Classifications

• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
  • C06B45/18—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
• • 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

Definitions

• the invention relates to a method for producing a functional high-energy Material with a layered grain containing an energy-rich plasticizer and a polymeric desensitizer.
• the invention further relates to such material.
• TLP Propellant powder
• the problem with deploying this required new high performance TLP is now to avoid unwanted side effects, i.e. on the required increased performance level still the full extended system compatibility regarding pipe (erosion, corrosion), weapon (peak gas pressures, cadence) and environment (avoidance to ensure environmentally problematic recipe components). That too should ballistic stability, i.e. the length of time within which the propellant powder filled ammunition can be fired safely and in accordance with requirements conventional propellant powders cannot be reduced.
• it is desirable that the required high-performance TLPs can be manufactured cost-effectively, i.e. starting from easily accessible, inexpensive starting materials and in particular no complex processing (such as rolling processes with multi-base TLP) need.
• the powders have a high kinetic Muzzle energy and a high thermal efficiency.
• the layered structure of the outer skin and the inner zones of the new types Powder has a burning behavior that is largely independent of the temperature of the powder body. This means that within a wide temperature range similarly high muzzle velocities and peak gas pressures result. This has to Consequence that regardless of the ambient temperature at which the ammunition fired a similarly high muzzle energy is available, i.e. the propellant powder behaves largely independent of temperature.
• the functional materials have very high bulk densities.
• the bulk density is a measure of which weight of propellant powder can be accommodated in a certain volume unit and is typically given in the unit g TLP / l. This positive property is of great importance because the shell volume of a given ammunition component is predetermined. The more amount of powder that can be accommodated in this given sleeve volume, the higher the potential that can be converted into kinetic energy. For example, with comparable peak gas pressure, a muzzle energy increased by up to 12% compared to conventional single-base TLP can be achieved.
• the object of the invention is to provide a method of the type mentioned at the outset, which allows the precise adjustment of the layer structure.
• the solution is defined by the features of claim 1.
• the plasticizer and / or the desensitizer in the form of an aqueous emulsion in the absorbent (unimpregnated) grain, i.e. diffused into the so-called green powder.
• the invention is based on the surprising finding that the impregnation
• the functional materials are also produced in an aqueous emulsion can, which also TLP with the desired layer-like structure result.
• the present invention therefore involves the process of impregnating an untreated single-base green powder in aqueous emulsion, as well as the subsequent completion to provide the functional, layered TLP.
• the invention thus differs significantly from the known methods in which Impregnations, by means of which the layer-like distribution of the explosive oil and the Have the desensitizers set specifically, typically in so-called polishing drums be performed.
• highly sensitive explosive oils such as nitroglycerin due to acute safety risks would arise and the production of larger quantities of functional high-energy Materials would complicate, if not make impossible avoided in the method according to the invention.
• the impregnation process can be carried out in a 2-step process or in a 1-step process be performed.
• the green grain is first in one aqueous emulsion treated with the explosive oil. After the exposure is finished the excess emulsion is pumped out.
• the liquid proportions in the reactor can by a Strainer to be drained. Then the powder mass (remaining in the reactor) is combined in one Another process step of an aqueous emulsion containing the polymeric desensitizer exposed. This procedure allows good control of the process parameters.
• the green grain is first of all with a treated aqueous emulsion of the explosive oil. After the exposure time, the remaining emulsion is not separated from the powder, but with the addition of the polymer Phlegmatizers continue to be used. By varying the addition times of the explosive oil or the polymeric desensitizer and the time, the concentration profiles be changed in a targeted manner.
• the 1-step process includes fewer process steps and is therefore more economical.
• auxiliaries stabilizers and / or wetting agents
• auxiliaries suppress foam formation, stabilize the emulsion or can specifically influence the penetration behavior of the active components.
• a large number of energetic plasticizers are known in powder technology. These include, in particular, low-molecular aliphatic nitric acid esters, nitro compounds, nitramines and azides.
• a class of substances which is particularly suitable for this purpose are the so-called 2-nitroxyethyl-nitramaines (alkyl-NENA) with the general structural formula I, where R 1 is an aliphatic radical.
• alkyl-NENA 2-nitroxyethyl-nitramaines
• Another particularly suitable class of substances for this are the so-called dinitro-diazaalkanes of the general formula II, where R 2 and R 3 are aliphatic radicals.
• the present invention also relates to novel functional materials which additionally contain a crystalline energy carrier in the basic matrix made of nitrocellulose.
• crystalline energy sources are known per se. These are, for example, so-called crystalline nitramines of the general formula III.
• the radical R 4 forms part of a ring system and can preferably contain further units of the structure (-CH 2 -N-NO 2 ).
• Particularly preferred compounds of structure III are hexogen IV, octogen V and CL-20 VI.
• the upper limit of the crystalline energy content is such that the maintain mechanical strength of the resulting powder grain even at low temperature remains. In order to ballistically recognize the expected positive effect, the amount should not be less than about 5%.
• These compounds of general structure III or mixtures of these therefore, in amounts between 5-80%, preferably 10-50% of the total powder mass, mixed with the nitrocellulose matrix and are homogeneously distributed in the finished grain.
• the powders pretreated in this way (which functionally correspond to the green powder) then through an impregnation process which corresponds to that described above results in layered grain structure and is also part of the present invention, treated with an energetic plasticizer and a desensitizer.
• the advantage of these layered functional materials is that they are opposite the functional materials that do not contain any crystalline energy in the grain matrix included, have an increased energy content, which thanks to the special Layer structure optimally converted into kinetic energy in a system-compatible manner can be.
• the impregnation process for the production of high-energy functional materials is described below.
• the impregnation process goes from untreated Green powder of any shape, which essentially consists of nitrocellulose with an N content between 11-13.5%.
• the green powder used can optionally be used in powder technology well-known additives for stabilization, pipe protection, softening and flare control contain.
• Known additives which are suitably used are sodium bicarbonate (CAS- #: 144-55-8), calcium carbonate to increase stability (CAS- #: 471-34-1), magnesium oxide (CAS- #: 1309-48-4), Akardit II (CAS- #: 724-18-5), Centralit I (CAS- #: 90-93-7), Centralit II (CAS- #: 611-92-7), 2-nitrodiphenylamine (CAS- #: 836-30-6) and diphenylamine (CAS- #: 122-39-4), for softening about diethyl phthalate (CAS- #: 84-66-2), camphor (CAS- #: 76-22-2), dibutyl phthalate (CAS- #: 84-74-2), Di-n-propyl adipate (CAS- #: 106-19-4) or methylphenyl urethane (CAS- #: 261-79-6), for Tube protection, e.g.
• magnesium oxide (CAS- #: 1303-48-4), molybdenum trioxide (CAS- #: 1313-27-5), Magnesium silicate (CAS- #: 14807-96-6), calcium carbonate (CAS- #: 471-34-1) or Titanium dioxide (CAS- #: 13463-67-7), and for fire suppression about sodium oxalate (CAS- #: 62-76-0), potassium bitarate (CAS- #: 868-14-4), sodium hydrogen carbonate (CAS- #: 144-55-8), Potassium hydrogen carbonate (CAS- #: 298-14-6), sodium oxalate (CAS- #: 62-76-0), potassium sulfate (CAS- #: 7778-80-5) or potassium nitrate (CAS- #: 7757-79-1).
• the green powder other known additives, for example to improve the ignition behavior and Modulation of the burning behavior, included. All of the additives mentioned are during added to the powder dough during green grain production, i.e. they are even in distributed the grain matrix. The total amount of these additives in the green grain is between 0-20% the nitrocellulose, preferably between 5-15%.
• Green powder is typically cylindrical single or multi-hole powder with a ratio of diameter / grain length between 0.5-2.0, preferably 0.9-1.5.
• the outside diameter of the green powder is in the range between 0.5-10 mm, preferably 0.5-5 mm.
• the hole diameter is between 0.03-0.7 mm.
• the green grain can known way by pressing a solvent-containing powder dough in an extruder or obtained by extrusion.
• the manufacturing method according to the invention can be one-stage or two-stage.
• the impregnation process should first be illustrated using the 2-step process:
• the above Green powder described is placed in a metallic reactor vessel, which with Lid inlet valve, bottom outlet valve, mechanical and static flow fittings and connections for vacuum and which is equipped with 1-5 times the amount Water (compared to the amount of powder to be treated) is loaded.
• the powder can first Pre-bathed with stirring for 4-24 hours at a temperature of 20-85 ° C become. Then a solution of the is for a period of 10-60 minutes Explosive oil (approx. 20% dissolved in a suitable solvent) was added, the proportion of the Explosive oil compared to the green grain used is in the range of 3-20%.
• the 1-step process is carried out analogously to the 2-step process described above with the only difference that after the exposure time of the explosive oil solution the liquid portions remain in the reactor and the desensitizing emulsion directly is added.
• the exposure times and the time the pressure drop can reduce the burn-off characteristics of the finished powder be influenced in a targeted manner.
• Suitable explosive oils can be nitroglycerin (CAS- #: 55-63-0) or diethylene glycol dinitrate (Dinitrodiglycol, CAS- #: 693-21-0) can be used. It is a multitude of connections possible, which can be used as suitable desensitizers. On the one hand the affinity with the nitrocellulose must be such that the desensitizer with the appropriate Diffuse solvent as transport medium (carrier) into the powder grain can. On the other hand, no further diffusion is allowed after the removal of the solvent occur, which would lead to a change in the distribution profile. As suitable have organic ether and ester compounds with a molecular weight between 100-100,000, preferably between 1000-10,000.
• a previously unknown novel class of functional energetic materials is obtained by replacing the explosive oils described above with less impact-sensitive (simply put: "insensitive") energetic plasticizers of the general structures I or II.
• these novel functional materials are distinguished by a particularly favorable ratio of Vo / Pmax.
• such functional materials have a favorable ratio of ⁇ Vo gTLP / ⁇ Pmax gTLP , ie the muzzle velocity per gram charge increases compared to the pressure more than with layer-like TLP based on explosive oils.
• these insensitive energetic plasticizers perform compared to conventional ones Blasting oils to lower the explosion heat by 150-200 J / g what a lowering of the flame temperature during the powder burn-up and thus an improvement the pipe life.
• R 1 C 1 -C 4 (methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl), R 2 / R 3 independently of one another C 1 -C 4 2 (methyl, ethyl).
• Another class of previously unknown functional energetic materials is obtained by adding a crystalline energy source to the green grain described above admits the general formula III.
• the crystalline energy sources can optionally Before incorporation into the powder dough, the size distribution is adjusted by grinding are or if necessary cleaned by recrystallization.
• the production The green grain is used to achieve a homogeneous distribution of the crystalline Energy sources in the matrix by means of known methods such as, for example, by extrusion with the help of static mixers or by processing in twin screw extruders.
• layer-like grain structure is used as propellant bulk powder, especially for medium and Small caliber applications, suitable.
• Example 1 Manufacturing process in aqueous emulsion
• the mixture is then heated to a temperature of 85 ° C and under constant Stir pre-bathed while maintaining the temperature for 15 hours. After that at 80 ° C a mixture containing 12.5 kg nitroglycerin and 0.25 kg 2-nitrodiphenylamine, dissolved in 60 liters of ethanol, added dropwise over a period of 30 minutes. You leave now for 2 1/4 hours with optimal backmix setting (powder bed completely in Treat) and then drip over a period of 15 minutes a suspension containing 1.97 kg of a non-solid, highly viscous at room temperature Average molecular weight polyester of 3000 (which is water soluble and as The desensitizer works in 30 kg of water. Then you leave while stirring Treat for a further 2 hours at a temperature of 80 ° C.
• the moist powder is now spread evenly on coarse-mesh metal sieves and with warm air flowing through at a temperature of 60 ° C for 24 hours dried.
• the TLP is finally polished by polishing approx. 0.3% graphite and, if necessary by treatment with special moderators in the known manner in the polishing drum completed.
• the completed TLP has an explosion heat of 3999 J / g, its bulk density is 1062 g / liter.
• a muzzle velocity of 1438 m / s can be achieved with a sub-caliber arrow projectile of mass 123 g at 21 ° C while observing the weapon-approved maximum gas pressure, which corresponds to a muzzle energy of 1271 J / g TLP .
• Example 2 Manufacturing process in aqueous emulsion
• Example 1 Analogously to Example 1, 200 kg of a 7-hole green powder with an outside diameter of 2.57 mm, 2.94 mm long and an average hole diameter of 0.16 mm from the solid proportions of 1.2% Akardit-ll, 0.2% calcium carbonate, 1.4% potassium sulfate and 97.2% nitrocellulose with a nitrogen content of 13.15%, with 14.4 kg nitroglycerin and Treated 3.3 kg of the same polyester as in Example 1. That after completion The propellant powder obtained as in Example 1 has a bulk density of 1063 g / l at an explosion heat of 3961 J / g.
• a muzzle velocity of 126 g and a charge mass of 44.5 g at 21 ° C can achieve a muzzle velocity of 1063 m / s at a peak gas pressure of 4146 bar (compliance with the weapon-permissible peak gas pressure), which is a kinetic muzzle energy of 1601 J / g TLP and a thermal efficiency of 0.404.
• the resulting propellant powder has a bulk density of 1070 g / l with a heat of explosion of 3799 J / g.
• a muzzle velocity of 908 m / s can be achieved with a bullet with a mass of 126 g and a load of 44.5 g at 21 ° C, while with a load of 42 g it can reach 853 m / s.
• the same ratio has a value of only 0.07.
• Example 4 TLP with grain matrix made of nitrocellulose + crystalline energy carrier
• the propellant charge powder resulting after completion, as in Example 1, has a bulk density of 1071
• TLP in addition to the manufacturing process itself, Known TLP also proposed new TLP in which the known explosive oils NGL and DEGN are replaced by reduced-sensitivity energetic plasticizers. These TLPs are less sensitive to vibrations. To optimize performance crystalline energy sources must be added to the grain matrix.
• the resulting layered TLPs show full system compatibility a higher level of performance than normal TLP and a balanced temperature behavior on.
• the TLP are cheaper to manufacture and compared to two-based TLP do not have the disadvantageous burning properties (pipe erosion) of nitramine-containing TLP on.

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• 2000
  • 2000-06-15 EP EP00810520A patent/EP1164116B1/fr not_active Expired - Lifetime
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