EP3548972B1 - Verfahren zur optimierung der tribologischen eigenschaften einer uhr - Google Patents

Verfahren zur optimierung der tribologischen eigenschaften einer uhr Download PDF

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Publication number
EP3548972B1
EP3548972B1 EP17808909.0A EP17808909A EP3548972B1 EP 3548972 B1 EP3548972 B1 EP 3548972B1 EP 17808909 A EP17808909 A EP 17808909A EP 3548972 B1 EP3548972 B1 EP 3548972B1
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EP
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Prior art keywords
ions
substrate
silicon
components
layer
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EP17808909.0A
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English (en)
French (fr)
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EP3548972A1 (de
Inventor
Frédéric Dreyer-Gonzales
Arnaud HOURIET
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Officine Panerai AG
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Officine Panerai AG
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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
    • G04B15/00—Escapements
    • G04B15/14—Component parts or constructional details, e.g. construction of the lever or the escape wheel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids

Definitions

  • the present invention relates to the field of watchmaking. It relates, more particularly, to a watch component intended to undergo dynamic friction and having improved tribological properties, as well as a method for optimizing the tribological properties of such a watch component.
  • This material also has the advantage of having interesting tribological properties, which suggested that it would be possible to have two silicon parts rub against each other, without having to resort to lubrication. Indeed, the interaction between moving parts, which is necessary for the operation of a timepiece mechanism, induces friction which is detrimental to the efficiency of the mechanism and which wears out the parts. It is therefore necessary to lubricate the parts of the components which undergo this friction. However, the oils traditionally used age and degrade, posing problems of maintenance of the movement, in particular.
  • improved tribological properties is meant a reduction in the coefficient of friction, a reduction in wear with respect to a given stress or to given conditions (surface condition, hygrometry, temperature, topology, etc.).
  • the purpose of the present invention is to propose an alternative to the methods proposed above, making it possible to obtain a watch component intended to undergo dynamic friction, which has improved tribological properties, in particular by the implementation of the ion implantation of certain elements. under specific conditions.
  • the document WO 2009/043391 describes a barrel spring for a mechanical watch, said barrel spring being made of a base material and comprising under at least part of its surface ions implanted in an associated implantation zone being made harder and more rigid than said material base, in order to increase the bending rigidity and thus the energy storage capacity of said barrel spring.
  • the invention relates to a method for optimizing the tribological properties of a watch component intended to undergo dynamic friction during its normal operation, produced on the basis of a substrate comprising a layer of silicon whose crystallographic structure comprises at least one of the monocrystalline, polycrystalline or amorphous forms, said substrate being reinforced by a protective layer produced on its surface during an operation for protecting the substrate, said method comprising a step of ion implantation of at least one ion, by ion bombardment on the surface of said component.
  • a toothed wheel meshing with another therefore undergoes dynamic friction at the level of the contact surfaces of its teeth, which is also the case between certain components of the escapement, in particular an anchor, an escape wheel or the part of the escapement.
  • a frictional resonator such as a platter peg, which experiences dynamic friction where it interacts with neighboring components.
  • a spiral spring being integral on the one hand with its peak and on the other hand with the balance shaft, it does not undergo any dynamic friction in the sense of the invention and is therefore excluded from its scope since no relative displacement is only present at the points of contact between the spring and the components with which it interacts.
  • silicon layer encompasses substrates for which, within the layer, the silicon does not form atomic bond with other atoms.
  • the different crystallographic natures of silicon are included in the scope of the invention and dopings or possible impurities present in the substrate are also possible and included in the scope of the claims.
  • a single layer of silicon, forming a silicon core, is also included in the scope of protection.
  • this protective layer is obtained by an effective protective operation and a natural oxidation layer is not a protective layer within the meaning of the present application, because it does not result from a protective operation as as such, carried out in an effective and positive manner.
  • a protective layer made of SiO 2 obtained by an oxidation step measures at least 50 nm in thickness, which cannot be obtained with natural oxidation.
  • the substrate takes the form of a single layer of silicon 10, covered with a protective layer 12.
  • the substrate takes the form of two layers of silicon 10, separated and covered with a protective layer 12. There could thus be an alternation of several layers of silicon.
  • the substrate comprises a core 14 covered with a layer of silicon 10 whose thickness is such that its tribological properties are equivalent to those of a silicon substrate.
  • the protection layer 12 covers the silicon layer.
  • the thickness of the silicon layer is greater than the depth of ion implantation, so that the ions do not penetrate into the core.
  • the invention relates to a method for optimizing the tribological properties of a watch component intended to undergo dynamic friction, produced on the basis of a substrate comprising a layer of silicon whose crystallographic structure comprises at least one of the forms monocrystalline, polycrystalline or amorphous, said substrate being reinforced by a protective layer produced on its surface during a substrate protection operation, said method comprising a step of ion implantation of at least one ion, by ion bombardment the surface of said component, in which the implantation step is carried out with C ions, at a dose greater than 5.10 17 ions/cm 2 and/or with N ions, at a dose greater than 1.10 16 ions/cm 2 .
  • the ion-implanted zone 16 is shared between the substrate, illustrated here in the form of a single layer of silicon 10, and the protective layer 12, the substrate having an implantation (in number of ions) greater than the protective layer.
  • the figure 4 has such a configuration. It is observed, more specifically, that the ions present in the protective layer are few, or even very few in number and that they are essentially concentrated in a precise zone of the substrate.
  • ion bombardment for example, ion beam, MEWA - Metal Vapor Vacuum Arc
  • the curve of density of the ions according to the depth of the component forms a narrow Gaussian showing this concentration in a precise region.
  • the distribution will be done with a concentration of ions with a decreasing tendency according to the depth reached.
  • a plasma atmosphere for example, Plasma Immersion Ion Implantation
  • one or the other of these general methods may be preferable, or even a combination of the two.
  • the implanted zone is located at least in the substrate.
  • the implanted zone 16 is located only in the protective layer 12 ( figure 5 ). This is particularly the case with a protective layer having a greater thickness than the implantation depth obtained with a given energy. More commonly, the implanted zone is located at least in the protective layer.
  • the ion-implanted zone can be located either in the protection layer only, or in the substrate only or shared between the protection layer and the substrate, that is to say in the region of the interface between the layer protection and the substrate.
  • the figure 1 shows the friction coefficient of a substrate on a ruby sphere, rolling on the substrate over a distance of 100m (abscissa).
  • the first centimeters of the curve correspond to a break-in and the establishment of regular conditions, and are not significant.
  • Curve A is the reference curve, obtained for a substrate without ion implantation.
  • Curve B is obtained for an identical substrate, implanted ionically with a dose of C ions of 2.10 17 ions/cm 2 , with an energy of 600 keV.
  • Curve C is obtained for an identical substrate, implanted ionically with a dose of C ions of 1.10 18 ions/cm 2 , with an energy of 600 keV. It can be seen that the coefficient of friction of the sample represented on curve B has a higher coefficient of friction than the reference sample, whereas the ion implantation of curve C makes it possible to reduce this coefficient of friction over almost all the length of the path traveled by the sphere.
  • the figure 2 shows the average coefficients of friction measured under conditions similar to those of the figure 1 , apart from the energy which in this case is 35keV, depending on the implantation dose, and on different substrates with a layer of SiO 2 of different thickness, which explains the results which are not directly comparable.
  • the effects obtained with a dose of 5.10 17 ions/cm 2 are already interesting.
  • the values of the dashed curve are extrapolations.
  • the nitrogen ions can be implanted in the protective layer, in the substrate, or in the region of the interface between the substrate and the protective layer, mainly in the substrate, or even only in the substrate if the energy is sufficient.
  • ion-implanted components as proposed above, to produce components subjected to repeated or significant shocks or friction, in particular the components of the escapement, in particular an anchor, a steering wheel anchor or part of a resonator subject to friction, such as a platter peg.
  • the invention also relates to the process for implanting the components described above, also defining a method for optimizing the tribological properties of a horological component as mentioned above, produced on the basis of a substrate comprising a layer of silicon 10 whose crystallographic structure comprises at least one of the monocrystalline, polycrystalline or amorphous forms, said substrate being reinforced by a protective layer 12 produced on its surface during a substrate protection operation.
  • the method comprises a step of ion implantation of at least one ion, by ion bombardment on the surface of said component.
  • the implantation step can be carried out with C ions, at a dose greater than 5.10 17 ions/cm 2 , preferably greater than 1.10 18 ions/cm 2 and with an energy greater than 600keV, or with ions N, at a dose greater than 1.10 16 ions/cm 2 and with an energy greater than 600keV.
  • the implantation is carried out on the components when, after etching, they have been detached from the base wafer in which they are etched.
  • the areas of the components that it is relevant to treat at the tribological level are the side faces which, in general in watchmaking, are those which are exposed to friction.
  • the side faces which, in general in watchmaking, are those which are exposed to friction.
  • the protection operation fundamental in the present application.
  • the lateral flanks of the components can pass at any place of the crystallographic lattice.
  • the ion implantation is directional and that the ion bombardment can have a variable angle of incidence on the side faces of the component, a tribological improvement is obtained which is averaged over the entire side surface. of the component and which is significant. Consequently, the method proposed in the present application can be applied with substrates of any crystallographic orientation, given that, at the level of the lateral surfaces, the part can assume all crystallographic orientations.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Physical Vapour Deposition (AREA)

Claims (5)

  1. Verfahren zur Optimierung der tribologischen Eigenschaften eines Uhrenbauteils, das dazu bestimmt ist, einer dynamischen Reibung zu unterliegen, hergestellt auf Basis eines Substrats, das eine Siliciumschicht (10) umfasst, deren kristallographische Struktur mindestens eine der Formen monokristallin, polykristallin oder amorph umfasst, wobei das Substrat mit einer im Lauf eines Arbeitsgangs zum Schützen des Substrats auf seiner Oberfläche hergestellten Schutzschicht (12) verstärkt wird, wobei das Verfahren einen Schritt der Ionenimplantation mindestens eines Ions durch Ionenbombardement der Oberfläche des Bauteils umfasst,
    wobei der Implantationsschritt mit C-Ionen in einer Dosis von mehr als 5-1017 Ionen/cm2 und/oder mit N-Ionen in einer Dosis von mehr als 1.1016 Ionen/cm2 durchgeführt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die C-Ionen-Dosis mehr als 1.1018 Ionen/cm2 beträgt.
  3. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass es an geformten Bauteilen durchgeführt wird, die mindestens teilweise von einem Basiswafer abgetrennt werden, um die Behandlung der Seitenflächen der Bauteile zu erlauben.
  4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Ionen mit einer Energie von mehr als 600 keV implantiert werden.
  5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schutzschicht aus durch einen Oxidationsschritt erhaltenes SiO2 hergestellt wird und eine Dicke von mindestens 50 nm aufweist.
EP17808909.0A 2016-12-05 2017-12-04 Verfahren zur optimierung der tribologischen eigenschaften einer uhr Active EP3548972B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH15872016 2016-12-05
PCT/EP2017/081407 WO2018104247A1 (fr) 2016-12-05 2017-12-04 Composant horloger presentant des proprietes tribologiques ameliorees et methode d'optimisation des proprietes tribologiques d'un composant horloger

Publications (2)

Publication Number Publication Date
EP3548972A1 EP3548972A1 (de) 2019-10-09
EP3548972B1 true EP3548972B1 (de) 2022-02-02

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EP (1) EP3548972B1 (de)
WO (1) WO2018104247A1 (de)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2165315B1 (es) * 2000-03-31 2003-08-01 Consejo Superior Investigacion Procedimiento de fabricacion de capas de carburo de silicio (sic) mediante implantacion ionica de carbono y recocidos.
US8339904B2 (en) * 2005-06-28 2012-12-25 Eta Sa Manufacture Horlogère Suisse Reinforced micro-mechanical part
WO2009043391A1 (fr) * 2007-10-05 2009-04-09 Creepservice Sarl Ressort de barillet a grande capacite de stockage d'energie et son procede de fabrication
CH708067B1 (fr) * 2008-10-22 2014-11-28 Richemont Int Sa Ressort spiral de montre autocompensé.
CH699780B1 (fr) * 2008-10-22 2014-02-14 Richemont Int Sa Ressort spiral de montre autocompensé.
CH705724B9 (fr) * 2011-11-03 2016-05-13 Sigatec Sa Pièce de micromécanique, notamment pour l'horlogerie.
CH709628B1 (fr) * 2015-08-27 2016-06-15 Csem Centre Suisse D'electronique Et De Microtechnique S A - Rech Et Développement Ressort spiral thermocompensé pour mouvement d'horlogerie.

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EP3548972A1 (de) 2019-10-09
WO2018104247A1 (fr) 2018-06-14

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