EP3601628B1 - Alliage de titane beta metastable, ressort d'horlogerie a base d'un tel alliage et son procede de fabrication - Google Patents

Alliage de titane beta metastable, ressort d'horlogerie a base d'un tel alliage et son procede de fabrication Download PDF

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EP3601628B1
EP3601628B1 EP18717524.5A EP18717524A EP3601628B1 EP 3601628 B1 EP3601628 B1 EP 3601628B1 EP 18717524 A EP18717524 A EP 18717524A EP 3601628 B1 EP3601628 B1 EP 3601628B1
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Prior art keywords
alloy
phase
less
spring
metastable
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German (de)
English (en)
French (fr)
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EP3601628A1 (fr
Inventor
Pascal Laheurte
Pierre Charbonnier
Laurent PELTIER
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Sas Inno Tech Conseils
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Sas Inno Tech Conseils
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    • 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
    • B21F3/08—Coiling wire into particular forms to flat spiral
    • 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
    • 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
    • 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
    • G04B17/32—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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite

Definitions

  • the present invention relates to a metastable ⁇ titanium alloy and its use as a clock spring.
  • the invention also relates to a method for implementing a clockwork spring made from a metastable ⁇ titanium alloy.
  • the invention also relates to a particular use of the metastable ⁇ -titanium alloy as a spiral spring and as a mainspring.
  • the balance-spring assembly is the regulating organ of the watch, it delivers a torque by oscillating around a position of equilibrium with a natural frequency.
  • the spiral spring In order for the watch to move as little as possible, the spiral spring must deliver a torque that is as constant as possible and has a natural frequency that varies as little as possible.
  • the spiral spring is characterized by its restoring torque which is directly proportional to the elastic limit of the spiral spring.
  • the barrel-barrel spring assembly is the component intended to supply the watch with energy.
  • the mainspring In order to provide the greatest possible constant quantity of energy, the mainspring must have the most constant possible torque and be capable of storing the greatest possible quantity of potentially releasable energy.
  • the mainspring is characterized by its elastic potential directly proportional to the elastic limit and the modulus of elasticity of the barrel spring.
  • the improvement in the performance of barrel springs lies in the use of materials having the highest possible elastic limit.
  • the springs must have the smallest possible size, they are therefore subject to extensive miniaturization during their shaping.
  • the process used for the shaping of such miniaturization must not be accompanied by a reduction in the mechanical properties of the material, nor by an irregularity in the size of the part, nor by a reduction in the quality of the surface condition of the part.
  • iron-nickel-based alloys are known in the state of the art, also referred to by those skilled in the art as “elinvar” alloys.
  • This type of alloy remains today mainly used for the manufacture of spiral springs, one finds, in particular, alloys of this type sold under the trade names of Nivarox and Nispan.
  • alloys of this type sold under the trade names of Nivarox and Nispan.
  • alloys of the same type with similar compositions and sold under the trade names of Mluslinvar and Isoval.
  • One of the main limitations of such alloys is linked to the fact that they have a high sensitivity to magnetic fields. As a result, the torque and the natural frequency of clock springs based on such materials can drift significantly in the presence of magnetic disturbances.
  • WO 2015 189278 discloses a spiral spring intended to equip a balance-spring of a mechanical timepiece, characterized in that the spiral spring is made of a titanium alloy comprising a titanium base, 10-40 at.% of at least one of Nb, Ta or V; 0-3 at.% oxygen; 0-6 at.% of Zr and 0-5 at.% of Hf.
  • Standard shaping processes for titanium-based alloys are also known in the state of the art. Nevertheless, taking into account the mechanical and tribological properties of such alloys, their in shape, and in particular their miniaturization, is extremely difficult and limited.
  • a metastable ⁇ titanium alloy comprising, as a mass percentage, between 24 and 45% niobium, between 0 and 20% zirconium, between 0 and 10% tantalum and/or between 0 and 1.5% silicon and/or less than 2% oxygen.
  • alloy used alone will be used to designate the metastable ⁇ titanium alloy according to the invention.
  • the alloy may comprise less than 10%, preferably less than 8%, more preferably less than 6%, more preferably less than 5% and even more preferably less than 3% of element (s) non-metallic(s).
  • the alloy only comprises titanium and niobium.
  • the alloy comprises titanium and between 35 and 45% niobium.
  • the alloy comprises titanium and 40.5% niobium.
  • austenitic phase in the alloy gives said alloy super-elastic properties.
  • austenitic phase is also referred to as beta phase by those skilled in the art.
  • Superelastic properties include consequent recoverable strain and high yield strength.
  • omega phase in the alloy makes it possible to harden said alloy.
  • the mixture of austenitic phase and alpha phase allows the alloy to have a low elastic modulus and a negligible sensitivity of the elastic modulus to temperature variations.
  • a presence of omega phase precipitates within the alloy does not affect the mechanical properties of the alloy when it is below a threshold quantity.
  • a quantity of omega phase precipitates within the alloy must be below a threshold value of 10% so that the alloy retains a low elastic modulus.
  • the volume fraction of the omega phase precipitates can be less than 5%, preferably less than 2%, more preferably less than 1%.
  • the metastable ⁇ titanium alloy may consist of titanium and niobium, and/or zirconium and/or tantalum, and/or silicon and/or oxygen.
  • the metastable ⁇ titanium alloy may consist of titanium and niobium.
  • the alpha phase of the alloy can have a volume fraction of between 1 and 40%, preferably between 2 and 35%, preferably between 5 and 30%.
  • the alpha phase and the omega phase are present in the form of precipitates within a matrix consisting of austenitic grains.
  • omega phase precipitates The presence of omega phase precipitates is necessary to initiate the appearance of alpha phase precipitates.
  • a grain size of the alloy can be less than 1 ⁇ m.
  • the alloy comprising grains with a size of less than 1 ⁇ m exhibits an increased elastic deformation limit.
  • the grains of the alloy can preferably be equiaxed.
  • the grain size of the alloy is less than 500 nm.
  • the grain size of the alloy of less than 500 nm makes it possible to improve the elastic limit of the alloy.
  • the size of alpha phase precipitates is less than 300 nm, preferably less than 200 nm, more preferably less than 150 nm.
  • the size of omega phase precipitates is less than 50 nm, preferably less than 30 nm.
  • omega phase within the beta matrix allows a better distribution of said alpha phase precipitates between the austenitic grains.
  • the better distribution of the alpha phase precipitates within the austenitic grains makes it possible to improve the mechanical properties of the alloy.
  • the omega and/or alpha phase has a different crystalline structure from the austenitic phase.
  • the alpha phase makes it possible to harden the material and thus increase the mechanical strength of the alloy.
  • the alloy has a constant modulus of elasticity over a temperature range between -10°C and 55°C.
  • the alloy has negligible magnetic susceptibility.
  • the alloy has a Young's modulus of less than 80 GPa (GigaPascal) over a temperature range between -70°C and 210°C.
  • the alloy has a maximum breaking strength of 1500 MPa and a reversible deformation greater than or equal to 2% for temperatures below 55°C.
  • a clock spring made of metastable ⁇ titanium alloy according to the first aspect of the invention.
  • spring used alone will be used to designate the clockwork spring according to the invention.
  • torque of a spring is meant a return torque of the spring.
  • the super-elastic properties of the alloy give the spring a more constant torque.
  • the negligible magnetic susceptibility of the alloy allows the torque and natural frequency of the spring to remain constant during exposures of the alloy to surrounding magnetic fields.
  • the alloy's negligible sensitivity to temperature allows the spring torque to remain constant over a temperature range of -10°C to 55°C.
  • the low Young's modulus and the low density of the alloy allow the spring to present a potentially restorable elastic energy greater than those of commonly used alloys.
  • the spring is a spiral spring.
  • the spring is a barrel spring.
  • the hardening rate is greater than or equal to 100%.
  • the heat treatment of the shaped alloy is carried out at a temperature of between 350°C and 550°C.
  • the heat treatment of the shaped alloy is carried out for a period of between 5 and 20 min.
  • the tooling used to work harden said alloy is heated to a temperature of between 200°C and 450°C.
  • the alloy is introduced into the tooling used to work harden said alloy at a temperature below 450°C.
  • the alloy is introduced into the tooling used to work harden said alloy at a temperature between 250°C and 400°C.
  • the hardening step can be repeated at least twice prior to the shaping step.
  • the work hardening rate of the alloy can decrease from one iteration to another.
  • the iteration of the hardening step can be defined as passing the alloy through the tool used to harden said alloy several times in succession.
  • the iteration of the work hardening step can be defined as the passage of the alloy through the tool used to work harden said alloy several times consecutively.
  • the work-hardening temperature range depending on the process between 150°C and 500°C, makes it possible to reduce the efforts of the passage of the alloy in the tooling.
  • the work hardening temperature range according to the process comprised between 150° C. and 500° C., makes it possible to avoid a generalized precipitation of phases while maintaining effective work hardening.
  • the inventors have discovered that the implementation of work hardening at a temperature range between 150° C. and 500° C. makes it possible to accelerate the precipitation of the alpha and omega phases during the heat treatment step subsequent to the strain hardening.
  • the inventors have discovered that (i) when the alloy has a temperature of less than 500°C when it is introduced into the tooling used for work hardening and (ii) the tooling is heated, there is a substantial reduction alloy breakage during the work hardening step.
  • the inventors have discovered that (i) when the alloy has a temperature of less than 500° C. when it is introduced into the tooling used for work hardening and (ii) the tooling is heated, it is possible to substantially increase the work hardening rate of the alloy.
  • the temperature range, between 300° C. and 600° C., used during the heat treatment step allows recrystallization of very small alpha phase grains, typically a size of recrystallized alpha phase grains may be less than 500 nm, preferably less than 300 nm.
  • the temperature range comprised (i) between 300° C. and 600° C., preferably (ii) between 350° C. and 550° C., used during the heat treatment step makes it possible to obtain a grain size of recrystallized alpha phase (i) less than 200 nm, (ii) less than 150 nm.
  • the heat treatment also allows precipitation of an alpha phase in the form of an alpha grain within a matrix consisting of austenitic grains.
  • the precipitation of the alpha phase during the heat treatment is initiated by the presence of the omega phase.
  • the combined processing parameters of the (i) strain hardening and (ii) heat treatment steps allow an optimal distribution of the alpha phase grains and omega phase grains within the matrix of austenitic grains.
  • the combination of the hyperdeformation and the heat treatment of the alloy make it possible to improve the breaking strength and the reversible deformation of the alloy.
  • the reduction rate of the alloy section can be between 8 and 25%.
  • the heat treatment carried out as part of the shaping step has the effect, among other things, of fixing the shape of the spring.
  • the heat treatment temperature may be between 300°C and 600°C, preferably between 350°C and 500°C.
  • the step of drying the alloy is implemented at a temperature between 250°C and 400°C.
  • the preparation step enables the alloy to resist, during work hardening, pressure exerted by the tool used to work harden the alloy, greater than those which it would resist if it were work hardened according to the processes strain hardening known to those skilled in the art.
  • the work hardening preparation step can be additional to the lubricating step, known to those skilled in the art, of the tool used to work harden a material.
  • the work hardening preparation step can replace the lubricating step, known to those skilled in the art, of the tool used to work harden a material.
  • the work hardening preparation step makes it possible to substantially improve the surface condition of the alloy obtained after work hardening.
  • the deposition temperature can be between 100°C and 500°C.
  • the deposition temperature is between 250°C and 400°C.
  • the graphite deposition can be carried out in the liquid phase.
  • the deposition can also be carried out by a vacuum deposition process, such as, inter alia, chemical vapor deposition or physical vapor deposition.
  • work hardening can be implemented by drawing.
  • the temperature range, between 150°C and 500°C, used during drawing allows the alloy to be shaped in the form of small diameter wires, typically with diameters less than 100 ⁇ m, by considerably limiting the risks of breakage of the son.
  • the successive passages of a thread in a die are preferably carried out always in the same direction.
  • the process for implementing the spring makes it possible to obtain regularity and precision of less than a micrometer, as well as a surface finish compatible with watchmaking applications.
  • the material to be cold-worked can be an alloy.
  • the material is introduced into the tooling used to work harden the material at a temperature below 350°C.
  • the material is introduced into the tooling used to work harden the material at a temperature below 150°C.
  • the material is introduced into the tooling used to work harden the material at room temperature.
  • Ambient temperature is understood to mean a temperature of an environment in which the method is implemented.
  • the material is introduced into the tooling used to work harden the material in the absence of a prior material heating step.
  • the drying temperature is above 250°C.
  • the deposition temperature can be higher than 100°C.
  • the deposition temperature is greater than 250°C.
  • the graphite deposition can be carried out in the liquid phase.
  • the deposition can also be carried out by a vacuum deposition process, such as, inter alia, chemical vapor deposition or physical vapor deposition.
  • variants of the invention may in particular be considered comprising only a selection of characteristics described, isolated from the other characteristics described (even if this selection is isolated within a sentence including these other features), if this selection of features is sufficient to confer a technical advantage or to differentiate the invention from the state of the prior art.
  • This selection includes at least one feature, preferably functional without structural details, or with only part of the structural details if only this part is sufficient to confer a technical advantage or to differentiate the invention from the state of the prior art.
  • the clockwork spring is obtained from a wire 2 to 3 mm in diameter in a metastable ⁇ titanium alloy comprising 40.5% Niobium in mass percentage.
  • the process for implementing the spring comprises heating the wire to a temperature of 350° C., followed by soaking the wire in an aqueous solution comprising graphite in suspension.
  • the yarn is then dried at a temperature of 400° C. for 5 to 30 seconds.
  • the wire is then drawn in a tungsten carbide or diamond die heated to a temperature of 400°C.
  • the wire is introduced without being heated into the die.
  • the thread is passed several times through the die. The deformation applied decreases progressively from one pass to another and varies from 25 to 8% in variation of the section of the wire.
  • the wire cross section reduction rate is 15% per pass
  • the wire cross section reduction rate is wire cross-section is 10% per pass
  • the wire cross-section reduction rate is 8% per pass.
  • the wire is always drawn in the same direction. All of the steps previously described constitute the drawing step denoted E1 and the alloy according to the embodiment having been subjected to step E1 is denoted A1.
  • the wire is then cold rolled, the reduction of the applied section is 10% so as to obtain an elastic metallic ribbon of rectangular section.
  • the ribbon is then strapped on a mandrel so as to form an Archimedean spiral comprising 15 turns.
  • the tape is then immobilized and then heat treated at a temperature of 475° C. for 600 seconds.
  • the heat treatment step constitutes the step denoted T1.
  • Alloy A2 corresponds to alloy A1 having subsequently been subjected to step T1.
  • the diffractogram of A1 shows only the characteristic peaks of the ⁇ (austenitic) phase.
  • the diffractogram of A2 shows the characteristic peaks of the ⁇ and a phases. The significant width of the base of the peaks indicates the presence of significant work hardening of the alloy.
  • the inventors have observed an optimum temperature range, between 200 and 450° C., for work hardening of the A1 alloy for which there is (i) an absence of generalized precipitation of phases and (i) work hardening of the effective alloy.
  • the inventors have also observed a range of optimal alpha phase volume fraction of the A1 alloy. This range corresponds to a volume fraction of alpha phase between 5 and 30%, it allows, after implementation of steps E1 and T1, (i) to obtain super-elastic properties, (ii) to increase the resistance mechanics of the alloy, (iii) to present a low elastic modulus and (iv) to obtain a negligible sensitivity of the elastic modulus to temperature variations.
  • FIGURE 2 an AFM image of the microstructure of an A2 alloy wire 285 ⁇ m in diameter is observed.
  • the FIGURE 2 shows the presence of recrystallized equiaxed grains with a size between 150 and 200 nm.
  • the inventors have observed that when a heat treatment is carried out under the conditions described above, that is to say at moderate temperatures and for a short time, it allows recrystallization of grains of very small diameters, typically grains smaller than at 150nm.
  • FIGURES 3 , 4 and 5 TEM images of the microstructure of an A2 alloy wire 285 ⁇ m in diameter are presented.
  • the FIGURE 3 reveals the presence of alpha-phase 1 grains within a matrix of beta-phase grains.
  • These alpha phase 1 grains are present in the form of equiaxed grains of 100 to 200 nm within ⁇ phase grains.
  • the grains 1 of phase alpha are few and homogeneously distributed among the ⁇ phase grains.
  • the inventors have observed that the heat treatment allows precipitation of an alpha phase and homogeneous germination of the alpha phase within the ⁇ phase precipitates.
  • These alpha phase grains 1 have an average size of less than 150 nm.
  • the FIGURE 4 confirms the presence of omega phase 2 grains within the matrix of beta phase grains.
  • These omega phase 2 grains have an average size of less than 50 nm.
  • the omega phase grains harmful for the mechanical properties of the alloy but necessary to initiate the precipitation of the alpha phase grains, (i) are dispersed within the beta phase grains, (ii) have a low volume fraction, typically less than 5% and (iii) have a low average grain size.
  • the FIGURE 5 confirms the combined presence of the alpha, beta and omega phases within the A2 alloy.
  • I1 located at the top right of the FIGURE 3 a selected area electron diffraction pattern is shown.
  • the diffractogram indicates the presence of alpha and omega phase grains within the matrix of beta phase grains.
  • the inventors have observed that the precipitation of the alpha phase grains is initiated by the presence of the omega phase grains.
  • step T1 the precipitation of omega and alpha phase during step T1 is accelerated by the prior work hardening step during warm wire drawing of step E1.
  • the evolution of the linear expansion coefficients of the A2 alloy and of an alloy sold under the trade name of Nispan is illustrated.
  • Curve 3 illustrates the evolution of the expansion coefficient of alloy A2 as a function of temperature
  • curve 4 illustrates the evolution of the expansion coefficient of Nispan as a function of temperature.
  • the value of the linear expansion coefficient is 9.10 -6 for the A2 alloy and 8.10 -6 for the Nispan.
  • the value of the coefficient of expansion of a material reflects the influence of temperature on the dimensions of the spring by the effects of contraction and expansion of the material.
  • the value of the expansion coefficient of a material therefore reflects the influence of temperature on the mechanical properties of the spring and therefore the influence of temperature on the torque delivered by a spring made of this material.
  • the coefficient of the A2 alloy is low and identical to that of Nispan.
  • the ultimate strength is 1000 MPa for the A2 alloy and 2000 MPa for the Nivaflex
  • the elastic modulus is 40 GPa for the A2 alloy and 270 GPa for the Nivaflex
  • the recoverable deformation is 3% for the A2 alloy and 0.7% for the Nivaflex.
  • the area under the unloading tensile curve makes it possible to calculate the potentially releasable elastic energy, this elastic energy is 10 Kj/mm 3 for the Nivaflex and 16 Kj/mm 3 for the A2 alloy. This characteristic indicates that an A2 alloy barrel spring can store a greater amount of energy than Nivaflex barrel springs.
  • the modulus of elasticity is almost constant between 200 and -50°C, it decreases from a value of 54 GPa for a temperature of 200°C to a value of 53 GPa for a temperature of -50°C.
  • This characteristic indicates that the torque of an A2 alloy spring has great stability over a temperature range between 200 and -50°C.
  • the breaking strength increases from a value of approximately 800 MPa for a temperature of 200°C to a value of 1350 MPa for a temperature of -50°C.
  • the evolution of the diameter of the A2 alloy wire as a function of the length of drawn wire is presented.
  • the maximum variation in diameter over the entire length of the wire is between 0.1 and 0.2 ⁇ m.
  • the regularity and the surface condition of the wires obtained by the drawing process according to the invention are compatible with the requirements required for watchmaking applications.
  • the moment induced in the material for an applied magnetic field of 3 T is about 0.15 emu/g.
  • the moment induced in the A2 alloy is 1000 times lower than the moment induced in Nispan.
  • the main drawback of the commercial alloys used today for making watch springs lies in the sensitivity of these alloys to the surrounding magnetic fields. This sensitivity introduces a continuous and cumulative drift of the spring torque.
  • the very low magnetic susceptibility of the A2 alloy makes it possible to significantly increase the constancy of the torque of the alloy clockwork springs according to the invention because the effect of the surrounding magnetic fields on the said springs is infinitesimal.

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EP18717524.5A 2017-03-24 2018-03-14 Alliage de titane beta metastable, ressort d'horlogerie a base d'un tel alliage et son procede de fabrication Active EP3601628B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1752503A FR3064281B1 (fr) 2017-03-24 2017-03-24 Alliage de titane beta metastable, ressort d'horlogerie a base d'un tel alliage et son procede de fabrication
PCT/EP2018/056440 WO2018172164A1 (fr) 2017-03-24 2018-03-14 ALLIAGE DE TITANE ß METASTABLE, RESSORT D'HORLOGERIE A BASE D'UN TEL ALLIAGE ET SON PROCEDE DE FABRICATION

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EP3601628A1 EP3601628A1 (fr) 2020-02-05
EP3601628B1 true EP3601628B1 (fr) 2022-05-04

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US (1) US11913106B2 (ja)
EP (1) EP3601628B1 (ja)
JP (1) JP7169336B2 (ja)
KR (2) KR20220156678A (ja)
CN (1) CN110573636B (ja)
FR (2) FR3064281B1 (ja)
RU (1) RU2764070C2 (ja)
WO (1) WO2018172164A1 (ja)

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EP3422115B1 (fr) 2017-06-26 2021-08-04 Nivarox-FAR S.A. Ressort spiralé d'horlogerie
EP3422116B1 (fr) 2017-06-26 2020-11-04 Nivarox-FAR S.A. Ressort spiral d'horlogerie
EP3502288B1 (fr) * 2017-12-21 2020-10-14 Nivarox-FAR S.A. Procédé de fabrication d'un ressort spiral pour mouvement d'horlogerie
EP3502785B1 (fr) * 2017-12-21 2020-08-12 Nivarox-FAR S.A. Ressort spiral pour mouvement d'horlogerie et son procédé de fabrication
EP3671359B1 (fr) * 2018-12-21 2023-04-26 Nivarox-FAR S.A. Procédé de formation d'un ressort spirale d'horlogerie à base titane
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
EP4060424A1 (fr) 2021-03-16 2022-09-21 Nivarox-FAR S.A. Spiral pour mouvement d'horlogerie
EP4123393A1 (fr) 2021-07-23 2023-01-25 Nivarox-FAR S.A. Ressort spiral pour mouvement d'horlogerie

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2095455C1 (ru) 1996-07-16 1997-11-10 Научно-производственный центр "ИНОР" Неферромагнитный инварный сплав и изделие, выполненное из него (их варианты)
ES2171872T3 (es) 1997-06-20 2002-09-16 Rolex Montres Espiral autocompensadora para oscilador mecanico de balancin-espiral para dispositivo de movimiento de relojeria y procedimiento de fabricacion de la espiral.
EP1445670A1 (fr) 2003-02-06 2004-08-11 ETA SA Manufacture Horlogère Suisse Spiral de résonateur balancier-spiral et son procédé de fabrication
FR2864107B1 (fr) 2003-12-22 2006-08-04 Univ Metz Fil en alliage de titane beta pour orthodontie, et procede d'obtention d'un tel fil.
CN100362122C (zh) 2004-05-17 2008-01-16 北京有色金属研究总院 β钛合金及其所制成的产品
US7837812B2 (en) 2004-05-21 2010-11-23 Ati Properties, Inc. Metastable beta-titanium alloys and methods of processing the same by direct aging
JP4302604B2 (ja) 2004-09-27 2009-07-29 株式会社古河テクノマテリアル 生体用超弾性チタン合金
CN101760669A (zh) 2009-12-29 2010-06-30 沈阳铸造研究所 一种低弹性模量的铸造钛合金
RU2485197C1 (ru) 2011-10-03 2013-06-20 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" Металлический наноструктурный сплав на основе титана и способ его обработки
FR2982617B1 (fr) 2011-11-10 2014-01-10 Univ Paul Verlaine Metz Procede d'elaboration d'un alliage de titane, alliage et prothese ainsi obtenus.
JP2013170304A (ja) 2012-02-22 2013-09-02 Toyota Central R&D Labs Inc β型チタン合金およびその製造方法
WO2015189278A2 (fr) * 2014-06-11 2015-12-17 Cartier Création Studio Sa Oscillateur pour un ensemble de balancier-spiral d'une pièce d'horlogerie
FR3027230B1 (fr) 2014-10-17 2016-11-04 Univ De Lorraine Ressort d'orthodontie helicoidal et son procede de fabrication.

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CREMASCO A ET AL: "Correlations between aging heat treatment, phase precipitation and mechanical properties of a cast TiNb alloy", MATERIALS AND DESIGN, LONDON, GB, vol. 32, no. 4, 5 November 2010 (2010-11-05), pages 2387 - 2390, XP028132484, ISSN: 0261-3069, [retrieved on 20101111], DOI: 10.1016/J.MATDES.2010.11.012 *
FRÉDÉRIC PRIMA ET AL: "Optimization of Superelastic Properties in Titanium-Niobium Alloys Using Short-Time Thermal Treatments", JOURNAL OF METASTABLE AND NANOCRYSTALLINE MATERIALS, vol. 738-739, 25 January 2013 (2013-01-25), CH, pages 554 - 558, XP055416349, ISSN: 1422-6375, DOI: 10.4028/www.scientific.net/MSF.738-739.554 *
JOSEF STR?SK? ET AL: "Plastic Deformation and Elastic Properties of Ti-Nb-Zr-Ta(-Fe-Si) Biomedical Alloys", ADVANCED MATERIALS RESEARCH, vol. 922, 1 May 2014 (2014-05-01), pages 734 - 739, XP055415995, DOI: 10.4028/www.scientific.net/AMR.922.734 *
KIM H Y ET AL: "Effect of thermo-mechanical treatment on mechanical properties and shape memory behavior of Ti-(26-28)at.% Nb alloys", MATERIALS SCIENCE AND ENGINEERING: A, ELSEVIER, AMSTERDAM, NL, vol. 438-440, 25 November 2006 (2006-11-25), pages 839 - 843, XP027953270, ISSN: 0921-5093, [retrieved on 20061125] *
SUN F ET AL: "A thermo-mechanical treatment to improve the superelastic performances of biomedical Ti 26Nb and Ti 20Nb 6Zr (at.%) alloys", JOURNAL OF THE MECHANICAL BEHAVIOR OF BIOMEDICAL MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 4, no. 8, 5 June 2011 (2011-06-05), pages 1864 - 1872, XP028112947, ISSN: 1751-6161, [retrieved on 20110612], DOI: 10.1016/J.JMBBM.2011.06.003 *
W. ELMAY ET AL: "Improvement of Superelastic Performance of Ti-Nb Binary Alloys for Biomedical Applications", JOURNAL OF MATERIALS ENGINEERING AND PERFORMANCE., vol. 23, no. 7, 1 July 2014 (2014-07-01), US, pages 2471 - 2476, XP055416345, ISSN: 1059-9495, DOI: 10.1007/s11665-014-0876-0 *

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FR3064281A1 (fr) 2018-09-28
RU2764070C2 (ru) 2022-01-13
JP2020515720A (ja) 2020-05-28
US20200308685A1 (en) 2020-10-01
KR20190131517A (ko) 2019-11-26
FR3126511A1 (fr) 2023-03-03
EP3601628A1 (fr) 2020-02-05
RU2019133673A (ru) 2021-04-26
KR102488776B1 (ko) 2023-01-13
CN110573636B (zh) 2022-04-08
KR20220156678A (ko) 2022-11-25
CN110573636A (zh) 2019-12-13
FR3064281B1 (fr) 2022-11-11
WO2018172164A1 (fr) 2018-09-27
RU2019133673A3 (ja) 2021-06-03
US11913106B2 (en) 2024-02-27
JP7169336B2 (ja) 2022-11-10
FR3126511B1 (fr) 2024-03-29

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