US3772099A - Phosphor combination and method, particularly adapted for use with explosives, for providing a distinctive information label - Google Patents

Phosphor combination and method, particularly adapted for use with explosives, for providing a distinctive information label Download PDF

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US3772099A
US3772099A US00143772A US3772099DA US3772099A US 3772099 A US3772099 A US 3772099A US 00143772 A US00143772 A US 00143772A US 3772099D A US3772099D A US 3772099DA US 3772099 A US3772099 A US 3772099A
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explosive
phosphor
finely divided
indicia
combination
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F Ryan
R Miller
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CBS Corp
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Westinghouse Electric Corp
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    • 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
    • F42B5/025—Cartridges, i.e. cases with charge and missile characterised by the dimension of the case or the missile
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
    • C09K11/75—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth containing antimony
    • C09K11/76—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth containing antimony also containing phosphorus and halogen, e.g. halophosphates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7784—Chalcogenides
    • C09K11/7787—Oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
    • F21K2/00—Non-electric light sources using luminescence; Light sources using electrochemiluminescence
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/123—Tagged compositions for identifying purposes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S252/00—Compositions
    • Y10S252/965—Retrospective product identification, e.g. tags and tracers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/13—Tracers or tags

Definitions

  • ABSTRACT Phosphor-explosive material combination and method wherein a small amount of inorganic phosphor is mixed with explosive material to provide an indicia or label of information regarding the explosive, either before or after detonation of same.
  • the phosphor can readily be located with an ultraviolet lamp even after the explosive has been detonate-d, and by correlating the phosphor emission spectra with data known about the explosive when it is manufactured, the explosive can be identified. Line-emitting phosphors are especially useful because of their distinctive emission characteristics, which provide a vast number of possible combinations of emission which are correlated against the data known about the explosive when it is manufactured.
  • the phosphor is formed as a combination of finely divided spotter phosphor and finely divided coding material held together by a binder in the form of small conglomerates, in order to facilitate initial location and later identification of same.
  • a binder in the form of small conglomerates, in order to facilitate initial location and later identification of same.
  • This invention generally relates to labeling of an item with an individualistic and readily identifiable indicia in order to provide an item identification at a location remote from that location at which the label was applied and, more particularly, to a combination explosive and method whereby explosive material is coded with information to permit an identification of the explosive material either before or after detonation of same.
  • US. Pat. No. 3,199,454 dated Aug. 10, 1965 discloses placing an organic fluorescent material such as sodium fluorescein about a small explosive charge which is to be detonated in water, in order to help control predatory fish.
  • the explosive charge is relatively small and the presence of the water in which the charge is detonated serves to protect the fluorescein from the blast effects of the detonation so that upon striking the water, the fluorescein immediately provides an indicative fluorescent response.
  • organic fluorescent dyes As tracer materials to commercial items and this is described in U.S. Pat. No. 2,920,202 dated Jan. 5, 1960. It should be noted, however, that organic fluorescent materials exhibit an extremely broadband type of fluorescent emission and such dyes are normally used to describe one to two possibilities, namely, the presence or lack of such dye.
  • a somewhat similar use of organic fluorescent dyes is described in US. Pat. No. 2,392,620, dated Jan. 8, 1946 wherein fluorescent dyes are placed in hydrocarbon products in order to show the presence or lack of undesirable crude oil in a desired crude oil.
  • explosive agent or explosive material which preferably has a form suitable for use.
  • Incorporated with the explosive material is a relatively small amount of inorganic phosphor means which is positioned in receptive proximity to the shock, pressures, hightemperatures and reactive atmospheres which result from the detonation of the explosive.
  • the phosphor survives the explosive blast and can readily be detected by ultraviolet light, for example, and the fluorescence of the phosphor comprises a readily identifiable indicia of information regarding the explosive.
  • the phosphor is in a finely divided state and along with other finely divided material is retained in intimate association in the form of small conglomerates.
  • the other finely divided material once it has been located, is readily identifiable by its line-emission fluorescent response or by other suitable techniques.
  • the foregoing requires that the particular individualistic fluorescent emission be correlated with data known about the explosive at the time it is manufactured, such as manufacturer, date of manufacture, type of explosive, etc., and such data is all readily available.
  • the foregoing technique of utilizing the line-emissions of fluorescent materials can be used to label any item with an individualistic and readily identifiable indicia in order to provide an item identification at a location which is remote from that location at which the label was applied. No specific orientation of such a label is required.
  • FIG. 1 is an elevational view, partly broken away, of an explosive cartridge such as a stick of dynamite, showing phosphor conglomerates of the present invention scattered throughout the dynamite;
  • FIG. 2 is a greatly enlarged view of one of the phosphor conglomerates of the present invention.
  • FIG. 3 is a flow chart illustrating the basic method steps which are utilized in coding explosives for later identification
  • FIG. 4 is a graph of energy versus wavelength showing the spectral distribution for a cool white halophosphate phosphor, which can be used as a spotting phosphor;
  • FIG. 5 is a graph similar to FIG. 4, but showing the spectral energy distribution for a calcium tungstate phosphor, which can be used as a spotting phosphor;
  • FIG. 6 is a graph similar to FIG. 4, but showing the spectral energy distribution for a zinc silicate phosphor, which can be usd as a spotting phosphor;
  • FIG. 7 is a graph or relative energy versus wavelength showing the excitation and emission spectra for trivalent europium-activated yttrium oxide, which can be used as a coding phosphor;
  • FIG. 8 is a view similar to FIG. 7, but shown for trivalent terbium-activated yttrium oxide
  • FIG. 9 is a graph similar to FIG. 7, but taken for a lanthanum oxide host which is activated by trivalent samarium;
  • FIG. 10 is a graph similar to FIG. 7, but taken for a trivalent dysprosium-activated phosphor
  • FIG. 11 is a graph similar to FIG. 7, but taken for a trivalent gadolinium-activated phosphor
  • FIG. 12 is a graph similarto FIG. 7, but taken for a trivalent erbium-activated phosphor
  • FIG. 13 is a graph similar to FIG. 7, but taken for a trivalent holmium-activated embodiment
  • FIG. 14 is a graph similar to FIG. 7, but taken for a lanthanum oxide host activated by trivalent praesodymium;
  • FIG. 15 is a graph similar to FIG. 7, but taken for a lanthanum oxide host activated by trivalent thulium;
  • FIG. 16 is a flow chart illustrating the basic steps utilized in labeling an item for later identification through the use of line-emitting phosphors
  • FIG. 17 is a schematic view of an apparatus which could be utilized for scanning a previously labeled item in order to derive the information which had previously been placed thereon;
  • FIG. 18 is a plan view of the item shown in FIG. 17,
  • FIG. 19 is an isometric view of an alternative excitation source and modified filter, as could be used with the scanning apparatus as shown in FIGS. 17 and 18.
  • a small amount of finely divided, particulate, inorganic phosphor means which comprises a readily identifiable indicia, as will be explained in detail hereinafter.
  • This fluorescence indicia is correlated against then-known predetermined data regarding the explosive material, for example the manufacturers indicia, the type of explosive, the year of manufacture, the month of manufacture, the week of manufacture, and if desired, even the day of manufacture in the case of high volume explosives.
  • the indicia which is provided by the phosphor can be correlated against the distribution of the explosive.
  • FIG. 1 a generally conventional dynamite cartridge 20 which comprises a fibrous casing 22 enclosing the dynamite 24 having scattered throughout small phosphor conglomerates 26, in accordance with the present invention.
  • the usual fluorescent phosphor materials such as are used in fluorescent lamps, are quite finely divided and a representative average particle diameter is in the order of 6-8 microns. If such very finely divided material, such as halophosphate phosphor, were to be scattered throughout the dynamite, the finely divided particles would survive the detonation and would be detectable at night as viewed under 254 nm ultraviolet radiations. They would be quite difficult to pick up, however, because of their extremely small size, and only one indicia of information would be available from any one fluorescent phosphor material.
  • fluorescent materials which have very distinctive emissions are utilized in combination to provide a vast number of different fluorescent emissions which can be readily detected.
  • the most distinctive fluorescent emitting materials are those of the lanthanide series of rare-earth metals which, apparently because of the incompletely filled IF-shells, possess a large number of sharp levels. The transitions between these provide a many-line spectrum, in contrast to the usual type of fluorescent materials which usually provide a continuous or so-called band-type emission.
  • typical commercial phosphors such as are used in fluorescent lamps, for example, are used as what can be termed spotting phosphors and there are mixed therewith a predetermined combination of different line-emitting coding phosphors which provide a very individualistic emission when excited by predetermined energy such as ultra-violet radiation.
  • the band-emitting phosphors and line-emitting phosphors are mixed together in the form of small conglomerates 26, such as shown in FIG. 2, and these small conglomerates are dispersed throughout the explosive, such as the dynamite cartridge.
  • a very finely divided commercial spotting phosphor 28 such as apatite structured cool-white halophosphate activated by antimony and manganese
  • very finely divided coding phosphor 30 an example of which is yttrium oxide activated by trivalent europium.
  • the foregoing finely divided phosphor mixture is mixed with an aqueous solution of potassium silicate (75 percent by weight H O) to form a very thick paste and this paste is spread in a layer approximately two mm thick and permitted to air dry for twelve hours.
  • the material After air drying, the material is baked at a temperature of approximately 80C for a period of three hours and then is allowed to cure for about 24 hours.
  • the cured mass comprises about 80 percent by weight phosphor and percent by weight potassium silicate.
  • the resulting hard mass is reduced to a particulate status, such as by grinding or hammer milling.
  • the resulting milled product is then passed over a sieve No. 20 and then over a sieve number 40 to separate the fines and coarses.
  • the resulting conglomerates have a particle size in the order of 0.5 to 0.7 mm. Because of the extremely fine state of division of the phosphor particles, each of the conglomerates 26 as shown in FIG.
  • the resulting conglomerates 26 are then thoroughly mixed into the explosive, such as dynamite, during its processing into a form suitable for use.
  • the conglomerates can be dispersed throughout the molten explosive and cast with same.
  • the amount of phosphor material which is incorporated into the dynamite is in no way critical and amounts of from 0.01 percent by weight to 1 percent by weight can be utilized. Smaller or larger amounts of phosphor also can be utilized.
  • the weight of the conglomerate will be approximately one milligram. If 0.1 percent by weight of conglomerates are used with a 200 gram stick of dynamite, there will be approximately 200 of the conglomerates 26 scattered throughout the dynamite stick.
  • the emission spectra of the lanthanide series of rareearth metals have been studied in detail and are set forth in comprehensive form in Applied Physics, Vol. 2, No. 7, July 1963 at page 608.
  • Table I are set forth the lanthanide rare-earth metals which can be utilized as activators in order to provide very distinctive line emissions of radiations, along with some other activator ions which provide line-appearing type emissions.
  • These activators can be used with many different host or matrix materials to :form a phosphor and, as an example, yttrium oxide has been found to be a very suitable host material for many of these metals to provide many different phosphors which can be used for coding purposes.
  • These phosphors are all well known and the general properties of rare-earth metal activated materials are described in the Journal of the Electrochemical Society, Volume 111, No. 3, March 1964, at pages 31l3l7.
  • the Cr ions are readily assimilated into an A1 0 host material.
  • a suitable host for Mn is magnesium fluorogermanate, and U0 is readily assimilated into a lithium fluoride host.
  • V is readily assimilated into a magnesium oxide host, and Fe into LiAl O Sm is read ily assimilated into CaF
  • the trivalent lanthanide rareearth metals normally can be used with one or more of an yttrium oxide host, an yttrium orthovanadate host, a lanthanum phosphate host, or a. gadolinium vanadate host.
  • the actual width of a fluorescent line as emitted by a rare-earth metal activated phosphor is generally in the order of three to ten Angstroms as measured at an intensity which is 50 percent of the maximum fluorescent intensity of the emission.
  • This narrow line of emission should be contrasted to the emission of calcium tungstate as shown in FIG. 5, wherein the width of the band, as measured at an emission intensity which is 50 percent of the maximum intensity, is 1250 Angstroms.
  • a line-emitting phosphor is described as one for which the emission, as viewed through a spectroscope, appears as one or more lines, in contrast to a band" which occupies a band in the visible spectrum, as viewed with a spectroscope.
  • the phosphor emission is not restricted to the visible and may occur in the ultraviolet or infrared.
  • each conglomerate 26 To enable the conglomerates 26 to be readily located after an explosive material is detonated, it is desirable to incorporate with each conglomerate a substantial proportion of fluorescent material which serves primarily as a spotter or locator. Most of the commercialphosphors which are used in fluorescent lamps can be used for such purpose and these phosphors normally have a continuous or band-type emission. Of course, the so-called spotter phosphor could also be used to provide information and, for example, a different spotter phosphor can be used to identify each different manufacturer of explosives.
  • magnesium tungstate phosphor could be included in small amount to provide an indicia of permissible explosive and manganese-activated calcium gallate could be utilized to provide an indicia of non-permissible explosive.
  • the number of phosphors which could be substituted for the foregoing specific examples are numerous and for further examples, reference is made to Leverenz, Luminescense of Solids, published by Wiley and Sons, New York (1950) see Table V following page 72 of this reference. As a general rule, phosphors which will oxidize readily desirably should be avoided.
  • the finely divided phosphor materials would be mixed in the proportion of 80 percent by weight calcium tungstate, percent by weight magnesium tungstate, and 2 percent by weight of each of the five remaining coding constituents. Since each conglomerate of phosphor contains well in excess of a million individual phosphor particles, each conglomerate is assured of having a representative sampling of each of the spotting and coding constituents which are utilized. After the blast under investigation has occurred, the investigators would wait until dark and them systematically irradiate the area of the blast with 254 nm ultraviolet radiations to which the spotter phorpher responds with a bright blue fluorescence.
  • the principal emission lines and the excitation spectra for various rare-earth metal activated phosphors are illustrated in FIGS. 8 through 115.
  • the emission lines as shown are only the primary lines and in most cases, the line emissions of these rare-earth metals are much more complex.
  • the phosphor In analyzing the located conglomerates for emission spectrum, the phosphor can be irradiated with energy which will excite the host, which energy is then transferred to the activators which provide characteristic emission.
  • each rare-earth ion can be excited directly by using a tunable excitation source whose output wavelength is scanned over the wavelengths containing the sharp absorption lines of the' various activators. The resulting fluorescence is monitored to determine the variation of fluorescent energy with excitation wavelength.
  • the host is yttrium oxide activated with europium and terbium
  • excitation peaks at 395.5 nm for europium and 309 nm for terbium are easily seen by monitoring the fluorescent output in the wavelength range of from 500-700 nm, which contains many of the fluorescent lines of the europium and terbium ions.
  • the presence or absence of europium is determined by exciting the conglomerate with a wavelength of 395.5 nm and observing the presence or absence of the europium fluorescent line at 611.2 nm.
  • the presence or absence of terbium is noted if an excitation at 309 nm produces, or fails to produce, a fluorescent emission line at 543 nm.
  • the detection of the presence or absence of a very minute quantity of phosphor is extremely accurate using the foregoing techniques.
  • the conglomerates need not use line-emitting fluorescent phosphors as coding indicia, but could readily use other forms of identifying indicia, provided such material could be located after a blast.
  • Relatively simple techniques for identification are those of emission spectroscopy or X-ray fluorescence.
  • the technique of atomic absorption spectroscopy is also well known and can be used to detect very minute: quantities of various elements and this is described in the book by Robinson entitled Atomic Absorption Spectroscopy published by Dekker, New York (1966).
  • Table VII are listed some elements which are suitable for detection utilizing this atomic absorption spectroscopy technique. These elements should be mixed in a stable form, such as the oxides, phosphates or silicates, for example, as very finely divided material comprising a part of the conglomerate 26 as shown in FIG. 2.
  • inorganic phosphor placed into an explosive in very finely divided form will provide one indicia of information
  • the very size of the conglomerate also facilitates their being readily segregated from the debris of the explosion.
  • the inorganic binder material which is used should be transmissive of at least that energy which excites the spotter phosphor and it should be transmissive of the radiations which the spotter V phosphor produces when excited. In the usual case, the
  • phosphor will be responsive to either short wavelength or long wavelength ultraviolet radiations, although other forms of phosphor excitation could be used if de-v sired.
  • potassium silicate as a phosphor binder which meets the foregoing requirements.
  • Many other inorganic binders could be utilized such as sodium silicates which range in composition from Na O-2SiO to Na O-4SiO These silicates air dry to hard films which do not readily dissolve and if they are heated, the binders will freeze into a solid foam type material.
  • the compositions range from K O-3.9SiO to K O-3.3SiO
  • Glass-forming inorganic materials can also be used as binders and these include the well known soda-lime-silica glasses of which there are numerous different compositions. Glass-ceramic compositions, which are well known, can also be used as binders.
  • refractory materials could be used as a binder fabricated about the phosphor particle with a sintering type of process. As a general rule, it has been found that the finer the phosphor particles, the stronger the particle conglomerate with respect to resisting the blast effects of the detonation. With most phosphor materials, it is a relatively simple matter to obtain ultimate particles which have a diameter in the order of two microns and less.
  • each conglomerate will contain all coding information which is initially placed therein.
  • the conglomerates can even be intermixed with RDX and, after detonation, the continuity of the conglomerates will still be preserved to a degree sufficient to insure that all coding information is present. This is about as extreme a test as the conglomerates can be subjected to, because of the extremely high velocity of detonation and high detonation pressures of this explosive material.
  • the line-emitting phosphors can be applied as separate patches to label any item with an individualistic and readily identifiable indicia to provide an item identification at a location which is remote from that location at which the label was applied. No specific orientation of the label is required.
  • a combination of different phosphor materials at least the substantial portion of which are inorganic phosphors activated by different ions which taken together provide a vast number of different known combination of distinctive line emissions when the phosphors are excited by predetermined energy other than visible light.
  • the known phosphor combination is then secured in intimate association, as a label for example, with the item to be identified.
  • FIGS. 17 and 18 are shown an example of a coded item 34 wherein each of the four patches 36, 38, 40 and 42 comprise a different rare-earth metal activated phosphor to comprise a coded label, 44.
  • the labeled item 34 is passed on a conveyor belt 46 beneath an ultraviolet lamp 48 and the fluorescence of the label 44 is scanned by a pick-up photocell 50 or similar conventional read-out device. 7
  • each line-emitting activator ion in two or more different hosts which have what the phosphor art terms larger band gap energies, with each host being capable of transferring energy to the line-emitter activator ion.
  • the phosphors would be excited sequentially with two or more wavelengths of light of progressively shorter wavelength. The first exciting longer wavelength would be capable of exciting only that host which had the lowest band gap energy, the next shorter wavelength would be capable of exciting the second host, and so forth.
  • yttrium oxide (Y O has a band gap energy of 5.8 ev; the host Y O S has a band gap energy less than 5.8 ev; the host Y OS has a band gap energy substantially less than 5.8 ev and greater than 2.5 ev; and the host Y S has a band gap energy of about 2.5 ev.
  • All of these hosts would be activated by a trivalent europium, for example, and they would be sequentially excited first with long wavelength energy and then with progressively shorter wavelength energy with the resulting fluorescence observed. For example, the label would be pumped sequentially with wavelengths of 3ev,'4ev, Sev and 6ev. In this manner, the total number .of possible combinations could be extended substantially.
  • a plurality of hosts which have progressively larger band gap energies would be utilized as in the previous example and these would be excited sequentially with successively higher energies (i.e., shorter wavelengthexcitations).
  • a set of filters each of which is capable of passing one and only one of the exciting energies.
  • one filter 52 is shown in FIG. 17. This would greatly extend the number of total combinations.
  • the use of more than one filter 52 will normally require a separate ultraviolet lamp 48. This technique could also be used to eliminate spurious emissions as might occur from a fluorescent dye actually incorporated as a part of an item to be detected.
  • the fluorescent dye would in all probability respond to all energies and by deliberately omitting from the label a phosphor which will respond to a predetermined excitation energy, the possibility of spurious signals could be eliminated since if the labeled item did respond to a predetermined excitation, the presence of the fluorescent dye would be indicated.
  • an excitation energy of 300 nm were used to excite a fluorescent dye such as sodium fluorescein, and no phosphor were present which would respond to such excitation, the presence of the fluorescent dye would be indicated, and the item would have to be specially handled.
  • excitation source 48a which for this embodiment is a reflectortype high-pressure mercury vapor lamp, modified to incorporate an ultraviolet transmitting faceplate.
  • This lamp emits strong radiations at 254 nm and 365 nm.
  • a rotating filter 52a one half portion 54 of which is a filter which passes only 254 nm radiations and the other half portion 56 of which passes only 365 nm radiations.
  • the label 44 can be sequentially excited with successively varying energies as the filter 52a is rotated.
  • the signal from the photocell 50 is read only when the items which comprise the label 44 are irradiated only with the 254 nm excitation or the 365 nm excitation.
  • the small conglomerates can be coated with a non-fluorescing, ultravioletradiation-absorbing organic combustible, such as polymethyl methacrylate. If the explosive cartridge is broken open and exposed to ultraviolet radiations, the coated conglomerates will not fluoresce and their detection and removal will be a most difficult task. When the explosive cartridge is detonated, however, the organic coating will burn in the reactive atmospheres, leaving the residual fluorescent conglomerates. Such a coating may also have benefit in forming a seal about the conglomerates to inhibit absorption of any material of the environment in which the conglomerates are intended to be used.
  • a non-fluorescing, ultravioletradiation-absorbing organic combustible such as polymethyl methacrylate.
  • the techniques described herein could also be used to code other types of explosives and propellent materials.
  • the coding techniques as described can also be used to identify explosive agents.
  • ammonium nitrate could be coded with the phosphor conglomerates. When this explosive agent is further processed into a form suitable for use, the conglomerates would remain in the resulting explosive material.
  • explosive agent or explosive material and associated means which will provide an indicia of information regarding said explosive agent or explosive material, said combination comprising:
  • inorganic phosphor means incorporated with and retained in intimate association with said explosive agent or explosive material and receptive to the shock, pressure, high temperature and reactive atmospheres resulting from the ultimate detonation thereof, and the fluorescence of said phosphor means comprising a readily identifiable indicia of information regarding said explosive agent or explosive material.
  • solid explosive material and associated individualistic and readily determinable phosphor means which will provide an indicia of information regarding said explosive material either before or after detonation of same, said combination comprising:
  • conglomerated particles comprising a first finely divided phosphor material which is excited by predetermined energy to produce a predetermined emission of readily detectable radiations, at least one finely divided second phoshor material which is excited by predetermined energy to produce a predetermined individualistic emission of radiations which is different from the emission of said first phosphor material, and inorganic binder material intimately holding together said first phosphor material and second phosphor material as a plurality of small particles each comprising said conglomerates of said first finely divided phosphor material and said second finely divided phosphor material, and said binder material transmissive of at least said predetermined energy which excites said first phosphor material and transmissive of said readily detectable radiations produced by said excited first phosphor material.
  • said explosive material comprises dynamite
  • said first phosphor material is efficiently excited by ultra-violet radiations to provide a band-type emission
  • said second phosphor material is excited by ultraviolet radiations to produce a line-type emission
  • the relative amount of said first phosphor material substantially exceeds the relative amount of said second phosphor material.
  • said conglomerates comprise from about 0.01 to l percent by weight of said dynamite, said conglomerates are of such size as to weigh about one milligram each, said first and second phosphor materials comprise about percent by weight of said conglomerates, said first phosphor material is apatite structured halophosphate activated by antimony and manganese, and said second phosphor material comprises yttrium oxide matrix activated by trivalent europ ium, and the weight ratio of said first phosphor material to said second phosphor material is about :10.
  • an explosive cartridge and associated means which will provide an indicia of information regarding said explosive cartridge, said combination comprising:
  • an explosive cartridge comprising a casing and explosive material enclosed by said casing
  • inorganic fluorescent phosphor means incorporated with and retained in intimate association with said explosive cartridge and receptive to the shock, pressure, high temperature and reactive atmospheres resulting from the ultimate detonation thereof, and-the fluorescence of said phosphor means comprising a readily locatable indicia of information regarding said explosive cartridge.
  • explosive agent or explosive material and associated means which will provide an indicia of information regarding said explosive agent or explosive material, said combination comprising:
  • inorganic phosphor means incorporated with and retained in intimate association with said explosive agent or explosive material and receptive to the shock, pressure, high temperature and reactive atmospheres resulting from the ultimate detonation thereof, and the fluorescence of said phosphor means comprising a readily identifiable indicia of information regarding said explosive agent or explosive material, said phosphor means is in finely divided form, and finely divided other material is retained in intimate association with said phosphor means in the form of small conglomerates, said finely divided other material upon identification providing individualistic indicia of information, and once said other material has been located, said other material is readily identifiable.
  • explosive agent or explosive material and associated means which will provide an indicia of information regarding said explosive agent or explosive material, said combination comprising:
  • inorganic phosphor means incorporated with and retained in intimate association with said explosive agent or explosive material and receptive to the shock, pressure, high temperature and reactive atmospheres resulting from the ultimate detonation thereof, and the fluorescence of said phosphor means comprising a readily identifiable indicia ofinformation regarding said explosive agent or explosive material, said phosphor means is in finely divided form, and finely divided other material is retained in intimate association with said phosphor means in the form of small conglomerates, said finely divided other material upon identification providing individualistic indicia of information, and once said other material has been located, said other material is readily identifiable by at least one of the procedures of emission spectroscopy, atomic absorption spectroscopy, X-ray fluorescence analysis, neutron irradiation and activation analysis, or distinctive fluorescent emission response.
  • explosive agent or explosive material and associated means which will provide an indicia of information regarding said explosive agent or explosive material, said combination comprising:
  • inorganic phosphor means incorporated with and retained in intimate association with said explosive agent or explosive material and receptive to the shock, pressure, high temperature and reactive atmospheres resulting from the ultimate detonation thereof, and the fluorescence of said phosphor means comprising a readily identifiable indicia of information regarding said explosive agent or explosive material
  • said phosphor means is in finely divided form, and finely divided other material is retained in intimate association with said phosphor means in the form of small conglomerates, said finely divided other material upon identification providing individualistic indicia of information, and once said other material has been located, said other material is readily identifiable by at least one of the procedures of emission spectroscopy, atomic absorption spectroscopy, X-ray fluorescence analysis, neutron irradiation and activation analysis, or distinctive fluorescent emission response, and said distinctive fluorescent emission response comprises line emission fluorescent response.
  • an explosive cartridge and associated means which will provide an indicia of information regarding said explosive cartridge, said combination comprising:
  • an explosive cartridge comprising a casing and explosive material enclosed by said casing
  • inorganic fluorescent phosphor means incorporated with and retained in intimate association with said explosive cartridge and receptive to the shock, pressure, high temperature and reactive atmospheres resulting from the ultimate detonation thereof, and the fluorescence of said phoshor means comprising a readily locatable indicia of information regarding said explosive cartridge, said phosphor means is in finely divided form, and finely divided other material is-retained in intimate association with said phosphor means in the form of small conglomerates, said finely divided other material upon identification providing individualistic indicia of information, and once said other material has been located, said other material is readily identifiable.
  • an explosive cartridge and associated means which will provide an indicia of information regarding said explosive cartridge, said combination comprising: a. an explosive cartridge comprising a casing and explosive material enclosed by said casing; and
  • inorganic fluorescent phosphor means incorporated with and retained in intimate association with said explosive cartridge and receptive to the shock, pressure, high temperature and reactive atmospheres resulting from the ultimate detonation thereof, and the fluorescence of said phosphor means comprising a readily locatable indicia of information regarding said explosive cartridge, said phosphor means is in finely divided form, and finely divided other material is retained in intimate association with said phosphor means in the form of small conglomerates, said finely divided other material upon identification providing individualistic indicia of information, and once said other material has been located, said other material is readily identifiable by at least one of the procedures of emission spectroscopy, atomic absorption spectroscopy, X-ray fluorescence analysis, neutron irradiation and activation analysis, or distinctive fluorescent emission response.
  • an explosive cartridge comprising a casing and explosive material enclosed by said casing
  • inorganic fluorescent phosphor means incorporated with and retained in intimate association with said explosive cartridge and receptive to the shock, pressure, high temperature and reactive atmospheres resulting from the ultimate detonation thereof, and the fluorescence of said phosphor means comprising a readily locatable indicia of information regarding said explosive cartridge
  • said phosphor means is in finely divided form, and finely divided other material is retained in intimate association with said phosphor means in the form of small conglomerates, said finely divided other material upon identification providing individualistic indicia of information, and once said other material has been located said other material able indicia of information regarding said explosive cartridge
  • said inorganic phosphor means comprises a plurality of conglomerated small particles, said conglomerated small particles comprising a is readily idfmiifiable y at least one P the W first finely divided phosphor material which is exdures of emlsslon Spectroscopy, atomic fbsorption cited by predetermined
  • an explosive cartridge comprising a casing and explosive material enclosed by said casing
  • inorganic fluorescent phosphor means incorporated with and retained in rial as a plurality of small particles each comprising said conglomerates of said first finely divided phosphor material and said second finely divided phosphor material, and said binder material transmissive of at least said predetermined energy which exintimate association with said explosive cartridge and receptive to the ho k, pressure, hi h temperacites said first phosphor material and transmissive ture and reactive atmospheres resulting from the of a d rea i y d tecta l radiations produced by ultimate detonation thereof, and the fluorescence said excited first phosphor material.
  • said phosphor means comprising a readily locat-

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US00143772A 1971-05-17 1971-05-17 Phosphor combination and method, particularly adapted for use with explosives, for providing a distinctive information label Expired - Lifetime US3772099A (en)

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US20040096911A1 (en) * 1999-04-15 2004-05-20 Oleg Siniaguine Particles with light-polarizing codes
US20040126773A1 (en) * 2002-05-23 2004-07-01 Beske Oren E. Assays with coded sensor particles to sense assay conditions
US20040171076A1 (en) * 2001-12-20 2004-09-02 Dejneka Matthew J. Detectable micro to nano sized structures, methods of manufacture and use
US20050026298A1 (en) * 2003-08-01 2005-02-03 Tim Bickett Dye solutions for use in methods to detect the prior evaporation of anhydrous ammonia and the production of illicit drugs
US20050042764A1 (en) * 2002-02-07 2005-02-24 Sailor Michael J Optically encoded particles
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US20080042106A1 (en) * 2004-06-04 2008-02-21 Basf Aktiengesellschaft Method for Marking Materials
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US3967990A (en) * 1975-03-03 1976-07-06 The United States Of America As Represented By The Secretary Of The Interior Combination of band-type and line-type emission phosphors with explosive
US3993838A (en) * 1975-03-03 1976-11-23 The United States Of America As Represented By The Secretary Of The Interior Wax or plastic coated phosphor grains
US4063510A (en) * 1975-08-29 1977-12-20 Taisei Kensetsu Kabushiki Kaisha Process for detecting a misfired explosive
US4238384A (en) * 1978-06-19 1980-12-09 Sandoz, Inc. Method of incorporating additives in polymeric materials
US4442017A (en) * 1978-06-19 1984-04-10 Sandoz, Inc. Additive blends for polymeric materials
US4198307A (en) * 1978-07-24 1980-04-15 General Electric Company Polymer based magnetic tags
US4197104A (en) * 1978-09-21 1980-04-08 General Electric Company Magnetic tag process
US4256038A (en) * 1979-02-06 1981-03-17 The United States Of America As Represented By The United States Department Of Energy Perfluorocarbon vapor tagging of blasting cap detonators
US4431766A (en) * 1979-11-05 1984-02-14 Stauffer Chemical Company Coded polymeric material and method
US4329393A (en) * 1980-05-21 1982-05-11 Minnesota Mining And Manufacturing Company Coating compositions for retrospective identification of articles
US5422538A (en) * 1992-01-07 1995-06-06 U.S. Philips Corporation Low-pressure mercury discharge lamp
US5849590A (en) * 1992-01-29 1998-12-15 Anderson, Ii; David K. Method of chemical tagging
US5677187A (en) * 1992-01-29 1997-10-14 Anderson, Ii; David K. Tagging chemical compositions
US5677186A (en) * 1992-01-29 1997-10-14 Anderson, Ii; David K. Method of identifying chemicals by use of non-radioactive isotopes
US5329127A (en) * 1992-04-23 1994-07-12 Bayer Ag Method for the identification of plastics
US5324940A (en) * 1992-07-01 1994-06-28 Northwest Marine Technology, Inc. Color-encoded fluorescent visible implant tags and method for identification of a macro-organism therewith
US5760394A (en) * 1996-05-17 1998-06-02 Welle; Richard P. Isotopic taggant method and composition
US20070138438A1 (en) * 1997-02-24 2007-06-21 Cabot Corporation Photoluminescent phosphor powders, methods for making phosphor powders and devices incorporating same
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Also Published As

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DE2223058C3 (de) 1979-08-30
NL7206577A (ja) 1972-11-21
JPS5261209A (en) 1977-05-20
GB1399009A (en) 1975-06-25
IT960194B (it) 1973-11-20
JPS5319642B2 (ja) 1978-06-22
JPS5261210A (en) 1977-05-20
FR2137955B1 (ja) 1977-03-18
CA985908A (en) 1976-03-23
JPS5144168B1 (ja) 1976-11-26
JPS5235723B2 (ja) 1977-09-10
NL166452B (nl) 1981-03-16
GB1399008A (en) 1975-06-25
GB1399007A (en) 1975-06-25
NL166452C (nl) 1981-08-17
DE2223058A1 (de) 1972-11-30
FR2137955A1 (ja) 1972-12-29
DE2223058B2 (ja) 1979-01-04

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