CH708030A2 - A method of manufacturing a color section; in particular orange; zirconia and colored decorative article based on zirconia obtained by this process. - Google Patents
A method of manufacturing a color section; in particular orange; zirconia and colored decorative article based on zirconia obtained by this process. Download PDFInfo
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- CH708030A2 CH708030A2 CH9082013A CH9082013A CH708030A2 CH 708030 A2 CH708030 A2 CH 708030A2 CH 9082013 A CH9082013 A CH 9082013A CH 9082013 A CH9082013 A CH 9082013A CH 708030 A2 CH708030 A2 CH 708030A2
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- Prior art keywords
- oxide
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- zirconia
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 24
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 23
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 19
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 15
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000292 calcium oxide Substances 0.000 claims abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 238000005498 polishing Methods 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000003247 decreasing effect Effects 0.000 claims description 3
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 239000003086 colorant Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910002020 Aerosil® OX 50 Inorganic materials 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- AQCDIIAORKRFCD-UHFFFAOYSA-N cadmium selenide Chemical compound [Cd]=[Se] AQCDIIAORKRFCD-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- PGWFQHBXMJMAPN-UHFFFAOYSA-N ctk4b5078 Chemical compound [Cd].OS(=O)(=O)[Se]S(O)(=O)=O PGWFQHBXMJMAPN-UHFFFAOYSA-N 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
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- 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
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
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- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- 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
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- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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- C04B2235/02—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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium oxides or oxide-forming salts thereof
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- 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
- C04B2235/6562—Heating rate
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- C04B2235/6582—Hydrogen containing atmosphere
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- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
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- 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
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Abstract
L’invention concerne un procédé de fabrication d’un article orange à base de zircone caractérisé par le fait qu’il comprend les étapes successives consistant à réaliser un premier mélange comprenant une poudre de zircone, 3 à 20% en poids d’au moins un stabilisant choisi parmi l’ensemble des oxydes comprenant l’oxyde d’yttrium, l’oxyde de magnésium, et l’oxyde de calcium seuls ou en combinaison, 0,1% à 5% en poids d’au moins un élément destiné à réaliser une phase vitreuse, et choisi parmi l’ensemble comprenant de l’oxyde de silicium, de l’oxyde d’aluminium, de l’oxyde lithium et de l’oxyde d’yttrium seuls ou en combinaison, 1% à 6% en poids d’une poudre d’oxyde de cérium; réaliser un deuxième mélange comprenant ledit premier mélange et un liant; réaliser un mélange granulé en opérant une granulation dudit deuxième mélange; former une ébauche en conférant à ce deuxième mélange granulé la forme de l’article désiré; fritter sous air pendant au moins trente minutes à une température comprise entre 1250 et 1500 DEG. C, et recuire l’article désiré à une température comprise entre 700 DEG. C et 1350 DEG. C pendant une période comprise entre 30 minutes et 20 heures dans une atmosphère réductrice et polir ladite ébauche frittée.The invention relates to a method for manufacturing an orange article based on zirconia, characterized in that it comprises the successive steps of producing a first mixture comprising a zirconia powder, 3 to 20% by weight of at least a stabilizer selected from the group of oxides comprising yttrium oxide, magnesium oxide, and calcium oxide alone or in combination, 0.1% to 5% by weight of at least one element for to achieve a glassy phase, and selected from the group consisting of silicon oxide, aluminum oxide, lithium oxide and yttrium oxide alone or in combination, 1% to 6 % by weight of a cerium oxide powder; producing a second mixture comprising said first mixture and a binder; producing a granulated mixture by granulating said second mixture; forming a blank by imparting to that second granulated mixture the shape of the desired article; sinter in air for at least 30 minutes at a temperature between 1250 and 1500 DEG. C, and annealing the desired article at a temperature between 700 DEG. C and 1350 DEG. C for a period of between 30 minutes and 20 hours in a reducing atmosphere and polishing said sintered blank.
Description
[0001] L’invention concerne un procédé de fabrication d’un article coloré à base de zircone, en particulier d’un tel article présentant une couleur comprise dans la gamme de l’orange vif au brun cuivreux et réalisé par frittage. Un tel article sera désigné dans la suite de la description «article orange «pour des raisons de commodités. The invention relates to a method of manufacturing a colored article based on zirconia, in particular of such an article having a color in the range of bright orange to cuprous brown and made by sintering. Such an article will be referred to in the rest of the description "orange article" for reasons of convenience.
[0002] L’invention concerne également un article décoratif orange à base de zircone notamment obtenu selon le procédé ci-dessus. The invention also relates to an orange decorative article based on zirconia especially obtained by the method above.
[0003] Il est déjà connu d’incorporer des agents colorants ou pigments tels que le sulfure de cadmium (CdS), le séléniure de cadmium (CdSe) et le sulfoséléniure de Cadmium dans des matériaux céramique pour obtenir des articles en céramique orange/rouge utilisés par exemple pour réaliser des émaux, des glaçures et des récipients à usage domestique ou des revêtements de sols. It is already known to incorporate coloring agents or pigments such as cadmium sulfide (CdS), cadmium selenide (CdSe) and cadmium sulfoselenide in ceramic materials to obtain orange / red ceramic articles. used for example to make enamels, glazes and containers for domestic use or floor coverings.
[0004] L’utilisation de ce type d’agents colorants présente de nombreux inconvénients dès lors que l’on souhaite incorporer ce type d’agents colorants dans des céramiques industrielles notamment à base de zircone frittée. The use of this type of coloring agents has many disadvantages since it is desired to incorporate this type of coloring agents in industrial ceramics including sintered zirconia base.
[0005] En effet, ces agents colorants manquent de stabilité à température élevée et ne présentent leurs caractéristiques colorantes que jusqu’à 1000 ou 1200 DEG. C. Cela limite grandement l’utilisation de ce type d’agents colorants et ne permet notamment pas la réalisation d’articles à base de zircone frittée, les températures de frittage de la zircone étant dans tous les cas supérieures à 1100 DEG. C. Indeed, these coloring agents lack stability at high temperature and have their coloring characteristics only up to 1000 or 1200 DEG. C. This greatly limits the use of this type of coloring agents and does not in particular allow the production of articles based on sintered zirconia, the sintering temperatures of the zirconia being in all cases greater than 1100 DEG. vs.
[0006] Par ailleurs, l’utilisation de ces types d’agents colorants, qui contiennent des métaux lourds, dans des objets destinés à être en contact avec la peau d’un utilisateur tel qu’une boîte de montre est sinon interdite légalement, du moins fortement déconseillée. Furthermore, the use of these types of coloring agents, which contain heavy metals, in objects intended to be in contact with the skin of a user such as a watch case is otherwise legally prohibited, at least strongly discouraged.
[0007] De plus, les agents colorants de ce type, disponibles commercialement ont une granulométrie incompatible pour l’obtention d’un mélange homogène avec la poudre de zircone. In addition, the coloring agents of this type, commercially available have an incompatible particle size to obtain a homogeneous mixture with the zirconia powder.
[0008] L’invention a donc pour but principal de fournir d’une part un procédé de fabrication d’un article orange vif à base de zircone frittée et d’autre part un tel article notamment obtenu selon ce procédé, cet article ayant des propriétés mécaniques satisfaisantes tout en présentant une coloration orange vive au moins sur une profondeur de 5 mm. The main purpose of the invention is therefore firstly to provide a method of manufacturing a bright orange article based on sintered zirconia and secondly such an article obtained in particular according to this method, this article having satisfactory mechanical properties while having a bright orange color at least to a depth of 5 mm.
[0009] A cet effet, l’invention a pour objet un procédé de fabrication d’un article orange vif à base de zircone caractérisé par le fait qu’il comprend les étapes successives consistant à: For this purpose, the subject of the invention is a method for manufacturing a bright orange article based on zirconia, characterized in that it comprises the successive steps consisting in:
[0010] réaliser un premier mélange comprenant. <tb>•<SEP>une poudre de zircone, <tb>•<SEP>3 à 20% en poids d’au moins un stabilisant choisi parmi l’ensemble des oxydes comprenant l’oxyde d’yttrium, l’oxyde de magnésium, et l’oxyde de calcium seuls ou en combinaison, <tb>•<SEP>0,1% à 5% en poids d’au moins un élément destiné à réaliser une phase vitreuse, et choisi parmi l’ensemble comprenant de l’oxyde de silicium, de l’oxyde d’aluminium, de l’oxyde lithium et de l’oxyde d’yttrium seuls ou en combinaison, <tb>•<SEP>1% à 6% en poids d’une poudre d’oxyde de cérium;Make a first mixture comprising. <tb> • <SEP> a zirconia powder, <tb> • <SEP> 3 to 20% by weight of at least one stabilizer chosen from the group of oxides comprising yttrium oxide, magnesium oxide and calcium oxide alone or in combination , <tb> • <SEP> 0.1% to 5% by weight of at least one element intended to produce a glassy phase, and chosen from the group comprising silicon oxide and aluminum oxide , lithium oxide and yttrium oxide alone or in combination, <tb> • <SEP> 1% to 6% by weight of a cerium oxide powder;
[0011] réaliser un deuxième mélange comprenant ledit premier mélange et un liant; [0011] producing a second mixture comprising said first mixture and a binder;
[0012] réaliser un mélange granulé en opérant une granulation dudit deuxième mélange; [0012] producing a granulated mixture by granulation of said second mixture;
[0013] former une ébauche en conférant à ce deuxième mélange granulé la forme de l’article désiré; Forming a blank by imparting to this second granulated mixture the shape of the desired article;
[0014] fritter sous air pendant au moins trente minutes à une température comprise entre 1250 et 1500 DEG. C, et Sinter in air for at least thirty minutes at a temperature between 1250 and 1500 DEG. C, and
[0015] recuire l’article désiré à une température comprise entre 700 DEG. C et 1350 DEG. C pendant une période comprise entre 30 minutes et 20 heures dans une atmosphère réductrice ayant une pression partielle d’oxygène comprise entre 10<-><6>et 10<-><1>atmosphère, et Annealing the desired article at a temperature between 700 DEG. C and 1350 DEG. C for a period of between 30 minutes and 20 hours in a reducing atmosphere having an oxygen partial pressure of between 10 <-> <6> and 10 <-> <1> atmosphere, and
[0016] polir ladite ébauche frittée. Polishing said sintered blank.
[0017] Le procédé de l’invention permet par l’incorporation de poudre d’oxyde de cérium (CeO2) dans le mélange à fritter, une diminution des températures de frittage. L’oxyde de cérium agit aussi comme un des éléments déterminant dans la coloration orange que l’on souhaite donner à l’article. The method of the invention allows the incorporation of cerium oxide powder (CeO2) in the sintered mixture, a decrease in sintering temperatures. Cerium oxide also acts as one of the determining elements in the orange color that one wishes to give to the article.
[0018] En effet, la couleur de l’article après l’opération de frittage en présence de CeO2est blanc ivoire. Puis au cours d’une étape ultérieure du procédé de l’invention, appelée étape de recuit, on profite de la présence de CeO2(état d’oxydation +4) pour le réduire en Ce2O3(état d’oxydation +3). Après cette étape de recuit l’article présente une couleur située dans la gamme allant du jaune orangé à l’orange vif en fonction des quantités respectives de cérium aux états d’oxydation +4, +3 présentes aux joints de grains. La couleur de l’oxyde de cérium (CeO2) correspondant à l’état d’oxydation +4 est blanc ivoire et la couleur de l’oxyde de cérium (Ce2O3) correspondant à l’état d’oxydation +3 est orange vif. Indeed, the color of the article after the sintering operation in the presence of CeO2 is ivory white. Then during a subsequent step of the process of the invention, called the annealing step, it takes advantage of the presence of CeO2 (+4 oxidation state) to reduce it to Ce2O3 (oxidation state +3). After this annealing step, the article has a color ranging from orange-yellow to bright orange depending on the respective amounts of cerium at the +4, +3 oxidation states present at the grain boundaries. The color of the cerium oxide (CeO2) corresponding to the oxidation state +4 is ivory white and the color of the cerium oxide (Ce2O3) corresponding to the oxidation state +3 is bright orange.
[0019] Les quantités respectives d’oxydes de cérium correspondant aux états d’oxydation +4, +3 présentes aux joints de grains sont déterminées par les conditions du recuit, plus précisément en faisant varier la pression partielle d’oxygène dans l’environnement du four où a lieu le recuit. The respective quantities of cerium oxides corresponding to the +4, +3 oxidation states present at the grain boundaries are determined by the annealing conditions, more specifically by varying the oxygen partial pressure in the environment. of the oven where the annealing takes place.
[0020] Selon un mode de réalisation, le premier mélange comprend entre 0,1 et 1% en poids de poudres d’oxydes pour la phase vitreuse et de préférence entre 4 et 5% en poids de poudre d’oxyde de cérium (Ce<+4>O2). According to one embodiment, the first mixture comprises between 0.1 and 1% by weight of oxide powders for the vitreous phase and preferably between 4 and 5% by weight of cerium oxide powder (Ce). <4> O2).
[0021] L’invention a également pour objet un article décoratif orange vif à base de zircone obtenu notamment selon le procédé décrit ci-dessus, caractérisé en ce qu’il est constitué d’une pièce frittée à partir d’une pièce moulée comprenant en substance une matrice d’oxyde de zirconium, 3 à 20% en poids d’au moins un stabilisant choisi parmi l’ensemble des oxydes comprenant l’oxyde d’yttrium, l’oxyde de magnésium, et l’oxyde de calcium seuls ou en combinaison, 0,1 à 5% en poids d’une phase vitreuse, comprenant au moins un élément choisi parmi l’ensemble comprenant de l’oxyde de silicium, de l’oxyde d’aluminium, de l’oxyde lithium et de l’oxyde d’yttrium, seuls ou en combinaison et 1% à 6% en poids d’oxyde de cérium. The invention also relates to a bright orange decorative article based on zirconia obtained in particular according to the method described above, characterized in that it consists of a sintered part from a molded part comprising in substance a zirconium oxide matrix, 3 to 20% by weight of at least one stabilizer chosen from the group of oxides comprising yttrium oxide, magnesium oxide and calcium oxide alone or in combination, 0.1 to 5% by weight of a glassy phase, comprising at least one member selected from the group consisting of silicon oxide, aluminum oxide, lithium oxide and yttrium oxide, alone or in combination and 1% to 6% by weight of cerium oxide.
[0022] De tels articles ont l’avantage de présenter un brillant intense après polissage et sont ainsi particulièrement adaptés à la réalisation d’articles décoratifs tels que des éléments constitutifs de boîtes de montre, des bijoux, des bracelets, des broches, des épingles de cravate, des colliers, des sacs à main, des téléphones, du mobilier, ou des ustensiles ménagers. Such articles have the advantage of having an intense gloss after polishing and are thus particularly suitable for producing decorative items such as constituent elements of watch cases, jewelry, bracelets, pins, pins tie, necklaces, purses, telephones, furniture, or household utensils.
[0023] D’autres caractéristiques et avantages de l’invention apparaîtront à la lumière de la description qui suit d’un exemple de réalisation du procédé de l’invention. Other features and advantages of the invention will become apparent in light of the following description of an embodiment of the method of the invention.
[0024] Le procédé de fabrication de l’invention qui va maintenant être décrit en détail est celui qui permet de réaliser un article à base de zircone frittée orange vif dont l’aspect et les propriétés mécaniques sont particulièrement adaptés à la réalisation de pièces constitutives de montres bracelet ou à la réalisation de tout autre article décoratif. The manufacturing process of the invention which will now be described in detail is that which makes it possible to produce a bright orange sintered zirconia article whose appearance and mechanical properties are particularly suitable for producing component parts. of wristwatch watches or the making of any other decorative item.
[0025] L’article en zircone orange vif obtenu selon ce procédé comprend 89 à 98,9% en poids de zircone stabilisée et le complément en poids c’est-à-dire 0,1 à 5% en poids d’une phase vitreuse réalisée à base d’oxyde de silicium, d’oxyde d’aluminium, d’oxyde d’yttrium et d’oxyde de lithium seuls ou en combinaison, et de 1% à 6% en poids d’oxyde de cérium. The bright orange zirconia article obtained according to this process comprises 89 to 98.9% by weight of stabilized zirconia and the complement in weight, that is to say 0.1 to 5% by weight of a phase. glassware made from silicon oxide, aluminum oxide, yttrium oxide and lithium oxide alone or in combination, and from 1% to 6% by weight of cerium oxide.
[0026] La zircone est stabilisée de façon classique en phase tétragonale par au moins un stabilisant choisi parmi l’ensemble des oxydes comprenant l’oxyde d’yttrium, l’oxyde de magnésium, et l’oxyde de calcium seuls ou en combinaison, ce stabilisant étant en quantité de 3 à 20% en poids par rapport à la zircone. The zirconia is conventionally stabilized in the tetragonal phase by at least one stabilizer chosen from the group of oxides comprising yttrium oxide, magnesium oxide, and calcium oxide alone or in combination, this stabilizer being in an amount of 3 to 20% by weight relative to the zirconia.
[0027] Pour réaliser cet article, on procède selon un exemple de mise en œuvre du procédé de l’invention de la façon suivante: To achieve this article, one proceeds according to an exemplary implementation of the method of the invention as follows:
[0028] On pèse 943 grammes de poudre de zircone stabilisée à 3% en poids d’oxyde d’yttrium. La poudre utilisée a une taille granulométrique moyenne de l’ordre du micromètre ou submicrométrique, typiquement, de 0,5 micromètre. Une telle poudre est vendue sous la référence TZ-3Y par la société Tosoh Corporation, Japon. Weigh 943 grams of zirconia powder stabilized at 3% by weight of yttrium oxide. The powder used has a mean particle size of the order of one micrometer or submicron, typically 0.5 micron. Such a powder is sold under the reference TZ-3Y by Tosoh Corporation, Japan.
[0029] On pèse ensuite 7 grammes d’un mélange de poudre d’oxyde de silicium, d’oxyde d’aluminium, et d’oxyde de lithium qui sera destiné à former une phase vitreuse au moment du frittage ultérieur. Then we weighed 7 grams of a mixture of silicon oxide powder, aluminum oxide, and lithium oxide which will be intended to form a glassy phase at the time of subsequent sintering.
[0030] De préférence, la phase vitreuse comprend à teneur décroissante en poids un mélange ou une combinaison de l’oxyde de silicium, de l’oxyde d’aluminium et de l’oxyde de lithium respectivement 47%, 40% et 13%, Preferably, the vitreous phase comprises at a decreasing weight content a mixture or a combination of silicon oxide, aluminum oxide and lithium oxide 47%, 40% and 13% respectively. ,
[0031] La poudre de silicium utilisée a une taille granulométrique moyenne inférieure au micromètre, typiquement 40 nanomètres et est vendue sous le nom Aerosil OX50 par la société Cerdec, Allemagne. The silicon powder used has a mean particle size less than one micrometer, typically 40 nanometers and is sold under the name Aerosil OX50 by Cerdec, Germany.
[0032] La poudre d’oxyde d’aluminium utilisée a une taille granulométrique moyenne de l’ordre de grandeur du micromètre ou submicrométrique typiquement 0,5 micromètre et est vendue sous le nom CR30 par la société Baikowski, France. The aluminum oxide powder used has a mean particle size of the order of magnitude of the micrometer or submicrometer typically 0.5 micrometer and is sold under the name CR30 by the company Baikowski, France.
[0033] La poudre d’oxyde de lithium utilisée a une taille granulométrique moyenne de l’ordre de grandeur du micromètre ou submicrométrique, typiquement de 2,4 micromètres et est vendue sous la référence No 374725 par la société Sigma Aldrich Chemie, Suisse. Le cas échéant la poudre est broyée pour atteindre la granulométrie souhaitée. The lithium oxide powder used has a mean particle size of the order of magnitude of the micrometer or submicrometer, typically 2.4 microns and is sold under the reference No. 374725 by Sigma Aldrich Chemie, Switzerland. If necessary, the powder is milled to reach the desired particle size.
[0034] On pèse enfin 50 grammes d’oxyde de cérium (Ce<4+>O), la poudre utilisée a une taille granulométrique de l’ordre de grandeur du micromètre ou submicrométrique, typiquement 0,5 micromètre et est vendue sous la référence No 202975 par Sigma Aldrich Chemie, Suisse. We finally weigh 50 grams of cerium oxide (Ce <4+> O), the powder used has a particle size of the order of magnitude of the micrometer or submicrometer, typically 0.5 micrometer and is sold under the Reference No. 202975 by Sigma Aldrich Chemie, Switzerland.
[0035] On notera que toutes ces poudres doivent de préférence présenter une pureté supérieure à 95%. Note that all these powders must preferably have a purity higher than 95%.
[0036] Une fois le pesage des poudres terminé, l’ensemble de ces poudres sont mélangées et homogénéisées en milieu humide. Dans la phase finale d’homogénéisation, on ajoute environ 50 grammes d’un liant, par exemple un alcool polyvinylique. Once weighing of the finished powders, all of these powders are mixed and homogenized in a humid medium. In the final phase of homogenization, about 50 grams of a binder, for example a polyvinyl alcohol, are added.
[0037] On procède ensuite au séchage du mélange par exemple dans un atomiseur classique. The mixture is then dried for example in a conventional atomizer.
[0038] Le granulé obtenu est tamisé pour conserver les particules ayant une granulométrie inférieure à 200 micromètres. The granule obtained is sieved to retain particles having a particle size less than 200 microns.
[0039] Le granulé tamisé est ensuite pressé dans un moule ayant la configuration de l’article que l’on désire obtenir afin de former une ébauche de ce dernier. The screened granulate is then pressed into a mold having the configuration of the article that is desired to obtain a blank of the latter.
[0040] L’article dans sa forme générale quasi finale est placé dans un four de frittage. On notera à ce propos que le frittage peut être effectué sous air. L’article est alors chauffé dans une première phase à une vitesse de 30 DEG. par heure jusqu’à environ 1000 DEG. C, puis dans une deuxième phase à une vitesse de 50 DEG. par heure jusqu’à la température de 1250 DEG. C. L’article est maintenu à cette température pendant au moins trente minutes et de préférence pendant une heure. The article in its almost final general form is placed in a sintering furnace. It should be noted in this connection that the sintering can be performed under air. The article is then heated in a first phase at a rate of 30 DEG. per hour up to about 1000 DEG. C, then in a second phase at a speed of 50 DEG. per hour up to the temperature of 1250 DEG. C. The article is maintained at this temperature for at least thirty minutes and preferably for one hour.
[0041] On notera que le frittage peut bien entendu être effectué à toute autre température supérieure ou égale à 1100 DEG. et inférieure à 1600 DEG. C. Note that the sintering can of course be performed at any other temperature greater than or equal to 1100 DEG. and less than 1600 DEG. vs.
[0042] Au cours du frittage, l’oxyde de silicium, l’oxyde d’aluminium, l’oxyde d’yttrium et l’oxyde de lithium forment une phase vitreuse qui vient se concentrer avec l’oxyde de cérium à l’état d’oxydation +4 aux joints de grains, ce qui confère une couleur ivoire à l’article après le frittage. During sintering, the silicon oxide, the aluminum oxide, the yttrium oxide and the lithium oxide form a vitreous phase which is concentrated with the cerium oxide at room temperature. oxidation state +4 at the grain boundaries, which gives the article an ivory color after sintering.
[0043] On notera que la présence notamment d’oxyde de lithium diminue avantageusement la température de frittage et permet limiter la transformation de la couleur de l’oxyde cérium et d’obtenir une couleur orange vif. Note that the presence of lithium oxide advantageously decreases the sintering temperature and allows to limit the transformation of the color of the cerium oxide and to obtain a bright orange color.
[0044] Après cette opération de frittage l’article est placé dans un four de recuit dans lequel il est possible de choisir l’atmosphère. L’article désiré est recuit soit dans une atmosphère d’hydrogène (H2), soit dans une atmosphère comportant un mélange d’azote et d’hydrogène (N2/H2) ou un mélange d’argon et d’hydrogène. After this sintering operation the article is placed in an annealing furnace in which it is possible to choose the atmosphere. The desired article is annealed either in a hydrogen atmosphere (H2), or in an atmosphere comprising a mixture of nitrogen and hydrogen (N2 / H2) or a mixture of argon and hydrogen.
[0045] Au cours de cette opération de recuit, la pression partielle d’oxygène dans le four est comprise entre 10<-6>et 10<-><1>atmosphère, la température de recuit est comprise entre 700 DEG. C et 1250 DEG. C et le temps de recuit est compris généralement entre 30 minutes et 20 heures. During this annealing operation, the oxygen partial pressure in the oven is between 10 <-6> and 10 <-> <1> atmosphere, the annealing temperature is between 700 DEG. C and 1250 DEG. C and the annealing time is generally between 30 minutes and 20 hours.
[0046] Selon un mode de mise en œuvre préféré du procédé de l’invention, l’atmosphère dans le four de recuit est l’hydrogène, la pression partielle d’oxygène est comprise entre 10<-><4>et 10<-1>atmosphère, la température de recuit est comprise entre 900 et 1*150 DEG.C et le temps de recuit est compris entre 4 et 6 heures. On comprendra que la profondeur de la coloration dans la masse de l’article varie proportionnellement avec le temps de recuit. According to a preferred embodiment of the process of the invention, the atmosphere in the annealing furnace is hydrogen, the oxygen partial pressure is between 10 <-> <4> and 10 < -1> atmosphere, the annealing temperature is between 900 and 1 * 150 DEG.C and the annealing time is between 4 and 6 hours. It will be understood that the depth of coloration in the mass of the article varies proportionally with the annealing time.
[0047] La couleur de l’article obtenu après l’opération de recuit est orange vif ou à une nuance de couleur comprise entre l’orange et le brun cuivré en fonction des conditions de recuit. The color of the article obtained after the annealing operation is bright orange or a shade of color between orange and brown copper depending on the annealing conditions.
[0048] L’article est alors refroidi puis usiné pour obtenir une forme adaptée à son utilisation finale. On notera que la coloration est réalisée dans la masse si bien qu’une opération d’usinage de l’article n’altère aucunement sa couleur. The article is then cooled and machined to obtain a shape adapted to its end use. Note that the coloring is performed in the mass so that a machining operation of the article does not alter its color.
[0049] Enfin, l’article est poli par exemple à l’aide d’une pâte de diamant, l’article ainsi obtenu a un aspect brillant orange vif ou une nuance comprise entre les couleurs citées plus haut en fonction des conditions du recuit de sorte qu’il présente des caractéristiques esthétiques attractives et intéressantes, notamment pour des applications dans le domaine horloger. Finally, the article is polished for example with a diamond paste, the article thus obtained has a bright orange bright appearance or a shade between the colors mentioned above depending on the annealing conditions. so that it has attractive and interesting aesthetic characteristics, especially for applications in the watchmaking field.
[0050] Selon un autre exemple de réalisation du procédé de l’invention, on a suivi le mode opératoire décrit précédemment pour réaliser des lunettes de montre circulaires de 45 mm de diamètre et de 4mm d’épaisseur. Dans cet exemple on a utilisé une combinaison de SiO2 (47%), de AI2 O3 (40%), et de Li2O (13%) formant un composé dont la proportion en poids de la composition totale est de 0.7%, le mélange formant la phase vitreuse, 6% en poids de CeO2, et le solde soit 93,3% en poids de ZrO2 stabilisée. Une fois configurées dans leur forme finale désirée, les lunettes ont été frittées sous air pendant 2 heures à 1450 DEG.C. Ces lunettes ont ensuite été recuites pendant 12 heures à 1000 DEG.C dans une atmosphère comprenant 5% d’hydrogène et 95% d’argon. Les lunettes ont été refroidies puis polies miroir. Les lunettes obtenues avaient un aspect brillant orange vif. On a également constaté après rupture d’une lunette que la coloration s’est faite dans la masse. According to another embodiment of the method of the invention, the procedure described above was followed to make circular watch glasses 45 mm in diameter and 4 mm thick. In this example, a combination of SiO 2 (47%), Al 2 O 3 (40%) and Li 2 O (13%) was used, forming a compound in which the proportion by weight of the total composition was 0.7%, the mixture forming the glassy phase, 6% by weight of CeO 2, and the balance is 93.3% by weight of stabilized ZrO 2. Once configured to their desired final shape, the glasses were sintered under air for 2 hours at 1450 ° C. These glasses were then annealed for 12 hours at 1000 ° C. in an atmosphere comprising 5% hydrogen and 95% argon. The glasses were cooled then polished mirror. The glasses obtained had a bright orange glossy appearance. It was also found after rupture of a telescope that the coloring was done in the mass.
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CN107922272A (en) * | 2015-09-03 | 2018-04-17 | 东曹株式会社 | Red oxidization zirconium sintered body and its manufacture method |
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CN107922272A (en) * | 2015-09-03 | 2018-04-17 | 东曹株式会社 | Red oxidization zirconium sintered body and its manufacture method |
EP3345883A4 (en) * | 2015-09-03 | 2019-01-09 | Tosoh Corporation | Red zirconia sintered body and method for manufacturing the same |
US10550040B2 (en) | 2015-09-03 | 2020-02-04 | Tosoh Corporation | Red zirconia sintered body and method for manufacturing the same |
CN107922272B (en) * | 2015-09-03 | 2021-05-25 | 东曹株式会社 | Red zirconia sintered body and method for producing same |
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