US20190292633A1 - High entropy alloy for external components - Google Patents
High entropy alloy for external components Download PDFInfo
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- US20190292633A1 US20190292633A1 US16/271,925 US201916271925A US2019292633A1 US 20190292633 A1 US20190292633 A1 US 20190292633A1 US 201916271925 A US201916271925 A US 201916271925A US 2019292633 A1 US2019292633 A1 US 2019292633A1
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 65
- 239000000956 alloy Substances 0.000 title claims abstract description 65
- 238000005275 alloying Methods 0.000 claims abstract description 48
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 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
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 230000005294 ferromagnetic effect Effects 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 5
- 239000011159 matrix material 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
- 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 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
- 238000001513 hot isostatic pressing 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
- 239000010970 precious metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000013566 allergen Substances 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
- 230000005291 magnetic effect 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
- 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
-
- 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
- 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
-
- 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 concerns a high entropy alloy and an external component for a watch or piece of jewellery made from this alloy.
- Austenitic stainless steels generally contain nickel and also have limited hardness ( ⁇ 300 HV in annealed condition). Martensitic stainless steels are hard (>600 HV) but ferromagnetic.
- titanium alloys like grade 5 titanium (Ti6Al4V), certainly represent the best compromise among the properties set out above, but they have a particular colour and a hardness (around 350 HV for grade 5 titanium) that is not significantly higher than some austenitic stainless steels, for example.
- amorphous metals which are also very advantageous for external components, can have a hardness of more than 500 HV.
- very specific implementations are required to obtain amorphous metal components, which further limits their use as external components.
- the high entropy resulting from mixing various major alloying elements should stabilise solid-solution phases relative to the formation of potentially embrittling intermetallic phases. Consequently, unique properties, seldom seen in traditional alloys based on one or two major alloying elements are obtained. For external timepiece components, obtaining simple solid-solution phases is very advantageous, since it promotes high polishability and high corrosion resistance. Further, the mixture of various elements produces solid-solution hardening. Among single-phase high entropy alloys, high hardnesses have therefore already been demonstrated, particularly for those that have a body-centred cubic structure.
- the present invention more particularly aims to develop an alloy which, after implementation, has a hardness higher than or equal to 400 HV, non-ferromagnetic behaviour and high corrosion resistance.
- the alloy contains 3 major alloying elements which are Cr, Fe and V, each having atomic compositions comprised between 20 and 40%. It also contains Al and/or Si as major alloying element, which has the effect of eliminating the ferromagnetic behaviour of the alloy. These elements each have an atomic concentration higher than or equal to 5% with a total atomic concentration of Al and Si of less than or equal to 25%.
- the alloy may also optionally contain one or more major alloying elements chosen from Mn, Mo, Ti and Ni, each in an atomic concentration higher than or equal to 5% with a total atomic concentration of all 4 major alloying elements of less than or equal to 35%.
- the Ni content is specifically maintained at a value of less than 20% to avoid, during implementation and especially during heat treatments, the formation of undesirable phases which embrittle the material and reduce corrosion resistance.
- Some grades are also free of Ni to ensure high biocompatibility.
- the remainder can be made up of any impurities and/or one or more minor alloying elements, each in an atomic concentration of less than 5%.
- the material obtained after implementation has a single-phase with a body-centred cubic structure, which promotes good corrosion resistance and high polishability for a better surface finish or, in the case of multi-phase alloys, a matrix (main phase) with a body-centred cubic structure reinforced by nanoprecipitates. It also has the advantage of having a colour close to that of austenitic stainless steels.
- FIG. 1 represents a watch case made with the alloy according to the invention.
- FIG. 2 represents the diffractogram of an Al6Cr30Fe30Mo5V29 alloy after casting and heat treatment for 3 hours at 1300° C. followed by cooling in a furnace with a mean cooling speed of around 100° C./min.
- FIG. 3 represents the hysteresis curve for this same alloy.
- the present invention relates to high entropy alloys and to their use for external components for watches or pieces of jewellery, especially for components intended to be in contact with the skin.
- the external component can be a case middle, a case back, a bezel, a pusher, a crown, a bracelet link, a dial, a hand, a how symbol, a clasp, etc.
- a watch case 1 made from the alloy according to the invention is represented in FIG. 1 .
- the alloys include between 4 and 9 major alloying elements.
- Major alloying elements means elements having an atomic concentration higher than or equal to 5%.
- the alloys include the following 3 major alloying elements: Cr, Fe, V in an atomic concentration comprised between 20 and 40%. They also include 1 or 2 major alloying elements chosen from among Al and Si with a total atomic concentration of these two elements of less than or equal to 25%. They also optionally include one or more major alloying elements chosen from among Mn, Mo, Ti and Ni with a total atomic concentration of these 4 major alloying elements of less than or equal to 35%.
- the total atomic concentration of all the aforecited major alloying elements is greater than or equal to 80%.
- the remainder may, optionally, contain minor alloying 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 alloying elements means elements having an atomic concentration of less than 5%.
- the remainder can also contain residual impurities arising from the implementation.
- any shaping methods can be envisaged. It is possible, in particular, to obtain these alloys by casting, by powder metallurgy processes, by additive manufacturing techniques or by layer deposition technologies. This also includes any thermomechanical treatments (heat treatment, hot deformation, cold deformation) and sintering and hot isostatic pressing steps (HIP).
- thermomechanical treatments heat treatment, hot deformation, cold deformation
- HIP hot isostatic pressing steps
- the alloys according to the invention After shaping and performance of any thermomechanical treatments, the alloys according to the invention mostly have a body-centred cubic structure (BCC), which may be disordered (structure A2, space group Im3m) or ordered (B2 structure, space group Pm3m).
- BCC body-centred cubic structure
- a single-phase microstructure can be obtained at ambient temperature for alloys according to the invention which contain neither Ni, nor Ti as major alloying elements, nor any minor alloying elements, which promotes corrosion resistance and polishability.
- the alloys according to the invention may have a microstructure with a second phase in the form of precipitates, which, in some cases, can improve mechanical properties (hardness, ductility, resistance to deformation, etc.).
- the precipitates are small with sizes that may be nanometric and when the matrix has a virtually unchanged composition, i.e. it has a composition that satisfies the definition of alloys according to the invention (multi-element solid-solution phases), the high polishability, high corrosion resistance and absence of ferromagnetism are maintained.
- the addition of Ni or of Ni and Ti is particularly interesting, since this makes it possible to obtain very hardening nanoprecipitates.
- the alloys of the invention have the following properties required for external components: non-ferromagnetic behaviour, hardness higher than or equal to 400 HV, high corrosion resistance, especially with no sign of corrosion after the salt spray test according to ISO standard 9227.
- alloy compositions which meet all these criteria after fabrication are given in Table 1 below.
- the alloys were fabricated by arc melting with no other heat treatment.
- the atomic fractions have been rounded to the nearest whole number and hardness has been rounded to the nearest ten.
- Hardness Compositions (at. %) (HV10) Al10Fe25Cr40V25 450 Al10Fe40Cr25V25 410 Al10Fe25Cr25V40 500 Al10Fe30Cr30V30 410 Al5Cr30Fe30Mo5V30 480 Al6Cr30Fe30Mo5V29 480 Al5Cr30Fe30Si5V30 460 Al5Cr30Fe30Mn5V30 410 Al13Cr25Fe25Ni12V25 650 Fe25Cr25V25Al10Ni10Ti5 630 Cr31Fe31V31Si7 500
Abstract
Description
- The present invention concerns a high entropy alloy and an external component for a watch or piece of jewellery made from this alloy.
- Various alloys are commonly used nowadays for the fabrication of external watch components which are components generally exposed to the external environment that may be in contact with the skin. These are, for example, austenitic stainless steels, titanium alloys or precious metals. Indeed, these alloys have certain important properties for this type of parts, namely high corrosion resistance, high polishability for aesthetic purposes, and no ferromagnetism. In addition to these characteristics, other properties are currently highly sought-after in horology. These characteristics are high biocompatibility, especially by reducing or eliminating potential allergens, such as nickel or cobalt, and a high hardness and scratch resistance. Alloys that meet all these criteria are rare. Precious metals have low hardness (<200 HV in annealed condition). Austenitic stainless steels generally contain nickel and also have limited hardness (<300 HV in annealed condition). Martensitic stainless steels are hard (>600 HV) but ferromagnetic. Finally, titanium alloys, like
grade 5 titanium (Ti6Al4V), certainly represent the best compromise among the properties set out above, but they have a particular colour and a hardness (around 350 HV forgrade 5 titanium) that is not significantly higher than some austenitic stainless steels, for example. For comparison, amorphous metals, which are also very advantageous for external components, can have a hardness of more than 500 HV. However, very specific implementations are required to obtain amorphous metal components, which further limits their use as external components. - In the field of external timepiece components, there therefore remains a strong interest in obtaining hard, crystalline ferromagnetic alloys (>400 HV in annealed condition), which are corrosion resistant and highly polishable. In this context, high entropy alloys, currently the subject of much research and which form a new class of alloys, are particularly promising. According to the initial definition, alloys containing at least 5 major alloying elements with an atomic fraction of between 5 and 35% were considered high entropy alloys and elements having an atomic fraction of less than 5% were considered minor. These days, it is accepted that alloys containing 4 major alloying elements can be considered high entropy alloys. As regards thermodynamics, the high entropy resulting from mixing various major alloying elements should stabilise solid-solution phases relative to the formation of potentially embrittling intermetallic phases. Consequently, unique properties, seldom seen in traditional alloys based on one or two major alloying elements are obtained. For external timepiece components, obtaining simple solid-solution phases is very advantageous, since it promotes high polishability and high corrosion resistance. Further, the mixture of various elements produces solid-solution hardening. Among single-phase high entropy alloys, high hardnesses have therefore already been demonstrated, particularly for those that have a body-centred cubic structure. These single-phase, body-centred cubic structure, high entropy alloys, such as, for example, NbTiVZr, AlNbTiV, Al0.4Hf0.6NbTaTiZr or Hf0.5Nb0.5Ta0.5Ti1.5Zr, are more specifically intended for high temperature applications, especially for aeronautics. However, they contain many elements that are expensive, very reactive or have high melting temperatures, such as Nb, Zr, Hf, Ta. To facilitate the implementation of external timepiece components, it is important to avoid or limit the quantity of these elements, since high temperature resistance is not a desired property.
- It is an object of the invention to propose a high entropy alloy with a composition specifically adapted to the needs of external components. The present invention more particularly aims to develop an alloy which, after implementation, has a hardness higher than or equal to 400 HV, non-ferromagnetic behaviour and high corrosion resistance.
- To this end, the alloy contains 3 major alloying elements which are Cr, Fe and V, each having atomic compositions comprised between 20 and 40%. It also contains Al and/or Si as major alloying element, which has the effect of eliminating the ferromagnetic behaviour of the alloy. These elements each have an atomic concentration higher than or equal to 5% with a total atomic concentration of Al and Si of less than or equal to 25%.
- The alloy may also optionally contain one or more major alloying elements chosen from Mn, Mo, Ti and Ni, each in an atomic concentration higher than or equal to 5% with a total atomic concentration of all 4 major alloying elements of less than or equal to 35%. According to the invention, the Ni content is specifically maintained at a value of less than 20% to avoid, during implementation and especially during heat treatments, the formation of undesirable phases which embrittle the material and reduce corrosion resistance. Some grades are also free of Ni to ensure high biocompatibility.
- The remainder can be made up of any impurities and/or one or more minor alloying elements, each in an atomic concentration of less than 5%.
- Depending on the composition and thermomechanical treatments, the material obtained after implementation has a single-phase with a body-centred cubic structure, which promotes good corrosion resistance and high polishability for a better surface finish or, in the case of multi-phase alloys, a matrix (main phase) with a body-centred cubic structure reinforced by nanoprecipitates. It also has the advantage of having a colour close to that of austenitic stainless steels.
- Other advantages will appear from the features set out in the claims, and from the detailed description of the invention illustrated hereinafter with reference to the annexed drawings, given as non-limiting examples.
-
FIG. 1 represents a watch case made with the alloy according to the invention. -
FIG. 2 represents the diffractogram of an Al6Cr30Fe30Mo5V29 alloy after casting and heat treatment for 3 hours at 1300° C. followed by cooling in a furnace with a mean cooling speed of around 100° C./min. -
FIG. 3 represents the hysteresis curve for this same alloy. - The present invention relates to high entropy alloys and to their use for external components for watches or pieces of jewellery, especially for components intended to be in contact with the skin. The external component can be a case middle, a case back, a bezel, a pusher, a crown, a bracelet link, a dial, a hand, a how symbol, a clasp, etc. By way of illustration, a
watch case 1 made from the alloy according to the invention is represented inFIG. 1 . - According to the invention, the alloys include between 4 and 9 major alloying elements. ‘Major alloying elements’ means elements having an atomic concentration higher than or equal to 5%. The alloys include the following 3 major alloying elements: Cr, Fe, V in an atomic concentration comprised between 20 and 40%. They also include 1 or 2 major alloying elements chosen from among Al and Si with a total atomic concentration of these two elements of less than or equal to 25%. They also optionally include one or more major alloying elements chosen from among Mn, Mo, Ti and Ni with a total atomic concentration of these 4 major alloying elements of less than or equal to 35%.
- According to the invention, the total atomic concentration of all the aforecited major alloying elements is greater than or equal to 80%. The remainder may, optionally, contain minor alloying 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 alloying elements’ means elements having an atomic concentration of less than 5%. The remainder can also contain residual impurities arising from the implementation.
- To obtain the alloys according to the invention, any shaping methods can be envisaged. It is possible, in particular, to obtain these alloys by casting, by powder metallurgy processes, by additive manufacturing techniques or by layer deposition technologies. This also includes any thermomechanical treatments (heat treatment, hot deformation, cold deformation) and sintering and hot isostatic pressing steps (HIP).
- After shaping and performance of any thermomechanical treatments, the alloys according to the invention mostly have a body-centred cubic structure (BCC), which may be disordered (structure A2, space group Im3m) or ordered (B2 structure, space group Pm3m). In particular, a single-phase microstructure can be obtained at ambient temperature for alloys according to the invention which contain neither Ni, nor Ti as major alloying elements, nor any minor alloying elements, which promotes corrosion resistance and polishability. Nonetheless, depending on the composition and 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 some cases, can improve mechanical properties (hardness, ductility, resistance to deformation, etc.). When the precipitates are small with sizes that may be nanometric and when the matrix has a virtually unchanged composition, i.e. it has a composition that satisfies the definition of alloys according to the invention (multi-element solid-solution phases), the high polishability, high corrosion resistance and absence of ferromagnetism are maintained. In particular, the addition of Ni or of Ni and Ti is particularly interesting, since this makes it possible to obtain very hardening nanoprecipitates.
- In short, after implementation, the alloys of the invention have the following properties required for external components: non-ferromagnetic behaviour, hardness higher than or equal to 400 HV, high corrosion resistance, especially with no sign of corrosion after the salt spray test according to ISO standard 9227.
- A few examples of alloy compositions which meet all these criteria after fabrication are given in Table 1 below. The alloys were fabricated by arc melting with no other heat treatment. In the table, the atomic fractions have been rounded to the nearest whole number and hardness has been rounded to the nearest ten.
-
TABLE 1 Hardness Compositions (at. %) (HV10) Al10Fe25Cr40V25 450 Al10Fe40Cr25V25 410 Al10Fe25Cr25V40 500 Al10Fe30Cr30V30 410 Al5Cr30Fe30Mo5V30 480 Al6Cr30Fe30Mo5V29 480 Al5Cr30Fe30Si5V30 460 Al5Cr30Fe30Mn5V30 410 Al13Cr25Fe25Ni12V25 650 Fe25Cr25V25Al10Ni10Ti5 630 Cr31Fe31V31Si7 500 - It is observed, in particular, that the addition of nickel makes it possible to significantly increase hardness, owing to the formation of nanoprecipitates of NiAl in the body-centred cubic structure matrix.
- After casting and a heat treatment for 3 hours under argon at 1300° C. to homogenise the casting structure, a single phase microstructure is obtained, particularly for alloys containing only major alloying elements without Ni or Ti, such as, for example, for the alloy Al6Cr30Fe30Mo5V29.
- An X ray diffraction analysis (Bragg-Brentano configuration) was performed on this alloy and confirmed that a single phase was present with three lines corresponding to the body-centred cubic structure. This diffractogram is represented in
FIG. 2 . - With regard to the magnetic properties of this alloy, a hysteresis curve was measured at ambient temperature with a vibrating sample magnetometer (magnetisation M according to the applied field H). Although the alloy has a relatively high volume susceptibility (4.8 10−3), the alloy exhibits linear behaviour, signature of paramagnetic behaviour, as shown in
FIG. 3 . - It is also possible to improve the properties, particularly the mechanical properties, by adding some minor alloying elements while maintaining a major phase that meets the definition of alloys according to the invention. It is, for example, possible to add a small amount of boron as minor alloying element. Adding 0.1 at. % of boron to the alloy Al10Cr30Fe30V30 leaves the hardness unchanged relative to the same alloy without boron (410 HV), however, the addition of boron reduces grain growth after heat treatment and thereby improves ductility and polishability. The addition of interstitial atoms such as C, N and 0 as minor alloying elements also makes it possible to increase hardness.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070284108A1 (en) * | 2006-04-21 | 2007-12-13 | Roes Augustinus W M | Compositions produced using an in situ heat treatment process |
CN105714353A (en) * | 2016-02-02 | 2016-06-29 | 北京科技大学 | Method for generating composite oxide nanotube array on high-entropy alloy surface |
CN108359948A (en) * | 2018-01-22 | 2018-08-03 | 北京科技大学 | A kind of high flux screening Cr-Fe-V-Ta-W systems high-entropy alloy film and preparation method thereof |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020159914A1 (en) * | 2000-11-07 | 2002-10-31 | Jien-Wei Yeh | High-entropy multielement alloys |
JP4190720B2 (en) * | 2000-11-29 | 2008-12-03 | 國立清華大學 | Multi-component alloy |
TWI347978B (en) * | 2007-09-19 | 2011-09-01 | Ind Tech Res Inst | Ultra-hard composite material and method for manufacturing the same |
CN101418394A (en) * | 2007-10-23 | 2009-04-29 | 财团法人工业技术研究院 | Superhard composite material and method for preparation thereof |
CN102776430B (en) * | 2012-08-20 | 2014-08-06 | 太原理工大学 | AlCoCrFeNiTix high-entropy alloy material and method for preparing same |
CN103194656A (en) * | 2013-04-19 | 2013-07-10 | 梧州漓佳铜棒有限公司 | AlxCrFeNiCuVTi high-entropy alloy material and preparation method thereof |
CN103757661A (en) * | 2014-01-24 | 2014-04-30 | 福建工程学院 | Aluminum electrolysis inert anode |
JP6432822B2 (en) * | 2014-07-25 | 2018-12-05 | 日立金属株式会社 | Alloy powder used for melt lamination molding |
JP6388381B2 (en) * | 2014-07-23 | 2018-09-12 | 日立金属株式会社 | Alloy structure |
JP6455700B2 (en) * | 2014-07-25 | 2019-01-23 | 日立金属株式会社 | Method for manufacturing alloy structure |
JP6455699B2 (en) * | 2014-07-25 | 2019-01-23 | 日立金属株式会社 | Method for manufacturing alloy structure |
JP6455701B2 (en) * | 2014-07-25 | 2019-01-23 | 日立金属株式会社 | Alloy structure |
US10190197B2 (en) * | 2015-12-11 | 2019-01-29 | The Trustees Of Dartmouth College | Oxidation resistant high-entropy alloys |
KR101831056B1 (en) * | 2016-06-01 | 2018-02-21 | 한국기계연구원 | High entropy alloy |
-
2018
- 2018-03-20 EP EP18162716.7A patent/EP3543368B1/en active Active
-
2019
- 2019-02-06 JP JP2019019528A patent/JP6802866B2/en active Active
- 2019-02-11 US US16/271,925 patent/US20190292633A1/en not_active Abandoned
- 2019-02-15 KR KR1020190017908A patent/KR102180486B1/en active IP Right Grant
- 2019-03-19 CN CN201910207000.1A patent/CN110306094A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070284108A1 (en) * | 2006-04-21 | 2007-12-13 | Roes Augustinus W M | Compositions produced using an in situ heat treatment process |
CN105714353A (en) * | 2016-02-02 | 2016-06-29 | 北京科技大学 | Method for generating composite oxide nanotube array on high-entropy alloy surface |
CN108359948A (en) * | 2018-01-22 | 2018-08-03 | 北京科技大学 | A kind of high flux screening Cr-Fe-V-Ta-W systems high-entropy alloy film and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
Miracle et al, "A critical review of high entropy alloys and related concepts", 2017. Acta Materialia, Vol 122, pp 448-511. (Year: 2017) * |
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