阅读说明：本技术 一种高接合强度陶瓷和玻璃连接材料及其制备方法 (High-bonding-strength ceramic and glass connecting material and preparation method thereof ) 是由 张乐 甄方正 邵岑 赵超 申冰磊 陈浩 于 2020-11-09 设计创作，主要内容包括：本发明提供了一种适合连接陶瓷-玻璃的高接合强度的连接材料及其制备方法。该材料通过加入V_2O_5,并通过控制球磨过程中的参数得到与V_2O_5与SiO_2的最佳粒径之比,最终制得了热膨胀系数匹配的连接材料,提高了接合强度,非常适合陶瓷-玻璃连接材料的(半)工业化生产。(The invention provides a connecting material with high bonding strength suitable for connecting ceramic-glass and a preparation method thereof. The material is prepared by adding V 2 O 5 And obtaining the product V by controlling parameters in the ball milling process 2 O 5 With SiO 2 The optimal grain diameter ratio of the ceramic-glass composite material, the connecting material with matched thermal expansion coefficient is finally prepared, the bonding strength is improved, and the ceramic-glass composite material is very suitable for (semi-) industrial production of ceramic-glass connecting materials.)

1. A preparation method of a high bonding strength ceramic-glass connecting material is characterized in that ball milling parameters are controlled to ensure that V is V₂O₅With SiO₂The grain size ratio of (3) to (4), and finally preparing the connecting material with high bonding strength and thermal conductivity gradient, wherein the components of the connecting material meet the following requirements:

(AO)_x(V₂O₅)_y(SiO₂)_1-x-y

wherein x is more than or equal to 0.1 and less than or equal to 0.4, x is more than or equal to 0.2 and less than or equal to 0.4, AO is ZnO or B₂O₃、Al₂O₃、Na₂O、Li₂One of O and CaO, which comprises the following specific steps:

the method comprises the following steps: reacting AO and V₂O₅And SiO₂Weighing the oxide powder according to the stoichiometric ratio;

step two: mixing the weighed oxide powder, ball-milling the mixture by using deionized water and zirconia, and drying the mixture; then placing the glass powder in a crucible for melting, and then quickly pouring the molten oxide powder into deionized water to form a glass material;

step three: and ball-milling the obtained glass frit by using deionized water and zirconia, drying, placing the ball-milled particles in a mold, pressing for 10-30 s under the pressure of 30-50 MPa, placing the glass frit blank body with a fixed shape in air, heating, melting and bonding, and connecting the ceramic and the glass as a connecting material to obtain the high-bonding-strength ceramic-glass connecting material.

2. The method of claim 1, wherein in step one, the purity of the selected oxide raw material is 99.9-99.99%.

3. The method of claim 1, wherein in the second step, the drying temperature after the first ball milling is 50 to 60 ℃^oC, drying for 0.5-2 h, performing first ball milling for 8-9 h, and performing ball milling at a rotating speed of 170-190 rpm; the temperature rise rate during melting is 5 to 15^oC/min, melting for 1-5 h; the temperature of the poured deionized water is room temperature; the ball milling mode is planetary ball milling.

4. The process of claim 1, wherein in step three, the second stepThe secondary ball milling time is 5-7 h, and the ball milling rotating speed is 180-200 r/min; 50 to 60^oC, drying in an oven for 0.5-2 h; the pressure during pressing is 80-120 Mpa; the ball milling mode is planetary ball milling.

5. The method of claim 1, wherein the temperature for melting in the third step is 500 to 600%^oC, the bonding time is 0.5-1 h.

6. A high bond strength ceramic-glass joining material prepared by the method of any one of claims 1 to 5.

7. The ceramic-glass joint material according to claim 6, wherein said joint material has a thermal expansion coefficient of 5 to 6 (10)^-6and/K), the bonding strength of the bonded ceramic-glass is 40-55 MPa.

Technical Field

The invention provides a high-bonding-strength ceramic and glass connecting material and a preparation method thereof, belonging to the technical field of preparation and application of connecting materials.

Background

The connection of ceramics and glass, especially the ceramics and glass with matched connection performance, is an indispensable connection product for occasions of high temperature, high pressure, sealing and the like. After the ceramic is connected with the glass, the mechanical strength is good, the sealing performance is excellent, the high temperature resistance, the corrosion resistance and the radiation resistance are stronger, the electrical performance parameters are good, and the ceramic is suitable for being used in various special and severe environments. With the rapid advance of industries such as aviation, aerospace, ships, exploration and the like, agriculture and military industries and the increase of various working environments and working equipment such as high temperature, high pressure, corrosion, radiation and the like, the demand of ceramic glass sintering sealing connectors is increasing day by day, and the ceramic glass sintering sealing connectors are sealing connectors which cannot be replaced on the occasions. However, the properties of ceramics, such as chemical inertness, low diffusion rate and high melting point, have hindered the application of ceramic-to-glass joining techniques. Due to the need to maintain stable properties of the ceramic after joining to the glass, it is important to ensure good wetting between the bonding interlayer and the ceramic and a low coefficient of thermal expansion adaptation. The ceramic-glass joining techniques so far mainly include diffusion bonding, active brazing, liquid phase bonding, and frit sandwich bonding, among others. The glass frit has high tolerance to the surface roughness of the ceramic substrate, low cost and high chemical stability, so that the glass frit interlayer connection is an excellent connection method.

However, the thermal expansion coefficient of ceramics is usually 6.5 to 9 (10)^-6K) and the coefficient of thermal expansion of the industrial glass is 3 to 5 (10)^-6and/K), the thermal expansion coefficients of the ceramic and the glass are often mismatched, so that when the ceramic and the glass are connected through the glass frit, the connection reliability is reduced due to the difference of the thermal expansion coefficients, namely, the stress between the interfaces is concentrated when the ceramic and the glass are connected, and the joint strength is reduced. However, different materials often have a non-uniform grain size, which also results in a large reduction in the joint strength. Yet another challenge in joining ceramic and glass is that when joining, at higher temperatures, the glass may deform at the interface due to excessive temperatures, which is often difficult for one skilled in the art to handle.

Disclosure of Invention

1. To solve the above-mentioned problem of bonding between different ceramic-glass joining materialsThe invention provides a preparation method and application of a high-bonding-strength ceramic-glass connecting material, which solves the problem of low strength by selecting a connecting material with gradient matching thermal conductivity and doping V₂O₅Then due to V₂O₅The hardness of the material is small, and the material is obtained by the ball milling parameters and the raw material proportion controlled by the invention₂V with the particle size being 3-4 times smaller₂O₅Granules at this size V during compaction₂O₅Can be used for filling the gap of the glass material, improves the density of the glass material and is doped with V₂O₅The melting point of the glass frit is effectively reduced, and the temperature required for bonding is reduced. The method has simple process, and the product produced by the method has stable performance.

2. The technical scheme of the invention is as follows:

first, AO and V are mixed₂O₅And SiO₂Weighing the oxide powder according to a stoichiometric ratio, mixing the weighed oxide powder, ball-milling the mixture by using deionized water and zirconia, and drying the mixture; then placing the glass powder in a crucible for melting, and then quickly pouring the molten oxide powder into deionized water to form a glass material; then ball-milling the obtained glass sample by using deionized water and zirconia, drying, placing the ball-milled particles in a mold, pressing for 10-30 s under the pressure of 30-50 MPa, placing the glass frit blank body with a fixed shape in air, heating and melting for bonding, and connecting the ceramic and the glass as a connecting material;

preferably, the purity of the selected oxide raw materials is 99.9-99.99%;

preferably, the drying temperature after the first ball milling is 50-60 ℃, the drying time is 0.5-2 h, the first ball milling time is 8-9 h, and the ball milling rotating speed is 170-190 r/min; the heating rate during melting is 5-15 ℃/min, and the melting is carried out for 1-5 h; the temperature of the poured deionized water is room temperature; the ball milling mode is planetary ball milling. .

Preferably, the secondary ball milling time is 5-7 h, and the ball milling rotating speed is 180-200 r/min; drying in an oven at 50-60 ℃ for 0.5-2 h; the pressure during pressing is 80-120 Mpa; the ball milling mode is planetary ball milling.

Preferably, the heating and melting temperature is 500-600 ℃, and the bonding time is 0.5-1 h.

Advantageous effects

1. The ceramic-glass connecting material prepared by the method provided by the invention has high bonding strength, the bonding strength is 40-55 MPa, and the ceramic-glass connecting material is very suitable for ceramic-glass connection.

2. In the process of preparing the connecting material, the method provided by the invention strictly controls the parameters during ball milling to achieve the optimal SiO₂And V₂O₅The grain diameter ratio of (2) further enhances the bonding strength, and the prepared connecting material has high bonding strength and is very suitable for preparing the connecting material.

3. The connecting material prepared by the preparation method provided by the invention has low temperature during bonding and has no obvious influence on bonding strength and material deformation, thereby being very suitable for bonding ceramic-glass.

Drawings

Fig. 1 is an SEM image of the connection material prepared in example 1 after the first ball milling.

FIG. 2 is a comparison of the thermal expansion coefficients of examples 1, 2, 3, 4, and 5.

FIG. 3 is a comparison of the bonding strengths of examples 1, 2, 3, 4, and 5.

Detailed Description

The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention.

Example 1: (ZnO)_0.3(V₂O₅)_0.3(SiO₂)_0.4

First, ZnO and V are mixed₂O₅And SiO₂Weighing the oxide powder according to a stoichiometric ratio, mixing the weighed oxide powder, ball-milling the mixture by using deionized water and zirconia, and drying the mixture; then placing the glass powder in a crucible for melting, and then quickly pouring the molten oxide powder into deionized water to form a glass material; then ball-milling the obtained glass sample by using deionized water and zirconia, drying, and placing the ball-milled particles into a containerPressing the glass blank in a mould for 30s under the pressure of 30MPa, and heating and melting the glass blank in the air to joint the glass blank and the ceramic and the glass as a connecting material;

preferably, the purity of the selected oxide raw materials is 99.9-99.99%;

preferably, the drying temperature after the first ball milling is 50 ℃, the drying time is 2 hours, the first ball milling time is 8 hours, and the ball milling speed is 190 r/min; the heating rate during melting is 5 ℃/min, and the melting is carried out for 5 h; the temperature of the poured deionized water is room temperature; the ball milling mode is planetary ball milling. .

Preferably, the time of the second ball milling is 5 hours, and the ball milling speed is 200 r/min; drying in a 50 ℃ oven for 2 h; the pressure during pressing is 80 Mpa; the ball milling mode is planetary ball milling.

Preferably, the temperature for heating and melting is 600 ℃, and the bonding time is 0.5 h.

As can be seen from FIG. 1 and Table 1, SiO after the first ball milling₂And V₂O₅Has a particle size ratio of 4.2, smaller is designated as V in the figure₂O₅And (3) granules. The connecting material prepared in this example had a coefficient of thermal expansion of 5.5 (10)^-6and/K), the bonded ceramic-glass has a bonding strength of 55 MPa.

Example 2: (B)₂O₃)_0.2(V₂O₅)_0.4(SiO₂)_0.4

Firstly, B is mixed₂O₃、V₂O₅And SiO₂Weighing the oxide powder according to a stoichiometric ratio, mixing the weighed oxide powder, ball-milling the mixture by using deionized water and zirconia, and drying the mixture; then placing the glass powder in a crucible for melting, and then quickly pouring the molten oxide powder into deionized water to form a glass material; then ball-milling the obtained glass sample by using deionized water and zirconia, drying, placing the ball-milled particles in a mould, pressing for 10s under the pressure of 50MPa, placing the glass frit blank with a fixed shape in air, heating and melting for bonding, and connecting the ceramic and the glass as a connecting material;

preferably, the purity of the selected oxide raw materials is 99.9-99.99%;

preferably, the drying temperature after the first ball milling is 60 ℃, the drying time is 0.5h, the first ball milling time is 9h, and the ball milling rotating speed is 170 r/min; the heating rate during melting is 15 ℃/min, and the melting is carried out for 1 h; the temperature of the poured deionized water is room temperature; the ball milling mode is planetary ball milling. .

Preferably, the time of the second ball milling is 7 hours, and the ball milling speed is 180 r/min; drying in an oven at 60 deg.C for 0.5 h; the pressure during pressing is 120 Mpa; the ball milling mode is planetary ball milling.

Preferably, the temperature for heating and melting is 500 ℃, and the bonding time is 1 h.

As can be seen from Table 1, the SiO after the first ball milling₂And V₂O₅The particle size ratio of (1) is 4.7, and the thermal expansion coefficient of the connecting material prepared in this example is 5 (10)^-6and/K), the bonded ceramic-glass has a bonding strength of 40 MPa.

Example 3: (Al)₂O₃)_0.1CaO)_0.2(SiO₂)_0.7

First, Al is added₂O₃、V₂O₅And SiO₂Weighing the oxide powder according to a stoichiometric ratio, mixing the weighed oxide powder, ball-milling the mixture by using deionized water and zirconia, and drying the mixture; then placing the glass powder in a crucible for melting, and then quickly pouring the molten oxide powder into deionized water to form a glass material; then ball-milling the obtained glass sample by using deionized water and zirconia, drying, placing the ball-milled particles in a mould, pressing for 20s under the pressure of 40MPa, placing the glass frit blank with a fixed shape in air, heating and melting for bonding, and connecting the ceramic and the glass as a connecting material;

preferably, the purity of the selected oxide raw materials is 99.9-99.99%;

preferably, the drying temperature after the first ball milling is 55 ℃, the drying time is 1.5h, the first ball milling time is 8h, and the ball milling rotating speed is 180 r/min; the heating rate during melting is 10 ℃/min, and the melting is carried out for 3 h; the temperature of the poured deionized water is room temperature; the ball milling mode is planetary ball milling. .

Preferably, the time of the second ball milling is 6 hours, and the ball milling speed is 190 r/min; drying in an oven at 55 ℃ for 1 h; the pressure during pressing is 90 Mpa; the ball milling mode is planetary ball milling.

Preferably, the temperature for heating and melting is 550 ℃, and the bonding time is 1 h.

As can be seen from Table 1, the SiO after the first ball milling₂And V₂O₅The particle size ratio of (1) is 4.6, and the thermal expansion coefficient of the connecting material prepared in this example is 6 (10)^-6and/K), the bonding strength of the bonded ceramic-glass is 50 MPa.

Example 4: (Al)₂O₃)_0.1(V₂O₅)_0.2(SiO₂)_0.7

First, Al is added₂O₃、V₂O₅And SiO₂Weighing the oxide powder according to a stoichiometric ratio, mixing the weighed oxide powder, ball-milling the mixture by using deionized water and zirconia, and drying the mixture; then placing the glass powder in a crucible for melting, and then quickly pouring the molten oxide powder into deionized water to form a glass material; then ball-milling the obtained glass sample by using deionized water and zirconia, drying, placing the ball-milled particles in a mould, pressing for 20s under the pressure of 40MPa, placing the glass frit blank with a fixed shape in air, heating and melting for bonding, and connecting the ceramic and the glass as a connecting material;

preferably, the purity of the selected oxide raw materials is 99.9-99.99%;

preferably, the drying temperature after the first ball milling is 55 ℃, the drying time is 1.5h, the first ball milling time is 10h, and the ball milling rotating speed is 200 r/min; the heating rate during melting is 10 ℃/min, and the melting is carried out for 3 h; the temperature of the poured deionized water is room temperature; the ball milling mode is planetary ball milling. .

Preferably, the time of the second ball milling is 6 hours, and the ball milling speed is 190 r/min; drying in an oven at 55 ℃ for 1 h; the pressure during pressing is 90 Mpa; the ball milling mode is planetary ball milling.

Preferably, the temperature for heating and melting is 550 ℃, and the bonding time is 1 h.

As can be seen from Table 1, the SiO after the first ball milling₂And V₂O₅Has a particle size ratio of 2, the connecting material prepared in this example has a thermal expansion coefficient of 4.7 (10)^-6/K), the bonding strength of the bonded ceramic-glass is 40-55 MPa when SiO is₂And V₂O₅When the particle diameter of (2) is small and the mass ratio is determined, a new gap is likely to be generated during the compaction process, which leads to a decrease in the bonding strength.

Example 5: (Al)₂O₃)_0.1CaO)_0.2(SiO₂)_0.7

First, Al is added₂O₃、V₂O₅And SiO₂Weighing the oxide powder according to a stoichiometric ratio, mixing the weighed oxide powder, ball-milling the mixture by using deionized water and zirconia, and drying the mixture; then placing the glass powder in a crucible for melting, and then quickly pouring the molten oxide powder into deionized water to form a glass material; then ball-milling the obtained glass sample by using deionized water and zirconia, drying, placing the ball-milled particles in a mould, pressing for 20s under the pressure of 40MPa, placing the glass frit blank with a fixed shape in air, heating and melting for bonding, and connecting the ceramic and the glass as a connecting material;

preferably, the purity of the selected oxide raw materials is 99.9-99.99%;

preferably, the drying temperature after the first ball milling is 55 ℃, the drying time is 1.5h, the first ball milling time is 5h, and the ball milling speed is 150 r/min; the heating rate during melting is 10 ℃/min, and the melting is carried out for 3 h; the temperature of the poured deionized water is room temperature; the ball milling mode is planetary ball milling. .

Preferably, the time of the second ball milling is 6 hours, and the ball milling speed is 190 r/min; drying in an oven at 55 ℃ for 1 h; the pressure during pressing is 90 Mpa; the ball milling mode is planetary ball milling.

Preferably, the temperature for heating and melting is 550 ℃, and the bonding time is 1 h.

As can be seen from Table 1, the SiO after the first ball milling₂And V₂O₅The particle size ratio of (2) is 6, and the thermal expansion coefficient of the connecting material prepared in this example is 6.8 (10)^-6and/K) has a thermal expansion coefficient close to that of glass and a large difference with that of ceramic, the bonding strength of the bonded ceramic-glass is 40-55 MPa, and the gap cannot be completely filled in the compacting process due to the large particle size ratio, so that the bonding strength is reduced.

From Table 1, it can be seen that the combination of the rotational speed and the milling time of the ball mill is on SiO₂And V₂O₅SiO under the ball milling time and the ball milling rotating speed defined by the invention₂And V₂O₅All of them satisfy the optimum particle size ratio, in examples 1 to 3, SiO is optimum₂And V₂O₅The particle size ratio ranges are all compacted, and matched thermal expansion coefficients and higher bonding strength are obtained.

Table 1: examples 1-5 SiO in the first ball milling under different parameters₂And V₂O₅The particle size ratio of (a).

The present invention and its embodiments have been described above, and the description is not intended to be limiting, and the drawings are only one embodiment of the present invention, and the actual structure is not limited thereto. In summary, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.