CH711882B1 - A process for hardening an iron-nickel-chromium-manganese alloy for horological applications. - Google Patents
A process for hardening an iron-nickel-chromium-manganese alloy for horological applications. Download PDFInfo
- Publication number
- CH711882B1 CH711882B1 CH01758/15A CH17582015A CH711882B1 CH 711882 B1 CH711882 B1 CH 711882B1 CH 01758/15 A CH01758/15 A CH 01758/15A CH 17582015 A CH17582015 A CH 17582015A CH 711882 B1 CH711882 B1 CH 711882B1
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- Switzerland
- Prior art keywords
- carbon
- nitrogen
- alloy
- chromium
- iron
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Classifications
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- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/02—Hardening articles or materials formed by forging or rolling, with no further heating beyond that required for the formation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C22/00—Alloys based on manganese
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- 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
- C22C27/06—Alloys based on chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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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
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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
- G04B43/00—Protecting clockworks by shields or other means against external influences, e.g. magnetic fields
- G04B43/007—Antimagnetic alloys
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
L’invention concerne un procédé d’amélioration d’un alliage fer-nickel-chrome-manganèse et l’utilisation d’un tel alliage pour la fabrication d’un spiral d’horlogerie choisit et on élabore un alliage de base comportant, en masse: de 9,0% à 13,0% de nickel, de 4,0% à 12,0% de chrome, de 21,0% à 25,0% de manganèse, le complément en fer, puis effectue un durcissement dudit alliage, tout en maintenant ses propriétés antiferromagnétiques, par introduction de carbone et d’azote en interstitiel, avec, en proportion de la masse dudit alliage de base: de 0,10% à 1,20% de carbone, et/ou de 0,10% à 1,20% d’azote.The invention relates to a process for improving an iron-nickel-chromium-manganese alloy, and the use of such an alloy for the manufacture of a watch hairspring chooses and produces a base alloy comprising, in mass: 9.0% to 13.0% nickel, 4.0% to 12.0% chromium, 21.0% to 25.0% manganese, the iron supplement, and then hardening said alloy, while maintaining its antiferromagnetic properties, by introducing carbon and nitrogen interstitial, with, in proportion to the mass of said base alloy: from 0.10% to 1.20% carbon, and / or 0.10% to 1.20% nitrogen.
Description
DescriptionDescription
Domaine de l’invention [0001] L’invention concerne un procédé d’amélioration d’un alliage fer-nickel-chrome-manganèse pour des applications horlogères.FIELD OF THE INVENTION [0001] The invention relates to a process for improving an iron-nickel-chromium-manganese alloy for horological applications.
[0002] L’invention concerne encore l’utilisation d’un tel alliage pour la réalisation d’un spiral.The invention also relates to the use of such an alloy for producing a spiral.
Arrière-plan de l’invention [0003] Les alliages thermo-compensateurs utilisés pour les spiraux d’horlogerie sont en grande majorité issus des travaux de Charles-Edouard Guillaume et basés sur l’Elinvar Fe-Ni-Cr. Des éléments durcissants ont, depuis, été ajoutés: W+C, ou Ti+AI, ou Be, ou Nb, qui ont notamment donné naissance aux alliages «Elinvar», «Ni-Span», «Nivarox», «Isoval».BACKGROUND OF THE INVENTION [0003] The thermo-compensating alloys used for clockwork spirals are for the most part derived from the work of Charles-Edouard Guillaume and based on the Elinvar Fe-Ni-Cr. Hardening elements have since been added: W + C, or Ti + Al, or Be, or Nb, which have in particular given rise to the alloys "Elinvar", "Ni-Span", "Nivarox", "Isoval".
[0004] Tous ces alliages, qui conviennent à l’application en raison de leurs propriétés mécaniques, sont toutefois ferromagnétiques, et donc sensibles aux champs magnétiques, ce qui est préjudiciable à la marche d’une montre.All these alloys, which are suitable for the application because of their mechanical properties, however, are ferromagnetic, and therefore sensitive to magnetic fields, which is detrimental to the running of a watch.
[0005] Dans les années 1970-1990, des travaux sur des alliages antiferromagnétiques ont été publiés mais n’ont pas donné lieu à des développements industriels. Ces alliages sont quasiment insensibles à l’effet d’un champ magnétique, mais présentent quelques difficultés industrielles et l’arrivée de la crise horlogère des années 80 a stoppé les développements. Résumé de l’invention [0006] On connaît, notamment par les travaux du Dr. Ing. Manfred Müller, une famille d’alliages antiferromagnétiques particulièrement intéressante, de type Fe-Mn-Ni-Cr.In the years 1970-1990, work on antiferromagnetic alloys have been published but have not given rise to industrial developments. These alloys are almost insensitive to the effect of a magnetic field, but present some industrial difficulties and the arrival of the crisis of the 1980's stopped the developments. SUMMARY OF THE INVENTION [0006] The work of Dr. Ing. Manfred Müller, a particularly interesting family of antiferromagnetic alloys, Fe-Mn-Ni-Cr type.
[0007] Il est possible de durcir de tels alliages par adjonction de Be, ou par adjonction de Ti+AI.It is possible to harden such alloys by adding Be, or by adding Ti + AI.
[0008] Le Be n’est pas souhaitable en raison de sa toxicité. Et l’ajout de Ti+AI est délicat, car Ti et Al réagissent avec le Ni présent dans l’alliage, et en modifient localement la composition, rendant par là-même difficile la maîtrise du coefficient thermique de l’alliage; de plus, le durcissement structural par précipitation de Ni3AI et Ti3AI tend à réduire la ductilité de l’alliage.The Be is undesirable because of its toxicity. And the addition of Ti + Al is difficult because Ti and Al react with the Ni present in the alloy, and modify the composition locally, thereby making it difficult to control the thermal coefficient of the alloy; in addition, the precipitation hardening of Ni3Al and Ti3Al tends to reduce the ductility of the alloy.
[0009] L’objet de l’invention est de trouver une alternative permettant un durcissement satisfaisant.The object of the invention is to find an alternative for satisfactory hardening.
[0010] A cet effet, l’invention concerne un procédé d’amélioration d’un alliage fer-nickel-chrome-manganèse pour des applications horlogères, selon la revendication 1.For this purpose, the invention relates to a method for improving an iron-nickel-chromium-manganese alloy for horological applications, according to claim 1.
[0011] En résumé, la présente invention permet de durcir un alliage de type Fe-Mn-Ni-Cr, par l’introduction de carbone et d’azote en interstitiel, selon le principe des aciers HIS.In summary, the present invention allows to harden a Fe-Mn-Ni-Cr type alloy, by the introduction of carbon and nitrogen interstitial, according to the principle of HIS steels.
[0012] Un tel durcissement par C+N permet le développement d’alliages comportant de bonnes propriétés mécaniques, qui sont antiferromagnétiques, et écologiques.Such hardening by C + N allows the development of alloys with good mechanical properties, which are antiferromagnetic, and ecological.
[0013] L’invention concerne encore l’utilisation d’un tel alliage pour la réalisation d’un spiral d’horlogerie.The invention also relates to the use of such an alloy for the production of a horological spiral.
Description détaillée des modes de réalisation préférés [0014] L’invention concerne un procédé d’amélioration d’un alliage fer-nickel-chrome-manganèse pour des applications horlogères.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0014] The invention relates to a method of improving an iron-nickel-chromium-manganese alloy for horological applications.
[0015] Selon l’invention, on choisit et on élabore un alliage de base comportant, en masse: - de 4,0% à 13,0% de nickel, - de 4,0% à 12,0% de chrome, - de 21,0% à 25,0% de manganèse, - le complément en fer, et on effectue un durcissement de cet alliage, tout en maintenant ses propriétés antiferromagnétiques, par introduction de carbone et d’azote en interstitiel, avec, en proportion de la masse de l’alliage de base: - de 0,10% à 1,20% de carbone, et/ou - de 0,10% à 1,20% d’azote.According to the invention, a basic alloy is selected and produced comprising, by weight: from 4.0% to 13.0% of nickel, from 4.0% to 12.0% of chromium, from 21.0% to 25.0% of manganese, the iron complement, and this alloy is cured, while maintaining its antiferromagnetic properties, by introducing carbon and nitrogen into interstitial, with, in proportion of the mass of the base alloy: from 0.10% to 1.20% of carbon, and / or from 0.10% to 1.20% of nitrogen.
[0016] Plus particulièrement, on ajuste cette introduction de carbone et d’azote, telle que la somme des proportions, en masse de l’alliage de base, du carbone et de l’azote, est comprise entre 0,60% et 0,95%.More particularly, it adjusts the introduction of carbon and nitrogen, such that the sum of the proportions, by weight of the base alloy, carbon and nitrogen, is between 0.60% and 0. 95%.
[0017] Plus particulièrement, on ajuste cette introduction de carbone et d’azote, telle que la somme des proportions, en masse de l’alliage de base, du carbone et de l’azote, est comprise entre 0,75% et 0,95%.More particularly, this introduction of carbon and nitrogen is adjusted, such that the sum of the proportions by weight of the base alloy, carbon and nitrogen is between 0.75% and 0. 95%.
[0018] Plus particulièrement, on ajuste cette introduction de carbone et d’azote, telle que la somme des proportions, en masse de l’alliage de base, du carbone et de l’azote, est comprise entre 0,80% et 0,85%.More particularly, this introduction of carbon and nitrogen is adjusted, such that the sum of the proportions by weight of the base alloy, carbon and nitrogen is between 0.80% and 0. 85%.
[0019] Plus particulièrement, on ajuste cette introduction de carbone et d’azote, telle que le rapport des pourcentages de carbone et d’azote en masse totale de l’alliage de base est compris entre 0,5 et 2,0.More particularly, it adjusts the introduction of carbon and nitrogen, such that the ratio of percentages of carbon and nitrogen in total mass of the base alloy is between 0.5 and 2.0.
Claims (13)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CH01758/15A CH711882B1 (en) | 2015-12-02 | 2015-12-02 | A process for hardening an iron-nickel-chromium-manganese alloy for horological applications. |
Applications Claiming Priority (1)
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CH01758/15A CH711882B1 (en) | 2015-12-02 | 2015-12-02 | A process for hardening an iron-nickel-chromium-manganese alloy for horological applications. |
Publications (2)
Publication Number | Publication Date |
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CH711882A2 CH711882A2 (en) | 2017-06-15 |
CH711882B1 true CH711882B1 (en) | 2019-06-28 |
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CH01758/15A CH711882B1 (en) | 2015-12-02 | 2015-12-02 | A process for hardening an iron-nickel-chromium-manganese alloy for horological applications. |
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Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP4009114A1 (en) * | 2019-12-31 | 2022-06-08 | Nivarox-FAR S.A. | Hairspring for clock movement and method for manufacturing same |
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