EP4123393A1 - Ressort spiral pour mouvement d'horlogerie - Google Patents

Ressort spiral pour mouvement d'horlogerie Download PDF

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Publication number
EP4123393A1
EP4123393A1 EP21187512.5A EP21187512A EP4123393A1 EP 4123393 A1 EP4123393 A1 EP 4123393A1 EP 21187512 A EP21187512 A EP 21187512A EP 4123393 A1 EP4123393 A1 EP 4123393A1
Authority
EP
European Patent Office
Prior art keywords
spiral spring
spring according
alloy
content
weight
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.)
Pending
Application number
EP21187512.5A
Other languages
German (de)
English (en)
French (fr)
Inventor
Lionel MICHELET
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
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 EP21187512.5A priority Critical patent/EP4123393A1/fr
Priority to JP2022044945A priority patent/JP7438252B2/ja
Priority to US17/657,664 priority patent/US11851737B2/en
Priority to KR1020220051605A priority patent/KR20230015833A/ko
Priority to CN202210857448.XA priority patent/CN115685717A/zh
Publication of EP4123393A1 publication Critical patent/EP4123393A1/fr
Pending legal-status Critical Current

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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
    • 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
    • C22F1/16—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

Definitions

  • the invention relates to a spiral spring intended to equip a balance wheel of a timepiece movement. It also relates to the manufacturing process of this spiral spring.
  • the alloy chosen for a spiral spring must also have properties guaranteeing the maintenance of chronometric performance despite the variation in the temperatures of use of a watch incorporating such a spiral spring.
  • the thermoelastic coefficient, also called CTE, of the alloy is then of great importance.
  • a CTE of +/- 10 ppm/°C must be achieved.
  • CT M 38 °C ⁇ M 8 °C 30 with a value which must be between - 0.6 and + 0.6 s/d°C.
  • spiral springs for watchmaking made of binary Nb-Ti alloys with percentages by weight of Ti typically between 40 and 60% and more specifically with a percentage of 47%.
  • this spiral spring has a two-phase microstructure comprising a solid solution of Nb and Ti in the beta phase and Ti in the form of precipitates in the alpha phase.
  • the solid solution of hardened beta-phase Nb and Ti exhibits a strong positive CTE while the alpha-phase Ti possesses a strongly negative CTE allowing the two-phase alloy to be reduced to a CTE close to zero, which is particularly favorable for the CT. .
  • Nb-Ti binary alloys for spiral springs.
  • the Nb-Ti binary alloy is particularly favorable for low CT as mentioned above.
  • the secondary error is +4.5 s/d whereas preferably it should be between -3 and +3 s/d.
  • the object of the invention is to propose a new manufacturing process and a new chemical composition for a spiral spring making it possible to reduce the secondary error while maintaining a thermal coefficient close to 0.
  • hydrogen is added to the Nb-Ti alloy by thermochemical treatment under a controlled atmosphere during the manufacturing process.
  • thermochemical treatment is carried out on a recrystallized structure.
  • the spiral spring thus produced comprises hydrogen mainly or exclusively in the form of interstitials.
  • the spiral spring produced with the method according to the invention has a breaking load Rm greater than or equal to 500 MPa and more precisely comprised between 800 and 1000 MPa.
  • Rm breaking load
  • the spiral spring produced with the method according to the invention has a modulus of elasticity greater than or equal to 80 GPa and preferably greater than or equal to 90 GPa.
  • the hydrogen content is between 0.2 and 1.5% by weight, more preferably between 0.5 and 1% by weight.
  • the titanium content is between 20 and 60%, preferably between 40 and 50% by weight.
  • the alloy used in the present invention does not include other elements than Ti, Nb and H with the exception of possible and unavoidable traces.
  • 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 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 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 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 even less than or equal to 0.0075% 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 copper content 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 alloy is enriched in hydrogen via a thermochemical treatment under an atmosphere comprising a hydrogen carrier gas.
  • the thermochemical treatment can be carried out during the solution heat treatment of step b), during a heat treatment of step c), during the final fixing heat treatment of step e ) or between steps a) and b), b) and c), c) and d), d) and e) or after step e).
  • this treatment is carried out during step e) at the end of the manufacturing process. Carrying out the thermochemical treatment at the end of the manufacturing process makes it possible to avoid a possible release of hydrogen into the atmosphere during a subsequent step which would be carried out, for example, under vacuum. This also makes it possible to fix the geometry of the spring, the thermal coefficient and the secondary error during a single heat treatment.
  • thermochemical treatment is carried out at a holding temperature of between 100 and 900° C., preferably between 500 and 800° C., more preferably between 600 and 700° C. in an atmosphere comprising hydrogen.
  • the thermochemical treatment can be carried out in an atmosphere containing 100% H 2 with an absolute pressure of between 5 mbar and 10 bar, preferably between 0.5 and 7 bar, more preferably between 1 and 6 bar, even more preferably between 3.5 and 4.5 bar.
  • thermochemical treatment can also be carried out in an atmosphere containing a mixture of gases, for example Ar and H 2 , under a total pressure of between 5 mbar and 10 bar, preferably between 0.5 and 7 bar, more preferably between 1 and 6 bar, even more preferentially between 3.5 and 4.5 bar, with a volume percentage of H 2 comprised between 5 and 90%.
  • a mixture of gases for example Ar and H 2
  • the thermochemical treatment is carried out for a time of between 1 minute and 5 hours.
  • the solution treatment and quenching, called beta type, prior to the deformation sequences is a vacuum treatment at a temperature between 600°C and 1000°C with a duration of between 5 minutes and 2 hours, followed by cooling under gas. More particularly still, the treatment is carried out at 800° C. for 1 hour under vacuum and followed by cooling under gas.
  • each deformation sequence 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 hardening beta, and where d is the diameter of the work-hardened wire.
  • the global cumulation of the deformations on the whole of this succession of sequences brings a total rate of deformation included between 1 and 14.
  • the method includes between one and five deformation sequences.
  • the first sequence includes a first deformation with at least 30% section reduction.
  • each sequence other than the first, comprises a deformation with at least 25% reduction in section.
  • This heat treatment can have several purposes: to carry out a beta-type solution treatment and quenching treatment as before, to precipitate the alpha phase of titanium or else to restore/recrystallize the structure.
  • the beta-type solution treatment and quenching is carried out under vacuum at a temperature of between 600° C. and 1000° C. with a duration of between 5 minutes and 2 hours, followed by cooling under gas.
  • the precipitation of the alpha phase of the titanium is carried out at a temperature of between 300 and 500° C. for a time of between 1 hour and 200 hours.
  • the restoration/recrystallization is carried out at a temperature between 500 and 600°C for a time between 30 minutes and 20 hours.
  • step e) the final heat treatment is carried out for a period of between 1 hour and 200 hours at a temperature of between 300°C and 700°C. More particularly, the duration is between 5 hours and 30 hours at a holding temperature between 400°C and 600°C.
  • the method can also advantageously comprise an additional step taking place after step a) of producing or making available said alloy blank, and before the deformation sequences of step c), is added to the outlines 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 similar, to facilitate shaping into wire form when deforming. And, between the last deformation sequences, after the deformation sequences or after step d) of strapping, we rids the wire of its layer of ductile material, in particular by chemical attack.
  • the surface layer of ductile material is deposited so as to constitute a spiral spring whose pitch is not a multiple of the thickness of the blade.
  • the surface layer of ductile material is deposited so as to form a spring whose pitch is variable.
  • ductile material is thus added at a given moment to facilitate shaping in the form of a wire, in such a way that a thickness of 10 to 500 micrometers remains on the wire at the final diameter. from 0.3 to 1 millimetres.
  • the wire is stripped of its layer of ductile material in particular by chemical attack, then is rolled flat before the manufacture of the actual spring by strapping. Alternatively, the layer of ductile material is removed after flat rolling and before strapping.
  • ductile material can be galvanic, or mechanical, it is then a shirt or a tube of ductile material which is adjusted on an alloy bar with a large diameter, then which is thinned during the stages of deformation of the composite bar.
  • the layer can be removed in particular by chemical attack, with a solution based on cyanides or based on acids, for example nitric acid.
  • thermochemical treatment was carried out during the final fixing heat treatment in step e) under an atmosphere comprising 100% H 2 with the conditions given in Table 1 below.
  • the thermochemical treatment was carried out either on a recrystallized structure (R) having been subjected to sequences of deformation terminated by a heat treatment for recrystallization, or on a hardened structure (E) following sequences of deformation without subsequent heat treatment for recrystallization.
  • CT M 38 °C ⁇ M 8 °C 30 with the same apparatus.
  • Samples 01 to 04 have hydrogen contents between 0.3 and 1% by weight. All the samples have a secondary error between - 3 and + 3 s/d as desired with values close to 0 for the samples treated under a hydrogen pressure of 4 bar.
  • the CT is also contained in the range between -0.6 and +0.6 s/d°C as desired. The optimum is obtained for sample 01 for which the thermochemical treatment was carried out on a recrystallized structure, the thermal coefficient and the secondary error being close of 0 expressed respectively in s/d°C and s/d.
  • This sample has a hydrogen content of the order of 0.6% by weight.
  • thermochemical treatment makes it possible to introduce hydrogen in the form of interstitials without forming hydrides. Furthermore, no precipitation of titanium in the alpha phase is observed. The absence of titanium precipitates is attributed to the presence of hydrogen which stabilizes the beta phase of titanium.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Springs (AREA)
EP21187512.5A 2021-07-23 2021-07-23 Ressort spiral pour mouvement d'horlogerie Pending EP4123393A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP21187512.5A EP4123393A1 (fr) 2021-07-23 2021-07-23 Ressort spiral pour mouvement d'horlogerie
JP2022044945A JP7438252B2 (ja) 2021-07-23 2022-03-22 計時器用ムーブメントのためのバランスばね
US17/657,664 US11851737B2 (en) 2021-07-23 2022-04-01 Balance spring for a horological movement
KR1020220051605A KR20230015833A (ko) 2021-07-23 2022-04-26 시계 무브먼트를 위한 밸런스 스프링
CN202210857448.XA CN115685717A (zh) 2021-07-23 2022-07-21 用于钟表机芯的摆轮游丝

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21187512.5A EP4123393A1 (fr) 2021-07-23 2021-07-23 Ressort spiral pour mouvement d'horlogerie

Publications (1)

Publication Number Publication Date
EP4123393A1 true EP4123393A1 (fr) 2023-01-25

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP21187512.5A Pending EP4123393A1 (fr) 2021-07-23 2021-07-23 Ressort spiral pour mouvement d'horlogerie

Country Status (5)

Country Link
US (1) US11851737B2 (ja)
EP (1) EP4123393A1 (ja)
JP (1) JP7438252B2 (ja)
KR (1) KR20230015833A (ja)
CN (1) CN115685717A (ja)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018172164A1 (fr) * 2017-03-24 2018-09-27 Universite De Lorraine ALLIAGE DE TITANE ß METASTABLE, RESSORT D'HORLOGERIE A BASE D'UN TEL ALLIAGE ET SON PROCEDE DE FABRICATION
CH714494A2 (fr) * 2017-12-21 2019-06-28 Nivarox Sa Ressort spiralé d'horlogerie, notamment un ressort de barillet ou un ressort-spiral.

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100567534C (zh) 2007-06-19 2009-12-09 中国科学院金属研究所 一种高热强性、高热稳定性的高温钛合金的热加工和热处理方法
JP2013163840A (ja) 2012-02-10 2013-08-22 Toyota Central R&D Labs Inc チタン合金およびその製造方法
EP3502289B1 (fr) 2017-12-21 2022-11-09 Nivarox-FAR S.A. Procédé de fabrication d'un ressort spiral pour mouvement d'horlogerie
EP3736639B1 (fr) 2019-05-07 2024-07-03 Nivarox-FAR S.A. Procede de fabrication d'un ressort spiral pour mouvement d'horlogerie
EP3796101A1 (fr) 2019-09-20 2021-03-24 Nivarox-FAR S.A. Ressort spiral pour mouvement d'horlogerie
EP3845971B1 (fr) 2019-12-31 2024-04-17 Nivarox-FAR S.A. Procede de fabrication de ressort spiral pour mouvement d'horlogerie

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018172164A1 (fr) * 2017-03-24 2018-09-27 Universite De Lorraine ALLIAGE DE TITANE ß METASTABLE, RESSORT D'HORLOGERIE A BASE D'UN TEL ALLIAGE ET SON PROCEDE DE FABRICATION
CH714494A2 (fr) * 2017-12-21 2019-06-28 Nivarox Sa Ressort spiralé d'horlogerie, notamment un ressort de barillet ou un ressort-spiral.

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Oscillateur pour pièce d'horlogerie ED - Darl Kuhn", IP.COM, IP.COM INC., WEST HENRIETTA, NY, US, 28 May 2021 (2021-05-28), XP013189494, ISSN: 1533-0001 *
ELIAZ N ET AL: "Hydrogen-assisted processing of materials", MATERIALS SCIENCE, vol. 289, no. 1-2, 1 September 2000 (2000-09-01), AMSTERDAM, NL, pages 41 - 53, XP055872626, ISSN: 0921-5093, DOI: 10.1016/S0921-5093(00)00906-0 *

Also Published As

Publication number Publication date
US11851737B2 (en) 2023-12-26
CN115685717A (zh) 2023-02-03
JP2023016679A (ja) 2023-02-02
US20230031063A1 (en) 2023-02-02
KR20230015833A (ko) 2023-01-31
JP7438252B2 (ja) 2024-02-26

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