EP3796101B1 - Spiralfeder für uhrwerk - Google Patents

Spiralfeder für uhrwerk Download PDF

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Publication number
EP3796101B1
EP3796101B1 EP19198759.3A EP19198759A EP3796101B1 EP 3796101 B1 EP3796101 B1 EP 3796101B1 EP 19198759 A EP19198759 A EP 19198759A EP 3796101 B1 EP3796101 B1 EP 3796101B1
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EP
European Patent Office
Prior art keywords
balance spring
deformation
producing
heat treatment
niobium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP19198759.3A
Other languages
English (en)
French (fr)
Other versions
EP3796101A1 (de
Inventor
Christian Charbon
Marco Verardo
Lionel MICHELET
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nivarox Far SA
Original Assignee
Nivarox Far SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nivarox Far SA filed Critical Nivarox Far SA
Priority to EP19198759.3A priority Critical patent/EP3796101B1/de
Priority to US16/936,682 priority patent/US12147195B2/en
Priority to JP2020136578A priority patent/JP7148577B2/ja
Priority to CN202210710467.XA priority patent/CN114990402A/zh
Priority to CN202010985588.6A priority patent/CN112538587B/zh
Publication of EP3796101A1 publication Critical patent/EP3796101A1/de
Application granted granted Critical
Publication of EP3796101B1 publication Critical patent/EP3796101B1/de
Active legal-status Critical Current
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Classifications

    • 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
    • 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
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • 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
    • 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 spiral spring intended to equip a balance wheel of a watch movement. It also relates to the method of manufacturing this spiral spring.
  • the invention aims to define a new type of watch spiral spring, based on the selection of a particular material, and to develop the appropriate manufacturing process.
  • the invention relates to a watch spiral spring made from an alloy of niobium and titanium defined by claim 1 of the patent.
  • the invention also relates to the method of manufacturing this watch spiral spring as claimed in the appendix.
  • the invention relates to a watch spiral spring made from a binary type alloy comprising niobium and titanium.
  • the weight percentage of oxygen is less than or equal to 0.10% of the total, or even less than or equal to 0.085% of the total.
  • the weight percentage of tantalum is less than or equal to 0.10% of the total.
  • the weight percentage of carbon is less than or equal to 0.04% of the total, in particular less than or equal to 0.020% of the total, or even less than or equal to 0.0175% of the total.
  • the percentage by weight of iron is less than or equal to 0.03% of the total, in particular less than or equal to 0.025% of the total, or even less than or equal to 0.020% of the total.
  • the percentage by weight of nitrogen is less than or equal to 0.02% of the total, in particular less than or equal to 0.015% of the total, or even less than or equal to 0.0075% of the total.
  • the weight percentage of hydrogen is less than or equal to 0.01% of the total, in particular less than or equal to 0.0035% of the total, or even less than or equal to 0.0005% of the total.
  • the weight percentage of nickel is less than or equal to 0.01% of the total.
  • the weight percentage of silicon is less than or equal to 0.01% of the total.
  • the weight percentage of nickel is less than or equal to 0.01% of the total, in particular less than or equal to 0.16% of the total.
  • the weight percentage of copper is less than or equal to 0.01% of the total, in particular less than or equal to 0.005% of the total.
  • the weight percentage of aluminum is less than or equal to 0.01% of the total.
  • this spiral spring has a two-phase microstructure comprising niobium in beta-body-centered cubic phase and titanium in alpha-body-centered hexagonal compact phase.
  • thermoelastic coefficient also called CTE of the alloy
  • CTE the thermoelastic coefficient
  • E is the Young's modulus of the spiral spring, and, in this formula, E, ß and a are expressed in °C -1 .
  • CT is the thermal coefficient of the oscillator
  • (1/E. dE/dT) is the CTE of the balance alloy
  • ⁇ is the coefficient of expansion of the balance and ⁇ that of the balance.
  • the work-hardened beta-phase alloy has a strongly positive CTE, and the precipitation of the alpha phase which has a strongly negative CTE allows the two-phase alloy to be brought back to a CTE close to zero, which is particularly favorable.
  • too high a percentage of titanium leads to the formation of fragile phases.
  • a percentage of titanium lower than 40% by weight allows a good compromise to be obtained between the different desired properties.
  • the spiral spring made with this alloy has an elastic limit greater than or equal to 500 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 110 GPa.
  • each deformation is carried out with a given deformation 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.
  • Each coupled strain-heat treatment sequence includes, each time, a heat treatment to precipitate the alpha Ti phase.
  • Beta quenching prior to the deformation and heat treatment sequences 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.
  • this beta quenching is a solution treatment, lasting 1 hour at 800°C under vacuum, followed by cooling under gas.
  • the heat treatment is a precipitation treatment lasting between 1 hour and 200 hours at a temperature between 300°C and 700°C. More specifically, the duration is between 5 hours and 30 hours at a temperature between 400°C and 600°C.
  • the process involves between one and five coupled deformation-heat treatment sequences.
  • the first coupled deformation-heat treatment sequence comprises a first deformation with at least 30% reduction in section.
  • each coupled deformation-heat treatment sequence includes a deformation between two heat treatments with at least 25% reduction in section.
  • a surface layer of ductile material taken from copper, nickel, cupro-nickel, cupro-magnanese, gold, silver, nickel-phosphorus Ni-P and nickel-boron Ni-B, or the like, is added to the blank to facilitate shaping into wire during deformation.
  • the wire is stripped of its layer of ductile material, in particular by chemical attack.
  • the surface layer of ductile material is deposited so as to form a spiral spring whose pitch is not a multiple of the thickness of the blade. In another variant, the surface layer of ductile material is deposited so as to form a spring whose pitch is variable.
  • ductile material or copper is thus added at a given moment to facilitate shaping into wire, so that a thickness of 10 to 500 micrometers remains on the wire with a final diameter of 0.3 to 1 millimeter.
  • the wire is stripped of its layer of ductile material or copper in particular by chemical attack, then is rolled flat before the manufacture of the spring itself by strapping.
  • ductile material or copper can be galvanic, or mechanical, in which case it is a jacket or tube of ductile material or copper which is adjusted on a bar of niobium-titanium alloy to a large diameter, then which is thinned during the stages of deformation of the composite bar.
  • a diffusion barrier layer for example nb, can be added between the nb-Ti and the Cu in order to avoid the formation of intermetallics harmful to the deformability of the material.
  • the thickness of this layer is chosen so as to correspond to a thickness of 100 nm to 1 ⁇ m on the wire with a diameter of 0.1 mm.
  • the removal of the layer can be achieved in particular by chemical attack, with a solution based on cyanides or acids, for example nitric acid.
  • a very fine, in particular nanometric, lamellar two-phase microstructure comprising or composed of beta niobium and alpha titanium.
  • This alloy combines a very high elastic limit, at least greater than 500 MPa, and a very low modulus of elasticity, of the order of 80 GPa to 120 GPa. This combination of properties is well suited for a spiral spring.
  • the alloy after the deformation-heat treatment sequences has a ⁇ 110> texture.
  • this niobium-titanium alloy according to the invention can easily be covered with ductile material or copper, which greatly facilitates its deformation by wire drawing.
  • a binary type alloy comprising niobium and titanium, of the type selected above for the implementation of the invention also exhibits an effect similar to that of "Elinvar", with a practically zero thermo-elastic coefficient in the usual temperature range of use of watches, and suitable for the manufacture of self-compensating balance springs.

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

Claims (15)

  1. Spiralfeder (1), die dazu bestimmt ist, eine Unruh eines Uhrwerks auszustatten, wobei die Spiralfeder (1) aus einer Niob- und Titanlegierung hergestellt ist, die aus folgendem Gewicht besteht:
    - Niob: der Rest bis zu 100 %;
    - Spuren anderer Elemente, die aus O, H, C, Fe, Ta, N, Ni, Si, Cu und/oder Al ausgewählt werden, wobei jedes der Elemente im Bereich zwischen 0 und 1.600 ppm des Gesamtgewichts liegt und die Summe der Spuren weniger oder gleich 0,3 Gew.-% ist,
    dadurch gekennzeichnet, dass die Nioblegierung Titan mit einem Anteil im Bereich zwischen 27 und 33 Gew.-% umfasst.
  2. Spiralfeder (1) nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass sie eine zweiphasige Mikrostruktur aufweist, die Niob in der Beta-Phase und Titan in der Alpha-Phase enthält.
  3. Spiralfeder (1) nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass sie eine Elastizitätsgrenze von größer oder gleich 500 MPa und einen Elastizitätsmodul von kleiner oder gleich 120 GPa, vorzugsweise kleiner oder gleich 110 GPa, aufweist.
  4. Verfahren zum Herstellen einer Spiralfeder (1), die dazu bestimmt ist, eine Unruh eines Uhrwerks auszustatten, das nacheinander Folgendes umfasst:
    - einen Schritt des Erstellens eines Rohwerks aus einer Niob- und Titanlegierung, die aus folgendem Gewicht besteht:
    - Niob: der Rest bis zu 100 %;
    - Titan mit einem Anteil im Bereich zwischen 27 und 33 Gew.-%;
    - Spuren anderer Elemente, die aus O, H, C, Fe, Ta, N, Ni, Si, Cu und/oder Al ausgewählt werden, wobei jedes der Elemente im Bereich zwischen 0 und 1.600 ppm des Gesamtgewichts liegt und die Summe der Spuren weniger oder gleich 0,3 Gew.-% ist,
    - einen Schritt des Beta-Abschreckens des Rohwerks, so dass das Titan der Legierung im Wesentlichen in Form einer festen Lösung mit dem Niob in der Beta-Phase vorliegt,
    - einen Schritt des Anwendens einer Abfolge von Verformungssequenzen auf die Legierung, gefolgt von einer zwischenzeitlichen Wärmebehandlung,
    - einen Schritt des Aufwindens, um die Spiralfeder (1) zu bilden,
    - einen Schritt der abschließenden Wärmebehandlung.
  5. Verfahren zum Herstellen einer Spiralfeder (1) nach Anspruch 4, dadurch gekennzeichnet, dass die Verformung während jeder Sequenz durch Drahtziehen und/oder Walzung durchgeführt wird.
  6. Verfahren zum Herstellen einer Spiralfeder (1) nach Anspruch 5, dadurch gekennzeichnet, dass die Verformung der letzten Sequenz durch Flachwalzung erfolgt.
  7. Verfahren zum Herstellen einer Spiralfeder (1) nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass die Verformung jeder Sequenz mit einer gegebenen Verformungsrate im Bereich zwischen 1 und 5 durchgeführt wird, wobei die Gesamtkumulation der Verformungen über die gesamte Abfolge von Sequenzen zu einer Gesamtverformungsrate im Bereich zwischen 1 und 14 führt.
  8. Verfahren zum Herstellen einer Spiralfeder (1) nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, dass es sich beim Beta-Abschrecken um ein Lösungsglühen mit einer Dauer im Bereich zwischen 5 Minuten und 2 Stunden bei einer Temperatur im Bereich zwischen 700 °C und 1.000 °C unter Vakuumbedingungen handelt, gefolgt von einem Kühlen unter Gas.
  9. Verfahren zum Herstellen einer Spiralfeder (1) nach einem der Ansprüche 4 bis 8, dadurch gekennzeichnet, dass es sich beim Beta-Abschrecken um ein 1-stündiges Lösungsglühen bei 800 °C unter Vakuumbedingungen handelt, gefolgt von einem Kühlen unter Gas.
  10. Verfahren zum Herstellen einer Spiralfeder (1) nach einem der Ansprüche 4 bis 9, dadurch gekennzeichnet, dass es sich bei der abschließenden Wärmebehandlung sowie der zwischenzeitlichen Wärmebehandlung jeder Sequenz um eine Ausscheidungsbehandlung von Ti in der Alpha-Phase mit einer Dauer im Bereich zwischen 1 Stunde und 200 Stunden bei einer Temperatur im Bereich zwischen 300 °C und 700 °C handelt.
  11. Verfahren zum Herstellen einer Spiralfeder (1) nach einem der Ansprüche 4 bis 10, dadurch gekennzeichnet, dass es sich bei der abschließenden Wärmebehandlung sowie der zwischenzeitlichen Wärmebehandlung jeder Sequenz um eine Ausscheidungsbehandlung von Ti in der Alpha-Phase mit einer Dauer im Bereich zwischen 5 Stunden und 30 Stunden bei einer Temperatur im Bereich zwischen 400 °C und 600 °C handelt.
  12. Verfahren zum Herstellen einer Spiralfeder (1) nach einem der Ansprüche 4 bis 11, dadurch gekennzeichnet, dass das Verfahren zwischen einer und fünf Verformungssequenzen, gefolgt von einer zwischenzeitlichen Wärmebehandlung, enthält.
  13. Verfahren zum Herstellen einer Spiralfeder (1) nach einem der Ansprüche 4 bis 12, dadurch gekennzeichnet, dass die erste Verformungssequenz, gefolgt von einer zwischenzeitlichen Wärmebehandlung, eine erste Verformung mit einer Querschnittsverringerung von mindestens 30 % enthält.
  14. Verfahren zum Herstellen einer Spiralfeder (1) nach Anspruch 13, dadurch gekennzeichnet, dass jede Verformungssequenz, gefolgt von einer zwischenzeitlichen Wärmebehandlung, abgesehen von der ersten, eine Verformung zwischen zwei zwischenzeitlichen Wärmebehandlungen mit einer Querschnittsverringerung von mindestens 25 % enthält.
  15. Verfahren zum Herstellen einer Spiralfeder (1) nach einem der Ansprüche 4 bis 14, dadurch gekennzeichnet, dass nach dem Schritt des Erstellens des Rohwerks aus der Legierung und vor dem Schritt des Anwendens einer Abfolge von Sequenzen dem Rohwerk eine Oberflächenschicht aus duktilem Material, das aus Kupfer, Nickel, Kupfernickel, Kupfer-Mangan, Gold, Silber, Nickel-Phosphor (NiP) und Nickel-Bor (NiB) ausgewählt wird, hinzugefügt wird, um das Formen in Drahtform zu erleichtern, und dass vor oder nach dem Schritt des Aufwindens die Schicht aus duktilem Material durch chemische Ätzung von dem Draht entfernt wird.
EP19198759.3A 2019-09-20 2019-09-20 Spiralfeder für uhrwerk Active EP3796101B1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP19198759.3A EP3796101B1 (de) 2019-09-20 2019-09-20 Spiralfeder für uhrwerk
US16/936,682 US12147195B2 (en) 2019-09-20 2020-07-23 Balance spring for a horological movement
JP2020136578A JP7148577B2 (ja) 2019-09-20 2020-08-13 計時器用ムーブメントのためのバランスばね
CN202210710467.XA CN114990402A (zh) 2019-09-20 2020-09-18 用于钟表机芯的摆轮游丝
CN202010985588.6A CN112538587B (zh) 2019-09-20 2020-09-18 用于钟表机芯的摆轮游丝

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19198759.3A EP3796101B1 (de) 2019-09-20 2019-09-20 Spiralfeder für uhrwerk

Publications (2)

Publication Number Publication Date
EP3796101A1 EP3796101A1 (de) 2021-03-24
EP3796101B1 true EP3796101B1 (de) 2025-02-19

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EP19198759.3A Active EP3796101B1 (de) 2019-09-20 2019-09-20 Spiralfeder für uhrwerk

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US (1) US12147195B2 (de)
EP (1) EP3796101B1 (de)
JP (1) JP7148577B2 (de)
CN (2) CN112538587B (de)

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EP3502289B1 (de) * 2017-12-21 2022-11-09 Nivarox-FAR S.A. Herstellungsverfahren einer spiralfeder für uhrwerk
EP4123393B1 (de) * 2021-07-23 2025-04-16 Nivarox-FAR S.A. Spiralfeder für uhrwerk

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EP3502288B1 (de) 2017-12-21 2020-10-14 Nivarox-FAR S.A. Herstellungsverfahren einer spiralfeder für uhrwerk
EP3796102B1 (de) * 2017-12-22 2022-04-20 The Swatch Group Research and Development Ltd Verfahren zur herstellung einer unruh für uhren

Also Published As

Publication number Publication date
CN112538587A (zh) 2021-03-23
JP2021051065A (ja) 2021-04-01
US20210088971A1 (en) 2021-03-25
US12147195B2 (en) 2024-11-19
EP3796101A1 (de) 2021-03-24
CN112538587B (zh) 2022-08-16
CN114990402A (zh) 2022-09-02
JP7148577B2 (ja) 2022-10-05

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