US3400026A - Thickened aqueous inorganic oxidizer salt explosive composition containing dissolvedproteinaceous material - Google Patents

Thickened aqueous inorganic oxidizer salt explosive composition containing dissolvedproteinaceous material Download PDF

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US3400026A
US3400026A US609329A US60932967A US3400026A US 3400026 A US3400026 A US 3400026A US 609329 A US609329 A US 609329A US 60932967 A US60932967 A US 60932967A US 3400026 A US3400026 A US 3400026A
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composition
explosive
compositions
added
proteinaceous material
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Philip W Fearnow
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to GB2173/68A priority patent/GB1188443A/en
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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

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  • ABSTRACT F THE DISCLOSURE Water-bearing explosive compositions containing inorganic oxidizing salt, fuel, thickener, water and a proteinaceous material which is soluble in the aqueous explosive composition of pH 3 to 10 and, preferably, foamable therein.
  • the aqueous inorganic oxidizing salt can be added to a mixer at a temperature between about l50170 R, fuel, proteinaceous material and thickening agents are added thereto and agitated until mixed.
  • aqueous explosive compositions comprising an aqueous solution of an inorganic oxidizing salt, at least partially dissolved in Water, together with one or more fuels and a gelling agent provided blasting operations with a variety of new explosive compositions having many desirable advantages such as a Wide variety of explosive properties, and better safety characteristics and economy, both in manufacture and use.
  • aqueous explosive compositions free of self-explosives, e.g., TNT and/or metallic fuels, e.g., aluminum have been proposed which olfer added safety features and low cost.
  • aqueous explosive compositions possess certain drawbacks with regard to their physical and explosive properties, particula ly at low temperatures, e.g., 32 to 40 F. (0 to 5 C.). After standing for a period of time, often as short a time as several hours, whether in storage or in open boreholes prior to detonation, water gels tend to separate or settle into layers and/or harden or solidify, instead of remaining soft and pliable.
  • Separation is defined as the tendency of a water-bearing explosive composition to separate or settle into layers, each layer containing different proportions of the various components. Such separation can occur under either hot or nited States Patent D "ice cold temperature conditions and is generally a result of a lack of mutual solubility of the various components.
  • hardening which may occur concommitantly with, or independently of, separation, is defined as the tendency of a water-bearing explosive composition to become stiff and hard and concurrently to exude liquid. Such hardening, which may occur at ambient temperatures but is more pronounced at lower temperatures, is a result of the salting out of crystals from the saturated inorganic oxidizing salt solution.
  • blasting agents which will provide stable, soft aqueous explosive compositions capable of reliable detonations even at low temperatures in small diameter holes, e.g., about 2 to 10 inches and usually diameters of 6 inches or less.
  • the present invention provides an improvement in water-bearing explosive compositions comprising inorganic oxidizing salt, fuel, thickener and water, the improvement comprising using a soluble proteinaceous material, said proteinaceous material being soluble in the aqueous explosive composition of pH 3 to 10.
  • the amount of proteinaceous material i.e., protein or protein derivative, can vary Within a rather wide range but at least about 0.01 percent by weight proteinaceous material is used. Although larger amounts can be used, no beneficial effect results when quantities greater than about 10 percent by weight proteinaceous material are incorporated in the explosive composition. and generally, less than about 3 percent by weight protein is sutficient.
  • the resulting waterbearing explosive compositions are rendered soft and pliable and consistently sensitive to detonation at low tem peratures due primarily to the presence of the proteinaceous material. Furthermore, these water-bearing explosive compositions retain their valuable properties at low temperatures even when used in boreholes having very small diameters, e. g., 2 inches due to the presence of proteinaceous material.
  • the improvement of the present invention is further characterized in that the use of a soluble proteinaceous material that is also foamable in aqueous explosive compositions can result in the incorporation of small gas bubbles in the gel structure when the mixture is sufiiciently agitated thus providing further sensitivity to the explosive composition.
  • a proteinaceous material is herein defined as any protein or protein derivative, such as those obtained by hydrolysis, amidation, acylation or other chemical reaction applied to a protein.
  • soluble is meant at least about by weight of the porteinaceous material added to the aqueous explosive composition having a pH of 3 to 10 dissolves therein, the balance of the proteinaceous material being either Water-soluble or Waterdispersible.
  • foamable is meant the protein or protein derivative in the explosive composition is capable of at least minimum observable foaming, i.e., increases the volume of the explosive composition at least about 5 percent when agitated by mechanical means in any conventional type of mixer.
  • a hot aqueous inorganic oxidizing salt neutral liquor e.g., a solution such as that obtained from the manufacture of ammonium nitrate prior to graining or prilling
  • the fuel and other additives such as thickening agent and crosslinking agent are generally added to the hot liquor at about 150170 F. with mixing and the resulting solution cooled.
  • the use of proteinaceous material does not alter the process procedures; any of the mixing procedures and order of mixings normally employed in explosive gel formulation can be used in the present invention.
  • the soluble proteinaceous material can be added to the mixture at any step in the process, preferably prior to or at the same time as the thickener is added.
  • the addition of the proteinaceous material is preferably accompanied by mixing, and an additional mixing time of about 0.5 to 5 minutes may be required depending on the type and operating speed of the mixer employed as well as the amount of material to be mixed and the foamability of the particular proteinaceous material.
  • an additional mixing time of about 0.5 to 5 minutes may be required depending on the type and operating speed of the mixer employed as well as the amount of material to be mixed and the foamability of the particular proteinaceous material.
  • an additional mixing time of about 0.5 to 5 minutes may be required depending on the type and operating speed of the mixer employed as well as the amount of material to be mixed and the foamability of the particular proteinaceous material.
  • an additional mixing time of about 0.5 to 5 minutes may be required depending on the type and operating speed of the mixer employed as well as the amount of material to be mixed and the foamability of the particular proteinaceous material.
  • the hot inorganic oxidizing salt liquor e.g., ammonium nitrate liquor
  • the water-bearing explosive compositions of the present invention comprise an inorganic oxidizing salt, fuel, thickener and a proteinaceous material that is soluble in the aqueous explosive composition of pH 3 to 10.
  • the inorganic oxidizing salt can be any of the soluble salts conventionally used in aqueous explosive compositions including alkali metal, alkaline earth metal and ammonium nitrates, chromates, dichromates, chlorates, perchlorates as well as mixtures of two or more such salts.
  • these salts are ammonium nitrate, ammonium perchlorate, ammonium chromate, ammonium dichromate, ammonium chlorate, sodium nitrate, sodium perchlorate, potassium nitrate, potassium perchlorate, potassium dichromate, magnesium nitrate, magnesium perchlorate, and calcium nitrate.
  • the inorganic oxidizing salt component contains at least 45% of at least one salt which is highly soluble in Water at room temperature, that is, at least as soluble as ammonium nitrate, and preferably, the aqueous phase in the composition contains a substantial portion of oxidizing salt, for example, 30 to 70% by weight thereof.
  • oxidizing salt for example, 30 to 70% by weight thereof.
  • compositions employing substantial amounts of undissolved oxidizing salts e.g., 20 to 70% ammonium nitrate prills, are also within the scope of the present invention.
  • Sodium nitrate is a preferred auxiliary salt; in a preferred embodiment of the invention the explosive composition contains about 20 to 70% ammonium nitrate and about 5'to sodium nitrate by weight based on the total weight of the composition.
  • the fuels employed in the compositions of this invention can be, for example, self-explosive fuels, non-explosive fuels and metallic fuels, as well as mixtures of the aforementioned types of fuels.
  • the fuel or fuels used in the compositions of this invention can be varied widely provided that in the composition in which any particular fuel is used, the fuel is stable, i.e., chemically inert with the system employed, during storage and preparation prior to detonation.
  • Self-explosive fuel refers to a substance which by itself is generally recognized in the art as an explosive.
  • self-explosive fuels include certain organic nitrates, nitrocompounds, and nitramines such as TNT, pentaerythritol tetranitrate (PETN), tetranitro N methylaniline (tetryl), cyclotrimethylene trinitrarnine (RDX), cyclotetramethylenetetramine (HMX), nitrostarch, explosive-grade nitrocellulose, smokeless powder, and mixtures of such explosives, e.g., pentolite (PETN/TNT), cyclotol (RDX/ TNT), and tetryltol (tetryl/TNT).
  • PTN pentaerythritol tetranitrate
  • tetryl tetranitro N methylaniline
  • RDX cyclotrimethylene trinitrarnine
  • HMX cyclotetramethylenetetramine
  • nitrostarch explosive-grade nitrocellulose,
  • the self-explosive fuel can be, for example, in any of the conventional flaked, pelleted, grained, crystalline or other particulate forms.
  • a self-explosive fuel up to and preferably about 10 to 40% by weight, based on the weight of the composition is used.
  • Non-explosive fuels include, for example, certain nitro aromatic hydrocarbons which provide sensitizing action when combined with the oxidizing salt, e.g., ammonium nitrate.
  • oxidizing salt e.g., ammonium nitrate.
  • fuels include the monoand di nitrobenzenes and the monoand di nitrotoluenes.
  • Such fuels may replace a part or all of the highexplosive fuel employed in the compositions of this invention.
  • some water-bearing explosive compositions contain no high explosive fuel and are prepared by dispersing a liquid nitro aromatic hydrocarbon in the gelled composition with a dispersing agent, as described in copending application Ser. No. 609,330, filed Jan. 16, 1967 the teachings of which are incorporated herein by reference.
  • nonexplosive fuels examples include sulfurous fuels including sulfur itself, siliceous fuels and carbonaceous fuels.
  • preferred carbonaceous fuels are finely divided coal and other forms of finely divided carbon, solid carbonaceous vegetable products such as starch, wood and paper pulps, sugar, ivory nut meal and bagasse; solid and liquid organic hydrocarbons such as powdered paraffin Waxes and fuel oils, including nitrogen-containing liquid organic hydrocarbons such as urea, formamide and other amides; fatty oils; vegetable oils; and mixtures of two or more of the foregoing carbonaceous nonexplosive fuels.
  • up to about 25%, and preferably from 2 to 20% by weight of such carbonaceous fuels are used.
  • Up to about 10% of sulfurous fuels and up to about 5% of siliceous fuels are generally used.
  • the metallic fuels which can be present include, for example, light elements such as aluminum, magnesium, zinc, boron and silicon both singly and in combination and heavier metallic compounds and alloys including ferrophosphorus and ferr-osilicon as well as mixtures of two or more of these metals or alloys.
  • a preformed coating e.g., of fatty acid and high viscosity oil as described in copending application Ser. No. 441,319, filed Mar. 19, 1965, now Patent No. 3,297,502, can be provided on particles of any of these types of metallic fuels.
  • Such a coating has been found to be of particular benefit for use with light elements and alloys thereof with minor amounts of each other and, for example, iron, manganese, silicon, copper, zinc, or chromium whose composition and purity vary considerably from lot to lot,
  • the amount of metallic fuel used varies with particular fuel employed and can constitute up to 50% by weight of the total composition.
  • the metallic fuel is aluminum, usually about from 1 to 25% by Weight is used, whereas with heavier metallic fuels, such as ferrosilicon or ferrophosphorus, usually about from to 30% by weight is used.
  • the average particle size can vary, for example, from -325 mesh to H- mesh, but preferably is on the order of -100 to --18 mesh.
  • the total amount of fuel usually about 5 to 50% by weight, i.e., the weight of the metallic, nonexplosive, and/or self-explosive fuel, alone or in combination, is usually adjusted so that the total composition has an oxygen balance of to l-10%, and excepting for those compositions containing the aforementioned heavier metallic fuels such as ferrophosphorus and ferrosilicon, preferably the oxygen balance is between -10 to 0%.
  • compositions of this invention generally containing 5 to 30% water, and preferably about 10 to 20%, are thickened by any of the thickeners conventionally used in water-bearing explosive compositions.
  • Thickened as used herein refers to compositions in which the viscosity of the aqueous phase has been materially increased, e.g., to 20,000 c.p.s. or more, as well as gelled products including those gels which are crosslinked.
  • the composition can vary in consistency from pourable, pumpable semifiuid solutions, slurries and dispersions to moldable, tough plastic masses.
  • Such thickeners are used in amounts ranging from about 0.2 to 5%.
  • thickeners include tree exudates such as gum arabic, ghatti, karaya and tragacanth; seaweed colloids such as agar-agar, Irish moss, carrageenin and the alginates; seed extracts such as locust bean, locust kernel, guar and quince seed gums; starches and modified starches such as dextrins, hydroxyethyl starch and British gums; water-dispersible derivatives of cellulose such as methylcellulose, sodium carboxymethylcellulose and sodium sulfoethylcellulose; gelatin; casein, polyvinyl alcohol; polyacrylamides; high molecular weight polyethylene oxides; exocellular heteropoly saccharides made by fermenting starch-derived sugars, silica gels as well as mixtures of two or more of the above thickening agents.
  • galactomannans such as guar and locust bean gum, and particularly guar gum, are preferred.
  • the galactomannan can be a self-complexing guar gum, e.g., EX-FC-SO and EX-FC- DP supplied by Stein-Hall Co. or a noncomplexing guar gum such as Stein-Halls Jaguar 100 in which no crosslinking agent is incorporated.
  • a noncomplexing guar gum small amounts, i.e., about 0.001 to 1% by weight of the total composition, of crosslinking agents, e.g., borax, sodium or potassium dichromate, for the gelling agent can be employed.
  • crosslinking agents are soluble antimony and bismuth compounds at a pH of 6 to 13 as described in USP 3,202,556 and transition metal compounds as in S.N. 343,140, filed Feb. 6, 1964, now Patent No. 3,301,723, the teachings of which are incorporated herein by reference.
  • thickening agents or gelling systems are those described in copending US. application Ser. No 579,852, filed Sept. 16, 1966, which are formed by polymerizing in situ a monoethylenically unsaturated monomer, e.g., acrylamide, with polyethylenically unsaturated monomer, e.g., methylenebisacrylamide.
  • a monoethylenically unsaturated monomer e.g., acrylamide
  • polyethylenically unsaturated monomer e.g., methylenebisacrylamide.
  • the proteinaceous material which includes both protein and protetin derivatives, used in the present invention must be soluble in the aqueous explosive composition having a pH of from 3 to 10.
  • Soluble proteinaceous ma terial means at least about 10% by weight of the amount of said proteinaceous material added to the aqueous explosive composition dissolves therein and the remainder of the proteinaceous material is either water-soluble or waterdispersible.
  • at least 0.01 percent proteinaceous material is incorporated into the waterbearing explosive composition in order to realize beneficial results.
  • proteinaceous material that are used in the invention include: simple proteins, that is proteins that yield, on complete hydrolysis, chiefiy alpha amino acids; conjugated proteins, that is, compounds of a protein with some other molecule or molecules referred to as a prosthetic group; and protein derivatives, i.e., derived proteins, namely, products formed by the action of heat or other physical forces, or by hydrolytic agents, such as denatured proteins or peptides.
  • the molecular weight of the proteinaceous material is generally within the range of from about 5000 to 200,000 and, most preferably, not over 100,000.
  • proteinaceous material is not critical. Whether the protein is naturally occurring or a derivative is immaterial, provided it is soluble in the explosive composition.
  • Representative simple proteins that are used in the invention are albumins such as ovalbumin and lactalbumin, occurring respectively, in egg white and milk; globulins such as ovoglobulin and lactoglobulin, conjugated proteins such as the glycoprotein mucin.
  • Representative protein derivatives that are incorporated into the explosive composition are partially bydrolyzed milk protein and extracted collagen derivatives.
  • Other suitable naturally occurring animal and vegetable proteins that can be used in the explosive compositions are, for example, cottonseed protein, fishmeal protein, soybean and nonfat milk solids.
  • Fluid Colloids 2225 and 2226 and Colloid 5V (dry) manufactured by Swift & Co. which are extracted and refined proteins of a collagen source, having a molecular weight of at least 20,000 and a pH of about 6 as well as the N-Z amines, pancreatic digests of casein, manufactured by Shefiield Chemical.
  • a large number of protein derivatives are commercially available andwith consideration of solubility and preferably at least a minimum degree of observable foamability as mentioned above, such proteins and derivatives thereof are applicable for use in the described aqueous explosive compositions.
  • egg albumin is especially preferred due to its wide range of solubility and its exceptional ability both in producing and maintaining a foamed structure.
  • dry powdered egg whites manufactured by Henningson & Co. are particularly suitable for incorporation in the explosive compositions of the present invention.
  • the proteinaceous material is foamable, i.e., the volume of the explosive composition is increased at least 5%, and generally not more than about 50%, when agitated with said material.
  • foaming of the protein is not absolutely necessary.
  • the proteinaceous materials of this invention are still found to improve the properties of aqueous blasting agents so that they are soft and pliable and capable of detonation at low temperatures, yet, the foaming action produced by the combination of the proteinaceous material and mixing as described herein, or by any of the conventional agitation methods used in the manufacture of water-bearing explosive compositions, serves to introduce and entrain small bubbles of a gas, commonly air, in the gel structure, thus making the explosive composition especially sensitive to detonation. Quite surprisingly then, the proteinaceous material can also function as an effective foaming agent for the water-bearing explosive composition.
  • the dimensions of the gas bubbles are small, e.g., they have a diameter not larger than about 3.5 mm. and are substantially uniformly distributed throughout the composition so as to preclude any discontinuities which might result in failures in detonation.
  • any of these supplementary methods for introducing air or other gas into the compositions, as well as the use of low-density fuels as described herein, which serve to lower the product density to a desired level, can be employed in formulating the explosive compositions of this invention,
  • About to 50%, and preferably about to 40%, by volume, of the composition will comprise gas, e.g., air, entrained in small cavities or bubbles with the density of the explosive composition being about 1.0 to 2.0 g./cc. and preferably about 1.1 to 1.7 g./cc
  • soluble proteinaceous materials While the use of soluble proteinaceous materials is beneficial to all types of aqueous blasting agents, the foaming ability of the proteinaceous materials is particularly beneficial in formulating water-bearing explosive compositions containing nonexplosive fuels, i.e., free of self-explosives and/or metallic fuels.
  • These explosive compositions known as Nitro-Carbo-Nitrates, or NCIN' gels tend to become insensitive to detonation at high density, usually densities above about l.41.5, depending on the particular composition of the NCN gel.
  • the use of high cost ingredients such as TNT or aluminum, can be avoided and the sensitivity to detonation maintained if the density of the NCN gel can be lowered to about 1.1 to 1.4 g./cc.
  • composition ingredients without sacrificing the composition ingredients.
  • proteinaceous materials e.g., egg albumin
  • NCN gels having densities of about 1.1 to 1.4 g./cc. are prepared which are sensitive to detonation, even at low temperatures, e.g., of the order of to F.
  • a soluble, foamable pr'oteinaceous material particularly egg albumin
  • the addition of a soluble, foamable pr'oteinaceous material, particularly egg albumin, to the explosive compositions of the present invention is found to provide an additional advantage in formulating those compositions which contain a finely divided form of a metallic fuel, e.g., fine flake aluminum.
  • a metallic fuel e.g., fine flake aluminum.
  • the use of small quantities of proteinaceous material is found to minimize the dusting problem which arises when incorporating a fine aluminum powder into a slurry-type explosive composition. It is believed that on foaming a composition by mixing in the proteinaceous material the fine metal particles are entrapped in the gas bubbles being formed thus eliminating metal dust and providing better dispersion of the metal throughout the gel composition.
  • the soluble proteinaceous materials described herein act to improve the properties of all types of water-bearing explosive compositions by reason of their ability to act as crystal habit modifiers for the predominant explosive ingredient, namely, the inorganic oxidizing salt, e.g., ammonium nitrate.
  • the inorganic oxidizing salt e.g., ammonium nitrate.
  • the particle size of crystallized oxidizing salt is altered and the resultant particle sensitivity enhanced.
  • the inorganic oxidizing salts predominantly ammonium nitrate
  • the crystallize-d salt on recrystallizing from aqueous solutions forms long, large, acicular crystals having a hard and brittle texture.
  • the crystals formed in the presence of the habit modifier are found to be in a more sensitive habit and are small, fine particles similar in appearance to the hedgehog dendritic habit described by Buckley, Crystal Growth, John Wiley & Sons, New York, p. 487. It is believed, therefore that the incorporation of a soluble proteinaceous material, in altering crystal size, shape and texture results in the salt being in a more sensitive habit and by eliminating the conventional long, brittle crystals it allows the gelled structure to remain soft and pliable. In addition to the habit modifying properties, it is believed that the proteinaceous materials may also act as so-called crystal lubricants.
  • the proteinaceous materials described in this invention are generally complex, high molecular weight, e.g., in the range of 5,000 to 200,000, organic materials, many of which are oilyviscous-, or slippery-type fluids themselves or in solution. Even when used in relatively small quantities, the proteins may act as lubricants, perhaps reducing friction between crystal faces, thus enabling individual crystals to slide easily over one another and allowing the encompassing gel structure to remain soft, even at'low temperatures where a considerable proportion of the inorganic salt may be out of solution.
  • PAT refers to potassium antimony tartrate
  • Ammonium nitrate liquor (7880% concentration, pH adjusted to 4.5-5.0 by addition of nitric acid) at ISO-170 F. is placed in the mixer and potassium antimony tartrate crosslinking agent added while agitation is begun.
  • a premixed composition of sodium nitrate and guar gum is added and mixed for about 4 to 5 minutes, or until thickening is observed.
  • Ammonium nitrate prills and/or solid carbonaceous fuels are added and mixed in.
  • Crosslinking agent sodium dichromate
  • compositions of Examples 2 and 3 are loaded into 6 inch diameter, 32 feet deep boreholes filled with 10 to 18 feet of water. Stemming consists of about 20 feet of sand.
  • the composition of Example 2 remains loaded for a period of 5 days before shooting; the composition of Example 3 for 4 days prior to shooting.
  • the composition of Example 4 is loaded into a 9 inch diameter, 50 feet deep borehole filled with 27 feet of water.
  • the compositions of Examples 1, 4, 5 and 6 are packaged in 6- inch, 40-lb. polyethylene bags. One bag of each composition is shot unconfined in air and the others placed in hot (ca. F.) and cold (20 F.) storage.
  • Example 1 without the addition of a soluble, foamable proteinaceous material is prepared and packaged as previously described and placed in hot and cold storage. No separation or hardening is observed, in the compositions of Examples 1, 5 and 6 containing the proteinaceous material even after 6 weeks storage, the maximum period of observation. The composition without the proteinaceous material gave evidence of hardening after 3 days storage and failed to detonate when shot unconfined in 6 inch diameter at 40 F.
  • compositions are initiated at the temperatures designated in Table 1 by conventional primers, e.g., 2 lb. (908 g.) of cast TNT.
  • primers e.g., 2 lb. (908 g.) of cast TNT.
  • the detonation velocity measurements are given in meters/second, D indicates the composition propagates a detonation.
  • Ammonium nitrate (AN) prills 19. 8 19. 8 18. 6 18. 6 18.6 Sodium nitrate 13. 9 13.9 18.1 14. 14.0 14.0 DNT (26) 7.9 3 10.9 11.0 11.0 11.0 Formamide 4. 9 1.9 1. 8 2. 0 2.0 2.0 Sugar (granulated) 4. 9 4. 9 5. 0 5. 0 5.0 5. 0 I g nith 0. 8 0. 8 0. 8 Egg albumin 0.2 0.2 0.2 0. 2 Extracted mllamm 0. 2 Hydrolyzed milk pro 0.2 The compositions also contain per hundred weight: Guar gum, lbs 1.0 1.0 1.0 1.0 1.0 PZ0xgazCr2O1, cc. 300 300 400 300 300 300 300 300 300 Density, g./cc.
  • compositions of the preceding examples are foamed by agitation of the proteinaceous material.
  • the composition of Example 2 is also loaded in dry boreholes and after 4 days standing, is detonated at a velocity of 4920 m./sec.
  • the composition of Example 2 is packed in polyethylene bags as described for 'the compositions of Examples 1, 4 and 5 and is detonated in air unconfined in 6" diameter at 76 F. at a velocity of 4500 m./sec. and at 40 F. at a velocity of 4000 m./ sec.
  • Example 1 The composition of Example 1 with 0.8 part bagasse pith added was also evaluated as a seismic blasting agent by packaging in 4 /2 -inch-diameter, 20 lb. metal cans and shooting underwater at a depth of 6 feet and a temperature of about 70 F. Five different shots recorded velocities of 4000-4400 m./sec. when primed with an 18.5 g. charge of RDX.
  • Example 2 when formulated at a density of 1.41 g./cc. detonated in air unconfined in 6- inch-diameter at 76 F. at a velocity of 3400 m./ sec. and at 40 F. at 3915 m./sec.
  • Ammonium nitrate liquor (about ammonium nitrate) at ISO-170 F. is placed in the mixer and agitation is begun.
  • a soluble, foamable proteinaceous material is added and mixed for about 1-5 minutes.
  • a premixed composition of sodium nitrate and guar gum is added and mixed for about 4-5 minutes, or until thickening is observed.
  • Crosslinking agents sodium dichromate and potassium antimony tartrate
  • Crosslinking agents sodium dichromate and potassium antimony tartrate
  • the compositions are mixed for several minutes and discharged into 6-inchdiameter, 50 lb. polyethylene bags, except the composition of Example 10 which is packaged in S-inch-diameter, 50 lb. bags.
  • the compositions After being subjected to both hot and cold storage for 6 weeks, the compositions are examined and found to be soft and pliable and completely homogeneous.
  • the compositions are detonated in air, unconfined in 2 1 l b. cast TNT primers. Detonation velocity measuremodified soy protein or about 0.3 of an enzymatic 55 ments are given in meters/ second.
  • the eolrlrilzpositions also contain per hundred weig Guar gum, lbs 1. 0 1. 0 l. 0 1. 5% NazCr201, cc 400 400 400 400 5% PAT, cc 200 200 200 300 Velocity, n1./sec.:
  • compositions After 5 days recycling in hot and cold storage, the compositions, still soft and pliable, are detonated in air, unconfined with g. of pressed Pentolite 50 PETN/ TNT). Velocity measurements could not be recorded; in
  • Water-bearing explosive composition of the formulation shown below is prepared in a rotary mixer by adding to the mixer parts ammonium nitrate prills, 8.8 parts sodium nitrate, 7 parts sugar, 4 parts fine coal, 1 part guar gum, and 0.05 part powdered egg albumin. After mixing for about 30 seconds, 9.15 parts water is added and the mixture agitated for 4-5 minutes. Sodium dichromate is added and mixed in for about 15 seconds, followed by the the table, D indicates the composition propagates a 10 addition of potassium antimony tartrate and an additional detonation at the specified temperatures.
  • Coal coarse Coal (fin Egg albumi The composition also co weight:
  • EXAMPLES 15-19 Water-bearing explosive compositions are prepared in a rotary mixer from the materials shown in Table 4 by the general procedures described in the preceeding examples. Aluminum is added after the addition of the premixed sodium nitrate and guar gum, at the same time as other optional solid, insoluble fuels and mixed into the composition. After addition of the specified crosslinking agents and additional mixing as heretofore described, the products of Table 4 are discharged into 2, 2 /2, 3 and 4 inch diameter polyethylene bags. The compositions are detonated in air, unconfined with g. of pressed pentolite.
  • AN prills 15. 8 Sodium nitrate. 15.8 11.9 15.9 15.8 DNT (2 11.0 8.0 10.9 10. 9 Fine flake aluminum. 2. 0 2.0 2. 0 2. 0 Sugar (granulated)- 5.0 5.0 3.0 2.0 Formamide 2. 0 5. 0 2. 0 2. 0 Coal (fine) 2 0 3.0 Bagasse pith. 1.0 Egg albumin 0.2 0.2 0 2 0 2 The compositions also contain per hundred weight;
  • Guar gum lbs 1.0 1. 0 1. 0 1. 0 5% N azCrzO 7, cc. 100 100 100 100 5% PAT, cc 200 200 200 250 Velocity, m.lsec.;
  • compositions of the preceding examples are foamed
  • the composition detonates at a velocity of 3350 m./sec.
  • a soluble, foamable protein and a premixed composition of sodium nitrate and guar gum are added and mixed for about 3 /2 minutes.
  • compositions also contain per hundrcd weight:
  • a water-bearing explosive composition comprising inorganic oxidizing salt, fuel, thickener and Water, the improvement which comprises said explosive composition containing at least about 0.01 percent proteinaceous material selected from the group consisting of albumin, extracted collagen and soybean protein at least percent of which is dissolved in the aqueous explosive composition having a pH of 3 to 10.
  • composition of claim 1 wherein the proteinaceous material is an albumin.
  • composition of claim 1 wherein the proteinaceous material is egg albumin.
  • composition of claim 3 wherein the fuel is a nonexplosive.
  • composition of claim 1 wherein the proteinaceous material is extracted collagen.
  • composition of claim 1 wherein the protein is lactalbumin.
  • composition of claim 1 wherein the molecular Weight of the protein is within the range of from about 5000 to 200,000.
  • a composition of claim 1 comprising, by weight, based on the total composition from about 20 to 70 percent ammonium nitrate, from about 5 to 25 percent sodium nitrate, from about 5 to fuel, from about 5 to 30 percent water, from about 0.2 to 5 percent thickener, and 'from about 0.01 to 10 percent egg albumin.
  • a composition of claim 12 having 0.1 to 3 percent egg albumin.
  • a composition of claim 13 containing a nonexplosive fuel 14.
  • a composition of claim 13 containing a metallic fuel 15.
  • a composition of claim 13 containing an explosive fuel 16.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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US609329A 1967-01-16 1967-01-16 Thickened aqueous inorganic oxidizer salt explosive composition containing dissolvedproteinaceous material Expired - Lifetime US3400026A (en)

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US609329A US3400026A (en) 1967-01-16 1967-01-16 Thickened aqueous inorganic oxidizer salt explosive composition containing dissolvedproteinaceous material
FR1550925D FR1550925A (enrdf_load_stackoverflow) 1967-01-16 1968-01-15
GB2173/68A GB1188443A (en) 1967-01-16 1968-01-15 Water-Bearing Explosive Compositions
BE725218D BE725218A (enrdf_load_stackoverflow) 1967-01-16 1968-12-10

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US (1) US3400026A (enrdf_load_stackoverflow)
BE (1) BE725218A (enrdf_load_stackoverflow)
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GB (1) GB1188443A (enrdf_load_stackoverflow)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3431154A (en) * 1968-07-31 1969-03-04 Canadian Ind Aqueous slurry explosive composition containing a chlorinated organic compound as sensitizer
US3462324A (en) * 1968-04-24 1969-08-19 Dow Chemical Co Explosive composition comprising a salt component contiguous to an over-fueled salt component
US3507718A (en) * 1969-03-26 1970-04-21 Intermountain Res & Eng Explosive slurry containing pulpy fibrous matter,finely divided carbonaceous material and powerful inorganic oxidizer salt
US3511726A (en) * 1968-04-09 1970-05-12 Sanyo Pulp Kk Slurried ammonium nitrate explosive composition containing a chrome-lignin
US3522117A (en) * 1968-08-07 1970-07-28 Du Pont Aerated water-bearing inorganic oxidizer salt blasting agent containing dissolved and undissolved carbonaceous fuel
US3617407A (en) * 1968-10-07 1971-11-02 Canadian Ind Aqueous slurry explosive containing a thickener of cross-linked galactomannan with psyllium flour
US3678140A (en) * 1969-12-03 1972-07-18 Du Pont Process for foaming aqueous protein-containing blasting agents
US3714306A (en) * 1968-09-25 1973-01-30 Olin Mathieson Method of treating spherical powder grains
DE4140619A1 (de) * 1990-12-10 1992-06-11 Dantex Explosives Sprengstoffzusammensetzung
WO1994000406A1 (en) * 1992-06-29 1994-01-06 United Technologies Corporation Beneficial use of energy-containing wastes
US6537399B2 (en) 1997-06-26 2003-03-25 Union Espanola De Explosivos, S.A. Process and mechanism for in situ sensitization of aqueous explosives
US6610158B2 (en) 1999-07-09 2003-08-26 Union Espanola De Explosivos, S.A. Procedure and installation for on-site manufacturing of explosives made from a water based oxidizing product
US20040016481A1 (en) * 2002-06-26 2004-01-29 Union Espanola De Explosivos, A Spanish Corporation Process for the "in situ" manufacturing of explosive mixtures
EP3556741A1 (en) 2018-04-16 2019-10-23 Maxamcorp Holding, S.L. Procedure and installation for loading boreholes with bulk water-based suspension or watergel type explosives
RU2715869C2 (ru) * 2015-02-10 2020-03-03 Максамкорп Холдинг, С.Л. Несенсибилизированная матричная суспензия для получения взрывчатого вещества на водной основе, взрывчатая суспензия на водной основе и способ ее получения (варианты)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1317328A (en) * 1970-11-30 1973-05-16 Ici Ltd Slurry explosives
GB1596889A (en) * 1977-06-24 1981-09-03 Ici Australia Ltd Slurry blasting explosive compositions

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US3153606A (en) * 1962-11-13 1964-10-20 Du Pont Aqueous explosive composition containing flake aluminum and ammonium nitrate
US3198677A (en) * 1962-07-27 1965-08-03 Atlantic Res Corp Foamed polyurethane gas-generating compositions containing inorganic oxidizer
US3235423A (en) * 1964-03-24 1966-02-15 Hercules Powder Co Ltd Stabilized aqueous slurry blasting agent and process

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US3198677A (en) * 1962-07-27 1965-08-03 Atlantic Res Corp Foamed polyurethane gas-generating compositions containing inorganic oxidizer
US3153606A (en) * 1962-11-13 1964-10-20 Du Pont Aqueous explosive composition containing flake aluminum and ammonium nitrate
US3235423A (en) * 1964-03-24 1966-02-15 Hercules Powder Co Ltd Stabilized aqueous slurry blasting agent and process

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3511726A (en) * 1968-04-09 1970-05-12 Sanyo Pulp Kk Slurried ammonium nitrate explosive composition containing a chrome-lignin
US3462324A (en) * 1968-04-24 1969-08-19 Dow Chemical Co Explosive composition comprising a salt component contiguous to an over-fueled salt component
US3431154A (en) * 1968-07-31 1969-03-04 Canadian Ind Aqueous slurry explosive composition containing a chlorinated organic compound as sensitizer
US3522117A (en) * 1968-08-07 1970-07-28 Du Pont Aerated water-bearing inorganic oxidizer salt blasting agent containing dissolved and undissolved carbonaceous fuel
US3714306A (en) * 1968-09-25 1973-01-30 Olin Mathieson Method of treating spherical powder grains
US3617407A (en) * 1968-10-07 1971-11-02 Canadian Ind Aqueous slurry explosive containing a thickener of cross-linked galactomannan with psyllium flour
US3507718A (en) * 1969-03-26 1970-04-21 Intermountain Res & Eng Explosive slurry containing pulpy fibrous matter,finely divided carbonaceous material and powerful inorganic oxidizer salt
US3678140A (en) * 1969-12-03 1972-07-18 Du Pont Process for foaming aqueous protein-containing blasting agents
DE4140619A1 (de) * 1990-12-10 1992-06-11 Dantex Explosives Sprengstoffzusammensetzung
AU644497B2 (en) * 1990-12-10 1993-12-09 Dantex Explosives (Proprietary) Limited Explosive composition
WO1994000406A1 (en) * 1992-06-29 1994-01-06 United Technologies Corporation Beneficial use of energy-containing wastes
US5612507A (en) * 1992-06-29 1997-03-18 United Technologies Corporation Beneficial use of energy-containing wastes
US6537399B2 (en) 1997-06-26 2003-03-25 Union Espanola De Explosivos, S.A. Process and mechanism for in situ sensitization of aqueous explosives
US6610158B2 (en) 1999-07-09 2003-08-26 Union Espanola De Explosivos, S.A. Procedure and installation for on-site manufacturing of explosives made from a water based oxidizing product
US20040016481A1 (en) * 2002-06-26 2004-01-29 Union Espanola De Explosivos, A Spanish Corporation Process for the "in situ" manufacturing of explosive mixtures
US6949153B2 (en) 2002-06-26 2005-09-27 Union Espanola De Explosivos S.A. Process for the “in situ” manufacturing of explosive mixtures
RU2715869C2 (ru) * 2015-02-10 2020-03-03 Максамкорп Холдинг, С.Л. Несенсибилизированная матричная суспензия для получения взрывчатого вещества на водной основе, взрывчатая суспензия на водной основе и способ ее получения (варианты)
US10793485B2 (en) 2015-02-10 2020-10-06 Maxamcorp Holding, S.L. Water-based explosive suspension
EP3556741A1 (en) 2018-04-16 2019-10-23 Maxamcorp Holding, S.L. Procedure and installation for loading boreholes with bulk water-based suspension or watergel type explosives
WO2019201851A1 (en) 2018-04-16 2019-10-24 Maxamcorp Holding, S.L. Procedure and installation for loading boreholes with bulk water-based suspension or watergel type explosives

Also Published As

Publication number Publication date
GB1188443A (en) 1970-04-15
FR1550925A (enrdf_load_stackoverflow) 1968-12-20
BE725218A (enrdf_load_stackoverflow) 1969-05-16

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