Anti-counterfeiting object

Abstract

The present invention relates to an anti-counterfeiting object comprising a surface (12) bearing an optical identification marking (14) readable by eye and / or machine, and an authentication volume extending in a thickness (z) direction from the surface (12) so as to be accessible from the surface (12) for reading by X-ray diffraction (XRD). The authentication volume is a composite of a first material, referred to as an authentication material, and at least one second material, the authentication volume having a thickness of at least 5 mm. 3 The authentication material comprises at least one amorphous phase, at least one crystalline phase, and at least one complex metal phase. The second material is typically a polymer. The invention can be advantageously implemented by 3D printing.

Description

Technical Field

[0001] The present invention generally relates to the field of object identification and authentication. More particularly, it relates to anti-counterfeiting objects that can be more securely authenticated.

Background Art

[0002] Counterfeiting is an increasingly problematic issue. For companies, counterfeiting is troublesome due to its impact on sales, brand value, and corporate reputation, as well as the company's ability to profit from technological innovation. Consumers are also victims of counterfeiting, finding fake products and products that pose significant safety and health risks, such as mechanical parts or drugs, despite the price they paid. At the state level, counterfeiting is a concern for governments due to the threat it poses to consumer well-being and health, its negative impact on innovation, and the significant resources dedicated to targeting criminal networks, organized crime, and other groups that disrupt and corrupt society.

[0003] Today, there are numerous technologies that can be used to combat counterfeiting. For example, nanotechnology and other cutting-edge technologies provide access to new ways of protecting brands and monitoring and tracking products: they offer the possibility of unique "digital fingerprints" for both the actual products (without affecting them) as well as for packaging. In this regard, the report "Nano and Other Innovative Anti-Counterfeiting Technologies" issued by the Technology Transfer Center in April 2016 describes over 40 solutions, most of which were developed during the period 2014 - 2016.

[0004] Current technological options for combating counterfeiting include a range of "open" and "hidden" countermeasures, including product authentication and security. The anti-counterfeiting market can be mainly divided into two segments: authentication technologies (technologies that provide visible or hidden security features) and "tracking and tracing technologies" that promote product visibility throughout the supply chain.

[0005] These technical options use serial numbers, barcodes, data systems, and RFID identifiers for identification, and holograms, biometric solutions, watermarks, and tags for security. These technologies have their own limitations at different levels and are not absolute.

[0006] One of the specific challenges of anti-counterfeiting measures is the difficulty of preventing the replication of RFID devices, markers, holograms, or any other authentication imprint.

[0007] Patent Document 1 describes a method of marking the identification of an article based on X-ray diffraction (XRD) analysis. This method uses an identification element formed by a powder crystal material in a binder to form an X-ray diffraction pattern representing the signature of the element when irradiated by an X-ray beam. The X-ray diffraction pattern represents a code determined by the selection and omission of one or several of four different crystal materials. This identification element can take various forms (beads, cylinders, fibers) and can be used for various purposes such as sorting, tracking, identification, verification, authentication, anti-theft or anti-counterfeiting protection, security, or anti-terrorism.

[0008] The proposed method allows for a large number of distinct codes and is interesting for using small objects. Furthermore, the XRD signature is readable regardless of orientation and can withstand difficult environments. Despite these advantages, the method described in Patent Document 1 does not seem to be sufficiently secure. In fact, X-ray diffraction is a conventional means for analyzing crystal materials. It would be relatively easy for a person skilled in the art to analyze such an identification element to detect various crystal materials and reproduce compounds with very similar or identical diffraction patterns.

[0009] Other object authentication methods are described, for example, in Patent Document 2, Patent Document 3, Patent Document 4, or Non-Patent Document 1.

[0010] Patent Document 5 describes an authentication method using radiation crystallography that is safer than that described in Patent Document 1. This method uses an authentication material containing at least one amorphous phase, at least one crystalline phase, and at least one Composite metallic phase. In fact, by X-ray crystallography, such authentication substances produce a unique diffraction pattern, form a unique signature or imprint, and the composition cannot be determined after the substance is manufactured. The strength of this technique is that it is not possible to reverse-engineer the recipe using analytical methods to produce the authentication substance. Therefore, authentication is performed by comparison with a reference diffractogram.

[0011] In practice, batches of the authentication substance are prepared, which are shaped, for example, into balls, cylinders, fibers, or in the form of tags, badges or other marking means, which are associated with the object to authenticate it. It is also possible to incorporate the authentication substance into the object by making the object wholly or partly from the authentication substance, or the components of the object are made from the authentication substance.

[0012] It then becomes possible to authenticate the object by analyzing a tag made from the authentication material, or a part of the object made from the authentication material.

[0013] This method is very interesting because of its anti-counterfeiting nature since it is not possible to use analytical methods to reverse-engineer the recipe to produce the authentication substance. Nevertheless, a high degree of precision is required in the manufacture of the batch in order to maintain the homogeneity of the batch and thus ensure the same signature for all products manufactured from the batch. Furthermore, the X-ray analysis method is an essentially hidden method, and it is not always clear whether the object is an anti-counterfeiting object. Finally, it is necessary to maintain a database with reference XRD signatures.

[0014] Object of the Invention The object of the present invention is to propose another concept for an anti-counterfeiting object that can be authenticated by X-ray diffraction and does not have the above-mentioned drawbacks.

Summary of the Invention

[0015] According to a first aspect, the present invention provides an anti-counterfeiting object comprising a surface having an optically distinguishable marking readable by an eye and / or a machine, and an authentication volume, wherein the authentication volume extends in the thickness direction (or depth with respect to the surface) of the object from the surface of the object, from the same surface or another surface of the object, so as to be accessible for reading by X-ray diffraction method (indicated by XRD). The authentication volume includes an immiscible mixture of a first material called an authentication material and at least one second material. The authentication material includes at least one amorphous phase, at least one crystalline phase, and at least one Composite metallic phase.

[0016] The term "authentication volume" refers to the volume of the body of the object that can take various forms, the body having a surface carrying the distinguishable marking and an outer surface from which the authentication volume extends. The authentication volume can be disposed below the surface having the distinguishable marking or below another surface.

[0017] The authentication volume has a predetermined volume that is determined during a recording time of 1 or several hours to 1 - 2 days based on the sensitivity of the selected XRD technique. Thus, the authentication volume represents the minimum volume of the continuous material of the object that combines the first and second materials to enable detection by the selected XRD method. Preferably, the predetermined volume is at least 5 mm 3 and in particular at least 10 mm 3 in size.

[0018] The present invention completes anti-counterfeiting measures by proposing a method of associating an optical identification marking and an authentication volume with an object to be authenticated. The identification area is intended to be read by optical reading means (generally automated) and is in particular visible by looking at the object. While the identification area is on the surface of the object, the authentication volume extends into the volume of the object's body and requires X-ray analysis across a given volume of material.

[0019] Since the authentication volume is not necessarily visible / recognizable to the eye and does not necessarily extend over the entire object, the authentication volume can be identified by the marking and thus this indicates the authentication area where XRD analysis should be performed. It can be a specific marking intended only to identify the authentication area. However, the identification and authentication areas may advantageously be arranged in proximity to each other (juxtaposed) or may be partially or wholly superimposed, in which case the identification marking also functions as a marking indicating the authentication area. Thus, in the case of superposition (at least partially), the measurement of the XRD signature is performed from the surface having the identification marking.

[0020] It will be understood that the authentication is based on a combination of the authentication material with a second material that generates an XRD signature resulting from the combination of the radiation of the two materials. The specific signature of the second material actually combines with the signature of the first material to give a composite XRD signature based on the distribution of the authentication material within the analyzed authentication volume, in particular its quantity and its spatial position (x, y and z). In practice, since XRD analysis is sensitive over a specific depth (typically on the order of millimeters), it is possible to act on the distribution along the Z-axis (depth) to define and modulate the XRD signature of the authentication volume.

[0021] Thus, the object according to the present invention constitutes an object that can be certified as "anti-counterfeiting" due to its use and is itself "anti-copying" since it cannot be reproduced.

[0022] Preferably, the authentication volume extends from the surface having the identification marking over a depth between 0 and 1.5 mm, preferably between 0 and 1 mm, more preferably between 0 and 600 μm, or between 0 and 400 μm.

[0023] The authentication material can be present on the surface and / or can be distributed in depth.

[0024] According to a variant, the authentication volume extends over a surface of at least 10 mm 2 , preferably at least 100 mm 2 taken in a plane substantially parallel to the said surface of the object.

[0025] For the sake of simplicity of expression, in the present specification, the term "substance" is used as a synonym for material.

[0026] In the present specification, the term "XRD signature" refers to at least a part of a diffractogram (X-ray diffraction pattern) corresponding to a given sample (reference or candidate) and containing characteristic values of XRD analysis. The XRD signature can generally be represented graphically or as a data set. Furthermore, the authentication can be carried out over the entire diffractogram or over one or several parts thereof. In practice, the XRD signature includes a set of characteristic pairs (angle; intensity) of the diffractogram representing the analyzed sample.

[0027] The identification marking can take various forms and can be made readable under visible light or under a predetermined light (e.g., infrared). The identification marking can include numbers and / or characters, which may or may not represent a code, or can include any type of index representing a code, such as bars, dots, circles, squares, etc. In particular, it is possible to use codes of types such as one-dimensional or two-dimensional codes, barcodes, QR codes (registered trademark), matrix codes, cyclic codes (e.g., "Bleem" type), etc. The identification marking represents information of different natures, in particular information regarding the nature of the object, such as its name, manufacturer's reference, regulatory data, etc., and combinations thereof.

[0028] According to a modification example, the optical identification marking is made from two materials each having a different color.

[0029] The identification marking is a two-color matrix marking, and the surface layer is made from first and second materials each having a different color.

[0030] According to a modification example, the identification marking includes a series of marks representing a code delimited by a peripheral line, and the authentication volume is located inside the contour of this peripheral line.

[0031] The authentication of the object is performed by comparing the measured XRD signature with a reference XRD signature in an automated or assisted manner based on graphs and / or numerical values. Generally, the measured XRD signature and the reference XRD signature are considered to match when their angular positions and intensities are the same or similar (within defined tolerance limits). Therefore, comparing the XRD signatures mainly includes comparing the angular positions of the characteristic / representative peaks and / or comparing the relative intensities of the characteristic / representative peaks.

[0032] Reference XRD signatures can be stored, for example, locally or online in a database. Of course, it is possible to hold a reference sample against which the reference XRD signature can be measured.

[0033] Notably, the optical identification marking can contain information regarding the XRD signature that must be obtained when the authentication volume is the subject of XRD analysis. The reliability of the object is then verified by comparing the XRD signature measured for the authentication volume with the XRD signature encoded in the information marking.

[0034] Thus, one important advantage of this approach is that the reference XRD signature is encoded in the identification marking and there is no need to access or maintain an online database to obtain the reference XRD signature.

[0035] Here, it should be noted that when the authentication volume is spaced apart from the identification marking, for example, when the authentication volume is located below a surface other than the surface having the identification marking, it is possible to encode information within the identification marking regarding the position of the authentication volume within the object and thus, for example, the measurement coordinates for performing an XRD analysis indicating the position of the measurement zone.

[0036] Furthermore, the use of XRD is related to so-called hidden anti-counterfeiting methods (such as WO 2019 / 011986), but the present invention proposes a method combining optical identification and XRD authentication, and the authentication area is preferably marked such that the location where the XRD measurement must be performed is known. This is particularly interesting because the amount of authentication material can be reduced to the amount required for authentication.

[0037] It should be recalled that the authentication material used in the present invention generates a unique X-ray diffractogram that constitutes a unique signature, similar to that described in WO 2019 / 011986 Pamphlet. Its composition cannot be determined after manufacturing. Current analysis techniques do not allow for qualitative and quantitative analysis of the individual materials that make up the authentication material. In particular, chemical analysis does not allow for the interpretation of the composition corresponding to a given diffractogram. Elemental analysis of the various existing crystal structures and phases is carried out without distinction. XRD analysis also does not provide access to the volume fractions of the different phases, so the composition of the authentication material cannot be determined.

[0038] Due to X-ray absorption phenomena and the overlap of diffraction peaks of different crystal and composite phases of metal alloys, it is impossible to accurately determine the volume fractions of the different phases contained in the authentication volume.

[0039] Unlike the WO 2019 / 011986 Pamphlet, the present invention also allows for material savings since the XRD signature results from a combination of an authentication material and a second material that can be any material and does not include a specific combination of phases of the authentication material in particular. Thus, the second material can be less expensive both in terms of purchase cost and implementation. This is particularly interesting since the composite XRD signature can be varied by changing the ratio between the two materials. In a variant, the second material is mainly present and may form a matrix in some cases, while in other variants, the authentication material may be mainly present.

[0040] In principle, the second material can be any material, such as a polymer, wood, fiber, metal, etc. Generally, the second material has a specific XRD signature that is different from the XRD signature of the authentication material. The second material preferably has a polymer base with, for example, one or two components, a filled composite, an elastomer, silicone, etc. The second material can then be an anti - counterfeiting material. The present invention can also be made of a plurality of second materials according to the same criterion of having an XRD signature different from the authentication material.

[0041] The respective volumes and spatial arrangements (within the authentication volume) of the first and second materials can be varied by design based on the signature to be constructed. It is possible to have between 1% and 99% of the authentication material within the authentication volume, and the rest is completed by the first material. The authentication volume preferably contains at least 10% of the authentication material.

[0042] The shape of the object is limited only by the minimum volume required for XRD analysis. All types of shapes can be envisaged. It is possible to manufacture large objects. However, the present invention is particularly well - suited for manufacturing objects in the form of tags, plates, stamps, strips, panels, labels, stamps, badges, etc.

[0043] The object can be designed such that the authentication volume is present uniformly throughout its volume or only over a part of it. In the latter case, the authentication volume is adjacent to and / or (partially) overlapped with the identification area. Here, "overlap" means that when viewed along the thickness direction, the authentication volume is at least partially located below the identification area (with respect to the code of the identification marking).

[0044] According to a variant, the optical identification marking and the authentication volume are at least partially (when viewed in the thickness direction) overlapped.

[0045] For certain applications, the authentication volume can be mounted on / within the support where the two assemblies form the anti-counterfeiting object.

[0046] The anti-counterfeiting object according to the present invention can be fabricated using any suitable technique.

[0047] Generally, the first and second materials are prepared independently of each other. They are then combined to produce all or part of a component and thus, in particular, to form the authentication volume. Thus, the first and second materials are combined within the authentication volume by associating them, and / or juxtaposing them, and / or overlaying them, in order to obtain a distribution within the space of the volume. This distribution within the space determines the composite signature of the authentication volume.

[0048] The first and second materials are added independently, simultaneously or sequentially, using any suitable technique, to form this combination within the authentication volume (which has a given spatial distribution). Examples include methods for implementing polymers such as injection (co-injection of two materials), extrusion (co-extrusion) processes. However, manufacturing by layering and thus layer assembly is also included. Of course, additive manufacturing from two different threads, one having the first material and the other having the second material, is also included.

[0049] Additive manufacturing techniques are particularly interesting because of their flexibility and ease of implementation. Furthermore, they allow for very precise control of the deposition of materials and thus, layer-by-layer control of the deposition of materials. Thus, 3D printing makes it possible to master the desired combination between the authentication material and the second material (or other materials), not only within the plane of the layer but also in depth. Fused deposition modeling (FDM) technology is particularly interesting for implementation using two (or more) different filaments, one of which contains the authentication material.

[0050] It should be noted that for this purpose, it is possible to manufacture threads of authentication material with very good uniformity.

[0051] According to a variant, the object is composed of a plurality of superimposed layers formed by 3D printing, and at least one of the layers is located at a depth between 0 and 0.6 mm from the surface containing at least a part of the authentication material.

[0052] As will be apparent to those skilled in the art, similar X-characteristic evaluation techniques (especially the same X-ray source) are advantageously used so that the diffractograms of different objects can be compared.

[0053] In this specification, the term "amorphous phase" is used in its conventional meaning, which generally refers to an aperiodic three-dimensional structural arrangement that does not have the long-range order characteristic of crystals. Typically, in the amorphous phase, X-rays are scattered in multiple directions, resulting in broad peaks that are not clearly defined.

[0054] In this specification, the term "crystalline phase" is used in its conventional meaning in crystallography, which refers to a crystal structure, that is, a regular arrangement of atoms, ions, or molecules that forms a symmetric pattern repeating periodically in the main directions of the three-dimensional space of the material. Therefore, in this specification, the term "crystalline phase" includes the historical definition of crystals, but does not include "quasicrystals" or more generally "composite metal alloys" as defined below. The crystalline phase has a diffractogram characterized by a set of discrete and strong peaks.

[0055] In this specification, the term "composite metal alloy" refers to an alloy that is strictly either a quasicrystalline phase or an approximant phase. The quasicrystalline phase is, strictly speaking, a phase having a rotational symmetry that does not normally conform to translational symmetry, that is, a symmetry having a rotational axis of order 5, 8, 10, or 12. Examples include the icosahedral phase having icosahedral group symmetry and the decagonal phase having decagonal group symmetry.

[0056] Quasi-phase or quasi-compounds are true crystals because their crystallographic structures remain compatible with translational symmetry, but in electron diffraction snapshots, their symmetry has a diffraction pattern close to 5-, 8-, 10-, or 12-fold asymmetry. These are phases characterized by elemental meshes containing dozens or even hundreds of atoms, and their local order has a nearly icosahedral or decagonal symmetry arrangement similar to that of the parent quasicrystalline phase. The composite metal phase has a powder diffractogram characterized by a significantly more complex, discrete, and intense set of high-density peaks than conventional metal alloys.

[0057] Among these phases, for example, there is the orthorhombic phase O1 characteristic of an alloy with the atomic composition Al 65 Cu 20 Fe 10 Cr5, and its mesh parameters (nm) are a0 (1) = 2.366, b0 (1) = 1.267, c0 (1) = 3.252. This orthorhombic phase O1 is said to approximate the decagonal phase. The properties of the two phases can be confirmed by transmission electron microscopy.

[0058] The rhombohedral phase can also be cited by the parameter a 64 Cu 24 Fe 12 = 3.208 nm, α = 36° existing in an alloy with an atomic composition close to Al R This phase is an approximation of the icosahedral phase.

[0059] The orthorhombic phases O2 and O3 with the respective parameters a0 63 Cu 17.5 Co 17.5 Si2 existing in an alloy, a0 (2) = 3.83, b0 (2) = 0.41, c0 (2) = 5.26, and a0 (3) = 3.25, b0 (3) = 0.41, c0 (3) = 9.8, or the atomic composition Al 63 Cu8Fe 12 Cr17 formed in an alloy having, a0 in nm (4) = 1.46, b0 (4) = 1.23, c0 (4) It is also possible to cite the orthorhombic phase O4 having parameters of = 1.24.

[0060] It is also possible to cite the cubic phase C whose coexistence with an approximate or true quasicrystalline phase is very frequently observed. This phase formed in certain Al-Cu-Fe and Al-Cu-Fe-Cr alloys is composed of a superstructure due to the chemical effect of alloying elements on aluminum sites, a Cs-Cl type structural phase, and a lattice parameter a1 = 0.297 nm. The atomic composition Al 65 Cu 20 Fe 15 For a pure cubic phase sample having, the diffraction pattern of this cubic phase has been published.

[0061] The hexagonal phase H directly derived from the C phase can also be cited, as demonstrated by the epitaxial relationship observed by electron microscopy between the C phase and the H phase in a simple relationship linking the lattice parameters of the crystal lattice, i.e., aH = ³√a1 / √3 (within 4.5%) and cH = ³√2·a1 / 2 (within 2.5%). This phase is an isotype of the hexagonal phase denoted as ΦAlMn, discovered in an Al-Mn alloy containing 40% by weight of Mn.

[0062] The cubic phase, its superstructure, and the phases derived therefrom constitute a class of approximate phases of the quasicrystalline phase of adjacent compositions.

[0063] Quasicrystalline alloys of the Al-Cu-Fe system are also suitable for the implementation of the present invention. In particular, alloys having one of the following atomic compositions can be cited. Al 62 Cu 25.5 Fe 12.5 , Al 59 Cu 25.5 Fe 12.5 B3, Al 71 Cu 9.7 Fe 8.7 Cr 10.6, and Al 71.3 Fe 8.1 CO 12.8 Cr 7.8 . These alloys are commercially available, for example, from Saint-Gobain (or Sigma-Aldrich). In particular, the alloy Al 59 Cu 25.5 Fe 12.5 B3 is sold under the name Cristome F1, and the alloy Al 71 Cu 9.7 Fe 8.7 Cr 10.6 is sold under the name Cristome A1, and the alloy Al 71.3 Fe 8.1 CO 12.8 Cr 7.8 is sold under the name Cristome BT1.

[0064] The alloys Cristome A1, F1 and BT1 are cited merely as examples.

[0065] In the context of the present invention, the composite metal alloy that can be used can be a metal alloy containing more than 50 atomic percent of aluminum.

[0066] According to another aspect, the present invention relates to a method for manufacturing an anti-counterfeiting object, wherein the object is manufactured by additive manufacturing using a filament of a certification material containing at least one amorphous phase, at least one crystalline phase, and at least one Composite metal phase, and at least one polymer-based filament of a different color. The manufacturing is performed by printing successively stacked layers. The surface layer is printed so as to form an identification marking. The method is implemented such that the material of the filament of the certification material is deposited in the surface layer and / or one or more layers below the surface layer so as to form a certified volume. According to another aspect, the present invention relates to a method for authenticating an anti-counterfeiting object disclosed in the present application, ​In order to obtain information, a step of reading an identification marking of an anti-counterfeiting object using a reader, a step of XRD-analyzing an authentication region of the anti-counterfeiting object by means of X-ray diffraction to determine its XRD signature,

[0067] comparing the XRD signature of the anti-counterfeiting object with a reference XRD signature, which relates to a method.

[0068] The identification marking typically takes the form of a one-dimensional or two-dimensional code. This is advantageously automatically readable using a reader.

[0069] The XRD signature is preferably compared with computer assistance.

[0070] The reference XRD signature can be obtained by accessing a local or online file or database. In this case, the identification marking can include an address, URL, or hyperlink that enables access to the XRD signature.

[0071] Alternatively, information regarding the reference XRD signature can be encoded in the identification marking. This is information regarding a diffractogram corresponding to the reference XRD signature, for example, characteristic peaks identified by (angle, intensity) pairs optionally completed by an indication of the wavelength of the X-ray source.

Brief Description of the Drawings

[0072] Other peculiarities and features of the present invention will become apparent from the detailed description of at least one advantageous embodiment presented below by way of example with reference to the accompanying drawings. These drawings show the following:

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[0073] A) Example To explain the principle of the present invention, several examples were conducted. Examples 1 to 3 use tags or chips having a QR code type pattern. These chips are manufactured using a conventional FDM type 3D printer and two filaments with a diameter of 1.75 mm. One filament is a certification material (a material containing at least one amorphous phase, at least one crystalline phase, and at least one Composite metal phase), and the other filament has a polymer base, such as PLA (polylactic acid), having a specific XRD signature different from that of the other filament.

[0074] XRD measurements were performed on a D8 Advance instrument by Bruker, using a copper anode X-ray tube, in a theta / 2theta Bragg Brentano configuration. The measurements were carried out over an angular range from 15° to 90° with a measurement pitch of 0.018627795° and a total scan time of 55 minutes and 50 seconds.

[0075] Example 1 In this example, the samples are produced by filament deposition (FDM) in the form of a "chip" with a thickness of 1 mm and a diameter of 25 mm, or 10 consecutive layers with a thickness of 100 μm. For this purpose, two threads corresponding to two different materials are used, one being a certified material and the other being conventional PLA. The filament of the certified material here contains: an amorphous phase given by 50 m% PLA, a crystalline phase of 25 m%, and a mixture of a quasicrystalline icosahedral phase and an approximate phase of 25 m%. The approximate alloy and the composite alloy are Al-Cu-Fe-based alloys containing appropriate additive elements (chromium or boron as described above).

[0076] A first control sample composed of 10 layers of PLA is produced.

[0077] Next, 9 layers of PLA are deposited and 9 other samples are produced, each containing a single layer composed of 100% certified material. For these 9 layers mentioned above, the position of the 100% certified material layer varies from the first layer (the topmost layer of the chip) to the tenth and final layer (the bottommost layer of the chip). Next, all the samples are analyzed using the XRD method (analysis from the top surface) to obtain their characteristic signatures.

[0078] Figure 1 shows the diffractograms obtained for the control sample ct and samples c1 to c4, where the certified layer is located at depths of 0 - 100 μm, 100 - 200 μm, 200 - 300 μm, and 300 - 400 μm respectively. As can be seen from the figure, the XRD signatures of samples c1 to c4 resulting from the combination of the certified material and PLA are different from each other and different from the signature of the control sample ct.

[0079] Therefore, the analysis reveals that changing the position of the layer of authentication material can change the resulting signature up to about 600 μm or up to the sixth layer. Beyond this step, the signature of the composite chip becomes very close to or identical to the signature of the control chip again. Therefore, it can be considered that the composite signature can be effectively measured up to 600 μm, which represents the detection limit of the selected XRD analysis conditions.

[0080] This first example enables the conclusion that the XRD signature is controllable within the object based on the position of the authentication material along the Z-axis and thus based on depth.

[0081] Example 2 This example aims to study the reproducibility of authentication measurements. A two-color QR code (registered trademark) is generated, which is printed using PLA filament on one side and authentication filament on the other side. Thus, it has black and light gray QR codes (registered trademark), where black corresponds to the authentication filament and light gray corresponds to the PLA filament.

[0082] i) Operation 2-A. Two QR codes (registered trademark) that are identical with respect to the pattern and the filaments used are printed. They are shown in Figure 2. The XRD signatures obtained after analysis are identical, see Figure 3. These results confirm that the same authentication signature is obtained for the same pattern and the same material distribution. Therefore, the signature is reproducible for the same identification area.

[0083] ii) Operation 2-B. Second, the same pattern is still retained and its color is inverted. As shown in FIG. 4, a second QR code (registered trademark) is printed, where light gray replaces black and vice versa. The resulting signatures are found to be very close and difficult to distinguish; refer to FIG. 5. In fact, when the distributions of the two colors are similar, for example, when the surface distribution is 50 / 50, the concentrations of the two materials are the same before and after the color inversion.

[0084] Therefore, two different patterns can be created, but the distribution of the material (color) is the same, and thus two identical XRD signatures can be obtained for two different identification information items.

[0085] Therefore, it can be concluded that the XRD signature is reproducible for different identification regions.

[0086] Example 3 This example demonstrates the possibility of changing the signature while maintaining the same identification pattern.

[0087] i) Operation 3-A. The first operation (2-A) of Example 2 is repeated, changing the PLA filament used to vary the color and opacity (e.g., red instead of light gray). Therefore, black is performed using the authentication material filament. The QR code (registered trademark) is shown in FIG. 6.

[0088] Therefore, for two QR codes (registered trademarks) having the same pattern containing the same information, two different signatures are obtained; refer to FIG. 7. Therefore, for the same item of identification information, the authentication changes: the XRD signature is different for the same identification region.

[0089] ii) Operation 3-B. Next, two QR code chips are printed on the same first layer (same pattern, same material, etc.). At this time, only intervene at the lower level to change the authentication volume information while retaining the same identification information (due to the same surface pattern). The composition of each layer is shown in the following table. Note that layers 2, 3, and 4 are different between the two manufactured chips.

[0090] The diffractograms of the two chips are shown in Figure 8. As can be seen from the figure, the signatures are different for the same identification area. Therefore, this example demonstrates the possibility of changing the XRD signature for the same identification information.

Table 1

[0091] Example 4

[0092] Different from the previous examples, this example uses screen printing (ink deposition) instead of 3D printing.

[0093] A mixture of screen printing ink {active substances (Ag, C, dielectric powder, etc.) + epoxy, acrylic, polyimide or phenolic resin} and an additive / powder of the authentication material is manufactured. Next, a mask is made from a PET sheet (thickness about 130 μm) with a desired pattern cut (e.g., a disk) using a laser cutting machine. The substrate used following screen printing is of the same nature as the mask: a PET sheet of about 130 μm.

[0094] Therefore, after manufacturing the objects of the present inventors by screen printing, an authentication deposit of about 130 μm is obtained on the PET substrate. This multi-layer sample (PET / authentication deposit) has a unique XRD signature. Three materials were analyzed, and one of them was prepared according to this protocol: -a1: Composite metal alloy 1 in powder form -a2: Composite metal alloy 2 in powder form -s: Samples prepared by screen printing using a PET substrate and an ink containing a certification powder, where both of them constitute a1 and a2 (two composite metal alloys).

[0095] The diffractograms of each sample are shown in Figure 9.

[0096] XRD analysis of samples performed by screen printing enables the detection of XRD signatures that enable the certification of the samples.

[0097] Example 5 This example attempts to determine the separation threshold of two identification patterns.

[0098] This example is based on the area analyzed during XRD analysis of 1 cm 2 and the limiting resolution of a basic FDM printer equipped with a nozzle having a diameter of 0.4 mm: about 1 mm in size. Thus, a slab of 1 cm 2 and a thickness of 1 mm is manufactured and made into a grid using 100 small cubes of 1 mm 3 .

[0099] The aim is to verify the threshold with respect to the volume (thus, the 1 mm 3 cube), from which the signature is sufficiently altered as detected by this XRD analyzer.

[0100] Then, slabs with 100% of the cubes printed using PLA filament, slabs with 100% of the cubes printed using the certification filament, and then slabs with 50 cubes from PLA and 50 from the authentication material (A.M.) are manufactured. Finally, from this last 50 / 50 slab, four other slabs are manufactured where this distribution changes by changing the composition of one or two cubes (e.g., 51 cubes from PLA and 49 cubes from the authentication material, where one of the cubes transitions from the composition of the authentication material to PLA).

[0101] After XRD analysis, changes in the composition of 1 to 4 out of 100 cubes (or 1 to 4% in the compositional variation) 体積 ) do not seem to enable separable XRD signatures to be obtained.

[0102] Therefore, the same protocol is repeated, this time increasing the pitch. The slabs are of the same dimensions but are grid - shaped into 5×5 cubes of 4 mm 3 or slabs of 25 cubes. When the composition of a single cube is changed, this represents a 4% 体積 variation in the composition.

[0103] XRD analysis shows that a pitch of 4 mm 3 between two cubes, i.e., an 8% 体積 variation in the composition, enables two different signatures to be obtained. This discretization threshold is clearly shown in Figure 14 showing the diffractograms of the various slabs generated, i.e., q0 = 100% PLA, q1 = 42% A.M., q2 = 46% A.M., q3 = 50% A.M., q4 = 54% A.M., q5 = 58% A.M., and q6 = 100% A.M. As clearly shown, an 8% 体積 difference in the upper authentication material is sufficient to distinguish the XRD signatures (e.g., between q3 and q5).

[0104] B) Embodiments The operating principle of the invention demonstrated based on the previous example is explained here using Figures 10 to 13, which show some possible embodiments of the anti - counterfeiting object of the invention in the form of a chip, also called a plate or a tag here.

[0105] Each of objects 10, 30, 50, and 70 includes a surface 12, 32, 52, and 72 having an identification area with identification markings 14, 34, 54, and 74. All of the identification markings are visible to the naked eye here under normal conditions. Surfaces 12, 32, 52, and 72 extend in a plane parallel to (x,y) in the example, and thus the thickness direction is typically the direction of the Z axis perpendicular to (x,y).

[0106] Each object includes a certification volume extending in the thickness direction (along the Z axis) from surfaces 12, 32, 52, and 72 so as to be accessible for reading by X-ray diffraction, XRD. The certification volume is a composite of a first material called the certification material and at least one second material. The certification material includes at least one amorphous phase, at least one crystalline phase, and at least one Composite metallic phase.

[0107] The certification material has an XRD signature that cannot be forged because qualitative and quantitative analysis becomes impossible when using a composite metal phase.

[0108] The second material is used to obtain a composite signature resulting from the combination of the two materials within the analysis volume, and thus this is different from the XRD signature of the first material alone.

[0109] Therefore, the certification volume is a composite volume of the first material and the second material. Both materials are present in this volume, but the first and second materials are not miscible. Thus, the certification volume includes the volumes of the first and second materials.

[0110] As can be understood from the figure, the certification volume is associated with the identification marking. The identification marking constitutes a visible surface marking, and the certification volume is an invisible marking extending within the volume. Generally, the certification volume is arranged near the identification marking (when viewed in the z direction) or at least partially overlapped with the identification marking.

[0111] An operator who knows the structure of this type of object knows that the object can be authenticated by analyzing the authentication volume by XRD analysis in the area attacked from the surface 12, which is located near the marking area or (partially or entirely) overlapped with the marking area.

[0112] Conventional 3D printing technologies of the FDM type (deposition of molten materials) are particularly interesting because they enable the acquisition of material combinations, for example, by using threads of authentication material and threads of a second material having, for example, a polymer base. The resolution of conventional 3D printing enables deposition within a layer or within layers by selecting the positioning of the materials in both the plane (X, Y) and thickness (Z) of the object. Thus, the distribution of the materials is fully mastered within the authentication volume with good accuracy, enabling excellent reproducibility of the structure. Mastering the deposition also enables mastering different structures (ratios and positions in X - Y - Z) of the authentication volume.

[0113] Figure 10 shows a coordinate system (X, Y, Z). The layers are parallel to the plane X, Y and are stacked along the Z - axis (thus, this is the axis of thickness). The thickness of the layer is, for example, about 100 μm, but typically, in a conventional printer, it can vary between 20 μm and 300 μm [as in the original text].

[0114] The object in Figure 10 is a QR - code chip having a parallelepiped body. The surface layer is obtained by printing with two PLA threads of different colors so as to form the desired QR - code (registered trademark). The surface layer C1 is placed on top of a plurality of printed layers C2 to Cn made of PLA, except for one layer, for example C4, which is entirely printed with the authentication material. Thus, there is a layer of authentication material that extends at a given distance below the surface but within the XRD detection limit (preferably less than 600 μm). During XRD analysis by the surface 12, a composite XRD signature resulting from the combination of PLA and the authentication material is obtained over the detection / penetration depth.

[0115] The authentication layer here is 100% authentication material, but it may be less when combined with PLA or another printable polymer. Generally, it is possible to have the authentication material in one or more layers from C1 to layer Ci located at the detection limit. In fact, in practice, it is possible to act on the presence of the authentication material in several layers in order to increase the number of signatures. Layer C1 may also be made using threads of the authentication material and threads of different colored polymer bases.

[0116] The object of Figure 11 is a simple tag (flat elliptical body) having an identification marking 34 that can be read by the eye and simply shows text that can be the brand of a product or service or the name of a company. This tag is manufactured by 3D printing with the same material as the chip of Figure 10, and the layer of 100% authentication material is integrated at a given depth within the detection limit of XRD analysis. The layer of identification material has the same surface as surface 34. Thus, XRD analysis can be performed at any position on surface 32 to obtain the XRD signature of the object.

[0117] In another embodiment, the tag can be manufactured from conventional plastic materials (or other materials: wood, leather, fabric, etc.) by printing or non-printing, i.e., without incorporating an inner layer of authentication material. Reference numeral 36 indicates a circular cavity having a diameter of about 10 to 20 mm and a depth of 100 to 200 μm filled with ink deposited by screen printing, as indicated by reference numeral 38. As in Example 4 above, the ink is strictly speaking a mixture of an ink compound and authentication material powder. Thus, the XRD signature of the object can be determined by XRD analysis in the ink deposit 38. The XRD signature is a composite signature resulting from the materials present, in particular the ink and the ink having the compound of the authentication material powder, and the underlying support.

[0118] In the variant of FIG. 12, the tag 50 (parallelepiped) is generated by 3D printing including an identification area having a linear barcode type identification marking 54 on its face 52. During its manufacture, the authentication material is deposited at a given depth on a part of the surface 52 of the tag 50. More specifically, the authentication material is deposited next to the barcode 54, here at the longitudinal end, in particular to the left of the dashed line 56 (virtual line).

[0119] Thus, the tag comprises an identification marking 54 and an authentication area 58 (symbolically indicated by the dashed rectangle) which is separate from but adjacent to the identification area 54. In order to indicate to the operator the location where the XRD analysis is to be performed, the line 56 or the box 58 can be drawn on the face 52.

[0120] The embodiment of FIG. 13 is carried out based on the same principle as the tag of FIG. 10. Here, it includes a pin 70 printed in the form of a disk from PLA. The surface layer includes a "bleem" type circular two-dimensional code 74 made of two different PLA threads. In order to enable XRD analysis, a layer having 100% authentication material is arranged at a predetermined depth. Thus, the XRD analysis can be performed at any position on the face 72 of the pin 70. The code 74 extends only over a part of the surface layer. Thus, the authentication and identification areas are partially overlapped.

[0121] The identification marking can represent information of different natures, in particular one or several of the following information items, namely the nature of the object, the name, the manufacturer's reference, the regulatory data, and the information regarding the XRD signature.

[0122] Regarding the information regarding the XRD signature, it is possible to include a link referring to a file or database containing the reference XRD signature. Alternatively, the reference XRD signature, i.e., the information representing the characteristic peaks (angle, intensity), may be directly encoded in the identification marking.

[0123] The above-presented results, in particular the diffractogram, were obtained using the above-presented given X-ray characterization technique, in particular a copper X-ray source. It is clear to those skilled in the art that the diffractogram may vary based on the wavelength of the incident X-ray depending on the material / composite material being analyzed. Therefore, to enable comparison of the diffractograms, it is ensured that the same X-ray source (same wavelength) and a similar X-characterization technique are used. If applicable, the information regarding the reference XRD signature can include the wavelength used and / or the type of X-ray source.

Prior Art Documents

Patent Documents

[0124]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Non-Patent Documents

[0125]

Non-Patent Document 1

Claims

1. An anti-counterfeiting object, comprising: a surface (12) having an optically distinguishable marking (14) readable by an eye and / or a machine; and an authentication volume extending in the thickness (z) direction from the surface (12) or from another surface of the anti-counterfeiting object so as to be accessible from this surface for being read by X-ray diffraction (XRD); The authentication volume is a composite of a first material called an authentication material and at least one second material, and the authentication volume has a material volume of at least 5 mm ３ and the authentication volume has an XRD signature resulting from a combination of emissions of two materials wherein the authentication material includes at least one amorphous phase, at least one crystalline phase, and at least one composite metal phase; wherein the second material has a unique XRD signature different from the XRD signature of the first material; wherein the authentication volume results from a non-miscible combination of the first material and the second material and from the association, juxtaposition, and / or superposition of the first and second materials provided separately; an anti-counterfeiting object, wherein the optically distinguishable marking marks or includes information regarding the position of the authentication volume within the object.

2. The anti-counterfeiting object according to claim 1, wherein the authentication material is present on the surface of the anti-counterfeiting object and / or is distributed within the thickness. The surface of the anti-counterfeiting object

3. The anti-counterfeiting object according to claim 1 or 2, wherein the authentication material is present within the authentication volume at a given depth or at several depths relative to the surface of the anti-counterfeiting object.

4. The authentication material occupies at least 10 mm ３ in volume, and is a forgery-preventing object according to any one of claims 1 to 3.

5. The anti-counterfeiting object according to any one of claims 1 to 4, wherein the authentication volume extends to a depth between 0 and 1.5 mm from the surface.

6. The authentication volume is at least 10 mm taken in a plane substantially parallel to the surface of the anti-counterfeiting object ２ An anti-counterfeiting object according to any one of claims 1 to 5, extending on the surface of

7. The anti-counterfeiting object according to any one of claims 1 to 6, wherein, when viewed in the direction of the thickness, the optically distinguishable marking and the authentication volume are at least partially superimposed for reading from the surface (12).

8. The anti-counterfeiting object according to any one of claims 1 to 4, wherein the optically distinguishable marking is made from two materials each having a different color.

9. The anti-counterfeiting object according to any one of claims 1 to 4, wherein the optically distinguishable marking is a two-color matrix marking, and the surface layer is made from the first material and the second material and each has a different color.

10. The anti-counterfeiting object according to any one of claims 1 to 4, wherein the optical identification marking includes a series of marks representing a code delimited by a peripheral line, and the authentication volume is located inside the contour of this peripheral line.

11. The anti-counterfeiting object according to any one of claims 1 to 4, wherein the anti-counterfeiting object is composed of a plurality of superimposed layers formed by 3D printing, and at least one of the layers is located at a depth between 0 and 0.6 mm from the surface of the anti-counterfeiting object including at least a part of the authentication material.

12. The anti-counterfeiting object according to any one of claims 1 to 4, wherein the optical identification marking includes measurement coordinates for performing XRD analysis indicating the position of a measurement zone.

13. A method for manufacturing an anti-counterfeiting object, wherein the anti-counterfeiting object is manufactured by additive manufacturing using a filament of an authentication material including at least one amorphous phase, at least one crystalline phase, and at least one composite metal phase, and at least one polymer-based filament of a different color called a second material, the anti-counterfeiting object is formed by continuous printing of a plurality of layers, the surface layer is printed to form an optical identification marking (14), and the material of the filament of the authentication material is deposited on the surface layer and / or one or more layers below the surface layer to form an authentication volume. The authentication volume has an XRD signature resulting from a combination of emissions of two materials. The second material has a unique XRD signature different from the XRD signature of the authentication material. The authentication volume results from a non-miscible combination of the authentication material and the second material, and from the association, juxtaposition, and / or superposition of the separately provided authentication material and second material. A method, wherein the optical identification marking marks or includes information regarding the position of the authentication volume within the object.

14. A method for authenticating an anti-counterfeiting object according to any one of claims 1 to 8, comprising: reading the optical identification marking of the anti-counterfeiting object using a reader to obtain information. To determine the XRD signature of the complex, XRD is used to analyze the authentication volume of the anti-counterfeiting object, and the XRD signature of the anti-counterfeiting object is compared with a reference XRD signature. A method comprising: **Claim 15** The method according to claim 14, wherein the optical identification marking comprises information regarding the reference XRD signature, particularly regarding the position and intensity of characteristic peaks. **Claim 16** The method according to claim 14, wherein the reference XRD signature is obtained from a database. **Claim 17** A method for manufacturing an anti-counterfeiting object, wherein at least a part of the anti-counterfeiting object is manufactured by immiscibly mixing a first material called an authentication material and at least one second material so as to form an authentication volume, and the authentication volume extends in the thickness (z) direction from one surface of the anti-counterfeiting object so as to be accessible from the one surface of the anti-counterfeiting object for being read by X-ray diffraction (XRD), the anti-counterfeiting object further comprises an optical identification marking (14) readable by the eye and / or a machine on the one surface or another surface, the authentication material comprises at least one amorphous phase, at least one crystalline phase, and at least one composite metal phase, the authentication volume has an XRD signature resulting from a combination of radiations of two materials, the second material has a unique XRD signature different from the XRD signature of the first material, the authentication volume results from the immiscible combination of the first material and the second material, as well as the association, juxtaposition, and / or superposition of the separately provided first and second materials, The method, wherein the optical identification marking marks or comprises information regarding the position of the authentication volume within the object. **Claim 18** The method according to claim 17, wherein the first and second materials are added separately to form the authentication volume, and in the authentication volume, they are associated, juxtaposed, and / or superposed. **Claim 19** The method according to claim 17, wherein the first and second materials are combined to control their respective volumes and positions within the authentication volume.

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