EP1241152A1 - Poudre propulsive insensible à la température - Google Patents

Poudre propulsive insensible à la température Download PDF

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Publication number
EP1241152A1
EP1241152A1 EP02405191A EP02405191A EP1241152A1 EP 1241152 A1 EP1241152 A1 EP 1241152A1 EP 02405191 A EP02405191 A EP 02405191A EP 02405191 A EP02405191 A EP 02405191A EP 1241152 A1 EP1241152 A1 EP 1241152A1
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EP
European Patent Office
Prior art keywords
tlp
temperature
grain
moderator
solid
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
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EP02405191A
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German (de)
English (en)
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EP1241152B1 (fr
Inventor
Markus Fahrni
Beat Dr. Vogelsanger
Alfred Dr. Steinmann
Bruno Ossola
Kurt Ryf
Ulrike Jeck-Prosch
Alexander Dr. Huber
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Nitrochemie Wimmis AG
Nitrochemie Aschau GmbH
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Nitrochemie Wimmis AG
Nitrochemie Aschau GmbH
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Priority claimed from EP01810255A external-priority patent/EP1241151A1/fr
Application filed by Nitrochemie Wimmis AG, Nitrochemie Aschau GmbH filed Critical Nitrochemie Wimmis AG
Priority to EP20020405191 priority Critical patent/EP1241152B1/fr
Publication of EP1241152A1 publication Critical patent/EP1241152A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0083—Treatment of solid structures, e.g. for coating or impregnating with a modifier
    • 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
    • C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
    • C06B45/20—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component
    • C06B45/22—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component the coating containing an organic compound
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B5/00—Cartridge ammunition, e.g. separately-loaded propellant charges
    • F42B5/02—Cartridges, i.e. cases with charge and missile
    • F42B5/16—Cartridges, i.e. cases with charge and missile characterised by composition or physical dimensions or form of propellant charge, with or without projectile, or powder

Definitions

  • the invention relates to a propellant powder, the grain of which has at least one with an opening has an opening opening to an outer surface of the grain, the opening is closed with a pin. Furthermore, the invention relates to a method for Production of such a powder.
  • TLP Propellant powder
  • system specific Factors system specific Factors
  • Large temperature differences when using weapons are one of the most important influences that a propellant charge manufacturer or an ammunition manufacturer has to consider. So it can easily happen that Local and / or global climate conditions Safe drive solutions in one temperature range from - 54 ° C to + 63 ° C / + 71 ° C (and even up to + 100 ° C in aircraft use).
  • tube weapons are in constant demand after increased performance (e.g. higher kinetic energy of the projectile in the tank, longer ranges for artillery shells, shorter flight times for anti-aircraft missiles [Machine gun], higher probability of first shot, etc.).
  • the desired performance improvements can only be achieved by exhausting all reserves and through a combination of suitable measures (optimization of internal ballistic Operations) can be achieved with the weapon-technical framework unchanged stay.
  • the required high performance TLP be inexpensive are producible, i.e. with easily accessible, inexpensive starting materials and with simple processes can be manufactured.
  • the burning speed depends on the Autoignition temperature and the initial temperature of the propellant body. This behavior leads to the well-known property of such classic blowing agents, that their linear burning speed more or less from the initial temperature depends. This inevitably also means that peak gas pressure and muzzle velocity have a more or less steep temperature gradient. This The temperature-dependent performance of such blowing agents has considerable disadvantages, e.g. small First shot hit probability and significantly lower projectile energy at normal and especially at low operating temperatures. The limiting factor is always that of maximum peak gas pressure occurring at high temperatures.
  • US Pat. No. 4,106,960 mentions a surface coating in which a 19 - hole propellant powder with 18% polymethyl methacrylate (mol. weight> 100,000), 3.4% titanium oxide, 1.9% diphenylcresyl phosphate and 100% toluene (all percentages based on the TLP) is coated in 20 application and drying cycles. About 10 to 20 parts by weight (based on the amount of TLP) are preferred inert material mounted on the TLP. This corresponds to an inert coating layer from 100 to 200 microns. This greatly delays the ignition of the TLP. You mix this highly treated TLP with untreated TLP, which is an instantaneous ignition has, it is possible to invert the temperature dependence of the propellant charge powder. A mixture of treated grain and untreated grain showed in the pressure bomb (where all material burns) a temperature-independent behavior, the burning time was not specified. The temperature-independent behavior was in the gunfire Not checked.
  • Another proposal for reducing the temperature dependency relates to the adaptation of the chamber volume depending on the powder temperature.
  • the object of the invention is to provide a propellant charge powder of the type mentioned in the introduction, that shows a largely temperature-independent combustion behavior without essential Losses in other properties have to be accepted. In particular neither the ignition behavior nor the chemical and ballistic stability of the Propellant powder deteriorate.
  • a propellant charge powder of the type mentioned at the outset is characterized in that that the peg has a temperature-dependent mobility that is such that at lower Application temperature there is a higher mobility than at a higher application temperature, so that the peg is stronger at a lower application temperature Hole burn-up permits than at higher application temperatures.
  • the effect mentioned is based on the temperature-dependent cone mobility during the ignition process of the TLP.
  • the cones remain at a high powder temperature (and thus at faster burning rate) in the perforated channels. So there is a minimal Surface available for burning.
  • the pins are all removed by the ignition shock wave and there is a maximum surface area available for burning.
  • it is Product of the burn-off speed times the surface constant at all firing temperatures, which equates to a temperature-independent combustion behavior.
  • the temperature-dependent cone mobility is determined by coordinating the relevant parameters in surface treatment and due to the temperature-dependent expansion the propellant grain matrix or the cone controlled. Two important parameters are in the amount of graphite used and the treatment time. The longer treated, the stronger the cones become. It should be noted that the inventive Effect cannot be created solely by introducing graphite. The graphite must also be compacted or glued to form a kind of solid. Add to that e.g. the use of solvents or desensitizers. (Is the grain soft, e.g. desensitizers can also be dispensed with.)
  • elastomers such as e.g. the two- or multi-base nitrocellulose, itself above their glass transition temperature (> -40 ° C) more or less proportionally with expand with increasing temperature.
  • the surface treatment to achieve an SCDB® effect is usually done with 30 ° C carried out. This means that the hole diameter of such propellant grains at 63 ° C because of the material expansion are smaller than at 30 ° C. Since the cone material, that sits in the perforated channels, expands with increasing temperature these have a larger diameter at 63 ° C. Thus, the pins are firmly stuck at 63 ° C. In addition, propellant grains and also the cones (where the solid passes through small amounts of explosive oil and nitrocellulose is glued) at high temperatures exhibit increased adhesive behavior. The cones can thus be ignited during the ignition process hardly move by the shock wave.
  • the hole diameters are contracted of the grain material larger than at 30 ° C.
  • the pin diameter increases at this temperature because of the material contraction.
  • the cones are therefore quite loose in the perforated channels.
  • the adhesive effect of the cold grain material is also reduced.
  • the ignition shock therefore drives the cones immediately into the hole or pulverizes them, because the brittleness the cones, which are mainly made of solid material, at low temperatures but increases significantly.
  • TLP composition and amount amount and grain size of the solid, polarity and amount of the solvent, amount and polarity of the desensitizer or moderator, duration of treatment and temperature
  • TLP composition and amount amount and grain size of the solid, polarity and amount of the solvent, amount and polarity of the desensitizer or moderator, duration of treatment and temperature
  • pin stability described above in the perforated channels is a represents statistical size. Not every peg shows the same behavior on the ignition pressure wave.
  • the hole erosion is used to characterize the extent to which the holes run out Combustion processes contribute to the rate of gas formation. The more holes released the more surface is available for the erosion. Accordingly more gas is produced from the grain per unit of time.
  • the invention has various approaches compared to the approaches proposed in the prior art Benefits.
  • TLP perforated propellant powder
  • It can be Manufacture propellant powder that has a temperature-independent combustion behavior, can be easily initiated by conventional means of ignition and also via a have high ballistic stability (service life). Because of the temperature independence (more or less constant gas formation rate) the powder energy Make optimal use of the entire temperature range.
  • the cone should preferably consist of a substance contained in the green grain (i.e. the untreated one perforated TLP), is not soluble. This ensures that the anchoring of the pin in the opening and thus the mobility of the pin is not can change through diffusion processes.
  • the anchoring is essentially determined by surface parameters at the level of the grain or cone structure.
  • the pin preferably consists essentially of an inert solid.
  • Powder temperature is more or less strongly affected by the pressure wave of the ignition pushed the cavity in.
  • the active surface becomes increases and consequently the gas development per unit of time.
  • the initial temperature quickly disengages from the anchor. Thereby the flammable TLP surface is increased almost instantaneously.
  • the anchorage of the peg is quite resistant and the flammable TLP surface is reduced to a minimum.
  • a solid with a grain size in the range of 0.01 to 100 micrometers can be used become.
  • the grain size will have to be matched to the size of the opening. If the grains of the solid are relatively large, it is difficult to enter the opening be introduced.
  • the grain size is typically in the range from 0.1 to 50 Microns.
  • the solid be inert. It can also contain energy. However, it has to burn and burn less quickly than the green grain.
  • Suitable inert solids are e.g. Graphite, talc, titanium oxide, carbon black, potassium sulfate, potassium cryolite and / or calcium carbonate.
  • Graphite e.g. Graphite, talc, titanium oxide, carbon black, potassium sulfate, potassium cryolite and / or calcium carbonate.
  • substances that can be used do not react with the green grain. The substances mentioned can both can be used individually as well as in connection with each other.
  • the invention is not limited to the fact that the pin consists exclusively of inert substances consists. It is quite possible to have small amounts of an energetic solid add in particular nitrocellulose hexogen octogen nitroguanidine nitrotriazole Ethylenedinitramine, ethyltetryl, ammonium picrate, trinitrotoluene, trinitrobenzene, Tetranitroaniline etc., strong oxidizing agents may also be included, such as Ammonium nitrate, potassium nitrate, ammonium perchlorate, potassium perchlorate etc., if these have no incompatibilities with the selected recipe. Attention should be paid to this be that the stability or resistance of the pegs formed in the openings (Perforations) compared to the ignition shock wave at higher powder temperatures get lost.
  • the pin preferably has a melting temperature which is above a manufacturing, Storage and / or application temperature, in particular above 90 ° C.
  • the propellant powder is typically a two- or multi-base single- or multi-hole powder. That is, the grain is cylindrical (with an outer diameter of, for example, 1 mm to 20 mm or preferably 3 mm to 15 mm) and preferably has 7 to 19 axially continuous Holes.
  • the ratio of grain diameter to grain length is usually in the range between 0.3-2.0, preferably 0.8-1.2.
  • Other powder geometries, e.g. Rosette shape, Hexagon shapes are also possible.
  • the diameter of the holes is z. B. in a range of 0.03 to 0.5 mm in particular 0.1 to 0.3 mm. Finer holes are advantageous in the context of the invention. It can then work with smaller amounts of inert material. In addition, the Better control the quality of the anchoring of the pins. Typically they are compact (compressed) cones have a length to diameter ratio in the range of 5 to 60.
  • the green grain can be made in a known manner by pressing a solvent-containing or solvent-free powder dough or wrap with or without explosive oil additives in one Extrusion press or obtained by extrusion.
  • the cavities closed off by the pins are axially continuous channels a void volume that is a multiple of a volume of a compact spigot is.
  • the peg has a temperature-dependent mobility that is such that at lower Application temperature given a higher mobility (displaceability in the hole) than at a higher application temperature, so that the pin at a lower application temperature allows faster hole erosion than at a higher temperature.
  • the solid is preferably in the grain with the help of a moderator, in particular one insoluble moderator, and a volatile liquid introduced into the opening.
  • a mixing apparatus e.g. B. a drum instead.
  • the mixture of moderator liquid and solid gradually by the powder mass pressure stuffed into the holes of the grain or the wet mixture works under Influence of the powder mass pressure into the holes. It can be said that fill the holes of the TLP relatively quickly with the dry solid.
  • it is important that there is a condensed at the entrance of the hole Section is formed from solid, which is the ignition pressure wave among the specific can also withstand the desired conditions. It has been shown that at finished grain the density of the solid in the holes from the outside towards the inside decreases, the relatively loose mass located under the compacted pin, for the control of the hole erosion is of no significant importance.
  • the green grain, the solid and the moderator are mixed in with a liquid a mixing apparatus at a temperature in the range of 0 ° C to 90 ° C during one Treatment duration between 10 minutes and 3 hours and with a rotation speed the mixing apparatus processed between 2 and 30 revolutions per minute.
  • a moderator who is radical can be networked.
  • a radical generator is also used to crosslink the solid.
  • the solid and the moderator are in the mixing apparatus in the smallest possible Amount of z. B. 0.001% by weight to 4% by weight based on the weight of the untreated Grünkorns used. Typically, the solid and the moderator are in one quantity of significantly less than 1% by weight in the drum of the mixing apparatus.
  • the low-viscosity liquid is also in a similar amount in the mixing apparatus added: 0.1% by weight to 5% by weight, based on the weight of the untreated grain.
  • Low viscosity is a liquid in the present context if it is associated with the dissolved moderator can be easily transported at room temperature. It can be low molecular weight common solvents such as water, alcohol, toluene, cyclohexane etc. can be used.
  • a radical generator can e.g. B. in an amount of 0.1 mol% to 5 mol% based on the molar amount of the networkable moderator are used, the radical generator at Surface treatment temperature in the mixing apparatus a high disintegration stability having.
  • the disintegration time during the surface treatment is for half of the radical generator for example greater than 10 hours.
  • the radical generator should quickly break down into radicals.
  • the decay time for the Half of the radical generator should be less than 1 hour.
  • the propellant powder must be flushed with inert gas or vacuum / flushed can be freed from atmospheric oxygen with inert gas at room temperature after it has been mixed with the networkable moderator and has been treated with an initiator.
  • the moderator is typically networked under inert gas at normal pressure a temperature of less than 90 ° C and for a period of less than that six-fold decay half-life of the radical generator was carried out at this temperature.
  • uncrosslinked moderators are polyvinyl alcohol, poly ( ⁇ -methylstyrene) Poly (vinyl alcohol-co-vinyl acetate), poly (vinyl alcohol-co-ethylene), Polybutadiene diol, polybutadiene diol dimethacrylate or polybutadiene diol diacrylate or longer chain Hydrocarbons such as waxes. Because these moderators in the TLP matrix don't are soluble, they remain in the cone and on the TLP surface. A diffusion into the TLP grain or away from the TLP interface does not take place.
  • the liquid is water, hexane, cyclohexane, toluene or a mixture of water / ethanol, Water / methanol, water / acetone, ethanol / cyclohexane or toluene / hexane used.
  • hexanediol diacrylate Dipropylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, Trimethylolpropane triacrylate, triethylene glycol diacrylate, propoxylated glycerol triacrylate, Pentaerythritol tetraacrylate, ethoxylated bisphenol A diacrylate, propoxylated Neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, polyethylene glycol diacrylate, Polybutadiene diol diacrylate, polybutadiene diol dimethacrylate, Polyethylene glycol dimethacrylate, polypropylene oxide diacrylate.
  • the liquid can be evaporated while rotating from the open mixer be removed.
  • the finished propellant powder is then during stored for several days at an elevated temperature (e.g. 3 days at 60 ° C) to remove residual solvent and remove other volatile components.
  • the perforated TLP can be of any recipe and dimension. So they can For example, be made from the following energy sources:
  • the perforated TLP can, if appropriate, be used for additives known in powder production Stabilization, pipe protection, softening and flare control included.
  • Known Additives to increase stability which are suitably used such as Akardit II (CAS No. 724-18-5), Centralit I (CAS No. 90-93-7), Centralit II (CAS No. 611-92-7), 2-Nitrodiphenylamine (CAS No. 836-30-6) and Diphenylamine (CAS No. 122-39-4), for Tube protection, e.g. talc (CAS No. 14807-96-6), titanium dioxide (CAS No. 13463-67-7), Calcium carbonate (CAS No. 1317-65-3) or magnesium silicate (CAS No.
  • the green powder can also contain other known additives to improve the ignition behavior and included to modulate the combustion behavior. All the additives mentioned can be added to the powder dough during green grain production, i.e. they are therefore evenly distributed in the grain matrix. The total amount of these additives in the Green grain is preferably between 0-20% by weight, based on the nitrocellulose content between 0.1-5% by weight. However, it is also possible to use the additives according to the invention To bring in surface treatment.
  • the perforated green grains in a polishing drum with a solid, a cone-stabilizing moderator and a low-viscosity liquid speak at a certain temperature for a certain time at a certain time speak Rotational speed mixed.
  • the individual surface treatment materials must be compatible with the TLP green grain.
  • the compatibility must be determined from case to case using suitable measurement methods. So z. B. intensive mixtures of green grain and surface treatment materials at 80 ° C in the heat flow calorimeter (WFK) for extensive heat development examined or the surface treatment material is in excess Quantities applied to the green grain or diffused into the green grain. These samples are subjected to the 90 ° C weight loss test or examined in the WFK. Another Test to determine the compatibility is the determination of the deflagration temperature such surface treatment materials / green grain mixtures.
  • WFK heat flow calorimeter
  • the solid used can be a pure substance or a mixture of substances act from different solids. It is important that the average grain size of the Solid or the solid mixture is in a favorable range if the solid or the solid mixture is not soluble in the low-viscosity liquid.
  • the solid or the solid mixture should be easily in the hole with the help of the mixing apparatus be insertable. Furthermore, it should compress well so that the pin is sufficient Has firmness. For example, the grain size of the solid should not be larger than 1/10 of the Hole diameter.
  • grain sizes are in the range between 0.01 microns and 200 microns, preferably in Range 0.1 to 50 microns. (In the experimental examples described below, the Grain size in the range of 0.5 to 45 microns.)
  • the liquid and the solid as well the solid / liquid ratio should be chosen so that the solid particles do not agglomerate, but keep their full mobility. This is important for one efficient closing of the perforations at their outer ends.
  • the average grain size does not matter.
  • Solids or solid mixtures in the liquid used are preferred are not soluble.
  • any solid or mixture of solids can be used chemically stable within the application temperature range of the TLP and with the TLP formulation is compatible and therefore does not negatively affect the chemical life.
  • the solid can be used in the entire manufacturing, bombardment and storage temperature range do not melt and do not become too essential during the entire service life Sublimate portions of the TLP grain and / or diffuse into it.
  • Substances with a melting point above are preferred have of 90 ° C and are insoluble in the TLP recipe or at most only very have low solubility in it.
  • the solids or their mixtures are primarily inert substances.
  • the TLP must be made of inert solids or their mixtures the smallest possible amounts are used. Relate to the green grain between 0.001 and 4 percent inert solids or solid mixtures are used, preferably between 0.01 and 2 percent.
  • inert solids that can be used pure or as mixtures, are graphite, talc, titanium oxide, potassium cryolite, tungsten trioxide, molybdenum trioxide, Magnesium oxide, boron nitride, potassium sulfate, acardite, centralite, calcium carbonate, oxalamide, Ammonium carbamate, ammonium oxalate, etc. Polymers and Copolymers with or without functional groups, linear, branched or cross-linked.
  • Solid or liquid substances are used as moderators. In doing so, the firm Moderators in the low-viscosity liquid, which is used as a third component will solve. Liquid moderators or moderator solutions can in the low-viscosity Liquid is also present as an emulsifier.
  • moderators eg vapor pressure at 21 ° C of ⁇ 10 -2 bar.
  • the moderator can be used as a pure substance or as a mixture of substances.
  • the moderators used are generally inert substances. But it is quite possible that energetic "moderators" can be used: However, these must be insensitive to the mechanical stress during the surface treatment process, in later ammunition processing or ammunition transport and its use.
  • the amounts of moderators or moderator mixtures used are between 0.001 and 4%, preferably between 0.01 and 2%.
  • the moderator can be either soluble or insoluble in the TLP matrix. Is the moderator soluble, it is also called a desensitizer and can also be used accordingly this function known per se can be used.
  • the inventive Surface treatment can be designed so that during TLP storage no or only a slight diffusion-related change in the interior ballistic properties occur. If moderately diffusing moderators are used, either sufficient small quantities are used, or it must be ensured that the diffusion process before the ammunition is finished is practically complete.
  • Suitable classes of substances include ethers, esters, Urethanes, ureas and ketones. Examples are camphor, dibutyl phthalate, Diamyl phthalate, centralite, dipropyl adipate, di (2-ethylhexyl) adipate, diphenyl urethane, Methylphenyl urethane, hexanediol diacrylate, ethylene glycol dimethacrylate, etc.
  • Oligomeric, soluble moderators such as polyether and polyester are also suitable Molecular weights from 500 to 3000 daltons. Examples are poly (tetrahydrofuran), Polymethyl vinyl ether, poly (oxyethylene), polyethylene glycol, poly (butanediol) divinyl ether, polyester such as SANTICIZER 431, PARAPLEX G-54, or poly [di (ethylene glycol) adipate, polyethylene glycol, Polyethylene glycol acrylate, polyethylene glycol methacrylate, polyethylene glycol diacrylate, Polyethylene glycol dimethacrylate, polyethylene glycol dimethyl ether, poly (propylene glycol), Poly (propylene glycol) acrylate, poly (propylene glycol) diacrylate, poly (propylene glycol) ether, Polycaprolactone diol, polycaprolactone triol and those derived therefrom Co-oligomers. There are none for the acrylates / methacrylates Polymerization reactions carried out.
  • These compounds are either insoluble in the TLP matrix and thus remain on the TLP surface or they are soluble and therefore diffuse in the course of the invention Surface treatment in the top layer of the TLP.
  • a suitable thermal activatable radical starter (initiator) must be added to the networkable moderator become.
  • the initiator should be so soluble in the moderator that it is is distributed homogeneously in the moderator.
  • the treatment conditions and the initiator must be chosen so that the initiator during the surface treatment process in the polishing drum, if possible, cannot disintegrate into radicals.
  • initiator and polymerizable moderator either present as a layer on the TLP surface or diffused into the outermost TLP layer, so the atmospheric oxygen and sometimes the Indian Outermost TLP layer of oxygen removed by vacuum at room temperature and replaced by inert gas. This is necessary so that the radical reactions (Polymerization, crosslinking) without annoying side reactions and with high yield expire. Under inert gas, the temperature of the TLP is increased to such an extent that the initiator breaks down into radicals as quickly and completely as possible. These radicals then start the Polymerization or the networking of moderators.
  • Initiators which are practical at room temperature are preferably used as radical initiators not, but at temperatures around 60 ° C to 90 ° C very quickly in the corresponding Radicals decay. This guarantees a quick, gentle and complete implementation of polymerizable moderators.
  • suitable radical initiators are tert. peroxyneodecanoate, Di (4-tert.butylcyclohexyl) peroxydicarbonate, tert. Butyl peroxypivalate, Dilauroyl peroxide, bis (aza-isobutyronitrile) etc.
  • the amount of the polymerization initiator used depends on the amount of deployed, networkable moderator. Between 0.1 and 5 mol% of initiator are obtained used on 1 mole of moderator. Initiator amounts between 1 and 4 mole%.
  • diacrylates, triacrylates, Tetraacrylates, dimethacrylates, trimethacrylates, tetramethacrylates diacrylamides, Triacrylamides, dimethacrylamides, trimethacrylamides, divinyl esters, trivinyl esters, Divinyl ethers, trivinyl ethers, divinyl aromatics, trivinyl aromatics etc. are suitable.
  • low molecular weight, radically crosslinkable moderators are Hexanediol diacrylate, hexanediol dimethacrylate, ethylene glycol dimethacrylate, Tetraethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, Trimethylolpropane triacrylate, pentaerythritol tetraacrylate etc.
  • oligomeric, radically crosslinkable moderators are low molecular weight ones Polyethylene glycol diacrylate, low molecular weight polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated Neopentyl glycol diacrylate, propoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate Etc.
  • polymeric, radically crosslinkable moderators examples include Polybutadiene diol diacrylate, high molecular weight polyethylene glycol diacrylate, high molecular weight Polyethylene glycol dimethacrylate, high molecular polypropylene oxide diacrylate etc.
  • the moderators who are not very soluble or completely insoluble in the TLP are solid or liquid compounds that are soluble in the low-viscosity liquid or at least are finely emulsifiable.
  • the connections in question can be act inert or energetic substances. It must be assumed that the Moderator concentration on the TLP surface not by sublimation or diffusion can change. This can be done by using either high-melting, low-melting the volatility in the case of insoluble compounds which have polymerizable groups, after application to the TLP grain additionally by a polymerization reaction (as described above).
  • Apolar polymers and oligomers or strongly polar are suitable as insoluble moderators Polymers and oligomers with or without polymerizable groups.
  • Examples include totally or partially hydrolyzed polyvinyl acetate, poly (vinyl alcohol-coethylene), Polybutadiene, polybutadiene diol, polybutadiene diol diacrylate, polystyrene, Polyvinylpyrrolidone, poly (acrylonitrile-co-butadiene), poly ( ⁇ -methylstyrene), poly (vinyltoluene-co- ⁇ -methylstyrene), Etc.
  • the surface treatments according to the invention it is a solvent or solvent mixture
  • the solid or liquid cone-stabilizing moderator very well dissolve or can be finely emulsified, but the TLP grain cannot or only very little is able to swell.
  • Liquids with high or low polarity are well suited.
  • the boiling point of the liquid must be higher than the surface treatment temperature. Nevertheless, the low-viscosity liquid should have a sufficiently high volatility that evaporation at the treatment temperature can take place in a short time (between 5 and 60 minutes).
  • the liquid can also with the help of Pressure reduction or be removed using a warm gas stream.
  • the liquid can be pure Solvent or a mixed solvent can be used.
  • For surface treatment amounts of 0.1% to 5% liquid (based on the amount of TLP) used. Between 0.5% and 2% liquid is preferably used.
  • low-viscosity liquids examples include water and mixtures from water and methanol, mixtures from water and ethanol, mixtures from water and Propanol, mixtures of water and acetone, mixtures of water and tetrahydrofuran, as well as pentane, hexane, heptane, cyclohexane, toluene, methylene chloride and mixtures thereof.
  • Perforated TLP are treated with the substances mentioned above in a polishing drum.
  • the desired degree of filling is between 5 and 50%, preferably between 10 and 40%.
  • the TLP can be ungraphited or graphitized. This is done by turning first the solid or the solid mixture is applied and homogeneous to the whole Distributed TLP surface. If the TLP used is already sufficiently graphitized, it can if necessary, a further introduction of solid material can be dispensed with or it can another solid is added. Then a solution from the low-viscosity Liquid and the moderator or the moderator mixture added. in the If a crosslinking of polymerizable moderators is desired, this contains Solution also the polymerization initiator.
  • the powder must always be covered with an electrically conductive material at least one of the solid components should be either graphite dust or Be acetylene black.
  • the solid consists of inert (non-energetic) material, it is only in small amounts (based on the TLP). So in the polishing drum between 0.01% and 2% solids homogeneously distributed on the TLP. In the case of an admixture of energetic material can because of the better ignitability of this mixture Concentration of more than 2% can be used.
  • the added substances act on the TLP surface.
  • the exposure process lasts between 5 minutes and 4 hours, preferably between 15 minutes and 120 minutes.
  • the polishing drum must (depending on the steam pressure of the used Liquid) must be gas-tight.
  • This evaporation process must also be precisely controlled in time.
  • the time period can be between 5 minutes and 4 hours, preferably between Evaporated for 10 minutes and 120 minutes.
  • the evaporation can by other Measures are additionally supported or promoted. For example, an air or flow of inert gas over the moist TLP.
  • the treated TLP then becomes subjected to a sharp drying process. This leaves the last traces of solvents removed and the treatment layer stabilized. This is how the TLP is typically Leave at 60 ° C for about 3 days in a convection oven. This allows e.g. ethanol Remove completely ( ⁇ 0.01%).
  • a radically polymerizable moderator is used and one If the polymerization reaction is to be carried out, a corresponding one is also used Polymerization initiator added.
  • the surface treatment of the TLP is as possible carried out at a lower temperature and the low-viscosity liquid at the same temperature away. The surface treatment is preferably carried out at room temperature.
  • the TLP is then vacuumed of solvent residues and atmospheric oxygen freed and placed under inert gas.
  • the TLP can only be used with the inert gas purged to displace atmospheric oxygen.
  • an inert gas e.g. argon or nitrogen can be used. Only then is the TLP mass applied to the under inert gas required polymerization temperature, which is usually around 30 ° C to 60 ° C above the treatment temperature.
  • a polymerization initiator is used, which is thermally stable at room temperature, but very quickly in at 50 ° C to 80 ° C the corresponding radicals disintegrate.
  • the decay half-life of a polymerization initiator is the time in which half of the Initiator has broken down into radicals at a certain temperature. This decay half-life is, because of its central importance, in all commercially available thermal Initiators known. So that the polymerization reactions are as complete as possible the polymerization time at a certain temperature to four to six times the decay half-life of the initiator used Temperature set. Then the TLP is opened directly in the air or under the inert gas Cooled to room temperature. Because preferred for applying the polymerizable moderator low-boiling, apolar solvents are used, the TLP is after Evacuation and polymerization practically solvent-free.
  • the low-viscosity liquid and / or the moderator soluble in the TLP causes this (Desensitizer) that the pin is additionally solidified and anchored in the perforated channel.
  • the burn in the perforations of the TLP is therefore due to the treatment-related influence slows down to the shape function with increasing powder temperatures. This works the with increasing temperature, the burning speed of the TLP becomes faster. Ideally, the two effects compensate, so that the surface-treated TLP has a temperature-independent burning behavior.
  • This mechanism of action according to the invention thus differs completely from that other mechanisms described in the literature for achieving a reduced Temperature dependence.
  • this mechanism is not based on the (dangerous) Embrittlement of the TLP at low temperatures.
  • the surface treatment according to the invention is different also has a favorable effect on the flowability and bulk density of the TLP. That's how they are Bulk densities of the treated TLP are up to 10% higher than the bulk densities of the untreated TLP.
  • a TLP that is subjected to a surface treatment according to the invention is therefore suitable was, significant and inexpensive combat value increases in existing weapon systems to realize without impairing the full system compatibility.
  • This treated TLP can also be used in newly developed weapon systems become. It can z. B. improves the ignition and / or pipe erosion can be reduced.
  • the treated TLP is dried at 60 ° C for 3 days.
  • FIG. 1a-c shows a comparison of the test results of the combustion behavior of a propellant powder in the ballistic bomb.
  • the ratio is on the abscissa of the current pressure P to the maximum pressure Pmax and on the ordinate is the dynamic one Liveness (1 / bar sec) x100 applied.
  • Fig. 1a is the behavior of the untreated Grünkorns can be seen at application temperatures of -40 ° C, + 21 ° C and + 50 ° C.
  • Fig. 1b the pressure bomb tests are immediately after the powder production and in Fig. 1c recorded after 5 years of storage at 21 ° C.
  • the surface-treated (SCDB) TLP FM 2032n / 9 shows in the 150 ml pressure bomb (loading density 0.2, shelling at -40 ° C, + 21 ° C and + 50 ° C) the three powder temperatures very small liveliness differences. That means that Burning is practically independent of temperature.
  • TLP Part of the treated TLP is 5 in a closed vessel at room temperature Stored for years. A pressure bomb is shot again from this stored TLP (Fig. 1c). The TLP shows practically the same dynamic vivacity as 5 years previously, i.e. the burn-off is still temperature-independent.
  • the TLP treated in this way is dried at 60 ° C. for 3 days.
  • Powder grains in an extinguishing bomb examined at different temperatures: A rupture disc opened the bomb at approx. 700 bar and the burnt-in TLP grains were thrown into a water bath and extinguished. The recuperated, partially burned TLP were photographed.
  • 3a again shows the pressure bomb results of the untreated green grain FM2708n.
  • 3b and 3c show the test results of the two samples FM 2712n and FM 2758n. It is clearly evident that the temperature dependence of the TLP burnup could be greatly reduced.
  • a solution consisting of 100 is then sprayed while rotating the powder mass Grams of cyclohexane (1.25% by weight based on the TLP), 40 grams of propoxylated Glycerol triacrylate (0.5% by weight based on the TLP) and 2 grams of di (4-tert.butylcyclohexyl) peroxydicarbonate (5% by weight based on the triacrylate).
  • the mass is at room temperature for 60 minutes touched. Then the lid of the treatment device is removed and the solvent evaporated while rotating for 30 minutes.
  • the treated TLP is transferred to a vacuum cabinet and there at room temperature evacuated until a final pressure of about 1 mbar is reached. Then the vacuum cabinet filled with nitrogen and the heating switched on. Once the TLP reaches a temperature of 70 ° C, this temperature is left to act for about two hours. The TLP is then allowed to cool to room temperature.
  • 1 kg of the treated TLP is sealed in a gas-tight bag and attached to Stored at 71 ° C for 4 weeks. This corresponds to storage at room temperature of several decades (50 to 100 years). The rest of the TLP is stored at room temperature.
  • a green grain was made with the matrix 11.0x (19x0.20) mm, treated with a networkable moderator.
  • Ethylene glycol dimethacrylate (1.3% by weight or TLP) was used.
  • the residual ethylene glycol dimethacrylate content was reduced determined by GC / MS. It was found that> 95% of the dimethacrylate was converted.
  • the TLP was stored at 71 ° C for 4 weeks and then with FTIR microspectroscopy its concentration profile compared to normally stored TLP. In the Fig. 7 concentration profiles of the networked moderator show that even under drastic storage conditions no diffusion can be determined. That means again that this TLP is ballistically stable.
  • the treated TLP is dried at 60 ° C for three days.
  • Fig. 8a-c are the pressure bombs at different powder temperatures of the Grünkorns (Fig. 8a: untreated), the treated powder (Fig. 8b: after storage at 21 ° C for 4 weeks) and the accelerated aged, treated powder (Fig. 8c: 4 weeks at 63 ° C).
  • the pressure bomb clearly shows the reduction in temperature dependence of powder burn-off after the surface treatment according to the invention. This reduction remains unchanged when the treated TLP undergoes artificial aging is subjected. Because of its insolubility, polyvinyl alcohol cannot enter the TLP matrix diffuse. This treated TLP is also ballistically stable.
  • the cap is then removed and the aqueous ethanol is turned while rotating Evaporated for 15 minutes.
  • the treated TLP is dried at 60 ° C for three days.
  • Fig. 9a-d the pressure bombing at different powder temperatures of the Grünkorns (Fig. 9a: untreated), the treated powder (Fig. 9b: after storage at 21 ° C for 4 weeks) and the accelerated aged, treated powder (Fig. 9c: 4 weeks at 63 ° C).
  • the pressure bomb clearly shows the reduction in temperature dependence of powder burn-off after the surface treatment according to the invention. This reduction remains unchanged when the treated TLP undergoes artificial aging is subjected. This treated TLP is also ballistically stable.
  • 9d is a mixture of 70% by weight of green grain and 30% by weight of treated Grain shown. With such mixtures, the liveliness of the TLP burnup can still can also be controlled.
  • the mass at room temperature will be 100 minutes long stirred. Then the lid of the treatment device is removed and the solvent evaporated while rotating for 20 minutes.
  • the treated TLP is then dried at 60 ° C for 3 days.
  • Part of this surface-treated TLP is at 71 ° C for 4 weeks in one gas-tight bag artificially aged (Fig. 10b), during which the other part of the TLP is gas-tight is stored at room temperature (Fig. 10a).
  • the effect according to the invention is achieved without a desensitizer.
  • the cap is then removed and the solvent is turned while rotating Evaporated for 30 minutes.
  • the treated TLP is dried at 60 ° C for three days.
  • Fig. 11a green grain
  • Fig. 11b after the treatment according to the invention
  • the pressure bomb clearly shows the reduction in the temperature dependence of the powder burn after the surface treatment according to the invention.
  • the good service life is particularly noteworthy. Storage for long periods or at high temperatures is possible without the burn-off characteristics essential to influence.
  • the treatment process is simple, reproducible and relatively inexpensive.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Air Bags (AREA)
EP20020405191 2001-03-13 2002-03-12 Poudre propulsive insensible à la température Expired - Lifetime EP1241152B1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100420657C (zh) * 2006-10-12 2008-09-24 新泰市安泰化工有限责任公司 连续自动混药机、生产粉状硝铵炸药的方法及生产线
WO2008148365A1 (fr) * 2007-06-04 2008-12-11 Rheinmetall Waffe Munition Gmbh Munition encartouchée, en particulier munition d'exercice
DE102011118547A1 (de) 2011-11-16 2013-05-16 Diehl Bgt Defence Gmbh & Co. Kg Verfahren zur Vorhersage des Abbrandverhaltens eines Treibladungspulvers
US10125057B2 (en) 2011-06-21 2018-11-13 Nitrochemie Aschau Gmbh Use of a solid for the production of a propellant powder
EP3495338A1 (fr) 2017-12-08 2019-06-12 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Charge propulsive

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5556119B2 (ja) * 2008-10-31 2014-07-23 日油株式会社 コーティング発射薬

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Publication number Priority date Publication date Assignee Title
GB508914A (en) * 1938-07-27 1939-07-07 Hercules Powder Co Ltd Improvements in or relating to the preparation of smokeless powder
FR1205433A (fr) * 1957-04-18 1960-02-02 Rech S Chimiques S A Procédé de fabrication de poudre propulsive à faible coefficient de température
US3506505A (en) * 1967-12-01 1970-04-14 Herzog Johanna Nitrocellulose base propellant coated with graphite,plasticizer,and inorganic pigment
DE3008196A1 (de) * 1980-03-04 1981-09-17 Wilhelm Dipl.-Chem. Dr. 5400 Koblenz Oversohl Ein- oder mehrbasiges treibladungspulver und verfahren zu seiner herstellung
US4597994A (en) * 1983-07-13 1986-07-01 Aktiebolaget Bofors Method of producing progressively burning artillery propellant powder and agent adapted thereto
DE2520882C1 (de) * 1975-05-10 1986-07-17 Dynamit Nobel Ag, 5210 Troisdorf Ein- oder mehrbasige Pulverk¦rper für Treibladungen und Verfahren zu ihrer Herstellung
EP0290718A1 (fr) * 1987-05-09 1988-11-17 Rheinmetall GmbH Grain de poudre en vrac à perforation pour chargement propulsif à progressivité de combustion variable
EP1031548A1 (fr) * 1999-02-24 2000-08-30 Nitrochemie Aschau GmbH Procédé de production de poudres à simple, double ou triple base pour munition pour armes à canon

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB508914A (en) * 1938-07-27 1939-07-07 Hercules Powder Co Ltd Improvements in or relating to the preparation of smokeless powder
FR1205433A (fr) * 1957-04-18 1960-02-02 Rech S Chimiques S A Procédé de fabrication de poudre propulsive à faible coefficient de température
US3506505A (en) * 1967-12-01 1970-04-14 Herzog Johanna Nitrocellulose base propellant coated with graphite,plasticizer,and inorganic pigment
DE2520882C1 (de) * 1975-05-10 1986-07-17 Dynamit Nobel Ag, 5210 Troisdorf Ein- oder mehrbasige Pulverk¦rper für Treibladungen und Verfahren zu ihrer Herstellung
DE3008196A1 (de) * 1980-03-04 1981-09-17 Wilhelm Dipl.-Chem. Dr. 5400 Koblenz Oversohl Ein- oder mehrbasiges treibladungspulver und verfahren zu seiner herstellung
US4597994A (en) * 1983-07-13 1986-07-01 Aktiebolaget Bofors Method of producing progressively burning artillery propellant powder and agent adapted thereto
EP0290718A1 (fr) * 1987-05-09 1988-11-17 Rheinmetall GmbH Grain de poudre en vrac à perforation pour chargement propulsif à progressivité de combustion variable
EP1031548A1 (fr) * 1999-02-24 2000-08-30 Nitrochemie Aschau GmbH Procédé de production de poudres à simple, double ou triple base pour munition pour armes à canon

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100420657C (zh) * 2006-10-12 2008-09-24 新泰市安泰化工有限责任公司 连续自动混药机、生产粉状硝铵炸药的方法及生产线
WO2008148365A1 (fr) * 2007-06-04 2008-12-11 Rheinmetall Waffe Munition Gmbh Munition encartouchée, en particulier munition d'exercice
US8042472B2 (en) 2007-06-04 2011-10-25 Rheimentall Waffe Munition Gmbh Cartridged ammunition, particularly blank ammunition
US10125057B2 (en) 2011-06-21 2018-11-13 Nitrochemie Aschau Gmbh Use of a solid for the production of a propellant powder
DE102011118547A1 (de) 2011-11-16 2013-05-16 Diehl Bgt Defence Gmbh & Co. Kg Verfahren zur Vorhersage des Abbrandverhaltens eines Treibladungspulvers
DE102011118547B4 (de) * 2011-11-16 2013-06-27 Diehl Bgt Defence Gmbh & Co. Kg Verfahren zur Vorhersage des Abbrandverhaltens eines Treibladungspulvers
EP3495338A1 (fr) 2017-12-08 2019-06-12 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Charge propulsive
WO2019112437A1 (fr) 2017-12-08 2019-06-13 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Charge propulsive

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