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  • 专利说明
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    • 专利摘要:
    The present invention relates to new technical ceramics and a process for the preparation of technical ceramics.The process of preparing a green body from this composition, optionally Delicate the green body, then subject the green body to be treated with one or more metals.The colored technical ceramic of the present invention comprises a first colored zone and a second colored zone contains a second pigment component in association with the first pigment component.
    公开号:CH707423B1
    申请号:CH02126/13
    申请日:2013-12-20
    公开日:2019-10-15
    发明作者:Pujol Ollivier；Bienvenu Carine
    申请人:Rolex Sa；
    IPC主号:
    专利说明:

    Description Technical Field [0001] The present invention relates to new colored ceramics. The present invention also relates to a process for producing these colored ceramics.
    State of the art Technical ceramics are well known in the state of the art. They have a number of properties that make them suitable for a variety of different applications. More specifically, these properties are hardness, physical stability, extreme heat resistance and chemical inertness, among others.
    In many applications, technical ceramics are supplied colored. The coloring of technical ceramics makes it possible to obtain products which combine the advantageous properties of technical ceramics with the aesthetics of a particular color. Among the applications where color increases the value of products, or, in other words, where aesthetic properties are relevant, there are applications related to jewelry or wristwatches.
    The impregnation of technical ceramic products in order to obtain a coloring of the product is described in patent DE 2012 304. Colored ceramic products are produced according to the teaching of the document by impregnating molded parts with aqueous solutions of compounds heavy coloring metals. The castings are prepared from suitable ceramic materials, such as clay and kaolin shaped into the desired shape and heat treated between 800 ° C and 1400 ° C. No pigment is present in the molded parts and the coloring is introduced during the impregnation phase with the aqueous solution.
    In WO 00/15 580, the impregnation of ceramics is described for materials comprising an uncolored metal oxide of spinel or rutile structure (TIO 2 , SnO 2 , ZrO 2 or ZrSiO) which serves as a host network for fixing bivalent or trivalent metal ions. The ions are introduced by impregnating an aqueous solution and make it possible to color the ceramic. No indication of conditions used for pre-sintering, impregnation and drying is given. All the examples relate to the impregnation of clay with Ti / Sb / Cr solutions and give yellow-ocher colors.
    Faulkner & Schwartz (in “High Performance Pigments”, Wiley-VCH Verlag GmbH, 2009) describe aluminate-based pigments as “the combination of cobalt and aluminum oxides in spinel type stoichiometry (AB 2 O 4 with A = Co and B = Al) which gives the blue spinel of cobalt and aluminate ”. The color of spinel can be changed by adding other metals such as zinc, magnesium, titanium or lithium.
    WO 2011/120 181 A1 describes the preparation of colored opaque ceramics based on alumina. Adding a metal oxide selected from chromium, cobalt, nickel, manganese, vanadium, titanium and iron gives a colored product. The preferred product described in the document is a red-colored technical ceramic prepared from alumina containing chromium oxide.
    Brief description of the diagrams [0008]
    Fig. 1: Microstructures of the "red" (a) and "blue" (b) zones after sintering of a ceramic according to the invention.
    Fig. 2: Reflectivity spectrum of the "red" and "blue" zones after sintering of a ceramic prepared according to the invention.
    Disclosure of the invention Problems to be solved by the invention [0009] An object of the present invention is to provide a process for producing colored technical ceramics which makes it possible to produce two-color or multi-color technical ceramics. The main challenges in the realization of such components are to obtain a suitable second color from a previously colored ceramic, and to guarantee that the demarcation between the different colored zones is clear and precise, while retaining very advantageous mechanical properties. .
    You can change the color of an alumina-based technical ceramic by impregnating the green body with a solution of metal salt.
    Means of Solving the Problems Following various intensive researches to achieve the above object, the present inventors have found that a process consisting in providing a composition comprising alumina and a pigment component, preparing a green body from this composition and treat part of the green body area with a preparation containing one or more
    CH 707 423 B1 metals, in particular impregnating part of the surface and / or a volume of the green body with a solution of at least one metal salt, makes it possible to obtain a final product of high technical quality and a beautiful external appearance.
    The present invention has been made on the basis of the above findings.
    1. Method for producing a colored technical ceramic, comprising the following steps:
    providing a composition comprising alumina, at least one pigment component and optionally binders, preparing a green body therefrom, optionally debinding the green body, then subjecting the green body to treatment with a preparation containing one or more metals as another pigment component, and sintering of the treated green body.
    2. Method according to aspect 1, where the composition comprises binders and where the method comprises the debinding step which consists in heat treating the green body, or in treating the green body with an aqueous solution, then in drying the body treated green.
    3. Method according to aspect 1 or 2, where the at least one pigment component is a metal chosen from the group consisting of chromium, nickel, manganese, vanadium, titanium and iron, which metal is present in substitution on one of the sites of the alumina network.
    4. Method according to one of the preceding aspects, where the composition supplied in the first step contains magnesium in the amount of 0.0008 to 5% by weight, calculated as the amount of magnesia in the composition.
    5. Method according to one of the preceding aspects, where the composition supplied in the first step consists of: 0.4-5% by weight of at least one of Cr, Co, Ni, Μη, V, Tl or Fe
    0.0008-0.5% by weight of Mg, 0.05-6% by weight of a lanthanide element, and supplemented with 100% by weight of alumina, these quantities being calculated on the basis of the oxides of the elements present .
    6. Method according to one of the preceding aspects, the composition consisting of:
    1.0-3% by weight of Cr 2 O 3 ,
    0.05-0.5% by weight of MgO,
    0.1-5% by weight of Er 2 O 3 and the rest in alumina.
    7. Method according to one of the preceding aspects, where the heat treatment for debinding of the green body is carried out at a temperature between 700 ° C and 1200 ° C.
    8. Method according to one of the preceding aspects, where the green body is partially subjected to a treatment with the preparation containing one or more metals.
    9. Method according to one of the preceding aspects, where the treatment with the preparation containing one or more metals is an impregnation with a solution of at least one metal salt as another pigment component, followed by drying of the impregnated ceramic.
    10. Method according to aspect 9, where the impregnation solution is a solution of at least one salt of a metal chosen from the group consisting of Co, Cu, Cr, Fe, Mg, Mn, Mo, Ni, Tl and Zn in water and / or, if appropriate, at least one organic solvent.
    11. Method according to aspect 9 or 10, where the drying step after impregnation is carried out at room temperature for 12 to 24 hours, or at 60-100 ° C for 1 to 60 minutes.
    12. Method according to one of the preceding aspects, where the green body which has been treated with a preparation containing one or more metals as another pigment component and has been optionally dried is sintered at a temperature between 1250 ° C and 1700 ° C, preferably at a temperature between 1550 ° C and 1670 ° C.
    13. Method according to one of the preceding aspects, where the colored technical ceramic is a watch component, in particular a watch bezel or a watch case.
    14. Colored technical ceramic, consisting of alumina as technical ceramic material,
    CH 707 423 B1 technical ceramics comprising a first colored zone and a second colored zone of a different color, where the first colored zone contains a first pigment component, and the second colored zone contains a second pigment component in association with the first component pigment.
    15. Technical ceramic colored according to aspect 14, where the first pigment component is Cr present in substitution in the crystal lattice of alumina, and the second pigment component is a mineral complex pigment component having a spinel crystal structure of the group of space Fd-3m.
    16. Technical ceramic colored according to aspect 14 or 15, where the first colored zone is red and the second colored zone is blue.
    17. Technical ceramic colored according to one of aspects 14 to 16 which is a watch bezel.
    DETAILED DESCRIPTION OF THE INVENTION First, the method of the present invention is described.
    The process of the present invention is linked to the preparation of colored technical ceramics.
    In a first step of the process of the present invention, a green body is prepared from a composition comprising a technical ceramic material and a pigment component, hereinafter "the composition".
    Generally, technical ceramic materials have a number of properties that make them suitable for a variety of different applications. More particularly, these properties are hardness, physical stability, extreme thermal resistance and chemical inertness.
    The technical ceramics produced in the process according to the present invention consist of a technical ceramic material. The technical ceramic material used in the process of the present invention can be, for example, the type of technical ceramic material described in WO 2011/120 181 A1. The technical ceramic material described in WO 2011/120 181 A1 consists of a doped alumina.
    According to the method of the present invention, the main component of the composition is alumina. As will be described later, the presence of aluminum is essential for creating colors in technical ceramics. The desired effect of the process of the present invention is to obtain a technical ceramic with zones of different colors, and this effect is obtained with alumina as the main component in technical ceramic. It may be possible to apply the concept of the present invention to other materials as a major component of the composition.
    The at least one pigment component which serves as the other component present in the composition is at least one coloring dopant or a coloring impurity, which is a transition metal or a rare earth, in particular a transition metal chosen from the group consisting of chromium, copper, cobalt, nickel, manganese, vanadium, titanium and iron. The coloring dopant (or several coloring dopants) is dispersed in the crystal lattice of the main component, and is generally present in substitution on one of the sites of the network, preferably in substitution for aluminum. These metal ions in the pigment component induce coloring of the material when they are dispersed in the crystal lattice with the appropriate coordination and degree of oxidation. The choice of these metals is important, because the choice of a metal from this selection determines the color of technical ceramics as the final product obtained by the process of the present invention. The preferred metal according to this choice is chromium. A technical ceramic prepared according to the present invention, which is made from a combination of alumina and chromium, has a red color and is therefore designated as a "ruby". This red color is advantageous in the context of the present invention. Choosing a different metal instead of chrome gives a final color that may be different from red. An alumina composition with iron, for example, can give a blue or green end product depending on the circumstances in the method of preparation.
    The amount of metal chosen from chromium, cobalt, nickel, manganese, vanadium, titanium and iron is preferably in the range of 0.4 to 5% by weight. This amount is calculated as the amount of metal oxide in the composition in proportion to the weight of the total final composition, including alumina and the other metallic components (reference may be made later to some of the other metallic components as " pigment components ”).
    Another component which may be present in the composition is magnesium. The amount of magnesium in the composition is from 0.0008 to 5% by weight, calculated as the amount of magnesia present in the composition.
    Yet another component optionally present in the composition is a lanthanide. Any lanthanide can be chosen in the context of the present invention, such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, erbium, dysprosium, holmium, thulium, ytterbium and lutetium, and combinations of these metals are possible. It has been found that the elements lanthanum, ytterbium and erbium are particularly suitable, and that erbium is particularly suitable.
    CH 707 423 B1 The amount of lanthanide in the composition of the present invention is 0.05 to 6% by weight, and preferably 0.1 to 5% by weight, and more preferably 0.5 to 2.5 % in weight.
    The above weight reports were all provided on the basis of the amount of metal calculated in the form of its oxide present in the composition. The amount of alumina present in the composition completes it up to 100% by weight; consequently, the total weight of alumina, of the metal oxide (s) chosen from chromium, nickel, manganese, vanadium, titanium and iron, magnesium and lanthanide (s) is 100% and the relative amounts of each of the components in the composition are calculated based on this total weight.
    In the process of the present invention, the preparation of the composition in the first step of the process does not necessarily require the immediate presence of the metals in the form of oxide. They can also be supplied in the form of different salts, if these salts can be obtained. These salts can be any of chlorides, nitrates, sulfates, or other suitable salt forms. The essential condition for the choice of these different salt forms is the necessity that, during the final phase of the process of the present invention, which is the sintering of a prepared intermediate product ("the green body"), the metal salts in the green bodies react with the other constituents to form the corresponding metal oxides.
    A particularly preferred composition of the green body comprises 96.5-97.9% by weight of alumina, 1.5-2.9% by weight of Cr 2 O 3 , 0.1% by weight of MgO and 0.5% by weight of Er 2 O 3 .
    The composition can be provided in the solid form of the various components. The different solid components can have different particle sizes.
    The adjustment of the preferred range of particle sizes can be carried out on the dry composition in a conventional manner described in the state of the art. It can also be carried out starting from a suspension of the particles in a suitable liquid, for example by ball atomizer or by attrition.
    The advantage of the above preferred composition is that technical ceramic has a number of favorable properties. Technical ceramics show great resistance and a beautiful red color.
    To prepare the green body, other components can be added to the composition comprising the technical ceramic material and the pigment component. For example, the presence of a binder can be an advantage in preparing the green body.
    The binders optionally used in the preparation of the green body are not particularly limited and one can use any suitable material to help the formation of the green body. Often, the binder is an organic material, and as such, a polymeric material such as polyethylene, polyethylene glycol (PEG), polyvinyl acetate, polyoxymethylene (POM), polyvinyl butyral (PVB), polytetrafluoroethylene or poly (methacrylate) -co-ethylene glycol dimethacrylate (PMMA) can be chosen.
    The presence of such an organic binder facilitates the formation of the green body, in the sense that it can be more easily shaped into a particular form. For the green body formation, any conventional process described in the state of the art can be chosen. These conventional green body preparation processes include injection molding, strip casting, dry pressing, slip casting and extrusion. In any of these processes, a product of a particular form is obtained which can be subjected to other treatments.
    For an injection feedstock, the quantity of binder material in the green body is preferably chosen from the range of 15 to 25 parts by weight, relative to 100 parts by weight of the composition comprising the technical ceramic material and the components pigments. The amount of binder material may be different for materials used in processes other than injection, such as in powders for pressing.
    After the formation and shaping of the green body, it is heat treated in a first stage of heat treatment or debinding. One of the objectives of this first step is to remove the binders, provided that there were some during the preparation of the green body. The first step is therefore regularly called the debinding step. This first heat treatment step has the additional objective of optimizing the volume of pores in the green body and of solidifying the material of the green body so as to allow subsequent treatment.
    The first step is carried out at a temperature in the range between at least 700 ° C and less than 1300 ° C. The purpose of this first heat treatment step is to generate the appropriate level of porosity in the heat-treated green body. What should not happen is an undesirable reduction in pore size, or even the complete disappearance of the pores. Consequently, an adequate balance between the desired effect and the avoidance of the undesirable effect will determine the temperature which will be chosen for the first stage. A preferential range for the temperature at the first sintering stage can be between 850 ° C. and less than 1300 ° C., and will have to be adapted and optimized according to the material and the type of binders used.
    The first step is regularly carried out at ambient pressure.
    Debinding involves the generation of open pores in the green body, which facilitates the subsequent treatment with a preparation containing one or more metals and gives a better final result. For the success of subsequent treatment, the presence of pores is necessary. Treatment at the highest temperatures of the preferred range
    CH 707 423 B1 rential may cause partial closure of the pores formed in the same treatment step. On the other hand, it can be recognized that large pores, and generally a capillary system of connected voids and pores can cause diffusion of the impregnating liquid in the lateral direction parallel to the surface of the impregnated article. This diffusion effect can cause the loss of the demarcation sharpness of the impregnated area, which constitutes an undesirable effect and will be described later in connection with the description of the colored ceramic of the present invention.
    There is another embodiment of the method of the present invention for obtaining the desired level of porosity. Instead of the heat treatment step, it is possible to treat the green body with an aqueous or acid solution to obtain the desired level of porosity. This possibility of treatment with an aqueous composition is a favorable embodiment since it can be carried out easily and it does not require careful control of the heating and of the time required for pre-sintering. A condition for treatment with the aqueous composition is that the green body is suitable for this kind of treatment. This may be the case if the binder which has been added to the composition for preparing the green body is easily water-soluble, or if at least one of the components which has been added as a binder is water-soluble. The binder material which is used in the state of the art regularly consists of water-soluble as well as non-water-soluble components. Treatment with the aqueous solution can dissolve the water-soluble components under the chosen conditions. Maintaining the presence of these non-dissolving components in water will help preserve the shape of the green body.
    As an aqueous composition for the treatment of the green body to make it porous, it is possible to use tap water, distilled water or demineralized water. The addition of other components, such as acids, salts or bases, may be considered depending on the conditions. The duration of treatment of the green body with the aqueous composition depends on the composition of the binder material and the desired level of porosity. The treatment temperature can be changed and it is clear that a higher temperature can speed up the process.
    In the case of treatment with the aqueous composition, the treated green body must be dried to remove any residual water from the pores. Optionally, a heat treatment can also be carried out after the treatment with the aqueous composition. The residual presence of water can have a negative effect on the treatment provided for in the next step of the process of the invention and, for this reason, its absence in the porous green body is preferable.
    In the next step, the green body which is unbound is subjected to a treatment with a preparation containing one or more metals. In the context of the process of the invention, the preparation containing one or more metals acts as another pigment component, where the term "other" distinguishes it from the first pigment component present in the composition for preparing the green body.
    Any form of treatment with a preparation containing one or more metals can be applied from the moment the desired effect is obtained, namely to bring the metal of the preparation containing one or more metals to the heat-treated green body. , so that it can interact with the material of the composition.
    Suitable methods of treatment with a preparation containing one or more metals are, for example, impregnation with a solution of metal salts, impregnation with a gel containing metal particles, impregnation with a gel containing metal oxide particles, the application of a suspension of nanoparticles on the surface of the heat-treated green body, the deposition of metals on the surface following the physical vapor deposition (PVD) process and the deposition of metals on the surface by chemical vapor deposition (CVD). These methods prove to be suitable in the process of the invention. In some cases it may be necessary to carry out a heat treatment after the application of metal to the unbound green body surface so that the metal in the preparation containing one or more metals diffuses into the green body and becomes available to interact with the material of the composition. The method which has proved to be the most favorable is the method of impregnation with a solution of another pigment component.
    Impregnation within the meaning of the present invention can be carried out by soaking the green body in an impregnation solution, but can also be carried out by inkjet printing, brushing spraying, screen printing or pad printing, or any another suitable method of applying a solution to the surface of an object.
    The impregnation solution is, for example, a solution of at least one metal salt.
    The metal salt in the impregnation solution can be any type of metal salt.
    The metal used in the preparation containing one or more metals, according to the preferred embodiment, the metal salt of the impregnating solution, must provide a color to the treated area which will be different from the color in the untreated area. As described above, the preferred color of the untreated end product of the process of the invention is red, giving a final product resembling a ruby. The treatment carried out on part of the total surface of the porous green body should give a color in the final product which contrasts with this red color, such as, for example, blue or black, or another shade of red.
    The metal in the preparation containing one or more metals, in the preferred embodiment, the metal salt of the impregnation solution, should be chosen from metals or metal salts which generate these different colors in the treated area.
    Metals suitable for the preparation of the treatment are Co, Cu, Cr, Fe, Mg, Mn, Mo, Ni, Ti and Zn, among others. The choice in this selection is based on the desired effect. It also depends on the composition of the green body.
    CH 707 423 B1 It has been found that in an embodiment where the composition of the green body comprises chromium, magnesium and erbium, the treatment with a preparation containing one or more metals comprising cobalt, zinc or iron leads to particularly favorable effects. The preparation containing one or more metals, such as the impregnating solution, may contain these metals in the form of metals or their salts or other suitable forms, alone or in combination.
    The treatment of a porous green body which contains chromium (ruby red type) with a cobalt preparation results in a blue color in the treated area. The treatment of the same type of porous green body with a preparation of a combination of cobalt and one of zinc or iron results in a blue coloring which may have the same quality or a slightly different quality.
    In the preferred embodiment of the treatment by impregnation with a solution of at least one metal salt, the type of metal salts in the impregnation solution can be any type of salt, provided that the desired effect is got. For the color to be obtained in the final technical ceramic product, the metal cation of the salt must be responsible and not so much the anionic part. However, a number of practical reasons play a role in selecting the right salt. Since the impregnation is usually carried out with an aqueous or water-based solution, the metal salt must be soluble in the solution. It may be disadvantageous to have to work with a toxic salt, as this may require complicated adaptation of working conditions; less toxic types of salt are therefore preferred. In addition, of course, not all types of salts may be available in every case and, if available, the level of purity may not meet the requirements of the process. Finally, a pH requirement of the salt solution which is not suitable for its use in impregnation can also disqualify a salt.
    Regular salts such as nitrates, chlorides and sulfates can be used, as well as salts of organic acids, such as citrates or oxalates. In most experiments, the nitrate salts have been found to be reliable and adequate and this type of salt is preferred for the process of the present invention.
    The concentration of the different elements in the solution must be adjusted to obtain the desired color, but also to avoid problems after cooking. The type of blue color obtained by impregnation with the solution of cobalt salt alone is a very intense blue, the addition of zinc salt to the impregnation solution gives less intensity. As described above, green bodies comprising chromium (in the form of a suitable salt or oxide) ultimately have a red color after sintering, with the chromium atoms as dispersed coloring dopant in the crystal lattice. Treatment with a preparation comprising cobalt gives the final technical ceramic a blue color in the treated area. When the treatment is carried out by impregnation, this effect can be obtained by impregnating the porous green body with a solution of a cobalt salt with a concentration of 0.1 mol / l to 1.5 mol / l (values included ), in particular with a solution of Co (NQ 3 ) 2 in this range of concentrations. The liquid for preparing this solution will normally be water, preferably distilled water, and / or if appropriate, at least one organic solvent.
    According to another embodiment of the method of the present invention, it is possible to treat the porous green body with a preparation comprising a combination of cobalt and zinc. In a preferred embodiment, the porous green body is impregnated with a solution containing a combination of cobalt and zinc salts. In these combined impregnation solutions, the concentration of the cobalt salt can vary between 0.1 mol / l and 1.5 mol / l (values included). The ratio of the concentration of the cobalt salt to the concentration of the zinc salt can vary between 0.33 and 1. A typical impregnation solution according to this embodiment contains Co (NQ 3 ) 2 up to a concentration of 0, 33 mol / l and Zn (NO 3 ) 2 up to a concentration of 0.66 mol / l.
    According to yet another embodiment of the process of the present invention, it is possible to impregnate the porous green body with a solution containing a combination of cobalt and iron salts. In these combined impregnation solutions, the concentration of the cobalt salt can vary between 0.1 mol / l and 1.5 mol / l (values included). The ratio between the concentration of the cobalt salt and the concentration of the iron salt can vary between 0.5 and 2. A typical impregnation solution according to this embodiment contains Co (NQ 3 ) 2 at a concentration of 0.85 mol / l and Fe (NO 3 ) 3 at a concentration of 0.5 mol / l.
    It is in principle possible to subject the entire porous green body to treatment, but a typical embodiment of the present invention consists in treating only part of the total surface of the porous green body. This partial impregnation of the porous green body gives, after final sintering, a two-color technical ceramic with different colors, in the sense that there is a first colored area and a second colored area having a different color. It is also possible to carry out several partial treatments of the porous green body, to give, after final sintering, a multicolored technical ceramic having different colors.
    The coloring can be located by physical masking and then soaking, p. ex. with an adhesive strip, with a photosensitive resin, by local deposition of the solution by pad printing or screen printing or inkjet, or by any other process suitable for the localized and controlled deposition of a liquid solution on a surface.
    The duration of the treatment must guarantee the sufficient application of the pigment component. When the treatment by soaking impregnation is chosen, the duration can generally be adjusted to be carried out for 0.25 to 20 minutes, preferably between 0.25 and 15 minutes and more preferably between 0.25 and 10 minutes. It has been observed with
    CH 707 423 B1 surprised that a soaking time of less than 1 minute gives a very satisfactory result. So impregnations for as short as 15 to 45 seconds can give the desired result.
    The treatment process with the preparation containing one or more metals according to the process of the invention, in particular the preferential impregnation with the impregnation solution, leads to penetration of the metallic component of the preparation containing one or more metals in the porous green body. This penetration into the depths of the porous green body, which means in a direction perpendicular to the surface of the porous green body, gives a good quality of coloring which, for example, is not adversely affected by a subsequent polishing treatment or by any other similar final treatment of the surface. On the other hand, the preparation containing one or more metals should preferably not diffuse laterally, that is to say in a direction parallel to the surface of the porous green body, since this would cause a loss of the precision of the demarcation of the colored areas. It was unexpectedly observed, in connection with the process of the present invention, a limited lateral diffusion and a clear demarcation between the colored zones of the sintered product.
    One property which can influence the diffusion observed in the impregnation treatment is the viscosity of the impregnation solution. An increased viscosity of the liquid results in less diffusion in the green body, and the quality of the result obtained is better. Any thickening agent can be used as an optional component in the context of the present invention. Suitable thickening agents are the different types of polyethylene glycol, but basically any conventional thickening agent can be used, such as cellulose ether, hydroxycellulose ether, glycerol, ethylene glycol, polyacrylic polymers, polymers polymethacrylics, vinyl polymers, polycarboxylic acids, polyimines and polyamides. The optionally present conventional thickening agent is burnt off during the heat treatment in the final sintering step. Another parameter which influences the diffusion is the temperature.
    The impregnation of the porous green body is usually carried out with a single impregnation solution. The impregnation solution contains all the necessary components in the appropriate concentration.
    It is also possible to carry out the treatment with the preparation containing one or more metals in a sequential manner, the impregnation in a basic manner as described above is carried out with two or more of two unique solutions one after the other. After each impregnation step in the sequential impregnation, any residual liquid is removed from the impregnated green body. The important drying step in the process of the present invention is carried out, in this particular embodiment, after the last impregnation in the sequence of separate impregnations. Another embodiment involving more than one processing step should be chosen when more than two colors are required in the final product. Different treatments involving different treated areas are possible and, in this embodiment, the method can be implemented for example by the separate coverage of selected areas in a number of subsequent steps, For example, by the separate coverage of selected areas in a number of subsequent steps, or by inkjet deposition of different solutions on different areas. In this way, different designs can be made for the final sintered product.
    After the impregnation of the green body with the impregnation solution, the resulting impregnated green body is subjected to an intensive drying procedure. A typical drying step in the context of the present invention consists of air drying for a few minutes to a few hours, for example 3 to 24 hours at room temperature. You can also choose other temperatures, such as any temperature between room temperature and 100 ° C. The duration of the drying step can be adapted to the chosen temperature. The drying step is essential in the process of the present invention using the impregnation, although the modification of the conditions does not lead to different colorings. In an industrial environment, it may be important to optimize the drying step to remove the water as completely as possible and HCl (if chloride salts are used in the impregnation solution) before sintering.
    Other methods of treatment with preparations containing one or more metals usually do not need a separate drying step.
    After treatment with the preparation containing one or more metals and, in the case of impregnation, after intensive drying, the treated green body is sintered. Conventional sintering, i.e. densification of the green body by a conventional sintering process, can be carried out at a temperature in the range between more than 1250 ° C and 1700 ° C, preferably at a temperature between 1550 ° C and 1670 ° C. Regularly, the sintering is carried out at a temperature of 1600 ° C. The temperature may depend on the conditions of the case. Consequently, the composition of the preparation containing one or more metals is a relevant parameter for determining the sintering conditions and, in particular, the sintering temperature.
    The sintering mode implies that the sintering temperature must be kept constant for a certain time; we are talking about holding time. Regularly, a hold time of 2 hours is sufficient to obtain the sintering effect. You can choose shorter or longer hold times, if necessary, such as between 1.5 and 3 hours. The full sintering procedure requires a heating period until the final sintering temperature has been reached followed by a cooling period after the hold time has expired. The duration of the total sintering procedure, including heating and cooling, can range from 24 to 32 hours.
    CH 707 423 B1 Sintering is carried out under oxidizing conditions, which means that there is preferably a presence of oxygen. Consequently, the sintering can be carried out in the presence of any gas containing oxygen, such as preferably air. It is possible to sinter under non-reducing conditions, such as a neutral atmosphere, provided that the coloring dopant is at the required degree of oxidation (eg Cr 3+ in the case of Cr in the ruby color).
    During sintering, the color of the substrate (namely the color of the area of the ceramic which is not treated with the preparation containing one or more metals), as well as the color of the area treated, are formed. According to the typical arrangement in the colored technical ceramic according to the invention, the colors in these two areas must be different.
    The color in the area of the ceramic which is not treated by the preparation containing one or more metals depends on the composition used in the preparation of the green body. The preferred color can be red, as in the case of the presence of Cr 3+ ions in alumina. The impregnated area has a different color. The color obtained in the treated area depends on the coloring dopant in the composition used to prepare the green body as well as on the metal in the preparation containing one or more metals, since the color after treatment will be generated by the association of the color generated by the coloring dopant in the composition used to prepare the green body and metal in the preparation containing one or more metals.
    According to a preferred embodiment of the present invention, the untreated surface is red, while the treated surface is blue. The association of the red color and the blue color is very preferable, because it gives an easily observed contrast.
    The effectiveness of the impregnation does not seem to depend on the type of counterions present in the impregnation solution. This aspect has been studied in connection with impregnation solutions containing Co or Zn. The salts of these metals have been supplied in the form of chlorides as well as nitrates and have been studied in different combinations and concentrations. All associations gave a blue color in the area impregnated in technical ceramics including Cr in alumina.
    In the treated area, pigment particles are identified in a separate spinel type phase. In this phase, the size of the pigment particles is typically 1-2 μm.
    It is observed that some of the materials present in the composition for preparing the green body and the metal salts contained in the impregnation solution form a phase of pigment component in the sintered product. The metal components in the preparation containing one or more metals seep into the porous structure of the green body. At the high temperature and under the oxidizing conditions of the sintering step, some of the materials, as well as the metallic components resulting from the preparation containing one or more metals, are converted into a phase of pigment component which is responsible for the final color. observed.
    One possible explanation is as follows: during sintering, a metal oxide formed from the metal salt in the impregnation solution can react with alumina as a component of the green body in the following manner: MO + AI 2 O 3 -> MAI2O4.
    In the case of the presence of a cobalt salt in the impregnation solution, chosen as the preferred embodiment of the impregnation solution, the reaction which takes place during sintering is probably as follows:
    CoO + AI 2 O 3 -> CoAI 2 0 4 .
    In the case of the presence of a cobalt salt and a zinc salt in the impregnation solution, chosen as the preferred embodiment of the impregnation solution, a compound Co x Zn 1 _ x AI 2 0 4 probably forms after sintering.
    Consequently, in this reaction, a spinel compound is generated. Commonly, this spinel compound corresponds to a cubic phase of the space group Fd-3m, which is the same phase as the pigment CoAI 2 0 4 of spinel type of blue ceramic. This phase is known to accept other elements on the Co 2+ and / or Al 3+ sites; these can be occupied, for example, by Al, Co, Cr, Cu, Fe, Mn, Mo, Ni or Zn with the corresponding degree of oxidation. Depending on the composition, the color and the mesh parameter will vary, which will shift the lines of the X-ray spectrum. This compound, which is formed according to this last reaction, gives a blue color in the case of metal salts containing Co, Zn and / or Fe, as illustrated in the examples.
    According to one of the embodiments of forming the porous green body, the green body was treated with an aqueous solution, whereupon the components of the binder which are soluble in water are dissolved and those which are not in them. chosen treatment conditions remain in the porous green body. In this case, sintering the impregnated and dried green body will remove the binder still present. In other cases of heat treatment during the pre-sintering step, normally no binder is observed after the pre-sintering step.
    Another embodiment of the method of the present invention consists in treating, in a first step, the entire surface of the ceramic, for example with a first impregnation solution, and in only treating in a second step a part of the surface, for example with a second impregnation solution. This double treatment, in particular in the form of a double impregnation, makes it possible to obtain two colors different from that obtained with the initial non-impregnated material. Such a double treatment may be advantageous, for example, for finely adjusting the color of the substrate. As an example, it is therefore possible to obtain a darker shade or shade (e.g. with solutions containing Fe, Ni, Cr, and / or Co in the case of impregnation) or a lighter shade or shade (e.g. with
    CH 707 423 B1 solutions containing Al in the case of impregnation) of the color of the initial non-impregnated material, in association with the second more contrasted color obtained with the combination of the first and the second impregnation solution. Alternatively, only part of the surface of the ceramic can be treated in a first step, for example with a first impregnating solution, and another part of the surface can be treated in a second step, for example with a second impregnation solution.
    Finally, as a last action in the production of colored technical ceramic, the products can be polished or subjected to any other final treatment to obtain an external appearance in accordance with the intended use. This last action is optional and depends on the intended use of the sintered product.
    The technical ceramics obtained according to the process of the invention are used in different applications. These applications are, for example, the manufacture of watches, for example the bezel or part of the watch case. These applications take particular advantage of the aesthetics of the process of the present invention for preparing a technical ceramic which has an advantageous combination of different colors. At the same time, these applications require considerable resistance from technical ceramics to make possible their use in watch manufacturing applications. It has been observed in the process of the present invention that the technical ceramics which are produced according to the process of the invention exhibit advantageous resistance, and that the impregnation treatment does not weaken the impregnated part of the technical ceramics. The high degree of mechanical resistance and hardness of technical ceramics make them suitable for any exposure to the elements, and common shocks will not damage them.
    The effect of the process of the present invention for obtaining technical ceramic with zones of different colors is unexpected. As described above, in the preferred embodiment according to the method of the present invention, the green body material comprises chromium in alumina as the base material. Such a composition gives a red color after sintering. The treatment of a green body of this preferred composition with a preparation containing one or more metals gives a blue color in the treated area. It was an unexpected effect. In technical ceramics produced from an alumina and chromium composition, it is believed that the red color observed after sintering results from the absorption (and for a small part of the re-emission) of light from electronic levels induced by the presence of dispersed metal ions. The coloration that appears in the treated area of technical ceramics is caused at least in part by particles of spinel compounds generated by the treatment and subsequent sintering, which form an additional phase in technical ceramic. As a result, the two colored areas in technical ceramics have a coloring effect based on different physical phenomena.
    It should also be noted that the final color can be influenced by several process and material parameters: the color of the substrate (concentration of Cr in the ruby), the sintering temperature, the pore size distribution of the substrate before treatment, in particular before the impregnation step in the case of the use of the impregnation, the viscosity of the impregnation liquid and the surface tension of the impregnation liquid and of the substrate, the concentration of metals and / or in metal salts in the preparation or in the solution, the kinetics and the drying conditions (temperature, duration, etc.), and the techniques and conditions used for the treatment (in the case of impregnation, the choice of soaking or inkjet - and in the case of inkjet, parameters such as drop size, resolution and number of print repetitions). It will therefore be necessary to adjust and optimize the process parameters for a given experimental situation.
    In conclusion, the method of the present invention has a number of surprising effects:
    - mechanical properties such as hardness, solidity and modulus of elasticity are not influenced by the impregnation;
    - the microstructure remains homogeneous and fine-grained;
    the added elements are located in the particles of the pigment component (structure of the CoAI 2 0 4 type ) dispersed in the matrix; and
    - the concentration of added elements is remarkably lower than that of commercially available samples of similar color.
    Next, the colored technical ceramics are described.
    The colored technical ceramics of the present invention contain alumina in the form of ceramic material, as described above in connection with the process for preparing colored technical ceramics.
    The colored technical ceramics according to the present invention are not particularly limited as regards their shape and can have any shape.
    The colored technical ceramics according to the present invention have different colored zones which are obtained by applying the method of the present invention as described above. Any combination of colors is possible: the first zone can, for example, be red, blue or green, the second blue, green or black zone. The two colored areas may also have different shades of red. The choice of colors depends on the intended use of technical ceramics, and technical or purely aesthetic reasons may play a role.
    CH 707 423 B1
    According to a preferred embodiment of technical ceramics, a first zone of technical ceramics is red, while a second zone is blue.
    Colored technical ceramics include a first colored zone and a second colored zone of a different color. The arrangement of the present invention makes it possible to obtain other zones of different colors, for example a third zone of another different color and / or and a fourth zone of the same kind. Although this option is specifically intended for another possible embodiment of the present invention, it will not be discussed further. The description of the realization of a technical ceramic with two different colors will make it clear to the skilled person how to obtain technical ceramics with more than two colored areas.
    The specific colors in the two different color zones are determined by the pigment components present. The pigment component in the first area is chosen based on the color you want in this first area as well as in the second area.
    It is particularly preferable to create a first zone of technical ceramic of red color, with a second zone of technical ceramic of blue color. Other possible colors for the first area are, for example, blue or green.
    A particular characteristic of the technical ceramics of the present invention is that the dividing line between the two zones of different colors is made along a thin line. It is one of the advantages of the process of the present invention to produce a colored technical ceramic allowing the formation of the second color in the second zone of technical ceramics along a fine line.
    The colored technical ceramics of the present invention are also distinguished by the usual properties of these materials, such as typically the density and the hardness. This includes, in particular, a favorable mechanical resistance which is very often the motivation for choosing ceramics for particular functions. Treatment with solutions can influence the properties of the final ceramic in any way, so that in principle deterioration of initially favorable properties is possible. It has surprisingly been observed that the colored technical ceramics of the present invention exhibit the same kind of mechanical properties as the same type of ceramic without treatment with the preparation containing one or more metals according to the process of the present invention.
    The colored technical ceramics of the present invention can be used in various applications. Since the colored technical ceramics of the present invention exhibit the usual properties of conventional colored technical ceramics, they can be used in all applications where technical ceramics are regularly used.
    Obviously, the additional aspect of the coloring makes the colored technical ceramics of the present invention very suitable for applications for which the coloring provides additional value. These applications are regularly found in ornamental items such as external components of watches, watch cases, brooches, tie pins, cuff links, external components of mobile phones and household appliances. Colored technical ceramics are particularly suitable for use in watch cases and two-tone watch components, in particular components for the watch case, such as red and blue or red and black glasses. The combination of mechanical properties with aesthetic properties make it a very suitable application.
    Examples [0098] Methods used in the examples:
    Density The density is measured according to the Archimedes method in absolute ethanol. Each sample is measured three times and the average value is measured.
    Colorimetry [0100] L * a * b * measurements are carried out after machining and polishing the sample, on the free face (namely the face which was not in contact with the sample holder during the heat treatment), with an opening of 7 mm in three different places. The equipment is a Minolta CM3610d with illuminant D65. The colorimetry is indicated as the color difference AE La b (or ΔΕ) between the measurement and the color of a reference sample (a commercial ceramic of the target color, obtained with a standard pigment).
    AE L ab is calculated by the formula ΔΕ = (AL 2 + Aa 2 + Ab 2 ) 0.5 .
    Hardness The hardness measurements were carried out by indentation with KB250 Prüftechnik GmbH equipment. The HV3 indentations were carried out under a load of 3 kg applied for 15 s. The hardness is evaluated by the formula proposed by K. Niihara:
    CH 707 423 B1
    K1c = 0.0089 (E / Hv) 2/5 P / (a / (ca) 0 · 5 ) where E is the modulus of elasticity (measured value: 390 GPa), Hv is the hardness in GPa, P is the load in N, a is the diagonal of the mark of the indentation and c is the length of the crack formed after indentation.
    Microhardness The microhardness HV1 was measured with LEICA VMHT MOT equipment under a load of 1 kg for 15 s. 10 measurements were made per sample.
    Young's modulus Young's modulus and Poisson's ratio were measured by acoustic microscopy (non-destructive control by ultrasound). The relative measurement uncertainty is 2% for the two parameters.
    Example 1 [0104] An injection raw material was prepared with the following composition:
    Mineral filler:
    97.9% by weight of alumina;
    1.5% by weight Cr 2 O 3 ;
    0.1% by weight MgO;
    0.5% by weight Er 2 O 3 ;
    to which are added binders up to a concentration of 20% by weight in the final raw material.
    The composition was injected into a mold and heat treated at 1050 ° C in air for 20 hours for debinding, which generated pores in the molded material. The porous green body had open porosity and enough mechanical strength to be handled safely.
    Then, the porous product was partially masked with adhesive tape and subjected to an impregnation treatment by soaking in an impregnation solution.
    The composition of the impregnation solution was 0.4 mol / l of Co (N0 3 ) 2 in distilled water. The impregnation time was a few seconds. The molded and impregnated green body was then extracted and dried at room temperature for 24 hours.
    In the next step, the molded green body, impregnated and then dried was sintered at 1600 ° C for 24 hours.
    The resulting technical ceramic had a red color on the part of its surface which had not been impregnated. The impregnated part of the surface had a deep blue color (“cobalt blue”).
    The line between the two areas was drawn along a straight line. The adhesive tape had made it possible to close the pores located directly under the tape and to prevent any leakage of the solution below the tape. The tape used was waterproof and, consequently, had prevented the impregnation of the part located below.
    The results of the example are shown in Table 1.
    EXAMPLES 2 TO 18 In Examples 2 to 18, the composition of the injection raw material and of the impregnating solution was varied relative to the preparation of Example 1.
    In Examples 2 to 4 and 16, the amount of chromium oxide in the raw material was 1.5% by weight, as in Example 1. In Examples 5 to 8 and 17, it had increased to 2.0% by weight. In Examples 9 to 15 and 18, it was brought to 2.88% by weight.
    In Examples 2 to 18, the composition of the impregnation solution was modified as indicated in Table 1. The pre-sintering treatment of the green body was the same as in Example 1 at 1200 ° C.
    The sintering temperature was the same as in Example 1 at 1600 ° C., except in Example 13.
    The other conditions were also identical to those of Example 1.
    Table 1.
    Ex. [Co (N0 3 ) 2 ] [Zn (NO 3 ) 2 ] [Fe (NO 3 ) 3 ] Cr 2 O 3 conc. in mineral load [wt%] Temp. sintering[° C] Color 1 0.4 0 0 1.5 1600 Cobalt blue 2 0.5 0.5 0 1.5 1600 Cobalt blue
    CH 707 423 B1
    Ex. [Co (N0 3 ) 2 ] [Zn (NO 3 ) 2 ] [Fe (NO 3 ) 3 ] Cr 2 O 3 conc. in mineral load [wt%] Temp. sintering[° C] Color 3 0.33 0.66 0 1.5 1600 Cobalt blue 4 0.25 0.75 0 1.5 1600 Cobalt blue 5 0.4 0 0 2.0 1600 Cobalt blue 6 0.5 0.5 0 2.0 1600 Cobalt blue 7 0.33 0.66 0 2.0 1600 Cobalt blue 8 0.25 0.75 0 2.0 1600 Cobalt blue 9 0.4 0 0 2.88 1600 Cobalt blue with red highlights 10 0.5 0.5 0 2.88 1600 Cobalt blue 11 0.33 0.66 0 2.88 1600 Cobalt blue 12 0.25 0.75 0 2.88 1600 Cobalt blue 13 1 0 0 2.88 1625 Cobalt blue 14 1,697 0 0 2.88 1600 Cobalt blue 15 0.5 0 0.85 2.88 1600 Midnight blue-black 16 0.25 0.25 0 1.5 1600 Cobalt blue 17 0.25 0.25 0 2.0 1600 Cobalt blue 18 0.25 0.25 0 2.88 1600 Cobalt blue
    The concentrations of Co (N0 3 ) 2 , Zn (NO 3 ) 2 and Fe (NO 3 ) 3 are given in the table in mol / 1.
    EXAMPLE 19 A two-color telescope was prepared as described in Example 1. This telescope was impregnated with a 0.5 mol.r 1 Co (N0 3 ) 2 solution . The final sintering was carried out at 1650 ° C.
    The red and blue regions of the two-color bezel obtained after the final sintering were characterized by scanning electron microscopy.
    Fig. 1 shows the microstructure after sintering of the non-impregnated (red) and impregnated (blue) zones. The "red" area is shown in fig. 1a, the clear points correspond to erbium-aluminate grains Er 3 AI 5 O 12 . An additional phase is detected in the "blue" zone shown in fig. 1b, which corresponds to the blue pigment synthesized in situ during sintering.
    Analysis by X-ray spectrography by EDX energy dispersive analysis confirmed that the additional phase in the "blue" zone included Co in addition to Al, Cr and O, which corresponds to the element added by impregnation. It is only present in this phase and not in the alumina matrix.
    Similar behavior was observed for a disc impregnated with a CoZn solution sintered at 1570 ° C with a soaking time of 2 h. Co and Zn were only present in grains with a typical grain size of 1 μm incorporated in the ruby matrix, with additional erbium-aluminate grains as in the non-impregnated regions.
    Example 20 A technical ceramic was prepared in the same manner as in Example 2. The porous green impregnated body was sintered at 1590 ° C for 2 h.
    A technical control ceramic was prepared in the same way, but without the impregnation step.
    The sintered technical ceramics obtained were subjected to the study of their reflectance spectrum.
    The results of the experiments are shown in fig. 2. In the impregnated sample, the reflection characteristics are observed in the blue (446-500 nm) and red (620-780 nm) parts of the spectrum. In comparison, the unimpregnated sample shows a reflectance peak in the red part only.
    CH 707 423 B1
    权利要求:
    Claims (18)
    [1]
    claims
    1. Method for producing a colored technical ceramic, comprising the following steps:
    providing a composition comprising alumina, at least one pigment component and optionally binders, preparing a green body therefrom, optionally debinding the green body, then subjecting the green body to treatment with a preparation containing one or more metals as another pigment component, and sintering of the treated green body.
    [2]
    2. The method of claim 1, wherein the composition comprises binders and wherein the method comprises the debinding step which consists in treating the green body thermally, or in treating the green body with an aqueous solution and then drying the treated green body .
    [3]
    3. Method according to claim 1 or 2, wherein the at least one pigment component is a metal chosen from the group consisting of chromium, nickel, manganese, vanadium, titanium and iron, which metal is present in substitution on one of the sites of the alumina network.
    [4]
    4. Method according to one of the preceding claims, wherein the composition provided in the first step contains magnesium in the amount of 0.0008 to 5% by weight, calculated as the amount of magnesia in the composition.
    [5]
    5. Method according to one of the preceding claims, wherein the composition provided in the first step consists of: 0.4-5% by weight of at least one of Cr, Co, Ni, Μη, V, Tl or Fe
    0.0008-0.5% by weight of Mg, 0.05-6% by weight of a lanthanide element, and supplemented with 100% by weight of alumina, these quantities being calculated on the basis of the oxides of the elements present .
    [6]
    6. Method according to one of the preceding claims, the composition consisting of:
    1.0-3.0% by weight of Cr 2 O 3 ,
    0.05-0.5% by weight of MgO,
    0.1-5% by weight of Er 2 O 3 and the rest in alumina.
    [7]
    7. Method according to one of the preceding claims, wherein the heat treatment for debinding of the green body is carried out at a temperature between 700 ° C and 1200 ° C.
    [8]
    8. Method according to one of the preceding claims, wherein the green body is partially subjected to a treatment with the preparation containing one or more metals.
    [9]
    9. Method according to one of the preceding claims, wherein the treatment with the preparation containing one or more metals is an impregnation with a solution of at least one metal salt as another pigment component, followed by drying of the impregnated ceramic.
    [10]
    10. The method of claim 9, wherein the impregnating solution is a solution of at least one salt of a metal selected from the group consisting of Co, Cu, Cr, Fe, Mg, Mn, Mo, Ni, Tl , and Zn, this at least one salt being dissolved in water and / or, if appropriate, in at least one organic solvent.
    [11]
    11. The method of claim 9 or 10, wherein the drying step after impregnation is carried out at room temperature for 12 to 24 hours, or at 60-100 ° C for 1 to 60 minutes.
    [12]
    12. Method according to one of the preceding claims, in which the green body which has been treated with a preparation containing one or more metals as another pigment component and has been optionally dried is sintered at a temperature between 1250 ° C and 1700 ° C, preferably at a temperature between 1550 ° C and 1670 ° C.
    [13]
    13. Method according to one of the preceding claims, wherein the colored technical ceramic is shaped so that it forms a watch component, in particular a watch bezel or a watch case.
    [14]
    14. Colored technical ceramic, consisting of alumina as a technical ceramic material, technical ceramic comprising a first colored zone and a second colored zone of a different color, where the first colored zone contains a first pigment component, and the second colored area contains a second pigment component comprising one or more metals in association with the first pigment component.
    [15]
    15. A colored technical ceramic according to claim 14, wherein the first pigment component is Cr present in substitution in the crystal lattice of alumina and the second pigment component is a mineral complex pigment component having a spinel crystal structure of the space group Fd -3m.
    [16]
    16. A colored technical ceramic according to claim 14 or 15, wherein the first colored area is red and the second colored area is blue.
    CH 707 423 B1
    [17]
    17. Colored technical ceramic according to one of claims 14 to 16 which is a watch bezel.
    [18]
    18. Watch, characterized in that it comprises a colored technical ceramic according to one of claims 14 to 17.
    CH 707 423 B1
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    同族专利:
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    EP2746243A1|2014-06-25|
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    JP2020007221A|2020-01-16|
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    JP2016500363A|2016-01-12|
    EP2746243B1|2018-10-31|
    CN105073686B|2018-09-25|
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    法律状态:
    2018-12-14| PFA| Name/firm changed|Owner name: ROLEX SA, CH Free format text: FORMER OWNER: ROLEX SA, CH |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12198975|2012-12-21|
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