JPH0446036A - Glass composite material and its manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a glass composite material used for bonding metal substrates together or coating the surface of a metal substrate with a glass layer, and a method for manufacturing the same. Although many types of sealing glasses have been developed and commercially available for bonding materials such as metals and ceramics, these glasses have different coefficients of thermal expansion and softening points depending on the application. When sealing a substrate using stainless steel, the coefficient of thermal expansion is 60 to 10.
The thermal expansion coefficient of the sealing glass is 20~SOx to
The reason for this is that glass is resistant to compressive stress. Therefore, metals with a relatively small coefficient of thermal expansion, such as iron and stainless steel, can be used to control the glass composition. By doing so, it is possible to obtain a glass with the desired coefficient of thermal expansion (this invention solves the problem of the fact that there is no sealing glass with excellent properties for metals with a large coefficient of thermal expansion). Thermal expansion coefficient method for aluminum, aluminum and copper alloys The thermal expansion coefficient is 180 to 230x 10-' compared to that of iron (120x 10-'/l: ) and stainless steel (160x 10-'/l: ) /l, and no sealing glass has been developed that is compatible with such metal substrates, and among the glasses developed so far, the ones with a large coefficient of thermal expansion are 150 x 10-'/l. Although it contains a large amount of alkali and lead components and is inferior in water resistance and mechanical strength, the present invention aims to provide a sealing glass that solves the above-mentioned problems and a method for manufacturing the same. The present invention is one of the most expensive glass materials, characterized by dispersing a metal powder having a coefficient of thermal expansion larger than that of the glass material.
In other words, by dispersing metal powder with a high coefficient of thermal expansion into a glass base material, the coefficient of thermal expansion can be increased without changing the characteristics of conventional glass, which has excellent water resistance and mechanical strength. It enables sealing to metal substrates with large thermal expansion coefficients such as aluminum alloys and copper alloys.When manufacturing the above-mentioned glass composites, colloidal silica is added to the mixture of each material. Alternatively, the glass composite material of the present invention is characterized by using a slurry to which colloidal alumina is added. The metal powder is dispersed in the glassy base material.A glass composite with a high expansion coefficient is used as a dispersion medium. Characteristics of the manufacturing method using inorganic materials such as colloidal silica or colloidal alumina (which enables easy application to unbonded substrates and the production of composites with excellent insulation resistance) The glass CL used in the present invention can be selected from commercially available glasses according to the thermal expansion of the metal substrate to be bonded, and is characterized in that it can be used on a metal substrate with a large coefficient of thermal expansion. The coefficient of linear expansion of the glass to be selected is 12
0X 10-'/l: It is desirable to use a glass having the above characteristics, but a metal powder having a higher coefficient of thermal expansion than this is dispersed in the glass powder having the above-mentioned characteristics.As a metal having a higher coefficient of thermal expansion, aluminum is used. (230x 10-
'/l), copper (200x 10-'/l), brass (
180 to 230 The larger the amount, the higher the coefficient of thermal expansion will be. However, if the amount added exceeds 5% by weight, the fluidity will decrease when applied to a metal substrate as a glass composite, and the bond between metal particles will deteriorate. The optimum amount of addition is 5% by weight or less, as addition I becomes easy to corrode and reduces insulation resistance.Additional I is 0.05%
If the amount of metal powder added is less than 0.05 to 5% by weight, the effect of increasing thermal expansion as a composite material cannot be expected. In order to reduce the amount added as much as possible, it is desirable to add a metal powder with a large coefficient of thermal expansion.Among the metal powders mentioned above, the most suitable metal is aluminum.The particle size of the metal powder to be added is:
In the present invention, it is necessary that the particle size is 1100 μm or less. If the particle size of the metal powder exceeds 100 μm or more, the metal will be exposed on the surface, and the probability that metal particles will come into contact with each other will increase, resulting in poor insulation and corrosion resistance. Due to reasons such as poor performance, Muji & Mi discussed the manufacturing method of glass composites, but the common method for applying sealing glass to a substrate is to mix it with a solvent such as water or terpineol. It is possible to use these conventional solvents as the glass composite material of the present invention. However, when the above-mentioned solvents are used, there are the following disadvantages. Water is the most common solvent. There are also disadvantages such as it is difficult to apply due to lack of viscosity, has a weak bonding force to the substrate and tends to peel off during the drying stage. After heating, the unburned carbon of the organic substance terpineol remains in the glass, reducing its insulation resistance. Colloidal alumina is made by dispersing fine particles of silica powder or alumina powder in a colloidal state, and it is possible to use what is commercially available as Snowtex (manufactured by Nichichi Kagaku).

Characteristics when using colloidal silica or colloidal alumina as a dispersion medium Table 1: By kneading with glass, it has a viscosity that makes it easy to apply, it has a certain degree of bonding force to the substrate even before firing, and after firing It also overcomes the drawbacks of silica and alumina, which are inorganic and reduce insulation resistance. Colloidal silica or colloidal alumina is added to the amorous glass powder and metal powder, and water is added as necessary to adjust it to the desired viscosity. This slurry will be described in detail below using specific examples.Example 1 The composition shown in Table 1 was kneaded in a mortar to prepare a slurry. 6mm
The sample was applied in a ring shape with a width of about 3 mm around the periphery of the sample, dried at room temperature, and then fired at 600℃ for 10 minutes.When the fired sample was observed under a microscope for cracks, no cracks were observed. One cycle consists of heating for 15 minutes and then pouring into ice water at 0°C. X.

Cracks were observed after 10 repetitions of the above-mentioned sample (No cracks were observed even after 10 thermal shocks. The optimum amount of aluminum was investigated as shown in Table 2, and the amount of colloidal silica and pure water added was the same as in Example 1. The amount of aluminum powder added was not included in the calculation of the amount of aluminum powder added.9 Therefore, the amount of aluminum powder added is the amount (wt%) added to the glass powder.The impact test of the sample was performed in the same manner as in Example 1. 9. Table 2 ○ indicates that no cracks occur even after 10 times.Those expressed in numerical values represent those that cracked after that number of times.From the above results, the amount of aluminum added i;L O, 0
If it is less than 5wtX, no cracks will occur in the glass composite. Therefore, the optimal addition amount of the metal powder of the present invention is 0.05 to 5wt%. λ 3 and No. 12 are reference examples (Example 3) In Example 1, aluminum powder was used with an average particle size of 120
This sample was subjected to a thermal shock test using μ nails of 200 μm, and no cracks appeared even after 10 cycles.The corrosion resistance was also examined together with the sample of Example 1 under an atmosphere of 80 tons and 80% RH.Average Particle size is 120μ
In Example 10, corrosion was observed after 100 hours on the grains of 80 μm or less (Example 4) In Example 1, corrosion was observed in the grains of 80 μm or less (example 4). Samples were prepared using brass powder and a thermal shock test was conducted. No cracks occurred in any of the samples even after 10 cycles. Example 5 In Example 1, ugly colloidal alumina was used instead of colloidal silica to create a slurry. Create t, f-.

The adhesion of aluminum to the metal wire is good, and 610
After firing at ℃ for 10 minutes, the sample was subjected to a thermal shock test, and no cracks appeared even after 10 cycles.As can be seen from the effects of the invention, according to the present invention, the glass was inserted into the glass powder. By containing metal powder with a higher coefficient of thermal expansion, it becomes possible to apply it to materials such as aluminum, which has a high coefficient of thermal expansion and which has been difficult to seal with glass.

Claims (6)

[Claims] (1) A glass composite material characterized in that a metal powder having a coefficient of thermal expansion larger than that of the glass is dispersed in a glass base material. (2) The glass composite material according to claim 1, wherein the metal powder has a particle size of 100 μm or less. (3) 0.05 to 5% by weight of metal powder in the glassy base material
The glass composite material according to claim 1 or 2, characterized in that it contains: (4) The glass composite material according to claim 1, 2 or 3, wherein the metal powder is aluminum. (5) A method for producing a glass composite material, which comprises adding and kneading glass powder, metal powder, and a dispersion medium, and then applying the mixture to a metal substrate and firing it. (6) The method for producing a glass composite material according to claim 5, wherein the dispersion medium comprises colloidal silica or colloidal alumina.