• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The present invention relates to a method of manufacturing a ceramic material product characterized in that it comprises the following steps of: a / - mixing a ceramic powder with a powder of cerium sulphide pigment so as to obtain a mixture homogeneous powders; b / - flash sintering of the homogeneous powders mixture for densifying said mixture, said sintering being carried out at a predetermined sintering temperature, said process comprising an intermediate step b1 / of heating said homogeneous powder mixture according to a temperature profile comprising: ○ a first phase of temperature rise at a first speed A during a first duration t1, ○ and a second phase of temperature rise at a second speed B lower than the first speed A for a second duration t2, until reaching the temperature sintering which is then maintained for a period t3.
    公开号:FR3060556A1
    申请号:FR1662951
    申请日:2016-12-20
    公开日:2018-06-22
    发明作者:Yannick Beynet；Romain EPHERRE；Florence Ansart；Pascal Lenormand；Claude Estournes
    申请人:Centre National de la Recherche Scientifique CNRS；Universite Paul Sabatier Toulouse III；Norimat SAS；
    IPC主号:
    专利说明:

    Holder (s): NORIMAT Simplified joint-stock company, UNIVERSITE PAUL SABATIER TOULOUSE III Public establishment, NATIONAL CENTER FOR SCIENTIFIC RESEARCH Public establishment.
    Extension request (s)
    Agent (s): IPSIDE.
    FR 3 060 556 - A1 (54) PROCESS FOR THE MANUFACTURE OF A RED-COLORED CERAMIC MATERIAL.
    ©) The present invention relates to a process for manufacturing a product made of ceramic material, characterized in that it comprises the following steps:
    a / - mixing a ceramic powder with a powder of Cerium Sulfide pigment so as to obtain a homogeneous powder mixture;
    b / - flash sintering of the homogeneous powder mixture to densify said mixture, said sintering being carried out at a so-called predetermined sintering temperature, said method comprising an intermediate step b ·, / of heating said homogeneous powder mixture according to a temperature profile comprising :
    O a first temperature rise phase at a first speed A for a first duration t · ,,
    O and a second phase of temperature rise at a second speed B lower than the first speed A for a second duration t 2 , until reaching the sintering temperature which is then maintained for a duration t 3 .
    Field of the invention
    The present invention applies to the field of ceramic materials. More particularly, the present invention applies to the field of methods for the production of ceramic materials.
    The present invention relates to a process for manufacturing a ceramic material of red color. The invention also relates to a ceramic material capable of being obtained by said process as well as to horological, jewelry or jewelry products comprising such a ceramic material.
    State of the art
    Among the processes for manufacturing ceramic materials, it is known today to use powder sintering processes.
    Assisted sintering techniques under an electric field are well known for the densification and assembly of new polymer materials, metals and nanostructured ceramics and nanocomposites. One of these techniques called flash sintering or “spark Plasma Sintering” (SPS) in English terminology, the most widespread in the world, is similar to conventional hot pressing, but it has the distinction of using series of pulses of high intensity electric current to generate the heating of tools generally conductive of electricity (eg graphite, carbide, steel ...) applying a uniaxial pressure on a sample to be densified placed in said tooling. The application of this current allows the heating of the sample by Joule effect. Either the sample is conductive and the current flows through the sample, which leads to its direct heating. Either the sample is insulating and the current then passes through a conductive graphite matrix in which the sample is placed beforehand, which in turn heats the sample by conduction.
    The advantage of this technique is that it allows materials to be densified very quickly in a few tens of minutes.
    A typical flash sintering device conventionally comprises a sintering chamber which is generally under vacuum (a few Pascals), two electrodes between which is inserted a column generally made of graphite containing the tools and which jointly make it possible to apply the electric current and the pressure uniaxial to the sample through the tools. The tools are made of a refractory and electrically conductive material, this material preferably has a coefficient of expansion lower than that of the material that one seeks to obtain by flash sintering. The tool has internal walls defining a cavity with a shape complementary to that of the part to be produced from the material thus produced.
    In the fields of jewelry, watchmaking and fine jewelry, ceramic materials are often used. For example, some watches have a case made of ceramic material or another part such as the middle, the back, the bezel, the insert, the crown, the bracelet, etc. Such ceramic materials need to have high mechanical strength, low density (lightness), high hardness, high rigidity, high resistance to wear, cracking, heat and chemical agents, but also to be inert and hypoallergenic.
    Most of the ceramic pieces used today are black, white, blue or even brown. For aesthetic reasons, it would be interesting to be able to have ceramic materials of homogeneous red color.
    However, today there is no known prior art method for obtaining in a controlled manner ceramic materials of uniform red color and having hardness properties compatible with their use in fields such as those of jewelry, watchmaking and fine jewelry.
    The present invention aims to propose such a method, which is easy and quick, making it possible to obtain a product made of ceramic material of homogeneous red color.
    Statement of the invention
    To this end, according to a first aspect, the present invention relates to a method of manufacturing a ceramic material characterized in that it comprises the following steps:
    a / - mixing a ceramic powder with a pigment powder
    Cerium sulphide so as to obtain a homogeneous powder mixture;
    b / - flash sintering of the homogeneous powder mixture to densify said mixture, said flash sintering being carried out at a so-called predetermined sintering temperature and comprising a prior step bi / of heating said homogeneous powder mixture according to a temperature profile comprising:
    o a first phase of temperature rise at a first speed A for a first period ti, o and a second phase of temperature rise at a second speed B lower than the first speed A for a second period t 2 , until reaching the sintering temperature.
    In a completely advantageous manner, it has been observed by the present inventors that such a process makes it possible to obtain a ceramic material of homogeneous red color, devoid in particular of dark spots detrimental to its aesthetic appearance. It also makes it possible to precisely control the colorimetry of the ceramic material formed.
    Adjusting the sintering conditions is within the competence of a person skilled in the art who knows perfectly well, depending on the ceramic material used, to determine the operating conditions, in particular the temperature, the duration, the compression, the intensity of the pulsed current, etc., to obtain the desired final densification.
    According to preferred modes of implementation, the invention also meets the following characteristics, implemented separately or in each of their technically operative combinations.
    In one embodiment, flash sintering is carried out until densification of the homogeneous powder mixture of between 90% and 100%, preferably between 95% and 100%, more preferably greater than or equal to 98%, is obtained.
    In a particular implementation, step b / flash sintering comprises applying to said homogeneous powder mixture a uniaxial pressure called sintering pressure between 25 and 130 MPa, preferably between 50 and 100 MPa.
    In a particular embodiment, the method comprises before and / or during the prior step bi /, a phase of rise in uniaxial pressure applied to said homogeneous powder mixture of duration t p up to uniaxial pressure sintering. For example, before the first temperature rise phase, the method can comprise a uniaxial pressure rise phase of duration t p of one minute at a temperature of 50 ° C., up to the uniaxial sintering pressure.
    In a particular embodiment, the sintering temperature is between 950 ° C and 1150 ° C. Preferably, the sintering temperature is between 1000 ° C and 1050 ° C.
    In a particular embodiment, the sintering temperature is maintained for a third duration t 3 of between one and ten minutes.
    In a particular embodiment, the method comprises, after step b / of sintering, a phase of descent in temperature and in uniaxial pressure for a fourth duration t4, to ambient temperature and zero uniaxial pressure. According to a particular embodiment, the duration t 4 is between one and ten minutes. Preferably, it is five minutes. The descent in temperature and in uniaxial pressure of such a fourth duration t 4 is recommended to accommodate the stresses in the ceramic and thus limit the risks of cracking.
    In a particular embodiment, the first duration ti is between five and ten minutes, and the second duration t 2 is between one and three minutes.
    In a particular implementation, the first duration ti is nine minutes, the second duration t 2 is two minutes, the sintering temperature is 1050 ° C, the uniaxial sintering pressure is 100 MPa and the third duration t 3 is five minutes.
    In a particular embodiment, the first speed A is greater than 10 ° C / min and less than or equal to 200 ° / min, preferably greater than 50 ° C / min and less than or equal to 150 ° / min, even more preferably greater than 90 ° C / min and less than or equal to 120 ° C / min. In one embodiment, the second speed B is greater than or equal to 10 ° C / min and less than 200 ° C / min, preferably greater than or equal to 50 ° C / min and less than 150 ° C / min, more preferably greater than or equal to 90 ° C / min and less than 120 ° C / min.
    In a particular embodiment, the first speed A is 100 ° C / min and the second speed B is 50 ° C / min.
    In a particular embodiment, the ceramic is chosen from zirconia, alumina and a mixture of zirconia and alumina.
    In a particular embodiment, the ceramic is zirconia reinforced with alumina (ATZ or "Alumine Toughened Zirconia" in English terminology).
    In a particular embodiment, the powder mixture comprises a mass percentage of the cerium sulphide pigment of between 1% and 20%, preferably between 5% and 20%.
    In a particular embodiment, the mixture of powders comprises a mass percentage of the Cerium Sulfide pigment equal to 5%, 10% or 20%.
    In a particular implementation, sintering additions, such as ΓΑΙ2Ο3, T1O3, Y2O3, MgO, CaO, CeO2, etc., are added to the powders during step a / of mixing to improve the sinterability of the mixture. of powders and / or the mechanical properties of the product made of ceramic material obtained by the process which is the subject of the present invention.
    According to a second aspect, the present invention relates to a ceramic material of homogeneous red color capable of being obtained by the process which is the subject of the present invention, said ceramic material comprising a ceramic chosen from zirconia, alumina and a mixture of zirconia and alumina, and further comprising a cerium sulphide pigment, the colorimetry of the ceramic material being between 30 and 60 for the parameter L, between 10 and 40 for the parameter a and between 0 and 20 for the parameter b, according to the L * a * b * system of the International Commission on Lighting, the hardness of the ceramic material being between 1000 and 1500
    Hv, preferably between 1200 and 1500 Hv, and the toughness of the ceramic material being between 4 and 10 MPa.m 1/2 .
    Such a red color with such hardness and toughness properties has never been achieved before for ceramic materials.
    Finally, according to a last aspect, the present invention relates to a product from the field of jewelery, watchmaking or fine jewelry, comprising a homogeneous red colored ceramic material which is the subject of the present invention.
    Presentation of the figures
    The invention will be better understood on reading the following description, given by way of nonlimiting example, and made with reference to the figures which represent:
    - Figure 1: Variation of the temperature parameter (1 A) and the uniaxial pressure parameter (1B) over time according to an implementation mode of the process object of the invention.
    - Figure 2: Image viewed with a scanning electron microscope (SEM) of a red ceramic material based on zirconia obtained by an implementation method of the object of the present invention.
    - Figure 3: Evolution curves of the value of the parameters L *, a * and b * of the ceramic material obtained by the process of the present invention implemented with zirconia, specular reflection included (SCI or “Specular Behavior Included” »In English terminology), according to the colorimetric system of the International Commission on Lighting, according to the percentage by mass of Cerium Sulfide pigment present in the homogeneous powder mixture.
    - Figure 4: SEM image of a ceramic material based on ATZ obtained by an implementation of the method of the present invention.
    Detailed description of the invention
    We note now that the figures are not to scale.
    More generally, the scope of the present invention is not limited to the embodiments and embodiments described above by way of nonlimiting examples, but on the contrary extends to all modifications to the scope of one skilled in the art. Each characteristic of an embodiment can be implemented in isolation or combined with any other characteristic of any other embodiment in an advantageous manner.
    The present invention relates, according to a first aspect, to a process for manufacturing a product made of ceramic material comprising the following steps:
    a / - mixing a ceramic powder with a pigment powder
    Cerium sulphide so as to obtain a homogeneous powder mixture;
    b / - flash sintering of the homogeneous powder mixture to densify said mixture, said sintering being carried out at a so-called predetermined sintering temperature and comprising a prior step bi / of heating said homogeneous powder mixture according to a temperature profile comprising:
    o a first phase of temperature rise at a first speed A for a first period ti, o and a second phase of temperature rise at a second speed B lower than the first speed A for a second period t 2 , until reaching the sintering temperature.
    The powder mixture must be homogeneous, that is to say that the distribution of the grains of cerium sulfide pigment powder among the grains of ceramic powder must be homogeneous. Such a homogeneity of the mixture can for example be obtained by the implementation of step a / of mixing the ceramic powder with the powder of pigment of Cerium Sulfide for a period of at least two hours. The mixing can be carried out dry in a mixer such as a Turbula® or in the wet process by attrition.
    Step b / flash sintering comprises applying to said homogeneous powder mixture a uniaxial pressure called predetermined sintering pressure.
    In the particular embodiment illustrated in FIG. 1, the step of b / flash sintering of the powder mixture is carried out at a uniaxial sintering pressure of 100 MPa (FIG. 1B) and a sintering temperature of 1050 ° C. (FIG. 1A).
    The process comprises before and / or during the prior step bi /, a phase of rise in uniaxial pressure on the homogeneous powder mixture of duration t p of one minute up to the uniaxial sintering pressure 100 MPa. This rise in uniaxial pressure takes place at a temperature of 50 ° C. in this embodiment.
    We also observe in this embodiment illustrated in FIG. 1, a first phase of temperature rise carried out at a first speed A of 100 ° C./min for a first period of nine minutes, and a second phase of temperature rise carried out at a second speed B of 50 ° C / min for a second duration fe of two minutes. The sintering temperature of 1050 ° C. is reached at the end of the second phase and is maintained for a third duration t 3 of five minutes. As illustrated in FIG. 1B, in this embodiment the uniaxial sintering pressure of 100 MPa is applied and maintained during the first, second and third duration t-ι, t 2 and t 3 , that is to say during the flash sintering comprising the duration t 3 , but also during the prior step bi / comprising the durations ti and t 2 . In other particular embodiments, the uniaxial sintering pressure is applied and maintained only during the duration t 3 , that is to say only during the flash sintering but not during the prior step bi /.
    The method also comprises, after step b / of flash sintering, a phase of descent in temperature and in uniaxial pressure for a fourth duration t 4 of five minutes up to ambient temperature and zero uniaxial pressure.
    The material used to carry out flash sintering is a flash sintering device commonly used, comprising a sintering chamber which is under vacuum or neutral atmosphere, two electrodes between which is inserted a graphite column containing the tools, said electrodes making it possible to apply an electric current and the pistons a uniaxial pressure, to the sample of powder mixture via the tools. The tools are made of a refractory material and conductor of the electric current, this material having a coefficient of expansion lower than that of the ceramic material that one seeks to obtain by flash sintering. The tools also have internal walls delimiting a cavity of shape complementary to that of the part to be produced in ceramic material.
    EXAMPLES
    Example: Manufacture of a red ceramic material based on zirconia.
    The ceramic powder used is TZ3Y zirconia powder (stabilized zirconia 3 mol% of yttrin). The grain size of the ceramic powder is 63 ± 8 nm.
    The grain size of the Cerium Sulfide powder is approximately 200 nm ± 24 nm.
    Different mixtures of these two powders with a final quantity equal to 15 g are produced:
    - TZ3Y (control) = Zirconia TZ3Y + 0% by mass of Ce 2 S 3 pigment;
    - TZ3Y5 = Zirconia TZ3Y + 5% by mass of Ce2S 3 pigment;
    - TZ3Y10 = Zirconia TZ3Y + 10% by mass of Ce2S 3 pigment;
    - TZ3Y20 = Zirconia TZ3Y + 20% by mass of Ce 2 S 3 pigment.
    In each mixture are added 15 g of attrition beads. Each powder mixture is then placed in a Turbula® type mixer to be mixed for two hours, without adding any binder or other organic compounds.
    After the mixing step, each of the powder mixtures is placed separately in a graphite matrix lined with a sheet of flexible graphite (for example of the Papersex® type from the manufacturer MERSEN) to ensure electrical contact during flash sintering.
    To avoid pollution of powder mixtures by residues of flexible graphite sheets, graphite is deposited in the form of a spray at the interface between the pistons and the powder mixtures. The aim is to protect the tools while limiting reactions with the powder mixture. This spray can be based on boron nitride.
    Each graphite matrix comprising a mixture of powders is placed in the flash sintering apparatus and densification by flash sintering is carried out according to the operating conditions set out in FIG. 1:
    - rise in uniaxial pressure on the homogeneous powder mixture for a duration t p of one minute up to the uniaxial sintering pressure 100 MPa. This rise in uniaxial pressure takes place at a temperature of 50 ° C;
    - always at uniaxial pressure of 100 MPa, a first temperature rise phase is carried out at a first speed A of 100 ° C / min for a first duration ΐ of nine minutes, and a second temperature rise phase is carried out at a second speed B of 50 ° C / min for a second duration t2 of two minutes;
    - always at a uniaxial pressure of 100 MPa, the sintering temperature of 1050 ° C is reached at the end of the second phase and is maintained for a third duration t 3 of five minutes;
    - descent in temperature and uniaxial pressure for a fourth duration t4 of five minutes to room temperature and zero uniaxial pressure.
    The different ceramic materials obtained are then polished using five diamond discs (grains 220, 500, 1200, 2000 and 4000) and a felt disc on which a silicate solution is deposited. The entire flexible graphite sheet is removed using an automatic polisher. The ceramic materials obtained are examined with a scanning electron microscope. Figure 2 illustrates an image viewed with a scanning electron microscope of the red ceramic material from the TZ3Y10 mixture.
    Mixture of powders TZ3Y10 Composition TZ3Y + 10% mass Ce 2 S 3 Grain size TZ3Y before sintering (nm) 63 + 8 Grain size TZ3Y after sintering (nm) 115 + 24
    Table 1: Evolution of the grain size after flash sintering for the mixture of TZ3Y10 powders.
    A slight growth of the grains is observed but which remains of 5 nanometric sizes (Table 1). The three important reasons are: the sintering temperature which is low (less than 1200 ° C.), the uniaxial pressure applied during sintering which lowers the reaction temperatures and the sintering time t3 of five minutes.
    Nomenclature Sintering temperature (° C) Densification rate(%) Hardness(H v) Hardness(GPa) Tenacity(MPa.ml/2) TZ3Y 1050 99% 1487 14.58 + 0.10 / TZ3Y5 1050 99% 1472 14.44 +0.30 6.21 +0.54 TZ3Y10 1050 99% 1332 13.06 + 0.19 5.41 +0.40 TZ3Y20 1050 98% 1224 12.00 +0.22 4.87 +0.33
    Table 2: Mechanical characterizations of the ceramic materials obtained.
    Density analyzes by the Archimedes method using a hydrostatic balance, Vickers hardness, and toughness by Vickers micro-indentation have shown that the ceramic materials obtained according to the process of the present invention have a rate of densification greater than or equal to
    98%, a hardness between 1220 and 1490 Hv, and a toughness between 4.5 and 6.8 MPa.m 1/2 (Table 2). The evolution of the parameters of colorimetry L *, a * and b * of the ceramic materials obtained by the process of the present invention implemented with zirconia, specular reflection included (SCI or “Specular Component Included” in English terminology) , according to the colorimetric system of the International Commission on Lighting, according to the mass percentage of pigment Sulfide of
    Cerium present in the powder mixture, is illustrated by the curves in Figure 3.
    It is noted that for the mixture of powders TZ3Y5 one obtains a colorimetry of parameters L * a * b * of 48/9/5, for the mixture of powder TZ3Y10 one obtains a colorimetry of parameters L * a * b * of 49/20 / 11 and, for the mixture of powders TZ3Y20, a colorimetry of parameters L * a * b * of 50/25/12 is obtained. TZ3Y zirconia powder alone gives a material whose colorimetry has parameters L * a * b * of 48/1/0.
    Example 2: Manufacture of a red ceramic material based on zirconia reinforced with alumina.
    The ceramic powder used is powder of zirconia reinforced with alumina (ATZ-20/80, 150 nm alpha alumina / 20 nm zirconia stabilized 2.5 mol%). The grain size of the ceramic powder is between 80 µm to 100 µm.
    The grain size of the Cerium Sulfide powder is approximately 200 nm ± 24 nm.
    Different mixtures of these two powders with a final quantity equal to 15 g are produced:
    - ATZ (control) = ATZ + 0% by mass of Ce 2 S3 pigment;
    - ATZ10 = ATZ + 10% by mass of Ce 2 S 3 pigment;
    In each mixture are added 15 g of attrition beads. Each powder mixture is then placed in a Turbula® type mixer to be mixed for two hours, without adding any binder or other organic compounds.
    After the mixing step, each of the powder mixtures is placed separately in a graphite matrix lined with a sheet of flexible graphite (for example of the Papersex® type from the manufacturer MERSEN) to ensure electrical contact during flash sintering.
    As in Example 1, graphite is deposited in the form of a spray at the interface between the pistons and the powder mixtures.
    Each graphite matrix comprising a mixture of powders is placed in the flash sintering apparatus and densification by flash sintering is carried out under the operating conditions set out in FIG. 1 and cited in Example 1.
    The different ceramic materials obtained are then polished in the same manner as described in Example 1. The entire flexible graphite sheet is also removed and the ceramic materials obtained are examined using a scanning electron microscope. Figure 4 illustrates an image viewed with a scanning electron microscope of the red ceramic material from the ATZ10 mixture.
    Samples ATZ10 Phase Alumina Yttria Zirconia Grain size before sintering (nm) 272 + 89 36 + 8 Grain size after sintering (nm) 262 + 78 264 + 34
    Table 3: Evolution of the grain size after flash sintering for the mixture of ATZ10 powders.
    We observe a certain growth of the zirconia grains (x7) but 15 which remain submicron sizes (Table 3).
    Nomenclature Sintering temperature (° C) Densification rate (%) Hardness(H v) Hardness(GPa) Tenacity(MPa.ml/2) ATZ 1050 95% 1391 13.64 +0.53 / ATZ10 1050 98% 1442 14.14 + 0.27 7.43 +0.66
    Table 4: Mechanical characterizations of the ceramic materials obtained.
    Density analyzes by the Archimedes method using a hydrostatic balance, Vickers hardness, and tenacity by Vickers micro-indentation, have shown that the ceramic materials obtained according to the process of the present invention exhibit densification rate greater than or equal to 98%, a hardness close to 1442 Hv, and a toughness between 6 and 8
    MPa.m 1/2 (Table 4).
    Example 3: Manufacture of a red ceramic material based on alumina.
    The ceramic powder used is alumina powder, the grain size of which is approximately 150 nm.
    The grain size of the Cerium Sulfide powder is approximately
    200 nm.
    Different mixtures of these two powders with a final quantity equal to 15 g are produced:
    - AA (control) = Alumina + 0% by mass of Ce2S3 pigment;
    - AA20 = Alumina + 20% by mass of Ce2S3 pigment;
    As in the previous examples, 15 g of attrition beads are added to each mixture. Each powder mixture is then placed in a Turbula® type mixer to be mixed for two hours, without adding any binder or other organic compounds.
    After the mixing step, each of the powder mixtures is placed separately in a graphite matrix lined with a sheet of flexible graphite (for example of the Papersex® type from the manufacturer MERSEN) to ensure electrical contact during flash sintering. graphite is also deposited in the form of a spray at the interface between the pistons and the powder mixtures.
    Each graphite matrix comprising a mixture of powders is placed in the flash sintering apparatus and a flash sintering is carried out under the operating conditions set out in FIG. 1 and cited in Example 1.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1 - Process for manufacturing a product made of ceramic material, characterized in that it comprises the following steps:
    a / - mixing a ceramic powder with a powder of Cerium Sulfide pigment so as to obtain a homogeneous powder mixture;
    b / - flash sintering of the homogeneous powder mixture to densify said mixture, said flash sintering being carried out at a so-called predetermined sintering temperature and comprising a prior step bi / of heating said homogeneous powder mixture according to a temperature profile comprising:
    o a first phase of temperature rise at a first speed A for a first period ti, o and a second phase of temperature rise at a second speed B lower than the first speed A for a second period t 2 , until reaching the sintering temperature.
    [2" id="c-fr-0002]
    2 - The manufacturing method according to claim 1, wherein step b / flash sintering comprises applying to said mixture of homogeneous powders a uniaxial pressure called predetermined sintering pressure between 25 and 130 MPa, preferably between 50 and 100 MPa.
    [3" id="c-fr-0003]
    3 - Process according to claim 2, comprising before and / or during the prior step bi /, a phase of rise in uniaxial pressure applied to said homogeneous powder mixture, of duration t p , until the uniaxial pressure of sintering.
    [4" id="c-fr-0004]
    4 - Process according to any one of claims 1 to 3, wherein the sintering temperature is between 950 ° C and 1150 ° C, preferably between 1000 ° C and 1050 ° C.
    [5" id="c-fr-0005]
    5 - Method according to any one of claims 1 to 4, wherein the sintering temperature is maintained for a third time t3 between one and ten minutes.
    [6" id="c-fr-0006]
    6 - Method according to any one of claims 1 to 5, comprising after step b / sintering, a phase of descent in temperature and in uniaxial pressure to room temperature and zero uniaxial pressure, for a fourth period t 4 between one and ten minutes, preferably being five minutes.
    [7" id="c-fr-0007]
    7 - Method according to any one of claims 1 to 6, wherein the first duration ti is between five and ten minutes, and the second duration t 2 is between one and three minutes.
    [8" id="c-fr-0008]
    8 - The manufacturing method according to any one of claims 1 to 7, wherein the first speed A is 100 ° C / min and the second speed B is 50 ° C / min.
    [9" id="c-fr-0009]
    9 - The manufacturing method according to any one of claims 1 to 8, wherein the ceramic is chosen from zirconia, alumina and a mixture of zirconia and alumina.
    [10" id="c-fr-0010]
    10- The method of claim 9, wherein the ceramic is zirconia reinforced with alumina (ATZ).
    [11" id="c-fr-0011]
    11 - The manufacturing method according to any one of claims 1 to 10, wherein the powder mixture comprises a mass percentage of pigment Cerium Sulfide between 1% and 20%, preferably between 5 and 20%.
    [12" id="c-fr-0012]
    12 - Manufacturing process according to any one of claims 1 to 10, wherein the powder mixture comprises a mass percentage of pigment Cerium Sulfide equal to 5%, 10% or 20%.
    [13" id="c-fr-0013]
    13 - Ceramic material of homogeneous red color capable of being obtained by a process according to any one of claims 1 to 12, comprising a ceramic chosen from zirconia, alumina and a
    5 mixture of zirconia and alumina, and further comprising a pigment of
    Cerium sulphide, the colorimetry of the ceramic material being between 30 and 60 for parameter L, between 10 and 40 for parameter a and between 0 and 20 for parameter b, according to the Commission's L * a * b * system lighting, the hardness of the material being
    10 between 1000 and 1500 Hv, preferably between 1200 and 1500 Hv, and the toughness of the ceramic material being between 4 and 10 MPa.m 1/2 .
    [14" id="c-fr-0014]
    14- Product in the field of jewelery, watchmaking or jewelry comprising a homogeneous red ceramic material depending on the
    [15" id="c-fr-0015]
    15 claim 13.
    1/2
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    同族专利:
    公开号 | 公开日
    FR3060556B1|2022-03-04|
    WO2018115649A1|2018-06-28|
    EP3558893A1|2019-10-30|
    EP3558893B1|2020-10-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2010146311A1|2009-06-19|2010-12-23|Electricite De France|Production of self-supporting ceramic materials having a reduced thickness and containing metal oxides|
    WO2011120181A1|2010-04-01|2011-10-06|Rolex S.A.|Alumina-based opaque ceramic|
    CN104261842A|2014-08-31|2015-01-07|吴雪健|Preparation method of long-service-life sand jet for blast furnace tapping|CN110294629A|2019-08-15|2019-10-01|内蒙古科技大学|A kind of chromic lanthanum ceramics and preparation method thereof|
    FR3082765A1|2018-06-25|2019-12-27|Safran Aircraft Engines|METHOD FOR MANUFACTURING AN ABRADABLE LAYER|
    FR3088637A1|2018-11-16|2020-05-22|Commissariat A L'energie Atomique Et Aux Energies Alternatives|METHOD FOR MANUFACTURING A RED COLORED ARTICLE, RED COLORED ARTICLE, USES THEREOF AND PART COMPRISING SUCH AN ARTICLE|
    法律状态:
    2017-12-29| PLFP| Fee payment|Year of fee payment: 2 |
    2018-06-22| PLSC| Publication of the preliminary search report|Effective date: 20180622 |
    2019-12-27| PLFP| Fee payment|Year of fee payment: 4 |
    2020-12-31| PLFP| Fee payment|Year of fee payment: 5 |
    2021-12-23| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1662951A|FR3060556B1|2016-12-20|2016-12-20|PROCESS FOR MANUFACTURING A RED COLORED CERAMIC MATERIAL|
    FR1662951|2016-12-20|FR1662951A| FR3060556B1|2016-12-20|2016-12-20|PROCESS FOR MANUFACTURING A RED COLORED CERAMIC MATERIAL|
    EP17825576.6A| EP3558893B1|2016-12-20|2017-12-14|Method for manufacturing a red ceramic material|
    PCT/FR2017/053590| WO2018115649A1|2016-12-20|2017-12-14|Method for manufacturing a red ceramic material|
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