EP3543368A1 - High-entropy alloys for covering components - Google Patents
High-entropy alloys for covering components Download PDFInfo
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- EP3543368A1 EP3543368A1 EP18162716.7A EP18162716A EP3543368A1 EP 3543368 A1 EP3543368 A1 EP 3543368A1 EP 18162716 A EP18162716 A EP 18162716A EP 3543368 A1 EP3543368 A1 EP 3543368A1
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 57
- 239000000956 alloy Substances 0.000 title claims abstract description 57
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000005260 corrosion Methods 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 11
- 230000005294 ferromagnetic effect Effects 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 235000019589 hardness Nutrition 0.000 description 14
- 239000010936 titanium Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002009 allergenic effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/006—Amorphous alloys with Cr as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/008—Amorphous alloys with Fe, Co or Ni as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/08—Amorphous alloys with aluminium as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B37/00—Cases
Definitions
- the present invention relates to a high entropy alloy and a dressing component for a watch or jewel made in this alloy.
- Austenitic stainless steels generally contain nickel and also have limited hardnesses ( ⁇ 300 HV in the annealed state). Martensitic stainless steels are hard (> 600 HV) but ferromagnetic.
- titanium alloys such as titanium grade 5 (Ti6Al4V)
- Ti6Al4V titanium grade 5
- amorphous metals also very interesting for the dressing components, may have hardnesses greater than 500 HV.
- very particular implementations are necessary to obtain amorphous metal components, which further limits their use as a trim element.
- high-entropy alloys are all alloys containing at least 5 main elements with an atomic fraction between 5 and 35%, elements with an atomic fraction of less than 5% being considered as minor. To date, it is accepted that alloys containing 4 main elements can also be considered as high entropy alloys.
- the high entropy resulting from the mixing of many main elements would make it possible to stabilize the phases in solid solution with respect to the formation of potentially embrittling intermetallic phases.
- unique and poorly observed properties in traditional alloys based on one or two major elements are obtained.
- obtaining simple phases in solid solution is very interesting because it promotes good polishability and good resistance to corrosion.
- the mixture of many different elements gives rise to hardening by solid solution.
- high-entropy single-phase alloys high hardness has already been demonstrated, particularly for those with a centered cubic structure.
- the object of the invention is to propose a high-entropy alloy with a composition specifically adapted to the needs of dressing components.
- the present invention thus aims more particularly at developing an alloy having, after use, a hardness greater than or equal to 400 HV, a non-ferromagnetic behavior and a high resistance to corrosion.
- the alloy contains 3 main elements which are Cr, Fe and V each having atomic concentrations of between 20 and 40%. It further contains as main element Al and / or Si having the effect of annihilating the ferromagnetic behavior of the alloy. These elements each have an atomic concentration greater than or equal to 5% with a total atomic concentration for Al and Si less than or equal to 25%.
- the alloy may, in addition, optionally comprise one or more main elements chosen from Mn, Mo, Ti and Ni each having an atomic concentration greater than or equal to 5% with a total atomic concentration for these 4 main elements less than or equal to 35%. %.
- the Ni content is specifically maintained at a value of less than 20% in order to avoid, during the implementation and in particular of the heat treatments, the formation of unwanted phases which weaken the material and reduce the resistance to corrosion. .
- Some grades are otherwise devoid of Ni to ensure high biocompatibility.
- the balance may be composed of possible impurities and / or one or more minor elements each having an atomic concentration of less than 5%.
- the material obtained after implementation has, depending on the composition and the thermomechanical treatments, a single phase with a cubic centered structure, which promotes a good resistance to corrosion and good polishability for a better surface finish or in the case of multiphase alloys, a matrix (main phase) with centered cubic structure reinforced with nanoprecipitates. It has the other advantage of having a color similar to that of austenitic stainless steels.
- the present invention relates to high entropy alloys and their use for display components for watches or jewelery, in particular for components intended to be in contact with the skin.
- the dressing component may be a middle part, a bottom, a bezel, a pusher, a crown, a bracelet link, a dial, a needle, a dial index, a clasp, etc.
- a watch case 1 made of the alloy according to the invention is represented in FIG. figure 1 .
- the alloys comprise between 4 and 9 main elements.
- principal elements are meant elements having an atomic concentration greater than or equal to 5%.
- the alloys have the following 3 main elements: Cr, Fe, V with an atomic concentration between 20 and 40%. They also comprise 1 or 2 main elements chosen from Al and Si with a total atomic concentration for these two elements of less than or equal to 25%. They also optionally include one or more main elements selected from the Mn, Mo, Ti and Ni with a total atomic concentration for these 4 main elements less than or equal to 35%.
- the total atomic concentration for all the aforementioned main elements is greater than or equal to 80%.
- the balance may, optionally, contain minor elements selected from the list including Si, Mn, Mo, Al, Nb, H, B, C, N, O, Mg, Sc, Ti, Cu, Ni, Zn, Ga, Ge, Sr, Y, Zr, Rh, Pd, Ag, Sn, Sb, Hf, Ta, W, Pt and Au. Minor elements are elements with an atomic concentration of less than 5%.
- the balance may also contain residual impurities from the implementation.
- the shaping processes are conceivable. It is in particular possible to obtain these alloys by casting, by powder metallurgy processes, by additive manufacturing techniques or by layer deposition technologies. This also includes possible thermomechanical treatments (heat treatment, hot deformation, cold deformation) and sintering and hot isostatic pressing (HIP) steps.
- thermomechanical treatments heat treatment, hot deformation, cold deformation
- HIP hot isostatic pressing
- the alloys according to the invention After shaping and carrying out possible thermomechanical treatments, the alloys according to the invention present predominantly a centered cubic structure (BCC), which can be disordered (structure A2, space group Im3m ) or ordered (structure B2, space group Pm3m ).
- BCC centered cubic structure
- a single-phase microstructure can be obtained at ambient temperature for the alloys according to the invention which contain neither Ni nor Ti as main elements, nor minor elements, which promotes resistance to corrosion and polishability .
- the alloys according to the invention may have a microstructure with a second phase in the form of precipitates which in certain cases make it possible to improve the mechanical properties (hardness, ductility, tenacity, etc. .).
- the precipitates are small with nanometric sizes and the matrix has a substantially unchanged composition, i.e. that it retains a composition which satisfies the definition of the alloys according to the invention (phases in solid multi-element solution), the good polishability, the high resistance to corrosion as well as the absence of ferromagnetism are preserved.
- the addition of Ni or Ni and Ti is particularly interesting, since this makes it possible to obtain very hardening nanoprecipitates.
- the alloys according to the invention have, after use, the following properties required for the covering components: non-ferromagnetic behavior, hardness greater than or equal to 400HV, high resistance to corrosion, with in particular no sign of corrosion after the Salt spray test according to ISO 9227.
- alloy compositions which fulfill all these criteria after elaboration are given in table 1 below.
- the alloys were developed by arc melting without further heat treatment.
- the atomic fractions have been rounded to the nearest integer and the hardnesses have been rounded to the nearest ten.
- the addition of nickel makes it possible to significantly increase the hardness, thanks to the formation of NiAI nanoprecipitates in the matrix with a cubic centered structure.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Adornments (AREA)
- Powder Metallurgy (AREA)
Abstract
L'invention concerne un alliage à haute entropie avec une composition contenant entre 4 et 9 éléments principaux choisis parmi la liste constituée du Cr, Fe, V, Al, Si, Mn, Mo, Ti et Ni avec:- 3 éléments principaux qui sont le Cr, Fe et le V ayant chacun une concentration atomique comprise entre 20 et 40%,- 1 ou 2 éléments principaux choisis parmi l'Al et le Si ayant chacun une concentration atomique supérieure ou égale à 5% avec une concentration totale pour ces 2 éléments principaux inférieure ou égale à 25%,- 0, 1, 2, 3 ou 4 éléments principaux choisis parmi le Mn, Mo, Ti et le Ni ayant chacun une concentration atomique supérieure ou égale à 5% avec une concentration atomique totale pour ces 4 éléments principaux inférieure ou égale à 35%,la concentration atomique totale pour les 4 à 9 éléments principaux étant supérieure ou égale à 80%,le solde étant composé d'impuretés éventuelles et/ou d'un ou plusieurs éléments mineurs ayant chacun une concentration atomique inférieure à 5%.The invention relates to a high entropy alloy with a composition containing between 4 and 9 main elements selected from the list consisting of Cr, Fe, V, Al, Si, Mn, Mo, Ti and Ni with: - 3 main elements which are Cr, Fe and V each having an atomic concentration of between 20 and 40%; - 1 or 2 main elements selected from Al and Si each having an atomic concentration greater than or equal to 5% with a total concentration for these 2 main elements less than or equal to 25%, - 0, 1, 2, 3 or 4 main elements chosen from Mn, Mo, Ti and Ni each having an atomic concentration greater than or equal to 5% with a total atomic concentration for these 4 main elements less than or equal to 35%, the total atomic concentration for the 4 to 9 main elements being greater than or equal to 80%, the balance being composed of possible impurities and / or of one or more minor elements each having a conc Atomic input less than 5%.
Description
La présente invention concerne un alliage à haute entropie et un composant d'habillage pour une montre ou un bijou réalisé dans cet alliage.The present invention relates to a high entropy alloy and a dressing component for a watch or jewel made in this alloy.
Différents alliages sont aujourd'hui couramment utilisés pour la fabrication de composants d'habillage de montres qui sont des composants généralement exposés à l'environnement extérieur et pouvant être en contact avec la peau. Il s'agit, par exemple, d'aciers inoxydables austénitiques, d'alliages de titane ou encore de métaux précieux. Ces alliages possèdent en effet certaines propriétés importantes pour ce type de pièces, à savoir une résistance à la corrosion élevée, une bonne polissabilité pour des raisons esthétiques, et pas de ferromagnétisme. Outre ces caractéristiques, d'autres propriétés sont actuellement très recherchées en horlogerie. Ces caractéristiques sont une biocompatibilité élevée, notamment en réduisant ou en éliminant les éléments potentiellement allergènes comme le nickel ou le cobalt, et, une dureté et une résistance aux rayures élevées. Les alliages qui remplissent tous ces critères sont rares. Les métaux précieux ont des duretés faibles (<200 HV à l'état recuit). Les aciers inoxydables austénitiques contiennent généralement du nickel et possèdent également des duretés limitées (<300 HV à l'état recuit). Les aciers inoxydables martensitiques sont durs (>600 HV) mais ferromagnétiques. Finalement, les alliages de titane, comme le titane grade 5 (Ti6Al4V), représentent certainement le meilleur compromis parmi les propriétés présentées ci-dessus mais ils ont une couleur particulière et des duretés (environ 350 HV pour le titane grade 5) pas significativement plus élevées que certains aciers inoxydables austénitiques par exemple. Pour comparaison, les métaux amorphes, également très intéressants pour les composants d'habillage, peuvent avoir des duretés supérieures à 500 HV. Toutefois, des mises en oeuvre très particulières sont nécessaires pour obtenir des composants en métal amorphe, ce qui limite encore leur utilisation en tant qu'élément d'habillage.Various alloys are nowadays commonly used for the manufacture of watch dressing components which are components generally exposed to the external environment and may be in contact with the skin. These are, for example, austenitic stainless steels, titanium alloys or precious metals. These alloys have indeed some important properties for this type of parts, namely a high resistance to corrosion, good polishability for aesthetic reasons, and no ferromagnetism. In addition to these characteristics, other properties are currently very much sought after in watchmaking. These features are high biocompatibility, including reducing or eliminating potentially allergenic elements such as nickel or cobalt, and high hardness and scratch resistance. Alloys that meet all these criteria are rare. Precious metals have low hardnesses (<200 HV in the annealed state). Austenitic stainless steels generally contain nickel and also have limited hardnesses (<300 HV in the annealed state). Martensitic stainless steels are hard (> 600 HV) but ferromagnetic. Finally, titanium alloys, such as titanium grade 5 (Ti6Al4V), certainly represent the best compromise among the properties presented above but they have a particular color and hardness (about 350 HV for grade 5 titanium) not significantly more high as some austenitic stainless steels for example. For comparison, amorphous metals, also very interesting for the dressing components, may have hardnesses greater than 500 HV. However, very particular implementations are necessary to obtain amorphous metal components, which further limits their use as a trim element.
Dans le domaine de l'habillage horloger, il demeure donc toujours un fort intérêt pour l'obtention d'alliages cristallins durs (>400 HV à l'état recuit), non ferromagnétiques, résistants à la corrosion et présentant une bonne polissabilité. Dans ce cadre, les alliages à haute entropie, actuellement très étudiés et qui constituent une nouvelle classe d'alliages, sont particulièrement prometteurs. Selon la définition initiale, sont considérés comme alliages à haute entropie tous les alliages contenant au moins 5 éléments principaux avec une fraction atomique entre 5 et 35%, les éléments présentant une fraction atomique inférieure à 5% étant considérés comme mineurs. A ce jour, il est admis que les alliages contenant 4 éléments principaux peuvent également être considérés comme alliages à haute entropie. Au niveau thermodynamique, la haute entropie résultant du mélange de nombreux éléments principaux permettrait de stabiliser les phases en solution solide par rapport à la formation de phases intermétalliques potentiellement fragilisantes. En conséquence, des propriétés uniques et peu observées dans les alliages traditionnels basés sur un ou deux éléments principaux sont obtenues. Pour l'habillage horloger, l'obtention de phases simples en solution solide est très intéressante, car cela favorise une bonne polissabilité et une bonne résistance à la corrosion. De plus, le mélange de nombreux éléments différents engendre un durcissement par solution solide. Parmi les alliages à haute entropie monophasés, des duretés élevées ont ainsi déjà été mises en évidence, particulièrement pour ceux qui présentent une structure cubique centrée. Ces alliages à haute entropie monophasés à structure cubique centrée, comme par exemple le NbTiVZr, AINbTiV, Al0.4Hf0.6NbTaTiZr ou encore le Hf0.5Nb0.5Ta0.5Ti1.5Zr, visent plus spécifiquement les applications à haute température, pour l'aéronautique notamment. Toutefois, ils contiennent beaucoup d'éléments chers, très réactifs ou ayant des températures de fusion élevées, comme le Nb, Zr, Hf, Ta. Pour faciliter la mise en oeuvre des composants d'habillage, il est important d'éviter ou de limiter la quantité de ces éléments, la résistance à haute température n'étant pas une propriété désirée.In the field of watchmaking, there remains therefore a strong interest in obtaining hard crystalline alloys (> 400 HV in the annealed state), non-ferromagnetic, resistant to corrosion and having good polishability. In this context, the high entropy alloys, currently very studied and which constitute a new class of alloys, are particularly promising. According to the original definition, high-entropy alloys are all alloys containing at least 5 main elements with an atomic fraction between 5 and 35%, elements with an atomic fraction of less than 5% being considered as minor. To date, it is accepted that alloys containing 4 main elements can also be considered as high entropy alloys. At the thermodynamic level, the high entropy resulting from the mixing of many main elements would make it possible to stabilize the phases in solid solution with respect to the formation of potentially embrittling intermetallic phases. As a result, unique and poorly observed properties in traditional alloys based on one or two major elements are obtained. For clockwork, obtaining simple phases in solid solution is very interesting because it promotes good polishability and good resistance to corrosion. In addition, the mixture of many different elements gives rise to hardening by solid solution. Among the high-entropy single-phase alloys, high hardness has already been demonstrated, particularly for those with a centered cubic structure. These single-phase high-entrained alloys with a cubic centered structure, such as NbTiVZr, AINbTiV, Al0.4Hf0.6NbTaTiZr or Hf0.5Nb0.5Ta0.5Ti1.5Zr, are more specifically aimed at high temperature applications for aeronautics. especially. However, they contain a lot of elements expensive, highly reactive or having high melting temperatures, such as Nb, Zr, Hf, Ta. To facilitate the implementation of the dressing components, it is important to avoid or limit the amount of these elements, the high temperature resistance is not a desired property.
L'invention a pour objet de proposer un alliage à haute entropie avec une composition spécifiquement adaptée aux besoins des composants d'habillage. La présente invention vise ainsi plus particulièrement à développer un alliage présentant après mise en oeuvre une dureté supérieure ou égale à 400 HV, un comportement non ferromagnétique et une résistance à la corrosion élevée.The object of the invention is to propose a high-entropy alloy with a composition specifically adapted to the needs of dressing components. The present invention thus aims more particularly at developing an alloy having, after use, a hardness greater than or equal to 400 HV, a non-ferromagnetic behavior and a high resistance to corrosion.
A cet effet, l'alliage contient 3 éléments principaux qui sont le Cr, le Fe et le V ayant chacun des concentrations atomiques comprises entre 20 et 40%. Il contient en outre comme élément principal de l'Al et/ou du Si ayant pour effet d'annihiler le comportement ferromagnétique de l'alliage. Ces éléments ont chacun une concentration atomique supérieure ou égale à 5% avec une concentration atomique totale pour l'Al et le Si inférieure ou égale à 25%.For this purpose, the alloy contains 3 main elements which are Cr, Fe and V each having atomic concentrations of between 20 and 40%. It further contains as main element Al and / or Si having the effect of annihilating the ferromagnetic behavior of the alloy. These elements each have an atomic concentration greater than or equal to 5% with a total atomic concentration for Al and Si less than or equal to 25%.
L'alliage peut en outre optionnellement comporter un ou plusieurs éléments principaux choisis parmi le Mn, Mo, Ti et le Ni ayant chacun une concentration atomique supérieure ou égale à 5% avec une concentration atomique totale pour ces 4 éléments principaux inférieure ou égale à 35%. Selon l'invention, la teneur en Ni est spécifiquement maintenue à une valeur inférieure à 20% pour éviter, lors de la mise en oeuvre et notamment des traitements thermiques, la formation de phases indésirables qui fragilisent le matériau et réduisent la résistance à la corrosion. Certaines nuances sont par ailleurs dépourvues de Ni pour garantir une biocompatibilité élevée.The alloy may, in addition, optionally comprise one or more main elements chosen from Mn, Mo, Ti and Ni each having an atomic concentration greater than or equal to 5% with a total atomic concentration for these 4 main elements less than or equal to 35%. %. According to the invention, the Ni content is specifically maintained at a value of less than 20% in order to avoid, during the implementation and in particular of the heat treatments, the formation of unwanted phases which weaken the material and reduce the resistance to corrosion. . Some grades are otherwise devoid of Ni to ensure high biocompatibility.
Le solde peut être composé d'impuretés éventuelles et/ou d'un ou plusieurs éléments mineurs ayant chacun une concentration atomique inférieure à 5%.The balance may be composed of possible impurities and / or one or more minor elements each having an atomic concentration of less than 5%.
Le matériau obtenu après mise en oeuvre présente, en fonction de la composition et des traitements thermomécaniques, une seule phase à structure cubique centrée, ce qui favorise une bonne résistance à la corrosion et une bonne polissabilité pour un meilleur fini de surface ou dans le cas d'alliages multiphasés, une matrice (phase principale) à structure cubique centrée renforcée avec des nanoprécipités. Il présente pour autre avantage d'avoir une couleur proche de celle des aciers inoxydables austénitiques.The material obtained after implementation has, depending on the composition and the thermomechanical treatments, a single phase with a cubic centered structure, which promotes a good resistance to corrosion and good polishability for a better surface finish or in the case of multiphase alloys, a matrix (main phase) with centered cubic structure reinforced with nanoprecipitates. It has the other advantage of having a color similar to that of austenitic stainless steels.
D'autres avantages ressortiront des caractéristiques exprimées dans les revendications, de la description détaillée de l'invention illustrée ci-après à l'aide des dessins annexés donnés à titre d'exemples nullement limitatifs.Other advantages will emerge from the features expressed in the claims, of the detailed description of the invention illustrated hereinafter with the aid of the accompanying drawings given by way of non-limiting examples.
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La
figure 1 représente une boîte de montre réalisée avec l'alliage selon l'invention.Thefigure 1 represents a watch case made with the alloy according to the invention. -
La
figure 2 représente le diffractogramme d'un alliage Al6Cr30Fe30Mo5V29 après coulée et traitement thermique de 3h à 1300°C suivi d'un refroidissement dans un four avec une vitesse de refroidissement moyenne de l'ordre de 100°C/min.Thefigure 2 represents the diffractogram of an alloy Al6Cr30Fe30Mo5V29 after casting and heat treatment from 3h to 1300 ° C followed by cooling in an oven with an average cooling rate of the order of 100 ° C / min. -
La
figure 3 représente pour ce même alliage la courbe d'hystérèse.Thefigure 3 represents for this same alloy the hysteresis curve.
La présente invention se rapporte à des alliages à haute entropie et à leur utilisation pour des composants d'habillage pour montre ou bijou, notamment pour des composants destinés à être en contact avec la peau. Le composant d'habillage peut être une carrure, un fond, une lunette, un poussoir, une couronne, un maillon de bracelet, un cadran, une aiguille, un index de cadran, un fermoir, etc. A titre illustratif, une boîte de montre 1 réalisée dans l'alliage selon l'invention est représentée à la
Selon l'invention, les alliages comportent entre 4 et 9 éléments principaux. On entend par éléments principaux, des éléments ayant une concentration atomique supérieure ou égale à 5%. Les alliages comportent les 3 éléments principaux suivants : Cr, Fe, V avec une concentration atomique comprise entre 20 et 40%. Ils comportent en outre 1 ou 2 éléments principaux choisis parmi l'Al et le Si avec une concentration atomique totale pour ces deux éléments inférieure ou égale à 25%. Ils comportent en outre optionnellement un ou plusieurs éléments principaux choisis parmi le Mn, Mo, Ti et le Ni avec une concentration atomique totale pour ces 4 éléments principaux inférieure ou égale à 35%.According to the invention, the alloys comprise between 4 and 9 main elements. By principal elements are meant elements having an atomic concentration greater than or equal to 5%. The alloys have the following 3 main elements: Cr, Fe, V with an atomic concentration between 20 and 40%. They also comprise 1 or 2 main elements chosen from Al and Si with a total atomic concentration for these two elements of less than or equal to 25%. They also optionally include one or more main elements selected from the Mn, Mo, Ti and Ni with a total atomic concentration for these 4 main elements less than or equal to 35%.
Selon l'invention, la concentration atomique totale pour l'ensemble des éléments principaux précités est supérieure ou égale à 80%. Le solde peut, à titre optionnel, contenir des éléments mineurs choisis parmi la liste comprenant le Si, Mn, Mo, Al, Nb, H, B, C, N, O, Mg, Sc, Ti, Cu, Ni, Zn, Ga, Ge, Sr, Y, Zr, Rh, Pd, Ag, Sn, Sb, Hf, Ta, W, Pt et Au. On entend par éléments mineurs des éléments ayant une concentration atomique inférieure à 5%. Le solde peut également contenir des impuretés résiduelles issues de la mise en oeuvre.According to the invention, the total atomic concentration for all the aforementioned main elements is greater than or equal to 80%. The balance may, optionally, contain minor elements selected from the list including Si, Mn, Mo, Al, Nb, H, B, C, N, O, Mg, Sc, Ti, Cu, Ni, Zn, Ga, Ge, Sr, Y, Zr, Rh, Pd, Ag, Sn, Sb, Hf, Ta, W, Pt and Au. Minor elements are elements with an atomic concentration of less than 5%. The balance may also contain residual impurities from the implementation.
Pour obtenir les alliages selon l'invention, tous les procédés de mise en forme sont envisageables. Il est notamment possible d'obtenir ces alliages par coulée, par des procédés de métallurgie des poudres, par des techniques de fabrication additive ou encore par des technologies de déposition de couches. Cela inclut également des éventuels traitements thermomécaniques (traitement thermique, déformation à chaud, déformation à froid) et des étapes de frittage et de compression isostatique à chaud (HIP).To obtain the alloys according to the invention, all the shaping processes are conceivable. It is in particular possible to obtain these alloys by casting, by powder metallurgy processes, by additive manufacturing techniques or by layer deposition technologies. This also includes possible thermomechanical treatments (heat treatment, hot deformation, cold deformation) and sintering and hot isostatic pressing (HIP) steps.
Après mise en forme et réalisation d'éventuels traitements thermomécaniques, les alliages selon l'invention présentent majoritairement une structure cubique centrée (BCC), qui peut être désordonnée (structure A2, space group Im3m) ou ordonnée (structure B2, space group Pm3m). En particulier, une microstructure monophasée peut être obtenue à température ambiante pour les alliages selon l'invention qui ne comportent ni du Ni, ni du Ti comme éléments principaux, ni d'éléments mineurs, ce qui favorise la résistance à la corrosion et la polissabilité. Néanmoins, en fonction de la composition et des traitements thermiques effectués, les alliages selon l'invention peuvent présenter une microstructure avec une seconde phase sous forme de précipités qui permettent dans certains cas d'améliorer les propriétés mécaniques (dureté, ductilité, ténacité, etc.). Lorsque les précipités sont petits avec des tailles pouvant être nanométriques et lorsque la matrice possède une composition quasi inchangée, c.à.d. qu'elle conserve une composition qui satisfait la définition des alliages selon l'invention (phases en solution solide multi-éléments), la bonne polissabilité, la résistance à la corrosion élevée ainsi que l'absence de ferromagnétisme sont conservées. En particulier, l'ajout de Ni ou de Ni et de Ti est particulièrement intéressant, puisque cela permet d'obtenir des nanoprécipités très durcissants.After shaping and carrying out possible thermomechanical treatments, the alloys according to the invention present predominantly a centered cubic structure (BCC), which can be disordered (structure A2, space group Im3m ) or ordered (structure B2, space group Pm3m ). In particular, a single-phase microstructure can be obtained at ambient temperature for the alloys according to the invention which contain neither Ni nor Ti as main elements, nor minor elements, which promotes resistance to corrosion and polishability . Nevertheless, depending on the composition and the heat treatments carried out, the alloys according to the invention may have a microstructure with a second phase in the form of precipitates which in certain cases make it possible to improve the mechanical properties (hardness, ductility, tenacity, etc. .). When the precipitates are small with nanometric sizes and the matrix has a substantially unchanged composition, i.e. that it retains a composition which satisfies the definition of the alloys according to the invention (phases in solid multi-element solution), the good polishability, the high resistance to corrosion as well as the absence of ferromagnetism are preserved. In particular, the addition of Ni or Ni and Ti is particularly interesting, since this makes it possible to obtain very hardening nanoprecipitates.
En résumé, les alliages selon l'invention présentent après mise en oeuvre les propriétés suivantes requises pour les composants d'habillage : comportement non ferromagnétique, dureté supérieure ou égale à 400HV, résistance à la corrosion élevée, avec notamment aucun signe de corrosion après le test au brouillard salin selon la norme ISO 9227.In summary, the alloys according to the invention have, after use, the following properties required for the covering components: non-ferromagnetic behavior, hardness greater than or equal to 400HV, high resistance to corrosion, with in particular no sign of corrosion after the Salt spray test according to ISO 9227.
Quelques exemples de compositions d'alliages qui remplissent tous ces critères après élaboration sont donnés dans la table 1 ci-après. Les alliages ont été élaborés par fusion à l'arc (arc melting) sans autre traitement thermique. Dans la table, les fractions atomiques ont été arrondies au nombre entier le plus proche et les duretés ont été arrondies à la dizaine la plus proche.
On observe notamment que l'ajout de nickel permet d'augmenter significativement la dureté, grâce à la formation de nanoprécipités de NiAI dans la matrice à structure cubique centrée.In particular, the addition of nickel makes it possible to significantly increase the hardness, thanks to the formation of NiAI nanoprecipitates in the matrix with a cubic centered structure.
Après coulée et un traitement thermique de 3h sous argon à 1300 °C pour homogénéiser la structure de coulée, une microstructure monophasée est obtenue, notamment pour les alliages contenant uniquement des éléments majeurs sans Ni ni Ti, comme, par exemple, pour l'alliage Al6Cr30Fe30Mo5V29.After casting and a heat treatment of 3 hours under argon at 1300 ° C. to homogenize the casting structure, a single-phase microstructure is obtained, in particular for alloys containing only major elements without Ni or Ti, such as, for example, for the alloy Al6Cr30Fe30Mo5V29.
Une analyse par diffraction des rayons X (configuration Bragg-Brentano) a été effectuée sur cet alliage et a confirmé qu'une seule phase est présente avec trois raies correspondant à la structure cubique centrée. Le diffractogramme est représenté à la
Concernant les propriétés magnétiques de ce même alliage, une courbe d'hystérèse a été mesurée à température ambiante avec un magnétomètre à échantillon vibrant (aimantation M en fonction du champ appliqué H). Bien que présentant une susceptibilité volumique relativement élevée (4.8 10-3), l'alliage présente un comportement linéaire signature du comportement paramagnétique comme montré à la
Il est encore possible d'améliorer les propriétés, particulièrement les propriétés mécaniques, en ajoutant certains éléments mineurs tout en maintenant une phase principale qui satisfait la définition des alliages selon l'invention. Il est, par exemple, possible d'ajouter une petite quantité de bore comme élément mineur. En ajoutant 0.1% at. de bore à l'alliage Al10Cr30Fe30V30, la dureté est inchangée par rapport au même alliage sans bore (410 HV) mais, par contre, l'ajout de bore permet de réduire la croissance granulaire après traitement thermique et par là-même d'améliorer la ductilité et la polissabilité. L'ajout d'atomes interstitiels tels que le C, N et l'O comme éléments mineurs permet également d'augmenter la dureté.It is still possible to improve the properties, particularly the mechanical properties, by adding certain minor elements while maintaining a main phase which satisfies the definition of the alloys according to the invention. For example, it is possible to add a small amount of boron as a minor element. Adding 0.1% at. from boron to Al10Cr30Fe30V30 alloy, the hardness is unchanged from the same boron-free alloy (410 HV) but, on the other hand, the addition of boron makes it possible to reduce the granular growth after heat treatment and thereby to improve ductility and polishability. Adding interstitial atoms such as C, N and O as minor elements also increases the hardness.
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| JP2019019528A JP6802866B2 (en) | 2018-03-20 | 2019-02-06 | High entropy alloy for exterior parts |
| US16/271,925 US20190292633A1 (en) | 2018-03-20 | 2019-02-11 | High entropy alloy for external components |
| KR1020190017908A KR102180486B1 (en) | 2018-03-20 | 2019-02-15 | High entropy alloy for external components |
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| CN110777273A (en) * | 2018-07-31 | 2020-02-11 | 哈尔滨工业大学 | Method for improving room temperature plasticity of refractory high-entropy alloy |
| CN110777273B (en) * | 2018-07-31 | 2020-10-16 | 哈尔滨工业大学 | Method for improving room temperature plasticity of refractory high-entropy alloy |
| CN111321335A (en) * | 2020-03-06 | 2020-06-23 | 中南大学 | High-corrosion-resistance high-toughness FeCrNi series multi-principal-element alloy and preparation method thereof |
| CN113444955A (en) * | 2021-06-01 | 2021-09-28 | 西安理工大学 | High-entropy alloy containing eutectic structure and preparation method thereof |
| CN113444955B (en) * | 2021-06-01 | 2022-03-22 | 西安理工大学 | High-entropy alloy containing eutectic structure and preparation method thereof |
| CN113564493A (en) * | 2021-08-10 | 2021-10-29 | 成都大学 | High-entropy alloy reinforced FeCrAl alloy cladding material and preparation process thereof |
| CN113774295A (en) * | 2021-09-24 | 2021-12-10 | 中国人民解放军军事科学院国防科技创新研究院 | Al-Ni-Zr-Y-Co high-entropy amorphous alloy and preparation method thereof |
| WO2023093464A1 (en) * | 2021-11-23 | 2023-06-01 | 燕山大学 | High-entropy austenitic stainless steel, and preparation method therefor |
| CN114657439A (en) * | 2022-04-19 | 2022-06-24 | 西安稀有金属材料研究院有限公司 | Refractory high-entropy alloy with good room-temperature plasticity and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019163535A (en) | 2019-09-26 |
| CN110306094A (en) | 2019-10-08 |
| JP6802866B2 (en) | 2020-12-23 |
| KR102180486B1 (en) | 2020-11-19 |
| US20190292633A1 (en) | 2019-09-26 |
| KR20190110432A (en) | 2019-09-30 |
| EP3543368B1 (en) | 2020-08-05 |
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