EP3889691B1 - Uhrspiralfeder aus nb-hf-legierung - Google Patents

Uhrspiralfeder aus nb-hf-legierung Download PDF

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Publication number
EP3889691B1
EP3889691B1 EP21170773.2A EP21170773A EP3889691B1 EP 3889691 B1 EP3889691 B1 EP 3889691B1 EP 21170773 A EP21170773 A EP 21170773A EP 3889691 B1 EP3889691 B1 EP 3889691B1
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EP
European Patent Office
Prior art keywords
weight
total
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alloy
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Active
Application number
EP21170773.2A
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English (en)
French (fr)
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EP3889691A1 (de
Inventor
Christian Charbon
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
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Nivarox Far SA
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Priority to EP21170773.2A priority Critical patent/EP3889691B1/de
Publication of EP3889691A1 publication Critical patent/EP3889691A1/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
    • G04B17/04—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 wheel with a watch movement. It also relates to the spiral spring resulting from this process made in an Nb-Hf alloy.
  • 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.
  • An object of the present invention is to propose a spiral spring intended to equip a balance wheel with a clock movement and for which deformations during its manufacture are facilitated and rolling is easy.
  • the invention relates to a spiral spring as defined in appended claim 1.
  • the invention relates to a spiral spring intended to equip a balance wheel with a watch movement and made from an alloy comprising niobium and hafnium.
  • the blank comprises by weight between 8 and 12% hafnium, Ti 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 for 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, 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 0.05% by weight of the total. 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 solution treatment, with a duration of preferably between 5 minutes and 2 hours at a temperature of between 650°C and 1750°C, under vacuum, followed by quenching for example under gas to obtain Hf in supersaturated solid solution in Nb ß.
  • natural cooling under vacuum can also be considered.
  • the deposition step of the process making it possible to manufacture the spiral spring which is more particularly the subject of the invention consists of 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 shaping into wire form.
  • 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 shaping into wire form.
  • the thickness of the layer of ductile material deposited is chosen so that the ratio of surface area of ductile material/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 can have a thickness of 7 ⁇ m for an NbHf alloy section of 0.086 mm in diameter. This corresponds to a ratio between the copper surface area (0.002 mm 2 ) and the NbHf surface area (0.0058 mm 2 ) of 0.35.
  • Such a thickness of ductile material, and in particular of copper makes it possible to easily stretch, draw and roll the Cu/NbHf composite material.
  • the copper thickness is optimized so that the tip, created by filing or hot drawing, necessary for introducing the wire into the die during drawing or drawing, is covered with copper.
  • the ductile material preferably copper, is thus deposited at a given moment to facilitate the shaping of the wire by drawing, drawing and rolling, in such a way that a thickness remains, preferably between 1 and 500 micrometers on the wire with a total diameter of 0.2 to 1 millimeter.
  • ductile material can be galvanic, by PVD or CVD, or mechanical, it is then a jacket or a tube of ductile material such as copper which is adjusted to an NbHf alloy bar with a large diameter, then which is thinned during the step(s) of deformation of the composite bar.
  • ductile material can be galvanic, by PVD or CVD, or mechanical, it is then a jacket or a tube of ductile material such as copper which is adjusted to an NbHf alloy bar with a large diameter, then which is thinned during the step(s) of deformation of the composite bar.
  • the deformation step generally designates 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 stage or during different deformation stages if necessary.
  • Drawing is carried out until a round section wire is obtained.
  • Rolling can be carried out 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 strapping pin.
  • the process may comprise one step or several deformation steps with a deformation rate for each step of between 1 and 5, preferably between 2 and 5, the deformation rate corresponding to the classic formula 2ln(d0/d) where d0 and d are respectively the diameter before and after deformation.
  • the total strain rate can be between 1 and 14.
  • the process may include intermediate annealing stages between the different deformation stages.
  • the method which makes it possible to manufacture the spiral spring according to the invention preferably comprises, after the deformation step, a step of eliminating said layer of ductile material.
  • the ductile material is eliminated once all the deformation operations have been carried out, that is to say after the last rolling, before strapping.
  • 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 stage as well as the intermediate annealing carried out between the deformation stages is carried out during a duration 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 strapping 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 centered cubic or two-phase type with a centered cubic structure and a compact hexagonal structure can be obtained at the end of this heat treatment.
  • the above process allows the production, and more particularly the shaping, of a spiral spring for a balance wheel made of a niobium-hafnium type alloy, as claimed.
  • 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 100 GPa. This combination of properties is well suited for a spiral spring.
  • 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 has an effect similar to that of "Elinvar", with a thermo-elastic coefficient practically zero in the usual temperature range of watches, and suitable for the manufacture of self-compensating hairsprings.

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

Claims (1)

  1. Spiralfeder, die dazu bestimmt ist, eine Unruh eines Uhrwerks auszustatten, wobei die Spiralfeder aus einer Niob- und Hafniumlegierung hergestellt ist, die aus Folgendem besteht:
    - Niob: bis zu 100 Gew.-%,
    - Hafnium: zwischen 8 und 12 Gew.-%,
    - Ti zwischen 0,5 und 1,5 Gew.-%,
    - Zr zwischen 0,5 und 0,9 Gew.-%,
    - Ta zwischen 0,3 und 0,7 Gew.-%,
    - W zwischen 0,3 und 0,7 % und
    - wobei Verunreinigungen mit einem Gesamtanteil zwischen 0 und 0,5 Gew.-% betragen.
EP21170773.2A 2019-05-07 2019-05-07 Uhrspiralfeder aus nb-hf-legierung Active EP3889691B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP21170773.2A EP3889691B1 (de) 2019-05-07 2019-05-07 Uhrspiralfeder aus nb-hf-legierung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21170773.2A EP3889691B1 (de) 2019-05-07 2019-05-07 Uhrspiralfeder aus nb-hf-legierung
EP19173114.0A EP3736639B1 (de) 2019-05-07 2019-05-07 Herstellungsverfahren einer spiralfeder für uhrwerk

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP19173114.0A Division EP3736639B1 (de) 2019-05-07 2019-05-07 Herstellungsverfahren einer spiralfeder für uhrwerk
EP19173114.0A Division-Into EP3736639B1 (de) 2019-05-07 2019-05-07 Herstellungsverfahren einer spiralfeder für uhrwerk

Publications (2)

Publication Number Publication Date
EP3889691A1 EP3889691A1 (de) 2021-10-06
EP3889691B1 true EP3889691B1 (de) 2024-02-21

Family

ID=66448420

Family Applications (2)

Application Number Title Priority Date Filing Date
EP21170773.2A Active EP3889691B1 (de) 2019-05-07 2019-05-07 Uhrspiralfeder aus nb-hf-legierung
EP19173114.0A Active EP3736639B1 (de) 2019-05-07 2019-05-07 Herstellungsverfahren einer spiralfeder für uhrwerk

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP19173114.0A Active EP3736639B1 (de) 2019-05-07 2019-05-07 Herstellungsverfahren einer spiralfeder für uhrwerk

Country Status (4)

Country Link
US (1) US11550263B2 (de)
EP (2) EP3889691B1 (de)
JP (1) JP2020183940A (de)
CN (2) CN119472216A (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4060425B1 (de) * 2021-03-16 2024-10-16 Nivarox-FAR S.A. Spiralfeder für uhrwerk
EP4060424B1 (de) * 2021-03-16 2024-11-20 Nivarox-FAR S.A. Spiralfeder für uhrwerk
EP4123393B1 (de) 2021-07-23 2025-04-16 Nivarox-FAR S.A. Spiralfeder für uhrwerk

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1521206A (fr) * 1966-06-08 1968-04-12 Vacuumschmelze Gmbh Procédé pour la préparation d'alliages non ferromagnétiques dont le coefficient de température du module d'élasticité est réglable, ainsi que les produits conformes à ceux obtenus par le présent procédé ou procédé similaire
DE69710445T2 (de) * 1997-06-20 2002-10-10 Manufacture Des Montres Rolex S.A., Biel/Bienne Selbstkompensierende Spiralfeder für mechanische Uhrwerkunruhspiralfederoszillator und Verfahren zu deren Herstellung
DE69911913T2 (de) * 1999-03-26 2004-09-09 Rolex Sa Selbstkompensierende Spiralfeder für Uhrwerkspiralfederunruh und Verfahren zur Behandlung derselben
DE1258786T1 (de) 2001-05-18 2003-08-14 Rolex S.A., Genf/Geneve Selbstkompensierende Feder für einen mechanischen Oszillator vom Unruh-Spiralfeder-Typ
JP2005140674A (ja) * 2003-11-07 2005-06-02 Seiko Epson Corp 時計用ばね、ぜんまい、ひげぜんまい、及び時計
EP4439193A3 (de) * 2012-07-06 2024-12-18 Rolex Sa Verfahren zur behandlung einer oberfläche einer uhrkomponente und durch solch ein verfahren erhaltene uhrkomponente
US9395692B2 (en) * 2012-08-31 2016-07-19 Citizen Holdings Co., Ltd. Hairspring material for mechanical timepiece and hairspring using the same
EP3040790A1 (de) * 2014-12-29 2016-07-06 Montres Breguet S.A. Uhr oder Schmuckgegenstand aus einer leichten hochwertigen Legierung auf Titanbasis
EP3252542B1 (de) * 2016-06-01 2022-05-18 Rolex Sa Teil zur befestigung einer unruhspirale
EP3422116B1 (de) * 2017-06-26 2020-11-04 Nivarox-FAR S.A. Spiralfeder eines uhrwerks

Also Published As

Publication number Publication date
JP2020183940A (ja) 2020-11-12
US20200356057A1 (en) 2020-11-12
CN111913380B (zh) 2025-01-17
US11550263B2 (en) 2023-01-10
CN111913380A (zh) 2020-11-10
EP3736639A1 (de) 2020-11-11
EP3889691A1 (de) 2021-10-06
EP3736639B1 (de) 2024-07-03
CN119472216A (zh) 2025-02-18

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