WO2023228190A1

WO2023228190A1 - Multi-signature xrf-responsive tag

Info

Publication number: WO2023228190A1
Application number: PCT/IL2023/050537
Authority: WO
Inventors: Haggai ALON; Zeren BROWNE; Nataly TAL; Tehila NACHUM; Ilan SCHAPIRO; Mor KAPLINSKY; Yekaterina ZELDICH; Bar PINCHAS; Hagit SADE
Original assignee: Security Matters Ltd.
Priority date: 2022-05-26
Filing date: 2023-05-24
Publication date: 2023-11-30

Abstract

The technology concerns an XRF tag comprising at least one XRF-readable material and uses thereof.

Description

MULTI-SIGNATURE XRF-RESPONSIVE TAG

TECHNOLOGICAL FIELD

The invention generally concerns tagging products and more specifically using XRF-responsive tag that can provide a vast variety of marker signatures.

GENERAL DESCRIPTION

The proliferation of counterfeit products has increased the need for a robust authentication method which can be implemented on-the-spot or during product manufacturing, in a variety of products, and in a way that does not cause harm to the product to be authenticated. Numerous methodologies exist that enable product authentication. Two of the modem tools of authentication make use of NFC tags and XRF labeling.

Near-Field Communication (NFC) tags are passive data stores that can be read and under some circumstances written to by an NFC device. Typically, NFC tag readers are enabled to read information stored on the NFC tags embedded in products of a variety of forms and for a variety of purposes. To enable an NFC device to work in NFC reader mode, requires cooperation with NFC-available application software.

X-ray fluorescent (XRF) marking has also been used to enable authentication of luxury products. In a typical method, an XRF marking material is applied to a surface region of the product or is embedded within the product itself to provide a latent signature unique to the product itself.

While both the NFC and XRF techniques in the art provide a suitable means for authentication, both techniques suffer from certain unresolved drawbacks. For example, while an XRF marking provides a robust signature that is typically latent and unaffected by the environment, the lifespan and performances of the NFC tag are significantly affected by the environment. Moreover, the conditions and environmental parameters associated with the manufacturing of a product and its lifetime cycle can be destructive to the NFC tag. While XRF marking provides superior marking and reading capabilities, not every product can or may be marked to embed therein a latent chemical marker.

XRF marking typically requires adaptation of the marking to the product onto which the marking is formed. Marker-product compatibility factors highly affect marker selection and marker adaptability to a particular product. While the choice of markers may be vast, the selected marker must not change a mechanical, chemical, optical, or a composition property of the product to an extent that the change will modify or damage the product in any way. Thus, marker selection may be limited and must be determined for every product and use. This means that each product or object to be XRF marked may have a narrow class of markers that would not impose such changes to the product.

To broaden the variety of XRF markers that may be used for every product or object, independent of the product or object’s mechanical, chemical, optical, compositional and other attributes. The inventors of the technology disclosed herein have developed a universal XRF tag that provides an unlimited number of XRF signatures. Each signature is unique and may be used with any product or object. The universal XRF tag of the invention is a reporter unit that is formed on a preselected surface or substrate that is not a surface region of the product or a surface embedded in the object to be marked. The preselected substrate or surface on which the tag is formed does not directly or indirectly induce mechanical, chemical, optical, compositional, or other changes to the product itself. The XRF tag is configured for attachment onto a target product or object or to an article that accommodates the product or object (such as a casing or a packaging unit) to be analyzed or evaluated. The tag may be configured to present a unique identification (ID) or signature that is used to uniquely pair the tag with the product or object. The ID of the reporter unit or tag is implemented by one or more XRF-identifiable materials that are deposited in a composition and/or amount and/or a sequence and/or a pattern that distinguishes one tag from another. Each unique tag may be associated with a different object or product by concealing the tag within the product in such a way that neither the process for producing the object or product nor the object or product lifespan causes deterioration of the tag or renders it inoperable.

Thus, in its broadest aspect the invention concerns an XRF-tag, wherein the tag comprises an invisible XRF marking of a unique characteristic X-ray or gamma-ray radiation response to a predetermined primary radiation and is configured to attach or be associated with a product or an object.

Further provided is a universal XRF tag, the tag comprising an invisible XRF marking formed of at least one XRF-identifiable material which selection is independent of a product or an object with which the tag is to be associated, wherein the marking having a unique characteristic X-ray or gamma-ray radiation response to a predetermined primary radiation.

The invention further provides a set of products each associated with a universal XRF tag comprising a substrate and an amount of an XRF-identifiable material, wherein the tag providing an X-ray or gamma-ray radiation response to a predetermined primary radiation, the response being indicative of the association of said product to the set of products.

The XRF tag is typically formed of a substrate material, typically a flexible material, such as polymeric, plastic, metalized plastic, or paper-based material. The substrate material is provided with one or more XRF marker materials. The substrate material is typically not a substrate of the product or object with which the tag is to be associated. However, the substrate material may be the same as the material from which the product or object is made. It is important to note that the XRF marker does not intend to identify the tag material itself. Rather the marker associated with the substrate material or tag is to identify or authenticate the product with which the tag is associated, independent of the material from which the tag itself is formed. For example, a transparent polymer substrate may be marked with a colored XRF marker or an XRF marker material that modifies its properties.

Each XRF marker material is provided in a predetermined amount and ratio (relative to another XRF marker material present) and is positioned on the substate material in a way which minimizes its loss or detachment from the substrate. In some embodiments, the substrate is provided with the one or more XRF marker materials is further provided with a protective coating, or is placed between sheets of a solid material protecting the marker materials from degrading or eliminated from the surface of the substate. The solid material may be a polymer laminate. In some configurations, the protective material is in the form of a polymeric pocket comprising the marker material(s).

In some embodiments, the substrate is in an internal region of a laminated surface, a polymeric pocket, or encased.

In some embodiments, the substrate provided with the XRF marker as a tag may be glued or associated to the product to be marked via an adhesive or mechanical association such as stitching. “Association” is defined as a tag in proximity to a product or object to understand that there is a relationship between the tag and the product or object. “Marking material” is defined as XRF-responsive material. “Marker” is used interchangeably with “Mark” that may be read with information concerning a product or object.

In some embodiments, the substrate material is a polymeric material. In some embodiments, the protective material is a polymeric material, which may be the same or different from the substrate material. The polymeric material may be a virgin material or a recyclable material. It may be selected amongst thermoplastic polymers, thermosetting polymers and elastomers. Non-limiting examples of polymeric materials which may be used for the substrate and/or for the protective coating, independently, include polyimides, polymethyl methacrylate (PMMA), polystyrene polyvinyl acetates, polyvinyl acetate copolymers, ethylene vinyl acetate (EVA) copolymers, polyvinyl alcohols, polyvinyl alcohol copolymers, celluloses (e.g., ethylcelluloses, methylcelluloses, hydroxymethylcelluloses, hydroxypropylcelluloses, and carboxymethylcelluloses), polyvinylpyrolidones, vinyl chloride, vinylidene chloride copolymers, acrylic copolymers, polyvinylacrylates, polyethylene oxide, acylamide polymers and copolymers, poly hydroxy ethyl acrylate, methylacrylamide monomers, poly chloroprene and others.

In some embodiments, the polymeric materials which may be used for the substrate and/or for the protective coating, independently, include polyethylene (PE), polypropylene (PP), the polystyrene (PS), polycarbonate (PC), polyethylene, polyesters and terephalate (PET), polyoxymethylene (POM), polyacetals or polyvinyl chloride (PVC), polyamide (PA) and polymethyl methacrylate (PMMA) or a combination thereof.

In some embodiments, the polymeric materials which may be used for the substrate and/or for the protective coating, independently, include polyamides, polycarbonates, polyolefins (e.g., polyethylene, polypropylene), acrylonitrile butadiene styrene (ABS) polymers, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyvinyl chloride (PVC).

In some embodiments, the polymeric materials used for the substrate and/or for the protective coating, independently, may include polyethylene terephtalate (PET), polytrimethylene terephtalate (PTT), polyethylene 2,5-furandicarboxylate (PEF), polytrimethylene 2,5-furandicarboxylate (PTF) or combinations thereof. The size and shape of the tag may vary and may depend on the product with which it is to be associated. In some embodiments, the tag may be of a size ranging from a few millimeters to a few centimeters. The tag may be of any shape.

Additionally, while the thickness of the tag may vary, it is typically desired to provide a tag that is configured to be sufficiently small and thin to be concealed within folding or crevasses or concealed pockets in the product. In some embodiments, the tag may be of a thickness that is between 0.1 and 3 mm.

In some embodiments, the associated tag is shaped and sized identically to a brand label designating a product or an object.

In some embodiments, the tag has a reporter unit with a shape and size that is configured to be concealed within a product in such a way that its presence in the product is not immediately evident, yet it can be read, as disclosed herein, from the surface of the product. The tag may be provided with adhesive surfaces to enable secured concealed attachment to the product.

In some embodiments, the tag is structured such that a XRF marker layer (e.g., formed by placing the XRF material on a substrate) is between a plastic laminate and a protective cover layer, wherein either the laminate or the cover or both are provided with an adhesive layer.

The invention further provides a process for manufacturing an XRF tag, the method comprising forming an XRF mark on a surface of a substrate and coating said substrate with a protective material to provide the tag.

In some embodiments, the substrate is of a predetermined size and shape. In some embodiments, the substrate is provided pre-shaped and pre-sized.

In some embodiments, the substrate is a material sheet and the XRF mark is formed on its surface.

In some embodiments, the process comprising forming a plurality of identical XRF marks on a surface of a substrate, coating said substrate with a protective material, cutting the substrate into a plurality of segments, wherein each segment comprises an XRF mark, such that each segment constitutes the tag.

In some embodiments, the protective material is a sheet of a solid material. The solid material may be a polymeric material. In some embodiments, the protective material is a laminating material sheet. In some embodiments, the protective material is coated on both faces of the substrate surface.

In some embodiments, the cut segment defining an XRF tag is of a size ranging from a few millimeters to a few centimeters.

In some embodiments, the tag is shaped and sized identically to a label designating a product or an object the tag is to be associated therewith.

In some embodiments, the protective material is a material sheet provided with an adhesive surface selected to adhere or associate to a surface region of the product or object.

In some embodiments, forming the XRF mark comprises deposition of one or more XRF identifiable material on the surface of the substrate. In some embodiments, deposition is by printing, liquid deposition, powder deposition, by dropping or by any other means.

XRF tags according to the invention may be associated or appended to any product or object which monitoring, authentication or evaluation is desired, wherein there is no requirement for compatibility between the tag’s XRF-identifiable marking material and the product or object.

The invention further provides a process comprising associating or appending an XRF tag according to the invention to an object or a product, thereby rendering said object or product XRF sensitive.

The invention further provides a method comprising applying a material deposition process to a substrate material and creating an XRF tag with at least one predetermined marking, said at least one predetermined marking being unique for a particular object or product, such that the tag with said at least one predetermined marking is characterized by a unique characteristic X-ray or gamma-ray radiation response to a predetermined primary radiation. This method allows for authentication and monitoring of the object or product with which the tag is associated, upon identifying the unique characteristic radiation response therefrom.

The method provides a tool of verification, determining authenticity, supply chain, recycling, brand ID, producer, country of manufacturing and other features relating to the use/attributes and/or history of the product or object with which the tag is associated. For verification, the unique characteristic X-ray or gamma-ray radiation response of said at least one predetermined marking is read. Thus, verification comprises forming the tag and irradiating same to induce secondary radiation in response to the primary radiation; detecting the secondary radiation and optionally recording data indicative thereof, enabling storage of the data or of a signature of the unique characteristic radiation response; and analyzing the detected secondary radiation to identify whether it matches the predetermined characteristic radiation response.

This verification method may be used as an authenticating method. Thus, in another aspect there is provided an authenticating method, the method comprising

-forming at least one XRF tag having a predefined marking profile;

-associating or appending said tag to a product or an object;

-applying a predetermined primary radiation to the product or object to induce secondary radiation in response to said primary radiation; and

-detecting the secondary radiation response and generating measured data indicative thereof.

The method further comprises:

-analyzing the measured data using reference data about various types of tags and their unique characteristic responses to said primary radiation stored in a database, for determining a match between the measured data and data in said database, and

-generating notification data indicative of whether the product or object has been identified or not.

The predetermined marking is in the form of an invisible XRF mark of a predefined marking profile, e.g., composition, concentration, mixture of markers, amount ratios, etc., wherein the marking profile is unique to the specific tag or a selection of tags. An XRF tag may comprise an amount of the XRF-identifiable marker that is between 0.1 to l,000ppm. In some embodiments, the amount may be between 5 and 500 ppm, between 10 and 400, between 10 and 350, between 10 and 300, between 10 and 250, between 10 and 200, between 10 and 150, between 10 and 100, between 10 and 90, between 10 and 80, between 10 and 70, between 10 and 60, between 10 and 50, between 10 and 40, between 20 and 400, between 30 and 400, between 40 and 400, between 50 and 400, between 60 and 400, between 70 and 400, between 80 and 400, between 90 and 400, between 100 and 400 ppm, between 30 and 100 ppm.

In some embodiments, the amount of the XRF-identifiable marker is between 1,000 ppm and 50,000ppm. In some embodiments, the amount of the XRF-identifiable marker is between 1,000 and 40,000ppm, 1,000 and 30,000ppm, 1,000 and 20,000ppm, 1,000 and 10,000ppm, 1,000 and 9,000ppm, 1,000 and 8,000ppm, 1,000 and 7,000ppm, 1,000 and 6,000ppm, 1,000 and 5,000ppm, 1,000 and 4,000ppm, 1,000 and 3,000ppm, or between 1,000 and 2,000ppm.

Where the tag comprises two or more different XRF marking materials, each XRF marking material may be in an amount as above. The two or more marking materials need not be present in the same amount. For example, where a certain tag is differentiated from another in the composition of the two or more marker materials and their amounts, the certain tag may comprise three marker materials A, B and C, in amounts X, Y and Z ppm, respectfully, such that an amount ratio between the amounts of X and Y is 2.5:1 and the amount ratio between Y and Z is 2.9:4. This certain tag differs from a tag comprising three marker materials B, C and E, in amounts F, G and H, respectfully, wherein the three materials are present in identical ppm amounts.

Thus, an XRF marking composition used in depositing the one or more marker materials on the XRF tag may comprise a single marking material or a mixture of marking materials which composition, concentrations and material ratios are predetermined. The marking composition may comprise the marking materials in neat forms or in a carrier material that does not affect the material signature signals. Alternatively, a tag may be formed by depositing predetermined volume amounts of different XRF marking compositions comprising each a single marker material at a predetermined concentration, to thereby provide a tag with a predetermined XRF profile.

The XRF markers may be inorganic salts, metal oxides, polyatomic ions, and organometallic molecules.

The marker can be water soluble or water-insoluble. The marker may be in the form of a metal atom, a metal oxide, or a metal salt such as a metal sulfide, a metal carbonate, metal sulfate, metal carbide and others; or in the form of an organometallic or an organohalide material. The organometallic material may be selected amongst organic anions that are ionically associated with at least one metal atom (metal cation). Nonlimiting examples include metal phenolates, metal acrylates, metal-associated anilines and others. The organohalide is at least one organic material substituted with at least one halide e.g., bromide, iodine, chloride. Such organohalides include halide-substituted phenols, halide substituted anilines, halide-substituted epoxies, halide-substituted acrylates, halide-substituted amides, halide-substituted acids, halide-substituted glycols and others.

The metal or atom used as a marker may be any atom of the periodic table. The atom may be presented as a salt, a complex, an organic compound, or an inorganic compound. For example, where the marker is a metal or a metal containing material, e.g., organometallic material, or metal salt, the metal atom may be selected from aluminum (provided as e.g., aluminum sulfate), titanium (provided as, e.g., titanium sulfate), cobalt (provided as e.g., cobalt nitrate hexahydrate, cobalt gluconate hydrate, cobalt glycinate), nickel (provided as nickel nitrate hydrate, nickel glycinate), yttrium provided as e.g., yttrium nitrate hexahydrate), cadmium (provided as e.g., cadmium nitrate tetrahydrate), tin (provided as e.g., tin chloride), scandium, niobium, silver, tungsten, zinc, zirconium, manganese, copper, lead, molybdenum, vanadium, bismuth, antimony, tantalum and cesium (provided as e.g., cesium carbonate).

Other metal-based markers may be provided in a water-insoluble form. Such include aluminum oxide, scandium acetate, titanium oxide, cobalt acetyl acetonate, cobalt carbonate, cobalt dibromo, nickel acetyl acetonate, nickel acrylate, yttrium oxide, niobium oxide, silver carbonate, silver chloride, tin ethyl hexanoate, tungsten oxide and others.

Halide-based markers include tri-iodine phenol (TIP), tribromophenol (TBP), tri chlorophenol (TCP), 2,2-bis(bromomethyl) propane- 1,3-diol, 2,4,6-tribromo aniline, pentabromobenzyl acrylate, 4,5,6,7-tetrabromoisobenzofuran-l,3-dione, ammonium bromide and others.

The XRF tag of the invention may be associated or appended to any product or object or to any article that accommodates the product (such as a casing or a packaging unit), which identification, authentication or generally evaluation is desired. Typically, the product is one that the tag can be provided concealed from the eye. Luxury products such as clothing, leather products, silk products, jewelry, and accessories; including shoes, sneakers, boots, bags, suitcases, wallets, leatherware, clothing, watches, and any other commercial product, or cases in which such products are accommodated, may be provided with an XRF tag that would identify the product over another and would provide an indication of origin, sites of production, manufacturing history, retailer ID, and so forth. By reading the tag, the embedded data is revealed ensuring traceability of the product along all manufacturing and commercialization steps. Each such reading is recorded on a block chain platform and provides real-time access and visibility of supply chain movements.

The tag may be positioned at any depth from the external surface of the product or object. It may be positioned immediately associated with the top surface of the product or object or may be contained, encased or associated with inner layers or features in the product or object. As the XRF-identifiable marker materials may be provided in a variety of concentrations, reading of the radiation emitted from the tag may be from any distance from the surface of the object.

In addition to marking a product with a tag, depending on the nature of the product, the product itself may be XRF-marked by a variety of means. Such means are disclosed for example in each of international application nos. W02022/029770, WO2022/029769 and WO2018/042427, and US applications derived therefrom, each being incorporated herein by reference.

A reading unit may be used for detecting the markers and/or measuring the concentrations or relative concentration of the markers in the tag. In an example the marking composition includes markers which are identifiable by XRF analysis and the verification unit comprises an XRF analyzer which emits an X-ray or Gamma-ray radiation towards the object and detects the X-ray signal (a response signal) that is emitted from the markers in response. Such an XRF analyzer may be configured to measure/estimate the concentration or relative concentration of each of the markers according to the detected response signal. The concentrations of the markers may be indicative of the information encoded by the marking composition on the tag and therefore on the product or object. Accordingly, based on the measured/estimated concentration the system may be configured and operable to verifying that the applied marker composition indeed matches/encodes the intended information/authentication data that should have had being marked on the product or object and possibly also verifies the quality of the marking applied by the marking device (i.e. the quality may be determined based on the signal to noise (SNR) of the detected signal).

As mentioned herein, the XRF marking can be detected and identified also when markers are present under the external surface of a product.

The marker may be detected and measured by X-Ray fluorescence (XRF) spectrometers (readers) which detect and identify the marker response (signature) signal(s). The XRF readers may be Energy Dispersive X-Ray fluorescence EDXRF spectrometers. XRF markers are flexible, namely, they may be combined, blended or form compounds with a huge range of carriers and materials.

The invention further provides a database, i.e., a storage device that is configured to be accessible via a communication network, the database comprising a plurality of electronic certificates assigned to a respective plurality of marked products or objects, each of the electronic certificates comprising data indicative of a corresponding unique radiation signature of the product or object. The plurality of products may be a plurality of products manufactured in a particular manufacturing facility; a plurality of raw materials that are manufactured at a particular date; a plurality of raw materials that are designed and manufactured for producing a particular type of final products, e.g., handbags or shoes; a plurality of raw materials designed and manufactured for a particular brand designer; a plurality of raw materials that are manufactured from components obtained from a particular source; and others.

The invention further provides a kit comprising one or more types of XRF tags according to the invention, wherein each tag in the one or more types of tags is identical to another in the same type; and instructions of use. Each type of tag has a unique XRF profile derived from a different XRF mark it is provided with.

Unlike direct marking of a product by an XRF-identifiable material, as known in the art, the present technology enables reuse of the XRF tags in case the product has been rendered unusable or recyclable. The tags in such products may be removed from the product, tested, and verified for continued use and then appended to another product of the same type.

The invention further provides product sets, wherein each product in said set is associated with a tag having same XRF-identifiable profile. Typically, each of the tags associated with each product in the set is of the same structure, size, shape and embedded or associated with the product in a way that is identical between the products. Each tag may provide information or may be indicative of data relating to the relations between the particular product and the set of products, e.g., the series number of the product in the set. The set may comprise one or more product units.

DETAILED DESCRIPTION OF EMBODIMENTS

The data and details examples provided hereinbelow are merely examples of certain embodiments of the invention. None of the examples should be taken as limiting. Markers used and their molecular source:

PPM of marker calculation:

Stock solution of 5% poly-acrylic acid (PAA) dissolved in ETOH:

1. add the amount of PAA necessary to obtain 5 wt%, while stirring, until a viscous clear solution is obtained.

Formulation procedure for a 2% PAA, 1 wt% marker molecule:

*The percentages represent the wt% from the entire solution, including solvents and solids.

1. Dissolve 1 wt% of salt in 39 wt% DIW.

2. after fully dissolved add 20 wt% ETOH.

3. when the solution is clear again add 40% of 5 wt% PAA stock.

Layer application method:

Equipment:

1. Eco-pen300 pre-flow by viscoTec.

2. A thin needle (Pink head) to enable the release of small volumes.

3. Syringe to add the solution into the feed cell.

The present tool has the ability of transferring accurately small doses, and by that we are able to control the marker amount added above SMX stickers.

To improve the adhesion and wetting of the layer over the sticker we perform a corona treatment for 10 seconds using a laboratory scale corona, model BD-20V, purchased from Electro-technic products inc.

During the development we used to add 5 drops of 5 uL each to create a continuous and homogenous layer. Then we dry the sticker in an oven at 50 °C, for 12 minutes, and apply additional layers as necessary to obtain the codes.

After optimizations we successfully proceeded to prepare layers in one dose of 50 uL (as minimal volume to successfully read it by XRF and obtain the desired separation between each concentration.

Exemplary Samples:

For all the following stickers the PAA concentration was 2 wt%, and the marker molecule was 1 wt%, with the ETOH-DIW ratio of 58-39, as previously explained.

5 stickers of 1 to 5 layers of Indium.

5 stickers of 1 to 5 layers of Holmium.

5 stickers of 1 to 5 layers of Gallium. The layers were etched probably due to the nitrate.

Study of the maximal volume to add per dose before drying:

Increasing Dose to 30, 50 uL and 250 uL, using the formulation with Holmium.

Claims

CLAIMS:

1. An XRF tag, the tag comprising an invisible XRF mark having a unique characteristic X-ray or gamma-ray radiation response to a predetermined primary radiation, the tag being configured to attach or associate with a product or an object.

2. A universal XRF tag, the tag comprising an invisible XRF-identifiable mark formed of at least one XRF marking material, wherein selection of XRF marking material is independent of a product or an object with which the tag is to be associated, wherein the marking having a unique characteristic X-ray or gamma-ray radiation response to a predetermined primary radiation.

3. The XRF tag according to claim 1 or 2, formed on a substrate material selected from flexible materials.

4. The XRF tag according to any one of the preceding claims, formed on a substrate is one of a polymeric, plastic, metalized plastic, and paper-based material.

5. The XRF tag according to any one of the preceding claims, comprising one or more XRF marker material provided on a substrate.

6. The XRF tag according to claim 5, wherein the one or more marker material is provided in a predetermined amount and ratio and is positioned on the substate.

7. The XRF tag according to any one of the preceding claims, comprising a substrate provided with the one or more XRF marking materials and the substrate further provided with a protective coating, or positioned between sheets of a solid material.

8. The XRF tag according to claim 7, wherein the solid material is a polymer laminate.

9. The XRF tag according to claim 7, wherein the protective coating is in a form of a polymeric pocket comprising the marker material(s).

10. The XRF tag according to any one of the preceding claims, wherein the substrate is an internal region of a laminate surface or an internal region of a polymeric pocket or an encasing.

11. The XRF tag according to any one of the preceding claims, wherein the substrate provided with the marker is glued or associated to a product to be marked via an adhesive or stitching.

12. The XRF tag according to claim 4, wherein the substrate is a polymeric material.

13. The XRF tag according to claim 7, wherein the protective coating is a polymeric material, which is same or different from the substrate material.

14. The XRF tag according to any one of the preceding claims, wherein the substrate material is a virgin polymeric material or a recyclable polymeric material.

15. The XRF tag according to any one of claims 4 to 14, wherein the polymeric material is selected from thermoplastic polymers, thermosetting polymers and elastomers.

16. The XRF tag according to claim 15, wherein the polymeric material is selected from polyimides, polymethyl methacrylate (PMMA), polystyrene polyvinyl acetates, polyvinyl acetate copolymers, ethylene vinyl acetate (EVA) copolymers, polyvinyl alcohols, polyvinyl alcohol copolymers, celluloses, polyvinylpyrolidones, vinyl chloride, vinylidene chloride copolymers, acrylic copolymers, polyvinylacrylates, polyethylene oxide, acylamide polymers and copolymers, poly hydroxy ethyl acrylate, methylacrylamide monomers, and poly chloroprene.

17. The XRF tag according to claim 16, wherein the polymeric material is selected from polyethylene (PE), polypropylene (PP), the polystyrene (PS), polycarbonate (PC), polyethylene, polyesters and terephalate (PET), polyoxymethylene (POM), polyacetals or polyvinyl chloride (PVC), polyamide (PA), polymethyl methacrylate (PMMA) and a combination thereof.

18. The XRF tag according to claim 16, wherein the polymeric material is selected from polyamides, polycarbonates, polyolefins (e.g., polyethylene, polypropylene), acrylonitrile butadiene styrene (ABS) polymers, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyvinyl chloride (PVC).

19. The XRF tag according to claim 16, wherein the polymeric material is selected from polyethylene terephtalate (PET), polytrimethylene terephtalate (PTT), polyethylene 2, 5 -furandicarboxy late (PEF), polytrimethylene 2,5-furandicarboxylate (PTF) and combinations thereof.

20. The XRF tag according to any one of the preceding claims, having a thickness between 0.1 and 3 mm.

21. The XRF tag according to any one of the preceding claims, shaped and sized identically to a brand label designating a product or an object the tag is to be associated therewith.

22. The XRF tag according to any one of the preceding claims, shaped and sized to be concealed within a product in such a way that its presence in the product is not immediately evident.

23. The XRF tag according to any one of the preceding claims, provided with adhesive surface to enable secured concealed attachment to a product.

24. The XRF tag according to any one of the preceding claims, wherein the marker is formed as a marker layer between a plastic laminate and a protective cover layer, wherein either the laminate or the cover or both are provided with an adhesive layer.

25. The XRF tag according to any one of claims 1 to 24, when appended or associated to a luxury product.

26. A method of manufacturing an XRF tag, the method comprising:

-forming an XRF mark on a surface of a substrate; and -coating the substrate with a protective material.

27. The method according to claim 26, wherein the substrate is of a predetermined size and shape.

28. The method according to claim 26, wherein the substrate is provided pre-shaped and pre- sized.

29. The method according to claim 26, wherein the substrate is a sheet and the XRF mark is formed on the sheet surface.

30. The method according to claim 26, wherein the process further comprising: -forming a plurality of identical XRF marks on a surface of a substrate; -coating said substrate with a protective material; and

-cutting the substrate into a plurality of segments, wherein each segment has an XRF mark, wherein each of the plurality of segments is an identical tag.

31. The method according to claim 26, wherein the protective material is a sheet.

32. The method according to claim 31, wherein the sheet is a polymeric material.

33. The method according to claim 26, wherein the protective material is a laminated sheet.

34. The method according to claim 33, wherein the substrate has two opposing face surfaces and the protective material is coated on each of the substrate face surfaces.

35. The method according to claim 30, wherein, the cut segment defining an XRF tag being of a size ranging from a few square millimeters to a few square centimeters.

36. The method according to claim 35, wherein the tag is shaped and sized identically to a label designating a product or an object that the tag is to be associated therewith.

37. The method according to claim 26, wherein the protective material is a sheet provided with an adhesive surface selected to adhere or associate to a surface region of the product or object.

38. The method according to claim 26, wherein forming the XRF mark further comprises deposition of one or more XRF identifiable materials on the surface of the substrate.

39. The method according to claim 38, wherein deposition is by printing, liquid deposition, or powder deposition.

40. A method according to any one of claims 1 to 25 further comprising associating or appending an XRF tag to an object or a product, thereby rendering the object or product XRF sensitive.

41. A method comprising:

-applying a material deposition process to a substrate material; and

-creating an XRF tag with at least one predetermined marking, the at least one predetermined marking is unique for a particular object or product, the unique marking is characterized by a unique characteristic X-ray or gamma-ray radiation response to a predetermined primary radiation.

42. The method according to claim 41, further comprising identifying the unique characteristic radiation response therefrom, and authenticating and monitoring of the object or product to which the tag is associated.

43. The method according to claim 42, wherein authenticating and monitoring includes verifying, determining authenticity, determining a history of the object or product relating to at least one or more of supply chain, recycling, brand ID, producer and country of manufacturing.

44. The method according to claim 43, wherein verifying further comprises:

-recording data of the detected secondary radiation;

-storing the recorded data and reference data of a tag having a signature of the unique characteristic radiation response; and

-analyzing the detected secondary radiation to identify whether it matches the unique predetermined characteristic radiation response.

45. An authenticating method, the method comprising

-forming at least one XRF tag having a predefined marking profile;

-associating or appending said tag to a product or an object; -applying a predetermined primary radiation to the product or object to induce secondary radiation in response to said primary radiation;

-detecting the secondary radiation response; and

-generating measured data of the detected secondary radiation response.

46. The method according to claim 45 further comprising:

-analyzing the measured data using reference data about various types of XRF tags and the XRF tag’s unique characteristic responses to the primary radiation, the reference data stored in a database;

-determining a match between the measured data and the reference data stored in the database; and

-generating a notification indicative of whether the associated product or object has been identified or not.

47. The method according to claim 45 or 46, wherein the predefined marking profile is an invisible mark, wherein the predefined marking profile is unique to the at least one tag.

48. The product or object according to claim 1-25, being selected from products where an XRF tag is concealed.

49. The product or object according to claim 48, wherein the product is selected from clothing, leather products, silk products, jewelry, and accessories.

50. A product set comprising a plurality of products, each product being associated with a tag according to any one of claims 1 to 24, wherein each tag associated with each product in the set is identical to another tag in another product in the set.

51. A kit comprising one or more XRF tags according to any one of claims 1 to 25, wherein each tag in the one or more tags is identical or different; and instructions of use.