Composite ceramic substrate and process for producing the same

Abstract

The application discloses a kind of composite ceramic substrate and its production process, belong to ceramic substrate production technical field, the composite ceramic substrate is composed of following raw materials: alumina 85-95 parts, praseodymium yttrium composite oxide 15-18 parts, zirconium oxide 13-15 parts, solvent 80-100 parts, dibutyl phthalate 5-10 parts, polyvinyl butyral 2-7 parts, composite dispersing agent 0.5-1 part.The application adds zirconium oxide and praseodymium yttrium composite oxide to alumina ceramic substrate, praseodymium yttrium composite oxide is prepared by glycine combustion method, then after mixing praseodymium yttrium composite oxide, zirconium oxide and alumina, flow casting sintering is formed, the addition of praseodymium yttrium composite oxide can promote the substance between particles in composite ceramic substrate to fill in pore, by reducing the porosity of composite ceramic substrate, and then improve density, to improve the bending strength and fracture toughness of composite ceramic substrate.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ceramic substrate production, and particularly relates to a composite ceramic substrate and a production process thereof. BACKGROUND

[0002] Alumina ceramic has excellent electrical properties, mechanical properties and chemical stability, and is one of the most widely used ceramic materials at present. However, its low fracture toughness seriously limits its application in a wider field, so enhancing the fracture toughness of alumina ceramic has become one of the current research hotspots.

[0003] Zirconia toughened alumina (ZTA) ceramic material is a kind of composite fine ceramic material formed by introducing a certain amount of phase change material zirconia into the alumina matrix substrate. Because alumina is hard and zirconia is tough, these two materials form an excellent composite with high bending strength and high fracture toughness. Therefore, this composite ceramic material has the characteristics of high toughness and high strength of zirconia ceramic, and the advantage of high hardness of alumina ceramic. Chinese patent CN114656245B discloses an alumina-based composite ceramic substrate and a preparation method thereof. The application further improves the mechanical properties such as bending strength and fracture toughness of the ceramic substrate by doping strontium titanate and bismuth titanate in the substrate material mainly composed of alumina and zirconia.

[0004] With the continuous development of the electronic chip manufacturing industry, the demand for bending strength and fracture toughness of alumina-based composite ceramic substrates is gradually increasing. SUMMARY

[0005] The application provides a composite ceramic substrate and a production process thereof, aiming to further improve the bending strength and fracture toughness of the composite ceramic substrate.

[0006] The purpose of the application is to provide a composite ceramic substrate.

[0007] Another purpose of the application is to provide a production process of the composite ceramic substrate.

[0008] The purpose of the application can be achieved by the following technical solutions.

[0009] A composite ceramic substrate is composed of the following raw materials:

[0010] 85-95 parts of alumina, 15-18 parts of praseodymium-yttrium composite oxide, 13-15 parts of zirconia, 80-100 parts of solvent, 5-10 parts of dibutyl phthalate, 2-7 parts of polyvinyl butyral, and 0.5-1 part of composite dispersant.

[0011] Further, the praseodymium-yttrium composite oxide is prepared by the following steps:

[0012] A1, adding praseodymium nitrate and yttrium nitrate into deionized water, stirring until the solid is completely dissolved, adding glycine into the stirring solution, continuously stirring to obtain a mixed solution;

[0013] A2, heating the mixed solution to 85 DEG C, constant temperature stirring for 2h, obtaining a composite gel, transferring the composite gel to a 200 DEG C hot plate and heating to combustion, after the combustion, obtaining a powder;

[0014] A3, grinding the powder and placing it in a muffle furnace, heat treating at 950-1100 DEG C for 2h, naturally cooling to room temperature, obtaining praseodymium yttrium composite oxide.

[0015] Further, the amount of deionized water, praseodymium nitrate, yttrium nitrate and glycine is 100mL: 13-15g: 13-15g: 45-50g.

[0016] Further, the solvent is a xylene-ethanol azeotrope solution, and the preparation process of the xylene-ethanol azeotrope solution is as follows: stirring and mixing equal mass of anhydrous ethanol and xylene, and then standing for 12h.

[0017] Further, the composite dispersant is prepared by stirring and mixing equal mass of terpineol, diethylene glycol butyl ether, tributyl citrate and butyl benzyl phthalate according to a mass ratio of 4:4:1:1.

[0018] As a preferred technical scheme of the present application, the production process of the composite ceramic substrate comprises the following steps:

[0019] (1) adding a composite dispersant into the xylene-ethanol azeotrope solution, heating to 55-65 DEG C, constant temperature stirring for 15min, adding aluminum oxide and praseodymium yttrium composite oxide into the solution, ball milling for 8h, adding zirconium oxide into the solution, continuing ball milling for 12h, adding dibutyl phthalate and polyvinyl butyral into the solution, continuing ball milling for 24h, obtaining a mixture, vacuumizing and defoaming the mixture to obtain a flowable slurry, flow casting the flowable slurry, flow casting film, drying the flow casting film, and obtaining a flow casting green sheet;

[0020] (2) sintering the flow casting green sheet, nitriding at 1400 DEG C for 2h in a nitrogen atmosphere, then heating to 1800 DEG C, holding for 2-4h, and cooling to obtain a composite ceramic substrate.

[0021] Further, the parameters of the flow casting are as follows: the doctor blade height is 1-2mm, and the flow casting rate is 200-300mm / min.

[0022] The present application has the following advantages:

[0023] The application realizes the purposes of improving the bending strength (>823MPa) and the fracture toughness (≥11.6MPa·m 1 / 2 ) of the composite ceramic substrate by adding zirconium oxide and praseodymium yttrium composite oxide into the alumina ceramic substrate, wherein the praseodymium yttrium composite oxide is prepared by the glycine combustion method, and then the praseodymium yttrium composite oxide, zirconium oxide and alumina are mixed, flow casted and sintered to form the composite ceramic substrate, and the addition of the praseodymium yttrium composite oxide can promote the filling of the substances between the particles in the composite ceramic substrate to the pores, thereby reducing the porosity of the composite ceramic substrate and further improving the density, so as to improve the bending strength and the fracture toughness of the composite ceramic substrate. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the application will be clearly and completely described below in combination with the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by a person of ordinary skill in the art without creative labor fall within the protection scope of the application.

[0025] Embodiment 1

[0026] Preparation of praseodymium yttrium composite oxide:

[0027] Preparation of praseodymium yttrium composite oxide by using the glycine-nitrate combustion method: 13g of praseodymium nitrate and 13g of yttrium nitrate are added into 100mL of deionized water, and stirred until the solid is completely dissolved. Then, 45g of glycine is added into the mixture under stirring, and the stirring is continued for 30min to obtain a mixed solution. The mixed solution is introduced into a reactor, and the reactor is heated to 85℃. The temperature is kept constant, and the stirring is continued for 2h to obtain a composite gel. The composite gel is transferred to a hot plate, and heated to combustion at 200℃. After the combustion is completed, a powder is obtained. The powder is ground through a 200 mesh sieve, and then placed in a muffle furnace for heat treatment at 950℃ for 2h. After natural cooling to room temperature, the praseodymium yttrium composite oxide is obtained.

[0028] Embodiment 2

[0029] Preparation of praseodymium yttrium composite oxide:

[0030] Praseodymium-yttrium composite oxide was prepared by the glycine-nitrate combustion method: 14g of praseodymium nitrate and 14g of yttrium nitrate were added to 100mL of deionized water and stirred until the solids were completely dissolved. 48g of glycine was then added to the mixture and stirred for 30min to obtain a mixed solution. The mixed solution was introduced into a reactor, which was heated to 85℃ and stirred at a constant temperature for 2h to obtain a composite gel. The composite gel was transferred to a 200℃ hot plate and heated to combustion. After combustion, powder was obtained. The powder was ground through a 200-mesh sieve and placed in a muffle furnace for heat treatment at 1050℃ for 2h. After natural cooling to room temperature, praseodymium-yttrium composite oxide was obtained.

[0031] Example 3

[0032] Preparation of praseodymium-yttrium composite oxides:

[0033] Praseodymium-yttrium composite oxide was prepared by the glycine-nitrate combustion method: 15g of praseodymium nitrate and 15g of yttrium nitrate were added to 100mL of deionized water and stirred until the solids were completely dissolved. 50g of glycine was then added to the mixture and stirred for 30min to obtain a mixed solution. The mixed solution was introduced into a reactor, which was heated to 85℃ and stirred at a constant temperature for 2h to obtain a composite gel. The composite gel was transferred to a 200℃ hot plate and heated to combustion. After combustion, powder was obtained. The powder was ground through a 200-mesh sieve and placed in a muffle furnace for heat treatment at 1100℃ for 2h. After natural cooling to room temperature, praseodymium-yttrium composite oxide was obtained.

[0034] Example 4

[0035] A manufacturing process for composite ceramic substrates:

[0036] First, the composite ceramic substrate is composed of the following raw materials:

[0037] 85 parts alumina, 15 parts praseodymium-yttrium composite oxide prepared in Example 1, 13 parts zirconium oxide, 80 parts solvent, 5 parts dibutyl phthalate, 2 parts polyvinyl butyral, and 0.5 parts composite dispersant.

[0038] Then, the manufacturing process of the composite ceramic substrate includes the following steps:

[0039] (1) Add xylene to the reaction vessel, add an equal mass of anhydrous ethanol to the reactor and stir for 30 min, let stand for 12 h to obtain xylene-ethanol azeotropic solution.

[0040] (2) adding the composite dispersant to the xylene-ethanol azeotrope solution, heating the reactor to 55°C, stirring and mixing at constant temperature for 15 min, adding the aluminum oxide and praseodymium-yttrium composite oxide to the reactor, using silicon nitride as the ball milling medium, ball milling in the ball mill at a speed of 42 r / min for 8 h, adding zirconium oxide to the ball mill, and continuing to ball mill at a constant speed for 12 h to obtain mixture A;

[0041] (3) adding dibutyl phthalate and polyvinyl butyral to mixture A, stirring uniformly, and continuing to ball mill at the speed in step (2) for 24 h to obtain slurry-like mixture B;

[0042] (4) pouring the slurry-like mixture B into a rotary bottle for vacuum degassing to obtain a casting slurry, and performing casting molding on the casting slurry, with a doctor blade height of 2 mm and a casting rate of 200 mm / min to obtain a casting film, and drying the casting film at 40°C for 6 h to obtain a green sheet;

[0043] (5) sintering the green sheet, heating to 1400°C at a heating rate of 6°C / min in a nitrogen atmosphere, and then heating to 1800°C at a constant rate, and holding for 2 h, and then naturally cooling to room temperature to obtain the composite ceramic substrate.

[0044] Example 5

[0045] A production process of a composite ceramic substrate:

[0046] First, the composite ceramic substrate is composed of the following raw materials:

[0047] aluminum oxide 90 parts, praseodymium-yttrium composite oxide prepared in Example 2 17 parts, zirconium oxide 14 parts, solvent 90 parts, dibutyl phthalate 8 parts, polyvinyl butyral 5 parts, and composite dispersant 0.8 parts.

[0048] Then, the production process of the composite ceramic substrate includes the following steps:

[0049] (1) adding xylene to a reaction container, stirring and adding anhydrous ethanol of equal mass to the reactor, stirring for 30 min, and standing for 12 h to obtain a xylene-ethanol azeotrope solution;

[0050] (2) adding the composite dispersant to the xylene-ethanol azeotrope solution, heating the reactor to 58°C, stirring and mixing at constant temperature for 15 min, adding the aluminum oxide and praseodymium-yttrium composite oxide to the reactor, using silicon nitride as the ball milling medium, ball milling in the ball mill at a speed of 44 r / min for 8 h, adding zirconium oxide to the ball mill, and continuing to ball mill at a constant speed for 12 h to obtain mixture A;

[0051] (3) adding dibutyl phthalate and polyvinyl butyral to the mixture A, stirring uniformly, and then ball milling at the ball milling rate in step (2) for 24 h to obtain a slurry-like mixture B;

[0052] (4) pouring the slurry-like mixture B into a rotary bottle for vacuum degassing to obtain a casting slurry, and then performing casting molding on the casting slurry at a doctor blade height of 2 mm and a casting rate of 250 mm / min to obtain a casting film, and then drying the casting film at 40℃ for 6 h to obtain a green sheet;

[0053] (5) sintering the green sheet at a temperature increasing rate of 7℃ / min to 1400℃ in a nitrogen atmosphere, and then performing nitriding at 1400℃ for 2 h, and then continuously increasing the temperature at a constant rate to 1800℃, and then performing sintering at 1800℃ for 3 h, and then naturally cooling to room temperature to obtain the composite ceramic substrate.

[0054] Example 6

[0055] A production process of a composite ceramic substrate:

[0056] Firstly, the composite ceramic substrate is composed of the following raw materials:

[0057] 95 parts of alumina, 18 parts of praseodymium-yttrium composite oxide prepared in Example 3, 15 parts of zirconium oxide, 100 parts of solvent, 10 parts of dibutyl phthalate, 7 parts of polyvinyl butyral, and 1 part of composite dispersant.

[0058] Then, the production process of the composite ceramic substrate includes the following steps:

[0059] (1) adding xylene into a reaction container, and then adding anhydrous ethanol into the reaction container at the same mass, stirring for 30 min, and then standing for 12 h to obtain a xylene-ethanol azeotrope solution;

[0060] (2) adding the composite dispersant into the xylene-ethanol azeotrope solution, increasing the temperature of the reactor to 60℃, and then stirring and mixing at constant temperature for 15 min, adding alumina and praseodymium-yttrium composite oxide into the reactor, using silicon nitride as a ball milling medium, and then ball milling in a ball mill at a rate of 45 r / min for 8 h, adding zirconium oxide into the ball mill, and then continuously ball milling at a constant rate for 12 h to obtain a mixture A;

[0061] (3) adding dibutyl phthalate and polyvinyl butyral into the mixture A, stirring uniformly, and then continuously ball milling at the ball milling rate in step (2) for 24 h to obtain a slurry-like mixture B;

[0062] (4) Pouring the mixture B in the form of slurry into a rotating bottle to perform vacuum degassing, to obtain a casting slurry, and the casting slurry is subjected to casting forming, the doctor blade height of the casting forming is 2 mm, the casting rate is 300 mm / min, to obtain a casting film, and the casting film is dried at 40℃ for 6 h, to prepare a casting green sheet;

[0063] (5) The casting green sheet is subjected to sintering, and the sintering is performed in a nitrogen atmosphere, the temperature is raised to 1400℃ at a heating rate of 8℃ / min, and then the temperature is continuously raised to 1800℃ at a constant rate, and the sintering is performed for 4 h, and after the sintering is completed, the sintering is naturally cooled to room temperature, to obtain a composite ceramic substrate.

[0064] Comparative Example 1

[0065] The zirconium oxide prepared in Example 1 in Example 4 is removed by 13 parts, and the remaining raw materials and production processes remain unchanged, and finally a composite ceramic substrate is obtained.

[0066] Comparative Example 2

[0067] The praseodymium-yttrium composite oxide prepared in Example 2 in Example 5 is removed by 17 parts, and the remaining raw materials and production processes remain unchanged, and finally a composite ceramic substrate is obtained.

[0068] Comparative Example 3

[0069] The praseodymium-yttrium composite oxide prepared in Example 3 in Example 6 is removed by 18 parts and the zirconium oxide is removed by 15 parts, and the remaining raw materials and production processes remain unchanged, and finally a composite ceramic substrate is obtained.

[0070] The composite ceramic substrates produced in Example 4-Example 6 and Comparative Example 1-Comparative Example 3 are sampled and detected, the sample size of the composite ceramic substrate is 10mm*10mm*2mm, and the detection contents are as follows, and the detection results are shown in Table 1:

[0071] Bending strength: The bending strength of the sample is measured by using a SGL-8000 type bending strength tester.

[0072] Fracture toughness detection: The fracture toughness of the sample is measured by using an HV-30RX fracture toughness analyzer.

[0073] Table 1

[0074] Item Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Bending strength (MPa) 823.3 831.6 828.4 771.1 682.2 320.5 Fracture toughness (MPa-m 1 / 2 )]]> 11.6 12.4 12.1 10.9 8.7 5.3

[0075] As can be seen from Table 1, the zirconium oxide and the praseodymium-yttrium composite oxide prepared in the application can significantly improve the bending strength and fracture toughness of the composite ceramic substrate.

[0076] It has to be noted that, as used herein, such terms as "including", "contains" or any other variations thereof are intended to cover a non-exclusive inclusion, such that processes, methods, articles, or apparatuses that comprise a list of elements are not required to comprise only those elements recited, but can also include other elements not expressly listed or inherent to such processes, methods, articles, or apparatuses.

[0077] While embodiments of the application have been shown and described, it is to be understood that the application is not limited to the details of the embodiments described, since numerous modifications and changes can be made to the embodiments without departing from the spirit and scope of the application as defined by the appended claims and their equivalents.

Claims

1. A composite ceramic substrate, characterized by, The composite ceramic substrate is composed of the following raw materials: 85-95 parts of alumina, 15-18 parts of praseodymium-yttrium composite oxide, 13-15 parts of zirconium oxide, 80-100 parts of solvent, 5-10 parts of dibutyl phthalate, 2-7 parts of polyvinyl butyral, and 0.5-1 part of composite dispersant. The praseodymium-yttrium composite oxide is prepared by the following steps: A1, adding praseodymium nitrate and yttrium nitrate to deionized water, stirring until the solid is completely dissolved, adding glycine to the stirring solution, and continuously stirring to obtain a mixed solution; A2, the mixed solution is heated to 85℃, and constant temperature stirring is carried out for 2h, and then the composite gel is obtained, and the composite gel is transferred to a 200℃ hot plate and heated to combustion, and after the combustion is completed, a powder is obtained; A3, the powder is ground and placed in a muffle furnace, and heat treated at 950-1100℃ for 2h, and naturally cooled to room temperature to obtain praseodymium-yttrium composite oxide.

2. The composite ceramic substrate of claim 1, wherein, The amount ratio of the deionized water, praseodymium nitrate, yttrium nitrate and glycine is 100mL:13-15g:13-15g:45-50g.

3. The composite ceramic substrate of claim 1, wherein, The solvent is a xylene-ethanol azeotrope solution, and the preparation process of the xylene-ethanol azeotrope solution is as follows: equal mass of anhydrous ethanol and xylene are stirred and mixed, and then left to stand for 12h.

4. The composite ceramic substrate of claim 1, wherein, The composite dispersant is prepared by stirring and mixing equal mass of terpineol, diethylene glycol butyl ether, tributyl citrate and butyl benzyl phthalate according to a mass ratio of 4:4:1:

1.

5. The production process of a composite ceramic substrate according to claim 1, wherein The method comprises the following steps: (1) adding the composite dispersant to the xylene-ethanol azeotrope solution, heating to 55-65℃, constant temperature stirring for 15min, adding alumina and praseodymium-yttrium composite oxide, ball milling for 8h, adding zirconium oxide, continuing to ball mill for 12h, adding dibutyl phthalate and polyvinyl butyral, and continuing to ball mill for 24h to obtain a mixture, vacuumizing and defoaming the mixture to obtain a casting slurry, and the casting slurry is subjected to casting forming, casting film, and drying the casting film to obtain a green sheet; (2) sintering the green sheet, nitriding at 1400℃ for 2h in a nitrogen atmosphere, then heating to 1800℃ and holding for 2-4h, and cooling to obtain the composite ceramic substrate.

6. The production process of a composite ceramic substrate according to claim 5, wherein The parameters of the casting forming are as follows: doctor blade height 1-2mm, and casting rate 200-300mm / min.