EP3889691A1 - Horological hairspring made of a ni-hf alloy - Google Patents

Horological hairspring made of a ni-hf alloy Download PDF

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Publication number
EP3889691A1
EP3889691A1 EP21170773.2A EP21170773A EP3889691A1 EP 3889691 A1 EP3889691 A1 EP 3889691A1 EP 21170773 A EP21170773 A EP 21170773A EP 3889691 A1 EP3889691 A1 EP 3889691A1
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European Patent Office
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weight
total
equal
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alloy
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EP21170773.2A
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German (de)
French (fr)
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EP3889691B1 (en
Inventor
Christian Charbon
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Nivarox Far SA
Nivarox SA
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Nivarox Far SA
Nivarox SA
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Classifications

    • 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
    • G04B17/00—Mechanisms for stabilising frequency
    • G04B17/04—Oscillators acting by spring tension
    • G04B17/06—Oscillators with hairsprings, e.g. balance
    • G04B17/066—Manufacture of the spiral spring
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • 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
    • G04B17/00—Mechanisms for stabilising frequency
    • G04B17/04—Oscillators acting by spring tension
    • G04B17/06—Oscillators with hairsprings, e.g. balance
    • 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
    • G04B17/00—Mechanisms for stabilising frequency
    • G04B17/04—Oscillators acting by spring tension
    • G04B17/06—Oscillators with hairsprings, e.g. balance
    • G04B17/063—Balance construction

Definitions

  • the invention relates to a method of manufacturing a spiral spring intended to equip a balance of a timepiece movement. It also relates to the spiral spring resulting from this process produced in an Nb-Hf alloy.
  • spiral springs are also centered on the concern for thermal compensation, so as to guarantee regular chronometric performance. This requires obtaining a thermoelastic coefficient close to zero. We are also looking to produce spiral springs exhibiting limited sensitivity to magnetic fields.
  • An object of the present invention is to provide a method of manufacturing a spiral spring intended to equip a balance with a clockwork movement making it possible to facilitate deformation, and more particularly to obtain easy rolling.
  • the method comprises, before the deformation step and after the annealing step, a step of depositing, on the blank, a layer of a ductile material chosen from the group comprising copper, nickel, cupro-nickel, cupro-manganese, gold, silver, nickel-phosphorus Ni-P and nickel-boron Ni-B, to facilitate wire shaping.
  • a ductile material chosen from the group comprising copper, nickel, cupro-nickel, cupro-manganese, gold, silver, nickel-phosphorus Ni-P and nickel-boron Ni-B, to facilitate wire shaping.
  • the thickness of the layer of ductile material deposited is chosen so that the ratio of ductile material surface / surface area of the NbHf alloy for a given wire section is less than 1, preferably less than 0.5, and more preferably between 0.01 and 0.4.
  • the invention relates to a method of manufacturing a spiral spring intended to equip a balance of a clockwork movement and made of an alloy comprising niobium and hafnium.
  • the blank comprises by weight between 8 and 12% of hafnium, Ti, Zr, Ta and W with a percentage for each element between 0.2 and 1.5%, and more preferably Ti included in a percentage between 0.5 and 1.5%, Zr in a percentage between 0.5 and 0.9%, Ta in a percentage between 0.3 and 0.7%, W in a percentage between 0.3 and 0.7%.
  • the NbHf alloy blank used in the present invention does not include other elements except for possible and inevitable traces. This makes it possible to avoid the formation of fragile phases.
  • the oxygen content is less than or equal to 0.10% by weight of the total, in particular less than or equal to 0.05% by weight of the total, or even less than or equal to 0.03% by weight of the total.
  • the carbon content is less than or equal to 0.04% by weight of the total, in particular less than or equal to 0.02% by weight of the total, or even less than or equal to 0.015% by weight of the total.
  • the iron content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.02% by weight of the total, or even less than or equal to 0.005% by weight of the total.
  • the nitrogen content is less than or equal to 0.04% by weight of the total, in particular less than or equal to 0.02% by weight of the total, or even less than or equal to 0.015% by weight of the total.
  • the hydrogen content is less than or equal to 0.01% by weight of the total, in particular less than or equal to 0.0035% by weight of the total, or even less than or equal to 0.001% by weight of the total.
  • the silicon content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.02% by weight of the total, or even less than or equal to 0.005% by weight of the total.
  • the nickel content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.
  • the content of element in ductile solid solution, such as copper, in the alloy is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to equal to 0.004% by weight of the total.
  • the aluminum content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.
  • the chromium content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.
  • the manganese content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.
  • the vanadium content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.
  • the tin content is less than or equal to 0.01% by weight of the total, in particular less than or equal to 0.0035% by weight of the total, or even less than or equal to 0.001% by weight of the total.
  • the magnesium content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.
  • the molybdenum content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.
  • the lead content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.
  • the cobalt content is less than or equal to 0.01% by weight of the total, in particular less than or equal to 0.0035% by weight of the total, or even less than or equal to 0.001% by weight of the total.
  • the boron content is less than or equal to 0.005% by weight of the total, in particular less than or equal to 0.0001% by weight of the total.
  • the annealing step is a dissolving treatment, with a duration preferably between 5 minutes and 2 hours at a temperature between 650 ° C and 1750 ° C, under vacuum, followed by quenching for example. under gas to obtain Hf in a supersaturated solid solution in Nb ⁇ .
  • natural cooling under vacuum can also be envisaged.
  • the deposition step which is more particularly the subject of the invention consists in depositing a layer of a ductile material chosen from the group comprising copper, nickel, cupro-nickel, cupro-manganese, gold , silver, nickel-phosphorus Ni-P and nickel-boron Ni-B, to facilitate wire forming.
  • a ductile material chosen from the group comprising copper, nickel, cupro-nickel, cupro-manganese, gold , silver, nickel-phosphorus Ni-P and nickel-boron Ni-B, to facilitate wire forming.
  • the thickness of the layer of ductile material deposited is chosen so that the ratio of ductile material surface / surface area of the NbHf alloy for a given wire section is less than 1, preferably less than 0.5, and more preferably between 0.01 and 0.4.
  • the layer of ductile material may have a thickness of 7 ⁇ m for an NbHf alloy section of 0.086 mm in diameter. This corresponds to a ratio between the area of copper (0.002 mm 2 ) and the area of NbHf (0.0058 mm 2 ) of 0.35.
  • Such a thickness of ductile material, and in particular copper makes it possible to easily stretch, draw and roll the Cu / NbHf composite material.
  • the thickness of copper is optimized so that the tip, created by filing or by hot drawing, necessary for the introduction of the wire into the die during drawing or drawing is covered with copper.
  • the ductile material preferably copper, is thus deposited at a given time to facilitate the shaping of the wire by drawing, drawing and rolling, so that a thickness thereof remains, preferably between 1 and 500. micrometers on the wire with a total diameter of 0.2 to 1 millimeter.
  • the supply of ductile material can be galvanic, by PVD or CVD, or else mechanical, it is then a jacket or a tube of ductile material such as copper which is fitted to a bar of NbHf alloy with a large diameter, then which is thinned during the step or steps of deformation of the composite bar.
  • ductile material such as copper which is fitted to a bar of NbHf alloy with a large diameter, then which is thinned during the step or steps of deformation of the composite bar.
  • one possibility is to form a composite billet by assembling an Nb-Hf bar and a copper jacket which is then extruded.
  • the deformation step generally refers to one or more deformation treatments, which may include wire drawing and / or rolling.
  • Wire drawing may require the use of one or more dies during the same deformation step or during different deformation steps if necessary.
  • the wire drawing is carried out until a wire of round section is obtained.
  • Rolling can be performed in the same deformation step as wire drawing or in another subsequent deformation step.
  • the last deformation treatment applied to the alloy is rolling, preferably with a rectangular profile compatible with the entry section of a stranding spindle.
  • the method may include one step or more deformation steps with a deformation rate for each step between 1 and 5, preferably between 2 and 5, the deformation rate corresponding to the conventional formula 2ln (d0 / d) where d0 and d are the diameter before and after deformation, respectively.
  • the total strain rate can be between 1 and 14.
  • the process may include intermediate annealing steps between the different deformation steps.
  • the method of the invention preferably comprises, after the deformation step, a step of removing said layer of ductile material.
  • the ductile material is removed once all the deformation operations have been carried out, that is to say after the last rolling, before the stretching.
  • the wire is freed from its layer of ductile material, such as copper, in particular by chemical attack, with a solution based on cyanides or based on acids, for example nitric acid.
  • the annealing prior to the deformation step as well as the intermediate annealing carried out between the deformation steps is carried out during a period of between 5 minutes and 2 hours, preferably between 10 minutes and 1 hour at a temperature of between 650 ° C and 1750 ° C.
  • the final heat treatment after the straddling is carried out at a temperature between 500 and 1250 ° C for a time between 30 minutes and 30 hours.
  • a single-phase structure of the centered or two-phase cubic type with a centered cubic structure and a compact hexagonal structure can be obtained at the end of this heat treatment.
  • the method of the invention allows the production, and more particularly the shaping, of a balance spring for a balance made of a niobium-hafnium type alloy.
  • This alloy has high mechanical properties, by combining a very high elastic limit, greater than 600 MPa, and a very low modulus of elasticity, of the order of 60 GPa to 100 GPa. This combination of properties is well suited for a spiral spring. In addition, such an alloy is paramagnetic.
  • a binary type alloy comprising niobium and hafnium, of the type selected above for the implementation of the invention also exhibits an effect similar to that of “Elinvar”, with a thermoelastic coefficient. practically zero in the temperature range of usual use of watches, and suitable for the manufacture of self-compensating balance springs.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Springs (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

La présente invention concerne un spiral horloger composé d'un alliage Ni-Hf et comportant également des basses pourcentages en poids de Ti, Zr, Ta et W.The present invention relates to a watch balance spring composed of an Ni-Hf alloy and also comprising low percentages by weight of Ti, Zr, Ta and W.

Description

Domaine de l'inventionField of the invention

L'invention concerne un procédé de fabrication d'un ressort spiral destiné à équiper un balancier d'un mouvement d'horlogerie. Elle se rapporte également au ressort spiral issu de ce procédé réalisé dans un alliage Nb-Hf.The invention relates to a method of manufacturing a spiral spring intended to equip a balance of a timepiece movement. It also relates to the spiral spring resulting from this process produced in an Nb-Hf alloy.

Arrière-plan de l'inventionBackground of the invention

La fabrication de ressorts spiraux pour l'horlogerie doit faire face à des contraintes souvent à première vue incompatibles :

  • nécessité d'obtention d'une limite élastique élevée,
  • facilité d'élaboration, notamment de tréfilage et de laminage,
  • excellente tenue en fatigue,
  • stabilité des performances dans le temps,
  • faibles sections.
The manufacture of spiral springs for watchmaking must face constraints that are often incompatible at first sight:
  • need to obtain a high elastic limit,
  • ease of production, especially wire drawing and rolling,
  • excellent resistance to fatigue,
  • performance stability over time,
  • low sections.

La réalisation de ressorts spiraux est en outre centrée sur le souci de la compensation thermique, de façon à garantir des performances chronométriques régulières. Il faut pour cela obtenir un coefficient thermoélastique proche de zéro. On recherche également à réaliser des ressorts spiraux présentant une sensibilité aux champs magnétiques limitée.The production of spiral springs is also centered on the concern for thermal compensation, so as to guarantee regular chronometric performance. This requires obtaining a thermoelastic coefficient close to zero. We are also looking to produce spiral springs exhibiting limited sensitivity to magnetic fields.

Des spiraux ont été développés à partir d'alliages de niobium et d'hafnium. Toutefois, ces alliages posent des problèmes de collement et de grippage dans les filières d'étirage ou de tréfilage (diamant ou métal dur) et contre les rouleaux de laminage (métal dur ou acier), ce qui les rend quasiment impossibles à transformer en fils fins par les procédés standards utilisés par exemple pour l'acier.Spirals have been developed from alloys of niobium and hafnium. However, these alloys pose problems of sticking and seizing in the drawing or drawing dies (diamond or hard metal) and against the rolling rolls (hard metal or steel), which makes them almost impossible to transform into wires. purposes by standard processes used for example for steel.

Toute amélioration sur au moins l'un de ces points, et en particulier sur la facilité d'élaboration, notamment de tréfilage et de laminage, représente donc une avancée significative.Any improvement on at least one of these points, and in particular on the ease of preparation, in particular of drawing and rolling, therefore represents a significant advance.

Résumé de l'inventionSummary of the invention

Un objet de la présente invention est de proposer un procédé de fabrication d'un ressort spiral destiné à équiper un balancier d'un mouvement d'horlogerie permettant de faciliter les déformations, et plus particulièrement d'obtenir un laminage aisé.An object of the present invention is to provide a method of manufacturing a spiral spring intended to equip a balance with a clockwork movement making it possible to facilitate deformation, and more particularly to obtain easy rolling.

A cet effet, l'invention concerne un procédé de fabrication d'un ressort spiral destiné à équiper un balancier d'un mouvement d'horlogerie qui comprend :

  • une étape d'élaboration d'une ébauche dans un alliage de niobium et d'hafnium constitué de :
    • niobium : balance à 100% en poids,
    • hafnium: entre 5 et 60% en poids, de préférence entre 5 et 30%, et plus préférentiellement entre 8 et 12% en poids,
    • un ou plusieurs éléments choisis parmi le Ti, Zr, Ta, W avec un pourcentage pour chaque élément compris entre 0 et 2%, de préférence entre 0.2 et 1.5% en poids,
    • impuretés avec un pourcentage total compris entre 0 et 0.5% en poids. Plus précisément, les impuretés peuvent être des traces d'éléments sélectionnés parmi le groupe constitué de O, H, C, Fe, N, Ni, Si, Cu, Al, Cr, Mn, V, Sn, Mg, Mo, Pb, Co, B, chacun desdits éléments étant présent dans une quantité comprise entre 0 et 1000 ppm en poids,
  • une étape de recuit et refroidissement de ladite ébauche suivie d'une étape de déformation de l'ébauche recuite pour former un fil, les étapes de recuit et de déformation pouvant être répétées plusieurs fois,
  • une étape d'estrapadage pour former le ressort-spiral,
  • une étape finale de traitement thermique.
To this end, the invention relates to a method of manufacturing a spiral spring intended to equip a balance of a timepiece movement which comprises:
  • a stage of preparation of a blank in an alloy of niobium and hafnium consisting of:
    • niobium: balance at 100% by weight,
    • hafnium: between 5 and 60% by weight, preferably between 5 and 30%, and more preferably between 8 and 12% by weight,
    • one or more elements chosen from Ti, Zr, Ta, W with a percentage for each element between 0 and 2%, preferably between 0.2 and 1.5% by weight,
    • impurities with a total percentage between 0 and 0.5% by weight. More precisely, the impurities can be traces of elements selected from the group consisting of O, H, C, Fe, N, Ni, Si, Cu, Al, Cr, Mn, V, Sn, Mg, Mo, Pb, Co, B, each of said elements being present in an amount between 0 and 1000 ppm by weight,
  • a step of annealing and cooling said blank followed by a step of deforming the annealed blank to form a wire, the annealing and deformation steps being able to be repeated several times,
  • a stepping step to form the spiral spring,
  • a final heat treatment step.

Selon l'invention, le procédé comprend avant l'étape de déformation et après l'étape de recuit, une étape de dépôt, sur l'ébauche, d'une couche d'un matériau ductile choisi parmi le groupe comprenant le cuivre, le nickel, le cupro-nickel, le cupro-manganèse, l'or, l'argent, le nickel-phosphore Ni-P et le nickel-bore Ni-B, pour faciliter la mise en forme sous forme de fil. Préférentiellement, l'épaisseur de la couche de matériau ductile déposée est choisie de sorte que le rapport surface de matériau ductile/surface de l'alliage NbHf pour une section de fil donnée est inférieur à 1, de préférence inférieur à 0.5, et plus préférentiellement compris entre 0.01 et 0.4.According to the invention, the method comprises, before the deformation step and after the annealing step, a step of depositing, on the blank, a layer of a ductile material chosen from the group comprising copper, nickel, cupro-nickel, cupro-manganese, gold, silver, nickel-phosphorus Ni-P and nickel-boron Ni-B, to facilitate wire shaping. Preferably, the thickness of the layer of ductile material deposited is chosen so that the ratio of ductile material surface / surface area of the NbHf alloy for a given wire section is less than 1, preferably less than 0.5, and more preferably between 0.01 and 0.4.

Un tel procédé de fabrication permet de faciliter la mise en forme sous forme de fil de l'ébauche en alliage NbHf, et plus spécifiquement de faciliter l'étirage, le tréfilage et le laminage. En particulier, ce procédé permet de faciliter la fabrication d'un ressort spiral ayant la composition suivante :

  • niobium: balance à 100% en poids,
  • hafnium: entre 5 et 15%, de préférence entre 8 et 12% en poids,
  • un ou plusieurs éléments choisis parmi le Ti, Zr, Ta, W avec un pourcentage pour chaque élément compris entre 0.2 et 1.5% en poids,
  • impuretés avec un pourcentage total de ces dernières compris entre 0 et 0.5% en poids.
Such a manufacturing process makes it possible to facilitate the shaping in wire form of the NbHf alloy blank, and more specifically to facilitate drawing, drawing and rolling. In particular, this process makes it possible to facilitate the manufacture of a spiral spring having the following composition:
  • niobium: balance at 100% by weight,
  • hafnium: between 5 and 15%, preferably between 8 and 12% by weight,
  • one or more elements chosen from Ti, Zr, Ta, W with a percentage for each element between 0.2 and 1.5% by weight,
  • impurities with a total percentage of the latter between 0 and 0.5% by weight.

Description de l'inventionDescription of the invention

L'invention concerne un procédé de fabrication d'un ressort spiral destiné à équiper un balancier d'un mouvement d'horlogerie et réalisé dans un alliage comportant du niobium et de l'hafnium.The invention relates to a method of manufacturing a spiral spring intended to equip a balance of a clockwork movement and made of an alloy comprising niobium and hafnium.

Le procédé comprend les étapes suivantes :

  • une étape d'élaboration d'une ébauche dans un alliage de niobium et d'hafnium constitué de :
    • niobium : balance à 100% en poids,
    • hafnium: entre 5 et 60% en poids, de préférence entre 5 et 30%, et plus préférentiellement entre 8 et 12% en poids,
    • un ou plusieurs éléments choisis parmi le Ti, Zr, Ta, W avec un pourcentage pour chaque élément compris entre 0 et 2%, de préférence entre 0.2 et 1.5% en poids,
    • impuretés avec un pourcentage total de ces dernières compris entre 0 et 0.5% en poids. Plus précisément, les impuretés peuvent être des traces d'éléments sélectionnés parmi le groupe constitué de O, H, C, Fe, N, Ni, Si, Cu, Al, Cr, Mn, V, Sn, Mg, Mo, Pb, Co, B, chacun desdits éléments étant présent dans une quantité comprise entre 0 et 1000 ppm en poids,
  • une étape de recuit suivi d'un refroidissement de ladite ébauche,
  • une étape de dépôt d'un matériau ductile sur l'ébauche,
  • au moins une étape de déformation de l'ébauche pour former un fil, avec une étape de recuit et refroidissement entre les étapes de déformation lorsqu'il y a plusieurs étapes de déformation,
  • une étape d'estrapadage pour former le ressort spiral,
  • une étape finale de traitement thermique permettant de fixer la forme du ressort spiral et d'ajuster le coefficient thermoélastique.
The process comprises the following steps:
  • a stage of preparation of a blank in an alloy of niobium and hafnium consisting of:
    • niobium: balance at 100% by weight,
    • hafnium: between 5 and 60% by weight, preferably between 5 and 30%, and more preferably between 8 and 12% by weight,
    • one or more elements chosen from Ti, Zr, Ta, W with a percentage for each element between 0 and 2%, preferably between 0.2 and 1.5% by weight,
    • impurities with a total percentage of the latter between 0 and 0.5% by weight. More precisely, the impurities can be traces of elements selected from the group consisting of O, H, C, Fe, N, Ni, Si, Cu, Al, Cr, Mn, V, Sn, Mg, Mo, Pb, Co, B, each of said elements being present in an amount between 0 and 1000 ppm by weight,
  • an annealing step followed by cooling of said blank,
  • a step of depositing a ductile material on the blank,
  • at least one step of deformation of the blank to form a wire, with a step of annealing and cooling between the deformation steps when there are several deformation steps,
  • a stepping step to form the spiral spring,
  • a final heat treatment step making it possible to fix the shape of the spiral spring and to adjust the thermoelastic coefficient.

De manière particulièrement préférée, l'ébauche comprend en poids entre 8 et 12% d'hafnium, du Ti, Zr, Ta et du W avec un pourcentage pour chaque élément compris entre 0.2 et 1.5%, et plus préférentiellement du Ti compris dans un pourcentage entre 0.5 et 1.5%, du Zr dans un pourcentage compris entre 0.5 et 0.9%, du Ta dans un pourcentage compris entre 0.3 et 0.7%, du W dans un pourcentage compris entre 0.3 et 0.7%.Particularly preferably, the blank comprises by weight between 8 and 12% of hafnium, Ti, Zr, Ta and W with a percentage for each element between 0.2 and 1.5%, and more preferably Ti included in a percentage between 0.5 and 1.5%, Zr in a percentage between 0.5 and 0.9%, Ta in a percentage between 0.3 and 0.7%, W in a percentage between 0.3 and 0.7%.

Préférentiellement, l'ébauche en alliage NbHf utilisé dans la présente invention ne comprend pas d'autres éléments à l'exception d'éventuelles et inévitables traces. Cela permet d'éviter la formation de phases fragiles.Preferably, the NbHf alloy blank used in the present invention does not include other elements except for possible and inevitable traces. This makes it possible to avoid the formation of fragile phases.

Plus particulièrement, la teneur en oxygène est inférieure ou égale à 0.10% en poids du total, notamment inférieure ou égale à 0.05% en poids du total, voire encore inférieure ou égale à 0.03% en poids du total.More particularly, the oxygen content is less than or equal to 0.10% by weight of the total, in particular less than or equal to 0.05% by weight of the total, or even less than or equal to 0.03% by weight of the total.

Plus particulièrement, la teneur en carbone est inférieure ou égale à 0.04% en poids du total, notamment inférieure ou égale à 0.02% en poids du total, voire encore inférieure ou égale à 0.015% en poids du total.More particularly, the carbon content is less than or equal to 0.04% by weight of the total, in particular less than or equal to 0.02% by weight of the total, or even less than or equal to 0.015% by weight of the total.

Plus particulièrement, la teneur en fer est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.02% en poids du total, voire encore inférieure ou égale à 0.005% en poids du total.More particularly, the iron content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.02% by weight of the total, or even less than or equal to 0.005% by weight of the total.

Plus particulièrement, la teneur en azote est inférieure ou égale à 0.04% en poids du total, notamment inférieure ou égale à 0.02% en poids du total, voire encore inférieure ou égale à 0.015% en poids du total.More particularly, the nitrogen content is less than or equal to 0.04% by weight of the total, in particular less than or equal to 0.02% by weight of the total, or even less than or equal to 0.015% by weight of the total.

Plus particulièrement, la teneur en hydrogène est inférieure ou égale à 0.01% en poids du total, notamment inférieure ou égale à 0.0035% en poids du total, voire encore inférieure ou égale à 0.001% en poids du total.More particularly, the hydrogen content is less than or equal to 0.01% by weight of the total, in particular less than or equal to 0.0035% by weight of the total, or even less than or equal to 0.001% by weight of the total.

Plus particulièrement, la teneur en silicium est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.02% en poids du total, voire encore inférieure ou égale à 0.005% en poids du total.More particularly, the silicon content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.02% by weight of the total, or even less than or equal to 0.005% by weight of the total.

Plus particulièrement, la teneur en nickel est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.01% en poids du total, voire encore inférieure ou égale à 0.002% en poids du total.More particularly, the nickel content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.

Plus particulièrement, la teneur en élément en solution solide ductile, tel que le cuivre, dans l'alliage, est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.01% en poids du total, voire encore inférieure ou égale à 0.004% en poids du total.More particularly, the content of element in ductile solid solution, such as copper, in the alloy is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to equal to 0.004% by weight of the total.

Plus particulièrement, la teneur en aluminium est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.01% en poids du total, voire encore inférieure ou égale à 0.002% en poids du total.More particularly, the aluminum content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.

Plus particulièrement, la teneur en chrome est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.01% en poids du total, voire encore inférieure ou égale à 0.002% en poids du total.More particularly, the chromium content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.

Plus particulièrement, la teneur en manganèse est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.01% en poids du total, voire encore inférieure ou égale à 0.002% en poids du total.More particularly, the manganese content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.

Plus particulièrement, la teneur en vanadium est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.01% en poids du total, voire encore inférieure ou égale à 0.002% en poids du total.More particularly, the vanadium content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.

Plus particulièrement, la teneur en étain est inférieure ou égale à 0.01% en poids du total, notamment inférieure ou égale à 0.0035% en poids du total, voire encore inférieure ou égale à 0.001% en poids du total.More particularly, the tin content is less than or equal to 0.01% by weight of the total, in particular less than or equal to 0.0035% by weight of the total, or even less than or equal to 0.001% by weight of the total.

Plus particulièrement, la teneur en magnésium est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.01% en poids du total, voire encore inférieure ou égale à 0.002% en poids du total.More particularly, the magnesium content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.

Plus particulièrement, la teneur en molybdène est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.01% en poids du total, voire encore inférieure ou égale à 0.002% en poids du total.More particularly, the molybdenum content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.

Plus particulièrement, la teneur en plomb est inférieure ou égale à 0.05% en poids du total, notamment inférieure ou égale à 0.01% en poids du total, voire encore inférieure ou égale à 0.002% en poids du total.More particularly, the lead content is less than or equal to 0.05% by weight of the total, in particular less than or equal to 0.01% by weight of the total, or even less than or equal to 0.002% by weight of the total.

Plus particulièrement, la teneur en cobalt est inférieure ou égale à 0.01% en poids du total, notamment inférieure ou égale à 0.0035% en poids du total, voire encore inférieure ou égale à 0.001% en poids du total.More particularly, the cobalt content is less than or equal to 0.01% by weight of the total, in particular less than or equal to 0.0035% by weight of the total, or even less than or equal to 0.001% by weight of the total.

Plus particulièrement, la teneur en bore est inférieure ou égale à 0.005% en poids du total, notamment inférieure ou égale à 0.0001% en poids du total.More particularly, the boron content is less than or equal to 0.005% by weight of the total, in particular less than or equal to 0.0001% by weight of the total.

L'étape de recuit est un traitement de mise en solution, avec une durée comprise, de préférence, entre 5 minutes et 2 heures à une température comprise entre 650°C et 1750°C, sous vide, suivie d'une trempe par exemple sous gaz pour obtenir l'Hf en solution solide sursaturée dans le Nb β. Selon une variante, un refroidissement naturel sous vide peut aussi être envisagé.The annealing step is a dissolving treatment, with a duration preferably between 5 minutes and 2 hours at a temperature between 650 ° C and 1750 ° C, under vacuum, followed by quenching for example. under gas to obtain Hf in a supersaturated solid solution in Nb β. According to one variant, natural cooling under vacuum can also be envisaged.

L'étape de dépôt qui fait plus particulièrement l'objet de l'invention consiste à déposer une couche d'un matériau ductile choisi parmi le groupe comprenant le cuivre, le nickel, le cupro-nickel, le cupro-manganèse, l'or, l'argent, le nickel-phosphore Ni-P et le nickel-bore Ni-B, pour faciliter la mise en forme sous forme de fil. Préférentiellement, l'épaisseur de la couche de matériau ductile déposée est choisie de sorte que le rapport surface de matériau ductile/surface de l'alliage NbHf pour une section de fil donnée est inférieur à 1, de préférence inférieur à 0.5, et plus préférentiellement compris entre 0.01 et 0.4. A titre d'exemple, pour un diamètre total du fil de 0.1 mm, la couche de matériau ductile peut avoir une épaisseur de 7 µm pour une section en alliage de NbHf de 0.086 mm de diamètre. Cela correspond à un rapport entre la surface de cuivre (0.002 mm2) et la surface de NbHf (0.0058 mm2) de 0.35.The deposition step which is more particularly the subject of the invention consists in depositing a layer of a ductile material chosen from the group comprising copper, nickel, cupro-nickel, cupro-manganese, gold , silver, nickel-phosphorus Ni-P and nickel-boron Ni-B, to facilitate wire forming. Preferably, the thickness of the layer of ductile material deposited is chosen so that the ratio of ductile material surface / surface area of the NbHf alloy for a given wire section is less than 1, preferably less than 0.5, and more preferably between 0.01 and 0.4. By way of example, for a total diameter of the wire of 0.1 mm, the layer of ductile material may have a thickness of 7 μm for an NbHf alloy section of 0.086 mm in diameter. This corresponds to a ratio between the area of copper (0.002 mm 2 ) and the area of NbHf (0.0058 mm 2 ) of 0.35.

Une telle épaisseur de matériau ductile, et notamment de cuivre, permet d'étirer, de tréfiler et de laminer aisément le matériau composite Cu/NbHf. En effet, l'épaisseur de cuivre est optimisée pour que la pointe, créée par limage ou par étirage à chaud, nécessaire à l'introduction du fil dans la filière lors de l'étirage ou du tréfilage soit recouverte de cuivre.Such a thickness of ductile material, and in particular copper, makes it possible to easily stretch, draw and roll the Cu / NbHf composite material. Indeed, the thickness of copper is optimized so that the tip, created by filing or by hot drawing, necessary for the introduction of the wire into the die during drawing or drawing is covered with copper.

Le matériau ductile, de préférence du cuivre, est ainsi déposé à un moment donné pour faciliter la mise en forme du fil par étirage, tréfilage et laminage, de telle manière à ce qu'il en reste une épaisseur de préférence comprise entre 1 et 500 micromètres sur le fil au diamètre total de 0.2 à 1 millimètre.The ductile material, preferably copper, is thus deposited at a given time to facilitate the shaping of the wire by drawing, drawing and rolling, so that a thickness thereof remains, preferably between 1 and 500. micrometers on the wire with a total diameter of 0.2 to 1 millimeter.

L'apport de matériau ductile peut être galvanique, par PVD ou CVD, ou bien mécanique, c'est alors une chemise ou un tube de matériau ductile tel que le cuivre qui est ajusté sur une barre d'alliage NbHf à un gros diamètre, puis qui est amincie au cours de la ou des étapes de déformation du barreau composite. Ainsi, une possibilité est de former une billette composite par assemblage d'une barre de Nb-Hf et d'une chemise de cuivre qui est ensuite extrudée.The supply of ductile material can be galvanic, by PVD or CVD, or else mechanical, it is then a jacket or a tube of ductile material such as copper which is fitted to a bar of NbHf alloy with a large diameter, then which is thinned during the step or steps of deformation of the composite bar. Thus, one possibility is to form a composite billet by assembling an Nb-Hf bar and a copper jacket which is then extruded.

L'étape de déformation désigne d'une manière globale un ou plusieurs traitements de déformation, qui peuvent comprendre le tréfilage et/ou le laminage. Le tréfilage peut nécessiter l'utilisation d'une ou plusieurs filières lors de la même étape de déformation ou lors de différentes étapes de déformation si nécessaire. Le tréfilage est réalisé jusqu'à l'obtention d'un fil de section ronde. Le laminage peut être effectué lors de la même étape de déformation que le tréfilage ou dans une autre étape de déformation ultérieure. Avantageusement, le dernier traitement de déformation appliqué à l'alliage est un laminage, de préférence à profil rectangulaire compatible avec la section d'entrée d'une broche d'estrapadage.The deformation step generally refers to one or more deformation treatments, which may include wire drawing and / or rolling. Wire drawing may require the use of one or more dies during the same deformation step or during different deformation steps if necessary. The wire drawing is carried out until a wire of round section is obtained. Rolling can be performed in the same deformation step as wire drawing or in another subsequent deformation step. Advantageously, the last deformation treatment applied to the alloy is rolling, preferably with a rectangular profile compatible with the entry section of a stranding spindle.

Le procédé peut comporter une étape ou plusieurs étapes de déformation avec un taux de déformation pour chaque étape compris entre 1 et 5, de préférence entre 2 et 5, le taux de déformation répondant à la formule classique 2ln(d0/d) où d0 et d sont respectivement le diamètre avant et après déformation. Le taux total de déformation peut être compris entre 1 et 14.The method may include one step or more deformation steps with a deformation rate for each step between 1 and 5, preferably between 2 and 5, the deformation rate corresponding to the conventional formula 2ln (d0 / d) where d0 and d are the diameter before and after deformation, respectively. The total strain rate can be between 1 and 14.

Le procédé peut comporter des étapes intermédiaires de recuit entre les différentes étapes de déformation.The process may include intermediate annealing steps between the different deformation steps.

Le procédé de l'invention comprend préférentiellement, après l'étape de déformation, une étape d'élimination de ladite couche de matériau ductile. De préférence, le matériau ductile est éliminé une fois toutes les opérations de déformation effectuées, c'est-à-dire après le dernier laminage, avant l'estrapadage. Cependant, il n'est pas exclu d'éliminer la couche de matériau ductile avant d'avoir finalisé toutes les opérations de déformation. Il est ainsi envisageable lors d'un laminage en plusieurs passes d'éliminer la couche de matériau ductile avant la dernière passe de laminage. De préférence, le fil est débarrassé de sa couche de matériau ductile, tel que le cuivre, notamment par attaque chimique, avec une solution à base de cyanures ou à base d'acides, par exemple d'acide nitrique.The method of the invention preferably comprises, after the deformation step, a step of removing said layer of ductile material. Preferably, the ductile material is removed once all the deformation operations have been carried out, that is to say after the last rolling, before the stretching. However, it is not excluded to remove the layer of ductile material before having finalized all the deformation operations. It is thus possible, during rolling in several passes, to eliminate the layer of ductile material before the last rolling pass. Preferably, the wire is freed from its layer of ductile material, such as copper, in particular by chemical attack, with a solution based on cyanides or based on acids, for example nitric acid.

Le recuit préalable à l'étape de déformation de même que les recuits intermédiaires effectués entre les étapes de déformation est réalisé pendant une durée comprise entre 5 minutes et 2 heures, de préférence entre 10 minutes et 1 heure à une température comprise entre 650°C et 1750°C.The annealing prior to the deformation step as well as the intermediate annealing carried out between the deformation steps is carried out during a period of between 5 minutes and 2 hours, preferably between 10 minutes and 1 hour at a temperature of between 650 ° C and 1750 ° C.

Le traitement thermique final après l'estrapadage est réalisé à une température comprise entre 500 et 1250°C pendant un temps compris entre 30 minutes et 30 heures. Selon la composition de l'alliage et les températures, une structure monophasée de type cubique centrée ou biphasée avec une structure cubique centrée et une structure hexagonale compacte peut être obtenue à l'issue de ce traitement thermique.The final heat treatment after the straddling is carried out at a temperature between 500 and 1250 ° C for a time between 30 minutes and 30 hours. Depending on the composition of the alloy and the temperatures, a single-phase structure of the centered or two-phase cubic type with a centered cubic structure and a compact hexagonal structure can be obtained at the end of this heat treatment.

Le procédé de l'invention permet la réalisation, et plus particulièrement la mise en forme, d'un ressort spiral pour balancier en alliage de type niobium-hafnium. Cet alliage présente des propriétés mécaniques élevées, en combinant une limite élastique très élevée, supérieure à 600 MPa, et un module d'élasticité très bas, de l'ordre de 60 GPa à 100 GPa. Cette combinaison de propriétés convient bien pour un ressort spiral. De plus, un tel alliage est paramagnétique.The method of the invention allows the production, and more particularly the shaping, of a balance spring for a balance made of a niobium-hafnium type alloy. This alloy has high mechanical properties, by combining a very high elastic limit, greater than 600 MPa, and a very low modulus of elasticity, of the order of 60 GPa to 100 GPa. This combination of properties is well suited for a spiral spring. In addition, such an alloy is paramagnetic.

Un alliage de type binaire comportant du niobium et de l'hafnium, du type sélectionné ci-dessus pour la mise en œuvre de l'invention, présente également un effet similaire à celui de l' « Elinvar », avec un coefficient thermo-élastique pratiquement nul dans la plage de températures d'utilisation usuelle de montres, et apte à la fabrication de spiraux auto-compensateurs.A binary type alloy comprising niobium and hafnium, of the type selected above for the implementation of the invention, also exhibits an effect similar to that of “Elinvar”, with a thermoelastic coefficient. practically zero in the temperature range of usual use of watches, and suitable for the manufacture of self-compensating balance springs.

Claims (3)

Ressort spiral destiné à équiper un balancier d'un mouvement d'horlogerie, le ressort spiral étant réalisé dans un alliage de niobium et d'hafnium constitué de : - niobium : balance à 100% en poids, - hafnium: entre 8 et 12% en poids, - un ou plusieurs éléments choisis parmi le Ti, Zr, Ta et le W avec un pourcentage pour chaque élément compris entre 0.2 et 1.5% en poids, - impuretés avec un pourcentage total compris entre 0 et 0.5% en poids. Spiral spring intended to equip a balance of a clockwork movement, the spiral spring being made of an alloy of niobium and hafnium consisting of: - niobium: balance at 100% by weight, - hafnium: between 8 and 12% by weight, - one or more elements chosen from Ti, Zr, Ta and W with a percentage for each element between 0.2 and 1.5% by weight, - impurities with a total percentage between 0 and 0.5% by weight. Ressort spiral selon la revendication 1, caractérisé en ce qu'il comprend du Ti, Zr, Ta et du W avec un pourcentage en poids pour chaque élément compris entre 0.2 et 1.5%.Spiral spring according to Claim 1, characterized in that it comprises Ti, Zr, Ta and W with a percentage by weight for each element of between 0.2 and 1.5%. Ressort spiral selon la revendication 2, caractérisé en ce que le Ti est compris dans un pourcentage en poids compris entre 0.5 et 1.5%, le Zr dans un pourcentage en poids compris entre 0.5 et 0.9%, le Ta dans un pourcentage en poids compris entre 0.3 et 0.7%, le W dans un pourcentage en poids compris entre 0.3 et 0.7%.Spiral spring according to Claim 2, characterized in that the Ti is included in a percentage by weight of between 0.5 and 1.5%, the Zr in a percentage by weight of between 0.5 and 0.9%, the Ta in a percentage by weight of between 0.3 and 0.7%, the W in a percentage by weight between 0.3 and 0.7%.
EP21170773.2A 2019-05-07 2019-05-07 Horological hairspring made of a nb-hf alloy Active EP3889691B1 (en)

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EP4060424A1 (en) * 2021-03-16 2022-09-21 Nivarox-FAR S.A. Hairspring for timepiece movement
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EP0886195A1 (en) * 1997-06-20 1998-12-23 Montres Rolex Sa Auto-compensating spring for mechanical oscillatory spiral spring of clockwork movement and method of manufacturing the same
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EP1258786A1 (en) * 2001-05-18 2002-11-20 Montres Rolex Sa Self-compensating spring for a mechanical oscillator of balance-spring type

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US20200356057A1 (en) 2020-11-12
EP3889691B1 (en) 2024-02-21
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EP3736639B1 (en) 2024-07-03
US11550263B2 (en) 2023-01-10

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