CH714796B1 - Brown-colored article and its manufacturing process. - Google Patents
Brown-colored article and its manufacturing process. Download PDFInfo
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- CH714796B1 CH714796B1 CH00342/18A CH3422018A CH714796B1 CH 714796 B1 CH714796 B1 CH 714796B1 CH 00342/18 A CH00342/18 A CH 00342/18A CH 3422018 A CH3422018 A CH 3422018A CH 714796 B1 CH714796 B1 CH 714796B1
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
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- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
L'invention concerne un procédé de fabrication d'un article décoratif, notamment d'un composant horloger, de couleur brune, comprenant les étapes successives consistant à : Réaliser un premier mélange avec une poudre de Si 3 N 4 , une poudre d'Y 2 O 3 , une poudre d'Al 2 O 3 et une poudre de TiO 2 , ledit premier mélange comprenant en poids entre 79 et 91% de Si 3 N 4 , entre 3 et 7% d'Y 2 O 3 , entre 3 et 7% d'Al 2 O 3 , entre 3 et 7% de TiO 2 , Réaliser un deuxième mélange comprenant le premier mélange et un liant, Former une ébauche en conférant à ce deuxième mélange la forme souhaitée de l'article, Délianter l'ébauche, Fritter l'ébauche déliantée à une température comprise entre 1650 et 1850°C sous une pression comprise entre 20 et 80 bars d'azote pendant une période comprise entre 30 minutes et 3 heures.The invention relates to a method of manufacturing a decorative article, in particular a watch component, of brown color, comprising the successive steps consisting in: Performing a first mixture with a powder of Si 3 N 4, a powder of Y 2 O 3, an Al 2 O 3 powder and a TiO 2 powder, said first mixture comprising by weight between 79 and 91% of Si 3 N 4, between 3 and 7% of Y 2 O 3, between 3 and 7% Al 2 O 3, between 3 and 7% TiO 2, Produce a second mixture comprising the first mixture and a binder, Form a blank by giving this second mixture the desired shape of the article, Debinding the 'blank, Sinter the debonded blank at a temperature of between 1650 and 1850 ° C. under a pressure of between 20 and 80 bars of nitrogen for a period of between 30 minutes and 3 hours.
Description
DOMAINE TECHNIQUETECHNICAL AREA
[0001] La présente invention se rapporte à un procédé de fabrication d'un article décoratif, notamment d'un composant horloger, de couleur brune à base de nitrure de silicium. Elle se rapporte également à l'article décoratif. The present invention relates to a method of manufacturing a decorative article, in particular a watch component, brown in color based on silicon nitride. It also relates to the decorative article.
ART ANTERIEURPRIOR ART
[0002] Dans le domaine horloger, il est connu de réaliser des composants d'habillage tels que des boîtes de montre en céramique à base d'oxyde de zirconium, autrement dénommée zircone, avec une couleur qui peut être ajustée en fonction de la composition de la céramique. Ainsi, les documents EP 3 012 239 et CH 708 030 divulguent respectivement des céramiques à base de zircone de couleur grise et de couleur orange. In the watchmaking field, it is known to produce trim components such as ceramic watch cases based on zirconium oxide, otherwise called zirconia, with a color which can be adjusted according to the composition. ceramics. Thus, documents EP 3 012 239 and CH 708 030 respectively disclose ceramics based on zirconia of gray color and orange color.
[0003] Une autre céramique qui est le nitrure de silicium est également utilisée dans les composants horlogers. Cette céramique présente pour avantage d'être moins dense que la zircone, ce qui permet de fabriquer des composants qui sont légers tout en étant durs. Par exemple, le document CH 699 793 divulgue un matériau céramique à base de nitrure de silicium utilisé comme substrat pour des carrures de boîte de montre ou des maillons de bracelet. Another ceramic which is silicon nitride is also used in watch components. This ceramic has the advantage of being less dense than zirconia, which makes it possible to manufacture components which are light while being hard. For example, document CH 699 793 discloses a ceramic material based on silicon nitride used as a substrate for watch case middle parts or bracelet links.
[0004] Le nitrure de silicium est de couleur grise. Pour des raisons esthétiques, d'autres couleurs peuvent être souhaitées. Silicon nitride is gray in color. For aesthetic reasons, other colors may be desired.
RESUME DE L'INVENTIONSUMMARY OF THE INVENTION
[0005] La présente invention a ainsi pour objet de proposer un procédé de fabrication d'un article fritté à base de nitrure de silicium qui est coloré dans sa masse et, en particulier, qui est de couleur brune. The object of the present invention is thus to provide a method of manufacturing a sintered article based on silicon nitride which is colored throughout and, in particular, which is brown in color.
[0006] A cet effet, la composition de la poudre céramique à base de nitrure de silicium (Si3N4) est adaptée. Elle comporte des oxydes de titane (TiO2), d'yttrium (Y2O3) et d'aluminium (Al2O3). L'oxyde de titane confère la couleur brune au produit issu du procédé. Les oxydes d'yttrium et d'aluminium forment une phase liquide lors du frittage qui joue le rôle de liant pour les grains de Si3N4tout en permettant de nuancer la couleur brune du produit final. Les différents oxydes sont ainsi présents dans des pourcentages choisis pour obtenir une couleur brune bien spécifique qui qualitativement peut être qualifiée de brun chocolat. Le pourcentage en poids de TiO2est maintenu dans une gamme comprise entre 3 et 7%, de préférence entre 4 et 6% et plus préférentiellement entre 4.5 et 5.5%. Les pourcentages en poids d'Y2O3et d'Al2O sont maintenus entre 3 et 7% et, de préférence, entre 4 et 6%. For this purpose, the composition of the ceramic powder based on silicon nitride (Si3N4) is suitable. It contains oxides of titanium (TiO2), yttrium (Y2O3) and aluminum (Al2O3). The titanium oxide imparts the brown color to the product resulting from the process. The oxides of yttrium and aluminum form a liquid phase during sintering which acts as a binder for the Si3N4 grains while making it possible to shade the brown color of the final product. The various oxides are thus present in percentages chosen to obtain a very specific brown color which qualitatively can be qualified as chocolate brown. The percentage by weight of TiO2 is maintained in a range of between 3 and 7%, preferably between 4 and 6% and more preferably between 4.5 and 5.5%. The percentages by weight of Y2O3 and Al2O are maintained between 3 and 7% and, preferably, between 4 and 6%.
[0007] D'autres caractéristiques et avantages de la présente invention apparaîtront dans la description suivante d'un mode de réalisation préféré, présenté à titre d'exemple non limitatif en référence au dessin annexé. [0007] Other characteristics and advantages of the present invention will become apparent from the following description of a preferred embodiment, presented by way of non-limiting example with reference to the accompanying drawing.
BREVE DESCRIPTION DE LA FIGUREBRIEF DESCRIPTION OF THE FIGURE
[0008] La figure 1 représente une boîte de montre réalisée avec le matériau céramique à base de nitrure de silicium selon l'invention.[0008] FIG. 1 represents a watch case produced with the ceramic material based on silicon nitride according to the invention.
DESCRIPTION DETAILLEEDETAILED DESCRIPTION
[0009] La présente invention se rapporte à un article de couleur brune réalisé en un matériau céramique à base de nitrure de silicium et à son procédé de fabrication. Cet article peut être un élément constitutif de montres, bijoux, bracelets, broches, colliers, sacs à main, etc. Dans le domaine horloger, cet article peut être une carrure, un fond, une lunette, un poussoir, un maillon de bracelet, un cadran, une aiguille, un index de cadran, etc. A titre illustratif, une boîte de montre 1 réalisée avec le matériau céramique selon l'invention est représentée à la figure 1. The present invention relates to a brown article made of a ceramic material based on silicon nitride and its manufacturing process. This item can be a component of watches, jewelry, bracelets, brooches, necklaces, handbags, etc. In the watchmaking field, this article can be a caseband, a caseback, a bezel, a push-piece, a bracelet link, a dial, a hand, a dial index, etc. By way of illustration, a watch case 1 made with the ceramic material according to the invention is shown in FIG. 1.
[0010] L'article est fabriqué par frittage avec le procédé consistant à: Réaliser un premier mélange avec une poudre de Si3N4, une poudre d'Y2O3, une poudre d'Al2O3et une poudre de TiO2. Le mélange comprend en poids entre 3 et 7%, de préférence entre 4 et 6%, d'Y2O3, entre 3 et 7%, de préférence entre 4 et 6% d'Al2O3, entre 3 et 7%, de préférence entre 4 et 6%, et plus préférentiellement entre 4.5 et 5.5% de TiO2, le complément étant la poudre de Si3N4. De manière particulièrement préférée, le mélange comprend en poids 85% de Si3N4, 5% d'Y2O3, 5% d'Al2O3et 5% de TiO2. Broyer le premier mélange pour obtenir un diamètre d100 des particules inférieur ou égal à 5 µm si le premier mélange présente un diamètre d100 supérieur à cette valeur. De préférence, le diamètre d100 des particules est inférieur ou égal à 3 µm pour obtenir au final un produit fritté très dense avec une microstructure très fine. Le temps de broyage peut être de l'ordre de l'heure avec, par exemple, un temps de 2h. Réaliser un deuxième mélange comprenant le premier mélange et un système de liant organique (paraffine, polyéthylène, etc.). Former une ébauche en conférant à ce deuxième mélange la forme de l'article désiré, par exemple, par injection ou pressage. Délianter l'ébauche par exemple avec un solvant. Fritter l'ébauche déliantée à une température comprise entre 1650 et 1850°C, de préférence entre 1700 et 1800 °C, sous une pression comprise entre 20 et 80, de préférence entre 50 et 70, bars d'azote pendant une période comprise entre 30 minutes et 3 heures et, de préférence, entre 1 et 2 heures.The article is manufactured by sintering with the process consisting of: First mix with Si3N4 powder, Y2O3 powder, Al2O3 powder and TiO2 powder. The mixture comprises by weight between 3 and 7%, preferably between 4 and 6%, of Y2O3, between 3 and 7%, preferably between 4 and 6% of Al2O3, between 3 and 7%, preferably between 4 and 6%, and more preferably between 4.5 and 5.5% of TiO2, the remainder being Si3N4 powder. Particularly preferably, the mixture comprises by weight 85% of Si3N4, 5% of Y2O3, 5% of Al2O3 and 5% of TiO2. Grind the first mixture to obtain a particle diameter d100 less than or equal to 5 μm if the first mixture has a diameter d100 greater than this value. Preferably, the diameter d100 of the particles is less than or equal to 3 μm to ultimately obtain a very dense sintered product with a very fine microstructure. The grinding time can be of the order of an hour with, for example, a time of 2 hours. Make a second mixture comprising the first mixture and an organic binder system (paraffin, polyethylene, etc.). Form a blank by shaping this second mixture into the shape of the desired article, for example, by injection or pressing. Unbind the blank, for example with a solvent. Sinter the debonded blank at a temperature between 1650 and 1850 ° C, preferably between 1700 and 1800 ° C, under a pressure between 20 and 80, preferably between 50 and 70, bars of nitrogen for a period between 30 minutes and 3 hours and preferably between 1 and 2 hours.
[0011] L'article issu du procédé a une couleur brune conférée par l'oxyde de titane. Plus spécifiquement, il a une couleur brun chocolat lorsque la poudre de départ comporte 85% de Si3N4, 5% d'Y2O3, 5% d'Al2O3et 5% de TiO2. La nuance de brun peut être modulée en ajustant la teneur en TiO2ainsi que la teneur en Y2O3qui tend à changer l'intensité de la couleur et la teneur en Al2O3qui tend à apporter des nuances de vert. Les oxydes d'yttrium et d'aluminium jouent un rôle de liant pour les grains de nitrure de silicium et forment une phase vitreuse dans le produit final. The article resulting from the process has a brown color imparted by titanium oxide. More specifically, it has a chocolate brown color when the starting powder contains 85% Si3N4, 5% Y2O3, 5% Al2O3 and 5% TiO2. The shade of brown can be modulated by adjusting the TiO2 content as well as the Y2O3 content which tends to change the intensity of the color and the Al2O3 content which tends to provide shades of green. The oxides of yttrium and aluminum act as a binder for the silicon nitride grains and form a glassy phase in the final product.
[0012] A titre d'exemple, le procédé selon l'invention a été mis en oeuvre pour fabriquer un fond de boîte de montre partant d'une poudre comprenant en poids 85% de Si3N4(UBE SNE10), 5% d'Y2O3(Starck Grade C), 5% d'Al2O3(Sumitomo AKP 50) et 5% TiO2(US Research Nanomaterials 300 nm), le mélange de poudres étant passé dans un attriteur durant 1 heure afin d'obtenir un d100 inférieur à 3 µm. Des mesures de dureté (HV30), de ténacité (Kic), de colorimétrie (CIELab conforme aux normes CIE n°15, ISO 7724/1, DIN 5033 Teil 7, ASTM E-1164) ont été réalisées. For example, the method according to the invention was implemented to manufacture a watch case back from a powder comprising by weight 85% of Si3N4 (UBE SNE10), 5% of Y2O3 (Starck Grade C), 5% Al2O3 (Sumitomo AKP 50) and 5% TiO2 (US Research Nanomaterials 300 nm), the mixture of powders being passed through an attritor for 1 hour in order to obtain a d100 of less than 3 µm . Measurements of hardness (HV30), toughness (Kic), colorimetry (CIELab in accordance with standards CIE No. 15, ISO 7724/1, DIN 5033 Teil 7, ASTM E-1164) were carried out.
[0013] La table 1 ci-dessous reprend les résultats des mesures de dureté et de ténacité. Les mesures de dureté ont été réalisées sur une coupe transversale du fond avec respectivement trois mesures sous la surface et trois mesures à coeur de l'échantillon. La ténacité a été déterminée sur base des mesures des longueurs des fissures aux quatre extrémités des diagonales de l'empreinte de dureté selon la formule : avec P qui est la charge appliquée (N), a qui est la demi-diagonale (m) et / qui est la longueur de la fissure mesurée (m). Table 1 below shows the results of the hardness and toughness measurements. The hardness measurements were carried out on a cross section of the bottom with respectively three measurements under the surface and three measurements at the core of the sample. The toughness was determined on the basis of the measurements of the lengths of the cracks at the four ends of the diagonals of the hardness indentation according to the formula: with P which is the applied load (N), a which is the half-diagonal (m) and / which is the length of the measured crack (m).
[0014] La dureté est supérieure à 1500 Vickers et la ténacité est supérieure à 4 MPa √m. Surface 1514 9.2 5.3 0.1 Coeur 1509 8 4.8 0.2The hardness is greater than 1500 Vickers and the toughness is greater than 4 MPa √m. Surface 1514 9.2 5.3 0.1 Core 1509 8 4.8 0.2
Table 1Table 1
[0015] Les valeurs colorimétriques Lab ont été mesurées avec un spectrophotomètre KONICA MINOLTA CM-5 dans les conditions suivantes : mesures SCI (réflexion spéculaire incluse) et SCE (réflexion spéculaire excluse), inclinaison de 8°, zone de mesure MAV de 8 mm de diamètre. Les valeurs L*a*b* sont respectivement de 43.32 0.42 et 2.42. The Lab colorimetric values were measured with a KONICA MINOLTA CM-5 spectrophotometer under the following conditions: SCI (specular reflection included) and SCE (specular reflection excluded) measurements, inclination of 8 °, MAV measurement area of 8 mm of diameter. The L * a * b * values are 43.32 0.42 and 2.42 respectively.
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