Aluminum oxide and zirconium oxide sintered plate and manufacturing method thereof

Abstract

Provided is a highly reliable alumina-zirconia sintered plate having high toughness. The present invention relates to an alumina-zirconia sintered plate, and more particularly, to an alumina-zirconia sintered plate, the alumina-zirconia sintered plate comprising, as the analysis result of the alumina-zirconia sintered plate, 4.54 to 8.02 wt% of ZrO2, 0.13 to 0.33 wt% of Y2O3, 0.20 to 0.44 wt% of SiO2, 0.09 to 0.25 wt% of MgO, 0.05 to 0.17 wt% of CaO, 0.09 to 0.17 wt% of HfO2, and the balance of Al2O3, and the breaking toughness of the sintered plate being 3.95 to 4.90 MPa.m < 1 / 2 >.

Description

Technical Field The invention relates to an alumina zirconia sintered plate. Background Art Patent Document 1 reports that when nano-zirconia particles are dispersed in a matrix of alumina particles, a high-strength alumina-zirconia composite ceramic body having a porosity of 2.2% is obtained. As for the alumina zirconia sintered substrate of patent document 2 previously proposed by the applicant of this application, the three-point bending strength is as high as 557 MPa in the sample of the embodiment with a porosity of 4.1% (in order to improve the light reflectivity for mounting the light-emitting element), and the three-point bending strength is 705 MPa in the sample of the comparison example with a porosity of 0.8%, which is very high. Prior art literature Patent Literature Patent Document 1: Japanese Patent Application Publication No. 2010-24128 Patent Document 2: Japanese Patent No. 5850450 Summary of the invention Problems to be solved by the invention However, when the strength of an alumina zirconia sintered plate is increased, the toughness is reduced, the impact resistance is weakened, and the reliability is impaired. Therefore, an object of the present invention is to provide an alumina zirconia sintered plate having high toughness and high reliability. Means for solving problems

[0001] An alumina zirconia sintered plate, wherein, as a result of analysis of the alumina zirconia sintered plate, it contains ZrO 2 :4.54~8.02wt%、Y 2 O 3 :0.13~0.33wt%、SiO 2 : 0.20~0.44wt%, MgO: 0.09~0.25wt%, CaO: 0.05~0.17wt%, HfO 2 :0.09~0.17wt%, and the balance is Al 2 O 3 The fracture toughness of the sintered plate is 3.95~4.90MPa·m 1 / 2 .

[0002] The alumina zirconia sintered plate according to [1] above, wherein Y 2 O 3 / ZrO 2 The mass ratio is 0.0280 to 0.0420.

[0003] The alumina zirconia sintered plate according to [1] or [2] above has a three-point bending strength of 500 to 600 MPa.

[0004] The alumina zirconia sintered plate according to any one of [1] to [3] above, wherein the specific gravity is 3.89 or more.

[0005] The alumina zirconia sintered plate according to any one of [1] to [4] above, wherein the porosity is 0.6% or less.

[0006] Alumina zirconia sintered plate, which contains Al 2 O 3 、ZrO 2 , Y 2 O 3 and CaO, as the analysis results of the alumina zirconia sintered plate, Y 2 O 3 / ZrO 2 The mass ratio is 0.0280-0.0420, and the fracture toughness is 3.95-4.90 MPa·m 1 / 2 , the three-point bending strength is 500~600MPa.

[0007] Alumina zirconia sintered plate, its fracture toughness is 3.95~4.90MPa·m 1 / 2 , three-point bending strength is 500-600MPa, and the porosity is less than 0.6%.

[0008] A circuit board using the alumina zirconia sintered plate according to any one of [1] to [7] above.

[0009] A heat dissipation member using the alumina zirconia sintered plate according to any one of [1] to [7] above.

[0010] An insulating member using the alumina zirconia sintered plate according to any one of [1] to [7] above.

[0011] A method for preparing an alumina-zirconia sintered plate, wherein, based on the feed amount, ZrO 2 :5.66~9.43wt%、Y 2 O 3 :0.14~0.35wt%、SiO 2 : 0.30~0.47wt%, MgO: 0.08~0.24wt%, CaO: 0.05~0.11wt%, HfO 2 :0.11~0.18wt% and the balance is Al 2 O 3The raw material powders are mixed and pulverized so that the average particle size (D50) after the mixed and pulverized mixture becomes 1.43 to 1.58 μm; and a compact composed of the mixed and pulverized raw material powders is fired to be sintered.

[0012] According to the method for producing an alumina zirconia sintered plate described in

[11] , wherein Y 2 O 3 / ZrO 2 The mass ratio is 0.0250 to 0.0380.

[0013] The method for producing an alumina zirconia sintered plate according to

[11] or

[12] , wherein the sintering is performed at a temperature of 1530 to 1600° C. and a time of 2 to 4 hours. [effect] It is believed that tetragonal ZrO 2 Helps with resilience. Y 2 O 3 Tetragonal ZrO 2 Partially stabilized, so in solid solution in ZrO 2 Partially stabilized ZrO 2 exists in the state of . However, through Y 2 O 3 The ratio of ZrO is moderately low. 2 The ratio is relatively increased and the toughness is improved. SiO 2 MgO and CaO are sintering aids, which can promote Al 2 O 3 The effect of grain growth and lowering the sintering temperature. In addition, by appropriately containing CaO, sinterability is improved and toughness is improved. If CaO is not contained, sinterability is reduced and pores are formed (Comparative Examples 4 and 5 described later). If CaO is contained excessively, particles become coarse and pores between particles increase. Effects of the Invention According to the present invention, it is possible to provide an alumina zirconia sintered plate having high toughness and high reliability. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 This is a SEM image of Example 1 (porosity: 0.4%). Figure 2 This is a SEM image of Comparative Example 6 (porosity: 0.8%). Figure 3 This is a SEM image of Comparative Example 7 (porosity 1.4%). Figure 4 This is a SEM image of Comparative Example 4 (porosity 3.0%). Figure 5 To show ZrO 2 Graph showing the relationship between the amount and the three-point bending strength and fracture toughness. Figure 6 This is a graph showing the relationship between the average particle size (D50) after the mixed and pulverized raw materials and the three-point bending strength and fracture toughness. DETAILED DESCRIPTION <1> Method for manufacturing alumina zirconia sintered plate (A)Y 2 O 3 / ZrO 2 The mass ratio is preferably 0.0280 to 0.0420, more preferably 0.0330 to 0.0360. This is because, through Y 2 O 3 The ratio of ZrO is moderately low. 2 The ratio is relatively increased and the toughness is improved. (B) Firing is preferably performed at a temperature of 1530 to 1600°C for 2 to 4 hours, and more preferably 2.5 to 4 hours. If the temperature is lower than 1530°C, sintering becomes insufficient and sufficient board strength cannot be obtained. On the other hand, if the temperature is higher than 1600°C, grain growth proceeds. <2>Alumina zirconia sintered plate (A) The plate thickness is not particularly limited, but preferably is 0.08 mm or more. If it is thinner than 0.08 mm, the resistance to external stress becomes weaker. If it is thicker, only the formability becomes difficult, so there is no particular upper limit, but if you have to say it, it is 5 mm. (B) The porosity is preferably 0.6% or less, more preferably 0.5% or less. If sintering is insufficient or excessive, the number of pores increases, so the porosity is an indicator of the degree of sintering. It is believed that if the porosity is low, strength and toughness can be ensured. (C) The fracture toughness is preferably 3.95 to 4.90 MPa·m 1 / 2 , more preferably 4.20 to 4.90 MPa·m 1 / 2 . The fracture toughness is 3.95MPa·m 1 / 2 As a result, the impact resistance becomes stronger and the reliability is improved. (D) The three-point bending strength is preferably 500 to 600 MPa, more preferably 530 to 600 MPa. The three-point bending strength of a general alumina sintered plate is about 450 MPa, while the three-point bending strength of the alumina zirconia sintered plate of the present invention is 500 MPa or more, so it can fully withstand large external stress that a general alumina sintered plate cannot withstand, and can also be made thinner. <3>Application The use of the alumina zirconia sintered plate of the present invention is not particularly limited, and examples thereof include circuit substrates, heat sinks, insulating plates, high-frequency windows, etc. used in semiconductor modules, LED packages, Peltier modules, printers, compound machines, semiconductor lasers, optical communications, high frequencies, etc. Example Next, examples of the present invention will be described in comparison with comparative examples. It should be noted that the materials, quantities, and conditions of each part of the examples are for illustration only and can be appropriately changed without departing from the gist of the invention. Alumina zirconia sintered plates of Examples 1 to 16 and Comparative Examples 1 to 7 shown in Tables 1 to 3 were produced. [Table 1] [Table 2] [Table 3] Initially, in the mixing process, the Al in the mixing ratio of the "Feeding Materials" column in Tables 1 to 3 is 2 O 3 、ZrO 2 , Y 2 O 3 、SiO 2 , MgO, CaO and HfO 2 To the raw material powder, 0.5 parts by weight of a surface active dispersant and 20 parts by weight of a mixed solvent of xylene and isopropyl alcohol were added, with the total amount of the raw material powder being 100 parts by weight. As ZrO 2 and Y 2 O 3 , use the following products. In Examples 1 to 3, 6 to 16 and Comparative Examples 1 and 4 to 7, 1.5 mol parts of Y 2 O 3 Powdered ZrO 2 Powder products (DURAZR series of zirconium oxide for fine ceramics manufactured by Daiichi Kizen Chemical Industry Co., Ltd.) 2 O 3 / ZrO 2 The mass ratio is 0.0318. In Example 4, in order to make ZrO 2 The mass ratio is lower than that of Example 1, and the above DURAZR series is mixed with Y 2 O 3 ZrO 2Powder blending use. In Example 5 and Comparative Examples 2 and 3, in order to make ZrO 2 The mass ratio is higher than that of Example 1. The above DURAZR series is mixed with 3 mol parts of Y 2 O 3 Powdered ZrO 2 The powder product (HSY-3F zirconia for fine ceramics manufactured by the same company) is blended for use. Examples 1 to 3 and Comparative Example 1 are obtained by changing the blending amount of the above-mentioned DURAZR series, mainly changing ZrO 2 and Y 2 O 3 The amount of group. ·Examples 4, 5 and Comparative Examples 2, 3 are obtained by changing the above blending amount and mainly changing Y 2 O 3 The amount of group. Examples 6 to 9 and Comparative Examples 4 to 7 are groups in which the amount of CaO was mainly changed. Examples 10 to 12 mainly change the SiO 2 , MgO, CaO amount group. The raw material powder after the addition was pulverized and mixed using alumina jade so that the particle size after pulverization and mixing would be as follows. In Example 1, the pulverization and mixing were performed for a predetermined time, and as a result, the particle sizes after the pulverization and mixing were D90: 3.02 μm, D50: 1.50 μm, and D10: 0.52 μm. In Examples 2 to 12 and Comparative Examples 1 to 7, the pulverization and mixing were performed for the same time as in Example 1, and therefore the particle size after pulverization and mixing is considered to be the same as that in Example 1 (thus, the measurement of the particle size was omitted). In Examples 13 to 16, the pulverization and mixing was performed for a shorter or longer time than in Example 1, and the particle sizes after pulverization and mixing were D90: 2.84 to 3.28 μm, D50: 1.43 to 1.58 μm, and D10: 0.51 to 0.52 μm. In Table 3, Example 1 is shown again, and Examples 13 to 16 are shown in between. It should be noted that for the measurement of particle size, 0.5 g of the raw material powder after crushing and mixing was put into 50 ml of a 0.1% by mass sodium pyrophosphate aqueous solution, and dispersed for 3 minutes at an output of 80% using US-300E manufactured by Nippon Seiki Co., Ltd., and then the laser diffraction scattering method was used for it using SALD-2200 manufactured by Shimadzu Corporation. Then, 7 parts by weight of polyvinyl butyral as a binder, 3 parts by weight of dioctyl adipate as a plasticizer, and 20 parts by weight of the same solvent as the above-mentioned solvent were added until the binder was completely dissolved and mixed, and stirred and mixed using a ball mill to prepare a slurry. The slurry is applied onto a film by a doctor blade method, and dried at 70 to 120° C. to evaporate the solvent. Thereafter, the slurry is peeled off from the film to obtain a green sheet. The obtained green sheet was cut into a predetermined shape by press working, the organic components were removed at 300-500°C, and it was fired at 1560°C for 3 hours to obtain an alumina zirconia sintered plate (ceramic sintered plate) with a thickness of 0.38 mm. The following analyses and measurements were performed on the obtained alumina zirconia sintered plates of Examples 1 to 16 and Comparative Examples 1 to 7. The analysis and measurement results are shown in Tables 1 to 3. (1) Composition analysis of alumina zirconia sintered plates The composition of the alumina zirconia sintered plate was analyzed using a scanning X-ray fluorescence analyzer (XRF) (ZSX Primus IV manufactured by Rigaku Corporation). (2) Specific gravity The specific gravity ρ is calculated by the Archimedean method as follows: The dry mass of the substrate is W1, the mass of the saturated substrate in water is W2, and the mass of the saturated substrate after the water attached to the surface of the saturated substrate is wiped off is W3, and the specific gravity ρ is calculated by the calculation formula ρ = W1 / (W3-W2). (3) Porosity The porosity was determined by observing the mirror-polished and thermally etched substrate surface with a scanning electron microscope, measuring the pore area for each of five arbitrary 5000x SEM images, and calculating the average of the pore occupied area relative to the observed area. (4) Three-point bending strength The three-point bending strength was measured using AGX-V manufactured by Shimadzu Corporation in accordance with JIS R1601:2008 (room temperature bending strength test method for fine ceramics). (5) Failure toughness The fracture toughness was measured by the IF method using HV-120B manufactured by Mi Tutoyo Co., Ltd. in accordance with JIS R1607:2015 (Test method for room temperature fracture toughness of fine ceramics). Figure 1 This is a SEM image of Example 1 (porosity: 0.4%). Figure 2 This is a SEM image of Comparative Example 6 (porosity: 0.8%). Figure 3 This is a SEM image of Comparative Example 7 (porosity 1.4%). Figure 4 This is a SEM image of Comparative Example 4 (porosity 3.0%). In these SEM images, the white part is ZrO 2 (Partially stabilized zirconia), the black part is the pores. Figure 5 The ZrO 2 Graph showing the relationship between feed rate and three-point bending strength and fracture toughness. Figure 6 This is a graph plotted for Examples 1 and 13 to 16, showing the relationship between the average particle size (D50) after the mixed and pulverized raw materials, the three-point bending strength, and the fracture toughness. In Comparative Examples 1 to 7, the three-point bending strength was less than 500 MPa and / or the fracture toughness was less than 3.95 MPa·m 1 / 2 . In Examples 1 to 16, the three-point bending strength is 500 MPa or more and the fracture toughness is 3.95 MPa·m 1 / 2 above. In particular, in Examples 1 to 5 and 8 to 16, the three-point bending strength was 516 MPa or more and the fracture toughness was 4.13 MPa·m 1 / 2 Above, particularly excellent. It should be noted that the present invention is not limited to the above-described embodiments, and can be embodied with appropriate changes without departing from the gist of the invention.

Claims

1. Alumina zirconia sintered plate, wherein: As an analysis result of the alumina zirconia sintered plate, it contains ZrO2: 4.54-8.02wt%, Y2O3: 0.13-0.33wt%, SiO2: 0.20-0.44wt%, MgO: 0.09-0.25wt%, CaO: 0.05-0.17wt%, HfO2: 0.09-0.17wt%, and the balance Al2O3, and the fracture toughness of the sintered plate is 3.95-4.90MPa·m 1 / 2 .

2. The alumina zirconia sintered plate according to claim 1, wherein: The mass ratio of Y2O3 / ZrO2 is 0.0280~0.0420.

3. The alumina zirconia sintered plate according to claim 1, wherein the three-point bending strength is 500-600 MPa. The alumina zirconia sintered plate according to claim 1 , which has a specific gravity of 3.89 or more. The alumina zirconia sintered plate according to claim 1 , which has a porosity of 0.6% or less.

6. An alumina zirconia sintered plate comprising Al2O3, ZrO2, Y2O3 and CaO, wherein as a result of analysis of the alumina zirconia sintered plate, the Y2O3 / ZrO2 mass ratio is 0.0280 to 0.0420, and the fracture toughness is 3.95 to 4.90 MPa·m 1 / 2 , the three-point bending strength is 500~600MPa.

7. Alumina zirconia sintered plate, its fracture toughness is 3.95~4.90MPa·m 1 / 2 , three-point bending strength is 500-600MPa, and the porosity is less than 0.6%.

8. A circuit board using the alumina zirconia sintered plate according to any one of claims 1 to 7.

9. A heat dissipation member using the alumina zirconia sintered plate according to any one of claims 1 to 7.

10. An insulating member using the alumina zirconia sintered plate according to any one of claims 1 to 7.

11. A method for producing an alumina-zirconia sintered plate, wherein: In terms of feed amount, raw material powders including 5.66-9.43wt% ZrO2, 0.14-0.35wt% Y2O3, 0.30-0.47wt% SiO2, 0.08-0.24wt% MgO, 0.05-0.11wt% CaO, 0.11-0.18wt% HfO2 and the remainder Al2O3 are mixed and pulverized so that the average particle size (D50) after the mixed pulverization becomes 1.43-1.58μm; the raw material powders after the mixed pulverization are molded into a plate-like molded body; and the plate-like molded body is sintered.

12. The method for manufacturing an alumina zirconia sintered plate according to claim 11, wherein: The mass ratio of Y2O3 / ZrO2 is 0.0250~0.0380.

13. The method for producing an alumina zirconia sintered plate according to claim 11 or 12, wherein: The sintering is carried out at a temperature of 1530 to 1600° C. and a time of 2 to 4 hours.

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