Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
  • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
  • C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
  • C04B35/5611—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
  • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
  • C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B19/00—Indicating the time by visual means
  • G04B19/04—Hands; Discs with a single mark or the like
  • G04B19/042—Construction and manufacture of the hands; arrangements for increasing reading accuracy
• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B19/00—Indicating the time by visual means
  • G04B19/06—Dials
  • G04B19/12—Selection of materials for dials or graduations markings
• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B19/00—Indicating the time by visual means
  • G04B19/28—Adjustable guide marks or pointers for indicating determined points of time
• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B29/00—Frameworks
  • G04B29/02—Plates; Bridges; Cocks
  • G04B29/027—Materials and manufacturing
• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B37/00—Cases
  • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
  • G04B37/225—Non-metallic cases
• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects
  • G04B45/0076—Decoration of the case and of parts thereof, e.g. as a method of manufacture thereof
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
  • C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
  • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
  • C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/38—Non-oxide ceramic constituents or additives
  • C04B2235/3817—Carbides
  • C04B2235/3839—Refractory metal carbides
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/38—Non-oxide ceramic constituents or additives
  • C04B2235/3817—Carbides
  • C04B2235/3839—Refractory metal carbides
  • C04B2235/3843—Titanium carbides
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/38—Non-oxide ceramic constituents or additives
  • C04B2235/3817—Carbides
  • C04B2235/3839—Refractory metal carbides
  • C04B2235/3847—Tungsten carbides
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
  • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
  • C04B2235/604—Pressing at temperatures other than sintering temperatures
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
  • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
  • C04B2235/6567—Treatment time
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
  • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
  • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
  • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
  • C04B2235/9646—Optical properties
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
  • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
  • C04B2235/9646—Optical properties
  • C04B2235/9661—Colour
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/64—Burning or sintering processes

Definitions

• the present invention relates to a decorative article and in particular to a cladding component in watchmaking, made of a ceramic composite material. It also relates to its manufacturing process.
• composite ceramic materials having, among other things, the advantage of having very high hardnesses which guarantee their ability not to be scratched.
• the literature mainly reports on composites consisting mainly of an oxide such as alumina to which carbides are added. It can, for example, be composites comprising by weight 70% of ALOs and 30% of TiC used as reinforcement. These composites have the characteristic of having little or no metallic luster compared to other materials such as stainless steels or cermets, which can be a disadvantage for decorative articles where this luster is desired.
• the present invention thus aims to overcome the aforementioned disadvantage by providing a ceramic material with a composition adapted to present this metallic luster.
• the present invention provides a decorative article produced in a ceramic mainly comprising a carbide phase and minority an oxide phase. More specifically, the present invention provides a decorative article made of a ceramic material comprising by volume a carbide phase in a percentage between 50 and 95%, preferably between 51 and 85%, and an oxide phase in a percentage included between 5 and 50%, preferably between 15 and 49%.
• the carbide phase comprises one or more carbides chosen from TiC, M02C and NbC and the oxide phase comprises one or more oxides chosen from I ⁇ I2O3, ZrÜ2, Cr2Ü3 and I ⁇ 2O3.
• the carbide phase mainly comprises TiC or M02C and the oxide phase mainly comprises I ⁇ I2O3, preferably in alpha phase mainly or a mixture of alpha phase and gamma phase, or ZrÜ2; the latter is preferably a stabilized zirconia, for example with Y2O3.
• the oxide phase comprising predominantly aluminum oxide also comprises predominantly chromium oxide.
• the decorative article comprises a carbide phase mainly comprising titanium carbide and said carbide phase mainly comprising titanium carbide is present in a percentage by volume of between 55 and 90% , preferably between 60 and 85%, the oxide phase being present in a percentage by volume of between 10 and 45%, preferably between 15 and 40%.
• said carbide phase can comprise niobium carbide in the minority.
• the decorative article comprises a phase of carbides predominantly comprising molybdenum carbide and said phase of carbides predominantly comprising molybdenum carbide is present in a percentage by volume of between 50 and 75%, preferably between 51 and 75%, the oxide phase being present in a percentage by volume of between 25 and 50%, preferably between 25 and 49%.
• said carbide phase consists of titanium carbide and said oxide phase consists of aluminum oxide, said carbide phase being present in a percentage by volume of between 65 and 85, preferably between 70 and 80%, and said oxide phase being present in a percentage by volume of between 15 and 35%, preferably between 20 and 30%.
• said carbide phase consists of titanium carbide and said oxide phase consists mainly of aluminum oxide and mainly chromium oxide, said carbide phase being present in a volume percentage of between 55 and 75%, preferably between 60 and 70%, and said oxide phase being present in a volume percentage of between 25 and 45%, preferably between 30 and 40%
• the composite material thus developed exhibits, after polishing, a metallic luster similar to that observed in stainless steels or cermets using nickel or cobalt as metallic binder.
• These composites have the other advantages of being free of allergenic elements such as Ni, of being resistant to corrosion and of not being magnetic. They also have high hardness and sufficient toughness for the production of covering elements. In addition, they can be shaped by conventional powder metallurgy methods such as pressing or injection in order to obtain “near-net shape” parts.
• FIG. 1 represents a timepiece comprising a middle part made with the ceramic material according to the invention.
• FIG. 2 represents an electron microscopy image of the ceramic material according to the invention.
• the present invention relates to a decorative article made of a ceramic composite material.
• the decorative article can be a component of watches, jewelry, bracelets, etc. or more generally an external part of a portable element such as a mobile phone.
• this article can be a piece of clothing such as a middle part, a back, a bezel, a pusher, a bracelet link, a dial, a hand, a dial index, etc.
• a middle part 1 produced with the ceramic material according to the invention is shown in FIG. 1.
• the ceramic material comprises a carbide type phase constituting the matrix and an oxide type phase distributed within the matrix.
• the carbide phase is present in the ceramic material in a volume percentage of between 50 and 95% and the complementary oxide phase is present in a volume percentage of between 5 and 50%.
• the carbide phase is present in the ceramic material in a percentage by volume of between 51 and 85% and the complementary oxide phase is present in a percentage by volume of between 15 and 49%.
• the carbide phase includes one or more types of carbides.
• the carbide phase comprises one or more carbides chosen from TiC, M02C and NbC.
• the carbide phase mainly comprises TiC or M02C.
• the oxide phase may comprise one or more oxides chosen, for example, from I ⁇ I2O3, ZrÜ2, Cr203, Y2O3, etc.
• the oxide phase comprises one or more oxides chosen from I ⁇ I2O3, ZrÜ2 and Cr203. More preferably, the oxide phase mainly comprises I ⁇ I2O3 or ZrÜ2.
• the ceramic article is produced by sintering starting from a mixture of carbide and oxide powders.
• the present invention therefore does not relate to a composite material with a ceramic matrix reinforced with a directional load such as ceramic fibers.
• the manufacturing process includes the steps of:
• the starting powders preferably have a d50 of less than 45 ⁇ m.
• the mixing can optionally be carried out in a grinder or ball mill, which reduces the d50 of the powder particles to a size of the order of a few microns ( ⁇ 5pm) after grinding.
• This mixture comprises by volume between 50 and 95% of a carbide powder and between 5 and 50% of an oxide powders, each powder comprising respectively one or more carbides and one or more oxides as indicated above.
• the carbide powder mainly comprises titanium carbide (TiC) or molybdenum carbide (M02C). It can, except for impurities, consist entirely of TiC or M02C.
• the oxide powder mainly comprises aluminum oxide (AI2O3) or zirconium oxide (ZrC). It can, apart from impurities, consist entirely of Al203 or ZrÜ2. As a variant, it may contain I ⁇ I2O3 or ZrÜ2 and another oxide such as Cr203, the latter being present in the majority in the oxide powder and having the object of modifying the properties obtained.
• the powder mixture may contain one of the following distributions by volume for a total of 100%:
• a second mixture comprising the above-mentioned mixture and an organic binder system (paraffin, polyethylene, etc.) can be produced.
• an organic binder system paraffin, polyethylene, etc.
• the blank thus obtained is cooled and polished. It can also be machined before sintering and / or before polishing to obtain the desired article.
• the article resulting from the manufacturing process comprises the phase comprising carbides and the phase comprising oxides in volume percentages close to those of the starting powders. Indeed, a priori, the carbide and oxide phases coexist without the formation of new phases during sintering. One cannot however exclude small variations in compositions and percentages between the basic powders and the material resulting from sintering following, for example, contamination.
• the article has a CIELAB color space (conforms to CIE standards n ° 15, ISO 7724/1, DIN 5033 Part 7, ASTM E-1164) with a luminance component L * , representative of the way in which the material reflects light , between 60 and 85 and preferably between 65 and 80.
• the components a * (red component) and b * (yellow component) can be modulated as desired depending on the choice of oxides.
• the components a * and b * are respectively between -1 and 5 and between -2 and 5.
• the component a * is between -0.5 and 2 and the component b * is between -0.5 and 3.
• a ceramic material with a white metallic appearance may be preferred. In which case, the components a * and b * are equal to 0.
• the ceramic material has an HV30 hardness of between 1200 and 1950 depending on the types and percentages of the constituents. It has a toughness KiC of between 2 and 8.5 MPa.m 1/2 , the toughness being determined on the basis of measurements of the lengths of the cracks at the four ends of the diagonals of the hardness imprint according to the formula:
• the ceramic material comprising a carbide phase consisting of TiC and an oxide phase consisting of ALC, apart from impurities, exhibits a very good toughness-hardness compromise. So when this carbide phase is present in a percentage volume between 65 and 85, preferably between 70 and 80%, with the complementary phase of A Os, the HV30 values are greater than or equal to 1800, or even 1900, and the Kic values are greater than or equal to 3.5 MPa. m 1/2 .
• the ceramic material comprising a carbide phase consisting of TiC and an oxide phase consisting of Al2C> 3 and O2O3, apart from impurities, exhibits a very good toughness-hardness compromise.
• this carbide phase is present in a percentage by volume of between 55 and 75%, preferably between 60 and 70%, with the complementary phase of Al203 and O2O3, the HV30 values are greater than or equal to 1800 and the Kic values are greater than or equal to 4.5, or even to 5 MPa.m 1/2 .
• Seven powder mixtures were prepared in a grinder in the presence of a solvent.
• the mixtures were made without a binder. They were shaped by pressing and sintered under a flow of argon at 60 mbar at a temperature which depends on the composition of the powders. After sintering, the samples were coated and plane polished.
• HV30 hardness measurements were carried out on the surface of the samples and the toughness was determined on the basis of the hardness measurements as described above.
• the powder mixture comprises by weight 80% TiC and 20% AI2O3 (in alpha phase) or by volume respectively 76% and 24%.
• the blank was sintered at 2000 ° C for 20 minutes.
• the sample has an average hardness of 1932 HV30 and a toughness of 4 MPa.m 1/2 .
• the Lab components are respectively equal to 66.3, 0.44 and 0.73.
• Example 2 (70% TiC. 10% NbC and 20% AI2O3 by weight).
• the powder mixture comprises by weight 70% TiC, 10% NbC and 20% AI2O3 (in alpha phase) or by volume respectively 69%, 6% and 25%.
• the blank was sintered at 1800 ° C for 30 minutes.
• the sample has an average hardness of 1255 HV30 and a toughness of 3.8 MPa.m 1/2 .
• the Lab components are respectively equal to 63.3, 0.00 and 0.09.
• the addition of NbC lowers the sintering temperature by 200 ° C but has the effect of reducing the hardness.
• Example 3 (70% TiC, 25% AI2O3 and 5% Cr203 by weight)
• the powder mixture comprises by weight 70% TiC, 25% AI2O3 (in alpha phase) and 5% Cr203, ie by volume respectively 66%, 29.5% and 4.5%.
• the blank was sintered at 1750 ° C for 90 minutes.
• the sample has an average hardness of 1830 HV30 and a toughness of 5.2 MPa.m 1/2 .
• the Lab components are respectively equal to 64.5, 0.34 and 0.92.
• the addition of 5% Cr2Ü3 makes it possible to obtain a high hardness and to increase the toughness.
• An electron microscopy image of this sample is shown in Figure 2, the gray phase represents the TiC matrix and the white phase represents the oxide phase.
• Example 4 (80% TiC and 20% ZrÜ2 by weight)
• the powder mixture comprises by weight 80% TiC and 20% ZrÜ2 (stabilized zirconia containing 3% molar of Y203), ie by volume 82% and 18% respectively.
• the blank was sintered at 1750 ° C for 90 minutes.
• the sample has an average hardness of 1617 HV30 and a toughness 2.5 MPa.m 1/2 .
• the Lab components are respectively equal to 66.5, -0.39 and -1.14.
• the replacement of aluminum oxide by zirconia makes it possible to reduce the components a * and b * but also has the effect of reducing the toughness.
• Example 5 (85% M02C and 15% AI2O3 by weight)
• the powder mixture comprises by weight 85% M02C and 15% AI2O3 (in the alpha phase), ie by volume 72% and 28% respectively.
• the blank was sintered at 1450 ° C for 90 minutes.
• the sample has an average hardness of 1319 HV30 and a toughness of 5.3 MPa.m 1/2 .
• the Lab components are respectively equal to 72.5, 0.21 and 2.
• the replacement of the titanium carbide by the molybdenum carbide makes it possible to greatly reduce the sintering temperature while increasing the value of the luminance index L * .
• Example 6 (70% M02C and 30% AI2O3 by weight)
• the powder mixture comprises by weight 70% M02C and 30% AI2O3
• the blank (in the alpha phase), ie by volume 51% and 49% respectively.
• the blank was sintered at 1450 ° C for 90 minutes.
• the sample has an average hardness of 1417 HV30 and a toughness of 5.0 MPa.m 1/2 .
• the Lab components are respectively equal to 63.8, 0.13 and 1.49.
• the increase in the proportion of aluminum oxide makes it possible to increase the hardness but leads to a decrease in the luminance index L * .
• Example 7 (80% TiC, 18% AhCb and 2% Cr2C> 3 by weight)
• the powder mixture comprises by weight 80% TiC, 18% AI2O3 (in alphaj phase and 2% Cr2C> 3, ie by volume respectively 76.5%, 21.5 and 2%.
• the blank was sintered at 1650 ° C for 90 minutes
• the sample has an average hardness of 1219 HV30 and a toughness of 7.8 MPa.m 1/2 .
• the Lab components are respectively equal to 65, 0.06 and 0.4.
• the addition in low proportion of chromium oxide allows improve toughness.
• samples 1 and 3 have a very good toughness-hardness compromise with hardness and toughness values greater than 1800 HVso and 3.5 MPa.m 1/2 respectively and that sample 7 has a very good toughness with a value greater than 7 MPa.m 1/2 .

Landscapes

• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Ceramic Engineering (AREA)
• Manufacturing & Machinery (AREA)
• General Physics & Mathematics (AREA)
• Physics & Mathematics (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Metallurgy (AREA)
• Compositions Of Oxide Ceramics (AREA)
• Ceramic Products (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=64901291

Family Applications (2)

Family Applications Before (1)

Country Status (5)

Families Citing this family (1)

Family Cites Families (11)

• 2018
  • 2018-12-07 EP EP18211003.1A patent/EP3663273A1/de not_active Withdrawn
• 2019
  • 2019-11-11 WO PCT/EP2019/080898 patent/WO2020114725A1/fr unknown
  • 2019-11-11 US US17/298,860 patent/US20220033312A1/en active Pending
  • 2019-11-11 JP JP2021527914A patent/JP7145330B2/ja active Active
  • 2019-11-11 CN CN201980080469.1A patent/CN113165983A/zh active Pending
  • 2019-11-11 EP EP19798116.0A patent/EP3891109A1/de active Pending

Also Published As

Similar Documents

Legal Events