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    • 专利摘要:
    The invention relates to a method of manufacturing a part, for example a watch bezel, comprising a substrate (2) made of a ceramic based on nitride or carbide, the method successively comprising the steps of: a) arrangement of said substrate (2), b) formation of an oxide layer (5) on the surface of said substrate (2), c) deposition of an electrically conductive layer (6) on at least part of the surface comprising the oxide layer (5). According to the invention, the formation of the oxide layer makes it possible to improve the adhesion between the ceramic substrate based on nitride or carbide and the electrically conductive layer, the latter being able to be used for a subsequent deposition of a layer. metallic exterior. The invention also relates to the part which comprises this oxide layer and at least one electrically conductive layer deposited on the oxide layer.
    公开号:CH715153A2
    申请号:CH00841/18
    申请日:2018-07-05
    公开日:2020-01-15
    发明作者:Le Boudouil Damien；Netuschill Alexandre
    申请人:Comadur Sa；
    IPC主号:
    专利说明:

    Description
    TECHNICAL FIELD The present invention relates to a process for manufacturing a part, in particular a timepiece component, comprising a ceramic substrate based on nitride or carbide. More particularly, the invention relates to a manufacturing process including a surface treatment step making it possible to increase the adhesion between the substrate and an electrically conductive layer deposited subsequently.
    PRIOR ART In the watchmaking field, it is known to produce covering components such as watch cases, glasses, etc., made of ceramic based on zirconium oxide, otherwise known as zirconia. To modify the properties (density, toughness, etc.) or the aesthetic appearance of the component, it may be desirable to use other ceramics such as silicon nitride which, inter alia, has the advantage of being less dense than zirconia, which makes it possible to manufacture components that are light while being hard.
    These trim components can be decorated. It can be a simple coating deposited by PVD which modifies the aesthetic appearance of the component. More elaborately, it can be a galvanic deposit of a metallic element within a recess formed in the component to produce a decoration. In this regard, document EP 2380 864 describes a process for manufacturing ceramic watch glasses decorated with indices produced by galvanic deposition of a metallic element within the recesses. The method consists of depositing two electrically conductive bonding layers by physical vapor deposition (PVD) on one face of the ceramic support comprising the recesses. Once the bonding layers have been deposited, the recesses are filled with the metallic material by electroforming. This process is more specifically described and adapted for a ceramic zirconia substrate. In the presence of a ceramic substrate based on nitride or carbide and no longer on oxide, the lack of chemical affinity between the substrate and the first conductive layer can cause adhesion problems between the substrate and said layer. This lack of adhesion between the substrate and the conductive layer can lead to a local detachment of the conductive material with, as a corollary, uneven galvanic growth on the substrate. This lack of adhesion can also lead to removal of the material deposited during a subsequent grinding of the part.
    SUMMARY OF THE INVENTION The object of the present invention is to propose a method of manufacturing a part including a step of surface treatment of the non-oxide based ceramic substrate making it possible to increase the adhesion between the substrate and a layer deposited later.
    To this end, the present invention proposes to form on the surface of the substrate an oxide layer improving the chemical affinity between the substrate and the layer deposited subsequently.
    Preferably, the oxide layer is formed by thermal oxidation and has a thickness between 10 and 60 μm and more preferably between 20 and 40 μm.
    [0007] Next, a first metallic layer or, more generally, a first electrically conductive layer is deposited. This layer can form a coating intended to improve the aesthetic appearance of the part. This layer can also serve as an intermediate layer within a set of layers formed on the part.
    Preferably, the substrate is made of a ceramic based on silicon nitride and the first electrically conductive layer deposited is a layer of titanium which has very good adhesion to the oxide layer.
    The better adhesion obtained thanks to the oxide layer makes it possible to increase the number of layers deposited on the substrate and to improve the yield of a subsequent galvanic deposition if necessary. In this regard, a second electrically conductive layer, for example made of gold, is advantageously deposited on the first electrically conductive layer before the galvanic deposition of a metallic material also still by way of example in gold. Preferably, the different layers are formed and deposited on the internal wall of a recess formed in the substrate before filling the recess with the metallic material to form a surface decoration on the surface of the substrate.
    Other features and advantages of the present invention will appear in the following description of preferred embodiments, presented by way of non-limiting example with reference to the accompanying drawings.
    BRIEF DESCRIPTION OF THE FIGURES [0011]
    Fig. 1 shows in plan a part, and in particular, a watch bezel comprising a ceramic substrate with a non-oxide base and indices produced with the manufacturing process according to the invention.
    Fig. 2 shows a partial sectional view of this same part.
    Fig. 3 schematically illustrates the step of forming the oxide layer on the surface of the nitride-based substrate with the method according to the invention.
    Fig. 4 schematically represents the different layers formed or deposited with the method according to the invention for a preferred variant.
    Figs. 5 to 8 schematically represent the manufacturing steps according to the invention of a part comprising recesses filled by electroforming to form decorative elements on the non-oxide based ceramic substrate.
    DETAILED DESCRIPTION The present invention relates to a method of manufacturing a part comprising a ceramic substrate based on non-oxide. It is more specifically described for a nitride-based substrate, but it also applies to carbide-based substrates. The present invention relates more particularly to the step implemented to improve the adhesion between the substrate and an electrically conductive layer deposited on the substrate. This layer may in itself be a purpose and be intended to improve the aesthetic appearance of the room. As a variant, this layer may be an intermediate layer used for its electrical conductivity properties with a view to subsequent galvanic deposition.
    The invention also relates to the part resulting from the manufacturing process. The piece may in particular be a component of watchmaking dressing such as a bezel, a dial, a box, a crown, a push-piece, a crystal, a bracelet element, etc. By way of example illustrated in FIG. 1, the part 1 is a watch bezel comprising an annular body forming the substrate 2. The substrate 2 has recesses 3 visible in FIG. 2, filled by electroforming with a metallic material 8 to form decorative elements 4 such as indices in the example illustrated. Between the surface of the substrate and the metallic material, several layers are present. These layers will be described in more detail below.
    The substrate is ceramic based on nitride or carbide. Depending on the color or the properties sought, it may, for example, be a silicon nitride (Si 3 N 4 ), a titanium nitride (TIN), a boron nitride (BN) or of a mixture of two or more of these ceramics. For a carbide-based substrate, it may, for example, be a titanium carbide (TIC) or silicon (SIC). The substrate is mainly (+ 80% by weight) based on nitride or carbide but could also contain oxides such as yttrium oxide and / or aluminum oxide.
    According to the invention, the method of manufacturing the part comprises a step of treating the surface of the substrate aimed at improving the adhesion to the surface of the substrate. The surface treatment consists in forming an oxide layer on this surface. Several routes (chemical, thermal, plasma, etc.) can be envisaged to form this layer. According to the invention, the choice is preferably made on the thermal route that can easily be carried out in an oven. When heated, the nitrogen or carbon atoms are replaced by oxygen atoms. There may be formation of a mixed oxynitride or oxycarbide compound at the interface respectively between the nitride or carbide substrate and the oxide layer. As shown in fig. 3 for a substrate 2 made of silicon nitride (Si 3 N 4 ), a layer of silicon oxide 5 (SIO 2 ) is formed with a mixed compound 5a of Si 2 N 2 O at the interface with the layer of Si 3 N 4 . It is assumed that this mixed compound improves the cohesion between the layers of SiO 2 and Si 3 N 4 .
    The oxide layer including the mixed compound preferably has a thickness between 10 and 60 μm and, more preferably, between 20 and 40 μm, the temperature and the annealing time making it possible to adapt the thickness of the layer . The oxidation temperature is chosen according to the composition of the ceramic. For a ceramic based on Si 3 N 4 , the oxidation temperature is preferably between 850 and 1500 ° C and, more preferably, between 1200 and 1300 ° C. The holding times are a function of the heating rate up to the aforementioned oxidation temperature, the oxidation being able to start during the rise ramp. These holding times are between 0 and 6 hours and preferably between 1.5 and 3 hours. A zero holding time can be envisaged if the heating rate is sufficiently slow (<200 ° C / h) only to allow oxidation to the desired thickness during the rise in temperature. For a TIN-based ceramic, the oxidation temperature is preferably between 500 and 900 ° C and more preferably between 600 and 700 ° C for holding times of the same order. For mixtures of non-oxide-based ceramics, the oxidation temperature is based on the lowest oxidation temperature for the different ceramics present. Thermal oxidations are carried out in an oven in an ambient atmosphere.
    Optionally, the thermal oxidation of the substrate can be followed by a step of depositing by PVD a layer of the corresponding oxide of the nitride or of the carbide (SiO 2 for Si 3 N 4 , TiO 2 for TIN, etc.). This layer, which has a thickness of a few tens of nanometers, makes it possible to reinforce the oxide layer formed.
    Then, a first electrically conductive layer is deposited on the oxide layer. Preferably, it is deposited by PVD deposition and has a thickness between 20 and 70 nm and, more preferably, between 40 and 60 nm with typically a value substantially equal to 50 nm. The material of this layer is chosen according to its affinity with the oxide of the layer formed. For example, the layer is Cr, Ni, Cu, Ti, Zr, TIW or NiP. In the case of a SiaN4 substrate, the choice is preferably made on titanium which is a reactive element with strong adhesion to silica. It is thus preferentially chosen because, compared to another reactive metal such as chromium, it is theoretically more reactive than the latter. It is moreover thermodynamically possible that the oxygen of silica can react with the metallic titanium to form an intermetallic allowing to reinforce the cohesion of the layers. Alternatively, this first layer forms a coating intended to remain visible for decorative purposes on the substrate. According to another preferred variant, this first layer consists of an intermediate layer for subsequent galvanic deposition. According to this preferred variant, a second electrically conductive layer is deposited on the first layer. This deposit is also preferably made by PVD. By way of example, this second layer can, for example, be gold, copper, silver, indium, platinum, palladium or nickel. It is chosen for its adhesion capacity and is preferably similar in nature to that of the metallic material subsequently deposited by electroforming. This second layer preferably has a thickness between 20 and 70 nm, and more preferably between 30 and 60 nm with typically a value of 50 nm.
    [0020] FIG. 4 preferably shows the different layers formed or deposited with the method according to the invention for a substrate 2 of Si 3 N 4 . There is formation of the layer of silicon oxide with the mixed compound 5a of oxynitride at the interface with the substrate 2, then deposition of the first electrically conductive layer 6 of Ti with probable formation of an intermetallic compound 6a of Ti and Si, then deposition of the second electrically conductive layer 7 of Au.
    The surface of the substrate is thus ready for the deposition of a metallic material by electroforming. The choice of material is varied. Depending on the desired visual rendering, the deposited material may, for example, include gold, copper, silver, indium, platinum, palladium or nickel. For the preferred example of fig. 4, the material chosen is gold. This galvanic deposition makes it possible to deposit a layer of thickness greater than 100 μm with values typically of the order of 200 μm.
    Then, the part is subjected to a mechanical correction such as polishing to remove the different layers outside the areas comprising the decorative elements or remove a surplus of material in the areas comprising the decorative elements.
    This process can be applied to make many decorations on the ceramic substrate. Returning to the example in fig. 1, the manufacturing process is illustrated in FIGS. 5 to 8 for producing the indices 4 on the watch bezel constituting the substrate 2. In FIG. 5, part of the substrate 2 is visible. This substrate is provided with at least one recess 3 with a thickness P greater than 100 μm. This recess can, for example, be achieved by laser engraving. Preferably, each recess is delimited by an internal wall without an edge, represented with a radius of curvature R in FIG. 5, to facilitate subsequent electroforming. The entire substrate is then subjected to thermal oxidation in an oven to form the oxide layer 5 with a thickness of the order of 30 μm (fig. 6). The two conductive layers 6,7 of a thickness substantially equal to 50 nm are then deposited on the face F of the substrate comprising the recess. The deposition of the two layers is preferably carried out by PVD within an enclosure. Then, as illustrated in fig. 7, the deposition of the metallic material 8 is carried out by electroforming on the face F with a thickness of the layer typically of the order of 200 nm. Finally, the process ends by removing the oxide layer 5 and the deposits 6,7,8 from the surface of the substrate outside the recess in order to leave only at the level of the recess. This step can be carried out by a usual surfacing method such as grinding or lapping to remove the excess material followed by polishing. Thus, the decorative element 4 is flush with the surface of the substrate 2.
    The process has been illustrated here to decorate a cladding component in watchmaking but it goes without saying that this applies in general to any room, including jewelry, where decor is desired.
    Legend to the figures (1) Part (2) Support (3) Recess (4) Decorative element (5) Oxide layer
    at. Oxynitride interface (6) First electrically conductive layer, also called first metallic layer
    at. Intermetallic interface (7) Second electrically conductive layer, also called second metallic layer (8) Galvanic layer, also called third metallic layer
    权利要求:
    Claims (28)
    [1]
    claims
    1. A method of manufacturing a part (1) comprising a substrate (2) made of a ceramic based on nitride or carbide, the method successively comprising the steps of;
    a) Provision of said substrate (2),
    b) Formation of an oxide layer (5) on the surface of said substrate (2),
    c) Depositing a first electrically conductive layer (6) on at least part of the surface comprising the oxide layer (5).
    [2]
    2. Method according to claim 1, characterized in that the oxide layer (5) is formed in step b) by thermal oxidation of the substrate (2).
    [3]
    3. Method according to claim 2, characterized in that the oxide layer (5) is formed in step b) by thermal oxidation of the substrate (2) followed by a vapor phase deposition of the same oxide as that obtained during thermal oxidation.
    [4]
    4. Method according to claim 2 or 3, characterized in that, for a nitride-based ceramic substrate, the step
    b) is carried out with an oxidation temperature which is, when the substrate (2) comprises as sole nitride: -nitride of silicon, between 850 and 1500 ° C and, preferably, between 1200 and 1300 ° C;
    - titanium nitride, between 500 and 900 ° C and preferably between 600 and 700 ° C;
    and that is, when the substrate (2) comprises several nitrides, equal to that of the nitride having the lowest oxidation temperature.
    [5]
    5. Method according to claim 4, characterized in that the holding time in step b) is between 0 and 6 hours and, preferably, between 1.5 and 3 hours.
    [6]
    6. Method according to any one of the preceding claims, characterized in that when the substrate (2) is made of ceramic based on silicon nitride, the first electrically conductive layer (6) deposited during the step
    c) is made of titanium.
    [7]
    7. Method according to any one of the preceding claims, characterized in that it further comprises a step
    d) depositing a second electrically conductive layer (7) on the first electrically conductive layer (6).
    [8]
    8. Method according to claim 7, characterized in that step d) of depositing the second electrically conductive layer (7) is followed by a step e) of depositing a metallic material (8) by electroforming.
    [9]
    9. Method according to any one of the preceding claims, characterized in that step c) is carried out by vapor deposition.
    [10]
    10. Method according to claim 7 or 8, characterized in that step d) is carried out by vapor deposition.
    [11]
    11. Method according to any one of claims 8 to 10, characterized in that the substrate (2) has on its surface at least one recess (3), the surface comprising said at least recess (3) being subjected to steps b ), c), d) and e) with the metallic material (8) filling said at least one recess (3) to form a decorative element (4) on the substrate (2).
    [12]
    12. Method according to any one of claims 8 to 11, characterized in that step e) is followed by a step f) of rectification to remove the oxide layer (5), the first layer (6) , the second layer (7) and the metallic material (8) on the surface of the substrate (2) not including said at least one recess (3).
    [13]
    13. Part (1) comprising a substrate (2) produced with a ceramic based on nitride or carbide, characterized in that the substrate (2) comprises on at least part of its surface several layers with successively a layer of oxide (5) and a first electrically conductive layer (6).
    [14]
    14. Part (1) according to claim 13, characterized in that the substrate (2) further comprises, following the first electrically conductive layer (6), a second electrically conductive layer (7) and a third metal layer (8).
    [15]
    15. Piece (1) according to claim 13 or 14, characterized in that the substrate (2) is a nitride-based ceramic and mainly comprises silicon nitride, titanium nitride, boron nitride or a mixture of two or more of these nitrides.
    [16]
    16. Piece (1) according to any one of claims 13 to 15, characterized in that the oxide layer (5) comprises the oxide corresponding to the nitride or carbide of the ceramic of the substrate (2).
    [17]
    17. Piece (1) according to claim 16, characterized in that the oxide layer (5) further comprises an oxynitride (5a) or an oxycarbide at the interface with said at least part of the surface of the substrate (2) .
    [18]
    18. Piece (1) according to any one of claims 13 to 17, characterized in that the first electrically conductive layer (6) comprises chromium, nickel, copper, titanium, zirconium, nickel-phosphorus or titanium-tungsten.
    [19]
    19. Part (T) according to any one of claims 14 to 18, characterized in that the second electrically conductive layer (7) and the third metallic layer (8) respectively comprise of Tor, copper, silver, indium, platinum, palladium or nickel.
    [20]
    20. Piece (1) according to any one of claims 13 to 19, characterized in that when the substrate (2) is a ceramic based on silicon nitride, the oxide layer (5) comprises oxide of silicon and the first electrically conductive layer (6) comprises titanium.
    [21]
    21. Part (1) according to claim 20, characterized in that the first electrically conductive layer (6) comprises metallic titanium and an intermetallic (5a) composed of titanium and silicon disposed at the interface with the oxide layer (5).
    [22]
    22. Piece (1) according to claim 20 or 21, characterized in that the second electrically conductive layer (7) and the third metallic layer (8) comprise gold.
    [23]
    23. Piece (1) according to any one of claims 13 to 22, characterized in that the oxide layer (5) has a thickness between 10 and 60 μm, preferably between 20 and 40 μm, and in this that the first electrically conductive layer (6) has a thickness between 20 and 70 nm and, preferably, between 40 and 60 nm.
    [24]
    24. Piece (1) according to any one of claims 14 to 22, characterized in that the second electrically conductive layer (7) has a thickness between 20 and 70 nm, preferably between 40 and 60 pm, and in that that the third metallic layer (8) has a minimum thickness of 100 μm.
    [25]
    25. Piece (1) according to any one of claims 14 to 24, characterized in that the substrate (2) is provided with at least one recess (3) successively comprising on its internal wall the oxide layer (5 ), the first electrically conductive layer (6), the second electrically conductive layer (7) and the third metal layer (8) with said third layer (8) completely filling said at least one recess (3) to form a decorative element (4 ) on the substrate (2).
    [26]
    26. Piece (1) according to any one of claims 13 to 25, characterized in that it is a covering component in watchmaking or in jewelry.
    [27]
    27. Piece (1) according to claim 26, characterized in that the component is a watch bezel forming the substrate (2) with at least one index forming the decorative element (4).
    [28]
    28. Watch or jewel comprising the part (1) according to any one of claims 13 to 27.
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    同族专利:
    公开号 | 公开日
    CH715153B1|2021-12-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH00841/18A|CH715153B1|2018-07-05|2018-07-05|Process for manufacturing a ceramic part coated at least partially with an electrically conductive layer.|CH00841/18A| CH715153B1|2018-07-05|2018-07-05|Process for manufacturing a ceramic part coated at least partially with an electrically conductive layer.|
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