PROCESS FOR PREPARATION AND USE OF INORGANIC MARKERS FOR SECURITY IDENTIFICATION/MARKING ON EXPLOSIVES, FUSES AND AMMUNITION AFTER DETONATION AND ON FIREARMS AND METAL PROJECTILES, PRODUCTS OBTAINED AND PROCESS OF INSERTING MARKERS ON EXPLOSIVES, FUSES AND AMMUNITION AND ON FIREARMS AND METAL PROJECTILES

Abstract

Development of different inorganic materials, having the capacity to generate visible colors when excited in the infrared region, which can be used to determine the origin of explosives, fuses and ammunition, even after detonation, and in weapons and metal projectiles, thus serving as a safety marking tool thereof. The following were developed: LaNbO.sub.4 (called Mark1), BiVO.sub.4, Sr.sub.3V.sub.2O.sub.8 and YNbO.sub.4 (called Mark2), doped with different rare earth ions (erbium, ytterbium, holmium and thulium). The markers were physically inserted inside the explosives and in the gunpowder and by carburizing and forging in steel or metal alloy, with which the weapon or metal projectile is manufactured. The parameter used to demonstrate the presence of the markers in the products, after detonation or scraping of the weapon, was the verification of the color identity of the marker fluorescence, before and after, via laser in the infrared region.

Claims

1-13. (canceled)

14. A method for preparation and use of inorganic markers for security identification/marking in explosives, fuses and ammunition after detonation and on firearms and metal projectiles, products obtained and process of inserting markers on explosives, fuses and ammunition and on firearms and metal projectiles, comprising: materials with capacity to generate visible colors when excited in the infrared region, which are used to determine the origin of explosives, fuses and ammunition, even after detonation, as well as in weapons and metal projectiles, which are prepared using the solid-state reaction method, wherein the inorganic oxides are mixed according to the desired stoichiometric proportions for obtaining LaNbO.sub.4 (Mark1), BiVO.sub.4, Sr.sub.3V.sub.2O.sub.8 and YNbO.sub.4 (Mark2), doped, respectively, with rare earth ions erbium and ytterbium, holmium and ytterbium, holmium and ytterbium and thulium and ytterbium, which are mechanically inserted into explosives and ammunition and by carburizing and forging on weapons and metal projectiles.

15. The method according to claim 14, wherein in the solid-state reaction method, the inorganic oxides are mixed according to the desired stoichiometric proportions; the oxides are packed into polyacetal reactors containing 0.1 mm diameter zirconia spheres and then the grinding process using a Pulverisette® planetary mill 5 at a speed of 360 rpm for 4 hours depending on the marker; the materials obtained are taken to Jung® resistive furnaces for calcinating and thus the desired markers are obtained; and the marker LaNbO.sub.4 (Mark1) was calcined at a temperature of 1100° C. for 4 hours, while the other markers were obtained at the same time and temperature.

16. The method according to claim 14, wherein the reaction for the formation of the markers are as follows: 0.89 La.sub.7O.sub.3+Nb.sub.2O.sub.5+0.01Er.sub.2O.sub.3+0.10Yb.sub.2O.sub.3.fwdarw.2La.sub.0.89Er.sub.0.01Yb.sub.0.10NbO.sub.4 0.845 Y.sub.2O.sub.3+Nb.sub.2O.sub.5+0.005Tm.sub.2O.sub.3+0.15Yb.sub.2O.sub.3.fwdarw.2Y.sub.0.845Tm.sub.0.005Yb.sub.0.15NbO.sub.4 0.89 Bi.sub.2O.sub.3+V.sub.2O.sub.5+0.01Ho.sub.2O.sub.3+0.10Yb.sub.2O.sub.3.fwdarw.2Bi.sub.0.89Ho.sub.0.01Yb.sub.0.10VO.sub.4 2.88 SrCO.sub.3+V.sub.2O.sub.5+0.03Ho.sub.2O.sub.3+0.09Yb.sub.2O.sub.3.fwdarw.Sr.sub.2.88Ho.sub.0.03Yb.sub.0.09V.sub.2O.sub.8+2.88 CO.sub.2

17. The method according to claim 16, further comprising physical insertion of 1 part of marker to 15000 parts per mass of explosive emulsion.

18. The method according to claim 16, further comprising physical insertion of 1% to 14% of marker in relation to ammunition gunpowder of the projectile.

19. The method according to claim 18, wherein the fluorescence obtained from the residues is visible to the naked eye after detonation using a commercial Diode-Pumped Solid State Laser (DPSSL) with excitation wavelength of 980 nm (infrared region).

20. The method according to claim 19, wherein the marker LaNbO.sub.4 (Mark1) is the color green, YNbO.sub.4 (Mark2) is the color blue, BiVO.sub.4 is the color red, and Sr.sub.3V.sub.2O.sub.8 is the color green.

21. The method according to claim 16, wherein the use of the markers on the steel or steel alloys of weapons, the insertion being by carburizing and forging.

22. The method according to claim 21, wherein the carburizing uses a mixture of 10 to 20% of marker in a mixture specifically for carburizing, which consists of commercial powder for carburizing.

23. The method according to claim 21, wherein mixture of powders is carried out manually using a spatula; a mass of 5 g of the mixture was used, of which lg of marker+4 g of the mixture for carburizing; the metal parts, steel 4140, were subjected to a temperature of 900° C., thereafter placed individually on the marking mixture for a period of one minute and subsequently subjected to oil quenching.

24. The method according to claim 21, wherein the forging used the same mixture for carburizing, the metal parts, steel 1020, are subjected to a temperature of 1100° C. and thereafter were positioned in a hydraulic press with the mixture of carburizing and marker, consisting of 0.2 g of marker+0.8 of mixture for carburizing; the parts were pressed at a force of 15 tons for two minutes.

25. The method according to claim 21, wherein the marker LaNbO.sub.4 (Mark1) is the color green, YNbO.sub.4 (Mark2) is the color blue, BiVO4 is the color red, Sr.sub.3V.sub.2O.sub.8 is the color green.

26. The method according to claim 21, wherein the markers LaNbO.sub.4(Mark1), BiVO.sub.4, Sr.sub.3V.sub.2O.sub.8 and YNbO.sub.4 (Mark2) are doped with different rare earth ions, comprising erbium, ytterbium, holmium and thulium, in the range of 1 part of marker to 30000 parts at 20%, for better adjustment to the efficacy in use of the product, both explosives, and ammunition and weapons.

Description

DESCRIPTION OF THE DRAWINGS

[0033] The figures set out below are for improved explanation of the patent application in an illustrative, non-limitative manner:

[0034] FIG. 1: X-ray diffraction result. Diffraction peaks characteristic of one of the inorganic matrices used as marker. No additional diffraction peaks were identified, which demonstrates that there is no presence of any reagent or spurious phase. The crystallographic pattern used to identify the phase in Rietveld refinement was ICSD 81616. The small residual difference between the theoretical (calculated) and the experimental (observed) results can be perceived in detail, that is, it is shown that the material formed is actually LaNbO.sub.4 doped with erbium and ytterbium (Mark1). The X axis is the diffraction angle and the Y-axis is the diffracted intensity.

[0035] FIG. 2: Photographs of the technical details of the explosives used in the tests, with the emulsion (dynamite), showing the emulsion fuse system (2A)—fuse+circulated fuse—, fuse and emulsion with different markers (2B) and final system inside the enclosure (2C).

[0036] FIG. 3: Perspective view of the polyacetal/metal casing used in explosives tests.

[0037] FIG. 4: Photograph of a polyacetal casing, after detonation, being excited by a commercial infrared emitting laser. The green color observed in the explosion residues refers to the presence of the inorganic marker Mark1 (4A) in one part and the inorganic marker Mark2 in the other part (4B).

[0038] FIG. 5: Graph of the fluorescence spectrum upconversion in the range of 450 to 600 nm, which was obtained for one of the samples of polyethylene post-detonation in comparison with the pure Mark1 spectrum. These fluorescence measurements were taken using a bench top laser.

[0039] FIG. 6: Photograph of a metal casing, after detonation, used in gunpowder test (munition), being excited by a commercial infrared emitting laser. The circled one, in the green color observed in the explosion residues, refers to the presence of the inorganic marker Mark1.

[0040] FIG. 7: Graph of the fluorescence spectrum upconversion in the range of 450 to 600 nm, which was obtained for one of the samples of the metal casing after detonation in comparison with the pure Mark1 spectrum. These fluorescence measurements were taken using a bench top laser.

[0041] FIG. 8: Sectional photograph illustrating the structure of an ammunition, composed of projectile (a), case (b), gunpowder (c) and fuse (d).

[0042] FIG. 9: Photograph of the ammunition of a caliber 380 pistol used in the tests.

[0043] FIG. 10: Photograph of the cases and projectiles of the caliber 380 pistol ammunition used in the tests.

[0044] FIG. 11: Photograph illustrating the color green on the projectile, after firing the ammunition, the concentration of 1%, when excited with an infrared laser.

[0045] FIG. 12: Photograph illustrating the color green on the case, after firing the ammunition, the concentration of 1%, when excited with an infrared laser.

[0046] FIG. 13: Photograph illustrating the color green on the glove, after firing the ammunition, the concentration of 1%, when excited with an infrared laser.

[0047] FIG. 14: Photograph illustrating the color green on the cotton swab, after firing the ammunition, the concentration of 1%, when excited with an infrared laser.

[0048] FIG. 15: Graph of the fluorescence spectra upconversion of 450 to 650 nm which was obtained from the projectiles with concentrations of 1% and 14% of the marker in the firing with the caliber 38 revolver, compared to the pure Mark1.

[0049] FIG. 16: Graph of the fluorescence spectra upconversion of 450 to 650 nm which was obtained cases and projectiles collected after the firing relating to the concentrations of 1 and 14% respectively, using the pistol 380 in comparison with the marker pure Mark1.

[0050] FIG. 17: Photograph illustrating the color blue observed for the material YNbO.sub.4 doped with thulium and ytterbium, when latter is excited with an infrared laser.

[0051] FIG. 18: Photograph of a metal part marked with marker Mark1 after the carburizing process at 900° C. and which underwent oil quenching.

[0052] FIG. 19: Photograph of a metal part marked with marker Mark1 in the carburizing process and the metal part after thinning in different layers (0.05 mm//five hundredths of a millimeter, 0.1 mm//one tenth of a millimeter and 0.2 mm//two tenths of a millimeter).

[0053] FIG. 20: Photograph of a metal part marked with the marker Mark1 in the process of forging and the metal part after thinning.

[0054] FIG. 21: Photograph showing fluorescence-emitting images from the thinned out metal parts marked by carburizing and forging, top and base respectively.

[0055] FIG. 22: Graph of the fluorescence spectrum upconversion in the range of 450 to 700 nm, which was obtained from the metal parts marked by the carburizing methodology and from the metal parts marked by forging.

DETAILED DESCRIPTION OF THE INVENTION

[0056] The PROCESS FOR PREPARATION AND USE OF INORGANIC MARKERS FOR SECURITY IDENTIFICATION/MARKING ON EXPLOSIVES, FUSES AND AMMUNITION AFTER DETONATION AND ON FIREARMS AND METAL PROJECTILES, PRODUCTS OBTAINED AND PROCESS OF INSERTING MARKERS ON EXPLOSIVES, FUSES AND AMMUNITION AND ON FIREARMS AND METAL PROJECTILES, consists of the development of different inorganic materials, with the ability to generate visible colors when excited in the infrared region, which can be used to determine the origin of explosives, fuses and ammunition, even after detonation, as well as in weapons and metal projectiles, thus serving as a safety marking tool thereof. LaNbO.sub.4 (called Mark1), BiVO.sub.4, Sr.sub.3V.sub.2O.sub.8 and YNbO.sub.4 (called Mark2), doped with different rare earth ions (erbium, ytterbium, holmium and thulium) were developed. The markers were physically inserted within the explosives and in the gunpowder and by carburizing and forging in steel or metal alloy, with which the metallic gun or projectile is manufactured. The parameter used to demonstrate the presence of markers in the products, after detonation or scraping of the weapon, was the verification of the color identity of the marker fluorescence, before and after, via laser in the infrared region.

[0057] More particularly, the invention consists of the development and preparation of inorganic materials used as markers. The materials were prepared using the solid-state reaction method, wherein the inorganic oxides were mixed according to the desired stoichiometric proportions. The oxides were packed in polyacetal reactors containing 0.1 mm diameter zirconia spheres and then the grinding process using a Pulverisette® planetary mill 5 at a speed of 360 rpm for 4 hours was carried out. The reaction to the formation of markers is as follows: [0058] 0.89 La.sub.2O.sub.3+Nb.sub.2O.sub.5+0.01Er.sub.2O.sub.3+0.10Yb.sub.2O.sub.3.fwdarw.2La.sub.0.89Er.sub.0.01Yb.sub.0.10NbO.sub.40.845 Y.sub.2O.sub.3+Nb.sub.2O.sub.5+0.005Tm.sub.2O.sub.3+0.15Yb.sub.2O.sub.3.fwdarw.2Y.sub.0.845Tm.sub.0.005Yb.sub.0.15NbO.sub.4 [0059] 0.89 Bi.sub.2O.sub.3+V.sub.2O.sub.5+0.01Ho.sub.2O.sub.3+0.10Yb.sub.2O.sub.3.fwdarw.2Bi.sub.0.89Ho.sub.0.01Yb.sub.0.10VO.sub.42.88 SrCO.sub.3+V.sub.2O.sub.5+0.03Ho.sub.2O.sub.3+0.09Yb.sub.2O.sub.3.fwdarw.Sr.sub.2.88Ho.sub.0.03Yb.sub.0.09V.sub.2O.sub.8+2.88 CO.sub.2

[0060] The materials obtained were then taken to Jung resistive furnaces® so that they could be calcined and thus the desired markers were obtained. The Mark1 marker was calcined at the temperature of 1100° C. for 4 hours, while the other markers were obtained at the same time and temperature.

[0061] The synthesis of the marker was monitored by the x-ray diffraction technique and the presence of latter was confirmed by the refinement of the experimental diphratogram by the Rietveld method. The parameters obtained for Rietveld refinement, for the synthesis of the LaNbO.sub.4 (Mark1) doped material are given as examples, and the values in this case were R.sub.wp=18.30%, S=1.12% and R.sub.Bra gg=4.22%, where only a crystalline phase was used and the values obtained are within the limits considered adequate for a good refinement procedure. FIG. 1 presents the result of Rietveld's refinement to the synthesized material LaNbO.sub.4 (Mark1), where it is possible to note a very small difference between the experimental diffraction profiles and that calculated from Rietveld refinement, which confirms the argument that the refinement carried out is reliable. The same procedure was carried out for the other phases with results that also confirmed their achievement.

[0062] In order to verify the marking capability of the inorganic materials, more specifically Mark1 and another marker, Mark2, they were inserted directly into two different regions of the tested explosives. FIG. 2 displays photos with test details. The tested marker was inserted in emulsion (A), mass of 110 g, cartridged/dynamite banana, now in fuse (B), mass of 0.8g, of explosives used in the test, both with different markers. The purpose of placing the marker in these two regions was to verify the possibility of detecting its presence, regardless of the mass of the marker used, since the concentration of the marker was directly related to the mass of the fuse or emulsion. A total of 1.1 g of marker was inserted into the emulsion (dynamite banana), and this presented mass of 110 g. In the other test, 0.008 g, or 8 mg, of marker only in the fuse, which had mass of 0.8 g was added. In both tests, the marker was detected after detonation in the residues of the explosion. Therefore, for the second test, with the marker inserted in the fuse and detonation was performed in the fuse+emulsion set, it was observed that the marker was diluted 13850 times, approximately, in relation to the explosive material, that is, 1 part of marker for 13750. It was also effectively possible to note the detection of the marker for detonations with dopings in the scale of 1 (one) part of marker to 15000 parts per mass of emulsion. After the insertion of the marker in the explosives, these were placed in polyacetal and metal casings and thereafter were detonated following the safety standards of the Brazilian Army. FIG. 3 shows the constructive detail of the casings used in the tests. The debris resulting from the explosions of the casings were collected and analyzed in order to detect the presence of the marker in the residues, which were embedded in the casings.

[0063] For the marker tests in the ammunition, two types of tests were performed. In the first, individual marker mixture was performed with gunpowder. In one of the tests, 0.01 g (10 mg) of each of the inorganic markers were mechanically mixed with 10 g of gunpowder. In the other test, 0.001 (1 mg) of markers were mixed with 10 g of gunpowder. This mixture was also detonated inside polyacetal and metal casings (structures equal to those used in the tests of dynamite detonation). After detonation, the debris from the casings was collected and taken for analysis in the laboratory. For both tests the markers were detected after the detonations in the residues of the casings (metal and plastic). For the second test, the marker was inserted into the gunpowder used in ammunition for revolvers and pistols to be described below.

[0064] For the explosives tests, the residues of the explosions were initially tested with a commercial laser, which emits infrared radiation with a length of 980 nm. In FIG. 4, a photograph is presented wherein the residues from the detonation of explosives in the polyacetal casing, demonstrate the color green when they are excited by the laser. This color green is characteristic of the inorganic marker Mark1 (4A), which was inserted in explosive artifacts, and this result confirms that the marker used in the tests, even after the explosion, remains present and demonstrates active fluorescence. It also features the lilac color for the marker Mark2 (4B). It is worth mentioning, as already commented, that the marketer did not cause any kind of interference in the result of the detonation of explosives, that is, markers are inert materials in light of the components present in the explosives. The explosives maintained all their detonation power characteristics.

[0065] For a more detailed analysis of fluorescence obtained from the residues, a Diode-Pumped Solid State Laser (DPSSL) model LD-WL206 with excitation wavelength of 980 nm (infrared region) was used. All residues of the casings tested with the laser presented the color green perceivable to the naked eye, and for demonstration is presented in FIG. 5, a fluorescence spectrum obtained for the residues of a polyacetal casing in comparison with the spectrum of the pure marker. The spectra obtained revealed the presence of fluorescent bands in the range of 500 to 600 nm, and this region refers to the color green.

[0066] For gunpowder tests, residues collected after detonation were also preliminary analyzed with commercial infrared radiation emitting laser. FIG. 6 shows a photograph, wherein the residues of the gunpowder explosion in the casing metal, demonstrate the color green when excitation occurs using the commercial laser. This color green is characteristic of the inorganic marker Mark1, which was placed in gunpowder and this result demonstrates that the markers used in the tests, even after the explosion, are still present and present active fluorescence (F). As in the tests of explosives, the markers used did not cause any kind of interference in the result of the explosion, that is, the inorganic materials used are inert in light of the chemical components present in the gunpowder.

[0067] A more detailed analysis of fluorescence obtained from the residues, was carried out by employing the same bench laser used to analyze the residues of explosives. Again it was noted that all casings tested with this laser, presented the color green perceivable by the naked eye. To demonstrate the results is shown in FIG. 7, a fluorescence spectrum obtained in the residues of a metal casing compared with the pure marker spectrum, wherein it is noted the presence of fluorescent bands in the range of 500 to 600 nm, which is the region referring to color green.

[0068] The ammunition can be described as a combination between the projectile (bullet), the propellant (gunpowder) and the initiator (fuse) that are packaged in a capsule/case, forming a single unit, as presented in FIG. 8.

[0069] This marking was obtained through the mechanical mixture of the marker (Mark1) with the gunpowder and subsequent assembly of the bullet.

[0070] After firing the weapon gases and other residues jointly with the projectile are expelled. These residues are products of the burning of gunpowder, the initiator, cartridge metals and metal originating from the weapon. After the shooting, the metal case, the projectile and the glove used in the test by the shooter were examined. Using an infrared laser, it was possible to detect the presence of the marker Mark1 in all these objects as presented in FIGS. 11, 12, 13 and 14. To verify the marking capacity of the inorganic materials, tests were performed where the marker was introduced into the gunpowder used in the ammunition. Mark1 was mechanically mixed with the gunpowder and this was added in some revolver caliber 38 (RT 86) and pistol 380 (PT 58) projectiles. For the caliber 38, a common case of this caliber was used, and the amount of gunpowder that is used in a bullet of this caliber was weighed to calculate the amount of marker to be used in the tests. It was established that the mass of gunpowder used in a bullet of caliber 38 was 330 mg and from this value different masses of Mark1 were weighed, in order to obtain concentrations of 1%,4%,6%,8%,10%, 12% and 14% of this marker in relation to mass of gunpowder. The marker was added to the gunpowder so that the total mass of gunpowder+Mark1 was kept constant at 330 mg (original mass of a 38 projectile) and 290 mg for the pistol.

[0071] Once the marker was added, the ammunition was closed by inserting the projectile into the case by a cartridge refill press. The marking was done in duplicate, for each of the concentrations of markers, so two sets of similar bullets were prepared for revolver and pistol.

[0072] In this way, the ammunition used was 38 caliber for the revolver. Two shots were fired with each marker concentration using an RT86 TAURUS revolver totaling 14 shots and a pistol 380 (PT 58) with 14 shots in the same concentrations. For each shot, the shooter used a disposable glove for further detection analysis of the residues. In addition to the gloves, residues were also collected in the barrel and in the cylinder of the revolver and in the loader after the shots using a cotton swab.

[0073] FIG. 8 illustrates the bullets used in the tests numbered 1,2,3,4,5,6 and 7 corresponding to the increase in the marker concentration of 1%, 4%, 6%, 8%, 10%, 12%, 14%, for use in the pistol and revolver. FIG. 10, illustrates the cases after the shots, jointly with the projectiles collected after the shots, for the pistol.

[0074] For the caliber 38, a common case of this caliber was used, and the amount of gunpowder that is used in a bullet of this caliber was weighed to calculate the amount of marker to be used in the tests. The mass of gunpowder used in a caliber 38 bullet is 330 mg and from this value different masses of Mark1 were weighed in order to obtain concentrations of 1%, 4%, 6%, 8%, 10%, 12%, 14% of this marker in relation to gunpowder. The marker was added to the gunpowder such that the total mass of gunpowder+marker=330 mg (original mass of a caliber 38 projectile). For the pistol 380, the procedure was the same, and the only change occurred in the mass of gunpowder used in the projectiles, which is 290 mg. After adding the marker, the ammunition was closed by inserting the projectile into the case by means of a cartridge refill press. The marking was done in duplicate, for each of the concentrations of markers. Thus, two sets of projectiles similar for revolver and pistol were prepared.

[0075] Thus, two shots were made with each concentration of marker Mark1, using an RT86 TAURUS revolver and a pistol 380 (PT 58) with 14 shots in the same concentrations. For each shot, the shooter used a disposable glove for further detection analysis of the residues. In addition to the gloves residues were also collected in the barrel and cylinder of the revolver and in the pistol loader, after the shots, using a cotton swab.

[0076] FIG. 15 shows the graph with the spectra fluorescence of the cases of the bullets with 1% and 14% of the tests with revolver 38 that were obtained after the shots in comparison with the Mark1. As can be observed, the fluorescence obtained is quite similar to that of the original marker, which confirms the presence of Mark1 in the projectiles even after the shots. In all other cases, with intermediate concentrations, the presence of Mark1 was noted after the shots both using the caliber 38 revolver and using the pistol 380, showing that the marker used is stable, is present after the firing of firearm and that the marking of the ammunition tested effectively occurred.

[0077] For the analysis of fluorescence emitted by the residues of ammunition marked with marker Mark1, a solid state diode bench laser (DPSSL)—model LD-WL206—with excitation wavelength at 980 nm was used. FIGS. 11 to 14 show a marking in the color green for the projectile and case of the shots from the caliber 38 revolver the concentration of 1% (lowest concentration of marker used in the tests), as well as residues on the glove and on the cotton swab, that is, residues were found, verified with active fluorescence (F), in all objects that came into contact with gunpowder after the shooting.

[0078] FIG. 16 shows the graph with spectra fluorescence of the cases of projectiles with 1% and 14% of the tests with pistol 380, which were obtained after shots in comparison with Mark1. It is observed that fluorescence is very similar to that of the original marker, which confirms the presence of the Mark1 in the projectiles even after the shots. In all other cases with intermediate concentrations, the presence of Mark1 was also noted after the shots, both in the caliber 38 revolver and in the pistol 380, which demonstrates that the Mark1 is stable, as it was found after the firing of the firearm and the marking of the ammunition tested effectively occurred.

[0079] The results presented for both explosives and gunpowder tests were with the use of the LaNbO.sub.4 marker (Mark1), and all other markers also proved to be efficient as well as their marking capacity. Since these other markers present as differential, the fact of generating different colors to LaNbO.sub.4 (Mark1). As an example, the marker YNbO.sub.4 (Mark2) doped, shown in FIG. 17, which features the color blue.

[0080] In the case of the use of markers in steel or steel alloys of weapons and metal projectiles, to verify the marking capacity of inorganic materials two types of tests were performed for inclusion of markers in the parts: carburizing and forging.

[0081] In carburizing, a mixture of 10% to 20% in marker was used in a mixture specifically for carburizing, which consists of powder for carburizing. The mixtures of powders were carried out manually using a spatula. Therefore, a mixture mass of 5 g (1 g of the marker+4 g of the mixture for carburizing) was used. The container used to insert the metal parts and a mixture was an alumina crucible with a height of 55.0 mm and diameter of 45.0 mm. The metal parts were immersed throughout the carburizing mixture. The metal parts, in this feasibility form of the invention, steel 4140, with dimensions of 50.0 mm in height and 19.0 mm diameter were subjected to the temperature of 900° C., thereafter placed individually on the marking mixture for the period of one minute and subsequently subjected to oil quenching (FIG. 18). The test part was thinned with depths of 0.05 mm (50 μm); 0.1 mm (100 μm) and 0.2 mm (200 μm) to check how deep the fluorescent marker signal could be observed. FIG. 19 shows the test part after carburizing and the test part after thinning.

[0082] The second method used to mark the metal parts was forging. In this procedure the same mixture was used as for carburizing. In this form of feasibility of the invention, the metal parts, steel 1020, were subjected to temperature of 1100° C. and thereafter were positioned in a hydraulic press with the mixture of carburizing and marker, consisting of 0.2 g of marker+0.8 mixture for carburizing. The parts were pressed to a force of 15 tons for two minutes. FIG. 20 shows the test part after pressing and part after thinning of 0.05 mm (50 μm).

[0083] To analyze the fluorescence emitted by the metal parts marked with the marker LaNbO.sub.4 (Mark1) a bench top laser was used—Diode-Pumped Solid State Laser (DPSSL) model LD-WL206—with an excitation wavelength at 980 nm. The metal parts marked using the two methodologies, carburizing and forging, presented characteristic fluorescence to the LaNbO.sub.4 marker (Mark1) even after the thinning processes. For the part marked using carburizing methodology it was possible to observe the fluorescent signal referring to LaNbO.sub.4 (Mark1) with a maximum thinning of 0.05 mm (50 μm). FIG. 21 shows the flourescence-emitting images (F) from the thinned out metal parts, marked by carburizing and forging, top and base respectively. FIG. 22 shows the emission spectrum of the pure marker LaNbO.sub.4 (Mark1), from the metal parts marked by the carburizing methodology and from the metal parts marked by forging. It was possible to observe the similarity of the fluorescence spectrum of the pure LaNbO.sub.4 (Mark1) marker in comparison to the signals obtained in the tests of marking by carburizing and forging. The little variation is due to the fact of the variation of excitation power used.

[0084] Thus, the proportions of markers, such as the marker LaNbO.sub.4 (Mark1), BiVO.sub.4, Sr.sub.3V.sub.2O.sub.8 and YNbO.sub.4 (called Mark2), doped with different rare earth ions (erbium, ytterbium, holmium and thulium) occurs in the range of 1 part of marker for 30000 parts to 20% explosives, ammunition, fuses and in the carburizing or forging of the steel with which the weapons are manufactured, preferably in the ratio of 1 part to 15000, to better suit the effectiveness in the use of the product, both explosives and ammunition and weapons. Depending on the product and its application the proportion is changed within the range stipulated above.