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EP-4735195-A1 - METHOD FOR PRODUCING A METAL PART COMPRISING A LUMINESCENT OPTICAL MARKING

EP4735195A1EP 4735195 A1EP4735195 A1EP 4735195A1EP-4735195-A1

Abstract

The present invention relates to a method for producing a metal part from a metal alloy powder, the metal part comprising a luminescent optical marking. This method comprises the following consecutive steps (a) to (c): (a) preparing a first mixture in the form of a powder, the mixture comprising: - at least one first oxide of one or more metals chosen from among Li, K, Mg, Ca, Sr, Ba, Sc, Y, La, Lu, Ti, Zr, Hf, V, Nb, Ta, Zn, Cd, B, Al, Ga, Si and Ge; and - at least one precursor of a luminescent cation added in the form of a second metal oxide; (b) preparing a second mixture comprising the metal alloy powder and the first mixture; and (c) transforming the second mixture via additive manufacturing, thereby forming a luminescent optical marking layer.

Inventors

  • BASLARI, Christina
  • DE SOUSA NOBRE CATTOEN, Sonia
  • MASKROT, HICHAM
  • PACQUENTIN, Wilfried

Assignees

  • Commissariat à l'Energie Atomique et aux Energies Alternatives

Dates

Publication Date
20260506
Application Date
20240730

Claims (14)

  1. Claims 1. A method of manufacturing a metal part from a metal alloy powder, said metal part comprising a luminescent optical marking, this method comprising the following successive steps (a) to (c): (a) preparing a first mixture in the form of a powder and comprising: - at least 90% by mass of at least one first oxide of one or more metals chosen from Li, K, Mg, Ca, Sr, Ba, Sc, Y, La, Lu, Ti, Zr, Hf, V, Nb, Ta, Zn, Cd, B, Al, Ga, Si and Ge, and - at least 0.1% by mass of at least one precursor of a luminescent cation, this precursor being introduced in the form of a second metal oxide; (b) preparing a second mixture comprising: - from 0.1% mass to 20% mass of the first mixture, and - from 80% mass to 99.9% mass of the metal alloy powder; and (c) transforming the second mixture obtained at the end of step (b) by additive manufacturing allowing the material to be consolidated by a laser source or an electron beam, whereby the formation of a luminescent optical marking layer is obtained.
  2. 2. The method of claim 1, wherein the first metal oxide(s ) are selected from Li2O , K2O , MgO, CaO, SrO, BaO , Sc2O3, Y2O3, La2O3, Lu2O3, TiO2, ZrO2 , HfO2 , V2O5 , Nb2O5, Ta2O5 , ZnO , CdO , B2O3 , Al2O3 , Ga2O3 , SiO2 , GeO2 , Y3Al5O12 , YAlO3 , Y4Al2O9 , Sr4Al2O7 , Sr3Al2O6 , SrAl2O4 , SrAl4O7 and Sr4Al12O19 .
  3. 3. A method according to claim 1 or 2, wherein the first mixture comprises Y 2 O 3 and Al 2 O 3 .
  4. 4. A method according to any one of claims 1 to 3, wherein the luminescent cation(s) are selected from In + , Sn 2+ , Pb 2+ , Sb 3+ , Bi 3+ , Ce 3+ , Ce 4+ , Pr 3+ , Nd 3+ , Sm2+, Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 2+ , Tm 3+ , Yb 2+ , Yb 3+ , Ti 3+ , V 2+ , V 3+ , V 4+ , Cr 3+ , Cr 4+ , Mn 2+ , Mn 3+ , Mn 4+ , Fe 3+ , Fe 4+ , Fe 5+ , Co 3+ , Co 4+ , Ni 2+ , Cu + , Ru 2+ , Ru 3+ , Pd 2+ , Ag + , Ir 3+ , Pt 2+ and Au + .
  5. 5. The method of any one of claims 1 to 4, wherein the second metal oxide(s) are selected from In2O, PbO, Sb2O3, Bi2O3, Ce2O3, CeO2, Pr2O3, Nd2O3, SmO, Sm2O3, EuO, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, TmO, Tm2O3, YbO, Yb 2 O 3 , Ti 2 O 3 , VO, V 2 O 3 , VO 2 , Cr 2 O 3 , CrO 2 , MnO, Mn 2 O 3 , MnO 2 , Fe 2 O 3 , FeO 2 , Fe 2 O 5 , Co2O3, CoO2, NiO, Cu2O, RuO, Ru2O3, PdO, Ag2O, Ir2O3, PtO and Au2O and, preferably, among CeO2, Cr2O3 and Eu2O3.
  6. 6. The method of claim 5, wherein the first mixture comprises Y2O3, Al2O3 and CeO2.
  7. 7. A method according to any one of claims 1 to 6, wherein the metal alloy of the metal alloy powder is selected from iron alloys, aluminum alloys, titanium alloys, nickel alloys, copper alloys and steels, in particular stainless steels.
  8. 8. Method according to claim 7, in which, when the metal alloy is a steel, this steel is an austenitic steel, advantageously chosen from 316L steel, 304L steel and 1.4404 steel.
  9. 9. Method according to any one of claims 1 to 8, in which the first mixture comprises: - between 95% mass and 99.5% mass and, preferably, between 97% mass and 99% mass of the first metal oxide(s), and - up to 10% mass, advantageously between 0.5% mass and 5% mass and, preferably, between 1% mass and 3% mass of the second metal oxide(s).
  10. 10. Method according to any one of claims 1 to 9, in which the second mixture comprises: - from 0.5% mass to 15% mass of the first mixture, and - from 85% mass to 99.5% mass of the metal alloy powder.
  11. 11. Method according to any one of claims 1 to 10, in which step (c) of transformation by additive manufacturing is carried out by laser fusion on a powder bed or by laser fusion of projected powder.
  12. 12. A method according to any one of claims 1 to 11, wherein step (c) is repeated as many times as necessary to give the desired thickness to the luminescent optical marking layer.
  13. 13. Method according to any one of claims 1 to 12, further comprising at least one step (i) of transformation of the metal alloy powder by additive manufacturing, this or these steps (i) being able to be implemented before and/or after step(s) (c) and, preferably, before and after step(s) (c).
  14. 14. The method of claim 13, wherein this or these steps (i) are carried out by laser powder bed fusion or by laser powder fusion projected from the metal alloy powder.

Description

Description Title: Method for manufacturing a metal part comprising a luminescent optical marking TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for manufacturing a metal part, in particular a steel part, comprising a luminescent optical marking. The method according to the invention makes it possible to manufacture metal parts characterized by a luminescent optical marking which is unique, complex, non-reproducible and which, when incorporated into the part, is non-degradable and, therefore, permanent. The metal parts manufactured by the method according to the invention thus have the advantage of being able to be easily identified and traced, whether in the context of procedures for monitoring and controlling the quality of these parts or in the context of the fight against counterfeiting. The present invention finds applications in particular in many industrial sectors and, in particular, in the fields of nuclear power, automotive, aeronautics, railways, luxury goods or even the food sector. STATE OF THE ART Traditionally, in industry, the traceability of metal parts is carried out by methods such as labeling, engraving (for example, by micro-percussion) or marking which can be inkjet marking, laser marking or even luminescent marking. Manufacturers therefore have the choice of marking their metal parts with a marking that can be read by everyone or with a codified marking, for example with two-dimensional barcodes such as QR codes or Data Matrix codes. However, these different markings all have a certain number of limitations insofar as they are generally made on the surface of the metal parts, as in document DE 102014117519 A1 for example. These surface markings can therefore deteriorate over time. In addition, these markings are more or less easily reproducible. Furthermore, the manufacturing processes for marked metal parts implement one or more additional steps necessary to produce such markings. The aim of the present invention is, therefore, to overcome the drawbacks of the methods for manufacturing marked metal parts of the prior art and to propose a method for manufacturing a metal part comprising a particular marking, in this case a luminescent optical marking, this luminescent optical marking being unique, non-reproducible, or even permanent, this method not necessarily requiring the implementation of additional steps to obtain this particular marking. Documents CN 113231649 A, CN 114559046 A, CN 115625345 A, CN 110711862 A, CN 110735065 A and CN 115846927 A describe methods for preparing, by additive manufacturing, materials from powders of metal alloys and metal oxides. DISCLOSURE OF THE INVENTION The aims stated above and others are achieved by a method for manufacturing a metal part from a metal alloy powder, said metal part comprising a luminescent optical marking. According to the invention, the method comprises the following successive steps (a) to (c): (a) preparing a first mixture in the form of a powder and comprising: - at least one first oxide of one or more metals chosen from Li, K, Mg, Ca, Sr, Ba, Sc, Y, La, Lu, Ti, Zr, Hf, V, Nb, Ta, Zn, Cd, B, Al, Ga, Si and Ge, and - at least one precursor of a luminescent cation, this precursor being introduced in the form of a second metal oxide; (b) preparing a second mixture comprising the metal alloy powder and the first mixture, and (c) transforming the second mixture obtained at the end of step (b) by additive manufacturing, whereby the formation of a luminescent optical marking layer is obtained. The method according to the invention makes it possible to manufacture a metal part comprising a luminescent optical marking which is obtained by implementing a step (c) of transforming, by additive manufacturing, the second specific mixture formed by a mixture of powders resulting from steps (a) and (b) of the method of the invention. More particularly, during step (c) of the method according to the invention, luminescent precipitates are formed in situ from the first non-luminescent metal oxide(s) and the second metal oxide(s) which form the first mixture, by interaction of these first and second metal oxides with each other and/or with the metal matrix formed from the metal alloy powder. These interactions between the first and second metal oxides and the metal matrix, under these high-temperature processing conditions which are implemented in additive manufacturing step (c) and which allow the complete fusion of these first and second metal oxides and the metal matrix, generate a multitude of phases formed from the first metal oxide(s) and doped with the luminescent cation(s) present in the second metal oxide(s) which make the corresponding precipitations luminescent. Since the precipitations and their doping by this cation(s) are not controlled, the signals emitted by the luminescent precipitates thus formed in situ are random and non-reproducible. In doing so, the metal part manufactured by the method accord