A corrosion-resistant multi-layer ceramic substrate and its preparation method

Abstract

The present invention relates to the technical field of ceramic substrates, and provides a corrosion-resistant multi-layer ceramic substrate and a preparation method thereof. A corrosion-resistant multi-layer ceramic substrate, the raw materials of which comprise the following components in parts by weight: 90-100 parts of aluminum nitride, 4-8 parts of plasticizer, 5-10 parts of sintering aid, 3-7 parts of binder, 2-5 parts of dispersant, 5-12 parts of reinforcing agent, and 60-70 parts of solvent; the reinforcing agent comprises metal powder and yttrium hydride; the metal powder comprises nickel powder and titanium powder. Through the above technical solution, the problem of poor flexural strength of ceramic substrates in the related art is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic substrates, and specifically, to a corrosion-resistant multi-layer ceramic substrate and a preparation method thereof. Background Art

[0002] At present, with the rapid development of the electronic information industry, ceramic substrates, as key electronic materials, play a crucial role in the fields of electronic packaging, integrated circuits, etc. Among them, aluminum nitride ceramic substrates have become the ideal choice for many high-end electronic devices due to their high thermal conductivity, good electrical insulation, and thermal expansion coefficient.

[0003] However, in actual application scenarios, aluminum nitride ceramic substrates face severe challenges. As electronic devices develop towards miniaturization and high performance, the requirements for the mechanical properties of ceramic substrates, especially the bending strength, are becoming increasingly stringent. Miniaturization means that the layout of electronic components is more compact, and the ceramic substrate needs to carry more electronic components in a limited space, which makes the stress distribution more complex and concentrated when the substrate is subjected to external forces. For example, in products such as smart phones and wearable devices, in order to pursue thinness, lightness, and portability, the thickness of the ceramic substrate is continuously reduced, while the bending stress it bears does not decrease accordingly, but increases due to the increased compactness of the internal structure of the device. Under the trend of high performance, the high heat generated during the operation of electronic devices needs to be discharged through an efficient heat dissipation system, which makes the ceramic substrate not only bear mechanical stress but also thermal stress caused by differences in thermal expansion coefficients. When the thermal stress and mechanical stress are superimposed, if the bending strength of the ceramic substrate is insufficient, it is very easy to crack under the action of these stresses.

[0004] In the chemical industry, ceramic substrates with corrosion-resistant properties are often used to manufacture key components such as reactor linings and pipelines to resist the erosion of various strongly corrosive chemical substances. However, under the complex working conditions of chemical production, these components not only have to withstand the continuous scouring of fluids and the interference of mechanical vibrations but also have to cope with thermal stresses caused by temperature changes. Due to the low bending strength of existing corrosion-resistant ceramic substrates, under the combined action of various factors, they are very likely to deform and crack, thereby triggering serious safety accidents such as leakage. This will not only lead to production interruption and reduced production efficiency but may also cause environmental pollution and pose a huge threat to personnel safety.

[0005] To meet these growing demands, it is urgent to develop a technology for corrosion-resistant aluminum nitride multi-layer ceramic substrates that can significantly improve the bending strength. Summary of the Invention

[0006] The present invention provides a corrosion-resistant multi-layer ceramic substrate and a preparation method thereof, which solve the problem of poor bending strength of ceramic substrates in related technologies.

[0007] The technical solution of the present invention is as follows:

[0008] The present invention provides a corrosion-resistant multi-layer ceramic substrate, and the raw materials include the following components in parts by weight: 90-100 parts of aluminum nitride, 4-8 parts of plasticizer, 5-10 parts of sintering aid, 3-7 parts of binder, 2-5 parts of dispersant, 5-12 parts of reinforcing agent, and 60-70 parts of solvent;

[0009] The reinforcing agent includes metal powder and yttrium hydride;

[0010] The metal powder includes nickel powder and titanium powder.

[0011] As a further technical solution, the mass ratio of the nickel powder, titanium powder and yttrium hydride is 5:2:3-5.

[0012] In the present invention, by adjusting the mass ratio of the nickel powder, titanium powder and yttrium hydride to 5:2:3-5, the bending strength of the ceramic substrate is further improved.

[0013] As a further technical solution, the metal powder is a sintered metal powder.

[0014] As a further technical solution, the preparation method of the sintered metal powder includes the following steps:

[0015] A1. Ball-mill the nickel powder and titanium powder to obtain a mixture;

[0016] A2. Perform spark plasma sintering on the mixture to obtain the sintered metal powder.

[0017] As a further technical solution, the ball-milling includes the first-stage ball-milling and the second-stage ball-milling;

[0018] During the first-stage ball-milling, the rotation speed is 100-200 rpm and the time is 2-5 h;

[0019] During the second-stage ball-milling, the rotation speed is 600-800 rpm and the time is 1-4 h.

[0020] As a further technical solution, the spark plasma sintering is carried out in an inert gas atmosphere;

[0021] The inert gas is one of argon and helium.

[0022] As a further technical solution, during the spark plasma sintering, the temperature is 1000-1200 °C, the pressure is 30-60 MPa, and the time is 15-20 min.

[0023] In the present invention, when the metal powder used is the sintered metal powder, strong metal bond connections are formed between the metal powders, improving the density of the metal powders, thereby enhancing the density of the ceramic substrate, preventing corrosive substances from corroding through pores, and improving the corrosion resistance of the ceramic substrate.

[0024] As a further technical solution, the plasticizer includes one of dibutyl phthalate and dioctyl phthalate;

[0025] The sintering aid includes one of calcium oxide and magnesium oxide;

[0026] The binder includes one of polyvinyl butyral and polymethyl methacrylate;

[0027] The dispersant includes one of sodium polyacrylate and dibutyl phosphate;

[0028] The solvent includes one of n-butanol, isopropanol, and ethanol.

[0029] In the present invention, when a plasticizer is added to the raw materials, the friction between the raw material particles is reduced, the plasticity and flexibility of the raw materials are increased, making it easier to process them into a specific shape during the forming process;

[0030] In the present invention, when a sintering aid is added to the raw materials, the sintering aid promotes the sintering process of aluminum nitride, reduces the sintering temperature, reduces energy consumption, and at the same time avoids problems such as excessive grain growth that may occur at high temperatures, which is beneficial to obtaining a ceramic substrate with good performance;

[0031] In the present invention, when a binder is added to the raw materials, the binder forms a bonding bridge between the raw material powder particles, firmly bonding each particle together, making the green body have a certain shape and strength;

[0032] In the present invention, when a dispersant is added to the raw materials, the dispersant can attach to the surface of the raw material particles, generating an electrostatic repulsive force or a steric hindrance effect between the particles, effectively preventing particle agglomeration, ensuring the uniform dispersion of the particles in the solvent, and improving the mixing uniformity of the raw materials.

[0033] The present invention also provides a method for preparing the corrosion-resistant multi-layer ceramic substrate, comprising the following steps:

[0034] S1. Mix aluminum nitride, plasticizer, sintering aid, dispersant, reinforcing agent, and solvent evenly, and then add the binder to obtain a slurry;

[0035] S2. Cast and form the slurry, and dry it to obtain a green body;

[0036] S3. Punch the green body, and through surface printing, lamination, vertical conduction, cutting, sintering, and cooling, obtain the corrosion-resistant multi-layer ceramic substrate.

[0037] As a further technical solution, the raw material for the surface printing is tungsten paste;

[0038] During the sintering, the temperature is 1650~1740°C.

[0039] The working principle and beneficial effects of the present invention are as follows:

[0040] In the present invention, nickel powder, titanium powder and yttrium hydride are added as reinforcing agents. Nickel powder and titanium powder are ductile metals. Yttrium hydride promotes densification during sintering. The synergistic effect of nickel powder, titanium powder and yttrium hydride improves the bending strength of the ceramic substrate, thereby significantly enhancing the reliability and service life of the ceramic substrate in electronic product applications, and also enabling the ceramic substrate to be applied in more scenarios with demanding material performance requirements. Specific embodiments

[0041] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of the present invention.

[0042] In the following examples and comparative examples, the nickel powder content is 99.9 wt%, the particle size is 300 mesh, the titanium powder content is 99.9 wt%, the particle size is 325 mesh, the yttrium hydride content is 99.9 wt%, the particle size is 200 mesh, the weight average molecular weight of polyvinyl butyral is 30,000, the model of polymethyl methacrylate is VH-001, and the weight average molecular weight of sodium polyacrylate is 10,000.

[0043] Example 1

[0044] A corrosion-resistant multi-layer ceramic substrate, the raw materials of which include the following components in parts by weight: 100 parts of aluminum nitride, 8 parts of plasticizer, 10 parts of sintering aid, 7 parts of binder, 5 parts of dispersant, 12 parts of reinforcing agent, and 70 parts of solvent;

[0045] The reinforcing agent includes nickel powder, titanium powder and yttrium hydride with a mass ratio of 5:2:7;

[0046] The plasticizer is dibutyl phthalate;

[0047] The sintering aid is calcium oxide;

[0048] The binder is polyvinyl butyral;

[0049] The dispersant is sodium polyacrylate;

[0050] The solvent is n-butanol;

[0051] Preparation method of corrosion-resistant multi-layer ceramic substrate, comprising the following steps:

[0052] S1. Mix aluminum nitride, plasticizer, sintering aid, dispersant, reinforcing agent and solvent evenly, then add binder and continue to mix evenly to obtain slurry;

[0053] S2. Perform tape casting on the slurry and dry it to obtain a green body;

[0054] S3. Drill holes in the green body, and through surface printing, lamination, vertical and horizontal conduction, cutting, sintering at 1740 °C and cooling, obtain a corrosion-resistant multi-layer ceramic substrate;

[0055] The raw material for surface printing is tungsten paste, and the printing thickness is 20 μm;

[0056] The number of layers of the multi-layer ceramic substrate is 30.

[0057] Example 2

[0058] A corrosion-resistant multi-layer ceramic substrate, the raw materials thereof comprising the following components in parts by weight: 90 parts of aluminum nitride, 4 parts of plasticizer, 5 parts of sintering aid, 3 parts of binder, 2 parts of dispersant, 5 parts of reinforcing agent, 60 parts of solvent;

[0059] The reinforcing agent comprises nickel powder, titanium powder and yttrium hydride with a mass ratio of 5:2:1;

[0060] The plasticizer is dioctyl phthalate;

[0061] The sintering aid is magnesium oxide;

[0062] The binder is polymethyl methacrylate;

[0063] The dispersant is dibutyl phosphate;

[0064] The solvent is isopropyl alcohol;

[0065] Preparation method of corrosion-resistant multi-layer ceramic substrate, comprising the following steps:

[0066] S1. Mix aluminum nitride, plasticizer, sintering aid, dispersant, reinforcing agent and solvent evenly, then add binder and continue to mix evenly to obtain slurry;

[0067] S2. Perform tape casting on the slurry and dry it to obtain a green body;

[0068] S3. Drill holes in the green body, and through surface printing, lamination, vertical and horizontal conduction, cutting, sintering at 1650 °C and cooling, obtain a corrosion-resistant multi-layer ceramic substrate;

[0069] The raw material for surface printing is tungsten paste, and the printing thickness is 15 μm;

[0070] The number of layers of the multi-layer ceramic substrate is 30.

[0071] Example 3

[0072] A corrosion-resistant multi-layer ceramic substrate, the raw materials of which include the following components in parts by weight: 95 parts of aluminum nitride, 6 parts of plasticizer, 8 parts of sintering aid, 5 parts of binder, 3 parts of dispersant, 10 parts of reinforcing agent, and 65 parts of solvent;

[0073] The reinforcing agent includes nickel powder, titanium powder and yttrium hydride with a mass ratio of 5:2:6;

[0074] The plasticizer is dibutyl phthalate;

[0075] The sintering aid is calcium oxide;

[0076] The binder is polyvinyl butyral;

[0077] The dispersant is dibutyl phosphate;

[0078] The solvent is ethanol;

[0079] A preparation method of a corrosion-resistant multi-layer ceramic substrate, comprising the following steps:

[0080] S1. Mix aluminum nitride, plasticizer, sintering aid, dispersant, reinforcing agent and solvent evenly, and then add the binder and continue to mix until uniform to obtain a slurry;

[0081] S2. Cast and form the slurry, and dry it to obtain a green body;

[0082] S3. Punch the green body, perform surface printing, lamination, upper and lower conduction, cutting, sintering at 1680 °C, and cooling to obtain a corrosion-resistant multi-layer ceramic substrate;

[0083] The raw material for surface printing is tungsten paste, and the printing thickness is 20 μm;

[0084] The number of layers of the multi-layer ceramic substrate is 30.

[0085] Example 4

[0086] The difference between this example and Example 3 is only that the reinforcing agent in this example includes nickel powder, titanium powder and yttrium hydride with a mass ratio of 5:2:2.

[0087] Example 5

[0088] The difference between this example and Example 3 is only that the reinforcing agent in this example includes nickel powder, titanium powder and yttrium hydride with a mass ratio of 5:2:3.

[0089] Example 6

[0090] The difference between this embodiment and Embodiment 3 is only that the enhancer in this embodiment comprises nickel powder, titanium powder, and yttrium hydride with a mass ratio of 5:2:5.

[0091] Embodiment 7

[0092] The difference between this embodiment and Embodiment 6 is only that the metal powder in this embodiment is the sintered metal powder;

[0093] The preparation method of the sintered metal powder comprises the following steps:

[0094] A1. Ball-mill the nickel powder and the titanium powder to obtain a mixture;

[0095] A2. Perform spark plasma sintering on the mixture to obtain the sintered metal powder;

[0096] The ball-milling is specifically first the first ball-milling and then the second ball-milling;

[0097] During the first-stage ball-milling, the rotation speed is 200 rpm and the time is 2 h;

[0098] During the second-stage ball-milling, the rotation speed is 800 rpm and the time is 1 h;

[0099] The spark plasma sintering is carried out in an inert gas atmosphere;

[0100] The inert gas is argon;

[0101] During the spark plasma sintering, the temperature is 1200 °C, the pressure is 60 MPa, and the time is 15 min.

[0102] Embodiment 8

[0103] The difference between this embodiment and Embodiment 6 is only that the metal powder in this embodiment is the sintered metal powder;

[0104] The preparation method of the sintered metal powder comprises the following steps:

[0105] A1. Ball-mill the nickel powder and the titanium powder to obtain a mixture;

[0106] A2. Perform spark plasma sintering on the mixture to obtain the sintered metal powder;

[0107] The ball-milling is specifically first the first ball-milling and then the second ball-milling;

[0108] During the first-stage ball-milling, the rotation speed is 100 rpm and the time is 5 h;

[0109] During the second-stage ball-milling, the rotation speed is 600 rpm and the time is 4 h;

[0110] The spark plasma sintering is carried out in an inert gas atmosphere;

[0111] The inert gas is helium;

[0112] During spark plasma sintering, the temperature is 1000 °C, the pressure is 30 MPa, and the time is 20 min.

[0113] Comparative Example 1

[0114] The difference between this comparative example and Example 3 is only that the reinforcing agent in this comparative example includes nickel powder and yttrium hydride with a mass ratio of 7:6.

[0115] Comparative Example 2

[0116] The difference between this comparative example and Example 3 is only that the reinforcing agent in this comparative example includes titanium powder and yttrium hydride with a mass ratio of 7:6.

[0117] Comparative Example 3

[0118] The difference between this comparative example and Example 3 is only that the reinforcing agent in this comparative example is yttrium hydride.

[0119] Comparative Example 4

[0120] The difference between this comparative example and Example 3 is only that the reinforcing agent in this comparative example includes nickel powder and titanium powder with a mass ratio of 5:2.

[0121] Comparative Example 5

[0122] The difference between this comparative example and Example 3 is only that this comparative example has no reinforcing agent.

[0123] Experimental Example 1

[0124] The flexural strength of the corrosion-resistant multi-layer ceramic substrates prepared in Examples 1 to 6 and Comparative Examples 1 to 5 was tested according to the test method specified in GB / T 6569-2006 "Test Method for Flexural Strength of Fine Ceramics". The test method was three-point bending. The test results are shown in Table 1.

[0125] Table 1 Flexural strength test results

[0126]

[0127] When comparing Example 3 with Comparative Examples 1 to 5, the nickel powder, titanium powder, and yttrium hydride in the raw materials of the corrosion-resistant multi-layer ceramic substrate of the present invention act synergistically to improve the flexural strength of the corrosion-resistant multi-layer ceramic substrate.

[0128] Experimental Example 2

[0129] The specimens of the corrosion-resistant multi-layer ceramic substrates prepared in Examples 6 to 8 were immersed in a sulfuric acid solution with a mass fraction of 20% at 90 °C for 1 h, and then the flexural strength test after acid corrosion test was carried out according to the above-mentioned flexural strength test method. The test results are shown in Table 2.

[0130] Table 2 Test Results of Acid Corrosion Experiment

[0131]

[0132] Comparing Examples 7 - 8 with Example 6 shows that using sintered metal powder instead of metal powder in the present invention improves the corrosion resistance of the corrosion - resistant multi - layer ceramic substrate.

[0133] Experimental Example 3

[0134] The corrosion - resistant multi - layer ceramic substrates prepared in Examples 1 - 8 were tested for dielectric loss using a broadband dielectric impedance analyzer E4990A. The test frequency was 10 6 Hz, and the dielectric loss values of the multi - layer ceramic substrates were read. The test results are shown in Table 3.

[0135] Table 3 Test Results of Dielectric Loss

[0136]

[0137] The experimental results show that the corrosion - resistant multi - layer ceramic substrate in the present invention meets the usage requirements.

[0138] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A corrosion-resistant multi-layer ceramic substrate, characterized in that, The raw materials include the following components in parts by weight: 90 - 100 parts of aluminum nitride, 4 - 8 parts of plasticizer, 5 - 10 parts of sintering aid, 3 - 7 parts of binder, 2 - 5 parts of dispersant, 5 - 12 parts of reinforcing agent, and 60 - 70 parts of solvent; The reinforcing agent includes metal powder and yttrium hydride; The metal powder includes nickel powder and titanium; The mass ratio of the nickel powder, titanium powder and yttrium hydride is 5:2:3 - 5; The metal powder is the sintered metal powder.

2. The corrosion-resistant multi-layer ceramic substrate according to claim 1, wherein, The preparation method of the sintered metal powder includes the following steps: A1. Ball - mill the nickel powder and titanium powder to obtain a mixture; A2. Perform spark plasma sintering on the mixture to obtain the sintered metal powder.

3. The corrosion-resistant multi-layer ceramic substrate according to claim 2, wherein The ball - milling includes the first - stage ball - milling and the second - stage ball - milling; During the first - stage ball - milling, the rotation speed is 100 - 200 rpm and the time is 2 - 5 h; During the second - stage ball - milling, the rotation speed is 600 - 800 rpm and the time is 1 - 4 h.

4. A corrosion-resistant multi-layer ceramic substrate according to claim 2, characterized in that, The spark plasma sintering is carried out in an inert gas atmosphere; The inert gas is one of argon and helium.

5. The corrosion-resistant multi-layer ceramic substrate according to claim 2, wherein During the spark plasma sintering, the temperature is 1000 - 1200 °C, the pressure is 30 - 60 MPa, and the time is 15 - 20 min.

6. The corrosion-resistant multi-layer ceramic substrate according to claim 1, wherein, The plasticizer includes one of dibutyl phthalate and dioctyl phthalate; The sintering aid includes one of calcium oxide and magnesium oxide; The binder includes one of polyvinyl butyral and polymethyl methacrylate; The dispersant includes one of sodium polyacrylate and dibutyl phosphate; The solvent includes one of n - butanol, isopropanol and ethanol.

7. The preparation method of a corrosion-resistant multi-layer ceramic substrate according to any one of claims 1 to 6, characterized in that, It includes the following steps: S1. Mix aluminum nitride, plasticizer, sintering aid, dispersant, reinforcing agent and solvent evenly, and then add the binder to obtain a slurry; S2. Carry out tape casting on the slurry and dry it to obtain a green body; S3. Punch the green body, and through surface printing, lamination, upper - lower conduction, cutting, sintering and cooling, obtain a corrosion - resistant multi - layer ceramic substrate.

8. The preparation method of a corrosion-resistant multi-layer ceramic substrate according to claim 7, characterized in that, The raw material for the surface printing is tungsten paste; During the sintering, the temperature is 1650 - 1740 °C.

Images