EP0068528A1 - Cold formable, plastics-bound high power explosive and process for preparing it - Google Patents
Cold formable, plastics-bound high power explosive and process for preparing it Download PDFInfo
- Publication number
- EP0068528A1 EP0068528A1 EP82200629A EP82200629A EP0068528A1 EP 0068528 A1 EP0068528 A1 EP 0068528A1 EP 82200629 A EP82200629 A EP 82200629A EP 82200629 A EP82200629 A EP 82200629A EP 0068528 A1 EP0068528 A1 EP 0068528A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- desensitizing
- binding agent
- dispersion
- poly
- 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.)
- Granted
Links
- 239000002360 explosive Substances 0.000 title claims abstract description 82
- 239000004033 plastic Substances 0.000 title claims abstract description 10
- 229920003023 plastic Polymers 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 71
- 239000003975 dentin desensitizing agent Substances 0.000 claims abstract description 54
- 239000006185 dispersion Substances 0.000 claims abstract description 54
- 239000012188 paraffin wax Substances 0.000 claims abstract description 32
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 28
- -1 Polytetrafluoroethylene Polymers 0.000 claims abstract description 27
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000000314 lubricant Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000000741 silica gel Substances 0.000 claims abstract description 14
- 239000004698 Polyethylene Substances 0.000 claims abstract description 11
- 229920000573 polyethylene Polymers 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 8
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 19
- 239000004815 dispersion polymer Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000586 desensitisation Methods 0.000 claims description 8
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 4
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims 2
- 239000000839 emulsion Substances 0.000 claims 1
- 239000000499 gel Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000000028 HMX Substances 0.000 abstract description 22
- 238000000465 moulding Methods 0.000 abstract description 8
- 238000005474 detonation Methods 0.000 abstract description 4
- 239000003995 emulsifying agent Substances 0.000 abstract description 4
- 239000000080 wetting agent Substances 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000002562 thickening agent Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 235000011132 calcium sulphate Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000007970 homogeneous dispersion Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 241000282693 Cercopithecidae Species 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007786 electrostatic charging Methods 0.000 description 1
- JROGBPMEKVAPEH-GXGBFOEMSA-N emetine dihydrochloride Chemical compound Cl.Cl.N1CCC2=CC(OC)=C(OC)C=C2[C@H]1C[C@H]1C[C@H]2C3=CC(OC)=C(OC)C=C3CCN2C[C@@H]1CC JROGBPMEKVAPEH-GXGBFOEMSA-N 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960004321 pentaerithrityl tetranitrate Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S149/00—Explosive and thermic compositions or charges
- Y10S149/11—Particle size of a component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S149/00—Explosive and thermic compositions or charges
- Y10S149/11—Particle size of a component
- Y10S149/114—Inorganic fuel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S149/00—Explosive and thermic compositions or charges
- Y10S149/11—Particle size of a component
- Y10S149/115—Organic fuel
Definitions
- a high-performance explosive such as cyclotetramethylene tetranitramine or cyclotrimethylene trinitramine
- a desensitizing and binding agent which contains an organic polymer
- the invention also relates to a plastic-bound high-performance explosive containing at least 90% by weight of a high-performance explosive such as cyclotetramethylene tetranitramine or cyclotrimethylene trinitramine and a maximum of 10% by weight (based in each case on the weight of the plastic-bound high-performance explosive) of a desensitizing and binding agent made from an organic polymer with additives like wax and paraffin.
- a high-performance explosive such as cyclotetramethylene tetranitramine or cyclotrimethylene trinitramine
- a desensitizing and binding agent made from an organic polymer with additives like wax and paraffin.
- the invention further relates to a method for producing a shaped body from the high-performance explosive in a mold by applying pressure.
- a high-performance explosive is obtained by dispersing a high-performance explosive such as octogen (in the following used trivial name for cyclotetramethylene tetranitramine) in a rubber-like two-component binder which is made from a prepolymer two preferably terminal carboxyl groups and an epoxy-based crosslinking agent.
- a Desensitizing agents such as wax are added, as well as other auxiliaries such as catalysts for crosslinking the desensitizing and binding agent, antioxidants and wetting agents.
- the known method is cumbersome in that the desensitizing and binding agent and the octogen have to be mixed under vacuum at elevated temperature in a kneading device and the subsequent casting process must also be carried out under vacuum. In addition, vibrations must be brought into effect in order to achieve the desired homogeneity.
- the hardening times of several days for the desensitizing and binding agent additionally make the whole process time-consuming.
- the high-performance explosive molded article thus obtained still contains more than 10% foreign matter, and its explosive power is therefore considerably reduced compared to that of the pure octogen.
- the object of the invention is to provide a high-performance explosive of the aforementioned type, the effectiveness of which is close to that of the pure octogen and which has high mechanical strength with high safety in handling, and to provide a process which can be carried out with simple means for its production and processing.
- Handling safety is understood to mean, among other things, both the harmlessness during manufacture and processing, as well as the insensitivity to external influences in use, such as the dimensional stability (e.g. under the effects of shocks when fired) and mechanical strength of molded articles made therefrom.
- an aqueous polymer dispersion in Anwe The mixture of auxiliaries and additives is mixed with a lubricant, with an aqueous paraffin dispersion and with a filler, such that the aqueous dispersion of the desensitizing and binding agent thus obtained is mixed with the dry explosive and that the mixture obtained is dried warm.
- the process according to the invention uses aqueous dispersions of the polymer and other constituents of the desensitizing and binding agent, so that these can be completely mixed with one another and with further constituents of the desensitizing and binding agent in a very short time using simple means at room temperature and under normal pressure.
- the aqueous dispersion of the desensitizing and binding agent is then effectively combined with the octogen in a mixing drum in a very short time, also at room temperature and under normal pressure; the product thus obtained is dried in a very simple manner by a warm air stream.
- the dry product is very safe to use.
- the aqueous polymer dispersion can be prepared by mixing an aqueous dispersion of poly-O-butyl acrylate (a butyl polyacrylic acid) with an aqueous dispersion of polyethylene and 5 to 15% by weight of polyethylene (based on the weight of the poly-O butyl acrylate) with an average particle size of 0.1 to 0.3 pm are added; polytetrafluoroethylene as a lubricant, highly disperse silica gel, paraffin and calcium carbonate with a particle size of approximately 1 pm can be added in succession as filler.
- poly-O-butyl acrylate a butyl polyacrylic acid
- polyethylene based on the weight of the poly-O butyl acrylate
- polytetrafluoroethylene as a lubricant
- highly disperse silica gel, paraffin and calcium carbonate with a particle size of approximately 1 pm can be added in succession as filler.
- Poorly soluble compounds of the alkaline earth group such as magnesium pyrophosphate, calcium carbonate, calcium sulfate and barium sulfate, are added as fillers.
- the aqueous polymer dispersion can be prepared from poly-O-alkyl acrylate or poly-0-alkyl methacrylate (polymethacrylic acid alkyl ester) with an alkyl group of at least 3 carbon atoms and preferably poly-O- contain butyl acrylate or isobutylacrylate.
- a first component containing part of the polymer, graphite as a lubricant and part of the paraffin and a second component containing calcium sulfate as a filler, the highly disperse silica gel and the rest of the paraffin can be used together and then with a third component of the aqueous dispersion of the desensitization - And binder are mixed, which contains cyclohexanone and the rest of the polymer in an isopropanol-water mixture.
- the plastic-bound high-performance explosive according to the invention achieves the aforementioned object in that the desensitizing and binding agent contains a polymer based on polyacrylate or polymethacrylate, a lubricant and a filler.
- the filler in the desensitization and binder of the plastic-bound high-performance explosive according to the invention is selected from poorly soluble compounds of the alkaline earth group and is preferably magnesium pyrophosphate, calcium carbonate, calcium sulfate or barium sulfate.
- the polymer can be a poly-O-alkyl acrylate or poly-O-alkyl methacrylate, preferably poly-O-butyl acrylate or isobutylacrylate, and the high-performance explosive with a desensitizing and binding agent composed of 18 to 50% by weight of poly-O- butyl acrylate, 0.9 to 8% by weight of polyethylene, 2 to 7% by weight of polytetrafluoroethylene, 20 to 65% by weight of calcium carbonate, 0.3 to 2.3% by weight of silica gel and 3.2 to 20% by weight .-% paraffin.
- a desensitizing and binding agent composed of 18 to 50% by weight of poly-O- butyl acrylate, 0.9 to 8% by weight of polyethylene, 2 to 7% by weight of polytetrafluoroethylene, 20 to 65% by weight of calcium carbonate, 0.3 to 2.3% by weight of silica gel and 3.2 to 20% by weight .-% paraffin.
- An antistatic variant of the high-performance explosive according to the invention can be made with a desensitizing and binding agent composed of 18 to 50% by weight of poly-O-butyl acrylate, 25 to 65% by weight of graphite with an average grain size of 2.5 ⁇ m and a grain size distribution corresponding to 95% less than 5 ⁇ m, 12 to 25% by weight calcium sulfate, 0.3 to 2.3% by weight silica gel and 3.5 to 20% by weight paraffin.
- a desensitizing and binding agent composed of 18 to 50% by weight of poly-O-butyl acrylate, 25 to 65% by weight of graphite with an average grain size of 2.5 ⁇ m and a grain size distribution corresponding to 95% less than 5 ⁇ m, 12 to 25% by weight calcium sulfate, 0.3 to 2.3% by weight silica gel and 3.5 to 20% by weight paraffin.
- the aforementioned object is achieved with regard to the method for further processing according to the invention in that the high-performance explosive is pressed in the mold at room temperature with a pressure in the range above 1.5 kbar.
- the high-performance explosive manufactured according to the invention can thus be processed by cold pressing to give shaped articles, for example also shaped charges. This particularly simple method has not yet been used successfully with explosives with high proportions of octogen.
- the molded articles produced according to the invention have densities above 1.8 g / cm 3 and detonation speeds above 8.6 km / s. They have improved mechanical strength and homogeneity and are less sensitive to impact or friction than expected; they are also thermally stable and, to a particular extent, are pressure-resistant and bulletproof.
- the poly-O-butyl acrylate increases the adhesion between the explosive particles in a sufficient manner for further processing and for the dimensional stability of the molded article ultimately produced.
- the polyethylene improves the mechanical properties of the plastic film with regard to its desensitizing effect.
- Neither polymer is known to date as a binding agent for octogen.
- the polytetrafluoroethylene known per se as a lubricant, is present in a proportion which is matched to the abovementioned constituents and is chosen so high that the dimensional stability of the ultimately produced shaped body is not impaired, but the shaped body is removed from the mold smoothly and without damage after shaping can be.
- Graphite especially with average particle sizes of 2.5 ⁇ m and particle size distributions corresponding to 95% below 5 ⁇ m, supports the desensitizing effect of the paraffin and prevents electrostatic charging of the explosive particles; it also acts as a lubricant and its amount is chosen so that the dimensional stability of the molded article ultimately produced is only insignificantly impaired, but the molded article can be removed from the mold smoothly and without damage after shaping.
- the octogen has a particle size of less than 1.68 mm, preferably less than 0.5 mm.
- the filler selected from poorly soluble compounds of the alkaline earth group is first added in order to increase the flowability of the particles of the high-performance explosive and to reduce their mutual adhesion through the binder coating.
- a filler has a considerable desensitizing effect which, in conjunction with the aforementioned polymers, enables safe handling of high-performance explosives with octogen proportions of more than 90% by weight.
- this addition unexpectedly increases the mechanical strength of the molded articles made from the high-performance explosive.
- the plastic-bound high-performance explosive with polytetrafluoroethylene as a lubricant contains 3 to 10% by weight of the desensitizing and binding agent, which essentially consists of 20 to 50% by weight of poly-O-alkyl acrylate, 0.9 to 8% by weight of polyethylene, 2 up to 7% by weight of polytetrafluoroethylene, up to 65% by weight of filler, at least 0.3% by weight of silica gel and 8 to 20% by weight of paraffin.
- the filler consists of a poorly soluble alkaline earth compound such as magnesium pyrophosphate, calcium carbonate, calcium sulfate, barium sulfate.
- the magnesium pyrophosphate is precipitated from aqueous solution by combining stoichiometric amounts of sodium pyrophosphate and magnesium sulfate, filtered off and ge dries, the rest are commercially available products.
- a preferred embodiment with 4% by weight of desensitizing and binding agent is obtained as follows:
- 39 kg of a commercially available aqueous dispersion of poly-O-butyl acrylate (24% by weight corresponding to 9.3 kg of poly-O-butyl acrylate) are diluted with 8 l of water with stirring and initially with 0.7 kg of a silicone-based defoamer (10 % By weight corresponding to 0.07 kg) and 0.3 kg of an alkanol polyglycol ether-based wetting agent.
- the mixture is stirred until it is homogeneous; 3.4 kg of a commercially available aqueous polyethylene dispersion (35% by weight, corresponding to 1.2 kg of polyethylene) are then added with further stirring.
- stirring speed is sufficiently low (to avoid flocculation)
- 2.5 kg of a commercially available aqueous dispersion of polytetrafluoroethylene (60% by weight corresponding to 1.5 kg of polytetrafluoroethylene; particle size 0.05 to 0.5 nm) are added.
- 0.5 kg of a commercially available colloidal silica gel (average particle size 12 nm) is added, in portions and at a low stirring speed until it is completely wetted and then at a high stirring speed until the complete formation of any lumps that may have formed.
- the first step is to work with a slow stirring speed and then to increase the viscosity of the initially pulpy mass until the mixture is thin.
- the high-performance explosive obtained in accordance with point 2 is cold-pressed in molds of conventional design under a pressure in the range from 1.5 to 4.2 kbar.
- a pressure of approx. 3.5 kbar gives optimal results, especially with regard to the safety and performance achieved.
- the moldings have a density of 1.81 g / cm 3 and above. Detonation speed: 8.6 km / s.
- the impact sensitivity was examined with the drop hammer method n-ch Koenen and Ide. With a 2 kg drop hammer and 10 mm 3 samples, only isolated, weak reactions were observed at a drop height of 25 cm and less than 30% or 50% reactions at 30 or 35 cm drop height. With a 5 kg drop hammer and 40 mm 3 samples, no reactions were observed at a fall height of 30 cm, only occasional reactions occurred at 35 cm and 0 - 20% reactions occurred at 40 cm.
- the antistatic plastic-bound high-performance explosive with graphite as a lubricant contains 3 to 10% by weight of the desensitizing and binding agent, which essentially consists of 18 to 40% by weight of poly-O-butyl acrylate, 25 to 65% by weight of graphite, 12 to 25% by weight of filler, at least 0.3% by weight of silica gel and 7 to 17% by weight of paraffin is composed.
- the filler consists of a poorly soluble alkaline earth compound such as magnesium pyrophosphate, calcium carbonate, calcium sulfate, barium sulfate.
- the magnesium pyrophosphate is precipitated from an aqueous solution by combining stoichiometric amounts of sodium pyrophosphate and magnesium sulfate, filtered off and dried, the rest are commercially available products.
- a preferred embodiment with 4.3% by weight of desensitizing and binding agent is obtained as follows:
- the desensitizing and binding agent can also be a prepared third component of the desensitizing and binding agent, which consists of 0.6 kg of cyclohexanone and 8.3 kg of a commercially available dispersion of poly-O-butyl acrylate (40% by weight corresponding to 3.3 kg of poly-O-butyl acrylate ) in isopropanol-water (mixing ratio 2: 1), the mixture of the first and second components of the desensitizing and binding agent are dispersed with an intensive stirrer. The stirring process is ended after 3 hours and repeated for 1 hour after one day. The desensitization and binder dispersion is then ready for use, but must be stirred before use.
- aqueous desensitization and binder dispersion 1.015 kg of the aqueous desensitization and binder dispersion are mixed with 7 kg of dry octogen and evenly distributed over the explosive.
- the mixture is then circulated in a mixing drum of the usual type, and after 10 minutes the desensitizing and binding agent is homogeneously distributed over the explosive.
- the mixture is removed from the mixing drum, spread out flat and with occasional stirring pre-dried by passing a warm air stream.
- the predried material is mixed in a rotating drum with 290 g of isopropanol-water (mixing ratio 1: 1) corresponding to about 4% by weight and the mixture is circulated for 15 to 30 minutes.
- the mixture is then removed from the mixing drum, spread out flat and, with occasional circulation, dried by passing a warm air stream over it.
- the last-mentioned processes can also be carried out using a fluidized bed method, if necessary, taking into account relevant safety measures.
- the high-performance explosive obtained in accordance with point 5 is cold-pressed in molds of conventional design under a pressure in the range from 1.5 to 4.2 kbar. Pressures of 2.2 to 3.5 kbar are usually sufficient, but the pressures can be increased for special requirements, even for shaped loads, high-performance loads.
- the compacts have densities above 1.80 g / cm 3 .
- the measured detonation speeds are 8.6 km / s and above.
- the impact sensitivity was examined with the monkey method according to Koenen and Ide.
- the results were particularly favorable for particle sizes below 0.5 mm: with a 2 kg drop hammer with an explosive volume of 10 mm 3 and with a 5 kg drop hammer with an explosive volume of 40 mm 3 , even with drop heights of 40 or 60 cm no reactions observed.
- the compressive strength was on explosive compacts (Pressing pressure 1.9 to 4.2 t / cm 2 ) measured with the shape of an equilateral cylinder at room temperature. With decreasing particle size and increasing pressure, increasing values for the compressive strength are obtained, which can be more than twice as high as the compressive strength of known wax-containing pressed bodies made of octogen. The compressive strength increases again by up to 30% as the compacts age (1 to 2 weeks at room temperature, 3 to 4 days at + 50 ° C).
- explosives with the desired high density are obtained from fine-grained material using fine press material, which have the additional advantage of increased strength and reduced impact sensitivity. For this reason, such explosives are particularly safe to handle, to which their surface conductivity also makes an important contribution (surface resistance, measured according to DIN 53482, at a measuring voltage of 6 V: a few kilo-ohms).
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Abstract
Ein kunststoffgebundener Hochleistungssprengstoff enthält 90 bis 97 Gew.-% eines hochbrisanten Sprengstoffs, z.B. Octogen, und 3 bis 10 Gew.-% eines neuen Phlegmatisierungs- und Bindemittels (jeweils bezogen auf das Gesamtgewicht des Hochleistungssprengstoffs = 100). Dieses wird auf der Basis wässriger Dispersionen hergestellt und enthält im wesentlichen (bezogen auf den Feststoffanteil) 18 bis 50 Gew.-% Poly-O-butylacrylat und 3,7 bis 20 Gew.-% Paraffin, sowie 2 bis 7 Gew.-% Polytetrafluorethylen als Gleitmittel, 20 bis 65 Gew.-% Calciumcarbonat als Füllstoff und 0.9 bis 7,5 Gew.-% Polyethylen oder, für einen antistatischen Hochleistungssprengstoff, 25 bis 65 Gew.-% Graphit als Gleitmittel und 15 bis 25 Gew.-% Calciumsulfat als Füllstoff. Zusätzlich werden Hilfs- und Zusatzstoffe wie Emulgatoren, Dispergiermittel, Entschäumer, Benetzungsmittel, Verdicker und kleine Mengen Kieselgel zugefügt. Das in wässriger Dispersion zübereitete Phlegmatisierungs- und Bindemittel wird mit dem Octogen in einer Mischtrommel vermischt und getrocknet oder vorgetrocknet und anschliessend nach Behandlung mit Isopropanol-Wasser (1 : 1) getrocknet. Bei Drücken im Bereich von 2,2 bis 4,2 t/cm² daraus kalt gepresste, homogene Formkörper haben Dichten über 1,8 g/cm³ und Detonationsgeschwindigkeiten von 8.6 km/s und mehr.A high performance plastic bound explosive contains 90 to 97% by weight of a high explosive, e.g. Octogen, and 3 to 10 wt .-% of a new desensitizing and binding agent (in each case based on the total weight of the high-performance explosive = 100). This is produced on the basis of aqueous dispersions and essentially contains (based on the solids content) 18 to 50% by weight of poly-O-butyl acrylate and 3.7 to 20% by weight of paraffin, and 2 to 7% by weight Polytetrafluoroethylene as a lubricant, 20 to 65% by weight calcium carbonate as a filler and 0.9 to 7.5% by weight polyethylene or, for an antistatic high-performance explosive, 25 to 65% by weight graphite as a lubricant and 15 to 25% by weight Calcium sulfate as a filler. In addition, auxiliaries and additives such as emulsifiers, dispersants, defoamers, wetting agents, thickeners and small amounts of silica gel are added. The desensitizing and binding agent prepared in aqueous dispersion is mixed with the octogen in a mixing drum and dried or predried and then dried after treatment with isopropanol-water (1: 1). At pressures in the range from 2.2 to 4.2 t / cm², homogeneous moldings cold-pressed therefrom have densities above 1.8 g / cm³ and detonation speeds of 8.6 km / s and more.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines Hochleistungssprengstoffs enthaltend mindestens 90 Gew.-% eines leistungsstarken Sprengstoffs wie Cyclotetramethylentetranitramin oder Cyclotrimethylentrinitramin und maximal 10 Gew.-% (jeweils bezogen auf das Gesamtgewicht = 100) eines Phlegmatisierungs- und Bindemittels, das ein organisches Polymer enthält, bei welchem Verfahren zunächst die Bestandteile des Phlegmatisierungs- und Bindemittels vermischt und dann das so erhaltene Gemisch mit dem leistungsstarken Sprengstoff vermengt wird.The invention relates to a method for producing a high-performance explosive containing at least 90% by weight of a high-performance explosive such as cyclotetramethylene tetranitramine or cyclotrimethylene trinitramine and at most 10% by weight (in each case based on the total weight = 100) of a desensitizing and binding agent which contains an organic polymer , in which method the components of the desensitizing and binding agent are first mixed and then the mixture thus obtained is mixed with the powerful explosive.
Die Erfindung betrifft auch einen kunststoffgebundenen Hochleistungssprengstoff, enthaltend mindestens 90 Gew.-% eines leistungsstarken Sprengstoffs wie Cyclotetramethylentetranitramin oder Cyclotrimethylentrinitramin und maximal 10 Gew.-% (jeweils bezogen auf das Gewicht des kunststoffgebundenen Hochleistungssprengstoffs) eines Phlegmatisierungs-und Bindemittels aus einem organischen Polymeren mit Zusatzstoffen wie Wachs und Paraffin.The invention also relates to a plastic-bound high-performance explosive containing at least 90% by weight of a high-performance explosive such as cyclotetramethylene tetranitramine or cyclotrimethylene trinitramine and a maximum of 10% by weight (based in each case on the weight of the plastic-bound high-performance explosive) of a desensitizing and binding agent made from an organic polymer with additives like wax and paraffin.
Ferner betrifft die Erfindung ein Verfahren zur Herstellung eines Formkörpers aus dem Hochleistungssprengstoff in einer Form durch Anwendung von Druck.The invention further relates to a method for producing a shaped body from the high-performance explosive in a mold by applying pressure.
Nach einem bekannten Verfahren der eingangs genannten Art (US-PS 3 839 106) wird ein Hochleistungssprengstoff dadurch erhalten, dass ein leistungsstarker Sprengstoff wie Octogen (im folgenden verwendeter Trivialname für Cyclotetramethylentetranitramin) in einem gummiartigen Zweikomponenten-Bindemittel dispergiert wird, das aus einem Präpolymer mit zwei vorzugsweise endständigen Carboxylgruppen und einem Vernetzungsmittel auf Epoxidbasis besteht. Zusätzlich werden ein Phlegmatisierungsmittel wie Wachs hinzugegeben, sowie weitere Hilfsstoffe wie Katalysatoren für die Vernetzung des Phlegmatisierungs- und Bindemittels, Antioxidantien und Netzmittel. Im einzelnen werden dabei zunächst die Bindemittelkomponenten in einer Kneteinrichtung bei erhöhten Temperaturen unter Vakuum vermengt; anschliessend wird das Phleg- matisierungs- und Bindemittel unter gleichen Bedingungen mit dem Octogen gemischt. Dabei wird eine giessfähige Masse erhalten, die unter Vakuum und unter Einwirkung von Vibrationen in Formen gegossen wird, in denen die Masse im Verlaufe einiger Tage durchhärtet. Auf diese Weise drucklos herstellbare Hochleistungssprengstoff-Formkörper enthalten bis zu 90 Gew.-% (bezogen auf das Gesamtgewicht = 100) Octogen.According to a known method of the type mentioned at the beginning (US Pat. No. 3,839,106), a high-performance explosive is obtained by dispersing a high-performance explosive such as octogen (in the following used trivial name for cyclotetramethylene tetranitramine) in a rubber-like two-component binder which is made from a prepolymer two preferably terminal carboxyl groups and an epoxy-based crosslinking agent. In addition, a Desensitizing agents such as wax are added, as well as other auxiliaries such as catalysts for crosslinking the desensitizing and binding agent, antioxidants and wetting agents. In detail, the binder components are first mixed in a kneader at elevated temperatures under vacuum; Subsequently, the P hleg- matisierungs- and binder is mixed under the same conditions with the octogen. A pourable mass is obtained, which is poured under vacuum and under the influence of vibrations into molds in which the mass hardens over the course of a few days. High-performance explosive moldings which can be produced without pressure contain up to 90% by weight (based on the total weight = 100) of octogen.
Ein ähnliches Verfahren (FR-Veröffentlichung Nr. 2 225 979) verwendet ein Zweikomponenten-Bindemittel aus Diisocyanaten und Polyolen; jedoch liegen bei den erhaltenen Hochleistungssprengstoff-Formkörpern die Mengenanteile von Octogen unter 90 Gew.-% (bezogen auf das Gesamtgewicht = 100).A similar process (FR Publication No. 2 225 979) uses a two-component binder made from diisocyanates and polyols; however, in the high-performance explosive moldings obtained, the proportions of octogen are below 90% by weight (based on the total weight = 100).
Das bekannte Verfahren ist dadurch umständlich, dass das Phlegmatisierungs- und Bindemittel und das Octogen unter Vakuum bei erhöhter Temperatur in einer Kneteinrichtung gemischt werden müssen und der anschliessende Giessvorgang ebenfalls unter Vakuum durchgeführt werden muss. Dabei müssen zusätzlich Vibrationen zur Einwirkung gebracht werden, um die gewünschte Homogenität zu erreichen. Die Härtezeiten von mehreren Tagen für das Phlegmatisierungs- und Bindemittel machen das ganze Verfahren zusätzlich zeitaufwendig. Der so schliesslich erhaltene Hochleistungssprengstoff-Formkörper enthält aber immer noch mehr als 10 % Fremdstoffe, und seine Sprengkraft ist daher gegenüber der des reinen Octogens erheblich vermindert.The known method is cumbersome in that the desensitizing and binding agent and the octogen have to be mixed under vacuum at elevated temperature in a kneading device and the subsequent casting process must also be carried out under vacuum. In addition, vibrations must be brought into effect in order to achieve the desired homogeneity. The hardening times of several days for the desensitizing and binding agent additionally make the whole process time-consuming. The high-performance explosive molded article thus obtained still contains more than 10% foreign matter, and its explosive power is therefore considerably reduced compared to that of the pure octogen.
Es ist bekannt, Hexogen (Cyclotrimethylentrinitramin) mit einer wässrigen Suspension von Polytetrafluorethylen umzusetzen; das warm getrocknete Umsetzungsprodukt besteht aus 97 Gew.-% Cyclotrimethylentrinitramin und 3 Gew.-% Polytetrafluorethylen (jeweils bezogen auf das Gesamtgewicht = 100) und ist bereits unter geringem Druck plastisch verformbar (DE-AS 1 571 227). Die Wirkung des Polytetrafluorethylens wird auf die niedrige Reibung zwischen den damit überzogenen Sprengstoffpartikeln zurückgeführt. Die geringe Haftung zwischen den Sprengstoffpartikeln bewirkt jedoch, dass daraus hergestellte Formkörper keine hinreichende Formbeständigkeit aufweisen.It is known to react hexogen (cyclotrimethylene trinitramine) with an aqueous suspension of polytetrafluoroethylene; the warm dried reaction product consists of 97% by weight of cyclotrimethylene trinitramine and 3% by weight of polytetrafluoroethylene (in each case based on the total weight = 100) and is plastically deformable even under low pressure (DE-AS 1 571 227). The effect of polytetrafluoroethylene is attributed to the low friction between the explosive particles coated with it. However, the low adhesion between the explosive particles means that molded articles produced from them do not have sufficient dimensional stability.
Es ist weiterhin bekannt, Graphit oder Talkum als Gleitmittel für Nitropentaerythrit (PETN) in Anteilen von 0,3 bis 5 % zu verwenden, wobei die Mischung auch in wässriger Suspension erfolgen kann. Zur Beseitigung elektrostatischer Aufladungen, u.a. bei Octogen, werden jedoch Spezialrusse mit einem spezifischen Widerstand unter 1 Ohm cm und einer spezifischen Oberfläche über 20 m2/g empfohlen, die in Anteilen von bis zu 0,5 % auf die Oberfläche der Sprengstoffe aufgebracht werden (DE-OS 14 46 875).It is also known to use graphite or talc as a lubricant for nitropentaerythritol (PETN) in proportions of 0.3 to 5%, it also being possible to mix in aqueous suspension. To remove electrostatic charges, including those from Octogen, special carbon blacks with a specific resistance of less than 1 Ohm cm and a specific surface area of over 20 m 2 / g are recommended, which are applied to the surface of the explosives in proportions of up to 0.5% ( DE-OS 14 46 875).
Die Aufgabe der Erfindung besteht darin, einen Hochleistungssprengstoff der vorgenannten Art zu schaffen, dessen Wirksamkeit an die des reinen Octogens heranreicht und der bei hoher mechanischer Festigkeit hohe Sicherheit in der Handhabung besitzt, und ein mit einfacher Mitteln durchführbares Verfahren zu seiner Herstellung und Verarbeitung anzugeben.The object of the invention is to provide a high-performance explosive of the aforementioned type, the effectiveness of which is close to that of the pure octogen and which has high mechanical strength with high safety in handling, and to provide a process which can be carried out with simple means for its production and processing.
Unter Handhabungssicherheit wird dabei unter anderem sowohl die Gefahrlosigkeit bei der Herstellung und Verarbeitung, als auch die Unempfindlichkeit gegen äussere Einwirkungen im Gebrauch, wie die Formbeständigkeit (z.B. unter Schockeinwirkungen beim Abschuss) und mechanische Festigkeit daraus hergestellter Formkörper, verstanden.Handling safety is understood to mean, among other things, both the harmlessness during manufacture and processing, as well as the insensitivity to external influences in use, such as the dimensional stability (e.g. under the effects of shocks when fired) and mechanical strength of molded articles made therefrom.
Diese Aufgabe wird nach dem erfindungsgemässen Verfahren dadurch gelöst, dass eine wässrige Polymerdispersion in Anwesenheit von Hilfs- und Zusatzstoffen mit einem Gleitmittel, mit einer wässrigen Paraffindispersion und mit einem Füllstoff gemischt wird, dass die so erhaltene wässrige Dispersion des Phlegmatisierungs- und Bindemittels mit dem trockenen Sprengstoff vermengt und dass das so erhaltene Gemenge warm getrocknet wird.This object is achieved according to the inventive method in that an aqueous polymer dispersion in Anwe The mixture of auxiliaries and additives is mixed with a lubricant, with an aqueous paraffin dispersion and with a filler, such that the aqueous dispersion of the desensitizing and binding agent thus obtained is mixed with the dry explosive and that the mixture obtained is dried warm.
Das erfindungsgemässe Verfahren benutzt wässrige Dispersionen des Polymeren und anderer Bestandteile des Phlegmatisierungs- und Bindemittels, so dass diese mit einfachen Mitteln bei Raumtemperatur und unter Normaldruck in kürzester Zeit untereinander und mit weiteren Bestandteilen des Phlegmatisierungs- und Bindemittels vollständig durchmischt werden können. Die wässrige Dispersion des Phlegmatisierungs- und Bindemittels wird anschliessend mit dem Octogen in einer Mischtrommel in sehr kurzer Zeit, ebenfalls bei Raumtemperatur und unter Normaldruck, wirksam verbunden; das so erhaltene Produkt wird auf ebenfalls sehr einfache Weise durch einen warmen Luftstrom getrocknet. Das trockene Produkt ist trotz seines hohen Mengenanteils an Octogen (97 Gew.-% bezogen auf das Gesamtgewicht = 100) in hohem Masse handhabungssicher.The process according to the invention uses aqueous dispersions of the polymer and other constituents of the desensitizing and binding agent, so that these can be completely mixed with one another and with further constituents of the desensitizing and binding agent in a very short time using simple means at room temperature and under normal pressure. The aqueous dispersion of the desensitizing and binding agent is then effectively combined with the octogen in a mixing drum in a very short time, also at room temperature and under normal pressure; the product thus obtained is dried in a very simple manner by a warm air stream. Despite its high proportion of octogen (97% by weight based on the total weight = 100), the dry product is very safe to use.
Vorteilhafte Ausbildungen des Verfahrens sind in abhängigen Ansprüchen gekennzeichnet.Advantageous developments of the method are characterized in the dependent claims.
In einer Variante des erfindungsgemässen Verfahrens kann die wässrige Polymerdispersion durch Vermischen einer wässrigen Dispersion von Poly-O-butylacrylat (ein Polyacrylsäurebutylester) mit einer wässrigen Dispersion von Polyethylen hergestellt und 5 bis 15 Gew.-% Polyethylen (bezogen auf das Gewicht des Poly-O-butylacrylats) mit einer mittleren Teilchengrösse von 0,1 bis 0,3 pm zugegeben werden; dabei können nacheinander Polytetrafluorethylen als Gleitmittel, hochdisperses Kieselgel, Paraffin und Calciumcarbonat einer Teilchengrösse von annähernd 1 pm als Füllstoff zugegeben werden.In a variant of the process according to the invention, the aqueous polymer dispersion can be prepared by mixing an aqueous dispersion of poly-O-butyl acrylate (a butyl polyacrylic acid) with an aqueous dispersion of polyethylene and 5 to 15% by weight of polyethylene (based on the weight of the poly-O butyl acrylate) with an average particle size of 0.1 to 0.3 pm are added; polytetrafluoroethylene as a lubricant, highly disperse silica gel, paraffin and calcium carbonate with a particle size of approximately 1 pm can be added in succession as filler.
Als Füllstoff werden dabei schwerlösliche Verbindungen der Erdalkaligruppe wie Magnesiumpyrophosphat, Calciumcarbonat, Calciumsulfat und Bariumsulfat zugesetzt.Poorly soluble compounds of the alkaline earth group, such as magnesium pyrophosphate, calcium carbonate, calcium sulfate and barium sulfate, are added as fillers.
In einer zweiten Variante des erfindungsgemässen Verfahrens, nach der ein antistatischer Hochleistungssprengstoff erhalten wird, kann die wässrige Polymerdispersion aus Poly-O-alkylacrylat oder Poly-0-alkylmethacrylat (Polymethacrylsäurealkylester) mit einer Alkylgruppe von wenigstens 3 Kohlenstoffatomen hergestellt werden und vorzugsweise Poly-O-butylacrylat oder -isobutylacrylat enthalten. Dabei können eine erste, einen Teil des Polymers, Graphit als Gleitmittel und einen Teil des Paraffins enthaltende Komponente und eine zweite, Calciumsulfat als Füllstoff, das hochdisperse Kieselgel und den Rest des Paraffins enthaltende Komponente miteinander und dann mit einer dritten Komponente der wässrigen Dispersion des Phlegmatisierungs- und Bindemittels vermischt werden, die Cyclohexanon und den Rest des Polymers in einer Isopropanol-Wasser-Mischung enthält.In a second variant of the method according to the invention, according to which an antistatic high-performance explosive is obtained, the aqueous polymer dispersion can be prepared from poly-O-alkyl acrylate or poly-0-alkyl methacrylate (polymethacrylic acid alkyl ester) with an alkyl group of at least 3 carbon atoms and preferably poly-O- contain butyl acrylate or isobutylacrylate. A first component containing part of the polymer, graphite as a lubricant and part of the paraffin and a second component containing calcium sulfate as a filler, the highly disperse silica gel and the rest of the paraffin can be used together and then with a third component of the aqueous dispersion of the desensitization - And binder are mixed, which contains cyclohexanone and the rest of the polymer in an isopropanol-water mixture.
Bei der zweiten Variante des erfindungsgemässen Verfahrens hat sich in der Praxis überraschenderweise herausgestellt, dass unabhängig von der Partikelgrösse des verwendeten Octogens eine völlig gleichmässige Verteilung des Phlegmatisierungs- und Bindemittels über die Octogenpartikel dadurch erzielt werden kann, dass das Gemenge aus Phlegmatisierungs-und Bindemittel mit Octogen unter Umwälzung vorgetrocknet, anschliessend in einer Mischtrommel mit 2 bis 10 Gew.-% (bezogen auf das Gewicht des Gemenges = 100) Alkanol-Wasser bevorzugt Isopropanol-Wasser (1 : 1-Gemisch) nachbehandelt und danach unter Umwälzen getrocknet wird.In practice, in the second variant of the method according to the invention, it has surprisingly been found that, regardless of the particle size of the octogen used, a completely uniform distribution of the desensitizing and binding agent over the octogen particles can be achieved in that the mixture of desensitizing and binding agent with octogen pre-dried with circulation, then treated in a mixing drum with 2 to 10% by weight (based on the weight of the batch = 100) alkanol-water, preferably isopropanol-water (1: 1 mixture) and then dried with circulation.
Der kunststoffgebundene Hochleistungssprengstoff nach der Erfindung löst die vorgenannte Aufgabe dadurch, dass das Phlegmatisierungs- und Bindemittel ein Polymer auf Polyacrylat- oder Polymethacrylatbasis, ein Gleitmittel und einen Füllstoff enthält. Der Füllstoff in dem Phlegmatisierungs-und Bindemittel des erfindungsgemässen kunststoffgebunden Hochleistungssprengstoffs ist aus schwerlöslichen Verbindungen der Erdalkaligruppe ausgewählt und ist vorzugsweise Magnesiumpyrophosphat, Calciumcarbonat, Calciumsulfat oder Bariumsulfat.The plastic-bound high-performance explosive according to the invention achieves the aforementioned object in that the desensitizing and binding agent contains a polymer based on polyacrylate or polymethacrylate, a lubricant and a filler. The filler in the desensitization and binder of the plastic-bound high-performance explosive according to the invention is selected from poorly soluble compounds of the alkaline earth group and is preferably magnesium pyrophosphate, calcium carbonate, calcium sulfate or barium sulfate.
Dabei kann das Polymer ein Poly-O-alkylacrylat oder Poly-O-alkylmethacrylat,-vorzugsweise Poly-O-butylacrylat oder -isobutylacrylat, sein und der Hochleistungssprengstoff mit einem Phlegmatisierungs- und Bindemittel aus 18 bis 50 Gew.-% Poly-O-butylacrylat, 0,9 bis 8 Gew.-% Polyethylen, 2 bis 7 Gew.-% Polytetrafluorethylen, 20 bis 65 Gew.-% Calciumcarbonat, 0,3 bis 2,3 Gew.-% Kieselgel und 3,2 bis 20 Gew.-% Paraffin versehen sein.The polymer can be a poly-O-alkyl acrylate or poly-O-alkyl methacrylate, preferably poly-O-butyl acrylate or isobutylacrylate, and the high-performance explosive with a desensitizing and binding agent composed of 18 to 50% by weight of poly-O- butyl acrylate, 0.9 to 8% by weight of polyethylene, 2 to 7% by weight of polytetrafluoroethylene, 20 to 65% by weight of calcium carbonate, 0.3 to 2.3% by weight of silica gel and 3.2 to 20% by weight .-% paraffin.
Eine antistatische Variante des erfindungsgemässen Hochleistungssprengstoffs kann mit einem Phlegmatisierungs- und Bindemittel aus 18 bis 50 Gew.-% Poly-O-butylacrylat, 25 bis 65 Gew.-% Graphit einer mittleren Korngrösse von 2,5 ,um und einer Korngrössenverteilung entsprechend 95 % unter 5 um, 12 bis 25 Gew.-% Calciumsulfat, 0,3 bis 2,3 Gew.-% Kieselgel und 3,5 bis 20 Gew.-% Paraffin versehen sein.An antistatic variant of the high-performance explosive according to the invention can be made with a desensitizing and binding agent composed of 18 to 50% by weight of poly-O-butyl acrylate, 25 to 65% by weight of graphite with an average grain size of 2.5 μm and a grain size distribution corresponding to 95% less than 5 µm, 12 to 25% by weight calcium sulfate, 0.3 to 2.3% by weight silica gel and 3.5 to 20% by weight paraffin.
Die vorgenannte Aufgabe wird hinsichtlich des Verfahrens zur Weiterverarbeitung nach der Erfindung dadurch gelöst, dass der Hochleistungssprengstoff in der Form bei Raumtemperatur mit einem Druck im Bereich über 1,5 kbar gepresst wird. Der nach der Erfindung hergestellte Hochleistungssprengstoff kann somit durch Kaltpressen zu Formkörpern, beispielsweise auch Hohlladungen, verarbeitet werden. Dieses besonders einfache Verfahren ist bisher bei Sprengstoffen mit hohen Mengenanteilen an Octogen noch nicht mit Erfolg angewendet worden.The aforementioned object is achieved with regard to the method for further processing according to the invention in that the high-performance explosive is pressed in the mold at room temperature with a pressure in the range above 1.5 kbar. The high-performance explosive manufactured according to the invention can thus be processed by cold pressing to give shaped articles, for example also shaped charges. This particularly simple method has not yet been used successfully with explosives with high proportions of octogen.
Es ist bekannt, aus einem Sprengstoff, der 95 Gew.-% Cyclotrimethylentrinitramin und 5 Gew.-% Wachs (jeweils bezogen auf das Gesamtgewicht = 100) enthält, Presskörper unter einem Pressdruck von 1,2 kbar herzustellen (DE-OS 24 34 252).It is known, from an explosive which contains 95% by weight of cyclotrimethylene trinitramine and 5% by weight of wax (in each case based on the total weight = 100), pressed bodies under egg to produce a pressing pressure of 1.2 kbar (DE-OS 24 34 252).
Die nach der Erfindung hergestellten Formkörper haben Dichten über 1,8 g/cm3 und Detonationsgeschwindigkeiten über 8,6 km/s. Sie haben eine verbesserte mechanische Festigkeit und Homogenität und sind in weiteren Grenzen als erwartet schlag- oder reibungsunempfindlich; sie sind auch thermisch stabil und in besonderem Umfang druckfest und beschusssicher.The molded articles produced according to the invention have densities above 1.8 g / cm 3 and detonation speeds above 8.6 km / s. They have improved mechanical strength and homogeneity and are less sensitive to impact or friction than expected; they are also thermally stable and, to a particular extent, are pressure-resistant and bulletproof.
Für die Zusammensetzung des Bindemittels ist von wesentlicher Bedeutung, dass das Poly-O-butylacrylat die Haftung zwischen den Sprengstoffpartikeln in für die Weiterverarbeitung und für die Formbeständigkeit des letztlich hergestellten Formkörpers ausreichender Weise erhöht. Das Polyethylen verbessert die mechanischen Eigenschaften des Kunststoff-Films bezüglich seiner phlegmatisierenden Wirkung. Beide Polymeren sind bisher nicht als Bindemittel für Octogen bekannt. Das an sich als Gleitmittel bekannte Polytetrafluorethylen ist in einem auf die vorgenannten Bestandteile abgestimmten Mengenanteil vorhanden, der gerade so hoch gewählt ist, dass die Formbeständigkeit des letztlich hergestellten Formkörpers nicht beeinträchtigt wird, der Formkörper aber glatt und ohne Beschädigungen nach der Formgebung aus der Form entnommen werden kann.It is essential for the composition of the binder that the poly-O-butyl acrylate increases the adhesion between the explosive particles in a sufficient manner for further processing and for the dimensional stability of the molded article ultimately produced. The polyethylene improves the mechanical properties of the plastic film with regard to its desensitizing effect. Neither polymer is known to date as a binding agent for octogen. The polytetrafluoroethylene, known per se as a lubricant, is present in a proportion which is matched to the abovementioned constituents and is chosen so high that the dimensional stability of the ultimately produced shaped body is not impaired, but the shaped body is removed from the mold smoothly and without damage after shaping can be.
Graphit, insbesondere bei mittleren Partikelgrössen von 2,5 µm und Partikelgrössenverteilungen entsprechend 95 % unter 5 ,um, unterstützt die phlegmatisierende Wirkung des Paraffins und verhindert die elektrostatische Aufladung der Sprengstoffpartikel; dabei wirkt er auch als Gleitmittel und ist in seiner Menge gerade so gewählt, dass die Formbeständigkeit des letztlich hergestellten Formkörpers nur unwesentlich beeinträchtigt wird, der Formkörper aber glatt und ohne Beschädigungen nach der Formgebung aus der Form entnommen werden kann.Graphite, especially with average particle sizes of 2.5 µm and particle size distributions corresponding to 95% below 5 µm, supports the desensitizing effect of the paraffin and prevents electrostatic charging of the explosive particles; it also acts as a lubricant and its amount is chosen so that the dimensional stability of the molded article ultimately produced is only insignificantly impaired, but the molded article can be removed from the mold smoothly and without damage after shaping.
Auch hat sich in der Praxis unerwarteterweise ergeben, dass besonders formbeständige Formkörper und insbesondere verhältnismässig wenig schlagempfindliche Formkörper dadurch erhalten werden, dass das Octogen eine Partikelgrösse von weniger als 1,68 mm, vorzugsweise weniger als 0,5 mm, hat.In practice, it has also unexpectedly emerged that particularly dimensionally stable moldings and, in particular, comparatively little impact-sensitive moldings are obtained in that the octogen has a particle size of less than 1.68 mm, preferably less than 0.5 mm.
Der aus schwerlöslichen Verbindungen der Erdalkaligruppe ausgewählte Füllstoff wird zunächst zugesetzt, um die Rieselfähigkeit der Partikeln des Hochleistungssprengstoffs zu erhöhen und deren gegenseitige Haftung durch den Bindemittelüberzug zu erniedrigen. Überraschenderweise hat sich jedoch gezeigt, dass ein solcher Füllstoff im Gegensatz zu anderen Weisspigmenten eine erhebliche phlegmatisierende Wirkung hat, die in Verbindung mit den vorgenannten Polymeren erst die sichere Handhabung von Hochleistungssprengstoffen mit Octogen-Mengenanteilen über 90 Gew.-% ermöglicht. Darüberhinaus wird durch diesen Zusatz unerwarteterweise auch die mechanische Festigkeit der aus dem Hochleistungssprengstoff hergestellten Formkörper vergrössert.The filler selected from poorly soluble compounds of the alkaline earth group is first added in order to increase the flowability of the particles of the high-performance explosive and to reduce their mutual adhesion through the binder coating. Surprisingly, however, it has been shown that, in contrast to other white pigments, such a filler has a considerable desensitizing effect which, in conjunction with the aforementioned polymers, enables safe handling of high-performance explosives with octogen proportions of more than 90% by weight. In addition, this addition unexpectedly increases the mechanical strength of the molded articles made from the high-performance explosive.
Nachfolgend werden die Herstellung eines erfindungsgemässen Hochleistungssprengstoffs und die Eigenschaften daraus hergestellter Formkörper anhand von Ausführungsbeispielen im einzelnen erläutert und beschrieben.The manufacture of a high-performance explosive according to the invention and the properties of moldings produced therefrom are explained and described in detail below using exemplary embodiments.
Der kunststoffgebundene Hochleistungssprengstoff mit Polytetrafluorethylen als Gleitmittel enthält 3 bis 10 Gew.-% des Phlegmatisierungs- und Bindemittels, das im wesentlichen aus 20 bis 50 Gew.-% Poly-O-alkylacrylat, 0,9 bis 8 Gew.-% Polyethylen, 2 bis 7 Gew.-% Polytetrafluorethylen, bis zu 65 Gew.-% Füllstoff, mindestens 0,3 Gew.-% Kieselgel und 8 bis 20 Gew.-% Paraffin zusammengesetzt ist. Der Füllstoff besteht aus einer schwerlöslichen Erdalkaliverbindung wie Magnesiumpyrophosphat, Calciumcarbonat, Calciumsulfat, Bariumsulfat. Das Magnesiumpyrophosphat wird aus wässriger Lösung durch Zusammengeben stöchiometrischer Mengen Natriumpyrophosphat und Magnesiumsulfat gefällt, abfiltriert und getrocknet, die übrigen sind handelsübliche Produkte. Ein bevorzugtes Ausführungsbeispiel mit 4 Gew.-% Phlegmatisierungs- und Bindemittel wird folgendermassen erhalten:The plastic-bound high-performance explosive with polytetrafluoroethylene as a lubricant contains 3 to 10% by weight of the desensitizing and binding agent, which essentially consists of 20 to 50% by weight of poly-O-alkyl acrylate, 0.9 to 8% by weight of polyethylene, 2 up to 7% by weight of polytetrafluoroethylene, up to 65% by weight of filler, at least 0.3% by weight of silica gel and 8 to 20% by weight of paraffin. The filler consists of a poorly soluble alkaline earth compound such as magnesium pyrophosphate, calcium carbonate, calcium sulfate, barium sulfate. The magnesium pyrophosphate is precipitated from aqueous solution by combining stoichiometric amounts of sodium pyrophosphate and magnesium sulfate, filtered off and ge dries, the rest are commercially available products. A preferred embodiment with 4% by weight of desensitizing and binding agent is obtained as follows:
39 kg einer handelsüblichen wässrigen Dispersion von Poly-O-butylacrylat (24 Gew.-% entsprechend 9,3 kg Poly-O-butylacrylat) werden unter Rühren mit 8 1 Wasser verdünnt und zunächst mit 0,7 kg eines Entschäumers auf Silikonbasis (10 Gew.-% entsprechend 0,07 kg) und 0,3 kg eines Netzmittels auf Alkanolpolyglykoletherbasis versetzt. Es wird bis zur Homogenität der Mischung gerührt; dann werden 3,4 kg einer handelsüblichen wässrigen Polyethylendispersion (35 Gew.-% entsprechend 1,2 kg Polyethylen) unter weiterem Rühren zugefügt.39 kg of a commercially available aqueous dispersion of poly-O-butyl acrylate (24% by weight corresponding to 9.3 kg of poly-O-butyl acrylate) are diluted with 8 l of water with stirring and initially with 0.7 kg of a silicone-based defoamer (10 % By weight corresponding to 0.07 kg) and 0.3 kg of an alkanol polyglycol ether-based wetting agent. The mixture is stirred until it is homogeneous; 3.4 kg of a commercially available aqueous polyethylene dispersion (35% by weight, corresponding to 1.2 kg of polyethylene) are then added with further stirring.
Bei hinreichend niedriger Rührgeschwindigkeit (zur Vermeidung des Ausflockens) werden 2,5 kg einer handelsüblichen wässrigen Dispersion von Polytetrafluorethylen (60 Gew.-% entsprechend 1,5 kg Polytetrafluorethylen; Teilchengrösse 0,05 bis 0,5 nm) zugegeben. Anschliessend wird mit 0,5 kg eines handelsüblichen kolloiden Kieselgels (mittlere Teilchengrösse 12 nm) versetzt, und zwar portionsweise und bei niedriger Rührgeschwindigkeit bis zu dessen völliger Benetzung und dann bei hoher Rührgeschwindigkeit bis zur völligen Verteilung eventuell gebildeter Klumpen.If the stirring speed is sufficiently low (to avoid flocculation), 2.5 kg of a commercially available aqueous dispersion of polytetrafluoroethylene (60% by weight corresponding to 1.5 kg of polytetrafluoroethylene; particle size 0.05 to 0.5 nm) are added. Then 0.5 kg of a commercially available colloidal silica gel (average particle size 12 nm) is added, in portions and at a low stirring speed until it is completely wetted and then at a high stirring speed until the complete formation of any lumps that may have formed.
Nach Zusatz des Kieselgels werden unter starkem Rühren, aber unter Vermeidung von Schaumbildung, 15 kg einer wässrigen Paraffindispersion zugesetzt (s.w.u.; 24 Gew.-% entsprechend 3,6 kg Paraffin (handelsüblich, Fp. ca. 52 °C) und 6 Gew.-% entsprechend 0,9 kg eines handelsüblichen Emulgiermittels auf Alkylpolyglykoletherbasis).After addition of the silica gel, 15 kg of an aqueous paraffin dispersion are added with vigorous stirring, but avoiding the formation of foam (swu; 24% by weight corresponding to 3.6 kg of paraffin (commercially available, mp. Approx. 52 ° C.) and 6% by weight. -% corresponding to 0.9 kg of a han commercially available emulsifier based on alkyl polyglycol ether).
Der so erhaltenen Mischung werden 25 kg Calciumcarbonat (Teilchengrösse i ,um, entsprechend der österreichischen oder belgischen Pharmakopoe ÖAB9 bzw. Ph.Belg.V) zugegeben; dabei wird zunächst mit geringer Rührgeschwindigkeit gearbeitet und diese dann mit abnehmender Viskosität der anfangs breiartigen Masse zunehmend erhöht, bis eine dünnflüssige Mischung erhalten wird.25 kg of calcium carbonate (particle size i, um, corresponding to the Austrian or Belgian pharmacopoeia ÖAB9 or Ph.Belg.V) are added to the mixture thus obtained; the first step is to work with a slow stirring speed and then to increase the viscosity of the initially pulpy mass until the mixture is thin.
Schliesslich werden der Dispersion noch 1,1 kg handelsüblicher Natriumcarboxymethylcellulose und 4,5 1 destilliertes Wasser hinzugefügt, und es wird dann weiter bis zur völligen Homogenität gerührt. Die ganze Mischung lässt man vorteilhafterweise noch ein Drei-Walzen-Mischwerk passieren, wodurch die Viskosität und die Schaumbildung günstig beeinflusst werden. Danach ist die Bindemitteldispersion nach weiteren 24 Stunden "Reifezeit" gebrauchsfertig.Finally, 1.1 kg of commercially available sodium carboxymethyl cellulose and 4.5 l of distilled water are added to the dispersion, and stirring is continued until it is completely homogeneous. The entire mixture is advantageously passed through a three-roller mixer, which has a favorable effect on the viscosity and foam formation. After that, the binder dispersion is ready for use after a further 24 hours of "maturing time".
6 kg handelsüblichen Paraffins (Fp. ca. 52 °C) werden unter Zugabe von 1,5 kg eines handelsüblichen Emulgiermittels auf Aklkylpolyglykoletherbasis geschmolzen, die Schmelze wird gut durchmischt und auf 95 °C erwärmt. Diese Mischung wird anschliessend portionenweise in 17,5 kg destilliertes Wasser von 85 °C eingerührt. Es wird bis zur Bildung einer homogenen Dispersion gerührt und danach erfolgt unter weiterem Rühren ein Abkühlen auf unterhalb 40 °C. Nach einem Tag weiterer "Reife" ist die wässrige Paraffindispersion gebrauchsfertig.6 kg of commercially available paraffins (mp. Approx. 52 ° C.) are melted with the addition of 1.5 kg of a commercially available emulsifier based on alkyl polyglycol ether, the melt is mixed well and heated to 95 ° C. This mixture is then stirred in portions into 17.5 kg of distilled water at 85 ° C. The mixture is stirred until a homogeneous dispersion is formed and then cooled to below 40 ° C. with further stirring. After a day of further "ripening", the aqueous paraffin dispersion is ready for use.
10 kg trockenes Octogen werden mit 1 kg der wässrigen Dispersion des Phlegmatisierungs- und Bindemittels versetzt. Die Masse wird zunächst von Hand umgewälzt und dann 10 min in einer Mischtrommel üblicher Bauart durchmischt. Die Mischung wird der Mischtrommel entnommen, flach ausgebreitet und unter gelegentlichem Umwälzen durch Überleiten eines warmen Luftstroms getrocknet.10 kg of dry octogen are mixed with 1 kg of the aqueous dispersion of the desensitizing and binding agent puts. The mass is first circulated by hand and then mixed for 10 minutes in a mixing drum of the usual type. The mixture is removed from the mixing drum, spread out flat and, with occasional circulation, dried by passing a warm air stream over it.
Der gemäss Punkt 2. erhaltene Hochleistungssprengstoff wird in Formen üblicher Bauart unter einem Druck im Bereich von 1,5 bis 4,2 kbar kalt gepresst. Ein Druck von ca. 3,5 kbar ergibt dabei optimale Ergebnisse, insbesondere in bezug auf die erzielte Sicherheit und Leistung.The high-performance explosive obtained in accordance with point 2 is cold-pressed in molds of conventional design under a pressure in the range from 1.5 to 4.2 kbar. A pressure of approx. 3.5 kbar gives optimal results, especially with regard to the safety and performance achieved.
Die Formkörper haben eine Dichte von 1,81 g/cm3 und darüber. Detonationsgeschwindigkeit: 8,6 km/s.The moldings have a density of 1.81 g / cm 3 and above. Detonation speed: 8.6 km / s.
Die Schlagempfindlichkeit wurde mit der Fallhammer-Methode n-ch Koenen und Ide untersucht. Mit einem 2 kg-Fallhammer und 10 mm3-Proben wurden nur vereinzelte, schwache Reaktionen bei einer Fallhöhe von 25 cm und weniger als 30 % bzw. 50 % Reaktionen bei 30 bzw. 35 cm Fallhöhe beobachtet. Mit einem 5 kg-Fallhammer und 40 mm3 Proben wurden keine Reaktionen bei 30 cm Fallhöhe beobachtet, bei 35 cm traten nur vereinzelt Reaktionen auf und bei 40 cm traten 0 - 20 % Reaktionen auf.The impact sensitivity was examined with the drop hammer method n-ch Koenen and Ide. With a 2 kg drop hammer and 10 mm 3 samples, only isolated, weak reactions were observed at a drop height of 25 cm and less than 30% or 50% reactions at 30 or 35 cm drop height. With a 5 kg drop hammer and 40 mm 3 samples, no reactions were observed at a fall height of 30 cm, only occasional reactions occurred at 35 cm and 0 - 20% reactions occurred at 40 cm.
Bei der Prüfung der Reibungsempfindlichkeit mit dem Peters-Apparat wurden keine Reaktionen bei Reibstiftbelastungen von 12 kg beobachtet, und zwischen 14 - 16 kg traten nur vereinzelt Anbrennreaktionen auf.When testing the sensitivity to friction with the Peters apparatus, no reactions were observed at rubbing pin loads of 12 kg, and there were only occasional burn-on reactions between 14 and 16 kg.
Die Druckfestigkeit wurde an Sprengstoffpresskörpern mit der Form eines gleichseitigen Zylinders (Durchmesser = Höhe) von 20 mm , 40 mm und 60 mm gemessen und ist mit über 100 kg/cm2 mindestens doppelt so hoch wie bei Formkörpern aus herkömmlichen Sprengstoffen.The compressive strength was measured on explosive compacts with the shape of an equilateral cylinder (diameter = height) of 20 mm, 40 mm and 60 mm and is with over 100 kg / cm 2 at least twice as high as for molded articles made from conventional explosives.
Der antistatische kunststoffgebundene Hochleistungssprengstoff mit Graphit als Gleitmittel enthält 3 bis 10 Gew.-% des Phlegmatisierungs- und Bindemittels, das im wesentlichen aus 18 bis 40 Gew.-% Poly-O-butylacrylat, 25 bis 65 Gew.-% Graphit, 12 bis 25 Gew.-% Füllstoff, mindestens 0,3 Gew.-% Kieselgel und 7 bis 17 Gew.-% Paraffin zusammengesetzt ist. Der Füllstoff besteht aus einer schwerlöslichen Erdalkaliverbindung wie Magnesiumpyrophosphat, Calciumcarbonat, Calciumsulfat, Bariumsulfat. Das Magnesiumpyrophosphat wird aus wässriger Lösung durch Zusammengeben stöchiometrischer Mengen Natriumpyrophosphat und Magnesiumsulfat gefällt, abfiltriert und getrocknet, die übrigen sind handelsübliche Produkte. Ein bevorzugtes Ausführungsbeispiel mit 4,3 Gew.-% Phlegmatisierungs- und Bindemittel wird folgendermassen erhalten:The antistatic plastic-bound high-performance explosive with graphite as a lubricant contains 3 to 10% by weight of the desensitizing and binding agent, which essentially consists of 18 to 40% by weight of poly-O-butyl acrylate, 25 to 65% by weight of graphite, 12 to 25% by weight of filler, at least 0.3% by weight of silica gel and 7 to 17% by weight of paraffin is composed. The filler consists of a poorly soluble alkaline earth compound such as magnesium pyrophosphate, calcium carbonate, calcium sulfate, barium sulfate. The magnesium pyrophosphate is precipitated from an aqueous solution by combining stoichiometric amounts of sodium pyrophosphate and magnesium sulfate, filtered off and dried, the rest are commercially available products. A preferred embodiment with 4.3% by weight of desensitizing and binding agent is obtained as follows:
24,2 kg Wasser werden mit 0,5 kg eines Entschäumers auf Silikonbasis (10 Gew.-% entsprechend 0,05 kg) und danach mit 15 kg einer handelsüblichen wässrigen Dispersion von Poly-O-butylacrylat (24 Gew.-% entsprechend 3,6 kg Poly-O-butylacrylat) mit einem Intensivrührer bis zur Homogenität der Mischung dispergiert. Dann werden unter zusätzlicher Einwirkung von Ultraschall (Eintauchen eines an sich bekannten Ultraschallgerätes) 12,5 kg Graphit (K 2,5; Lonza; mittlere Teilchengrösse 2,5 µm; Teilchengrösseverteilung: 95 % < 5 pm), danach 2 kg einer wässrigen Paraffindispersion (s.w.u.) und schliesslich 0,3 kg handelsüblicher Natriumcarboxymethylcellulose unter gleichen Umständen der Dispersion zugefügt. Ungefähr 1 Stunde nach Zusatz des letzten Bestandteils liegt eine homogene Dispersion vor.24.2 kg of water are mixed with 0.5 kg of a silicone-based defoamer (10% by weight corresponding to 0.05 kg) and then with 15 kg of a commercially available aqueous dispersion of poly-O-butyl acrylate (24% by weight corresponding to 3 , 6 kg of poly-O-butyl acrylate) with an intensive stirrer until the mixture is homogeneous. Then, with the additional action of ultrasound (immersion of an ultrasound device known per se), 12.5 kg of graphite (K 2.5; Lonza; average particle size 2.5 μm; particle size distribution: 95% <5 pm), then 2 kg of an aqueous paraffin dispersion (swu) and finally 0.3 kg of commercially available sodium carboxymethyl cellulose same circumstances added to the dispersion. Approximately 1 hour after adding the last ingredient there is a homogeneous dispersion.
In 16,7 kg Wasser werden nacheinander unter Einwirkung eines eingetauchten Ultraschallgerätes und unter Anwendung eines Intensivrührers 0,03 kg eines Netzmittels auf Alkanolpolyglykoletherbasis, 0,2 kg eines Dispergiermittels z.B. auf Polyalkylenglykolbasis und 0,6 kg des unter Punkt 4a. genannten Entschäumers dispergiert. Anschliessend werden unter den gleichen Bedingungen nacheinander die folgenden Bestandteile zudispergiert: 5 kg Calciumsulfat (gefälltes Calciumsulfat purum oder p.a.; Fluka AG), 0,4 kg eines handelsüblichen kolloiden Kieselgels (mittlere Teilchengrösse 12 nm), 13,35 kg der unter Punkt 4a. genannten wässrigen Paraffindispersion (s.w.u.) und schliesslich 0,4 kg der handelsüblichen Natriumcarboxymethylcellulose. Ungefähr 1 Stunde nach Zusatz des letzten Bestandteils liegt eine homogene Dispersion vor.In 16.7 kg of water, 0.03 kg of an alkanol polyglycol ether-based wetting agent, 0.2 kg of a dispersing agent, e.g. based on polyalkylene glycol and 0.6 kg of the item 4a. mentioned defoamer dispersed. The following constituents are then dispersed in succession under the same conditions: 5 kg of calcium sulphate (precipitated calcium sulphate purum or p.a .; Fluka AG), 0.4 kg of a commercially available colloidal silica gel (average particle size 12 nm), 13.35 kg of that described under 4a. aqueous paraffin dispersion (see below) and finally 0.4 kg of the commercially available sodium carboxymethyl cellulose. Approximately 1 hour after adding the last ingredient there is a homogeneous dispersion.
Die nach Punkt 4a. und 4b. erhaltenen Komponenten werden zusammengegeben, auf ca. 35 °C erwärmt und miteinander vermischt. Diese Operation kann wegen der Zähigkeit des Produktes auch mit einer Knetvorrichtung ausgeführt werden. In der so erhaltenen Dispersion werden 0,4 kg der handelsüblichen Natriumcarboxymethylcellulose durch einen Intensivrührer homogen dispergiert, was nach ca. 1 Stunde der Fall ist.The according to point 4a. and 4b. components obtained are combined, heated to about 35 ° C and mixed together. Because of the toughness of the product, this operation can also be carried out with a kneading device. In the dispersion obtained in this way, 0.4 kg of the commercially available sodium carboxymethyl cellulose is homogeneously dispersed by an intensive stirrer, which is the case after about 1 hour.
Es werden dann nacheinander 0,6 kg Cyclohexanon und 8,3 kg einer handelsüblichen Dispersion von Poly-O-butylacrylat (40 Gew.-% entsprechend 3,3 kg Poly-O-butylacrylat) in Isopropanol-Nasser (Mischungsverhältnis 2 : 1) mit einem Intensivrührer zudispergiert. Stattdessen. kann aber auch eine vorbereitete dritte Komponente des Phlegmatisierungs- und Bindemittels, die aus 0,6 kg Cyclohexanon und 8,3 kg einer handelsüblichen Dispersion von Poly-O-butylacrylat (40 Gew.-% entsprechend 3,3 kg Poly-O-butylacrylat) in Isopropanol-Wasser (Mischungsverhältnis 2 : 1) besteht, dem Gemisch aus der ersten und zweiten Komponente des Phlegmatisierungs- und Bindemittels mit einem Intensivrührer zudispergiert werden. Der Rührvorgang wird nach 3 Stunden beendet und nach einem Tag für 1 Stunde wiederholt. Die Phlegmatisierungs-und Bindemitteldispersion ist dann gebrauchsfertig, muss aber vor dem Gebrauch gerührt werden.Then 0.6 kg of cyclohexanone and 8.3 kg of a commercially available dispersion of poly-O-butyl acrylate (40% by weight, corresponding to 3.3 kg of poly-O-butyl acrylate) in isopropanol-Nasser (mixing ratio 2: 1) with an intensive stirrer. Instead. can also be a prepared third component of the desensitizing and binding agent, which consists of 0.6 kg of cyclohexanone and 8.3 kg of a commercially available dispersion of poly-O-butyl acrylate (40% by weight corresponding to 3.3 kg of poly-O-butyl acrylate ) in isopropanol-water (mixing ratio 2: 1), the mixture of the first and second components of the desensitizing and binding agent are dispersed with an intensive stirrer. The stirring process is ended after 3 hours and repeated for 1 hour after one day. The desensitization and binder dispersion is then ready for use, but must be stirred before use.
3,7 kg handelsüblichen Paraffins (Fp. ca. 52 °C) werden unter Zugabe von 0,9 kg eines handelsüblichen Emulgiermittels auf Alkylpolyglykoletherbasis geschmolzen, die Schmelze wird gut durchmischt und auf 95 °C erwärmt. Diese Mischung wird anschliessend portionsweise in 10,5 kg destilliertes Wasser von 85 °C eingerührt. Es wird bis zur Bildung einer homogenen Dispersion gerührt und danach erfolgt unter weiterem Rühren ein Abkühlen auf unterhalb 40 °C. Nach einem Tag weiterer "Reife" ist die wässrige Paraffindispersion gebrauchsfertig.3.7 kg of commercially available paraffins (melting point approx. 52 ° C.) are melted with the addition of 0.9 kg of a commercially available emulsifier based on alkyl polyglycol ether, the melt is mixed well and heated to 95 ° C. This mixture is then stirred in portions in 10.5 kg of distilled water at 85 ° C. The mixture is stirred until a homogeneous dispersion is formed and then cooled to below 40 ° C. with further stirring. After a day of further "ripening", the aqueous paraffin dispersion is ready for use.
1,015 kg der wässrigen Phlegmatisierungs- und Bindemitteldispersion werden mit 7 kg trockenem Octogen versetzt und gleichmässig über den Sprengstoff verteilt. Anschliessend wird das Gemisch in einer Mischtrommel üblicher Bauart umgewälzt, und nach 10 min ist das Phlegmatisierungs- und Bindemittel homogen über den Sprengstoff verteilt. Die Mischung wird der Mischtrommel entnommen, flach ausgebreitet und unter gelegentlichem Umwälzen durch Überleiten eines warmen Luftstroms vorgetrocknet.1.015 kg of the aqueous desensitization and binder dispersion are mixed with 7 kg of dry octogen and evenly distributed over the explosive. The mixture is then circulated in a mixing drum of the usual type, and after 10 minutes the desensitizing and binding agent is homogeneously distributed over the explosive. The mixture is removed from the mixing drum, spread out flat and with occasional stirring pre-dried by passing a warm air stream.
Das vorgetrocknete Material wird in einer rotierenden Trommel mit 290 g Isopropanol-Wasser (Mischungsverhältnis 1 : 1) entsprechend ca. 4 Gew.-% versetzt und die Mischung 15 bis 30 min umgewälzt. Anschliessend wird die Mischung der Mischtrommel entnommen, flach ausgebreitet und unter gelegentlichem Umwälzen durch Überleiten eines warmen Luftstroms getrocknet.The predried material is mixed in a rotating drum with 290 g of isopropanol-water (mixing ratio 1: 1) corresponding to about 4% by weight and the mixture is circulated for 15 to 30 minutes. The mixture is then removed from the mixing drum, spread out flat and, with occasional circulation, dried by passing a warm air stream over it.
Die zuletzt genannten Vorgänge können gegebenenfalls und unter Beachtung einschlägiger Sicherheitsmassnahmen auch nach einem Fliessbettverfahren durchgeführt werden.The last-mentioned processes can also be carried out using a fluidized bed method, if necessary, taking into account relevant safety measures.
Der nach Punkt 5. erhaltene Hochleistungssprengstoff wird in Formen üblicher Bauart unter einem Druck im Bereich von 1,5 bis 4,2 kbar kalt gepresst. Drücke von 2,2 bis 3,5 kbar reichen normalerweise aus, doch können die Pressdrücke bei speziellen Anforderungen auch bei geformten Ladungen, Hochleistungsladungen, gesteigert werden.The high-performance explosive obtained in accordance with point 5 is cold-pressed in molds of conventional design under a pressure in the range from 1.5 to 4.2 kbar. Pressures of 2.2 to 3.5 kbar are usually sufficient, but the pressures can be increased for special requirements, even for shaped loads, high-performance loads.
Die Presskörper haben Dichten über 1,80 g/cm3. Die gemessenen Detonationsgeschwindigkeiten liegen bei 8,6 km/s und darüber.The compacts have densities above 1.80 g / cm 3 . The measured detonation speeds are 8.6 km / s and above.
Die Schlagempfindlichkeit wurde mit der Fallhammer-Methode nach Koenen und Ide untersucht. Dabei waren die Ergebnisse bei Partikelgrössen unter 0,5 mm besonders günstig: Mit einem 2 kg-Fallhammer bei einem Sprengstoffvolumen von 10 mm3 und mit einem 5 kg-Fallhammer bei einem Sprengstoffvolumen von 40 mm3 wurden auch bei Fallhöhen von 40 bzw. 60 cm keine Reaktionen beobachtet.The impact sensitivity was examined with the monkey method according to Koenen and Ide. The results were particularly favorable for particle sizes below 0.5 mm: with a 2 kg drop hammer with an explosive volume of 10 mm 3 and with a 5 kg drop hammer with an explosive volume of 40 mm 3 , even with drop heights of 40 or 60 cm no reactions observed.
Die Druckfestigkeit wurde an Sprengstoffpresskörpern (Pressdruck 1,9 bis 4,2 t/cm2) mit der Form eines gleichseitigen Zylinders bei Raumtemperatur gemessen. Dabei werden mit abnehmender Partikelgrösse und zunehmendem Pressdruck zunehmende Werte für die Druckfestigkeit erhalten, die mehr als doppelt so hoch sein können wie die Druckfestigkeit bekannter wachshaltiger Presskörper aus Octogen. Die Druckfestigkeit erfährt nochmals eine Erhöhung um bis zu 30 %, wenn die Presskörper altern (1 bis 2 Wochen bei Raumtemperatur, 3 bis 4 Tage bei + 50 °C).The compressive strength was on explosive compacts (Pressing pressure 1.9 to 4.2 t / cm 2 ) measured with the shape of an equilateral cylinder at room temperature. With decreasing particle size and increasing pressure, increasing values for the compressive strength are obtained, which can be more than twice as high as the compressive strength of known wax-containing pressed bodies made of octogen. The compressive strength increases again by up to 30% as the compacts age (1 to 2 weeks at room temperature, 3 to 4 days at + 50 ° C).
Insgesamt werden nach dem vorstehend beschriebenen Verfahren auch aus feinkörnigem Material bei Anwendung praktikabler Pressdrücke Sprengstoffe mit der erwünscht hohen Dichte erhalten, die den zusätzlichen Vorteil erhöhter Festigkeit und verringerter Schlagempfindlichkeit besitzen. Aus diesem Grunde sind solche Sprengstoffe besonders handhabungssicher, wozu auch ihre Oberflächenleitfähigkeit einen wichtigen Beitrag liefert (Oberflächenwiderstand, gemessen nach DIN 53482, bei einer Messpannung von 6 V: einige Kilo-Ohm).Overall, explosives with the desired high density are obtained from fine-grained material using fine press material, which have the additional advantage of increased strength and reduced impact sensitivity. For this reason, such explosives are particularly safe to handle, to which their surface conductivity also makes an important contribution (surface resistance, measured according to DIN 53482, at a measuring voltage of 6 V: a few kilo-ohms).
Claims (38)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT82200629T ATE11906T1 (en) | 1981-05-25 | 1982-05-24 | COLD-FORMABLE, PLASTIC-BOND, HIGH-PERFORMANCE EXPLOSIVE AND ITS PRODUCTION PROCESS. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH340381 | 1981-05-25 | ||
| CH3403/81 | 1981-05-25 | ||
| CH1423/82 | 1982-03-09 | ||
| CH142382 | 1982-03-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0068528A1 true EP0068528A1 (en) | 1983-01-05 |
| EP0068528B1 EP0068528B1 (en) | 1985-02-20 |
Family
ID=25687608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82200629A Expired EP0068528B1 (en) | 1981-05-25 | 1982-05-24 | Cold formable, plastics-bound high power explosive and process for preparing it |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4428786A (en) |
| EP (1) | EP0068528B1 (en) |
| CA (1) | CA1195122A (en) |
| DE (1) | DE3262399D1 (en) |
| DK (1) | DK153388C (en) |
| ES (1) | ES512486A0 (en) |
| FI (1) | FI73661C (en) |
| GR (1) | GR76805B (en) |
| NO (1) | NO153452C (en) |
| PT (1) | PT74948B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0152280A2 (en) * | 1984-02-08 | 1985-08-21 | Dyno Industrier A.S. | A method for coating high energy explosive crystals |
| DE3625412A1 (en) * | 1986-07-26 | 1988-02-04 | Messerschmitt Boelkow Blohm | METHOD FOR PRODUCING A PLASTIC-TIED EXPLOSIVE |
| EP0509200A1 (en) * | 1991-04-11 | 1992-10-21 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Process for the fabrication of phlegmatized explosives |
| WO2012028288A3 (en) * | 2010-09-03 | 2012-06-07 | Rheinmetall Waffe Munition Gmbh | Plastic-bonded explosive formulation |
| EP3312546A1 (en) | 2016-10-20 | 2018-04-25 | RUAG Ammotec AG | Multi-purpose projectile |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4526633A (en) * | 1982-11-08 | 1985-07-02 | Ireco Incorporated | Formulating and delivery system for emulsion blasting |
| US4503004A (en) * | 1984-03-12 | 1985-03-05 | The United States Of America As Represented By The Secretary Of The Army | Method of molding a red phosphorous pyrotechnic composition |
| SE460901B (en) * | 1987-06-04 | 1989-12-04 | Exploweld Ab | WATER RESISTANT ELASTIC EXPLOSIVE MATERIAL |
| CH673704A5 (en) * | 1987-06-17 | 1990-03-30 | Eidgenoess Munitionsfab Thun | |
| JPH07112537B2 (en) * | 1987-11-27 | 1995-12-06 | ダイセル化学工業株式会社 | Method for mixing raw material composition of highly ignitable or explosive substance |
| US5547526A (en) * | 1990-03-06 | 1996-08-20 | Daimler-Benz Aerospace Ag | Pressable explosive granular product and pressed explosive charge |
| US5445690A (en) * | 1993-03-29 | 1995-08-29 | D. S. Wulfman & Associates, Inc. | Environmentally neutral reformulation of military explosives and propellants |
| US5487851A (en) * | 1993-12-20 | 1996-01-30 | Thiokol Corporation | Composite gun propellant processing technique |
| FR2749851B1 (en) | 1996-06-13 | 2000-02-25 | Valeo Systemes Dessuyage | METHOD FOR MANUFACTURING A PROFILE HAVING A SURFACE LAYER REDUCING THE COEFFICIENT OF FRICTION WITH A GLASS SURFACE TO BE WIPED AND WIPING BLADE OBTAINED BY SUCH A PROCESS |
| FR2749852B1 (en) * | 1996-06-13 | 2004-01-23 | Valeo Systemes Dessuyage | SOLUTION FOR REALIZING A COATING ON A PROFILE, WIPING BLADE COATED WITH SUCH A SOLUTION, METHOD FOR COATING A PROFILE WITH SUCH A COATING AND WIPING BLADE COATED WITH A COATING, OBTAINED BY SUCH A PROCESS |
| DE19823999C2 (en) * | 1998-05-28 | 2002-07-18 | Nico Pyrotechnik | Process for the manufacture of pyrotechnic igniters |
| US6009810A (en) * | 1998-07-08 | 2000-01-04 | The United States Of America As Represented By The Secretary Of The Navy | Airbag propellant |
| US6315930B1 (en) | 1999-09-24 | 2001-11-13 | Autoliv Asp, Inc. | Method for making a propellant having a relatively low burn rate exponent and high gas yield for use in a vehicle inflator |
| US6402864B1 (en) | 2000-10-27 | 2002-06-11 | The United States Of America As Represented By The Secretary Of The Navy | Low slag, reduced hazard, high temperature incendiary |
| US6485586B1 (en) | 2000-10-27 | 2002-11-26 | The United States Of America As Represented By The Secretary Of The Navy | Lower burning rate, reduced hazard, high temperature incendiary |
| US20100294113A1 (en) * | 2007-10-30 | 2010-11-25 | Mcpherson Michael D | Propellant and Explosives Production Method by Use of Resonant Acoustic Mix Process |
| FR2954309B1 (en) * | 2009-12-21 | 2012-03-23 | Eurenco France | MALLEABLE SOLID EXPLOSIVE AND ITS OBTAINING |
| RU2703204C1 (en) * | 2018-06-27 | 2019-10-15 | Акционерное общество "Взрывгеосервис" | Explosive composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE722144C (en) * | 1933-06-28 | 1942-07-02 | Dynamit Act Ges Vormals Alfred | Process for the production of non-caking powdered ammonium nitrate explosives |
| US2597926A (en) * | 1947-07-05 | 1952-05-27 | Atlas Powder Co | Pentaerythritol tetranitrate product |
| DE1239968B (en) * | 1963-03-14 | 1967-05-03 | Delet | Self-supporting explosive mass with viscous-elastic binding agent, as well as process for their production |
| DE1446875A1 (en) * | 1965-12-24 | 1968-11-21 | Dynamit Nobel Ag | Process to increase the electrical surface conductivity and pourability of crystalline explosives |
| FR2017104A1 (en) * | 1968-08-30 | 1970-05-15 | Dynamit Nobel Ag | Moulded binder - contng compressed parts - made from powdered high explosives |
| DE1571227A1 (en) * | 1965-07-23 | 1971-02-25 | Ici Ltd | Explosives |
-
1982
- 1982-05-07 CA CA000402500A patent/CA1195122A/en not_active Expired
- 1982-05-10 US US06/376,916 patent/US4428786A/en not_active Expired - Fee Related
- 1982-05-21 FI FI821814A patent/FI73661C/en not_active IP Right Cessation
- 1982-05-24 NO NO821716A patent/NO153452C/en unknown
- 1982-05-24 DE DE8282200629T patent/DE3262399D1/en not_active Expired
- 1982-05-24 EP EP82200629A patent/EP0068528B1/en not_active Expired
- 1982-05-24 ES ES512486A patent/ES512486A0/en active Granted
- 1982-05-24 PT PT74948A patent/PT74948B/en not_active IP Right Cessation
- 1982-05-24 GR GR68227A patent/GR76805B/el unknown
- 1982-05-25 DK DK235882A patent/DK153388C/en not_active Application Discontinuation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE722144C (en) * | 1933-06-28 | 1942-07-02 | Dynamit Act Ges Vormals Alfred | Process for the production of non-caking powdered ammonium nitrate explosives |
| US2597926A (en) * | 1947-07-05 | 1952-05-27 | Atlas Powder Co | Pentaerythritol tetranitrate product |
| DE1239968B (en) * | 1963-03-14 | 1967-05-03 | Delet | Self-supporting explosive mass with viscous-elastic binding agent, as well as process for their production |
| DE1571227A1 (en) * | 1965-07-23 | 1971-02-25 | Ici Ltd | Explosives |
| DE1446875A1 (en) * | 1965-12-24 | 1968-11-21 | Dynamit Nobel Ag | Process to increase the electrical surface conductivity and pourability of crystalline explosives |
| FR2017104A1 (en) * | 1968-08-30 | 1970-05-15 | Dynamit Nobel Ag | Moulded binder - contng compressed parts - made from powdered high explosives |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 90, Nr. 10, 5. März 1979, Seite 121, Nr. 74076j, Columbus Ohio (USA); & JP - A - 78 124 604 (CHUGOKU KAYAKU CO., LTD.) (31.10.1978) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0152280A2 (en) * | 1984-02-08 | 1985-08-21 | Dyno Industrier A.S. | A method for coating high energy explosive crystals |
| EP0152280A3 (en) * | 1984-02-08 | 1985-09-18 | Dyno Industrier A.S. | A method for coating high energy explosive crystals |
| DE3625412A1 (en) * | 1986-07-26 | 1988-02-04 | Messerschmitt Boelkow Blohm | METHOD FOR PRODUCING A PLASTIC-TIED EXPLOSIVE |
| EP0509200A1 (en) * | 1991-04-11 | 1992-10-21 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Process for the fabrication of phlegmatized explosives |
| WO2012028288A3 (en) * | 2010-09-03 | 2012-06-07 | Rheinmetall Waffe Munition Gmbh | Plastic-bonded explosive formulation |
| EP3312546A1 (en) | 2016-10-20 | 2018-04-25 | RUAG Ammotec AG | Multi-purpose projectile |
Also Published As
| Publication number | Publication date |
|---|---|
| GR76805B (en) | 1984-09-04 |
| ES8404668A1 (en) | 1984-05-01 |
| DK235882A (en) | 1982-11-26 |
| DK153388C (en) | 1988-11-28 |
| FI73661B (en) | 1987-07-31 |
| PT74948A (en) | 1982-06-01 |
| DE3262399D1 (en) | 1985-03-28 |
| US4428786A (en) | 1984-01-31 |
| FI821814A0 (en) | 1982-05-21 |
| EP0068528B1 (en) | 1985-02-20 |
| CA1195122A (en) | 1985-10-15 |
| FI73661C (en) | 1987-11-09 |
| ES512486A0 (en) | 1984-05-01 |
| NO821716L (en) | 1982-12-26 |
| DK153388B (en) | 1988-07-11 |
| PT74948B (en) | 1984-11-26 |
| NO153452C (en) | 1986-05-07 |
| NO153452B (en) | 1985-12-16 |
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