EP1616845A1 - Pourable propellant powder - Google Patents
Pourable propellant powder Download PDFInfo
- Publication number
- EP1616845A1 EP1616845A1 EP04405460A EP04405460A EP1616845A1 EP 1616845 A1 EP1616845 A1 EP 1616845A1 EP 04405460 A EP04405460 A EP 04405460A EP 04405460 A EP04405460 A EP 04405460A EP 1616845 A1 EP1616845 A1 EP 1616845A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bismuth
- grains
- powder according
- propellant
- powder
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 141
- 239000003380 propellant Substances 0.000 title claims abstract description 34
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 36
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 239000002344 surface layer Substances 0.000 claims abstract description 15
- 239000000020 Nitrocellulose Substances 0.000 claims abstract description 13
- 229920001220 nitrocellulos Polymers 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 238000007517 polishing process Methods 0.000 claims abstract description 3
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000006 Nitroglycerin Substances 0.000 claims description 18
- 229960003711 glyceryl trinitrate Drugs 0.000 claims description 18
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 17
- MSBGPEACXKBQSX-UHFFFAOYSA-N (4-fluorophenyl) carbonochloridate Chemical compound FC1=CC=C(OC(Cl)=O)C=C1 MSBGPEACXKBQSX-UHFFFAOYSA-N 0.000 claims description 16
- 239000004014 plasticizer Substances 0.000 claims description 14
- 238000004898 kneading Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 5
- LYAGTVMJGHTIDH-UHFFFAOYSA-N diethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCO[N+]([O-])=O LYAGTVMJGHTIDH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 4
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 claims description 4
- 238000005422 blasting Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 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 3
- 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 3
- 239000000028 HMX Substances 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 description 57
- 238000004519 manufacturing process Methods 0.000 description 32
- 238000002360 preparation method Methods 0.000 description 23
- 238000004140 cleaning Methods 0.000 description 15
- 238000005498 polishing Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229910000416 bismuth oxide Inorganic materials 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 8
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 8
- 238000013459 approach Methods 0.000 description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 7
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229910000994 Tombac Inorganic materials 0.000 description 5
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 5
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 4
- ADCBKYIHQQCFHE-UHFFFAOYSA-N 1,3-dimethyl-1,3-diphenylurea Chemical compound C=1C=CC=CC=1N(C)C(=O)N(C)C1=CC=CC=C1 ADCBKYIHQQCFHE-UHFFFAOYSA-N 0.000 description 4
- NKOUWLLFHNBUDW-UHFFFAOYSA-N Dipropyl hexanedioate Chemical compound CCCOC(=O)CCCCC(=O)OCCC NKOUWLLFHNBUDW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 241000723346 Cinnamomum camphora Species 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002611 lead compounds Chemical class 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- 230000002110 toxicologic effect Effects 0.000 description 3
- 231100000027 toxicology Toxicity 0.000 description 3
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229940039790 sodium oxalate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- -1 aliphatic nitric acid esters Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- QHGZFCAIXRVHID-UHFFFAOYSA-N ethyl n-methyl-n-phenylcarbamate Chemical compound CCOC(=O)N(C)C1=CC=CC=C1 QHGZFCAIXRVHID-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- IAGUPODHENSJEZ-UHFFFAOYSA-N methyl n-phenylcarbamate Chemical compound COC(=O)NC1=CC=CC=C1 IAGUPODHENSJEZ-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- AFQPDONMRFOLIJ-UHFFFAOYSA-N oxobismuthanylium Chemical compound [Bi+]=O AFQPDONMRFOLIJ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/04—Compositions characterised by non-explosive or non-thermic constituents for cooling the explosion gases including antifouling and flash suppressing agents
Definitions
- the invention relates to a pourable propellant charge powder with grains based on nitrocellulose containing bismuth as Entkupferungsadditiv. Furthermore, the invention relates to a process for the preparation of the propellant charge powder and to an ammunition with such a propellant powder.
- Free-flowing, nitrated cellulose-based propellant powders are used in the caliber ranges from 5.56 mm (small caliber) to 80 mm (medium caliber) in a wide front as drive for accelerating the respective projectile.
- Such bulk powders have been routinely used for several years and have proven themselves due to their high ballistic performance (high muzzle velocity), excellent chemical and ballistic stability (use in warm climates), cheap availability (good price / performance ratio, renewable raw materials, available in large quantities ) and good properties with respect to bombardment resistance (no detonative reaction when exposed to hollow charge jet or hot splinters).
- the use of lead has been widely used in several ammunition components.
- the bullet often contained lead to improve end-effect and trajectory.
- the double-core projectile which is made up of two lead cores of different hardness and a bullet jacket made of Tombak.
- the tombac sheath ensures a lower throughput resistance of the projectile and thus a reduced running load, since tombac alloys, which are composed of the elements copper and tin (Tombak is thus brass with a copper content of 70-90%), are very good cold formable.
- Lead compounds have also often been used for ignition, e.g. Bleiazide.
- Bi203 is suitable as an additive in the production of perforated propellant charge powder for decoppering.
- the additives should be in a range of 0-15 wt .-% move.
- the decoloring additive may be added separately to the powder mass.
- lead foils were used, which due to their toxicity may not be used in the future.
- Entkupferungsadditive be bismuth, indium, zinc and titanium metal resp. Alloys thereof mentioned.
- the application of the described method is problematic, since the significant difference in density between the additive composite and the bulk powder known to lead to a separation of the two different types of grain, resulting in an uncontrolled respectively. incomplete burning of the powder mass result.
- the addition of an additive composite to a normal bulk powder is technically more complex and therefore more expensive than the use of a uniformly structured drive.
- the additive composite burns only incomplete because of its high content of inert material, which can lead to increased residue formation.
- the object of the invention is to provide a pourable propellant powder belonging to the technical field mentioned at the outset, which leaves less copper deposits in the barrel of the rifle or gun and is environmentally harmless.
- the bismuth compound is contained in the grains in an amount of 0.1-2% by weight.
- metallic / elemental bismuth may be used alone (i.e., without any other metal such as tin or the like) as a decoloring additive.
- bismuth (III) oxide as bismuth compound.
- bismuth oxide (Bi 2 O 3 , melting point 817 ° C, boiling point 1'890 ° C, Density 8.9 g / ccm, CAS no. 1304-76-3, EINECS no. 215-134-7) with a mean grain diameter of 10 microns.
- elemental bismuth (CAS No. 7440-69-9, EINECS No. 231-177-4)
- bismuth carbonate oxide CAS No. 5891-10-4, EINECS No. 227-567-9) a surprisingly clear decolouring effect.
- the bismuth or the bismuth compound should in any case be present in the form of very fine grains ( ⁇ 100 microns). A particle size of less than 20 micrometers is preferred.
- the bismuth compound (or elemental bismuth) may be distributed in the grain matrix underlying the grains or on the surface or in a surface forming layer of the grains.
- the bismuth compound is added during the surface treatment so that the bismuth compound and the metallic bismuth, respectively, have a higher concentration in the near-surface layer than in the grain matrix.
- the surface layer in question is e.g. formed together with the graphite powder and has a thickness of typically up to 50 microns. However, other solids may also be included in the surface layer (such as lime or potassium sulfate).
- the graphite powder is used in a known amount ( ⁇ 1 wt .-%).
- the bismuth compound or metallic bismuth should be present as powders having a particle size of less than 100 microns, more preferably 20 microns or less. Fine bismuth powders have proven to be particularly effective.
- the total amount of bismuth compound contained in the powder grain is incorporated in about half of the total amount in the grain matrix and about half in the near-surface layer. The concentration is thus greater immediately below the surface than inside the grain.
- the bismuth (III) oxide is preferably present in a concentration of between 0.5% and 1.2% by weight.
- the small, medium and large caliber based bulk powder is based on nitrocellulose with a nitrogen content between 11-13.5% by weight and can be used as further energetic additives Explosive oils (NGL or DEGN or their combination) or energetic plasticizers (Bu-NENA, Et-NENA or Me-NENA or their combination).
- nitroglycerin (NGL) is provided in an amount between 3-20% by weight in a near-surface layer.
- the size of the near-surface layer depends on the depth of diffusion that the NGL achieves during surface treatment (eg, diffusion depth d between 100-500 microns).
- the nitroglycerin content is in the range of 4-8 wt% for medium caliber and 10-17 wt% for small caliber.
- Blasting oils can be homogeneously distributed in the grain matrix (2-base bulk powder) or concentrated in the outer layer of the grain matrix (so-called EI® powder, see EP 1 164 116 A1). If the grain matrix no energetic plasticizer resp. Contains explosive oils, it is 1-base bulk powders.
- the grains have e.g. a maximum geometric extension of 20 mm. If the geometry of the grains is cylindrical, the ratio of length (L) to diameter (D) is 0.25-5, with a length of the grain between 0.3-10 mm and the diameter of the circular cylindrical grain between 0.3-10 mm. If the geometry of the grains is spherical, the diameter of the grains usually ranges between 0.2-20 mm, preferably between 1-5 mm.
- the thickness is between 0.3-5 mm and the diagonal between 1-15 mm.
- the grains may contain crystalline energy carriers and / or energetic plasticizers or blasting oils as further main components.
- crystalline energy carrier for example, one of the following substances is used: nitroguanidine (CAS #: 556-88-7), hexogen (CAS #: 121-82-4) and octogen (CAS #: 2691-41-0).
- Suitable energy softeners are nitroglycerin, diethylene glycol dinitrate, Me-NENA, Et-NENA, Bu-NENA. Of course, two or more of these substances can be combined.
- the total amount of these energetic liquid additives is between 0-40 wt .-% compared to the nitrocellulose, preferably between 5-20 wt .-%.
- the crystalline energy carriers can be added during the kneading of the dough mass.
- the weight percentages of the crystalline energy carriers are between 0-45 wt .-% of the powder mass, the weight percentages of energy plasticizers between 0-45 wt .-%. Together, the weight should not be more than 75 wt .-% of the powder mass.
- bismuth (III) oxide in a concentration between 0.1-2 wt .-%
- the energetic plasticizer in a concentration between 0-25 wt .-%
- the crystalline energy sources in a concentration between 0-30 wt .-% in front.
- the energetic plasticizer and the crystalline Energy sources represent a proportion of not more than 50 wt .-%. If neither an energetic plasticiser nor a crystalline energy source are provided (both 0%), then one speaks of a one-base propellant charge powder (only NC as energy carrier).
- a method according to the invention for the production of a propellant charge powder is characterized in a first embodiment in that the bismuth compound or the metallic bismuth is introduced into a near-surface layer of the grain during the polishing process (finishing). If the bismuth or bismuth compound is to be homogeneously distributed in the grain matrix, the said decoloring additive is added to the kneading compound prior to extrusion. Thereafter, the green grain can be formed by extrusion.
- the propellant powder makes it possible to produce small, medium and large caliber ammunition which has a lead-free bullet and a lead-free igniter.
- the green powder may contain other known additives, for example for improving the ignition behavior and for modulating the burn-off behavior.
- All of the additives mentioned are added to the dough mass during green grain production, i. they are evenly distributed in the grain matrix.
- the total amount of these additives in the green grain is between 0-20 wt .-% compared to the nitrocellulose, preferably between 5-15 wt .-%.
- the production of the bulk powders according to the invention comprises the known process steps "kneading with solvents”, “extrusion by die”, “drying” and “finishing” (surface treatment).
- the bismuth compound is added either during kneading (homogeneous distribution in the grain matrix) or during finishing (enrichment at grain surface).
- the bulk powder may optionally be accompanied by other additives.
- additives include on the one hand the classic blasting oils nitroglycerin (NGL, CAS #: 55-63-0) or diethylene glycol dinitrate (DEGN, CAS #: 693-21-0).
- NGL classic blasting oils
- DEGN diethylene glycol dinitrate
- a variety of other energetic plasticizers is also known. These include in particular low molecular weight aliphatic nitric acid esters, nitro compounds, nitramines and azides.
- a particularly suitable class of substances are the so-called 2-nitroxyethyl-nitramines (alkyl-NE-NA) having the general structural formula (1), where R 1 is an aliphatic radical:
- the total amount of these energetic liquid additives is between 0-40 wt .-% compared to the nitrocellulose, preferably between 5-20 wt .-%.
- the liquid additives are either distributed homogeneously in the grain matrix, wherein the powder production is carried out by the known processes kneading / rolling / pressing.
- an enrichment in the outer zones of the powder grain is conceivable, whereby the production of such bulk powder by impregnation of a green grain in aqueous emulsion takes place (see, EP 1 164 116 A 1).
- the bulk powders according to the invention have the following geometries: Cylindrical with 0-30 (preferably 1-19) axial longitudinal channels.
- the outer diameters are between 0.3-15 mm (preferably 0.5-7.5 mm), the lengths are 0.3-15 mm (preferably 0.5-7.5 mm).
- the ratio of grain length to grain diameter is 0.5-3.0 (preferably 1.0-1.5).
- the diameters of the longitudinal channels are between 0.05-0.5 mm (preferably 0.1-0.4 mm). In the case of the spherical grain geometry, the diameters are in the range of 0.3-5.0 mm (preferably 0.5-2.0 mm).
- the geometric dimensions of the bulk powders included in the present application are primarily determined by the caliber range. So can the powder grains for Small caliber applications (caliber range from about 5.56 to about 20 mm) on the one hand have cylindrical geometries with a diameter of about 0.5-3 mm, wherein the length of a powder grain is typically about 0.5 to 2.0 times the value of the respective grain diameter.
- the cylindrical powders may contain longitudinal channels extending in the axial direction for influencing the burning behavior.
- 1- and 7-hole geometries have proven particularly useful, wherein the diameter of the hole zones is typically between 0.05 to 0.5 mm.
- the spherical grain geometry has also proven successful in the small bore range, with the ball diameters typically ranging from 0.3 to 2.0 mm, depending on the caliber range.
- Fig. 1 the course of the bismuth (III) oxide concentration of a preferred embodiment is shown schematically.
- the bismuth compound acting as a decoloring additive in this example is one half in the grain matrix (i.e., in the whole grain volume) and the other half in the surface layer.
- the outer diameter D is e.g. 0.7-1 mm.
- the surface layer thickness d is e.g. 50 microns. ( Figure 1 is not drawn to scale.)
- Production Example 1 (0.35% by weight of bismuth oxide on the grain surface and 0.35% by weight in the interior of the grain, NGL on the grain surface)
- a 1-hole green powder with 0.73 mm outside diameter, 0.93 mm length and 0.10 mm hole diameter composed of the solid portions of 1.5% by weight of acardite II, 1% by weight potassium sulfate, 0.35% by weight bismuth (III) oxide and 97.4 wt .-% nitrocellulose having a nitrogen content of 13.15 wt .-% and prepared in the manner known in the powder art by pressing a solvent-moist kneading dough through a die, are equipped in a 1'000 liter steel reactor equipped with mechanical paddle , Lid inlet valve, bottom outlet valve and vacuum connections, with twice the amount of water added.
- the batch is heated to a temperature of 80 ° C. Thereafter, a mixture containing 25 kg of nitroglycerin (12.5 wt .-%) and 0.5 kg (0.25 wt .-%) 2-nitrodiphenylamine, dissolved in ethanol, added dropwise. It is allowed at optimal baking mix adjustment (powder bed completely in suspension) and then drips a suspension containing 6.0 kg (3 wt .-%) of a highly viscous at room temperature polyester compound having an average molecular weight of 1'500 g / mol in water. Then allowed to aftertreat stirring. Subsequently, the pressure in the reactor vessel is slowly reduced and distilled off parts of the solvent from the liquor.
- the vacuum is broken and cooled the approach.
- the remaining liquid Parts of the approach drained by opening the bottom valve.
- the liquid portions are drained again through the bottom valve and the remaining wet powder matrix is then removed from the reactor.
- the wet powder is dried and then finished by polishing about 0.3 wt .-% graphite, 0.35 wt .-% finely pulverized bismuth (III) oxide and optionally other special moderators in a known manner in the polishing drum.
- the resulting bulk powder has a bulk density of 940 g / l with an energy content of 3893 J / g.
- a 1-hole green powder having an outer diameter of 0.64 mm, a length of 1.03 mm and a hole diameter of 0.12 mm is first prepared, but in which no bismuth compound is added.
- This green powder is then treated analogously to Preparation Example 1 with nitroclycerol and the highly viscous at room temperature polyester compound having an average molecular weight of 1'500 g / mol.
- the polishing is carried out analogously to Preparation Example 1, but no bismuth compound is used.
- the finished bulk powder has a bulk density of 943 g / l with an energy content of 3,943 J / g.
- a 1-hole green powder having an outer diameter of 0.64 mm, a length of 1.03 mm and a hole diameter of 0.12 mm is first prepared, but in which no bismuth compound is added.
- This green powder is then treated analogously to Preparation Example 1 with nitroclycerol and the highly viscous at room temperature polyester compound having an average molecular weight of 1'500 g / mol.
- the polishing is carried out analogously to Preparation Example 1, during which, however, 0.7% by weight of finely powdered bismuth powder is used during the polishing.
- the finished bulk powder has a bulk density of 940 g / l with an energy content of 3'918 J / g.
- a bulk powder is prepared analogously to Preparation Example 2, but 0.7% by weight of finely powdered bismuth carbonate oxide is used during the polishing.
- the finished bulk powder has a bulk density of 920 g / l with an energy content of 3'919J / g.
- a bulk powder is prepared analogously to Preparation Example 2, but during the refinement, however, 0.7% by weight of finely powdered bismuth (III) oxide is used.
- the finished bulk powder has a bulk density of 945 g / l with an energy content of 3,923 J / g.
- a bulk powder is prepared analogously to Preparation Example 2, but 0.7% by weight of finely powdered tin dioxide is used during the polishing.
- the finished bulk powder has a bulk density of 925 g / l with an energy content of 3'919 J / g.
- a 1-hole green powder with 0.75 mm outside diameter, 0.97 mm length and 0.12 mm hole diameter is first produced, in which, however, 0.7 wt .-% bismuth (III) oxide is added.
- This green powder is then treated analogously to Preparation Example 1 with nitroclycerol and the polyester at room temperature highly viscous compound having an average molecular weight of 3,000 g / mol.
- the polishing is carried out analogously to Preparation Example 1, but no bismuth compound is used.
- the finished bulk powder has a bulk density of 923 g / l with an energy content of 3,921 J / g.
- a laboratory polishing drum made of glass with 1 liter internal volume and a drum temperature of 60 ° C to 100 g of a finished spherical powder with 0.39 mm diameter, a bulk density of 990 g / l and an energy content of 3'812 J / g, which in addition to nitrocellulose with a nitrogen content of 13.15 wt .-% as further main ingredients nitroglycerin (10 wt .-%), dibutyl phthalate (4.5 wt .-%), a mixture of 0.7g (0.7 wt .-%) bismuth (III) oxide and 0.1 g (0.1 wt.%) of graphite dispersed in 5 ml of ethanol.
- the bulk powder is then allowed to turn for 1 hour with the lid closed. Thereafter, continue to rotate with the removal opening open until the bulk powder shows a shiny surface. The bulk powder is then removed from the polishing drum and then dried for 20 hours at a temperature of 60 ° C. The finished bulk powder has a bulk density of 966 g / l and an energy content of 3'782 J / g.
- the bulk powder is then allowed to turn for 1 hour with the lid closed. Then, with the removal opening open, continue to turn until the bulk powder has a shiny surface. The bulk powder is then removed from the polishing drum and then dried for 20 hours at a temperature of 60 ° C. The finished bulk powder has a bulk density of 1'025 g / l and an energy content of 3'236 J / g.
- a polishing drum made of copper with 50 liters internal volume and a drum temperature of 60 ° C to 5 kg of a finished 19-hole powder with a mean outer diameter of 3.61 mm, a mean grain length of 3.80 mm, a mean hole diameter of 0.12 mm and a average wall thickness of 0.58 mm, a bulk density of 1'060 g / l and an energy content of 3'956 J / g, which in addition to nitrocellulose with a nitrogen content of 13.15 wt .-% as further main ingredients nitroguanidine (5.0 wt .-%) and Diethylene glycol dinitrate (18% by weight), a mixture of 35 g (0.7% by weight) of bismuth (III) oxide and 5 g (0.1% by weight) of graphite dispersed in 300 ml 94% by weight industrial spirit, added.
- the bulk powder is then allowed to turn for 1 hour with the lid closed. Thereafter, continue to rotate with the removal opening open until the bulk powder shows a shiny surface. The bulk powder is then removed from the polishing drum and then dried for 20 hours at a temperature of 60 ° C. The finished bulk powder has a bulk density of 1,055 g / l and an energy content of 3,932 J / g.
- Production Example 11 (0.35% by weight of bismuth oxide in grain matrix, NGL on grain surface)
- a 1-hole green powder with 0.73 mm outside diameter, 0.93 mm in length and 0.10 mm hole diameter is first produced.
- This green powder is then treated analogously to Preparation Example 1 with nitroglycerin and the polyester at room temperature highly viscous compound having an average molecular weight of 3000 g / mol.
- the polishing is carried out analogously to Preparation Example 1, but no bismuth compound is used.
- the finished bulk powder has a bulk density of 891 g / l with an energy content of 3'892 J / g.
- Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 130 double strokes.
- Application example 2 Powder from production example 6, cleaning effort in lead-free 5.56 mm cartridge with Sintox ignition.
- Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 110 double strokes.
- Cartridge casings filled with sintered ignition elements were filled with bulk powder from Production Example 3 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 20 double strokes.
- Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 4 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 30 double strokes.
- Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 5 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 10 double strokes.
- Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet. This was 1,500 cartridges fired, the cleaning effort was determined after every 100 shots. The cleaning effort required to produce the original tube condition was between 10 and 20 double strokes for the shot loads examined (100 rounds, 200 rounds, 300 rounds, etc.). When using a non-bismuth-containing reference powder when using the same cartridge and ignition element is the weapon barrel after the same shot load no longer clean and is therefore unusable.
- Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet. This was 1,500 cartridges fired, the caliber at the mouth of the muzzle was determined after every 100 shots. After 800 shots occurred in the use of a non-bismuth-containing reference powder, a caliber extension of 5.54 mm to 5.55 mm, in the powder of Preparation Example 1, however, the caliber at the mouth after 1'500 shots compared to the initial state unchanged at 5.54 mm.
- Example of Use 8 Powder from Production Example 1, Free Flight with Lead-Free 5.56 mm Cartridge with Lead-Free Ignition.
- Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet.
- 1,400 cartridges were fired, whereby the free flight (distance between sleeve mouth and introduction into running trains) after every 100 shots was determined.
- the free flight increased from 3.0 to 3.1 mm, after 800 shots from 3.1 to 3.2 mm and after 1 400 shots from 3.2 to 3.3 mm.
- the first enlargement of the free flight by 0.1 mm only occurred after 700 shots, until 1,400 shots no longer changed.
Abstract
Description
Die Erfindung betrifft ein schüttbares Treibladungspulver mit Körnern auf der Basis von Nitrocellulose enthaltend Bismuth als Entkupferungsadditiv. Weiter bezieht sich die Erfindung auf ein Verfahren zur Herstellung des Treibladungspulvers und auf eine Munition mit einem solchen Treibladungspulver.The invention relates to a pourable propellant charge powder with grains based on nitrocellulose containing bismuth as Entkupferungsadditiv. Furthermore, the invention relates to a process for the preparation of the propellant charge powder and to an ammunition with such a propellant powder.
Rieselfähige, auf nitrierter Cellulose basierende Treibladungspulver werden in den Kaliberbereichen von 5.56 mm (Kleinkaliber) bis gegen 80 mm (Mittelkaliber) in breiter Front als Antrieb zur Beschleunigung des jeweiligen Geschosses eingesetzt. Derartige Schüttpulver sind seit mehreren Jahren routinemässig im Einsatz und haben sich bewährt aufgrund ihrer hohen ballistischen Leistungsfähigkeit (hohe Mündungsgeschwindigkeit), ausgezeichneten chemischen und ballistischen Stabilität (Einsatz in warmen Klimazonen), günstigen Verfügbarkeit (gutes Preis/Leistungsverhältnis, erneuerbare Rohstoffe, in grossen Mengen verfügbar) und guten Eigenschaften bezüglich Beschussfestigkeit (keine detonative Umsetzung bei Einwirkung von Hohlladungsstrahl oder heissen Splittern).Free-flowing, nitrated cellulose-based propellant powders are used in the caliber ranges from 5.56 mm (small caliber) to 80 mm (medium caliber) in a wide front as drive for accelerating the respective projectile. Such bulk powders have been routinely used for several years and have proven themselves due to their high ballistic performance (high muzzle velocity), excellent chemical and ballistic stability (use in warm climates), cheap availability (good price / performance ratio, renewable raw materials, available in large quantities ) and good properties with respect to bombardment resistance (no detonative reaction when exposed to hollow charge jet or hot splinters).
Insbesondere im Kleinkaliberbereich ist die Verwendung von Blei bisher in mehreren Munitionskomponenten allgemein verbreitet. So enthielt das Geschoss zur Verbesserung von Endzielwirkung und Flugbahn oftmals Blei. Als Beispiel sei z.B. das Doppelkerngeschoss erwähnt, welches aus zwei Bleikernen unterschiedlicher Härte und einem Geschossmantel aus Tombak aufgebaut ist. Der Tombakmantel sorgt für einen geringeren Durchpresswiderstand des Geschosses und damit für eine reduzierte Laufbelastung, da Tombaklegierungen, die sich aus den Elementen Kupfer und Zinn zusammensetzen (Tombak ist somit Messing mit einem Kupfergehalt von 70-90 %), sehr gut kalt verformbar sind. Auch für die Anzündung wurden häufig Bleiverbindungen eingesetzt, z.B. Bleiazide.Especially in the small caliber area, the use of lead has been widely used in several ammunition components. Thus, the bullet often contained lead to improve end-effect and trajectory. As an example, see mentions the double-core projectile, which is made up of two lead cores of different hardness and a bullet jacket made of Tombak. The tombac sheath ensures a lower throughput resistance of the projectile and thus a reduced running load, since tombac alloys, which are composed of the elements copper and tin (Tombak is thus brass with a copper content of 70-90%), are very good cold formable. Lead compounds have also often been used for ignition, e.g. Bleiazide.
In neuerer Zeit werden bezüglich umweltbelastender Emissionen, welche durch die Anwendung resp. Verwendung von bleihaltiger Munition ausgehen, verschärfte Vorschriften eingeführt. So hat z.B. Schweden beschlossen, ab 2007 nur noch bleifreie Geschosse zuzulassen.More recently, with respect to polluting emissions, which by the application resp. Use of leaded ammunition emanated, tightened regulations introduced. For example, Sweden decided to allow only unleaded bullets from 2007 onwards.
Seit mehreren Jahren sind daher Entwicklungen im Gange, welche darauf abzielen, die Verwendung von Blei und dessen Verbindungen gänzlich zu umgehen. So wurde in neuerer Zeit eine neue Generation bleifreier Geschosse und bleifreier Anzündungen entwickelt. Charakteristisch für derartige moderne Geschosse ist das Fehlen des traditionellen Bleikerns. Dieser wurde durch plastisch verformbare, homogene Werkstoffe ersetzt, welche typischerweise aus Kupfer oder einer Kupferlegierung bestehen. Auch bei diesen neuen Geschossen kann der Geschossmantel aus Tombak bestehen. Anzündungsseitig sind mittlerweile toxikologisch verbesserte Varianten entwickelt worden, z.B. der blei- und bariumfreie Sintox-Zündsatz der Firma RUAG Ammotec.For several years now, developments have been underway aimed at completely circumventing the use of lead and its compounds. Thus, a new generation of lead-free bullets and lead-free ignitions has recently been developed. Characteristic of such modern projectiles is the absence of the traditional lead core. This was replaced by plastically deformable, homogeneous materials, which typically made of copper or a copper alloy. Even with these new floors, the bullet jacket can consist of Tombak. On the ignition side, toxicologically improved variants have now been developed, for example the lead- and barium-free Sintox ignition set from RUAG Ammotec.
Es ist aus Erfahrung bekannt, dass beim Verschiessen kupferhaltiger Geschosse unerwünschte Verengungen im Lauf entstehen können. Diese bestehen aus Ablagerungen von Kupfer, welche auch bei grossem Reinigungsaufwand nicht mehr vollständig entfernt werden können und bewirken, dass das Rohr bereits nach einer relativ tiefen Schussbelastung ersetzt werden muss. Das Geschoss wird durch den enormen Gasdruck durch den Lauf getrieben, woraus eine äusserst starke Reibung zwischen dem Geschossmaterial und dem Stahl des Laufs resultiert. Auch ein spiegelblanker Lauf hat mikrofeine Poren, welche vom Geschossmaterial zugeschmiert werden. Zudem hat sich gezeigt, dass abgeschmiertes Material zu weiteren Ablagerungen führt. Züge- und Feldkanten werden mit der Zeit abgerundet, wodurch natürlich nach und nach die Präzision des Laufes beeinträchtigt wird. Der Reibungswiderstand wächst und die Geschossgeschwindigkeit fällt dabei entsprechend ab. Zunehmende Ablagerungen führen zu Präzisionsabfall. Diese allgemeinen Betrachtungen gelten grundsätzlich für Gross-, Mittel-wie auch Kleinkaliber-Applikationen.It is known from experience that when copper-containing projectiles are fired, unwanted narrowing can occur in the barrel. These consist of deposits of copper, which can not be completely removed even with great cleaning effort and cause the pipe to be replaced after a relatively low load. The bullet is driven through the barrel by the tremendous gas pressure resulting in an extremely strong friction between the bullet material and the steel of the barrel. A mirror-like barrel also has microfine pores, which are smeared by the bullet material. In addition, it has been shown that lubricated material leads to further deposits. Trace and field edges are rounded off over time, which of course gradually reduces the precision of the barrel. The frictional resistance increases and the projectile velocity drops accordingly. Increasing deposits lead to precision waste. These general considerations apply in principle to large, medium and small caliber applications.
Es ist weiter bekannt, dass Blei oder dessen Verbindungen, welche zusammen mit der Munition verschossen werden, derartige Rohr-Aufkupferungen wirkungsvoll zu unterbinden vermag (W.M. Robertson, Decoppering of gun tubes by lead, Army Armament Command, Rock Island, IL, USA, Gov. Rep. Announce. Index (US) 1975, 75(23), 164, CAS 1976: 139485). Es versteht sich von selbst, dass die Möglichkeit einer Blei-Zugabe zur Verhinderung des unerwünschten Aufkupferungs-Effekts bei bleifreier Munition entfällt.It is also known that lead or its compounds, which are shot together with the ammunition, can effectively suppress such tube copper plating (WM Robertson, Decoppering of gun tubes by lead, Army Armament Command, Rock Island, IL, USA, Gov Rep. Announce Index (US) 1975, 75 (23), 164, CAS 1976: 139485). It goes without saying that there is no possibility of lead addition to prevent the unwanted copper-up effect of lead-free ammunition.
Ein möglicher Ansatz zur Umgehung der Aufkupferungs-Problematik besteht darin, in gewissen Abständen ein sogenanntes "Entkupferungsgeschoss" zu verschiessen. Dieses Vorgehen weist jedoch erhebliche logistische Nachteile auf. Zum Erreichen eines maximalen Entkupferungseffekts kann das "Entkupferungsgeschoss" zudem hohe Anteile von Bleiverbindungen enthalten, was umwelttoxikologisch nicht erwünscht ist. Eine weitere Möglichkeit besteht in der mechanischen Entfernung mit speziellen Reinigungsgeräten, welche z.B. als Bürste mit stark abrasivem Drahtmaterial aufgebaut sein können.One possible approach to circumvent the copper-plating problem is to shoot a so-called "decoupling bullet" at intervals. However, this approach has significant logistical disadvantages. To achieve a maximum Entkupferungseffekts the "Entkopferungsgeschoss" may also contain high levels of lead compounds, which is not environmentally toxicologically desirable. Another possibility is the mechanical removal with special cleaning equipment, which may be constructed, for example, as a brush with highly abrasive wire material.
Ein weiterer Ansatz besteht in der direkten Einarbeitung des Entkupferungsadditivs in das Schüttpulver (WO 03/066544, Nexplo Bofors AB). Hierbei gelangen Kombinationen aus Zinn und Bismuth zum Einsatz, wobei Zinn bzw. Bismuth in metallischer Form, in legierter Form oder in Verbindungen vorgeschlagen werden. Der Zinnanteil soll 10-62 % und der Bismuthanteil 38-90 % betragen. Da die Umwelttoxizität von Zinn-Verbindungen jedoch deutlich höher ist als bei Bismuth-Verbindungen, stellt sich bei diesem Ansatz der umwelttoxikologische Fortschritt nur eingeschränkt ein.Another approach is the direct incorporation of the Entkupferungsadditivs in the bulk powder (WO 03/066544, Nexplo Bofors AB). In this case, combinations of tin and bismuth are used, with tin or bismuth being proposed in metallic form, in alloyed form or in compounds. The tin content should be 10-62% and the bismuth fraction 38-90%. However, since the environmental toxicity of tin compounds is significantly higher than that of bismuth compounds, this approach has limited environmental toxicological progress.
Aus der EP 1 031 547 A1 bzw. der US 2001/0042576 A1 ist bekannt, dass Bi203 als Zusatzstoff bei der Herstellung von perforierten Treibladungspulver zur Entkupferung geeignet ist. Die Additive sollen sich dabei in einem Bereich von 0-15 Gew.-% bewegen.It is known from
In Grosskaliber-Anwendungen kann das Entkupferungsadditiv separat der Pulvermasse zugegeben werden. Hierbei wurden früher Bleifolien verwendet, welche wegen deren Toxizität in Zukunft jedoch nicht mehr verwendet werden dürfen. Als Alternative wird die Zugabe einer Additiv-Compositeverbindung (=Zusatzstoff) beschrieben, in welcher das Entkupferungsadditiv in Mengen von 5-95 % in einen energetischen Binder eingearbeitet wird (US 5,565,643, EP 0 805 943 B1). Als Entkupferungsadditive werden Bismuth-, Indium-, Zink- und Titan-Metall resp. Legierungen hiervon erwähnt. In der Praxis ist die Anwendung des beschriebenen Verfahrens jedoch problematisch, da der deutliche Dichteunterschied zwischen dem Additiv-Composite und dem Schüttpulver bekanntermassen zu einer Entmischung der beiden verschiedenen Korntypen führt, was einen unkontrollierten resp. unvollständigen Abbrand der Pulvermasse zur Folge hat. Zudem ist die Zugabe eines Additiv-Composits zu einem normalen Schüttpulver technisch aufwändiger und daher teurer als die Verwendung eines einheitlich aufgebauten Antriebs. Ferner brennt das Additiv-Composite wegen dessen hohen Anteil an Inertmaterial nur unvollständig ab, was zu erhöhter Rückstandbildung führen kann.In large caliber applications, the decoloring additive may be added separately to the powder mass. In the past lead foils were used, which due to their toxicity may not be used in the future. As an alternative, the addition of an additive composite compound (= additive) is described in which the Entkupferungsadditiv is incorporated in amounts of 5-95% in an energetic binder (US 5,565,643,
Es besteht daher in der Schüttpulver-Technik nach wie vor ein klarer Bedarf für eine effiziente technische Lösung, mit welcher sich die Rohraufkupferung wirkungsvoll und kosteneffizient unterbindenden lässt und welche die zuvor beschriebenen Nachteile wie etwa geringer toxikologischer Vorteil gegenüber bisherigen Bleiverbindungen, teurer Herstellungsprozess oder eingeschränkte Einsatzmöglichkeit bei Wärme und Kälte nicht aufweist.There is therefore still a clear need in the bulk powder technology for an efficient technical solution with which the copper oxide copper can be effectively and cost effectively prevented and which have the disadvantages described above such as low toxicological advantage over existing lead compounds, expensive manufacturing process or limited use does not have heat and cold.
Aufgabe der Erfindung ist es, ein dem eingangs genannten technischen Gebiet zugehörendes schüttbares Treibladungspulver zu schaffen, welches weniger Kupferablagerungen im Rohrlauf des Gewehrs bzw. Geschützes zurücklässt und umwelttoxikologisch unbedenklich ist.The object of the invention is to provide a pourable propellant powder belonging to the technical field mentioned at the outset, which leaves less copper deposits in the barrel of the rifle or gun and is environmentally harmless.
Die Lösung der Aufgabe ist durch die Merkmale des Anspruchs 1 definiert. Gemäss der Erfindung ist die Bismuth-Verbindung in einer Menge von 0.1-2 Gew.-% in den Körnern enthalten. Es kann auch metallisches/elementares Bismuth in Alleinstellung (d.h. ohne ein anderes Metall wie Zinn oder dergl.) als Entkupferungsadditiv eingesetzt werden.The solution of the problem is defined by the features of
Gegenüber dem Stand der Technik bietet die vorliegende Erfindung unter anderem folgende Vorteile:
- Kostengünstige Herstellung der die Rohraufkupferung unterbindenden Schüttpulvers (analog konventionellem Schüttpulver ohne Additiv)
- Keine Entmischung während Lagerung (da kein Zusatzstoff notwendig)
- Keine Empfindlichkeit gegenüber Einwirkung von Wärme und Kälte (Liner an Patronenwand, bei welchem Additiv in Binder eingearbeitet ist)
- Regelmässiger und rückstandfreier Abbrand der gesamten Pulvermasse (kein schwerverbrennbarer Additivzusatz, welcher das Entkupferungsadditiv enthält)
- Bestmögliche umwelttoxikologische Entlastung, da das Entkupferungsadditiv eine reine Bismuth-Verbindung ist, keine Zinnverbindungen enthält und bei tiefen Additiv-Konzentrationen von ca. 0.2-1.0 Gew.-% eingesetzt werden kann.
- Überraschenderweise tritt bei den erfindungsgemässen, das Entkupferungs-Additiv enthaltenden Schüttpulvern zusätzlich ein rohrschonender Effekt auf.
- Cost-effective production of bulk bulk copper powder (analog conventional bulk powder without additive)
- No segregation during storage (no additive necessary)
- No sensitivity to the effects of heat and cold (liner on cartridge wall, in which additive is incorporated in binder)
- Regular and residue-free burning off of the entire powder mass (no heavy-burnable additive additive containing the de-coppering additive)
- Best possible environmental toxicological relief, since the Entkupferungsadditiv is a pure bismuth compound, contains no tin compounds and can be used at low additive concentrations of about 0.2-1.0 wt .-%.
- Surprisingly, in addition, a tube-sparing effect occurs in the bulk powders according to the invention containing the de-coupling additive.
Sehr gute Resultate hat die Verwendung von Bismuth-(III)-oxid als Bismuthverbindung ergeben. In der Praxis wird Bismuth-oxid (Bi2O3, Schmelzpunkt 817°C, Siedepunkt 1'890°C, Dichte 8.9 g/ccm, CAS-Nr. 1304-76-3, EINECS-Nr. 215-134-7) mit einem mittleren Korn-durchmesser von 10 Mikrometer verwendet. Auch elementares Bismuth (CAS-Nr. 7440-69-9, EINECS-Nr. 231-177-4) und Bismuth-Carbonatoxid (CAS-Nr. 5891-10-4, EINECS-Nr. 227-567-9) zeigten einen überraschend deutlichen Entkupferungseffekt. Das Bismuth bzw. die Bismuthverbindung sollen in jedem Fall in Form feinster Körner (<100 Mikrometer) vorhanden sein. Bevorzugt ist eine Korngrösse von unter 20 Mikrometern.Very good results have resulted from the use of bismuth (III) oxide as bismuth compound. In practice, bismuth oxide (Bi 2 O 3 , melting point 817 ° C, boiling point 1'890 ° C, Density 8.9 g / ccm, CAS no. 1304-76-3, EINECS no. 215-134-7) with a mean grain diameter of 10 microns. Also, elemental bismuth (CAS No. 7440-69-9, EINECS No. 231-177-4) and bismuth carbonate oxide (CAS No. 5891-10-4, EINECS No. 227-567-9) a surprisingly clear decolouring effect. The bismuth or the bismuth compound should in any case be present in the form of very fine grains (<100 microns). A particle size of less than 20 micrometers is preferred.
Die Bismuth-Verbindung (bzw. das elementare Bismuth) kann in der Kornmatrix, welche den Körnern zugrunde liegt, verteilt sein oder auf der Oberfläche bzw. in einer die Oberfläche bildenden Schicht der Körner. Im erstgenannten Fall wird die Bismuth-Verbindung der Knetmasse während der TLP-Herstellung zugegeben (TLP = Treibladungspulver). Im zweitgenannten Fall wird die Bismuth-Verbindung während der Oberflächenbehandlung zugegeben, so dass die Bismuth-Verbindung bzw. das metallische Bismuth in der oberflächennahen Schicht eine höhere Konzentration hat als in der Kornmatrix. Die fragliche Oberflächenschicht wird z.B. zusammen mit dem Graphitpulver gebildet und hat eine Dicke von typischerweise bis zu 50 µm. Es können in der Oberflächenschicht aber auch noch andere Feststoffe enthalten sein (wie z.B. Kalk oder Kaliumsulfat). Das Graphitpulver wird in einer an sich bekannten Menge (< 1 Gew.-%) verwendet.The bismuth compound (or elemental bismuth) may be distributed in the grain matrix underlying the grains or on the surface or in a surface forming layer of the grains. In the former case, the bismuth compound is added to the kneading mass during the preparation of the TLP (TLP = propellant charge powder). In the latter case, the bismuth compound is added during the surface treatment so that the bismuth compound and the metallic bismuth, respectively, have a higher concentration in the near-surface layer than in the grain matrix. The surface layer in question is e.g. formed together with the graphite powder and has a thickness of typically up to 50 microns. However, other solids may also be included in the surface layer (such as lime or potassium sulfate). The graphite powder is used in a known amount (<1 wt .-%).
Die Bismuth-Verbindung bzw. das metallische Bismuth sollen als Pulver mit einer Korngrösse von unter 100 Mikrometern, insbesondere von 20 Mikrometern oder weniger vorhanden sein. Feine Bismuth-Pulver haben sich als besonders wirkungsvoll erwiesen.The bismuth compound or metallic bismuth should be present as powders having a particle size of less than 100 microns, more preferably 20 microns or less. Fine bismuth powders have proven to be particularly effective.
Gemäss einer bevorzugten Ausführungsform ist die insgesamt im Pulverkorn enthaltene Menge der Bismuth-Verbindung etwa zur Hälfte der Gesamtmenge in der Kornmatrix und etwa zur Hälfte in der oberflächennahen Schicht eingebracht. Die Konzentration ist also unmittelbar unter der Oberfläche grösser als im Inneren des Korns.According to a preferred embodiment, the total amount of bismuth compound contained in the powder grain is incorporated in about half of the total amount in the grain matrix and about half in the near-surface layer. The concentration is thus greater immediately below the surface than inside the grain.
Das Bismuth-(111)-oxid liegt vorzugsweise in einer Konzentration zwischen 0.5 Gew.-% und 1.2 Gew.-% vor.The bismuth (III) oxide is preferably present in a concentration of between 0.5% and 1.2% by weight.
Das Schüttpulver für Klein-, Mittel- und Grosskaliberbasis basiert auf Nitrocellulose mit einem Stickstoffgehalt zwischen 11-13.5 Gew.-% und kann als weitere energetische Zusatzstoffe Sprengöle (NGL oder DEGN resp. deren Kombination) oder energetische Weichmacher (Bu-NENA, Et-NENA oder Me-NENA resp. deren Kombination) enthalten. Vorzugsweise ist Nitroglycerin (NGL) in einer Menge zwischen 3-20 Gew.-% in einer oberflächennahen Schicht vorgesehen. Die Grösse der oberflächennahen Schicht hängt von der Diffusionstiefe ab, welche das NGL bei der Oberflächenbehandlung erreicht (z.B. Diffusionstiefe d zwischen 100-500 Mikrometer). Vorzugsweise liegt der Nitroglycerin-Anteil im Bereich von 4-8 Gew.-% für Mittelkaliber bzw. 10-17 Gew.-% für Kleinkaliber. Gegebenenfalls in der Kornmatrix vorhandenen energetischen Weichmacher resp. Sprengöle können homogen in der Kornmatrix verteilt sein (2-basige Schüttpulver) oder in der äusseren Schicht der Kornmatrix konzentriert sein (sogenannte EI®-Pulver, vgl. EP 1 164 116 A1). Falls die Kornmatrix keine energetischen Weichmacher resp. Sprengöle enthält, handelt es sich um 1-basige Schüttpulver.The small, medium and large caliber based bulk powder is based on nitrocellulose with a nitrogen content between 11-13.5% by weight and can be used as further energetic additives Explosive oils (NGL or DEGN or their combination) or energetic plasticizers (Bu-NENA, Et-NENA or Me-NENA or their combination). Preferably, nitroglycerin (NGL) is provided in an amount between 3-20% by weight in a near-surface layer. The size of the near-surface layer depends on the depth of diffusion that the NGL achieves during surface treatment (eg, diffusion depth d between 100-500 microns). Preferably, the nitroglycerin content is in the range of 4-8 wt% for medium caliber and 10-17 wt% for small caliber. Optionally in the grain matrix existing energetic plasticizer resp. Blasting oils can be homogeneously distributed in the grain matrix (2-base bulk powder) or concentrated in the outer layer of the grain matrix (so-called EI® powder, see
Die Form der Schüttpulver ist der jeweiligen Anwendung angepasst und kann sein: Zylindrisch mit in axialer Richtung verlaufenden Längskanälen (Lochzahl = 0-30), sphärisch oder blattartig flach (gewalzt).The shape of the bulk powders is adapted to the respective application and can be: Cylindrical with axial channels running in the axial direction (number of holes = 0-30), spherical or sheet-like flat (rolled).
Die Körner haben z.B. eine maximale geometrische Ausdehnung 20 mm. Wenn die Geometrie der Körner zylindrisch ist, beträgt das Verhältnis von Länge (L) zu Durchmesser (D) 0.25-5, wobei eine Länge des Korns zwischen 0.3-10 mm und der Durchmesser des kreiszylindrischen Korns zwischen 0.3-10 mm beträgt. Ist die Geometrie der Körner sphärisch, bewegt sich der Durchmesser der Körner in aller Regel zwischen 0.2-20 mm, bevorzugterweise zwischen 1-5 mm.The grains have e.g. a maximum geometric extension of 20 mm. If the geometry of the grains is cylindrical, the ratio of length (L) to diameter (D) is 0.25-5, with a length of the grain between 0.3-10 mm and the diameter of the circular cylindrical grain between 0.3-10 mm. If the geometry of the grains is spherical, the diameter of the grains usually ranges between 0.2-20 mm, preferably between 1-5 mm.
Wenn die Geometrie der Körner blattförmig ist, beträgt die Dicke zwischen 0.3-5 mm und die Diagonale zwischen 1-15 mm.If the geometry of the grains is leaf-shaped, the thickness is between 0.3-5 mm and the diagonal between 1-15 mm.
Die Körner können neben Nitrocellulose als weitere Hauptkomponenten kristalline Energieträger und/oder energetische Weichmacher bzw. Sprengöle enthalten. Als kristalliner Energieträger wird z.B. einer der folgenden Stoffe verwendet: Nitroguanidin (CAS-#: 556-88-7), Hexogen (CAS-#: 121-82-4) und Oktogen (CAS-#: 2691-41-0). Als energetische Weichmacher eignen sich Nitroglycerin, Diethylenglykoldinitrat, Me-NENA, Et-NENA, Bu-NENA. Es können natürlich auch zwei oder mehrere dieser Stoffe kombiniert werden.In addition to nitrocellulose, the grains may contain crystalline energy carriers and / or energetic plasticizers or blasting oils as further main components. As a crystalline energy carrier, for example, one of the following substances is used: nitroguanidine (CAS #: 556-88-7), hexogen (CAS #: 121-82-4) and octogen (CAS #: 2691-41-0). Suitable energy softeners are nitroglycerin, diethylene glycol dinitrate, Me-NENA, Et-NENA, Bu-NENA. Of course, two or more of these substances can be combined.
Die Gesamtmenge dieser energetischen Flüssigzusätze liegt zwischen 0-40 Gew.-% gegenüber der Nitrocellulose, bevorzugt zwischen 5-20 Gew.-%. Die kristallinen Energieträger können während der Knetung der Teigmasse zugegeben werden.The total amount of these energetic liquid additives is between 0-40 wt .-% compared to the nitrocellulose, preferably between 5-20 wt .-%. The crystalline energy carriers can be added during the kneading of the dough mass.
Die gewichtsmässigen Anteile der kristallinen Energieträger betragen zwischen 0-45 Gew.-% der Pulvermasse, die gewichtsmässigen Anteile der energetischen Weichmacher zwischen 0-45 Gew.-%. Zusammen sollten die Gewichtsanteile nicht mehr als 75 Gew.-% der Pulvermasse betragen.The weight percentages of the crystalline energy carriers are between 0-45 wt .-% of the powder mass, the weight percentages of energy plasticizers between 0-45 wt .-%. Together, the weight should not be more than 75 wt .-% of the powder mass.
Insgesamt liegen Bismuth-(III)-oxid in einer Konzentration zwischen 0.1-2 Gew.-%, der energetische Weichmacher in einer Konzentration zwischen 0-25 Gew.-% und der kristalline Energieträger in einer Konzentration zwischen 0-30 Gew.-% vor. Zusammen sollen der energetische Weichmacher und der kristalline Energieträeger einen Anteil von nicht mehr als 50 Gew.-% darstellen. Wenn weder ein energetischer Weichmacher noch ein kristalliner Energieträger vorgesehen sind (beide 0 %), dann spricht man von einem einbasigen Treibladungspulver (nur NC als Energieträger).Overall, bismuth (III) oxide in a concentration between 0.1-2 wt .-%, the energetic plasticizer in a concentration between 0-25 wt .-% and the crystalline energy sources in a concentration between 0-30 wt .-% in front. Together, the energetic plasticizer and the crystalline Energieträeger represent a proportion of not more than 50 wt .-%. If neither an energetic plasticiser nor a crystalline energy source are provided (both 0%), then one speaks of a one-base propellant charge powder (only NC as energy carrier).
Ein erfindungsgemässes Verfahren zur Herstellung eines Treibladungspulvers zeichnet sich in einer ersten Ausprägung dadurch aus, dass die Bismuth-Verbindung oder das metallische Bismuth während dem Polierprozess (Finishing) in eine oberflächennahe Schicht des Korns eingebracht wird. Soll das Bismuth bzw. die Bismuth-Verbindung in der Kornmatrix homogen verteilt sein, wird das genannte Entkupferungsadditiv der Knetmasse vor der Extrusion zugegeben. Danach kann das Grünkorn durch Extrusion geformt werden.A method according to the invention for the production of a propellant charge powder is characterized in a first embodiment in that the bismuth compound or the metallic bismuth is introduced into a near-surface layer of the grain during the polishing process (finishing). If the bismuth or bismuth compound is to be homogeneously distributed in the grain matrix, the said decoloring additive is added to the kneading compound prior to extrusion. Thereafter, the green grain can be formed by extrusion.
Mit dem Treibladungspulver kann eine Munition für Klein-, Mittel- und Grosskaliber hergestellt werden, welche ein bleifreies Geschoss und eine bleifreie Anzündung aufweist.The propellant powder makes it possible to produce small, medium and large caliber ammunition which has a lead-free bullet and a lead-free igniter.
Es können in der Pulvertechnik bekannte Zusätze zur Stabilisierung, Rohrschonung, Weichmachung und Feuerscheindämpfung verwendet werden:
- Zusätze zur Stabilitätserhöhung sind z.B. Natriumhydrogenkarbonat (CAS-#: 144-55-8), Calziumkarbonat (CAS-#: 471-34-1), Magnesiumoxid (CAS-#: 1309-48-4), Akardit II (CAS-#: 724-18-5), Centralit I (CAS-#: 90-93-7), Centralit II (CAS-#: 611-92-7), 2-Nitrodiphenylamin (CAS-#: 836-30-6) und Diphenylamin (CAS-#: 122-39-4).
- Zusätze zur Weichmachung sind z.B. Diethylphthalat (CAS-#: 84-66-2), Campher (CAS-#: 76-22-2), Dibutylphthalat (CAS-#: 84-74-2), Di-n-propyladipat (CAS-#: 106-19-4) oder Methylphenylurethan (CAS-#: 261-79-6).
- Zusätze zur Rohrschonung sind z.B. Magnesiumoxid (CAS-#: 1303-48-4), Molybdäntrioxid (CAS-#: 1313-27-5), Magnesiumsilikat (CAS-#: 14807-96-6), Calciumkarbonat (CAS-#: 471-34-1) oder Titandioxid (CAS-#: 13463-67-7).
- Zusätze zur Feuerscheindämpfung sind z.B. Natriumoxalat (CAS-#: 62-76-0), Katiumbitarat (CAS-#: 868-14-4), Natriumhydrogenkarbonat (CAS-#: 144-55-8), Kaliumhydrogenkarbonat (CAS-#: 298-14-6), Natriumoxalat (CAS-#: 62-76-0), Kaliumsulfat (CAS-#: 7778-80-5) oder Kaliumnitrat (CAS-#: 7757-79-1).
- Additives for increasing stability include sodium hydrogen carbonate (CAS #: 144-55-8), calcium carbonate (CAS #: 471-34-1), magnesium oxide (CAS #: 1309-48-4), acardite II (CAS # : 724-18-5), Centralit I (CAS #: 90-93-7), Centralit II (CAS #: 611-92-7), 2-Nitrodiphenylamine (CAS #: 836-30-6) and diphenylamine (CAS #: 122-39-4).
- Plasticizer additives include, for example, diethyl phthalate (CAS #: 84-66-2), camphor (CAS #: 76-22-2), dibutyl phthalate (CAS #: 84-74-2), di-n-propyl adipate ( CAS #: 106-19-4) or methylphenylurethane (CAS #: 261-79-6).
- For example, magnesium oxide (CAS #: 1303-48-4), molybdenum trioxide (CAS #: 1313-27-5), magnesium silicate (CAS #: 14807-96-6), calcium carbonate (CAS #: 471-34-1) or titanium dioxide (CAS #: 13463-67-7).
- Additives for fire suppression are, for example, sodium oxalate (CAS #: 62-76-0), catium bitarate (CAS #: 868-14-4), sodium hydrogen carbonate (CAS #: 144-55-8), potassium bicarbonate (CAS #: 298-14-6), sodium oxalate (CAS #: 62-76-0), potassium sulfate (CAS #: 7778-80-5) or potassium nitrate (CAS #: 7757-79-1).
Ferner kann das Grünpulver noch weitere bekannte Zusätze, etwa zur Verbesserung des Anzündverhaltens und zur Modulierung des Abbrandverhaltens, enthalten.Furthermore, the green powder may contain other known additives, for example for improving the ignition behavior and for modulating the burn-off behavior.
Alle die erwähnten Zusätze werden während der Grünkornherstellung der Teigmasse zugegeben, d.h. sie sind gleichmässig in der Kornmatrix verteilt. Die Gesamtmenge dieser Zusätze im Grünkorn liegt zwischen 0-20 Gew.-% gegenüber der Nitrocellulose, bevorzugt zwischen 5-15 Gew.-%. Die Herstellung der erfindungsgemässen Schüttpulver beinhaltet die bekannten Prozessschritte "Kneten mit Lösungsmitteln", "Extrusion durch Matrize", "Trocknung" und "Finishing" (Oberflächenbehandlung). Die Zugabe der Bismuth-Verbindung erfolgt entweder während der Knetung (homogene Verteilung in der Kornmatrix) oder während des Finishings (Anreicherung an Korn-Oberfläche).All of the additives mentioned are added to the dough mass during green grain production, i. they are evenly distributed in the grain matrix. The total amount of these additives in the green grain is between 0-20 wt .-% compared to the nitrocellulose, preferably between 5-15 wt .-%. The production of the bulk powders according to the invention comprises the known process steps "kneading with solvents", "extrusion by die", "drying" and "finishing" (surface treatment). The bismuth compound is added either during kneading (homogeneous distribution in the grain matrix) or during finishing (enrichment at grain surface).
Dem Schüttpulver können gegebenenfalls weitere Zusätze beigefügt sein. Hierzu gehören einerseits die klassischen Sprengöle Nitroglyzerin (NGL, CAS-#: 55-63-0) oder Diethylenglykoldinitrat (DEGN, CAS-#: 693-21-0). In der Pulvertechnik ist zudem eine Vielzahl weiterer energetischer Weichmachern bekannt. Hierzu gehören insbesondere niedermolekulare aliphatische Salpetersäureester, Nitroverbindungen, Nitramine und Azide. Eine hierzu besonders geeignete Stoffklasse bilden die sogenannten 2-Nitroxyethyl-nitramine (Alkyl-NE-NA) mit der allgemeinen Strukturformel (1), wobei R1 ein aliphatischer Rest darstellt:
Eine weitere besonders geeignete Stoffklasse hierfür bilden die sogenannten Dinitro-diazaalkane der allgemeinen Formel (II), wobei R2 und R3 für aliphatische Reste stehen:
Die Gesamtmenge dieser energetischen Flüssigzusätze liegt zwischen 0-40 Gew.-% gegenüber der Nitrocellulose, bevorzugt zwischen 5-20 Gew.-%. Die Flüssigzusätze sind entweder homogen in der Kornmatrix verteilt, wobei die Pulverherstellung durch die bekannten Abläufe Kneten/Walzen/Pressen erfolgt. Zudem ist auch eine Anreicherung in den Aussenzonen des Pulverkorns denkbar, wobei die Fertigung derartiger Schüttpulver durch Imprägnierung eines Grünkorns in wässriger Emulsion erfolgt (vgl. EP 1 164 116 A 1).The total amount of these energetic liquid additives is between 0-40 wt .-% compared to the nitrocellulose, preferably between 5-20 wt .-%. The liquid additives are either distributed homogeneously in the grain matrix, wherein the powder production is carried out by the known processes kneading / rolling / pressing. In addition, an enrichment in the outer zones of the powder grain is conceivable, whereby the production of such bulk powder by impregnation of a green grain in aqueous emulsion takes place (see,
Die erfindungsgemässen Schüttpulver weisen folgende Geometrien auf: Zylinderförmig mit 0-30 (bevorzugt 1-19) axialen Längskänalen. Die Aussendurchmesser liegen zwischen 0.3-15 mm (bevorzugt 0.5-7.5 mm), die Längen betragen 0.3-15 mm (bevorzugt 0.5-7.5 mm). Das Verhältnis von Korn-Länge zu Korn-Durchmesser beträgt 0.5-3.0 (bevorzugt 1.0-1.5). Die Durchmesser der Längskanäle liegen zwischen 0.05-0.5 mm (bevorzugt 0.1-0.4 mm). Bei der sphärischen Korngeometrie liegen die Durchmesser im Bereich von 0.3-5.0 mm (bevorzugt 0.5-2.0 mm).The bulk powders according to the invention have the following geometries: Cylindrical with 0-30 (preferably 1-19) axial longitudinal channels. The outer diameters are between 0.3-15 mm (preferably 0.5-7.5 mm), the lengths are 0.3-15 mm (preferably 0.5-7.5 mm). The ratio of grain length to grain diameter is 0.5-3.0 (preferably 1.0-1.5). The diameters of the longitudinal channels are between 0.05-0.5 mm (preferably 0.1-0.4 mm). In the case of the spherical grain geometry, the diameters are in the range of 0.3-5.0 mm (preferably 0.5-2.0 mm).
Die geometrischen Abmessungen der in der vorliegenden Anmeldung umfassten Schüttpulver werden primär durch den Kaliberbereich bestimmt. So können die Pulverkörner für Kleinkaliber-Anwendungen (Kaliberbereich von ca. 5.56 bis ca. 20 mm) einerseits zylinderförmige Geometrien mit Durchmesser von ca. 0.5-3 mm aufweisen, wobei die Länge eines Pulverkorns typischerweise ca. 0.5 bis 2.0 Mal des Wertes des jeweiligen Korndurchmessers beträgt. Zudem können die zylinderförmigen Pulver zur Beeinflussung des Abbrandverhaltens in axialer Richtung verlaufende Längskanäle enthalten. In der Praxis haben sich 1- und 7-Lochgeometrien besonders bewährt, wobei der Durchmesser der Lochzonen typischerweise zwischen 0.05 bis 0.5 mm beträgt. Neben der zylindrischen Korngeometrie hat sich im Kleinkaliberbereich zudem die sphärische Korngeometrie bewährt, wobei die Kugeldurchmesser je nach Kaliberbereich typischerweise zwischen 0.3-2.0 mm betragen.The geometric dimensions of the bulk powders included in the present application are primarily determined by the caliber range. So can the powder grains for Small caliber applications (caliber range from about 5.56 to about 20 mm) on the one hand have cylindrical geometries with a diameter of about 0.5-3 mm, wherein the length of a powder grain is typically about 0.5 to 2.0 times the value of the respective grain diameter. In addition, the cylindrical powders may contain longitudinal channels extending in the axial direction for influencing the burning behavior. In practice, 1- and 7-hole geometries have proven particularly useful, wherein the diameter of the hole zones is typically between 0.05 to 0.5 mm. In addition to the cylindrical grain geometry, the spherical grain geometry has also proven successful in the small bore range, with the ball diameters typically ranging from 0.3 to 2.0 mm, depending on the caliber range.
Für Mittelkaliber-Anwendungen (Kaliberbereich von 20-ca. 80 mm) hat sich erfahrungsgemäss die zylinderförmige Korngeometrie als vorteilhaft erwiesen, wobei zur Steuerung der Abbrandcharakteristik normalerweise mehrere in axialer Richtung verlaufende Längskanäle im Pulverkorn enthalten sind. Besonders bewährt haben sich Pulverkörner mit 1, 7 oder 19 Längskanälen, deren Durchmesser typischerweise 0.05-0.5 mm beträgt. Auch im Mittelkaliber-Bereich können jedoch für gewisse Anwendungen schüttbare Pulver mit sphärischer Korngeometrie eingesetzt werden.For central caliber applications (caliber range from 20 to approximately 80 mm), experience has shown that the cylindrical grain geometry has proved advantageous, with a plurality of longitudinal channels extending in the axial direction normally being contained in the powder grain for controlling the burnup characteristic. Powder grains with 1, 7 or 19 longitudinal channels, whose diameter is typically 0.05-0.5 mm, have proved to be particularly suitable. Even in the medium caliber range, however, pourable powders with spherical grain geometry can be used for certain applications.
Aus der nachfolgenden Detailbeschreibung und der Gesamtheit der Patentansprüche ergeben sich weitere vorteilhafte Ausführungsformen und Merkmalskombinationen der Erfindung.From the following detailed description and the totality of the claims, further advantageous embodiments and feature combinations of the invention result.
Die zur Erläuterung des Ausführungsbeispiels verwendeten Zeichnungen zeigen:
- Fig. 1
- eine schematische Darstellung der Bismuth-(III)-oxid Konzentration bei einem bevorzugten Pulverkorn;
- Fig. 2
- eine tabellarische Zusammenstellung der Herstellungsbeispiele 1
bis 10.
- Fig. 1
- a schematic representation of bismuth (III) oxide concentration in a preferred powder grain;
- Fig. 2
- a tabular summary of Preparation Examples 1 to 10.
In Fig. 1 ist schematisch der Verlauf der Bismuth-(III)-oxid-Konzentration einer bevorzugten Ausführungsform dargestellt. Die als Entkupferungsadditiv wirkende Bismuthverbindung ist in diesem Beispiel zu einer Hälfte in der Kornmatrix (d.h. im ganzen Kornvolumen) und zur anderen Hälfte in der Oberflächenschicht eingebracht. Der Aussendurchmesser D beträgt z.B. 0.7-1 mm. Die Oberflächenschichtdicke d beträgt z.B. 50 Mikrometer. (Fig. 1 ist nicht massstäblich gezeichnet.)In Fig. 1, the course of the bismuth (III) oxide concentration of a preferred embodiment is shown schematically. The bismuth compound acting as a decoloring additive in this example is one half in the grain matrix (i.e., in the whole grain volume) and the other half in the surface layer. The outer diameter D is e.g. 0.7-1 mm. The surface layer thickness d is e.g. 50 microns. (Figure 1 is not drawn to scale.)
Im Folgenden werden mehrere Ausführungsbeispiele gegeben. Sie sind in Fig. 2 tabellarisch zusammengefasst.In the following, several embodiments are given. They are summarized in Fig. 2 in tabular form.
200 kg eines 1-Loch-Grünpulvers mit 0.73 mm Aussendurchmesser, 0.93 mm Länge und 0.10 mm Lochdurchmesser, aufgebaut aus den festen Anteilen von 1.5 Gew.-% Akardit-II, 1 Gew.-% Kaliumsulfat, 0.35 Gew.-% Bismuth-(III)-oxid und 97.4 Gew.-% Nitrocellulose mit einem Stickstoffgehalt von 13.15 Gew.-% und hergestellt auf in der Pulvertechnik bekannte Weise durch Verpressen eines lösungsmittelfeuchten Knetteigs durch eine Matrize, werden in einem 1'000 Liter Stahlreaktor ausgerüstet mit mechanischem Flügelrührer, Deckeleinlassventil, Bodenauslassventil sowie und Anschlüssen für Vakuum, mit der zweifachen Menge Wasser versetzt.200 kg of a 1-hole green powder with 0.73 mm outside diameter, 0.93 mm length and 0.10 mm hole diameter, composed of the solid portions of 1.5% by weight of acardite II, 1% by weight potassium sulfate, 0.35% by weight bismuth (III) oxide and 97.4 wt .-% nitrocellulose having a nitrogen content of 13.15 wt .-% and prepared in the manner known in the powder art by pressing a solvent-moist kneading dough through a die, are equipped in a 1'000 liter steel reactor equipped with mechanical paddle , Lid inlet valve, bottom outlet valve and vacuum connections, with twice the amount of water added.
Anschliessend wird der Ansatz auf eine Temperatur von 80°C erwärmt. Danach wird eine Mischung enthaltend 25 kg Nitroglycerin (12.5 Gew.-%) und 0.5 kg (0.25 Gew.-%) 2-Nitrodiphenylamin, gelöst in Ethanol, zugetropft. Man lässt bei optimaler Backmixeinstellung (Pulverbett vollständig in Schwebe) behandeln und tropft anschliessend eine Suspension enthaltend 6.0 kg (3 Gew.-%) einer bei Raumtemperatur hochviskosen Polyester-Verbindung mit einem mittleren Molekulargewicht von 1'500 g/mol in Wasser zu. Anschliessend lässt man unter Rühren nachbehandeln. Anschliessend wird der Druck im Reaktorkessel langsam reduziert und Teile des Lösungsmittels aus der Flotte abdestilliert. Danach wird das Vakuum gebrochen und der Ansatz abgekühlt. Danach werden die verbleibenden flüssigen Anteile des Ansatzes durch Öffnen des Bodenventils abgelassen. Zum Schluss werden die flüssigen Anteile erneut durch das Bodenventil abgelassen und die verbleibende feuchte Pulvermatrix anschliessend aus dem Reaktor entfernt. Das feuchte Pulver wird getrocknet und hiernach durch Aufpolieren von ca. 0.3 Gew.-% Graphit, 0.35 Gew.-% fein pulverisiertes Bismuth-(III)-oxid und gegebenenfalls weiterer speziellen Moderatoren auf bekannte Weise in der Poliertrommel fertiggestellt. Das resultierende Schüttpulver hat eine Schüttdichte von 940 g/l bei einem Energieinhalt von 3'893 J/g.Subsequently, the batch is heated to a temperature of 80 ° C. Thereafter, a mixture containing 25 kg of nitroglycerin (12.5 wt .-%) and 0.5 kg (0.25 wt .-%) 2-nitrodiphenylamine, dissolved in ethanol, added dropwise. It is allowed at optimal baking mix adjustment (powder bed completely in suspension) and then drips a suspension containing 6.0 kg (3 wt .-%) of a highly viscous at room temperature polyester compound having an average molecular weight of 1'500 g / mol in water. Then allowed to aftertreat stirring. Subsequently, the pressure in the reactor vessel is slowly reduced and distilled off parts of the solvent from the liquor. Thereafter, the vacuum is broken and cooled the approach. After that, the remaining liquid Parts of the approach drained by opening the bottom valve. Finally, the liquid portions are drained again through the bottom valve and the remaining wet powder matrix is then removed from the reactor. The wet powder is dried and then finished by polishing about 0.3 wt .-% graphite, 0.35 wt .-% finely pulverized bismuth (III) oxide and optionally other special moderators in a known manner in the polishing drum. The resulting bulk powder has a bulk density of 940 g / l with an energy content of 3893 J / g.
Analog Herstellungsbeispiel 1 wird zunächst ein 1-Loch-Grünpulvers mit 0.64 mm Aussendurchmesser, 1.03 mm Länge und 0.12 mm Lochdurchmesser hergestellt, bei welchem jedoch keine Bismuth-Verbindung zugegeben wird. Dieses Grünpulver wird anschliessend analog Herstellungsbeispiel 1 mit Nitroclycerin und der bei Raumtemperatur hochviskosen Polyester-Verbindung mit einem mittleren Molekulargewicht von 1'500 g/mol behandelt. Die Aufpolierung erfolgt analog Herstellungsbeispiel 1, wobei jedoch keine Bismuth-Verbindung verwendet wird. Das fertige Schüttpulver hat eine Schüttdichte von 943 g/l bei einem Energieinhalt von 3'943 J/g.Analogously to Preparation Example 1, a 1-hole green powder having an outer diameter of 0.64 mm, a length of 1.03 mm and a hole diameter of 0.12 mm is first prepared, but in which no bismuth compound is added. This green powder is then treated analogously to Preparation Example 1 with nitroclycerol and the highly viscous at room temperature polyester compound having an average molecular weight of 1'500 g / mol. The polishing is carried out analogously to Preparation Example 1, but no bismuth compound is used. The finished bulk powder has a bulk density of 943 g / l with an energy content of 3,943 J / g.
Analog Herstellungsbeispiel 1 wird zunächst ein 1-Loch-Grünpulvers mit 0.64 mm Aussendurchmesser, 1.03 mm Länge und 0.12 mm Lochdurchmesser hergestellt, bei welchem jedoch keine Bismuth-Verbindung zugegeben wird. Dieses Grünpulver wird anschliessend analog Herstellungsbeispiel 1 mit Nitroclycerin und der bei Raumtemperatur hochviskosen Polyester-Verbindung mit einem mittleren Molekulargewicht von 1'500 g/mol behandelt. Die Aufpolierung erfolgt analog Herstellungsbeispiel 1, wobei während der Aufpolierung jedoch 0.7 Gew.-% feinpulvriges Bismuth-Pulver verwendet werden. Das fertige Schüttpulver hat eine Schüttdichte von 940 g/l bei einem Energieinhalt von 3'918 J/g.Analogously to Preparation Example 1, a 1-hole green powder having an outer diameter of 0.64 mm, a length of 1.03 mm and a hole diameter of 0.12 mm is first prepared, but in which no bismuth compound is added. This green powder is then treated analogously to Preparation Example 1 with nitroclycerol and the highly viscous at room temperature polyester compound having an average molecular weight of 1'500 g / mol. The polishing is carried out analogously to Preparation Example 1, during which, however, 0.7% by weight of finely powdered bismuth powder is used during the polishing. The finished bulk powder has a bulk density of 940 g / l with an energy content of 3'918 J / g.
Es wird ein Schüttpulver analog Herstellungsbeispiel 2 hergestellt, wobei während der Aufpolierung jedoch 0.7 Gew.-% feinpulvriges Bismuth-carbonat-oxid verwendet werden. Das fertige Schüttpulver hat eine Schüttdichte von 920 g/l bei einem Energieinhalt von 3'919J/g.A bulk powder is prepared analogously to Preparation Example 2, but 0.7% by weight of finely powdered bismuth carbonate oxide is used during the polishing. The finished bulk powder has a bulk density of 920 g / l with an energy content of 3'919J / g.
Es wird ein Schüttpulver analog Herstellungsbeispiel 2 hergestellt, wobei während der Aufpolierung jedoch 0.7 Gew.-% feinpulvriges Bismuth-(III)-oxid verwendet werden. Das fertige Schüttpulver hat eine Schüttdichte von 945 g/l bei einem Energieinhalt von 3'923 J/g.A bulk powder is prepared analogously to Preparation Example 2, but during the refinement, however, 0.7% by weight of finely powdered bismuth (III) oxide is used. The finished bulk powder has a bulk density of 945 g / l with an energy content of 3,923 J / g.
Es wird ein Schüttpulver analog Herstellungsbeispiel 2 hergestellt, wobei während der Aufpolierung jedoch 0.7 Gew.-% feinpulvriges Zinn-dioxid verwendet werden. Das fertige Schüttpulver hat eine Schüttdichte von 925 g/l bei einem Energieinhalt von 3'919 J/g.A bulk powder is prepared analogously to Preparation Example 2, but 0.7% by weight of finely powdered tin dioxide is used during the polishing. The finished bulk powder has a bulk density of 925 g / l with an energy content of 3'919 J / g.
Analog Herstellungsbeispiel 1 wird zunächst ein 1-Loch-Grünpulvers mit 0.75 mm Aussendurchmesser, 0.97 mm Länge und 0.12 mm Lochdurchmesser hergestellt, bei welchem jedoch 0.7 Gew.-% Bismuth-(III)-oxid zugegeben wird. Dieses Grünpulver wird anschliessend analog Herstellungsbeispiel 1 mit Nitroclycerin und der bei Raumtemperatur hochviskosen Polyester-Verbindung mit einem mittleren Molekulargewicht von 3'000 g/mol behandelt. Die Aufpolierung erfolgt analog Herstellungsbeispiel 1, wobei jedoch keine Bismuth-Verbindung verwendet wird. Das fertige Schüttpulver hat eine Schüttdichte von 923 g/l bei einem Energieinhalt von 3'921 J/g.Analogously to Preparation Example 1, a 1-hole green powder with 0.75 mm outside diameter, 0.97 mm length and 0.12 mm hole diameter is first produced, in which, however, 0.7 wt .-% bismuth (III) oxide is added. This green powder is then treated analogously to Preparation Example 1 with nitroclycerol and the polyester at room temperature highly viscous compound having an average molecular weight of 3,000 g / mol. The polishing is carried out analogously to Preparation Example 1, but no bismuth compound is used. The finished bulk powder has a bulk density of 923 g / l with an energy content of 3,921 J / g.
In einer Labor-Poliertrommel aus Glas mit 1 Liter Innenvolumen und einer Trommeltemperatur von 60°C werden zu 100 g eines fertiggestellten sphärischen Pulvers mit 0.39 mm Durchmesser, einer Schüttdichte von 990 g/l und einem Energieinhalt von 3'812 J/g, welches neben Nitrocellulose mit einem Stickstoffgehalt von 13.15 Gew.-% als weitere Hauptinhaltsstoffe Nitroglycerin (10 Gew.-%), Dibutylphthalat (4.5 Gew.-%) enthält, eine Mischung von 0.7g (0.7 Gew.-%) Bismuth-(III)-oxid und 0.1g (0.1 Gew.-%) Graphit, dispergiert in 5 ml Ethanol, zugegeben. Man lässt zuerst während 1 Stunde mit verschlossenem Deckel drehen. Danach wird mit offener Entnahmeöffnung solange weitergedreht, bis das Schüttpulver eine glänzige Oberfläche zeigt. Das Schüttpulver wird hiernach aus der Poliertrommel entnommen und danach während 20 Stunden bei einer Temperatur von 60°C getrocknet. Das fertige Schüttpulver hat eine Schüttdichte von 966 g/l und einen Energieinhalt von 3'782 J/g.In a laboratory polishing drum made of glass with 1 liter internal volume and a drum temperature of 60 ° C to 100 g of a finished spherical powder with 0.39 mm diameter, a bulk density of 990 g / l and an energy content of 3'812 J / g, which in addition to nitrocellulose with a nitrogen content of 13.15 wt .-% as further main ingredients nitroglycerin (10 wt .-%), dibutyl phthalate (4.5 wt .-%), a mixture of 0.7g (0.7 wt .-%) bismuth (III) oxide and 0.1 g (0.1 wt.%) of graphite dispersed in 5 ml of ethanol. It is first allowed to turn for 1 hour with the lid closed. Thereafter, continue to rotate with the removal opening open until the bulk powder shows a shiny surface. The bulk powder is then removed from the polishing drum and then dried for 20 hours at a temperature of 60 ° C. The finished bulk powder has a bulk density of 966 g / l and an energy content of 3'782 J / g.
In einer Labor-Poliertrommel aus Glas mit 1 Liter Innenvolumen und einer Trommeltemperatur von 60°C werden zu 100 g eines fertiggestellten 7-Loch-Pulvers mit einem Aussendurchmesser von 2.21 mm, einer Länge von 2.32 mm, einem Lochdurchmesser von 0.16 mm und einer mittleren Wandstärke von 0.47 mm, einer Schüttdichte von 1'034 g/l und einem Energieinhalt von 3'256 J/g, welches neben Nitrocellulose mit einem Stickstoffgehalt von 13.15 Gew.-% als weitere Hauptinhaltsstoffe Campher (6.5 Gew.-%) und Diphenylamin (1.5 Gew.-%) enthält, eine Mischung von 0.7 g (0.7 Gew.-%) Bismuth-(III)-oxid und 0.1 g (0.1 Gew.-%) Graphit, dispergiert in 5 ml 94 % Industriesprit, zugegeben. Man lässt zuerst während 1 Stunde mit verschlossenem Deckel drehen. Danach wird bei offener Entnahmeöffnung solange weitergedreht, bis das Schüttpulver eine glänzige Oberfläche zeigt. Das Schüttpulver wird hiernach aus der Poliertrommel entnommen und danach während 20 Stunden bei einer Temperatur von 60°C getrocknet. Das fertige Schüttpulver hat eine Schüttdichte von 1'025 g/l und einen Energieinhalt von 3'236 J/g.In a laboratory polishing drum made of glass with 1 liter internal volume and a drum temperature of 60 ° C to 100 g of a finished 7-hole powder with an outer diameter of 2.21 mm, a length of 2.32 mm, a hole diameter of 0.16 mm and a middle Wall thickness of 0.47 mm, a bulk density of 1'034 g / l and an energy content of 3'256 J / g, which in addition to nitrocellulose with a nitrogen content of 13.15 wt .-% as further main ingredients camphor (6.5 wt .-%) and diphenylamine (1.5 wt%), a mixture of 0.7 g (0.7 wt%) of bismuth (III) oxide and 0.1 g (0.1 wt%) of graphite dispersed in 5 ml of 94% industrial spirit was added. It is first allowed to turn for 1 hour with the lid closed. Then, with the removal opening open, continue to turn until the bulk powder has a shiny surface. The bulk powder is then removed from the polishing drum and then dried for 20 hours at a temperature of 60 ° C. The finished bulk powder has a bulk density of 1'025 g / l and an energy content of 3'236 J / g.
In einer Poliertrommel aus Kupfer mit 50 Liter Innenvolumen und einer Trommeltemperatur von 60°C werden zu 5 kg eines fertiggestellten 19-Loch-Pulvers mit einem mittleren Aussendurchmesser von 3.61 mm, einer mittleren Kornlänge von 3.80 mm, einem mittleren Lochdurchmesser von 0.12 mm und einer mittleren Wandstärke von 0.58 mm, einer Schüttdichte von 1'060 g/l und einem Energieinhalt von 3'956 J/g, welches neben Nitrocellulose mit einem Stickstoffgehalt von 13.15 Gew.-% als weitere Hauptinhaltsstoffe Nitroguanidin (5.0 Gew.-%) und Diethylenglykoldinitrat (18 Gew.-%) enthält, eine Mischung von 35 g (0.7 Gew.-%) Bismuth-(III)-oxid und 5 g (0.1 Gew.-%) Graphit, dispergiert in 300 ml 94 Gew.-% Industriesprit, zugegeben. Man lässt zuerst während 1 Stunde mit verschlossenem Deckel drehen. Danach wird mit offener Entnahmeöffnung solange weitergedreht, bis das Schüttpulver eine glänzige Oberfläche zeigt. Das Schüttpulver wird hiernach aus der Poliertrommel entnommen und danach während 20 Stunden bei einer Temperatur von 60°C getrocknet. Das fertige Schüttpulver hat eine Schüttdichte von 1'055 g/l und einen Energieinhalt von 3'932 J/g.In a polishing drum made of copper with 50 liters internal volume and a drum temperature of 60 ° C to 5 kg of a finished 19-hole powder with a mean outer diameter of 3.61 mm, a mean grain length of 3.80 mm, a mean hole diameter of 0.12 mm and a average wall thickness of 0.58 mm, a bulk density of 1'060 g / l and an energy content of 3'956 J / g, which in addition to nitrocellulose with a nitrogen content of 13.15 wt .-% as further main ingredients nitroguanidine (5.0 wt .-%) and Diethylene glycol dinitrate (18% by weight), a mixture of 35 g (0.7% by weight) of bismuth (III) oxide and 5 g (0.1% by weight) of graphite dispersed in 300 ml 94% by weight industrial spirit, added. It is first allowed to turn for 1 hour with the lid closed. Thereafter, continue to rotate with the removal opening open until the bulk powder shows a shiny surface. The bulk powder is then removed from the polishing drum and then dried for 20 hours at a temperature of 60 ° C. The finished bulk powder has a bulk density of 1,055 g / l and an energy content of 3,932 J / g.
Analog Herstellungsbeispiel 1 wird zunächst ein 1-Loch-Grünpulver mit 0.73 mm Aussendurchmesser, 0.93 mm Länge und 0.10 mm Lochdurchmesser hergestellt. Dieses Grünpulver wird anschliessend analog Herstellungsbeispiel 1 mit Nitroglycerin und der bei Raumtemperatur hochviskosen Polyester-Verbindung mit einem mittleren Molekulargewicht von 3'000 g/mol behandelt. Die Aufpolierung erfolgt analog Herstellungsbeispiel 1, wobei jedoch keine Bismuth-Verbindung verwendet wird. Das fertige Schüttpulver hat eine Schüttdichte von 891 g/l bei einem Energieinhalt von 3'892 J/g.Analogously to Preparation Example 1, a 1-hole green powder with 0.73 mm outside diameter, 0.93 mm in length and 0.10 mm hole diameter is first produced. This green powder is then treated analogously to Preparation Example 1 with nitroglycerin and the polyester at room temperature highly viscous compound having an average molecular weight of 3000 g / mol. The polishing is carried out analogously to Preparation Example 1, but no bismuth compound is used. The finished bulk powder has a bulk density of 891 g / l with an energy content of 3'892 J / g.
Anwendungsbeispiel 1: Pulver aus Herstellungsbeispiel 2, Reinigungsaufwand in bleifreier 5.56 mm Patrone mit Sintox-Anzündung. Use Example 1 Powder from Production Example 2, Cleaning Efficiency in Lead-Free 5.56 mm Cartridge with Sintox Ignition.
Es wurden mit Sintox-Zündelementen beschickte Patronenhülsen mit Schüttpulver aus Herstellungsbeispiel 1 gefüllt und mit einem bleifreien Geschoss verschlossen. Hierauf wurden 200 Patronen verschossen. Der Reinigungsaufwand zur Herstellung des ursprünglichen Rohrzustandes betrug 130 Doppelhübe.Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 130 double strokes.
Anwendungsbeispiel 2: Pulver aus Herstellungsbeispiel 6, Reinigungsaufwand in bleifreier 5.56 mm Patrone mit Sintox-Anzündung. Application example 2 : Powder from production example 6, cleaning effort in lead-free 5.56 mm cartridge with Sintox ignition.
Es wurden mit Sintox-Zündelementen beschickte Patronenhülsen mit Schüttpulver aus Herstellungsbeispiel 1 gefüllt und mit einem bleifreien Geschoss verschlossen. Hierauf wurden 200 Patronen verschossen. Der Reinigungsaufwand zur Herstellung des ursprünglichen Rohrzustandes betrug 110 Doppelhübe.Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 110 double strokes.
Anwendungsbeispiel 3: Pulver aus Herstellungsbeispiel 3, Reinigungsaufwand in bleifreier 5.56 mm Patrone mit Sintox-Anzündung.Example of
Es wurden mit Sintox-Zündelementen beschickte Patronenhülsen mit Schüttpulver aus Herstellungsbeispiel 3 gefüllt und mit einem bleifreien Geschoss verschlossen. Hierauf wurden 200 Patronen verschossen. Der Reinigungsaufwand zur Herstellung des ursprünglichen Rohrzustandes betrug 20 Doppelhübe.Cartridge casings filled with sintered ignition elements were filled with bulk powder from Production Example 3 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 20 double strokes.
Anwendungsbeispiel 4: Pulver aus Herstellungsbeispiel 4, Reinigungsaufwand in bleifreier 5.56 mm Patrone mit Sintox-Anzündung. Use Example 4: Powder from Preparation Example 4, cleaning effort in lead-free 5.56 mm cartridge with Sintox ignition.
Es wurden mit Sintox-Zündelementen beschickte Patronenhülsen mit Schüttpulver aus Herstellungsbeispiel 4 gefüllt und mit einem bleifreien Geschoss verschlossen. Hierauf wurden 200 Patronen verschossen. Der Reinigungsaufwand zur Herstellung des ursprünglichen Rohrzustandes betrug 30 Doppelhübe.Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 4 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 30 double strokes.
Anwendungsbeispiel 5: Pulver aus Herstellungsbeispiel 3, Reinigungsaufwand in bleifreier 5.56 mm Patrone mit Sintox-Anzündung. Use Example 5 Powder from Production Example 3, Cleaning Efficiency in Lead-Free 5.56 mm Cartridge with Sintox Ignition.
Es wurden mit Sintox-Zündelementen beschickte Patronenhülsen mit Schüttpulver aus Herstellungsbeispiel 5 gefüllt und mit einem bleifreien Geschoss verschlossen. Hierauf wurden 200 Patronen verschossen. Der Reinigungsaufwand zur Herstellung des ursprünglichen Rohrzustandes betrug 10 Doppelhübe.Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 5 and sealed with a lead-free bullet. After that, 200 cartridges were fired. The cleaning effort to produce the original tube state was 10 double strokes.
Anwendungsbeispiel 6: Pulver aus Herstellungsbeispiel 1, Reinigungsaufwand in bleifreier 5.56 mm Patrone mit bleifreier Anzündung. Use Example 6: Powder from Preparation Example 1, cleaning effort in lead-free 5.56 mm cartridge with lead-free ignition.
Es wurden mit Sintox-Zündelementen beschickte Patronenhülsen mit Schüttpulver aus Herstellungsbeispiel 1 gefüllt und mit einem bleifreien Geschoss verschlossen. Hierauf wurden 1'500 Patronen verschossen, wobei der Reinigungsaufwand nach jeweils 100 Schuss ermittelt wurde. Der Reinigungsaufwand zur Herstellung des ursprünglichen Rohrzustandes lag bei den untersuchten Schussbelastungen (100 Schuss, 200 Schuss, 300 Schuss, usw.) zwischen 10 und 20 Doppelhüben. Bei Verwendung eines nicht-bismuthhaltigen Referenzpulvers ist bei Verwendung von derselben Patrone und Zündelement das Waffenrohr nach derselben Schussbelastung nicht mehr zu reinigen und ist hiermit unbrauchbar.Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet. This was 1,500 cartridges fired, the cleaning effort was determined after every 100 shots. The cleaning effort required to produce the original tube condition was between 10 and 20 double strokes for the shot loads examined (100 rounds, 200 rounds, 300 rounds, etc.). When using a non-bismuth-containing reference powder when using the same cartridge and ignition element is the weapon barrel after the same shot load no longer clean and is therefore unusable.
Anwendungsbeispiel 7: Pulver aus Herstellungsbeispiel 1, Kalibervergrösserung an Mündung (Rohrausbrand) in bleifreier 5.56 mm Patrone mit bleifreier Anzündung. Use Example 7 Powder from Production Example 1, Caliber Enlargement at the Orifice (Pipe Outwash) in a Lead-Free 5.56 mm Cartridge with Lead-Free Ignition.
Es wurden mit Sintox-Zündelementen beschickte Patronenhülsen mit Schüttpulver aus Herstellungsbeispiel 1 gefüllt und mit einem bleifreien Geschoss verschlossen. Hierauf wurden 1'500 Patronen verschossen, wobei das Kaliber an der Rohrmündung nach jeweils 100 Schuss ermittelt wurde. Nach 800 Schuss trat bei der Verwendungen eines nicht-bismuthhaltigen Referenzpulvers eine Kalibererweiterung von 5.54 mm auf 5.55 mm ein, beim Pulver aus Herstellungsbeispiel 1 dagegen blieb das Kaliber an der Mündung nach 1'500 Schuss gegenüber dem Ausgangszustand unverändert bei 5.54 mm.Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet. This was 1,500 cartridges fired, the caliber at the mouth of the muzzle was determined after every 100 shots. After 800 shots occurred in the use of a non-bismuth-containing reference powder, a caliber extension of 5.54 mm to 5.55 mm, in the powder of Preparation Example 1, however, the caliber at the mouth after 1'500 shots compared to the initial state unchanged at 5.54 mm.
Anwendungsbeispiel 8: Pulver aus Herstellungsbeispiel 1, Freiflug mit bleifreier 5.56 mm Patrone mit bleifreier Anzündung. Example of Use 8 : Powder from Production Example 1, Free Flight with Lead-Free 5.56 mm Cartridge with Lead-Free Ignition.
Es wurden mit Sintox-Zündelementen beschickte Patronenhülsen mit Schüttpulver aus Herstellungsbeispiel 1 gefüllt und mit einem bleifreien Geschoss verschlossen. Hierauf wurden 1'400 Patronen verschossen, wobei der Freiflug (Distanz zwischen Hülsenmund und Einführung in Laufzüge) nach jeweils 100 Schuss ermittelt wurde. Nach 300 Schuss trat bei der Verwendung eines nicht-bismuthhaltigen Referenzpulvers eine Vergrösserung des Freiflugs von 3.0 auf 3.1 mm ein, nach 800 Schuss von 3.1 auf 3.2 mm und nach 1'400 Schuss von 3.2 auf 3.3 mm. Beim Pulver aus Herstellungsbeispiel 1 trat die erste Vergrösserung des Freiflugs um 0.1 mm erst nach 700 Schuss auf, bis 1'400 Schuss trat keine Veränderung mehr ein.Cartridge casings loaded with Sintox ignition elements were filled with bulk powder from Production Example 1 and sealed with a lead-free bullet. Hereupon 1,400 cartridges were fired, whereby the free flight (distance between sleeve mouth and introduction into running trains) after every 100 shots was determined. After 300 shots, when using a non-bismuth-containing reference powder, the free flight increased from 3.0 to 3.1 mm, after 800 shots from 3.1 to 3.2 mm and after 1 400 shots from 3.2 to 3.3 mm. In the case of the powder from Production Example 1, the first enlargement of the free flight by 0.1 mm only occurred after 700 shots, until 1,400 shots no longer changed.
Die Beimischung der untersuchten Bismuth-Verbindungen zu den erfindungsgemässen Schüttpulvern bewirkt keine Verträglichkeits- resp. Stabilitätsprobleme. Alle hergestellten Mustern liegen bei Wärmefluss-Kalorimetrie-Messungen, durchgeführt gemäss STANAG 4582, unterhalb der maximal erlaubten Wärmeentwicklung von 114 µW, und zwar unabhängig von der räumlichen Verteilung der Bismuth-Verbindung im TLP-Korn.The admixture of the investigated bismuth compounds to the inventive bulk powders causes no compatibility resp. Stability problems. All fabricated samples are below the maximum allowable heat development of 114 μW in heat flow calorimetry measurements performed according to STANAG 4582, regardless of the spatial distribution of the bismuth compound in the TLP grain.
Zusammenfassend ist festzustellen, dass ein neuer technischer Ansatz zur Verhinderung der Rohraufkupferung bei Verwendung von bleifreier Munition gefunden wurde. Dieser basiert auf der Verwendung von neuartigen Schüttpulvern, in welchen eine Bismuth-Verbindung oder elementares Bismuth (ohne anderes Metall) eingearbeitet ist und welche die bei Verwendung bleifreier Geschosse und Anzündungen auftretende Rohraufkupferung wirkungsvoll zu unterbinden vermögen. Die Schüttpulver sind prinzipiell für Klein-, Mittel- und Grosskaliber-Anwendungen einsetzbar.In summary, a new technical approach has been found to prevent pipe coppering when using lead-free ammunition. This is based on the use of novel bulk powders in which a bismuth compound or elemental bismuth (without other metal) is incorporated and which are able to effectively prevent the Rohraufkupferung occurring when using lead-free projectiles and ignitions. The bulk powders can be used in principle for small, medium and large caliber applications.
Claims (21)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20040405460 EP1616845B1 (en) | 2004-07-16 | 2004-07-16 | Pourable propellant powder |
DK04405460T DK1616845T3 (en) | 2004-07-16 | 2004-07-16 | Pourable pourable powder |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20040405460 EP1616845B1 (en) | 2004-07-16 | 2004-07-16 | Pourable propellant powder |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1616845A1 true EP1616845A1 (en) | 2006-01-18 |
EP1616845B1 EP1616845B1 (en) | 2013-10-30 |
Family
ID=34932208
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20040405460 Active EP1616845B1 (en) | 2004-07-16 | 2004-07-16 | Pourable propellant powder |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP1616845B1 (en) |
DK (1) | DK1616845T3 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1857429A1 (en) * | 2006-05-19 | 2007-11-21 | Nitrochemie Wimmis AG | Propulsive means for accelerating projectiles |
RU2561082C1 (en) * | 2014-01-27 | 2015-08-20 | Федеральное казенное предприятие "Государственный научно-исследовательский институт химических продуктов" (ФКП "ГосНИИХП") | Spherical powder for 5,6 mm rifle high-efficiency cartridge |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5565643A (en) * | 1994-12-16 | 1996-10-15 | Olin Corporation | Composite decoppering additive for a propellant |
US5747723A (en) * | 1996-11-26 | 1998-05-05 | The United States Of America As Represented By The Secretary Of The Army | Modular artillery charge system |
US6024810A (en) * | 1998-10-06 | 2000-02-15 | Atlantic Research Corporation | Castable double base solid rocket propellant containing ballistic modifier pasted in an inert polymer |
EP1031547A1 (en) * | 1999-02-23 | 2000-08-30 | Primex Technologies, Inc. | Perforated propellant and method of manufacturing same |
-
2004
- 2004-07-16 DK DK04405460T patent/DK1616845T3/en active
- 2004-07-16 EP EP20040405460 patent/EP1616845B1/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5565643A (en) * | 1994-12-16 | 1996-10-15 | Olin Corporation | Composite decoppering additive for a propellant |
US5747723A (en) * | 1996-11-26 | 1998-05-05 | The United States Of America As Represented By The Secretary Of The Army | Modular artillery charge system |
US6024810A (en) * | 1998-10-06 | 2000-02-15 | Atlantic Research Corporation | Castable double base solid rocket propellant containing ballistic modifier pasted in an inert polymer |
EP1031547A1 (en) * | 1999-02-23 | 2000-08-30 | Primex Technologies, Inc. | Perforated propellant and method of manufacturing same |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1857429A1 (en) * | 2006-05-19 | 2007-11-21 | Nitrochemie Wimmis AG | Propulsive means for accelerating projectiles |
US8353994B2 (en) | 2006-05-19 | 2013-01-15 | Nitrochemie Wimmis Ag | Propulsion system for the acceleration of projectiles |
RU2561082C1 (en) * | 2014-01-27 | 2015-08-20 | Федеральное казенное предприятие "Государственный научно-исследовательский институт химических продуктов" (ФКП "ГосНИИХП") | Spherical powder for 5,6 mm rifle high-efficiency cartridge |
Also Published As
Publication number | Publication date |
---|---|
EP1616845B1 (en) | 2013-10-30 |
DK1616845T3 (en) | 2014-02-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0129081B1 (en) | Primers free of lead and barium | |
EP1857429B1 (en) | Propulsive means for accelerating projectiles | |
DE3500784A1 (en) | METHOD FOR PRODUCING PROGRESSIVELY BURNING ARTILLERY POWDER POWDER AND AGENT SUITABLE FOR THIS | |
DE69531960T2 (en) | DECOUPLER ADDITIVE MIXTURE FOR FUEL | |
EP0238959B1 (en) | Self-supporting propellant body and compact charge produced therefrom | |
EP2951137B1 (en) | Powder for accelerating projectiles for mortar systems | |
EP1616845B1 (en) | Pourable propellant powder | |
DE60221659T2 (en) | TROLLEY POWDER FOR PIPE WEAPONS | |
EP1876160A1 (en) | Active blasting charge | |
EP3317606B1 (en) | Propellant charge system for artillery shells | |
DE2900020C2 (en) | Process for the production of a polybasic propellant charge powder | |
EP1164116B1 (en) | Process for producing a functional high-energy material | |
EP2352710B1 (en) | Ignition sets with improved ignition performance | |
DE4342428C2 (en) | Gun ammunition with a flammable cartridge case | |
EP3939952A1 (en) | Fast burning solid propellant comprising an oxidizer, an energetic binder and a metallic burn-off modifier and method for its preparation | |
DE3242106C1 (en) | Propellent charge compositions for barrel-type weapons | |
EP2580175B1 (en) | Method for producing and using an explosive substance mixture containing fuel | |
US2304037A (en) | Propellent explosive charge | |
CH685940A5 (en) | Perkussionszundsatz for handguns, process for its preparation and its use. | |
DE2644987C1 (en) | Nitrocellulose-free propellant powder | |
EP2695870B1 (en) | Active pyrotechnic materials containing a combustion accelerating agent | |
DE2921212C2 (en) | ||
DE2449777A1 (en) | Inhibited propellant powders - with cellulose binder and inhibitor coating of polyol-isocyanate compsn. | |
DE60007799T2 (en) | Propellant charge sleeve made of metal, which is provided with an inner erosion protection layer | |
DE102010022982B3 (en) | Pressure-increasing explosive charge and ammunition containing this charge |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL HR LT LV MK |
|
AKX | Designation fees paid | ||
17P | Request for examination filed |
Effective date: 20060712 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: 8566 |
|
17Q | First examination report despatched |
Effective date: 20070209 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20130708 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: SCHAEDELI, ULRICH Inventor name: VAMOS, ATTILA Inventor name: ANDRES, HANSPETER |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: KELLER AND PARTNER PATENTANWAELTE AG, CH Ref country code: AT Ref legal event code: REF Ref document number: 638440 Country of ref document: AT Kind code of ref document: T Effective date: 20131115 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 502004014415 Country of ref document: DE Representative=s name: OTTEN, ROTH, DOBLER & PARTNER PATENTANWAELTE, DE Ref country code: DE Ref legal event code: R082 Ref document number: 502004014415 Country of ref document: DE Representative=s name: OTTEN, ROTH, DOBLER & PARTNER MBB PATENTANWAEL, DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502004014415 Country of ref document: DE Effective date: 20131224 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 Effective date: 20140130 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20131030 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502004014415 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20140731 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502004014415 Country of ref document: DE Effective date: 20140731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140716 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PCAR Free format text: NEW ADDRESS: EIGERSTRASSE 2 POSTFACH, 3000 BERN 14 (CH) |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140716 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131030 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20040716 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20170628 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20170726 Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP Effective date: 20180731 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 638440 Country of ref document: AT Kind code of ref document: T Effective date: 20180716 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180716 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180731 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Owner name: NITROCHEMIE WIMMIS AG, CH Free format text: FORMER OWNER: NITROCHEMIE WIMMIS AG, CH |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 502004014415 Country of ref document: DE Representative=s name: MUELLER SCHUPFNER & PARTNER PATENT- UND RECHTS, DE |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230724 Year of fee payment: 20 Ref country code: GB Payment date: 20230719 Year of fee payment: 20 Ref country code: CH Payment date: 20230801 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20230719 Year of fee payment: 20 Ref country code: FR Payment date: 20230725 Year of fee payment: 20 Ref country code: DE Payment date: 20230719 Year of fee payment: 20 Ref country code: BE Payment date: 20230719 Year of fee payment: 20 |