EP4009114B1 - Spiralfeder für uhrwerk und ihr herstellungsverfahren - Google Patents

Spiralfeder für uhrwerk und ihr herstellungsverfahren Download PDF

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Publication number
EP4009114B1
EP4009114B1 EP21218349.5A EP21218349A EP4009114B1 EP 4009114 B1 EP4009114 B1 EP 4009114B1 EP 21218349 A EP21218349 A EP 21218349A EP 4009114 B1 EP4009114 B1 EP 4009114B1
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Prior art keywords
weight
niobium
layer
core
equal
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EP21218349.5A
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English (en)
French (fr)
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EP4009114A1 (de
Inventor
Christian Charbon
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Nivarox Far SA
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Nivarox Far 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
    • G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21F—WORKING OR PROCESSING OF METAL WIRE
    • B21F3/00—Coiling wire into particular forms
    • B21F3/02—Coiling wire into particular forms helically
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • 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
    • C22F1/02—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
    • 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
    • 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
    • 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
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium 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
    • 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
    • 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
    • G04B17/20—Compensation of mechanisms for stabilising frequency
    • G04B17/22—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature
    • G04B17/227—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature composition and manufacture of the material used
    • 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
    • G04B17/32—Component parts or constructional details, e.g. collet, stud, virole or piton
    • G04B17/34—Component parts or constructional details, e.g. collet, stud, virole or piton for fastening the hairspring onto the balance
    • G—PHYSICS
    • G04—HOROLOGY
    • G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0002—Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe
    • G04D3/0035—Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the regulating mechanism
    • G04D3/0041—Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the regulating mechanism for coil-springs
    • G—PHYSICS
    • G04—HOROLOGY
    • G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0069—Watchmakers' or watch-repairers' machines or tools for working materials for working with non-mechanical means, e.g. chemical, electrochemical, metallising, vapourising; with electron beams, laser beams

Definitions

  • the invention relates to a spiral spring intended to equip a balance wheel of a clock movement.
  • spiral springs are also focused on the concern for thermal compensation, in order to guarantee regular chronometric performances. To achieve this, it is necessary to obtain a thermoelastic coefficient close to zero. We are also looking to produce spiral springs with limited sensitivity to magnetic fields.
  • New balance springs have been developed from niobium and titanium alloys.
  • these alloys have problems with sticking and seizing in the drawing or wire-drawing dies and against the rolling rollers, making them almost impossible to process into fine wire by standard processes used, for example, for steel.
  • This copper layer on the wire has a disadvantage: it must be deposited in a thick layer (typically 10 microns for a Nb-Ti diameter of 0.1 mm) to play its role as an anti-sticking agent during the deformation steps. It does not allow fine control of the wire geometry during calibration and rolling of the wire. These dimensional variations of the Nb-Ti core of the wire result in significant variations in the torque of the balance springs.
  • the layer of the first material has a thickness of between 300 nm and 1.5 ⁇ m and preferably of between 400 nm and 800 nm.
  • the first material is niobium.
  • the Ti content is between 40 and 65% by weight, preferably between 40 and 49% by weight and more preferably between 46 and 48% by weight.
  • the Nb-Ti core has a two-phase microstructure comprising niobium in beta phase and titanium in alpha phase.
  • the spring has an elastic limit greater than or equal to 500 MPa, preferably 600 MPa, and a modulus of elasticity less than or equal to 120 GPa, preferably less than or equal to 100 GPa.
  • the invention relates to a spiral spring intended to equip a balance wheel of a watch movement.
  • This spiral spring is made of a binary type alloy comprising niobium and titanium. It also relates to the spiral spring resulting from this process.
  • niobium as a first material and copper as a second material.
  • the method further comprises a step h) of removing said copper layer formed in step c), at a time in step c) at which the blank has reached a diameter such that said blank can still be passed at least through one die and preferably through two dies with a rate of elongation of the blank of approximately 10% at each die before the first rolling step d2) or at the latest before the last pass of step d2).
  • the core is made of an Nb-Ti alloy comprising between 5 and 95% by weight of titanium.
  • the alloy used in the present invention comprises between 40 and 60% by weight of titanium.
  • it comprises between 40 and 49% by weight of titanium, and more preferably between 46% and 48% by weight of titanium.
  • the percentage of titanium is sufficient to obtain a maximum proportion of Ti precipitates in the form of alpha phase while being reduced to avoid the formation of martensitic phase leading to problems of brittleness of the alloy during its implementation.
  • the Nb-Ti alloy used in the present invention does not comprise other elements except for possible and unavoidable 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, or even less than or equal to 0.085% by weight of the total.
  • the tantalum content is less than or equal to 0.10% 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 0.020% by weight of the total, or even less than or equal to 0.0175% by weight of the total.
  • the iron content is less than or equal to 0.03% by weight of the total, in particular less than or equal to 0.025% by weight of the total, or even less than or equal to 0.020% by weight of the total.
  • the nitrogen content is less than or equal to 0.02% by weight of the total, in particular less than or equal to 0.015% by weight of the total, or even less than or equal to 0.0075% 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 0.0005% by weight of the total.
  • the silicon content is less than or equal to 0.01% by weight of the total.
  • the nickel content is less than or equal to 0.01% by weight of the total, in particular less than or equal to 0.16% by weight of the total.
  • the content of ductile material, such as copper, in the alloy is less than or equal to 0.01% by weight of the total, in particular less than or equal to 0.005% by weight of the total.
  • the aluminum content is less than or equal to 0.01% by weight of the total.
  • the Nb-Ti core of the blank in step a) is coated with a layer of niobium.
  • the niobium layer can be applied around the core by galvanic means, by PVD, CVD or by mechanical means. In the latter case, a niobium tube is fitted onto a bar of the Nb-Ti alloy. The assembly is deformed by hammering, stretching and/or wire drawing to thin the bar and form the blank that was made available in step a).
  • the thickness of the niobium layer is chosen so that the niobium surface/Nb-Ti core surface ratio for a given wire section is less than 1, preferably less than 0.5, and more preferably between 0.01 and 0.4. For example, the thickness is preferably between 1 and 500 micrometers for a wire having a total diameter of 0.2 to 1 millimeter.
  • the niobium layer may be made by wrapping a niobium strip around the Nb-Ti core, the niobium strip/Nb-Ti core assembly then being deformed by hammering, stretching and/or wire drawing to thin the bar and form the blank that was made available at the end of step a).
  • the Nb-Ti core of the blank obtained in step b) is coated with a layer of copper during a step c) .
  • the copper layer can be applied around the core by galvanic means, by PVD, CVD or by mechanical means. In the latter case, a copper tube is fitted onto a bar of the Nb-Ti alloy coated with the niobium layer. The assembly is deformed by hammering, stretching and/or wire drawing to thin the bar and form the blank that was made available at the end of step b).
  • the thickness of the copper layer is chosen so that the ratio of copper surface area/surface area of the Nb-Ti core covered with the niobium layer for a given wire section is less than 1, preferably less than 0.5, and more preferably between 0.01 and 0.4.
  • the thickness is preferably between 1 and 500 micrometers for a wire having a total diameter of 0.2 to 1 millimeter.
  • the copper layer may be made by wrapping a copper strip around the Nb-Ti core covered with the niobium layer, the niobium strip/Nb-Ti core assembly then being deformed by hammering, stretching and/or wire drawing to thin the bar and form the blank that was made available at the end of step b).
  • the Nb-Ti core covered with the niobium strip can be introduced into a copper tube, the whole being co-extruded hot at a temperature of the order of 600 to 900 degrees through a die.
  • a beta quenching consisting of a solution treatment is carried out at least before the subsequent deformation steps.
  • This treatment is carried out so that the titanium of the alloy is essentially in the form of a solid solution with the niobium in the beta phase.
  • it is carried out for a period of between 5 minutes and 2 hours at a temperature of between 700°C and 1000°C, under vacuum, followed by cooling under gas.
  • this beta quenching is a solution treatment at 800°C under vacuum for 5 minutes to 1 hour, followed by cooling under gas.
  • Step d) of deformation is carried out in several sequences.
  • Deformation means deformation by wire drawing and/or rolling.
  • the deformation step comprises at least successive deformation sequences, preferably cold, by hammering and/or drawing and/or calibration wire drawing designated by step d1).
  • Step d1) makes it possible to bring the blank obtained at the end of step c) to a determined diameter called the wire calibration diameter.
  • the method further comprises a step h) which consists in removing the copper layer formed in step c), when during step d1), the blank has reached a diameter such that said blank can still be passed at least through a die with a blank elongation rate of approximately 10% before the first subsequent rolling step d2).
  • This step of removing the copper layer is carried out by chemical etching in a solution based on cyanides or acids, for example in a bath of nitric acid at a concentration of 53% by mass in water.
  • a sequence of rolling operations preferably with a rectangular profile compatible with the entry section of a rolling spindle, is then carried out, this sequence forming step d2).
  • Each sequence of steps d1) and d2) is carried out with a given strain rate between 1 and 5, this strain rate corresponding to the classic formula 2ln(d0/d), where d0 is the diameter of the last beta quench, and where d is the diameter of the work-hardened wire.
  • the overall accumulation of strains over this entire succession of sequences leads to a total strain rate between 1 and 14.
  • the niobium layer coating the Nb-Ti core has a thickness of between 20 nm and 10 ⁇ m, preferably between 300 nm and 1.5 ⁇ m, more preferably between 400 and 800 nm.
  • the rolled wire obtained at the end of step d2) is then cut to a length determined during step e) .
  • Step f) of stripping to form the spiral spring is followed by step g) of final heat treatment on the spiral spring.
  • This final heat treatment is a Ti precipitation treatment in alpha phase lasting between 1 and 80 hours, preferably between 5 and 30 hours, at a temperature between 350 and 700°C, preferably between 400 and 600°C.
  • the method may further comprise, between each sequence or between certain sequences of the deformation steps d1) and/or d2), an intermediate heat treatment for precipitation of the titanium in alpha phase lasting between 1 hour and 80 hours at a temperature between 350°C and 700°C, preferably between 5 hours and 30 hours between 400°C and 600°C.
  • this intermediate treatment is carried out in step d1) between the first drawing sequence and the second calibration drawing sequence.
  • the spiral spring of the invention produced according to this method has an elastic limit greater than or equal to 500 MPa, preferably greater than 600 MPa, and more precisely between 500 and 1000 MPa.
  • it has a modulus of elasticity less than or equal to 120 GPa, and preferably less than or equal to 100 GPa.
  • the spiral spring comprises a core of Nb-Ti coated with a layer of niobium, said layer having a thickness of between 50 nm and 5 ⁇ m, preferably between 200 nm and 1.5 ⁇ m, more preferably between 800 nm and 1.2 ⁇ m.
  • the core of the spiral spring has a two-phase microstructure comprising niobium in beta phase and titanium in alpha phase.
  • the spiral spring has a thermoelastic coefficient, also called CTE, allowing it to guarantee the maintenance of chronometric performance despite the variation in operating temperatures of a watch incorporating such a spiral spring.
  • the process allows the production, and more particularly the shaping, of a spiral spring for a balance wheel in a niobium-titanium alloy, typically containing 47% titanium by weight (40-60%).
  • This alloy has high mechanical properties, combining a very high elastic limit high, greater than 600 MPa, and a very low modulus of elasticity, of the order of 60 GPa to 80 GPa. This combination of properties is well suited for a spiral spring.
  • such an alloy is paramagnetic.
  • the Nb-Ti core of the blank in step a) is coated with a layer of niobium.
  • the niobium layer can be applied around the core by galvanic means, by PVD, CVD or by mechanical means. In the latter case, a niobium tube is fitted onto a bar of the Nb-Ti alloy. The assembly is deformed by hammering, stretching and/or wire drawing to thin the bar and form the blank that was made available in step a).
  • the thickness of the niobium layer is chosen so that the niobium surface/Nb-Ti core surface ratio for a given wire section is less than 1, preferably less than 0.5, and more preferably between 0.01 and 0.4. For example, the thickness is preferably between 1 and 500 micrometers for a wire having a total diameter of 0.2 to 1 millimeter.
  • the niobium layer may be made by wrapping a niobium strip around the Nb-Ti core, the niobium strip/Nb-Ti core assembly then being deformed by hammering, stretching and/or wire drawing to thin the bar and form the blank that was made available at the end of step a).
  • the Nb-Ti core of the blank obtained in step b) is coated with a layer of copper during a step c) .
  • the copper layer can be applied around the core by galvanic means, by PVD, CVD or by mechanical means. In the latter case, a copper tube is fitted onto a bar of the Nb-Ti alloy coated with the niobium layer. The assembly is deformed by hammering, stretching and/or wire drawing to thin the bar and form the blank that was made available at the end of step b).
  • the thickness of the copper layer is chosen so that the ratio of copper surface area/surface area of the Nb-Ti core covered with the niobium layer for a given wire section is less than 1, preferably less than 0.5, and more preferably between 0.01 and 0.4.
  • the thickness is preferably between 1 and 500 micrometers for a wire having a total diameter of 0.2 to 1 millimeter.
  • the copper layer may be made by wrapping a copper strip around the Nb-Ti core covered with the niobium layer, the niobium strip/Nb-Ti core assembly then being deformed by hammering, stretching and/or wire drawing to thin the bar and form the blank that was made available at the end of step b).
  • the Nb-Ti core covered with the niobium strip can be introduced into a copper tube, the whole being co-extruded hot at a temperature of the order of 600 to 900 degrees through a die.
  • a beta quenching consisting of a solution treatment is carried out at least before the subsequent deformation steps.
  • This treatment is carried out so that the titanium of the alloy is essentially in the form of a solid solution with the niobium in the beta phase.
  • it is carried out for a period of between 5 minutes and 2 hours at a temperature of between 700°C and 1000°C, under vacuum, followed by cooling under gas.
  • this beta quenching is a solution treatment at 800°C under vacuum for 5 minutes to 1 hour, followed by cooling under gas.
  • Step d) of deformation is carried out in several sequences.
  • Deformation means deformation by wire drawing and/or rolling.
  • the deformation step comprises at least successive deformation sequences, preferably cold, by hammering and/or drawing and/or calibration wire drawing designated by step d1 ).
  • Step d1) makes it possible to bring the blank obtained at the end of step c) to a determined diameter called the wire calibration diameter.
  • the method further comprises a step h) which consists in removing the copper layer formed in step c), when during step d1), the blank has reached a diameter such that said blank can still be passed at least through a die with a rate of elongation of the blank of approximately 10% before the first subsequent rolling step d2).
  • This step of removing the copper layer is carried out by chemical attack in a solution based on cyanides or acids, for example in a bath of nitric acid at a concentration of 53% by mass in water.
  • a sequence of rolling operations preferably with a rectangular profile compatible with the entry section of a rolling spindle, is then carried out, this sequence forming step d2).
  • Each sequence of steps d1) and d2) is carried out with a given strain rate between 1 and 5, this strain rate corresponding to the classic formula 2ln(d0/d), where d0 is the diameter of the last beta quench, and where d is the diameter of the work-hardened wire.
  • the overall accumulation of strains over this entire succession of sequences leads to a total strain rate between 1 and 14.
  • the niobium layer coating the Nb-Ti core has a thickness of between 20 nm and 10 ⁇ m, preferably between 300 nm and 1.5 ⁇ m, more preferably between 400 and 800 nm.
  • the rolled wire obtained at the end of step d2) is then cut to a length determined during step e) .
  • Step f) of stripping to form the spiral spring is followed by step g) of final heat treatment on the spiral spring.
  • This final heat treatment is a Ti precipitation treatment in alpha phase lasting between 1 and 80 hours, preferably between 5 and 30 hours, at a temperature between 350 and 700°C, preferably between 400 and 600°C.
  • the method may further comprise, between each sequence or between certain sequences of the deformation steps d1) and/or d2), an intermediate heat treatment for precipitation of titanium in alpha phase lasting between 1 hour and 80 hours at a temperature between 350°C and 700°C, preferably between 5 hours and 30 hours between 400°C and 600°C.
  • this intermediate treatment is carried out in step d1) between the first drawing sequence and the second calibration drawing sequence.
  • the spiral spring produced according to this method has an elastic limit greater than or equal to 500 MPa, preferably greater than 600 MPa, and more precisely between 500 and 1000 MPa.
  • it has a modulus of elasticity less than or equal to 120 GPa, and preferably less than or equal to 100 GPa.
  • the spiral spring comprises a core of Nb-Ti coated with a layer of niobium, said layer having a thickness of between 50 nm and 5 ⁇ m, preferably between 200 nm and 1.5 ⁇ m, more preferably between 800 nm and 1.2 ⁇ m.
  • the core of the spiral spring has a two-phase microstructure comprising niobium in beta phase and titanium in alpha phase.
  • the spiral spring produced according to the invention has a thermoelastic coefficient, also called CTE, allowing it to guarantee the maintenance of chronometric performance despite the variation in operating temperatures of a watch incorporating such a spiral spring.
  • the method of the invention allows the production, and more particularly the shaping, of a spiral spring for a balance wheel made of a niobium-titanium alloy, typically containing 47% by weight of titanium (40-60%).
  • 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 80 GPa. This combination of properties is well suited for a spiral spring.
  • such an alloy is paramagnetic.

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  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
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  • Heat Treatment Of Steel (AREA)
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Claims (7)

  1. Spiralfeder, die dazu bestimmt ist, eine Unruh eines Uhrwerks auszustatten, mit einem Kern aus Nb-Ti, der aus einer Legierung hergestellt ist, die aus Folgendem besteht:
    - Niob: Rest bis 100 Gew.-%,
    - Titan: zwischen 5 und 95 Gew.-%,
    - Spuren von Elementen, die aus der Gruppe ausgewählt sind, die aus O, H, C, Fe, Ta, N, Ni, Si, Cu, Al besteht, wobei jedes der Elemente in einer Menge zwischen 0 und 1600 Gew.-ppm vorhanden ist, wobei die Gesamtmenge, die aus allen diesen Elementen besteht, zwischen 0 und 0,3 Gew.-% liegt,
    dadurch gekennzeichnet, dass der Nb-Ti-Kern mit einer Schicht aus einem ersten Material ummantelt ist, das aus der Reihe ausgewählt ist, die Niob, Tantal, Vanadium, einen rostfreien austenitischen Stahl, insbesondere Stahl der Sorte 316L, umfasst, wobei die Schicht aus dem ersten Material eine Dicke zwischen 20 nm und 10 µm aufweist.
  2. Spiralfeder nach Anspruch 1, dadurch gekennzeichnet, dass die Schicht aus dem ersten Material eine Dicke zwischen 300 nm und 1,5 µm aufweist.
  3. Spiralfeder nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Schicht aus dem ersten Material eine Dicke zwischen 400 nm und 800 nm aufweist.
  4. Spiralfeder nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das erste Material Niob ist.
  5. Spiralfeder nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Ti-Gehalt zwischen 40 und 65 Gew.-%, vorzugsweise zwischen 40 und 49 Gew.-% und besonders bevorzugt zwischen 46 und 48 Gew.-% liegt.
  6. Spiralfeder nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Nb-Ti-Kern eine Zweiphasen-Mikrostruktur mit Niob in der Beta-Phase und Titan in der Alpha-Phase umfasst.
  7. Spiralfeder nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass sie eine Streckgrenze von größer oder gleich 500 MPa, vorzugsweise 600 MPa, und einen Elastizitätsmodul von kleiner oder gleich 120 GPa, vorzugsweise kleiner oder gleich 100 GPa, aufweist.
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EP4123393B1 (de) * 2021-07-23 2025-04-16 Nivarox-FAR S.A. Spiralfeder für uhrwerk
CN117004854B (zh) * 2023-07-28 2025-11-04 深圳市飞亚达精密科技有限公司 顺磁性恒弹性合金材料和机械手表游丝及用途、制备方法
CN117403099A (zh) * 2023-08-18 2024-01-16 中南大学 一种富氮高强韧Ti-Nb合金及其制备方法和应用

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US20210200153A1 (en) 2021-07-01
JP7051979B2 (ja) 2022-04-11
KR102431406B1 (ko) 2022-08-10
CN113126466A (zh) 2021-07-16
US12105475B2 (en) 2024-10-01
CN113126466B (zh) 2023-01-24
EP3845971B1 (de) 2024-04-17
JP2021110726A (ja) 2021-08-02
KR20210086949A (ko) 2021-07-09
KR102502785B1 (ko) 2023-02-23
EP3845971A1 (de) 2021-07-07
RU2756785C1 (ru) 2021-10-05
EP4009114A1 (de) 2022-06-08
KR20220088652A (ko) 2022-06-28

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