fructose Potassium Nitrate Sodium Gluconate
Fructose Potassium Sulfate Sodium Gluconate Fructose Sodium
Perchlorate Sodium Gluconate Fructose Sodium Chlorate Sodium
Gluconate Fructose Sodium Nitrate Sodium Gluconate Fructose Sodium
Sulfate Sodium Gluconate Fructose Ammonium Perchlorate Sodium
Gluconate Fructose Ammonium Nitrate Sodium Gluconate Fructose Other
Alternative Oxidizer Sodium Gluconate Fructose Potassium
Perchlorate Potassium Benzoate Fructose Potassium Chlorate
Potassium Benzoate Fructose Potassium Nitrate Potassium Benzoate
Fructose Potassium Sulfate Potassium Benzoate Fructose Sodium
Perchlorate Potassium Benzoate Fructose Sodium Chlorate Potassium
Benzoate Fructose Sodium Nitrate Potassium Benzoate Fructose Sodium
Sulfate Potassium Benzoate Fructose Ammonium Perchlorate Potassium
Benzoate Fructose Ammonium Nitrate Potassium Benzoate Fructose
Other Alternative Oxidizer Potassium Benzoate Fructose Potassium
Perchlorate Potassium Nitrobenzoate Fructose Potassium Chlorate
Potassium Nitrobenzoate Fructose Potassium Nitrate Potassium
Nitrobenzoate Fructose Potassium Sulfate Potassium Nitrobenzoate
Fructose Sodium Perchlorate Potassium Nitrobenzoate Fructose Sodium
Chlorate Potassium Nitrobenzoate Fructose Sodium Nitrate Potassium
Nitrobenzoate Fructose Sodium Sulfate Potassium Nitrobenzoate
Fructose Ammonium Perchlorate Potassium Nitrobenzoate Fructose
Ammonium Nitrate Potassium Nitrobenzoate Fructose Other Alternative
Oxidizer Potassium Nitrobenzoate Fructose Potassium Perchlorate
Potassium Gluconate Fructose Potassium Chlorate Potassium Gluconate
Fructose Potassium Nitrate Potassium Gluconate Fructose Potassium
Sulfate Potassium Gluconate Fructose Sodium Perchlorate Potassium
Gluconate Fructose Sodium Chlorate Potassium Gluconate Fructose
Sodium Nitrate Potassium Gluconate Fructose Sodium Sulfate
Potassium Gluconate Fructose Ammonium Perchlorate Potassium
Gluconate Fructose Ammonium Nitrate Potassium Gluconate Fructose
Other Alternative Oxidizer Potassium Gluconate Fructose Potassium
Perchlorate Iron oxide Fructose Potassium Chlorate Iron oxide
Fructose Potassium Nitrate Iron oxide Fructose Potassium Sulfate
Iron oxide Fructose Sodium Perchlorate Iron oxide Fructose Sodium
Chlorate Iron oxide Fructose Sodium Nitrate Iron oxide Fructose
Sodium Sulfate Iron oxide Fructose Ammonium Perchlorate Iron oxide
Fructose Ammonium Nitrate Iron oxide Fructose Other Alternative
Oxidizer Iron oxide Ascorbic Acid Potassium Perchlorate None
Ascorbic Acid Potassium Chlorate None Ascorbic Acid Potassium
Nitrate None Ascorbic Acid Potassium Sulfate None Ascorbic Acid
Sodium Perchlorate None Ascorbic Acid Sodium Chlorate None Ascorbic
Acid Sodium Nitrate None Ascorbic Acid Sodium Sulfate None Ascorbic
Acid Ammonium Perchlorate None Ascorbic Acid Ammonium Nitrate None
Ascorbic Acid Other Alternative Oxidizer None Ascorbic Acid
Potassium Perchlorate Ferrosilicon Ascorbic Acid Potassium Chlorate
Ferrosilicon Ascorbic Acid Potassium Nitrate Ferrosilicon Ascorbic
Acid Potassium Sulfate Ferrosilicon Ascorbic Acid Sodium
Perchlorate Ferrosilicon Ascorbic Acid Sodium Chlorate Ferrosilicon
Ascorbic Acid Sodium Nitrate Ferrosilicon Ascorbic Acid Sodium
Sulfate Ferrosilicon Ascorbic Acid Ammonium Perchlorate
Ferrosilicon Ascorbic Acid Ammonium Nitrate Ferrosilicon Ascorbic
Acid Other Alternative Oxidizer Ferrosilicon Ascorbic Acid
Potassium Perchlorate Magnalium Ascorbic Acid Potassium Chlorate
Magnalium Ascorbic Acid Potassium Nitrate Magnalium Ascorbic Acid
Potassium Sulfate Magnalium Ascorbic Acid Sodium Perchlorate
Magnalium Ascorbic Acid Sodium Chlorate Magnalium Ascorbic Acid
Sodium Nitrate Magnalium Ascorbic Acid Sodium Sulfate Magnalium
Ascorbic Acid Ammonium Perchlorate Magnalium Ascorbic Acid Ammonium
Nitrate Magnalium Ascorbic Acid Other Alternative Oxidizer
Magnalium Ascorbic Acid Potassium Perchlorate Aluminum Ascorbic
Acid Potassium Chlorate Aluminum Ascorbic Acid Potassium Nitrate
Aluminum Ascorbic Acid Potassium Sulfate Aluminum Ascorbic Acid
Sodium Perchlorate Aluminum Ascorbic Acid Sodium Chlorate Aluminum
Ascorbic Acid Sodium Nitrate Aluminum Ascorbic Acid Sodium Sulfate
Aluminum Ascorbic Acid Ammonium Perchlorate Aluminum Ascorbic Acid
Ammonium Nitrate Aluminum Ascorbic Acid Other Alternative Oxidizer
Aluminum Ascorbic Acid Potassium Perchlorate Magnesium Ascorbic
Acid Potassium Chlorate Magnesium Ascorbic Acid Potassium Nitrate
Magnesium Ascorbic Acid Potassium Sulfate Magnesium Ascorbic Acid
Sodium Perchlorate Magnesium Ascorbic Acid Sodium Chlorate
Magnesium Ascorbic Acid Sodium Nitrate Magnesium Ascorbic Acid
Sodium Sulfate Magnesium Ascorbic Acid Ammonium Perchlorate
Magnesium Ascorbic Acid Ammonium Nitrate Magnesium Ascorbic Acid
Other Alternative Oxidizer Magnesium Ascorbic Acid Potassium
Perchlorate Sodium Benzoate Ascorbic Acid Potassium Chlorate Sodium
Benzoate Ascorbic Acid Potassium Nitrate Sodium Benzoate Ascorbic
Acid Potassium Sulfate Sodium Benzoate Ascorbic Acid Sodium
Perchlorate Sodium Benzoate Ascorbic Acid Sodium Chlorate Sodium
Benzoate Ascorbic Acid Sodium Nitrate Sodium Benzoate Ascorbic Acid
Sodium Sulfate Sodium Benzoate Ascorbic Acid Ammonium Perchlorate
Sodium Benzoate Ascorbic Acid Ammonium Nitrate Sodium Benzoate
Ascorbic Acid Other Alternative Oxidizer Sodium Benzoate Ascorbic
Acid Potassium Perchlorate Sodium Nitrobenzoate Ascorbic Acid
Potassium Chlorate Sodium Nitrobenzoate Ascorbic Acid Potassium
Nitrate Sodium Nitrobenzoate Ascorbic Acid Potassium Sulfate Sodium
Nitrobenzoate Ascorbic Acid Sodium Perchlorate Sodium Nitrobenzoate
Ascorbic Acid Sodium Chlorate Sodium Nitrobenzoate Ascorbic Acid
Sodium Nitrate Sodium Nitrobenzoate Ascorbic Acid Sodium Sulfate
Sodium Nitrobenzoate Ascorbic Acid Ammonium Perchlorate Sodium
Nitrobenzoate Ascorbic Acid Ammonium Nitrate Sodium Nitrobenzoate
Ascorbic Acid Other Alternative Oxidizer Sodium Nitrobenzoate
Ascorbic Acid Potassium Perchlorate Sodium Gluconate Ascorbic Acid
Potassium Chlorate Sodium Gluconate Ascorbic Acid Potassium Nitrate
Sodium Gluconate Ascorbic Acid Potassium Sulfate Sodium Gluconate
Ascorbic Acid Sodium Perchlorate Sodium Gluconate Ascorbic Acid
Sodium Chlorate Sodium Gluconate Ascorbic Acid Sodium Nitrate
Sodium Gluconate Ascorbic Acid Sodium Sulfate Sodium Gluconate
Ascorbic Acid Ammonium Perchlorate Sodium Gluconate Ascorbic Acid
Ammonium Nitrate Sodium Gluconate Ascorbic Acid Other Alternative
Oxidizer Sodium Gluconate Ascorbic Acid Potassium Perchlorate
Potassium Benzoate Ascorbic Acid Potassium Chlorate Potassium
Benzoate Ascorbic Acid Potassium Nitrate Potassium Benzoate
Ascorbic Acid Potassium Sulfate Potassium Benzoate Ascorbic Acid
Sodium Perchlorate Potassium Benzoate Ascorbic Acid Sodium Chlorate
Potassium Benzoate Ascorbic Acid Sodium Nitrate Potassium Benzoate
Ascorbic Acid Sodium Sulfate Potassium Benzoate Ascorbic Acid
Ammonium Perchlorate Potassium Benzoate Ascorbic Acid Ammonium
Nitrate Potassium Benzoate Ascorbic Acid Other Alternative Oxidizer
Potassium Benzoate Ascorbic Acid Potassium Perchlorate Potassium
Nitrobenzoate Ascorbic Acid Potassium Chlorate Potassium
Nitrobenzoate Ascorbic Acid Potassium Nitrate Potassium
Nitrobenzoate Ascorbic Acid Potassium Sulfate Potassium
Nitrobenzoate Ascorbic Acid Sodium Perchlorate Potassium
Nitrobenzoate Ascorbic Acid Sodium Chlorate Potassium Nitrobenzoate
Ascorbic Acid Sodium Nitrate Potassium Nitrobenzoate Ascorbic Acid
Sodium Sulfate Potassium Nitrobenzoate Ascorbic Acid Ammonium
Perchlorate Potassium Nitrobenzoate Ascorbic Acid Ammonium Nitrate
Potassium Nitrobenzoate Ascorbic Acid Other Alternative Oxidizer
Potassium Nitrobenzoate Ascorbic Acid Potassium Perchlorate
Potassium Gluconate Ascorbic Acid Potassium Chlorate Potassium
Gluconate Ascorbic Acid Potassium Nitrate Potassium Gluconate
Ascorbic Acid Potassium Sulfate Potassium Gluconate Ascorbic Acid
Sodium Perchlorate Potassium Gluconate Ascorbic Acid Sodium
Chlorate Potassium Gluconate Ascorbic Acid Sodium Nitrate Potassium
Gluconate Ascorbic Acid Sodium Sulfate Potassium Gluconate Ascorbic
Acid Ammonium Perchlorate Potassium Gluconate Ascorbic Acid
Ammonium Nitrate Potassium Gluconate Ascorbic Acid Other
Alternative Oxidizer Potassium Gluconate Ascorbic Acid Potassium
Perchlorate Iron oxide Ascorbic Acid Potassium Chlorate Iron oxide
Ascorbic Acid Potassium Nitrate Iron oxide Ascorbic Acid Potassium
Sulfate Iron oxide Ascorbic Acid Sodium Perchlorate Iron oxide
Ascorbic Acid Sodium Chlorate Iron oxide Ascorbic Acid Sodium
Nitrate Iron oxide Ascorbic Acid Sodium Sulfate Iron oxide Ascorbic
Acid Ammonium Perchlorate Iron oxide Ascorbic Acid Ammonium Nitrate
Iron oxide Ascorbic Acid Other Alternative Oxidizer Iron oxide
Erythroscorbic Acid Potassium Perchlorate None Erythroscorbic Acid
Potassium Chlorate None Erythroscorbic Acid Potassium Nitrate None
Erythroscorbic Acid Potassium Sulfate None Erythroscorbic Acid
Sodium Perchlorate None Erythroscorbic Acid Sodium Chlorate None
Erythroscorbic Acid Sodium Nitrate None Erythroscorbic Acid Sodium
Sulfate None Erythroscorbic Acid Ammonium Perchlorate None
Erythroscorbic Acid Ammonium Nitrate None Erythroscorbic Acid Other
Alternative Oxidizer None Erythroscorbic Acid Potassium Perchlorate
Ferrosilicon Erythroscorbic Acid Potassium Chlorate Ferrosilicon
Erythroscorbic Acid Potassium Nitrate Ferrosilicon Erythroscorbic
Acid Potassium Sulfate Ferrosilicon Erythroscorbic Acid Sodium
Perchlorate Ferrosilicon Erythroscorbic Acid Sodium Chlorate
Ferrosilicon Erythroscorbic Acid Sodium Nitrate Ferrosilicon
Erythroscorbic Acid Sodium Sulfate Ferrosilicon Erythroscorbic Acid
Ammonium Perchlorate Ferrosilicon Erythroscorbic Acid Ammonium
Nitrate Ferrosilicon Erythroscorbic Acid Other Alternative Oxidizer
Ferrosilicon Erythroscorbic Acid Potassium Perchlorate Magnalium
Erythroscorbic Acid Potassium Chlorate Magnalium Erythroscorbic
Acid Potassium Nitrate Magnalium Erythroscorbic Acid Potassium
Sulfate Magnalium Erythroscorbic Acid Sodium Perchlorate Magnalium
Erythroscorbic Acid Sodium Chlorate Magnalium Erythroscorbic Acid
Sodium Nitrate Magnalium Erythroscorbic Acid Sodium Sulfate
Magnalium Erythroscorbic Acid Ammonium Perchlorate Magnalium
Erythroscorbic Acid Ammonium Nitrate Magnalium Erythroscorbic Acid
Other Alternative Oxidizer Magnalium Erythroscorbic Acid Potassium
Perchlorate Aluminum Erythroscorbic Acid Potassium Chlorate
Aluminum Erythroscorbic Acid Potassium Nitrate Aluminum
Erythroscorbic Acid Potassium Sulfate Aluminum Erythroscorbic Acid
Sodium Perchlorate Aluminum Erythroscorbic Acid Sodium Chlorate
Aluminum Erythroscorbic Acid Sodium Nitrate Aluminum Erythroscorbic
Acid Sodium Sulfate Aluminum Erythroscorbic Acid Ammonium
Perchlorate Aluminum Erythroscorbic Acid Ammonium Nitrate Aluminum
Erythroscorbic Acid Other Alternative Oxidizer Aluminum
Erythroscorbic Acid Potassium Perchlorate Magnesium Erythroscorbic
Acid Potassium Chlorate Magnesium Erythroscorbic Acid Potassium
Nitrate Magnesium Erythroscorbic Acid Potassium Sulfate Magnesium
Erythroscorbic Acid Sodium Perchlorate Magnesium Erythroscorbic
Acid Sodium Chlorate Magnesium Erythroscorbic Acid Sodium Nitrate
Magnesium Erythroscorbic Acid Sodium Sulfate Magnesium
Erythroscorbic Acid Ammonium Perchlorate Magnesium Erythroscorbic
Acid Ammonium Nitrate Magnesium Erythroscorbic Acid Other
Alternative Oxidizer Magnesium Erythroscorbic Acid Potassium
Perchlorate Sodium Benzoate Erythroscorbic Acid Potassium Chlorate
Sodium Benzoate Erythroscorbic Acid Potassium Nitrate Sodium
Benzoate Erythroscorbic Acid Potassium Sulfate Sodium Benzoate
Erythroscorbic Acid Sodium Perchlorate Sodium Benzoate
Erythroscorbic Acid Sodium Chlorate Sodium Benzoate Erythroscorbic
Acid Sodium Nitrate Sodium Benzoate Erythroscorbic Acid Sodium
Sulfate Sodium Benzoate Erythroscorbic Acid Ammonium Perchlorate
Sodium Benzoate Erythroscorbic Acid Ammonium Nitrate Sodium
Benzoate Erythroscorbic Acid Other Alternative Oxidizer Sodium
Benzoate Erythroscorbic Acid Potassium Perchlorate Sodium
Nitrobenzoate Erythroscorbic Acid Potassium Chlorate Sodium
Nitrobenzoate Erythroscorbic Acid Potassium Nitrate Sodium
Nitrobenzoate Erythroscorbic Acid Potassium Sulfate Sodium
Nitrobenzoate Erythroscorbic Acid Sodium Perchlorate Sodium
Nitrobenzoate Erythroscorbic Acid Sodium Chlorate Sodium
Nitrobenzoate Erythroscorbic Acid Sodium Nitrate Sodium
Nitrobenzoate Erythroscorbic Acid Sodium Sulfate Sodium
Nitrobenzoate Erythroscorbic Acid Ammonium Perchlorate Sodium
Nitrobenzoate Erythroscorbic Acid Ammonium Nitrate Sodium
Nitrobenzoate Erythroscorbic Acid Other Alternative Oxidizer Sodium
Nitrobenzoate Erythroscorbic Acid Potassium Perchlorate Sodium
Gluconate Erythroscorbic Acid Potassium Chlorate Sodium Gluconate
Erythroscorbic Acid Potassium Nitrate Sodium Gluconate
Erythroscorbic Acid Potassium Sulfate Sodium Gluconate
Erythroscorbic Acid Sodium Perchlorate Sodium Gluconate
Erythroscorbic Acid Sodium Chlorate Sodium Gluconate Erythroscorbic
Acid Sodium Nitrate Sodium Gluconate Erythroscorbic Acid Sodium
Sulfate Sodium Gluconate Erythroscorbic Acid Ammonium Perchlorate
Sodium Gluconate Erythroscorbic Acid Ammonium Nitrate Sodium
Gluconate Erythroscorbic Acid Other Alternative Oxidizer Sodium
Gluconate Erythroscorbic Acid Potassium Perchlorate Potassium
Benzoate Erythroscorbic Acid Potassium Chlorate Potassium Benzoate
Erythroscorbic Acid Potassium Nitrate Potassium Benzoate
Erythroscorbic Acid Potassium Sulfate Potassium Benzoate
Erythroscorbic Acid Sodium Perchlorate Potassium Benzoate
Erythroscorbic Acid Sodium Chlorate Potassium Benzoate
Erythroscorbic Acid Sodium Nitrate Potassium Benzoate
Erythroscorbic Acid Sodium Sulfate Potassium Benzoate
Erythroscorbic Acid Ammonium Perchlorate Potassium Benzoate
Erythroscorbic Acid Ammonium Nitrate Potassium Benzoate
Erythroscorbic Acid Other Alternative Oxidizer Potassium Benzoate
Erythroscorbic Acid Potassium Perchlorate Potassium Nitrobenzoate
Erythroscorbic Acid Potassium Chlorate Potassium Nitrobenzoate
Erythroscorbic Acid Potassium Nitrate Potassium Nitrobenzoate
Erythroscorbic Acid Potassium Sulfate Potassium Nitrobenzoate
Erythroscorbic Acid Sodium Perchlorate Potassium Nitrobenzoate
Erythroscorbic Acid Sodium Chlorate Potassium Nitrobenzoate
Erythroscorbic Acid Sodium Nitrate Potassium Nitrobenzoate
Erythroscorbic Acid Sodium Sulfate Potassium Nitrobenzoate
Erythroscorbic Acid Ammonium Perchlorate Potassium Nitrobenzoate
Erythroscorbic Acid Ammonium Nitrate Potassium Nitrobenzoate
Erythroscorbic Acid Other Alternative Oxidizer Potassium
Nitrobenzoate Erythroscorbic Acid Potassium Perchlorate Potassium
Gluconate Erythroscorbic Acid Potassium Chlorate Potassium
Gluconate Erythroscorbic Acid Potassium Nitrate Potassium Gluconate
Erythroscorbic Acid Potassium Sulfate Potassium Gluconate
Erythroscorbic Acid Sodium Perchlorate Potassium Gluconate
Erythroscorbic Acid Sodium Chlorate Potassium Gluconate
Erythroscorbic Acid Sodium Nitrate Potassium Gluconate
Erythroscorbic Acid Sodium Sulfate Potassium Gluconate
Erythroscorbic Acid Ammonium Perchlorate Potassium Gluconate
Erythroscorbic Acid Ammonium Nitrate Potassium Gluconate
Erythroscorbic Acid Other Alternative Oxidizer Potassium Gluconate
Erythroscorbic Acid Potassium Perchlorate Iron oxide Erythroscorbic
Acid Potassium Chlorate Iron oxide Erythroscorbic Acid Potassium
Nitrate Iron oxide Erythroscorbic Acid Potassium Sulfate Iron oxide
Erythroscorbic Acid Sodium Perchlorate Iron oxide Erythroscorbic
Acid Sodium Chlorate Iron oxide Erythroscorbic Acid Sodium Nitrate
Iron oxide Erythroscorbic Acid Sodium Sulfate Iron oxide
Erythroscorbic Acid Ammonium Perchlorate Iron oxide Erythroscorbic
Acid Ammonium Nitrate Iron oxide Erythroscorbic Acid Other
Alternative Oxidizer Iron oxide Other Carbohydrate Sugar Potassium
Perchlorate None Other Carbohydrate Sugar Potassium Chlorate None
Other Carbohydrate Sugar Potassium Nitrate None Other Carbohydrate
Sugar Potassium Sulfate None Other Carbohydrate Sugar Sodium
Perchlorate None Other Carbohydrate Sugar Sodium Chlorate None
Other Carbohydrate Sugar Sodium Nitrate None Other Carbohydrate
Sugar Sodium Sulfate None Other Carbohydrate Sugar Ammonium
Perchlorate None Other Carbohydrate Sugar Ammonium Nitrate None
Other Carbohydrate Sugar Other Alternative Oxidizer None Other
Carbohydrate Sugar Potassium Perchlorate Ferrosilicon Other
Carbohydrate Sugar Potassium Chlorate Ferrosilicon Other
Carbohydrate Sugar Potassium Nitrate Ferrosilicon Other
Carbohydrate Sugar Potassium Sulfate Ferrosilicon Other
Carbohydrate Sugar Sodium Perchlorate Ferrosilicon Other
Carbohydrate Sugar Sodium Chlorate Ferrosilicon Other Carbohydrate
Sugar Sodium Nitrate Ferrosilicon Other Carbohydrate Sugar Sodium
Sulfate Ferrosilicon Other Carbohydrate Sugar Ammonium Perchlorate
Ferrosilicon Other Carbohydrate Sugar Ammonium Nitrate Ferrosilicon
Other Carbohydrate Sugar Other Alternative Oxidizer Ferrosilicon
Other Carbohydrate Sugar Potassium Perchlorate Magnalium Other
Carbohydrate Sugar Potassium Chlorate Magnalium Other Carbohydrate
Sugar Potassium Nitrate Magnalium Other Carbohydrate Sugar
Potassium Sulfate Magnalium Other Carbohydrate Sugar Sodium
Perchlorate Magnalium Other Carbohydrate Sugar Sodium Chlorate
Magnalium Other Carbohydrate Sugar Sodium Nitrate Magnalium Other
Carbohydrate Sugar Sodium Sulfate Magnalium Other Carbohydrate
Sugar Ammonium Perchlorate Magnalium Other Carbohydrate Sugar
Ammonium Nitrate Magnalium Other Carbohydrate Sugar Other
Alternative Oxidizer Magnalium Other Carbohydrate Sugar Potassium
Perchlorate Aluminum Other Carbohydrate Sugar Potassium Chlorate
Aluminum Other Carbohydrate Sugar Potassium Nitrate Aluminum Other
Carbohydrate Sugar Potassium Sulfate Aluminum Other Carbohydrate
Sugar Sodium Perchlorate Aluminum Other Carbohydrate Sugar Sodium
Chlorate Aluminum Other Carbohydrate Sugar Sodium Nitrate Aluminum
Other Carbohydrate Sugar Sodium Sulfate Aluminum Other Carbohydrate
Sugar Ammonium Perchlorate Aluminum Other Carbohydrate Sugar
Ammonium Nitrate Aluminum Other Carbohydrate Sugar Other
Alternative Oxidizer Aluminum Other Carbohydrate Sugar Potassium
Perchlorate Magnesium Other Carbohydrate Sugar Potassium Chlorate
Magnesium Other Carbohydrate Sugar Potassium Nitrate Magnesium
Other Carbohydrate Sugar Potassium Sulfate Magnesium Other
Carbohydrate Sugar Sodium Perchlorate Magnesium Other Carbohydrate
Sugar Sodium Chlorate Magnesium Other Carbohydrate Sugar Sodium
Nitrate Magnesium Other Carbohydrate Sugar Sodium Sulfate Magnesium
Other Carbohydrate Sugar Ammonium Perchlorate Magnesium Other
Carbohydrate Sugar Ammonium Nitrate Magnesium Other Carbohydrate
Sugar Other Alternative Oxidizer Magnesium Other Carbohydrate Sugar
Potassium Perchlorate Sodium Benzoate Other Carbohydrate Sugar
Potassium Chlorate Sodium Benzoate Other Carbohydrate Sugar
Potassium Nitrate Sodium Benzoate Other Carbohydrate Sugar
Potassium Sulfate Sodium Benzoate Other Carbohydrate Sugar Sodium
Perchlorate Sodium Benzoate Other Carbohydrate Sugar Sodium
Chlorate Sodium Benzoate Other Carbohydrate Sugar Sodium Nitrate
Sodium Benzoate Other Carbohydrate Sugar Sodium Sulfate Sodium
Benzoate Other Carbohydrate Sugar Ammonium Perchlorate Sodium
Benzoate Other Carbohydrate Sugar Ammonium Nitrate Sodium Benzoate
Other Carbohydrate Sugar Other Alternative Oxidizer Sodium Benzoate
Other Carbohydrate Sugar Potassium Perchlorate Sodium Nitrobenzoate
Other Carbohydrate Sugar Potassium Chlorate Sodium Nitrobenzoate
Other Carbohydrate Sugar Potassium Nitrate Sodium Nitrobenzoate
Other Carbohydrate Sugar Potassium Sulfate Sodium Nitrobenzoate
Other Carbohydrate Sugar Sodium Perchlorate Sodium Nitrobenzoate
Other Carbohydrate Sugar Sodium Chlorate Sodium Nitrobenzoate Other
Carbohydrate Sugar Sodium Nitrate Sodium Nitrobenzoate Other
Carbohydrate Sugar Sodium Sulfate Sodium Nitrobenzoate Other
Carbohydrate Sugar Ammonium Perchlorate Sodium Nitrobenzoate Other
Carbohydrate Sugar Ammonium Nitrate Sodium Nitrobenzoate Other
Carbohydrate Sugar Other Alternative Oxidizer Sodium Nitrobenzoate
Other Carbohydrate Sugar Potassium Perchlorate Sodium Gluconate
Other Carbohydrate Sugar Potassium Chlorate Sodium Gluconate Other
Carbohydrate Sugar Potassium Nitrate Sodium Gluconate Other
Carbohydrate Sugar Potassium Sulfate Sodium Gluconate Other
Carbohydrate Sugar Sodium Perchlorate Sodium Gluconate Other
Carbohydrate Sugar Sodium Chlorate Sodium Gluconate Other
Carbohydrate Sugar Sodium Nitrate Sodium Gluconate Other
Carbohydrate Sugar Sodium Sulfate Sodium Gluconate Other
Carbohydrate Sugar Ammonium Perchlorate Sodium Gluconate Other
Carbohydrate Sugar Ammonium Nitrate Sodium Gluconate Other
Carbohydrate Sugar Other Alternative Oxidizer Sodium Gluconate
Other Carbohydrate Sugar Potassium Perchlorate Potassium Benzoate
Other Carbohydrate Sugar Potassium Chlorate Potassium Benzoate
Other Carbohydrate Sugar Potassium Nitrate Potassium Benzoate Other
Carbohydrate Sugar Potassium Sulfate Potassium Benzoate Other
Carbohydrate Sugar Sodium Perchlorate Potassium Benzoate Other
Carbohydrate Sugar Sodium Chlorate Potassium Benzoate Other
Carbohydrate Sugar Sodium Nitrate Potassium Benzoate Other
Carbohydrate Sugar Sodium Sulfate Potassium Benzoate Other
Carbohydrate Sugar Ammonium Perchlorate Potassium Benzoate Other
Carbohydrate Sugar Ammonium Nitrate Potassium Benzoate Other
Carbohydrate Sugar Other Alternative Oxidizer Potassium Benzoate
Other Carbohydrate Sugar Potassium Perchlorate Potassium
Nitrobenzoate Other Carbohydrate Sugar Potassium Chlorate Potassium
Nitrobenzoate Other Carbohydrate Sugar Potassium Nitrate Potassium
Nitrobenzoate Other Carbohydrate Sugar Potassium Sulfate Potassium
Nitrobenzoate Other Carbohydrate Sugar Sodium Perchlorate Potassium
Nitrobenzoate Other Carbohydrate Sugar Sodium Chlorate Potassium
Nitrobenzoate Other Carbohydrate Sugar Sodium Nitrate Potassium
Nitrobenzoate Other Carbohydrate Sugar Sodium Sulfate Potassium
Nitrobenzoate Other Carbohydrate Sugar Ammonium Perchlorate
Potassium Nitrobenzoate Other Carbohydrate Sugar Ammonium Nitrate
Potassium Nitrobenzoate Other Carbohydrate Sugar Other Alternative
Oxidizer Potassium Nitrobenzoate Other Carbohydrate Sugar Potassium
Perchlorate Potassium Gluconate Other Carbohydrate Sugar Potassium
Chlorate Potassium Gluconate Other Carbohydrate Sugar Potassium
Nitrate Potassium Gluconate Other Carbohydrate Sugar Potassium
Sulfate Potassium Gluconate Other Carbohydrate Sugar Sodium
Perchlorate Potassium Gluconate Other Carbohydrate Sugar Sodium
Chlorate Potassium Gluconate Other Carbohydrate Sugar Sodium
Nitrate Potassium Gluconate Other Carbohydrate Sugar Sodium Sulfate
Potassium Gluconate Other Carbohydrate Sugar Ammonium Perchlorate
Potassium Gluconate Other Carbohydrate Sugar Ammonium Nitrate
Potassium Gluconate Other Carbohydrate Sugar Other Alternative
Oxidizer Potassium Gluconate Other Carbohydrate Sugar Potassium
Perchlorate Iron oxide Other Carbohydrate Sugar Potassium Chlorate
Iron oxide Other Carbohydrate Sugar Potassium Nitrate Iron oxide
Other Carbohydrate Sugar Potassium Sulfate Iron oxide Other
Carbohydrate Sugar Sodium Perchlorate Iron oxide Other Carbohydrate
Sugar Sodium Chlorate Iron oxide Other Carbohydrate Sugar Sodium
Nitrate Iron oxide Other Carbohydrate Sugar Sodium Sulfate Iron
oxide Other Carbohydrate Sugar Ammonium Perchlorate Iron oxide
Other Carbohydrate Sugar Ammonium Nitrate Iron oxide Other
Carbohydrate Sugar Other Alternative Oxidizer Iron oxide Other
Starch Potassium Perchlorate None Other Starch Potassium Chlorate
None Other Starch Potassium Nitrate None Other Starch Potassium
Sulfate None Other Starch Sodium Perchlorate None Other Starch
Sodium Chlorate None Other Starch Sodium Nitrate None Other Starch
Sodium Sulfate None Other Starch Ammonium Perchlorate None Other
Starch Ammonium Nitrate None Other Starch Other Alternative
Oxidizer None Other Starch Potassium Perchlorate Ferrosilicon Other
Starch Potassium Chlorate Ferrosilicon Other Starch Potassium
Nitrate Ferrosilicon Other Starch Potassium Sulfate Ferrosilicon
Other Starch Sodium Perchlorate Ferrosilicon Other Starch Sodium
Chlorate Ferrosilicon Other Starch Sodium Nitrate Ferrosilicon
Other Starch Sodium Sulfate Ferrosilicon Other Starch Ammonium
Perchlorate Ferrosilicon Other Starch Ammonium Nitrate Ferrosilicon
Other Starch Other Alternative Oxidizer Ferrosilicon Other Starch
Potassium Perchlorate Magnalium Other Starch Potassium Chlorate
Magnalium Other Starch Potassium Nitrate Magnalium Other Starch
Potassium Sulfate Magnalium Other Starch Sodium Perchlorate
Magnalium Other Starch Sodium Chlorate Magnalium Other Starch
Sodium Nitrate Magnalium Other Starch Sodium Sulfate Magnalium
Other Starch Ammonium Perchlorate Magnalium Other Starch Ammonium
Nitrate Magnalium Other Starch Other Alternative Oxidizer Magnalium
Other Starch Potassium Perchlorate Aluminum Other Starch Potassium
Chlorate Aluminum Other Starch Potassium Nitrate Aluminum Other
Starch Potassium Sulfate Aluminum Other Starch Sodium Perchlorate
Aluminum Other Starch Sodium Chlorate Aluminum Other Starch Sodium
Nitrate Aluminum Other Starch Sodium Sulfate Aluminum Other Starch
Ammonium Perchlorate Aluminum Other Starch Ammonium Nitrate
Aluminum Other Starch Other Alternative Oxidizer Aluminum Other
Starch Potassium Perchlorate Magnesium
Other Starch Potassium Chlorate Magnesium Other Starch Potassium
Nitrate Magnesium Other Starch Potassium Sulfate Magnesium Other
Starch Sodium Perchlorate Magnesium Other Starch Sodium Chlorate
Magnesium Other Starch Sodium Nitrate Magnesium Other Starch Sodium
Sulfate Magnesium Other Starch Ammonium Perchlorate Magnesium Other
Starch Ammonium Nitrate Magnesium Other Starch Other Alternative
Oxidizer Magnesium Other Starch Potassium Perchlorate Sodium
Benzoate Other Starch Potassium Chlorate Sodium Benzoate Other
Starch Potassium Nitrate Sodium Benzoate Other Starch Potassium
Sulfate Sodium Benzoate Other Starch Sodium Perchlorate Sodium
Benzoate Other Starch Sodium Chlorate Sodium Benzoate Other Starch
Sodium Nitrate Sodium Benzoate Other Starch Sodium Sulfate Sodium
Benzoate Other Starch Ammonium Perchlorate Sodium Benzoate Other
Starch Ammonium Nitrate Sodium Benzoate Other Starch Other
Alternative Oxidizer Sodium Benzoate Other Starch Potassium
Perchlorate Sodium Nitrobenzoate Other Starch Potassium Chlorate
Sodium Nitrobenzoate Other Starch Potassium Nitrate Sodium
Nitrobenzoate Other Starch Potassium Sulfate Sodium Nitrobenzoate
Other Starch Sodium Perchlorate Sodium Nitrobenzoate Other Starch
Sodium Chlorate Sodium Nitrobenzoate Other Starch Sodium Nitrate
Sodium Nitrobenzoate Other Starch Sodium Sulfate Sodium
Nitrobenzoate Other Starch Ammonium Perchlorate Sodium
Nitrobenzoate Other Starch Ammonium Nitrate Sodium Nitrobenzoate
Other Starch Other Alternative Oxidizer Sodium Nitrobenzoate Other
Starch Potassium Perchlorate Sodium Gluconate Other Starch
Potassium Chlorate Sodium Gluconate Other Starch Potassium Nitrate
Sodium Gluconate Other Starch Potassium Sulfate Sodium Gluconate
Other Starch Sodium Perchlorate Sodium Gluconate Other Starch
Sodium Chlorate Sodium Gluconate Other Starch Sodium Nitrate Sodium
Gluconate Other Starch Sodium Sulfate Sodium Gluconate Other Starch
Ammonium Perchlorate Sodium Gluconate Other Starch Ammonium Nitrate
Sodium Gluconate Other Starch Other Alternative Oxidizer Sodium
Gluconate Other Starch Potassium Perchlorate Potassium Benzoate
Other Starch Potassium Chlorate Potassium Benzoate Other Starch
Potassium Nitrate Potassium Benzoate Other Starch Potassium Sulfate
Potassium Benzoate Other Starch Sodium Perchlorate Potassium
Benzoate Other Starch Sodium Chlorate Potassium Benzoate Other
Starch Sodium Nitrate Potassium Benzoate Other Starch Sodium
Sulfate Potassium Benzoate Other Starch Ammonium Perchlorate
Potassium Benzoate Other Starch Ammonium Nitrate Potassium Benzoate
Other Starch Other Alternative Oxidizer Potassium Benzoate Other
Starch Potassium Perchlorate Potassium Nitrobenzoate Other Starch
Potassium Chlorate Potassium Nitrobenzoate Other Starch Potassium
Nitrate Potassium Nitrobenzoate Other Starch Potassium Sulfate
Potassium Nitrobenzoate Other Starch Sodium Perchlorate Potassium
Nitrobenzoate Other Starch Sodium Chlorate Potassium Nitrobenzoate
Other Starch Sodium Nitrate Potassium Nitrobenzoate Other Starch
Sodium Sulfate Potassium Nitrobenzoate Other Starch Ammonium
Perchlorate Potassium Nitrobenzoate Other Starch Ammonium Nitrate
Potassium Nitrobenzoate Other Starch Other Alternative Oxidizer
Potassium Nitrobenzoate Other Starch Potassium Perchlorate
Potassium Gluconate Other Starch Potassium Chlorate Potassium
Gluconate Other Starch Potassium Nitrate Potassium Gluconate Other
Starch Potassium Sulfate Potassium Gluconate Other Starch Sodium
Perchlorate Potassium Gluconate Other Starch Sodium Chlorate
Potassium Gluconate Other Starch Sodium Nitrate Potassium Gluconate
Other Starch Sodium Sulfate Potassium Gluconate Other Starch
Ammonium Perchlorate Potassium Gluconate Other Starch Ammonium
Nitrate Potassium Gluconate Other Starch Other Alternative Oxidizer
Potassium Gluconate Other Starch Potassium Perchlorate Iron oxide
Other Starch Potassium Chlorate Iron oxide Other Starch Potassium
Nitrate Iron oxide Other Starch Potassium Sulfate Iron oxide Other
Starch Sodium Perchlorate Iron oxide Other Starch Sodium Chlorate
Iron oxide Other Starch Sodium Nitrate Iron oxide Other Starch
Sodium Sulfate Iron oxide Other Starch Ammonium Perchlorate Iron
oxide Other Starch Ammonium Nitrate Iron oxide Other Starch Other
Alternative Oxidizer Iron oxide Other Fuel Potassium Perchlorate
None Other Fuel Potassium Chlorate None Other Fuel Potassium
Nitrate None Other Fuel Potassium Sulfate None Other Fuel Sodium
Perchlorate None Other Fuel Sodium Chlorate None Other Fuel Sodium
Nitrate None Other Fuel Sodium Sulfate None Other Fuel Ammonium
Perchlorate None Other Fuel Ammonium Nitrate None Other Fuel Other
Alternative Oxidizer None Other Fuel Potassium Perchlorate
Ferrosilicon Other Fuel Potassium Chlorate Ferrosilicon Other Fuel
Potassium Nitrate Ferrosilicon Other Fuel Potassium Sulfate
Ferrosilicon Other Fuel Sodium Perchlorate Ferrosilicon Other Fuel
Sodium Chlorate Ferrosilicon Other Fuel Sodium Nitrate Ferrosilicon
Other Fuel Sodium Sulfate Ferrosilicon Other Fuel Ammonium
Perchlorate Ferrosilicon Other Fuel Ammonium Nitrate Ferrosilicon
Other Fuel Other Alternative Oxidizer Ferrosilicon Other Fuel
Potassium Perchlorate Magnalium Other Fuel Potassium Chlorate
Magnalium Other Fuel Potassium Nitrate Magnalium Other Fuel
Potassium Sulfate Magnalium Other Fuel Sodium Perchlorate Magnalium
Other Fuel Sodium Chlorate Magnalium Other Fuel Sodium Nitrate
Magnalium Other Fuel Sodium Sulfate Magnalium Other Fuel Ammonium
Perchlorate Magnalium Other Fuel Ammonium Nitrate Magnalium Other
Fuel Other Alternative Oxidizer Magnalium Other Fuel Potassium
Perchlorate Aluminum Other Fuel Potassium Chlorate Aluminum Other
Fuel Potassium Nitrate Aluminum Other Fuel Potassium Sulfate
Aluminum Other Fuel Sodium Perchlorate Aluminum Other Fuel Sodium
Chlorate Aluminum Other Fuel Sodium Nitrate Aluminum Other Fuel
Sodium Sulfate Aluminum Other Fuel Ammonium Perchlorate Aluminum
Other Fuel Ammonium Nitrate Aluminum Other Fuel Other Alternative
Oxidizer Aluminum Other Fuel Potassium Perchlorate Magnesium Other
Fuel Potassium Chlorate Magnesium Other Fuel Potassium Nitrate
Magnesium Other Fuel Potassium Sulfate Magnesium Other Fuel Sodium
Perchlorate Magnesium Other Fuel Sodium Chlorate Magnesium Other
Fuel Sodium Nitrate Magnesium Other Fuel Sodium Sulfate Magnesium
Other Fuel Ammonium Perchlorate Magnesium Other Fuel Ammonium
Nitrate Magnesium Other Fuel Other Alternative Oxidizer Magnesium
Other Fuel Potassium Perchlorate Sodium Benzoate Other Fuel
Potassium Chlorate Sodium Benzoate Other Fuel Potassium Nitrate
Sodium Benzoate Other Fuel Potassium Sulfate Sodium Benzoate Other
Fuel Sodium Perchlorate Sodium Benzoate Other Fuel Sodium Chlorate
Sodium Benzoate Other Fuel Sodium Nitrate Sodium Benzoate Other
Fuel Sodium Sulfate Sodium Benzoate Other Fuel Ammonium Perchlorate
Sodium Benzoate Other Fuel Ammonium Nitrate Sodium Benzoate Other
Fuel Other Alternative Oxidizer Sodium Benzoate Other Fuel
Potassium Perchlorate Sodium Nitrobenzoate Other Fuel Potassium
Chlorate Sodium Nitrobenzoate Other Fuel Potassium Nitrate Sodium
Nitrobenzoate Other Fuel Potassium Sulfate Sodium Nitrobenzoate
Other Fuel Sodium Perchlorate Sodium Nitrobenzoate Other Fuel
Sodium Chlorate Sodium Nitrobenzoate Other Fuel Sodium Nitrate
Sodium Nitrobenzoate Other Fuel Sodium Sulfate Sodium Nitrobenzoate
Other Fuel Ammonium Perchlorate Sodium Nitrobenzoate Other Fuel
Ammonium Nitrate Sodium Nitrobenzoate Other Fuel Other Alternative
Oxidizer Sodium Nitrobenzoate Other Fuel Potassium Perchlorate
Sodium Gluconate Other Fuel Potassium Chlorate Sodium Gluconate
Other Fuel Potassium Nitrate Sodium Gluconate Other Fuel Potassium
Sulfate Sodium Gluconate Other Fuel Sodium Perchlorate Sodium
Gluconate Other Fuel Sodium Chlorate Sodium Gluconate Other Fuel
Sodium Nitrate Sodium Gluconate Other Fuel Sodium Sulfate Sodium
Gluconate Other Fuel Ammonium Perchlorate Sodium Gluconate Other
Fuel Ammonium Nitrate Sodium Gluconate Other Fuel Other Alternative
Oxidizer Sodium Gluconate Other Fuel Potassium Perchlorate
Potassium Benzoate Other Fuel Potassium Chlorate Potassium Benzoate
Other Fuel Potassium Nitrate Potassium Benzoate Other Fuel
Potassium Sulfate Potassium Benzoate Other Fuel Sodium Perchlorate
Potassium Benzoate Other Fuel Sodium Chlorate Potassium Benzoate
Other Fuel Sodium Nitrate Potassium Benzoate Other Fuel Sodium
Sulfate Potassium Benzoate Other Fuel Ammonium Perchlorate
Potassium Benzoate Other Fuel Ammonium Nitrate Potassium Benzoate
Other Fuel Other Alternative Oxidizer Potassium Benzoate Other Fuel
Potassium Perchlorate Potassium Nitrobenzoate Other Fuel Potassium
Chlorate Potassium Nitrobenzoate Other Fuel Potassium Nitrate
Potassium Nitrobenzoate Other Fuel Potassium Sulfate Potassium
Nitrobenzoate Other Fuel Sodium Perchlorate Potassium Nitrobenzoate
Other Fuel Sodium Chlorate Potassium Nitrobenzoate Other Fuel
Sodium Nitrate Potassium Nitrobenzoate Other Fuel Sodium Sulfate
Potassium Nitrobenzoate Other Fuel Ammonium Perchlorate Potassium
Nitrobenzoate Other Fuel Ammonium Nitrate Potassium Nitrobenzoate
Other Fuel Other Alternative Oxidizer Potassium Nitrobenzoate Other
Fuel Potassium Perchlorate Potassium Gluconate Other Fuel Potassium
Chlorate Potassium Gluconate Other Fuel Potassium Nitrate Potassium
Gluconate Other Fuel Potassium Sulfate Potassium Gluconate Other
Fuel Sodium Perchlorate Potassium Gluconate Other Fuel Sodium
Chlorate Potassium Gluconate Other Fuel Sodium Nitrate Potassium
Gluconate Other Fuel Sodium Sulfate Potassium Gluconate Other Fuel
Ammonium Perchlorate Potassium Gluconate Other Fuel Ammonium
Nitrate Potassium Gluconate Other Fuel Other Alternative Oxidizer
Potassium Gluconate Other Fuel Potassium Perchlorate Iron oxide
Other Fuel Potassium Chlorate Iron oxide Other Fuel Potassium
Nitrate Iron oxide Other Fuel Potassium Sulfate Iron oxide Other
Fuel Sodium Perchlorate Iron oxide Other Fuel Sodium Chlorate Iron
oxide Other Fuel Sodium Nitrate Iron oxide Other Fuel Sodium
Sulfate Iron oxide Other Fuel Ammonium Perchlorate Iron oxide Other
Fuel Ammonium Nitrate Iron oxide Other Fuel Other Alternative
Oxidizer Iron oxide
[0060] Any of the compositions in Table 1 or elsewhere may be
present in a gas-generating composition in any weight percentage,
such as the weight percentages described above. The total weight
percentage of a composition is generally about 100. Accordingly,
components of a composition are generally chosen in weight
percentages such that the total weight percentage of a given
composition is about 100. For instance, the gas-generating
composition can contain a fuel, oxidizer and additional components
in the weight percentage ranges shown in Table 2, and may contain
further components, such as less than 5 weight percent or about 1
weight percent flow agent such as Neosil, provided that the total
sum of weight percentages of all components of the composition is
100 or about 100%.
[0061] Weight percentages are generally measured by the weight of a
commercially available chemical composition, with no drying steps
or extra precautions being taken during storage or weighing to
guard against absorption of moisture, such as from moisture in the
air. In this way, the dry weight percentage of a given component in
a composition may vary slightly according to small changes in
moisture content of the commercially available component.
[0062] Table 2 lists representative examples of fuel, oxidizer and
additional components, although it is recognized that all fuel,
oxidizers and additional agents disclosed herein may be used in the
gas-generating compositions in the ranges indicated. TABLE-US-00002
TABLE 2 Example ranges and substitute components in weight percent.
Component Representative Examples Range 1 Range 2 Range 3 Range 4
Oxidizer Potassium Perchlorate, 45-75% 30-80% 40-50% 50-65% sodium
sulfate, ammonium chlorate Fuel Lactose, glucose, glycogen, 10-30%
1-40% 25-35% 15-25% amylase, chitin, heparin, cellulose, Adenosyl
First Additional Ferrosilicon, sodium 0-15% 0-25% 10-15% 15-25%
Component benzoate, potassium gluconate, magnalium Second or
greater than Ferrosilicon, sodium 0-10% 0-25% 6-12% 0-10% second
Additional benzoate, potassium Component gluconate, magnalium
[0063] Additional examples of gas-generating compositions are
listed below in Table 3 as gas-generating compositions A-H. In one
variation, each of the weight percentages listed in Table 3 can be
increased or decreased by about 30% or by about 25% or by about 20%
or by about 15% or by about 10% or by about 5% of the values
listed. For instance, in one variation, a composition can comprise
56 weight %.+-.10% potassium perchlorate such that potassium
perchlorate may be present in the composition in about 50 weight %
or about 62 weight %. In another variation, each of the weight
percentages listed in Table 3 can be increased or decreased by
between about 5-10% or between about 5-20% or between about 5-30%
or between about 10-20% or between about 10-30% or between about
15-25% or between about 15-30% or between about 20-40% or between
about 30-40% of the values listed. In yet another variation, each
of the weight percentages listed in Table 3 can be increased or
decreased by less than 30% or less than 25% or less than 20% or
less than 15% or less than 10% or less than 5% or less than 3% of
the values listed. TABLE-US-00003 TABLE 3 Example gas-generating
compositions, listed in weight percentage. A B C D E F G H
Potassium Perchlorate 56% 45.5% 68% 71% 71% 63% 65% 45% Lactose 22%
30.8% 18% 17% 15% 10% 5% 32% Sodium Benzoate -- -- 6% -- 5% -- --
-- Sodium Nitrobenzoate -- -- 7% -- 5% -- -- -- Sodium Gluconate --
-- -- 11% -- 20% 15% -- Ferrosilicon 21% 13.6% -- -- 3% 6% 14% 13%
Magnalium -- 9.1% -- -- -- -- -- -- Flow agent (Neosil, etc.) 1%
1.0% 1% 1% 1% 1% 1% -- Magnesium Powder -- -- -- -- -- -- -- 5%
Aluminum Powder -- -- -- -- -- -- -- 5%
Composition Preparation
[0064] The gas-generating compositions may be prepared in any
suitable mixing apparatus known to those of skill in the art, such
as an apparatus comprising a rotating stainless steel drum with no
mixing fins, or any powder mixing apparatus of suitable size that
is commonly known to those skilled in the art. The compositions are
generally in the form of a powder, which can be loose, loosely
packed or packed to at least a density that allows shaping of the
powder composition into a desirable shape, such as a bar or tapered
shape such as a cone.
[0065] The gas-generating composition can be made in any batch
size, such as about a 10 or 20 or 30 or 40 or 50 or 60 or 70 or 80
or 90 or 100 pound or more batch size. In preparing the
gas-generating compositions, it was found that increasing the batch
size in the mixing apparatus from 40 lb to 100 lb, corresponding to
the total weight of the mixture, had the effect of increasing the
powder density by as much as 40%. Therefore, a larger mixing batch
is preferred. It is believed that a higher density of powder serves
to increase the burn rate and reduce the gas volume available in
the cartridge, thereby increasing the fracturing efficiency of the
cartridge. By scaling up the mixing apparatus to larger batch
sizes, it is expected that the powder density may increase further,
and the beneficial properties obtained therein may be further
improved.
[0066] In one variation, the composition is made such that at least
a portion of the composition exhibits a tap density of about 0.5
g/cc or about 0.6 g/cc or about 0.7 g/cc or about 0.8 g/cc or about
0.9 g/cc or about 1.0 g/cc or about 1.03 g/cc or about 1.5 g/cc or
greater than about 1.5 g/cc or greater than about 1.0 g/cc or
between about 0.06 g/cc and about 1.8 g/cc or between about 0.08
g/cc and about 1.6 g/cc or between about 1.0 g/cc and about 1.4
g/cc or between about 1.1 g/cc and about 1.3 g/cc or between about
1.2 g/cc and about 1.8 g/cc or between about 1.2 g/cc and about 1.6
g/cc or between about 1.0 g/cc and about 2.0 g/cc or between about
1.0 g/cc and about 3.0 g/cc or less than about 2.0 g/cc or less
than about 1.8 g/cc or less than about 1.5 g/cc.
[0067] A method of making a composition is also described wherein
the method comprises the steps of providing at least one fuel, such
as a carbohydrate fuel, providing at least oxidizer, such as
potassium perchlorate, potassium nitrate, potassium chlorate,
potassium sulfate or a perchlorate salt, providing at least one
additional component, such as of ferrosilicon and/or magnalium and
combining the compounds in amounts and under conditions sufficient
to produce a composition having a tap density according to any of
the values described herein, such as a tap density greater than
about 1.2 g/cc.
System
[0068] In general, a gas-generating system comprises a
gas-generating composition within a container, such as cartridge.
The system can also include a material to be fractured such that
the gas-generating system comprises a container, a gas-generating
composition within the container and a material to be fractured. In
addition, the system can also include a stemming material such that
the gas-generating system comprises a container, a gas-generating
composition within the container, a material to be fractured and a
stemming material.
[0069] The gas-generating composition system may comprise several
component parts, each of which is discussed in turn below. Examples
of the system are found in FIGS. 1-3.
[0070] Referring to FIG. 1, the system can comprise a cartridge 1
filled with gas generating formulation 7. A wick 2 can be attached
to an igniter 3, such as via a string 4. The igniter 3 can be
electric and employ an ignition wire 6, which is connected to the
igniter and extends through the cartridge via a hole in an end-cap
5. An example of an assembled cartridge is shown in FIG. 2, which
shows the cartridge comprising a cylindrical housing closed with
end caps 5 equipped with friction ribs 11. The lead wire extends
out a hole in an end cap, which is sealed by a sealing material 12.
FIG. 3 shows an assembled cartridge 1 inside a hole 9 in a material
to be fractured 8 where the hole is covered with a blasting mat 10
and filled with a stemming material 13.
Material
[0071] The gas-generating compositions may be used in the systems
and methods disclosed herein to fracture a material. The material
can be any material for which fractioning is desired. The material
to be fractured includes any hard material such as solid or
semi-fractured rock, concrete, granite, marble, hard clay,
sandstone, limestone, dolomite, basalt, mineral deposits, diamond,
gold or silver, precious or semi-precious stone and quartz. The
compositions are useful in certain applications, including but not
limited to, excavation of hard materials in such applications as
surface mining, open pits and quarries, earth moving and allied
construction works, and in civil demolition projects. The
compressive strengths of the material can be greater than 20 MPa,
and often greater than 100 MPa. When the compressive strengths
exceed 100 MPa, mechanical breaking such as by impact hammers
becomes impractical and costly, making the proposed system a more
desirable choice. The concrete materials may include foundations,
piers, and reinforced structural concrete as found in bridges or
other structures.
Charging Material with Gas-Generating Composition:
[0072] In one variation, the material to be fractured is charged
with a gas-generating composition by positioning the gas-generating
composition in a hole present in the material. The gas-generating
composition may be contained within a cartridge, which is described
in more detail below under the section entitled `cartridge`.
Positioning the gas-generating cartridge allows control over
factors such as orienting the igniter, such as at the bottom of the
hole, keeping moisture out of the composition, and preventing
mixing between the stemming material and the powder. However, the
gas-generating compositions can be used as a loose powder and/or
shaped powder, including a bar of powder. A bar of powder can be
made with a mold as known to those of skill in the art. Generally a
very small amount of moisture is added to the gas-generating
composition to allow it to clump or bind in a mold. After the
moistened powder is pressed into a mold and the desired shape is
obtained, the shaped powder can be baked to dryness to ensure that
moisture has been driven from the powder prior to use.
Hole
[0073] The material to be fractured can be charged with the
gas-generating composition by placing the composition in a hole
present or made in the material. The hole may be created by any
methods known to those skilled in the art, such as drilling using a
pneumatic or impact drill equipped with a steel drill. The depth of
the hole from the surface of the material may be any depth that
allows a desired volume of the material to be fractured. In one
variation, the hole is at least about 2 feet deep from the surface
of the material to provide sufficient length for the stemming
material, and may be deeper to allow for a greater volume of
material to be fractured. In one variation, the hole length is
greater than 10 or about 10 or about 8 or about 6 or about 4 or
about 3 or about 1 times the length of the cartridge.
[0074] The length of the cartridge can vary, and can hold varying
amount of gas-generating composition, depending on both the length
and diameter of the cartridge. For instance, a cartridge can be
about 11/2'' or about 2'' or about 21/4'' or about 5'' or about
10'' or about 12'' or about 15'' or about 18'' or more in length. A
cartridge with a longer length may contain the same amount of
material as a cartridge of shorter length, provided that the
diameter of the cartridge is smaller in the longer cartridge than
in the shorter cartridge. For instance, a 21/4'' in length
cartridge may contain about 50 g of gas-generating composition, a
15'' in length cartridge may contain about 600 g of gas-generating
composition, and an 18'' in length composition may contain about
300 g of gas-generating composition. In this example, the 18''
cartridge has a diameter that is smaller than the diameter of the
15'' in length cartridge.
[0075] In order for gas-generating system to be optimized, care is
usually taken to minimize the available volume within the cartridge
and drill hole. By reducing the free volume of air, the expanding
gas is able to perform more work on the surrounding rock by
achieving a higher total pressure before a fracture occurs, which
releases the gas.
[0076] To this end, the diameter of the drill hole that will
contain the gas-generating composition or cartridge may be a
diameter that minimizes the available volume with in the drill
hole. In one variation, the drill hole will not exceed 0.75'' more
than the outer diameter of the cartridge, preferably less than
0.5'' more, and more preferably less the 0.25'' more than the outer
diameter of the cartridge housing. In one variation, a hole is
created having a diameter of about 11/4'' and in another variation,
a hole is created having a diameter of about 2''. In yet another
variation, the drill hole is no greater than about 2''. In one
variation, a cartridge of diameter of about 11/8'' is used in
connection with a drill hole having a diameter of about 11/4''. In
another variation, a cartridge having a diameter of about 13/4'' is
used in connection with a drill hole having a diameter of about
17/8''. In yet another variation, the ratio of cartridge diameter
to drill hole diameter is about 0.5 to about 0.9.
[0077] The depth of the drill hole can be any depth that is
required to fracture the material. The depth of the drill from the
surface of the material to be fractured can be, for example, about
two or about three times the length of the cartridge containing the
gas-generating composition. The depth of the hole is generally a
depth that is sufficiently deep that, e.g., the stemming material
effectively seals the hole over the short time period required for
the composition to ignite and generate a large volume of gas to
fracture or break the material.
[0078] More than one cartridge can be place in a single hole and
multiple holes may be created for a single cartridge. When multiple
holes are created for use with a single cartridge, one of the holes
will contain the cartridge and the remaining holes act as weak
spots. For instance, a series of holes can be created in a material
to be fractured, where every other hole in the series contains a
cartridge. In this way, fracturing or breaking occurs toward the
weak spots formed by the holes that are not charged with
cartridges, allowing the user to control the breakage and create a
straight line split along the line of drill holes. If multiple
cartridges are used in a single hole, a stemming material can be
placed between the charges. As known to one of skill in the art,
placing a stemming material between multiple charges tends to
distribute the gas pressure evenly along the length of the hole,
leading to improved fracturing efficiency in longer holes. If the
energy is concentrated at the bottom of the hole for example, large
un-fractured chunks of material to be fractured could remain
unbroken near the surface of the material. Multiple charges include
two or three or four or five or six or more charges for use in a
single hole.
[0079] In one variation, a hole is created in the material to be
fractured such that the "free volume" or total volume of the hole
minus the volume taken up by the gas-generating carrier, such as a
cartridge, is less than about 55% of the total volume. In one
variation the free volume inside the hole less than about 65% or
less than about 50% or less than about 40% or less than about 30%
of the total volume. The free volume is generally filled with
stemming material.
Cartridge
[0080] The gas-generating composition may be contained in any
suitable way, such as in a cartridge, which aids in the ease of
transporting and/or storing and/or charging and/or igniting the
gas-generating composition. In one variation, the gas-generating
composition may be contained in a cartridge, which aids in the ease
of transporting and storing and charging and igniting the
gas-generating composition. In one variation, the cartridge is
constructed such that the cartridge does not break in the
conditions in the hole until the pressure inside the cartridge
reaches the first pressure indicating a change in burn rate as a
function of ln(p).
[0081] The cartridge can be any shape, including a bar, a rod, a
cone, a sphere, a trapezoid or any rectangular, square or tapered
shape having any number of sides.
[0082] In one variation, the cartridge has at least one closable
end. The cartridge can include a housing, such as in the shape of a
tube, made of or coated by any material, including water-proof or
water-repellant materials such as high-density polyethylene (HDPE).
The wall thickness of the cartridge can be any thickness, and will
vary according to the cartridge material. For example, a HDPE or
other polymer-based cartridge can have a wall thickness of
approximately 0.05''. It is desirable for the cartridge to have
sufficient strength so as to be durable during transport and
loading, but not so strong as to allow high-pressure gasses to
build-up in the case of an accidental ignition outside the drill
hole. The wall thickness may be less than 0.2'', less than 0.1'',
or less than 0.05''. It is intended for the cartridge to pass the
UN classification of 1.4S or 1.4C, meaning there is no significant
danger for explosion while the cartridge is being transported. By
limiting the strength of the cartridge, the tendency of creating an
explosion is reduced and the beneficial classification of 1.4 can
be obtained.
[0083] In one variation, the cartridge can be a tube having at
least one closable end, which can be permanently closed, such as
when a tube is manufactured as a single unit with at least one
closed end, or removably closed, such as when a hollow tube can be
closed by one or more end caps that can be put on or taken off of
the open ends of the tube. The end caps can be inserted into the
inner hollow portion of a cartridge tube to create a seal or can be
fitted over the housing body. If the cartridge has removable ends,
any closable end can be employed, including friction or other
suitable end caps that screw or clamp or glue into place. In one
variation, the cartridge is closed with end caps that are also
comprised of HDPE, and which may have 1 or 2 or more friction ribs
to hold the caps in place and create a seal.
[0084] When an igniter wire is used, a hole can be created in an
end cap, such as punched or drilled into one cap to allow an
igniter wire, which is discussed in more detail below, to pass
through. The hole is typically just large enough to allow the
thickness of the wire to pass through. Once the igniter wire is in
place, a bead of hot glue, silicone, or epoxy may be applied to the
area to seal the hole against the passage of moist air and water.
The glue may be allowed to seep into the hole and create a tight
seal up into and around the top portion of the cartridge. Care is
often taken to minimize the available volume within the cartridge
and drill hole. By reducing the free volume of air, the expanding
gas is able to perform more work on the surrounding rock by
achieving a higher total pressure before a fracture occurs,
releasing the gas.
[0085] The gas-generating composition can be inserted into the
cartridge in loose powder form or can be shaped, for instance, into
a bar. When the cartridges are filled with powder gas-generating
compositions, the free space left in the cartridge is generally
less than about 5 or less than about 10%, but can be as much as
about 20%.
[0086] For a cartridge containing a loose powder form of the
gas-generating compositions, the igniter, ignition wire and black
powder wick may be inserted into the loose powder. Generally, the
ignition wire and igniter are inserted into the cartridge via a
hole in an end cap. The igniter can then be attached to the wick,
such as a black powder wick, via a tie wrap, a string, an adhesive
or any other material that allows the wick to stay in proximity to
the igniter. The wick can be, e.g., about 1-5 inches in length, or
about 2 or about 3 or about 4 inches in length. While not wishing
to be bound by theory, it is believed that the igniter generally
ignites both the wick and the gas-generating composition. However,
a close proximity of the wick to the igniter decreases the
incidence of misfires in that even if the gas-generating
composition powder were to move away from the igniter, such as
could happen during movement involved in transport, the wick when
ignited by the igniter will ensure ignition of the composition.
Igniter Wire
[0087] The wire extending from the electric igniter out of the
cartridge through the end cap is preferably 22 gauge or thicker to
prevent breakage during loading of the cartridge and the
compression of the stemming material. The igniter wire can be
extended as far as necessary to provide for a safe distance to
ignite the gas-generating formula, typically a few hundred feet. In
general, a cartridge includes about 10 or about 15 feet of igniter
wire extending from the cartridge, enabling a cartridge placed into
a drill hole to have at least some igniter wire exposed outside of
the hole. In one variation, multiple cartridges are linked together
via their extension wires. The ignition wires are generally
connected to a power source or interlinked with each other by
stripping at least a portion of an outer coating of a wire and
contacting the wire to the power source or another ignition wire,
such as by twisting two wires together. However, the ignition wires
may also comprise a quick fit connector or plug/socket connection
to connect the ignition wire to a power source or to another
ignition wire.
Sealing
[0088] An optional bead of hot glue, epoxy, or silicone, or similar
material may be used to seal the cartridge from water egress. The
entire cartridge can be dipped into a rubber-like substance, or
encased in a plastic bag before loading into the hole to seal out
any standing water which may be present at the bottom of the hole
or elsewhere.
Stemming
[0089] Once the material to be fractured is charged with the
gas-generating composition, e.g., by placing the sealed cartridge
equipped with a wire into a hole of the material as described
above, the hole is covered using stemming material, such as
aggregate stone or other composition commonly known to those
skilled in the art. The stemming material contains the gases from
the ignited gas-generating composition in the hole for a time
sufficient to cause fracturing of the rock.
[0090] The stemming material can be any material that is stable
under the conditions present in the hole during ignition and
deflagration. Examples of suitable stemming material include resin,
water-based gel, cementitious material, grout, concrete, metal or
composite bar, clay, gravel, sand, and dirt. One variation of the
stemming includes coarse damp sand composition having grit ranging
from 15 to 25. Other stemming compositions may include a rubber
plug filled with sand, or fly ash in combination with aggregate
stone. When using unconsolidated stemming material such as wet
gravel, sand or dirt, a firm compaction of the stemming composition
by hand during the loading process using a wooden or steel rod can
help prevent the stemming composition from rifling out of the hole,
as known to those skilled in the art. Due to the ability of the
gas-generating compositions to generate gas sufficient to fracture
material in a shorter time than is known for other deflagrating
materials, wet sand is generally a sufficient stemming material and
does not experience a high incidence of rifling. A blast mat known
to those of skill in the art can be placed over the stemmed
hole.
Igniter
[0091] Ignition of the gas-generating composition may occur by
methods known in the art. An igniter for use in the system can be
of any suitable design, and can be electronic, electric or
non-electric and can ignite a material in any way, such as
electrically, thermally or by generating a spark. The igniter can
include a timer that can control ignition time and delay ignition
until a pre-programmed time and can also include a microprocessor
and/or memory. In one variation, the igniter is used in connection
with ignition wires. In another variation, the igniter is remotely
activated and does not require use of ignition wires.
[0092] In one variation, the igniter is an electric igniter, such
as an electric igniter of a pyrotechnic composition. Ignition of
the gas-generating composition using an electric igniter allows
ignition at a safe distance from the material to be fractured,
generally several hundred feet or more.
Black Powder
[0093] An electric igniter has been found to be sufficient to
ignite the gas-generating pyrotechnic formula within the cartridge.
However, the presence of a wick, such as a black powder wick
connected to the igniter has been found to reduce the tendency for
misfires, which can be a dangerous and costly situation given the
time required for extraction and the expense of a lost cartridge.
The black powder wick is typically rolled paper containing black
powder, approximately 2'' to 4'' long. While not wishing to be
bound by any theory, it is believed that the relatively fast burn
rate of the black powder wick rapidly ignites the first several
inches of the gas-generating composition after ignition, allowing
the heat and pressure in the cartridge to rise more rapidly than by
the electric ignition alone, which in turn increases the burn rate
of the remaining gas-generating composition. By achieving this
small improvement in the time to peak pressure, it is believed that
the fracturing efficiency is thus improved. Furthermore, in cases
where the electric igniter would not otherwise be in contact with
the gas-generating composition due to settling, manufacturing
defects or improper orientation of the cartridge in the hole
(upside down), the extended black powder wick serves to ensure
proper ignition.
[0094] The wick can be made of other materials, including any of
the black powder substitutes known to those of skill in the arts,
such as Pyrodex.RTM., Triple Seven.RTM., Cordite, Ballistite or any
material having the desired characteristics of a fast burn-rate at
atmospheric pressure and a low ignition temperature (<500
C).
[0095] The systems disclosed can be used in a method of breaking or
fracturing hard materials. While not wishing to be bound by theory,
the gas-generating systems disclosed herein are believed to break
or fracture hard material by creating or enhancing structural
discontinuities or other weak spots within the material, resulting
in material breaks and fractures. The forces created by the
gas-generating compositions within the material create, disturb or
otherwise act on weak spots within the material.
[0096] In one variation, a method for fracturing material involves
creating a hole in the material, inserting a cartridge with a
gas-generating composition within the cartridge into the hole, at
least partially filling the hole with stemming material and
igniting the composition. The gas-generating compositions for use
in the methods can be any composition described herein, including a
composition that comprises (a) at least one fuel, such as a
carbohydrate; (b) at least one oxidizer, such as a compound
selected from the group consisting of potassium perchlorate,
potassium nitrate, potassium chlorate, potassium sulfate and a
perchlorate salt; (c) at least one additional component, such as a
compound selected from the group consisting of ferrosilicon,
magnalium, aluminum metal and magnesium metal and (d) less than 5
weight percent ammonium oxalate. The gas-generating compositions
for use in the methods can also be a composition comprising (a) at
least one fuel, such as a carbohydrate; (b) at least one oxidizer,
such as a compound selected from the group consisting of potassium
perchlorate, potassium nitrate, potassium chlorate, potassium
sulfate and a perchlorate salt; (c) at least one additional
component, such as a compound selected from the group consisting of
ferrosilicon, magnalium, aluminum metal and magnesium metal and (d)
less than 12 weight percent ammonium oxalate, wherein the ignited
composition generates gas sufficient to fracture the material. The
gas-generating compositions for use in the methods can also be a
composition that, when ignited, exhibits a first change in burn
rate as a function of ln(p) to a first pressure and a second change
in burn rate as a function of ln(p) at pressures greater than the
first pressure, and wherein the second change in burn rate as a
function of ln(p) is greater than the first change in burn rate as
a function of ln(p).
[0097] In one variation, the method comprises the steps of charging
a material to be fractured with a gas-generating composition and
igniting the gas-generating composition. The method may comprise
the steps of placing a cartridge filled with gas-generating
composition into a hole located in the material to be fractured,
and igniting the gas-generation composition. Any one or more
additional steps may be employed, such as the steps of filling a
cartridge with the gas-generating material, placing end caps on the
cartridge, puncturing a hole into the end cap of the cartridge,
placing an igniter wire into the gas-generation composition via the
hole in the end cap, contacting the igniter wire with an electric
igniter, and igniting the gas-generating composition.
[0098] The amount of gas-generating composition used in the systems
and methods will vary depending on the application, as one skilled
in the art will readily recognize. In one variation, the amount of
gas-generating composition utilized to fracture material is the
amount of gas-generating composition known as the powder factor.
The powder factor is the weight of powder required to break a given
volume of material, a value that is known to be dependant on
factors such as the strength of the material to be fractured and/or
the degree of confinement of the material and/or the amount of
fracturing required in the given application. However, those of
skill in the art will recognize and appreciate that the powder
factor required to fracture material can change from one
application to the next. For instance, a free-standing boulder may
require a powder factor of only about 20 percent of the powder
factor needed for use in fracturing a solid rock face or embedded
material. In one variation, the gas-generating composition powder
factor is about 100 g of gas-generating composition per cubic yard
of material to be fractured. In one variation, the powder factor is
more than about 100 g of gas-generating composition per cubic yard
of material to be fractured. In one variation, the powder factor is
less than about 100 g of gas-generating composition per cubic yard
of material to be fractured.
[0099] A test can be conducted prior to first-time use of the
disclosed systems and compositions to enable the operator to
categorize the type of breakage desired for the particular type of
application. In one application, the material to be fractured is a
free standing boulder and the amount of gas-generating composition
for use in fracturing the material is about 50 or about 60 or about
40 or between about 40-60 or more than 50 or less than 80 grams per
cubic yard. In another application, the material to be fractured is
an imbedded material with at least one free face and the amount of
gas-generating composition for fracturing the material is about 100
or about 80 or about 110 or about 120 or more than about 100 or
more than about 120 or less than about 160 or less than about 125
grams per cubic yard.
EXAMPLE 1
Closed-Bomb Burn Rate Test
[0100] A closed bomb burn rate test was performed on a
gas-generating composition. The burn rate test was conducted by
Safety Management Services, Inc. In the test, a composition
comprising lactose, ferrosilicon and potassium perchlorate was
provided to Safety Management Services, Inc. as sticks of brittle
white powder that fractured easily. For comparison, a commercially
available propellant, Triple Seven pyrotechnic mixture manufactured
by Hodgdon Powder Co., Inc., was also supplied for testing.
[0101] A sample of the tested composition was coated with
Krylon.TM. UV-resistant clear acrylic coating to inhibit the flame
from flashing down the sides of the sample, encouraging a linear
burn. The sample was loaded into a vessel held at an isothermal
temperature, after which the vessel was closed and sealed. Inert
nitrogen gas was used to pressurize the vessel. The sample was
ignited using a hot wire or small torch at one end. Pressure
sensors were used to record the pressure increase per time. Burn
rate was calculated by dividing the sample length by the measured
burn time.
[0102] A test of the composition comprising lactose, ferrosilicon
and potassium perchlorate was performed at 25.degree. C., varying
the pressure from 62 psig to 4,000 psig. Testing was concluded at
4,000 psig since the reaction was proceeding quicker than the
instrumentation and data acquisition system could effectively
measure. A plot of the burn rate data against the natural log of
pressure (ln(p)) for this sample is included as FIG. 4, and a Table
of the burn rate data is shown below as Table 4. TABLE-US-00004
TABLE 4 Burn rate data for composition comprising lactose,
ferrosilicon and potassium perchlorate. Burn Reference Average
Pressure Sample Length Burn Time Rate Pressure (psig) (psig) (in)
(sec) (in/sec) 62 106 0.73 1.392 0.52 250 320 0.81 0.746 1.09 500
651 0.74 0.590 1.25 1,000 1,168 1.32 0.168 7.86 2,000 2,227 0.75
0.047 15.90 4,000 4,123 0.31 0.013 23.41
[0103] A test of the comparison propellant was performed at
25.degree. C., varying the pressure from 250 psig to 7,000 psig.
Testing was concluded at 7,000 psig since the sample showed a
consistent trend in the burn rate. A plot of the burn rate data as
a function of the natural log of pressure (ln(p)) for this sample
is included as FIG. 5 and a Table of the burn rate data is shown
below as Table 5. TABLE-US-00005 TABLE 5 Burn rate data for
comparative composition. Burn Reference Average Pressure Sample
Length Burn Time Rate Pressure (psig) (psig) (in) (sec) (in/sec)
250 342 1.38 1.412 0.98 1000 1150 1.37 0.670 2.05 2500 2677 0.85
0.264 3.22 4000 4225 1.17 0.276 4.24 7000 7309 0.81 0.138 5.86
[0104] All references, publications, patents and patent
applications disclosed herein are hereby orated by reference in
their entirety.
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