• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a spiral watch spring with bi-phased structure, made of niobium and titanium alloy, and a method of manufacturing this spring. The material of said spring is a binary alloy comprising niobium and titanium, with: niobium: 100% balance; titanium between 40.0% and 60.0% by mass of the total, traces of components among O, H, C, Fe, Ta, N, Ni, Si, Cu, Al, between 0 and 1600 ppm of total mass in individual, with cumulative less than 0.3% by mass. The manufacturing method comprises: the application of alternating deformations to heat treatments for obtaining a bi-phased microstructure comprising niobium beta and alpha titanium, with an elastic limit greater than 1000 MPa, lower modulus of elasticity at 80 GPa; wire drawing to obtain calenderable wire; calendering or ringing to form a barrel spring, ground key before its first winding, or strapping to form a spiral spring.
    公开号:CH713935A2
    申请号:CH00861/17
    申请日:2017-07-03
    公开日:2018-12-28
    发明作者:Charbon Christian
    申请人:Nivarox Sa；
    IPC主号:
    专利说明:

    Description
    FIELD OF THE DISCLOSURE [0001] The invention relates to a clockwork spiral spring, in particular a mainspring or a spiral spring, with a bi-phased structure.
    The invention also relates to a method of manufacturing a clockwork spiral spring.
    The invention relates to the field of the manufacture of clock springs, in particular energy storage springs, such as barrel springs or coil springs motor or ring, or oscillator springs, such as than spirals.
    BACKGROUND OF THE INVENTION [0004] The manufacture of energy storage springs for the watch industry must face constraints that are often at first incompatible: - need to obtain a very high elastic limit, - necessity to obtain a low modulus of elasticity, - easy processing, in particular wire drawing, - excellent fatigue strength, - wear over time, - small sections, - end arrangement: bung hook and sliding flange, with local fragilities and difficulty of elaboration.
    The embodiment of spiral springs is centered on the concern of thermal compensation, so as to ensure regular chronometric performance. This requires a thermoelastic coefficient close to zero.
    Any improvement on at least one of the points, and in particular on the mechanical strength of the alloy used, therefore represents a significant advance. SUMMARY OF THE INVENTION [0007] The invention proposes to define a new type of spiral clock spring, based on the selection of a particular material, and to develop the appropriate manufacturing process.
    For this purpose, the invention relates to a spiral watch spring with a two-phase structure, according to claim 1.
    The invention also relates to a method of manufacturing such a spiral clockwork spring, according to claim 9.
    BRIEF DESCRIPTION OF THE DRAWINGS [0010] Other features and advantages of the invention will appear on reading the detailed description which follows, with reference to the appended drawings, in which: FIG. 1 shows, schematically and in plan view before its first winding, a mainspring which is a spiral spring according to the invention; fig. 2 schematically shows a spiral spring which is a spiral spring according to the invention; fig. 3 represents the sequence of the main operations of the method according to the invention.
    DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0011] The invention relates to a spiral watch spring with a bi-phased structure.
    According to the invention, the material of this spiral spring is a binary type alloy comprising niobium and titanium.
    In an advantageous embodiment, this alloy comprises: - niobium: 100% balance; - a mass proportion of titanium greater than or equal to 40.0% of the total and less than or equal to 60.0% of the total, - traces of other components among O, H, C, Fe, Ta, N, Ni, Si, Cu , Al, each of said trace components being between 0 and 1600 ppm of the total by mass, and the sum of these traces being less than or equal to 0.3% by mass.
    More particularly, this alloy has a mass proportion of titanium greater than or equal to 45.0% of the total and less than or equal to 48.0% of the total.
    Advantageously, this spiral spring has a bi-phased microstructure comprising centered cubic niobium beta and compact hexagonal alpha titanium.
    To obtain such a structure, and suitable for the development of a spring, it is necessary to precipitate a portion of the alpha phase by heat treatment.
    The higher the titanium content, the higher the maximum proportion of alpha phase that can be precipitated by heat treatment is high, which encourages the search for a high proportion of titanium. But on the other hand, the higher the titanium content, the more difficult it is to obtain only a precipitation of the alpha phase at the intersections of the grain boundaries. The appearance of Widmastätten alpha-Ti intragranular type precipitates or the intragranular phase phase makes the deformation of the material difficult or impossible, which is then not suitable for producing a spiral spring, and it should not be incorporated. too much titanium in the alloy. The development of the invention has made it possible to determine a compromise, with an optimum between these two characteristics close to 47% by weight of titanium.
    Also, more particularly, the proportion by weight of titanium is greater than or equal to 46.5% of the total.
    More particularly, the mass proportion of titanium is less than or equal to 47.5% of the total.
    In an alternative, the balance at 100% of the total mass is made by titanium, and the mass proportion of niobium is greater than or equal to 51.7% of the total and less than or equal to 55.0% of the total.
    In another composition variant, the mass proportion of titanium is greater than or equal to 46.0% of the total and less than or equal to 50.0% of the total.
    In yet another variant of composition, the mass proportion of titanium is greater than or equal to 53.5% of the total and less than or equal to 56.5% of the total, and the proportion by mass of niobium is greater than or equal to 43.5% of the total and less than or equal to 46.5% of the total.
    More particularly, in each variant, the total proportions by weight of titanium and niobium is between 99.7% and 100% of the total.
    More particularly, the mass ratio 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.
    More particularly, the mass proportion of tantalum is less than or equal to 0.10% of the total.
    More particularly, the proportion by weight of carbon is less than or equal to 0.04% of the total, especially less than or equal to 0.020% of the total, or even less than or equal to 0.0175% of the total.
    More particularly, the mass proportion of iron is less than or equal to 0.03% of the total, especially less than or equal to 0.025% of the total, or even less than or equal to 0.020% of the total.
    More particularly, the proportion by weight of nitrogen is less than or equal to 0.02% of the total, especially less than or equal to 0.015% of the total, or even less than or equal to 0.0075% of the total.
    More particularly, the mass proportion of hydrogen is less than or equal to 0.01% of the total, especially less than or equal to 0.0035% of the total, or even less than or equal to 0.0005% of the total.
    More particularly, the proportion by weight of nickel is less than or equal to 0.01% of the total.
    More particularly, the mass proportion of silicon is less than or equal to 0.01% of the total.
    More particularly, the proportion by weight of nickel is less than or equal to 0.01% of the total, especially less than or equal to 0.16% of the total.
    More particularly, the mass proportion of ductile material or copper is less than or equal to 0.01% of the total, especially less than or equal to 0.005% of the total.
    More particularly, the proportion by weight of aluminum is less than or equal to 0.01% of the total.
    This spiral spring has a yield strength greater than or equal to 1000 MPa.
    More particularly, the spiral spring has a yield strength greater than or equal to 1500 MPa.
    More particularly, the spiral spring has a yield strength greater than or equal to 2000 MPa.
    Advantageously, this spiral spring has a modulus of elasticity greater than 60 GPa and less than or equal to 80 GPa.
    The alloy thus determined allows, according to the treatment applied during development, the production of spiral springs which are spiral springs with an elastic limit greater than or equal to 1000 MPa, or barrel springs, especially when the yield strength greater than or equal to 1500 MPa.
    The application to a spiral spring requires properties capable of ensuring the maintenance of chronometric performance despite the variation of the operating temperature of a watch incorporating such a spiral spring. The thermoelastic coefficient, also called CTE of the alloy, then has a great importance. The hardened beta phase alloy has a strongly positive CTE, and the precipitation of the alpha phase which has a strongly negative CTE makes it possible to reduce the two-phase alloy to a CTE close to zero, which is particularly favorable. To form a chronometric oscillator with a CuBe or nickel silver balance, a CTE of +/- 10 ppm / ° C must be achieved. The formula that binds the CTE of the alloy and the coefficients of expansion of the spiral is the pendulum is the following one:
    The variables M and T are the step and the temperature respectively. E is the Young's modulus of the spiral spring, and in this formula E, β and a are expressed in ° C_1.
    CT is the thermal coefficient of the oscillator, (1 / E, dE / dT) is the CTE of the spiral alloy, ß is the coefficient of expansion of the balance and that of the spiral.
    The invention also relates to a method of manufacturing a spiral clock spring, characterized in that it implements successively the following steps: - (10) elaboration of a blank in an alloy comprising niobium and titanium, which is a binary type alloy comprising niobium and titanium, and which comprises: - niobium: 100% balance; - a mass proportion of titanium greater than or equal to 45.0% of the total and less than or equal to 48.0% of the total, - traces of other components among 0, H, C, Fe, Ta, N, Ni, Si, Cu , Al, each of said trace components being between 0 and 1600 ppm of the total by mass, and the sum of said traces being less than or equal to 0.3% by mass; - (20) application to said alloy of coupled deformation-heat treatment precipitation sequences, involving the application of alternating deformations to heat treatments, until a bi-phased microstructure comprising niobium beta is obtained and alpha titanium, with an elastic limit greater than or equal to 1000 MPa, and a modulus of elasticity greater than 60 GPa and less than or equal to 80 GPa; - (30) drawing to obtain a round section wire, and rectangular profile rolling compatible with the inlet section of a calender or a pinning pin or with a setting ring in the case of a mainspring; - (40) key-way calendering of the turns to form a barrel spring before its first winding, or strapping to form a spiral spring, or setting ring and heat treatment for a mainspring.
    In particular, the application is made to this alloy of coupled deformation-heat treatment precipitation sequences, comprising the application of alternating deformations (21) to heat treatments (22), up to the obtaining a bi-phased microstructure comprising niobium beta and alpha titanium, with an elastic limit greater than or equal to 2000 MPa. More particularly, the treatment cycle then comprises a beta quench (15) at a given diameter, so that the entire structure of the alloy is beta, then a succession of these coupled deformation-heat treatment precipitation sequences. .
    In these coupled deformation-heat treatment precipitation sequences, each deformation is carried out with a given deformation rate of between 1 and 5, this deformation rate corresponding to the conventional formula 2ln (d0 / d), where dO is the diameter of the last beta quench, and where d is the diameter of the hardened wire. The overall accumulation of the deformations over the whole of this succession of phases brings a total deformation rate of between 1 and 14. Each coupled deformation-heat treatment precipitation sequence comprises, in each case, a heat treatment of precipitation of the phase. alpha Ti (300-700 ° C, 1 h-30h).
    This variant of the method comprising a beta quench is particularly suitable for the manufacture of barrel springs. More particularly, this beta quench is a solution treatment, with a duration of between 5 minutes and 2 hours at a temperature between 700 ° C and 1000 ° C, under vacuum, followed by cooling under gas.
    More particularly, this beta quench is a solution treatment, with 1 hour at 800 ° C under vacuum, followed by cooling under gas.
    To return to the coupled deformation-heat treatment precipitation sequences, more particularly each coupled deformation-precipitation heat treatment sequence comprises a precipitation treatment of a duration of precipitation treatment of a duration of between 1 hour and 1 hour. 80 hours at a temperature between 350 ° C and 700 ° C. More particularly, the time is between 1 hour and 10 hours at a temperature between 380 ° C and 650 ° C. More particularly, the time is from 1 hour to 12 hours, at a temperature of 380 ° C.
    More particularly, the process comprises between one and five coupled deformation-heat treatment precipitation sequences.
    More particularly, the first coupled deformation-heat treatment precipitation sequence comprises a first deformation with at least 30% section reduction.
    More particularly, each coupled deformation-heat treatment precipitation sequence, other than the first, comprises a deformation between two thermal precipitation treatments with at least 25% reduction of section.
    More particularly, after this elaboration of said alloy blank, and before the drawing, in an additional step 25, is added to the blank 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, to facilitate the
    forming of wire by drawing and drawing and rolling. And, after drawing, or after rolling, or after a subsequent calendering or strapping operation, or ring setting and heat treatment in the case of a mainspring, the wire is stripped of its layer of ductile material , in particular by etching, in a step 50.
    For the barrel spring, it is indeed possible to perform the manufacture by setting ring and heat treatment, where the ring setting replaces the calendering. The mainspring is still generally heat-treated after ringing or after calendering.
    As for a spiral spring, it is generally still heat-treated after strapping.
    More particularly, the last phase of deformation is carried out in the form of a flat rolling, and the last heat treatment is carried out on the calender spring or set in a ring or estrapade. More particularly, after drawing, the wire is rolled flat, before the manufacture of the spring itself by calendering or strapping or setting ring.
    In a variant, 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. In another variant, the surface layer of ductile material is deposited so as to form a spring whose pitch is variable.
    In a particular watch application, ductile material or copper is thus added at a given moment to facilitate the shaping of the wire by drawing and drawing, so that there remains a thickness of 10 to 500 micrometers on the wire to the final diameter of 0.3 to 1 millimeters. The wire is stripped of its layer of ductile material or copper especially by etching, and is rolled flat before the manufacture of the actual spring.
    The supply of ductile material or copper may be galvanic, or mechanical, it is then a jacket or a ductile material or copper tube which is fitted on a niobium-titanium alloy bar to a large diameter, then which is thinned during the steps of deformation of the composite bar.
    The removal of the layer is particularly achievable by etching, with a solution based on cyanides or acid-based, for example nitric acid.
    The invention thus allows, in particular the embodiment of a barrel spiral spring of niobium-titanium type alloy, typically 47% by weight of titanium (46-50%). By an appropriate combination of deformation and heat treatment steps, it is possible to obtain a very fine lamellar bi-phased microstructure, in particular nanometric, comprising or composed of niobium beta and alpha titanium. This alloy combines a very high elastic limit, greater than at least 1000 MPa, or greater than 1500 MPa, or even 2000 MPa on wire, 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 mainspring or sprung spring. This niobium-titanium type alloy is easily coated with ductile or copper material, which greatly facilitates its deformation by drawing.
    Such an alloy is known and used for the manufacture of superconductors, such as magnetic resonance imaging apparatus, or particle accelerators), but is not used in watchmaking. Its fine and bi-phased microstructure is sought in the case of superconductors for physical reasons and has the collateral effect of improving the mechanical properties of the alloy.
    An NbTi47 type alloy is particularly suitable for the realization of a mainspring, and also for the production of spiral springs.
    A binary type alloy comprising niobium and titanium, of the type selected above for the implementation of the invention, is also likely to be used as a spiral wire, it has an effect similar to that of "Elinvar", with a thermo-elastic coefficient practically zero in the range of temperatures of usual use of watches, and suitable for the manufacture of self-compensating spirals, in particular for niobium-titanium alloys with a proportion by mass 40%, 50%, or 65% titanium.
    The selection of composition according to the invention has also been imposed also for the superconducting application, and is favorable because of the titanium content, which avoids the disadvantages: - alloys too charged in titanium, where appears a martensitic phase, where one encounters difficulties in shaping; - Alloys too low titanium, which result in less alpha phase during the heat treatment or precipitation.
    Formatting the lace of a spiral spring involves avoiding high titanium alloys, and the need to achieve the spiral thermal compensation involves avoiding low titanium alloys.
    权利要求:
    Claims (22)
    [1]
    1. Spiral watch spring with bi-phased structure, characterized in that the material of said spiral spring is a binary type alloy comprising niobium and titanium, and which comprises: - niobium: 100% balance; - a mass proportion of titanium greater than or equal to 40.0% of the total and less than or equal to 60.0% of the total, - traces of other components among O, H, C, Fe, Ta, N, Ni, Si, Cu , Al, each of said trace components being between 0 and 1600 ppm of the total by mass, and the sum of said traces being less than or equal to 0.3% by mass.
    [2]
    2. Spiral spring according to claim 1, characterized in that said alloy comprises a mass proportion of titanium greater than or equal to 45.0% of the total and less than or equal to 48.0% of the total.
    [3]
    3. Spiral spring according to claim 1 or 2, characterized in that the total proportions by weight of titanium and niobium is between 99.7% and 100% of the total.
    [4]
    4. Spiral spring according to one of claims 1 to 3, characterized in that said spiral spring has a bi-phased microstructure comprising niobium beta and alpha titanium.
    [5]
    5. Spiral spring according to one of claims 1 to 4, characterized in that the mass proportion of titanium is greater than or equal to 46.5% of the total.
    [6]
    6. Spiral spring according to one of claims 1 to 4, characterized in that the mass proportion of titanium is less than or equal to 47.5% of the total.
    [7]
    7. Spiral spring according to one of claims 1 to 6, characterized in that said spiral spring is a mainspring.
    [8]
    8. Spiral spring according to one of claims 1 to 6, characterized in that said spiral spring is a spiral spring.
    [9]
    9. A method of manufacturing a spiral spring clock, characterized in that it implements successively the following steps: - development of a blank in a binary type alloy comprising niobium and titanium, and which comprises : - niobium: 100% balance; a proportion by mass of titanium greater than or equal to 45.0% of the total and less than or equal to 48.0% of the total, - traces of other components among O, H, C, Fe, Ta, N, Ni, Si, Cu, Al, each of said trace components being between 0 and 1600 ppm of the total by mass, and the sum of said traces being less than or equal to 0.3% by mass; - Performing a treatment cycle having previously a beta quench at a given diameter, so that the entire structure of the alloy is beta, then application to said alloy of a succession of coupled sequences deformation-heat treatment of precipitation, involving the application of alternating deformations to heat treatments, until obtaining a two-phase microstructure comprising niobium beta and alpha titanium, with an elastic limit greater than or equal to 1000 MPa, and a modulus of elasticity greater than 60 GPa and less than or equal to 80 GPa; - drawing until a round section of wire, and rolling rectangular profile compatible with the inlet section of a calender or pin or banding; key-ring calendering of the turns to form a mainspring before its first winding, or strapping to form a spiral spring, or ring-setting and heat-treating for a mainspring.
    [10]
    10. A method of manufacturing a spiral spring according to claim 9, characterized in that the final phase of deformation is carried out in the form of a flat rolling, and in that the last heat treatment on the calender spring or put in ring or estrapade.
    [11]
    11. A method of manufacturing a spiral spring according to claim 9 or 10, characterized in that the application to said alloy of coupled sequences deformation-precipitation heat treatment, comprising the application of alternating deformations to treatments up to a bi-phased microstructure comprising niobium beta and alpha titanium, with an elastic limit greater than or equal to 2000 MPa, the treatment cycle having previously a beta quench at a given diameter, of so that the entire structure of the alloy is beta, then a succession of said coupled deformation-precipitation heat treatment sequences, where each deformation is carried out with a given deformation rate of between 1 and 5, the global accumulation of the deformations over all of said succession of phases bringing a total deformation rate of between 1 and 14, and which compo Each time a heat treatment of precipitation of the alpha phase Ti.
    [12]
    12. A method of manufacturing a spiral spring according to claim 11, characterized in that said beta quench is a solution treatment, with a duration between 5 minutes and 2 hours at a temperature between 700 ° C and 1000 ° C, under vacuum, followed by cooling under gas.
    [13]
    13. A method of manufacturing a spiral spring according to claim 12, characterized in that said quenching beta is a solution treatment, with 1 hour at 800 ° C under vacuum, followed by cooling under gas.
    [14]
    14. A method of manufacturing a spiral spring according to one of claims 9 to 13, characterized in that each coupled deformation-precipitation heat treatment sequence comprises a precipitation treatment of a duration of between 1 hour and 80 hours. at a temperature of between 350 ° C and 700 ° C.
    [15]
    15. A method of manufacturing a spiral spring according to claim 14, characterized in that each coupled deformation-heat treatment precipitation sequence comprises a precipitation treatment of a duration of between 1 hour and 10 hours at a temperature between 380 ° C and 650 ° C.
    [16]
    16. A method of manufacturing a spiral spring according to claim 15, characterized in that each coupled deformation-precipitation heat treatment sequence comprises a precipitation treatment lasting from 1 hour to 12 hours at 450 ° C.
    [17]
    17. A method of manufacturing a spiral spring according to one of claims 9 to 16, characterized in that said method comprises between one and five said coupled deformation-heat treatment precipitation sequences.
    [18]
    18. A method of manufacturing a spiral spring according to one of claims 9 to 17, characterized in that the first said coupled deformation-precipitation heat treatment sequence comprises a first deformation with at least 30% reduction of section.
    [19]
    19. A method of manufacturing a spiral spring according to claim 18, characterized in that each said coupled deformation-heat treatment precipitation sequence, other than the first, comprises a deformation between two thermal precipitation treatments with at least 25% section reduction.
    [20]
    20. A method of manufacturing a spiral spring according to one of claims 9 to 19, characterized in that, after said elaboration of said alloy blank, and before said drawing, is added to said blank 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, to facilitate wire shaping by drawing and drawing and rolling, and in that, after said drawing, or after said rolling, or after a subsequent calendering or stripping or ringing operation, said wire is removed from its layer of said ductile material by etching.
    [21]
    21. A method of manufacturing a spiral spring according to claim 20, characterized in that, after said wire drawing, said wire is rolled flat, before the manufacture of the actual spring by calendering or strapping or setting ring.
    [22]
    22. A method of manufacturing a spiral spring according to claim 20 or 21, characterized in that said surface layer of ductile material is deposited so as to constitute a spring whose pitch is constant and is not a multiple of blade thickness.
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    引用文献:
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    FR3064281A1|2017-03-24|2018-09-28|Universite De Lorraine|BETA METASTABLE TITANIUM ALLOY, WATCH-OUT SPRING BASED ON SUCH ALLOY AND PROCESS FOR PRODUCING THE SAME|EP3502785B1|2017-12-21|2020-08-12|Nivarox-FAR S.A.|Hairspring for clock movement and method for manufacturing same|
    法律状态:
    优先权:
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