EP3845971A1 - Spiralfeder für uhrwerk und ihr herstellungsverfahren - Google Patents
Spiralfeder für uhrwerk und ihr herstellungsverfahren Download PDFInfo
- Publication number
- EP3845971A1 EP3845971A1 EP19220163.0A EP19220163A EP3845971A1 EP 3845971 A1 EP3845971 A1 EP 3845971A1 EP 19220163 A EP19220163 A EP 19220163A EP 3845971 A1 EP3845971 A1 EP 3845971A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- blank
- weight
- niobium
- spiral spring
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 21
- 239000010955 niobium Substances 0.000 claims abstract description 54
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 52
- 229910020012 Nb—Ti Inorganic materials 0.000 claims abstract description 50
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 claims abstract description 37
- 239000010936 titanium Substances 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 54
- 239000010949 copper Substances 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 26
- 238000005096 rolling process Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- 238000009825 accumulation Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000005491 wire drawing Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 229910001275 Niobium-titanium Inorganic materials 0.000 description 1
- 241000287107 Passer Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 229940082150 encore Drugs 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 150000002821 niobium Chemical class 0.000 description 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B17/00—Mechanisms for stabilising frequency
- G04B17/04—Oscillators acting by spring tension
- G04B17/06—Oscillators with hairsprings, e.g. balance
-
- 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
-
- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- 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
-
- 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
- G04B17/063—Balance construction
-
- 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
-
- 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
- G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects
-
- G—PHYSICS
- G04—HOROLOGY
- G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
- G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
- G04D3/0002—Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe
- G04D3/0035—Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the regulating mechanism
- G04D3/0041—Watchmakers' or watch-repairers' machines or tools for working materials for mechanical working other than with a lathe for components of the regulating mechanism for coil-springs
-
- G—PHYSICS
- G04—HOROLOGY
- G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
- G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
- G04D3/0069—Watchmakers' or watch-repairers' machines or tools for working materials for working with non-mechanical means, e.g. chemical, electrochemical, metallising, vapourising; with electron beams, laser beams
Definitions
- the invention relates to a method of manufacturing a spiral spring intended to equip a balance of a timepiece movement and the spiral spring resulting from the method.
- spiral springs are also centered on the concern for thermal compensation, so as to guarantee regular chronometric performance. This requires obtaining a thermoelastic coefficient close to zero. We are also looking to produce spiral springs exhibiting limited sensitivity to magnetic fields.
- New balance springs have been developed from alloys of niobium and titanium.
- these alloys pose problems of sticking and seizing in the drawing or drawing dies and against the lamination rolls, which makes them almost impossible to transform into fine wires by the standard processes used, for example, for the production. 'steel.
- This copper layer on the wire has a disadvantage: it must be deposited in a thick layer (typically 10 microns for a diameter of Nb-Ti of 0.1 mm) to play its role of anti-sticking agent during the deformation steps. It does not allow fine control of the wire geometry during wire calibration and rolling. These dimensional variations of the Nb-Ti core of the wire result in significant variations in the torque of the balance springs.
- the present invention provides a method of manufacturing a spiral spring which makes it possible to facilitate shaping by deformation while avoiding the drawbacks associated with the copper layer.
- the blank As the blank undergoes a large number of deformation passes to bring it to specific dimensions and geometry, the blank must be coated with a layer preventing sticking in the successive dies thick enough not to be damaged during these successive deformations.
- the thickness of the copper layer for producing watch spiral springs is of the order of 10 microns. The Applicant has however observed that the external dimensions of the blank covered with the copper layer were well controlled during the successive deformation passes of the blank but on the other hand that the dimensions of the Nb-Ti core were not not mastered.
- the applicant therefore had the inventive idea which consists in coating the Nb-Ti blank with a thin layer (typically chosen between 800 nm and 1.2 microns when the blank has reached a diameter of between 15 and 50 microns) d '' a first anti-sticking material and preferably compatible with the thermoelastic coefficient (CTE) of the Nb-Ti core, before coating the blank with a layer of a second ductile material thicker than the layer of the first material to perform the first deformation steps and then to remove the "thick" layer of the second material before the final steps while retaining the "thin” layer of the first material.
- This “thin” layer will make it possible to carry out the final stages of deformation of the wire without sticking in the dies while perfectly controlling the dimensions of the Nb-Ti core.
- the first material is preferably chosen from the set comprising niobium, gold, tantalum, vanadium, austenitic stainless steels, grade 316L steel
- the second material is chosen from the set comprising copper , silver, copper and nickel alloys, alpha single phase copper and zinc alloys (eg CuZn30).
- the first material is niobium and the second material is copper (ETP (electrolytic tough pitch), OF (oxygen-free) or OFE (oxygen free electronic) grade, for example).
- ETP electrolytic tough pitch
- OF oxygen-free
- OFE oxygen free electronic grade
- a preferred embodiment of the method of manufacturing the spiral spring according to the invention therefore comprises a step aimed at forming a thin layer of niobium coating the Nb-Ti core, then at forming a thick layer. of copper, partially deforming the coated core, removing the remaining Cu layer, and then completing the deformation of the Nb-Ti core simply coated with niobium.
- This niobium layer then forms the outer layer which is in contact with the dies and the rolling rolls. It is chemically inert and ductile and makes it easy to draw and roll the spiral wire. It has the other advantage of facilitating the separation between the hairsprings after the fixing step following the slipping step.
- the niobium layer is retained on the hairspring at the end of the manufacturing process. It is sufficiently thin with a thickness of between 50 nm and 5 ⁇ m and preferably 200 nm and 1.5 ⁇ m and more preferably between 800 nm and 1.2 ⁇ m, so as not to significantly modify the thermoelastic coefficient (CTE) of the hairspring.
- CTE thermoelastic coefficient
- Nb has a CTE similar to that of Nb-Ti, which makes it easier to obtain a balance spring.
- Nb-Ti core It is also perfectly adherent to the Nb-Ti core.
- These thicknesses of the niobium layer are typically suitable for Nb-Ti cores having diameters of between 15 and 100 ⁇ m.
- step d1) of the method of the invention consists in cold deforming by hammering and / or stretching and / or drawing the blank obtained in step c).
- a beta-type hardening step of said blank is carried out, so that the titanium of said alloy is essentially in the form of a solid solution with the niobium in beta phase and preferably, the ⁇ quenching step 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 gas cooling.
- the step of removing the layer of the second material is carried out by etching.
- the final heat treatment of step g) is a treatment of precipitation of titanium in the alpha phase for a duration of between 1 hour and 80 hours at a temperature of between 350 ° C and 700 ° C, preferably between 5 hours and 30 hours between 400 ° C and 600 ° C.
- step g) consists of a heat treatment of precipitation of titanium in the alpha phase for a duration of between 1 hour and 80 hours at a temperature of between 350 ° C and 700 ° C, preferably between 5 hours and 30 hours between 400 ° C and 600 ° C.
- C and 600 ° C can also be carried out after each or certain sequences of the deformation step d1) and / or d2)
- the layer of the second material typically copper formed in step c
- each sequence of steps d1) and / or d2) is carried out with a strain rate of between 1 and 5, the global accumulation of strains over all the sequences leading to a total strain rate of between 1 and 14.
- the strain rate for each sequence g) corresponding to the classic formula 2ln (d0 / d), where d0 is the diameter of the last beta hardening, and where d is the diameter of the hardened wire
- step b) of forming the layer of the first material is carried out by winding a strip of the first material, for example. niobium, around the Nb-Ti core and step c) of forming the layer of the second material, typically a layer of copper, is carried out by introducing the blank obtained at after step b) in a tube of the second material, e.g. copper, followed by drawing and / or hammering and / or drawing of the entire tube and of the blank obtained at the end of step b).
- a tube of the second material e.g. copper
- the layer of the first material has a thickness between 300 nm and 1.5 ⁇ m and preferably between 400 nm and 800 nm.
- the first material is niobium.
- the Ti content is between 40 and 65% by weight, preferably between 40 and 49% by weight and more preferably between 46 and 48% by weight.
- the Nb-Ti core has a two-phase microstructure comprising niobium in the beta phase and titanium in the alpha phase.
- the spring has an elastic limit greater than or equal to 500 MPa, preferably 600 MPa, and an elastic modulus less than or equal to 120 GPa, preferably less than or equal to 100 GPa.
- the invention relates to a method of manufacturing a spiral spring intended to equip a balance of a timepiece movement.
- This spiral spring is made of a binary type alloy comprising niobium and titanium. It also relates to the spiral spring resulting from this process.
- niobium as a first material and copper as a second material.
- the method of the invention further comprises a step h) consisting in removing said copper layer formed in step c), at a time in step c) at which the blank has reached a diameter such that one can still pass said blank at least through one die and preferably through two dies with an elongation rate of the blank of about 10% at each die before the first rolling step d2) or at the latest before the last pass of step d2).
- the core is made from an Nb-Ti alloy comprising between 5 and 95% by weight of titanium.
- the alloy used in the present invention comprises by weight between 40 and 60% titanium.
- it comprises between 40% and 49% by weight of titanium, and more preferably between 46% and 48% by weight of titanium.
- the percentage of titanium is sufficient to obtain a maximum proportion of Ti precipitates in the form of alpha phase while being reduced to avoid the formation of a martensitic phase causing problems of fragility of the alloy during its use.
- the Nb-Ti alloy used in the present invention does not comprise other elements except for possible and inevitable traces. This makes it possible to avoid the formation of fragile phases.
- the oxygen content is less than or equal to 0.10% by weight of the total, or even less than or equal to 0.085% by weight of the total.
- the tantalum content is less than or equal to 0.10% 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 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 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 less than or equal to 0.0075% by weight of the total.
- the hydrogen content is less than or equal to 0.01% by weight of the total, in particular less than or equal to 0.0035% by weight of the total, or even less than or equal to 0.0005% 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 content of ductile material, such as copper, in the alloy 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 Nb-Ti core of the blank in step a) is coated with a layer of niobium.
- the addition of the niobium layer around the core can be achieved galvanically, by PVD, CVD or mechanically. In the latter case, a niobium tube is fitted to a bar of the Nb-Ti alloy. The assembly is deformed by hammering, stretching and / or wire drawing to thin the bar and form the blank which was made available in step a).
- the thickness of the niobium layer is chosen so that the niobium area / area ratio of the Nb-Ti core for a given wire section is less than 1, preferably less than 0.5, and more preferably between 0.01 and 0.4. For example, the thickness is preferably between 1 and 500 micrometers for a wire having a total diameter of 0.2 to 1 millimeter.
- the niobium layer can be produced by winding a niobium strip around the Nb-Ti core, the niobium strip / Nb-Ti core assembly then being deformed by hammering, stretching and / or wire drawing. to thin the bar and form the blank which was made available at the end of step a).
- the Nb-Ti core of the blank obtained in step b) is coated with a layer of copper during step c) .
- the addition of the copper layer around the core can be achieved galvanically, by PVD, CVD or mechanically. In the latter case, a copper tube is fitted to a bar of the Nb-Ti alloy coated with the niobium layer. The assembly is deformed by hammering, stretching and / or wire drawing to thin the bar and form the blank which was made available at the end of step b).
- the thickness of the copper layer is chosen so that the ratio of copper surface / surface area of the Nb-Ti core covered with the niobium layer for a given wire section is less than 1, preferably less than 0.5 , and more preferably between 0.01 and 0.4.
- the thickness is preferably between 1 and 500 micrometers for a wire having a total diameter of 0.2 to 1 millimeter.
- the copper layer can be produced by winding a copper strip around the Nb-Ti core covered with the niobium layer, the niobium strip / Nb-Ti core assembly then being deformed by hammering. , stretching and / or wire drawing to thin the bar and form the blank which was made available at the end of step b).
- the Nb-Ti core covered with the niobium strip can be introduced into a copper tube, the assembly being hot co-extruded at a temperature of the order of 600 to 900 degrees through a pathway.
- Beta-type quenching consisting of a solution treatment is carried out at least before the subsequent deformation steps.
- This treatment is carried out so that the titanium of the alloy is essentially in the form of a solid solution with the niobium in the beta phase.
- it is carried out for a period of between 5 minutes and 2 hours at a temperature of between 700 ° C and 1000 ° C, under vacuum, followed by cooling under gas.
- this beta quench is a dissolving treatment at 800 ° C. under vacuum for 5 minutes to 1 hour, followed by cooling under gas.
- Deformation step d) is carried out in several sequences.
- deformation is meant a deformation by wire drawing and / or rolling.
- the deformation step comprises at least successively sequences of deformation, preferably cold, by hammering and / or stretching and / or calibration drawing designated by step d1 ).
- Step d1) makes it possible to bring the blank obtained at the end of step c) to a determined diameter called the wire calibration diameter.
- the method further comprises a step h) which consists in removing the copper layer formed in step c), when during step d1), the blank has reached a diameter such that one can still pass said blank at least through a die with a degree of elongation of the blank of about 10% before the first subsequent rolling step d2).
- This step of removing the copper layer is carried out by chemical attack in a solution based on cyanides or acids, for example in a nitric acid bath at a concentration of 53% by mass in water.
- a sequence of rolling operations preferably with a rectangular profile compatible with the entry section of a stepping spindle is then carried out, this sequence forming step d2 ).
- Each sequence of steps d1) and d2) is carried out with a given strain rate between 1 and 5, this strain rate corresponding to the classic formula 2ln (d0 / d), where d0 is the diameter of the last beta hardening, and where d is the diameter of the hardened wire.
- the global accumulation of deformations over the whole of this succession of sequences leads to a total rate of deformation between 1 and 14.
- the niobium layer coating the Nb-Ti core to a thickness between 20 nm and 10 ⁇ m, preferably between 300 nm and 1.5 ⁇ m, more preferably between 400 and 800 nm .
- the laminated wire strip obtained at the end of step d2) is then cut to a length determined during step e) .
- Step f) of slipping to form the spiral spring is followed by step g) of final heat treatment on the spiral spring.
- This final heat treatment is a precipitation treatment of Ti in the alpha phase lasting between 1 and 80 hours, preferably between 5 and 30 hours, at a temperature between 350 and 700 ° C, preferably between 400 and 600. ° C.
- the process can also comprise, between each sequence or between certain sequences of the deformation steps d1) and / or d2), an intermediate heat treatment for precipitation of titanium in the alpha phase for a duration of between 1 hour and 80 minutes. hours at a temperature between 350 ° C and 700 ° C, preferably between 5 hours and 30 hours between 400 ° C and 600 ° C.
- this intermediate treatment is carried out in step d1) between the first wire drawing sequence and the second calibration wire drawing sequence.
- the spiral spring produced according to this process has an elastic limit greater than or equal to 500 MPa, preferably greater than 600 MPa, and more precisely between 500 and 1000 MPa.
- it has a modulus of elasticity less than or equal to 120 GPa, and preferably less than or equal to 100 GPa.
- the spiral spring comprises an Nb-Ti core coated with a layer of niobium, said layer having a thickness between 50 nm and 5 ⁇ m, preferably between 200 nm and 1.5 ⁇ m, more preferably between 800 nm and 1.2 ⁇ m .
- the spiral spring core has a two-phase microstructure comprising niobium in the beta phase and titanium in the alpha phase.
- the spiral spring produced according to the invention has a thermoelastic coefficient, also called CTE, allowing it to guarantee the maintenance of chronometric performance despite the variation in the temperatures of use of a watch incorporating such a spiral spring.
- the method of the invention allows the production, and more particularly the shaping, of a balance spring for a balance in a niobium-titanium type alloy, typically containing 47% by weight of titanium (40-60%).
- This alloy has high mechanical properties, by combining a very high elastic limit, greater than 600 MPa, 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 spiral spring.
- such an alloy is paramagnetic.
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21218349.5A EP4009114A1 (de) | 2019-12-31 | 2019-12-31 | Spiralfeder für uhrwerk und ihr herstellungsverfahren |
EP19220163.0A EP3845971B1 (de) | 2019-12-31 | 2019-12-31 | Herstellungsverfahren für eine spiralfeder für ein uhrwerk |
US17/084,210 US20210200153A1 (en) | 2019-12-31 | 2020-10-29 | Balance-spring for horological movement and method for manufacturing same |
JP2020183437A JP7051979B2 (ja) | 2019-12-31 | 2020-11-02 | 計時器用ムーブメントのためのバランスばね及びその製造方法 |
KR1020200147991A KR102431406B1 (ko) | 2019-12-31 | 2020-11-06 | 시계 무브먼트를 위한 밸런스 스프링 및 그 제조 방법 |
RU2020142723A RU2756785C1 (ru) | 2019-12-31 | 2020-12-23 | Балансная пружина для часового механизма и способ ее изготовления |
CN202011629549.9A CN113126466B (zh) | 2019-12-31 | 2020-12-31 | 用于钟表机芯的摆轮游丝及其制造方法 |
KR1020220072366A KR102502785B1 (ko) | 2019-12-31 | 2022-06-14 | 시계 무브먼트를 위한 밸런스 스프링 및 그 제조 방법 |
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EP19220163.0A EP3845971B1 (de) | 2019-12-31 | 2019-12-31 | Herstellungsverfahren für eine spiralfeder für ein uhrwerk |
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EP21218349.5A Division EP4009114A1 (de) | 2019-12-31 | 2019-12-31 | Spiralfeder für uhrwerk und ihr herstellungsverfahren |
EP21218349.5A Division-Into EP4009114A1 (de) | 2019-12-31 | 2019-12-31 | Spiralfeder für uhrwerk und ihr herstellungsverfahren |
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EP3845971A1 true EP3845971A1 (de) | 2021-07-07 |
EP3845971B1 EP3845971B1 (de) | 2024-04-17 |
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EP21218349.5A Pending EP4009114A1 (de) | 2019-12-31 | 2019-12-31 | Spiralfeder für uhrwerk und ihr herstellungsverfahren |
EP19220163.0A Active EP3845971B1 (de) | 2019-12-31 | 2019-12-31 | Herstellungsverfahren für eine spiralfeder für ein uhrwerk |
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EP21218349.5A Pending EP4009114A1 (de) | 2019-12-31 | 2019-12-31 | Spiralfeder für uhrwerk und ihr herstellungsverfahren |
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US (1) | US20210200153A1 (de) |
EP (2) | EP4009114A1 (de) |
JP (1) | JP7051979B2 (de) |
KR (2) | KR102431406B1 (de) |
CN (1) | CN113126466B (de) |
RU (1) | RU2756785C1 (de) |
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EP4123393A1 (de) | 2021-07-23 | 2023-01-25 | Nivarox-FAR S.A. | Spiralfeder für uhrwerk |
Citations (4)
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EP1039352A1 (de) * | 1999-03-26 | 2000-09-27 | Montres Rolex Sa | Selbstkompensierende Spiralfeder für Uhrwerkspiralfederunruh und Verfahren zur Behandlung derselben |
TWI615690B (zh) * | 2012-11-16 | 2018-02-21 | 尼瓦克斯 法爾公司 | 對氣候變化之敏感度降低之共振器 |
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 |
EP3502288A1 (de) * | 2017-12-21 | 2019-06-26 | Nivarox-FAR S.A. | Herstellungsverfahren einer spiralfeder für uhrwerk |
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JPS604879A (ja) * | 1983-06-23 | 1985-01-11 | Seiko Instr & Electronics Ltd | 腕時計用飾り板の製造方法 |
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. |
US6402859B1 (en) * | 1999-09-10 | 2002-06-11 | Terumo Corporation | β-titanium alloy wire, method for its production and medical instruments made by said β-titanium alloy wire |
JP2004502910A (ja) * | 2000-07-11 | 2004-01-29 | セイコーエプソン株式会社 | バネ、このバネを利用した駆動機構、機器および時計 |
DE10237446B4 (de) * | 2002-08-16 | 2004-07-29 | Stahlwerk Ergste Westig Gmbh | Verwendung eines Chrom-Stahls und dessen Herstellung |
US20120214016A1 (en) * | 2011-02-22 | 2012-08-23 | General Electric Company | Constrained metal flanges and methods for making the same |
EP2717103B1 (de) * | 2012-10-04 | 2017-01-11 | The Swatch Group Research and Development Ltd. | Leuchtende Spiralfeder |
JP6444059B2 (ja) * | 2014-05-23 | 2018-12-26 | セイコーインスツル株式会社 | てんぷ、調速機、ムーブメントおよび時計 |
WO2015189278A2 (fr) * | 2014-06-11 | 2015-12-17 | Cartier Création Studio Sa | Oscillateur pour un ensemble de balancier-spiral d'une pièce d'horlogerie |
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EP3502785B1 (de) | 2017-12-21 | 2020-08-12 | Nivarox-FAR S.A. | Spiralfeder für uhrwerk, und ihr herstellungsverfahren |
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- 2019-12-31 EP EP21218349.5A patent/EP4009114A1/de active Pending
- 2019-12-31 EP EP19220163.0A patent/EP3845971B1/de active Active
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- 2020-10-29 US US17/084,210 patent/US20210200153A1/en active Pending
- 2020-11-02 JP JP2020183437A patent/JP7051979B2/ja active Active
- 2020-11-06 KR KR1020200147991A patent/KR102431406B1/ko active IP Right Grant
- 2020-12-23 RU RU2020142723A patent/RU2756785C1/ru active
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EP3502288A1 (de) * | 2017-12-21 | 2019-06-26 | Nivarox-FAR S.A. | Herstellungsverfahren einer spiralfeder für uhrwerk |
Also Published As
Publication number | Publication date |
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EP4009114A1 (de) | 2022-06-08 |
EP3845971B1 (de) | 2024-04-17 |
KR102502785B1 (ko) | 2023-02-23 |
JP2021110726A (ja) | 2021-08-02 |
RU2756785C1 (ru) | 2021-10-05 |
KR20220088652A (ko) | 2022-06-28 |
CN113126466A (zh) | 2021-07-16 |
CN113126466B (zh) | 2023-01-24 |
KR20210086949A (ko) | 2021-07-09 |
KR102431406B1 (ko) | 2022-08-10 |
JP7051979B2 (ja) | 2022-04-11 |
US20210200153A1 (en) | 2021-07-01 |
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