EP3092531A2 - Device for securing a crystal to a watch case - Google Patents

Device for securing a crystal to a watch case

Info

Publication number
EP3092531A2
EP3092531A2 EP15700185.0A EP15700185A EP3092531A2 EP 3092531 A2 EP3092531 A2 EP 3092531A2 EP 15700185 A EP15700185 A EP 15700185A EP 3092531 A2 EP3092531 A2 EP 3092531A2
Authority
EP
European Patent Office
Prior art keywords
watch case
ice
electrode
intermediate layer
layer
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
Application number
EP15700185.0A
Other languages
German (de)
French (fr)
Other versions
EP3092531B1 (en
Inventor
Sébastien BRUN
Sandrine GUERIN DELETANG
Herbert Keppner
Sophie FARINE
Eric Guyot
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.)
Cartier International AG
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
Publication of EP3092531A2 publication Critical patent/EP3092531A2/en
Application granted granted Critical
Publication of EP3092531B1 publication Critical patent/EP3092531B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • G04B39/00—Watch crystals; Fastening or sealing of crystals; Clock glasses
    • G04B39/02—Sealing crystals or glasses
    • 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
    • G04D3/06—Devices for shaping or setting watch glasses

Definitions

  • the present invention relates to a method of fixing an upper and / or lower window on a watch case, more precisely on a bezel or on a middle case bezel of a watch case, without using a seal or glue while ensuring a tight and resistant fixing.
  • the present invention relates to a method of fixing an ice on a watch case which is distinguished by the characteristics listed in claim 1.
  • the specificity and purpose of the present invention is to produce a gas-tight, fluid-free, solderless, solder-free and organic compound (glue) seal.
  • Several preparations of the surfaces are necessary and illustrated in the accompanying drawing which illustrates schematically and by way of example, the successive steps of an execution of the method of fixing an ice on a watch case according to the invention.
  • the present method makes it possible to fix a watch glass that can be typically made of mineral glass, sapphire or other transparent or translucent ceramics with or without anti-reflective coating on a part or the whole of the surface, to a bezel or middle-bezel of a box watch by the technique of anodic bonding.
  • the area of the watch case on which the ice is attached is typically stainless steel, platinum or gold, or includes the various alloys associated with these materials.
  • the aforementioned materials may be indifferently coated with rhodium or any other material used for the manufacture of watch cases or jewelry or jewelery products.
  • the anodic bonding process is used in the general field of microtechnology, more particularly in the biomedical, aerospace and electronics sectors, where connections are made between materials that are compatible from a point of view of near thermal expansion coefficients with anodic joining technology.
  • anode assemblies is mainly used for films and thin and flat layers such as wafers of metal, glass and silicon.
  • JP 08166469A By the same principle of stress limitation, anodic assemblies of small size and low mass or elements not subject to external mechanical forces, have been described in the watch industry in JP 08166469A, for fixing a glass plate on a metal or silicon dial. JP 05080163A also discloses the attachment of silicon indexes affixed to a glass plate of the dial by the anode assembly.
  • the assembly proposed by the present invention is carried out by means of intermediate layers, in order to consolidate the link, increase the speed of diffusion and allow assembly for a wider range of materials. and more massive parts, subjected to strong constraints and having to withstand shocks.
  • the present fixing method is applied to mechanical components subjected to high mechanical stresses, in particular between a watch glass on a watch case made of steel, gold or platinum in particular.
  • the process for fixing a watch crystal on a watch case according to the invention consists in producing a permanent and sealed anode assembly between the box and the ice by the use of surface treatment on the ice zones and / or the contacting box allowing the migration of ions and electrons.
  • An electrode is connected to the ice and a counter-electrode is connected to the watch case then a voltage of between 1 kV and 15kV is applied to improve the intimate contact between the partners and to bring a kinetic energy assisted by the electric field to the particles. loaded for enable them to diffuse and create new ionic or covalent metal bonds.
  • the ice and / or the watch case are provided in the contacting areas of a semiconductor element or insulating promoting migration such as glasses or silicon.
  • the process is carried out at a low temperature ensuring that none of the materials of the system, watch case, ice or intermediate layers, leaves its solid phase.
  • the electrodes are adapted to the geometry of the contact surface.
  • the geometry of the electrode is considered in three dimensions, the part in contact with the sapphire is without edges and without tip, typically of curved shape.
  • a surface treatment allowing a structural modification of the substrates typically comprising heat treatments, activation plasma, pickling plasma or sonochemical can be used to facilitate the diffusion phenomena.
  • the assembly described is done by anodic bonding only, no element is melted, even partially. This differentiates the assembly obtained in a significant way assemblies obtained by laser or ultrasound welding.
  • the assembly described makes it possible to produce metal-to-metal, metal-to-metal and non-metal to non-metal bonds.
  • the intermediate semiconductor element may be attached by a separate part or deposited by physical or chemical means (PVD, PE-CVD, Sol-gel, electroplating).
  • Thin intermediate layers considered have non-constant stoichiometry.
  • the degree of nitriding or carburizing oxidation varies with the thickness of the layer.
  • the thin layer of the telescope may also contain its natural or forced passivation layer.
  • a masking layer is deposited on the ice to mask the contact area.
  • This layer may consist of metallic elements and alloys of at least one of the following elements: Ti, Fe, Al, Cr, V, Pt, Ta, W, Ga, Sn, Zn, Au and Ag.
  • watch case also includes other trim components such as the bottom and middle part. Is considered watch box all components to enclose the movement in a sealed manner.
  • the ice in question consists of at least one of the following elements: aluminum oxide such as sapphire, spinel, AlON spinel aluminum oxynitride, yttria, YAG (Yttrium Aluminum Garnet) and Nd : YAG or silicon oxide such as mineral glass or pyrex.
  • aluminum oxide such as sapphire, spinel, AlON spinel aluminum oxynitride, yttria, YAG (Yttrium Aluminum Garnet) and Nd : YAG or silicon oxide such as mineral glass or pyrex.
  • the temperature of the partners, watch case and ice, during the bonding process is less than 380 ° C, and preferably less than 250 ° C.
  • the temperature may vary during assembly, for example from 120 ° C to 250 ° C.
  • the expansion speed of the anode link is for example greater than 1 mm 2 / minute.
  • the surface roughness of the bezel is obtained by mechanical machining or fine stamping supplemented with electro-chemical polishing.
  • Figure 1 is a diagram of the partners, box and ice, and intermediate layers.
  • Figure 2 illustrates the steps of a particular embodiment of the method.
  • the method of fixing a watch glass on a watch case comprises, in a preferred embodiment, the following steps (see FIG. 2 of the drawing):
  • the roughness of the face in contact with the bezel is obtained by stamping and / or machining steps and the surface is finished by mechanical and / or electrochemical polishing;
  • PVD PVD
  • Sol-Gel Sol-Gel
  • ALD electroplating one or more intermediate layers are developed, stoichiometric or not on the area of the surface making the anodic connection of the bezel of the watch case.
  • the composition of this or these intermediate layers depends on the material of the telescope.
  • the ice is connected to an electrode and the telescope is connected to a counter electrode, then the voltage is raised, preferably a DC voltage, at a value between 1 kV and 15kV, which binds the partners anodically. More particularly, the voltage produces an electric field which causes an ion migration between the ice and the watch case.
  • step No. 2 is the polishing of the upper face of the bezel.
  • the telescope can be replaced by a case bezel or any other part of the watch case on which the ice must be fixed,
  • the intermediate layer is deposited on the upper face of the bezel by the physical or chemical technology mentioned above and the composition of the matrix of this intermediate layer.
  • typically consists of TixOy, SixOy, Si x N y , Al x O y or mixtures of oxides containing atoms / ions of light metals such as Li, Na, K, Ca, Be, or halogens promoting the migration of ions.
  • the addition of a thin metal layer is possible before the deposition of the intermediate layer to better ensure the brightness and visual metallic appearance under the transparent ice. This can by its choice increase the adhesion between the intermediate layer, the transition between the materials can even be done gradually.
  • the anode assembly is carried out under a voltage of less than 15kV.
  • the anode assembly will take place at a temperature below 250 ° C.
  • Determining the nature of the intermediate layer or layers requires the qualification of the materials to be assembled typically its physico-chemical composition, mechanical properties, surface condition, in order to optimize the characteristics of the deposit which will serve as the first intermediate layer. This being qualified by the following factors: adhesion with the raw materials, types of defects and gaps allowing the diffusion of the ions and the migration, electronegativity of the ions contained within the intermediate layer (s), concentration of ions and gaps, orientation of these same gaps.
  • the layer or layers may contain alkaline, alkaline-earth and halogenated materials because of their ease of migration and the size of their atoms.
  • the intermediate layer (s) will define the quality of the bond, its mechanical properties and the seal, but also its aesthetic properties. To grasp the importance of this or these intermediate layers and to differentiate an assembly according to the present invention from conventional soldering or brazing techniques where there is no question of using an electric field, it is a matter of understanding specific atomic transfers during the process of anodic assembly.
  • any charged particle placed under the influence of a uniform electric field moves at a rate proportional to this field, the proportionality factor being called the electric mobility of the particle.
  • This migration will take place from the anode to the cathode for the positively charged particles, in the opposite direction for the negatively charged particles.
  • there is a potential difference between the partners which causes a plating between the induced partners under the effect of electrostatic forces. If this plating is insufficient, the application of a mechanical load to force contact between the partners is considered.
  • the electric field increases the diffusion process, the assembly speeds are reduced by a few minutes, which encourages increased yield and reproducibility.
  • Disturbance of the thermodynamic equilibrium influences the populations of charge carriers located in the parts to be assembled and the intermediate layer.
  • the origins of the disturbances can be:
  • transport phenomena The properties relating to electric currents and to the displacement of charge carriers under the influence of applied forces are called transport phenomena.
  • transport phenomena mobility, whether it be for example gaps, impurities, charge carriers (the materials are differentiated by the Debye length of the majority carriers and their behavior is described in particular by the continuity equation ) as well as diffusion (based on Fick's laws) are the key mechanisms of anodic assembly.
  • the parameters which most influence the mobility of the charge carriers are the temperature and the volume number of impurities.
  • impurities and gaps are the same gaps, Schottky or Frenkel defects, among others, which facilitate the diffusion of charge carriers and which define the energy necessary for their diffusion.
  • moving a gap through a crystal requires much less work than constraining an ion to move through a dense ion network of a crystal. Ion conduction depends on the movement of the gaps.
  • the impurities that contribute to the charge carrier density are called "donors” if they bring additional electrons and “acceptors” if they bring additional holes. It should be noted that the speed of the phenomenon of the anode assembly depends on the quantity of defects and the temperature in particular.
  • the choice of the intermediate layer or layers depends strongly on the "properties" of the charge carriers.
  • the chemical composition of the layer or layers is naturally important since the transport phenomena depend on the characteristics of the atomic bonds.
  • the bonds created during the anodic assembly process are predominantly covalent bonds. These strong links are established by pooling a pair of electrons from each of the charge carriers.
  • PVD deposition method is preferred, but an intermediate layer (mono or multilayer) may be deposited by another physical or chemical deposition process.
  • the temperature and the applied voltage as well as the contact time are closely related and complementary since they control the electrostatic force required for the chemical reaction between the parts to be assembled.
  • the voltage will not go beyond 15 kV, and the temperature does not exceed 250 ° C.
  • Thicknesses depend on glasses and ice tolerances and are between 10-10000 angstroms.
  • the gap between the parts to be assembled has a significant effect on the magnitude of the electrostatic force, which implies that the quality of the bond formed by anodic assembly also depends on the surface condition.
  • mechanical finishing processes of the electrochemically polished, electrochemically polished surface of the contact surface are used.
  • the layer deposition mimicking the material of the bezel is deposited on ice before functional layer deposition.
  • Such a deposit is selective, masking the assembly area, with an aesthetic function.
  • This selectivity is obtained by masking technique, typically by lithography, stamping, selective etching or by promoting adhesion.
  • optical rendering surface appearance color
  • the optical rendering, surface appearance color is obtained by an adaptation of the layers, in particular by their thickness, their composition and their pretreatments.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention relates to a method for securing a crystal to a watch case, in which: at least one thin intermediate layer is attached by means of surface treatment to a zone of the surface of the crystal that is intended to come into contact with a corresponding zone of the watch case and/or to said corresponding zone of the watch case, said thin intermediate layer allowing the migration of ions and/or electrons; the aforementioned zones of the watch case and the crystal are applied against one another; the watch case/crystal assembly is heated to a sufficiently low heating temperature to guarantee that none of the materials forming the system leaves the solid phase; the crystal is connected to an electrode and the watch case is connected to a counter-electrode, and a voltage is applied between the electrode and the counter-electrode that accelerates the diffusion of the charged particles and thus creates new metallic, ionic or covalent bonds. The invention also relates to a watch case obtained using this method.

Description

Procédé de fixation d'une glace sur une boîte de montre  Method of fixing an ice on a watch case
La présente invention se rapporte à un procédé de fixation d'une glace supérieur et/ou inférieur sur une boîte de montre, plus précisément sur une lunette ou sur une carrure lunette d'une boîte de montre, sans utiliser de joint ou de colle tout en assurant une fixation étanche et résistante. The present invention relates to a method of fixing an upper and / or lower window on a watch case, more precisely on a bezel or on a middle case bezel of a watch case, without using a seal or glue while ensuring a tight and resistant fixing.
La présente invention a pour objet un procédé de fixation d'une glace sur une boîte de montre qui se distingue par les caractéristiques énumérées à la revendication 1 .  The present invention relates to a method of fixing an ice on a watch case which is distinguished by the characteristics listed in claim 1.
La spécificité et le but de la présente invention est de produire un assemblage étanche aux gaz et aux liquides sans soudure, sans brasure et sans composé organique (colle). Plusieurs préparations des surfaces sont nécessaires et illustrées au dessin annexé qui illustre schématiquement et à titre d'exemple, les étapes successives d'une exécution du procédé de fixation d'une glace sur une boîte de montre selon l'invention.  The specificity and purpose of the present invention is to produce a gas-tight, fluid-free, solderless, solder-free and organic compound (glue) seal. Several preparations of the surfaces are necessary and illustrated in the accompanying drawing which illustrates schematically and by way of example, the successive steps of an execution of the method of fixing an ice on a watch case according to the invention.
Le présent procédé permet de fixer une glace de montre pouvant être typiquement en verre minéral, saphir ou autres céramiques transparente ou translucide avec ou sans revêtement antireflets sur une partie ou la totalité de la surface, à une lunette ou carrure-lunette d'une boîte de montre par la technique de l'assemblage anodique (anodic bonding). La zone de la boîte de montre sur laquelle est fixée la glace est typiquement en acier inoxydable, en platine ou en or, ou comprend les différents alliages associés à ces matériaux. Les matériaux précités peuvent indifféremment être revêtus de rhodium ou toute autre matière utilisée pour la fabrication de boîtes de montres ou de produits de bijouterie ou de joaillerie.  The present method makes it possible to fix a watch glass that can be typically made of mineral glass, sapphire or other transparent or translucent ceramics with or without anti-reflective coating on a part or the whole of the surface, to a bezel or middle-bezel of a box watch by the technique of anodic bonding. The area of the watch case on which the ice is attached is typically stainless steel, platinum or gold, or includes the various alloys associated with these materials. The aforementioned materials may be indifferently coated with rhodium or any other material used for the manufacture of watch cases or jewelry or jewelery products.
Le procédé d'assemblage par anodique (anodic bonding) est utilisé dans le domaine général de la microtechnique, plus particulièrement dans les secteurs biomédicaux, aérospatiaux et en électronique, où l'on réalise des liaisons entre des matériaux compatibles d'un point de vue de coefficients de dilatation thermique proche avec la technologie d'assemblage par anodique. The anodic bonding process is used in the general field of microtechnology, more particularly in the biomedical, aerospace and electronics sectors, where connections are made between materials that are compatible from a point of view of near thermal expansion coefficients with anodic joining technology.
Dans ces domaines, notamment en microélectronique et les domaines voisins, l'utilisation d'assemblages anodiques est surtout utilisée pour les films et couches minces et plates notamment comme des wafers de métal, de verre et de silicium.  In these fields, particularly in microelectronics and neighboring fields, the use of anode assemblies is mainly used for films and thin and flat layers such as wafers of metal, glass and silicon.
Par le même principe de limitation des contraintes, des assemblages anodiques de petites tailles et de faible masse ou des éléments non soumis à des forces mécaniques externes, ont été décrits dans le secteur horloger dans le document JP 08166469A, pour fixer une plaque de verre sur un cadran métallique ou en silicium. Le brevet JP 05080163A décrit également la fixation d'index en silicium apposés sur une plaque en verre du cadran par l'assemblage anodique.  By the same principle of stress limitation, anodic assemblies of small size and low mass or elements not subject to external mechanical forces, have been described in the watch industry in JP 08166469A, for fixing a glass plate on a metal or silicon dial. JP 05080163A also discloses the attachment of silicon indexes affixed to a glass plate of the dial by the anode assembly.
Contrairement à ces réalisations, l'assemblage proposé par la présente invention se réalise par le biais de couches intermédiaires, ceci dans l'objectif de consolider le lien, augmenter la vitesse de diffusion et de permettre l'assemblage pour une plus grande gamme de matériaux et des pièces plus massives, soumises à de fortes contraintes et devant résister aux chocs.  In contrast to these embodiments, the assembly proposed by the present invention is carried out by means of intermediate layers, in order to consolidate the link, increase the speed of diffusion and allow assembly for a wider range of materials. and more massive parts, subjected to strong constraints and having to withstand shocks.
Le présent procédé de fixation est appliqué à des composants mécaniques soumis à des contraintes mécaniques élevées, en particulier entre une glace de montre sur une boîte de montre en acier, or ou platine notamment.  The present fixing method is applied to mechanical components subjected to high mechanical stresses, in particular between a watch glass on a watch case made of steel, gold or platinum in particular.
Le procédé de fixation d'une glace de montre sur une boîte de montre selon l'invention consiste à réaliser un assemblage anodique permanent et étanche entre la boîte et la glace par l'utilisation de traitement de surface sur les zones de la glace et/ou de la boîte entrant en contact permettant la migration des ions et des électrons.  The process for fixing a watch crystal on a watch case according to the invention consists in producing a permanent and sealed anode assembly between the box and the ice by the use of surface treatment on the ice zones and / or the contacting box allowing the migration of ions and electrons.
Une électrode est connectée à la glace et une contre-électrode est connectée à la boîte de montre puis on applique une tension comprise entre 1 kV et 15kV pour améliorer le contact intime entre les partenaires et amener une énergie cinétique assistée par le champ électrique aux particules chargées pour leur permettre de diffuser et de créer de nouvelles liaisons métalliques ioniques ou covalentes. An electrode is connected to the ice and a counter-electrode is connected to the watch case then a voltage of between 1 kV and 15kV is applied to improve the intimate contact between the partners and to bring a kinetic energy assisted by the electric field to the particles. loaded for enable them to diffuse and create new ionic or covalent metal bonds.
Préalablement à leur mise en place, la glace et/ou la boîte de montre sont munies dans les zones entrant en contact d'un élément semi-conducteur ou isolant favorisant la migration tel que des verres ou du silicium.  Prior to their introduction, the ice and / or the watch case are provided in the contacting areas of a semiconductor element or insulating promoting migration such as glasses or silicon.
Le processus s'effectue à basse température garantissant qu'aucun des matériaux du système, boîte de montre, glace ou couches intermédiaires, ne quitte sa phase solide.  The process is carried out at a low temperature ensuring that none of the materials of the system, watch case, ice or intermediate layers, leaves its solid phase.
La spécificité de la couche déposée sur la glace tient dans l'évolution chimique et structurelle, la partie en contact avec le substrat est de nature purement métallique et au fur et à mesure de sa croissance son degré d'oxydation évolue de manière progressive pour se terminer en surface avec un état d'oxydation complet ΤΊΟ2.  The specificity of the layer deposited on the ice is in the chemical and structural evolution, the part in contact with the substrate is purely metallic in nature and as it grows its degree of oxidation evolves gradually to finish at the surface with a complete oxidation state ΤΊΟ2.
De préférence, les électrodes sont adaptées à la géométrie de la surface de contact. La géométrie de l'électrode est considérée en trois dimensions, la partie en contact avec le saphir est sans arrêtes et sans pointe, typiquement de forme incurvée.  Preferably, the electrodes are adapted to the geometry of the contact surface. The geometry of the electrode is considered in three dimensions, the part in contact with the sapphire is without edges and without tip, typically of curved shape.
Une fonctionnalisation de surface par implantation ionique permet d'améliorer les phénomènes de diffusion par l'apport d'élément dans la matrice et par la perturbation du réseau cristallin ou de la stoechiométrie.  Surface functionalization by ion implantation makes it possible to improve the diffusion phenomena by adding element into the matrix and by disturbing the crystal lattice or the stoichiometry.
Une fonctionnalisation de surface par exposition UV permet d'améliorer les phénomènes de diffusion par la perturbation du réseau cristallin ou de la stœchiométrie résultant de l'apport d'énergie dans la matrice.  Surface functionalization by UV exposure makes it possible to improve diffusion phenomena by disturbing the crystal lattice or the stoichiometry resulting from the supply of energy into the matrix.
Un traitement de surface permettant une modification structurelle des substrats comprenant typiquement des traitements thermique, plasma d'activation, plasma de décapage ou sonochimique peut être utilisé pour faciliter les phénomènes de diffusion.  A surface treatment allowing a structural modification of the substrates typically comprising heat treatments, activation plasma, pickling plasma or sonochemical can be used to facilitate the diffusion phenomena.
L'assemblage décrit est effectué par anodic bonding uniquement, aucun élément n'est mis en fusion, même partiellement. Ceci différencie l'assemblage obtenu d'une manière importante des assemblages obtenus par soudures laser ou ultrasons. The assembly described is done by anodic bonding only, no element is melted, even partially. This differentiates the assembly obtained in a significant way assemblies obtained by laser or ultrasound welding.
L'assemblage décrit permet de réaliser des liaisons métal sur métal, métal sur non-métal et non métal sur non métal.  The assembly described makes it possible to produce metal-to-metal, metal-to-metal and non-metal to non-metal bonds.
L'élément semi-conducteur intermédiaire peut être rapporté par une pièce séparée ou déposé par voie physique ou chimique (PVD, PE-CVD, Sol-gel, galvanoplastie).  The intermediate semiconductor element may be attached by a separate part or deposited by physical or chemical means (PVD, PE-CVD, Sol-gel, electroplating).
Les couches intermédiaires minces considérées possèdent une stœchiométrie non constante. Le degré d'oxydation de nitruration ou de cémentation varie avec l'épaisseur de la couche.  Thin intermediate layers considered have non-constant stoichiometry. The degree of nitriding or carburizing oxidation varies with the thickness of the layer.
La couche mince de la lunette peut également contenir sa couche de passivation naturelle ou forcée.  The thin layer of the telescope may also contain its natural or forced passivation layer.
Une couche de masquage est déposée sur la glace afin de masquer la zone de contact. Cette couche peut être constituée d'éléments métalliques et des alliages d'au moins un des éléments suivants : Ti, Fe, Al, Cr, V, Pt, Ta, W, Ga, Sn, Zn, Au et Ag.  A masking layer is deposited on the ice to mask the contact area. This layer may consist of metallic elements and alloys of at least one of the following elements: Ti, Fe, Al, Cr, V, Pt, Ta, W, Ga, Sn, Zn, Au and Ag.
Le terme boîte de montre comprend également les autres composants de rhabillage tel que le fond et la carrure. Est considéré comme boîte de montre tous les composants permettant d'enfermer le mouvement de manière étanche.  The term watch case also includes other trim components such as the bottom and middle part. Is considered watch box all components to enclose the movement in a sealed manner.
La glace considérée est constituée d'au moins un des éléments suivants: d'oxyde d'aluminium comme le saphir, de spinelle, AlON spinelle d'oxynitride d'aluminium, d'yttria, d'YAG (Yttrium Aluminium Garnet) et Nd:YAG ou d'oxyde de silicium comme le verre minéral ou le pyrex.  The ice in question consists of at least one of the following elements: aluminum oxide such as sapphire, spinel, AlON spinel aluminum oxynitride, yttria, YAG (Yttrium Aluminum Garnet) and Nd : YAG or silicon oxide such as mineral glass or pyrex.
La température des partenaires, boîte de montre et glace, lors du processus de liaison est inférieure à 380°C, et de préférence inférieure à 250°C. La température peut varier pendant l'assemblage, par exemple de 120°C à 250°C.  The temperature of the partners, watch case and ice, during the bonding process is less than 380 ° C, and preferably less than 250 ° C. The temperature may vary during assembly, for example from 120 ° C to 250 ° C.
La vitesse d'extension du lien anodique est par exemple supérieure à 1 mm2/minute. La rugosité de surface de la lunette est obtenue par un usinage mécanique ou un étampage fin additionné d'un électro polissage chimique. The expansion speed of the anode link is for example greater than 1 mm 2 / minute. The surface roughness of the bezel is obtained by mechanical machining or fine stamping supplemented with electro-chemical polishing.
Le dessin annexé illustre schématiquement et à titre d'exemple l'assemblage anodique selon l'invention.  The accompanying drawing illustrates schematically and by way of example the anode assembly according to the invention.
La figure 1 est un schéma des partenaires, boîte et glace, et des couches intermédiaires.  Figure 1 is a diagram of the partners, box and ice, and intermediate layers.
La figure 2 illustre les étapes d'une forme d'exécution particulière du procédé.  Figure 2 illustrates the steps of a particular embodiment of the method.
Le procédé de fixation d'une glace de montre sur une boîte de montre comporte, dans une forme d'exécution préférée, les étapes suivantes (voir figure 2 du dessin) :  The method of fixing a watch glass on a watch case comprises, in a preferred embodiment, the following steps (see FIG. 2 of the drawing):
1 . On choisit une pièce d'une boîte de montre devant recevoir la glace, par exemple la lunette;  1. We choose a piece of a watch case to receive the ice, for example the bezel;
2. La rugosité de la face en contact avec la lunette est obtenue par des étapes d'étampage et/ou d'usinage puis la surface est terminée par polissage mécanique et/ou électrochimique;  2. The roughness of the face in contact with the bezel is obtained by stamping and / or machining steps and the surface is finished by mechanical and / or electrochemical polishing;
3. Par des procédés physique ou chimique principalement CVD,  3. By physical or chemical processes mainly CVD,
PVD, Sol-Gel, ALD, galvanoplastie on développe une ou plusieurs couches intermédiaires, stœchiométrique ou non sur la zone de la surface effectuant le lien anodique de la lunette de la boîte de montre. La composition de cette ou ces couches intermédiaires dépend de la matière de la lunette.  PVD, Sol-Gel, ALD, electroplating one or more intermediate layers are developed, stoichiometric or not on the area of the surface making the anodic connection of the bezel of the watch case. The composition of this or these intermediate layers depends on the material of the telescope.
Alternativement ou de manière complémentaire, un processus similaire peut être effectué sur la zone de la glace venant en contact avec la boîte de montre.  Alternatively or in a complementary manner, a similar process can be performed on the area of the ice that comes into contact with the watch case.
4. On positionne la glace sur la face supérieure de la lunette à une température inférieure à 250°C.  4. Position the ice on the upper face of the telescope at a temperature below 250 ° C.
5. La glace est connectée à une électrode et la lunette est connectée à une contre électrode, puis on élève la tension, de préférence une tension DC, à une valeur comprise en 1 kV et 15kV, ce qui lie les partenaires de manière anodique. Plus particulièrement, la tension produit un champ électrique qui engendre une migration des ions entre la glace et la boîte de montre. 5. The ice is connected to an electrode and the telescope is connected to a counter electrode, then the voltage is raised, preferably a DC voltage, at a value between 1 kV and 15kV, which binds the partners anodically. More particularly, the voltage produces an electric field which causes an ion migration between the ice and the watch case.
Dans une variante du procédé de fixation de la glace de montre sur une lunette d'une boîte de montre on peut supprimer l'étape N° 2 soit le polissage de la face supérieure de la lunette.  In a variant of the method of fixing the watch glass on a bezel of a watch case can be removed step No. 2 is the polishing of the upper face of the bezel.
Bien évidemment la lunette peut être remplacée par une carrure lunette ou toute autre partie de la boîte de montre sur laquelle la glace doit être fixée,  Of course, the telescope can be replaced by a case bezel or any other part of the watch case on which the ice must be fixed,
Une alternative consiste en l'utilisation d'un matériau rapporté en verre entre la glace et la carrure revêtues selon la figure 1 .  An alternative is the use of a glass material added between the ice and the middle part coated according to Figure 1.
Dans une forme d'exécution particulière du procédé de fixation d'une glace sur une boîte de montre on dépose la couche intermédiaire sur la face supérieure de la lunette par la technologie physique ou chimique évoquée précédemment et la composition de la matrice de cette couche intermédiaire est typiquement constituée de TixOy, SixOy, SixNy, de AlxOy ou des mélanges d'oxydes contenant des atomes / ions de métaux légers tels que Li, Na, K, Ca, Be, ou halogènes favorisant la migration des ions. In a particular embodiment of the process for fixing an ice on a watch case, the intermediate layer is deposited on the upper face of the bezel by the physical or chemical technology mentioned above and the composition of the matrix of this intermediate layer. typically consists of TixOy, SixOy, Si x N y , Al x O y or mixtures of oxides containing atoms / ions of light metals such as Li, Na, K, Ca, Be, or halogens promoting the migration of ions.
Pour un souci d'esthétisme, l'addition d'une couche mince métallique est possible avant la déposition de la couche intermédiaire afin de mieux garantir l'éclat et l'aspect métallique visuel sous la glace transparente. Celle-ci peut de par son choix augmenter l'adhésion entre la couche intermédiaire, la transition entre les matériaux pouvant même se faire de manière graduelle.  For the sake of aesthetics, the addition of a thin metal layer is possible before the deposition of the intermediate layer to better ensure the brightness and visual metallic appearance under the transparent ice. This can by its choice increase the adhesion between the intermediate layer, the transition between the materials can even be done gradually.
Dans une forme d'exécution particulière du procédé de fixation d'une glace sur une boîte de montre l'assemblage anodique s'effectue sous une tension inférieure à 15kV.  In a particular embodiment of the method of fixing an ice on a watch case the anode assembly is carried out under a voltage of less than 15kV.
Dans une forme d'exécution particulière du procédé, l'assemblage anodique s'effectuera sous une température inférieure à 250°C. La détermination de la nature de la ou des couches intermédiaires nécessite la qualification des matériaux à assembler typiquement sa composition physico-chimique, les propriétés mécaniques, l'état de surface, afin d'optimiser les caractéristiques du dépôt qui servira de première couche intermédiaire. Celle-ci étant qualifiée par les facteurs suivants: adhérence avec les matières premières, types de défauts et lacunes permettant la diffusion des ions et la migration, électronégativité des ions contenus au sein de la ou des couches intermédiaires, concentration en ions et en lacunes, orientation de ces mêmes lacunes. Au vu de l'ensemble des particularités que l'interface doit posséder, la ou les couches peuvent contenir des matériaux alcalins, alcalino-terreux et halogénés en raison de leurs facilités à migrer et de la taille de leurs atomes. In a particular embodiment of the process, the anode assembly will take place at a temperature below 250 ° C. Determining the nature of the intermediate layer or layers requires the qualification of the materials to be assembled typically its physico-chemical composition, mechanical properties, surface condition, in order to optimize the characteristics of the deposit which will serve as the first intermediate layer. This being qualified by the following factors: adhesion with the raw materials, types of defects and gaps allowing the diffusion of the ions and the migration, electronegativity of the ions contained within the intermediate layer (s), concentration of ions and gaps, orientation of these same gaps. In view of all the features that the interface must have, the layer or layers may contain alkaline, alkaline-earth and halogenated materials because of their ease of migration and the size of their atoms.
La ou les couches intermédiaires définiront la qualité du lien, ses propriétés mécaniques et l'étanchéité mais également ses propriétés esthétiques. Pour saisir l'importance de cette ou ces couches intermédiaires et pour différencier un assemblage selon la présente invention des techniques de soudure ou de brasure conventionnelles où il n'est pas question d'utilisation d'un champ électrique, il s'agit de comprendre les transferts atomiques spécifiques lors du processus de l'assemblage anodique.  The intermediate layer (s) will define the quality of the bond, its mechanical properties and the seal, but also its aesthetic properties. To grasp the importance of this or these intermediate layers and to differentiate an assembly according to the present invention from conventional soldering or brazing techniques where there is no question of using an electric field, it is a matter of understanding specific atomic transfers during the process of anodic assembly.
Toute particule chargée placée sous l'influence d'un champ électrique uniforme se déplace à une vitesse proportionnelle à ce champ, le facteur de proportionnalité étant appelé la mobilité électrique de la particule. Cette migration va s'effectuer de l'anode vers la cathode pour les particules chargées positivement, dans le sens opposé pour les particules chargées négativement. Sous l'effet de la migration des ions, on observe une différence de potentiel entre les partenaires, ce qui engendre un plaquage entre les partenaires induit sous l'effet de forces électrostatiques. Si ce plaquage est insuffisant, l'application d'une charge mécanique pour forcer le contact entre les partenaires est envisagée. Le champ électrique augmente le processus de diffusion, les vitesses d'assemblages sont réduites de l'ordre de quelques minutes, ce qui encourage un rendement accru et une meilleure reproductibilité. Any charged particle placed under the influence of a uniform electric field moves at a rate proportional to this field, the proportionality factor being called the electric mobility of the particle. This migration will take place from the anode to the cathode for the positively charged particles, in the opposite direction for the negatively charged particles. Under the effect of ion migration, there is a potential difference between the partners, which causes a plating between the induced partners under the effect of electrostatic forces. If this plating is insufficient, the application of a mechanical load to force contact between the partners is considered. The electric field increases the diffusion process, the assembly speeds are reduced by a few minutes, which encourages increased yield and reproducibility.
La perturbation de l'équilibre thermodynamique influence les populations de porteurs de charge localisés au sein des pièces à assembler et de la couche intermédiaire. Les origines des perturbations peuvent être:  Disturbance of the thermodynamic equilibrium influences the populations of charge carriers located in the parts to be assembled and the intermediate layer. The origins of the disturbances can be:
- les inhomogénéités de dopage, d'impuretés, de défauts structuraux et les déformations locales (principalement au voisinage de surface), des contacts et des jonctions  - inhomogeneities of doping, impurities, structural defects and local deformations (mainly near the surface), contacts and junctions
- les forces de champ électrique  - electric field strengths
- les gradients de température.  - the temperature gradients.
Lorsque le champ électrique ainsi que la température sont interrompues, les porteurs de charges tendent vers un état d'équilibre correspondant à des régimes permanents définis par des conditions initiales et aux bords, selon des mécanismes typiques :  When the electric field and the temperature are interrupted, the charge carriers tend towards a state of equilibrium corresponding to permanent regimes defined by initial conditions and at the edges, according to typical mechanisms:
- la diffusion des porteurs dans des gradients de concentration  - the diffusion of carriers in concentration gradients
- le déplacement des porteurs dans des champs électriques internes  - the movement of carriers in internal electric fields
- la génération et la recombinaison de porteurs qui peuvent être intrinsèques ou faire intervenir des centres de recombinaison et des pièges.  the generation and recombination of carriers that may be intrinsic or involve recombination centers and traps.
Les propriétés relatives aux courants électriques et aux déplacements de porteurs de charge sous l'influence de forces appliquées sont appelées phénomènes de transport. Parmi les phénomènes de transport, la mobilité, qu'elle soit par exemple des lacunes, des impuretés, des porteurs de charges (les matériaux sont différentiés par la longueur de Debye des porteurs majoritaires et leur comportement est notamment décrit par l'équation de continuité) ainsi que la diffusion (basée sur les lois de Fick) sont les mécanismes clés d'assemblage anodique.  The properties relating to electric currents and to the displacement of charge carriers under the influence of applied forces are called transport phenomena. Among the transport phenomena, mobility, whether it be for example gaps, impurities, charge carriers (the materials are differentiated by the Debye length of the majority carriers and their behavior is described in particular by the continuity equation ) as well as diffusion (based on Fick's laws) are the key mechanisms of anodic assembly.
Les paramètres qui influencent le plus la mobilité des porteurs de charge sont la température et le nombre volumique d'impuretés. Parmi les défauts on peut distinguer les impuretés et les lacunes. Il s'agit de ces mêmes lacunes, défauts de Schottky ou de Frenkel entre autres qui facilitent la diffusion des porteurs de charges et qui définissent l'énergie nécessaire à leur diffusion. De plus déplacer une lacune à travers un cristal demande beaucoup moins de travail que de contraindre un ion à se déplacer à travers un réseau d'ion dense d'un cristal. La conduction ionique dépend du mouvement des lacunes. Les impuretés qui contribuent à la densité de porteurs de charge sont appelées « donneurs » si elles apportent des électrons supplémentaires et « accepteurs » si elles apportent des trous supplémentaires. A noter que la vitesse du phénomène de l'assemblage anodique dépend de la quantité de défauts et de la température notamment. The parameters which most influence the mobility of the charge carriers are the temperature and the volume number of impurities. Among the defects we can distinguish impurities and gaps. These are the same gaps, Schottky or Frenkel defects, among others, which facilitate the diffusion of charge carriers and which define the energy necessary for their diffusion. Moreover, moving a gap through a crystal requires much less work than constraining an ion to move through a dense ion network of a crystal. Ion conduction depends on the movement of the gaps. The impurities that contribute to the charge carrier density are called "donors" if they bring additional electrons and "acceptors" if they bring additional holes. It should be noted that the speed of the phenomenon of the anode assembly depends on the quantity of defects and the temperature in particular.
Le choix de la ou des couches intermédiaires dépend fortement des « propriétés » des porteurs de charge. La composition chimique de la ou des couches est naturellement importante puisque les phénomènes de transport dépendent des caractéristiques des liaisons atomiques. Les liaisons créées lors du processus d'assemblage anodique sont des liaisons de type covalentes majoritairement. Ces liaisons fortes s'établissent par la mise en commun d'une paire d'électrons issus de chacun des porteurs de charges.  The choice of the intermediate layer or layers depends strongly on the "properties" of the charge carriers. The chemical composition of the layer or layers is naturally important since the transport phenomena depend on the characteristics of the atomic bonds. The bonds created during the anodic assembly process are predominantly covalent bonds. These strong links are established by pooling a pair of electrons from each of the charge carriers.
Il faut donc prendre en compte les mécanismes permettant l'assemblage anodique ainsi que la nature des pièces à assembler pour déterminer la constitution de la ou des couches intermédiaires. La méthode de déposition PVD est privilégiée, mais une couche intermédiaire (mono ou multicouche) peut être déposée par un autre procédé de déposition physique ou chimique.  It is therefore necessary to take into account the mechanisms allowing the anodic assembly as well as the nature of the parts to be assembled to determine the constitution of the intermediate layer or layers. The PVD deposition method is preferred, but an intermediate layer (mono or multilayer) may be deposited by another physical or chemical deposition process.
La température et la tension appliquée ainsi que le temps de contact sont étroitement liés et complémentaires puisqu'ils contrôlent la force électrostatique nécessaire pour la réaction chimique entre les pièces à assembler. Ainsi, de préférence, la tension n'ira pas au-delà de 15 kV, et la température ne dépasse pas les 250°C.  The temperature and the applied voltage as well as the contact time are closely related and complementary since they control the electrostatic force required for the chemical reaction between the parts to be assembled. Thus, preferably, the voltage will not go beyond 15 kV, and the temperature does not exceed 250 ° C.
D'autres paramètres ont leurs importances telles que l'épaisseur des pièces à assembler ainsi que l'épaisseur de la zone de déplétion. Les limitations d'épaisseurs dépendent des tolérances au plan des lunettes et des glaces et sont comprises entre 10-10000 angstrôms. Other parameters have their importance such as the thickness of the parts to be assembled and the thickness of the depletion zone. Limitations Thicknesses depend on glasses and ice tolerances and are between 10-10000 angstroms.
Il est à noter que l'écart entre les pièces à assembler a un effet significatif sur la grandeur de la force électrostatique, ce qui implique que la qualité de la liaison formée par assemblage anodique dépend aussi de l'état de surface. Ainsi des processus de finition mécaniques de la surface de contact additionnée, en fonction de la matière, de polissage électrochimique est utilisé.  It should be noted that the gap between the parts to be assembled has a significant effect on the magnitude of the electrostatic force, which implies that the quality of the bond formed by anodic assembly also depends on the surface condition. Thus, mechanical finishing processes of the electrochemically polished, electrochemically polished surface of the contact surface are used.
Quelle que soit la pièce sur laquelle le dépôt est effectué, des complications d'ordre esthétique sont évitées par la couleur intrinsèque des couches et de l'assemblage des couches, le cas échéant le dépôt de couche mimant la matière de la lunette est déposé sur la glace avant le dépôt de couche fonctionnelle. Un tel dépôt est sélectif, masquant la zone d'assemblage, avec une fonction esthétique.  Whatever the part on which the deposit is made, aesthetic complications are avoided by the intrinsic color of the layers and the assembly of the layers, where appropriate the layer deposition mimicking the material of the bezel is deposited on ice before functional layer deposition. Such a deposit is selective, masking the assembly area, with an aesthetic function.
Cette sélectivité est obtenue par technique de masquage, typiquement par lithographie, stamping, décapage sélectif ou par promotion d'adhérence.  This selectivity is obtained by masking technique, typically by lithography, stamping, selective etching or by promoting adhesion.
Le rendu optique, couleur aspect de surface, est obtenu par une adaptation des couches, notamment par leur épaisseur, leur composition et leurs prétraitements.  The optical rendering, surface appearance color, is obtained by an adaptation of the layers, in particular by their thickness, their composition and their pretreatments.

Claims

REVENDICATIONS
1 . Procédé de fixation d'une glace sur une boîte de montre selon lequel : 1. A method of fixing an ice on a watch case according to which:
on appose par traitement de surface sur une zone de la surface de la glace destinée à entrer en contact avec une zone correspondante de la boîte de montre et/ou sur ladite zone correspondante de la boîte de montre au moins une couche intermédiaire mince permettant la migration des ions et/ou des électrons ;  is applied by surface treatment on an area of the surface of the ice intended to come into contact with a corresponding zone of the watch case and / or on said corresponding zone of the watch case at least one thin intermediate layer allowing migration ions and / or electrons;
on applique ces zones de la boîte de montre et de la glace l'une contre l'autre ;  these areas of the watch case and ice are applied against each other;
on chauffe l'ensemble boîte de montre-glace à une température de chauffage suffisamment basse pour garantir qu'aucun matériau du système ne quitte sa phase solide ; et on connecte la glace à une électrode et la boîte de montre à une contre-électrode et applique entre cette électrode et cette contre-électrode une tension accélérant la diffusion des particules chargées et créant ainsi de nouvelles liaisons métalliques, ioniques ou covalentes.  the icebox assembly is heated to a sufficiently low heating temperature to ensure that no material in the system leaves its solid phase; and connecting the ice to an electrode and the watch case to a counter-electrode and applying between the electrode and the counter electrode a voltage accelerating the diffusion of the charged particles and thereby creating new metallic, ionic or covalent bonds.
2. Procédé selon la revendication 1 , caractérisé par le fait que la tension est une tension DC entre 1 kV et 15kV. 2. Method according to claim 1, characterized in that the voltage is a DC voltage between 1 kV and 15kV.
3. Procédé selon l'une des revendications précédentes, caractérisé par le fait que la température de chauffage n'excède pas 250°C et/ou qu'elle varie entre 120°C et 250°C. 3. Method according to one of the preceding claims, characterized in that the heating temperature does not exceed 250 ° C and / or it varies between 120 ° C and 250 ° C.
4. Procédé selon l'une des revendications précédentes, selon lequel, avant d'appliquer lesdites zones de la boîte de montre et de la glace l'une contre l'autre, on dispose une couche d'un élément semi-conducteur ou isolant favorisant la migration tel que des verres, des siliciums entre ladite zone de la glace et ladite zone de la boîte de montre. 4. Method according to one of the preceding claims, wherein, before applying said zones of the watch case and the ice against each other, there is a layer of a semiconductor or insulating element. promoting migration such as glasses, silicas between said ice zone and said zone of the watch case.
5. Procédé selon la revendication 4, caractérisé par le fait que l'élément semiconducteur ou isolant est rapporté par une pièce séparée ou déposé par voie physique ou chimique (PVD, PE-CVD, Sol-gel, galvanoplastie). 5. Method according to claim 4, characterized in that the semiconductor or insulating element is reported by a separate part or deposited by physical or chemical means (PVD, PE-CVD, Sol-gel, electroplating).
6. Procédé selon l'une des revendications précédentes, caractérisé par le fait que ladite au moins une couche intermédiaire comprend une couche apposée sur la glace et présentant une évolution chimique et structurelle, la partie en contact avec la glace étant de nature purement métallique et au fur et à mesure de sa croissance, son degré d'oxydation évolue de manière progressive pour se terminer en surface avec un état d'oxydation complet ΤΊΟ2. 6. Method according to one of the preceding claims, characterized in that said at least one intermediate layer comprises a layer affixed to the ice and having a chemical and structural evolution, the part in contact with the ice being purely metallic in nature and as it grows, its degree of oxidation evolves gradually and ends at the surface with a complete oxidation state ΤΊΟ2.
7. Procédé selon l'une des revendications précédentes, caractérisé par le fait que chaque électrode a une géométrie adaptée à la surface avec laquelle elle est en contact. 7. Method according to one of the preceding claims, characterized in that each electrode has a geometry adapted to the surface with which it is in contact.
8. Procédé selon la revendication 7, caractérisé par le fait que la géométrie de l'électrode en contact avec la glace est de forme incurvée, exempte de pointes. 8. Method according to claim 7, characterized in that the geometry of the electrode in contact with the ice is of curved shape, free of spikes.
9. Procédé selon l'une des revendications précédentes, caractérisé par le fait que ladite au moins une couche intermédiaire possède une stœchiométrie non constante, le degré d'oxydation de nitruration ou de cémentation variant avec l'épaisseur de la couche. 9. Method according to one of the preceding claims, characterized in that said at least one intermediate layer has a non-constant stoichiometry, the degree of nitriding oxidation or cementation varying with the thickness of the layer.
10. Procédé selon l'une des revendications précédentes, caractérisé par le fait que ladite au moins une couche intermédiaire comprend une couche mince apposée sur la boîte et contenant une couche de passivation naturelle ou forcée. 10. Method according to one of the preceding claims, characterized in that said at least one intermediate layer comprises a thin layer affixed to the box and containing a natural or forced passivation layer.
1 1 . Procédé selon l'une des revendications précédentes, caractérisé par le fait ladite au moins une couche intermédiaire comprend une couche de masquage déposée sur la glace afin de masquer sa zone de contact, cette couche étant constituée d'éléments métalliques et des alliages d'au moins un des éléments suivants : Ti, Fe, Al, Cr, V, Pt, Ta, W, Ga, Sn, Zn, Au et Ag. 1 1. Method according to one of the preceding claims, characterized in that said at least one intermediate layer comprises a masking layer deposited on the ice in order to mask its contact zone, this layer consisting of metallic elements and alloys of at least one of Ti, Fe, Al, Cr, V, Pt, Ta, W, Ga, Sn, Zn, Au and Ag.
12. Procédé selon l'une des revendications précédentes, caractérisé par le fait que la glace est constituée d'au moins un des éléments suivants: d'oxyde d'aluminium comme le saphir, de spinelle, AION spinelle d'oxynitride d'aluminium, d'yttria, d'YAG (Yttrium Aluminium Garnet) et Nd:YAG ou d'oxyde de silicium comme le verre minéral ou le pyrex. 12. Method according to one of the preceding claims, characterized in that the ice consists of at least one of the following elements: aluminum oxide such as sapphire, spinel, AION spinel aluminum oxynitride , yttria, YAG (Yttrium Aluminum Garnet) and Nd: YAG or silicon oxide such as mineral glass or pyrex.
13. Procédé selon l'une des revendications précédentes, caractérisé par le fait que la rugosité de surface de la boîte est obtenue par un usinage mécanique ou un étampage fin additionné d'un électro polissage chimique. 13. Method according to one of the preceding claims, characterized in that the surface roughness of the box is obtained by mechanical machining or fine stamping plus a chemical electro polishing.
14. Boîte de montre obtenue par le procédé selon l'une des revendications 14. Watch case obtained by the method according to one of the claims
précédentes.  preceding.
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