EP2655291A2 - Piece frittee coloree - Google Patents

Piece frittee coloree

Info

Publication number
EP2655291A2
EP2655291A2 EP11810692.1A EP11810692A EP2655291A2 EP 2655291 A2 EP2655291 A2 EP 2655291A2 EP 11810692 A EP11810692 A EP 11810692A EP 2655291 A2 EP2655291 A2 EP 2655291A2
Authority
EP
European Patent Office
Prior art keywords
mixtures
chromium
cobalt
group
manganese
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11810692.1A
Other languages
German (de)
English (en)
French (fr)
Inventor
Nabil Nahas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Original Assignee
Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Centre de Recherche et dEtudes Europeen SAS filed Critical Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Priority to EP14157518.3A priority Critical patent/EP2740717A3/fr
Publication of EP2655291A2 publication Critical patent/EP2655291A2/fr
Withdrawn legal-status Critical Current

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    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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Definitions

  • the invention relates to a particulate mixture, a sintered part obtained from such a particulate mixture and a method of manufacturing such a sintered part.
  • Sintered pieces made from zirconia are commonly used for the manufacture of decorative items such as jewelery, watches, bracelets, brooches, tie pins, necklaces, handbags, telephones, furniture, or household utensils.
  • a pigment can be added.
  • WO 2010024275 discloses a stabilized zirconia product which may contain between 1 and 30% of alumina, incorporating a pigment based on cobalt oxide and chromium oxide, nickel oxide or iron oxide.
  • JP 2005306678, JP 2004059374 provide other examples of pigments.
  • alumina-zirconia products in particular those having an alumina content of between 10 and 50%, are known to have good mechanical properties, in particular hardness and mechanical strength.
  • a pigment added in an alumina-zirconia product generally tends to degrade during sintering of alumina-zirconia because of the high sintering temperatures required, which can lead to a difficultly controllable modification of the color.
  • alumina-zirconia products intended to be decorative articles must also have good resistance to scratches and shocks, as well as a beautiful appearance with well-developed and homogeneous colors. They must also be biocompatible, that is to say, not contain elements that can be released and that could be dangerous for humans.
  • An object of the invention is to satisfy, at least partially, this need.
  • this object is achieved by means of a particulate mixture having the following chemical composition, in weight percentages based on the oxides: zirconia Zr0 2 : ⁇ 10.0%;
  • said group G s oxide (1) and / or said group G s (2) oxide and / or alumina being wholly or partly exchangeable with an equivalent amount of precursor (s) for these oxides,
  • said particulate mixture comprising a pigment, in an amount between 0.5 and 10.0%, the particles of said pigment comprising a material selected from
  • the oxide (s) of perovskite structure optionally substituted (s), wholly or in part, by an equivalent quantity of precursor (s) of these oxides, the spinel structure oxides,
  • the oxides with a hematite structure E 2 0 3 the element E being chosen from the group G E (1) formed by the mixtures of aluminum and chromium, the mixtures of aluminum and of manganese, and their mixtures
  • oxides with rutile structure F0 2 the element F being chosen from the group G F (1) formed by mixtures of tin and vanadium, mixtures of titanium and chromium and niobium, mixtures of titanium and chromium and tungsten, mixtures of titanium and niobium and manganese, mixtures of tin and chromium, and mixtures thereof,
  • orthosilicates chosen from the group of zirconium and praseodymium (Zr, Pr) SiO 4 orthosilicates, zirconium and vanadium (Zr, V) SiO 4 orthosilicates, zirconium orthosilicates in which there is iron in inclusion, and mixtures thereof.
  • the constituents of said perovskite structure oxide, spinel, hematite, rutile or orthosilicate represent more than 98%, more than 99%, or even substantially 100% by weight of said material.
  • the 100% complement consists of impurities.
  • the alumina content may be less than or equal to 2%.
  • the inventors have found that a particulate mixture according to the invention makes it possible to manufacture, by sintering, a colored alumina-zirconia product perfectly adapted to the manufacture of decorative articles.
  • the zirconia content is greater than 15%, preferably greater than 20%, even greater than 30%, greater than 40%, greater than 50%, greater than 60%, or greater than 70%, by weight percentage.
  • the alumina content is greater than 5%, preferably greater than 10%, or even greater than 15%, greater than 20%, greater than 25%, greater than 30%, by weight percentage.
  • the oxide of group G s (1) is chosen from the group formed by Y 2 0 3 , Sc 2 0 3 and their mixtures and, preferably, the content of said oxide of group G s (1) is less than 8; %, preferably less than 6.5%.
  • the oxide of group G s (1) is chosen from the group formed by MgO, CaO and their mixtures and, preferably, the content of said oxide of group G s (1) is less than 4%.
  • the oxide of group G s (1) is CeO 2 and, preferably, the content of said oxide of group G s (1) is greater than 10% and less than 15%.
  • the oxide of the group G s (1) is chosen from the group formed by Y 2 0 3 , Ce0 2 and their mixtures, and preferably preferably respects the relationship 10% ⁇ 3.Y 2 0 3 + Ce0 2 ⁇ 20%.
  • the oxide of group G s (1) is Y 2 0 3 and, preferably, its content is greater than 3%, preferably greater than 4% and / or less than 8%, preferably less than 6.5 %.
  • the oxide of group G s (1) is a stabilizer of zirconia.
  • the oxide of group G s (1) is chosen from the group formed by Y 2 0 3 , Sc 2 0 3 and their mixtures and, preferably, the content of said oxide of group G s (1) is less than
  • the oxide of group G s (1) is chosen from the group formed by MgO, CaO and mixtures thereof and, preferably, the content of said oxide of group G s (1) is less than 4%, on the basis of the sum of Zr0 2 , Y 2 0 3 , Sc 2 0 3 , MgO, CaO and CeO 2 .
  • the oxide of group G s (1) is CeO 2 and its content is greater than 10% and less than
  • the oxide of the group G s (1) is chosen from the group formed by Y 2 0 3 , Ce0 2 and their mixtures, and preferably preferably respects the relationship 10% ⁇ 3.Y 2 0 3 + Ce0 2
  • the zirconia stabilizer is Y 2 0 3 , i.e. the particulate mixture contains only Y 2 0 3 as a zirconia stabilizer.
  • the content of Y 2 O 3 is greater than 3%, preferably greater than 4% and / or less than 8%, preferably less than 6.5%, based on the sum of Zr0 2 , Y 2 0 3 Sc 2 0 3 , MgO, CaO and CeO 2 .
  • the particulate mixture comprises zirconia stabilized with said stabilizer, or a mixture of zirconia particles, stabilized or not, and particles of said stabilizer, or a mixture of particles in which zirconia, stabilized or otherwise, and said stabilizer are intimately mixed.
  • Such an intimate mixture can for example be obtained by co-precipitation or atomization, possibly consolidated by a heat treatment.
  • the stabilizer may be replaced by an equivalent amount of precursor (s) of this stabilizer.
  • the alumina content is greater than 10%, preferably greater than 15% and less than 60%, preferably less than preferably less than 50%, preferably less than 40%, more preferably less than 30%. In a particular embodiment, the alumina content is between 2% and 10%. In another particular embodiment, the alumina content is between 10% and 20%. Finally, in another particular embodiment, the alumina content is between 20% and 80%.
  • Group oxide s (2) is selected from the group consisting of ZnO and lanthanide oxides except CeO 2 , and mixtures thereof, and preferably the content of said Group S oxide (2) is less than 15. %, preferably less than 10%, preferably less than 8%, preferably less than 5%.
  • the oxide of group G s (2) is La 3 O 3 and, preferably, its content is less than 15%, preferably less than 10%, preferably less than 8%, preferably less than 5%, and / or preferably greater than 0.5%.
  • the Group G oxide s (2) is a stabilizer of alumina.
  • Group oxide s (2) is selected from the group consisting of ZnO and lanthanide oxides except CeO 2 , and mixtures thereof, and preferably the content of said Group S oxide (2) is less than 15. %, preferably less than 10%, preferably less than 8%, preferably less than 5%, based on the sum of Al 2 O 3 , ZnO and lanthanide oxides with the exception of CeO 2 .
  • the oxide of group G s (2) is La 3 O 3 and, preferably, its content is less than 15%, preferably less than 10%, preferably less than 8%, preferably less than 5%, and or preferably greater than 0.5%, based on the sum of Al 2 O 3 , ZnO and lanthanide oxides except Ce0 2 .
  • the stabilizing of the alumina is La 2 0 3, that is to say the particulate mixture contains only La 2 0 3 as a stabilizer to the alumina.
  • the particulate mixture comprises alumina stabilized with said stabilizer, or a mixture of alumina particles, stabilized or not, and particles of said stabilizer, or a mixture of particles in which alumina, stabilized or otherwise, and said stabilizer are intimately mixed.
  • Such an intimate mixture can for example be obtained by co-precipitation or atomization, possibly consolidated by a heat treatment.
  • the stabilizer may be replaced by an equivalent amount of precursor (s) of this stabilizer.
  • the particulate mixture comprises alumina in the form of an alumina precursor, such as, for example, an aluminum hydroxide, an aluminum salt.
  • the alumina of the particulate mixture is alpha alumina.
  • the particulate mixture comprises particles in which zirconia, stabilized or otherwise, and zirconia stabilizer are intimately mixed.
  • the particulate mixture comprises particles in which zirconia, stabilized or otherwise, and zirconia stabilizer are intimately mixed.
  • Such an intimate mixture can for example be obtained by coprecipitation or atomization, possibly consolidated by a heat treatment.
  • the stabilizer may be replaced by an equivalent amount of precursor (s) of this stabilizer.
  • the particulate mixture does not have a zirconia stabilizer precursor.
  • the particulate mixture has a median size of less than 10 ⁇ , or even less than 5 ⁇ , or even less than 3 ⁇ , or even less than 1 ⁇ and / or preferably greater than 0,05 ⁇ .
  • the median size of the particulate mixture is adapted to the shaping process used to make the sintered workpiece.
  • the powder consisting of the pigment particles has a median size of less than 5 ⁇ , preferably less than 1 ⁇ , preferably less than 0,5 ⁇ .
  • the pigment content is greater than 3%, preferably greater than 4%, preferably greater than 5% and / or less than 8%, as a percentage by weight based on the particulate mixture.
  • the particulate mixture does not contain a pigment containing the aluminum element.
  • the oxides represent more than 98%, more than 99%, or even substantially 100% of the mass of the particulate mixture.
  • the pigment is an oxide of perovskite structure AB0 3 and the particulate mixture according to the invention may also comprise one or more of the following optional characteristics:
  • element A at site A of the perovskite structure is chosen from the group G A (1) formed by calcium Ca, strontium Sr, barium Ba, lanthanum La, praseodymium Pr, neodymium Nd, bismuth Bi, Ce cerium, and mixtures thereof.
  • A is selected from the group G A (2) formed by lanthanum, praseodymium, neodymium, bismuth, cerium, and mixtures thereof.
  • A is selected from the group GA (3) formed by lanthanum.
  • group G B (1) formed by mixtures of cobalt and iron, mixtures of cobalt and manganese, mixtures of cobalt and chromium, mixtures cobalt and nickel, chromium and manganese mixtures, chromium and nickel mixtures, chromium and iron mixtures, manganese and iron mixtures, manganese and nickel mixtures, nickel mixtures and iron, mixtures of cobalt and titanium, mixtures of cobalt and copper, cobalt, mixtures of chromium and titanium, mixtures of chromium and copper, mixtures of nickel and titanium, chromium, nickel, copper, iron, nickel and copper mixtures, and mixtures thereof.
  • the element B is chosen from the group G B (2) formed by mixtures of cobalt and iron, mixtures of cobalt and manganese, mixtures of chromium and manganese, mixtures of chromium and iron, mixtures of cobalt and chromium and iron, mixtures of cobalt and chromium and iron and manganese, mixtures of cobalt and iron and manganese, mixtures of cobalt and chromium, cobalt mixtures and nickel, cobalt-titanium blends, cobalt-copper blends, cobalt, chromium-nickel blends, chromium-titanium blends, chromium-copper mixtures, blends of chromium and iron and manganese, nickel and iron mixtures, nickel and manganese mixtures, nickel and cobalt mixtures, nickel and titanium mixtures, nickel and cobalt and chromium mixtures , mixtures of nickel and cobalt and chromium and manganese, mixtures of nickel
  • the level of perovskite in the 0.5 to 10% of pigment of oxide (s) of perovskite structure and / or in precursor (s) of such oxides is greater than 90%, preferably greater than 95%, preferably greater than 99%, preferably substantially 100%.
  • the content of pigment perovskite oxide (s) and / or precursor (s) of such oxides is preferably greater than 3%, preferably greater than 4%, preferably greater than 5% and / or preferably less than 8%. Also generally, for a content of pigment perovskite oxide (s) and / or precursor (s) of such oxides constant, the alumina content is increased to lighten the color.
  • the pigment is an oxide of spinel structure CD 2 0 4 or D (C, D) O 4 and the particulate mixture according to the invention may also comprise one or more of the following optional characteristics:
  • the element C of the spinel structure is chosen from the group G c (1) formed by nickel Ni in a molar fraction of between 0 and 0.2 or in a molar fraction equal to 1, copper Cu in a fraction between 0.2 and 0.6 or in a molar fraction equal to 1, zinc Zn in a molar fraction of between 0 and 0.2 or in a molar fraction of between 0 and 0.2; a molar fraction equal to 1, manganese Mn in a mole fraction of between 0 and 0.4, cobalt Co in a mole fraction of between 0 and 0.4 or in a mole fraction of between 0.4 and 1.1; tin in a mole fraction of between 0 and 0.2 or in a mole fraction of 1, mixtures of zinc and iron, mixtures of iron and manganese, mixtures of zinc and manganese, mixtures of cobalt and zinc, and their mixtures.
  • the element C is chosen from the group G c (2) formed by nickel Ni in a mole fraction of between 0 and 0.2 or in a molar fraction equal to 1, Fe iron in a molar fraction. between 0.2 and 0.6 or in a molar fraction equal to 1, zinc Zn in a molar fraction equal to 1, manganese Mn in a molar fraction of between 0 and 0.4, cobalt Co in a fraction between 0 and 0.4 or in a mole fraction of between 0.4 and 1, tin Sn in a mole fraction of between 0 and 0.2 or in a mole fraction of 1, mixtures of zinc and iron, manganese and iron mixtures, zinc and manganese mixtures, cobalt and zinc mixtures, and mixtures thereof.
  • the element D of the spinel structure is chosen from the group G D (1) formed by the manganese Mn in a molar fraction of between 0 and 0.4, the Fe iron in a molar fraction between 0 and 0.6; or in a molar fraction equal to 1 (that is to say that D is the Fe element), chromium Cr in a mole fraction of between 0.2 and 0.6 and in a molar fraction equal to 1, aluminum Al in a molar fraction of between 0 and 1, titanium Ti in a molar fraction of between 0 and 1, cobalt in a molar fraction of 1 unless element C is cobalt, iron mixtures and chromium, iron and chromium and manganese mixtures, manganese and chromium mixtures, aluminum and chromium mixtures, and mixtures thereof.
  • the element D is chosen from the group G D (2) formed by the manganese Mn in a mole fraction of between 0 and 0.4, the Fe iron in a mole fraction of between 0.2 and 0, 6 and in a molar fraction equal to 1, chromium Cr in a mole fraction of between 0 and 0.6 and in a molar fraction equal to 1, aluminum Al in a molar fraction equal to 1, titanium Ti in a molar fraction equal to 1, cobalt in a molar fraction equal to 1 unless element C is cobalt, mixtures of iron and chromium, mixtures of iron and chromium and manganese, mixtures of manganese and chromium, aluminum and chromium mixtures, and mixtures thereof.
  • the spinel content in the 0.5 to 10% pigment in oxide (s) of spinel structure is greater than 90%, preferably greater than 95%, preferably greater than 99%, preferably substantially 100%.
  • the pigment content of oxide (s) of spinel structure is preferably greater than 3%, preferably greater than 4%, preferably greater than 5% and / or preferably less than 8%. Also generally, for a pigment content of oxide (s) of constant spinel structure, the alumina content is increased to lighten the color.
  • the pigment is an oxide of hematite structure E 2 0 3 , the element E being chosen from the group G E (1) formed by the mixtures of aluminum and chromium, the mixtures of aluminum and manganese, and mixtures thereof, and the particulate mixture according to the invention may further comprise one or more of the following optional characteristics: -
  • the hematite content in the 0.5 to 10% pigment in oxide (s) of hematite structure is greater than 90%, preferably greater than 95%, preferably greater than 99%, preferably substantially 100%.
  • the pigment content of oxide (s) hematite structure is preferably greater than 3%, preferably greater than 4%, preferably greater than 5% and / or preferably less than 8%. Also generally, for a pigment content of oxide (s) of hematite structure, the alumina content is increased to lighten the color.
  • the pigment is in an oxide of rutile structure F0 2 , the element F being chosen from the group G F (1) formed by mixtures of tin and vanadium, mixtures of titanium and of chromium and niobium, mixtures of titanium and chromium and tungsten, mixtures of titanium and niobium and manganese, mixtures of tin and chromium, and mixtures thereof, and the particulate mixture according to the invention may further have one or more of the following optional features:
  • the level of rutile in the 0.5 to 10% of pigment of oxide (s) of rutile structure is greater than 90%, preferably greater than 95%, preferably greater than 99%, preferably substantially 100%.
  • the pigment content of oxide (s) of rutile structure is preferably greater than 3%, preferably greater than 4%, preferably greater than 5% and / or preferably less than 8%. Also generally, for a pigment content of oxide (s) of constant rutile structure, the alumina content is increased to lighten the color.
  • the pigment is an orthosilicate selected from the group of orthosilicates of zirconium and praseodymium (Zr, Pr) SiO 4 , zirconium and vanadium orthosilicates (Zr, V) SiO 4 , orthosilicates of zirconium in which there is iron oxide in inclusion.
  • the content of orthosilicate pigment (s) is preferably greater than 3%, preferably greater than 4%, preferably greater than 5% and / or preferably less than 8%.
  • the alumina content is increased to lighten the color.
  • the pigment is a mixture of several pigments according to the first to fifth embodiments above.
  • the pigment can be chosen as follows:
  • the pigment is in an oxide of perovskite structure such that A and B are chosen in the following manner:
  • A may be chosen from the group G A '(1) formed by calcium Ca, strontium Sr, barium Ba, lanthanum La, praseodymium Pr, neodymium Nd, bismuth Bi, cerium Ce, and mixtures thereof .
  • A is selected from the group G A '(2) formed by lanthanum, praseodymium, neodymium, bismuth, cerium, and mixtures thereof.
  • A is selected from the group GA '(3) formed by lanthanum.
  • B can be chosen from the group G B '(1) formed by the mixtures of cobalt and iron Co x Fei -X, with x ranging from 0.2 to 0.4, the mixtures of cobalt and manganese Co x Mn 1-X , with x between 0.2 and 0.4, the chromium and manganese mixtures Cr x Mn 1-X, with x ranging from 0.2 to 0.4, the chromium and iron mixtures Cr x Fei -X, with x between 0.3 and 0.5, the manganese and iron Mn x Fei -X mixtures , with x ranging from 0.4 to 0.7, and the nickel and iron Ni mixtures x Fei -X, with x ranging from 0.4 to 0.7, and mixtures thereof.
  • a particulate mixture according to the invention may comprise a quantity of pigment perovskite oxide (s) and / or precursor (s) of such oxides , A and B being preferably selected from groups G A '(1) to (3) and G B ' (1) to (2) above:
  • a particulate mixture according to the invention may comprise a quantity of pigment of oxide (s) of perovskite structure and / or precursor (s) of such oxides, A and B being preferably selected from groups G A '(1) to (3) and and G B ' (1) to (2) above:
  • the pigment is an oxide of spinel structure such that C and D are chosen in the following manner:
  • C can be chosen from the group G c '(1) formed by nickel Ni in a mole fraction of between 0 and 0.2, copper Cu in a mole fraction of between 0 and 0.2, Fe iron in a molar fraction between 0.2 and 0.6, zinc Zn in a molar fraction of between 0 and 0.2, manganese Mn in a molar fraction of between 0 and 0.4, cobalt Co in a molar fraction of between between 0 and 0.4, and mixtures thereof.
  • C is chosen from the group G c '(2) formed by nickel Ni in a mole fraction of between 0 and 0.2, Fe iron in a mole fraction of between 0.2 and 0.6, and Mn manganese in a mole fraction of 0 to 0.4, cobalt Co in a mole fraction of 0 to 0.4, and mixtures thereof.
  • D can be chosen from the group G D '(1) formed by the manganese Mn in a mole fraction of between 0 and 0.4, the Fe iron in a mole fraction of between 0.2 and 0.6, the chromium Cr in a molar fraction between 0.2 and 0.6, Al aluminum in a mole fraction of 0 to 0.4, Ti titanium in a mole fraction of 0 to 0.4, and mixtures thereof.
  • D is chosen from the group G D '(2) formed by the manganese Mn in a mole fraction of between 0 and 0.4, the Fe iron in a mole fraction of between 0.2 and 0.6, the chromium Cr in a molar fraction between
  • a particulate mixture according to the invention may comprise a quantity of pigment in oxide (s) of spinel structure, C and D being preferably selected from the groups G c '(1) to (2) and and G D ' (1) to (2) above, greater than 3%.
  • a particulate mixture according to the invention may comprise a quantity of oxide pigment (s) of spinel structure, C and D being preferably selected in the groups G c '(1) to (2) and G D ' (1) to (2) above, less than 3%.
  • the pigment can be chosen as follows:
  • the pigment is an oxide of perovskite structure such that A and B are chosen as follows:
  • A may be chosen from the group G A - (1) formed by calcium Ca, strontium Sr, barium Ba, lanthanum La, praseodymium Pr, neodymium Nd, bismuth Bi, cerium Ce, and mixtures thereof .
  • A is selected from the group G A "(2) formed by lanthanum, praseodymium, neodymium, bismuth, cerium, and mixtures thereof.
  • A is selected from the group G A "(3) formed by lanthanum.
  • B can be selected from the group G B "(1) formed by the mixtures of cobalt and iron Co x Fei -X, with x ranging from 0.5 to 0.95, the mixtures of cobalt and manganese Co x Mn 1-X , with x between 0.5 and 0.95, the cobalt-chromium mixtures Co x Cr 1 -X , with x ranging from 0.5 to 0.95, the cobalt-nickel mixtures x Ni 1-X, with x between 0.5 and 0.95, cobalt and titanium mixtures
  • B is selected from the group GB (2) formed by mixtures of cobalt and iron Co x Fei -X, with x ranging from 0.8 to 0.95, mixtures of cobalt and manganese Co x Mn 1-X , with x between 0.8 and 0.95, cobalt-chromium mixtures Co x Cr 1 -X , with x ranging from 0.8 to 0.95, cobalt-nickel mixtures Co x Ni 1-X, with x ranging from 0.8 to 0.95, cobalt-titanium mixtures Co x Ti 1-X, with x ranging from 0.8 to 0.95, cobalt mixtures and of copper Cu x Cui -X, with x ranging from 0.8 to 0.95, cobalt, mixtures of cobalt, mixtures of cobalt, mixtures of cobalt, mixtures of cobalt, mixtures of cobalt, mixtures of cobalt, mixtures of cobalt, mixtures of cobalt, mixtures of cobalt, mixtures
  • a particulate mixture according to the invention may comprise a quantity of pigment perovskite oxide (s) and / or precursor (s) such oxides, A and B being preferably selected from groups G A "(1) to (3) and G B " (1) to (2) above:
  • a particulate mixture according to the invention may comprise a quantity of pigment perovskite oxide (s) and / or precursor (s) such oxides, A and B being preferably selected from groups G A "(1) to (3) and and G B " (1) to (2) above:
  • the pigment is an oxide of spinel structure such that C and D are chosen as follows:
  • C can be chosen from the group Gc "(1) formed by nickel Ni in a molar fraction of between 0 and 0.2, zinc Zn in a molar fraction of between 0 and 0.2, cobalt Co in a fraction of molar ratio between 0.4 and 1, tin Sn in a mole fraction of between 0 and 0.2 and in a mole fraction of 1, mixtures of cobalt and zinc, and mixtures thereof.
  • C is selected from the group Gc "(2) formed by cobalt Co in a molar fraction equal to 1, tin Sn in a molar fraction equal to 1, mixtures of cobalt and zinc, and mixtures thereof. .
  • D can be chosen from the group GD "(1) formed by chromium Cr in a molar fraction of between 0 and 0.4, aluminum Al in a molar fraction of between 0 and 1, titanium Ti in a molar fraction between 0 and 1, cobalt in a molar fraction equal to 1 unless element C is cobalt, mixtures of aluminum and chromium, and mixtures thereof.
  • D is chosen from the group GD "(2) formed by Al aluminum in a molar fraction equal to 1, cobalt in a molar fraction equal to 1 unless element C is cobalt, mixtures of aluminum and chromium, and mixtures thereof.
  • the spinel structure oxide is selected from the group consisting of Co 2 SnO 4 , CoAl 2 O 4 , Co (Cr, Al) 2 O 4 , (Co, Zn) Al 2 O 4 and mixtures thereof.
  • the pigment is an orthosilicate of zirconium and vanadium (Zr, V) SiO 4 .
  • the pigment can be chosen as follows:
  • the pigment is an oxide of perovskite structure such that A and B are chosen as follows:
  • A may be selected from group G A '' (1) formed by calcium Ca, strontium Sr, barium Ba, lanthanum La, praseodymium Pr, neodymium Nd, bismuth Bi, cerium Ce, and their mixtures.
  • A is selected from the group consisting of lanthanum, praseodymium, neodymium, bismuth, cerium, and mixtures thereof.
  • A is selected from the group consisting of lanthanum GA (3)
  • B may be selected from the group GB (1) formed by chromium and iron Cr x Fei- X mixtures with x between 0.5 and 0.95, mixtures of chromium and manganese Mn x Cr 1-x, with x between 0.5 and 0.95, mixtures of chromium and cobalt Cr x -x Coi, with x between 0.5 and 0.95, chromium and nickel mixtures Cr x Ni 1-X, with x between 0.5 and 0.95, chromium and titanium mixtures Cr x Ti 1- X, with x between 0.5 and 0.95, the chromium and copper mixtures Cr x Cui -X, with x between 0.5 and 0.95, the nickel and iron mixtures
  • Ni x Fei -X with x between 0.5 and 0.95, the Ni x Mn 1-X nickel and manganese mixtures, with x ranging from 0.5 to 0.95, the nickel and Coi -x Ni x cobalt, with x between 0.5 and 0.95, nickel and mixtures of titanium Ni x Ti 1-x, with x between 0.5 and 0.95, chromium, nickel , and their mixtures.
  • B is selected from the group GB (2) formed by chromium and iron Cr x Fei- X mixtures , with x ranging from 0.8 to 0.95, chromium and Cr manganese mixtures.
  • a particulate mixture according to the invention may comprise a quantity of oxide powder (s) of perovskite structure and / or precursor (s) of such oxides, A and B being preferably selected from the groups G A "(1) to (3) and G B" (1) to (2) above:
  • a particulate mixture according to the invention may comprise a quantity of oxide powder (s) of perovskite structure and / or precursor (s) of such oxides, A and B being preferably selected from groups G A '"(1) to (3) and and G B '" (1) to (2) above:
  • the pigment is an oxide of spinel structure selected from the group consisting of CoCr 2 0 4 , TiCo 2 0 4 , and mixtures thereof.
  • the pigment may be a pigment of perovskite structure such that A and B are chosen in the following manner:
  • A may be chosen from the group G A 4 '(1) formed by calcium Ca, strontium Sr, barium Ba, lanthanum La, praseodymium Pr, neodymium Nd, bismuth Bi, cerium Ce, and their mixtures.
  • A is selected from the group GA 4 '(2) formed by lanthanum, praseodymium, neodymium, bismuth, cerium, and mixtures thereof.
  • A is selected from the group GA 4 '(3) formed by lanthanum La.
  • B may be selected from the group GB 4 ' (1) formed by chromium and cobalt mixtures Cr x Coi- x , with x between 0.3 and 0.8, the nickel-cobalt mixtures Ni x Co-x, with x between 0.3 and 0.8, the chromium and copper mixtures Cr x Cui- X, with x between 0.3 and 0.8, nickel-copper mixtures Ni x Cu- X , with x ranging from 0.3 to 0.8, nickel-titanium mixtures Ni x T. x, with x ranging from 0.3 to 0.8, copper, and mixtures thereof.
  • a particulate mixture according to the invention may in particular comprise a quantity of oxide powder (s) of perovskite structure and / or precursor (s) of such oxides greater than 3%, preferably greater than 4%, and / or less than 6%, A and B being preferably selected from groups G A 4 '(1) to (3) and G B 4 ' (1) to (2) ) above.
  • the pigment can be chosen as follows:
  • the pigment is an oxide of perovskite structure such that A and B are chosen as follows:
  • A may be chosen from the group G A 5 '(1) formed by calcium Ca, strontium Sr, barium Ba, lanthanum La, praseodymium Pr, neodymium Nd, bismuth Bi, cerium Ce, and their mixtures.
  • A is selected from the group G A 5 '(2) formed by lanthanum, praseodymium, bismuth, cerium, and mixtures thereof.
  • B may be selected from the group G B 5 '(1) formed by iron.
  • the pigment is an oxide of rutile structure such that F is selected from the group G F '(1) formed by mixtures of titanium and chromium and niobium, mixtures of titanium and chromium and tungsten , and their mixtures.
  • the pigment can be chosen as follows:
  • the pigment is an oxide of perovskite structure such that A and B are chosen as follows:
  • A may be chosen from the group G A 6 '(1) formed by calcium Ca, strontium Sr, barium Ba, lanthanum La, praseodymium Pr, neodymium Nd, bismuth Bi, cerium Ce, and their mixtures.
  • A is selected from the group GA 6 '(2) formed by lanthanum, praseodymium, neodymium, bismuth, cerium, and mixtures thereof.
  • A is selected from the group GA 6 '(3) formed by lanthanum.
  • B can be selected from the group GB 6 '(1) formed by the chromium and iron mixtures Cr x Fei -X, with x ranging from 0.05 to 0.5, the mixtures of nickel and iron Ni x Fei -X , with x ranging from 0.05 to 0.5, the manganese and iron Mn x Fei -X mixtures, with x ranging from 0.05 to 0.5, and mixtures thereof.
  • a particulate mixture according to the invention may comprise a quantity of oxide powder (s) of perovskite structure and / or precursor (s) of such oxides, A and B being preferably selected from groups G A 6 '(1) to (3) and G B 6 ' (1) above:
  • a particulate mixture according to the invention may comprise a quantity of oxide powder (s) of perovskite structure and / or precursor (s) of such oxides, A and B being preferably selected from groups G A 6 '(1) to (3) and G B 6 ' (1) above:
  • the pigment is an oxide of spinel structure selected from the group formed by Fe (Fe, Cr) 20 4! Fe 2 Ti0 4, NiFe 2 0 4, (Zn, Fe) Fe 2 0 4, (Fe, Mn) (Fe? Mn? Cr) 2 0 4! (Zn, Mn) (Mn, Cr) 2 O 4 and mixtures thereof.
  • the pigment is an oxide of rutile structure such that F is selected from the group G F "(1) formed by mixtures of titanium and niobium and manganese.
  • the pigment can be chosen as follows:
  • the pigment is an oxide of spinel structure such that C and D are chosen as follows:
  • the C element at site C of the spinel structure is zinc Zn.
  • the D element at site D of the spinel structure is the mixtures of aluminum and chromium.
  • the pigment is an oxide of hematite structure such that element E at site E of the hematite structure is selected from group G E (1) formed by mixtures of aluminum and chromium, aluminum and manganese.
  • the pigment is an oxide of rutile structure such that F is selected from the group G F '"(1) formed by mixtures of tin and chromium.
  • the pigment is a zirconium orthosilicate in which there is iron oxide in inclusion.
  • the pigment can be chosen as follows:
  • the pigment is an oxide of perovskite structure such that A and B are chosen as follows: A may be chosen from group G A 7 '(1) formed by calcium Ca, strontium Sr, barium Ba, lanthanum La, praseodymium Pr, neodymium Nd, bismuth Bi, cerium Ce, and their mixtures.
  • A is selected from the group GA 7 '(2) formed by lanthanum, neodymium, and mixtures thereof.
  • B may be selected from GB 7 '(1) formed by mixtures of cobalt and manganese Co x Mn 1-X, with x ranging from 0.05 to 0.2.
  • the pigment can be chosen as follows:
  • the pigment is an oxide of rutile structure such that F is selected from the group G F 4 '(1) formed by mixtures of tin and vanadium.
  • the invention also relates to an assembly comprising a particulate mixture according to the invention and a notice, for example in the form of a label affixed to a packaging of the particulate mixture or a booklet attached to the particulate mixture, the notice indicating that the particulate mixture is intended for the manufacture of decorative sintered parts.
  • the notice may for example indicate “powder for decorative ceramics", or
  • the record provides one or more of the following instructions:
  • the packaging can be for example a bag, for example of "big bag” type, a can, a drum, or a carton.
  • the invention also relates to a method for manufacturing a sintered part comprising the following steps:
  • e) optionally, checking the color of the sintered part, in particular by measuring the parameters L * and / or a * , and / or b * ,
  • the starting charge comprises a particulate mixture according to the invention.
  • the starting charge in step a) (and in particular the nature and composition of the pigment) is determined according to a desired color for said sintered part.
  • a powder of oxide (s) of perovskite structure and / or of spinel structure oxides and / or an oxide of hematite structure E 2 O 3 powder is added to the feedstock.
  • E element being selected from group G E (1) formed by mixtures of aluminum and chromium, mixtures of aluminum and manganese, and mixtures thereof, and / or an oxide powder of rutile structure F0 2 , the element F being chosen from the group G F (1) formed by mixtures of tin and vanadium, mixtures of titanium and chromium and niobium, mixtures of titanium and chromium and tungsten, mixtures titanium and niobium and manganese, mixtures of tin and chromium, and mixtures thereof, and / or a powder of an orthosilicate selected from the group of orthosilicates of zirconium and praseodymium (Zr, Pr) SiO 4 , orthosilicates of zirconium and vanadium (Zr,
  • the oxide (s) of perovskite structure may be replaced, totally or partially, by an equivalent amount of precursor (s) of these oxides.
  • the quantity and the nature of said orthosilicate (s) and / or of said oxide (s) of perovskite structure and / or of said oxide (s) of spinel structure and / or of said oxide (s) of structure hematite and / or of said oxide (s) of rutile structure can be determined in particular according to the rules, in particular (R1) to (R29), and their variants defined above. Adapting the starting load to comply with these rules does not pose any particular difficulty.
  • a sintered part of a given color by adding in the starting charge pigment powders described above as appropriate to obtain other colors.
  • a green-colored sintered part may be obtained by the method by adding in the starting charge a zirconium and praseodymium (Zr, Pr) SiO 4 orthosilicate described above as being suitable for obtaining a yellow color.
  • a zirconium and vanadium (Zr, V) SiO 4 orthosilicate described above as suitable for obtaining a blue color.
  • This method can be used in particular to manufacture a decorative article according to the invention.
  • this process can be used to manufacture a sintered part whose sum of alumina and zirconia content is greater than 70%, in weight percent on the oxide basis, and having a specific color.
  • the method is implemented for the manufacture of a plurality of sintered parts, a color verification step e) is carried out on a sampling of said sintered parts, and the initial charge is adapted as a function of the difference between the color of the sintered pieces of the sample and the desired color so that the color of sintered pieces manufactured later are closer to the desired color.
  • the starting load is modified so that the index ⁇ evaluating the difference in color between the sintered parts manufactured and the desired color is less than 5, less than 2, or even less than 1.
  • the feedstock contains particles in which zirconia, stabilized or otherwise, and an oxide selected from the group G s (1) (a mixture of oxides being itself an “oxide”) are intimately mixed, and an alumina powder, stabilized or not, and an oxide selected from the group G s (2) are intimately mixed.
  • the preform is sintered, preferably in air, preferably at atmospheric pressure or under pressure (hot pressing) or hot isostatic pressing ("hot isostatic pressing”). , or HIP)) and at a temperature of between 1200 ° C. and 1500 ° C., preferably greater than 1350 ° C., or even 1400 ° C. and / or less than 1450 ° C.
  • the invention also relates to a sintered part having the following chemical composition, in mass percentages on the basis of the oxides:
  • said sintered part comprising 0.5 to 10.0% of a pigment of a material selected from - perovskite oxide (s),
  • the oxides with a hematite structure E 2 0 3 the element E being chosen from the group G E (1) formed by the mixtures of aluminum and chromium, the mixtures of aluminum and of manganese, and their mixtures
  • oxides with rutile structure F0 2 the element F being chosen from the group G F (1) formed by mixtures of tin and vanadium, mixtures of titanium and chromium and niobium, mixtures of titanium and chromium and tungsten, mixtures of titanium and niobium and manganese, mixtures of tin and chromium, and mixtures thereof,
  • the Group G oxide s (1) is a stabilizer of zirconia.
  • the Group G oxide s (2) is a stabilizer of alumina.
  • the invention relates in particular to a sintered part obtained or obtainable from a particulate mixture according to the invention, in particular manufactured according to a manufacturing method according to the invention.
  • Such a sintered part has a particularly suitable appearance for use in a decorative article when the roughness Ra of its surface is less than 0.05 ⁇ , preferably less than 0.02 ⁇ , and even lower at 0.01 ⁇ , or is between 0.1 and 0.5 ⁇ .
  • this sintered part has a density greater than 98%, preferably greater than 99%, preferably greater than 99.5% of the theoretical density.
  • the inventors have indeed discovered that a high density advantageously leads to a good development of the color in the sintered part, and to good mechanical properties.
  • the zirconia of this sintered part consists of more than 80%, preferably more than 90%, preferably more than 95%, by volume, of quadratic and / or cubic phase, the complement being 100% being consisting of monoclinic phase.
  • the median size of the zirconia grains is less than 2 ⁇ , preferably less than 1 ⁇ , or even less than 0.5 ⁇ .
  • the median size of the alumina grains is less than 2 ⁇ , preferably less than 1 ⁇ , or even less than 0.5 ⁇ .
  • the median size of the pigment grains is less than 2 ⁇ , preferably less than 1 ⁇ , or even less than 0.5 ⁇ .
  • the pigment may be chosen from oxides of perovskite structures such that A and B belong to groups G A (1) to (3) and G B (1) to (2), the spinel structure oxides such as C and D belong to in groups G c (1) to (2) and G D (1) to (2), the oxides of hematite structure such that E belongs to the group G E (1), the oxides of rutile structure such that F belongs to the group G F (1), an orthosilicate of zirconium and praseodymium (Zr, Pr) SiO 4 , a zirconium and vanadium orthosilicate (Zr, V) SiO 4 , a zirconium orthosilicate in which iron oxide is found in inclusion, and mixtures thereof, as described above.
  • oxides of perovskite structures such that A and B belong to groups G A (1) to (3) and G B (1) to (2)
  • the spinel structure oxides such as C and D belong to in groups G c (1) to (2) and G D (1) to (2)
  • a sintered part according to the invention can in particular be black or even gray, in particular by choosing the oxides of perovskite structure such that A and B belong to groups G A '(1) to (3) and G B ' (1). ) to (2), and / or by selecting the spinel structure oxides such that C and D belong to groups G c '(1) to (2) and G D ' (1) to (2), as described above. above. It can in particular present the following color parameters, measured according to the NF ISO 7724 standard:
  • a sintered part according to the invention can also be blue in color, in particular by choosing the oxides of perovskite structure such that A and B belong to groups G A "(1) to (3) and G B " (1) to (2) ) and / or by choosing the spinel structure oxides such that C and D belong to groups G c "(1) to (2) and G D " (1) to (2), in particular by choosing said structural oxides spinel in the group consisting of Co 2 SnO 4 , CoAl 2 O 4 , Co (Cr, Al) 2 O 4 , (Co, Zn) Al 2 O 4 and mixtures thereof, and / or selecting a zirconium orthosilicate and vanadium (Zr, V) SiO 4 , as described above.
  • 10 ⁇ L * ⁇ 30 preferably 10 ⁇ L * ⁇ 20 for the dark blue, and if the light blue color is sought: 30 ⁇ L * ⁇ 70, preferably 30 ⁇ L * ⁇ 50, and / or * ⁇ 5, preferably a * ⁇ 0, and / or
  • a sintered part according to the invention can also be green in color, in particular by choosing the perovskite structure oxides such that A and B belong to groups G A '"(1) to (3) and G B '" (1) to (2), and / or by selecting the spinel structure oxides in the group formed by CoCr 2 O 4 , TiCo 2 O 4 , and mixtures thereof, as described above.
  • 10 ⁇ L * ⁇ 30 preferably 10 ⁇ L * ⁇ 20 for the dark green color, and if the light green color is desired: 30 ⁇ L * ⁇ 70, preferably 30 ⁇ L * ⁇ 50, and / or * ⁇ -5, preferably a * ⁇ -10, and / or
  • a sintered part according to the invention can also be turquoise, in particular by choosing the perovskite structure oxides such that A and B belong to groups G A 4 '(1) to (3) and GB 4 ' (1) to (3). 2), as described above.
  • a sintered part according to the invention can also be orange in color, in particular by choosing the perovskite structure oxides such that A and B belong to groups G A 5 '(1) to (2) and G B 5 ' (1), and / or by choosing oxides of rutile structure such that F belongs to G F '(1), as described above.
  • ⁇ L * ⁇ 70 preferably 30 ⁇ L * ⁇ 50 for the light orange color, and / or a * > 5, preferably a * > 10, and / or
  • a sintered part according to the invention may also be brown in color, in particular by choosing the oxides of perovskite structure such that A and B belong to groups G A 6 '(1). to (3) and G B 6 '(1), and / or by selecting the oxides of spinel structure in the group formed by Fe (Fe, Cr) 2 O 4 , Fe 2 TiO 4 , NiFe 2 O 4 , (Zn , Fe) Fe 2 O 4 , (Fe, Mn) (Fe, Mn, Cr) 2 O 4 , (Zn, Mn) (Mn, Cr) 2 O 4 and mixtures thereof, and / or by selecting structural oxides rutile such that F belongs to the group G F "(1), as described above.
  • a sintered part according to the invention may also be red in color, in particular by choosing oxides of spinel structure such that C is zinc and D is a mixture of aluminum and chromium, and / or by choosing oxides of hematite structure such that E belongs to the group G E (1), and / or by choosing oxides of rutile structure such that F belongs to the group GF " (1), and / or by choosing a zirconium orthosilicate in which there is inclusion iron oxide, as described above.
  • a sintered part according to the invention can also be dark violet in color, in particular by choosing the oxides of perovskite structure such that A and B belong to groups G A 7 '(1) to (2) and G B 7 ' (1) as described above.
  • a sintered part according to the invention can also be yellow in color, in particular by choosing oxides of rutile structure such that F belongs to the group G F 4 '(1), and / or by choosing an orthosilicate of zirconium and praseodymium (Zr , Pr) Si0 4 , as described above.
  • ⁇ L * ⁇ 70 preferably 30 ⁇ L * ⁇ 50 for the light yellow color, and / or
  • composition of a sintered part according to the invention may be identical to that of a particulate mixture according to the invention, by not considering the temporary constituents, in particular considering only the oxides.
  • the sintered part may have the following optional features:
  • the sintered part comprises 0.5 to 10.0% of oxide (s) of perovskite structure.
  • the perovskite level in the oxide (s) of perovskite structure is greater than 90%, preferably greater than 95%, preferably greater than 99%, preferably substantially 100%.
  • the oxide content (s) perovskite structure is greater than 3%, preferably greater than 4% and / or less than 9%, preferably less than 6%.
  • the stabilizer of zirconia is selected from the group consisting of Y 2 0 3 , Sc 2 0 3 and mixtures thereof and the content of said zirconia stabilizer is less than 8%, preferably less than 6.5%, based on the sum of Zr0 2 , Y2O3, Sc 2 0 3 , MgO, CaO and Ce0 2 .
  • the zirconia stabilizer is selected from the group consisting of MgO, CaO and mixtures thereof and the content of said zirconia stabilizer is less than 4%, based on the sum of Zr0 2 , Y 2 0 3 , Sc 2 0 3 , MgO, CaO and Ce0 2 .
  • the zirconia stabilizer is Ce0 2 and the content of said zirconia stabilizer is greater than 10% and less than 15%, based on the sum of Zr0 2 , Y 2 0 3 , Sc 2 0 3 , MgO, CaO and Ce0 2 .
  • the stabilizer of zirconia is selected from the group consisting of Y 2 0 3 , CeO 2 and mixtures thereof, and preferably respects the relationship 10% ⁇ 3.Y 2 0 3 + Ce0 2 ⁇ 20%, based on the sum of Zr0 2 , Y 2 0 3 , Sc 2 0 3 , MgO, CaO and CeO 2 .
  • the stabilizer of zirconia is Y 2 0 3 .
  • the content of Y 2 O 3 is greater than 3%, preferably greater than 4% and / or less than 8%, preferably less than 6.5%, based on the sum of Zr0 2 , Y 2 0 3 Sc 2 0 3 , MgO, CaO and CeO 2 .
  • the alumina content is greater than 10%, preferably greater than 15% and less than 60%, preferably less than 55%, preferably less than 50%, preferably less than 40%, more preferably less than 30%. In a particular embodiment, the alumina content is between 2% and 10%. In another particular embodiment, the alumina content is between 10% and 20%. Finally, in another particular embodiment, the alumina content is between 20% and 80%.
  • the stabilizer of alumina is selected from the group consisting of ZnO and lanthanide oxides except CeO 2 , and mixtures thereof, and the content of said stabilizer of alumina is less than 15%, preferably less than 10%, of preferably less than 8%, preferably less than 5%, based on the sum of Al 2 O 3 , ZnO and lanthanide oxides with the exception of CeO 2 .
  • the stabilizing of the alumina is La 2 0 3, that is to say the particulate mixture contains only La 2 0 3 as a stabilizer to the alumina.
  • the stabilizer of the alumina is La 3 O 3 and its content is less than 15%, preferably less than 10%, preferably less than 8%, preferably less than 5%, and / or preferably greater than 0%. , 5%, based on the sum of Al 2 O 3 , ZnO and lanthanide oxides except Ce0 2 .
  • the oxides of perovskite structure are preferably chosen from groups G A '(1) to (3) and G B ' (1) to (2), G A '' (1) to (3) and G B '' ( 1) to (2), G A '"(1) to (3) and G B '" (1) to (2), GA 4 '(1) to (3) and G B 4, (1) to (2), G A 5 '(1) to (2) and G B 5 ' (1), G A 6 '(1) to (3) and G B 6 ' (1), G A 7 '(1) ) to (2) and G B 7 '(1) above.
  • the invention further relates to an article selected from the group consisting of a jewel, a watch, a bracelet, a necklace, a ring, a brooch, a tie pin, a purse, a telephone, a piece of furniture and a household utensil such as a knife or chisel, a handle (in a car like a door handle, a gearbox knob, in the home like a door handle and / or window), a button (like a cufflink, a button for an action (window lift, car radio, ...), a veneer (car dashboard, a musical instrument, for example a guitar, a tool,.
  • a jewel a watch, a bracelet, a necklace, a ring, a brooch, a tie pin, a purse, a telephone, a piece of furniture and a household utensil
  • a handle in a car like a door handle, a gearbox knob, in the home like a door handle and / or window
  • a visible part of consumer goods equipment such as computer or telephone keys, the outer casing of a computer, Certainly, a frame part glasses, even glasses frames, an article of crockery, a frame (frame of a photo frame), a cover of a common device hertzian waves of frequencies between 800 MHz to 3GHz, said hood being exposed, at least in part, to the external environment of the device and traversed by at least a portion of said waves during use of the device, said article comprising a sintered part according to the invention.
  • 0.05 ⁇ preferably less than 0.02 ⁇ , more preferably less than 0.01 ⁇ , is considered to be particularly advantageous.
  • the mechanical properties render a sintered part according to the invention well suited to an application in which it is caused to undergo abrasive stresses and / or shocks and in which it must maintain its appearance despite these constraints and / or shocks. .
  • the invention also relates to such an application.
  • a sintered part according to the invention has:
  • the invention also relates to an article comprising a sintered part according to the invention, said sintered part being apparent (that is to say exposed to the outside), except disassemble, at least partially, said article.
  • the sintered part does not participate substantially in the main function of the article, that is to say that said sintered part takes part in a mainly decorative function, or purely decorative.
  • the choice of the sintered part results mainly from an aesthetic choice.
  • the sintered part performs a technical function.
  • the sintered part may be a support for another part, and / or be a protection part, in particular against shocks, in particular to protect a transmitter and / or a receiver able to transmit and / or receive radio waves. frequencies between 800 MHz and 3GHz.
  • the decorative article may have a support on which the sintered part is glued, clipped, sewn or inserted in force.
  • the sintered part can also be cofired with its support.
  • the decorative article comprises a plurality of sintered parts according to the invention.
  • the values of L * , and / or a * and / or b * measured a first of said sintered parts according to the invention different from less than 10%, preferably less than 5% of the corresponding measured values. on a second of said sintered parts according to the invention.
  • this proximity of the values of L * , and / or a * and / or b * is respected regardless of the first and second sintered parts according to the invention considered.
  • the index ⁇ measuring the color difference between the first and second parts is such that ⁇ ⁇ 5, preferably ⁇ ⁇ 2, or even ⁇ ⁇ 1.
  • the decorative article is packaged, for example in a bag, a box, or a container, for example in a package comprising, or even constituted by, paper and / or cardboard and / or plastic or metal, preferably sheet, preferably flexible sheet.
  • the package carries information indicating the destination of the decorative article and / or the technical characteristics of the decorative article.
  • the invention also relates to a method of manufacturing a decorative article comprising the following steps: i) preparation of a support;
  • iii) optionally, checking the color of said sintered part, preferably by measuring at least one, preferably all, of the following parameters: L * , a * , and b * ;
  • the preparation of the sintered part according to the invention (step ii)) comprises
  • the mixed raw materials and in particular the nature and composition of the pigment, being determined depending on the desired color and / or uniformity of the desired color for the sintered part, preferably by measurements of L *, a * and b *; and or
  • a selection operation of the sintered part, according to a desired color and / or uniformity of the desired color, among a plurality of sintered parts according to the invention it is preferable to check the color of a plurality of sintered parts according to the invention, preferably by measuring at least one, preferably all, of the following parameters: L * , a * , and b * , then select the sintered part whose color is closest to the desired color.
  • index ⁇ the mean squared difference between the parameters L * , a * and b * measured on an object (L obj , obi and bo bj ) and the corresponding parameters of the desired color (L, a and b), that is:
  • the sintered parts are selected so that ⁇ ⁇ 5, preferably ⁇ ⁇ 2, or even ⁇ ⁇ 1.
  • alumina-zirconia a product containing zirconia and more than 2% alumina.
  • Zirconia products reinforced with alumina or “alumina- zirconia (or “ATZ” in English) and zirconia-enhanced alumina products (or “zirconia-toughned alumina” or “ZTA") are alumina-zirconia products, well known to the skilled person.
  • “Sintering” is a consolidation by heat treatment at more than 1100 ° C of a particulate agglomerate, possibly with a partial or total melting of some of the constituents of this agglomerate (but not all of these constituents).
  • a perovskite crystallographic structure corresponds to a particular arrangement of elements in sites conventionally called “A sites” and “B sites”. The elements located at sites A and B, respectively, are commonly referred to as “A” and "B” elements.
  • oxides of perovskite structure include especially compounds of formula AB0 3 . All sites A and / or B are not always occupied by elements A and / or B, respectively.
  • a perovskite lanthanum-manganese oxide is a compound where A is lanthanum and B is manganese. Its structure is conventionally defined by a formula of t peLaMn0 3 .
  • a spinel crystallographic structure corresponds to a particular arrangement of elements C and D in sites conventionally called “octahedral sites” and “tetrahedral sites”.
  • the compounds exhibiting a spinel crystallographic structure include, in particular, the compounds of formula CD 2 0 4 referred to as “direct spinels", in which the element C occupies a tetrahedral site and the element D occupies an octahedral site, and the compounds of formulas D ( C, D) 0 4 , called “inverse spinels”, in which element D occupies tetrahedral and octahedral sites and element C occupies an octahedral site.
  • a cobalt - chromium oxide of direct spinel structure is a compound where C is cobalt, located at sites C, and D of chromium, arranged on sites D.
  • Its structure is conventionally defined by a formula of the CoCr 2 0 A type .
  • Another example of spinel is TiFe 2 O 4 inverse spinel, where C is titanium on D sites, and D is iron on C sites and D sites.
  • a hematite crystallographic structure corresponds to a particular arrangement of elements in sites conventionally called "E sites".
  • the elements located on the E sites are usually called "E elements”.
  • oxides of hematite structure include especially compounds of formula E 2 0 3 .
  • a rutile crystallographic structure corresponds to a particular arrangement of elements in sites conventionally called "F sites". The elements located on the F sites are usually called "F elements".
  • oxides of rutile structure include especially compounds of formula F0 2 .
  • An element A, B, C, D, E, or F may comprise several constituents.
  • a molar fraction of one of these constituents refers to the molar fraction of this component in said element.
  • “Lanthanide oxides” are the oxides of elements No. 57 (lanthanum) to No. 71 (lutetium) of the periodic table of elements.
  • a pigment is a powder which, when incorporated into a preform, leads, during sintering, to said preform, with a particular coloring.
  • a pigment is a powder whose median particle size is less than 50 ⁇ .
  • pigment is also used to refer to the grains corresponding, in the sintered part, to the pigment introduced into the feedstock.
  • the "rate” of perovskite, spinel, hematite, rutile or orthosilicate, excluding impurities, is defined in%, according to formula (1) below:
  • o APIG is the area measured on an X-ray diffraction diagram obtained from a BRUKER D5000 diffractometer type apparatus provided with a tube Copper DX, without deconvolution treatment, of the main peak or the main diffraction multiplet of the considered structure (perovskite, spinel, hematite, rutile or orthosilicate, respectively);
  • Secondary aphase is the area measured on the same chart, without deconvolution treatment, of the principal peak or main multiplet of diffraction of the secondary phase.
  • the secondary phase is the phase presenting the main peak or the largest multiplet of area, without taking into account said considered structure.
  • a multiplet is the partial superposition of several peaks. For example, a multiplet composed of two peaks is a doublet, a multiplet composed of three peaks is a triplet.
  • the oxide contents relate to the overall contents for each of the corresponding chemical elements, expressed in the form of the most stable oxide, according to the usual convention of the industry; therefore include sub-oxides and optionally nitrides, oxynitrides, carbides, oxycarbides, carbonitrides, or even the metallic species of the aforementioned elements.
  • impurities is meant the inevitable constituents, necessarily introduced with the raw materials or resulting from reactions with these constituents. Impurities are not necessary constituents, but only tolerated.
  • the compounds forming part of the group of oxides, nitrides, oxynitrides, carbides, oxycarbides, carbonitrides and metallic species of sodium and other alkalis are impurities.
  • hafnium oxide is not considered as an impurity. It is considered that a total content of impurities of less than 2% does not substantially modify the results obtained.
  • Hf0 2 is not chemically separable from Zr0 2 .
  • Zr0 2 conventionally refers to the total content of these two oxides. according to the present invention, Hf0 2 is not voluntarily added to the feedstock. Hf0 2 therefore only designates traces of hafnium oxide, this oxide always being naturally present in zirconia sources at levels generally less than 2%. For the sake of clarity, the zirconia content and traces of hafnium oxide can be referred to either by “Zr0 2 " or by "zirconia content”.
  • Stabilized zirconia is a zirconia stabilized with a stabilizer and constituted for more than 80% or even more than 90% or even more than 95%, or even substantially 100%, by volume, of quadratic and / or cubic phase, 100% complement consisting of monoclinic phase.
  • the amount of stabilized zirconia is measured by X-ray diffraction.
  • the measuring surface is polished, the last polishing step being carried out with a Mecaprex LD32-E 1 ⁇ diamond preparation marketed by the company PRESI after the piece was heat treated at 1000 ° C for 1 hour and cooled to room temperature.
  • the measurement is carried out directly on the powder, without preliminary grinding.
  • a precursor of a product is a compound or a set of compounds which, during sintering, in air, lead to the formation of said product.
  • a precursor of said perovskite structure oxide is a compound consisting of an intimate mixture of the oxides and / or precursors of the oxides comprising said perovskite structure oxide.
  • Such an intimate mixture can for example be obtained by coprecipitation or atomization.
  • the intimate mixture is consolidated by a heat treatment.
  • a precursor of this perovskite structure oxide is an intimate mixture of lanthanum oxide, cobalt oxide, iron oxide and manganese oxide.
  • Another possible precursor is an intimate mixture of precursors of these oxides, such as, for example, an intimate mixture of lanthanum nitrate, cobalt nitrate, iron nitrate and manganese nitrate. The mixture must be intimate.
  • a powder which comprises particles of Ti0 2 and MgO particles would not be a precursor of MgTi0 3 .
  • Ti0 2 and MgO are intimately mixed within the same particle.
  • An intimate mixture of precipitated salts may also serve as a precursor.
  • An amount of a precursor of a product is said to be "equivalent” to a quantity of said product when, during sintering, it leads to said quantity of said product.
  • Temporal means “capable of being removed from the preform during sintering”.
  • the “median size” of the grains of a sintered part the dimension measured according to the method of "Mean Linear Intercept” described in the ASTM method E1382.
  • the “median size” of a set of particles generally denoted D 50 , the size dividing the particles of this set into first and second populations equal in mass, these first and second populations comprising only particles having a larger size. , or lower respectively, at the median size.
  • the percentiles or "percentiles" (D 10 ) and 90 (D 90 ) are the particle sizes corresponding to percentages, by mass, of 10% and 90%, respectively, on the cumulative particle size distribution curve of the particle sizes. powder, the particle sizes being ranked in ascending order. For example, 10% by weight of the particles of the powder have a size less than D 10 and 90% of the particles by mass have a size greater than D 10 . Percentiles can be determined using a particle size distribution using a laser granulometer.
  • the specific surface area is calculated by the BET method (Brunauer Emmet Teller) as described in Journal of American Chemical Society 60 (1938), pages 309 to 316.
  • a particulate mixture according to the invention may thus comprise, for example, a first pigment in an oxide of perovskite structure and a second pigment in an oxide of spinel structure.
  • a particulate mixture according to the invention is preferably made up of more than 95%, more than 98%, or even substantially 100% of oxides.
  • the particulate mixture has a specific surface area, calculated by the BET method, greater than 3 m 2 / g, preferably greater than 5 m 2 / g and / or less than 30 m 2 / g, preferably less than 25 m 2 / g, preferably less than 20 m 2 / g.
  • D 50 median size less than 10 ⁇ , or even less than 5 ⁇ , or even less than 3 ⁇ , or even less than 1 ⁇ and / or preferably greater than 0,05 ⁇ .
  • the particulate mixture may be in a dry form, i.e. be obtained directly by mixing the appropriate raw materials. It may also have undergone an additional step, for example an atomization step, in particular to improve the chemical homogeneity.
  • the main constituents (i.e., the highest contents) of the particulate mixture are zirconia and alumina.
  • the median size of the zirconia is preferably less than 10 ⁇ , or even less than 5 ⁇ , or even less than 3 ⁇ , or even less than 1 ⁇ and / or preferably greater than 0,05 ⁇ .
  • the median size of the alumina is preferably less than 10 ⁇ , or even less than 5 ⁇ , or even less than 3 ⁇ , or even less than 1 ⁇ and / or preferably greater than 0,05 ⁇ .
  • the zirconia In the sintered part, the zirconia must be stabilized. In the particulate mixture, the zirconia can therefore preferably be stabilized with said zirconia stabilizer, preferably with Y 2 O 3 .
  • the stabilizer of the zirconia and / or a precursor of such a stabilizer may also, partially or totally, be incorporated in the particulate mixture in the form of a powder, that is to say in a form separate from the zirconia, so that, during sintering, at least a portion of the zirconia is stabilized.
  • the particulate mixture comprises a zirconia stabilizer selected from the group consisting of Y 2 O 3 , CeO 2 and mixtures thereof.
  • the amount of Y 2 0 3 , Ce0 2 respects the relationship 10% ⁇ 3.Y 2 0 3 + Ce0 2 ⁇ 20%, based on the sum of Zr0 2 , Y 2 0 3 , Sc 2 0 3 , MgO, CaO and Ce0 2 .
  • said zirconia stabilizer is Y 2 0 3 .
  • the content of Y 2 O 3 may especially be greater than 3%, preferably greater than 4% and / or less than 8%, preferably less than 6.5%, based on the sum of Zr0 2 , Y 2 0 3 , Sc 2 O 3 , MgO, CaO and CeO 2 .
  • the median size of the stabilizer powder of zirconia and / or a precursor of such a zirconia stabilizer is preferably less than 1 ⁇ , preferably less than 0.5 ⁇ , more preferably less than 0, 1 ⁇ .
  • the effectiveness of the stabilizer of zirconia is advantageously improved during sintering.
  • the alumina in the sintered part, can be stabilized.
  • the alumina in the particulate mixture, can thus be stabilized with said alumina stabilizer, preferably with La 3 O 3 .
  • the stabilizer of the alumina and / or a precursor of such a stabilizer may also, partially or totally, be incorporated in the particulate mixture in the form of a powder, that is to say in a form separate from the alumina, so that, during sintering, at least a portion of the alumina is stabilized.
  • the particulate mixture comprises La 3 0 3 as a stabilizer for alumina in an amount of less than 15%, preferably less than 10%, preferably less than 8%, preferably less than 5%, and / or preferably greater than 0.5%, based on the sum of Al 2 O 3 , ZnO and lanthanide oxides except CeO 2 .
  • the median size of the stabilizer powder of alumina and / or a precursor of such an alumina stabilizer is preferably less than 1 ⁇ , preferably less than 0.5 ⁇ , more preferably less than 0.1 ⁇ .
  • the effectiveness of the stabilizer of alumina is advantageously improved during sintering.
  • the particulate mixture also comprises one or more pigments of oxide (s) of perovskite structure and / or precursor (s) of such oxides and / or one or more pigments of oxide (s) of spinel structure and / or or one or more pigments of oxide (s) of hematite structure E 2 0 3 , the element E being chosen from the group G E (1) formed by mixtures of aluminum and chromium, mixtures of aluminum and aluminum, manganese, and mixtures thereof and / or one or more pigments of oxide (s) of rutile structure F0 2 , the element F being chosen from the group G F (1) formed by mixtures of tin and vanadium, the mixtures titanium and chromium and niobium, mixtures of titanium and chromium and tungsten, mixtures of titanium and niobium and manganese, mixtures of tin and chromium, and mixtures thereof and / or one or more pigments to an orthosilicate selected from the group of
  • a minimum content of 0.5% of said pigments in the particulate mixture is considered essential for obtaining a sintered part having good scratch and impact resistance, as well as a good appearance with well-developed and homogeneous colors. .
  • the pigment used preferably has a median size of less than 5 ⁇ , preferably less than 1 ⁇ , preferably less than 0,5 ⁇ .
  • the effectiveness of said pigments in the sintered part is improved.
  • the "other oxides" are preferably only pigments and impurities.
  • the impurities preferably represent less than 1, 5%, preferably less than 1%, more preferably less than 0.5%, preferably less than 0.2%, preferably less than 0.1%.
  • a particulate mixture according to the invention may also comprise one or more deflocculant (s) and / or binder (s) and / or lubricants, preferably temporary, conventionally used in forming processes for the production of preforms to be sintered, for example an acrylic resin, polyethylene glycol (PEG), or polyvinyl alcohol (PVA).
  • deflocculant s
  • binder s
  • lubricants preferably temporary, conventionally used in forming processes for the production of preforms to be sintered, for example an acrylic resin, polyethylene glycol (PEG), or polyvinyl alcohol (PVA).
  • a sintered part according to the invention may be manufactured from a particulate mixture according to the invention according to a process conventionally comprising steps a) to c).
  • this process comprises, prior to step a), a grinding step to achieve the particle size characteristics necessary for good subsequent densification of the material.
  • a grinding may be implemented so that each of the powders used in step a) or for the mixture particle of all these powders has a median size (D 50 ) less than 1 ⁇ .
  • step a a particulate mixture according to the invention "ready-to-use" can be implemented. Alternatively, all raw materials can be dosed at the time of preparation of the feedstock.
  • the feedstock can also comprise one or more deflocculant (s) and / or binder (s) and / or lubricants, preferably temporary, conventionally used in forming processes for the production of preforms to be sintered, for example a acrylic resin, polyethylene glycol (PEG), or polyvinyl alcohol (PVA).
  • deflocculant s
  • binder s
  • lubricants preferably temporary, conventionally used in forming processes for the production of preforms to be sintered, for example a acrylic resin, polyethylene glycol (PEG), or polyvinyl alcohol (PVA).
  • the mixture of raw materials can optionally be atomized before proceeding to step b).
  • the atomization makes it possible to improve the chemical homogeneity of said mixture.
  • step b) the mixture is then shaped, for example by cold isostatic pressing, to form blocks of desired size.
  • the preform is sintered, preferably under air, at atmospheric pressure or under pressure (hot pressing) or hot isostatic pressing ("hot isostatic pressing"), or HIP)) and at a temperature between 1200 ° C and 1500 ° C, preferably between 1350 ° C or 1400 ° C and 1450 ° C.
  • sintering in this temperature range promotes a good development of the color.
  • the holding time at this temperature is preferably between 2 and 8 hours.
  • the rise speed is typically between 10 and 100 ° C / h.
  • the descent speed can be free.
  • the sintering cycle preferably comprises a step of 1 to 4 hours at a temperature of between 400 ° C. and 800 ° C. in order to promote elimination of said products.
  • the parameters of the manufacturing process in particular the particle size of the feedstock, the sintering additive, the compression for making the preform and the sintering temperature can be adapted, in a known manner, to adapt the density of the sintered part to the intended application.
  • the sintered part obtained at the end of step c) may be machined and / or subjected to a surface treatment, such as, for example, polishing or sanding, according to any technique known to those skilled in the art.
  • the chemical analyzes were performed by X-ray fluorescence with respect to constituents with a content greater than 0.5%.
  • the content of the constituents present in an amount of less than 0.5% was determined by AES-ICP ("Atomic Emission Spectoscopy-Inductively Coupled Plasma").
  • the specific surface area was measured by nitrogen adsorption at 77 K and calculated by the BET 1-point method.
  • the samples are pre-treated at 300 ° C. under a stream of nitrogen for 2 hours before analysis.
  • the crystalline phases in a powder or in a sintered part were determined by X-ray diffraction on a Brucker D5000 apparatus (with a setting of 2 ⁇ from 5 ° to 80 °, with a pitch of 0.02 ° and 1 second per step).
  • the sintered alumina-zirconia part was polished, the last polishing step having been carried out with a Mecaprex LD32-E 1 ⁇ diamond preparation marketed by the company PRESI, then heat-treated at 1000 ° C. for 1 hour. hour and cooled to room temperature.
  • the particle size distributions were determined by sedigraphy, using a Sedigraph Sedigraph 5100 of the company Micromeritics ®, having dispersed under ultrasound suspension powders to characterize the presence of sodium metaphosphate.
  • EDS Energy Dispersive Spectroscopy
  • X-ray diffraction analysis X-ray diffraction analysis
  • elementary microprobe mapping may also be performed to identify the nature of the pigments present in a particulate mixture, as well as in the sintered part.
  • EDS Energy Dispersive Spectroscopy
  • the median grain size of a sintered part was measured by a Mean Linear Intercept method, according to ASTM E1382. According to this standard, lines of analysis are drawn on images of said sintered part, then, along each line of analysis, the so-called “intercepts" lengths are measured between two consecutive grain boundaries intersecting said line of 'analysis. The average length " ⁇ " of the "I" intercepts is then determined. For the tests below, the intercepts were measured on images, obtained by scanning electron microscopy, of sections of the sintered part, said sections having previously been polished until obtaining a mirror quality and then thermally etched at a temperature of 100 ° C below the sintering temperature, for reveal the grain boundaries. The magnification used for taking the images was chosen to display about 500 grains on an image. 5 images per sintered part were made.
  • the color measurements were carried out according to the NF ISO 7724 standard on polished pieces whose last polishing step was carried out with a Mecaprex LD32-E 1 ⁇ diamond preparation marketed by the company PRESI, using a device CM-2500d, manufactured by Konica Minolta, with illuminant D65 (natural light), 10 ° observer, and specular reflection excluded.
  • the hardness and toughness of the sintered parts tested were measured by Vickers indentation on polished sintered parts, the last polishing step having been carried out with a diamond paste of 1 ⁇ .
  • Flexural strength was measured at room temperature by 3-point bending on machined webs of dimensions 45 mm x 4 mm x 3 mm.
  • the powders of the various oxides of perovskite structure used in Examples 1 to 12 and 21 are prepared by solid-phase reaction of different nitrates co-precipitated in basic medium with ammonia.
  • the salts employed, provided by Sigma Aldrich, are hydrated lanthanum nitrate La (NO 3 ) 3 , xH 2 0, hydrated manganese nitrate Mn (NO 3 ) 2 , xH 2 O, cobalt nitrate hexahydrate, Co ( N0 3 ) 2 , 6H 2 0, iron nitrate nonahydrate Fe (N0 3 ) 3 , 9H 2 0, chromium nitrate nonahydrate Cr (NO 3 ) 3 , 9H 2 0.
  • the hydrates are dissolved in water. distilled water at a total concentration of 1 mol / l.
  • the masses of the various nitrates introduced are shown in Table 1 below: (Coo, 3Fe 0, 4Co, 3) O 3 LaCo0 3 LaFe0 3 La (Co 0 , 2Fe O , 2I lno, 6) O.
  • the ammonia is added gradually with stirring to a pH of 9.
  • the precipitate obtained is then filtered on Buchner and dried in an oven at 110 ° C for 1 night.
  • the precipitates are then dried for at least 12 hours in an oven at 110.degree.
  • the powders thus obtained are heat-treated in air at a temperature allowing the formation of the perovskite phase, generally between 1000 ° C. and 1400 ° C. (A lower temperature would have been possible, but would have led to a perovskite precursor). In this case, the temperature was 1300 ° C. After heat treatment, the perovskite level measured by X-ray diffraction on each of the powders was greater than or equal to 90%.
  • perovskite phase structure content was determined by the method previously described in the present description. For example, the determination of the perovskite rate of lanthanum-chromium-cobalt La (Cr 0.9 Co 0 , i) O 3 was carried out from X diffraction diagrams acquired with a D5000 diffractometer. BRUKER company with a copper DX tube. After synthesis, the products obtained may comprise the perovskite phase as well as other phases, in smaller amounts, such as Cr 2 0 3 .
  • the perovskite phases of the lanthanum - chromium - cobalt oxides are identified, according to the conventional protocol, by X - ray diffraction, using International Center for Diffraction Data (ICDD) sheets.
  • ICDD record 00-024-1016 is that of the perovskite phase of lanthanum - chromium - cobalt oxide La (Cr 0 , 9Co 0 , i) O 3 .
  • the perovskite level is equal to 100%.
  • the perovskite La (Cr 0.9 Co 0, i) O 3 calculated according to the formula (1) is 95%.
  • the spinel powder (Co, Fe) (Fe, Cr) 2 O 4 used in Examples 13 to 20 is prepared by solid phase reaction of different nitrates co-precipitated in basic medium with ammonia. Hydrates employed, provided by Sigma Aldrich, are cobalt nitrate hexahydrate, Co (NO 3 ) 2 , 6H 2 0, iron nitrate nonahydrate Fe (NO 3 ) 3 , 9H 2 0 and chromium nitrate nonahydrate Cr ( N0 3 ) 3 , 9H 2 0. The hydrates are dissolved in distilled water at a total concentration of 1 mol / l. The masses of the various hydrates introduced are shown in Table 2 below:
  • the ammonia is added gradually with stirring to a pH of 9.
  • the precipitate obtained is then filtered on Buchner and dried in an oven at 110 ° C for 1 night.
  • the precipitate is then dried for at least 12 hours in an oven at 110.degree.
  • the powder thus obtained is heat-treated in air at a temperature of 1200 ° C., allowing the formation of the spinel phase.
  • the spinel content measured by X-ray diffraction on this powder was greater than 95%, the determination of the content of spinel structure phase having been determined by the method described previously in the present description, and calculated according to the formula ( 1).
  • the Fe 2 0 3 powder, oxide of hematite structure, used in Example 22 is a Fe 2 O 3 iron oxide powder sold by BASF.
  • the powder of Mn 2 0 3 , oxide of hematite structure, used in Example 23 is a manganese oxide powder Mn 2 0 3 , obtained after heat treatment at 800 ° C for 2 hours in air MnO 2 , electrolytic grade , marketed by the EMD delta company.
  • the zirconium orthosilicate powder of praseodymium (Zr, Pr) SiO 4 used in Example 24 is a zirconium orthosilicate powder of praseodymium grade SICOCER F YELLOW 2255, sold by the company BASF.
  • the zirconium orthosilicate powder in which there is embedded iron oxide used in Example 25 is a zirconium orthoxide and iron oxide powder, grade SICOCER F RED 2355, marketed by the Company. BASF company.
  • the pigment powder of perovskite structure or pigment with a spinel structure or a pigment with a hematite structure or with an orthosilicate pigment is mixed with a yttria-containing zirconia powder and with an alumina powder whose main characteristics are shown in FIG. Table 3, by micromilling of the zirconia powder ytria with the alumina powder and with the perovskite structure pigment powder or spinel structure pigment or hematite structure pigment or orthosilicate pigment.
  • This microbrilling is carried out in a wet ball mill (zirconia beads 3 mol% Y 2 0 3 , diameter 0.8 mm) or "attritor".
  • the grinding conditions used for each mixture are as follows:
  • Mill volume 800 ml
  • volume of demineralized water 200 ml
  • Mass of powder to microbrease 50 g.
  • the powders After micromilling, the powders have a median size, measured by sedigraphy, of 0.25 ⁇ .
  • the various suspensions are then spray-dried, with an inlet atomizer temperature of 300 ° C. and an outlet temperature of the atomizer of 110 ° C., the flow rate of the suspension being 6 l / h.
  • the powders thus obtained are then screened with a sieve of 250 ⁇ .
  • Preforms in the form of pellets 32 mm in diameter and 8 grams in weight, were made by uniaxial pressing at a pressure of 100 MPa of the particulate mixtures of the examples. Said preforms were then sintered according to the following cycle:
  • the zirconia of the sintered parts obtained from the particulate mixtures 1 to 25 consists of more than 95%, in volume, of quadratic and / or cubic phase, the complement to 100% consisting of monoclinic phase.
  • the alumina of the sintered pieces obtained from the particulate mixtures 1 to 25 consists of substantially 100% alpha phase.
  • Table 5 shows that the sintered parts according to the invention tested have good mechanical properties and are dense.
  • a comparison of Examples 1 and 2, 9 and 10, 13 and 14, 16 to 18 shows a decrease in toughness and an increase in hardness when the alumina content increases, perovskite structure pigment content or pigment content of constant spinel structure.
  • Example 21 outside the invention shows that a perovskite content of pigment equal to 15% degrades the toughness to a prohibitive level for an application where the impact resistance is necessary.
  • the sintered parts according to the invention are particularly well suited for use as a decorative ornament in articles such as watches, bracelets, brooches, tie pins, necklaces, telephones, furniture or household utensils such as knives or scissors and as a hood in a radio communication device of frequencies between 800 MHz to 3GHz, said hood being exposed, at least in part, to the external environment of the device and traversed by at least a part of said waves when using the device.

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JP5718481B2 (ja) 2015-05-13
KR20130093173A (ko) 2013-08-21
CN103384652B (zh) 2015-05-20
CN103384652A (zh) 2013-11-06
US9340679B2 (en) 2016-05-17
US20130284065A1 (en) 2013-10-31
WO2012085875A2 (fr) 2012-06-28
KR101528861B1 (ko) 2015-06-15

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