US3926698A - Explosive compositions containing metallic fuel particles and method of preparation thereof - Google Patents

Explosive compositions containing metallic fuel particles and method of preparation thereof Download PDF

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Publication number
US3926698A
US3926698A US444691A US44469174A US3926698A US 3926698 A US3926698 A US 3926698A US 444691 A US444691 A US 444691A US 44469174 A US44469174 A US 44469174A US 3926698 A US3926698 A US 3926698A
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composition
collector
solution phase
metallic particles
sensitivity
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US444691A
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Melvin A Cook
Mark J Hagmann
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Ireco Inc
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Ireco Chemicals
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Priority to US444691A priority Critical patent/US3926698A/en
Priority to CA220,469A priority patent/CA1054799A/en
Priority to JP50021393A priority patent/JPS5811400B2/ja
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Assigned to IRECO INCORPORATED reassignment IRECO INCORPORATED ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: IRECO CHEMICALS
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Classifications

    • 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
    • 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
    • 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
    • C06B23/006—Stabilisers (e.g. thermal stabilisers)

Definitions

  • An explosive blasting composition of the gel or slurry type which retains its sensitivity to detonation after being agitated or worked and method of making such composition are provided wherein a small amount of collector is added to the composition comprised of a stable dispersion of a metallic sensitizer and/or fuel particle throughout a thickened solution or fluid phase containing at least one inorganic oxidizer salt. The collector remains in solution throughout the fluid phase of the composition.
  • the present invention relates to method of obtaining explosive blasting compositions of the gel or slurry type which retain their sensitivity to detonation after being agitated or worked, and to the resulting explosive compositions.
  • it concerns the addition of a small amount of a collector to an explosive blasting composition comprised of a stable dispersion of metallic sensitizer and/or fuel particles throughout a thickened solution or fluid phase containing at least one inorganic oxidizer salt.
  • the collector which is in solution throughout the fluid phase, prevents wetting of the surface of the metallic particles by the solution. Prevention of wetting allows explosive compositions to retain their sensitivity with working as will be more fully explained below.
  • 3,249,474 discloses a method of regulating density and sensitivity of aqueous explosive blasting compositions whereby such coated fuel is used with an aqueous solution containing at least one dissolved inorganic oxidizer salt.
  • a coated lyophobic metallic fuel in this manner, coupled with mechanical or chemical aeration or gassing, results in the inclusion of air or gas bubbles which adhere to the surface of the metal particles thereby forming an interface between the metal surface and the aqueous solvent. This adherence of included gas bubbles lowers the bulk density of the composition and provides for significantly enhanced sensitivity in comparison to similar compositions not containing lyophobic, coated, metallic fuel.
  • Such hot spots can be sufficient in number and are high enough in temperature, owing to essentially adiabatic compression, to initiate rapid combustion or chemical reaction of the adjacent reactive material, i.e., oxidizer salt in solution and aluminum particles.
  • oxidizer salt in solution and aluminum particles.
  • This loosely termed hot spot theory is an explanation of the significant sensitizing effect that a small amount of very fine, coated lyophobic aluminum particles having a relatively high surface area (for increased entrapment of gas bubbles in addition to kindling effect) have been found to have in a fluid-phase-based explosive blasting composition.
  • Empirical data coupled with direct density measurements and visual observation substantiate that lyophobic, coated metallic fuel particles vastly increase slurry or viscous liquid explosive composition sensitivity due to the incorporation of small gas or air bubbles into the composition which adhere to the surfaces of the particles.
  • Gas bubbles are therefore preferably dispersed throughout an aqueous or fluid solution phase of a slurry explosive composition and can be formed either by chemical gassing or mechanical entrainment as is well known in the art.
  • metallic fuel particles are admixed into a liquid oxidizer salt solution exposed to air or gas, particularly one which has been prethickened by thickeners such as galactomannan gums, starches, etc.
  • thickeners such as galactomannan gums, starches, etc.
  • small gas or air bubbles are entrained or incorporated into the solution phase. Further, such bubbles will be stably held in place in a viscous, prethickened solution.
  • Chemical gassing agents such as decomposing hydrogen peroxide and alkali salts or nitrous acid, which agents can be present in the solution, comprise an in situ gassing means for explosive compositions.
  • the present invention relates to explosive compositions which contain a fine dispersion of air or gas bubbles.
  • composition sensitivity is greatly dependent upon adequate dispersion of the coated metallic particles containing attached gas bubbles throughout the aqueous or fluid phase, it is also greatly dependent upon the maintenance of these gas bubbles in this desired arrangement. It has been found that prolonged storage of explosive compositions containing finely dispersed gas bubbles, initially adhering to the surfaces of a coated metallic particle when first formed, has in some instances resulted in a loss of composition sensitivity and in many instances without a noticeable change in bulk density. Presumably, this phenomenon is a result of bubble separation from the metallic surface and possible subsequent migration and coalescence into larger, less sensitizing bubbles. Thus while 3 gas is still contained in the composition, the gas bubbles are no longer uniformly small and widely dispersed or in adherence to the metallic surfaces. Proper thickening and cross-linking of the fluid phase can, in most instances, prevent migration, coalescence and bubble separation to a significant degree.
  • a onceformed composition of the coated, metallic fuel and/or sensitizer type is subsequently subjected to some type of agitation.
  • packaged slurry or aqueous explosive composition is oftentimes compactly loaded into boreholes by tamping which results in a working or agitation of the composition.
  • a once-formed composition may be subjected to repumping, or in other words, pumping after initial formation.
  • a composition may be formulated and loaded into a container and then subsequently pumped or repumped from the container into a borehole or other receptacle. This repumping constitutes another example of working.
  • this wetting phenomenon is that working results in a loss of the lyophobic coating (e.g. stearic acid, fatty acids, etc.) perhaps due to friction and consequential rubbing off" of the coating. Without this coating, the metallic surface is no longer lyophobic and becomes wetted by the liquid solution which displaces the adhering gas bubbles.
  • the lyophobic coating e.g. stearic acid, fatty acids, etc.
  • the collector used in the present invention may be similar to the coatings heretofore described in the above referenced patents.
  • the collector can be any substance which will cause the flotation of a metallic, preferably aluminum, particle in the liquid menstrum of the explosive composition,
  • the only essential requirement of the collector is that it remain in solution, i.e., be a miscible liquid in the explosive composition solution at temperatures of working of the explosive. Liquidity and miscibility are necessary in order that the collector can actively seek out metallic surfaces as they become exposed and thereby continually prevent their wetting as working continues.
  • collectors of the present invention which have been found to be effective in various degrees in preventing loss of sensitivity are as follows: oleic, caprylic, linoleic and other fatty acids; red, tall and cod liver oils; green soap (vegetable oil-potassium hydroxide soap); Fels-naptha', xanthogen ester; sodium sulfated fatty amide derivatives; anionic sulphonates; and sodium lauryl sulfates,
  • compositions of the present invention also contain, in solution and in addition, a collector which acts as an in situ, continuous coater or wetting inhibitor of the metal particles.
  • the present invention has solved a problem which has been prevalent with the use of slurry or viscous liquid explosive compositions containing metallic fuel and/or sensitizer; that problem being loss of explosive sensitivity due to working. It has been discovered that the use of a collector in the liquid menstruum enables such compositions to retain their sensitivity upon working.
  • frothers found effective for their conjunctive use with collector(s) are polypropylene glycol methyl ethers such as Dowfroth 250 and lOl2 which are represented by the following formula:
  • a procedure for determining the relative effectiveness of a collector in preventing wetting of metallic particles was devised wherein two solutions, one containing water and the other containing dissolved ammonium nitrate (AN) were admixed with atomized aluminum particles and a collector and the degree of subsequent flotation of the particles in the solutions was observed.
  • the atomized aluminum tested did not contain a preformed coating. ln this simplified test 200 ml of solution was placed in a 300 ml flask and 5 gms of atomized aluminum were added. Thereafter, each collector was added in an experimentally optimum amount which was about one-hundredth of the mass of the particles (0.05 gm) for the collectors tested (although each collector differed slightly).
  • Flotation results are shown in Table I.
  • green soap was found to be the best collector in AN containing solutions.
  • Fels-Naptha was equivalent to green soap, but, when tested, it was not compatible with solutions containing calcium nitrate (CN).
  • the fatty acids tested and reported in Table l were liquid at room temperatures (oleic, caprylic and linoleic).
  • Other fatty acids with greater chain length such as capric, lauric, myristic, palmitic and stearic were found to work equally well at temperatures above their solidification temperatures even through they are solids at room temperature. The degree of flotation was substantially lessened when these longer-chained fatty acids were used in solutions having temperatures below their solidification temperatures.
  • the optimum quantity of oleic acid is about one-hundredth the mass of the atomized aluminum for maximum flotation and is further roughly proportional to the surface area of the aluminum particles used.
  • the fraction of flotation obtained as well as its stability was found to increase with increasing fineness of the atomized aluminum.
  • the finest atomized aluminum tested had a particle size distribution such that 62% was 325 Tyler mesh. [t is possible that too fine of particles would not have sufficient surface for bubble contact; however, such an effect was not observed down to the particle size range tested.
  • Hydrophilic colloid thickeners such as galactomannan gums, flours, starches, xanthomonas gums produced from the bacteria Xanthomonas campesrris, etc., are commonly used in aqueous slurry explosive compositions. Such thickeners render the aqueous solution viscous thereby preventing segregation of dispersed solid ingredients such as metallic fuels and/or sensitizers, undissolved oxidiizer salts. carbonaceous fuels, etc., as well as preventing migration and coalescence of finely dispersed gas bubbles. Such thickeners also provide water resistance to the compositions to prevent breakdown of the compositions and leaching of oxidizer salts in the presence of water.
  • thickeners are almost essential for stability, homogeneity and water resistance of aqueous gel or slurry type explosive blasting compositions.
  • thickeners can be cross-linked by cross-linkers such as metallic ions.
  • Slurry explosive cross-linkers and thickeners are widely used and common in the art.
  • Thickeners are essential to compositions of the present invention particularly for preventing metallic particle segregation and gas bubble migration.
  • atomized aluminum was found to have good flotation characteristics in water thickened with small quantities (concentrations were just below the values at which the viscosity of the solution would significantly interfere with particulate mobility and thus degree of flotation) of Brazilian tapioca flour, guar gum derivative of low molecular weight (Stein-Hall L808) and xanthomonas gum (General Mills XB23) and containing oleic acid as a collector.
  • Other collectors were found to be similarly compatible with hydrophilic colloid thickeners.
  • Table ll summarizes test results obtained for slurry or gel type explosive blasting compositions using various collector/frother combinations. All percentages refer to weight percent based on the total composition.
  • the CN refers to Norsk Hyro calcium nitrate which is a commercial grade CN consisting of about 80% CN, about 15% water (as water of crystallization) and about AN.
  • the thickener was General Mills XB-23, a biopolymer gum produced from the bacteria Xanthonomonas campestris.
  • compositions of Table II were prepared by first dissolving the oxidizer salt(s) in an aqueous solution containing water, liquid fuels (if any), thiourea as a nitrate gassing agent accelerator (if used), the thickening agent, a collector or combination of collectors, and frother (if used). Such dissolution was accomplished at a temperature preferably of about at least C higher than the fudge point or crystallization temperature of the solution. Thereafter, the remaining solid ingredients were added to the thickened solution (i.e., aluminum, gilsonite, ground AN) along with the nitrate gassing agent. The composition was subsequently mixed to provide a uniform, homogeneous dispersion of solid ingredients throughout an aqueous fluid phase.
  • the detonation results of Table II indicate the minimum booster required to detonate a 2-inch diameter explosive charge at 5C.
  • the symbol F stands for failure of the charge to detonate and Det" stands for effective charge detonation.
  • the No.” 5, 6, etc. stands for the size of a standard commercial blasting cap used as the booster with the larger the number corresponding to the greater the cap boostering power.
  • a number such as 5" followed by a g" represents that the charge would not detonate with a regular cap and thus stands for the amount of grams of a pentolite booster required for detonation.
  • Minimum booster required for detonation is a direct measure of an explosive compositions relative sensitivity. The smaller the booster. the more sensitive the composition.
  • compositions were tested for relative sensitivity both before and after working.
  • Working was accomplished by repumping an explosive composition through a Model H724 Viking pump at a rate of 80 pounds per minute. A 40-pound sample of slurry was used and thus was cycled through the pump two times per minute.
  • a comparison of the detonation results of mixes A. B and C shows that oleic acid as a collector has little effect on sensitivity of a composition which has not been worked or repumped, but greatly enhances the sensitivity of a composition which has been worked relative to a composition not containing the collector.
  • a comparison of the results of mixes E and F shows that when a frother is used with an oleic acid collector, the sensitivity of the composition after repumping or working is greater than if the frother is not used.
  • a comparison of the results of mixes G and H shows that when fuel oil is used with oleic acid the sensitivity of the composition after working is greater than if the fuel oil is not, used.
  • the results for mixes H and l surprisingly show that sensitivity is even increased upon working. Fiyrthermore, it is also greatly significant, as evident from the results of mixes H and I, that aqueous explosive composition sensitivity may be obtained at higher than nonnal slurry densities due to the control of bubble size and location by the use of frothers and collectors.
  • a soap was used as a collector which increased the compositions sensitivity upon working. Such result is significant since soaps have been generally regarded as desensitizing agents for slurries sensitized by paint grade aluminum.
  • the explosive compositions of the present invention are designed to retain their sensitivity after being subjected to working. They are also capable of stability over prolonged storage due in some respect to the ability of a collector to maintain adherence of fine gas bubbles to the surfaces of metallic fuels and/or sensitizers.
  • the explosive compositions of the invention may, if desired, be used, i.e., detonated, immediately after being placed into a borehole, they also remain stable and this may be detonated even after encountering water in the borehole and/or being allowed to re main in the borehole for many days.
  • compositions may also be packaged in any suitable container, for example, plastic bags or cardboard tubes, and thereafter detonated in either vertical or horizontal boreholes or any other desired location.
  • frother is selected from the group which consists of polypropylene glycol methyl ether and silicone resin.
  • an explosive composition comprising a thickened solution phase of at least one oxidizing salt and coated (stearic acid) atomized aluminum and a rating of 5 indicates no flotation.
  • mfitanic part cles as fue an sensitizer dispersed throughout the solution phase the improvement com- Table ll AN 27.
  • a method for preventing the loss of sensitivity of a gas-containing blasting composition upon being worked which composition comprises a continuous thickened solution phase having dissolved therein at least one inorganic oxidizer salt and metallic particles as fuel and/or sensitizer dispersed throughout the solution phase which method includes incorporating into the solution phase a small amount of a miscible, liquid collector, which is capable of causing floatation of the metallic particles in the solution phase when such phase is not thickened and which retains its liquidity and miscibility at intended temperatures of working.
  • a method according to claim 1 which includes the additional step of adding a frother to the fluid phase to stabilize and control bubble size.
  • a miscible, liquid collector which is capable of causing flotation of the metallic particles in the solution phase when such solution phase is not thickened and which retains its liquidity and miscibility at intended temperatures of working, to prevent the metallic particles from becoming wetted upon working thereby causing the composition to lose its sensitivity.
  • composition according to claim 8 wherein the collector is a fatty acid.
  • composition according to claim 9 wherein the fatty acid is oleic acid.
  • a composition according to claim 8 containing, in addition. a small amount of a frother to stabilize and control bubble size.
  • a composition according to claim 11 wherein the frother is selected from the group which consists of polypropylene glycol methyl ether and silicone resin.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Lubricants (AREA)
  • Liquid Carbonaceous Fuels (AREA)
US444691A 1974-02-21 1974-02-21 Explosive compositions containing metallic fuel particles and method of preparation thereof Expired - Lifetime US3926698A (en)

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Application Number Priority Date Filing Date Title
US444691A US3926698A (en) 1974-02-21 1974-02-21 Explosive compositions containing metallic fuel particles and method of preparation thereof
CA220,469A CA1054799A (en) 1974-02-21 1975-02-20 Explosive compositions containing metallic fuel particles and method of preparation thereof
JP50021393A JPS5811400B2 (ja) 1974-02-21 1975-02-20 バクハツソセイブツト ソノセイホウ

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2463110A1 (fr) * 1979-08-06 1981-02-20 Du Pont Composition explosive du type en emulsion et procede pour sa preparation
FR2490213A1 (fr) * 1980-09-12 1982-03-19 Ireco Chemicals Composition explosive antigrisouteuse contenant du nitrate de calcium
US5007973A (en) * 1989-10-12 1991-04-16 Atlas Powder Company Multicomponent explosives
USRE33788E (en) * 1977-09-19 1992-01-07 Hanex Products, Inc. Water-in-oil blasting composition
US5226986A (en) * 1991-11-12 1993-07-13 Hansen Gary L Formulation of multi-component explosives
US6361629B2 (en) * 1998-11-12 2002-03-26 The United States Of America As Represented By The Secretary Of The Air Force Flowable solid propellant
US20030084753A1 (en) * 2001-11-05 2003-05-08 Kim Chang Sun Rapidly expanding metallic mixture treated to prevent oxidation thereof at room temperature
US8585812B2 (en) * 2011-05-26 2013-11-19 Jackson State University Oxygen displacement technology (ODT) to remove rust from iron and iron-based tools and structures
US9573857B2 (en) 2012-03-12 2017-02-21 University Of Central Florida Research Foundation, Inc. Compositions having aluminum particles dispersed in a continuous phase

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711345A (en) * 1970-08-18 1973-01-16 Du Pont Chemical foaming of water-bearing explosives
US3713919A (en) * 1970-08-17 1973-01-30 Du Pont Chemical foaming of water-bearing explosives with n,n'-dimitrosopentamethylene-tetramine
US3770522A (en) * 1970-08-18 1973-11-06 Du Pont Emulsion type explosive composition containing ammonium stearate or alkali metal stearate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3713919A (en) * 1970-08-17 1973-01-30 Du Pont Chemical foaming of water-bearing explosives with n,n'-dimitrosopentamethylene-tetramine
US3711345A (en) * 1970-08-18 1973-01-16 Du Pont Chemical foaming of water-bearing explosives
US3770522A (en) * 1970-08-18 1973-11-06 Du Pont Emulsion type explosive composition containing ammonium stearate or alkali metal stearate

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE33788E (en) * 1977-09-19 1992-01-07 Hanex Products, Inc. Water-in-oil blasting composition
FR2463110A1 (fr) * 1979-08-06 1981-02-20 Du Pont Composition explosive du type en emulsion et procede pour sa preparation
FR2490213A1 (fr) * 1980-09-12 1982-03-19 Ireco Chemicals Composition explosive antigrisouteuse contenant du nitrate de calcium
US4364782A (en) * 1980-09-12 1982-12-21 Ireco Chemicals Permissible slurry explosive
US5007973A (en) * 1989-10-12 1991-04-16 Atlas Powder Company Multicomponent explosives
US5226986A (en) * 1991-11-12 1993-07-13 Hansen Gary L Formulation of multi-component explosives
US6361629B2 (en) * 1998-11-12 2002-03-26 The United States Of America As Represented By The Secretary Of The Air Force Flowable solid propellant
US20030084753A1 (en) * 2001-11-05 2003-05-08 Kim Chang Sun Rapidly expanding metallic mixture treated to prevent oxidation thereof at room temperature
US6849103B2 (en) * 2001-11-05 2005-02-01 Chang Sun Kim Rapidly expanding metallic mixture treated to prevent oxidation thereof at room temperature
US8585812B2 (en) * 2011-05-26 2013-11-19 Jackson State University Oxygen displacement technology (ODT) to remove rust from iron and iron-based tools and structures
US9573857B2 (en) 2012-03-12 2017-02-21 University Of Central Florida Research Foundation, Inc. Compositions having aluminum particles dispersed in a continuous phase

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Publication number Publication date
JPS5811400B2 (ja) 1983-03-02
CA1054799A (en) 1979-05-22
JPS50117906A (enrdf_load_stackoverflow) 1975-09-16

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