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WO2001025767A1 - Procedes d'identification et de verification - Google Patents

Procedes d'identification et de verification Download PDF

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Publication number
WO2001025767A1
WO2001025767A1 PCT/US2000/027491 US0027491W WO0125767A1 WO 2001025767 A1 WO2001025767 A1 WO 2001025767A1 US 0027491 W US0027491 W US 0027491W WO 0125767 A1 WO0125767 A1 WO 0125767A1
Authority
WO
WIPO (PCT)
Prior art keywords
taggant
article
ticket
ray
providing
Prior art date
Application number
PCT/US2000/027491
Other languages
English (en)
Other versions
WO2001025767A9 (fr
Inventor
Bruce John Kaiser
L. Stephen Price
Don Kenning
David J. Watson
Robert D. Kuhlman
Original Assignee
Edax Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Edax Inc. filed Critical Edax Inc.
Priority to AU24228/01A priority Critical patent/AU2422801A/en
Publication of WO2001025767A1 publication Critical patent/WO2001025767A1/fr
Publication of WO2001025767A9 publication Critical patent/WO2001025767A9/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
    • G01N23/06—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption
    • G01N23/083—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption the radiation being X-rays
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/07—Investigating materials by wave or particle radiation secondary emission
    • G01N2223/076—X-ray fluorescence

Definitions

  • the present invention generally relates to apparatus and methods for identification and verification. More particularly, the present invention relates to apparatus and methods for detecting an element or compound intrinsically present — or extrinsically added — in an article or product by using X-ray fluorescence to identify and verify that article or product.
  • inks which are transparent in visible light are sometimes applied to materials and the presence (or absence) of the ink is revealed by ultraviolet or infrared fluorescence.
  • Other methods include implanting microscopic additives which can be detected optically. However, detecting these materials is primarily based on optical or photometric measurements.
  • taggants many of the apparatus and methods for identifying and verifying articles using such materials (called taggants) are unsatisfactory for several reasons. First, they are often difficult and time-consuming. In many instances, a sample of the article must be sent to an off-site laboratory for analysis. In other instances, the apparatus are often expensive, large, and difficult to operate. In yet other instances, the taggant used is radioactive, causing serious health concerns.
  • the present invention provides an apparatus and method in which one or more taggants that are intrinsically located — or extrinsically placed — in an article or product are detected by x-ray fluorescence analysis to identify or verify the article or its point of manufacture.
  • the taggants are manufactured as part of the article or the taggant is placed into a coating, packaging, label, or otherwise embedded within the article for the purpose of later verifying the presence or absence of these elements by x-ray fluorescence to determine the unique elemental composition of the taggant within these articles.
  • the apparatus and methods of the present invention are simple and easy to use, as well as provide detection by a non line-of- sight method to establish the origin of materials, point of manufacture, authenticity, verification, or product security.
  • the present invention is extremely advantageous because it is difficult to replicate, simulate, alter, transpose, or tamper. Further, it is easily recognizable by a user in either overt or covert form, verifiable by a manufacturer or issuer, and is easily applicable to various forms of media in the articles.
  • Figures 1, 2a, 2b, 3, 4a, 4b, and 5-7 are views of apparatus and methods for identification and verification according to the present invention.
  • Figures 1, 2a, 2b, 3, 4a, 4b, and 5-7 are views of apparatus and methods for identification and verification according to the present invention.
  • Figures 1, 2a, 2b, 3, 4a, 4b, and 5-7 are views of apparatus and methods for identification and verification according to the present invention.
  • Figures 1, 2a, 2b, 3, 4a, 4b, and 5-7 are views of apparatus and methods for identification and verification according to the present invention.
  • Figures 1, 2a, 2b, 3, 4a, 4b, and 5-7 are views of apparatus and methods for identification and verification according to the present invention.
  • Figures 1, 2a, 2b, 3, 4a, 4b, and 5-7 are views of apparatus and methods for identification and verification according to the present invention.
  • Figures 1, 2a, 2b, 3, 4a, 4b, and 5-7 are views of apparatus and methods for identification and verification according to the
  • the present invention uses x-ray fluorescence analysis to detect at least one taggant which is intrinsically or extrinsically present in the material of a product or article.
  • XRF x-ray fluorescence
  • the x-rays emitted from each element bear a specific and unique spectral signature, allowing one to determine whether that specific taggant is present in the product or article.
  • Figures 1, 2a, and 2b represent how it is believed XRF generally operates.
  • primary x-rays or gamma rays 40 are i ⁇ adiated on a sample of a target material 46 of article 42.
  • Secondary x-rays 44 are emitted from that sample of target material 46.
  • atom 48 of a taggant located within target material 46 has nucleus 50 surrounded by electrons 52 at discrete distances from nucleus 50
  • Electron 54 is located within K shell 56.
  • Primary x-ray or gamma ray photon 40 impacting atom 48 has a given energy. If that energy is greater than the binding energy level of K shell 56, the energy of x- ray photon 40 is absorbed by atom 48, and one of the electrons in K shell 56 (i.e., electron 54) is ejected. With a vacancy now in K shell 56 left by electron 54, atom 48 is energetic and unstable. To become more stable, that vacancy in K shell 56 can be — and usually is — filled by an electron located in a shell with a lower binding energy level, such as L-shell electron 58 in L shell 60. As L-shell electron 58 fills the vacancy in K shell 56, atom 48 emits a secondary x-ray photon 44.
  • the energy levels (or corresponding wavelengths) of such secondary x-ray photons are uniquely characteristic to each taggant, allowing the presence or absence of any specific taggant to be determined.
  • the at least one taggant can be intrinsically or extrinsically present in the product (or article) to be detected (the "target material").
  • the taggant(s) is intrinsically present, it is a component (either as an element, compound, or other type of composition) in at least one portion of that target material.
  • the taggant(s) is extrinsically present, it can be added, incorporated, or inserted into the target material as described below.
  • the at least one taggant employed in the present invention can be any suitable taggant known in the art. See, for example, U.S. Patent Nos. 5,474,937, 5,760,394, and 6,025,200, the disclosures of which are incorporated herein by reference.
  • Suitable taggants include any element or compound which is capable of being detected via XRF.
  • the type of elements that can be used as the taggant are theoretically any of those listed in the periodic table, but the lower energy emitted by electrons in the lower atomic-number elements could be a limiting factor. Such lower energies can be re-absorbed much easier into its own material matrix or, in come cases, into the ambient atmosphere (e.g, air). Further, different isotopes of an element, as well as elements which "excite" only under certain conditions — such as specific temperature ranges — could be employed as the taggant in the present invention.
  • Example of taggants that could be used in the present invention include any element with an atomic number ranging from 6 to 94.
  • rare earth metals are used as the at least one taggant in the present invention. More preferably, samarium (Sm) and/or lanthanum (La) are used as the at least one taggant in the present invention.
  • the type of taggant depends, among other things, on the target material in which it is located.
  • the target material can interfere with the XRF detection because, as described below, backscattering and peaks emitted by the composition of the target material during XRF analysis can interfere with the taggant peaks. For example, if paper packaging contained an As taggant and trace amounts of Pb existed in the paper, the K-level electrons of As and L-level electrons of Pb could give confusing readings during XRF detection.
  • the type of taggant should be selected based on the ability of the taggant and/or the substance in which it is located (i.e., a coating) to attach or bond to the target material.
  • the target material will be used, handled, and/or washed extensively. If the taggant (or the substance in which is located) is removed from the target material under such conditions, tagging the target material is of little value.
  • a film or coating e.g., paint
  • the taggant and coating should be selected so that they will not be removed by the conditions to which the target material is periodically subjected.
  • the coating and/or the taggant is selected in this aspect of the invention so that it chemically attaches or bonds to the target material, like paint attaches and bonds with a wall.
  • the type of taggant should be selected based on the ability of the taggant and/or the substance in which it is located (i.e., a coating) to be removed from the target material.
  • the purpose for which the target material is tagged will be temporary. After this purpose is completed, the taggant is no longer needed and can optionally be removed.
  • the coating and/or the taggant is selected in this aspect of the invention so that it is removable by mechanical or chemical means.
  • the amount and concentration of the taggant in the target material can also vary depending on the number of elements used and energy needed.
  • the amount of taggant employed in the present invention is determined by the minimum amount needed for XRF detection. Additional amounts of taggant can be used as described below.
  • the concentration of the taggant is at least about 1 part per million (ppm), and can range from about 1-100 ppm. Larger taggant amounts can be used, but for economic reasons, a small amount is sufficient. Even lower taggant concentrations can be used (i.e, less than 1 ppm) as improved XRF devices and techniques become available.
  • the form of the taggant in the target material can also vary.
  • the form can be any compound (i.e., salt) or molecule — either small or large — containing the element that is added by itself or with other components.
  • the taggant can be combined with various components and/or additives to make a mixture and/or solution.
  • these other components or additives can be selected for various purposes, e.g., to modify the XRF properties, to modify the ability to be inserted into an article/product, to stabilize the mixture or solution, or other purpose known in the chemical arts.
  • the taggant could be in the form of a salt of the taggant, such as iodide or chloride.
  • the at least one taggant is a combination or plurality of taggants.
  • a plurality of taggants could include more than one taggant of the same type, e.g., the same element or compound.
  • a combination of taggants could also be more than one type of taggant, e.g., a different element or compound in different media. For example, a taggant dispersed in ink which has been placed on paper which also contains the same or different taggant.
  • the plurality of taggants could also include a combination of at least one intrinsic and at least one extrinsic taggant.
  • the at least one taggant incorporated in the target material can provide a distinctive code.
  • a code could be based on the number and types of taggants present or absent, an abundance ratio (i.e., concentrations) of the same or different taggants, the location of the taggants within the material (i.e., a barcode made of a series of taggants with a space, where the space could be part of the code), the presence of multiple types or forms of a single taggant, or a combination thereof.
  • the present invention can include a system in which the concentration of one taggant in a targeted material is controlled to provide a distinctive code.
  • a specific taggant can be used for tagging ten commercially prepared batches of a product.
  • Ten unique codes could then be created for these ten batches by preparing samples of the target material containing various concentrations (i.e., 10 ppm, 20 ppm, ... 100 ppm) of that taggant.
  • concentrations i.e. 10 ppm, 20 ppm, ... 100 ppm
  • 10 unique codes i.e., 10 ppm, 20 ppm, ... 100 ppm
  • Additional codes could be created for larger concentration ranges, e.g., 100 codes of a concentration ranging from 10 ppm to 1000 ppm in 10 ppm increments.
  • concentration ranges e.g. 100 codes of a concentration ranging from 10 ppm to 1000 ppm in 10 ppm increments.
  • the number of unique codes can be increased by adding additional types and concentrations of the same or different taggants.
  • a significant increase in the number of possible codes can be achieved by using more than one taggant in creating the code.
  • the code can be expanded by adding another taggant with its own specific concentrations.
  • the number of codes can be further expanded by adding a third taggant with its own specific concentrations. Additional taggants could be used to provide even more codes. This coding system depends on the concentration increments of each of the taggants.
  • the number of codes available in the coding system could also be increased by varying the location of the taggant(s) within the material to be detected.
  • the detected material could be divided into any number of portions (i.e., quadrants) with certain taggants (or codes) being placed in certain of those portions, and optionally not in others, to signify additional information during the XRF analysis.
  • taggants include elements or compounds that may be found in the target material or in the environment to which the target material may be exposed
  • taggant contamination may occur and possibly render the taggant code difficult to read.
  • the taggant comprising lanthanum is located in a target material, it is possible that additional amounts of the taggant(s) could be present in the target material as a result of environmental contamination, an internal chemical reaction, or other contamination. If this contamination occurs, there will be a change in the concentration of that taggant in the target material. Subsequent measurement of this taggant could yield a value corresponding to an incorrect code.
  • Suitable target material can be employed in the present invention.
  • Suitable target materials include those which intrinsically contain the desired taggant(s) or in which the desired taggant(s) can be incorporated. Because XRF detection measures changes in the inner shell(s) of the taggant, it will not be significantly modified by chemical reactions that normally occur in the outer shells. Thus, it possible to tag chemicals and have the taggant code be carried in any product manufactured with those chemicals.
  • Target materials should be comprised of a material in which XRF detection is easy, e.g., little chance of background contamination, taggant deterioration, taggant destruction, contamination, or other deteriorating condition.
  • suitable target materials include: paper products like documents, currency, or tickets; solid products like jewelry, carpets, packaging (films, labels, and adhesives), metals, rubbers (tires), woods, or plastics (credit cards); liquid products like lubricating fluids, resins, sprays, paints, oils, inks; hazardous wastes; drugs or pharmaceuticals; gaseous products; or combinations or hybrids of these materials.
  • suitable target materials such as paper documents, drugs, or counterfeit manufactured items — include those that will be subsequently changed.
  • a target material that is suspected might be destroyed could be tagged with elements known to be present in the residue from the destruction. Since the taggant is not usually changed by the chemical process in destruction, a connection between the target material and its residue could be established after destruction.
  • the target material of the present invention is paper and paper-based products. Examples of paper and paper products include tickets and coupons.
  • the target materials containing the at least one taggant can be used for a wide number of applications.
  • tagging paints would allow any article coated with that paint to be identified.
  • tagging paper and ink used in the paper (or applied to the paper) can be used to establish the authenticity of documents and cu ⁇ ency.
  • many manufactured items prone to counterfeiting or theft could benefit from tagging.
  • Tagged threads in clothing could be used to encode information about the date, time, and place of manufacture. Tagging the bulk materials used in the manufacture of such items as compact disks, computer disks, video tapes, audio tapes, electronic circuits, and other items would be useful in tracing and prosecuting theft and counterfeiting cases involving these items. Tagging the packaging placed on products would allow quick and easy tracking of the packaged products.
  • the at least one taggant can be incorporated into the target material in any suitable form.
  • suitable forms include those which place that taggant in the target material with little to no damage (either chemical or physical) to the target material. See, for example, the description in U.S. Patent Nos. 5,208,630, 5,760,394, and 6,030,657, the disclosures of which are incorporated herein by reference.
  • Other suitable forms include using materials containing the taggant such as particulates like microparticles; solvents; coatings and films; adhesives; sprays; or a hybrid or combination of these methods.
  • the at least one taggant can be incorporated by itself or with another agent.
  • the at least one taggant can be incorporated in the target material using any suitable technique.
  • Many existing tagging techniques involve the use of microparticles containing the elements, or compounds or compositions of the elements, comprising the at least one taggant.
  • particles can be manufactured wherein smaller particles, or compounds or compositions of the elements, containing the taggant.
  • Such particles could be made of: magnetic or fluorescent materials to facilitate collection; refractory materials to enhance particle survival in an explosion; or chemically inert materials to enhance particle survival in a chemical reaction.
  • Such particles could be made of non-durable, soluble, or reactive materials to enhance taggant dispersal in a fluid, aerosol, or powder system.
  • the at least one taggant can be incorporated as an element or compound in solution with the liquid.
  • the at least one taggant can be incorporated in elemental or compound form either in solution or suspension in the target material.
  • the at least one taggant could also be dissolved or suspended in a solvent used in making the target material so that when that solvent evaporates, the residue left behind would contain the at least one taggant.
  • the taggant can be inserted into the target material of an article either during or after the article (or a part thereof) has been manufactured.
  • the taggant can be manufactured as a component of the article or as part of a component of the article.
  • the at least one taggant can also be incorporated into another material which comprises part of the article. Indeed, the at least one taggant could also be an element or compound of the article itself.
  • the taggant can be incorporated into any location (including surfaces) of the article. Two (and three) dimensional shapes and patterns of the at least one taggant can be constructed using any desired combination of types and numbers of taggants.
  • the at least one taggant could also be incorporated after manufacture of the target material of the article.
  • the taggant can be implanted into the article or deposited as a coating or film on the article. Additionally, the at least one taggant could be incorporated into the already formed article as a dopant.
  • the at least one taggant could be physically or chemically deposited by itself.
  • the at least one taggant could also be incorporated as one ingredient (or contaminant) of another material (such as a mixture or solution) which forms a coating or film.
  • the at least one taggant can be incorporated as an element or compound in solution (or suspension) with a liquid which is applied, such as by spraying or dipping, to the article.
  • the at least one taggant could be dissolved or suspended in a solvent so that when that solvent evaporates after being applied to the article, the residue left behind would contain the at least one taggant.
  • the present invention has the ability to easily tag small batches of target materials with a code unique to that batch. This can be done manually or in an automated system where each batch (or select batches) of the target material receives a different code. For example, 1000 (or 100) compact discs could be manufacture and each could be tagged with a code of a number from 1 to 1000 (or 1 to 100). Economic and processing considerations, however, might limit the minimum size of each batch and the number of batches which could be tagged.
  • any product or article as the target material can have at least one extrinsic or intrinsic taggant located therein.
  • the target material of the present invention could be a commercially- available product which can be modified with the processes described herein.
  • the target material could be paper tickets which are purchased and then at least one taggant is incorporated in or on the tickets.
  • the target material of the present invention can be made with the processes described herein.
  • the target material could be paper tickets which are manufactured with the at least one taggant already incorporated in or on such tickets.
  • the at least one taggant could also be incorporated into the paper or ink of a ticket by any suitable implantation or diffusion method.
  • the at least one taggant could be incorporated into the components of the paper from which the tickets are made. Paper is made from cellulose as well as other components. These components are used in well known processes to make paper sheets or rolls. Thus, the at least one taggant could be added to the cellulose (or the other components) before or during this conversion process so that the paper rolls or sheets have the at least one taggant incorporated therein. The at least one taggant could also be incorporated into the paper before the tickets are made. For example, the at least one taggant could be added during the sizing process. Sizing is a well-known process by which the paper surface is made resistant to moisture and abrasion while improving the finish, printability, smoothness and surface bonding strength.
  • the components of the sizing liquid i.e., starch
  • Adding the taggant to the sizing liquid could ensure that the taggant permanently bonds to the paper.
  • the at least one taggant could be incorporated into the ink or other writing on the tickets. After the paper sheet or tickets are made, the ink (or other writing) is respectively deposited on the paper sheet(s) or tickets. The at least one taggant could be incorporated into the ink (or other writing) before, during, or after the process of its deposition.
  • the at least one taggant could also be incorporated into a film or coating which is placed on the tickets. Often, a coating or film is placed on the tickets for many reasons.
  • the at least one taggant can be first dispersed in a solution containing a suitable solvent. This solution is then placed on the ticket(s) and allowed to dry, with the solution (including solvent) partially or fully evaporating and leaving the at least one taggant as a component of the coating or film.
  • the solution can be placed on the tickets using any suitable chemical deposition method, such as by spraying or by dipping.
  • the at least one taggant could be incorporated into tickets with each ticket (or group of tickets) having its own code.
  • tickets for different events or geographical locations could have a different taggant mix incorporated therein.
  • a number of automated reservoirs having varying concentrations of the two taggants could be included in the sizing stage of the paper making process.
  • Each reservoir would contain a distinctive mix of taggant concentrations, e.g., 5/5, 5/10, 5/15,...10/5, 10/10, 10/15, ... 95/85, 95/90, 95/95.
  • any particular paper sheet passes through the assembly line, it would receive the taggants from the desired reservoir.
  • each paper sheet and the tickets cut from that sheet could receive a unique combination of taggants for its code.
  • the taggant(s) is detected to identify or verify the target material using XRF analysis as illustrated in Figure 1.
  • Primary x-rays 40 are used to excite a sample of the target material 46, and the secondary x-rays 44 that are emitted by the sample are detected and analyzed.
  • the x-rays which are detected have various energies, e.g., there is a broad band of scattered x-rays with energies less than and greater than those of the exciting atom.
  • Figure 3 illustrates this spectrum for paper as the target material. Within this broad band, there are peaks due to the excitation of the taggant(s) in the sample.
  • the ratio of the intensity of the radiation in any peak to the intensity of the background at the same energy is a measure of the concentration of the element which has characteristic X-rays at the energy of that peak, e.g., the taggant.
  • At least one target material believing to contain known concentrations of the taggant(s) of interest is selected.
  • the XRF analysis is performed on that target material (or a sample thereof) using a detection device or apparatus containing an x-ray radiation source ("source”), x-ray radiation detector (“detector”), support means, analyzer means, and calibration means.
  • source x-ray radiation source
  • detector x-ray radiation detector
  • the detection apparatus 25 has an ordinary x-ray fluorescence spectrometer capable of detecting elements present in a coating or packaging material.
  • X-rays 29 from a source (e.g., either x-ray tube or radioactive isotope) 20 impinge on a sample 11 which absorbs the radiation and emits x-rays 31 to an x-ray detector 21 and analyzer 23 capable of energy or wavelength discrimination.
  • a source e.g., either x-ray tube or radioactive isotope
  • analyzer 23 capable of energy or wavelength discrimination.
  • This is accomplished by using a commercially available x-ray spectrometer such as an Edax DX-95 or a MAP-4 portable analyzer, commercially available from Edax Inc., Mahwah, New Jersey.
  • Part of analyzer 23 includes a computerized system 27.
  • the detection apparatus 25 has an instrument housing 15 which contains the various components.
  • Gamma rays or x-rays 30 from a source (e.g., either x-ray tube or radioactive isotope) 20 are optionally focused by aperture 10 to impinge on a sample 11.
  • Sample 11 contains the at least one taggant which absorbs the radiation and emits x-rays 31 to an x-ray detector 21.
  • analyzing means can be incorporated within housing 15.
  • the present invention is not limited to the detection apparatus depicted in Figures 4a and 4b. Any suitable source, or plurality of sources, known in the art can be used as the source in the detection device of the present.
  • the source bombards the taggant with a high energy beam.
  • the beam may be an electron beam or electromagnetic radiation such as X-rays or gamma rays.
  • the source therefore, may be any material which emits such high energy beams.
  • these have been x-ray emitting devices such as x-ray tubes or radioactive sources.
  • the beam can be focused and directed properly by any suitable means such as an orifice or an aperture.
  • the configuration (size, length, diameter%) of the beam should be controlled, as known in the art, to obtain the desired XRF detection.
  • the power (or energy level) of the source should also be controlled, as known in the art, to obtain the desired XRF detection.
  • the source(s) can be shielded and emit radiation in a space limited by the shape of the shield.
  • the presence, configuration, and the material used for shielding the source should be controlled for consistent XRF detection.
  • Any suitable material and configuration for that shield known in the art can be employed in the present invention.
  • any high-density materials used as the material for the shield e.g, tungsten or brass.
  • Any suitable detector, or plurality of detectors, known in the art can be used as the detector in the detection device of the present invention. See, for example, U.S. Patent Nos. 4,862,143, 4,045,676, and 6,005,915, the disclosures of which are incorporated herein by reference.
  • Any type of material capable of detecting the photons omitted by the taggant may be used.
  • Silicon and CZT (cadmium-zinc- telluride) detectors have been conventionally used, but others such as proportional counters, germanium detectors, or mercuric iodide crystals can be used.
  • the geometry between the detector and the target material should be controlled.
  • the XRF detection also depend on the presence, configuration, and material — such as tungsten and beryllium — used as a window to allow x-rays photons to strike the detector.
  • the age of the detector, voltage, humidity, variations in exposure, and temperature can also impact the XRF detection and, therefore, these conditions should be controlled.
  • the analyzer means sorts the radiation detected by the detector into one or more energy bands and measures its intensity.
  • any analyzer means performing this function could be used in the present invention.
  • the analyzer means can be a multi-channel analyzer for measurements of the detected radiation in the characteristic band and any other bands necessary to compute the value of the characteristic radiation as distinct from the scattered or background radiation. See, for example, U.S. Patent Nos. 4,862,143, 4,045,676, and 6,005,915, the disclosures of which are incorporated herein by reference.
  • the XRF also depends on the resolution of the x-rays. Background and other noise must be filtered from the x-rays for proper measurement, e.g., the signals must be separated into the proper number of channels and excess noise removed.
  • the resolution can be improved by cooling the detector using a thermoelectric cooler — such as a nitrogen or a peltier cooler — and/or by filtering. Another way to improve this resolution is to use pre-amplifiers.
  • the support means supports the source and detector in predetermined positions relatively to a sample of the target material to be i ⁇ adiated.
  • the support means comprises two housings, where the source and detector are mounted in a first housing which is connected by a flexible cable to a second housing in which the analyzer means is positioned as illustrated in Figure 4a. If desired, the first housing may then be adapted to be hand-held.
  • the source and detector as well as the other components of the detection device are mounted in a single housing as illustrated in Figure 4b.
  • the calibration means are used to calibrate the detection apparatus, thus insuring accuracy of the XRF analysis.
  • the various parameters which could be modified and effect the measurement are isolated and calibrated.
  • the geometrical conditions or arrangements can be isolated and calibrated.
  • the material matrix are isolated and calibrated.
  • internal (in situ) calibration during detection is employed as the calibration means in the present invention.
  • Components, such as tungsten shielding, are already present to internally calibrate during the XRF analysis.
  • Other methods such as fluorescence peak or Compton backscattering, could be used for internal calibration in the present invention.
  • Analyzer means which includes a computerized system 27, is coupled to, receives, and processes the output signals produced by detector 21.
  • the energy range of interest which includes the energy levels of the secondary x-ray photons 44 emitted by the taggant(s), is divided into several energy subranges.
  • Computerized system 27 maintains counts of the number of X-ray photons detected within each subrange using specific software programs, such as those to analyze the detection and x-ray interaction and to analyze backscatter data. After the desired exposure time, computerized system 27 with display menus stops receiving and processing output signals and produces a graph of the counts associated with each subrange.
  • Figure 5 is a representative graph of the counts associated with each subrange. This graph is essentially a histogram representing the frequency distribution of the energy levels El, E2, and E3 of the detected x-ray photons. Peaks in the frequency distribution (i.e., relatively high numbers of counts) occur at energy levels of scattered primary x-ray photons as well as the secondary x-ray photons from the taggant(s).
  • a primary x-ray photon incident upon a target material may be absorbed or scattered.
  • the desired secondary x-ray photons are emitted only when the primary x-ray photons are absorbed.
  • the scattered primary x-ray photons which reach the detector of the system create an unwanted background intensity level.
  • the sensitivity of XRF analysis is dependent on the background intensity level, and the sensitivity of XRF detection may be improved by reducing the amount of scattered primary x-ray photons reaching the detector.
  • the peak occurring at energy levels of scattered primary x-ray photons is basically ignored, while the other peaks — those occurring at El, E2, and E3 — are used to identify the at least one taggant present in the target material.
  • the media such as air
  • the gamma rays (and x-rays) must travel also impacts the XRF. Therefore, the different types of media must be considered when performing the XRF analysis.
  • the methods used to interpret and analyze the x-rays depend, in large part, on the algorithms and software used. Thus, methods must be adopted to employ software and algorithms that will consistently perform the XRF detection.
  • FIG. 6 illustrates a prefe ⁇ ed apparatus and detection method according to the present invention.
  • detection apparatus 25 is capable of detecting at least one taggant present in target material 10, such as a ticket.
  • Detection apparatus 25 is a portable device which can be small enough to be hand-held.
  • Detection apparatus 25 contains all the components discussed above (i.e., source, detector, analyzer means, and calibration means) in a single housing, thus allowing the portability and smaller size.
  • the present invention is not limited to any specific XRF analysis. Any type of XRF, such as total reflection x-ray fluorescence (TXRF), can be employed in the present invention.
  • TXRF total reflection x-ray fluorescence
  • the apparatus and method used identify an article once it has been tagged. The ability to invisibly tag an article and read the tag, especially with a non line-of-sight method, would provide an invaluable asset in any industry that authenticates, verifies, tracks, labels, or distributes goods of any kind. Indeed, having an invisible taggant(s) could further prevent copying and counterfeiting of goods.
  • the apparatus and method of the present invention could be used for these same purposes, but for those products that have the desired taggant already located therein.
  • the present inventions could analyze liquid flows for contaminant particles or pinpoint via 3-D analysis the exact location of a contaminant(s) in an article. The following non-limiting examples illustrate the present invention.
  • Example 1 A dispersion of lanthanum oxide (taggant) particles in water was added to a sizing bath at a paper-manufacturing mill to obtain a taggant concentration in the bath of 7500 ppm lanthanum.
  • the web was then heat dried to drive off the water through evaporation, leaving the "size” and taggant as integral parts of the paper fiber.
  • a specialty ink base was prepared by adding a phosphomolybdic acid complex pigment to water which also contained resin and de-foaming agents.
  • the concentration of the taggant in the base was 35 wt% molybdenum (taggant). Two liters of this base was sent to a ticket printer to make a black printing ink for tickets.
  • the printer applied the black printing ink to card stock tickets using a flexographic printing press.
  • the ink was allowed to dry on the card stock tickets, leaving the taggant as part of the dried ink.
  • Example 3 The tagged ticket from Example 2 was analyzed for the presence of the molybdenum taggant.
  • a portable, hand-held detection apparatus similar to that illustrated in Figure 6 was used to detect the presence of the taggant using XRF analysis.
  • the detection apparatus contained several components.
  • a trigger actuated tungsten shutter block containing an americium 241 gamma ray point source and a silicon pin x-ray detector were located within the front of the instrument. Circuit boards, necessary for acquiring and processing the data from the detector were located within the rest of the housing.
  • the instrument had a red and a green light to indicate whether the carpet was tagged or not and a read out to inform the user that the carpet was tagged or not.
  • a keypad on the top of the instrument allowed the user to turn the electronics of the instrument on and off, while a key operated lock on the side of the instrument kept the user from inadvertently opening the shutter block, exposing the radioactive source.
  • This detection apparatus was used for an XRF analysis on the tagged ticket.
  • the result of the XRF analysis for the tagged ticket is reported in Figure 7.
  • the peaks indicating the presence of the molybdenum taggant in Figure 7 are labeled.

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  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
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Abstract

L'invention concerne un appareil et un procédé consistant à placer un ou plusieurs traceurs instrinsèquement ou extrinsèquement dans un article ou un produit (11). On détecte ces traceurs grâce à une analyse par fluorescence X (20, 21), d'où l'identification ou la vérification de l'article ou de son lieu de fabrication. On peut intégrer ces traceurs à l'article en cours de fabrication ou les placer dans un revêtement, une étiquette ou tout autre élément ajouté à cet article, de façon à vérifier ultérieurement la présence ou l'absence desdits traceurs par fluorescence X. On détermine ainsi la composition élémentaire unique du traceur à l'intérieur de l'article en question.
PCT/US2000/027491 1999-10-04 2000-10-04 Procedes d'identification et de verification WO2001025767A1 (fr)

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PCT/US2000/026461 WO2001025763A1 (fr) 1999-10-04 2000-09-27 Procede d'identification et de verification
PCT/US2000/026784 WO2001025764A1 (fr) 1999-10-04 2000-09-28 Procedes d'identification et de verification
PCT/US2000/027151 WO2001025765A1 (fr) 1999-10-04 2000-10-03 Procedes d'identification et de verification
PCT/US2000/027492 WO2001025768A1 (fr) 1999-10-04 2000-10-04 Procedes d'identification et de verification
PCT/US2000/027491 WO2001025767A1 (fr) 1999-10-04 2000-10-04 Procedes d'identification et de verification
PCT/US2000/027420 WO2001025766A1 (fr) 1999-10-04 2000-10-04 Procede d'identification et de verification
PCT/US2000/027418 WO2001025747A2 (fr) 1999-10-04 2000-10-04 Procede d'identification et de verification
PCT/US2000/027423 WO2001025748A2 (fr) 1999-10-04 2000-10-04 Procedes d'identification et de verification
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PCT/US2000/026784 WO2001025764A1 (fr) 1999-10-04 2000-09-28 Procedes d'identification et de verification
PCT/US2000/027151 WO2001025765A1 (fr) 1999-10-04 2000-10-03 Procedes d'identification et de verification
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PCT/US2000/027423 WO2001025748A2 (fr) 1999-10-04 2000-10-04 Procedes d'identification et de verification
PCT/US2000/027624 WO2001025821A2 (fr) 1999-10-04 2000-10-04 Procedes d'identification et de verification

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US6909770B2 (en) 2001-12-05 2005-06-21 The United States Of America As Represented By The United States National Aeronautics And Space Administration Methods for identification and verification using vacuum XRF system
US9073091B2 (en) 2013-03-15 2015-07-07 Altria Client Services Inc. On-line oil and foreign matter detection system and method
US9080987B2 (en) 2011-05-26 2015-07-14 Altria Client Services, Inc. Oil soluble taggants
US9097668B2 (en) 2013-03-15 2015-08-04 Altria Client Services Inc. Menthol detection on tobacco
US9244017B2 (en) 2011-05-26 2016-01-26 Altria Client Services Llc Oil detection process and apparatus
US10782279B2 (en) 2014-11-11 2020-09-22 Altria Client Services Llc Method for detecting oil on tobacco products and packaging
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CN104101697A (zh) * 2013-04-10 2014-10-15 苏州华觉智能科技有限公司 检测装置
US10650630B2 (en) 2014-10-31 2020-05-12 Honeywell International Inc. Authentication systems, authentication devices, and methods for authenticating a value article
WO2016157185A1 (fr) * 2015-04-02 2016-10-06 Soreq Nuclear Research Center Système et procédé permettant de lire un marquage de fluorescence aux rayons x
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Publication number Priority date Publication date Assignee Title
US6909770B2 (en) 2001-12-05 2005-06-21 The United States Of America As Represented By The United States National Aeronautics And Space Administration Methods for identification and verification using vacuum XRF system
US6850592B2 (en) 2002-04-12 2005-02-01 Keymaster Technologies, Inc. Methods for identification and verification using digital equivalent data system
US10866194B2 (en) 2011-05-26 2020-12-15 Altria Client Services Llc Oil soluble taggants
US10209201B2 (en) 2011-05-26 2019-02-19 Altria Client Services Llc Oil detection process and apparatus
US11555790B2 (en) 2011-05-26 2023-01-17 Altria Client Services Llc Oil soluble taggants
US9244017B2 (en) 2011-05-26 2016-01-26 Altria Client Services Llc Oil detection process and apparatus
US9080987B2 (en) 2011-05-26 2015-07-14 Altria Client Services, Inc. Oil soluble taggants
US9546966B2 (en) 2011-05-26 2017-01-17 Altria Client Serices Llc Oil detection process, apparatus and taggant therefor
US9733197B2 (en) 2011-05-26 2017-08-15 Altria Client Services Llc Oil detection process and apparatus
US10330607B2 (en) 2011-05-26 2019-06-25 Altria Client Services Llc Oil detection process and apparatus
US10900897B2 (en) 2012-05-29 2021-01-26 Altria Client Services Llc Oil detection process
US9488580B2 (en) 2013-03-15 2016-11-08 Altria Client Services Llc Menthol detection on tobacco
US10082467B2 (en) 2013-03-15 2018-09-25 Altria Client Services Llc Menthol detection on tobacco
US10724955B2 (en) 2013-03-15 2020-07-28 Altria Client Services Llc Menthol detection on tobacco
US9073091B2 (en) 2013-03-15 2015-07-07 Altria Client Services Inc. On-line oil and foreign matter detection system and method
US9381545B2 (en) 2013-03-15 2016-07-05 Altria Client Services Llc On-line oil and foreign matter detection system and method
US11340168B2 (en) 2013-03-15 2022-05-24 Altria Client Services Llc Menthol detection on tobacco
US9097668B2 (en) 2013-03-15 2015-08-04 Altria Client Services Inc. Menthol detection on tobacco
US10782279B2 (en) 2014-11-11 2020-09-22 Altria Client Services Llc Method for detecting oil on tobacco products and packaging
US11549932B2 (en) 2014-11-11 2023-01-10 Altria Client Services Llc Method for detecting oil on tobacco products and packaging

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AU2247001A (en) 2001-05-10
CA2386400A1 (fr) 2001-04-12
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NO20012656D0 (no) 2001-05-30
WO2001025747A3 (fr) 2001-10-25
MXPA02003424A (es) 2003-10-15
EP1218731A1 (fr) 2002-07-03
WO2001025820A2 (fr) 2001-04-12
JP2003511667A (ja) 2003-03-25
WO2001025765A1 (fr) 2001-04-12
WO2001025766A1 (fr) 2001-04-12
EP1257815A2 (fr) 2002-11-20
WO2001025768A1 (fr) 2001-04-12
NO20012656L (no) 2001-08-01
AU2572701A (en) 2001-05-10
AU2247101A (en) 2001-05-10
EP1137930A1 (fr) 2001-10-04
WO2001025747A2 (fr) 2001-04-12
EP1224459A2 (fr) 2002-07-24
SE0101893D0 (sv) 2001-05-30
WO2001025747A9 (fr) 2002-09-26
WO2001025748A3 (fr) 2001-10-18
AU2422901A (en) 2001-05-10
WO2001025821A3 (fr) 2001-06-07
AU2247201A (en) 2001-05-10
CA2386454A1 (fr) 2001-04-12
KR20010090856A (ko) 2001-10-19
CA2386391A1 (fr) 2001-04-12
ES2184652B1 (es) 2004-09-16
AU2572601A (en) 2001-05-10
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BR0007567A (pt) 2001-08-21
DE10083295T1 (de) 2002-02-14
DK200100797A (da) 2001-07-24
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WO2001025763A1 (fr) 2001-04-12
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SE0101893L (sv) 2001-07-31
WO2001025768A9 (fr) 2002-05-16
CA2386402A1 (fr) 2001-04-12
CA2352357A1 (fr) 2001-04-12
WO2001025764A9 (fr) 2002-09-26
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WO2001025764A1 (fr) 2001-04-12

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