EP4244059A1 - Verfahren zur herstellung eines keramischen gehäuseelementes, insbesondere für die uhrenherstellung, und entsprechendes gehäuseelement - Google Patents

Verfahren zur herstellung eines keramischen gehäuseelementes, insbesondere für die uhrenherstellung, und entsprechendes gehäuseelement

Info

Publication number
EP4244059A1
EP4244059A1 EP21811340.5A EP21811340A EP4244059A1 EP 4244059 A1 EP4244059 A1 EP 4244059A1 EP 21811340 A EP21811340 A EP 21811340A EP 4244059 A1 EP4244059 A1 EP 4244059A1
Authority
EP
European Patent Office
Prior art keywords
ceramic
sintering operation
reagents
interface
mold
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.)
Pending
Application number
EP21811340.5A
Other languages
English (en)
French (fr)
Inventor
Thibaut Le Loarer
Maxime GOVAERTS
Duncan DELEZINIER
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.)
Manufacture dHorlogerie Audemars Piguet SA
Original Assignee
Manufacture dHorlogerie Audemars Piguet SA
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 Manufacture dHorlogerie Audemars Piguet SA filed Critical Manufacture dHorlogerie Audemars Piguet SA
Publication of EP4244059A1 publication Critical patent/EP4244059A1/de
Pending legal-status Critical Current

Links

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
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • G04B37/225—Non-metallic cases
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • C04B35/4885—Composites with aluminium oxide
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • 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
    • G04B19/00—Indicating the time by visual means
    • G04B19/06—Dials
    • G04B19/12—Selection of materials for dials or graduations markings
    • 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
    • G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects
    • G04B45/0015—Light-, colour-, line- or spot-effects caused by or on stationary parts
    • 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
    • G04D3/0069—Watchmakers' or watch-repairers' machines or tools for working materials for working with non-mechanical means, e.g. chemical, electrochemical, metallising, vapourising; with electron beams, laser beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/02—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
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    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
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Definitions

  • the present invention relates to a method of manufacturing a ceramic trim element, for the watchmaking or jewelery fields, making it possible to obtain a substantially homogeneous trim element from the point of view of its structure and its mechanical properties and presenting variations in shade and/or color on its surface.
  • the present invention also relates to such a trim element intended to be used in the fields of watchmaking or jewelry.
  • patent CH707424 B1 discloses a process for manufacturing ceramic covering elements for watchmaking, making it possible to obtain such covering elements having two portions of different colors.
  • a composition comprising a powder intended to undergo a sintering operation to produce a ceramic as well as a first pigment, is prepared and then shaped.
  • the shaped part is partially exposed to a treatment aimed at doping the exposed portion with a second pigment, preferably one or more metals, so that the covering element finally obtained after the sintering operation has two different colors between the portion treated with the second pigment and the untreated portion.
  • this method advantageously makes it possible to produce covering elements having a clear and precise demarcation between the two portions, which is particularly suitable for the manufacture of two-tone bezels for diving watches or watches with a GMT function, for example.
  • a color is associated with daytime hours and the other color is associated with nighttime hours.
  • the publication JP 2014-12615 A discloses another process for producing casing elements, in particular for watchmaking, such as for example a bezel for a diver's watch.
  • This document describes embodiments according to which such a bezel can be manufactured so as to have a general envelope formed of a first ceramic, having a first predefined color and, inside which are made inscriptions composed of a second ceramic having a second predefined color.
  • the corresponding invention consists in injecting two different compositions into the same mold before subjecting them, together, to a conventional sintering operation.
  • HIP Het Isostatic Pressure
  • hot isostatic compression a treatment operation that is essential to ensure good densification of the ceramic finally obtained, and therefore good cohesion between the different regions of the final product respectively made on the basis of different compositions.
  • the process presented in this Japanese publication aims to produce a precise, predefined pattern for display or decoration purposes.
  • the method disclosed in the first prior document also relates to the manufacture of a covering element having display functionalities, which involves the implementation of a precise distribution between the ceramics of different colors, as is also the case in the realization of a predefined pattern.
  • these two processes are part of the general trend of industrial research, which aims to define manufacturing process parameters allowing the implementation of reproducible operating conditions to produce parts, produced in more or less large series, which are identical to each other.
  • a main object of the present invention is to provide a method for manufacturing a ceramic cladding element that is an alternative to methods already known, making it possible to obtain trim elements having an original and unique appearance.
  • Another object of the invention is to propose a ceramic covering element, for a timepiece or for a jewel, substantially homogeneous from the point of view of its structure and its mechanical properties and having an original appearance with reference to known trim elements of the prior art, in particular at least two different shades and/or colors obtained in the mass.
  • the present invention relates more particularly to a method of manufacturing a ceramic trim element for the fields of watchmaking or jewelry, of the type indicated above, comprising the steps consisting of:
  • first and second base compositions prior to the implementation of the sintering operation, in order to introduce therein at least one pigment and to define respective first and second reagents, the first and second reagents having of respective natures similar but different from each other such that, when they are subjected together to a sintering operation, a substantially homogeneous ceramic product is obtained from the point of view of its structure and its mechanical properties, and that the ceramic product finally obtained has variations in shade and/or color,
  • the method according to the invention is characterized in that it comprises at least one step of machining the ceramic product obtained after the sintering operation, comprising at least one material removal operation along a path intersecting the interface, such that at least a portion of the interface is visible on the surface of the covering element and that the latter has a unique appearance with variations in shade and/or color on its surface, the distribution of which appears to be substantially random and is independent of any predefined pattern or of any function linked to the display of an indication.
  • the different colors can for example be identified conventionally by their coordinates in the L*a*b* space.
  • each base composition comprises a powder intended to form a ceramic when it is subjected to a sintering operation, as well as a stabilizer and optionally a binder, in known manner, in such a way that after introduction of the pigment(s), a reagent of the green body type is obtained.
  • the subsequent machining step also makes it possible to produce two trim elements with distinctly different appearances from the same ceramic product resulting from sintering, depending on the path followed to carry out the removal of material. .
  • the manufacturer can choose to accentuate even more or, on the contrary, to attenuate the variations in shade and/or color on the surface of the trim element on the basis of the same ceramic product from the sintering.
  • the process according to the present invention is clearly distinguished from the prior processes mentioned above not only by the objective aimed at, that is to say the production of unique products rather than that of products which are all identical. to each other, but also by greatly simplifying the operation of placing the reagents in the mold before the sintering operation since the covering element according to the invention is not intended to comprise a predefined pattern , as is the case of the covering elements obtained by the implementation of the prior methods mentioned above.
  • the machining step is significantly simplified compared to that disclosed in the aforementioned Japanese document since it aims only to release the general shape of the trim element to be manufactured, without specific consideration of the distribution of colors or shades from the different reagents placed in the mold before sintering which would be essential for obtaining a predefined pattern.
  • first and second reagents are placed in the mold in the absence of any precise control over the way in which they are distributed relative to each other. inside the mold and which would aim to produce a predefined pattern.
  • the interface between the layers placed in the mold can have a mean plane and for the machining step to be carried out in such a way that the covering element has at least one side defining an average general plane having an inclination with reference to the average plane of the interface comprised between 10 and 90°.
  • the method according to the invention may comprise an additional step of preparing a third reagent, comprising a powder intended to undergo a sintering operation aimed at producing a ceramic, the third reagent having a similar nature but different from that of at least one of the first and second reactants and being chosen in such a way that, when the first, second and third reactants are subjected together to a sintering operation, a substantially homogeneous ceramic product of the point of view of its structure and mechanical properties.
  • the third reagent is then also placed in the mold with the first and second reagents, defining at least one additional interface with at least one of them, to be subjected with them to the sintering operation, at least one portion of the additional interface or interfaces being made visible on the surface of the trim element during the implementation of the material removal operation.
  • each of the reactants can also be made for each of the reactants to comprise a maximum proportion by mass of pigment(s) of 15%.
  • the sintering operation consists of a flash sintering operation.
  • the flash sintering operation includes a step consisting in using an electrically conductive mold connected to two electrodes located at a distance from each other and between which an electrical voltage is applied. greater than 1 Volt and less than or equal to 10 Volts, preferably associated with an electric current of between 1 and 25,000 A, and between which a pressure of between 5 and 1,000 MPa is preferably applied, for a period of between 2 and 30 minutes.
  • the flash sintering operation then constitutes the only heat treatment operation of the process applied to the mold while it contains the reactants.
  • the present invention also relates to a ceramic trim element, for the fields of watchmaking or jewellery, comprising first and second portions adjacent via an interface at least partially visible on the surface. of the trim element, the first and second portions having different respective shades and/or colors and respective natures such that the trim element is substantially homogeneous from the point of view of its structure and its mechanical properties.
  • the covering element according to the invention is characterized in that it has at least two cross-sectional planes orthogonal to each other and each of which intersects the two portions, and in that it has a unique appearance with variations in shade and/or color on its surface whose the distribution appears as substantially random and is independent of any predefined pattern or any function related to the display of an indication.
  • the covering element according to the invention has a structure such that the smallest dimension of each of the portions of different colors is less than or substantially equal to 5 mm.
  • the trim element according to the invention can be a watch trim element, in particular a component of a watch case such as a middle part, a bezel or a back, or a bracelet for a wristwatch such as a link, a stud or a buckle, or even an element for adorning a piece of jewellery.
  • the tenacity between two adjacent portions varies by a maximum of 5% depending on the extent of their interface.
  • FIG. 1 shows a schematic diagram illustrating a first step of implementing a method according to a preferred embodiment of the present invention
  • FIG. 2 shows a schematic diagram illustrating a second step of implementing the method according to the preferred embodiment of the present invention
  • FIG. 3 shows a schematic diagram illustrating a third step of implementing a method according to the preferred embodiment of the present invention
  • FIG. 4 shows a schematic diagram illustrating a step of implementing the method according to the preferred embodiment of the present invention, in connection with a further example, and
  • Figures 5a and 5b represent schematic diagrams illustrating a preferred mode of characterization of a trim element according to the present invention, Figure 5a corresponding to a trim element not meeting the characteristics of the invention and Figure 5b corresponding to a trim element according to the invention.
  • the manufacturing process according to the present invention consists in particular in combining several reagents, at least one of which contains at least one pigment, with a view to performing simultaneous sintering of all of the reagents and obtain a ceramic product having portions having different shades and/or colors with respect to each other.
  • trim element obtained has structural homogeneity, that is to say that it does not include any junction that could weaken it, and properties, in particular mechanical, uniform over its entire surface, even in its entire volume.
  • the different sintering temperatures of the different reagents used should preferably be within a range of the order of 20°C.
  • compositions in the form of powders having similar sintering temperatures should preferably be used in this process.
  • binders are preferably chosen from the same family of binders, or even one and the same binder can be used for the different compositions to be combined with each other. The same goes for the stabilizing agent used in the different compositions involved.
  • the respective proportions of binders, if any, and of stabilizing agents used in the different compositions must be chosen in such a way that the sintering temperatures of the different compositions remain close to each other.
  • the covering element 1 manufactured by the implementation of the manufacturing method has the shape of a bezel for a watch case but, of course, the a person skilled in the art will be able to implement the manufacturing method according to the invention, as defined in the claims, to produce other trim elements without departing from the scope of the present invention.
  • the method according to the invention consists in preparing different reagents or green bodies, with a view to carrying out their sintering when they are placed together in a mold, by introducing at least one pigment into at least one base composition to define the one of the reactants or green bodies.
  • At least one other green body can be used as reagent without necessarily comprising pigment.
  • Figures 1 to 3 represent schematic diagrams illustrating different stages of a manufacturing process according to the preferred embodiment, in which one and the same pigment or one and the same mixture of pigments is added to the same composition of base, but in different proportions, to define four different reagents or green bodies, whose respective sintering temperatures are close.
  • a base composition intended to lead to a ceramic after a sintering operation from a zirconia (ZrO2), with in particular a particle size adapted to the desired properties for the ceramic obtained.
  • ZrO2 zirconia
  • a person skilled in the art will not encounter any particular difficulty in choosing a powder and its particle size according to his own needs.
  • the base composition can comprise a stabilizing agent, for example here yttrium oxide (Y2O3), optionally, as well as a binder, for example polyvinyl alcohol (PVA) , each in proportions ranging from 0 to 10% by mass.
  • a stabilizing agent for example here yttrium oxide (Y2O3)
  • a binder for example polyvinyl alcohol (PVA)
  • the mass share of zirconia in the final green body preferably being between 80 and 98%.
  • an iron oxide red, or brown to black coloring depending on the degree of oxidation of the iron
  • an aluminum oxide white coloring
  • an oxide bismuth blue coloring
  • a chromium oxide green coloring
  • the introduction of the pigment or of the mixture of pigments can preferably be carried out so as to obtain green bodies in which the pigment or pigments represent a proportion of the order of 0 to 15% by mass.
  • the pigment or pigments represent a proportion of the order of 0 to 15% by mass.
  • Each layer may advantageously have an average thickness of the order of 0.5 to 5 mm, preferably 0.5 to 3 mm.
  • the distribution of the layers here substantially flat, gives rise to four interfaces 2, 4, 6 and 8, each interface being defined at the junction between two adjacent layers.
  • interfaces 2, 4, 6 and 8 are all substantially planar and parallel here, by way of non-limiting illustration, defining the orientation of a mean plane for all of the interfaces.
  • those skilled in the art could deposit different layers according to their own needs, in particular layers of variable thickness, possibly defining interfaces which would not necessarily be parallel to each other.
  • the placement of the different reagents in the mold does not require any particular precise control of the way in which the different layers are arranged relative to each other, given that the method according to the invention does not aim to produce a predefined pattern on the trim element finally obtained.
  • the sintering operation leads to a ceramic product, in the form of a block 10 whose shape is defined by the shape of the mold used, illustrated schematically in Figure 2.
  • this ceramic product has different portions, in its mass, having different colors from each other, depending on the proportion of pigment (s) used for doping the corresponding reagent.
  • the sintering operation according to the present invention preferably takes the form of a flash sintering operation (or SPS, “Spark Plasma Sintering", or electric current-assisted sintering or FAST, “Field-Assisted Sintering Technique”).
  • this flash sintering operation can include a step consisting in using an electrically conductive mold connected to two electrodes located at a distance from each other and between which an electrical voltage greater than 0 is applied. Volt and less than or equal to 10 Volts, preferably associated with the passage of an electric current of between 1 and 25,000 A between the two electrodes. This electric current makes it possible at least to heat the mold, with a heating which can be very rapid (of the order of 500 to T000° C./min), or even also the reagents when they are electrically conductive.
  • a pressure between 5 and 1000 MPa makes it possible to accelerate the sintering, sometimes to reduce the sintering temperature (thus the intensity of the current applied) and to improve the densification of the product obtained. after sintering.
  • the pressure is applied directly by the electrodes themselves and is therefore unidirectional.
  • the flash sintering operation typically lasts between 2 and 30 minutes depending on the nature of the reagents and the operating conditions selected. It can be carried out while the mold is maintained under vacuum or under a controlled atmosphere (for example under argon, hydrogen or nitrogen).
  • the flash sintering operation constitutes the only heat treatment operation applied to the mold while it is contains the reagents, since no debinding step is required.
  • the present method not only makes it possible to reduce the duration of the sintering operation, going from several hours to a few tens of minutes at most, and it also makes it possible to dispense with the hot isostatic pressing (HIP) step, which is essential in the prior process to obtain the mechanical properties desired for the final product.
  • HIP hot isostatic pressing
  • the manufacturing method according to the present invention provides for a step of machining the ceramic product obtained, making it possible to obtain a covering element 1, here a bezel for a watch case, having variations in color and/or color on its surface.
  • the machining step advantageously comprises at least one material removal operation along a path intersecting at least one of the interfaces 2, 4, 6 and 8, such that at least one portion of this interface is visible on the surface of the trim element 1.
  • FIG. 2 schematically illustrates a possible positioning of the bezel in the ceramic block 10 making it possible to simultaneously make visible all the interfaces 2, 4, 6 and 8 on the surface of the bezel once the machining step has been completed.
  • the bezel is octagonal here, by way of non-limiting illustrative example, which explains the presence of ridges regularly distributed around its periphery.
  • the trim element 1 here having a general shape making it possible to define an average general plane, the path followed by the removal of material is preferably chosen in such a way that this average general plane is inclined with respect to in the mean plane for all the interfaces.
  • the block 10 comprises at least two interfaces, they advantageously define two respective mean planes having a relative inclination of the order of 0 to 20°. Furthermore, provision may also be made for the average general plane of the covering element 1, or of at least one of its faces where applicable, to present an inclination with reference to the average plane of all the interfaces between 10 and 90°.
  • the ceramic block 10 is then machined, preferably using a CNC machine or possibly by laser, to release the bezel as shown in Figure 3.
  • the machining step according to the present invention is therefore relatively simple, depending on the shape of the covering element to be manufactured, since it simply consists in releasing the covering element from the ceramic block obtained. after the sintering operation. Once the overall shape of the trim element has been defined, it simply has to be applied to the ceramic block with an orientation allowing the interface or interfaces between the regions of different colors to be cut.
  • a binder may advantageously be added to obtain a ceramic paste including a mass proportion of binder between 0 and 7% compared to ceramic paste.
  • the binder may be chosen from the group comprising polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyoxymethylene (POM), or even polyvinyl pyrrolidine.
  • the pigments mentioned above may be used, in particular an iron oxide (red or brown to black coloring depending on the degree of oxidation of the iron), an aluminum oxide (white coloring), an oxide of bismuth (blue coloring) and/or a chromium oxide (green coloring).
  • the addition of pigment(s) may preferably be carried out so as to obtain green bodies in which the pigment(s) represent a proportion of the order of 0 to 15% by mass.
  • the green bodies thus obtained are mutually compatible from the point of view of the present invention, that is to say they have respective sintering temperatures close to each other.
  • the green bodies can be arranged alternately in a mold in the form of layers, as described above, preferably by injection under pressure.
  • white, green, red (and/or brown to black) and blue layers can be placed alternately from the reagents described above, in any order.
  • Each layer may preferably have a thickness of the order of 0.5 to 5mm.
  • a conventional sintering operation is then applied to the mold containing the various layers of reagents or green bodies, at a temperature of between 800 and 1600°C.
  • no binder is used and the powders are placed in a mold for flash sintering (typically graphite, silicon carbide or tungsten carbide for example), the latter being then subjected to a flash sintering operation.
  • a mold for flash sintering typically graphite, silicon carbide or tungsten carbide for example
  • the flash sintering operation may include one or more temperature rise ramps, depending on the nature of the reactants to be treated, without departing from the scope of the present invention as defined by the appended claims.
  • the ceramic block obtained after sintering is machined, for example using a CNC machine, to release therefrom the desired cladding element, in particular intended for use in the fields of watches or jewellery.
  • the average general plane of the trim element, or at least one of its faces, if applicable, has an inclination with reference to the mean plane of all the interfaces of between 10 and 90°.
  • this additional example provides for the production of a ceramic cladding element comprising six different portions having different respective colors and shades, due to the use of two different pigments or mixtures of pigments (C1 and C2), in varying proportions, as indicated in the following table.
  • FIG. 4 represents a schematic view of a ceramic block 40 obtained in accordance with the operating conditions presented above.
  • this additional embodiment provides for the preparation of several different green bodies by adding to the same basic composition different proportions of two pigments or of two mixtures of different pigments, according to variable proportions, before disposing these green bodies in a mold in the form of superimposed layers, and subjecting them to a sintering operation.
  • the block 40 is then obtained, with six different portions corresponding to the layers 104, 204, 304, 404, 504 and 604, as illustrated in figure 4.
  • a measurement of the toughness can be carried out to define an acceptable level of structural homogeneity of the block 40, by applying a load to the latter in a direction transverse to the different layers, that is to say substantially parallel to the plane P referenced in FIG. .
  • FIG. 5a represents a schematic diagram illustrating the relationship between the toughness at different points of a ceramic block not corresponding to the present invention, in a direction parallel to the plane P, and the toughness of the first layer 104.
  • the toughness varies significantly along the ceramic block, which reflects a certain structural heterogeneity which can give rise to a rupture of the block under certain mechanical stresses. particular, which is not desirable in the context of the present invention.
  • FIG. 5b represents a schematic diagram illustrating the relationship between the toughness at different points of a ceramic block according to the present invention, along a direction parallel to the plane P, and the toughness of the first layer 104.
  • FIG. 5b schematizes the ideal case according to which the toughness is constant all along the plane P, which reflects the fact that the corresponding ceramic block is homogeneous from the point of view of its structure and its properties. mechanical, in accordance with the criterion of the present invention.
  • the homogeneity criterion according to the present invention is fulfilled when the toughness between two adjacent layers varies by a maximum of 5%.

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EP21811340.5A 2020-11-16 2021-11-16 Verfahren zur herstellung eines keramischen gehäuseelementes, insbesondere für die uhrenherstellung, und entsprechendes gehäuseelement Pending EP4244059A1 (de)

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CH01461/20A CH718069A1 (fr) 2020-11-16 2020-11-16 Procédé de fabrication d'un élément d'habillage en céramique, notamment pour l'horlogerie, et élément d'habillage correspondant.
PCT/EP2021/081855 WO2022101504A1 (fr) 2020-11-16 2021-11-16 Procede de fabrication d'un element d'habillage en ceramique, notamment pour l'horlogerie, et element d'habillage correspondant

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