EP2388244A1 - Propellant - Google Patents

Propellant Download PDF

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Publication number
EP2388244A1
EP2388244A1 EP11003843A EP11003843A EP2388244A1 EP 2388244 A1 EP2388244 A1 EP 2388244A1 EP 11003843 A EP11003843 A EP 11003843A EP 11003843 A EP11003843 A EP 11003843A EP 2388244 A1 EP2388244 A1 EP 2388244A1
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EP
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Prior art keywords
weight
concentration
soluble
alcohol
cab
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Granted
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EP11003843A
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German (de)
French (fr)
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EP2388244B1 (en
Inventor
Dietmar Müller
Walter Langlotz
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Diehl BGT Defence GmbH and Co KG
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Diehl BGT Defence GmbH and Co KG
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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 from -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 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 .-%, contained ,
  • 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.
  • At least 80% by weight, in particular at least 90% by weight, in particular at least 95% by weight, in particular 100% by weight, of the NC is alcohol-soluble NC.
  • 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 may have a melting point above 200 ° C and a glass transition temperature above 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-saturated 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 cross-section as strands with 1-hole, 7-hole or 19-hole geometry 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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Abstract

Propellant comprises at least one energy carrier, nitrocellulose and cellulose acetate butyrate, where the nitrocellulose is an alcohol soluble and serves as a binder and the concentration of nitrocellulose is at least 15 wt.%.

Description

Die Erfindung betrifft eine Treibladung (TL) für Rohrwaffen mit mindestens einem Energieträger sowie Nitrocellulose (NC) und Celluloseacetatbutyrat (CAB).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).

Aus der EP 0 960 083 B1 ist ein Treibladungspulver für Rohrwaffen mit einem Weichmacher auf der Basis von Nitramin und energetischem oder nicht-energetischem Kunststoffbinder bekannt. Bei dem Weichmacher handelt es sich um ein Gemisch aus zumindest drei chemisch unterschiedlichen Dinitro-diazaverbindungen. Bei dem nichtenergetischen Binder kann es sich um CAB handeln. Auf Grund der Eigenschaften des Weichmachers ermöglicht ein derartiges Treibladungspulver den Verschuss von Rohrwaffenmunition mit nahezu konstanten Werten von Maximaldruck und Geschossgeschwindigkeit im gesamten Temperaturbereich von -50°C bis +70°C.From the EP 0 960 083 B1 For example, 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 from -50 ° C to + 70 ° C.

Aus der WO 95/17358 ist ein Treibladungsgemisch für Geschütze bekannt, welches eine hohe Resistenz gegenüber ungewollter Zündung durch Hitze, Flamme, Einschlag, Reibung und chemischen Einfluss zeigt. Neben RDX sind darin CAB, NC, Ethylcentralit, ein Feuchtigkeitsbindemittel und ein energetischer Weichmacher enthalten. Die Zutaten sind bei der Herstellung mit einem Ethylacetat/Ethylalkohol-Gemisch befeuchtet bzw. im Falle von CAB und NC darin gelöst. Das Ethylacetat/Ethylalkohol-Gemisch dient dabei dazu, die Masse mischfähig zu halten und durch einen Extruder extrudieren zu können. Die NC ist mit einem Anteil von 2 Gew.-% bis 6,3 Gew.-% in dem Treibladungsgemisch enthalten. Sie dient dazu, das Treibladungsgemisch zäh zu machen. CAB dient als Bindemittel und ist in einer Konzentration von 10 Gew.-% bis 15 Gew.-% enthalten. Die Treibladung ist verhältnismäßig teuer in der Herstellung.From the WO 95/17358 For example, a propellant charge mixture for guns is known which exhibits high resistance to unwanted ignition by heat, flame, impact, friction and chemical influence. In addition to RDX, it 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.

Aufgabe der vorliegenden Erfindung ist es, eine günstig herzustellende Treibladung und ein Verfahren zu deren Herstellung anzugeben.The object of the present invention is to specify a propellant charge which is inexpensive to produce and a method for the production thereof.

Die Aufgabe wird durch die Merkmale der Ansprüche 1 und 17 gelöst. Zweckmäßige Ausgestaltungen der Erfindung ergeben sich aus den Merkmalen der Ansprüche 2 bis 16, 18 und 19.The object is solved by the features of claims 1 and 17. Advantageous embodiments of the invention will become apparent from the features of claims 2 to 16, 18 and 19.

Erfindungsgemäß ist eine Treibladung (TL) für Rohrwaffen mit mindestens einem Energieträger sowie Nitrocellulose (NC) und Celluloseacetatbutyrat (CAB) vorgesehen. Bei dem Energieträger handelt es sich nicht um die NC. Zumindest ein Teil der NC ist alkohollösliche NC. Die NC dient dabei als Bindemittel und ist dazu in einer Konzentration von mindestens 15 Gewichtsprozent (Gew.-%) in der Treibladung enthalten.According to the invention, a propellant charge (TL) is provided 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.

Im Stand der Technik wird NC mit einem deutlich geringeren Anteil am Gesamtgewicht der TL eingesetzt. Es dient dabei üblicherweise der Verbesserung der Zündfähigkeit, jedoch nicht als Bindemittel. Zur Herstellung einer insensitiven TL mit erhöhter Verpuffungstemperatur und günstigem Cook-off-Verhalten hat es sich als vorteilhaft erwiesen, CAB zur NC zuzumischen. Bei der Ermittlung der Cook-off-Temperatur wird die Temperatur schrittweise definiert erhöht bis es zu einer Umsetzung durch Abbrand, Deflagration oder Detonation kommt. Das Cook-off-Verhalten ist umso günstiger je höher die Temperatur ist, bei der die Umsetzung eintritt. Das CAB verbessert bei Alterung der TL auch den Wärmefluss. Eine lokale Überhitzung in der TL wird dadurch verhindert. Dies ist insbesondere dann vorteilhaft, wenn Munition mit der TL in heißen Gebieten eingesetzt wird, wo die Munition in Fahrzeugen häufig Temperaturen von 60 bis 70°C ausgesetzt ist. Die Erfinder haben jedoch festgestellt, dass die TL bei Erhöhung des CAB-Gehalts auf über 2 Gew.-% verhältnismäßig spröde wird, so dass eine Sprödbruchgefahr besteht. NC ist, abhängig vom Veresterungsgrad, löslich in Alkoholen, Estern oder Ketonen. Es gibt NC, die in Aceton aber nicht in Alkohol löslich ist. In Alkohol lösliche NC ist jedoch stets auch in Aceton oder Ethylacetat löslich. Im Sinne der vorliegenden Erfindung wird unter einer acetonlöslichen NC stets eine NC verstanden, die nicht alkohollöslich ist. Unter Alkohol im Sinne der vorliegenden Erfindung wird im Allgemeinen Ethanol verstanden.In the prior art 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. To produce an insensitive TL with increased deflagration temperature and favorable cook-off behavior, it has proven to be advantageous to mix CAB to NC. In the determination of the cook-off temperature, 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. The inventors have found, however, that the TL becomes relatively brittle when the CAB content is increased above 2% by weight, so that there is a risk of brittle fracture. 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.

Bisher ist es üblich, für Treibladungen acetonlösliche NC einzusetzen. Die Erfinder haben erkannt, dass man bei Einsatz einer alkohollöslichen NC bei CAB-Konzentrationen über 2 Gew.-% eine deutlich weniger spröde TL erhält als bei Einsatz acetonlöslicher NC. Die Gefahr eines Sprödbruchs ist dadurch deutlich vermindert. Der erhöhte CAB-Anteil verbessert die thermischen Eigenschaften der TL durch eine Erhöhung der Verpuffungstemperatur und der Cook-off-Temperatur und verringert die Empfindlichkeit gegenüber Schlag, Reibung und der Wirkung von Projektileinschlägen, Hohlladungen und Splittern.So far, it is customary to use 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.

Weiterhin sind durch den erhöhten CAB-Anteil Treibladungen unterschiedlicher Energiedichten, die je nach Einsatzgebiet erforderlich sind, herstellbar. Die Energiedichte kann von etwa 900 J/g bis etwa 1350 J/g eingestellt werden. Weiterhin kann durch den erhöhten CAB-Anteil die Verbrennungstemperatur (adiabatische Flammtemperatur) um etwa 500 K bis 600 K im Vergleich zu Treibladungen mit gleicher Energiedichte reduziert werden. Durch die verringerte Verbrennungstemperatur zeigt die TL beim Einsatz ein stark reduziertes Erosionsverhalten, d. h. es kommt zu einer verringerten Abtragung von Material im Rohr der Rohrwaffe während der Geschossbewegung im Rohr.Furthermore, by the increased CAB share 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. Furthermore, the combustion temperature (adiabatic flame temperature) can be reduced by about 500 K to 600 K compared to propellant charges with the same energy density due to the increased CAB content. Due to the reduced combustion 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.

Es besteht die Möglichkeit, ausschließlich alkohollösliche NC oder ein Gemisch aus alkohollöslicher und acetonlöslicher NC einzusetzen. Die acetonlösliche NC wird üblicherweise alkoholfeucht geliefert während die alkohollösliche NC üblicherweise wasserfeucht geliefert wird. Alkohollösliche NC wird bisher hauptsächlich in der Lackindustrie eingesetzt und ist wesentlich preisgünstiger als acetonlösliche NC. Typische acetonlösliche NC ist z. B. Schieß- oder Pyrowolle. Die acetonlösliche NC wird häufig als sogenannte E-Wolle (esterlösliche Wolle) verkauft während alkohollösliche NC häufig als sogenannte A-Wolle verkauft wird.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.

Je nach eingesetztem Energieträger kann es vorteilhaft sein, eine niederviskose alkohollösliche NC oder eine hochviskose alkohollösliche NC einzusetzen. Bei einem hohen Anteil eines kristallinen Energieträgers, wie z. B. RDX, ist der Einsatz einer niederviskosen alkohollöslichen NC vorteilhaft. Eine niederviskose alkohollösliche NC zeigt eine Viskosität von unter 425 cP bei 20°C und 34 Gew.-% NC mit einem Stickstoffgehalt von 11,7% in Aceton gelöst. Eine hochviskose alkohollösliche NC weist eine Viskosität von unter 425 cP bei 20°C und 18 Gew.-% NC mit einem Stickstoffgehalt von 11,7% in Aceton gelöst auf. Für eine TL mit geringer Leistung kann auch alkohollösliche NC mit einem Stickstoffgehalt von 11,3% verwendet werden, deren Viskosität unter 450 cP bei 9 Gew.-% NC in Aceton gelöst oder unter 425 cP bei 23 Gew.-% NC in Aceton gelöst liegt.Depending on the energy source used, it may be advantageous to use a low-viscosity alcohol-soluble NC or a high-viscosity alcohol-soluble NC. At a high proportion of 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. For a low power TL, 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.

Ein weiterer wesentlicher Vorteil bei der Herstellung der TL besteht beim Einsatz der alkohollöslichen NC, insbesondere bei gleichzeitigem Einsatz eines alkoholfeuchten Energieträgers darin, dass der Energieträger keiner zeit- und energieaufwändigen Trocknung unterzogen werden muss. Darüber hinaus besteht nicht die beim Einsatz von wasserfeuchtem Energieträger, insbesondere RDX, häufig bestehende Gefahr einer Agglomeratbildung. Durch die nicht erforderliche Trocknung und den günstigeren Preis der alkohollöslichen NC ist die Produktion der erfindungsgemäßen TL um bis zu 30% günstiger als die Produktion bisheriger Treibladungen.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.

Ein weiterer Vorteil der erfindungsgemäßen TL ist, dass bei deren Herstellung die Fließfähigkeit des Gemischs der Komponenten auch bei sehr hohem Anteil eines kristallinen Energieträgers, wie RDX, durch den Zusatz von Ethanol gewährleistet werden kann. Die Fließfähigkeit ist für die üblicherweise bei der Verarbeitung des Gemischs zur Herstellung der TL eingesetzten Extrusion von entscheidender Bedeutung. Darüber hinaus ist die Prozesskontrolle beim Einsatz von Ethanol als Lösungsmittel einfacher und genauer als beim Einsatz von Aceton als Lösungsmittel. Ethanol kann jedoch nur beim Einsatz alkohollöslicher NC als Lösungsmittel verwendet werden.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. In addition, process control using ethanol as a solvent is simpler and more accurate than using acetone as a solvent. However, ethanol can only be used as a solvent when using alcohol-soluble NC.

Mit der alkohollöslichen NC besteht die Möglichkeit, die erfindungsgemäße TL im Batch-Verfahren in einem Kneter oder in einer Presse in einem sogenannten "Pulver mit Lösungsmittel"-Prozess (PmL-Prozess) oder einem "Pulver ohne Lösungsmittel"-Prozess (PoL-Prozess) herzustellen. Beim PoL-Prozess wird mit wasserfeuchtem Material gearbeitet. Dabei sollte das CAB mit alkoholfeuchter NC zu einem Basisgranulat verarbeitet werden, das dann in die wasserfeuchte Masse eingemischt und zu einem PoL-Pulver bei gleichzeitiger Entwässerung und Plastifizierung verarbeitet wird. Dazu kann eine Scherwalze eingesetzt werden, wobei ein entwässertes, plastifiziertes Granulat erhalten wird, das dann mit einem Doppelschneckenextruder zu einer TL gewünschter Geometrie verarbeitet wird.With the alcohol-soluble NC it is possible, 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. For this purpose, 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.

Vorzugsweise ist die NC in der TL in einer Konzentration von 15 Gew.-% bis 48 Gew.-%, insbesondere 20 Gew.-% bis 35 Gew.-%, insbesondere 22 Gew.-% bis 28 Gew.-%, enthalten.Preferably, the NC 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 .-%, contained ,

Diese NC-Konzentration hat sich als besonders vorteilhaft erwiesen, um die CAB-Konzentration so einstellen zu können, dass dadurch eine verhältnismäßig insensitive aber dennoch hochenergetische TL bereitgestellt werden kann.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.

Vorzugsweise ist zumindest 80 Gew.-%, insbesondere zumindest 90 Gew.-%, insbesondere zumindest 95 Gew.-%, insbesondere 100 Gew.-%, der NC alkohollösliche NC.Preferably, at least 80% by weight, in particular at least 90% by weight, in particular at least 95% by weight, in particular 100% by weight, of the NC is alcohol-soluble NC.

Der Stickstoffgehalt der NC kann 11,2% bis 12,8%, insbesondere 11,6% bis 12,7%, betragen. Bei NC wird der Substitutionsgrad indirekt über den auf die Trockensubstanz bezogenen Stickstoffgehalt angegeben. Theoretisch beträgt der Stickstoffgehalt wenn alle drei Positionen einer Anhydroglucose-Einheit substituiert sind 14,14%. Praktisch lässt sich jedoch nur ein Stickstoffgehalt von ca. 13,6% erreichen.The nitrogen content of the NC may be 11.2% to 12.8%, especially 11.6% to 12.7%. In the case of NC, 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.

Das CAB ist in der TL vorzugsweise in einer Konzentration von mindestens 2 Gew.-%, insbesondere in einer Konzentration von 2 Gew.-% bis 14 Gew.-%, insbesondere in einer Konzentration von 3 Gew.-% bis 8 Gew.-%, insbesondere in einer Konzentration von 3,5 Gew.-% bis 6 Gew.-%, enthalten.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.

Das CAB in der TL kann einen Schmelzpunkt von über 200°C und einer Glasübergangstemperatur von über 130°C aufweisen. Vorzugsweise weist das CAB einen Schmelzpunkt von über 230°C und eine Glasübergangstemperatur von über 160°C auf.The CAB in the TL may have a melting point above 200 ° C and a glass transition temperature above 130 ° C. Preferably, the CAB has a melting point above 230 ° C and a glass transition temperature above 160 ° C.

Bei dem Energieträger kann es sich um einen in kristalliner Form vorliegenden Energieträger handeln. Bei einem Ausführungsbeispiel ist der Energieträger Hexogen (RDX), Oktogen (HMX), Nitroguanidin, FOX-7 (1,1-Diamino-2,2-dinitroethylen), FOX-12 (Guarnylureadinitramid) oder ADN (Ammoniumdinitramid). Vorzugsweise ist der Energieträger in einer Konzentration von 11 Gew.-% bis 69 Gew.-%, insbesondere 25 Gew.-% bis 55 Gew.-%, insbesondere 35 Gew.-% bis 45 Gew.-%, in der TL enthalten.The energy carrier may be an energy source in crystalline form. In one embodiment, 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). Preferably, 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 ,

Weiterhin kann in der TL mindestens ein Stabilisator, insbesondere Magnesiumoxid, Diphenylamin, Diphenylurethan, N,N-Diphenylharnstoff (Arkadit I), N-Methyl-N,N-diphenylharnstoff (Arkadit II), 1,3-Diethyl,1',3'-Diphenylharnstoff (Centralit I), 1,3-Dimethyl-1'3'-Diphenylharnstoff (Centralit II) oder N-Methyl-N'-ethyl-N,N'-diphenylharnstoff (Centralit III), enthalten sein. Darüber hinaus kann in der TL mindestens ein Mündungsfeuerdämpfer, insbesondere ein Kryolith, Natriumoxalat, Kaliumsulfat, Kaliumnitrat, ein sonstiges Kaliumsalz oder ein Gemisch aus mindestens zwei der genannten Substanzen, enthalten sein. Der Stabilisator und der Mündungsfeuerdämpfer können in der TL in einer Gesamtkonzentration von etwa 2 Gew.-% bis 6 Gew.-% enthalten sein.Furthermore, in 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). In addition, in the TL 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.

Vorzugsweise ist in der TL mindestens ein, insbesondere energetischer, Weichmacher, insbesondere bis-(2,2 dinitropropyl) acetal/formal (BDNPA/F) oder eine Dinitrodiazaverbindung, enthalten. Besonders bevorzugt besteht der Weichmacher aus folgenden Komponenten:

  • 30 Gew.-% bis 50 Gew.-% 2,4-Dinitro-2,4-diazapentan,
  • 35 Gew.-% bis 55 Gew.-% 2,4-Dinitro-2,4-diazahexan und
  • 0 Gew.-% bis 30 Gew.-% 2,4-Dinitro-2,4-diazaheptan.
The TL preferably contains at least one, in particular energetic, plasticizer, in particular bis- (2,2-dinitropropyl) acetal / formal (BDNPA / F) or a dinitrodiaza compound. The plasticizer particularly preferably consists of the following components:
  • From 30% to 50% by weight of 2,4-dinitro-2,4-diazapentane,
  • 35 wt .-% to 55 wt .-% 2,4-dinitro-2,4-diazahexan and
  • 0% to 30% by weight of 2,4-dinitro-2,4-diazaheptane.

Ein aus diesen Komponenten bestehender Weichmacher wird als DNDA 5,7 bezeichnet.A plasticizer consisting of these components is referred to as DNDA 5.7.

Der Weichmacher kann in der TL in einer Konzentration von 9 Gew.-% bis 39 Gew.-%, insbesondere 14 Gew.-% bis 34 Gew.-%, insbesondere 29 Gew.-% bis 19 Gew.-%, enthalten sein. Durch die genannten Weichmacher lässt sich eine TL herstellen, bei welcher beim Verschießen der entstehende Maximaldruck und die bewirkte Geschossgeschwindigkeit nur gering von der Temperatur der TL abhängen. Dadurch wird ein Verschuss von Rohrwaffenmunition mit nahezu konstanten Werten von Maximaldruck und Geschossgeschwindigkeit in einem Temperaturbereich von -50°C bis +70°C ermöglicht.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 , By the said plasticizers, 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.

In der TL kann weiterhin mindestens ein energetisches weiteres Bindemittel, insbesondere Poly-3-nitratomethyl-3-methyloxetan (PolyNIMMO), Polyglycidylnitratester (Polyglyn), Glycidylazidpolymer (GAP), Poly-3-azidomethyl-3'-methyloxetan (AMMO), Poly-3,3'-bis-azidomethyloxetan (BAMO) oder ein Gemisch derselben, oder ein nicht-energetisches weiteres Bindemittel, insbesondere Polybutadien mit endständigen Hydroxylgruppen (HTPB), enthalten sein. Die erfindungsgemäße TL kann in Form von Formkörpern oder einem Granulat vorliegen. Das Granulat wird häufig auch als Treibladungspulver bezeichnet.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.

Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung einer erfindungsgemäßen TL, bei welchem einem mindestens einen Energieträger enthaltenden Gemisch eine CAB und alkohollösliche NC enthaltende vorgefertigte Mischung beigemischt wird. Das Beimischen kann beim Kneten des Gemischs erfolgen. Dadurch ist eine einfache Verarbeitung möglich. Vorzugsweise enthält das Gemisch weiterhin acetonlösliche NC, mindestens einen Stabilisator, mindestens einen Mündungsfeuerdämpfer, mindestens einen Weichmacher und/oder mindestens ein energetisches oder nicht-energetisches weiteres Bindemittel.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. This is a simple one Processing possible. Preferably, 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.

Das Gemisch kann wasserfeucht und unter thermischer Plastifizierung verarbeitet werden. Die thermische Plastifizierung kann bei Temperaturen von 55°C bis 100°C erfolgen.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.

Nachfolgend wird die Erfindung anhand von Ausführungsbeispielen näher erläutert.The invention will be explained in more detail by means of exemplary embodiments.

Die erfindungsgemäße TL kann in Form der folgenden Formulierungen vorliegen:The TL according to the invention may be in the form of the following formulations:

Formulierung AFormulation A

Gew.-%Wt .-% RDXRDX 52 +/- 1452 +/- 14 DNDA 5,7DNDA 5.7 20 +/- 720 +/- 7 NCNC 22 +/-722 +/- 7 CABCAB 4 +3/-24 + 3 / -2 Additive, wie z. B. Stabilisatoren und MündungsfeuerdämpferAdditives, such as. B. stabilizers and muzzle fire damper 2 +1/-02 + 1 / -0

Formulierung BFormulation B

Gew.-%Wt .-% RDXRDX 43 +/- 1243 +/- 12 DNDA 5,7DNDA 5.7 27 +/- 627 +/- 6 NCNC 26 +/- 626 +/- 6 CABCAB 4 +2/-04 + 2 / -0 Additive, wie z. B. Stabilisatoren und MündungsfeuerdämpferAdditives, such as. B. stabilizers and muzzle fire damper 2 +1/-02 + 1 / -0

Formulierung CFormulation C

Gew.-%Wt .-% RDXRDX 44,8 +/- 1244.8 +/- 12 DNDA 5,7DNDA 5.7 26 +/- 626 +/- 6 NCNC 25 +/- 625 +/- 6 CABCAB 2 +2/-02 + 2 / -0 Additive, wie z. B. Stabilisatoren und MündungsfeuerdämpferAdditives, such as. B. stabilizers and muzzle fire damper 2,2 +1/-02.2 + 1 / -0

Formulierung DFormulation D

Gew.-%Wt .-% RDXRDX 44,8 +/- 1244.8 +/- 12 DNDA 5,7DNDA 5.7 23 +/- 623 +/- 6 NCNC 22 +/- 622 +/- 6 CABCAB 8 +0/-48 + 0 / -4 Additive, wie z. B. Stabilisatoren und MündungsfeuerdämpferAdditives, such as. B. stabilizers and muzzle fire damper 2,2 +1/-02.2 + 1 / -0

Für alle genannten Formulierungen gilt:

  • Bei der NC kann es sich um alkohollösliche NC oder eine Mischung aus alkohollöslicher und acetonlöslicher NC handeln.
For all mentioned formulations applies:
  • The NC may be alcohol soluble NC or a mixture of alcohol soluble and acetone soluble NC.

Es ist vorteilhaft, wenn das RDX vor einem Einmischen in die sonstigen Komponenten der Formulierung mit alkohollöslicher NC beschichtet wird. Diese Beschichtung kann mit ca. 5% des nominalen NC-Gehalts der jeweiligen Formulierung erfolgen. Die am Ende zu Formkörpern oder einem Granulat geformte Formulierung kann, insbesondere zur Vermeidung statische Aufladungen und zur Verminderung eines Aneinanderreibens mit ca. 0,02 Gew.-% Grafit beschichtet werden.It is advantageous if 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.

Technologie 1Technology 1

Zur Herstellung von Treibladungen geringer Leistung, d. h. mit Energiedichten unter 1100 J/g, wird bei allen obigen Formulierungen ausschließlich alkohollösliche NC eingesetzt.For the production of low power propellants, d. H. with energy densities below 1100 J / g, in all the above formulations only alcohol-soluble NC is used.

Zur Herstellung von Treibladungen höherer Leistung können die nachfolgenden Technologien 2 und 3 zum Einsatz kommen.To produce higher power propellants, the following technologies 2 and 3 can be used.

Technologie 2Technology 2

Das RDX wird alkoholfeucht, d. h. mit ca. 20 Gew.-% bis 30 Gew.-% Ethanol benetzt eingesetzt. Es wird mit dem gesamten in der Formulierung vorgesehenen CAB und 5 Gew.-% bis 10 Gew.-% der Gesamtmasse der Formulierung an alkohollöslicher NC gemischt und in einem sogenannten Batch-Kneter geknetet. Dabei erfolgt eine Plastifizierung durch den das RDX benetzenden Alkohol. Das nicht-alkohollösliche CAB wird nicht gelöst. Anschließend wird der bisher nicht zugesetzte, gemäß der jeweiligen Formulierung vorgesehene Anteil an NC in Form acetonlöslicher NC, die höher als die alkohollösliche NC nitriert ist und einen höheren Stickstoffgehalt als diese aufweist, zusammen mit DNDA 5,7 und den Additiven zugegeben und weiter gemischt. Abschließend wird eine geringe Menge Aceton zugesetzt. Die vermischte Masse wird dann über eine Strangpresse mit geeigneter Matrize und eingebautem Nadelträger extrudiert. Der Nadelträger bewirkt, dass Stränge, beispielsweise mit 1-Loch-, 7-Loch-oder 19-Loch-Geometrie im Querschnitt, entstehen. Das Extrakt wird durch Schneiden auf die gewünschte Größe gebracht. Abschließend erfolgt eine Trocknung der gebildeten Formkörper bei 30°C bis 60°C.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. Finally, a small amount of 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.

Technologie 3Technology 3

Zu mit 20 Gew.-% bis 30 Gew.-% Ethanol benetztem RDX und dem CAB werden ausschließlich alkohollösliche NC oder eine mit Alkohol plastifizierte Mischung aus alkohollöslicher und alkoholunlöslicher NC sowie DNDA 5,7 und die Additive gegeben und in einem Batch-Kneter vermischt. Die Mischung wird nur durch Zugabe von weiterem Alkohol plastifiziert. Die vermischte Masse wird dann, wie bei Technologie 2 beschrieben, durch Extrusion, anschließendes Schneiden und Trocknen weiterverarbeitet.To 20 wt .-% to 30 wt .-% ethanol wetted RDX and the CAB exclusively alcohol-soluble NC or a plasticized with alcohol mixture of alcohol-soluble and alcohol-insoluble NC and DNDA 5.7 and the additives are added and mixed in a batch kneader , The mixture is plasticized only by adding more alcohol. The mixed mass is then further processed by extrusion as described in Technology 2, followed by cutting and drying.

Technologie 4Technology 4

Alkoholfeuchtes RDX, alkohollösliche NC mit CAB und den Additiven, DNDA 5,7 sowie weiterer Alkohol werden im Einzelstromverfahren einem gleichlaufenden Doppelschneckenextruder zudosiert, im Extruder plastifiziert und als Stränge mit 1-Loch-, 7-Loch- oder 19-Loch-Geometrie im Querschnitt über geeignete Matrizen kontinuierlich extrudiert. Die entstandenen Stränge werden zu Formkörpern geschnitten und getrocknet.Alcohol-saturated 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 cross-section as strands with 1-hole, 7-hole or 19-hole geometry Continuously extruded through suitable matrices. The resulting strands are cut into shaped bodies and dried.

Technologie 5Technology 5

Wie unter Technologie 2 beschrieben, wird ein Vorprodukt aus alkoholfeuchtem RDX, CAB und geringem Anteil alkohollöslicher NC hergestellt.As described under Technology 2, a precursor is made from alcohol wet RDX, CAB, and low levels of alcohol soluble NC.

Dieses Vorprodukt wird zu einer nicht-alkohollöslichen, wasserfeuchten NC (mit ca. 20 Gew.-% bis 30 Gew.-% Wasser benetzte NC) mit einem Stickstoffgehalt von über 12,5%, sowie DNDA 5,7, RDX und Additiven zugegeben und mit weiterem Wasser benetzt, so dass ein Wassergehalt von 20 Gew.-% bis 30 Gew.-% erreicht wird.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.

Die wasserfeuchte Masse wird auf eine kontinuierlich arbeitende Scherwalze aufgegeben.The water-moist mass is applied to a continuous shear roller.

Hierzu eignet sich mindestens eine gravimetrische Dosierwaage mit Blattschnecken-oder Spiralaustrag oder ein Förderband. Auf der Scherwalze wird die wasserfeuchte Masse durch Temperatur und Friktion plastifiziert und kontinuierlich über einen Granulier-Ring mit Messerabstreifer zu plastifiziertem Granulat verarbeitet.For this purpose, at least one gravimetric metering balance with leaf screw or spiral discharge or a conveyor belt is suitable. On the shear roller, the water-moist mass is plasticized by temperature and friction and continuously processed via a granulating ring with knife wiper to plasticized granules.

Dieses Granulat kann kontinuierlich einem gleichlaufenden Doppelschneckenextruder zugeführt werden und dann zu Treibladungssträngen ohne Zugabe von Lösungsmitteln verarbeitet und anschließend getrocknet werden.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.

Ebenso kann das Granulat einer Simultan- oder Feinwalze zugeführt werden, wobei nur durch Einfluss von Temperatur und Friktion ein plastifiziertes Fell erhalten wird.Likewise, 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.

Dieses wird zu einem Wickel gerollt, der dann in einer temperierten Strangpresse zu Strängen verarbeitet wird.This is rolled into a roll, which is then processed into strands in a tempered extruder.

Die Temperatur zur Verarbeitung der wasserfeuchten Rohmasse mit DNDA 5,7 liegt bei der Scherwalze, dem Walzwerk und der Strangpresse im Bereich von 60°C bis 90°C.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.

Technologie 5 kann auch so modifiziert werden, dass nur wasserfeuchtes RDX eingesetzt wird und die alkohollösliche NC (A-NC) nur thermisch mit DNDA 5,7 und CAB plastifiziert wird.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.

Claims (15)

Treibladung (TL) für Rohrwaffen mit mindestens einem Energieträger sowie Nitrocellulose (NC) und Celluloseacetatbutyrat (CAB),
dadurch gekennzeichnet,
dass zumindest ein Teil der NC alkohollösliche NC ist, wobei die NC als Bindemittel dient und dazu in einer Konzentration von mindestens 15 Gewichtsprozent (Gew.-%) in der TL enthalten ist.Propellant charge (TL) for tube weapons with at least one energy source as well as nitrocellulose (NC) and cellulose acetate butyrate (CAB),
characterized,
in that at least part of the NC is alcohol-soluble NC, the NC serving as a binder and being contained in the TL in a concentration of at least 15% by weight (wt.%). TL nach Anspruch 1,
dadurch gekennzeichnet,
dass die NC darin in einer Konzentration von 15 Gew.-% bis 48 Gew.-%, insbesondere 20 Gew.-% bis 35 Gew.-%, insbesondere 22 Gew.-% bis 28 Gew.-%, enthalten ist.TL according to claim 1,
characterized,
the NC is contained therein in a concentration of 15 wt .-% to 48 wt .-%, in particular 20 wt .-% to 35 wt .-%, in particular 22 wt .-% to 28 wt .-%. TL nach Anspruch 1 oder 2,
dadurch gekennzeichnet,
dass zumindest 80 Gew.-%, insbesondere zumindest 90 Gew.%, insbesondere zumindest 95 Gew.-%, insbesondere 100 Gew.-%, der NC alkohollösliche NC ist.TL according to claim 1 or 2,
characterized,
in that at least 80% by weight, in particular at least 90% by weight, in particular at least 95% by weight, in particular 100% by weight, of the NC is alcohol-soluble NC. TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass der Stickstoffgehalt der NC 11,2% bis 12,8%, insbesondere 11,6% bis 12,7%, beträgt.TL according to one of the preceding claims,
characterized,
that the nitrogen content of the NC 11.2% to 12.8%, especially 11.6% to 12.7% by weight,. TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass das CAB darin in einer Konzentration von mindestens 2 Gew.-%, insbesondere in einer Konzentration von 2 Gew.-% bis 14 Gew.-%, insbesondere in einer Konzentration von 3 Gew.-% bis 8 Gew.-%, insbesondere in einer Konzentration von 3,5 Gew.-% bis 6 Gew.-%, enthalten ist.TL according to one of the preceding claims,
characterized,
that the CAB therein 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 .-%, is contained. TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass das CAB einen Schmelzpunkt von über 200°C und eine Glasübergangstemperatur von über 130°C, insbesondere einen Schmelzpunkt von über 230°C und eine Glasübergangstemperatur von über 160°C, aufweist.TL according to one of the preceding claims,
characterized,
that the CAB has a melting point of over 200 ° C and a glass transition temperature of about 130 ° C, in particular a melting point of about 230 ° C and a glass transition temperature of about 160 ° C. TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass der Energieträger Hexogen (RDX), Oktogen (HMX), Nitroguanidin, FOX-7 (1,1-Diamino-2,2-dinitroethylen), FOX-12 (Guarnylureadinitramid) oder ADN (Ammoniumdinitramid) ist.TL according to one of the preceding claims,
characterized,
that the energy source is hexogen (RDX), octogen (HMX), nitroguanidine, FOX-7 (1,1-diamino-2,2-dinitroethylene), FOX-12 (guarnyl ureadinitramide) or ADN (ammonium dinitramide). TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass der Energieträger darin in einer Konzentration von 11 Gew.-% bis 69 Gew.-%, insbesondere 25 Gew.-% bis 55 Gew.-%, insbesondere 35 Gew.-% bis 45 Gew.-%, enthalten ist.TL according to one of the preceding claims,
characterized,
that the energy carrier is contained therein in a concentration of 11 wt .-% to 69 wt .-%, in particular 25 wt .-% to 55 wt .-%, in particular 35 wt .-% to 45 wt .-%. TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass darin mindestens ein Stabilisator, insbesondere Magnesiumoxid, Diphenylamin, Diphenylurethan, N,N-Diphenylharnstoff (Arkadit I), N-Methyl-N,N-diphenylharnstoff (Arkadit II), 1,3-Diethyl,1',3'-Diphenylharnstoff (Centralit I), 1,3-Dimethyl-1`3`-Diphenylharnstoff (Centralit II) oder N-Methyl-N'-ethyl-N,N'-diphenylharnstoff (Centralit III), enthalten ist.TL according to one of the preceding claims,
characterized,
in that 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). TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass darin mindestens ein Mündungsfeuerdämpfer, insbesondere ein Kryolith, Natriumoxalat, Kaliumsulfat, Kaliumnitrat, ein sonstiges Kaliumsalz oder ein Gemisch aus mindestens zwei der genannten Substanzen, enthalten ist.TL according to one of the preceding claims,
characterized,
in that it contains 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 the substances mentioned. TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass darin mindestens ein, insbesondere energetischer, Weichmacher, insbesondere bis-(2,2 dinitropropyl) acetal/formal (BDNPA/F) oder eine Dinitrodiazaverbindung, enthalten ist.TL according to one of the preceding claims,
characterized,
in that it contains at least one, in particular energetic, plasticizer, in particular bis- (2,2-dinitropropyl) acetal / formal (BDNPA / F) or a dinitrodiaza compound. TL nach Anspruch 11,
dadurch gekennzeichnet,
dass der Weichmacher aus folgenden Komponenten besteht: - 30 Gew.-% bis 50 Gew.-% 2,4-Dinitro-2,4-diazapentan, - 35 Gew.-% bis 55 Gew.-% 2,4-Dinitro-2,4-diazahexan und - 0 Gew.% bis 30 Gew.-% 2,4-Dinitro-2,4-diazaheptan. TL according to claim 11,
characterized,
that the plasticizer consists of the following components: From 30% by weight to 50% by weight of 2,4-dinitro-2,4-diazapentane, From 35% to 55% by weight of 2,4-dinitro-2,4-diazahexane and From 0% to 30% by weight of 2,4-dinitro-2,4-diazaheptane. TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass der Weichmacher darin in einer Konzentration von 9 Gew.-% bis 39 Gew.-%, insbesondere 14 Gew.-% bis 34 Gew.-%, insbesondere 29 Gew.-% bis 19 Gew.-%, enthalten ist.TL according to one of the preceding claims,
characterized,
that the plasticizer is contained therein in a concentration of 9 wt .-% to 39 wt .-%, in particular 14 wt .-% to 34 wt .-%, in particular 29 wt .-% to 19 wt .-%. TL nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
dass darin mindestens ein energetisches weiteres Bindemittel, insbesondere Poly-3-nitratomethyl-3-methyloxetan (PolyNIMMO), Polyglycidylnitratester (Polyglyn), Glycidylazidpolymer (GAP), Poly-3-azidomethyl-3'-methyloxetan (AMMO), Poly-3,3'-bis-azidomethyloxetan (BAMO) oder ein Gemisch derselben, oder ein nicht-energetisches weiteres Bindemittel, insbesondere Polybutadien mit endständigen Hydroxylgruppen (HTPB), enthalten ist.TL according to one of the preceding claims,
characterized,
that is at least an energetic further binder, in particular poly-3-nitratomethyl-3-methyloxetane (polyNIMMO), Polyglycidylnitratester (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, especially hydroxyl-terminated polybutadiene (HTPB). Verfahren zur Herstellung einer TL nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet,
dass einem mindestens einen Energieträger enthaltenden Gemisch eine CAB und alkohollösliche NC enthaltende vorgefertigte Mischung beigemischt wird.Method for producing a TL according to one of the preceding claims, characterized in that
in that a mixture comprising at least one energy carrier is admixed with a CAB and alcohol-soluble NC-containing prefabricated mixture.
EP11003843A 2010-05-18 2011-05-11 Propellant Not-in-force EP2388244B1 (en)

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US20110284140A1 (en) 2011-11-24

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