EP1528051A2 - Cartridge with a dopant allowing detection - Google Patents

Cartridge with a dopant allowing detection Download PDF

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Publication number
EP1528051A2
EP1528051A2 EP04102902A EP04102902A EP1528051A2 EP 1528051 A2 EP1528051 A2 EP 1528051A2 EP 04102902 A EP04102902 A EP 04102902A EP 04102902 A EP04102902 A EP 04102902A EP 1528051 A2 EP1528051 A2 EP 1528051A2
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EP
European Patent Office
Prior art keywords
powder
doping material
propellant
doping
propellant charge
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Granted
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EP04102902A
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German (de)
French (fr)
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EP1528051B1 (en
EP1528051A3 (en
Inventor
Dr. Norbert Buchholz
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Metallwerk Elisenhuette GmbH
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Metallwerk Elisenhuette GmbH
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Priority to PL04102902T priority Critical patent/PL1528051T3/en
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/008—Tagging additives
    • 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 present invention relates to propellant charge powder for Bullet ammunition, respectively, a cartridge for firearms as well Process for the production of propellant charge powder.
  • the Composition of a cartridge or the propellant charge powder is instrumental for the forensic reconstruction of the Shot events, for example, with regard to shot removal and determination of the shooter.
  • These allow next to the refined optical analysis of the Geunterspuren also a statement about the exact chemical composition of the smoke, the ejected in a minimal amount during the shot. Depending on Ammunition, these mixtures differ. Only the analysis The specific composition allows a precise assignment. This is especially crucial in cases where the murder weapon is not can be ensured.
  • the different ones Substance components of the smoke are in the respective ignition charge the ammunition available. Ammunition remains in the form of Waste traces provide evidence for the circle of offenders.
  • the scanning electron microscope (SEM) developed accordingly in forensics to the routine device. Because of its high, many thousand magnification and the very high depth of field It delivers meaningful images from the smallest traces to the most Submicrometer range.
  • EDX energy dispersive X - ray microanalysis
  • In a high vacuum is generates an electron beam and finely focused across a grid guided the object of investigation.
  • the interaction between Electron and object generates a series of signals such as. B. reflected electrons, secondary electrons, characteristic X-rays, visible light, infrared radiation, electrical Electricity, heat radiation.
  • the claimed propellant charge powder has dopant material on.
  • it is in the Propellant powder around nitrocellulose powder. It is for example in a cartridge used and used in fast burning and the resulting dynamic pressure to accelerate the Projectile.
  • the doping material causes firing an emission of particles having a composition which are largely absent in the environment.
  • copper and tin also come as a component in alloys often in technically oriented environments.
  • In order to These emissions of bullet ammunition so doped can be considered as be classified as one for bullet ammunition characteristic particulate particle emission is effected.
  • a alternative or additional embodiment of the invention occurs in X-ray fluorescence spectrum of the doping material of one of the three strongest intensity lines between 1 keV and 15keV significantly in Spectrum.
  • a further advantageous embodiment provides a copper-containing Dopant material before. This ensures that the Doping material in wet chemical analysis particularly light can be detected. Copper can with the Detecting reagents Chlorindanzone and Zincon with good detectable color change. A proof succeeds under the usual for smut residues Detection conditions, for example direct detection on foil and filter paper.
  • stabilizing elements are in Doping material provided. This is for example achieved that significantly fluorescent, but very reactive
  • elements are not bound to be harmful Reaction with the cartridge case to be able to. That's gallium when used as a dopant material due to its low Melting point difficult to handle. In addition, it works a lot strong alloying and tends to be harmful to the most Brass bullet ammunition existing shell.
  • gallium separates after the launch of the ammunition due to the low melting point not in particulate form but as swaths on the neighboring objects and is therefore bad in the scanning electron microscopy To establish investigation.
  • These disadvantages are caused by the stabilizing element avoided in the doping material.
  • copper may be provided as a stabilizing element be.
  • An alloy of gallium and copper may be the avoid the aforementioned disadvantages.
  • a mass ratio of 2: 1 of Copper to gallium is particularly beneficial
  • Another embodiment sees an element with the atomic number greater than or equal to 50 as the doping material. This can the workload and analysis times advantageously reduced become.
  • the proof of the smoke takes place over the X-ray microanalysis.
  • the finding of the particles happens however, with the automatic particle search in the Scanning electron microscope over the material contrast selective Backscatter detector (BSE detector), i. about the electron density.
  • BSE detector material contrast selective Backscatter detector
  • the ubiquitous Impurities such as iron oxides (rust) or mineral Components (silicon compounds) by appropriate Adjustment of the backscatter detector for electron-rich elements be eliminated in the particle search.
  • Tin is metallurgically easy to handle and furthermore non-toxic.
  • an existing tin Surface coating of the copper-gallium alloy by Triturate with tin at temperatures slightly above that Melting point can be achieved.
  • the doping material has a Polymer which is at least partially soluble in solvent is.
  • solvent which is preferably inexpensive and non-toxic as possible, is dissolved and after curing with the Propellant powder glued. A segregation in the technical Further processing of the propellant charge mixture can thereby in improved way to be avoided.
  • the doping material according to another variant of the Invention advantageously a polymer which in cured Shape is tough and brittle.
  • the polymer is in common with milled the doping material and thus can also easily t and mixed in precise amounts with the propellant charge powder become.
  • the propellant powder can be used in all forms of projectile ammunition find use under the aforementioned advantages.
  • cartridges of handguns and rifles are with provided the propellant powder according to the invention to here advantageous the requirements that are due to criminological Investigations show to be fulfilled.
  • the disadvantages that arise due to the use of lead-free or low-emission ammunition with regard to are revealed by the criminal proof propellant powder according to the invention or the Firearm cartridge picked up.
  • the doping material is a Gallium-copper-tin alloy.
  • the gallium component becomes achieved that with a firing with one with the material according to the invention doped cartridge not in the Environment naturally occurring, d, h, for the above Cartridge specific, particulate element combination emitted and that by the very characteristic x-ray radiation in the Fluorescence spectrum at 9.2429 keV, which is not by X-ray lines of other naturally occurring elements superimposed, the evidence by energy-dispersive X-ray Microanalysis (EDX) can be done easily.
  • EDX energy-dispersive X-ray Microanalysis
  • the copper component avoids the disadvantages that arise compared to the use of pure gallium. tin Due to its high electron density, it allows the selective Finding the specific particles in the automatic Tracing in the REM in a matrix of compounds easier Elements, such as silicon compounds, by appropriate setting of the material contrast selective Backscatter detector (BSE detector).
  • BSE detector material contrast selective Backscatter detector
  • the Propellant powder particles platelet-shaped and have a Diameter of 0.5mm and a height of 0.15mm. Due to the above requirements has become For example, a maximum grain size of 80 microns for the single alloy particles and a grain size of Doping powder as a conglomerate of several alloy particles from 1 20 to 125 microns proved advantageous, inter alia because it at the latter, the next higher level of commercial available sieve sizes.
  • the propellant charge powder is as possible large area but area covering, d, h, in a layer thickness in the covering the area with propellant powder just one Contamination of the substrate with doping material excludes, spread out and by means of a suitable Pulver atomizer dusted evenly with doping material.
  • the propellant charge powder with the Doping powder with a solvent e.g. Water wets with a solvent e.g. Water wets.
  • a solvent e.g. Water wets.
  • the solvent becomes similar to fine droplets atomized the air-brush method.
  • the propellant charge powder becomes dried at room temperature.

Abstract

A friction loading powder, for projected munitions, contains a doping material which, on firing, results in particle emission having a composition not excessively emitted into the environment and/or a composition in which the three intensity strength lines of the X-ray fluorescence spectrum of the doping material between 1 keV and 15 keV stand out. Independent claims are included for: (1) A firearm cartridge for hand and rifle fire weapons using the above powder; (2) A process for production of the above powder, by embedding the doping material in a polymer.

Description

Die vorliegende Erfindung betrifft Treibladungspulver für Geschossmunition, bzw, eine Patrone für Schusswaffen sowie ein Verfahren zur Herstellung von Treibladungspulver. Die Zusammensetzung einer Patrone bzw. des Treibladungspulvers ist maßgeblich für die kriminaltechnische Rekonstruktion des Schussgeschehens beispielsweise im Hinblick auf Schussentfernung und Feststellung des Schützens. Dazu dienen u,a, rasterelektonenmikrsoskopische und röntgenfluoereszenzspektroskopische Untersuchungen an den auffindbaren Schmauchrückständen. Diese erlauben neben der verfeinerten optischen Analyse der Geschossspuren auch eine Aussage über die genaue chemische Zusammensetzung des Schmauchs, der beim Schuss in minimaler Menge ausgeworfen wird. Je nach Munitionsart unterscheiden sich diese Gemische. Nur die Analyse der spezifischen Komposition erlaubt eine genaue Zuordnung. Dies ist vor allem in Fällen entscheidend, bei denen die Tatwaffe nicht sichergestellt werden kann. Die unterschiedlichen Stoffkomponenten des Schmauchs sind im jeweiligen Anzündsatz der Munition vorhanden. Munitionsreste in Form von Schmauchspuren liefern Indizien für den Täterkreis.The present invention relates to propellant charge powder for Bullet ammunition, respectively, a cartridge for firearms as well Process for the production of propellant charge powder. The Composition of a cartridge or the propellant charge powder is instrumental for the forensic reconstruction of the Shot events, for example, with regard to shot removal and determination of the shooter. Serve u, a, Raster electron microscopic and X-ray fluorescence spectroscopic Investigations on the detectable Schmauchrückständen. These allow next to the refined optical analysis of the Geschossspuren also a statement about the exact chemical composition of the smoke, the ejected in a minimal amount during the shot. Depending on Ammunition, these mixtures differ. Only the analysis The specific composition allows a precise assignment. This is especially crucial in cases where the murder weapon is not can be ensured. The different ones Substance components of the smoke are in the respective ignition charge the ammunition available. Ammunition remains in the form of Waste traces provide evidence for the circle of offenders.

Das Rasterelektronenmikroskop ( REM ) entwickelte sich demzufolge in der Kriminaltechnik zum Routinegerät. Wegen seiner hohen, vieltausendfachen Vergrößerung und der sehr hohen Tiefenschärfe liefert es aussagekräftige Abbildungen von kleinsten Spuren bis in den Submikrometer - Bereich. Durch die Verbindung des REM mit der energiedispersiven Röntgen - Mikroanalyse ( EDX ) ist es das geeignete Instrument, um die chemischen Bestandteile einer Spur bis in den Picogrammbereich zu bestimmen. Im Hochvakuum wird ein Elektronenstrahl erzeugt und fein fokussiert rasterförmig über das Untersuchungsobjekt geführt. Die Wechselwirkung zwischen Elektronen und Objekt erzeugt eine Reihe von Signalen wie z. B. reflektierte Elektronen, Sekundärelektronen, charakteristische Röntgenstrahlung, sichtbares Licht, Infrarotstrahlung, elektrischen Strom, Wärmestrahlung. Diese Signale werden mit geeigneten Detektoren aufgefangen und elektronisch zu Abbildungen und Spektren verarbeitet. Eine solche Abbildung zeigt die Morphologie der Oberfläche unter Ausnutzung verschiedener Bereiche des elektromagnetischen Spektrums, die Spektroskopie der charakteristischen Röntgenstrahlung liefert Informationen über die elementare Zusammensetzung der Probe. Es ist eine Bildauflösung von wenigen Nanometern erreichbar, die kleinste nachweisbare Masse eines chemischen Elements beträgt weniger als ein millionstel Mikrogramm.The scanning electron microscope (SEM) developed accordingly in forensics to the routine device. Because of its high, many thousand magnification and the very high depth of field It delivers meaningful images from the smallest traces to the most Submicrometer range. By connecting the REM with This is the energy dispersive X - ray microanalysis (EDX) appropriate instrument to the chemical constituents of a trace to determine the picogram area. In a high vacuum is generates an electron beam and finely focused across a grid guided the object of investigation. The interaction between Electron and object generates a series of signals such as. B. reflected electrons, secondary electrons, characteristic X-rays, visible light, infrared radiation, electrical Electricity, heat radiation. These signals are provided with appropriate Detectors collected and electronically to pictures and Spectra processed. Such a picture shows the morphology the surface taking advantage of different areas of the electromagnetic spectrum, the spectroscopy of characteristic X-ray provides information about the elementary composition of the sample. It is an image resolution reachable from a few nanometers, the smallest detectable Mass of a chemical element is less than one millionth microgram.

Bei bekannter bleihaltiger Munition entstehen beim Abschuss durch den Abbrand des Zündelementes oder gegebenenfalls durch das Abdampfen von Blei aus dem Geschossheck bleihaltige Schmauchspuren, die aufgrund des Bleigehalts leicht nachzuweisen sind. Bei schadstoffarmer bzw. bleifreier Munition ist der Nachweis nachteilig schwieriger bzw. nicht eindeutig möglich.With known leaded ammunition incurred by the launch the burnup of the ignition element or optionally by the Evaporation of lead from the bullet tail leaded Traces of smoke, due to the lead content easily be demonstrated. For low-emission or lead-free ammunition the evidence disadvantageous difficult or not clearly possible.

Es ist Aufgabe der vorliegenden Erfindung, Treibladungspulver bzw. eine Patrone sowie ein Verfahren zu schaffen, bei der die Nachweisbedingungen in Schmauchrückständen verbessert sind. It is an object of the present invention, propellant powder or to create a cartridge as well as a method in which the Detection conditions are improved in smut residues.

Diese Aufgabe wird durch eine gattungsgemäße Vorrichtung mit den Merkmalen des Anspruchs 1 bzw. 10 sowie durch ein Verfahren gemäß Anspruch 1 2 gelöst. Vorteilhafte Ausgestaltungen ergeben sich aus den Unteransprüchen.This object is achieved by a generic device the features of claim 1 or 10 and by a Process according to claim 1 2 solved. Advantageous embodiments emerge from the dependent claims.

Das anspruchsgemäße Treibladungspulver weist Dotierungsmaterial auf. Beispielsweise handelt es sich bei dem Treibladungspulver um Nitrozellulosepulver. Es wird beispielsweise in einer Patrone verwendet und dient bei schnellem Abbrennen und dem dadurch entstehenden Staudruck zur Beschleunigung des Geschosses. Das Dotierungsmaterial bewirkt bei Schussabgabe eine Emission von Teilchen, die eine Zusammensetzung aufweisen, die in der Umwelt weitgehend nicht vorkommen. Im Gegensatz hierzu kommen beispielsweise Kupfer und Zinn auch als Bestandteil in Legierungen häufig in technisch orientierter Umwelt vor. Damit können diese Emissionen der so dotierten Geschossmunition als spezifisch eingestuft werden, da eine für die Geschossmunition charakteristische partikuläre Teilchenemission bewirkt wird. In einer alternativen bzw. zusätzlichen Ausgestaltung der Erfindung tritt im Röntgenfluoreszenzspektrum des Dotierungsmaterials einer der drei intensitätsstärksten Linien zwischen 1 keV und 15keV signifikant im Spektrum hervor. Ein signifikantes Hervortreten liegt beispielsweise dann vor, wenn diese Linie nicht von Linien anderer in der Natur häufig vorkommender Elemente überlagert wird. Dadurch können die Schmauchspuren aufgrund der erfindungsgemäßen Zusammensetzung des Treibladungspulvers leicht nachgewiesen werden. Durch die oben genannten Eigenschaften verbessern diese einzeln oder gemeinsam die Nachweisbedingungen in Schmauchrückständen im Sinne der Aufgabe der Erfindung.The claimed propellant charge powder has dopant material on. For example, it is in the Propellant powder around nitrocellulose powder. It is for example in a cartridge used and used in fast burning and the resulting dynamic pressure to accelerate the Projectile. The doping material causes firing an emission of particles having a composition which are largely absent in the environment. In contrast For example, copper and tin also come as a component in alloys often in technically oriented environments. In order to These emissions of bullet ammunition so doped can be considered as be classified as one for bullet ammunition characteristic particulate particle emission is effected. In a alternative or additional embodiment of the invention occurs in X-ray fluorescence spectrum of the doping material of one of the three strongest intensity lines between 1 keV and 15keV significantly in Spectrum. A significant emergence is for example then before, if this line is not from lines of others in nature frequently occurring elements is superimposed. Thereby can the traces of smoke due to the invention Composition of the propellant charge powder easily detected become. Improve by the above properties these individually or together the detection conditions in Smudge residues in the sense of the object of the invention.

In einer vorteilhaften Ausgestaltung der Erfindung ist das Dotierungsmaterial galliumhaltig. Dadurch wird erreicht, dass einerseits bei einer Schussabgabe mit einer mit dem erfindungsgemäßen Material dotierten Patrone eine nicht in der Umwelt naturgemäß vorkommende, d,h, für die oben genannte Patrone spezifische, partikuläre Elementenkombination emittiert wird. Andererseits kann durch die sehr charakteristische Röntgenstrahlung im Fluoreszenzspektrum bei 9,2429 keV, welches nicht durch Röntgenlinien anderer, in der Natur vorkommender Elemente überlagert wird, der Nachweis durch energiedispersive Röntgen - Mikroanalyse (EDX) leicht erfolgen. Ferner ist Gallium ein für die Natur und den Menschen unschädliches Element, so dass sich der Schadstoffgehalt der Treibladung durch das Dotierungsmaterial nicht erhöht, sofern er überhaupt noch vorhanden ist.In an advantageous embodiment of the invention that is Doping material containing gallium. This ensures that on the one hand in a firing with a with the material according to the invention doped cartridge not in the Environment naturally occurring, d, h, for the above Cartridge specific, particulate element combination emitted becomes. On the other hand, by the very characteristic X-radiation in the fluorescence spectrum at 9.2429 keV, which not by x-rays of other, naturally occurring ones Elements are superimposed, the proof by energy-dispersive X - ray microanalysis (EDX) done easily. Furthermore, gallium is a for nature and man harmless element, so that the pollutant content of the propellant charge through the Doping material not increased, if he still has is available.

Eine weitere vorteilhafte Ausgestaltung sieht ein kupferhaltiges Dotierungsmaterial vor. Dadurch wird erreicht, dass das Dotierungsmaterial in nasschemischer Analyse besonders leicht nachgewiesen werden kann. Kupfer kann mit den Nachweisreagenzien Chlorindanzon und Zincon mit gut erkennbarem Farbumschlag nachgewiesen werden. Ein Nachweis gelingt so unter den für Schmauchrückstände üblichen Nachweisbedingungen, beispielsweise direkter Nachweis auf Folie und Filterpapier.A further advantageous embodiment provides a copper-containing Dopant material before. This ensures that the Doping material in wet chemical analysis particularly light can be detected. Copper can with the Detecting reagents Chlorindanzone and Zincon with good detectable color change. A proof succeeds under the usual for smut residues Detection conditions, for example direct detection on foil and filter paper.

Ferner sind in einer Ausführungsform stabilisierende Elemente im Dotierungsmaterial vorgesehen. Dadurch wird beispielsweise erreicht, dass signifikant fluoreszierende, aber sehr reaktive Elemente gebunden werden um so beispielsweise keine schädliche Reaktion mit der Patronenhülse eingehen zu können. So ist Gallium bei Verwendung als Dotierungsmaterial aufgrund seines niedrigen Schmelzpunktes schwer handhabbar. Darüber hinaus wirkt es sehr stark legierungsbildend und neigt dazu schädlich auf die meist aus Messing bestehende Hülse der Geschossmunition einzuwirken. Ferner scheidet sich Gallium nach dem Abschuss der Munition aufgrund des niedrigen Schmelzpunktes nicht in partikulärer Form sondern als Schwaden auf den benachbarten Objekten ab und ist daher schlecht in der rasterelektronenmikroskopischen Untersuchung festzustellen. Diese Nachteile werden durch das stabilisierende Element im Dotierungsmaterial vermieden. Beispielsweise kann Kupfer als stabilisierendes Element vorgesehen sein. Eine Legierung aus Gallium und Kupfer kann die vorgenannten Nachteile vermeiden. Ein Massenverhältnis 2:1 von Kupfer zu Gallium ist besonders vorteilhaft,Furthermore, in one embodiment stabilizing elements are in Doping material provided. This is for example achieved that significantly fluorescent, but very reactive For example, elements are not bound to be harmful Reaction with the cartridge case to be able to. That's gallium when used as a dopant material due to its low Melting point difficult to handle. In addition, it works a lot strong alloying and tends to be harmful to the most Brass bullet ammunition existing shell. Furthermore, gallium separates after the launch of the ammunition due to the low melting point not in particulate form but as swaths on the neighboring objects and is therefore bad in the scanning electron microscopy To establish investigation. These disadvantages are caused by the stabilizing element avoided in the doping material. For example, copper may be provided as a stabilizing element be. An alloy of gallium and copper may be the avoid the aforementioned disadvantages. A mass ratio of 2: 1 of Copper to gallium is particularly beneficial

Eine weitere Ausgestaltung sieht ein Element mit der Ordnungszahl größer oder gleich 50 als Dotierungsmaterial vor. Dadurch kann der Arbeitsaufwand und die Analysezeiten vorteilhaft reduziert werden. Der Nachweis des Schmauchs erfolgt über die Röntgenmikroanalyse. Das Auffinden der Partikel geschieht hingegen bei der automatischen Partikelsuche im Rasterelektronenmikroskop über den materialkontrastselektiven Rückstreudetektor (BSE-Detektor), d.h. über die Elektronendichte. Bei Elementen mit hoher Ordnungszahl ist diese vorteilhaft groß und somit wird die automatische Detektion im REM verbessert. Ferner können über den Materialkontrast die ubiquitären Verunreinigungen wie Eisenoxide (Rost) oder mineralische Bestandteile (Siliziumverbindungen) durch entsprechende Einstellung des Rückstreudetektors auf elektronenreiche Elemente bei der Partikelsuche eliminiert werden.Another embodiment sees an element with the atomic number greater than or equal to 50 as the doping material. This can the workload and analysis times advantageously reduced become. The proof of the smoke takes place over the X-ray microanalysis. The finding of the particles happens however, with the automatic particle search in the Scanning electron microscope over the material contrast selective Backscatter detector (BSE detector), i. about the electron density. For elements with a high atomic number, this is advantageously large and thus the automatic detection in the SEM is improved. Furthermore, over the material contrast the ubiquitous Impurities such as iron oxides (rust) or mineral Components (silicon compounds) by appropriate Adjustment of the backscatter detector for electron-rich elements be eliminated in the particle search.

Beispielsweise handelt es sich dabei um Zinn als Bestandteil des Dotierungsmaterials. Zinn ist metallurgisch leicht handhabbar und darüber hinaus ungiftig.For example, it is tin as part of the Dopant. Tin is metallurgically easy to handle and furthermore non-toxic.

Beispielweise kann eine aus Zinn bestehende Oberflächenbeschichtung der Kupfer-Gallium-Legierung durch Verreiben mit Zinn bei Temperaturen leicht oberhalb dessen Schmelzpunktes erreicht werden. Dabei liegt der Zinnanteil des metallischen Anteils des Dotierungsmaterials in der gleichen Größenordnung wie der Galliumanteil.For example, an existing tin Surface coating of the copper-gallium alloy by Triturate with tin at temperatures slightly above that Melting point can be achieved. The tin content of the metallic portion of the dopant in the same Magnitude as the gallium content.

Das Dotierungsmaterial weist in einer weiteren Ausführungsform ein Polymer auf, welches an Treibladungspulver, insbesondere an graphitiertem Pulver, haftet. Beispielsweise werden Gallium-Kupfer-Zinn-Legierungspartikel in Polyvinylakohol in einem Gewichtsverhältnis von 10:1 eingebettet. Durch die Haftung zwischen Treibladungspulver und Polymer kann eine Entmischung im Herstellungsprozess aufgrund des unterschiedlichen spezifischen Gewichtes von Partikeln des Dotierungsmaterials und des Treibladungspulvers verhindert werden. Dadurch wird erreicht, dass die Menge an Dotierungsmaterial in jeder Patrone gleich groß ist und somit die einzelne Geschoßmunition in Bezug auf die vorgenannten Untersuchungen nur unwesentlich differiert, d.h. es wird bei jedem Abschuss eine im Wesentlichen übereinstimmende Partikelemission erreicht, was beispielsweise wiederum Voraussetzung für die Reproduzierbarkeit bei einer Schussentfernungsbestimmung ist.The doping material has in a further embodiment Polymer, which of propellant powder, in particular to graphitized powder, adheres. For example, gallium-copper-tin alloy particles in polyvinyl alcohol in one Embedded weight ratio of 10: 1. By liability between propellant powder and polymer can segregation in the manufacturing process due to the different specific Weight of particles of the doping material and the Propellant powder can be prevented. This ensures that the amount of dopant in each cartridge is the same and thus the single projectile ammunition in relation to the aforementioned studies differs only insignificantly, i. it will be a substantially consistent one at each kill Particle emission achieved, which, for example, turn Prerequisite for the reproducibility in a Shot removal determination is.

In einer weiteren Ausführungsform weist das Dotierungsmaterial ein Polymer auf, welches in Lösungsmittel wenigstens teilweise löslich ist. Beispielsweise ist Polyvinylalkohol in Wasser löslich. Dadurch kann erreicht werden, dass das Polymer durch ein Lösungsmittel, welches bevorzugt kostengünstig und möglichst ungiftiges ist, angelöst wird und nach dem Aushärten mit dem Treibladungspulver verklebt. Eine Entmischung bei der technischen Weiterverarbeitung des Treibladungsgemisches kann dadurch in verbesserter Weise vermieden werden.In a further embodiment, the doping material has a Polymer which is at least partially soluble in solvent is. For example, polyvinyl alcohol is soluble in water. Thereby can be achieved that the polymer by a solvent, which is preferably inexpensive and non-toxic as possible, is dissolved and after curing with the Propellant powder glued. A segregation in the technical Further processing of the propellant charge mixture can thereby in improved way to be avoided.

Das Dotierungsmaterial weist gemäß einer weiteren Variante der Erfindung vorteilhaft ein Polymer auf, welches in ausgehärteter Form hart und spröde ist. Dadurch ist das Polymer gemeinsam mit dem Dotierungsmaterial vermahlbar und kann somit auch leicht t und in genauen Mengen mit dem Treibladungspulver vermischt werden.The doping material according to another variant of the Invention advantageously a polymer which in cured Shape is tough and brittle. As a result, the polymer is in common with milled the doping material and thus can also easily t and mixed in precise amounts with the propellant charge powder become.

Das Treibladungspulver kann in allen Formen von Geschossmunition unter den zuvor genannten Vorteilen Verwendung finden. Insbesondere sind Patronen von hand- und Gewehrfeuerwaffen mit dem erfindungsgemäßen Treibladungspulver versehen, um hier vorteilhaft die Anforderungen, die sich aufgrund kriminalistischer Untersuchungen ergeben, zu erfüllen. Vorteilhaft findet das Treibladungspulver Verwendung in Munition vom Kaliber 9mm. Dieses findet weite Verbreitung insbesondere in Armeen und Polizeidiensten. Den Nachteilen, die sich aufgrund der Verwendung von bleifreier bzw. schadstoffarmer Munition hinsichtlich des kriminalistischen Nachweises ergeben, werden durch das erfindungsgemäße Treibladungspulver bzw. die Schusswaffenpatrone aufgehoben.The propellant powder can be used in all forms of projectile ammunition find use under the aforementioned advantages. In particular, cartridges of handguns and rifles are with provided the propellant powder according to the invention to here advantageous the requirements that are due to criminological Investigations show to be fulfilled. This is advantageous Propellant powder Use in 9mm caliber ammunition. This finds widespread use especially in armies and Police services. The disadvantages that arise due to the use of lead-free or low-emission ammunition with regard to are revealed by the criminal proof propellant powder according to the invention or the Firearm cartridge picked up.

Im erfindungsgemäßen Verfahren zur Herstellung von Treibladungspulver wird in einem ersten Schritt Dotierungsmaterial in einem Polymer, beispielsweise Polyvinylalkohol, eingebettet. Beispielsweise handelt es sich bei dem Dotierungsmaterial um eine Gallium-Kupfer-Zinn-Legierung. Durch den Gallium-Bestandteil wird erreicht, dass bei einer Schussabgabe mit einer mit dem erfindungsgemäßen Material dotierten Patrone eine nicht in der Umwelt naturgemäß vorkommende, d,h, für die oben genannte Patrone spezifische, partikuläre Elementenkombination emittiert wird und dass durch die sehr charakteristische Röntgenstrahlung im Fluoreszenzspektrum bei 9,2429 keV, welches nicht durch Röntgenlinien anderer, in der Natur vorkommender Elemente überlagert wird, der Nachweis durch energiedispersive Röntgen - Mikroanalyse ( EDX ) leicht erfolgen kann. Kupfer kann mit den Nachweisreagenzien Chlorindanzon und Zincon mit gut erkennbarem Farbumschlag nachgewiesen werden. Darüber hinaus vermeidet der Kupferbestandteil die Nachteile, die sich gegenüber der Verwendung von reinem Gallium ergeben. Zinn ermöglicht aufgrund seiner hohen Elektronendichte das selektive Auffinden der spezifischen Partikel bei der automatischen Spurensuche im REM in einer Matrix von Verbindungen leichterer Elemente, beispielsweise Siliziumverbindungen, durch entsprechende Einstellung des materialkontrastselektiven Rückstreudetektor (BSE-Detektor). Nach vollständiger Durchtrocknung des Polymers, beispielsweise bei 100°C über 12h, wird in einem zweiten Schritt das Dotierungsmaterial samt Polymer zu Dotierungspulver, beispielsweise in einer Korngröße von ≤ 0,1 25 mm, vermahlen. Die Korngröße des Dotierungspulvers ergibt sich aus den Forderungen für die Korngröße der Dotierungslegierung. Sie sollte einerseits möglichst groß sein, um einer Entmischung der Legierung während des Verfeuerungsprozesses entgegenzuwirken und mit den damit größeren und massereicheren Teilchen eine größere Reichweite zu erzielen. Andererseits ist wegen der beabsichtigten und im Folgenden später beschriebenen Haftung des Dotierungspulvers am Treibladungspulver eine unter der Größe eines Treibladungspulverspartikels liegende Dimensionierung des Dotierungspulvers zu bevorzugen. Beispielsweise sind die Treibladungspulverpartikel plättchenförmig und weisen einen Durchmesser von 0,5 mm und eine Höhe von 0,15mm auf. Aufgrund der oben genannten Anforderungen hat sich beispielsweise eine maximale Korngröße von 80 µm für die einzelnen Legierungspartikel und eine Korngröße des Dotierungspulvers als Konglomerat mehrerer Legierungsteilchen von 1 20 bis 125 µm als vorteilhaft erwiesen, unter anderem weil es sich bei letzterer um die nächst höhere Stufe der handelsüblich erhältlichen Siebgrößen handelt.In the inventive method for the preparation of Propellant powder becomes doping material in a first step embedded in a polymer, for example polyvinyl alcohol. For example, the doping material is a Gallium-copper-tin alloy. By the gallium component becomes achieved that with a firing with one with the material according to the invention doped cartridge not in the Environment naturally occurring, d, h, for the above Cartridge specific, particulate element combination emitted and that by the very characteristic x-ray radiation in the Fluorescence spectrum at 9.2429 keV, which is not by X-ray lines of other naturally occurring elements superimposed, the evidence by energy-dispersive X-ray Microanalysis (EDX) can be done easily. Copper can with the Detecting reagents Chlorindanzone and Zincon with good detectable color change. About that In addition, the copper component avoids the disadvantages that arise compared to the use of pure gallium. tin Due to its high electron density, it allows the selective Finding the specific particles in the automatic Tracing in the REM in a matrix of compounds easier Elements, such as silicon compounds, by appropriate setting of the material contrast selective Backscatter detector (BSE detector). After complete Drying of the polymer, for example at 100 ° C for 12h, In a second step, the doping material together with polymer to doping powder, for example in a grain size of ≤ 0.1 25 mm, ground. The grain size of the doping powder results from the requirements for the grain size of the doping alloy. On the one hand, it should be as large as possible to avoid segregation Counteract alloy during the firing process and with the larger and more massive particles one to achieve greater range. On the other hand, because of the intended and subsequently described liability of the dopant powder on the propellant powder, one below the size dimension of the propellant charge powder particle Doping powder to be preferred. For example, the Propellant powder particles platelet-shaped and have a Diameter of 0.5mm and a height of 0.15mm. Due to the above requirements has become For example, a maximum grain size of 80 microns for the single alloy particles and a grain size of Doping powder as a conglomerate of several alloy particles from 1 20 to 125 microns proved advantageous, inter alia because it at the latter, the next higher level of commercial available sieve sizes.

In einem dritten Schritt wird das Treibladungspulver möglichst großflächig aber flächendeckend, d,h, in einer Schichtdicke in der die Bedeckung der Fläche mit Treibladungspulver gerade eine Kontamination des Untergrundes mit Dotierungsmaterial ausschließt, ausgebreitet und mittels eines geeigneten Pulverzerstäubers gleichmäßig mit Dotierungsmaterial bestäubt.In a third step, the propellant charge powder is as possible large area but area covering, d, h, in a layer thickness in the covering the area with propellant powder just one Contamination of the substrate with doping material excludes, spread out and by means of a suitable Pulver atomizer dusted evenly with doping material.

in einem vierten Schritt wird das Treibladungspulver mit dem Dotierungspulver mit einem Lösungsmittel z.B. Wasser benetzt. Beispielsweise wird das Lösungsmittel zu feinsten Tröpfchen ähnlich dem air-brush-Verfahren zerstäubt.in a fourth step, the propellant charge powder with the Doping powder with a solvent e.g. Water wets. For example, the solvent becomes similar to fine droplets atomized the air-brush method.

In einem fünften Schritt wird das Treibladungspulver beispielsweise bei Raumtemperatur getrocknet.For example, in a fifth step, the propellant charge powder becomes dried at room temperature.

Durch das Lösungsmittel wird der Polymeranteil des Dotierungspulvers angelöst und führt nach dem Trocknen zu einer intensiven Haftung des Dotierungsmaterials am Treibladungspulver, so dass bei der technischen Weiterverarbeitung eine Entmischung nicht mehr möglich ist. Dadurch wird erreicht, dass die Menge an Dotierungsmaterial in jeder Patrone gleich groß ist und somit die einzelne Geschoßmunition in Bezug auf die vorgenannten Untersuchungen nur unwesentlich differiert, d,h, es wird bei jedem Abschuss eine im Wesentlichen übereinstimmende Partikelemission erreicht, was beispielsweise wiederum Voraussetzung für die Reproduzierbarkeit bei einer Schussentfernungsbestimmung ist.Due to the solvent, the polymer content of Doping powder dissolved and leads after drying to a intensive adhesion of the doping material to the propellant powder, so that in the technical processing a segregation is no longer possible. This will achieve that amount Doping material in each cartridge is the same size and thus the single projectile ammunition in relation to the aforementioned Investigations differ only insignificantly, d, h, it is at each Launch a substantially consistent particulate emission achieved, which in turn is a prerequisite for the Reproducibility in a Schussentfernungsbestimmung is.

Claims (12)

Treibladungspulver für Geschossmunition, welches ein Dotierungsmaterial aufweist, wobei dieses bei Schussabgabe eine Emission von Teilchen bewirkt, die eine Zusammensetzung aufweisen, die in der Umwelt weitgehend nicht vorkommen und / oder einer der drei intensitätsstärksten Linien im Röntgenfluoreszenzspektrum zwischen 1keV und 15keV des Dotierungsmaterials signifikant im Spektrum hervortritt.Propellant powder for bullet ammunition, which a Having dopant material, which this firing a Emission of particles causes a composition which are largely absent in the environment and / or one of the three strongest intensity lines in the X - ray fluorescence spectrum between 1keV and 15keV of the Doping material emerges significantly in the spectrum. Treibladungspulver für Geschossmunition nach dem vorhergehenden Anspruch, wobei das Dotierungsmaterial galliumhaltig ist.Propellant charge for projectile ammunition after the preceding claim, wherein the doping material is gallium. Treibladungspulver für Geschossmunition nach einem der vorhergehenden Ansprüche, wobei das Dotierungsmaterial kupferhaltig ist.Propellant charge for projectile ammunition after one of preceding claims, wherein the doping material is copper-containing. Treibladungspulver für Geschossmunition nach einem der vorhergehenden Ansprüche, wobei das Dotierungsmaterial stabilisierende Elemente enthält.Propellant charge for projectile ammunition after one of preceding claims, wherein the doping material contains stabilizing elements. Treibladungspulver für Geschossmunition nach einem der vorhergehenden Ansprüche, wobei das Dotierungsmaterial ein Element mit der Ordnungszahl größer oder gleich 50 aufweist. Propellant charge for projectile ammunition after one of preceding claims, wherein the doping material is a Element with the atomic number greater than or equal to 50 has. Treibladungspulver für Geschossmunition nach einem der vorhergehenden Ansprüche, wobei das Dotierungsmaterial Zinn aufweist.Propellant charge for projectile ammunition after one of preceding claims, wherein the dopant material is tin having. Treibladungspulver für Geschossmunition nach einem der vorhergehenden Ansprüche, wobei das Dotierungsmaterial ein Polymer aufweist, welches an Treibladungspulver haftet.Propellant charge for projectile ammunition after one of preceding claims, wherein the doping material is a Having polymer which adheres to propellant charge powder. Treibladungspulver für Geschossmunition nach einem der vorhergehenden Ansprüche, wobei das Dotierungsmaterial ein Polymer aufweist, welches in Lösungsmittel wenigstens teilweise löslich ist.Propellant charge for projectile ammunition after one of preceding claims, wherein the doping material is a Polymer, which in solvent at least partially is soluble. Treibladungspulver für Geschossmunition nach einem der vorhergehenden Ansprüche, wobei das Dotierungsmaterial ein Polymer aufweist, welches in ausgehärteter Form hart und spröde ist.Propellant charge for projectile ammunition after one of preceding claims, wherein the doping material is a Polymer having hard and brittle in cured form is. Schusswaffenpatrone für Hand- und Gewehrfeuerwaffen mit Treibladungspulver gemäß einer der vorhergehenden Ansprüche.Firearms cartridge for hand and gun firearms with Propellant powder according to one of the preceding claims. Schusswaffenpatrone nach dem vorhergehenden Anspruch, wobei diese vom Kaliber 9mm ist.Firearm cartridge according to the preceding claim, this is 9mm caliber. Verfahren zur Herstellung von Treibladungspulver gemäß einer der Ansprüche 1 bis 9 wobei in einem ersten Schritt Dotierungsmaterial in einem Polymer eingebettet wird, in einem zweiten Schritt das Dotierungsmaterial samt Polymer zu Dotierungspulver vermahlen wird, in einem dritten Schritt flächig verteiltes Treibladungspulver mit dem Dotierungspulver besprüht wird, in einem vierten Schritt das Treibladungspulver mit dem Dotierungspulver mit einem Lösungsmittel benetzt wird und in einem fünften Schritt getrocknet wird.Process for the preparation of propellant powder according to of claims 1 to 9 wherein in a first step Doping material is embedded in a polymer, in one second step, the doping material together with polymer Doping powder is ground, in a third step surface sprayed dispersed propellant powder with the doping powder is, in a fourth step, the propellant powder with the Doping powder is wetted with a solvent and in dried a fifth step.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010135998A1 (en) * 2009-05-29 2010-12-02 Sellier & Bellot A.S. Marking of combustion products after firing

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008058177A1 (en) * 2008-11-20 2010-06-24 Eos Gmbh Electro Optical Systems Method for identifying laser sintering powders
RU2466975C1 (en) * 2011-03-23 2012-11-20 Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) Propellant charge
DE102017103780A1 (en) 2017-02-23 2018-08-23 Tailorlux Gmbh Method for identifying a material or material mixture
DE102020120318A1 (en) 2020-07-31 2022-02-03 Ruag Ammotec Ag Identifiable projectile and method of manufacture

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1441419A (en) * 1973-08-21 1976-06-30 Minnesota Mining & Mfg Method of tagging units of production of a substance
GB1487967A (en) * 1975-02-04 1977-10-05 Minnesota Mining & Mfg Tagging explosives with organic microparticles
DE3301357C1 (en) * 1983-01-18 1984-08-16 Plast-Labor S.A., 1630 Bulle Marking agents, processes for their preparation and their use for marking finely dispersed systems
US5677187A (en) * 1992-01-29 1997-10-14 Anderson, Ii; David K. Tagging chemical compositions
DE10046150A1 (en) * 1999-09-15 2001-03-22 Dynamit Nobel Ag Ammunition, comprises at least one substance e.g. cesium which, after firing, is simple to detect, ensuring a high recovery rate.
US6501825B2 (en) * 2001-01-19 2002-12-31 Keymaster Technologies, Inc. Methods for identification and verification

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897284A (en) * 1971-04-30 1975-07-29 Minnesota Mining & Mfg Tagging explosives with organic microparticles
US3835782A (en) * 1972-09-22 1974-09-17 Commercial Solvents Corp Product and method
DD258472A1 (en) * 1987-03-06 1988-07-20 Mdi METHOD FOR DETERMINING THE WELDING AGENT BY CONCENTRATION DETERMINATION OF GAS-FORMED ELASTIC COMPONENTS
DD259250A1 (en) * 1987-03-19 1988-08-17 Univ Berlin Humboldt COMPUTER-ASSESSED METHOD FOR STUDYING AND EVALUATING MALFUNCTIONS
US5565643A (en) * 1994-12-16 1996-10-15 Olin Corporation Composite decoppering additive for a propellant
EP0905218A3 (en) * 1997-09-26 1999-11-03 IRT-Innovative Recycling Technologie GmbH Process for making a granulate for generate ignition germs in fuel and propellants
SE523997C2 (en) * 2002-02-08 2004-06-15 Nexplo Bofors Ab decoppering

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1441419A (en) * 1973-08-21 1976-06-30 Minnesota Mining & Mfg Method of tagging units of production of a substance
GB1487967A (en) * 1975-02-04 1977-10-05 Minnesota Mining & Mfg Tagging explosives with organic microparticles
DE3301357C1 (en) * 1983-01-18 1984-08-16 Plast-Labor S.A., 1630 Bulle Marking agents, processes for their preparation and their use for marking finely dispersed systems
US5677187A (en) * 1992-01-29 1997-10-14 Anderson, Ii; David K. Tagging chemical compositions
DE10046150A1 (en) * 1999-09-15 2001-03-22 Dynamit Nobel Ag Ammunition, comprises at least one substance e.g. cesium which, after firing, is simple to detect, ensuring a high recovery rate.
US6501825B2 (en) * 2001-01-19 2002-12-31 Keymaster Technologies, Inc. Methods for identification and verification

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010135998A1 (en) * 2009-05-29 2010-12-02 Sellier & Bellot A.S. Marking of combustion products after firing

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PL1528051T3 (en) 2011-07-29
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