US2674526A - Gelatin dynamite composition containing sulfur - Google Patents
Gelatin dynamite composition containing sulfur Download PDFInfo
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- US2674526A US2674526A US174579A US17457950A US2674526A US 2674526 A US2674526 A US 2674526A US 174579 A US174579 A US 174579A US 17457950 A US17457950 A US 17457950A US 2674526 A US2674526 A US 2674526A
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- United States
- Prior art keywords
- sulphur
- pellets
- screen
- amount
- explosive
- Prior art date
- 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.)
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 49
- 239000000203 mixture Substances 0.000 title claims description 40
- 229920000159 gelatin Polymers 0.000 title claims description 25
- 235000019322 gelatine Nutrition 0.000 title claims description 25
- 108010010803 Gelatin Proteins 0.000 title description 23
- 239000008273 gelatin Substances 0.000 title description 23
- 235000011852 gelatine desserts Nutrition 0.000 title description 23
- 229910052717 sulfur Inorganic materials 0.000 title description 2
- 239000011593 sulfur Substances 0.000 title description 2
- 239000005864 Sulphur Substances 0.000 claims description 47
- 239000008188 pellet Substances 0.000 claims description 38
- 239000002360 explosive Substances 0.000 claims description 32
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 claims description 18
- 229960003711 glyceryl trinitrate Drugs 0.000 claims description 18
- 239000001828 Gelatine Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 229910001868 water Inorganic materials 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 229920001220 nitrocellulos Polymers 0.000 description 15
- 230000000717 retained effect Effects 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- 239000004202 carbamide Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 8
- 239000004927 clay Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004317 sodium nitrate Substances 0.000 description 6
- 235000010344 sodium nitrate Nutrition 0.000 description 6
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 244000018633 Prunus armeniaca Species 0.000 description 2
- 235000009827 Prunus armeniaca Nutrition 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000005474 detonation Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012260 resinous material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 241001579016 Nanoa Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- NINIDFKCEFEMDL-RNFDNDRNSA-N Sulfur-36 Chemical compound [36S] NINIDFKCEFEMDL-RNFDNDRNSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 ammonium chloride Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- 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
- C06B25/28—Compositions containing a nitrated organic compound the compound being nitrocellulose present as less than 10% by weight of the total composition
- C06B25/30—Compositions containing a nitrated organic compound the compound being nitrocellulose present as less than 10% by weight of the total composition with nitroglycerine
-
- 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
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
- C06B31/04—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with carbon or sulfur
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/32—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound
- C06B31/56—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound the compound being nitrocellulose present as less than 10% by weight of the total composition
Definitions
- the present invention relates to an improvement in gelatin dynamite compositions, and, in particular, to a gelatin dynamite explosive composition especially advantageous for use in 011- Well blasting and prospecting, which explosive will not be rendered insensitive by prolongedexposure to pressure and water. It has long been known that gelatin dynamite explosives, upon the application of continued pressure, become passified or insensitive and cannot be detonated in the intended manner by commercial detonators. Such passification' is a serious detriment to the use of gelatin dynamite explosives in certain important applications, for instance in seismic prospecting.
- Seismic prospecting In seismic prospecting, explosive charges are detonated at the bottoms of bore holes and from the rate and direction of propagation of the resulting shock waves, the geological structure of the given area can be constructed. Seismic prospecting is an important geological tool,- particularly in the discovery'of petroleum.
- an object of the present invention to provide an explosive composition having improved resistance to pressure and water.
- a further object is the formulation of a gelatin dynamite which will retain, after long storage, its ability to detonate when subjected to high water pressures.
- a further object of the invention is to provide agelatin dynamite explosive having improved utility for seismic prospecting.
- a gelatin dynamite explosive composition having improved resistance to high water pressures and increased stability in storage is provided by including in the gelatin dynamite composition comprising the usual ingredients thereof, a substantial portion of pelleted interio'rly ca'vitated elemental sul-.
- Gelatin dynamite accord- .500 ft. 2l5 p. s.i 9 days. Detonation in all ing to invention. cases.
- nitrocotton usually from about 0.4% to about the amount of nitrocotton being sufficient to provide a viscous liquid or a gel of the desired consistency with the nitroglycerine as is standard practice.
- the particular proportions of nitroglycerine to nitrocotton selected will depend, as is well known; upon the amount of solid ingredients included in the 'explosive. When substantial amounts of solid ingredients are present the proportion of nitrocotton to nitroglycerine may be such as to provide a more or less viscous liquid, the adsorption and absorption of the solid ingredients being relied upon to render the mixture plastic.
- nitrocotton to nitroglycerine As the proportion of nitrocotton to nitroglycerine is increased the mixture becomes more viscous until a gel isobtained, and this gel may be relied upon to render the composition plastic. At any rate the amounts and proportions of nitroglycerine and of nitrocotton, as well as any solid ingredients, will be selected in accordance with common practice to provide a plastic, solid mass.
- sodium nitrate is employed, it will generally be present in an amount from about 3% to about 65%, While fuels will usually be between about 3% and about 25%. In accordance with conventional practice the proportions of fuel and of sodium nitrate, when used, may be varied to provide a desirable oxygen. balance in the explosive. If ammonium nitrate is used, it may be present in an amount from about 2.0% to about 50%, depending upon the particular grade of ammonia gelatin dynamite desired.
- the nitroglycerine used in the present compositions may be relatively pure nitroglycerine or it may be a nitrated mixture of glycerine, ethylene glycol and corn or sugar or other nitratable substances, as is usually employed in the :art.
- the aforesaid nitrated mixture, as well as relatively pure nitroglycerine, is designated in the trade as nitroglycerine and that term is used herein to include both materials.
- pelleted sulphur small interiorly cavitated (hollow) pellets or beads of elemental sulphur the interiors of which are air-filled. Such pellets can be obtained by spraying molten sulphur into air in fine droplets with subsequent solidification or freezing of the droplets in flight. While the size of the sulphur pellets employed in the composition of the invention may vary over a wide range, the pellets are usually smaller than a U. S. S. No. 6 screen aperture and larger than a U. S. S. No. 80 screen apering the hollow sulphur pellets.
- this is accomplished by providing the sulphur pellets in the composition with an exterior coating of a water-resistant film-forming substance, for ex ample, a coating of wax or of a resinous material of the type hereinafter described.
- a coating appears to seal off the pores of the sulphur and increase the resistance of the resulting composition to water pressure.
- a microcrystalline hydrocarbon Wax or a convertible urea reaction product for example, a convertible urea-formaldehyde reaction product ineluding dimethylolurea, a convertible urea-melture.
- they are smaller than a U. S. S. H
- the quantity of pelleted sulphur present in the novel composition may vary widely depending upon the particular conditions of use to which the explosive is intended but generally the pelleted sulphur will be present in an amount from about 5% to about 50% by weight, preferably from about 10% to about 45% by weight.
- the composition contains a material which serves to prevent water from enter- It has been found that v amine reaction product or a convertible ureamelamine-formaldehyde reaction product is employed, to provide the water resistant coating although other film-forming materials may be used if desired.
- a convertible material conventional curing catalysts, for example, an ammonium salt, such as ammonium chloride, may be employed to facilitate the conversion of the reaction product into the insoluble state, but even in the absence of a catalyst, the convertible urea reaction product will be converted as cured with the passage of time.
- the amount of coating material added may vary, but generally from about 0.5% to about 5.0% will be used, and the preferable range is from about 1.0% to about 3.0% by weight of the sulphur.
- a coating of clay may be applied following the treatment with the wax. If used, the amount of clay will depend on the amount of wax used and may comprise from about 1% to 3% by weight of the sulphur. In place of coating the sulphur pellets, prevention of water-penetration into the sulphur pellets may be accomplished by adding a convertible reaction product of the stated type to the dry dope used in preparing the composition, as hereinafter described.
- a stabilizer is preferably added.
- organic amines are preferred, in particular urea, carbazole and diphenylamine. While the amount of stabilizer added to the composition will vary with the particular composition and the length of time and conditions of storage (especially temperature), in general from about 0.5% to about 5.0% may be employed.
- the pelleted sulphur used in the present invention may, as stated above, be prepared by blowing molten sulphur upwardly through a nozzle into the atmosphere. For best results, it is desirable that the temperature of the sulphur as it leaves the nozzle be as near to the crystallizing temperature as possible. After the pellets have formed, they are gathered and classifled according to size.
- pelleted sulphur of the desired size may then be provided with the water-resistant coating, for example, the wax or wax and clay, or the resin. This may be accomplished, for example, by adding the molten wax to a quantity of pellets in a heated paddle type mixer and mixing until a uniform coating is obtained. If a clay coat is also desired, the clay may then be added and mixing continued until the clay coat is evenly distributed.
- the water-resistant coating for example, the wax or wax and clay, or the resin.
- the material providing the resin in finely divided form in suspension or slightly moistened or rendered slightly sticky by heating or in solution, may be mixed with the pelleted sulphur in a suitable mixing device.
- a particularly advantageous way of applying a resin coating to the sulphur pellets is as a suspension or partial solution in water.
- the pellets thus treated can be dried to provide the water resistant coating.
- the pellets may be heated to convert the resin coating to the insoluble state.
- a convenient method of applying a coating on the pellets is to suspend or partially dissolve the convertible reaction product in cool water containing a conversion catalyst such as about of ammonium chloride based on the dry weight of the reaction product, and to apply the resulting liquid to the pellets which have been heated to an elevated temperature, for'example to about 150 F.
- the heat contained in the pellets is suiiicient to dry'the coating and to convert the reaction product into an insoluble resin coating.
- the material providing the resin, in dry finely divided condition may be mixed with the other dry ingredients to form a dry dope and it will be found that the resin will be distributed through the mixture and will serve to prevent water-penetration into the interior of the sulphur pellets.
- the pelleted sulphur, desired is then added to coated or 'uncoated, as the secondary ingredients, as, for example, sodium nitrate or ammo- Q nium nitrate, wood pulp. pit meal. corn flour, stabilizer, etc, to form a dry dope which in turn is worked into the nitric ester base (which is prepared according to standard practice) until the desired consistency is obtained. It may then be packed into cardboard cartridges which may be sealed by crimping in the usual manner.
- the secondary ingredients as, for example, sodium nitrate or ammo- Q nium nitrate, wood pulp. pit meal. corn flour, stabilizer, etc, to form a dry dope which in turn is worked into the nitric ester base (which is prepared according to standard practice) until the desired consistency is obtained. It may then be packed into cardboard cartridges which may be sealed by crimping in the usual manner.
- a charge preferably two cartridges 2" in diameter and 14%; long, together with an electric ca are loaded end to end into a steel bomb 3" in diameter and about 40 long, the cap leads being arranged for detonating the bomb.
- the cap leads being arranged for detonating the bomb.
- two or more cartridges are employed they are preferably joined together with a cardboard sleeve to assure proper alignment and end to end contact.
- the bomb is then filled with water under the desired pressure and kept at that pressure, by the addition of water to compensate for that absorbed by the explosivev composition, for the desired time. It is then sealed oif and, while still at the desired pressure, taken to a bombproof structure for firing.
- Composition 2 contains In Table III, compositions compQSitions while comcompositions of the in- 6 Seisnon-pelleted sulphur. 1, 3 and 5 are prior art positions 2, 4 and .6 are vention. All tests were made with a. N0. mograph Electric Blasting Cap.
- Table III about 20% and 80% and nitrocotton in an amount between about 0.3% and about 7%, and containing from about 5% to about 50% by Weight of hollow sulphur pellets, said hollow sulphur pellets being smaller in size than a No. 6
- a gelatin dynamite explosive comprising nitroglycerine in an amount between about pression.
- a gelatin dynamite explosive comprising nitroglycerine in an amount between about 20% 1 2 and about 80% and nitrocotton in an amount between about 0.3% and about 7%, and containing from about 5% to about 50% by weight of Ntrcglyce'rme 1:: &3 &3 hollow sulphur pellets, said hollow sulphur pelg-g 8-? lets being smaller in size than a U. S. S. No. 6 1 screen aperture and larger than a U. S. S. No.
- a gelatin dynamite explosive composition ig' comprising nitroglycerine in an amount between Q 6 3% about 20% and about 80% and nitrocotton in an 0 22 40 amount between about 0.3% and about 7%, and containing from about 5% to about by 1 Passing through a u. s. s. No. 14 and retained on a U. s. s. No. weight of hollow sulphur pellets, said hollow sul- 35 screen and coated with 2% of a partially polymerized reaction phur pellets being Smaller in Size than a No. 6
- U S S Screen aperture and larger than a U S s As will be apparent to those skilled in the art, 5 No. 80 screen aperture and containing a reaction compositions according to the invention are susproduct of formaldehyde and at least one comceptible of considerable variations in ingredients pound selected from the group consisting of urea and percentages without departing from the feaand melamine present in an amount from about tures of the invention. 0.5% to about 5.0% by weight of the sulphur, I claim: 50 and containing from about 0.5% to about 5% of 1.
- a gelatine dynamite explosive composition a stabilizing organic amine. comprising nitroglycerine in an amount between 9.
- a gelatin dynamite explosive composition about 20% and about 80%, and nitrocotton in an comprising nitroglycerine in an amount between amount between about 0.3% and about 7%, and about 20% and about 80% and nitrocotton in an containing from about 5% to about 50% of holamount between about 0.3% and about 7%, and low sulphur pellets, said hollow sulphur pellets containing from about 10% to about 45% by being smaller in size than a U. S. S. No. 6 screen weight of hollow sulphur pellets, said hollow aperture and larger than a U. S. S. No. 80 screen sulphur pellets being smaller in size than a aperture. U. S. S. No. 14 screen aperture and larger than 2.
- a gelatin dynamite explosive composition a U. S. S. No. 45 screen aperture and having a comprising nitroglycerine in an amount between wax coating comprising from about, 1 0-% to about a about and nitrocotton in an about 3.0% by weight of the sulphur; and from amount between about 0.3% and about 7%, and about 95% t about 5 f a Stabilizing organic containing from about 5% to about 50% by amine weight of hollow sulphur pellets, said hollow sul- 5 10 A i a gelatin dynamite explosive comprising P 3 g fi a nitroglycerine in an amount between about 20% p61 g a and about 80% and nitrocotton in an amount be- No.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Patented Apr. 6, 1954 GELATIN DYNAMITE ,ooMi os'iTIoN CONTAINING SULFUR Walter L. Reinhart, McKeansbur'g, Pa., assignor to Atlas Powder Company, Wilmington, Del., a
corporation of Delaware No Drawing. Applicatio'iiJuly it, 1950',
Serial No. 174,579
14 Claims.
1 The present invention relates to an improvement in gelatin dynamite compositions, and, in particular, to a gelatin dynamite explosive composition especially advantageous for use in 011- Well blasting and prospecting, which explosive will not be rendered insensitive by prolongedexposure to pressure and water. It has long been known that gelatin dynamite explosives, upon the application of continued pressure, become passified or insensitive and cannot be detonated in the intended manner by commercial detonators. Such passification' is a serious detriment to the use of gelatin dynamite explosives in certain important applications, for instance in seismic prospecting.
In seismic prospecting, explosive charges are detonated at the bottoms of bore holes and from the rate and direction of propagation of the resulting shock waves, the geological structure of the given area can be constructed. Seismic prospecting is an important geological tool,- particularly in the discovery'of petroleum.
The bore holes within which theexplosives are fired are usually of great depth and filled to a considerable extent with water or drilling" mud. Commercial practice in seismic prospecting often demands that the explosive remain under this mud or water and subjected to the pressure thereof for days.- beena common experience for gelatin dynamite to become passi'fied or insensitize'd and fail to fire with commercial detonators.- While the exact reason for such passification has not been determined, it is theorized that the extended subjection of the gelatin dynamite to high water In such cases; it has- 2 tered in seismic prospecting, pelleted alkali metal nitrates are, at times, not sufficiently resistant to compression and in particular that they are not mechanically stable when exposed to water. In addition, they often do not stand up satisfactorily in storage.
It is, therefore, an object of the present invention to provide an explosive composition having improved resistance to pressure and water.
A further object is the formulation of a gelatin dynamite which will retain, after long storage, its ability to detonate when subjected to high water pressures.
A further object of the invention is to provide agelatin dynamite explosive having improved utility for seismic prospecting.
Other objects of the invention will be apparent from aconsid'eration of the following specification and claims.
According to the invention, a gelatin dynamite explosive composition having improved resistance to high water pressures and increased stability in storage is provided by including in the gelatin dynamite composition comprising the usual ingredients thereof, a substantial portion of pelleted interio'rly ca'vitated elemental sul-.
phur. By including pelleted interiorly cavitated elemental sulphur in the gelatindynamite, explosives may be obtained which exhibit markedly superior propagation-sustaining properties under high water pressure, in comparison with compositions hitherto employed. To illustrate this, the following general comparison may be made (for a more detailed comparison see the tables of specific examples):
Explosive Head Time Results Ordinary gelatin dynamite; 200 ft.-87 p. s. i
2 hrs. N0 detonation in ials.
Gelatin cynamite contain- 300 it.=l30p. s.i 24 hrs..- Do.
ing pelleted NaNOa,
Gelatin dynamite accord- .500 ft.=2l5 p. s.i 9 days. Detonation in all ing to invention. cases.
pressures renders the air particles; normally'dis tributed throughout the composition, inoperative as propagation-sustaining media.
Normally gelatin-dynamite explosives'have had included in their composition cork, bag'asse' pulp, and the like in anattempt to offset this passifying effect. However; this has not in general been effective in retaining the sensitivity of the explosive under high water pressures for more than a few hours. in U. S. Patent No. 1,77 8-,7-18 'that thisproblem might be solved by the use ofhollow pellets of alkali metalnitrates as ingredientsofthe-explosive mix. Experience has indicated; how ever, that under the severe-conditions encoun- Ithas been suggested" to about 7% nitrocotton, usually from about 0.4% to about the amount of nitrocotton being sufficient to provide a viscous liquid or a gel of the desired consistency with the nitroglycerine as is standard practice. The particular proportions of nitroglycerine to nitrocotton selected will depend, as is well known; upon the amount of solid ingredients included in the 'explosive. When substantial amounts of solid ingredients are present the proportion of nitrocotton to nitroglycerine may be such as to provide a more or less viscous liquid, the adsorption and absorption of the solid ingredients being relied upon to render the mixture plastic. As the proportion of nitrocotton to nitroglycerine is increased the mixture becomes more viscous until a gel isobtained, and this gel may be relied upon to render the composition plastic. At any rate the amounts and proportions of nitroglycerine and of nitrocotton, as well as any solid ingredients, will be selected in accordance with common practice to provide a plastic, solid mass.
If sodium nitrate is employed, it will generally be present in an amount from about 3% to about 65%, While fuels will usually be between about 3% and about 25%. In accordance with conventional practice the proportions of fuel and of sodium nitrate, when used, may be varied to provide a desirable oxygen. balance in the explosive. If ammonium nitrate is used, it may be present in an amount from about 2.0% to about 50%, depending upon the particular grade of ammonia gelatin dynamite desired.
The nitroglycerine used in the present compositions may be relatively pure nitroglycerine or it may be a nitrated mixture of glycerine, ethylene glycol and corn or sugar or other nitratable substances, as is usually employed in the :art. The aforesaid nitrated mixture, as well as relatively pure nitroglycerine, is designated in the trade as nitroglycerine and that term is used herein to include both materials.
By pelleted sulphur is meant small interiorly cavitated (hollow) pellets or beads of elemental sulphur the interiors of which are air-filled. Such pellets can be obtained by spraying molten sulphur into air in fine droplets with subsequent solidification or freezing of the droplets in flight. While the size of the sulphur pellets employed in the composition of the invention may vary over a wide range, the pellets are usually smaller than a U. S. S. No. 6 screen aperture and larger than a U. S. S. No. 80 screen apering the hollow sulphur pellets. Preferably, this is accomplished by providing the sulphur pellets in the composition with an exterior coating of a water-resistant film-forming substance, for ex ample, a coating of wax or of a resinous material of the type hereinafter described. Such a coating appears to seal off the pores of the sulphur and increase the resistance of the resulting composition to water pressure. Preferably, a microcrystalline hydrocarbon Wax or a convertible urea reaction product, for example, a convertible urea-formaldehyde reaction product ineluding dimethylolurea, a convertible urea-melture. Preferably, they are smaller than a U. S. S. H
No. 14 screen aperture and larger than, a U. S. S. No. 45 screen aperture. pellets larger than those which will pass through a U. S. S. No. 6 screen tend to break upon handling or milling. To the extent that such breakage occurs, the advantages of the invention are not realized. This tendency to breakis not found in the smaller particles, but, when the pellet size is less than that which will be retained on a U. S. S. No. 80 screen, the pellets tend to be ineifective to prevent pressure passification.
The quantity of pelleted sulphur present in the novel composition may vary widely depending upon the particular conditions of use to which the explosive is intended but generally the pelleted sulphur will be present in an amount from about 5% to about 50% by weight, preferably from about 10% to about 45% by weight.
It has been found that improved results are obtained when the composition contains a material which serves to prevent water from enter- It has been found that v amine reaction product or a convertible ureamelamine-formaldehyde reaction product is employed, to provide the water resistant coating although other film-forming materials may be used if desired. In the event a convertible material is employed, conventional curing catalysts, for example, an ammonium salt, such as ammonium chloride, may be employed to facilitate the conversion of the reaction product into the insoluble state, but even in the absence of a catalyst, the convertible urea reaction product will be converted as cured with the passage of time. The amount of coating material added may vary, but generally from about 0.5% to about 5.0% will be used, and the preferable range is from about 1.0% to about 3.0% by weight of the sulphur.
To prevent the pellets from sticking or agglomerating when treated with wax, a coating of clay may be applied following the treatment with the wax. If used, the amount of clay will depend on the amount of wax used and may comprise from about 1% to 3% by weight of the sulphur. In place of coating the sulphur pellets, prevention of water-penetration into the sulphur pellets may be accomplished by adding a convertible reaction product of the stated type to the dry dope used in preparing the composition, as hereinafter described.
To aid in preventing the deterioration of the compositions on storage, a stabilizer is preferably added. For this function, organic amines are preferred, in particular urea, carbazole and diphenylamine. While the amount of stabilizer added to the composition will vary with the particular composition and the length of time and conditions of storage (especially temperature), in general from about 0.5% to about 5.0% may be employed.
The pelleted sulphur used in the present invention may, as stated above, be prepared by blowing molten sulphur upwardly through a nozzle into the atmosphere. For best results, it is desirable that the temperature of the sulphur as it leaves the nozzle be as near to the crystallizing temperature as possible. After the pellets have formed, they are gathered and classifled according to size.
If desired, pelleted sulphur of the desired size may then be provided with the water-resistant coating, for example, the wax or wax and clay, or the resin. This may be accomplished, for example, by adding the molten wax to a quantity of pellets in a heated paddle type mixer and mixing until a uniform coating is obtained. If a clay coat is also desired, the clay may then be added and mixing continued until the clay coat is evenly distributed.
If the pelleted sulphur is to be provided with a coating of resinous material, the material providing the resin, in finely divided form in suspension or slightly moistened or rendered slightly sticky by heating or in solution, may be mixed with the pelleted sulphur in a suitable mixing device. A particularly advantageous way of applying a resin coating to the sulphur pellets is as a suspension or partial solution in water. The pellets thus treated can be dried to provide the water resistant coating. In the event a thermosetting resin is employed the pellets may be heated to convert the resin coating to the insoluble state. A convenient method of applying a coating on the pellets is to suspend or partially dissolve the convertible reaction product in cool water containing a conversion catalyst such as about of ammonium chloride based on the dry weight of the reaction product, and to apply the resulting liquid to the pellets which have been heated to an elevated temperature, for'example to about 150 F. The heat contained in the pellets is suiiicient to dry'the coating and to convert the reaction product into an insoluble resin coating. Alternatively, the material providing the resin, in dry finely divided condition, may be mixed with the other dry ingredients to form a dry dope and it will be found that the resin will be distributed through the mixture and will serve to prevent water-penetration into the interior of the sulphur pellets.
The pelleted sulphur, desired, is then added to coated or 'uncoated, as the secondary ingredients, as, for example, sodium nitrate or ammo- Q nium nitrate, wood pulp. pit meal. corn flour, stabilizer, etc, to form a dry dope which in turn is worked into the nitric ester base (which is prepared according to standard practice) until the desired consistency is obtained. It may then be packed into cardboard cartridges which may be sealed by crimping in the usual manner.
To test the explosive effect of the novel mixtures, the following conventional procedure may be followed:
A charge, preferably two cartridges 2" in diameter and 14%; long, together with an electric ca are loaded end to end into a steel bomb 3" in diameter and about 40 long, the cap leads being arranged for detonating the bomb. When two or more cartridges are employed they are preferably joined together with a cardboard sleeve to assure proper alignment and end to end contact. The bomb is then filled with water under the desired pressure and kept at that pressure, by the addition of water to compensate for that absorbed by the explosivev composition, for the desired time. It is then sealed oif and, while still at the desired pressure, taken to a bombproof structure for firing.
To determine whether the explosive composition propagates completely through the full length of the column, use is, made of three lead crusher cylinders about '2" in diameter by 4" in length. The cylinders are each placed on a steel base plate under the bombs in an upright position and on a straight line on 12" centers and the explosive composition lies directly above them. To prevent their deformation when the bomb shatters, a steel cap plate about 1" thick and 3" square is interposed between each of the cylinders and the bomb. In this manner, the transmitted compression effect is recorded on each lead block. Complete or partial failures are shown by uncompressed or very slightly compressed lead cylinders. The bomb'is detonated andthe linear compression of the, lead cylinders measured and. then converted into, percent compression.
nitrate, respectively. Composition 2 contains In Table III, compositions compQSitions while comcompositions of the in- 6 Seisnon-pelleted sulphur. 1, 3 and 5 are prior art positions 2, 4 and .6 are vention. All tests were made with a. N0. mograph Electric Blasting Cap.
Table I Nitr0g1ycerine Nitr0cott0n. Sulphur 36. 6. Burnt IO-mesh, retained on 35-mesh) 1.0 Ground sodium nitrate Coarse sodium nitrate 35. 7 agasse 4.1
alk 1.0
Hydrostatic Pressure tests:
Pressure in ft., H20. Time (hrs) Percent Compression:
1 Non-pelleted sulphur passing through a U. S. S. No. 14 and re tamed on a. U. S. S. No. 35 screen.
2 Pclleted sodium nitrate coated with 2% wax and passing through a U. S. S. No. 14 and retained on a U. S. S. No. 35 screen.
3 Pcllcted sulphur interiorly cavitated passing through a U. S. S. N0. 14 and retained on a U. S. S. No. 35 screen.
4 Pelleted sulphur interiorly cavitated passing through a. U. S. S. N o. 8 and retained on a U. S. S. No. 20 screen.
Table II' Nitroglycerinc Nitrocotton Pelleted sulphur interiorly cavitated Ground sodium niate sure tests:
Pressure in it,
H2O Time (hrs.). Percent compres- 1 Passing through a U. S. S. No. 14 and retained'on a, U. S. S. No. 35 screen and coated with 2% of a microcrystalline hydrocarbon wax.
2 Passing through a U. S. S. N o. 8 screen and retained on a U; S. S. No. 14 screen.
3 Passing through a U. S. S. N o. 20 screen and retained on a U. S. S. No. screen.
4 Passing through a U. S. S. N o. 14 and retained on a No. 35 screen and coated with 2% of a microcrystalline hydrocarbon wax. and with an exterior coating of finely divided clay.
5 Passing through a U. S. S. N o. 14 and retained on a U'. S: S1No. 35 screen and coated with 2% of a partially polymerized reaction product of urea and formaldehyde (Cascamite-a watei soluble ureaiormaldehyde resin adhesive in dry powder form).
2, 4, 7: 8 T Table III about 20% and 80% and nitrocotton in an amount between about 0.3% and about 7%, and containing from about 5% to about 50% by Weight of hollow sulphur pellets, said hollow sulphur pellets being smaller in size than a No. 6
gitroglytgerine. l roco on Ground Sodium mtme U. S. S. screen aperture and larger than a U. S S. g fifi nitratem I No. 80 screen aperture and containing a reaction p p Come Apricot Pit Meal product of formaldehyde and at least one com Fine Apricot Pit Meal p nd selected from the group consisting of g Flour urea and melamine.
rea .0 Pu1verizedSu1phur A gelatm dynam1te explosive as claime in 3 x 3 5 35 e claim 4 wherein said reaction product is provided ohnik I I as a coating for the sulphur pellets and is a urea- Hydrostatic Pressure f ld h d resin Tests.
Pressureinit, 1120.- 6. A gelatin dynamite explosive comprising nitroglycerine in an amount between about pression.
Lead No.1 and about 80% and nitrocotton in an amount figg 1 1%.-
11 between about 0.3% and about 7%, and containing from about 5% to about 50% of hollow sul- 20 phur pellets and from about 0.5% to about 5.0%
Passing through a U. S. S. No. 14 and retained on a U. S. S.
lgllgkglgzfifixirgdeidzggivgglgigfl ogffialgicgogiigggigge hydrocarbon of a stabilizing organic amine, Said sulphur pel- 1 Passing through a U. S. S No. 14 End retained o n a U. S. S. lets bem'g smaller 1n S128 than U S- S 6 No. 35 screen and coated with 2% of apartially polymerized reaction screen aperture and larger than a. U. S. S. No. 80 product of urea and formaldehyde (Oascamite"). Screen aperture Table IV 7. A gelatin dynamite explosive comprising nitroglycerine in an amount between about 20% 1 2 and about 80% and nitrocotton in an amount between about 0.3% and about 7%, and containing from about 5% to about 50% by weight of Ntrcglyce'rme 1:: &3 &3 hollow sulphur pellets, said hollow sulphur pelg-g 8-? lets being smaller in size than a U. S. S. No. 6 1 screen aperture and larger than a U. S. S. No. 80 screen aperture and having a wax coating com- 1 j prising from about 0.5% to about 5.0% by weight 23 of the sulphur; and from about 0.5% to 5.0% of n arsllil'i'frlin'e' fiisl a Sta l zi an c am egggjz gf 20 2 9 8. A gelatin dynamite explosive composition ig' comprising nitroglycerine in an amount between Q 6 3% about 20% and about 80% and nitrocotton in an 0 22 40 amount between about 0.3% and about 7%, and containing from about 5% to about by 1 Passing through a u. s. s. No. 14 and retained on a U. s. s. No. weight of hollow sulphur pellets, said hollow sul- 35 screen and coated with 2% of a partially polymerized reaction phur pellets being Smaller in Size than a No. 6
product of urea and formaldehyde (Cascamite). U S S Screen aperture and larger than a U S s As will be apparent to those skilled in the art, 5 No. 80 screen aperture and containing a reaction compositions according to the invention are susproduct of formaldehyde and at least one comceptible of considerable variations in ingredients pound selected from the group consisting of urea and percentages without departing from the feaand melamine present in an amount from about tures of the invention. 0.5% to about 5.0% by weight of the sulphur, I claim: 50 and containing from about 0.5% to about 5% of 1. A gelatine dynamite explosive composition a stabilizing organic amine. comprising nitroglycerine in an amount between 9. A gelatin dynamite explosive composition about 20% and about 80%, and nitrocotton in an comprising nitroglycerine in an amount between amount between about 0.3% and about 7%, and about 20% and about 80% and nitrocotton in an containing from about 5% to about 50% of holamount between about 0.3% and about 7%, and low sulphur pellets, said hollow sulphur pellets containing from about 10% to about 45% by being smaller in size than a U. S. S. No. 6 screen weight of hollow sulphur pellets, said hollow aperture and larger than a U. S. S. No. 80 screen sulphur pellets being smaller in size than a aperture. U. S. S. No. 14 screen aperture and larger than 2. A gelatin dynamite explosive composition a U. S. S. No. 45 screen aperture and having a comprising nitroglycerine in an amount between wax coating comprising from about, 1 0-% to about a about and nitrocotton in an about 3.0% by weight of the sulphur; and from amount between about 0.3% and about 7%, and about 95% t about 5 f a Stabilizing organic containing from about 5% to about 50% by amine weight of hollow sulphur pellets, said hollow sul- 5 10 A i a gelatin dynamite explosive comprising P 3 g fi a nitroglycerine in an amount between about 20% p61 g a and about 80% and nitrocotton in an amount be- No. 80 screen aperture and having a wax coating -om ri n from 0.5 to 5 b Wei ht of the g g if g y g from about 10% to about 4.5% by weight of hol- A gelatin dynamite explosive as claimed in low sulphur pellets, said hollow sulphur pellets claim 2 wherein the ax coated ulphur ellets Smaller in Size than a: U- S. S. No. Screen are also coated it c1a,y aperture and larger than a U. S. S. No. 45 screen 4. A gelatin dynamite explosive composition aperture and ha a coating comprising a comprising nitroglycerine in an amount between action product of urea and formaldehyde present tween about 0.3% and about 7% and containing 14. The explosive of claim 7 wherein said sta- 0 bilizing organic amine is urea.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date Perry Nov. 19, 1918 Bacon et a1 May 17, 1921 Stoops Oct. 27, 1931 Seil May 24, 1932 Stratton Sept. 27, 1932 Jones Mar. 2, 1937 Tapley Sept. 27, 1938
Claims (1)
1. A GELATINE DYNAMITE EXPLOSIVE COMPOSITION COMPRISING NITROGLYCERINE IN AN AMOUNT BETWEEN ABOUT 20% AND ABOUT 80%, AND INTROCOTTON IN AN AMOUNT BETWEEN ABOUT 0.3% AND ABOUT 7%, AND CONTAINING FROM ABOUT 5% TO ABOUT 50% OF HOLLOW SULPHUR PELLETS, SAID HOLLOW SULPHUR PELLETS BEING SMALLER IN SIZE THAN A U. S. S. NO. 6 SCREEN APERTURE AND LARGER THAN A U. S. S. NO. 80 SCREEN APERTURE.
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US174579A US2674526A (en) | 1950-07-18 | 1950-07-18 | Gelatin dynamite composition containing sulfur |
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US174579A US2674526A (en) | 1950-07-18 | 1950-07-18 | Gelatin dynamite composition containing sulfur |
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US2674526A true US2674526A (en) | 1954-04-06 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2966405A (en) * | 1955-01-03 | 1960-12-27 | Atlantic Res Corp | Cellulose ester propellant compositions |
US3101288A (en) * | 1957-04-18 | 1963-08-20 | Du Pont | Explosive composition |
US3456589A (en) * | 1967-03-20 | 1969-07-22 | Dow Chemical Co | High pressure explosive compositions and method using hollow glass spheres |
DE1696382B1 (en) * | 1965-11-12 | 1970-06-18 | Wasagchemie Ag | Explosives foils |
US20130055918A1 (en) * | 2011-09-02 | 2013-03-07 | Alliant Techsystems Inc. | Energetic compositions including nitrate esters, methods of forming such energetic compositions, and articles including such energetic compositions |
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US1285358A (en) * | 1917-10-11 | 1918-11-19 | Barrett Co | Sulfur in globular form and process of producing the same. |
US1378084A (en) * | 1919-10-06 | 1921-05-17 | Texas Gulf Sulphur Co | Refining sulfur |
US1828788A (en) * | 1927-12-08 | 1931-10-27 | Hercules Powder Co Ltd | Explosive |
US1859992A (en) * | 1926-04-01 | 1932-05-24 | Gilbert E Seil | Method of and apparatus for subdividing material |
US1880116A (en) * | 1931-02-27 | 1932-09-27 | Atlas Powder Co | Explosive composition |
US2072263A (en) * | 1933-01-13 | 1937-03-02 | Ind Associates Inc | Process and apparatus for producing comminuted sulphur |
US2131574A (en) * | 1935-11-19 | 1938-09-27 | Du Pont | Explosive |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US1285358A (en) * | 1917-10-11 | 1918-11-19 | Barrett Co | Sulfur in globular form and process of producing the same. |
US1378084A (en) * | 1919-10-06 | 1921-05-17 | Texas Gulf Sulphur Co | Refining sulfur |
US1859992A (en) * | 1926-04-01 | 1932-05-24 | Gilbert E Seil | Method of and apparatus for subdividing material |
US1828788A (en) * | 1927-12-08 | 1931-10-27 | Hercules Powder Co Ltd | Explosive |
US1880116A (en) * | 1931-02-27 | 1932-09-27 | Atlas Powder Co | Explosive composition |
US2072263A (en) * | 1933-01-13 | 1937-03-02 | Ind Associates Inc | Process and apparatus for producing comminuted sulphur |
US2131574A (en) * | 1935-11-19 | 1938-09-27 | Du Pont | Explosive |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2966405A (en) * | 1955-01-03 | 1960-12-27 | Atlantic Res Corp | Cellulose ester propellant compositions |
US3101288A (en) * | 1957-04-18 | 1963-08-20 | Du Pont | Explosive composition |
DE1696382B1 (en) * | 1965-11-12 | 1970-06-18 | Wasagchemie Ag | Explosives foils |
US3456589A (en) * | 1967-03-20 | 1969-07-22 | Dow Chemical Co | High pressure explosive compositions and method using hollow glass spheres |
US20130055918A1 (en) * | 2011-09-02 | 2013-03-07 | Alliant Techsystems Inc. | Energetic compositions including nitrate esters, methods of forming such energetic compositions, and articles including such energetic compositions |
US8778103B2 (en) * | 2011-09-02 | 2014-07-15 | Alliant Techsystems Inc. | Energetic compositions including nitrate esters and articles including such energetic compositions |
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