Abrasive particle friction low-temperature metallization method of ceramic in atmospheric environment

Abstract

The invention discloses an abrasive particle friction low-temperature metallization method for ceramic in an atmospheric environment, and belongs to metallization methods. In order to improve the components of Sn-based low-temperature metal, the invention provides the abrasive particle friction low-temperature metallization method of the ceramic in the atmospheric environment; according to the low-temperature metallization material containing the ceramic particles, the friction effect between the ceramic particles in the liquid metal and the ceramic matrix is utilized, combination between the low-temperature Sn-based metal and the ceramic matrix is achieved in the atmospheric environment, and metallization of the ceramic is achieved. The method comprises the following steps: 1, pre-treating a to-be-metalized ceramic substrate; 2, preparing a low-temperature metallization material containing ceramic particles; thirdly, Sn9Zn alloy melt containing ceramic particles is prepared; 4, rubbing; and 5, cooling in the atmospheric environment to obtain the metalized ceramic matrix. The metalized layer obtained by the method is well combined with the ceramic, and the interface has no bad defects such as pores and cracks.

Description

Technical Field

[0001] The invention belongs to a metallization method, and in particular relates to a low-temperature metallization method of ceramics by abrasive friction in an atmospheric environment. Background Art

[0002] Ceramic materials, as a common inorganic non-metallic material, usually have high melting point, high hardness, good corrosion resistance and chemical stability. Some specific ceramics also have excellent electrical and thermal properties, and have important applications in communications, biology, chemical industry, construction and other industries. Under actual service conditions, ceramic materials are often connected with metal materials to form complex components. However, due to the different chemical bonds between metal and ceramic materials, it is difficult for metal to wet ceramic materials, and the ceramic surface needs to be metallized.

[0003] Patent 201510679841.4 uses Ti-Si alloy to metallize silicon-based ceramics in a vacuum furnace. During the metallization process, a Ti-Si alloy sheet is placed on the surface of the silicon-based ceramic, heated to a temperature of more than 1400°C, and kept warm for 10 to 30 minutes. After the metal sheet is melted, it gradually spreads and wets on the surface of the substrate during the insulation process. This method effectively reduces the thermal stress caused by the inconsistency of the thermal expansion coefficient between the ceramic and metal layers by controlling the heating and cooling rates, but only one surface can be metallized at a time, which is not convenient for irregularly shaped ceramics.

[0004] Patent 202010146104.9 uses laser cladding to metalize the surface of silicon nitride ceramics. First, the configured metal powder is pre-placed on the surface of the silicon nitride ceramic, and then laser cladding is performed in a vacuum or nitrogen atmosphere. This method can achieve the effect of controlling the metallization position by controlling the preset area of ​​the metal powder and the walking path of the laser. Due to the need to pre-set powder and the limitation of the position of the laser heating table, it is not possible to achieve metallization of all surfaces of the ceramic at once.

[0005] Patent 201611072947.9 proposes a method for metallization of microwave dielectric ceramic surface. The experiment adopts the method of magnetron sputtering, which can realize the deposition of multi-layer metal film system on the ceramic surface. The process is relatively simple and the sputtering film forming speed is fast. The sputtering gas pressure needs to be controlled during the sputtering process, so the airtightness of the equipment is strictly required. In addition, the cost of sputtering equipment is relatively high.

[0006] Patent 201210282340.9 introduces a sintering metallization method for alumina ceramics, and the obtained metallization layer is uniform and dense. In the preparation process, powder making, powder screen printing on the ceramic surface, high-temperature sintering and nickel plating are carried out in sequence according to the composition requirements of the surface metallization layer. The ball milling time is more than 96 hours, the sintering needs to be carried out in a reducing atmosphere, the sintering temperature is above 1400℃, and the sintering time is more than 30 minutes.

[0007] In patent 201910840365.8, a metal film is chemically electroplated on the ceramic surface, and the ceramic needs to be activated before electroplating. The temperature is low during the preparation of the metal film, which can effectively reduce the thermal stress between the film layer and the ceramic matrix, and there are no strict requirements on the shape of the ceramic. The main disadvantage of this method is that a large amount of chemical reagents are used, and the treatment of waste liquid is more troublesome, which is not conducive to environmental protection.

[0008] From the above analysis, it can be seen that the current different surface metallization methods of ceramics such as magnetron sputtering, high temperature sintering, laser cladding, and chemical plating have certain limitations, and there are one or more of the following disadvantages:

[0009] 1. Higher experimental temperature causes thermal stress problems;

[0010] 2. The metallization time is long, which reduces the experimental efficiency;

[0011] 3. The experimental atmosphere (vacuum, protective gas, etc.) needs to be controlled, and strict requirements are placed on the airtightness of the equipment;

[0012] 4. The use of chemical reagents is not conducive to environmental protection. Summary of the invention

[0013] In order to solve the above technical problems, the present invention provides a method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment.

[0014] The present invention starts from improving the composition of Sn-based low-temperature metal and proposes a method for abrasive friction low-temperature metallization of ceramics in an atmospheric environment; the present invention prepares a low-temperature metallization material containing ceramic particles, utilizes the friction between the ceramic particles in the liquid metal and the ceramic matrix, realizes the bonding between the low-temperature Sn-based metal and the ceramic matrix in the atmospheric environment, and realizes the metallization of the ceramic.

[0015] A method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment is specifically completed by the following steps:

[0016] 1. Cleaning the ceramic substrate to be metallized and then drying it to obtain the pre-treated ceramic substrate to be metallized;

[0017] 2. Mixing Sn powder, Zn particles and ceramic particles in a certain mass ratio to obtain a low-temperature metallization material containing ceramic particles;

[0018] 3. Put the low-temperature metallization material containing ceramic particles into the TC4 mold, and then place the mold on the heating platform for heating and melting. Stir continuously during the heating process until the Sn powder and Zn particles are melted to obtain a Sn9Zn alloy melt containing ceramic particles;

[0019] Fourth, immerse the pretreated ceramic substrate to be metallized into a Sn9Zn alloy melt containing ceramic particles at a temperature of 220°C to 230°C, use a tool to clamp the ceramic substrate, and rub it repeatedly on the bottom of the TC4 mold to promote the wetting and bonding of the alloy melt on the surface of the ceramic substrate, and evenly adhere a layer of Sn-based metal melt on the friction surface of the ceramic substrate;

[0020] 5. Taking the ceramic matrix out of the Sn9Zn alloy melt containing ceramic particles, and naturally cooling it to room temperature in an atmospheric environment to obtain a metallized ceramic matrix.

[0021] Principle of the present invention:

[0022] Ceramics are covalent bond materials with very stable surfaces. The atoms of metal materials are metallic bonds. The difference between the two bond energies is very large. Therefore, liquid metal has poor wettability to ceramics, and often requires long-term high-temperature treatment, or the introduction of high-energy fields such as lasers, magnetic fields, and electric fields to promote the combination between metals and ceramics. The present invention starts with the most common low-temperature Sn-based metal. First, the powder is mixed evenly and then heated and stirred to make the ceramic particles evenly dispersed in the liquid Sn-based metal. At low temperatures (200-300°C) where the Sn-based metal can form a liquid, the metallization of the surface of the ceramic base is achieved under atmospheric conditions through friction between the ceramic particles and the ceramic base, avoiding high-temperature heating and the use of an inert atmosphere to prevent oxidation of the material at high temperatures. At the same time, the metallization efficiency is high, and the addition of ceramic particles also greatly reduces the thermal stress between the ceramic base and the metallization layer.

[0023] Beneficial effects of the present invention:

[0024] 1. The ceramic substrate to be metallized in the present invention may be an oxide ceramic, a carbide ceramic or a nitride ceramic;

[0025] Second, the ceramic particles in the present invention can be oxide ceramics, carbide ceramics or nitride ceramics, and the range of material selection is wide;

[0026] 3. The metal material containing ceramic particles used in the present invention can be any Sn-based alloy or other low melting point metal;

[0027] Fourth, the experimental temperature in the present invention can be 20°C to 30°C above the melting point of the metal;

[0028] 5. The present invention can achieve wetting of the ceramic substrate at a lower temperature, effectively reducing thermal stress;

[0029] 6. The present invention introduces ceramic particles into the metallization layer, which alleviates the difference in thermal expansion coefficient between the ceramic substrate and the metallization layer, and further reduces thermal stress;

[0030] 7. The present invention can complete the metallization process of the ceramic substrate within a few tens of seconds to one minute, thereby improving the experimental efficiency;

[0031] 8. The operation in the present invention is carried out in an atmospheric environment, and no protective gas or vacuum environment is required;

[0032] 9. The present invention does not involve the use of harmful chemical reagents and meets environmental protection requirements;

[0033] 10. The metallization layer obtained by the present invention has good bonding with the ceramic, and there are no defects such as pores and cracks on the interface. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The morphology of the bonding interface between the AlN ceramic substrate and the Sn9Zn metal layer containing SiC in Example 1 under an optical microscope;

[0035] Figure 2 The morphology of the bonding interface between the AlN ceramic substrate and the Sn9Zn metal layer containing SiC in Example 1 under a scanning electron microscope;

[0036] Figure 3 The morphology of the bonding interface between the AlN ceramic substrate and the Sn9Zn metal layer without ceramic particles in Comparative Example 1 under a scanning electron microscope. DETAILED DESCRIPTION

[0037] Specific implementation method 1: This implementation method is a method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment, which is specifically completed in the following steps:

[0038] 1. Cleaning the ceramic substrate to be metallized and then drying it to obtain the pre-treated ceramic substrate to be metallized;

[0039] 2. Mixing Sn powder, Zn particles and ceramic particles in a certain mass ratio to obtain a low-temperature metallization material containing ceramic particles;

[0040] 3. Put the low-temperature metallization material containing ceramic particles into the TC4 mold, and then place the mold on the heating platform for heating and melting. Stir continuously during the heating process until the Sn powder and Zn particles are melted to obtain a Sn9Zn alloy melt containing ceramic particles;

[0041] Fourth, immerse the pretreated ceramic substrate to be metallized into a Sn9Zn alloy melt containing ceramic particles at a temperature of 220°C to 230°C, use a tool to clamp the ceramic substrate, and rub it repeatedly on the bottom of the TC4 mold to promote the wetting and bonding of the alloy melt on the surface of the ceramic substrate, and evenly adhere a layer of Sn-based metal melt on the friction surface of the ceramic substrate;

[0042] 5. Taking the ceramic matrix out of the Sn9Zn alloy melt containing ceramic particles, and naturally cooling it to room temperature in an atmospheric environment to obtain a metallized ceramic matrix.

[0043] Specific implementation method 2: This implementation method is different from specific implementation method 1 in that the ceramic substrate to be metallized in step 1 is AlN ceramic or SiC ceramic. The other steps are the same as those in specific implementation method 1.

[0044] Specific implementation method 3: This implementation method is different from specific implementation method 1 or 2 in that: in step 1, acetone is used as a cleaning agent to perform ultrasonic cleaning on the metallized ceramic substrate for 3 minutes to 5 minutes. The other steps are the same as those of specific implementation method 1 or 2.

[0045] Specific embodiment 4: This embodiment differs from specific embodiments 1 to 3 in that: in step 1, a hair dryer is used to dry the acetone on the surface to obtain a pre-treated ceramic substrate to be metallized. The other steps are the same as those of specific embodiments 1 to 3.

[0046] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that the ceramic particles described in step 2 are SiC ceramic particles. The other steps are the same as those of specific embodiments 1 to 4.

[0047] Specific embodiment 6: This embodiment differs from specific embodiments 1 to 5 in that the mass ratio of Sn powder, Zn particles and ceramic particles in step 2 is (85-90): (5-10): (2-5). The other steps are the same as those of specific embodiments 1 to 5.

[0048] Specific embodiment 7: This embodiment differs from specific embodiments 1 to 6 in that the particle size of the Sn powder in step 2 is 50 μm to 150 μm. The other steps are the same as those of specific embodiments 1 to 6.

[0049] Specific embodiment 8: This embodiment differs from specific embodiments 1 to 7 in that the particle size of the Zn particles in step 2 is 0.5 mm to 1 mm, and the particle size of the ceramic particles is 2 μm to 50 μm. The other steps are the same as those of specific embodiments 1 to 7.

[0050] Specific embodiment 9: This embodiment differs from specific embodiments 1 to 8 in that the temperature of heating and melting in step 3 is 220° C. to 230° C. The other steps are the same as those in specific embodiments 1 to 8.

[0051] Specific embodiment 10: This embodiment differs from specific embodiments 1 to 9 in that the friction time in step 4 is 60s to 100s. The other steps are the same as those in specific embodiments 1 to 9.

[0052] The following examples are used to verify the beneficial effects of the present invention:

[0053] Embodiment 1: A method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment is specifically accomplished by the following steps:

[0054] 1. Using acetone as a cleaning agent, ultrasonically cleaning the AlN ceramic substrate to be metallized for 3 minutes, and then using a hair dryer to dry the acetone on its surface to obtain the pretreated AlN ceramic substrate to be metallized;

[0055] 2. Mixing Sn powder, Zn particles and SiC ceramic particles in a certain mass ratio to obtain a low-temperature metallization material containing SiC ceramic particles;

[0056] The mass ratio of Sn powder, Zn particles and SiC ceramic particles described in step 2 is 89:9:2;

[0057] The particle size of the Sn powder in step 2 is 70 μm to 150 μm, the particle size of the Zn particles is 0.8 mm, and the particle size of the ceramic particles is 5 μm;

[0058] 3. Put the low-temperature metallization material containing SiC ceramic particles into the TC4 mold, and then place the mold on the heating platform for heating and melting. Stir continuously during the heating process until the Sn powder and Zn particles are melted to obtain a Sn9Zn alloy melt containing SiC;

[0059] The heating and melting temperature in step 3 is 230°C;

[0060] Fourth, immerse the pretreated AlN ceramic substrate to be metallized into a Sn9Zn alloy melt containing SiC at a temperature of 230°C, use a tool to clamp the ceramic substrate, and rub it repeatedly on the bottom of the TC4 mold to promote the wetting and bonding of the alloy melt on the surface of the ceramic substrate, and evenly adhere a layer of Sn-based metal melt on the friction surface of the ceramic substrate;

[0061] The friction time described in step 4 is 60s;

[0062] 5. The ceramic substrate is taken out from the Sn9Zn alloy melt containing SiC, and is naturally cooled to room temperature in an atmospheric environment to obtain an AlN ceramic substrate having a Sn9Zn metal layer containing SiC on the surface.

[0063] Figure 1 The morphology of the bonding interface between the AlN ceramic substrate and the Sn9Zn metal layer containing SiC in Example 1 under an optical microscope;

[0064] Figure 2 The morphology of the bonding interface between the AlN ceramic substrate and the Sn9Zn metal layer containing SiC in Example 1 under a scanning electron microscope.

[0065] from Figure 1 and Figure 2 It can be seen that: there are no defects such as pores and cracks on the interface, and the bonding is good; the bonding strength between the Sn9Zn metal layer of SiC and the ceramic substrate is 9.71MPa.

[0066] Comparative Example 1: A method for preparing an AlN ceramic substrate having a Sn9Zn metal layer on the surface is specifically completed by the following steps:

[0067] 1. Using acetone as a cleaning agent, ultrasonically cleaning the AlN ceramic substrate to be metallized for 3 minutes, and then using a hair dryer to dry the acetone on its surface to obtain the pretreated AlN ceramic substrate to be metallized;

[0068] 2. Mixing Sn powder and Zn particles in a certain mass ratio to obtain a low-temperature metallization material;

[0069] The mass ratio of Sn powder to Zn particles described in step 2 is 91:9;

[0070] The particle size of the Sn powder in step 2 is 70 μm to 150 μm, and the particle size of the Zn particles is 0.8 mm;

[0071] 3. Put the low-temperature metallization material into the TC4 mold, and then place the mold on the heating platform for heating and melting. Stir continuously during the heating process until the Sn powder and Zn particles are melted to obtain a Sn9Zn alloy melt;

[0072] The heating and melting temperature in step 3 is 230°C;

[0073] Fourth, immerse the pretreated AlN ceramic substrate to be metallized in a Sn9Zn alloy melt at a temperature of 230°C for 300s, and evenly adhere a layer of Sn9Zn alloy melt to the friction surface of the ceramic substrate;

[0074] The friction time described in step 4 is 60s;

[0075] 5. The ceramic substrate is taken out from the Sn9Zn alloy melt and naturally cooled to room temperature in an atmospheric environment to obtain an AlN ceramic substrate having a Sn9Zn metal layer on the surface.

[0076] Figure 3 The morphology of the bonding interface between the AlN ceramic substrate and the Sn9Zn metal layer without ceramic particles in Comparative Example 1 under a scanning electron microscope.

[0077] from Figure 3 It can be seen that the surface of the ceramic matrix is ​​not bonded to Sn9Zn and there are obvious cracks.

Claims

1. A method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment, characterized in that The method is specifically completed according to the following steps:

1. Cleaning the ceramic substrate to be metallized and then drying it to obtain the pre-treated ceramic substrate to be metallized; 2. Mixing Sn powder, Zn particles and ceramic particles in a certain mass ratio to obtain a low-temperature metallization material containing ceramic particles; 3. Put the low-temperature metallization material containing ceramic particles into the TC4 mold, and then place the mold on the heating platform for heating and melting. Stir continuously during the heating process until the Sn powder and Zn particles are melted to obtain a Sn9Zn alloy melt containing ceramic particles; Fourth, immerse the pretreated ceramic substrate to be metallized into a Sn9Zn alloy melt containing ceramic particles at a temperature of 220°C to 230°C, use a tool to clamp the ceramic substrate, and rub it repeatedly on the bottom of the TC4 mold to promote the wetting and bonding of the alloy melt on the surface of the ceramic substrate, and evenly adhere a layer of Sn-based metal melt on the friction surface of the ceramic substrate; 5. Taking the ceramic matrix out of the Sn9Zn alloy melt containing ceramic particles, and naturally cooling it to room temperature in an atmospheric environment to obtain a metallized ceramic matrix.

2. The method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment according to claim 1, characterized in that The ceramic substrate to be metallized in step 1 is AlN ceramic or SiC ceramic.

3. The method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment according to claim 1, characterized in that In step 1, acetone is used as a cleaning agent to perform ultrasonic cleaning on the ceramic substrate to be metallized for 3 minutes to 5 minutes.

4. The method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment according to claim 1, characterized in that In step 1, a hair dryer is used to dry the acetone on the surface to obtain a pretreated ceramic substrate to be metallized.

5. The method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment according to claim 1, characterized in that The ceramic particles described in step 2 are SiC ceramic particles.

6. The method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment according to claim 1, characterized in that The mass ratio of Sn powder, Zn particles and ceramic particles described in step 2 is (85-90):(5-10):(2-5).

7. The method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment according to claim 1, characterized in that The particle size of the Sn powder described in step 2 is 50 μm to 150 μm.

8. The method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment according to claim 1, characterized in that The particle size of the Zn particles described in step 2 is 0.5 mm to 1 mm, and the particle size of the ceramic particles is 2 μm to 50 μm.

9. The method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment according to claim 1, characterized in that The heating and melting temperature in step 3 is 220°C to 230°C.

10. The method for low-temperature metallization of ceramics by abrasive friction in an atmospheric environment according to claim 1, characterized in that The friction time in step 4 is 60s to 100s.

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