EP2510405B1 - Verfahren zur formung einer feder für eine uhr - Google Patents

Verfahren zur formung einer feder für eine uhr Download PDF

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Publication number
EP2510405B1
EP2510405B1 EP10801554.6A EP10801554A EP2510405B1 EP 2510405 B1 EP2510405 B1 EP 2510405B1 EP 10801554 A EP10801554 A EP 10801554A EP 2510405 B1 EP2510405 B1 EP 2510405B1
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EP
European Patent Office
Prior art keywords
spring
ribbon
fixing
plastic deformation
alloy
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EP10801554.6A
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English (en)
French (fr)
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EP2510405A1 (de
Inventor
Thomas Gyger
Vincent von Niederhäusern
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Rolex SA
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Rolex SA
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    • 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
    • G04B1/00—Driving mechanisms
    • G04B1/10—Driving mechanisms with mainspring
    • G04B1/14—Mainsprings; Bridles therefor
    • G04B1/145—Composition and manufacture of the springs
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49579—Watch or clock making

Definitions

  • the present invention relates to a method of manufacturing a spring for a timepiece which comprises at least one monolithic ribbon of metal glass comprising at least one curvature.
  • the international application published under number WO 2007/038882 discloses a composite material composed of a substantially continuous amorphous matrix comprising graphite particles. This composite material is supposed it can be used to make especially springs, however, no indication is given as to the method of manufacturing such springs. In addition, the size of the particles dispersed in the matrix of the composite is of the same order of magnitude as the typical thickness of watch springs, which raises doubts about the use of such a composite for this application.
  • the US patent no. US 5,772,803 relates to an object comprising a torsion spring obtainable by cooling at a speed less than 500 ° C / s of a liquid metal alloy to obtain a massive amorphous metal alloy, and then shaped of this alloy.
  • the only formatting mentioned in this document is casting in a mold. It turns out that the casting of an alloy with high mechanical performance, in particular with a high elastic limit, produces ribbons that are flexibly brittle in the dimensions necessary to make a mainspring.
  • French Patent No. FR 1 553 876 relates to a device and a method for the manufacture of watch spirals. The nature of the strips used for the manufacture of these spirals is not indicated in this document. Given the age of the document, it can be assumed that it is a polycrystalline metal alloy for Invar®-type self-compensating coil springs, such as the Nivarox® alloy (FeNi base alloy).
  • US Patent No. US 3,624,883 a relates to a method of manufacturing a spirally wound spring and attached to a ferrule comprising attaching a ribbon to a ferrule and then rotating the latter and subjecting the assembly to heat treatment to freeze the ribbon in its wound position.
  • the nature of the ribbon is not indicated in this document.
  • This patent claiming a priority dated 1968, and given the description, it is likely that the ribbon was polycrystalline metal alloy for spiral springs (hair spring) of the same type as that described in French Patent No. FR 1 553 876 cited above. It is known to those skilled in the art that the role and therefore the properties of the spiral spring are very different from that of the mainspring or mainspring.
  • plastic deformation of an amorphous metal alloy is only possible by the creation of sliding strips. This deformation mechanism is totally different from that of crystalline metal alloys. A plastic deformation of an amorphous metal alloy is generally undesired because it results in a rapid breakage of the stressed part.
  • the elastic limit is a limit not to be crossed under pain to damage the material. Therefore, for the skilled person, any plastic deformation of a solid metal glass is prohibited.
  • Nivaflex® CoNiCr base high performance alloy
  • amorphous metal alloy Another fundamental difference between a multi-phase polycrystalline alloy such as Nivaflex® (CoNiCr base high performance alloy) and an amorphous metal alloy is that, in order to achieve its maximum mechanical properties, the Nivaflex® alloy must be hardened by hardening and by precipitation of phases during a heat treatment. In the case of an amorphous metal alloy, its mechanical characteristics are obtained during solidification and its mechanical properties can not be improved by plastic deformation and / or a subsequent heat treatment. Thus, it is necessary to apply heat treatment Nivaflex® barrel springs to obtain the desired mechanical properties, which is not the case for a metal glass spring.
  • the inventors discovered with surprise that it was possible to plastically deform a metal glass ribbon, and to use it industrially with its plastic deformation, especially in the form of a spring mechanically stressed repeatedly in the barrel of a watch movement.
  • This method therefore makes it possible to manufacture functional clock springs made of metal glass, in particular cylinder springs, on an industrial scale.
  • metal alloy capable of forming, by cooling an amorphous or essentially amorphous metal alloy, called "metallic glass", in because of the excellent mechanical properties resulting from their particular structure.
  • metal glasses whose mechanical properties are superior to those of conventional polycrystalline alloys used in the prior art, such as the Nivaflex® alloy.
  • the invention presented below relates more particularly to metal glasses whose elastic limit is greater than 2400 MPa.
  • Such amorphous metal alloys include alloys based on Ni, Co and / or Fe.
  • the inventors have also found that to achieve a functional spring, that is to say guaranteeing a certain restoring torque and good reliability when used in a timepiece, the ribbon must preferably be made of an amorphous or essentially amorphous alloy with the thickness required to achieve the functional properties and to be initially ductile in flexion. Indeed, beyond a certain thickness, the ribbon can show a fragile behavior in bending, which would degrade the reliability of the spring.
  • the thickness of the ribbon will advantageously be at least 50 ⁇ m, since smaller thicknesses do not make it possible to obtain a sufficient return torque. Likewise, the thickness will advantageously be at most 150 ⁇ m.
  • Such a projection can be achieved for example by implementing a method such as "Planar flow casting”, “Melt-spinning” and “Twin roll casting”.
  • the parameters of the projection and the cooling are chosen so as to obtain a cooling rate of the liquid metal alloy greater than 10000 ° C./s.
  • a cooling rate obtained by hyper-quenching, indeed favors the ductility by the formation of "free volume" in the structure of the metallic glass.
  • the cooling rates obtained using a molding technique are significantly lower and do not allow, for high-strength metal glasses of which we have knowledge, to obtain both a sufficient thickness and ductility to the good function of a high performance watch spring.
  • the projection is performed so as to obtain a monolithic ribbon having a thickness between 50 and 150 microns, preferably between 50 and 120 microns, and more preferably between 50 and 100 microns.
  • the metal glass obtained under these conditions is then clearly different from solid metallic glass ("Bulk metallic glass (BMG)") whose thickness is greater than 1 mm.
  • the spring can not be used directly after the casting in the form of straight ribbon, but must be shaped in order to develop the desired torque, as described in the document WO 2010 / 000081A1 . We must therefore be able to format the ribbon so that it takes a given free form, before the stages of strapping and winding in a barrel.
  • the plastic deformation is advantageously carried out at ambient temperature and under ambient atmosphere. This plastic deformation must not degrade the mechanical properties of the tape, so as to allow its repeated mechanical stress, for example in a barrel.
  • an additional curvature is achieved by deforming the tape elastically, for example in a setting, and fixing the new shape obtained with a heat treatment to a temperature and for a duration not leading to weakening of the spring.
  • This additional curvature can in particular be carried out on the portions of the ribbon which are not curved by plastic deformation.
  • the heat treatment can be carried out before or after the plastic deformation, advantageously before the plastic deformation, in particular if the heat treatment affects the plastically deformed zone.
  • Tapes of Ni 53 Nb 20 Zr 8 Ti 10 Co 6 Cu 3 were made by "planar flow casting", which consists in forming a flow of liquid metal on a cooled wheel. From 10 to 20 g of alloy are placed in a dispensing nozzle heated between 1050 and 1150 ° C. The slit width of the nozzle is between 0.2 and 0.8mm. The distance between the nozzle and the wheel is between 0.1 and 0.3mm. The wheel on which the molten alloy is deposited is a copper alloy wheel and driven at a speed of 5 to 20m / s. The pressure exerted to bring the molten alloy out through the nozzle is between 10 and 50kPa.
  • Table 1 gives the characteristics of three ribbons obtained.
  • Table 1 - Characteristics of three ribbons used in alloy Ni ⁇ sub> 53 ⁇ / sub> Nb ⁇ sub> 20 ⁇ / sub> Zr ⁇ sub> 8 ⁇ / sub> Ti ⁇ sub> 10 ⁇ / sub> Co ⁇ sub> 6 ⁇ / sub> Cu ⁇ sub> 3 ⁇ / sub> Ribbon length thickness Variat. thick. height Variat. high. ductile / fragile [Cm] [.Mu.m] [.Mu.m] [Mm] [Mm] [- - ] 1 900 0.8 1.23 0.01 ductile 2 500 109 1.1 1.44 0.02 ductile 3 1700 81 0.8 1.37 0.02 ductile
  • Tg and Tx are little influenced by the conditions of elaboration of the ribbons.
  • a ribbon is wound in a ring of internal diameter D 0 and the diameter taken by the ribbon after the heat treatment is measured in its free state, or diameter "fixed" D f .
  • the fixing coefficient is calculated by the ratio between the fully relaxed diameter, assumed equal to the inside diameter of the ring D 0 , and the diameter of curvature of the fixed tape D f .
  • Form fixing relaxation annealing was performed on 30mm long tapes wound inside aluminum rings with an internal diameter of 7.8mm, which is close to typical spring bending diameters. barrel.
  • a logotherm® resistance furnace in ambient atmosphere was used.
  • the rings are placed on thermostatic alumina studs in the center of the oven to ensure temperature homogeneity and rapid heat transfer.
  • the treatment time is counted from the moment of closure of the oven door. One second before the end of the countdown, we take the ring with a pair of pliers and soak it very quickly in about 2 liters of water at room temperature.
  • the bending diameter of the relaxed tape is measured with a vernier caliper with an accuracy of 0.2mm.
  • the tape attached between the two parallel surfaces of the caliper is placed as in a 2-point bend test.
  • the gap at break is noted by slowly bringing the two parallel surfaces of the caliper closer together.
  • the sample is considered fragile if the breaking strain is less than 2% (without any prior plastic deformation).
  • the figure 1 represents the mechanical behavior of the Ni 53 Nb 20 Zr 8 Ti 10 Co 6 Cu 3 alloy strips with a thickness of 81 microns at the different temperatures and annealing times to which they were subjected. It can be seen that there is a window of annealing parameters that does not weaken the ribbons. This window is large enough to allow formatting reproducibly.
  • the time limit increases by decreasing the temperature. For annealing in an oven, it is necessary to place in the case of this alloy at more than 50 °, advantageously 100 ° C., below Tg to have a suitable time from the technological point of view, ie a duration of several minutes at least. With hot air heating followed by quenching, the technologically suitable treatment time is shorter (less than one minute) and the temperature may be accordingly higher.
  • Tg 740 ° C.
  • Tx 768 ° C.
  • an alloy must satisfy a necessary condition so that the shaping below Tg, respectively below Tx for an alloy does not show Tg or with Tg> Tx, can be used for a spring: the superimposition of "fixing" and "ductility" windows.
  • the time required to fix the shape is significantly less than the time limit which corresponds to the transition to a fragile state.
  • the fixing coefficient depends on the thickness of the ribbon but not on the imposed curvature.
  • the inventors have verified that it is possible to obtain the theoretical free form of a mainspring using a single fixing coefficient by performing a copper setting.
  • a 0.3 mm thick slit was electroeroded in a 1.5 mm thick copper plate, with a profile corresponding to the desired free shape of the spring but with curvature radii contracted to 60% to account for the expansion D 0 / D f , while maintaining the length of the different segments of the free form at 100%.
  • a metal glass ribbon was placed in the slit of the installation by making it undergo an elastic deformation and the fixing process was carried out in an oven under ambient atmosphere between two ceramic studs thermostated at 430 ° C., for 3 min, followed by the tempering of the pose.
  • the ribbon once out of his pose, shows a free form corresponding almost perfectly to the desired free form.
  • the Figures 5a, 5b represent respectively the desired free form and the free form with the curvatures contracted at 60% of the setting.
  • the spring is shaped not in an oven but by hot gas jet.
  • a device of type "Sylvania Heater SureHeat Jet 074719" with a power of 8kW is used to heat compressed air and project it against the setting containing the tape.
  • the apparatus makes it possible to heat a gas (air, or a neutral gas such as argon, nitrogen or helium) up to 700 ° C., the ribbon being inserted into the slot of the copper setting by elastic deformation as previously.
  • the copper installation is placed perpendicular to the hot gas distribution tube. It could also be maintained with a certain inclination, for example 45 °.
  • the fixture is mounted on a three-position linear guiding system for i) placing the copper fixture in a raised position, out of range of the gas jet ii) positioning it in the hot gas jet and iii) immersing it immediately in a cooling liquid, such as water for example, at the end of hot treatment.
  • the setting containing the tape is placed in a vacuum oven, or between two ceramic heating plates, these modes being given by way of non-limiting examples.
  • the shaping can also be carried out in two or more stages of heat treatment.
  • this step can not be transposed directly to the metal glass ribbons: as indicated above, the plastic deformation of the metal glasses is strongly discouraged.
  • Such a ribbon can then be used as a spring, in particular as a high performance spring, more particularly as a mainspring.
  • This unexpected finding thus makes it possible to give the desired final shapes by cold plastic deformation before or after a possible heat treatment for fixing.
  • This shaping by plastic deformation can be limited to the shells (internal end, see below), but can also be performed on a larger part of the spring, or even on the whole of the shape given to the spring.
  • the squab (cut at the inner end of the spring which allows it to hang on the pin of the plug of the barrel shaft) is cut by stamping in a traditional way.
  • Other methods of attaching the spring to the barrel shaft can of course be used, such as welding.
  • a sliding flange intended to be fixed to the outer end of the spring is made in a strip 110 ⁇ m thick of the same alloy as the ribbon, obtained by the same technique of "planar flow casting” and shaped by deformation cold plastic (see below) to give it the typical curvature of a self-winding, self-locking barrel spring flange.
  • the welding is carried out by resistance (by point) as usual.
  • Other fixing modes are of course also conceivable, such as laser welding for example.
  • the figure 6a shows the armoring and disarming characteristic of a spring of alloy Ni 53 Nb 20 Zr 8 Ti 10 Co 6 Cu 3 of 81 ⁇ m thick shaped by cold plastic deformation for the internal end (shell), then by heating hot gas jet in a setting as described above, with conditions corresponding to a fixing coefficient of 60%.
  • the spring gives a completely satisfactory behavior, making it possible to reach the desired torque and number of turns, and shows a good fatigue behavior.
  • the spring measured at figure 6a comprises a shell formed by cold plastic deformation over a greater or lesser length (typically 40 mm in the case of the figure 6a ) with good reproducibility, and the barrel spring obtained shows good performance.
  • the inventors therefore wanted to know if the method of obtaining the curvature of the shell by plastic deformation was applicable to the entire spring.
  • the technique of shelling consists of deforming the blade by hammering.
  • the adjustment of the curvature is effected by two parameters: the step of displacement of the ribbon between two hammer strokes and the amplitude of the deformation, regulated by the angle of rotation of the hammer around its axis. It is necessary to adjust the parameters according to the alloy and the thickness of the ribbon.
  • the shaping by cold plastic deformation takes place in two stages: first, the outer end of the ribbon is introduced in order to apply a negative curvature according to the desired theoretical curvature up to the point of inflection. Then the inner end is introduced to apply a positive curvature according to the theoretical curvature.
  • the figure 6b shows the armoring and disarming characteristic of a Ni 53 Nb 20 Zr 8 Ti 10 Co 6 Cu 3 alloy spring of 81 ⁇ m thickness shaped by cold plastic deformation only. Despite the absence of fixing by heat treatment, the behavior of the spring is in all respects comparable to that of the figure 6a .
  • the shaping of metallic glass alloy ribbons by plastic deformation is not limited to the alloy Ni 53 Nb 20 Zr 8 Ti 10 Co 6 Cu 3 .
  • alloys figures 3 and 4 can also be shaped by plastic deformation.
  • Other amorphous Ni base alloys, Fe and / or Co may also be shaped with at least one plastic deformation step, and may be heat-treated to obtain additional curvature.
  • the fixing annealing must not make the ribbon fragile and must therefore be at a temperature and for a period less than the point of weakness.
  • Ni-based amorphous alloys as mentioned herein, but also based on Fe or Co, exhibit sufficient annealing embrittlement resistance to apply hot forming to them.
  • the method described above can also be applied to the shaping of other springs than the mainspring, whether for components of the watch movement (jumper spring, or sliding flange for a mainspring, for example) or watchmaking clothing, case or bracelet.

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  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
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Claims (18)

  1. Verfahren zur Herstellung einer Feder für eine Uhr, umfassend mindestens ein monolithisches Band aus metallischem Glas mit mindestens einer Krümmung,
    dadurch gekennzeichnet, dass
    das Verfahren einen Formungsschritt durch plastische Kaltverformung des genannten monolithischen Bandes umfasst, um mindestens einen Teil der genannten Krümmung zu erhalten.
  2. Verfahren gemäß Anspruch 1, bei welchem dem Formungsschritt durch plastische Kaltverformung des monolithischen Bandes ein Schritt zur Gewinnung dieses Bandes vorangeht, der das Spritzen einer flüssigen, zur Bildung eines metallischen Glases geeigneten Metall-Legierung auf ein erkaltetes und in Bewegung befindliches Substrat umfasst.
  3. Verfahren gemäß Anspruch 2, bei welchem das monolithische Band aus metallischem Glas durch Abschrecken erhalten wird, gemäß einer der wie folgt genannten Methoden: "Planar flow casting", "Melt-spinning", und "Twin roll casting".
  4. Verfahren gemäß einem der Ansprüche 2 oder 3, bei welchem das Spritzverfahren so durchgeführt wird, dass die Abkühlungsgeschwindigkeit der flüssigen Metall-Legierung mehr als 10000°C/s beträgt.
  5. Verfahren gemäß einem der Ansprüche 1 bis 4, bei welchem das Spritzverfahren so durchgeführt wird, dass das monolithische Band eine Stärke zwischen 50 und 150 µm aufweist.
  6. Verfahren gemäß einem der Ansprüche 1 bis 5, bei welchem dem Formungsschritt durch plastische Kaltverformung ein Schritt zur Fixierung zumindest eines Teils des monolithischen Bandes vorgeschaltet oder nachgeschaltet ist.
  7. Verfahren gemäß einem der Ansprüche 1 bis 5, bei welchem dem Formungsschritt durch plastische Kaltverformung ein Schritt zur Fixierung des genannten Teils der Krümmung durch thermische Behandlung zumindest dieses Teils der Krümmung vorgeschaltet oder nachgeschaltet ist.
  8. Verfahren gemäß Anspruch 7, bei welchem der Fixierungsschritt durch eine elastische Verformung des genannten Bandes auf einem Träger erfolgt, gefolgt von einer Fixierung der Form durch die genannte thermische Behandlung.
  9. Verfahren gemäß einem der Ansprüche 7 und 8, bei welchem die thermische Behandlung bei einer Temperatur und innerhalb einer Zeitspanne vorgenommen wird, die einer Bruchdehnung des metallischen Glases von über 2% entspricht.
  10. Verfahren gemäß Anspruch 9, bei welchem die Temperatur der thermischen Behandlung weniger als 50°C unterhalb der Glasübergangstemperatur Tg des genannten metallischen Glases liegt oder unterhalb der Kristallisationstemperatur Tx für eine Legierung liegt, die keine Glasübergangstemperatur Tg aufweist oder bei der Tg>Tx ist.
  11. Verfahren gemäß Anspruch 10, bei welchem die genannte Temperatur der thermischen Behandlung weniger als 100°C unterhalb der Glasübergangstemperatur Tg des genannten metallischen Glases liegt oder unterhalb der Kristallisationstemperatur Tx für eine Legierung, die keine Glasübergangstemperatur Tg aufweist oder bei der Tg>Tx ist.
  12. Verfahren gemäß Anspruch 8 oder einem der Ansprüche 9 bis 11, soweit sie sich auf Anspruch 8 beziehen, bei welchem der für die Formung der Feder verwendete Träger das Profil der Feder umfasst, welches im Wesentlichen der freien, für die Feder vorgesehenen Form entspricht, mit den gespannten Krümmungsradien in Funktion von dem Fixierungskoeffizienten, der von der Dicke und der Legierung des genannten Bandes abhängt und von der für die Fixierung gewählten Temperatur und Dauer, wobei die Länge der Segmente des genannten Profils der reellen Länge der freien Form entsprechen.
  13. Verfahren gemäß Anspruch 6 bis 12, bei welchem der Fixierungskoeffizient zwischen 60% und 90% liegt, bevorzugter Weise zwischen 85% und 90%.
  14. Verfahren gemäß einem der vorangehenden Ansprüche, bei welchem die plastische Verformung in Umgebungstemperatur durchgeführt wird.
  15. Verfahren gemäß einem der vorangehenden Ansprüche, bei welchem ein metallisches Glas verwendet wird, das eine Elastizitätsgrenze von über 2400 MPa aufweist.
  16. Verfahren gemäß einem der vorangehenden Ansprüche, bei welchem die Feder eine Antriebsfeder ist und die plastische Verformung zumindest auf seinen inneren Teil angewendet wird.
  17. Verfahren gemäß einem der Ansprüche 1 bis 16, bei welchem die Gesamtheit der Feder durch plastische Verformung geformt wird.
  18. Verfahren gemäß einem der vorangehenden Ansprüche, bei welchem die Feder eine Antriebsfeder ist, die positive Krümmungen aufweist, ebenso negative, von beiden Seiten eines Wendepunktes.
EP10801554.6A 2009-12-09 2010-12-09 Verfahren zur formung einer feder für eine uhr Active EP2510405B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10801554.6A EP2510405B1 (de) 2009-12-09 2010-12-09 Verfahren zur formung einer feder für eine uhr

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09405221 2009-12-09
PCT/CH2010/000309 WO2011069273A1 (fr) 2009-12-09 2010-12-09 Procédé de fabrication d'un ressort pour pièce d'horlogerie
EP10801554.6A EP2510405B1 (de) 2009-12-09 2010-12-09 Verfahren zur formung einer feder für eine uhr

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EP2510405A1 EP2510405A1 (de) 2012-10-17
EP2510405B1 true EP2510405B1 (de) 2016-03-30

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US (1) US9104178B2 (de)
EP (1) EP2510405B1 (de)
JP (1) JP5744050B2 (de)
CN (1) CN102713770B (de)
CH (1) CH704391B1 (de)
WO (1) WO2011069273A1 (de)

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DE102013008396B4 (de) * 2013-05-17 2015-04-02 G. Rau Gmbh & Co. Kg Verfahren und Vorrichtung zum Umschmelzen und/oder Umschmelzlegieren metallischer Werkstoffe, insbesondere von Nitinol
CH710545B1 (de) * 2013-11-28 2020-06-15 Adamant Namiki Prec Jewel Co Ltd Uhrenarmband und Verfahren zum Herstellen desselben.
KR20160021579A (ko) * 2014-08-18 2016-02-26 서울대학교산학협력단 고탄성 비정질 합금 유연성 기판과 그 제조방법 및 이를 이용한 전자소자
EP2998799A1 (de) * 2014-09-18 2016-03-23 Montres Breguet SA Kontaktlose Rastung
JP7133909B2 (ja) * 2016-07-04 2022-09-09 ロレックス・ソシエテ・アノニム 時計用組立体の製造方法、及び該製造方法により得られる時計用組立体
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EP2510405A1 (de) 2012-10-17
JP2013513781A (ja) 2013-04-22
JP5744050B2 (ja) 2015-07-01
CH704391B1 (fr) 2016-01-29
WO2011069273A1 (fr) 2011-06-16
CN102713770A (zh) 2012-10-03
US20120281510A1 (en) 2012-11-08
US9104178B2 (en) 2015-08-11
CN102713770B (zh) 2015-11-25

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