EP0068528B1 - 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
- EP0068528B1 EP0068528B1 EP82200629A EP82200629A EP0068528B1 EP 0068528 B1 EP0068528 B1 EP 0068528B1 EP 82200629 A EP82200629 A EP 82200629A EP 82200629 A EP82200629 A EP 82200629A EP 0068528 B1 EP0068528 B1 EP 0068528B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- desensitizing
- binding agent
- dispersion
- process according
- 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.)
- Expired
Links
- 239000002360 explosive Substances 0.000 claims description 77
- 239000011230 binding agent Substances 0.000 claims description 68
- 239000003975 dentin desensitizing agent Substances 0.000 claims description 55
- 239000006185 dispersion Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 45
- 229920002125 SokalanĀ® Polymers 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 32
- 239000004584 polyacrylic acid Substances 0.000 claims description 32
- 239000012188 paraffin wax Substances 0.000 claims description 31
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- -1 isobutyl ester Chemical class 0.000 claims description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- 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 description 24
- 239000000945 filler Substances 0.000 claims description 23
- 239000000314 lubricant Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000004815 dispersion polymer Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910002027 silica gel Inorganic materials 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 235000011132 calcium sulphate Nutrition 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 125000005907 alkyl ester group Chemical group 0.000 claims description 9
- 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
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000001175 calcium sulphate Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 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
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 235000010216 calcium carbonate Nutrition 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 4
- 150000002148 esters Chemical class 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000028 HMX Substances 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000586 desensitisation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000465 moulding Methods 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
- 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
- 239000013530 defoamer Substances 0.000 description 3
- 238000005474 detonation Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- OXIKLRTYAYRAOE-CMDGGOBGSA-N (e)-3-(1-benzyl-3-pyridin-3-ylpyrazol-4-yl)prop-2-enoic acid Chemical compound N1=C(C=2C=NC=CC=2)C(/C=C/C(=O)O)=CN1CC1=CC=CC=C1 OXIKLRTYAYRAOE-CMDGGOBGSA-N 0.000 description 2
- 241000282693 Cercopithecidae Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000015572 biosynthetic process Effects 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
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000003825 pressing Methods 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
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000004593 Epoxy Chemical group 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000003963 antioxidant agent 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
- 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
- 239000002270 dispersing agent Substances 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
- 238000010304 firing Methods 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 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 (in each case based 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 agent such as wax is added, as well as other auxiliaries such as catalysts for crosslinking the desensitizing and binding agent, antioxidants and wetting agents.
- the binder components are first mixed in a kneader at elevated temperatures under vacuum; the desensitizing and binding agent is then mixed with the octogen under the same conditions. This gives a pourable mass, which is poured under vacuum and under the action of vibrations into molds in which the mass hardens over the course of a few days.
- 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 safety 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 shock when firing) and the mechanical strength of molded articles made therefrom.
- an aqueous polymer dispersion in the presence of Auxiliaries and additives are mixed with a lubricant, with an aqueous paraffin dispersion and with a filler in such a way that the aqueous dispersion of the desensitizing and binding agent thus obtained is mixed with the dry explosive and that the mixture thus obtained is dried warm.
- the inventive method uses aqueous dispersions of 'polymers and other components of the Phlegmatmaschines- and binder. so that they can be completely mixed with one another and with other 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 extremely safe to use.
- the aqueous polymer dispersion can be prepared by mixing an aqueous dispersion of polyacrylic acid butyl ester with an aqueous dispersion of polyethylene and 5 to 15% by weight of polyethylene (based on the weight of the polyacrylic acid butyl ester) having an average particle size of 0.1 to 0 , 3 pm can be added; polytetrafluoroethylene as a lubricant, highly disperse silica gel, paraffin and calcium carbonate with a particle size of approximately 1 J.Lm can be added as a 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 alkyl polyacrylate or alkyl polymethacrylate with an alkyl group of at least 3 carbon atoms and preferably contain butyl or isobutyl polyacrylate.
- 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 desensitizing and binding agent 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 polyacrylic acid alkyl ester or polymethacrylic acid alkyl ester, preferably polyacrylic acid butyl ester -acrylic acid isobutyl ester, and the high-performance explosive with a desensitizing and binding agent composed of 18 to 50% by weight of butyl polyacrylic acid, 0.9 to 8% by weight of polyethylene, 2 to 7% by weight. -% polytetrafluoroethylene, 20 to 65% by weight calcium carbonate, 0.3 to 2.3% by weight silica gel and 3.2 to 20% by weight paraffin.
- a desensitizing and binding agent composed of 18 to 50% by weight of butyl polyacrylic acid, 0.9 to 8% by weight of polyethylene, 2 to 7% by weight.
- -% polytetrafluoroethylene 20 to 65% by weight calcium carbonate, 0.3 to 2.3% by weight 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 butyl polyacrylic acid, 25 to 65% by weight of graphite with an average particle size of 2.5 f.lm and a particle size distribution corresponding to 95% below 5 ā m , 12 to 25% by weight of calcium sulfate, 0.3 to 2.3% by weight of silica gel and 3.5 to 20% by weight of paraffin.
- a desensitizing and binding agent composed of 18 to 50% by weight of butyl polyacrylic acid, 25 to 65% by weight of graphite with an average particle size of 2.5 f.lm and a particle size distribution corresponding to 95% below 5 ā m , 12 to 25% by weight of calcium sulfate, 0.3 to 2.3% by weight of silica gel and 3.5 to 20% by weight of 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 to shaped articles, for example also shaped charges, by cold pressing. This particularly simple method has not yet been used successfully with explosives with high proportions of octogen.
- Bodies have densities above 1.8 g f 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 polyacrylic acid butyl ester increases the adhesion between the explosive particles in a manner sufficient 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 binder 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 f Lm and particle size distributions corresponding to 95% below 5 ā 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 is one. 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.
- 39 kg of a commercially available aqueous dispersion of butyl polyacrylic acid (24% by weight, corresponding to 9.3 kg of butyl polyacrylic acid) are diluted with 8 l of water while 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 a wetting agent based on alkanol polyglycol ether.
- 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 clumps that may have formed are completely distributed.
- 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.
- 10 kg of dry octogen are mixed with 1 kg of the aqueous dispersion of the desensitizing and binding agent.
- 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.
- 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 monkey method according to Koenen and Ide.
- 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.
- a 5 kg drop hammer and 40 mm 3 samples no reactions were observed at a drop height of 30 cm, only occasional reactions occurred at 3 5 cm and 0-20% reactions occurred at 40 cm.
- 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 polyacrylic acid butyl acrylate (40% by weight, corresponding to 3.3 kg of polyacrylic acid butyl acrylate) in isopropanol-water (mixture ratio 2: 1) consists of dispersing the mixture of the first and second components of the desensitizing and binding agent 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 pre-dried with occasional circulation by passing a warm air stream over it.
- 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 measured on explosive compacts (compression pressure 1.9 to 4.2 ticm 2 ) 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 Ā° 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 6V: a few kilo-ohms).
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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 enthƤlt, bei welchem Verfahren zunƤchst 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 (in each case based 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 Formkƶrpers 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 fĆ¼r Cyclotetramethylentetranitramin) in einem gummiartigen Zweikomponenten-Bindemittel dispergiert wird, das aus einem PrƤpolymer mit zwei vorzugsweise endstƤndigen Carboxylgruppen und einem Vernetzungsmittel auf Epoxidbasis besteht. ZusƤtzlich werden ein Phlegmatisierungsmittel wie Wachs hinzugegeben, sowie weitere Hilfsstoffe wie Katalysatoren fĆ¼r die Vernetzung des Phlegmatisierungs- und Bindemittels, Antioxidantien und Netzmittel. Im einzelnen werden dabei zunƤchst die Bindemittelkomponenten in einer Kneteinrichtung bei erhƶhten Temperaturen unter Vakuum vermengt ; anschliessend wird das Phlegmatisierungs- und Bindemittel unter gleichen Bedingungen mit dem Octogen gemischt. Dabei wird eine giessfƤhige Masse erhalten, die unter Vakuum und unter Einwirkung von Vibrationen in Formen gegossen wird, in denen die Masse im Verlaufe einiger Tage durchhƤrtet. Auf diese Weise drucklos herstellbare Hochleistungssprengstoff-Formkƶrper 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 agent such as wax is added, as well as other auxiliaries such as catalysts for crosslinking the desensitizing and binding agent, antioxidants and wetting agents. Specifically, the binder components are first mixed in a kneader at elevated temperatures under vacuum; the desensitizing and binding agent is then mixed with the octogen under the same conditions. This gives a pourable mass, which is poured under vacuum and under the action of vibrations into molds in which the mass hardens over the course of a few days. High-performance explosive molded articles which can be produced without pressure contain up to 90% by weight (based on the total weight = 100) of octogen.
Ein Ƥhnliches Verfahren (FR-Verƶffentlichung Nr. 2225979) verwendet ein Zweikomponenten-Bindemittel aus Diisocyanaten und Polyolen ; jedoch liegen bei den erhaltenen Hochleistungssprengstoff-Formkƶrpern die Mengenanteile von Octogen unter 90 Gew.-% (bezogen auf das Gesamtgewicht = 100).A similar process (FR Publication No. 2225979) 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 umstƤndlich, dass das Phlegmatisierungs- und Bindemittel und das Octogen unter Vakuum bei erhƶhter Temperatur in einer Kneteinrichtung gemischt werden mĆ¼ssen und der anschliessende Giessvorgang ebenfalls unter Vakuum durchgefĆ¼hrt werden muss. Dabei mĆ¼ssen zusƤtzlich Vibrationen zur Einwirkung gebracht werden, um die gewĆ¼nschte HomogenitƤt zu erreichen. Die HƤrtezeiten von mehreren Tagen fĆ¼r das Phlegmatisierungs- und Bindemittel machen das ganze Verfahren zusƤtzlich zeitaufwendig. Der so schliesslich erhaltene Hochleistungssprengstoff-Formkƶrper enthƤlt aber immer noch mehr als 10 % Fremdstoffe, und seine Sprengkraft ist daher gegenĆ¼ber 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 wƤssrigen 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 Ć¼berzogenen Sprengstoffpartikeln zurĆ¼ckgefĆ¼hrt. Die geringe Haftung zwischen den Sprengstoffpartikeln bewirkt jedoch, dass daraus hergestellte Formkƶrper keine hinreichende FormbestƤndigkeit 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 fĆ¼r Nitropentaerythrit (PETN) in Anteilen von 0,3 bis 5 % zu verwenden, wobei die Mischung auch in wƤssriger 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 OberflƤche Ć¼ber 20 m2/g empfohlen, die in Anteilen von bis zu 0,5 % auf die OberflƤche der Sprengstoffe aufgebracht werden (DE-OS 1446875)'.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 1446875) ' .
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 einfachen Mitteln durchfĆ¼hrbares 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 Ƥussere Einwirkungen im Gebrauch, wie die FormbestƤndigkeit (z. B. unter Schockeinwirkungen beim Abschuss) und mechanische Festigkeit daraus hergestellter Formkƶrper, verstanden.Handling safety is understood to mean, among other things, both the safety 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 shock when firing) and the mechanical strength of molded articles made therefrom.
Diese Aufgabe wird nach dem erfindungsgemƤssen Verfahren dadurch gelƶst, dass eine wƤssrige Polymerdispersion in Anwesenheit von Hilfs- und Zusatzstoffen mit einem Gleitmittel, mit einer wƤssrigen Paraffindispersion und mit einem FĆ¼llstoff gemischt wird, dass die so erhaltene wƤssrige 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 the presence of Auxiliaries and additives are mixed with a lubricant, with an aqueous paraffin dispersion and with a filler in such a way that the aqueous dispersion of the desensitizing and binding agent thus obtained is mixed with the dry explosive and that the mixture thus obtained is dried warm.
Das erfindungsgemƤsse Verfahren benutzt wƤssrige Dispersionen des'Polymeren und anderer Bestandteile des Phlegmatisierungs- und Bindemittels. so dass diese mit einfachen Mitteln bei Raumtemperatur und unter Normaldruck in kĆ¼rzester Zeit untereinander und mit weiteren Bestandteilen des Phlegmatisierungs- und Bindemittels vollstƤndig durchmischt werden kƶnnen. Die wƤssrige 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 inventive method uses aqueous dispersions of 'polymers and other components of the Phlegmatisierungs- and binder. so that they can be completely mixed with one another and with other 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 extremely safe to use.
Vorteilhafte Ausbildungen des Verfahrens sind in abhƤngigen AnsprĆ¼chen gekennzeichnet.Advantageous developments of the method are characterized in the dependent claims.
In einer Variante des erfindungsgemƤssen Verfahrens kann die wƤssrige Polymerdispersion durch Vermischen einer wƤssrigen Dispersion von PolyacrylsƤurebutylester mit einer wƤssrigen Dispersion von Polyethylen hergestellt und 5 bis 15 Gew.-% Polyethylen (bezogen auf das Gewicht des PolyacrylsƤurebutylester) einer mittleren Teilchengrƶsse von 0,1 bis 0,3 p.m zugegeben werden ; dabei kƶnnen nacheinander Polytetrafluorethylen als Gleitmittel, hochdisperses Kieselgel, Paraffin und Calciumcarbonat einer Teilchengrƶsse von annƤhernd 1 J.Lm als FĆ¼llstoff 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 polyacrylic acid butyl ester with an aqueous dispersion of polyethylene and 5 to 15% by weight of polyethylene (based on the weight of the polyacrylic acid butyl ester) having an average particle size of 0.1 to 0 , 3 pm can be added; polytetrafluoroethylene as a lubricant, highly disperse silica gel, paraffin and calcium carbonate with a particle size of approximately 1 J.Lm can be added as a filler.
Als FĆ¼llstoff werden dabei schwerlƶsliche 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 erfindungsgemƤssen Verfahrens, nach der ein antistatischer Hochleistungssprengstoff erhalten wird, kann die wƤssrige Polymerdispersion aus PolyacrylsƤurealkylester oder PolymethacrylsƤurealkylester mit einer Alkylgruppe von wenigstens 3 Kohlenstoffatomen hergestellt werden und vorzugsweise PolyacrylsƤurebutylester oder -isobutylester enthalten. Dabei kƶnnen eine erste, einen Teil des Polymers, Graphit als Gleitmittel und einen Teil des Paraffins enthaltende Komponente und eine zweite, Calciurnsulfat als FĆ¼llstoff, das hochdisperse Kieselgel und den Rest des Paraffins enthaltende Komponente miteinander und dann mit einer dritten Komponente der wƤssrigen Dispersion des Phlegmatisierungs- und Bindemittels vermischt werden, die Cyclohexanon und den Rest des Polymers in einer Isopropanol-Wasser-Mischung enthƤlt.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 alkyl polyacrylate or alkyl polymethacrylate with an alkyl group of at least 3 carbon atoms and preferably contain butyl or isobutyl polyacrylate. 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 erfindungsgemƤssen Verfahrens hat sich in der Praxis Ć¼berraschenderweise herausgestellt, dass unabhƤngig von der Partikelgrƶsse des verwendeten Octogens eine vƶllig gleichmƤssige Verteilung des Phlegmatisierungs- und Bindemittels Ć¼ber die Octogenpartikel dadurch erzielt werden kann, dass das Gemenge aus Phlegmatisierungs- und Bindemittel mit Octogen unter UmwƤlzung 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 UmwƤlzen getrocknet wird.In practice, the second variant of the method according to the invention surprisingly 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 lƶst die vorgenannte Aufgabe dadurch, dass das Phlegmatisierungs- und Bindemittel ein Polymer auf Polyacrylat- oder Polymethacrylatbasis, ein Gleitmittel und einen FĆ¼llstoff enthƤlt. Der FĆ¼llstoff in dem Phlegmatisierungs- und Bindemittel des erfindungsgemƤssen kunststoffgebunden Hochleistungssprengstoffs ist aus schwerlƶslichen Verbindungen der Erdalkaligruppe ausgewƤhlt 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 desensitizing and binding agent 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 PolyacrylsƤurealkylester oder PolymethacrylsƤurealkylester, vorzugsweise PolyacrylsƤurebutylester -acrylsƤureisobutylester, sein und der Hochleistungssprengstoff mit einem Phlegmatisierungs- und Bindemittel aus 18 bis 50 Gew.-% PolyacrylsƤurebutylester, 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 polyacrylic acid alkyl ester or polymethacrylic acid alkyl ester, preferably polyacrylic acid butyl ester -acrylic acid isobutyl ester, and the high-performance explosive with a desensitizing and binding agent composed of 18 to 50% by weight of butyl polyacrylic acid, 0.9 to 8% by weight of polyethylene, 2 to 7% by weight. -% polytetrafluoroethylene, 20 to 65% by weight calcium carbonate, 0.3 to 2.3% by weight silica gel and 3.2 to 20% by weight paraffin.
Eine antistatische Variante des erfindungsgemƤssen Hochleistungssprengstoffs kann mit einem Phlegmatisierungs- und Bindemittel aus 18 bis 50 Gew.-% PolyacrylsƤurebutylester, 25 bis 65 Gew.-% Graphit einer mittleren Korngrƶsse von 2,5 f.Lm und einer Korngrƶssenverteilung entsprechend 95 % unter 5 Āµm, 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 butyl polyacrylic acid, 25 to 65% by weight of graphite with an average particle size of 2.5 f.lm and a particle size distribution corresponding to 95% below 5 Āµm , 12 to 25% by weight of calcium sulfate, 0.3 to 2.3% by weight of silica gel and 3.5 to 20% by weight of paraffin.
Die vorgenannte Aufgabe wird hinsichtlich des Verfahrens zur Weiterverarbeitung nach der Erfindung dadurch gelƶst, dass der Hochleistungssprengstoff in der Form bei Raumtemperatur mit einem Druck im Bereich Ć¼ber 1,5 kbar gepresst wird. Der nach der Erfindung hergestellte Hochleistungssprengtoff kann somit durch Kaltpressen zu Formkƶrpern, 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 to shaped articles, for example also shaped charges, by cold pressing. 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) enthƤlt, Presskƶrper unter einem Pressdruck von 1,2 kbar herzustellen (DE-OS 24 34 252).It is known to use 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) to produce pressed bodies under a pressure of 1.2 kbar (DE-OS 24 34 252 ).
Die nach der Erfindung hergestellten Formkƶrper haben Dichten Ć¼ber 1,8 gfcm3 und Detonationsgeschwindigkeiten Ć¼ber 8.6 km/s. Sie haben eine verbesserte mechanische Festigkeit und HomogenitƤt und sind in weiteren Grenzen als erwartet schlag- oder reibungsunempfindlich ; sie sind auch thermisch stabil und in besonderem Umfang druckfest und beschussicher.The shape produced according to the invention Bodies have densities above 1.8 g f 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.
FĆ¼r die Zusammensetzung des Bindemittels ist von wesentlicher Bedeutung, dass das PolyacrylsƤurebutylester die Haftung zwischen den Sprengstoffpartikeln in fĆ¼r die Weiterverarbeitung und fĆ¼r die FormbestƤndigkeit des letztlich hergestellten Formkƶrpers ausreichender Weise erhƶht. Das Polyethylen verbessert die mechanischen Eigenschaften des Kunststoff-Films bezĆ¼glich seiner phlegmatisierenden Wirkung. Beide Polymeren sind bisher nicht als Bindemittel fĆ¼r Octogen bekannt. Das an sich als Gleitmittel bekannte Polytetrafluorethylen ist in einem auf die vorgenannten Bestandteile abgestimmten Mengenanteil vorhanden, der gerade so hoch gewƤhlt ist, dass die FormbestƤndigkeit des letztlich hergestellten Formkƶrpers nicht beeintrƤchtigt wird, der Formkƶrper aber glatt und ohne BeschƤdigungen nach der Formgebung aus der Form entnommen werden kann.It is essential for the composition of the binder that the polyacrylic acid butyl ester increases the adhesion between the explosive particles in a manner sufficient 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 binder 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 Partikelgrƶssen von 2,5 fLm und Partikelgrƶssenverteilungen entsprechend 95 % unter 5 Āµm, unterstĆ¼tzt 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 gewƤhlt, dass die FormbestƤndigkeit des letztlich hergestellten Formkƶrpers nur unwesentlich beeintrƤchtigt wird, der Formkƶrper aber glatt und ohne BeschƤdigungen nach der Formgebung aus der Form entnommen werden kann.Graphite, especially with average particle sizes of 2.5 f Lm and particle size distributions corresponding to 95% below 5 Āµm, 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 formbestƤndige Formkƶrper und insbesondere verhƤltnismƤssig wenig schlagempfindliche Formkƶrper dadurch erhalten werden, dass das Octogen eine Partikelgrƶsse 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 schwerlƶslichen Verbindungen der Erdalkaligruppe ausgewƤhlte FĆ¼llstoff wird zunƤchst zugesetzt, um die RieselfƤhigkeit der Partikeln des Hochleistungssprengstoffs zu erhƶhen und deren gegenseitige Haftung durch den BindemittelĆ¼berzug zu erniedrigen. Ćberraschenderweise hat sich jedoch gezeigt, dass ein solcher FĆ¼llstoff 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 Ć¼ber 90 Gew.-% ermƶglicht. DarĆ¼berhinaus wird durch diesen Zusatz unerwarteterweise auch die mechanische Festigkeit der aus dem Hochleistungssprengstoff hergestellten Formkƶrper vergrƶssert.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, unlike other white pigments, such a filler is one. 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 erfindungsgemƤssen Hochleistungssprengstoffs und die Eigenschaften daraus hergestellter Formkƶrper anhand von AusfĆ¼hrungsbeispielen im einzelnen erlƤutert 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 enthƤlt 3 bis 10 Gew.-% des Phlegmatisierungs-und Bindemittels, das im wesentlichen aus 20 bis 50 Gew.-% PolyacrylsƤurealkylester, 0,9 bis 8 Gew.-% Polyethylen, 2 bis 7 Gew.-% Polytetrafluorethylen, bis zu 65 Gew.-% FĆ¼llstoff, mindestens 0,3 Gew.-% Kieselgel und 8 bis 20 Gew.-% Paraffin zusammengesetzt ist. Der FĆ¼llstoff besteht aus einer schwerlƶslichen Erdalkaliverbindung wie Magnesiumpyrophosphat, Calciumcarbonat, Calciumsulfat, Bariumsulfat. Das Magnesiumpyrophosphat wird aus wƤssriger Lƶsung durch Zusammengeben stƶchiometrischer Mengen Natriumpyrophosphat und Magnesiumsulfat gefƤllt, abfiltriert und getrocknet. die Ć¼brigen sind handelsĆ¼bliche Produkte. Ein bevorzugtes AusfĆ¼hrungsbeispiel mit 4 Gew.-% Phlegmatisierungs- und Bindemittel wird folgendermassen erhalten :
- 1. Herstellung von 100 kg einer Dispersion des Phlegmatisierungs- und Bindemittels
- 1a. Herstellung der wƤssrigen Polymerdispersion.
- 1. Production of 100 kg of a dispersion of the desensitizing and binding agent
- 1a. Preparation of the aqueous polymer dispersion.
39 kg einer handelsĆ¼blichen wƤssrigen Dispersion von PolyacrylsƤurebutylester (24 Gew.-% entsprechend 9,3 kg PolyacrylsƤurebutylester) werden unter RĆ¼hren mit 8 I Wasser verdĆ¼nnt und zunƤchst mit 0,7 kg eines EntschƤumers auf Silikonbasis (10 Gew.-% entsprechend 0,07 kg) und 0,3 kg eines Netzmittels auf Alkanolpolyglykoletherbasis versetzt. Es wird bis zur HomogenitƤt der Mischung gerĆ¼hrt: dann werden 3,4 kg einer handelsĆ¼blichen wƤssrigen Polyethylendispersion (35 Gew.-% entsprechend 1,2 kg Polyethylen) unter weiterem RĆ¼hren zugefĆ¼gt.39 kg of a commercially available aqueous dispersion of butyl polyacrylic acid (24% by weight, corresponding to 9.3 kg of butyl polyacrylic acid) are diluted with 8 l of water while 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 a wetting agent based on alkanol polyglycol ether. 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 RĆ¼hrgeschwindigkeit (zur Vermeidung des Ausflockens) werden 2,5 kg einer handelsĆ¼blichen wƤssrigen Dispersion von Polytetrafluorethylen (60 Gew.-% entsprechend 1,5 kg Polytetrafluorethylen ; Teilchengrƶsse 0,05 bis 0,5 nm) zugegeben. Anschliessend wird mit 0,5 kg eines handelsĆ¼blichen kolloiden Kieselgels (mittlere Teilchengrƶsse 12 nm) versetzt, und zwar portionsweise und bei niedriger RĆ¼hrgeschwindigkeit bis zu dessen vƶlliger Benetzung und dann bei hoher RĆ¼hrgeschwindigkeit bis zur vƶlligen 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 clumps that may have formed are completely distributed.
Nach Zusatz des Kieselgels werden unter starkem RĆ¼hren, aber unter Vermeidung von Schaumbildung, 15 kg einer wƤssrigen Paraffindispersion zugesetzt (s.w.u. ; 24 Gew.-% entsprechend 3,6 kg Paraffin (handelsĆ¼blich, Schmelzpunkt von ca. 52 Ā°C) und 6 Gew.-% entsprechend 0,9 kg eines handelsĆ¼blichen Emulgiermittels auf Alkylpolyglykoletherbasis).After adding 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, melting point of approx. 52 Ā° C.) and 6% by weight. -% corresponding to 0.9 kg of a commercially available Emulsifier based on alkyl polyglycol ether).
Der so erhaltenen Mischung werden 25 kg Calciumcarbonat (Teilchengrƶsse 1 Āµm, entsprechend der ƶsterreichischen oder belgischen Pharmakopoe ĆAB9 bzw. Ph. Belg. V) zugegeben ; dabei wird zunƤchst mit geringer RĆ¼hrgeschwindigkeit gearbeitet und diese dann mit abnehmender ViskositƤt der anfangs breiartigen Masse zunehmend erhƶht, bis eine dĆ¼nnflĆ¼ssige Mischung erhalten wird.25 kg of calcium carbonate (particle size 1 Ī¼m, corresponding to the Austrian or Belgian pharmacopoeia ĆAB9 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 handelsĆ¼blicher Natriumcarboxymethylcellulose und 4,5 I destilliertes Wasser hinzugefĆ¼gt, und es wird dann weiter bis zur vƶlligen HomogenitƤt gerĆ¼hrt. Die ganze Mischung lƤsst man vorteilhafterweise noch ein Drei-Walzen-Mischwerk passieren, wodurch die ViskositƤt und die Schaumbildung gĆ¼nstig beeinflusst werden. Danach ist die Bindemitteldispersion nach weiteren 24 Stunden Ā« 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 ripening.
6 kg handelsĆ¼blichen Paraffins (Schmelzpunkt von ca. 52 Ā°C) werden unter Zugabe von 1,5 kg eines handelsĆ¼blichen Emulgiermittels auf Alkylpolyglykoletherbasis geschmolzen, die Schmelze wird gut durchmischt und auf 95 Ā°C erwƤrmt. Diese Mischung wird anschliessend portionenweise in 17,5 kg destilliertes Wasser von 85 Ā°C eingerĆ¼hrt. Es wird bis zur Bildung einer homogenen Dispersion gerĆ¼hrt und danach erfolgt unter weiterem RĆ¼hren ein AbkĆ¼hlen auf unterhalb 40 Ā°C. Nach einem Tag weitere Ā« Reife ist die wƤssrige Paraffindispersion gebrauchsfertig.6 kg of commercially available paraffins (melting point of approx. 52 Ā° 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 Ā° C. This mixture is then stirred in portions into 17.5 kg of distilled water at 85 Ā° C. The mixture is stirred until a homogeneous dispersion is formed and then cooled to below 40 Ā° 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 wƤssrigen Dispersion des Phlegmatisierungs-und Bindemittels versetzt. Die Masse wird zunƤchst von Hand umgewƤlzt und dann 10 min in einer Mischtrommel Ć¼blicher Bauart durchmischt. Die Mischung wird der Mischtrommel entnommen, flach ausgebreitet und unter gelegentlichem UmwƤlzen durch Ćberleiten eines warmen Luftstroms getrocknet.10 kg of dry octogen are mixed with 1 kg of the aqueous dispersion of the desensitizing and binding agent. 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 gemƤss Punkt 2. erhaltene Hochleistungssprengstoff wird in Formen Ć¼blicher 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 Formkƶrper haben eine Dichte von 1,81 g/cm3 und darĆ¼ber. 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 nach Koenen und Ide untersucht. Mit einem 2 kg-Fallhammer und 10 mm3- Proben wurden nur vereinzelte, schwache Reaktionen bei einer Fallhƶhe von 25 cm und weniger als 30 % bzw. 50 % Reaktionen bei 30 bzw. 35 cm Fallhƶhe beobachtet. Mit einem 5 kg-Fallhammer und 40 mm3 Proben wurden keine Reaktionen bei 30 cm Fallhƶhe 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 monkey method according to 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 drop height of 30 cm, only occasional reactions occurred at 3 5 cm and 0-20% reactions occurred at 40 cm.
Bei der PrĆ¼fung 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 12 kg friction pin loads, and only occasional burn-on reactions occurred between 14-16 kg.
Die Druckfestigkeit wurde an Sprengstoffpresskƶrpern mit der Form eines gleichseitigen Zylinders (Durchmesser = Hƶhe) von 20 mm, 40 mm und 60 mm gemessen und ist mit Ć¼ber 100 kg/cm2 mindestens doppelt so hoch wie bei Formkƶrpern aus herkƶmmlichen 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, at over 100 kg / cm 2, is at least twice as high as for molded articles made of conventional explosives.
Der antistatische kunststoffgebundene Hochleistungssprengstoff mit Graphit als Gleitmittel enthƤlt 3 bis 10 Gew.-% des Phlegmatisierungs-und Bindemittels, das im wesentlichen aus 18 bis 40 Gew.-% PolyacrylsƤurebutylester, 25 bis 65 Gew.-% Graphit, 12 bis 25 Gew.-% FĆ¼llstoff, mindestens 0,3 Gew.-% Kieselgel und 7 bis 17 Gew.-% Paraffin zusammengesetzt ist. Der FĆ¼llstoff besteht aus einer schwerlƶslichen Erdalkaliverbindung wie Magnesiumpyrophosphat, Calciumcarbonat, Calciumsulfat, Bariumsulfat. Das Magnesiumpyrophosphat wird aus wƤssriger Lƶsung durch Zusammegeben stƶchiometrischer Mengen Natriumpyrophosphat und Magnesiumsulfat gefƤllt, abfiltriert und getrocknet. die ubrigen sind handelsĆ¼bliche Produkte. Ein bevorzugtes AusfĆ¼hrungsbeispiel mit 4,3 Gew.-% Phlegmatisierungs- und Bindemittel wird folgendermassen erhalten :
- 4. Herstellung von 100 kg einer Dispersion des Phlegmatisierungs- und Bindemittels
- 4a. Herstellung der ersten Komponente der Phlegmatisierungs- und Bindemitteldispersion.
- 4. Production of 100 kg of a dispersion of the desensitizing and binding agent
- 4a. Production of the first component of the desensitization and binder dispersion.
24,2 kg Wasser werden mit 0,5 kg eines EntschƤumers auf Silikonbasis (10 Gew.-% entsprechend 0,05 kg) und danach mit 15 kg einer handelsĆ¼blichen wƤssrigen Dispersion von PolyacrylsƤurebutylester (24 Gew.-% entsprechend 3,6 kg PolyacrylsƤurebutylester) mit einem IntensivrĆ¼hrer bis zur HomogenitƤt der Mischung dispergiert. Dann werden unter zusƤtzlicher Einwirkung von Ultraschall (Eintauchen eines an sich bekannten UltraschallgerƤtes) 12,5 kg Graphit (K 2,5 ; Lonza ; mittlere Teilchengrƶsse 2,5 Āµm ; Teilchengrƶsseverteilung : 95 % < 5 ktm), danach 2 kg einer wƤssrigen Paraffindispersion (s.w.u.) und schliesslich 0,3 kg handelsĆ¼blicher Natriumcarboxymethylcellulose unter gleichen UmstƤnden der Dispersion zugefĆ¼gt. UngefƤhr 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 butyl polyacrylic acid (24% by weight, corresponding to 3.6 kg of butyl polyacrylic acid) ) dispersed 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 Ī¼m; particle size distribution: 95% <5 kt m), then 2 kg of an aqueous Paraffin dispersion (swu) and finally 0.3 kg of commercially available sodium carboxymethyl cellulose were added to the dispersion under the same circumstances adds. Approximately 1 hour after adding the last ingredient there is a homogeneous dispersion.
4b. Herstellung der zweiten Komponente der Phlegmatisierungs- und Bindemitteldispersion.4b. Production of the second component of the desensitization and binder dispersion.
In 16,7 kg Wasser werden nacheinander unter Einwirkung eines eingetauchten UltraschallgerƤtes und unter Anwendung eines IntensivrĆ¼hrers 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 EntschƤumers dispergiert. Anschliessend werden unter den gleichen Bedingungen nacheinander die folgenden Bestandteile zudispergiert : 5 kg Calciumsulfat (gefƤlltes Calciumsulfat purum oder p.a. ; Fluka AG), 0,4 kg eines handelsĆ¼blichen kolloiden Kieselgels (mittlere Teilchengrƶsse 12 nm), 13,35 kg der unter Punkt 4a. genannten wƤssrigen Paraffindispersion (s.w.u.) und schliesslich 0,4 kg der handelsĆ¼blichen Natriumcarboxymethylcellulose. UngefƤhr 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. B. 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 point 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.
4c. Herstellung der eigentlichen Phlegmatisierungs- und Bindemitteldispersion.4c. Production of the actual desensitization and binder dispersion.
Die nach Punkt 4a. und 4b. erhaltenen Komponenten werden zusammengegeben, auf ca. 35 Ā°C erwƤrmt und miteinander vermischt. Diese Operation kann wegen der ZƤhigkeit des Produktes auch mit einer Knetvorrichtung ausgefĆ¼hrt werden. In der so erhaltenen Dispersion werden 0,4 kg der handelsĆ¼blichen Natriumcarboxymethylcellulose durch einen IntensivrĆ¼hrer 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 Ā° 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 handelsĆ¼blichen Dispersion von PolyacrylsƤurebutylester (40 Gew.-% entsprechend 3,3 kg PolyacrylsƤurebutylester) in Isopropanol-Wasser (MischungsverhƤltnis 2 : 1) mit einem IntensivrĆ¼hrer zudispergiert. Stattdessen kann aber auch eine vorbereitete dritte Komponente des Phlegmatisierungs- und Bindemittels, die aus 0,6 kg Cyclohexanon und 8,3 kg einer handelsĆ¼blichen Dispersion von PolyacrylsƤurebutylacrylat (40 Gew.-% entsprechend 3,3 kg PolyacrylsƤurebutylacrylat) in Isopropanol-Wasser (MischungsverhƤltnis 2:1) besteht, dem Gemisch aus der ersten und zweiten Komponente des Phlegmatisierungs- und Bindemittels mit einem IntensivrĆ¼hrer zudispergiert werden. Der RĆ¼hrvorgang wird nach 3 Stunden beendet und nach einem Tag fĆ¼r 1 Stunde wiederholt. Die Phlegmatisierungs- und Bindemitteldispersion ist dann gebrauchsfertig, muss aber vor dem Gebrauch gerĆ¼hrt werden.0.6 kg of cyclohexanone and 8.3 kg of a commercially available dispersion of butyl polyacrylic acid (40% by weight, corresponding to 3.3 kg of butyl polyacrylic acid) are then successively dispersed in isopropanol / water (mixing ratio 2: 1) using an intensive stirrer. Instead, 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 polyacrylic acid butyl acrylate (40% by weight, corresponding to 3.3 kg of polyacrylic acid butyl acrylate) in isopropanol-water (mixture ratio 2: 1) consists of dispersing the mixture of the first and second components of the desensitizing and binding agent 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.
4d. Herstellung der wƤssrigen Paraffindispersion.4d. Preparation of the aqueous paraffin dispersion.
3,7 kg handelsĆ¼blichen Paraffins (Fp. ca. 52 Ā°C) werden unter Zugabe von 0,9 kg eines handelsĆ¼blichen Emulgiermittels auf Alkylpolyglykoletherbasis geschmolzen, die Schmelze wird gut durchmischt und auf 95 Ā°C erwƤrmt. Diese Mischung wird anschliessend portionsweise in 10,5 kg destilliertes Wasser von 85 Ā°C eingerĆ¼hrt. Es wird bis zur Bildung einer homogenen Dispersion gerĆ¼hrt und danach erfolgt unter weiterem RĆ¼hren ein AbkĆ¼hlen auf unterhalb 40 Ā°C. Nach einem Tag weiterer Ā« Reife ist die wƤssrige Paraffindispersion gebrauchsfertig.3.7 kg of commercially available paraffins (melting point approx. 52 Ā° 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 Ā° C. This mixture is then stirred in portions in 10.5 kg of distilled water at 85 Ā° C. The mixture is stirred until a homogeneous dispersion is formed and then cooled to below 40 Ā° C. with further stirring. After a day of further Ā«ripening, the aqueous paraffin dispersion is ready for use.
5. Herstellung des Hochleistungssprengstoffs5. Manufacture of high performance explosives
1,015 kg der wƤssrigen Phlegmatisierungs- und Bindemitteldispersion werden mit 7 kg trockenem Octogen versetzt und gleichmƤssig Ć¼ber den Sprengstoff verteilt. Anschliessend wird das Gemisch in einer Mischtrommel Ć¼blicher Bauart umgewƤlzt, und nach 10 min ist das Phlegmatisierungs- und Bindemittel homogen Ć¼ber den Sprengstoff verteilt. Die Mischung wird der Mischtrommel entnommen, flach ausgebreitet und unter gelegentlichem UmwƤlzen durch Ćberleiten 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 pre-dried with occasional circulation by passing a warm air stream over it.
Das vorgetrocknete Material wird in einer rotierenden Trommel mit 290 g Isopropanol-Wasser (MischungsverhƤltnis 1 1) entsprechend ca. 4 Gew.-% versetzt und die Mischung 15 bis 30 min umgewƤlzt. Anschliessend wird die Mischung der Mischtrommel entnommen, flach ausgebreitet und unter gelegentlichem UmwƤlzen durch Ćberleiten 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 VorgƤnge kƶnnen gegebenenfalls und unter Beachtung einschlƤgiger Sicherheitsmassnahmen auch nach einem Fliessbettverfahren durchgefĆ¼hrt werden.The last-mentioned processes can also be carried out using a fluidized bed method, if necessary, taking into account relevant safety measures.
6a. Herstellung von Hochleistungssprengstoff-Presskƶrpern6a. Manufacture of high-performance explosive compacts
Der nach Punkt 5. erhaltene Hochleistungssprengstoff wird in Formen Ć¼blicher Bauart unter einem Druck im Bereich von 1,5 bis 4,2 kbar kalt gepresst. DrĆ¼cke von 2,2 bis 3,5 kbar reichen normalerweise aus, doch kƶnnen die PressdrĆ¼cke 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.
6b. Eigenschaften der Hochleistungssprengstoff-Presskƶrper6b. Properties of the high-performance explosive compacts
Die Presskƶrper haben Dichten Ć¼ber 1,80 g/cm3. Die gemessenen Detonationsgeschwindigkeiten liegen bei 8,6 km/s und darĆ¼ber.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 Partikelgrƶssen unter 0,5 mm besonders gĆ¼nstig : 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 Fallhƶhen 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 Sprengstoffpresskƶrpern (Pressdruck 1,9 bis 4,2 ticm2) mit der Form eines gleichseitigen Zylinders bei Raumtemperatur gemessen. Dabei werden mit abnehmender Partikelgrƶsse und zunehmendem Pressdruck zunehmende Werte fĆ¼r die Druckfestigkeit erhalten, die mehr als doppelt so hoch sein kƶnnen wie die Druckfestigkeit bekannter wachshaltiger Presskƶrper aus Octogen. Die Druckfestigkeit erfƤhrt nochmals eine Erhƶhung um bis zu 30 %, wenn die Presskƶrper altern (1 bis 2 Wochen bei Raumtemperatur, 3 bis 4 Tage bei + 50 Ā°C).The compressive strength was measured on explosive compacts (compression pressure 1.9 to 4.2 ticm 2 ) 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 Ā° C).
Insgesamt werden nach dem vorstehend beschriebenen Verfahren auch aus feinkƶrnigem Material bei Anwendung praktikabler PressdrĆ¼cke Sprengstoffe mit der erwĆ¼nscht hohen Dichte erhalten, die den zusƤtzlichen Vorteil erhƶhter Festigkeit und verringerter Schlagempfindlichkeit besitzen. Aus diesem Grunde sind solche Sprengstoffe besonders handhabungssicher, wozu auch ihre OberflƤchenleitfƤhigkeit einen wichtigen Beitrag liefert (OberflƤchenwiderstand, gemessen nach DIN 53482, bei einer Messpannung von 6V : 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 6V: 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 EP0068528A1 (en) | 1983-01-05 |
| EP0068528B1 true 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) |
Families Citing this family (23)
| 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 |
| NO153804C (en) * | 1984-02-08 | 1986-05-28 | Dyno Indusrtrier A S Nitroglyc | PROCEDURE FOR THE COATING OF CRYSTALLINE HEAD EXPLOSIVES. |
| 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 |
| DE3625412A1 (en) * | 1986-07-26 | 1988-02-04 | Messerschmitt Boelkow Blohm | METHOD FOR PRODUCING A PLASTIC-TIED EXPLOSIVE |
| 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 | ćć¤ć»ć«åå¦å·„ę„ę Ŗå¼ä¼ē¤¾ | 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 |
| DE4111752C1 (en) * | 1991-04-11 | 1992-09-17 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De | |
| 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 |
| 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 |
| 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 |
| 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 |
| DE102010044344A1 (en) * | 2010-09-03 | 2012-03-08 | Rheinmetall Waffe Munition Gmbh | Plastic-bound explosive formulation |
| HUE044204T2 (en) | 2016-10-20 | 2019-10-28 | Ruag Ammotec Ag | Multi-purpose projectile |
| RU2703204C1 (en) * | 2018-06-27 | 2019-10-15 | ŠŠŗŃŠøŠ¾Š½ŠµŃŠ½Š¾Šµ Š¾Š±ŃŠµŃŃŠ²Š¾ "ŠŠ·ŃŃŠ²Š³ŠµŠ¾ŃŠµŃŠ²ŠøŃ" | Explosive composition |
Family Cites Families (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 |
| GB1089403A (en) * | 1965-07-23 | 1967-11-01 | Ici Ltd | Explosive compositions |
| 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 |
-
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 GR GR68227A patent/GR76805B/el 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 PT PT74948A patent/PT74948B/en not_active IP Right Cessation
- 1982-05-24 ES ES512486A patent/ES512486A0/en active Granted
- 1982-05-25 DK DK235882A patent/DK153388C/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3262399D1 (en) | 1985-03-28 |
| EP0068528A1 (en) | 1983-01-05 |
| NO821716L (en) | 1982-12-26 |
| FI821814A0 (en) | 1982-05-21 |
| GR76805B (en) | 1984-09-04 |
| NO153452C (en) | 1986-05-07 |
| DK235882A (en) | 1982-11-26 |
| DK153388C (en) | 1988-11-28 |
| US4428786A (en) | 1984-01-31 |
| PT74948B (en) | 1984-11-26 |
| NO153452B (en) | 1985-12-16 |
| ES8404668A1 (en) | 1984-05-01 |
| PT74948A (en) | 1982-06-01 |
| FI73661C (en) | 1987-11-09 |
| CA1195122A (en) | 1985-10-15 |
| FI73661B (en) | 1987-07-31 |
| DK153388B (en) | 1988-07-11 |
| ES512486A0 (en) | 1984-05-01 |
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