EP3663867A1 - Kompensierende spiralfeder für eine uhr oder grossuhr aus einer niob-molybdän-legierung - Google Patents

Kompensierende spiralfeder für eine uhr oder grossuhr aus einer niob-molybdän-legierung Download PDF

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Publication number
EP3663867A1
EP3663867A1 EP18210512.2A EP18210512A EP3663867A1 EP 3663867 A1 EP3663867 A1 EP 3663867A1 EP 18210512 A EP18210512 A EP 18210512A EP 3663867 A1 EP3663867 A1 EP 3663867A1
Authority
EP
European Patent Office
Prior art keywords
balance spring
alloy
formula
niobium
spring according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18210512.2A
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English (en)
French (fr)
Inventor
Michael Stuer
Laurane CHEVALLIER
Philipp KEUTER
Jochen M. SCHNEIDER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Richemont International SA
Original Assignee
Cartier International AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cartier International AG filed Critical Cartier International AG
Priority to EP18210512.2A priority Critical patent/EP3663867A1/de
Publication of EP3663867A1 publication Critical patent/EP3663867A1/de
Pending legal-status Critical Current

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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
    • 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
    • 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
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • 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
    • 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

Definitions

  • the invention relates to the field of horology and more particularly to a balance spring of a regulating organ, made of a niobium-molybdenum alloy.
  • Mechanical watch movements include a regulating organ comprising a balance wheel and a balance spring. Since these movements must accurately function between 8 °C and 38 °C as defined by the COSC (Swiss Official Chronometer Testing), they require materials having elastic properties that do not change with temperature or materials that self-compensate any temperature induced change in their dynamic behavior and the ones of the balance wheel. More precisely, the thermal dilatations of the balance wheel and of the spiral are compensated by a thermal increase of spiral Young's modulus as the temperature increases. Actually, most of materials present a Young's modulus that decreases when the temperature increases. Hence, materials of interest for making balance springs are commonly defined as materials having an anomalous thermoelastic behavior.
  • the balance spring may be made of Elinvar material, which has a temperature independent Young's modulus within a certain temperature range.
  • Elinvar material includes an alloy containing 56% of iron, 36% of nickel and 5% of chromium.
  • EP 0 886 195 discloses a balance spring that is insensitive to magnetic fields since it is made of a paramagnetic niobium-zirconium based alloy.
  • the properties of this alloy result from specific heat treatments and doping elements such as 500 ppm or more of an oxygen based interstitial agent.
  • this kind of alloys exhibits some precipitates that are difficult to control.
  • EP 1 422 436 discloses a silicon based balance spring, which is also insensitive to magnetic fields but with a Young's modulus very sensitive to temperature variations. Thermal compensation can be obtained by a silicon core and an external layer made of silicon oxide.
  • silicon based balance springs remain fragile and require additional care with respect to their handling and to the assembly of the regulating organ.
  • the present invention relates to an alloy having an anomalous thermal behavior of the Young's modulus. As opposed to some of the prior art alloys, this alloy does not require a method of preparation involving specific heat treatments. It can be made according to conventional metallurgic methods since its anomalous behavior results from the combination of its alloying elements, and eventually from the texture of the grains in the alloy.
  • the present invention relates to a specific niobium-molybdenum (Nb-Mo) based alloy that exhibits an anomalous thermoelastic behavior. As opposed to Nb-Zr alloys, precipitations do not take place within Nb-Mo alloys. Indeed, the Nb-Mo alloys form a solid solution over the whole composition range.
  • Nb-Mo niobium-molybdenum
  • the invention relates to a balance spring for a watch or clock movement made of a niobium-molybdenum alloy of formula (I): (Nb 1-x M 1 x ) n (Mo 1-y M 2 y ) m M 3 z M 4 u (I) wherein
  • Amounts x, n, y, m, z and u relate to the respective molar amounts of elements Nb, M 1 , Mo, M 2 , M 3 and M 4 within formula (I). For instance, for every (1-x) moles of niobium, the alloy of formula (I) contains x moles of M 1 .
  • the thermal coefficient of elasticity (CTE) of this alloy has an anomalous behavior preferably between -10 °C and 40 °C, more preferably between 8 °C and 38 °C. Due to its anomaly, the alloy does not get more and more flexible as the temperature increases.
  • pure niobium exhibits an anomalous elastic behavior due to its c 44 elastic coefficient from about 500 K. Alloying element(s), such as molybdenum, allow(s) shifting this anomaly to lower temperatures. However, pure molybdenum does not exhibit an anomalous thermoelastic behavior.
  • the alloy of formula (I) has an anomalous thermoelastic behavior that is, at least, due to its shear elastic coefficient c 44 and/or to its shear coefficient constant c'.
  • alloying elements such as M 1 , M 2 , M 3 and M 4 are added so as to adjust the properties required for a balance spring e.g. elasticity, deformability or a low coefficient of expansion. They may also affect the thermoelastic anomaly of the alloy.
  • the alloy of formula (I) has a coefficient of expansion that is preferably less than 10.10 -6 /°C enabling the thermo-compensation of a spring balance assembly.
  • n and m correspond to the respective amounts of alloying elements Nb + M 1 and Mo + M 2 .
  • the n amount of alloying element(s) Nb+M 1 ranges from more than 0.6 to 0.98 or less.
  • M 1 is Ta, V or both.
  • the amount "x" of element M 1 is strictly less than 1, preferably between 0 and 0.5 (0 ⁇ x ⁇ 0.5), more preferably between 0 and 0.2 (0 ⁇ x ⁇ 0.2). Larger amounts of M 1 may cause precipitation, hence, strongly affect the thermoelastic behavior and impede deformability. In general, vanadium maintains the thermoelastic anomaly while tantalum reduces it.
  • Element M 1 is preferably vanadium.
  • the m amount of alloying element(s) Mo+M 2 ranges from between 0.02 and 0.4.
  • M 3 is a strengthening alloying element. It improves the mechanical properties of the alloy. It can also ensure the shift of the thermoelastic anomaly of the alloy, typically to lower temperatures i.e. from -10 °C to 40 °C.
  • M 3 is a metalloid or a metal other than Nb, Ta, V, Mo and W.
  • Metals include alkali metals, alkaline earth metals, transition metals, lanthanides and actinides.
  • metalloids include B, Si, Ge, As, Sb, Te and At.
  • M 3 is preferably any one of: Be, Al, Si, Ge, Sc, Y, La, Ti, Hf, Cr, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, or a mixture thereof.
  • any one of means "at least one selected from the group comprising.".
  • the alloy of formula (I) exhibits ductility properties that are advantageous in the formation of a balance spring. Indeed, many deformation steps are carried out, for instance the reduction of the section of a wire. Accordingly, the alloy comprises Nb, Mo and preferably any one of Zr, Ta, or Ti, which improve the ductility of the alloy.
  • the presence of any one of V, Ta, Pd, Pt, Ti, Rh and Zr can enhance the shift of the anomaly of the elastic behavior to temperatures that preferably range between -10 °C and 40 °C.
  • the amount "z" of the M 3 element within formula (I) is preferably between 0 and 0.02 (0 ⁇ z ⁇ 0.02).
  • M 4 is hardening alloying element.
  • M 4 is preferably any one of: O, N, C, B, P, H or a mixture thereof.
  • the amount "u" of the M 4 element within formula (I) is preferably between 0 and 0.01 (0 ⁇ u ⁇ 0.01).
  • the niobium-molybdenum alloy of formula (I) may contain either or both of M 3 and M 4 . Accordingly, z + u may be strictly greater than 0.
  • M 3 is preferably any one of Cu, Ti, Al, Cr, Mn, Si, or a mixture thereof. These alloying elements, as well as W and V, allow refining the microstructure of the alloy.
  • M 3 can be any one of Cr, Ni, Mn, Ti, Zr, Hf or a mixture thereof while M 4 can be any one of C, O, B, N or a mixture thereof.
  • the conditions (kinetics and/or temperature) for preparing and transforming the alloy may be adjusted thanks to these alloying elements, as well as Ta, Mo, V and W.
  • the balance spring made of the alloy of formula (I) may also comprise an oxide layer. This oxide layer acts as a passivation layer and therefore protects the balance spring from corrosion for instance.
  • the niobium-molybdenum alloy of formula (I) may be zirconium free and/or chromium free.
  • It can be free of magnetic elements such as Fe, Co and Ni.
  • the alloy of formula (I) is preferably insensitive to magnetic fields.
  • the metal elements of the alloy may have similar size and same crystal structure in elemental form in order to enhance the probability to form a solid solution and in order to reduce the probability of forming secondary phases.
  • Elements having the same crystal structure for instance cubic materials, e.g. body-centered cubic materials, include V, Cr, Mn, Fe, Ta, W, and mixtures thereof, preferably any one of V, Cr, Mn, Ta, W and mixtures thereof, and even more preferably any one of V, Cr, Ta, W and mixtures thereof.
  • the niobium-molybdenum alloy may be of formula Nb n Mo m M 4 u .
  • the invention also relates to a timepiece movement comprising a balance spring made of the niobium-molybdenum alloy of formula (I).
  • this timepiece movement may be a watch or a clock.
  • the invention also relates to a process for preparing a balance spring made of the niobium-molybdenum alloy of formula (I).
  • the above steps include cold/semi-hot transformations of the alloy, which generally texture the alloy.
  • temperature, transformation rates and heat treatments may be chosen and adjusted to favor and/or preserve the degree of texture.
  • Texturing the alloy may be useful in order to adjust the anomaly of the alloy when it depends on the c 44 elastic coefficient. Indeed, since the c 44 elastic coefficient is anisotropic, a texturing step may allow adjusting the anomaly of the alloy.
  • the anomaly of the alloy of formula (I) depends on the c 44 and/or on the c' elastic coefficients. As opposed to prior art alloys, the anomaly can be adjusted at two different levels since these two elastic coefficients can be independently adjusted thanks to the alloying elements (c 44 and c' coefficients) and thanks to a texturing step (c 44 ).
  • Niobium-molybdenum alloys have been compared to pure niobium and pure molybdenum using DFT calculations (density functional theory).
  • Figure 2 shows that the presence of Mo in the Nb-Mo alloys shifts the minimum c 44 from 500 K to temperatures close to 0 K as compared to pure Nb. Above 15 % and below 41 % in molybdenum, we observe an increase in the temperature behavior of c', which is not the case for elemental Nb and Mo.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Springs (AREA)
EP18210512.2A 2018-12-05 2018-12-05 Kompensierende spiralfeder für eine uhr oder grossuhr aus einer niob-molybdän-legierung Pending EP3663867A1 (de)

Priority Applications (1)

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EP18210512.2A EP3663867A1 (de) 2018-12-05 2018-12-05 Kompensierende spiralfeder für eine uhr oder grossuhr aus einer niob-molybdän-legierung

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EP18210512.2A EP3663867A1 (de) 2018-12-05 2018-12-05 Kompensierende spiralfeder für eine uhr oder grossuhr aus einer niob-molybdän-legierung

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EP3663867A1 true EP3663867A1 (de) 2020-06-10

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1521737A (fr) * 1966-04-22 1968-04-19 Straumann Inst Ag Alliage de métaux ou de semi-conducteurs ayant un faible coefficient du module d'élasticité en fonction des variations de température
US3547713A (en) * 1966-04-22 1970-12-15 Straumann Inst Ag Methods of making structural materials having a low temperature coefficient of the modulus of elasticity
EP0886195A1 (de) 1997-06-20 1998-12-23 Montres Rolex Sa Selbstkompensierende Spiralfeder für mechanische Uhrwerkunruhspiralfederoszillator und Verfahren zu deren Herstellung
EP1258786A1 (de) * 2001-05-18 2002-11-20 Montres Rolex Sa Selbstkompensierende Feder für einen mechanischen Oszillator vom Unruh-Spiralfeder-Typ
US6503341B2 (en) 1999-03-26 2003-01-07 Montres Rolex S.A. Self-compensating spiral for a spiral balance-wheel in watchwork and process for treating this spiral
EP1422436A1 (de) 2002-11-25 2004-05-26 CSEM Centre Suisse d'Electronique et de Microtechnique SA Spiraluhrwerkfeder und Verfahren zu deren Herstellung
US9227834B2 (en) 2011-04-12 2016-01-05 Diamaze Microtechnology S.A. Edge-reinforced micromechanical component

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1521737A (fr) * 1966-04-22 1968-04-19 Straumann Inst Ag Alliage de métaux ou de semi-conducteurs ayant un faible coefficient du module d'élasticité en fonction des variations de température
US3547713A (en) * 1966-04-22 1970-12-15 Straumann Inst Ag Methods of making structural materials having a low temperature coefficient of the modulus of elasticity
EP0886195A1 (de) 1997-06-20 1998-12-23 Montres Rolex Sa Selbstkompensierende Spiralfeder für mechanische Uhrwerkunruhspiralfederoszillator und Verfahren zu deren Herstellung
US5881026A (en) 1997-06-20 1999-03-09 Montres Rolex S.A. Self-compensating balance spring for a mechanical oscillator of a balance-spring/balance assembly of a watch movement and process for manufacturing this balance-spring
US6503341B2 (en) 1999-03-26 2003-01-07 Montres Rolex S.A. Self-compensating spiral for a spiral balance-wheel in watchwork and process for treating this spiral
EP1258786A1 (de) * 2001-05-18 2002-11-20 Montres Rolex Sa Selbstkompensierende Feder für einen mechanischen Oszillator vom Unruh-Spiralfeder-Typ
US6705601B2 (en) 2001-05-18 2004-03-16 Rolex S.A. Self-compensating spiral spring for a mechanical balance-spiral spring oscillator
EP1422436A1 (de) 2002-11-25 2004-05-26 CSEM Centre Suisse d'Electronique et de Microtechnique SA Spiraluhrwerkfeder und Verfahren zu deren Herstellung
US9227834B2 (en) 2011-04-12 2016-01-05 Diamaze Microtechnology S.A. Edge-reinforced micromechanical component

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HUBBELL W. C, F. R. BROTZEN: "Elastic constants of niobium-molibdenum alloys in the temperature range -190 to+100 °C", CJ. APPL. PHYS., vol. 43, no. 8, 1 August 1972 (1972-08-01), pages 3306 - 3312, XP055876108
LANDOLT-BMSTEIN: "New Series III/29a", 1972, article "Nb-Mo alloys", pages: 332 - 334, XP055876111

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