EP2388244B1 - Charge propulsive - Google Patents

Charge propulsive Download PDF

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Publication number
EP2388244B1
EP2388244B1 EP11003843A EP11003843A EP2388244B1 EP 2388244 B1 EP2388244 B1 EP 2388244B1 EP 11003843 A EP11003843 A EP 11003843A EP 11003843 A EP11003843 A EP 11003843A EP 2388244 B1 EP2388244 B1 EP 2388244B1
Authority
EP
European Patent Office
Prior art keywords
weight
soluble
alcohol
cab
concentration
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.)
Not-in-force
Application number
EP11003843A
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German (de)
English (en)
Other versions
EP2388244A1 (fr
Inventor
Dietmar Müller
Walter Langlotz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Diehl BGT Defence GmbH and Co KG
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Diehl BGT Defence GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
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Application filed by Diehl BGT Defence GmbH and Co KG filed Critical Diehl BGT Defence GmbH and Co KG
Publication of EP2388244A1 publication Critical patent/EP2388244A1/fr
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Publication of EP2388244B1 publication Critical patent/EP2388244B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/18—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
    • C06B25/20—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with a non-explosive or a non-explosive or a non-thermic component
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive

Definitions

  • the invention relates to a propellant charge (TL) for pipe weapons with at least one energy source and nitrocellulose (NC) and cellulose acetate butyrate (CAB).
  • TL propellant charge
  • NC nitrocellulose
  • CAB cellulose acetate butyrate
  • a gunpowder powder for guns is known with a nitramine based plasticizer and energetic or non-energetic plastic binder.
  • the plasticizer is a mixture of at least three chemically different dinitro diaza compounds.
  • the non-energetic binder can be CAB. Due to the properties of the plasticizer, such a propellant charge powder enables the firing of rifle ammunition with almost constant values of maximum pressure and bullet speed over the entire temperature range of -50 ° C to + 70 ° C.
  • a propellant charge mixture for guns which exhibits high resistance to unwanted ignition by heat, flame, impact, friction and chemical influence.
  • RDX contains CAB, NC, ethyl centralite, a moisture binder and an energetic plasticizer.
  • the ingredients are moistened in the preparation with an ethyl acetate / ethyl alcohol mixture or in the case of CAB and NC dissolved therein.
  • the ethyl acetate / ethyl alcohol mixture serves to keep the mass capable of being mixed and extruded through an extruder.
  • the NC is contained in the propellant charge mixture at a level of from 2% to 6.3% by weight. It serves to make the propellant charge mixture tough.
  • CAB serves as a binder and is contained in a concentration of 10 wt .-% to 15 wt .-%.
  • the propellant charge is relatively expensive to manufacture.
  • the object of the present invention is to specify a propellant charge which is inexpensive to produce and a method for the production thereof.
  • a propellant charge for pipe weapons with at least one energy source as well as nitrocellulose (NC) and cellulose acetate butyrate (CAB).
  • the energy source is not the NC.
  • At least part of the NC is alcohol-soluble NC.
  • the NC serves as a binder and is contained in a concentration of at least 15 weight percent (wt .-%) in the propellant charge.
  • NC is used with a significantly lower proportion of the total weight of the TL. It usually serves to improve the ignitability, but not as a binder.
  • CAB chemical vapor deposition
  • the temperature is gradually increased defined until it comes to a conversion by burning, deflagration or detonation.
  • the cook-off behavior is the better the higher the temperature at which the reaction occurs.
  • the CAB also improves the heat flow as the TL ages. Local overheating in the TL is thereby prevented. This is particularly advantageous when ammunition is used with the TL in hot areas where the ammunition in vehicles is often exposed to temperatures of 60 to 70 ° C.
  • NC is, depending on the degree of esterification, soluble in alcohols, esters or ketones. There is NC which is soluble in acetone but not in alcohol. However, alcohol-soluble NC is always soluble in acetone or ethyl acetate. For the purposes of the present invention, an acetone-soluble NC is always understood to mean an NC which is not alcohol-soluble. For the purposes of the present invention, alcohol is generally understood as meaning ethanol.
  • acetone-soluble NC for propellants.
  • the inventors have recognized that when using an alcohol-soluble NC at CAB concentrations above 2 wt .-%, a significantly less brittle TL is replaced when used acetone-soluble NC. The risk of brittle fracture is significantly reduced.
  • the increased CAB content improves the thermal properties of the TL by increasing the deflagration temperature and the cook-off temperature and reduces the sensitivity to impact, friction, and the effect of projectile impacts, shaped charges, and splinters.
  • propellant charges of different energy densities which are required depending on the application, can be produced.
  • the energy density can be adjusted from about 900 J / g to about 1350 J / g.
  • the combustion temperature adiabatic flame temperature
  • the TL shows a greatly reduced erosion behavior during use, i. H. There is a reduced removal of material in the tube of the gun during the projectile movement in the pipe.
  • Alcohol-soluble NC It is possible to use exclusively alcohol-soluble NC or a mixture of alcohol-soluble and acetone-soluble NC.
  • the acetone-soluble NC is usually supplied moisturized while the alcohol-soluble NC is usually supplied wet with water.
  • Alcohol-soluble NC has been used mainly in the paint industry and is much cheaper than acetone-soluble NC.
  • Typical acetone-soluble NC is z. B. shooting or Pyrowolle.
  • the acetone-soluble NC is often sold as so-called E-wool (ester-soluble wool) while alcohol-soluble NC is often sold as so-called A-wool.
  • a low-viscosity alcohol-soluble NC or a high-viscosity alcohol-soluble NC.
  • a crystalline energy carrier such as RDX
  • the use of a low-viscosity alcohol-soluble NC is advantageous.
  • a low-viscosity alcohol-soluble NC shows a viscosity of below 425 cP at 20 ° C and 34 wt .-% NC with a nitrogen content of 11.7% dissolved in acetone.
  • a high-viscosity alcohol-soluble NC has a viscosity of below 425 cP at 20 ° C and 18 wt .-% NC with a nitrogen content of 11.7% dissolved in acetone.
  • alcohol soluble NC with a nitrogen content of 11.3% can be used, whose viscosity is below 450 cP at 9 wt .-% NC dissolved in acetone or dissolved under 425 cP at 23 wt .-% NC in acetone lies.
  • TL Another significant advantage in the production of TL is the use of alcohol-soluble NC, especially when using an alcohol-moist energy carrier is that the energy must be subjected to no time and energy consuming drying. Moreover, there is no danger of agglomeration when using water-moist energy sources, in particular RDX. Due to the unnecessary drying and the lower price of the alcohol-soluble NC, the production of the TL according to the invention is up to 30% cheaper than the production of previous propellant charges.
  • a further advantage of the TL according to the invention is that in the production thereof, the flowability of the mixture of components can be ensured even with a very high proportion of a crystalline energy carrier, such as RDX, by the addition of ethanol. Flowability is critical to the extrusion commonly used in the processing of the blend to make the TL.
  • process control using ethanol as a solvent is simpler and more accurate than using acetone as a solvent.
  • ethanol can only be used as a solvent when using alcohol-soluble NC.
  • the TL according to the invention in a batch process in a kneader or in a press in a so-called "powder with solvent” process (PmL process) or a “powder without solvent” process (PoL process ).
  • the PoL process uses water-wet material.
  • the CAB was to be processed with alcohol wet NC to a basic granulate, which is then mixed into the water-moist mass and processed into a PoL powder with simultaneous dewatering and plasticization.
  • a shear roller can be used, wherein a dewatered, plasticized granules is obtained, which is then processed with a twin-screw extruder to a TL desired geometry.
  • the NC is contained in the TL in a concentration of 15 wt .-% to 48 wt .-%, in particular 20 wt .-% to 35 wt .-%, in particular 22 wt .-% to 28 wt .-%.
  • This NC concentration has proven to be particularly advantageous in order to be able to set the CAB concentration in such a way that a relatively insensitive but nevertheless high-energy TL can be provided.
  • the nitrogen content of the NC may be 11.2% to 12.8%, especially 11.6% to 12.7%.
  • the degree of substitution is indicated indirectly via the nitrogen content based on the dry substance. Theoretically, when all three positions of an anhydroglucose unit are substituted, the nitrogen content is 14.14%. In practice, however, only a nitrogen content of about 13.6% can be achieved.
  • the CAB is preferably in the TL in a concentration of at least 2 wt .-%, in particular in a concentration of 2 wt .-% to 14 wt .-%, in particular in a concentration of 3 wt .-% to 8 wt. %, in particular in a concentration of 3.5 wt .-% to 6 wt .-%, included.
  • the CAB in the TL has a melting point of over 200 ° C and a glass transition temperature of over 130 ° C.
  • the CAB has a melting point above 230 ° C and a glass transition temperature above 160 ° C.
  • the energy carrier may be an energy source in crystalline form.
  • the energy carrier is hexogen (RDX), octogen (HMX), nitroguanidine, FOX-7 (1,1-diamino-2,2-dinitroethylene), FOX-12 (guarnyl ureadinitramide) or ADN (ammonium dinitramide).
  • the energy carrier in a concentration of 11 wt .-% to 69 wt .-%, in particular 25 wt .-% to 55 wt .-%, in particular 35 wt .-% to 45 wt .-%, contained in the TL ,
  • At least one stabilizer in particular magnesium oxide, diphenylamine, diphenylurethane, N, N-diphenylurea (Arkadit I), N-methyl-N, N-diphenylurea (Arkadit II), 1,3-diethyl, 1 ', 3 Diphenylurea (Centralit I), 1,3-dimethyl-1'3'-diphenylurea (Centralit II) or N-methyl-N'-ethyl-N, N'-diphenylurea (Centralit III).
  • At least one muzzle fire damper in particular a cryolite, sodium oxalate, potassium sulfate, potassium nitrate, another potassium salt or a mixture of at least two of said substances may be included.
  • the stabilizer and the Mouthfire suppressants may be included in the TL in a total concentration of about 2% to 6% by weight.
  • a plasticizer consisting of these components is referred to as DNDA 5.7.
  • the plasticizer may be present in the TL in a concentration of 9% by weight to 39% by weight, in particular 14% by weight to 34% by weight, in particular 29% by weight to 19% by weight ,
  • a TL can be produced in which the maximum pressure which results during firing and the velocity of the projectile caused depend only slightly on the temperature of the TL. This allows a firing of gun ammunition with almost constant values of maximum pressure and bullet velocity in a temperature range of -50 ° C to + 70 ° C.
  • the TL may further comprise at least one additional energetic binder, in particular poly-3-nitratomethyl-3-methyloxetane (PolyNIMMO), polyglycidyl nitrate ester (Polyglyn), glycidyl azide polymer (GAP), poly-3-azidomethyl-3'-methyloxetane (AMMO), poly 3,3'-bis-azidomethyloxetane (BAMO) or a mixture thereof, or a non-energetic further binder, in particular hydroxyl-terminated polybutadiene (HTPB).
  • the TL according to the invention may be in the form of shaped bodies or granules. The granules are often referred to as propellant powder.
  • the invention further relates to a method for producing a TL according to the invention, in which a mixture containing at least one energy carrier is admixed with a CAB and alcohol-soluble NC-containing prefabricated mixture.
  • the mixing can take place when the mixture is kneaded.
  • the mixture further contains acetone-soluble NC, at least one stabilizer, at least one muzzle-fire damper, at least one plasticizer and / or at least one energetic or non-energetic further binder.
  • the mixture can be water-moist and processed under thermal plasticization.
  • the thermal plasticization can be carried out at temperatures of 55 ° C to 100 ° C.
  • the TL according to the invention may be in the form of the following formulations:
  • the RDX is coated with alcohol-soluble NC before being mixed into the other components of the formulation.
  • This coating can be done with about 5% of the nominal NC content of the respective formulation.
  • the formulation formed at the end into moldings or granules can be coated with about 0.02% by weight of graphite, in particular to avoid static charges and to reduce rubbing together.
  • the RDX becomes alcohol wet, d. H. used wetted with about 20 wt .-% to 30 wt .-% ethanol. It is mixed with the total provided in the formulation CAB and 5 wt .-% to 10 wt .-% of the total mass of the formulation of alcohol-soluble NC and kneaded in a so-called batch kneader. This plasticization is carried out by the RDX wetting alcohol. The non-alcohol soluble CAB is not solved. Subsequently, the proportion of NC in the form of acetone-soluble NC, which is nitrated higher than the alcohol-soluble NC and has a higher nitrogen content than this, is added together with DNDA 5,7 and the additives and mixed further.
  • acetone is added.
  • the blended mass is then extruded via an extruder with suitable die and built-in needle carrier.
  • the needle carrier causes strands, for example, with a 1-hole, 7-hole or 19-hole geometry in cross section, arise.
  • the extract is brought to the desired size by cutting. Finally, a drying of the shaped body formed at 30 ° C to 60 ° C.
  • Alcohol-moist RDX, alcohol-soluble NC with CAB and the additives, DNDA 5.7 and further alcohol are metered in a single-flow process to a co-rotating twin-screw extruder, plasticized in the extruder and in the form of strands with 1-hole, 7-hole or 19-hole geometry in cross section Continuously extruded through suitable matrices. The resulting strands are cut into shaped bodies and dried.
  • a precursor is made from alcohol wet RDX, CAB, and low levels of alcohol soluble NC.
  • This precursor is added to a non-alcohol soluble, water wet NC (with about 20 wt .-% to 30 wt .-% water wetted NC) having a nitrogen content of about 12.5%, and DNDA 5.7, RDX and additives and wetted with more water, so that a water content of 20 wt .-% to 30 wt .-% is achieved.
  • a non-alcohol soluble, water wet NC (with about 20 wt .-% to 30 wt .-% water wetted NC) having a nitrogen content of about 12.5%, and DNDA 5.7, RDX and additives and wetted with more water, so that a water content of 20 wt .-% to 30 wt .-% is achieved.
  • the water-moist mass is applied to a continuous shear roller.
  • At least one gravimetric metering balance with leaf screw or spiral discharge or a conveyor belt is suitable.
  • the water-moist mass is plasticized by temperature and friction and continuously processed via a granulating ring with knife wiper to plasticized granules.
  • This granulate can be continuously fed to a co-rotating twin-screw extruder and then processed into propellant charge strands without the addition of solvents and then dried.
  • the granules of a simultaneous or fine roll can be supplied, whereby only by the influence of temperature and friction, a plasticized coat is obtained.
  • This is rolled into a roll, which is then processed into strands in a tempered extruder.
  • the temperature for processing the water-wet raw material with DNDA 5.7 in the shear roll, the rolling mill and the extruder in the range of 60 ° C to 90 ° C.
  • Technology 5 can also be modified so that only water-wet RDX is used and the alcohol-soluble NC (A-NC) is only thermally plasticized with DNDA 5.7 and CAB.
  • A-NC alcohol-soluble NC

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (15)

  1. Charge propulsive (CP) pour armes tubulaires, comportant au moins une source d'énergie ainsi que de la nitrocellulose (NC) et de l'acétate-butyrate de cellulose (ABC),
    caractérisée en ce que 80 % en poids de la NC consistent en NC soluble dans un alcool, la NC servant de liant et étant à cette fin contenue à une concentration d'au moins 15 pour cent en poids (% en poids) dans la CP,
    l'ABC présentant un point de fusion supérieur à 200 °C et une température de transition vitreuse supérieure à 130 °C.
  2. CP selon la revendication 1,
    caractérisée en ce que
    la NC est contenue dans celle-ci à une concentration de 15 % en poids à 48 % en poids, en particulier de 20 % en poids à 35 % en poids, en particulier de 22 % en poids à 28 % en poids.
  3. CP selon la revendication 1 ou 2,
    caractérisée en ce
    qu'au moins 90 % en poids, en particulier au moins 95 % en poids, en particulier 100 % en poids, de la NC sont solubles dans un alcool.
  4. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    la teneur en azote de la NC vaut de 11,2 % à 12,8 %, en particulier de 11,6 % à 12,7 %.
  5. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    l'ABC est contenu dans celle-ci à une concentration d'au moins 2 % en poids, en particulier à une concentration de 2 % en poids à 14 % en poids, en particulier à une concentration de 3 % en poids à 8 % en poids, en particulier à une concentration de 3,5 % en poids à 6 % en poids.
  6. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    l'ABC présente un point de fusion supérieur à 230 °C et une température de transition vitreuse supérieure à 160 °C.
  7. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    la source d'énergie est l'hexogène (RDX), l'octogène (HMX), la nitroguanidine, le FOX-7 (1,1-diamino-2,2-dinitroéthylène), le FOX-12 (dinitramidure de guarnylurée) ou le DNA (dinitramidure d'ammonium).
  8. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    la source d'énergie est contenue dans celle-ci à une concentration de 11 % en poids à 69 % en poids, en particulier de 25 % en poids à 55 % en poids, en particulier de 35 % en poids à 45 % en poids.
  9. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    dans celle-ci est contenu au moins un stabilisant, en particulier de l'oxyde de magnésium, de la diphénylamine, du diphényluréthane, de la N,N-diphénylurée (arkadite I), de la N-méthyl-N,N-diphénylurée (arkadite II), de la 1,3-diéthyl-1',3'-diphénylurée (centralite I), de la 1,3-diméthyl-l',3'-diphénylurée (centralite II) ou de la N-méthyl-N'-éthyl-N,N'-diphénylurée (centralite III).
  10. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    dans celle-ci est contenu au moins un antilueur, en particulier une cryolithe, de l'oxalate de sodium, du sulfate de potassium, du nitrate de potassium, un autre sel de potassium ou un mélange d'au moins deux desdites substances.
  11. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    dans celle-ci est contenu au moins un plastifiant, en particulier énergétique, en particulier l'acétal/formal de bis-(2,2-dinitropropyle) (BDNPA/F) ou un composé dinitro-diaza.
  12. CP selon la revendication 11,
    caractérisée en ce que
    le plastifiant consiste en les composants suivants :
    - 30 % en poids à 50 % en poids de 2,4-dinitro-2,4-diazapentane,
    - 35 % en poids à 55 % en poids de 2,4-dinitro-2,4-diazahexane et
    - 0 % en poids à 30 % en poids de 2,4-dinitro-2,4-diazaheptane.
  13. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    le plastifiant est contenu dans celle-ci à une concentration de 9 % en poids à 39 % en poids, en particulier de 14 % en poids à 34 % en poids, en particulier de 29 % en poids à 19 % en poids.
  14. CP selon l'une quelconque des revendications précédentes,
    caractérisée en ce que
    dans celle-ci est contenu au moins un autre liant énergétique, en particulier du poly-3-nitratométhyl-3-méthyloxétane (polyNIMMO), du polynitrate de glycidyle (polyglyn), du polymère glycidylazide (GAP), du poly-3-azidométhyl-3'-méthyloxétane (AMMO), du poly-3,3'-bis-azidométhyloxétane (BAMO) ou un mélange de ceux-ci, ou un autre liant non énergétique, en particulier du polybutadiène à groupes hydroxy en bout de chaîne (HTPB).
  15. Procédé pour la préparation d'une CP selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on incorpore à un mélange contenant au moins une source d'énergie un mélange préparé au préalable, contenant de l'ABC et de la NC soluble dans un alcool, au moins 80 % en poids de la NC utilisée étant de la NC soluble dans un alcool, et l'ABC présentant un point de fusion supérieur à 200 °C et une température de transition vitreuse supérieure à 130 °C.
EP11003843A 2010-05-18 2011-05-11 Charge propulsive Not-in-force EP2388244B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102010020776.4A DE102010020776B4 (de) 2010-05-18 2010-05-18 Treibladung und Verfahren zu ihrer Herstellung

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Publication Number Publication Date
EP2388244A1 EP2388244A1 (fr) 2011-11-23
EP2388244B1 true EP2388244B1 (fr) 2013-03-06

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DE (1) DE102010020776B4 (fr)

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DE102005037017B4 (de) * 2005-08-05 2007-09-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Pulvervorkonzentrat und dessen Verwendung
EP1932817A1 (fr) * 2006-12-12 2008-06-18 Nitrochemie Wimmis AG Propergol constitué de nitratoéthyle nitramine pour systèmes de sécurité pour automobiles

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DE102010020776A1 (de) 2011-11-24
EP2388244A1 (fr) 2011-11-23
US20110284140A1 (en) 2011-11-24
DE102010020776B4 (de) 2015-03-05
US8795451B2 (en) 2014-08-05

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