EP0844539A1 - Decorative element particularly component of a timepiece - Google Patents

Decorative element particularly component of a timepiece Download PDF

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Publication number
EP0844539A1
EP0844539A1 EP96118796A EP96118796A EP0844539A1 EP 0844539 A1 EP0844539 A1 EP 0844539A1 EP 96118796 A EP96118796 A EP 96118796A EP 96118796 A EP96118796 A EP 96118796A EP 0844539 A1 EP0844539 A1 EP 0844539A1
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EP
European Patent Office
Prior art keywords
decorative element
substrate
element according
hard
layer
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Granted
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EP96118796A
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German (de)
French (fr)
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EP0844539B1 (en
Inventor
Michael Bach
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Rado Uhren AG
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Rado Uhren AG
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Application filed by Rado Uhren AG filed Critical Rado Uhren AG
Priority to EP96118796A priority Critical patent/EP0844539B1/en
Priority to DE69630792T priority patent/DE69630792T2/en
Priority to TW086115393A priority patent/TW346557B/en
Priority to KR1019970055762A priority patent/KR100547850B1/en
Priority to US08/966,481 priority patent/US6123450A/en
Priority to JP32085797A priority patent/JP4476371B2/en
Priority to CNB971141363A priority patent/CN1161673C/en
Priority to SG1997004122A priority patent/SG67443A1/en
Publication of EP0844539A1 publication Critical patent/EP0844539A1/en
Priority to HK98115089A priority patent/HK1013779A1/en
Application granted granted Critical
Publication of EP0844539B1 publication Critical patent/EP0844539B1/en
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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
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • 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
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • G04B37/223—Materials or processes of manufacturing pocket watch or wrist watch cases metallic cases coated with a nonmetallic layer

Definitions

  • the present invention relates to a decorative element comprising a surface coated with a protective layer and decorative in hard material, more particularly a component of a timepiece having a layer of hard material which is not very rough and which can be if necessary, polished without undue difficulty.
  • patent EP-A-0 199 207 it has already been proposed to make decorative elements such as a box of watch, including parts of the visible outer surface, likely to come into contact with foreign bodies, for example the upper sides of the box, have a unalterable aspect, that is to say that they can neither be scratched in contact with such bodies, nor oxidize or tarnish on contact with air so that it is possible to give these parts of the box a fine appearance and neat.
  • the cited patent proposes the use of metal carbide inserts (carbide tungsten or titanium carbide) coated with polycrystalline diamond layer having a thickness typically between 0.4 and 0.8 mm, these plates being attached to the watch case by gluing or welding.
  • the platelets are obtained from pellets of maximum diameter equal to 51 mm.
  • the manufacture of such lozenges requires the use of the equivalent around 4000 diamonds, the equivalent of 16.5 carats. These diamonds are first processed into powder and the powder is sintered at around 1,500 ° C and at a pressure of around 5,000 MPa on a hard metal substrate (carbide metallic). The pellets are then sanded and planned using a discharge process electric, and finally polished during a long process of polishing with diamond wheels. Then the lozenges are carefully selected, especially when these pastilles are intended for the realization of parts or components of wristwatches, in order to control the thickness and appearance visual, in particular the homogeneity of the color of the layer diamond. The pellets obtained are then machined, to using methods known as EDM machining or laser machining, in their form final to obtain the desired plate or ring. Finally, the sharp edges of the insert are removed during a final chamfering operation using of a diamond wheel.
  • the quantity of diamond powder and the amount of energy required to transform the powder by sintering, polish the diamond layer obtained, machine and chamfer the pellet to obtain a wafer finished are such that the cost price of the pellet is very high and leads to increasing so prohibitive the cost of products in which are integrated such plates.
  • this process requires the use of a sintered hard metal substrate comprising cobalt as binder for reasons of adhesion with the powder diamond.
  • cobalt as a binder in the substrate makes the latter easily oxidizable, which requires the deposition of a protective layer on the substrate and further increases the cost price of the pastille.
  • the topography of the layer obtained according to this process presents a multitude of microcrystals of diamond with dimensions of the order of 5 ⁇ m, in shape parallelepipedic with extremely hard edges (of around 10,000 Vickers) and extremely resistant to wear.
  • This hardness and high wear resistance are due to the almost exclusive presence of type bond SP3 between the carbon atoms that form the layer diamond.
  • the multitude of well-defined edges on the surface of these diamond layers therefore forms a multitude of anchor points for rubbed material.
  • a stripe of a commonly used material, i.e. soft compared to diamond leaves traces visible on the surface of the hard layer, which cannot be eliminated completely, for example using a simple means, such as a damp cloth, available of all consumers.
  • the main aim of the invention is therefore to remedy the disadvantages of the aforementioned prior art in providing a decorative element, particularly a component of a timepiece, comprising a surface layer of a very large material hardness having a microcrystalline structure and having a very regular topography and very little abrasive.
  • the subject of the invention is an element decorative comprising at least one coated substrate partially with a protective and decorative layer in hard material, characterized in that the hard material of said layer has a microcrystalline structure and a outer surface with a regular topography of the cauliflower type.
  • the hard layer has the advantage not to have sharp edges or deep hollows, even before polishing the surface of this layer.
  • the marks left of softer material deposits at the surface of the coating following a scratch can thus be easily reduced or even eliminated by a means simple, such as a cloth or finger, available to any consumer. Note that we can advantageously use such unpolished coatings without fear of mark the surface of the coating almost indelibly as was the case in interior art.
  • the hard material layer is specularly polished.
  • the hard material is diamond or nitride cubic boron.
  • the surface hardness of covered surfaces is around 8,000 HV, which leads to abrasion resistance four times superior to that of diamond art coatings which have hardnesses of the order of 6,000 to 8,000 HV.
  • a decorative element according to the invention now goes be described in detail as part of an application to the production of a component part of watchmaking and more particularly of a bezel of a wristwatch shown in Figure 1 and designated by the general reference number 1.
  • Wristwatch 1 includes four pieces main: an inner middle 2, a bezel 4, a glass 6 and a back 8.
  • the inner middle 2 and the glasses 4 have shapes which are determined from so that the manufacturing operations are simplified and those of assembly facilitated.
  • the inner middle part 2 is made of a metal easily machinable, for example stainless steel.
  • the middle 2 which is intended to contain a movement 10 surmounted by a dial 12 includes an upper part 14 and a lower part 16.
  • the lower part 16 surrounds and carries movement 10 and dial 12 of a classic way which will not be described further in detail.
  • the bottom 8 is also fixed to the part lower 16 conventionally through a seal 18.
  • the middle part 2 is fixed to the bezel 4 by a ring 20 of deformable material engaged in a radial clearance provided between facing coaxial cylindrical surfaces 22, 24 case 2 and bezel 4 respectively.
  • the glass 6 is fixed in the opening of the bezel 4 by means of an intermediate seal 26 and is not supported on the upper face 28 of the middle part interior 2.
  • the outer surface 30 of the bezel 4, which is in the embodiment describes the surface to be coated of hard material, includes a first parallel face 32 on the dial plane.
  • the face 32 is extended by a second side 34 frustoconical, then by a third side lateral circular 36 perpendicular to the plane of the dial.
  • the sides 32, 34, and 36 of the bezel are coated according to the invention a thin layer 38 of material very hard such as a layer of diamond or boron nitride.
  • layer 38 has a thickness of between 1 and 20 micrometers and a hardness of the order of 8,000 to 10,000 HV.
  • a method will be described below for carrying out a component of a timepiece according to the invention such as the telescope 4 on a certain part of which we are going to deposit a layer of diamond having a microcrystalline structure and surface topography cauliflower type.
  • the substrate has a hardness greater than 800 HV, and typically a metal substrate hard sintered or ceramic is quite suitable. In effect if the substrate material is too soft, shock on the thin layer 38 will cause deformation of the substrate and in most cases a crack in the layer 38, due to poor properties elastic.
  • a metal substrate hard preferably a hard stainless metal such as than a sintered hard metal based on tungsten carbide or of titanium carbide, these carbides being bonded using metallic binders such as nickel, chromium, cobalt or molybdenum or a mixture thereof.
  • the surfaces to be coated are subjected to a surface treatment in order to reduce the concentration of binder on the surface (over a few tens of micrometers).
  • this surface treatment can consist of a vacuum heat treatment during which the binder on the surface evaporates, or alternatively a chemical treatment in a solution of H 2 SO 4 / H 2 O 2 at a respective concentration of 5% and 35%.
  • ceramics having high impact resistance based on carbide or nitride.
  • ceramic based on carbide silicon and / or silicon nitride will be appropriate.
  • Oxide-based ceramic substrates can also be used, however prior treatment to obtain a carbide on the surface which must be coated is required.
  • this treatment may consist of heat treatment in an atmosphere controlled, chemical or plasma treatment.
  • the substrate is introduced into the enclosure of a phase chemical deposition installation steam, the substrate being arranged on a suitable assembly to deposit a layer of diamond and obtain a layer having a topography or structure of the type cauliflower.
  • a method for obtaining such a layer is described in detail in the publication called “The role of hydrogen in diamond synthesis from carbon dioxide-hydrocarbon gases by micro wave plasma chemical vapor deposition "by Chia-Fu Chen and Tsao-Ming hong, published in 1992 in Surface and Coatings Technology 54/55, pages 368 to 373, which is incorporated here in its entirety by reference. It is understood that any other method for depositing layers of hard material having a structure or topography of the type cauliflower on a substrate are possible.
  • the surface of the diamond layer obtained has a topography comprising an agglomerate of microglobules, as shown in Figure 4 which represents a micrograph of the surface of a diamond layer of the type cauliflower at a magnification of 2,000 times.
  • Figure 4 represents a micrograph of the surface of a diamond layer of the type cauliflower at a magnification of 2,000 times.
  • the bonds between the carbon atoms are almost exclusively of type SP3 and having a hardness of around 10,000 HV
  • the cauliflower type diamond layers used in the decorative element according to the invention comprises a high proportion of carbon atoms linked by SP2 type bonds with a low proportion of bonds type SP3 and have a hardness of the order of 8,000 HV.
  • This mixture of carbon-carbon bonds of the type SP3 and SP2 is in fact a fault which appears during the growth formation on the substrate surface of the layer of diamond and which leads to a structure in slightly rough microglobules such as those shown in Figure 4.
  • the cauliflower-like layer therefore has a primary advantage in use on element constituting a timepiece, namely that the hard coat can be specularly polished using a diamond wheel without excessive difficulty.
  • the decorative element according to the invention is not limited to the production of an element constituting a timepiece described above and than other decorative elements such as the link bracelet 38 shown in Figure 2 can be considered.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Vapour Deposition (AREA)
  • Powder Metallurgy (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Adornments (AREA)
  • Physical Vapour Deposition (AREA)
  • Electric Clocks (AREA)

Abstract

The wrist watch comprises four main pieces: an internal frame (2), an outer frame (4), a glass (6) and a base (8). The internal frame is made of a machined metal such as stainless steel and contains the mechanism. A part of the outer frame (4) is coated with a diamond layer having a micro-crystalline structure and 'cauliflower' type surface. This coating may be applied to specific surfaces of the frame (32,24,26). The coating offers a surface hardness of more than 800 HV, and is applied to a substrate of hard sintered metal or ceramic. If the material is too soft, then a shock to the outer casing can cause a fracture, since the outer thin coating does not have the elasticity which a soft substrate offers. If a metal substrate is used, then hard stainless steel may be used, sintered with tungsten carbide or titanium carbide, the carbides being attached with the aid of softer metals such as nickel, chromium, cobalt, molybdenum or a mixture of these.

Description

La présente invention concerne un élément décoratif comprenant une surface revêtue d'une couche protectrice et décorative en matériau dur, plus particulièrement un élément constitutif d'une pièce d'horlogerie ayant une couche de matériau dur peu rugueuse et qui peut être, le cas échéant, polie sans difficulté excessive.The present invention relates to a decorative element comprising a surface coated with a protective layer and decorative in hard material, more particularly a component of a timepiece having a layer of hard material which is not very rough and which can be if necessary, polished without undue difficulty.

Dans le brevet EP-A-0 199 207, on a déjà proposé de réaliser des éléments décoratifs tels qu'une boíte de montre, dont des parties de la surface extérieure visible, susceptibles de venir en contact avec des corps étrangers, par exemple les faces supérieures de la boíte, ont un aspect inaltérable, c'est-à-dire qu'elles ne peuvent ni être rayées au contact de tels corps, ni s'oxyder ou se ternir au contact de l'air, de façon qu'il soit possible de donner à ces parties de la boíte une apparence fine et soignée. Pour parvenir à ce but, le brevet cité propose de l'utilisation de plaquettes de carbure métallique (carbure de tungstène ou carbure de titane) recouvertes d'une couche de diamant polycristallin présentant une épaisseur typiquement comprise entre 0,4 et 0,8 mm, ces plaquettes étant rapportées sur la boíte de montre par collage ou soudage.In patent EP-A-0 199 207, it has already been proposed to make decorative elements such as a box of watch, including parts of the visible outer surface, likely to come into contact with foreign bodies, for example the upper sides of the box, have a unalterable aspect, that is to say that they can neither be scratched in contact with such bodies, nor oxidize or tarnish on contact with air so that it is possible to give these parts of the box a fine appearance and neat. To achieve this goal, the cited patent proposes the use of metal carbide inserts (carbide tungsten or titanium carbide) coated with polycrystalline diamond layer having a thickness typically between 0.4 and 0.8 mm, these plates being attached to the watch case by gluing or welding.

Les plaquettes sont obtenues à partir de pastilles de diamètre maximum égal à 51 mm. La fabrication de telles pastilles nécessite l'utilisation de l'équivalent d'environ 4000 diamants soit l'équivalent de 16,5 carats. Ces diamants sont tout d'abord transformés en poudre et la poudre est frittée à environ 1'500°C et à une pression de l'ordre de 5'000 MPa sur un substrat en métal dur (carbure métallique). Les pastilles sont ensuite sablées et planéifiées en ayant recours à un procédé à décharge électrique, et enfin polies au cours d'un long procédé de polissage à l'aide de meules à diamants. Ensuite les pastilles sont soigneusement sélectionnées, en particulier lorsque ces pastilles sont destinées à la réalisation d'éléments ou de parties constitutives de montres-bracelets, afin de contrôler l'épaisseur et l'aspect visuel, notamment l'homogénéité de la couleur de la couche de diamant. Les pastilles obtenues sont ensuite usinées, à l'aide de procédés connus comme l'usinage par électroérosion ou encore l'usinage au laser, dans leur forme finale pour obtenir la plaquette ou l'anneau désiré. Enfin, les arêtes vives de la plaquette sont supprimées au cours d'une dernière opération de chanfreinage à l'aide d'une meule à diamants.The platelets are obtained from pellets of maximum diameter equal to 51 mm. The manufacture of such lozenges requires the use of the equivalent around 4000 diamonds, the equivalent of 16.5 carats. These diamonds are first processed into powder and the powder is sintered at around 1,500 ° C and at a pressure of around 5,000 MPa on a hard metal substrate (carbide metallic). The pellets are then sanded and planned using a discharge process electric, and finally polished during a long process of polishing with diamond wheels. Then the lozenges are carefully selected, especially when these pastilles are intended for the realization of parts or components of wristwatches, in order to control the thickness and appearance visual, in particular the homogeneity of the color of the layer diamond. The pellets obtained are then machined, to using methods known as EDM machining or laser machining, in their form final to obtain the desired plate or ring. Finally, the sharp edges of the insert are removed during a final chamfering operation using of a diamond wheel.

La réalisation de ces plaquettes présente de nombreux inconvénients.The production of these brochures presents many disadvantages.

En effet, la quantité de poudre de diamant et la quantité d'énergie nécessaire pour transformer la poudre par frittage, polir la couche de diamant obtenue, usiner et chanfreiner la pastille afin obtenir une plaquette finie sont telles que le prix de revient de la pastille est très élevé et conduit à augmenter de manière prohibitive le coût des produits dans lesquels sont intégrées de telles plaquettes.Indeed, the quantity of diamond powder and the amount of energy required to transform the powder by sintering, polish the diamond layer obtained, machine and chamfer the pellet to obtain a wafer finished are such that the cost price of the pellet is very high and leads to increasing so prohibitive the cost of products in which are integrated such plates.

Un autre inconvénient de ce procédé consiste en qu'il n'est pas possible de d'obtenir des pastilles de couleur exactement identique, si bien que les plaquettes utilisées pour une montre-bracelet doivent provenir d'une même pastille. Cela limite donc pratiquement l'utilisation de telles pastilles à la réalisation de lunettes de montre ou à des plaquettes conformes à ce qui est représenté aux figures 2 et 3 du brevet EP-A-0 199 207.Another disadvantage of this process is that it it is not possible to obtain colored discs exactly the same, so that the pads used for a wristwatch must come from the same pastille. This therefore practically limits the use of such lozenges for the production of watch glasses or to plates conforming to what is shown in Figures 2 and 3 of patent EP-A-0 199 207.

Par ailleurs, ce procédé nécessite l'utilisation d'un substrat en métal dur fritté comprenant le cobalt comme liant pour des raisons d'adhérence avec la poudre de diamant. Or la présence de cobalt en tant que liant dans le substrat rend ce dernier facilement oxydable, ce qui nécessite le dépôt d'une couche de protection sur le substrat et augmente encore le prix de revient de la pastille. Furthermore, this process requires the use of a sintered hard metal substrate comprising cobalt as binder for reasons of adhesion with the powder diamond. The presence of cobalt as a binder in the substrate makes the latter easily oxidizable, which requires the deposition of a protective layer on the substrate and further increases the cost price of the pastille.

De plus, de par sa nature ce procédé de formation d'une couche de diamant par compression et frittage est limité à la réalisation de plaquettes de surface plane et de formes géométriques relativement simples.In addition, by its nature this training process of a layer of diamond by compression and sintering is limited to the production of flat surface plates and relatively simple geometric shapes.

Il a été déjà envisagé d'autres procédés pour revêtir des substrats avec couches de matériaux durs. On connaít notamment du document US 4'734'339 un procédé de dépôt chimique en phase vapeur d'une couche de diamant sur un substrat pour réaliser des outils de coupe. La topographie des couches de diamant obtenues selon ce procédé est mate, rugueuse et irrégulière, de sorte que ces couches agissent comme une lime sur les matériaux d'usage courant avec lesquels elles peuvent venir en contact.Other methods for coating have already been considered substrates with layers of hard materials. We know in particular from document US 4,734,339, a deposition process chemical vapor phase of a diamond layer on a substrate for making cutting tools. Topography diamond layers obtained according to this process is matt, rough and irregular, so these layers act like a file on everyday materials with which they can come in contact with.

En effet, la topographie de la couche obtenue selon ce procédé présente une multitude de microcristaux de diamant ayant des dimensions de l'ordre de 5 µm, de forme parallélipipédique avec des arêtes extrêmement dures (de l'ordre de 10'000 Vickers) et extrêmement résistantes à l'usure. Cette dureté et cette résistance à l'usure élevée sont dues à la présence quasi exclusive de liaison du type SP3 entre les atomes de carbone qui forment la couche diamant. La multitude d'arêtes bien définies à la surface de ces couches de diamant, forme donc une multitude de points d'ancrage pour un matériau frotté. Un rayage d'un matériau d'usage courant, c'est à dire tendre par rapport au diamant, a pour conséquence de laisser des traces visibles sur la surface de la couche dure, qui ne peuvent être éliminées complètement, par exemple à l'aide d'un moyen simple, tel qu'un chiffon humide, à la disposition de tous les consommateurs.Indeed, the topography of the layer obtained according to this process presents a multitude of microcrystals of diamond with dimensions of the order of 5 µm, in shape parallelepipedic with extremely hard edges (of around 10,000 Vickers) and extremely resistant to wear. This hardness and high wear resistance are due to the almost exclusive presence of type bond SP3 between the carbon atoms that form the layer diamond. The multitude of well-defined edges on the surface of these diamond layers, therefore forms a multitude of anchor points for rubbed material. A stripe of a commonly used material, i.e. soft compared to diamond, leaves traces visible on the surface of the hard layer, which cannot be eliminated completely, for example using a simple means, such as a damp cloth, available of all consumers.

On comprend donc aisément qu'une application de telles couches dures à un objet décoratif tel qu'une boíte de montre ou un bracelet ne peut pas être envisagée. En effet, il n'est pas admissible pour un consommateur ayant l'impression d'avoir acquis un objet "inrayable" de voir des marques laissées sur son objet par un rayage d'un autre matériau plus tendre. It is therefore easy to understand that an application of such hard layers to a decorative object such as a box watch or bracelet cannot be considered. In indeed, it is not eligible for a consumer having the impression of having acquired a "scratchproof" object of seeing marks left on its object by a striping of a other softer material.

Cet inconvénient peut être atténué sans être éliminé en procédant à un polissage de la couche obtenue. Toutefois, le polissage de telles couches est long et coûteux dans la mesure où les arêtes à éliminer sont les parties les plus dures de la couche. L'élimination des arêtes pour obtenir une topographie plus régulière par polissage est une opération économiquement prohibitive et par conséquent peu réaliste.This disadvantage can be mitigated without being eliminated by polishing the layer obtained. However, the polishing of such layers is long and costly since the edges to be removed are the hardest parts of the diaper. Elimination of edges to obtain a more regular topography by polishing is an economically prohibitive operation and therefore unrealistic.

On notera à ce propos que le polissage d'une telle surface facettée est contraire au but recherché pour une application de la couche de diamant aux outils de coupe, pour laquelle il est souhaitable d'augmenter le plus possible l'abrasion de la couche. Ceci va bien entendu à l'encontre de la réalisation d'une surface ayant une topographie facilement polissable qui pourrait être appliquée à la réalisation d'un élément décoratif.Note in this connection that the polishing of such faceted surface is contrary to the goal sought for a applying the diamond layer to the cutting tools, for which it is desirable to increase the most possible abrasion of the diaper. This goes of course to against achieving a surface with a easily polishable topography which could be applied to the production of a decorative element.

L'invention a donc pour but principal de remédier aux inconvénients de l'art antérieur susmentionné en fournissant un élément décoratif, particulièrement un élément constitutif d'une pièce d'horlogerie, comportant une couche superficielle en un matériau à très grande dureté ayant une structure microcristalline et ayant une topographie très régulière et très peu abrasive.The main aim of the invention is therefore to remedy the disadvantages of the aforementioned prior art in providing a decorative element, particularly a component of a timepiece, comprising a surface layer of a very large material hardness having a microcrystalline structure and having a very regular topography and very little abrasive.

A cet effet l'invention a pour objet un élément décoratif comprenant un substrat revêtu au moins partiellement d'une couche protectrice et décorative en matériau dur, caractérisé en ce que le matériau dur de ladite couche a une structure microcristalline et une surface extérieure présentant une topographie régulière du type chou-fleur.To this end, the subject of the invention is an element decorative comprising at least one coated substrate partially with a protective and decorative layer in hard material, characterized in that the hard material of said layer has a microcrystalline structure and a outer surface with a regular topography of the cauliflower type.

La topographie particulière dite en chou-fleur, plus connue dans la technique sous sa désignation anglaise "cauliflower structure", de la couche dure a pour avantage de ne pas présenter d'arêtes vives ni de creux profonds, même avant polissage de la surface de cette couche. Les marques laissées des dépôts de matériau plus tendre à la surface du revêtement suite à une rayure peuvent ainsi être facilement réduites voire éliminées par un moyen simple, tel qu'un chiffon ou le doigt, à la disposition de tout consommateur. On notera que l'on peut avantageusement utiliser de tels revêtements non polis sans craindre de marquer de façon quasi indélébile la surface du revêtement comme cela était le cas dans l'art intérieur.The particular topography known as cauliflower, plus known in the art under its English designation "cauliflower structure", the hard layer has the advantage not to have sharp edges or deep hollows, even before polishing the surface of this layer. The marks left of softer material deposits at the surface of the coating following a scratch can thus be easily reduced or even eliminated by a means simple, such as a cloth or finger, available to any consumer. Note that we can advantageously use such unpolished coatings without fear of mark the surface of the coating almost indelibly as was the case in interior art.

Selon une caractéristique préférée de l'invention, la couche de matériau dur est polie spéculairement.According to a preferred characteristic of the invention, the hard material layer is specularly polished.

Selon une autre caractéristique préférée de l'invention, le matériau dur est le diamant ou du nitrure de bore cubique.According to another preferred characteristic of the invention the hard material is diamond or nitride cubic boron.

En utilisant le diamant de type chou-fleur pour revêtir lesdits éléments, la dureté superficielle des surfaces recouvertes est de l'ordre 8'000 HV, ce qui conduit à une résistance à l'abrasion quatre fois supérieure à celle des revêtements de diamant de l'art antérieur qui présentent des duretés de l'ordre de 6'000 à 8'000 HV.Using the cauliflower type diamond for coating said elements, the surface hardness of covered surfaces is around 8,000 HV, which leads to abrasion resistance four times superior to that of diamond art coatings which have hardnesses of the order of 6,000 to 8,000 HV.

D'autres caractéristiques et avantages de l'invention apparaítront plus clairement à lecture de la description suivante d'un mode de réalisation de l'invention, présenté à titre purement illustratif et non limitatif, cette description étant faite en liaison avec les dessins dans lesquels:

  • la figure 1 est une coupe partielle d'une montre-bracelet équipée d'un élément décoratif selon l'invention;
  • la figure 2 est une coupe d'un autre élément décoratif selon l'invention sous la forme d'un maillon de bracelet dont est équipée la montre-bracelet représentée à la figure 1; et
  • les figures 3 et 4 sont des micrographies de couches de diamant, respectivement du type facetté et du type chou-fleur.
Other characteristics and advantages of the invention will appear more clearly on reading the following description of an embodiment of the invention, presented purely by way of non-limiting illustration, this description being made in conjunction with the drawings in which :
  • Figure 1 is a partial section of a wristwatch equipped with a decorative element according to the invention;
  • FIG. 2 is a section through another decorative element according to the invention in the form of a bracelet link with which the wristwatch shown in FIG. 1 is fitted; and
  • Figures 3 and 4 are micrographs of diamond layers, respectively of the faceted type and the cauliflower type.

Un élément décoratif selon l'invention va maintenant être décrit en détail dans le cadre d'une application à la réalisation d'un élément constitutif d'une pièce d'horlogerie et plus particulièrement d'une lunette d'une montre-bracelet représentée à la figure 1 et désignée par la référence numérique générale 1. A decorative element according to the invention now goes be described in detail as part of an application to the production of a component part of watchmaking and more particularly of a bezel of a wristwatch shown in Figure 1 and designated by the general reference number 1.

La montre-bracelet 1 comprend quatre pièces principales: une carrure intérieure 2, une lunette 4, un verre 6 et un fond 8. La carrure intérieure 2 et la lunette 4 présentent des formes qui sont déterminées de manière que les opérations de fabrication soient simplifiées et celles d'assemblage facilitées.Wristwatch 1 includes four pieces main: an inner middle 2, a bezel 4, a glass 6 and a back 8. The inner middle 2 and the glasses 4 have shapes which are determined from so that the manufacturing operations are simplified and those of assembly facilitated.

La carrure intérieure 2 est réalisé en un métal facilement usinable, par exemple en acier inoxydable. La carrure 2 qui est destinée à contenir un mouvement 10 surmonté d'un cadran 12 comprend une partie supérieure 14 et une partie inférieure 16. La partie inférieure 16 entoure et porte le mouvement 10 et le cadran 12 d'une manière classique qui ne sera donc pas décrite plus en détail. Le fond 8 est par ailleurs fixé à la partie inférieure 16 classiquement par l'intermédiaire d'une garniture d'étanchéité 18.The inner middle part 2 is made of a metal easily machinable, for example stainless steel. The middle 2 which is intended to contain a movement 10 surmounted by a dial 12 includes an upper part 14 and a lower part 16. The lower part 16 surrounds and carries movement 10 and dial 12 of a classic way which will not be described further in detail. The bottom 8 is also fixed to the part lower 16 conventionally through a seal 18.

La carrure 2 est fixée à la lunette 4 par une bague 20 en matière déformable engagée dans un jeu radial prévu entre des surfaces cylindriques coaxiales en regard 22, 24 respectivement de la carrure 2 et de la lunette 4.The middle part 2 is fixed to the bezel 4 by a ring 20 of deformable material engaged in a radial clearance provided between facing coaxial cylindrical surfaces 22, 24 case 2 and bezel 4 respectively.

Le verre 6 est fixé dans l'ouverture de la lunette 4 au moyen d'une garniture d'étanchéité 26 intercalaire et est ne appui sur la face supérieure 28 de la carrure intérieure 2.The glass 6 is fixed in the opening of the bezel 4 by means of an intermediate seal 26 and is not supported on the upper face 28 of the middle part interior 2.

La surface extérieure 30 de la lunette 4, qui est dans l'exemple de réalisation décrit la surface à revêtir d'un matériau dur, comprend une première face 32 parallèle au plan du cadran. La face 32 se prolonge par une deuxième face 34 tronconique, puis par une troisième face circulaire latérale 36 perpendiculaire au plan du cadran.The outer surface 30 of the bezel 4, which is in the embodiment describes the surface to be coated of hard material, includes a first parallel face 32 on the dial plane. The face 32 is extended by a second side 34 frustoconical, then by a third side lateral circular 36 perpendicular to the plane of the dial.

Les faces 32, 34, et 36 de la lunette sont revêtues selon l'invention d'une mince couche 38 de matériau très dur tel qu'une couche de diamant ou de nitrure de bore. Typiquement la couche 38 a une épaisseur comprise entre 1 et 20 micromètres et une dureté de l'ordre de 8'000 à 10'000 HV.The sides 32, 34, and 36 of the bezel are coated according to the invention a thin layer 38 of material very hard such as a layer of diamond or boron nitride. Typically layer 38 has a thickness of between 1 and 20 micrometers and a hardness of the order of 8,000 to 10,000 HV.

On décrira ci-après un procédé pour réaliser un élément constitutif d'une pièce d'horlogerie selon l'invention telle que la lunette 4 sur une certaine partie de laquelle on va déposer une couche de diamant ayant une structure microcristalline et une topographie de surface du type chou-fleur.A method will be described below for carrying out a component of a timepiece according to the invention such as the telescope 4 on a certain part of which we are going to deposit a layer of diamond having a microcrystalline structure and surface topography cauliflower type.

Pour ce faire, on se muni tout d'abord d'un substrat ayant notamment la ou les surfaces que l'on souhaite revêtir dans leur forme finie. Dans l'exemple décrit il s'agit des faces 32, 34 et 36 de la lunette 4.To do this, we first need a substrate having in particular the surface or surfaces that one wishes take on their finished form. In the example described there these are the faces 32, 34 and 36 of the telescope 4.

Par forme finie, on entend que les surfaces ont donc été préparées par des techniques de mises en forme classiques dans leur forme finale d'utilisation. Ces techniques de mise en forme seront bien entendu adaptées à la matière dont est constitué le substratBy finite form is meant that the surfaces therefore have been prepared by shaping techniques classics in their final form of use. These shaping techniques will of course be adapted to the material from which the substrate is made

De préférence, le substrat présente une dureté supérieure à 800 HV, et typiquement un substrat en métal dur fritté ou en céramique est tout a fait approprié. En effet si le matériau du substrat est trop tendre, un choc sur la couche mince 38 entraínera une déformation du substrat et dans la plupart des cas une fissure dans la couche 38, compte tenu des mauvaises propriétés élastiques.Preferably, the substrate has a hardness greater than 800 HV, and typically a metal substrate hard sintered or ceramic is quite suitable. In effect if the substrate material is too soft, shock on the thin layer 38 will cause deformation of the substrate and in most cases a crack in the layer 38, due to poor properties elastic.

Dans le cas où l'on souhaite un substrat en métal dur, on choisira de préférence un métal dur inoxydable tel qu'un métal dur fritté à base de carbure de tungstène ou de carbure de titane, ces carbures étant liés à l'aide de liants métalliques tels que le nickel, le chrome, le cobalt ou le molybdène ou un mélange de ceux-ci.If you want a metal substrate hard, preferably a hard stainless metal such as than a sintered hard metal based on tungsten carbide or of titanium carbide, these carbides being bonded using metallic binders such as nickel, chromium, cobalt or molybdenum or a mixture thereof.

Pour augmenter l'adhésion avec la couche dure à déposer, les surfaces à revêtir sont soumises à un traitement de surface afin de diminuer la concentration en liant à la surface (sur environ quelques dizaines de micromètres). A titre d'exemple, ce traitement de surface peut consister en un traitement thermique sous vide au cours duquel le liant à la surface s'évapore, ou encore en un traitement chimique dans une solution de H2SO4/H2O2 à une concentration respective de 5 % et 35 %.To increase adhesion with the hard layer to be deposited, the surfaces to be coated are subjected to a surface treatment in order to reduce the concentration of binder on the surface (over a few tens of micrometers). By way of example, this surface treatment can consist of a vacuum heat treatment during which the binder on the surface evaporates, or alternatively a chemical treatment in a solution of H 2 SO 4 / H 2 O 2 at a respective concentration of 5% and 35%.

Dans le cas où l'on souhaite un substrat en céramique, on choisira de préférence des céramiques ayant une grande résistance au choc, à base de carbure ou de nitrure. Par exemple des céramiques à base de carbure de silicium et/ou de nitrure de silicium seront appropriées.In the case where a substrate is desired ceramic, we will preferably choose ceramics having high impact resistance, based on carbide or nitride. For example ceramic based on carbide silicon and / or silicon nitride will be appropriate.

Des substrats en céramique à base d'oxydes peuvent être également utilisés, toutefois un traitement préalable permettant d'obtenir un carbure à la surface qui doit être revêtue est nécessaire. A titre d'exemple, ce traitement peut consister en un traitement thermique sous atmosphère contrôlée, un traitement chimique ou par plasma.Oxide-based ceramic substrates can also be used, however prior treatment to obtain a carbide on the surface which must be coated is required. As an example, this treatment may consist of heat treatment in an atmosphere controlled, chemical or plasma treatment.

Une fois le substrat préparé, il est introduit dans l'enceinte d'une installation de dépôt chimique en phase vapeur, le substrat étant disposé sur un montage approprié pour procéder au dépôt d'une couche de diamant et obtenir une couche ayant une topographie ou structure du type chou-fleur. Un procédé permettant d'obtenir une telle couche est décrit en détail dans la publication intitulée "The role of hydrogen in diamond synthesis from carbon dioxyde-hydrocarbon gases by micro wave plasma chemical vapor deposition" de Chia-Fu Chen et Tsao-Ming hong, publiée en 1992 dans la revue Surface and Coatings Technology 54/55, pages 368 à 373, qui est incorporée ici dans sa totalité par référence. Il est bien entendu que tout autre procédé permettant de déposer des couches de matériau dur ayant une structure ou topographie de type chou-fleur sur un substrat sont envisageables.Once the substrate is prepared, it is introduced into the enclosure of a phase chemical deposition installation steam, the substrate being arranged on a suitable assembly to deposit a layer of diamond and obtain a layer having a topography or structure of the type cauliflower. A method for obtaining such a layer is described in detail in the publication called "The role of hydrogen in diamond synthesis from carbon dioxide-hydrocarbon gases by micro wave plasma chemical vapor deposition "by Chia-Fu Chen and Tsao-Ming hong, published in 1992 in Surface and Coatings Technology 54/55, pages 368 to 373, which is incorporated here in its entirety by reference. It is understood that any other method for depositing layers of hard material having a structure or topography of the type cauliflower on a substrate are possible.

La surface de la couche de diamant obtenue présente une topographie comportant un agglomérat de microglobules, comme cela ressort de la figure 4 qui représente une micrographie de la surface d'une couche de diamant du type chou-fleur à un grossissement de 2'000 fois. Alors que dans les couches de diamant du type facetté, les liaisons entre les atomes de carbone sont quasi exclusivement du type SP3 et présentant une dureté d'environ 10'000 HV, les couches de diamant du type chou-fleur utilisées dans l'élément décoratif selon l'invention comprennent une proportion élevée d'atomes de carbone reliés par des liaisons du type SP2 avec une faible proportion de liaison de type SP3 et présentent une dureté de l'ordre de 8'000 HV. Ce mélange de liaisons carbone-carbone du type SP3 et SP2 est en fait un défaut qui apparaít lors de la formation par croissance à la surface du substrat de la couche de diamant et qui conduit à une structure en microglobules peu rugueuses telles que celles représentées à la figure 4.The surface of the diamond layer obtained has a topography comprising an agglomerate of microglobules, as shown in Figure 4 which represents a micrograph of the surface of a diamond layer of the type cauliflower at a magnification of 2,000 times. While in facet-type diamond layers, the bonds between the carbon atoms are almost exclusively of type SP3 and having a hardness of around 10,000 HV, the cauliflower type diamond layers used in the decorative element according to the invention comprises a high proportion of carbon atoms linked by SP2 type bonds with a low proportion of bonds type SP3 and have a hardness of the order of 8,000 HV. This mixture of carbon-carbon bonds of the type SP3 and SP2 is in fact a fault which appears during the growth formation on the substrate surface of the layer of diamond and which leads to a structure in slightly rough microglobules such as those shown in Figure 4.

En revanche, les couches de diamant déposées chimiquement en phase vapeur selon le procédé décrit dans le document US 4'734'339, ou une topographie qui comporte une multitude d'arêtes vives et de creux profonds disposés de façon aléatoire comme cela est visible à la figure 3 qui représente une micrographie de la surface d'une couche du type facette de diamant à un grossissement de 2'000 fois.On the other hand, the layers of diamond deposited chemically in the vapor phase according to the process described in document US 4,734,339, or a topography which includes a multitude of sharp edges and deep recesses arranged randomly as shown in Figure 3 which represents a micrograph of the surface of a layer of the diamond facet type at a magnification of 2,000 time.

La couche du type chou-fleur présente donc un avantage primordial dans une utilisation sur élément constitutif d'une pièce d'horlogerie, à savoir que la couche dure peut être polie spéculairement à l'aide d'une meule au diamant sans difficulté excessive.The cauliflower-like layer therefore has a primary advantage in use on element constituting a timepiece, namely that the hard coat can be specularly polished using a diamond wheel without excessive difficulty.

Bien entendu, dans le cas où l'on ne souhaite pas que toutes les faces du substrat soient revêtues du matériau dur, on peut prévoir un posage qui protège les faces sur lesquelles aucun matériau ne doit être déposé.Of course, if you do not want all sides of the substrate are coated with the material hard, we can provide a fitting that protects the faces on which no material should be deposited.

Il va de soi que l'élément décoratif selon l'invention n'est pas limité à la réalisation d'un élément constitutif d'une pièce d'horlogerie décrit plus haut et que d'autres éléments décoratifs tels que le maillon de bracelet 38 représenté à la figure 2 peuvent être envisagés.It goes without saying that the decorative element according to the invention is not limited to the production of an element constituting a timepiece described above and than other decorative elements such as the link bracelet 38 shown in Figure 2 can be considered.

Claims (12)

Elément décoratif comprenant un substrat revêtu au moins partiellement d'une couche protectrice et décorative en matériau dur, caractérisé en ce que le matériau dur de ladite couche a une structure microcristalline et une surface extérieure présentant une topographie régulière du type chou-fleur.Decorative element comprising a coated substrate at least partially with a protective layer and decorative in hard material, characterized in that the hard material of said layer has a structure microcrystalline and an outer surface having a regular topography of the cauliflower type. Elément décoratif selon la revendication 1, caractérisé en ce qu'il est un élément constitutif d'une pièce d'horlogerie.Decorative element according to claim 1, characterized in that it is a constituent element of a timepiece. Elément décoratif selon la revendication 1 ou 2, caractérisé en ce que la couche en matériau dur est polie spéculairement.Decorative element according to claim 1 or 2, characterized in that the hard material layer is polished specularly. Elément décoratif selon l'une des revendications 1 à 3, caractérisé en ce que ledit matériau dur est du diamant.Decorative element according to one of claims 1 to 3, characterized in that said hard material is diamond. Elément décoratif selon l'une des revendications 1 à 3, caractérisé en ce que ledit matériau dur est du nitrure de bore cubique.Decorative element according to one of claims 1 to 3, characterized in that said hard material is cubic boron nitride. Elément décoratif selon l'une des revendications 1 à 5, caractérisé en ce que le substrat présente une dureté supérieure ou égale à 800 HV.Decorative element according to one of claims 1 to 5, characterized in that the substrate has a hardness greater than or equal to 800 HV. Elément décoratif selon l'une des revendications 1 à 6, caractérisé en ce que le substrat est réalisé en un métal dur inoxydable.Decorative element according to one of claims 1 to 6, characterized in that the substrate is produced in a hard stainless steel. Elément décoratif selon l'une des revendications 1 à 6, caractérisé en ce que le substrat est réalisé par frittage d'un mélange d'un métal dur et d'un liant.Decorative element according to one of claims 1 to 6, characterized in that the substrate is produced by sintering a mixture of a hard metal and a binder. Elément décoratif selon l'une des revendications 1 à 6, caractérisé en ce que le substrat est réalisé en un matériau céramique.Decorative element according to one of claims 1 to 6, characterized in that the substrate is produced in a ceramic material. Elément décoratif selon la revendication 9, caractérisé en ce que ledit matériau céramique est du nitrure de silicium ou du carbure de silicium.Decorative element according to claim 9, characterized in that said ceramic material is silicon nitride or silicon carbide. Elément décoratif selon l'une quelconque des revendications précédentes, caractérisé en ce que ledit élément est une carrure-lunette destinée à une boíte de montre.Decorative element according to any one of previous claims, characterized in that said element is a middle-bezel intended for a box of watch. Elément décoratif selon l'une quelconque des revendications 1 à 10, caractérisé en ce que ledit élément est un maillon de bracelet.Decorative element according to any one of claims 1 to 10, characterized in that said element is a bracelet link.
EP96118796A 1996-11-22 1996-11-22 Decorative element particularly component of a timepiece Expired - Lifetime EP0844539B1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP96118796A EP0844539B1 (en) 1996-11-22 1996-11-22 Decorative element particularly component of a timepiece
DE69630792T DE69630792T2 (en) 1996-11-22 1996-11-22 Decorative element, in particular component of a clock
TW086115393A TW346557B (en) 1996-11-22 1997-10-18 Decorative element, in particular an element forming a part of a timepiece
KR1019970055762A KR100547850B1 (en) 1996-11-22 1997-10-29 Decorative element, in particular an element forming a part of a timerpiece
US08/966,481 US6123450A (en) 1996-11-22 1997-11-07 Decorative element, in particular an element forming a part of a timepiece
JP32085797A JP4476371B2 (en) 1996-11-22 1997-11-21 Decorative elements, especially those that form part of a watch
CNB971141363A CN1161673C (en) 1996-11-22 1997-11-21 Decorative part being as part of clock
SG1997004122A SG67443A1 (en) 1996-11-22 1997-11-22 Decorative element in particular an element forming a part of a timepiece
HK98115089A HK1013779A1 (en) 1996-11-22 1998-12-23 Decorative element, in particular an element forming a part of a timepiece.

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EP96118796A EP0844539B1 (en) 1996-11-22 1996-11-22 Decorative element particularly component of a timepiece

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DE69630792T2 (en) 2004-09-23
US6123450A (en) 2000-09-26
DE69630792D1 (en) 2003-12-24
TW346557B (en) 1998-12-01
EP0844539B1 (en) 2003-11-19
HK1013779A1 (en) 1999-09-10
CN1185599A (en) 1998-06-24
KR19980041971A (en) 1998-08-17
JP4476371B2 (en) 2010-06-09
SG67443A1 (en) 1999-09-21
JPH10160863A (en) 1998-06-19
CN1161673C (en) 2004-08-11
KR100547850B1 (en) 2006-04-14

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