阅读说明：本技术 彩色陶瓷 (Color ceramic ) 是由 谷淑人 于 2018-06-22 设计创作，主要内容包括：本发明提供一种彩色陶瓷,其中,包含稳定剂的氧化锆的含量为80质量％以上。并且该彩色陶瓷含有铝酸钴晶体中固溶有锰的固溶体晶体和氧化锆晶体。(The present invention provides a colored ceramic, wherein the content of zirconia containing a stabilizer is 80 mass% or more. And the colored ceramic contains solid solution crystals of manganese and zirconia crystals dissolved in the cobalt aluminate crystals.)

1. A colored ceramic, wherein,

the content of the stabilizer-containing zirconia is 80 mass% or more, and

it contains solid solution crystal of manganese dissolved in cobalt aluminate crystal and zirconia crystal.

2. The colored ceramic according to claim 1,

the solid solution crystal has an area occupancy of 1.5 area% or more and 7.5 area% or less in a cross section.

3. The colored ceramic according to claim 1 or 2, wherein,

the average crystal particle diameter of the solid solution crystal is 0.8 [ mu ] m or less.

4. The colored ceramic according to any one of claims 1 to 3,

the maximum value of the crystal particle diameter of the solid solution crystal is 1.2 [ mu ] m or less.

5. The colored ceramic according to any one of claims 1 to 4,

the average value of the distance between the centers of gravity of the adjacent solid solution crystals is 1.5 to 4 [ mu ] m.

6. The colored ceramic of claim 5,

the standard deviation of the distance between the centers of gravity of adjacent solid solution crystals is 1.5 [ mu ] m or less.

7. The colored ceramic according to any one of claims 1 to 6,

the ratio of monoclinic crystals of the zirconia crystals at the surface is greater than the ratio of monoclinic crystals of the zirconia crystals at the inside.

8. The colored ceramic of claim 7,

the ratio of monoclinic crystals of the zirconia crystals at the surface is 3 times or more and 10 times or less the ratio of monoclinic crystals of the zirconia crystals at the interior.

Technical Field

The invention relates to a colored ceramic.

Background

Zirconia ceramics are ceramics with high mechanical properties that give people a sense of high quality and aesthetic satisfaction. Therefore, in recent years, the decorative member has been widely used in various fields as a bezel of a glass insert of a timepiece, a key of a cellular phone, a headrest, and the like. In addition, various coloring components have been studied in order to form various hues in accordance with the diversification of preference.

Thus, the applicant has proposed a colored zirconia ceramic containing a blue-colored CoO-Al₂O₃A dye source of the above composition (see patent document 1).

Disclosure of Invention

The colored ceramic of the present invention contains zirconia as a stabilizer in an amount of 80 mass% or more. Further, the material contains a solid solution crystal in which manganese is dissolved in a cobalt aluminate crystal and a zirconia crystal.

Detailed Description

There are various preferences for color tone, and in recent years, a deep blue zirconia ceramic has been desired. In order to make the color dark blue, it is known to make the color light blue cobalt aluminate (e.g., C)_oO-Al₂O₃) In addition, the presence of particles made of manganese oxide, which serve to darken, makes it possible to achieve a deep blue color. However, since manganese oxide has a hardness lower than that of zirconium oxide and cobalt aluminate, when a zirconium oxide ceramic containing particles made of manganese oxide is processed into a decorative part, the particles are easily threshed. Further, the surrounding crystals are threshed from the threshed portion, and thereby large depressions (hereinafter referred to as pinholes) are easily generated. Here, the processed product in which the pin hole is generated is a defective product. In addition, even if the zirconia ceramics containing the particles made of manganese oxide do not generate pinholes due to processing, when the zirconia ceramics is worn on the body, the zirconia ceramics may be threshed when the zirconia ceramics collide with or come into contact with other objects. Therefore, at present, zirconia ceramics which exhibit a deep blue color tone and can give a high degree of aesthetic satisfaction over a long period of time are sought after.

The colored ceramic of the present invention exhibits a deep blue hue and can give a high degree of aesthetic satisfaction over a long period of time. The colored ceramic of the present invention will be described in detail below.

The colored ceramic of the present invention contains zirconia as a stabilizer in an amount of 80 mass% or more, and contains a solid solution crystal in which manganese is dissolved in a cobalt aluminate crystal and a zirconia crystal.

The colored ceramics of the present invention satisfies the above constitution, and therefore, there is no particle composed of manganese oxide which is easy to be threshed, and instead, there is cobalt aluminate crystal in which manganese is dissolved in solid, thereby exhibiting a deep blue color tone. Further, since the cobalt aluminate crystal is less likely to be degranulated, pinholes are less likely to be generated during processing. Thus, the colored ceramic of the present invention is less likely to cause pinholes due to processing, has a low possibility of grain shedding during use, and can withstand long-term use. Thus, the colored ceramic of the present invention can exhibit a deep blue color tone and can give a high aesthetic satisfaction over a long period of time.

Here, dark blue refers to a color tone in CIE1976L a b color space in which the luminance index L is 5 or more and 25 or less, the chromaticity index a is-20 or more and 10 or less, and the chromaticity index b is-40 or more and-5 or less.

The stabilizer is a substance for maintaining zirconia in a stable phase state (tetragonal crystal or cubic crystal), and is selected from, for example, yttria (Y)₂O₃) Cerium oxide (CeO)₂) Dysprosium oxide (Dy)₂O₃) At least one of magnesium oxide (MgO) and calcium oxide (CaO). In particular, if the stabilizer is yttria, the degree of stabilization is high because the ionic radius is close to that of zirconia, and coarse crystals of zirconia are less likely to be generated, and therefore the mechanical properties of the colored ceramic can be made excellent.

Next, various measurement methods and confirmation methods will be described.

First, as for the content of zirconia containing a stabilizer, the content of zirconium (Zr) was determined by semiquantitative analysis of the color ceramics using a fluorescence X-ray analyzer (XRF), and the zirconium was converted into zirconia (ZrO)₂) To perform the calculation.

Next, as for the content of the stabilizer, semi-quantitative analysis of the color ceramic was performed using XRF in the same manner as for zirconia, and for example, if yttrium (Y) is detected, the content of yttrium may be calculated by converting the yttrium content into yttrium oxide. Then, the content of zirconia containing the stabilizer can be calculated by summing the contents of zirconia and the stabilizer calculated by the above-described method.

In addition, the presence or absence of the zirconia crystal may be confirmed by measuring with an X-ray diffraction apparatus (XRD) and comparing with JCPDS data.

Further, the presence or absence of solid solution crystals in which manganese is solid-dissolved in cobalt aluminate crystals can be confirmed by the following method. First, the presence of cobalt aluminate crystals was confirmed by measurement using XRD and comparison with JCPDS data. Then, the colored ceramics are cut, mirror-polished on the cut cross section, and then heat-treated at 1360 to 1410 ℃ for 10 to 20 minutes, and the surface after heat treatment is used as a measurement surface, and surface analysis is performed by an electron beam microanalyzer (EPMA). Then, in the obtained color map, the presence or absence of solid solution crystals can be confirmed by whether or not manganese is detected in a region where aluminum, cobalt and oxygen overlap, which indicates the presence position of cobalt aluminate crystals. As another method of confirming the presence or absence of manganese in the cobalt aluminate crystal, energy dispersive X-ray analysis (EDS) was performed on the cobalt aluminate crystal on the measurement surface.

The color tone of the colored ceramic may be determined by using a color difference meter (CM-700 d manufactured by konica minolt, inc., or a model following it) according to JIS Z8722-. The measurement conditions may be set to CIE standard light source D65 for the light source, condition a ((45-n) [45-0]) for the illumination and light receiving method, and 3mm for the measurement diameter.

In addition, the solid solution crystal in the colored ceramic of the present invention may have an area occupancy of 1.5 area% or more and 7.5 area% or less in a cross section. If such a constitution is satisfied, pinholes are less likely to be generated by processing, the possibility of threshing during use is low, and a deep dark blue color tone is exhibited, so that a higher aesthetic satisfaction can be provided.

Here, deep blue refers to a color tone having a luminance index L of 7 or more and 22 or less, a chromaticity index a of-13 or more and 0 or less, and a chromaticity index b of-30 or more and-10 or less in the CIE1976L a b color space.

In addition, the area occupancy of solid solution crystals (in other words, the area occupancy of solid solution crystals) in the cross section of the colored ceramic can be calculated by the following method. First, the presence of solid solution crystals was confirmed by the above method. Then, in the photograph of the measurement surface taken by SEM, the solid solution crystal was painted black, and read as image data, and the area occupancy of the solid solution crystal was calculated by performing image analysis by a method of particle analysis by image analysis software "A image Jun" (Japanese: A image く, registered trademark, manufactured by Asahi Kasei corporation). As the analysis conditions of the image analysis software "a image man", for example, the brightness of the particles may be set to "dark", the binarization method may be set to "manual", the small pattern removal may be set to "0.1 μm", and the threshold may be set to "150".

In the colored ceramic of the present invention, the average crystal grain size of the solid solution crystal may be 0.8 μm or less. If such a constitution is satisfied, the solid solution crystals become a size that is less likely to be exfoliated, and therefore the colored ceramic of the present invention is less likely to cause pinholes due to processing, and the possibility of exfoliation during use becomes smaller.

Here, the average crystal grain size of the solid solution crystal may be calculated by a method such as particle analysis using the image analysis software "a is a monarch" in the same manner as when the area occupancy of the solid solution crystal is determined.

In the colored ceramic of the present invention, the maximum value of the crystal grain size of the solid solution crystal may be 1.2 μm or less. If such a constitution is satisfied, solid solution crystals having a size that is easy to be exfoliated are reduced, and therefore, the colored ceramic of the present invention is less likely to cause pinholes due to processing, and the possibility of exfoliation during use is reduced.

Here, the maximum value of the crystal grain size of the solid solution crystal may be calculated by a method such as particle analysis using the image analysis software "a is a monarch" in the same manner as when the area occupancy of the solid solution crystal is determined.

In the colored ceramic of the present invention, the average value of the distance between the centers of gravity of adjacent solid solution crystals may be 1.5 μm or more and 4 μm or less. The average value of the distances between the centers of gravity herein means an average value of the shortest distances between the centers of gravity of adjacent solid solution crystals. Thus, if such a constitution is satisfied, the solid solution crystals are dispersed, so that the colored ceramic of the present invention can suppress color variation and give a high aesthetic satisfaction to consumers.

Regarding the color deviation, the following isThe values of the luminance index L, the chromaticity indexes a, and b in the color space are measured in CIE1976L a b at a plurality of positions of the cross section of the color ceramic, and the minimum values of L, a, and b are subtracted from the maximum values of L, a, and b to calculate Δ L, Δ a, and Δ b, respectively, and Δ E is calculated from the calculated values ((Δ L)²+(Δa*)²+(Δb*)²)^1/2The color deviation Δ E may be obtained.

The average value of the inter-center-of-gravity distances of adjacent solid solution crystals may be calculated by the inter-center-of-gravity distance method of the image analysis software "a man", in the same manner as when the area occupancy of the solid solution crystals is determined.

In the colored ceramic of the present invention, the standard deviation of the distance between the centers of gravity of adjacent solid solution crystals may be 1.5 μm or less. The standard deviation of the distance between the centers of gravity herein refers to an index indicating the degree of dispersion of solid solution crystals. Thus, if such a constitution is satisfied, the solid solution crystals are more dispersed, and therefore the colored ceramic of the present invention can further suppress color variation and give a high aesthetic satisfaction to consumers.

The standard deviation of the distance between the centers of gravity of adjacent solid solution crystals may be calculated by the method of the distance between the centers of gravity method of the image analysis software "a-image" as in the case of obtaining the area occupancy of the solid solution crystals.

In addition, in the colored ceramic of the present invention, the ratio of monoclinic crystals of zirconia crystals at the surface may be greater than the ratio of monoclinic crystals of zirconia crystals at the inside. Here, the inside means a portion having a depth of 1.0mm or more from the surface of the colored ceramic of the present invention. The ratio of monoclinic crystals of zirconia crystals refers to the ratio to the total of tetragonal crystals, cubic crystals and monoclinic crystals of zirconia crystals.

Further, if such a constitution is satisfied, a compressive stress due to the presence of monoclinic crystals on the surface can be effectively applied, and cracks are less likely to be generated on the surface of the color ceramic due to the compressive stress. Therefore, the color ceramic of the present invention has improved mechanical strength and is not easily broken even after long-term use, and therefore can provide a high aesthetic satisfaction for a long term.

In the colored ceramic of the present invention, the ratio of monoclinic crystals of zirconia crystals on the surface may be 3 times or more and 10 times or less the ratio of monoclinic crystals of zirconia crystals inside. If such a constitution is satisfied, the compressive stress due to the presence of monoclinic crystals on the surface can be applied more effectively, and the mechanical strength of the colored ceramic of the present invention is further improved.

The ratio of monoclinic crystals of zirconia crystals on the surface of the colored ceramic of the present invention may be, for example, 0.3% or more and 30% or less. On the other hand, the ratio of monoclinic crystals of zirconia crystals in the colored ceramic of the present invention may be, for example, 0.1% or more and 3.0% or less.

Here, the ratio of monoclinic crystals of the zirconia crystals on the surface and in the interior can be determined from the obtained X-ray diffraction intensity by measuring the surface and in the interior of the colored ceramic by XRD, respectively.

Ratio (%) of monoclinic crystal (Im1+ Im2)/(Im1+ Im2+ It + Ic)

It: x-ray diffraction intensity of tetragonal crystal (111) plane

Ic: intensity of X-ray diffraction of cubic crystal (111) plane

Im 1: x-ray diffraction intensity of monoclinic crystal (111) plane

Im 2: x-ray diffraction intensity of monoclinic crystal (11-1) plane

In addition, the colored ceramic of the present invention may contain alumina. In particular, if the content of alumina is 0.5 mass% or more and 11 mass% or less in 100 mass% of all the components constituting the color ceramic, the grain growth of zirconia crystals can be suppressed, and therefore the mechanical strength of the color ceramic can be further improved.

Further, if the three-point bending strength of the color ceramic of the present invention is 900MPa or more as determined in accordance with JIS R1601-2008 and the Vickers hardness Hv is 13GPa or more as determined in accordance with JIS R1610-2003, it is less likely to be damaged even if it comes into contact with a substance having high hardness such as glass or metal dust.

Further, if the apparent density of the colored ceramic of the present invention is 5.7g/cm³As described above, the number of open pores on the surface is reduced, and the occurrence of degranulation from the outline of the open pores can be suppressed. The apparent density can be determined in accordance with JIS R1634-1998.

The colored ceramics of the present invention can be used as a timepiece component such as a bezel of a glass insert for a timepiece, a band link for a timepiece, a mobile phone component such as various keys, a headrest, an exterior component for performing a pressing operation, a fishing line guide component such as a fishing line guide ring, a decoration component such as a brooch, a necklace, an earring, a ring, a tie pin, a tie clip, a medal, and a button, a building material component such as a tile for decorating a floor, a wall, or a ceiling, a handle for a door, a kitchen component such as a spoon and a fork, a decorative component for other home appliances, and an automobile component such as a car badge.

Next, an example of the method for producing a color ceramic of the present invention will be described.

First, stabilized zirconia powder having an average particle diameter of 0.25 μm or more and 0.55 μm or less is prepared. The stabilized zirconia powder is a powder produced by a coprecipitation method by adding at least 1 stabilizer selected from the group consisting of yttria, ceria, dysprosia, magnesia, and calcia, and contains 95 to 99 mol% of zirconia and 1 to 10 mol% of a stabilizer. The stabilized zirconia powder may contain hafnium oxide in an amount of about 2 mass%.

Next, an alumina powder having an average particle size of 2 μm or less, a cobalt oxide powder having an average particle size of 2 μm or less, and a manganese oxide powder having an average particle size of 3 μm or less are prepared.

Then, raw material powders were prepared by weighing stabilized zirconia powder, alumina powder, cobalt oxide powder and manganese oxide powder so that the amount of zirconia containing a stabilizer in the color ceramic was 80 mass% or more. Here, in order to make the area occupancy rate of the solid solution crystals be 1.5% by area or more and 7.5% by area or less, the raw material powder is weighed so that the alumina powder is 0.5% by mass or more and 4.0% by mass or less, the cobalt oxide powder is 0.5% by mass or more and 1.3% by mass or less, and the manganese oxide powder is 0.3% by mass or more and 0.7% by mass or less in 100% by mass.

Next, the raw material powder and water as a solvent are put into a vibration mill, a ball mill, or the like, and mixed and pulverized, thereby obtaining a slurry. Here, in order to set the average value of the distance between the centers of gravity of adjacent solid solution crystals to 1.5 μm or more and 4 μm or less, the dispersant may be added in a range of 0.2 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the raw material powder in the mixing and pulverization. Further, in order to make the standard deviation of the distance between the centers of gravity of adjacent solid solution crystals to be 1.5 μm or less, the alumina powder, the cobalt oxide powder and the manganese oxide powder may be preliminarily pulverized before the mixed pulverization, and the preliminary pulverization time may be set to 40 hours or more.

Next, a predetermined amount of polyvinyl alcohol as a binder was added to the slurry, and the mixture was sprayed and dried using a spray dryer, thereby obtaining granulated particles. Then, using the pellets, a molded body having a desired shape such as a disk, a flat plate, a cylinder, or a torus is obtained by a desired molding method such as dry press molding or cold isostatic press molding. Alternatively, a solvent, a binder, or the like may be added to the slurry, and molding may be performed by a casting molding method or an injection molding method, thereby obtaining a molded article having a complicated shape.

Next, the obtained molded body is degreased as necessary, and then held at a specific temperature in a temperature range of 1000 ℃ to 1300 ℃ in an atmospheric atmosphere for 2 hours or more. Thereby, a cobalt aluminate crystal can be formed, and manganese in the manganese oxide powder can be made to be solid-soluble in the cobalt aluminate crystal. Then, the colored ceramic of the present invention can be obtained by sintering at a temperature ranging from 1400 ℃ to 1600 ℃. By adjusting the sintering temperature, the crystal grain size of the solid solution crystal can be made to be an arbitrary size.

After firing, the colored ceramics are put into a barrel mill together with a grinding medium and water and barrel-milled, whereby the transformation of the zirconia crystals on the surface of the colored ceramics is promoted, the ratio of monoclinic crystals in the zirconia crystals can be increased, and the ratio of monoclinic crystals of the zirconia crystals on the surface can be made larger than the ratio of monoclinic crystals of the zirconia crystals inside.

Here, by using the spherical polishing media, the effective phase transition of the zirconia crystals can be promoted on the surface of the colored ceramic, and the ratio of monoclinic crystals in the zirconia crystals can be greatly increased. Therefore, by appropriately adjusting the barrel polishing time using the spherical polishing medium, the ratio of monoclinic crystals of zirconia crystals on the surface can be made 3 times or more and 10 times or less the ratio of monoclinic crystals of zirconia crystals inside.

The following specifically describes examples of the present invention, but the present invention is not limited to these examples.