US3338165A - Gelled nitromethane explosive containing fluid encapsulations - Google Patents

Gelled nitromethane explosive containing fluid encapsulations Download PDF

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Publication number
US3338165A
US3338165A US571735A US57173566A US3338165A US 3338165 A US3338165 A US 3338165A US 571735 A US571735 A US 571735A US 57173566 A US57173566 A US 57173566A US 3338165 A US3338165 A US 3338165A
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United States
Prior art keywords
nitromethane
explosive
gelled
composition
balloons
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US571735A
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English (en)
Inventor
Minnick Joseph James
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Commercial Solvents Corp
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Commercial Solvents Corp
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Publication date
Application filed by Commercial Solvents Corp filed Critical Commercial Solvents Corp
Priority to US571735A priority Critical patent/US3338165A/en
Priority to IL28378A priority patent/IL28378A/he
Priority to GB34141/67A priority patent/GB1147307A/en
Application granted granted Critical
Publication of US3338165A publication Critical patent/US3338165A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C5/00—Fuses, e.g. fuse cords
    • C06C5/04—Detonating fuses
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
    • C06B23/003—Porous or hollow inert particles
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/36—Compositions containing a nitrated organic compound the compound being a nitroparaffin
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C5/00—Fuses, e.g. fuse cords
    • C06C5/06—Fuse igniting means; Fuse connectors
    • 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
    • Y10S149/118—Gel contains resin

Definitions

  • This invention relates to stable, sensitized explosive compositions comprising nitromethane and as sensitizer, resin balloons.
  • this invention relates to stable, gelled explosive compositions comprising nitromethane and as sensitizer, resin balloons.
  • this invention relates to stable, gelled explosive compositions in the form of the explosive core for detonator cord comprising nitromethane and as sensitizer, a finely divided, air-entrapping material.
  • this invention relates to novel detonating cord having a stable, sensitized explosive core in gelled form comprising nitromethane and a finely divided airentrapping material.
  • Explosive compositions comprising nitromethane and a sensitizer for the nitromethane are well-known and are used in a variety of applications.
  • Sensitized nitromethane explosive compositions are used in either the normally liquid form or in gelled form.
  • Normally liquid nitromethane compositions are readily converted to semi-solid or thickened form typically referred to as gelled form nitromethane by incorporation with a suitable gelling agent for the nitromethane, such as for example nitrocellulose.
  • suitable gelling agent for the nitromethane such as for example nitrocellulose.
  • Other gelling or thickening agents for nitromethane are disclosed in application Ser. No. 446,736, filed Apr. 8, 1965, for L. R. Jones and in US. Patent 2,954,- 350, issued Sept. 27, 1960 to R. F. Purcell.
  • nitromethane Numerous materials are known to sensitize nitromethane, of which the nitromethane soluble amines, in particular lower alkylimine, arylalkyleneamine, monoethanolamine, alkylphosphorousamide, aryldiamine, aminopyridine, N,N'-diethyl-p-phenylenediamine, hydrazine and alkylarylidiamine are generally most effective
  • nitromethane containing explosive compositions sensitized for detonation with conventional blasting caps are desired.
  • Nitromethane explosive compositions sensitized with the aforestated amines are generally unstable and decompose after storage for several days.
  • the instability of the explosive compositions is a particular drawback when the compositions are used in gelled form as the explosive material in the explosive core of d t at cord.
  • Detonator cord typically comprises an explosive core in the form of a solid explosive composition, a sheath, e.g.
  • nitromethane sensitized by the aforestated amines is used in gelled form as the explosive core of detonator cord, pressure from gases formed from the decomposition of the nitromethane often causes ballooning or rupture of the outer covering of the detonator cord.
  • the present invention in a first embodiment resides in the discovery that sensitized nitromethane explosive compositions which are stable against decomposition are obtained by incorporating into the explosive composition a sensitizing amount of resin balloon.
  • the present invention in a second embodiment resides in the discovery that gelled, sensitized nitromethane explosive compositions which are stable against decomposition are obtained by incorporating into the gelled explosive composition a sensitizing amount of resin balloon.
  • the present invention in a third embodiment resides in the discovery that gelled, sensitized nitromethane eX- plosive compositions which are stable against decomposition and suitable as explosive core of detonator cord are obtained by incorporating into the gelled explosive composition a sensitizing amount of a finely divided, air-entrapping material.
  • finely divided, airentrapping materials include bagasse, wood flour, ground balsa, resin balloons and the like. Because of the excellent results obtained therewith resin balloons are preferred.
  • the resin balloons of use in the explosive compositions of the present invention are water insoluble and nitromethane insoluble, thin-walled, hollow, spherical balloons of a polymerized thermosetting resin-selected from the group consisting of urea-formaldehyde and phenolformaldehyde.
  • the resin balloons are of low density and small particle size. Typical resin balloons have a bulk density of less than 0.3 gr./cc. and a diameter of from about 2 to about 360 microns. Resin balloons are more fully described in US. Patent 3,101,288 to Coursen et al. issued Aug. 20, 1963. Such resin balloons are commercially available.
  • the amount of resin balloons required to sensitize mtromethane explosive compositions will vary and will depend chiefly on the use desired for the particular explosive composition. Typically suitable amounts of resin balloons in the explosive compositions of the present invention are in the range of from about 0.1 to about 20% by weight based on the weight of the explosive composition. While amounts greater than 20% by weight of resin balloons may be included in the explosive compositions of the present invention, such amounts are considered excess. For most applications and in particular when the explosive composition is used in gelled form as the eX- plosive core of detonator cord, amounts of resin balloons 1n the range of from about 1.5 to about 10% are preferred.
  • Explosive compositions comprising nitromethane and resin balloons may be prepared in any suitable manner, as for example by mixing the resin balloons with the nitromethane. It is Well understood in the art that high temperatures during mixing should be avoided.
  • Examples of fuels include elemental carbon in various forms, such as carbon black, graphite and the like; aliphatic hydrocarbons such as pentane,-octane, dodecane and .cyclohexane; organic polymers such as liquid and solid polymers of ethylene and propylene; organic ketones such as diethyl ketone, ethyl butyl ketone, cyclohexanone and the like; and alkyl ethers of saturated glycols such as the monomethyl ether of ethylene glycol and the monoethyl ether of ethylene glycol and the like.
  • oxidizers include ammonium nitrate, sodium nitrate, lithium nitrate and the like.
  • additives examples include guanidine nitrate, pentaerythritol tetranitrate, and cyclotrimethylene trinitramine.
  • the explosive compositions of the present invention may be used in either the normally liquid or in gelled form. Normally liquid nitromethane is readily converted to gelled form by incorporation of a suitable thickening or gelling agent into the nitromethane as previously indicated.
  • the explosive compositions of the present invention have a variety of uses well-known to the art. As previously indicated, gelled explosive compositions of the present invention are especially useful as the explosive core of detonator cord. The compositions of the present invention also are particularly useful in oil wells to fracture oil bearing formations.
  • the resin balloons used were prepared from phenol-formaldehyde resins and were commercially sold by the Bakelite Company, a Division of Union Carbide Corporation under the trademark Microballoons.
  • the resin balloons were of small particle size and low bulk density.
  • Microballoons manufactured from ureaformaldehyde resins are also commercially available and if desired can be substituted for Microballoons manufactured from phenol-formaldehyde resins.
  • Example 1 Tests were conducted to show the effectiveness of resin balloons in sensitizing nitromethane explosive compositions.
  • the sensitized explosive compositions used in the tests designated A-G inclusive in the table below were prepared by blending resin balloons into a gelled nitromethane explosive composition prepared by blending 95 parts by weight nitromethane with 5 parts by weight nitrocellulose.
  • the composition used in test H contained no resin balloons and was prepared by blending 95 parts by weight nitromethane with 5 parts by weight nitrocellulose.
  • Example 2 A detonator cord was prepared by loading a piece of polyethylene tubing 14 inches in length and 4; inch in diameter (inside) with a gelled, sensitized nitromethane explosive composition comprising 95 parts by weight nitromethane, 5 parts by weight nitrocellulose and 5 parts Q by weight resin balloons. The cord was detonated with a No. 6 blasting cap. Detonation of the entire cord was obtained. The rate of detonation was in excess of 18,000 feet per second.
  • Example 3 The following is an example of a stable, sensitized nitromethane explosive composition.
  • Example 4 The following is an example of a stable, sensitized nitromethane explosive composition in gelled form.
  • Example 5 The following is an example of a stable, sensitized nitromethane explosive composition in gelled form suitable for use as the explosive core in detonator cord.
  • nitromethane explosive composition in gelled form suitable for use as the explosive core in detonator cord.
  • An explosive composition comprising nitromethane and a sensitizing amount of a water-insoluble and nitromethane-insoluble polymerized thermosetting resin selected from the group consisting of phenol-formaldehyde and urea-formaldehyde resins in the form of thin-walled, hollow, spherical balloons.
  • a gelled explosive composition comprising nitromethane, a gelling agent for the nitromethane and a sensitizing amount of water-insoluble and nitromethaneinsoluble polymerized thermosetting resin selected from the group consisting of phenol-formaldehyde and ureaformaldehyde resins in the form of thin-walled, hollow, spherical balloons.
  • composition of claim 2 wherein the said balloons have a bulk density of less than about 0.3 g. per cc. and a diameter in the range of from about 2 to about 360 microns.
  • composition of claim 2 wherein the amount of said balloons in the said composition is in the range of from about 0.1 to about 20% by weight based on the weight of the composition.
  • composition of claim 2 wherein the said gelling agent is nitrocellulose.
  • composition of claim 2 in the form of an explosive core for detonator cord.
  • composition of claim 6 wherein the amount of said spherical balloons in said composition is in the range of from about 1.5 to about 10% by weight based on the weight of the composition.
  • a detonator cord including an explosive core, a sheath for said core and a cover for said sheath, the composition of said core comprising nitromethane, a gelling agent for said nitromethane and a sensitizing amount of a finely divided, air-entrapping material.
  • the finely divided, air-entrapping material is a water-insoluble and nitromethane-insoluble, polymerized thermosetting resin selected from the group consisting of phenol-formaldehyde and urea-formaldehyde resins in the form of thinwalled, hollow, spherical balloons.
  • the detonator cord of claim 10 wherein the said balloons have a bulk density of less than 0.3 g. per cc. and a diameter in the range of from about 2 to about 360 microns.
  • the detonator cord of claim 10 wherein the amount of said resin balloons in the composition of said core is in the range of from about 0.1 to about 20% by weight based on the weight of the composition.

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  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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US571735A 1966-08-11 1966-08-11 Gelled nitromethane explosive containing fluid encapsulations Expired - Lifetime US3338165A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US571735A US3338165A (en) 1966-08-11 1966-08-11 Gelled nitromethane explosive containing fluid encapsulations
IL28378A IL28378A (he) 1966-08-11 1967-07-23 תערובות מתפוצצות
GB34141/67A GB1147307A (en) 1966-08-11 1967-07-25 Improvements in or relating to explosive compositions

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3409484A (en) * 1967-09-15 1968-11-05 Commercial Solvents Corp Thickened inorganic oxidizer salt slurried explosive containing an alkylamine nitrate and an air-entrapping material
US3409485A (en) * 1967-09-15 1968-11-05 Commercial Solvents Corp Thickened inorganic oxidizer salt slurried explosive containing tris(hydroxymethyl)-nitromethaneand air-entrapping material
US3419444A (en) * 1967-05-03 1968-12-31 Commercial Solvents Corp Thickened aqueous inorganic nitrate salt-nitroparaffin explosive composition sensitized with an air entrapping material
US3447978A (en) * 1967-08-03 1969-06-03 Atlas Chem Ind Ammonium nitrate emulsion blasting agent and method of preparing same
US3457126A (en) * 1967-05-16 1969-07-22 Ici Australia Ltd Aqueous explosive composition containing a porous water insoluble synthetic organic polymeric cellular material
US3475236A (en) * 1968-04-17 1969-10-28 Seispower Corp Non-aqueous cap-sensitive explosive containing gelled nitromethane and inorganic nitrate oxidizer salt
US3546034A (en) * 1968-06-19 1970-12-08 Commercial Solvents Corp Ammonium nitrate-nitromethane type blasting agent containing urea as a crystallization inhibitor
US3619306A (en) * 1967-09-13 1971-11-09 Dynamit Nobel Ag Molded explosive bodies having variable detonation speeds
US3663324A (en) * 1969-10-27 1972-05-16 Talley Frac Corp Liquid explosive containing a nitramine explosive dissolved in a nitroparaffin
US3718512A (en) * 1970-10-08 1973-02-27 Kinetics Int Corp Porous particles containing dispersed organic liquid and gaseous components
US4038112A (en) * 1975-05-12 1977-07-26 Talley-Frac Corporation Well-fracturing explosive composition
FR2518086A1 (fr) * 1981-12-15 1983-06-17 France Etat Materiau pyrotechnique alveolaire agglomere
US4394199A (en) * 1981-09-08 1983-07-19 Agnus Chemical Company Explosive emulsion composition
US5202051A (en) * 1987-04-29 1993-04-13 Shell Oil Company Stabilization of epoxy/nitroparaffin solutions
US20040200372A1 (en) * 2001-04-24 2004-10-14 Gladden Ernest L. Non-electric detonator
US6960267B1 (en) 2003-06-26 2005-11-01 Nixon Iii William P Multi-component liquid explosive composition and method
US20070214990A1 (en) * 2000-05-24 2007-09-20 Barkley Thomas L Detonating cord and methods of making and using the same
WO2014076099A3 (de) * 2012-11-14 2014-07-31 EST Energetics GmbH Sprengkapselempfindliche konfektionierte initiierungsladungen für sprengtechnische anwendungen und deren verwendung
US9175933B2 (en) 2014-02-21 2015-11-03 The United States Of America, As Represented By The Secretary Of The Army Simple low-cost hand-held landmine neutralization device
EP3228972A1 (fr) 2016-04-06 2017-10-11 Nitrates & Innovation Ensemble de deux reservoirs prêts a être assembles par vissage pour former une cartouche d'explosif bi-composant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3035948A (en) * 1959-04-29 1962-05-22 Phillips Petroleum Co Gelled nitroalkane propellants
US3143446A (en) * 1959-11-27 1964-08-04 Gen Electric Propellant charge containing fluid encapsulations
US3204560A (en) * 1961-04-24 1965-09-07 Lockheed Aircraft Corp Solid rocket propellant containing metal encapsulated gas
US3242022A (en) * 1963-09-27 1966-03-22 Dow Chemical Co Gelled nitroalkane compositions for blasting

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3035948A (en) * 1959-04-29 1962-05-22 Phillips Petroleum Co Gelled nitroalkane propellants
US3143446A (en) * 1959-11-27 1964-08-04 Gen Electric Propellant charge containing fluid encapsulations
US3204560A (en) * 1961-04-24 1965-09-07 Lockheed Aircraft Corp Solid rocket propellant containing metal encapsulated gas
US3242022A (en) * 1963-09-27 1966-03-22 Dow Chemical Co Gelled nitroalkane compositions for blasting

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419444A (en) * 1967-05-03 1968-12-31 Commercial Solvents Corp Thickened aqueous inorganic nitrate salt-nitroparaffin explosive composition sensitized with an air entrapping material
US3457126A (en) * 1967-05-16 1969-07-22 Ici Australia Ltd Aqueous explosive composition containing a porous water insoluble synthetic organic polymeric cellular material
US3447978A (en) * 1967-08-03 1969-06-03 Atlas Chem Ind Ammonium nitrate emulsion blasting agent and method of preparing same
US3619306A (en) * 1967-09-13 1971-11-09 Dynamit Nobel Ag Molded explosive bodies having variable detonation speeds
US3409484A (en) * 1967-09-15 1968-11-05 Commercial Solvents Corp Thickened inorganic oxidizer salt slurried explosive containing an alkylamine nitrate and an air-entrapping material
US3409485A (en) * 1967-09-15 1968-11-05 Commercial Solvents Corp Thickened inorganic oxidizer salt slurried explosive containing tris(hydroxymethyl)-nitromethaneand air-entrapping material
US3475236A (en) * 1968-04-17 1969-10-28 Seispower Corp Non-aqueous cap-sensitive explosive containing gelled nitromethane and inorganic nitrate oxidizer salt
US3546034A (en) * 1968-06-19 1970-12-08 Commercial Solvents Corp Ammonium nitrate-nitromethane type blasting agent containing urea as a crystallization inhibitor
US3663324A (en) * 1969-10-27 1972-05-16 Talley Frac Corp Liquid explosive containing a nitramine explosive dissolved in a nitroparaffin
US3718512A (en) * 1970-10-08 1973-02-27 Kinetics Int Corp Porous particles containing dispersed organic liquid and gaseous components
US4038112A (en) * 1975-05-12 1977-07-26 Talley-Frac Corporation Well-fracturing explosive composition
US4394199A (en) * 1981-09-08 1983-07-19 Agnus Chemical Company Explosive emulsion composition
FR2518086A1 (fr) * 1981-12-15 1983-06-17 France Etat Materiau pyrotechnique alveolaire agglomere
US5202051A (en) * 1987-04-29 1993-04-13 Shell Oil Company Stabilization of epoxy/nitroparaffin solutions
US20100037793A1 (en) * 2000-05-24 2010-02-18 Lee Robert A Detonating cord and methods of making and using the same
US20070214990A1 (en) * 2000-05-24 2007-09-20 Barkley Thomas L Detonating cord and methods of making and using the same
US20040200372A1 (en) * 2001-04-24 2004-10-14 Gladden Ernest L. Non-electric detonator
US7188566B2 (en) 2001-04-24 2007-03-13 Dyno Nobel Inc. Non-electric detonator
US6960267B1 (en) 2003-06-26 2005-11-01 Nixon Iii William P Multi-component liquid explosive composition and method
WO2014076099A3 (de) * 2012-11-14 2014-07-31 EST Energetics GmbH Sprengkapselempfindliche konfektionierte initiierungsladungen für sprengtechnische anwendungen und deren verwendung
AU2013346947B2 (en) * 2012-11-14 2017-06-15 EST Energetics GmbH Detonator-sensitive assembled booster charges for use in blasting engineering and the use thereof
US10227266B2 (en) 2012-11-14 2019-03-12 EST Energetics GmbH Detonator-sensitive assembled booster charges for use in blasting engineering and the use thereof
US9175933B2 (en) 2014-02-21 2015-11-03 The United States Of America, As Represented By The Secretary Of The Army Simple low-cost hand-held landmine neutralization device
US9506729B2 (en) 2014-02-21 2016-11-29 The United States Of America, As Represented By The Secretary Of The Army Field mixable two-component liquid explosive
US9797693B1 (en) 2014-02-21 2017-10-24 The United States Of America, As Represented By The Secretary Of The Army Adjustable stand for holding a liquid explosive
EP3228972A1 (fr) 2016-04-06 2017-10-11 Nitrates & Innovation Ensemble de deux reservoirs prêts a être assembles par vissage pour former une cartouche d'explosif bi-composant

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Publication number Publication date
IL28378A (he) 1971-02-25
GB1147307A (en) 1969-04-02

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