EP3845971B1 - Herstellungsverfahren für eine spiralfeder für ein uhrwerk - Google Patents

Herstellungsverfahren für eine spiralfeder für ein uhrwerk Download PDF

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Publication number
EP3845971B1
EP3845971B1 EP19220163.0A EP19220163A EP3845971B1 EP 3845971 B1 EP3845971 B1 EP 3845971B1 EP 19220163 A EP19220163 A EP 19220163A EP 3845971 B1 EP3845971 B1 EP 3845971B1
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EP
European Patent Office
Prior art keywords
blank
layer
manufacturing
previous
niobium
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EP19220163.0A
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English (en)
French (fr)
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EP3845971A1 (de
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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Priority to EP21218349.5A priority Critical patent/EP4009114B1/de
Priority to EP19220163.0A priority patent/EP3845971B1/de
Priority to US17/084,210 priority patent/US12105475B2/en
Priority to JP2020183437A priority patent/JP7051979B2/ja
Priority to KR1020200147991A priority patent/KR102431406B1/ko
Priority to RU2020142723A priority patent/RU2756785C1/ru
Priority to CN202011629549.9A priority patent/CN113126466B/zh
Publication of EP3845971A1 publication Critical patent/EP3845971A1/de
Priority to KR1020220072366A priority patent/KR102502785B1/ko
Application granted granted Critical
Publication of EP3845971B1 publication Critical patent/EP3845971B1/de
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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
    • G04B17/20—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
    • G04B17/04—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
    • G04B17/04—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
    • 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
    • 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
    • G04B17/32—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 method of manufacturing a spiral spring intended to equip a balance wheel with a clock movement and the spiral spring resulting from the method.
  • spiral springs are also centered on the concern for thermal compensation, so as to guarantee regular chronometric performance. To do this, it is necessary to obtain a thermoelastic coefficient close to zero. We are also seeking to produce spiral springs with limited sensitivity to magnetic fields.
  • New hairsprings have been developed from niobium and titanium alloys.
  • these alloys pose problems of sticking and galling in the drawing or drawing dies and against the rolling rolls, which makes them almost impossible to transform into fine wires by the standard processes used, for example, for 'steel.
  • This layer of copper on the wire has a disadvantage: it must be deposited in a thick layer (typically 10 microns for an Nb-Ti diameter of 0.1 mm) to play its role as an anti-sticking agent during the deformation stages. It does not allow fine control of the geometry of the wire 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 hairsprings.
  • the document EP 3 502 288 A1 shows all the features of the preamble of claim 1.
  • the present invention proposes a method of manufacturing a spiral spring which makes it possible to facilitate shaping by deformation while avoiding the drawbacks linked to the copper layer.
  • the blank As the blank undergoes a large number of deformation passes to bring it to specific dimensions and geometry, the blank must be coated with a layer preventing sticking in successive dies that is sufficiently thick so as not to be damaged during processing. these successive deformations.
  • it is planned to coat the blank with a layer of a ductile material such as copper.
  • the thickness of the copper layer for the production of watch spiral springs is of the order of 10 microns. The applicant, however, noted that the external dimensions of the blank covered with the copper layer were well controlled during the successive deformation passes of the blank but on the other hand that the dimensions of the Nb-Ti core were not not controlled.
  • the applicant therefore had the inventive idea which consists of coating the Nb-Ti blank with a thin layer (typically chosen between 800 nm and 1.2 microns when the blank has reached a diameter of between 15 and 50 microns) 'a first anti-sticking material and preferably compatible with the thermo elastic coefficient (CTE) of the Nb-Ti core, before coating the blank with a layer of a second ductile material thicker than the layer of the first material to carry out the first stages of deformation then to eliminate the “thick” layer of the second material before the final stages while retaining the “thin” layer of the first material.
  • This “thin” layer will make it possible to carry out the final stages of deformation of the wire without sticking in the dies while perfectly controlling the dimensions of the Nb-Ti core.
  • the first material is preferably chosen from the set comprising niobium, gold, tantalum, vanadium, stainless austenitic steels, grade 316L steel
  • the second material is chosen from the set comprising copper , silver, copper and nickel alloys, alpha single-phase copper and zinc alloys (e.g. CuZn30).
  • the first material is niobium and the second material is copper (ETP (electrolytic tough pitch), OF (oxygen-free) or OFE (oxygen free electronic) grade, for example).
  • ETP electrolytic tough pitch
  • OF oxygen-free
  • OFE oxygen free electronic grade
  • a preferred embodiment of the method of manufacturing the spiral spring according to the invention therefore comprises a step aimed at forming a thin layer of niobium coating the Nb-Ti core, then at forming a thick layer of copper, to partially deform the coated core, to remove the remaining Cu layer, then to complete the deformation of the Nb-Ti core simply coated with niobium.
  • This layer of niobium then forms the outer layer which is in contact with the dies and the rolling rollers. It is chemically inert and ductile and easily allows the spiral wire to be drawn and rolled. It has the other advantage of facilitating the separation between the spirals after the fixing step following the strapping step.
  • the niobium layer is retained on the hairspring at the end of the manufacturing process. It is sufficiently thin with a thickness of between 50 nm and 5 ⁇ m and preferably 200 nm and 1.5 ⁇ m and more preferably between 800 nm and 1.2 ⁇ m, so as not to significantly modify the thermoelastic coefficient (CTE) of the hairspring.
  • CTE thermoelastic coefficient
  • Nb has a CTE similar to that of Nb-Ti, which facilitates obtaining a compensating hairspring.
  • Nb-Ti core It is also perfectly adherent to the Nb-Ti core.
  • These thicknesses of the niobium layer are typically suitable for Nb-Ti cores having diameters between 15 and 100 ⁇ m.
  • step d1) of the process of the invention consists of cold deforming by hammering and/or stretching and/or drawing the blank obtained in step c).
  • a beta-type quenching step of said blank is carried out, so that the titanium of said alloy is essentially in the form of a solid solution with the niobium in the beta phase and preferably, the quenching step ⁇ is a solution treatment, with a duration of between 5 minutes and 2 hours at a temperature of between 700°C and 1000 °C, under vacuum, followed by cooling under gas.
  • the step of removing the layer of the second material is carried out by attack chemical in a solution based on cyanides or acids, for example nitric acid.
  • the final heat treatment of step g) is an alpha-phase precipitation treatment of titanium with a duration of between 1 hour and 80 hours at a temperature of between 350°C and 700°C, preferably between 5 hours and 30 hours between 400°C and 600°C.
  • step g) consists of a heat treatment for precipitation of titanium in alpha phase for a duration of between 1 hour and 80 hours at a temperature of between 350°C and 700°C, preferably between 5 hours and 30 hours between 400°C and 600°C.
  • an intermediate heat treatment for precipitation of titanium in alpha phase for a duration of between 1 hour and 80 hours at a temperature of between 350°C and 700°C, preferably between 5 hours and 30 hours between 400°C C and 600°C can also be carried out after each or certain sequences of the deformation step d1) and/or d2)
  • the layer of the second material typically copper formed in step c) has a thickness of between 1 ⁇ m and 100 ⁇ m when the diameter of the core of the Nb-Ti wire is 100 ⁇ m.
  • each sequence of steps d1) and/or d2) is carried out with a deformation rate of between 1 and 5, the overall accumulation of deformations over all the sequences leading to a total deformation rate of between 1 and 14.
  • the deformation rate for each sequence g) 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 hardened wire
  • step b) of forming the layer of the first material is carried out by winding a strip of the first material, for example. of niobium, around the Nb-Ti core
  • step c) of forming the layer of the second material is carried out by introducing the blank obtained at the outcome of step b) in a tube of the second material, e.g. of copper, followed by drawing and/or hammering and/or drawing of the entire tube and the blank obtained at the end of step b).
  • the invention relates to a method of manufacturing a spiral spring intended to equip a balance wheel with a watch movement.
  • This spiral spring is made of a binary type alloy comprising niobium and titanium.
  • niobium as a first material and copper as a second material.
  • the method of the invention further comprises a step h) consisting of removing said layer of copper formed in step c), at a moment in step c) at which the blank has reached a diameter such that can still pass said blank at least through one die and preferably through two dies with an elongation rate 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).
  • a step h) consisting of removing said layer of copper formed in step c), at a moment in step c) at which the blank has reached a diameter such that can still pass said blank at least through one die and preferably through two dies with an elongation rate 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 by weight between 40 and 60% 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 fragility of the alloy during its implementation.
  • the Nb-Ti alloy used in the present invention does not include other elements with the exception of 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, 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 addition of the niobium layer around the core can be carried out galvanically, by PVD, CVD or mechanically. In the latter case, a niobium tube is fitted to a bar of the Nb-Ti alloy. The assembly is deformed by hammering, stretching and/or drawing to thin the bar and form the blank which was made available in step a).
  • the thickness of the niobium layer is chosen so that the niobium surface/surface ratio of the Nb-Ti core 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 can be produced by winding 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 which 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 step c) .
  • the addition of the copper layer around the core can be done galvanically, by PVD, CVD or mechanically. In the latter case, a copper tube is fitted to a bar of Nb-Ti alloy coated with the niobium layer. The assembly is deformed by hammering, stretching and/or drawing to thin the bar and form the blank which was made available at the end of step b).
  • the thickness of the copper layer is chosen so that the ratio of copper surface/surface 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. 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 copper layer can be produced by winding 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 drawing to thin the bar and form the blank which 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 assembly being co-extruded hot at a temperature of the order of 600 to 900 degrees through a pathway.
  • a beta-type quenching consisting of a solution treatment is carried out at least before the subsequent deformation stages.
  • This treatment is carried out so that the titanium in 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.
  • Deformation step d) is carried out in several sequences.
  • deformation we mean deformation by drawing and/or rolling.
  • the deformation step comprises at least successively deformation sequences, preferably cold, by hammering and/or stretching and/or calibration 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 calibration diameter of the wire.
  • the method further comprises a step h) which consists of removing the layer of copper formed in step c), when during step d1), the blank has reached a diameter such that we can still pass said blank at least through a die with an elongation rate 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 weight in water.
  • a sequence of rolling operations preferably with a rectangular profile compatible with the entry section of a strapping spindle, is then carried out, this sequence forming step d2 ).
  • Each sequence of steps d1) and d2) is carried out with a given deformation rate between 1 and 5, this deformation 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 hardened wire.
  • the overall accumulation of deformations over this entire succession of sequences gives a total deformation rate of 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 blade obtained at the end of step d2) is then cut to a determined length during step e) .
  • Step f) of strapping to form the spiral spring is followed by step g) of final heat treatment on the spiral spring.
  • This final heat treatment is an alpha phase Ti precipitation treatment 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. °C.
  • the process may further comprise, between each sequence or between certain sequences of deformation steps d1) and/or d2), an intermediate heat treatment for precipitation of titanium in alpha phase with a duration of 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 process 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 an elastic modulus less than or equal to 120 GPa, and preferably less than or equal to 100 GPa.
  • the spiral spring comprises an Nb-Ti core 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 the beta phase and titanium in the alpha phase.
  • the spiral spring produced according to this process has a thermoelastic coefficient, also called CTE, allowing it to guarantee the maintenance of chronometric performance despite the variation in the temperatures of use of a watch incorporating such a spiral spring.
  • the process of the invention allows the production, and more particularly the shaping, of a spiral spring for a balance wheel made of a niobium-titanium type alloy, typically containing 47% by weight of titanium (40-60%).
  • This alloy has high mechanical properties, 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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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • General Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • 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 (15)

  1. Verfahren zur Herstellung einer Spiralfeder, die dazu bestimmt ist, eine Unruh eines Uhrwerks auszustatten, umfassend:
    a) einen Schritt zum Bereitstellen eines Rohwerks mit einem Kern aus Nb-Ti, der aus einer Legierung gefertigt ist, bestehend aus:
    - Niob: Balance zu 100 Gew.-%,
    - Titan: zwischen 5 Gew.-% und 95 Gew.-%,
    - Spuren eines oder mehrerer Elemente, die aus der Gruppe ausgewählt sind, die aus O, H, C, Fe, Ta, N, Ni, Si, Cu und Al besteht, wobei jedes der Elemente in einer Menge vorhanden ist, die zwischen 0 ppm und 1600 ppm, bezogen auf das Gewicht, liegt, wobei die Gesamtmenge, die aus der Gesamtheit der Elemente besteht, zwischen 0 Gew.-% und 0,3 Gew.-% liegt,
    b) einen Schritt zum Bilden einer Schicht aus einem ersten Werkstoff, die eine erste Dicke aufweist, um das Rohwerk mit dem Kern aus Nb-Ti herum,
    c) einen Schritt zum Bilden einer Schicht aus einem zweiten Werkstoff, wobei das Verfahren dadurch gekennzeichnet ist, dass die Schicht aus dem zweiten Werkstoff eine zweite Dicke aufweist, die größer als die Dicke der Schicht aus dem ersten Werkstoff um das aus Schritt b) erhaltene Rohwerk herum ist, wobei der erste und zweite Werkstoff ausgewählt sind, damit der zweite Werkstoff selektiv physikalisch oder chemisch entfernt werden kann, ohne den ersten Werkstoff wesentlich anzugreifen
    d) einen Schritt zum Verformen des Rohwerks in mehreren Abfolgen, umfassend:
    d1) eine Abfolge von Verformungsdurchgangsschritten, um das in Schritt c) erhaltene Rohwerk auf einen bestimmten, Kalibrierungsdurchmesser genannten, Durchmesser zu bringen, und
    d2) eine Abfolge von Flachwalzschritten des in Schritt d1) erhaltenen runden Rohwerks
    e) einen Schritt zum Schneiden des gewalzten Drahts in Klingen mit einer bestimmten Länge
    f) einen Schritt zum Aufwinden, um die Spiralfeder zu bilden,
    g) einen abschließenden Wärmebehandlungsschritt an der Spiralfeder,
    und wobei das Verfahren weiter einen Schritt h) umfasst, der darin besteht, die in Schritt c) gebildete Schicht aus dem zweiten Werkstoff zu entfernen, wenn das Rohwerk einen solchen Durchmesser erreicht hat, dass das Rohwerk vor dem ersten Walzschritt d2) oder spätestens vor dem letzten Durchgang des Schritts d2) noch durch mindestens einen Ziehstein mit einer Dehnungsrate des Rohwerks von etwa 10 % geführt werden kann.
  2. Verfahren nach Anspruch 1, wobei der erste Werkstoff aus der Einheit von Niob, Gold, Tantal, Vanadium, rostfreiem austenitischem Stahl, wie Stahl der Sorte 316L, ausgewählt ist, und dadurch, dass der zweite Werkstoff aus der Einheit ausgewählt ist, welche Kupfer, Silber, eine Kupfer-Nickel-Legierung, eine einphasige Alpha-Kupfer-Zink-Legierung, insbesondere die Cu-Zn30-Legierung, umfasst.
  3. Verfahren nach Anspruch 1 oder 2, wobei der erste Werkstoff Niob ist und dadurch, dass der zweite Werkstoff Kupfer ist.
  4. Verfahren nach einem der vorstehenden Ansprüche, wobei der Schritt h) durchgeführt wird, wenn das Rohwerk einen solchen Durchmesser erreicht hat, dass das Rohwerk vor dem ersten Walzschritt d2) noch durch zwei Ziehsteine mit einer Dehnungsrate des Rohwerks von jeweils etwa 10 % geführt werden kann.
  5. Verfahren nach einem der vorstehenden Ansprüche, wobei der Schritt d1) darin besteht, das in Schritt c) erhaltene Rohwerk durch Hämmern und/oder Ziehen und/oder Drahtziehen kalt zu verformen.
  6. Verfahren zur Herstellung nach einem der vorstehenden Ansprüche in Verbindung mit den Ansprüchen 2 oder 3, wobei der Schritt des Entfernens der Kupferschicht durch einen chemischen Angriff in einer Lösung auf Basis von Cyanid oder Säuren durchgeführt wird.
  7. Verfahren nach einem der vorstehenden Ansprüche, wobei zumindest vor dem Schritt d1) und/oder d2) ein Beta-Abschreckungsschritt des Rohwerks durchgeführt wird, sodass das Titan der Legierung im Wesentlichen in Form einer festen Lösung mit dem Niob in einer Beta-Phase vorliegt.
  8. Verfahren zur Herstellung nach Anspruch 7, wobei der Abschreckschritt β eine Behandlung durch Lösungsglühen mit einer Dauer, die zwischen 5 Minuten und 2 Stunden liegt, bei einer Temperatur zwischen 700 °C und 1000 °C unter Vakuum, gefolgt von einer Abkühlung unter Gas ist.
  9. Verfahren zur Herstellung nach einem der vorstehenden Ansprüche, wobei die abschließende Wärmebehandlung von Schritt g) eine Ausfällungsbehandlung von Titan in Alpha-Phase mit einer Dauer, die zwischen 1 Stunde und 80 Stunden liegt, bei einer Temperatur zwischen 350 °C und 700 °C, vorzugsweise zwischen 5 Stunden und 30 Stunden zwischen 400 °C und 600 °C, ist.
  10. Verfahren zur Herstellung nach einem der vorstehenden Ansprüche, das weiter zwischen jeder Abfolge oder zwischen bestimmten Abfolgen der Verformungsschritte d1) und/oder d2) eine Zwischenwärmebehandlung zur Ausfällung des Titans in der Alpha-Phase mit einer Dauer, die zwischen 1 Stunde und 80 Stunden liegt, bei einer Temperatur zwischen 350 °C und 700 °C, vorzugsweise zwischen 5 Stunden und 30 Stunden zwischen 400 °C und 600 °C, beinhaltet.
  11. Verfahren zur Herstellung nach einem der vorstehenden Ansprüche, wobei die Schicht aus dem ersten Werkstoff am Ende von Schritt d2) eine Dicke aufweist, die zwischen 50 nm und 5 µm und vorzugsweise 200 nm und 1,5 µm und bevorzugter zwischen 800 nm und 1,2 µm liegt, und dadurch, dass der Kern aus Nb-Ti einen Durchmesser aufweist, der zwischen 15 und 50 µm liegt.
  12. Verfahren zur Herstellung nach einem der vorstehenden Ansprüche, wobei die in Schritt c) gebildete Schicht aus dem zweiten Werkstoff eine Dicke aufweist, die zwischen 1 µm und 100 µm liegt, wenn der Durchmesser des Kerns des Drahtes aus Nb -Ti 100 µm beträgt.
  13. Verfahren zur Herstellung nach einem der vorstehenden Ansprüche, wobei jede Abfolge mit einer Verformungsrate durchgeführt wird, die zwischen 1 und 5 liegt, wobei die Gesamtsumme der Verformungen über die Gesamtheit der Abfolgen zu einer Gesamtverformungsrate führt, die zwischen 1 und 14 liegt.
  14. Verfahren zur Herstellung nach einem der vorstehenden Ansprüche, wobei der Schritt b) zur Bildung der Schicht aus dem ersten Werkstoff durch Aufwickeln eines Bandes aus dem ersten Werkstoff um den Kern aus Nb-Ti durchgeführt wird.
  15. Verfahren zur Herstellung nach einem der vorstehenden Ansprüche, wobei der Schritt c) zur Bildung der Schicht aus dem zweiten Werkstoff durch Einführen des am Ende des Schrittes b) erhaltenen Rohwerks in ein Rohr aus dem zweiten Werkstoff und anschließendes Ziehen und/oder Hämmern und/oder Strecken des gesamten Rohres und des nach Schritt b) erhaltenen Rohwerks durchgeführt wird.
EP19220163.0A 2019-12-31 2019-12-31 Herstellungsverfahren für eine spiralfeder für ein uhrwerk Active EP3845971B1 (de)

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EP21218349.5A EP4009114B1 (de) 2019-12-31 2019-12-31 Spiralfeder für uhrwerk und ihr herstellungsverfahren
EP19220163.0A EP3845971B1 (de) 2019-12-31 2019-12-31 Herstellungsverfahren für eine spiralfeder für ein uhrwerk
US17/084,210 US12105475B2 (en) 2019-12-31 2020-10-29 Balance-spring for horological movement and method for manufacturing same
JP2020183437A JP7051979B2 (ja) 2019-12-31 2020-11-02 計時器用ムーブメントのためのバランスばね及びその製造方法
KR1020200147991A KR102431406B1 (ko) 2019-12-31 2020-11-06 시계 무브먼트를 위한 밸런스 스프링 및 그 제조 방법
RU2020142723A RU2756785C1 (ru) 2019-12-31 2020-12-23 Балансная пружина для часового механизма и способ ее изготовления
CN202011629549.9A CN113126466B (zh) 2019-12-31 2020-12-31 用于钟表机芯的摆轮游丝及其制造方法
KR1020220072366A KR102502785B1 (ko) 2019-12-31 2022-06-14 시계 무브먼트를 위한 밸런스 스프링 및 그 제조 방법

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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
CN117403099B (zh) * 2023-08-18 2026-05-26 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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CN113126466B (zh) 2023-01-24
JP2021110726A (ja) 2021-08-02
KR20210086949A (ko) 2021-07-09
EP3845971A1 (de) 2021-07-07
CN113126466A (zh) 2021-07-16
RU2756785C1 (ru) 2021-10-05
KR102502785B1 (ko) 2023-02-23
US20210200153A1 (en) 2021-07-01
EP4009114A1 (de) 2022-06-08
EP4009114B1 (de) 2024-10-16
KR20220088652A (ko) 2022-06-28
KR102431406B1 (ko) 2022-08-10
US12105475B2 (en) 2024-10-01

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