US3459608A - Water-containing,nitric ester-free ammonium nitrate explosives - Google Patents

Water-containing,nitric ester-free ammonium nitrate explosives Download PDF

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US3459608A
US3459608A US702505*A US3459608DA US3459608A US 3459608 A US3459608 A US 3459608A US 3459608D A US3459608D A US 3459608DA US 3459608 A US3459608 A US 3459608A
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water
ammonium nitrate
parts
explosive
explosives
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US702505*A
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Erich Ludolphy
Gerhard Martin
Adolf Berthmann
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Dynamit Nobel AG
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Dynamit Nobel AG
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/11—Particle size of a component
    • Y10S149/111—Nitrated organic compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/11—Particle size of a component
    • Y10S149/112—Inorganic nitrogen-oxygen salt

Definitions

  • This invention relates to water-containing, nitric esterfree ammonium nitrate explosives. More particularly, this invention relates to water-containing, nitric ester-free ammonium nitrate explosives of increased sensitivity.
  • alkali metal nitrates e.g. sodium potassium, lithium-nitrate and/or alkaline earth metal nitrates e.g. calcium, strontium, barium-nitrate,
  • the brisant explosives may not be nitric esters because of the easy hydrolyzability of the latter:
  • Aromatic nitro compounds such as, trinitrotoluene, trinitroanisole, trinitrobenzene, trinitrocresol, trinitrophentole, trinitronaphthaline, trinitromethylaniline, picric acid, trinitrorosorcinol, trinitrophloroglucine, hexanitrodiphenyl, hexanitrodiphenylamine, hexanitrodiphenyl oxide, hexanitrodiphenyl sulfide, hexanitrophenylsulfone, hexanitrodiphenylsulfoxide, hexanitroazobenzene and tetranitromethylaniline (tetryl), Nitramines, such as, ethylenedinitramine, hexogen (cyclotrimethylenetrinitramine), octogen and tetranitromethylaniline (tetryl), and the Nitrosamines, such as, cyclotrimethylene'trinitrosamine.
  • tertiary amines are the following: tn'methylamine, triethylamine, triethanolamine, N-nbutyldlethanolamine, N-methyldiethanolamine, di-(2-hydroxypropyl)-ethanolamine, di-(Z-hydroxybutyl)-ethanolamine, triisopropanolamine, N-methylmorpholine, N- methylpyridine, N-methylpiperdine, N-methylpyrroline, N-methylpyrrolidine, N-fi-hydroxyethylmorpholine, and 1,2-dimorpholylethane.
  • the tertiary amines can also be advantageously in the form of their nitrates as a component of the explosives in accordance with the invention.
  • the nitrates of ammonia and of the alkali and alkalineearth metals, the perchlorates of ammonia and of the alkali metals, and the brisant explosives are used in the grain size which is conventionally employed in the formation of this type of explosives by the explosives industry namely in a grain-size smaller than 1 mm. in diameter (18 mesh), preferably 0.5-0.05 mm. (35-300 mesh).
  • guar meal agar-agar
  • water-soluble cellulose ethers e.g. methyl-carboxymethylcellulose (tylose types)
  • water-soluble polymers on the basis of vinyl alcohol, 1,2-vinylenediol, methylolated acrylic amide, and the like.
  • ionogenic and non-ionogenic emulsifiers which are conventionally employed in the explosives industry can be used as emulsifiers in the compositions in accordance with the invention in the percentages as stated above.
  • the water-containing, nitric ester-free ammonium nitrate explosives of. the invention are characterized, as stated previously, by an increased sensitivity.
  • the sensitivity of the slurries as herein taught is so great that they can even be ignited -by a No. 9 copper blasting cap.
  • An additional advantage of the explosive slurries of the invention consists in that they are considerably more fluid with higher power than the corresponding waterammonium-nitrate-TNT types.
  • EXAMPLE 1a.EXPLOSIVE ACCORDING TO THE INVENTION Composition 0.36 part by wt. of a water-soluble cellulose ether commercially obtainable under the name Tylose MH 50,
  • Tonogenic emulsifiers are, e.g., fatty amine salt, fatty acid salt; non-inogenic emulsifiers are, e.g., ethoxylated fatty amines, ethoxylated phenols or naphthols.
  • EXAMPLE 1b (For comparison with la) Composition 0.36 part by wt. of a water-soluble cellulose ether commercially obtainable under the name Tylose MH 50,
  • EXAMPLE 2 Composition 0.39 part by wt. of a water-soluble cellulose ether commercially obtainable under the name Tylose MH 50,
  • a water-containing, nitric ester-free ammonium nitrate explosive of increased sensitivity comprising:
  • An explosive according to claim 1 ' Wherein there is additionally present 0.2-1 wt. percent of at least one member selected from the group consisting of swelling agents and emulsifiers.
  • solid brisant explosive is a member selected from the group consisting of aromatic nitro compounds, nitramines and nitrosamines.
  • tertiary amine is a member selected from the group consisting of: trimethylamine, triethylamine, triethanolamine, N-n-butyldiethanolamine, N-methyldiethanolamine, di-(2- hydroxypropyl) -ethanolamine, di- Z-hydroxybutyl -ethanolamine, triisopropanolamine, N-methylmorpholine, N- methylpyridine, N-methylpiperidine, N-methylpyrroline, N-methylpyrrolidine, N fi hydroxyethylmorpholine and 1,2-dimorpholylethane.
  • said swelling agent is a member selected from the group consisting of guar meal, agar-agar, water-soluble cellulose ethers, water-soluble polymers on the basis of vinyl alcohol, 1,2-vinylene diol and methylolated acrylic amide.
  • a water-containing, nitric ester-free ammonium nitrate explosive of increased sensitivity comprising:
  • a water-containing, nitric ester-free ammonium nitrate explosive of increased sensitivity comprising:
  • ammonium nitrate (grain size under References Cited UNITED STATES PATENTS 3,369,944 2/ 1968 Berthmann et al. 149-47 X BENJAMIN R. PADGETT, Primary Examiner S. J. LECHERT, Assistant Examiner US. Cl. X.R.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

United States Patent Int. Cl. C06b 1/04 US. Cl. 149-56 8 Claims ABSTRACT OF THE DISCLOSURE Water-containing, nitric ester-free ammonium nitrate explosives of increased sensitivity composed of water, ammonium nitrate, a brisant explosive, tertiary amines or nitrates thereof, ammonium and/or alkali metal perchlorates, and a swelling agent and/or emulsifier.
This invention relates to water-containing, nitric esterfree ammonium nitrate explosives. More particularly, this invention relates to water-containing, nitric ester-free ammonium nitrate explosives of increased sensitivity.
Water-containing, nitric ester-free ammonium nitrate explosives prepared on the basis of water, ammonium nitrate and trinitrotoluene are known. Explosives of this type, of a quasi-liquid consistency, are generally known as slurries. The known slurries of this type, however, have the disadvantage of low sensitivity, and can be brought to detonation only by means of relatively large initiating charges.
It is an object of this invention to provide explosives of the aforesaid type which are not associated with the disadvantages as above noted.
It is a further object of this invention to provide water-containing, nitric ester-free ammonium nitrate explosives of increased sensitivity.
These are still further objects will appear from the description of this invention as hereinafter disclosed.
The above objects can be accomplished in accordance with the invention by providing an explosive having the following composition:
-15 wt. percent water,
30-80 wt. percent ammonium nitrate, of which up to 10 wt. percent can be replaced by alkali metal nitrates e.g. sodium potassium, lithium-nitrate and/or alkaline earth metal nitrates e.g. calcium, strontium, barium-nitrate,
2-15 wt. percent of a brisant explosive having a detonation rate greater than 5000 m./sec.,
2-10 wt. percent tertiary amines or nitrates thereof,
5-25 wt. percent perchlorates of ammonium and/ or alkali metals, and
0.2-1 wt. percent of swelling agent and/or emulsifier.
The following are illustrat-ive brisant explosives having a detonation rate greater than 5000 m./sec., which are suitable for use in accordance with the invention. The brisant explosives may not be nitric esters because of the easy hydrolyzability of the latter:
Aromatic nitro compounds, such as, trinitrotoluene, trinitroanisole, trinitrobenzene, trinitrocresol, trinitrophentole, trinitronaphthaline, trinitromethylaniline, picric acid, trinitrorosorcinol, trinitrophloroglucine, hexanitrodiphenyl, hexanitrodiphenylamine, hexanitrodiphenyl oxide, hexanitrodiphenyl sulfide, hexanitrophenylsulfone, hexanitrodiphenylsulfoxide, hexanitroazobenzene and tetranitromethylaniline (tetryl), Nitramines, such as, ethylenedinitramine, hexogen (cyclotrimethylenetrinitramine), octogen and tetranitromethylaniline (tetryl), and the Nitrosamines, such as, cyclotrimethylene'trinitrosamine.
The instances of suitable tertiary amines are the following: tn'methylamine, triethylamine, triethanolamine, N-nbutyldlethanolamine, N-methyldiethanolamine, di-(2-hydroxypropyl)-ethanolamine, di-(Z-hydroxybutyl)-ethanolamine, triisopropanolamine, N-methylmorpholine, N- methylpyridine, N-methylpiperdine, N-methylpyrroline, N-methylpyrrolidine, N-fi-hydroxyethylmorpholine, and 1,2-dimorpholylethane.
The tertiary amines can also be advantageously in the form of their nitrates as a component of the explosives in accordance with the invention.
The nitrates of ammonia and of the alkali and alkalineearth metals, the perchlorates of ammonia and of the alkali metals, and the brisant explosives, are used in the grain size which is conventionally employed in the formation of this type of explosives by the explosives industry namely in a grain-size smaller than 1 mm. in diameter (18 mesh), preferably 0.5-0.05 mm. (35-300 mesh).
The following, for example, are illustrative of the swelling agents which can be used in the manufacture of the explosives of the invention: guar meal, agar-agar, water-soluble cellulose ethers e.g. methyl-carboxymethylcellulose (tylose types), water-soluble polymers on the basis of vinyl alcohol, 1,2-vinylenediol, methylolated acrylic amide, and the like.
The ionogenic and non-ionogenic emulsifiers which are conventionally employed in the explosives industry can be used as emulsifiers in the compositions in accordance with the invention in the percentages as stated above.
The water-containing, nitric ester-free ammonium nitrate explosives of. the invention are characterized, as stated previously, by an increased sensitivity. The sensitivity of the slurries as herein taught is so great that they can even be ignited -by a No. 9 copper blasting cap.
An additional advantage of the explosive slurries of the invention consists in that they are considerably more fluid with higher power than the corresponding waterammonium-nitrate-TNT types.
The following examples are given to illustrate the in vention, it being understood that these examples are not intended to be limitative with respect to the specific details thereof:
EXAMPLE 1a.EXPLOSIVE ACCORDING TO THE INVENTION) Composition 0.36 part by wt. of a water-soluble cellulose ether commercially obtainable under the name Tylose MH 50,
13.29' parts by wt. water,
0.076 part by wt. ethoxylated p-nonylphenol (having an average of 9 ethoxyl radicals),
0.076 partby wt. castor oil,
0.55 part by wt. sodium nitrate (grain size less than 0.2
4.14 parts by Wt. calcium nitrate-4H O,
10.66 parts by wt. trinitrotoluene (grain size less than 1 Tonogenic emulsifiers are, e.g., fatty amine salt, fatty acid salt; non-inogenic emulsifiers are, e.g., ethoxylated fatty amines, ethoxylated phenols or naphthols.
3 47.43 parts by wt. ammonium nitrate (grain size less than 0.2 mm.), 5.07 parts by wt. triisopropanolamine (1:1 molar ratio),
and 18.34 parts by wt. sodium perchlorate (1:1 molar ratio).
Explosive characteristics Oxygen balance of the explosive: -l.4% Consistency of the explosive: liquid Trauzl lead block expansion: 279 ccm.
EXAMPLE 1b.(For comparison with la) Composition 0.36 part by wt. of a water-soluble cellulose ether commercially obtainable under the name Tylose MH 50,
13.29 parts by wt. water,
0.076 part by wt. ethoxylated p-nonylphenol (having an average of 9 ethoxyl radicals),
0.55 part by wt. sodium nitrate (grain size under 0.2
4.14 parts by wt. calcium nitrate-4H O,
10.66 parts by wt. trinitrotoluene (grain size under 0.2
mm.), and
47.43 parts by wt. ammonium nitrate (grain size under Explosive characteristics Consistency of the explosive: liquid Trauzl lead block expansion: 30 ccm.
EXAMPLE 2 Composition 0.39 part by wt. of a water-soluble cellulose ether commercially obtainable under the name Tylose MH 50,
7.82 parts by wt. water,
0.078 part by wt. ethoxylated p-nonylphenol (having an average of 9 ethoxyl radicals),
0.078 part by wt. castor oil,
5.39 parts by wt. triisopropanolamine,
19.50 parts by wt. sodium perchlorate,
0.59 part by wt. sodium nitrate (grain size under 0.2
4.4 parts by wt. calcium nitrate-4H O,
11.34 parts by wt. trinitrotoluene (grain size under 0.2
mm.), and
50.42 parts by wt. ammonium nitrate (grain size under Explosive characteristics Oxygen balance of the explosive: -1.4% Consistency of the explosive: thick liquid Trauzl lead block expansion: 415 ccm.
What is claimed is: 1. A water-containing, nitric ester-free ammonium nitrate explosive of increased sensitivity comprising:
5-15 wt. percent water,
30-80 wt. percent ammonium nitrate,
2-15 wt. percent of a solid organic brisant explosive having a detonation rate in excess of 5000 m./scc.,
2-10 wt. percent of a member selected from the group consisting of tertiary amines and the nitrates thereof, and
5-25 wt. percent of at least one member selected from the group consisting of ammonium and alkali metal perchlorates.
2. An explosive according to claim 1 wherein up to wt. percent of said ammonium nitrate is replaced by at least one member selected from the group consisting of alkali metal and alkaline earth metal nitrates,
3. An explosive according to claim 1 'Wherein there is additionally present 0.2-1 wt. percent of at least one member selected from the group consisting of swelling agents and emulsifiers.
4. An explosive according to claim 1 wherein said solid brisant explosive is a member selected from the group consisting of aromatic nitro compounds, nitramines and nitrosamines.
5. An explosive according to claim 1 wherein said tertiary amine is a member selected from the group consisting of: trimethylamine, triethylamine, triethanolamine, N-n-butyldiethanolamine, N-methyldiethanolamine, di-(2- hydroxypropyl) -ethanolamine, di- Z-hydroxybutyl -ethanolamine, triisopropanolamine, N-methylmorpholine, N- methylpyridine, N-methylpiperidine, N-methylpyrroline, N-methylpyrrolidine, N fi hydroxyethylmorpholine and 1,2-dimorpholylethane.
6. An explosive according to claim 3 wherein said swelling agent is a member selected from the group consisting of guar meal, agar-agar, water-soluble cellulose ethers, water-soluble polymers on the basis of vinyl alcohol, 1,2-vinylene diol and methylolated acrylic amide.
7. A water-containing, nitric ester-free ammonium nitrate explosive of increased sensitivity comprising:
0.36 part by weight of a water-soluble ethoxylated methyl cellulose,
13.29 parts by weight water,
0.076 part by weight ethoxylated p-nonylphenol (having an average of 9 ethoxyl radicals),
0.076 part by weight castor oil,
0.55 part by weight sodium nitrate (grain size less than 4.14 parts by weight calcium nitrate-4H O,
10.66 parts by weight trinitrotoluene (grain size less than 47.43 parts by weight ammonium nitrate (grain size less than 0.2 mm.),
5.07 parts by weight triisopropanolamine (1:1 molar ratio), and
18.34 parts by weight sodium perchlorate (1:1 molar ratio). '8. A water-containing, nitric ester-free ammonium nitrate explosive of increased sensitivity comprising:
0.39 part by weight of a water-soluble ethoxylated methyl cellulose,
7.82 parts by weight water,
0.078 part by weight ethoxylated p-nonylphenol (having an average of 9 ethoxyl radicals),
0.078 part by weight castor oil,
5.39 parts by weight triisopropanolamine,
19.50 parts by weight sodium perchlorate,
0.59 part by weight sodium nitrate (grain size under 0.2
4.4 parts by weight calcium nitrate-4H O,
1 1.34 parts by weight trinitrotoluene (grain size under 0.2 mm.), and
50.42 parts by weight ammonium nitrate (grain size under References Cited UNITED STATES PATENTS 3,369,944 2/ 1968 Berthmann et al. 149-47 X BENJAMIN R. PADGETT, Primary Examiner S. J. LECHERT, Assistant Examiner US. Cl. X.R.
l4946, 47, s5, s7, 60, 61, 62, 67, 69, 70, 76, 77, 78, 80,92, 105, 111, 112
US702505*A 1967-02-01 1968-01-31 Water-containing,nitric ester-free ammonium nitrate explosives Expired - Lifetime US3459608A (en)

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NL (1) NL6801421A (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3765964A (en) * 1972-10-06 1973-10-16 Ici America Inc Water-in-oil emulsion type explosive compositions having strontium-ion detonation catalysts
US3807973A (en) * 1970-12-02 1974-04-30 Mitsubishi Oil Co Gelled hydrocarbon fuels and process of preparing the same
US4426238A (en) 1979-09-14 1984-01-17 Ireco Chemicals Blasting composition containing particulate oxidizer salts
US4528049A (en) * 1984-07-09 1985-07-09 Udy Lex L Seismic explosive composition
US4708753A (en) * 1985-12-06 1987-11-24 The Lubrizol Corporation Water-in-oil emulsions
US4828633A (en) * 1987-12-23 1989-05-09 The Lubrizol Corporation Salt compositions for explosives
US4840687A (en) * 1986-11-14 1989-06-20 The Lubrizol Corporation Explosive compositions
US4844756A (en) * 1985-12-06 1989-07-04 The Lubrizol Corporation Water-in-oil emulsions
US4863534A (en) * 1987-12-23 1989-09-05 The Lubrizol Corporation Explosive compositions using a combination of emulsifying salts
US5047175A (en) * 1987-12-23 1991-09-10 The Lubrizol Corporation Salt composition and explosives using same
US5129972A (en) * 1987-12-23 1992-07-14 The Lubrizol Corporation Emulsifiers and explosive emulsions containing same
US5527491A (en) * 1986-11-14 1996-06-18 The Lubrizol Corporation Emulsifiers and explosive emulsions containing same
US6214140B1 (en) * 1999-09-22 2001-04-10 Universal Tech Corporation Development of new high energy blasting products using demilitarized ammonium picrate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3369944A (en) * 1963-06-12 1968-02-20 Dynamit Nobel Ag Patentabteilu Thickened aqueous detonator composition containing a brisant explosive

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3369944A (en) * 1963-06-12 1968-02-20 Dynamit Nobel Ag Patentabteilu Thickened aqueous detonator composition containing a brisant explosive

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3807973A (en) * 1970-12-02 1974-04-30 Mitsubishi Oil Co Gelled hydrocarbon fuels and process of preparing the same
US3765964A (en) * 1972-10-06 1973-10-16 Ici America Inc Water-in-oil emulsion type explosive compositions having strontium-ion detonation catalysts
US4426238A (en) 1979-09-14 1984-01-17 Ireco Chemicals Blasting composition containing particulate oxidizer salts
US4528049A (en) * 1984-07-09 1985-07-09 Udy Lex L Seismic explosive composition
US4708753A (en) * 1985-12-06 1987-11-24 The Lubrizol Corporation Water-in-oil emulsions
US4844756A (en) * 1985-12-06 1989-07-04 The Lubrizol Corporation Water-in-oil emulsions
US4840687A (en) * 1986-11-14 1989-06-20 The Lubrizol Corporation Explosive compositions
US5527491A (en) * 1986-11-14 1996-06-18 The Lubrizol Corporation Emulsifiers and explosive emulsions containing same
US4828633A (en) * 1987-12-23 1989-05-09 The Lubrizol Corporation Salt compositions for explosives
US4863534A (en) * 1987-12-23 1989-09-05 The Lubrizol Corporation Explosive compositions using a combination of emulsifying salts
US5047175A (en) * 1987-12-23 1991-09-10 The Lubrizol Corporation Salt composition and explosives using same
US5129972A (en) * 1987-12-23 1992-07-14 The Lubrizol Corporation Emulsifiers and explosive emulsions containing same
US6214140B1 (en) * 1999-09-22 2001-04-10 Universal Tech Corporation Development of new high energy blasting products using demilitarized ammonium picrate

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DE1646273A1 (en) 1970-11-26
DE1646273B2 (en) 1974-11-21
DE1646273C3 (en) 1975-07-10
FR1556471A (en) 1969-02-07
NL6801421A (en) 1968-08-02
BE710175A (en) 1968-05-30

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