EP1386144A1

EP1386144A1 - Methods for identification and verification

Info

Publication number: EP1386144A1
Application number: EP02723211A
Authority: EP
Inventors: Bruce J. Kaiser; Gerhard A. Meyer; Stephen L. Price; David J. Watson; Don Kenning; Robert D. Kuhlman; Dan Schoepflin; Robert Shannon
Original assignee: KeyMaster Technologies Inc
Current assignee: KeyMaster Technologies Inc
Priority date: 2001-01-16
Filing date: 2002-01-16
Publication date: 2004-02-04
Also published as: WO2002068945A1; EP1386144A4

Abstract

Apparatus and methods in which one or more taggants that are intrinsically located-or extrinsically placed-in an object (11), such as a personal identification device like a badge, a plastic material, or a secure document. The taggants are detected by x-ray fluorescence analysis (20, 21) to identify or verify the object or its point of manufacture. The taggants are manufactured as part of the article or the taggant is placed into a coating, label, or otherwise embedded within the object for the purpose of later verifying the presence or absence of these elements by x-ray fluorescence, thus determining the unique elemental composition of the taggant within the object.

Description

METHODS FOR IDENTIFICATION AND VERIFICATION

FIELD OF THE INVENTION

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, product, or object by using X-ray fluorescence to identify and verify that article, product, or object. Even more particularly, the present invention relates to: secure documents and methods and apparatus for making ands detecting the same; apparatus and methods for controlling the quality of a manufacturing process and the resulting product by using XRF analysis; secure personal identification devices and methods and apparatus for making and detecting the same.

BACKGROUND OF THE INVENTION

There has been significant interest in apparatus and methods for identifying and verifying various objects, articles, or products such as explosives, ammunition, paint, petroleum products, and documents. Known methods used to identify and verify generally involve adding and detecting materials like code-bearing microparticles, bulk chemical substances, and radioactive substances. Other methods used for identifying and verifying articles include those described in U.S. Patent Nos. 6,106,021, 6,082,775, 6,030,657, 6,024,200, 6,007,744, 6,005,915, 5,849,590,

5,760,394, 5,677,187, 5,474,937, 5,301,044, 5,208,630, 5,057,268, 4,862,143,

4,485,308, 4,445,225, 4,390,452, 4,363,965, 4,136,778, and 4,045,676, as well as

European Patent Application Nos. 0911626 and 0911627, the disclosures of which are incorporated herein by reference. It is also known to apply materials to articles in order to track, for example, point of origin, authenticity, and their distribution. In one method, inks that 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 that can be detected optically. However, detecting these materials is primarily based on optical or photometric measurements.

Unfortunately, many of the apparatus and methods for identifying objects 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 known apparatus and methods for identification and verification are also unsatisfactory because they require a "line-of-sight" analysis method. This line of sight requirement entails that the apparatus must be able to "see" the taggant in order to detect it. This can be detracting when it would be desirable to detect the taggant without having to see the taggant, e.g., such as when the taggant is located in the middle of large package with packaging and labels "covering" the taggant.

SUMMARY OF THE INVENTION

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 taggant is 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.

By using x-ray fluorescence analysis, 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 with. Further, it can be easily recognized by a user in either overt or covert form, easily verified by a manufacturer or issuer, and easily applied to various forms of media in the articles. BRIEF DESCRIPTION OF THE DRAWINGS Figures 1, 2a, 2b, 3, 4a, 4b, and 5-14 are views of apparatus and methods for providing x-rays according to the invention, in which: Figure 1 generally depicts the operation of XRF; Figure 2a and 2b illustrate the operation of XRF at the molecular level;

Figure 3 shows an exemplary x-ray spectrum, e.g., for paper; Figure 4a and 4b depict two aspects of the of the XRF apparatus of the invention;

Figure 5 illustrates exemplary energy levels of x-rays in an x-ray spectrum; Figure 6 shows another aspect of the XRF apparatus of the invention;

Figures 7 and 8 illustrate the XRF spectrum for two components used in a process for making a plastic material in one aspect of the invention;

Figure 9 illustrates the XRF spectrum of a high-quality plastic material in one aspect of the invention; Figures 10 and 11 illustrate the XRF spectrum of a low-quality plastic material in one aspect of the invention;

Figure 12 illustrates an XRF spectrum of a secure document in one aspect of the invention;

Figure 13 illustrates an exemplary personal identification device that has been made according to the invention; and

Figure 14 illustrates a comparative XRF spectrum for a "secure" badge and a "false" badge.

Figures 1, 2a, 2b, 3, 4a, 4b, and 5-14 presented in conjunction with this description are views of only particular — rather than complete — portions of apparatus and methods for providing x-rays according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

The following description provides specific details in order to provide a thorough understanding of the present invention. The skilled artisan would understand, however, that the present invention can be practiced without employing these specific details. Indeed, the present invention can be practiced by modifying the illustrated apparatus and method and can be used in conjunction with apparatus and techniques conventionally used in the industry.

For example, the invention is described with respect to paper documents printed from a computer, and methods and apparatus process for printing such documents. But a skilled artisan could easily adapt the invention for other paper documents and their associated processes and apparatus for printing, such as paper documents from a copiers, facsimiles, plotters, scanners, and any printing press. As another example, the invention is also described with respect to a manufacturing process for making plastic materials and the products produced from such processes. But a skilled artisan could easily adapt the present invention for other manufacturing processes and other products. As another example, the invention is described with respect to apparatus and methods for identifying and verifying personal identification devices. The invention described below, however, could be easily modified for any manufactured good and trade good. The present invention uses x-ray fluorescence analysis to detect at least one taggant intrinsically or extrinsically present in the material of a product or article. With x-ray fluorescence (XRF) analysis, x-rays produced from electron shifts in the inner shell(s) of atoms of the taggants and, therefore, are not affected by the form (chemical bonding) of the article being analyzed. 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. In Figure 1, primary gamma rays or x-rays 40 are irradiated on a sample of a target material 46 of article 42. Secondary x-rays 44 are emitted from that sample of target material 46.

In Figures 2a and 2b, atom 48 of a taggant located within target material 46 has nucleus 50 surrounded by electrons 52 at discrete distances from nucleus 50 (called electron shells). Each electron shell has a binding energy level equal to the amount of energy required to remove that electron from its corresponding shell. The innermost shell is the K shell, and has the highest binding energy level associated with it. 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 to be detected (the "target material"). When 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. When 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 some cases, into the ambient atmosphere (e.g, air). Further, different isotopes of an element, as well as elements which "excite" only under certain conditions 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. Preferably, any element above iron on the periodic element, yet within the above range, can be used as the at least one taggant in the present invention. More preferably, any transition elements between germanium and silver can be 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 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. In one aspect of the invention, 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. In many instances, 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. For example, if a film or coating (e.g., ink) containing a taggant is applied to a target material (e.g., paper), 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 (e.g., extensive contact with hands). Preferably, 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.

In another aspect of the invention, the type of taggant can be selected based on the ability of the taggant and/or the substance in which it is located, such as a coating, to be removed from the target material. In many instances, 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. For example, if an identifying film or coating containing a taggant is applied to a target material, once the target material has been identified, the identifying film of coating may no longer be needed and can be removed by suitable means. Preferably, 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. Indeed, 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.

In one aspect of the invention, 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 can be dispersed in ink that has been placed on paper that 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. Such 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. As one example of such a code, 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. For example, for tagging ten commercially prepared batches of carpeting, the taggant yttrium oxide can be used. 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.

The number of unique codes available with the use of just a single taggant depends on the precision with which that concentration can be controlled and measured in the sample. For example, if techniques allow concentrations in about 10 ppm increments, 10 unique codes (i.e., 10 ppm, 20 ppm, ... 100 ppm) can readily be constructed from a single taggant for that concentration range. 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. With the advent of superior concentration and detection techniques (e.g, for smaller increments), more codes may be constructed.

Further, 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. For example, 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. For example, 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.

When 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. For example, if a taggant comprising titanium oxide is located in carpet as the targeted material, it is possible that additional amounts of the taggant(s) could be present in the targeted 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. i such an instance, it is difficult to determine what amount of the taggant present in the targeted material is "contamination" as opposed to taggant present before contamination. This problem can be solved in target materials for which contamination might be suspected by using a backup (i.e., duplicate or otherwise) or secondary system, such as a backup or secondary taggant(s), backup or secondary code, or backup or secondary location. See, for example, the description in U.S. Patent No. 5,760,394, the disclosure of which is incorporated herein by reference. If desired, more than one such backup or secondary system can be used. The backup or secondary system can also be used for other purposes, e.g., to verify the original coding system.

Any suitable target material or target object 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 is 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.

Examples of suitable target objects include any manufactured goods or trade goods. Examples of manufactured goods include any of those goods listed in the 2000 and 3000 series of the SIC classification index. Examples of trade goods include any of those goods listed in the 5000 series of the SIC classification index. Manufactured goods include the following textile mill goods: cotton, manmade, and wool broadwoven fabric mills; narrow fabric mills; knitting mills like hosiery and women's hosiery, knit outerwear and underwear mills, weft-knit fabric mills, lace & warp knit fabric mills, and knitting mills; non-wool textile finishing like cotton and manmade finishing plants; carpets and rugs; yam and thread mills like yam spinning mills, thread mills, and throwing and winding mills; and miscellaneous textiles goods like coated fabrics (not rubberized), tire cord and fabrics, and non- woven fabrics, and cordage and twine.

Manufactured goods also include the following apparel and other textile goods: men's and boys' suits and coats; men's and boys' furnishings including shirts, underwear and nightwear, trousers and slacks, work clothing, and other clothing; women's and misses' outerwear like blouses, shirts, dresses, suits, and coats; woman's and children's undergarments like underwear, bras, girdles, and allied garments; hats and caps (and millinery); girls' and children's outerwear like dresses and blouses; fur goods; other miscellaneous apparel and accessories like fabric dress and work gloves, robes and dressing gowns, waterproof outerwear, leather and sheep- lined clothing, and belts; as well as other fabricated textile products like curtains, house furnishings, textile bags, canvas and related goods, pleating and stitching, automotive and apparel trimmings, and machine embroidery. Manufactured goods also include the following lumber and wood-based goods: logging goods; sawmills and planing mills including flooring mills and special product mills; millwork/plywood and structural members like millwork, wood kitchen cabinets, hardwood veneer and plywood, softwood veneer and plywood, and structural wood members; wood containers like nailed wood boxes and shook, as well as wood pallets and skids; wood buildings (includes those prefabricated) and mobile homes); and other wood products like wood preserving and reconstituted wood products.

Manufactured goods also include the following furnitures and fixtures: household furniture like wood furniture, upholstered furniture, metal furniture, mattresses and bedsprings, wood televisions, and wood radio cabinets; office furniture like wood furniture, upholstered furniture, and metal furniture; public building & related furniture; partitions and fixtures including wood partitions and fixtures, non- wood partitions and fixtures, and drapery hardware and blinds and shades.

Manufactured goods also include the following paper and allied products: pulp mills; paper mills; paperboard mills; paper board container and boxes including setup paperboard boxes, corrugated and solid fiber boxes, fiber cans and drums (and similar products), sanitary food containers, and folding paperboard boxes; converted paper products like coated or laminated paper (including packaging), plastic, laminated or coated bags, uncoated paper (and multiwall) bags, die-cut paper and board, sanitary paper products, envelopes, and stationary products. Manufactured goods also include the following printing and publishing goods: newspapers; periodicals; books (both publishing and printing); miscellaneous publishing; commercial printing including lithographic printing and gravure printing; manifold business forms; greeting cards; blankbooks and bookbinding like blankbooks, looseleaf binders, and bookbinding and related work; and printing trade services including typesetting and platemaking goods.

Manufactured goods also include the following chemicals and allied products: industrial inorganic chemicals including alkalies and chlorine, industrial gases, inorganic pigments, and industrial inorganic chemicals; plastic materials and synthetics including plastics materials and resins, synthetic rubber, cellulosic manmade fibers, and non- cellulosic organic fibers; drugs and pharmaceuticals including medicinals and botanicals, pharmaceutical preparations, diagnostic substances, and non-diagnostic biological products; soaps, cleaners and toilet goods like soaps and other detergents, polishes and sanitation goods, surface-active agents, and toilet preparations; paints and allied products; industrial organic chemicals including gum and wood chemicals, and cyclic and crude and intermediates; agricultural chemicals including nitrogenous fertilizers, phosphatic fertilizers, and mixing fertilizers; and other chemical products including adhesives and sealants, explosives, inks, carbon blacks, and other chemical preparations.

Manufactured goods also include the following petroleum and coal products: petroleum refining goods; asphalt paving and roofing materials including asphalt paving mixtures and blocks and asphalt felts and coatings; as well as lubricating oils and greases.

Manufactured goods also include the following rubber and miscellaneous plastics products: tires and inner tubes; rubber and plastics footwear; hose and belting and gaskets and packing including rubber and plastic hoses and belting, as well as gaskets, packing and sealing devices; fabricated rubber products including mechanical rubber goods; and other plastics products including unsupported plastics film & sheets, unsupported plastics profile shapes, laminated plastics plate & sheet, plastic pipes, plastic bottles, plastic foam products, custom compound purchased resins, and plastics plumbing fixtures.

Manufactured goods also include the following leather and leather products: leather tanning and finishing goods; footwear cut stock; non-rubber footwear including house slippers, non-athletic men's footwear, and non-athletic women's footwear; leather gloves and mittens; luggage; handbags and personal leather goods including women's handbags and purses; and other leather goods.

Manufactured goods also include the following stone, clay, and glass goods: flat glass; pressed or blown glass and glassware including glass containers; purchased glass products including hydraulic cement; structural clay products including brick and structural clay tile, ceramic wall and floor tile, and clay refractories; pottery and related products including vitreous plumbing fixtures, vitreous china table and kitchenware, semi-vitreous table & kitchenware, and porcelain electrical supplies; concrete, gypsum and plaster products including concrete block and brick, ready- mixed concrete, lime, other concrete products, and gypsum products; cut stone and stone products; and other nonmetallic mineral products including abrasive products, asbestos products, minerals, ground or treated goods, mineral wool, nonclay refractories, and other nonmetallic mineral products.

Manufactured goods also include the following primary metal industrial goods: blast furnace and basic steel products including blast furnaces and steel mills, electrometallurgical products, steel wire and related products, cold finishing of steel shapes, and steel pipe and tubes; iron and steel foundry goods including gray and ductile iron foundries, malleable iron foundries, and steel investment foundries; primary nonferrous metals including primary copper and primary aluminum; secondary nonferrous metals; nonferrous rolling and drawing goods including copper rolling and drawing, aluminum sheet, plate, and foil goods, aluminum extruded products, other aluminum rolling and drawing goods, nonferrous rolling and drawing goods, and nonferrous wiredrawing & insulating; nonferrous foundries including aluminum die-castings, nonferrous die-casting except aluminum, aluminum foundries, copper foundries, and other nonferrous foundries; and miscellaneous primary metal products including metal heat treating.

Manufactured goods also include the following fabricated metal products: metal cans and shipping containers including metal cans and metal barrels, drums, and pails; cutlery, handtools and hardware including cutlery, hand and edge tools, saw blades and handsaws, and other hardware; plumbing and heating goods including metal sanitary ware, plumbing fixture fittings and trim, and non-electric heating equipment; fabricated structural metal products including fabricated structural metal, metal doors, sash, and trim, fabricated plate work (boiler shops), sheet metalwork, architectural metal work, prefabricated metal buildings, and miscellaneous metal work; screw machine products including bolts, nuts, and washers; metal forgings and stampings including iron and steel forgings; nonferrous forgings; automotive stampings, crowns and closures, and other metal stampings; metal services including plating, polishing, and metal coating and allied services; ordnance and accessories including ammunition, small arms ammunition, and small arms; miscellaneous fabricated metal products including industrial valves, fluid power valves & hose fittings, non-wire steel springs, valves and pipe fittings, wire springs, miscellaneous fabricated wire products, metal foil and leaf, fabricated pipe and fittings, and other fabricated metal products.

Manufactured goods also include the following industrial machinery and equipment: engines and turbines including turbines and turbine generator sets, as well as internal combustion engines; farm and gardening machinery including farm machinery and equipment, as well as lawn and garden equipment; conduction and related machinery including construction machinery, mining machinery oil and gas field machinery, elevators and moving stairways, conveyors and conveying equipment, hoists, cranes and monorails, and industrial trucks and tractors; metal working machinery including metal-cutting machine tools, metal forming machine tools, industrial patterns, special dies, tools, jigs and fixtures, machine tools accessories, power-driven hand tools, rolling mill machinery, welding apparatus, and other metalworking machinery; special industry machinery including textile machinery, woodworking machinery, paper industries machinery, printing trades machinery, food products machinery, and other special industry machinery; general industrial machinery including pumps and pumping equipment, ball and roller bearings, air and gas compressors, blowers and fans, packaging machinery, speed changers, drives, and gears, industrial furnaces and ovens, other power transmission equipment, and other general industrial machinery; computer and office equipment including electronic computers, computer storage devices, computer terminals, computer peripheral equipment, calculating and accounting equipment, and other office machines; refrigeration and service machinery including automatic vending machines, commercial laundry equipment, refrigeration and heating equipment, measuring and dispensing pumps, and other service industry machinery; industrial machinery including carburetors, pistons, rings, and valves, fluid power cylinders and actuators, fluid power pumps and motors, non-laboratory scales, and other industrial machinery. Manufactured goods also include the following electronic and electric equipment: electric distribution equipment like non-electronic transformers and switchgear and switchboard apparatus; electrical industrial apparatus including motors and generators, carbon and graphite products, relays and industrial controls, and other electrical industrial apparatus; household appliances including cooking equipment, refrigerators and freezers, laundry equipment, electric housewares and fans, vacuum cleaners, and other household appliances; electric lighting and wiring equipment including electric lamps, current-carrying (and non current-carrying) wiring devices, residential lighting fixtures, commercial lighting fixtures, vehicular lighting equipment, and other lighting equipment; household audio and video equipment including pre-recorded records and tapes; communications equipment including telephone and telegraph apparatus, radio and telephone communications equipment, and other communications equipment; electronic components and accessories including electron tubes, printed circuit boards, semiconductors and related devices, electronic capacitors, electronic resistors, electronic coils and transformers, electronic controllers, and other electronic components; and miscellaneous electrical equipment and supplies including storage batteries, dry and wet primary batteries, engine electrical equipment, magnetic and optical recording media, and other electrical equipment and supplies.

Manufactured goods also include the following transportation equipment: motor vehicles and equipment including motor vehicles and car bodies, truck and bus bodies, motor vehicle parts and accessories, truck trailers, and motor homes; aircraft and parts including aircrafts, aircraft engines and engine parts, and aircraft parts and equipment; ship and boat building and repairing; railroad equipment; motorcycles, bicycles, and parts; guided missiles, space vehicles and parts including guided missiles and space vehicles, space propulsion units and parts, and other space vehicle equipment; miscellaneous transportation equipment including travel trailers and campers, tanks and tank components, and other transportation equipment.

Manufactured goods also include the following instruments and related products: search and navigation equipment, measuring and controlling devices including laboratory apparatus and furniture, environmental controls, process control instruments, fluid meters and counting devices, electricity-measuring instruments, analytical instruments, optical instruments and lenses, and other measuring and controlling devices; medical instruments and supplies including surgical and medical instruments, surgical appliances and supplies, dental equipment and supplies, x-ray apparatus and tubes, and electromedical equipment; ophthalmic goods; photographic equipment and supplies; watches, clocks, watchcases and parts.

Manufactured goods also include the following miscellaneous manufacturing goods: jewelry, silverware and plate ware including precious metal jewelry, silverware and plated ware, and jewelers' materials and lapidary work; musical instruments; toys and sporting goods including dolls and stuffed toys, games, toys and children's vehicles, and sporting and athletic goods; pens, pencils, office and art supplies including pens and mechanical pencils, lead pencils and art goods, marking devices, and carbon paper and inked ribbons; costume jewelry and notions including costume jewelry and fasteners, buttons, needles and pins; and miscellaneous manufactured goods including brooms and brushes, signs and advertising specialties, burial caskets, hard surface floor coverings, and other manufactured goods. Trade goods include both durable goods and nondurable goods. Durable goods include the following motor vehicles, parts, and supplies including automobiles and other motor vehicles, motor vehicle supplies and new part, tires and tubes, and used motor vehicle parts; furniture and homefurnishings; lumber and construction materials including lumber, plywood and millwork, brick, stone and related materials, roofing, siding and insulation, and other construction materials; professional and commercial equipment including photographic equipment and supplies, office equipment, computers, peripheral and software, other commercial equipment, medical and hospital equipment, ophthalmic goods, and other professional equipment; non- petroleum metals and minerals including metals service centers and offices, as well as coals and other minerals and ores; electrical goods including electrical apparatus and equipment, electrical appliances, television and radios, and electronic parts and equipment; hardware, plumbing and heating equipment including hardware, plumbing and hydronic heating supplies, warm air heating and air-conditioning, and refrigeration equipment and supplies; machinery, equipment and supplies including constmction and mining machinery, farm and garden machinery, industrial machinery and equipment, industrial supplies, service establishment equipment, and transportation equipment and supplies.

Durable goods include the following miscellaneous durable goods: sporting and recreational goods, toys and hobby goods and supplies, scrap and waste materials, jewelry and precious stones, and other durable goods.

Non- durable goods include the following goods: paper and paper products including printing and writing paper, stationary and office supplies, and industrial and personal service paper; drugs, proprietaries and sundries; apparel, piece goods and notions including men's and boy's clothing, women's and children's clothing, and footwear; groceries and related products including general groceries, packaged frozen foods, non-dried or non-canned dairy products, poultry and poultry products, confectionaries, fish and seafood, meats and meat products, fresh fruits and vegetables, and other groceries and related products; farm-product war materials including grain and field beans and livestock; chemicals and allied products including plastic materials and basic shapes and chemical and allied products; petroleum and petroleum products including petroleum bulk stations and terminals, as well as petroleum products; beer wine and distilled beverages including beer and ale, as well as wine and distilled beverages; and miscellaneous nondurable goods including farm supplies, books, periodicals and newspapers, flowers and florist supplies, tobacco and tobacco products, paints, varnishes and supplies, and other nondurable goods. Other examples of suitable target materials or objects 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. Additionally, suitable target materials — such as paper documents, drugs, or counterfeit manufactured items — include those that will be subsequently changed. For example, 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. In one aspect of the invention, the target material of the invention is printed paper documents. In another aspect of the invention, the target material of the invention is plastics and plastic materials. In yet another aspect of the invention, the target material or object of the invention is personal identification devices, such as badges, passports, visas, drivers licenses, and swipe tags.

The target materials containing the at least one taggant can be used for a wide number of applications. For example, tagging paints would allow any article coated with that paint to be identified. In another example, tagging paper and ink used in the paper (or applied to the paper) can be used to establish the authenticity of documents and currency. In yet another example, 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 discs, 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. In the present invention, 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. In any of these forms, 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. Additionally, 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. Indeed, such particles could be made of non-durable, soluble, or reactive materials to enhance taggant dispersal in a fluid, aerosol, or powder system.

When the target material is a liquid article like paints or inks, or adhesives, or has a liquid component, the at least one taggant can be incorporated as an element or compound in solution with the liquid. Thus, 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. During manufacture, the at least one taggant can also be incorporated into another material which comprises part of the target material. Indeed, the at least one taggant could also be an element or compound of the target material 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 at least one taggant could be incorporated into the already formed target material as a dopant. Additionally, the taggant can be implanted into the article or deposited as a coating or film on the article. As a coating or film, 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. In this aspect of the invention, 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, to the article. For example, 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.

As apparent from the description above, 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 that could be tagged.

In one aspect of the invention, the target object could be a personal identification device such as those described above. Personal identification devices that can be used in the invention include any of those known in the art that operate to identify the owner or carrier of the device, such as badges, documents, visas, licenses, and passports. To describe the invention, the following description focuses on paper badges, but the invention could be easily adapted for other personal identification devices as well as non-paper badges. In one aspect of the invention, the badge can be made or purchased and then at least one taggant is incorporated in or on the badge. In this aspect of the invention, for examples, an existing badge for an individual could be obtained and then laminated with a taggant in the lamination, or alternatively the taggant could be implanted or diffused into the badge or lamination. In another aspect of the invention, the personal identification device can be made with the processes described herein to include the taggant during the manufacturing process. In this aspect of the invention, for example, the paper of the badge could be manufactured with the taggant incorporated in the fibers of the paper or alternatively the taggant could be present in the ink used in printing the badge. The taggant could be incorporated into any of the components from which badges are made, e.g., the paper, the ink, the lamination (or other coating). 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 be incorporated into the paper before the badges are made. For example, the 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. This is accomplished by spraying a sizing liquid on the paper sheet, compressing it, and drying it. As the sizing liquid penetrates the fibers of the paper, the components of the sizing liquid (i.e., starch) interweaves with the fibers in a permanent bond. Adding the taggant to the sizing liquid could ensure that the taggant permanently bonds to the paper. In another example, after the paper sheet has been made, it is cut to the desired size. The taggant could also be added during this cutting operation.

The taggant could be incorporated into the ink or other writing of the badge. After the paper sheet or tickets are made, the ink (or other writing) is respectively deposited on the paper sheet(s). The 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 badge. Often, a coating or film is placed on the badge for many reasons. In this aspect of the invention, the at least one taggant can be first dispersed in a solution containing a suitable solvent. This solution is then placed on the badge 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 badge using any suitable chemical deposition method, such as by spraying or by dipping. One of the most common coating or films that is applied to badges is laminations. These laminations serve to protect the badge and extend the life of the badge. The laminations are often made from a plastic material in sheets. The sheets are cut to size for the badge, a single sheet is layed over and another under the badge and then heated so the two sheets encapsulate the badge, and then (if necessary) the final lamination is trimmed or cut. The taggant could be incorporated into the lamination before, during, or after this process of making the sheets and applying them to the badge.

In a preferred aspect of the invention, the badge is made with more than a single taggant. Even more preferably, the badge is made with the taggants located in separate parts or components of the badge. For example, one taggant (or set of taggants) could be located in the paper (or other substrate used) of the badge, another taggant (or set of taggants) could be located in the ink, another taggant (or set of taggants) could be located in the lamination or plastic sleeve, another taggant (or set of taggants) could be located in an attachment to the badge, another taggant (or set of taggants) could be located in the photograph or a similar identifying mark of the badge (including a finger print). By placing a taggant(s) in more than one location, the identification of the badge can be custom-fit. As well, by requiring several taggants in different locations of the badge, it is virtually impossible to duplicate or change any part of the badge without detection. As well, by using a central database with "codes" for all badges for a particular entity or organization, the badge can be quickly and securely verified as described in detail below.

In another aspect of the invention, the quality of a product (or a process for manufacturing that product) can be controlled by detecting or analyzing the at least one taggant in a target material — or a component thereof — during its manufacture. The quality of the product (and accompanying manufacturing process) can be controlled by detecting and analyzing the presence, concentration, and location of the taggant at any point in the manufacturing process. For example, the at least one taggant can be either a component of any raw material used to make the product or can be added to the raw material to "track" the presence of the raw material. In one aspect of the present invention, the presence, concentration, and location of those materials comprising plastics can be detected and analyzed during its manufacture. Plastics include any of various organic compounds produced by polymerization that can be molded, extruded, cast into various shapes or films, or drawn into filaments. Plastics encompass a variety of natural and synthetic organic materials that are based on polymers.

Plastics are generally produced in the following manner. First, hydrocarbon materials are heated in a "cracking" process, converting the hydrocarbons into monomers such as ethylene, propylene, butene, and styrene. These monomers are then chemically bonded into chains called polymers. The polymers can then be formed, usually by molding, to produce different kinds of plastic products with a wide variety of applications.

Optionally, the plastic is subjected to further treatment and inclusion of additives that are selected to yield specific properties, such as altering or improving their mechanical, physical, or chemical characteristics. For example, additives can be incorporated to protect from the degrading effects of light, heat, or bacteria; to change the polymer properties (such as flow); to provide color; or to provide special characteristics such as improved surface appearance or reduced friction. Examples of types of additives include antioxidants, colorants, foaming agents, and plasticizers.

While other processes are known, there are at least four different methods used to convert (or form) the polymers into finished products: extrusion; injection molding; blow molding; and rotational molding. In extrusion, plastic material is first loaded into a hopper and then fed into a long heated chamber through which it is moved by the action of a continuously revolving screw. At the end of the heated chamber, the molten plastic is forced out through a small opening called a die that is cast in the shape of the finished product. As the plastic extrusion comes from the die, it is fed onto a conveyor belt where it is cooled.

Blow molding is a process used in conjunction with extrusion. The die forms a molten tube of material. Using compressed air, the tube is then blown to conform tot he interior of a chilled mold which clamps around the tube.

In injection molding, plastic material is also put into a hopper, which feeds into a heating chamber. A plunger pushes the plastic through the heating chamber where the material is then softened into a fluid state. At the end of the chamber, the resin is forced into a closed mold. Once the plastic cools to a solid state, the mold opens and the finished product is ejected.

Rotational molding uses heat to melt and fuse the polymer inside a closed mold without using pressure. Rotational molding contains a mold mounted on a machine capable of rotating on two axes simultaneously. The solid or liquid polymer is then placed within the mold and heat is then applied. Rotation distributes the plastic into a uniform shape on the inside of the mold until it cools and sets.

The at least one taggant of the present invention, therefore, could be present in the hydrocarbons, the monomers, the polymers, and/or the additives. For example, the at least one taggant could be present in the hydrocarbon materials before the cracking process. In another example, the at least one taggant could be incorporated into the process of making the monomers from the hydrocarbons. In yet another example, the at least one taggant could be incorporated into the process of making the polymers from the monomers. In still another example, the at least one taggant could be incorporated into the process of making the final product from the polymers. In even another example, the at least one taggant could be added as an additive or incorporated into an additive that is used to make the plastic product. In another example, a taggant could be incorporated into all the various stages above, yielding a plurality of taggants. The at least one taggant could be detected and analyzed at any point during the manufacturing process of the plastic. For example, the at least one taggant could be detected during the cracking process. In another example, the at least one taggant could be detected during the process of making the monomers from the hydrocarbons. In yet another example, the at least one taggant could be detected during the process of making the polymers from the monomers. In still another example, the at least one taggant could be detected during the process of making the final product from the polymers. As well, the at least one taggant could be detected at any time after the plastic product is made.

Based on the detection and analysis of the taggant, the manufacturing process for making the plastic product could be modified as desired. For example, where the taggant is a component of a first polymer of several polymers used to make the plastic during an extrusion process, the detection and subsequent analysis could provide important information about the concentration of the first polymer. If the concentration of the first polymer in the process for making the plastic product was too high, the process could be modified to decrease the concentration of that polymer. A similar analysis and modification could occur when the taggant has been added to the first polymer for the purpose of measuring the concentration.

Indeed, multiple taggants could be used with each taggant being associated with a different component (i.e., polymer) in the product or process. For example, a first taggant could be added to (or present in) a first polymer, a second taggant could be added to (or present in) a second polymer, and a third taggant could be added to an additive. By using different taggants for different components of the product (or different parts of the manufacturing process), one is better able to monitor and control that part of the product (or process) where the quality is deficient. As an example, a protective coating (such as a shrink-wrap) is often applied to plastics after they have been manufactured. The shrink-wrap forms a coating on the plastic which, among other functions, covers and protects the plastic material. It is important for consumers to have a high quality coating so the protective functions can be maximized. Thus, it important for manufacturers to know as much as possible about the quality of the shrink-wrap. To that end, at least one taggant can be incorporated into the shrink-wrap to help control the quality of the process used in wrapping the shrink-wrap on the plastic material. Using the taggant, a manufacturer can detect the taggant before, during, or after applying the shrink-wrap to assess the quality of how it is applied and the quality of the resulting coating.

In another example, a plastic product could be made by extrusion molding a polymer mixture of a first polymer and a second polymer, along with at least one additive. The first and second polymers could be selected from any of the numerous polymers known in the art that can be extrusion molded. For example, typical materials that may be extruded include high temperature thermoplastics such as acrylonitrile-butadiene-styrene (ABS), polycarbonate, polycarbonate/ ABS blend, a co- polycarbonate-polyester, acrylic-styrene-acrylonitrile (ASA), acrylonitrile-(ethylene- propylene diamine modified) -styrene (AES), polyalkylene terephthalate such as polybutylene terephthalate (PBT) or polyethylene terephthalate (PET) or blends thereof, blends of polyphenylene ether/polyamide (NORYL GTX Registered TM from General Electric Company), blends of polycarbonate/polybutylene terephthalate and impact modifier (XENOY Registered TM resin from General Electric Company), blends of polycarbonate/PBT/ PET, etc., or blends thereof. The at least one additive includes fillers, impact modifiers, pigments, stabilizer, reinforcing agents, etc.

Prior to and during the extrusion molding process, the first polymer (such as polyphenylene ether) could contain a first taggant (such as yttrium or an yttrium compound), the second polymer (such as polybutylene terephthalate) could contain a second taggant (such as lanthanum or a lanthanum compound), and the additive (such as pigment) could contain a third taggant (such as iodine). During the extrusion process, the relative concentrations of the first and second polymer and the additive should be held within a tightly controlled range to obtain the desired plastic product. To obtain the desired ranges, the taggants could be monitored and used to report the relative concentration of each component. If any given component is not within the desired range, the extrusion process could be modified to increase the amount of that component and, therefore, its relative concentration.

As another example of the above concepts, a taggant could be added to a hydrocarbon by injecting a solid (i.e., microparticle) or liquid (e.g., solvent) containing the at least one taggant into the bulk material of the hydrocarbon. Alternatively, the hydrocarbon could be selected to already contain the taggant. The tagged hydrocarbon could then be incorporated in an already existing process for making a plastic product, such as the process using a first and second polymer and an additive as described immediately above. The hydrocarbon could then be converted to a monomer and subsequently to the first polymer under specified conditions. At each stage, the taggant could be detected and analyzed and then used to report on a desired chemical or physical parameter of the conversion process. In addition, numerous locations along the length and width of the final plastic product could be selected for XRF detection and analysis. The difference in taggant concentration over the locations could be measured to find the concentration and, therefore, consistency of the first polymer in the plastic product. If the desired consistency was not obtained, the process could be modified until the desired consistency is obtained.

The ability to monitor and assess the quality of a product and its accompanying manufacturing process using XRF detection of taggants becomes even more important with certain materials. Some materials are troublesome because they are "low z" materials, e.g., they have a low atomic number, which are difficult to detect via XRF. For that matter, many materials are troublesome because they are difficult to detect using an "online" method. By incorporating a taggant which is more easily detected — by having a high atomic number — with such low z materials, the quality of a product containing low z materials (and the accompanying manufacturing process) becomes possible and easier to control and monitor. As well, the quality of a product/materials becomes possible and easier to control and monitor using an online method.

The quality of a product and its accompanying manufacturing process can be controlled and monitored either through an off-line or an on-line process. In an off- line process, a sample of the desired product/material is removed from the desired location of the process and then subjected to XRF detection and analysis. In an on- line process, the sample of the desired product/material remains in the process and is subjected to XRF detection and analysis at the desired location. The on-line detection and analysis can be performed using a hand-held apparatus or an apparatus that is part of — or attached to — the equipment used in the manufacturing process. In yet another aspect of the invention, the present invention can be incorporated into a process for printing a document from a computer (i.e., digital printing), as well as the document printed by such a process. All printed output from a computer is technically digital. However, the term digital printing refers more to printing finished pages on the computer in contrast to using an offset printing press and commercial printer. Digital printing eliminates numerous mechanical steps present in the conventional printing process (such as newspaper and magazine presses), including making films, color proofs, manually stripping the pieces together, making plates and running the paper through the press four or five times.

For computers, a printer is an output device that accepts text and graphic output from the computer — whether stand-alone or part of a network of computers (like the Internet) — and transfers the information to paper, usually to standard size sheets of paper. Computer printers can generally be distinguished as impact or nonimpact printers. Impact printers operate similar an automatic typewriter, with a key or other apparatus striking an inked impression on paper for each printed character. With non-impact printers, the ink is applied to the paper without any such impact. Examples of impact printers include the dot-matrix (serial dot, line dot, and dot band), drum, character, serial, as well as band, chain and train printers.

Examples of non-impact printing include electrophotographic (laser and LED), electrosensitive, electrostatic, ink jet (including IRIS printers which can print on fabric), ionographic, magnetographic, direct thermal, thermal wax transfer, dye sublimation, solid ink, and electron beam imaging. Perhaps the best-known nonimpact printers are the inkjet printer, which sprays ink from an ink cartridge at very close range to the paper as it rolls by, and the laser printer, which uses a laser beam reflected from a mirror to attract ink (called toner) to selected paper areas as a sheet rolls over a drum. If desired, some of these printers can be made to print colors by using ink cartridges that contain colors. The taggant can be incorporated into the printed document in any suitable manner. In one aspect of the invention, the taggant is incorporated into the paper or document before the printing process by manufacturing the paper with the taggant or by incorporating the taggant (such as, by coating) after the paper is made. In another aspect of the invention, the taggant is incorporated into the ink in the printer. When the printer prints the document, the taggant is applied to the paper document along with the ink.

For example, when using a laser printer, the taggant can be incorporated into the ink cartridge either by manufacturing the cartridge with the taggant as a component of the ink or by later adding the taggant to the ink and then mixing until a homogenous mixture is obtained. In the latter instance, the taggant is preferably a powder that is of a finer consistency that the ink powder. When the laser printer prints the document, the ink (along with the taggant) is applied to the paper, thereby creating the paper document with a taggant contained in the ink. This aspect of the invention could be applied to printers other than just the laser printer in a similar manner, e.g., by incorporating the taggant into the ink source (such as a ribbon). For example, with ink-jet printers, the taggant could be incorporated into the ink by bonding the taggant to the ink. This bonding would be required because of the differences between the inks used in laser printers and the inks used in ink-jet printers. In a similar manner, this aspect of the invention could be used in color printers by incorporated the taggant with the color ink.

The resulting printed document would contain the taggant in the ink which has been applied to the paper. In one aspect of the invention, a single taggant could be present in the ink that has been printed on the paper. In another aspect of the invention, a plurality of taggants could be present in the printed ink by incorporating a plurality of taggants in a single ink source (i.e., cartridge) or by incorporating taggant(s) in a plurality of different ink cartridges.

In one aspect of the invention, a single taggant is present in a consistent concentration in all of the ink. In another aspect, however, the taggant concentration could be varied by using different cartridges with different taggant concentrations and varying the respective amounts of taggant-containing ink while printing. For example, a first ink cartridge (or first portion of a cartridge) could contain a first taggant concentration (ranging from 0% to 100%) and a second cartridge (or second portions of a cartridge) could contain a second taggant concentration (ranging from 100% to 0%). When printing, the taggant concentration in the printed ink could be changed by modifying the respective amount(s) of ink being printed from the first and second cartridges (or portions).

In another aspect of the invention, the taggant can be incorporated into color printing. In a color printing apparatus, a plurality of primary colors (i.e., yellow, cyan, and magenta) are superimposed to produce a desired color, thus providing for a variety of colored images. These colors are produced using various inorganic pigments that are mixed with the ink powder. Black ink has often been used with the above three colors to produce images with enhanced properties, such as additional brightness, as well as to print particularly solid black portions in images. The different colors of ink can come from different cartridges of from different portions (or reservoirs) within the same cartridge. Different taggants could be incorporated into the different colors to produce a printed, color ink containing the taggant(s) in the desired concentration(s).

The present invention could be used for any document containing ink and method for making the same. For example, the present invention could be used for any apparatus which produces a printed document by applying ink from a source (or reservoir) to paper. In particular, the present invention could be used in facsimile apparatus, as well as copiers.

The present invention could also used for documents other than just conventional paper. For example, the present invention could be used to make tickets or any other document that can be printed using the apparatus mentioned above.

Once the paper or document has been printed with the ink containing the taggant(s), the presence, concentration, and location of the taggant(s) can be detected and analyzed for the various purposes mentioned above. For example, the taggant in the printed ink of the document could be detected and analyzed to determine the authenticity of the document. After the at least one taggant is extrinsically or intrinsically present in the target material(s), 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.

As shown in Figure 3, 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 (known as the peak-to-background ratio) is a measure of the concentration of the element which has characteristic X-rays at the energy of that peak, e.g., the taggant.

In one aspect of the detection method of the present invention, 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. One aspect of the detection device of the present invention is illustrated in

Figure 4a. In this Figure, the detection apparatus 25 has an ordinary x-ray fluorescence spectrometer capable of detecting elements present in a coating, package or 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. 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.

Another aspect of the detection apparatus of the present invention is illustrated in Figure 4b. In this Figure, 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. Optionally, analyzing means can be incorporated within housing 15. The present invention, however, 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. 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. During the XRF detection process, 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. Typically, these have been x-ray emitting devices such as x-ray tubes or radioactive sources.

To target, 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. Thus, 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. Preferably, 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. Several aspects of the detector should be controlled to obtain the desired XRF detection. First, 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. Thus, 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 irradiated. Thus, any support means performing this function could be used in the present invention. In one example, 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. In another example, 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. In this calibration, the various parameters that could be modified and effect the measurement are isolated and calibrated. For example, the geometrical conditions or arrangements can be isolated and calibrated. In another example, the material matrix are isolated and calibrated. Preferably, 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 reaching the detector of the system create an unwanted background intensity level. Accordingly, 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.

Besides the parameters described above, at least two other parameters must be controlled during the process of XRF detection. First, the media (such as air) through which 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. Second, 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. These two parameters, plus those described above, must be carefully accounted for and controlled to obtain accurate measurements. In one aspect of the intention, these parameters could be varied and controlled to another provide a distinct code. For example, using a specific source and a specific detector with a specific measuring geometry and a specific algorithm could provide one distinct code. Changing the source, detector, geometry, or algorithm could provide a whole new set of distinct codes.

Figure 6 illustrates a preferred apparatus and detection method according to the present invention. In this Figure, detection apparatus 25 is capable of detecting at least one taggant present in target material 10, such as a document. 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.

In one aspect of the invention, 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 through 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. In another aspect of the invention, 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. Thus, 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 invention.

Example 1

A two-component epoxy compound comprising a resin and a hardener was obtained. XRF spectra were take of the resin and hardener and showed no constituents sensitive to the XRF analyzer. This was expected since epoxy is a plastic and contains only light (low Z) elements which are not sensitive to the XRF instrument.

The resin was tagged with a small quantity of Nal and the hardener was tagged with a small quantity of ZrO₂ powder. XRF Spectra were then taken of the tagged material in several configurations. A portable, hand-held detection apparatus similar to that illustrated in Figure 6 was used to detect the presence of the taggant(s) using XRF analysis.

The detection apparatus contained several components. A trigger actuated tungsten shutter block containing an Iron 55 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 sample was tagged or not and a read out to inform the user that the sample was tagged. 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.

The spectra for the tagged resin is depicted in Figure 7, with prominent peaks for IK. The spectra for the tagged hardener is depicted in Figure 8, with prominent peaks for ZrK. The tagged resin and the tagged hardener were then mixed together in the recommended ratio of 1 : 1. The epoxy formed a hard plastic within a few minutes, as expected. The spectra for the epoxy is depicted in Figure 9.

The tagged resin and the tagged hardener were then mixed together in a ratio of 1 :3.5. The epoxy did not harden. The spectra for the resulting un-hardened epoxy is depicted in Figure 10. There was a large shift in relative peak heights when compared to the 1 :1 epoxy mixture depicted in Figure 9.

The tagged resin and the tagged hardener were then mixed together in a ratio of 3.5:1. The epoxy did not harden. The spectra for the resulting un-hardened epoxy is depicted in Figure 11. Again, there was a large shift in relative peak heights when compared to the 1 :1 epoxy mixture depicted in Figure 9. Example 2

A conventional computer system containing a laser printer was obtained. A document was then prepared and printed using the computer system and the laser printer. A table-top detection apparatus, similar to a flat bed scanner, to was used to analyze the document using XRF analysis. The XRF spectra showed no constituents sensitive to the XRF analyzer. This was expected since paper contains only light (low Z) elements which are not sensitive to the XRF detection apparatus.

The toner cartridge was then removed from the laser printer and opened. A teaspoon of ZrO₂ powder was added to the toner cartridge, which contained about two pounds toner. The ZrO₂ powder was finer (smaller in particle size) than the toner powder. The toner powder and ZrO powder were mixed until a homogenous mixture was obtained. The "tagged" cartridge was then closed and replaced in the laser printer.

The same document was then printed using the tagged cartridge to make a "tagged" document. The tagged document appeared substantially identical to the untagged document in terms of the visual and physical properties. The tagged document was then detected using the same detection apparatus. The spectra of the tagged document is illustrated in Figure 12, with a prominent peak present for the Zr taggant which was not present in the spectra for the un-tagged document.

EXAMPLE 3 Two badges were made by first obtaining a sample of photograph paper with an original picture (Fuji Film Pictro Paper). The paper sample was analysed and found to contain trace amounts of Titanium (Ti) and Bromine (Br).

Next, the location of the picture on the paper was tagged with Zinc (Zn) and Zirconium (Zr). First, a thin layer of powdered ZnO was applied at 0.6mg/ cm followed by a layer of powder ZrO₂ applied at 0.2mg/cm . A first badge was then laminated to keep the taggant from being rubbed off. Figure 13 illustrates a sample badge made by this process. The other badge (the second badge) was then falsified by placing a different picture over the original picture before laminating to demonstrate what would happen if a photo was placed over the original. Clearly if the original photo was removed, the tag would be removed with it. The first and second badges were then detected with a portable TRACeR™

XRF instrument. The source for the x-rays was an x-ray tube manufactured by PEC running at 30KeV and 12μA. The spectrum was collected with a pettier cooled silicon detector manufactured by Ampptek. Figure 14 illustrates the results of the XRF detection of the first and second badges. The relative signal from Ti and Br compared to the tag of Zn and Zr demonstrates that the second badge is a forgery. Specifically, the Br signal in the forgery is stronger than in the valid badge while the signal from the tag is partially blocked by the added photo. The AgL and NiKα peaks are from the instrument. The silicon detector is housed in a Ni casing, and the collimator/tube shielding is manufactured out of silver (Ag). Having described the preferred aspects of the present invention, it is understood that the invention defined by the appended claims is not to be limited by particular details set forth in the above description, as many apparent variations thereof are possible without departing from the spirit or scope thereof.

Claims

CLAIMSWe claim:

1. A method for detecting a taggant on an object, comprising: providing a taggant on at least a portion of an object; causing the taggant to radiate at least one x-ray; and analyzing whether the at least one x-ray has a specific energy.

2. The method of claim 1, wherein the object is a manufactured good or trade good.

3. A method of analyzing an object, comprising providing a portion of the object; irradiating that portion with an energy beam; and analyzing whether that portion irradiates an x-ray with a specific energy.

4. The method of claim 3, wherein the object is a manufactured good or trade good.

5. A method for coating an object with a taggant, comprising: providing a portion of an object; and providing a coating on the portion of the object, the coating comprising a taggant which radiates an x-ray when an energy beam is impinged thereon.

6. The method of claim 5, wherein the object is a manufactured good or trade good.

7. A coating for an object, the coating comprising a taggant which radiates an x-ray when an energy beam is impinged thereon.

8. The coating of claim 7, wherein the object is a manufactured good or trade good.

9. A method ofmanufacturing an object containing a taggant, comprising: providing a portion of the object; and providing a coating on the portion of the object, the coating comprising a taggant which radiates an x-ray when an energy beam is impinged thereon.

10. The method of claim 9, wherein the object is a manufactured good or trade good.

11. An object containing a taggant made by the method comprising: providing a portion of the object; and providing a coating on the portion of the obvject, the coating comprising a taggant which radiates an x-ray when an energy beam is impinged thereon.

12. The object of claim 16, wherein the object is a manufactured good or trade good.

13. An object comprising a coating containing a taggant, the taggant radiating an x-ray when an energy beam is impinged thereon.

14. The object of claim 13, wherein the object is a manufactured good or trade good.

15. The object of claim 14, wherein the object is a personal identification device.

16. The object of claim 15, wherein the personal identification device is a badge.

17. A method of tagging an object with a taggant comprising: providing a portion of the object; and providing a coating containing a taggant on that portion of the object, the taggant radiating an x-ray when an energy beam is impinged thereon.

18. The method of claim 17, wherein the object is a manufactured good or trade good.

19. A method for detecting a taggant in an object, comprising: providing a taggant in a portion of an object; causing the taggant to radiate at least one x-ray; and analyzing whether the at least one x-ray has a specific energy.

20. The method of claim 19, wherein the object is a manufactured good or trade good.

21. A method of tagging an object with a taggant comprising: providing a portion of an object; and providing a taggant in a portion of the object, the taggant radiating an x-ray when an energy beam is impinged thereon.

22. The method of claim 21, wherein the object is a manufactured good or trade good.

23. A method for detecting a taggant on an article, comprising: providing a taggant on at least a portion of an article; causing the taggant to radiate at least one x-ray; and analyzing whether the at least one x-ray has a specific energy.

24. The method of claim 23, wherein the article is a document.

25. A method of analyzing an article, comprising providing a portion of the article; irradiating that portion with an energy beam; and analyzing whether that portion irradiates at least one x-ray with a specific energy.

26 The method of claim 25, wherein the at least one article is a document.

27. A method for coating an article with at least taggant, comprising: providing a portion of an article; and providing a coating on the portion of the article, the coating comprising at least one taggant which radiates at least one x-ray when an energy beam is impinged thereon.

28. The method of claim 27, wherein the at least one article is a document.

29. A coating for an article, the coating comprising at least one taggant which radiates at least one x-ray when an energy beam is impinged thereon.

30. The coating of claim 29, wherein the at least one article is a document.

31. A taggant mixture, comprising: an ink; and a taggant, the taggant radiating at least one x-ray when an energy beam is impinged thereon.

32. The taggant mixture of claim 31, wherein the ink comprises colored ink.

33. A method of manufacturing an article containing a taggant, comprising: providing a portion of the article; and providing a coating on the portion of the article, the coating comprising a taggant which radiates at least one x-ray when an energy beam is impinged thereon.

34. The method of claim 33, wherein the article is a document.

35. An article containing a taggant made by the method comprising: providing a portion of the article; and providing a coating on the portion of the article, the coating comprising at least one taggant which radiates at least one x-ray when an energy beam is impinged thereon.

36. The article of claim 35, wherein the article is a document.

37. An article comprising a coating containing a taggant, the taggant radiating at least one x-ray when an energy beam is impinged thereon.

38. The article of claim 37, wherein the article is a document.

39. A method of tagging an article with a taggant comprising: providing a portion of the article; and providing a coating containing a taggant on that portion of the article, the taggant radiating at least one x-ray when an energy beam is impinged thereon.

40. The method of claim 39, wherein the article is a document.

41. A method for detecting a taggant in an article, comprising: providing a taggant in a portion of an article; causing the taggant to radiate at least one x-ray; and analyzing whether the at least one x-ray has a specific energy.

42. The method of claim 41, wherein the article is a document.

43. A method of tagging an article with a taggant comprising: providing a portion of an article; and providing a taggant in a portion of the article, the taggant radiating at least one x-ray when an energy beam is impinged thereon.

44. The method of claim 43, wherein the article is a document.

45. A method for making a document containing a taggant, comprising: providing paper comprising a taggant which radiates at least one x-ray when an energy beam is impinged thereon; and providing ink on the paper.

46. A method for making a document containing a taggant, comprising: providing paper; and providing ink on the paper, the ink comprising a taggant which radiates at least one x-ray when an energy beam is impinged thereon.

47. The method of claim 46, including providing the ink on the paper using a device which applies ink from a reservoir to the paper.

48. The method of claim 47, the reservoir of ink containing the taggant.

49. The method of claim 48, including obtaining a reservoir of ink without a taggant and subsequently adding the taggant thereto.

50. The method of claim 47, wherein the device is a laser printer or an ink- jet printer.

51. A document containing a taggant made by the method comprising: providing paper comprising a taggant which radiates at least one x-ray when an energy beam is impinged thereon; and providing ink on the paper.

52. A document containing a taggant made by the method comprising: providing paper; and providing ink on the paper, the ink comprising a taggant which radiates at least one x-ray when an energy beam is impinged thereon.

53. A document comprising a taggant which radiates at least one x-ray when an energy beam is impinged thereon.

54. A method for controlling the quality of a process, comprising: providing a process having at least one range of operation; incorporating a taggant into the process to trace the at least one range; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the process operates within the at least one range.

55. The method of claim 54, further including modifying the process if the process does not operate within the at least one range.

56. The method of claim 54, the process making a plastic material.

57. An article made by a method for controlling the quality of a process, comprising: providing a process having at least one range of operation; incorporating a taggant into the process to trace the at least one range; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the process operates within the at least one range.

58. A method for controlling the quality of an article, comprising: providing a process for making an article having at least one characteristic; incorporating a taggant into the process to trace the at least one characteristic; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the article exhibits the at least one characteristic.

59. The method of claim 58, further including modifying the process if the article does not exhibit the at least one characteristic.

60. The method of claim 58, the process making a plastic material.

61. An article made by the method for controlling the quality of an article, comprising: providing a process for making an article having at least one characteristic; incorporating a taggant into the process to trace the at least one characteristic; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the article exhibits the at least one characteristic.

62. A method for measuring the quality of a process, comprising: providing a process having at least one range of operation; incorporating a taggant into the process to trace the at least one range; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the process operates within the at least one range.

63. The method of claim 62, the process making a plastic material.

64. A method for measuring the quality of an article, comprising: providing a process for making an article having at least one characteristic; incorporating a taggant into the process to trace the at least one characteristic; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the article exhibits the at least one characteristic.

65. The method of claim 64, the process making a plastic material.

66. A method for monitoring the quality of a process, comprising: providing a process having at least one range of operation; incorporating a taggant into the process to trace the at least one range; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the process operates within the at least one range.

67. The method of claim 66, the process making a plastic material.

68. A method for monitoring the quality of an article, comprising: providing a process for making an article having at least one characteristic; incorporating a taggant into the process to trace the at least one characteristic; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the article exhibits the at least one characteristic.

69. The method of claim 68, the process making a plastic material.

70. A method for controlling the quality of a process, comprising: providing a process with a taggant to trace at least one range of operation; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the process operates within the at least one range.

71. The method of claim 70, further including modifying the process if the process does not operate within the at least one range.

72. An article made by a method for controlling the quality of a process, comprising: providing a process with a taggant to trace at least one range of operation; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the process operates within the at least one range.

73. A method for controlling the quality of an article, comprising: providing a process for making an article having at least one characteristic; the process having a taggant to trace the at least one characteristic; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the article exhibits the at least one characteristic.

74. The method of claim 73, further including modifying the process if the article does not exhibit the at least one characteristic.

75. An article made by the method for controlling the quality of an article, comprising: providing a process for making an article having at least one characteristic; the process having a taggant to trace the at least one characteristic; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the article exhibits the at least one characteristic.

76. A method for measuring the quality of a process, comprising: providing a process with a taggant to trace at least one range of operation; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the process operates within the at least one range.

77. A method for measuring the quality of an article, comprising: providing a process for making an article having at least one characteristic; the process having a taggant to trace the at least one characteristic; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the article exhibits the at least one characteristic.

78. A method for monitoring the quality of a process, comprising: providing a process with a taggant to trace at least one range of operation; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the process operates within the at least one range.

79. A method for monitoring the quality of an article, comprising: providing a process for making an article having at least one characteristic; the process having a taggant to trace the at least one characteristic; causing the taggant to radiate at least one x-ray and analyzing whether the at least one x-ray has a specific energy; and determining whether the article exhibits the at least one characteristic.