Ceramic sintered body

Abstract

Provided is a ceramic sintered body comprising at least 90 mass% Al in terms of Al2O3, 0.4-2.5 mass% Si in terms of SiO2, 3.0-3.7 mass% Mn in terms of MnO2, 1.1-1.7 mass% Ti in terms of TiO2, 1.1-1.7 mass% Fe in terms of Fe2O3, and 0.05-0.3 mass% Mg in terms of MgO, wherein ΔE calculated on the basis of a*, b*, and L* is 0-36.

Description

[Technical Field]

[0001] The present disclosure relates to a ceramic sintered body. [Background Art]

[0002] Conventionally, as disclosed in Patent Document 1, ceramic sintered bodies used for mounting substrates, members for exposure processing apparatuses, light shielding materials, heat absorbing materials, and the like are known. Such a ceramic sintered body is, for example, black and includes a composite oxide containing a plurality of metal elements. [Prior Art Documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-open No. 1-42359 [Summary of the Invention]

[0004] A ceramic sintered body according to one aspect of the embodiment contains 90 mass% or more of Al in terms of Al2O3, 0.4 mass% or more and 2.5 mass% or less of Si in terms of SiO2, 3.0 mass% or more and 3.7 mass% or less of Mn in terms of MnO2, 1.1 mass% or more and 1.7 mass% or less of Ti in terms of TiO2, 1.1 mass% or more and 1.7 mass% or less of Fe in terms of Fe2O3, and 0.05 mass% or more and 0.3 mass% or less of Mg in terms of MgO. a * , b * and ΔE calculated based on L * is 0 or more and 36 or less. [Mode for Carrying Out the Invention]

[0005] The above-mentioned ceramic sintered body has, for example, poor bending strength, leaving room for improvement.

[0006] Accordingly, provision of a black ceramic sintered body having excellent bending strength is expected.

[0007] Hereinafter, embodiments of the ceramic sintered body disclosed in the present application will be described in detail. It should be noted that the present invention is not limited by the embodiments shown below.

[0008] The ceramic sintered body of the present disclosure contains Al, Si, Mn, Ti, Fe and Mg. The ceramic sintered body of the present disclosure contains a plurality of metal oxides.

[0009] The ceramic sintered body of the present disclosure exhibits a black color. Specifically, the ceramic sintered body of the present disclosure has a * , b * and L * ΔE calculated based on the above is 36 or less. Here, a * , b * and L * are CIE1976 (L * a * b * ) values based on the color space in accordance with JIS Z 8781-4 2013. a * , b * and L * can be measured at a wavelength of 400 nm to 700 nm using a spectrophotometer, for example, CM-700d manufactured by Konica Minolta. The visual field for measurement may be 10°. The main light source may be D65, and measurement may be performed under measurement conditions such that the illumination diameter has an opening diameter of φ6 mm (SAV), SCE (specular reflected light removal), and measurement is performed after white calibration. Further, the reflectance may be measured, for example, using CM-2600d manufactured by Konica Minolta under the conditions of SCE (specular reflected light removal) and a wavelength of 360 nm to 740 nm. Note that a * , b * and L * can be adjusted not only by the composition of the metal oxide contained in the ceramic sintered body of the present disclosure, but also by the firing temperature and firing time. ΔE is defined as ΔE=(a *2 +b *2 +L *2 ) 0.5 is a value calculated based on the calculation formula. If the value of ΔE is 0, a * , b * , L *A value of 0 for all of the parameters means that the color is black. Conversely, a larger value of ΔE means that the color is further away from black. A ΔE of 36 or less means that the color is sufficiently close to black.

[0010] The ceramic sintered body of this disclosure contains 90% by mass or more of Al on an Al2O3 basis. The ceramic sintered body of this disclosure may contain 90% by mass or more and 95% by mass or less of Al. The Al content may be adjusted according to the content of other components described later.

[0011] Furthermore, the ceramic sintered body of this disclosure contains 0.4% to 2.5% by mass of Si on an SiO2 basis. This makes it easier to obtain a sufficient density suitable for the application and a ceramic sintered body with excellent flexural strength. The ceramic sintered body of this disclosure may also contain 0.9% to 2.0% by mass of Si on an SiO2 basis. With such a composition, it is particularly easy to obtain a ceramic sintered body with high strength.

[0012] Furthermore, the ceramic sintered body of this disclosure contains 3.0% to 3.7% by mass of Mn in terms of MnO2. This makes it easier to obtain a ceramic sintered body with a ΔE of 36 or less. * and b * is between -2.0 and 2.0, L * A ceramic sintered body with a value between 0 and 36, possessing excellent bending strength and high volume resistivity, is more likely to be obtained.

[0013] Furthermore, the ceramic sintered body of this disclosure contains 1.1% to 1.7% by mass of Ti in terms of TiO2. This makes it easier to obtain a ceramic sintered body with a ΔE of 36 or less. * and b * is between -2.0 and 2.0, L * A ceramic sintered body with a value between 0 and 36 and excellent bending strength is more easily obtained.

[0014] Furthermore, the ceramic sintered body of this disclosure contains 1.1% by mass or more and 1.7% by mass or less in terms of Fe2O3. Fe It contains [a]. This makes it easier to obtain ceramic sintered bodies with a ΔE of 36 or less. Also, a * and b * is between -2.0 and 2.0, L * A ceramic sintered body with a value between 0 and 36, possessing excellent bending strength and high volume resistivity, is more likely to be obtained.

[0015] Furthermore, the ceramic sintered body of this disclosure contains 0.05% to 0.3% by mass of Mg in terms of MgO. As a result, the ceramic sintered body of this disclosure is less prone to grain growth and tends to have excellent flexural strength.

[0016] Furthermore, the ceramic sintered body of this disclosure may have a Mn content, calculated as MnO2, that is 2 to 5 times the Fe content, calculated as Fe2O3. * and b * The resistivity tends to approach zero, and the material tends to have excellent bending strength and a high volume resistivity, making it easier to obtain an insulating ceramic sintered body. Furthermore, because Mn is dispersed at the grain boundaries of the alumina matrix, it becomes easier to absorb low-wavelength to medium-wavelength visible light, which relatively increases the reflection of long-wavelength visible light. For this reason, the ceramic sintered body of this disclosure tends to reflect infrared light, for example. In particular, the above effect is significant when the Mn content (calculated as MnO2) is 2.5 times or more the Fe content (calculated as Fe2O3).

[0017] Furthermore, the ceramic sintered body of this disclosure has a volume resistivity of 10 9 The resistance may be Ω·m or greater, and the three-point bending strength may be 310 MPa or greater. This results in a ceramic sintered body suitable for applications requiring relatively high insulation resistance and physical strength.

[0018] Furthermore, the ceramic sintered body of this disclosure is a * and b *The value may be between -1.5 and 1.5. This results in a ceramic sintered body that is particularly suitable for applications requiring a black color.

[0019] Furthermore, the ceramic sintered body of this disclosure has a sum of Mn content (calculated as MnO2) and Fe content (calculated as Fe2O3) of 4.5% by mass or more and 6.9% by mass. the following This may also be the case. * and b * This makes it easier to obtain an insulating ceramic sintered body that is close to zero, has excellent bending strength, and has high volume resistivity.

[0020] The metallic elements contained in the ceramic sintered body of this disclosure can be quantified using an X-ray fluorescence analyzer (XRF). The content of each metallic element obtained by measurement is converted to a metallic oxide and expressed as the content of each metallic element. Specifically, for example, Al is converted to Al2O3, Si to SiO2, Mn to MnO2, Ti to TiO2, Fe to Fe2O3, and Mg to MgO. If the ceramic sintered body contains other metallic elements, they can be converted to representative metallic oxides of each element.

[0021] Furthermore, the ceramic sintered body of this disclosure does not need to contain Co and Cr. In such cases, the ceramic sintered body of this disclosure can be provided at a low cost because it does not use expensive Co and Cr. Note that "not containing Co and Cr" means that the Co and Cr content is below the detection limit of an X-ray fluorescence analyzer (XRF).

[0022] Next, an example of a method for manufacturing the ceramic sintered body of this disclosure will be described.

[0023] Al2O3, Fe2O3, and MnO2 are mixed in particulate or powder form, and TiO2, SiO2, and MgO are added as sintering aids. The particle size of each raw material powder may be, for example, 0.1 μm to 5 μm. Water and an optional binder are added and mixed and stirred, and a molded body of the desired shape is made using the resulting slurry. By firing in an oxidizing atmosphere, the ceramic sintered body of this disclosure is obtained. Known methods such as press molding can be used to make the molded body.

[0024] The firing temperature may be, for example, between 1350°C and 1550°C. The firing time may also be, for example, about 2 hours. The firing atmosphere may be air.

[0025] Next, the applications of the ceramic sintered body of this disclosure will be described. For example, the ceramic sintered body of this disclosure can be used as a component for exposure processing equipment, a light-shielding material, and a heat-absorbing material, taking advantage of its black color. It can also be used as a mounting substrate, a structural component, or a functional component for industrial machinery, taking advantage of the excellent mechanical and electrical properties of the ceramic sintered body of this disclosure. Furthermore, the ceramic sintered body of this disclosure can be used as a sliding component or decorative component for fishing gear, taking advantage of its black color and excellent mechanical properties. [Examples]

[0026] Ceramic sintered bodies with different compositions were fabricated, and their mechanical strength (three-point bending strength), volume resistivity, and a * , b * and L * Measurements were taken. The obtained a * , b * and L * Based on this, ΔE was calculated. ΔE was calculated based on the following relation (Equation 1). a * , b * and L * Unless otherwise specified, measurements were taken on the sintered surface of the sintered body.

[0027] (Equation 1) ΔE=(a*2 +b *2 +L *2 ) 0.5

[0028] First, we prepared Al2O3 powder, SiO2 powder, MnO2 powder, TiO2 powder, Fe2O3 powder, and MgO powder.

[0029] Then, the sintered ceramics were weighed so that the mass ratios of Al oxide (Al2O3), Si oxide (SiO2), Mn oxide (MnO2), Ti oxide (TiO2), Fe oxide (Fe2O3), and Mg oxide (MgO) matched the values ​​in Table 1.

[0030] Next, the weighed powders were mixed and molded to obtain a molded body of the desired shape.

[0031] Next, the molded bodies were fired in a firing furnace under an atmospheric (oxidizing) atmosphere to obtain sintered bodies that would become each sample.

[0032] Next, XRD measurements were performed on each sample to confirm the presence of aluminum oxide (alumina). Furthermore, after mirror polishing each sample, XRF measurements were performed to determine the content of Al, Si, Mn, Ti, Fe, and Mg. The content of each element was then converted from these determined elemental content values ​​to the content of each oxide, resulting in the elemental content percentages shown in Table 1.

[0033] Furthermore, the three-point bending strength was measured using the obtained sintered body in accordance with JIS R 1601-2008, and the results are shown in Table 1.

[0034] Furthermore, using the obtained sintered body, CIE1976(L) was performed in accordance with JIS Z 8722-2000. * a * b * ) a based on color space * , b * and L * Each of these parameters was measured, and ΔE was calculated using (Equation 1) described above. The results are shown in Table 1.

[0035] [Table 1]

[0036] As shown in samples No. 1 and 4, when the Si content was less than 0.4 mass% or more than 2.5 mass% in terms of SiO2, the three-point bending strength was less than 310 MPa, resulting in a ceramic sintered body with poor bending strength.

[0037] Furthermore, as shown in samples No. 5 and 8, when the Mg content was less than 0.05% by mass or more than 0.3% by mass in terms of MgO, the three-point bending strength was less than 310 MPa, resulting in a ceramic sintered body with poor bending strength.

[0038] Furthermore, as shown in sample No. 9, when the Ti content was less than 1.1% by mass in terms of TiO2, ΔE exceeded 36. Also, a * and b * is over 2.0, L * A ceramic sintered body with a bending strength of over 36 was obtained. Furthermore, as shown in sample No. 12, when the material contained more than 1.7 mass% of Ti in terms of TiO2, the three-point bending strength was less than 310 MPa, resulting in a ceramic sintered body with poor bending strength.

[0039] Furthermore, as shown in sample No. 13, if the sample contains less than 3.0% by mass of Mn in terms of MnO2, then b * A ceramic sintered body with a value greater than 2.0 was obtained. Furthermore, as shown in sample No. 17, when the material contained more than 3.7 mass% of Mn in terms of MnO2, the three-point bending strength was less than 310 MPa, resulting in a ceramic sintered body with poor bending strength.

[0040] Furthermore, as shown in sample No. 18, when the Fe content was less than 1.1% by mass in terms of Fe2O3, ΔE exceeded 36. Also, L * A ceramic sintered body with a ratio of over 36 was obtained. Also, as shown in sample No. 21, when the Fe content exceeds 1.7 mass% in terms of Fe2O3, a* and b * A ceramic sintered body with a coefficient of 2.0 or higher was obtained.

[0041] In contrast, as shown in samples No. 2, 3, 6, 7, 10, 11, 14-16, and 19, a ceramic sintered body containing 90% or more by mass of Al (in terms of Al2O3), 0.4% to 2.5% by mass of Si (in terms of SiO2), 3.0% to 3.7% by mass of Mn (in terms of MnO2), 1.1% to 1.7% by mass of Ti (in terms of TiO2), 1.1% to 1.7% by mass of Fe (in terms of Fe2O3), and 0.05% to 0.3% by mass of Mg (in terms of MgO) has a volume resistivity of 10 9 The resistance was Ω·m or greater, and the three-point bending strength was 310 MPa or greater. Thus, the ceramic sintered body of this disclosure has relatively high insulation resistance and physical strength. Furthermore, the ceramic sintered body of this disclosure had a ΔE of 36 or less. Also, a * and b * If it is 0 or greater and 2.0 or less, L * The value was between 0 and 36, and exhibited a black color.

[0042] Furthermore, if the MnO2 content is more than twice the Fe2O3 content ((MnO2 / Fe2O3)≧2), then a * and b * A ceramic sintered body with low performance was obtained.

[0043] Next, a molded body with the same composition as sample No. 15 in Table 1 was fired at a temperature 50°C lower than that of sample No. 15 to produce a ceramic sintered body. The properties of this sintered body are shown in Table 2.

[0044] [Table 2]

[0045] Sample No. 22a in Table 2 * , b * , L * And ΔE are values ​​obtained by measuring the surface of the fired area, as in the case of Table 1. Table 2, sample No. 23 a* , b * , L * And ΔE is the value measured on the mirror-finished surface, i.e., the mirror surface. In the ceramic sintered body of this disclosure, when mirror finishing is performed, L is obtained compared to the fired surface. * And ΔE tended to be small. On the other hand, in the ceramic sintered body of this disclosure, when mirror polishing is performed, a * and b * The value tended to increase. Furthermore, the strength of the ceramic sintered body of this disclosure was not significantly affected by the firing temperature. In terms of reflectivity, the ceramic sintered body of this disclosure exhibited a reflectivity of 15% or less. Additionally, the mirror surface of the ceramic sintered body of this disclosure exhibited a reflectivity of 12% or less. Furthermore, when comparing the fired surface and the mirror surface of the ceramic sintered body of this disclosure, the mirror surface tended to have a lower reflectivity.

[0046] Although the present disclosure has been described in detail above, this disclosure is not limited to the embodiments described above, and various modifications and improvements are possible without departing from the gist of this disclosure.

[0047] Further effects and modifications can be readily derived by those skilled in the art. Therefore, broader aspects of the present invention are not limited to the specific details and representative embodiments expressed and described above. Accordingly, various modifications are possible without departing from the spirit or scope of the overall concept of the invention as defined by the appended claims and their equivalents. For example, the black color of the ceramic sintered body of this disclosure can be utilized in components for exposure processing equipment, light-shielding materials, and heat-absorbing materials. Furthermore, the excellent mechanical and electrical properties of the ceramic sintered body of this disclosure can be utilized in mounting substrates, structural components, and functional components of industrial machinery. Additionally, the black color and excellent mechanical properties of the ceramic sintered body of this disclosure can be utilized in sliding members and decorative members of line guides, fishing tackle, and other similar products.

Claims

1. Al ２ O ３ In terms of equivalent, more than 90% by mass of Al, SiO ２ In terms of conversion, 0.4% by mass or more and 2.5% by mass or less of Si, MnO ２ In terms of conversion, Mn is between 3.0% by mass and 3.7% by mass, TiO ２ Ti in an equivalent amount of 1.1% by mass or more and 1.7% by mass or less, Fe ２ O ３ In terms of conversion, 1.1% by mass or more and 1.7% by mass or less of Fe, Mg in MgO equivalent amounts of 0.05% to 0.3% by mass and It contains, a ＊ , b ＊ and L ＊ ΔE calculated based on the above is 0 or more and 36 or less Ceramic sintered body.

2. The a ＊ and the b ＊ is between -2.0 and 2.0, Said L ＊ The value is between 0 and 36. The ceramic sintered body according to claim 1.

3. MnO ２ The converted Mn content is Fe ２ O ３ The amount of Fe converted is between two and five times the amount of Fe. The ceramic sintered body according to claim 1.

4. Volume resistivity is 10 ９ It is greater than or equal to Ω・m, The three-point bending strength is 310 MPa or higher. The ceramic sintered body according to claim 1.

5. The a ＊ and the b ＊ is 1.5 or less A ceramic sintered body according to any one of claims 1 to 4.

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