JPS6296373A - Joined body of non-oxide base ceramic and metal and joining 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] [Industrial Application Field] The present invention relates to non-oxide ceramics mainly composed of nitrides and carbides, and metals such as iron, copper, nickel, and stainless steel.
Or an alloy (in this specification, alloys are also referred to as metals)
The present invention relates to a bonded body and a bonding method.

[Conventional technology]

Ceramics have excellent heat resistance, corrosion resistance, and abrasion resistance, but when trying to utilize them effectively, the difficulty is that ceramics are brittle, which means they are susceptible to impact. In many cases, it is more convenient to use it in conjunction with other metals, which in turn expands its use.

Various studies have been conducted regarding the bonding of ceramics and metals. That is, there are organic and inorganic adhesives, as well as mechanical bonding such as shrink fitting, and excellent adhesives have been developed and are being evaluated to a certain extent. However, from the viewpoint of heat resistance, etc., chemical reactions, bonding by diffusion and penetration effects, and the so-called metallization method in which metal is formed on the surface of ceramics are attracting attention.

This metallization method is broadly classified as follows.

■It is also called the high melting point metal method, and Mo, M.

- Mn, W, W-Mo or kaolin etc. are added to these, mixed with a binder, heated to around 1600℃ in humidified hydrogen to infiltrate Mo and W, plated with Ni etc., and then bonded. How to braze metal.

The bonding mechanism is that Mn becomes Mn◯ and melts into the ceramic, and MO is slightly oxidized and penetrates into the glass phase of the ceramic phase and the Ni plating layer to bond.

■ A method of joining ceramics and metal by interposing an intermediate insert material that easily reacts with the material. As the insert material, a mixture of a copper compound such as copper sulfide and kaolin is generally known. When joining,
The insert material is inserted between the ceramic and the metal to be joined, and heated to a temperature equal to or higher than the melting point of the insert material.

Mechanically, method (■) requires a lot of man-hours, so method (■) is attracting attention.

[Problem that the invention seeks to solve]

In methods using insert materials, various examples have been reported in which oxide-based ceramics such as alumina-based, magnesia-based, and silica-based ceramics have been successfully joined.

However, sufficient bonding strength has not been achieved with non-oxide ceramics.

The present invention aims to propose a bonded body of non-oxide ceramics and a metal and a bonding method therefor.

[Means for solving problems]

The inventor focused on the stability of Sialon, and as a result of considering the phase formed by forced reduction, Ca 15 to 80% by weight,
The remainder SL and unavoidable impurities, or Ca 1 in wt%
A thin plate or powder consisting of 5-80% Ti, 15% or less Ti, the balance Si and unavoidable impurities, or a binder added to the powder, is inserted between the non-oxide ceramic and metal to be joined as an insert material, By heat-treating in a non-oxidizing atmosphere at a temperature of 900°C or higher and below the melting point of the metals to be joined, non-oxide ceramics and metals, including sialon, which have traditionally been difficult to bond firmly, can be bonded to the insert material. We succeeded in obtaining a bonded body in which the constituent elements of the metal are integrated with non-oxide ceramics and a layer containing the constituent elements of the metal.

In the present invention, the surface of the ceramic is reduced with calcium, which is a strong reducing agent, and a structure of metal or a structure similar to the metal, which is a component element of the ceramic, is generated on the surface of the ceramic, and a metal structure is formed by the compound of this and the insert material. It is expected that it will be joined with

Possible substances that can effectively reduce the surface of non-oxide ceramics include Ca, Be, Sr, Y, rare earth elements, etc. However, there are difficulties in handling other than Ca. It may be effective if measures are taken to prevent oxidation.

A temperature of 900°C or higher is required for the diffusion of the metal, which is a component element of the ceramic produced by reduction, or a similar structure to the metal to be bonded, and the insert material is heated before this bonding reaction occurs. If the insert material melts, uniform bonding cannot be achieved due to wettability, so the melting point of the insert material must be 900° C. or higher.

The melting point of Ca is about 800°C, but by alloying it,
It is necessary to have a melting point of 00° C. or higher, and a suitable alloy component may be one in which Si is appropriately added to Ca in consideration of reducing performance. Furthermore, considering the wettability of the insert material, it is also conceivable to add Ti within a range of 15% by weight or less without raising the melting point of the insert material excessively.

Next, the reason for limiting the Ca content will be described. If the Ca content is less than 1 nishiki, a sufficient reduction reaction cannot be obtained, and if it exceeds 80%, the melting point will be below 900°C, making it impossible to form a good bond, so the Ca content was set to 15 to 80%. . In addition, in the present invention, even if elements other than the above-mentioned Ca, SL, and T1 are contained, the strong reducing power and melting point of Ca are 900
As long as the temperature is above ℃, the presence of other elements is considered not to be a problem.

As mentioned above, the heat treatment temperature needs to be 900° C. or higher in order to reduce the non-oxide ceramics and also to diffuse the produced Si and metal. The upper limit was set to be below the melting point of the metals to be joined.

It is important that the heating atmosphere be an atmosphere in which Ca in the insert material is not oxidized, such as a dry hydrogen atmosphere, an inert gas atmosphere, or a vacuum, that is, a non-oxidizing atmosphere.

The present invention also considers applying a slight pressure to the bonded body during the heat treatment, which contributes to improving the bonding strength.

〔Example〕

The present invention will be explained below based on Examples.

Example 1 A Ca-3j alloy having the composition shown in sample No. 081.2 in Table 1 was ground to 150 mesh or less, made into a paste with inpropyl alcohol, and 50 mg/g was applied to a Sialon plate.
It was applied at a ratio of cx&. A Cu plate (thickness 0,5 nu) was placed on top of the Ca-Si alloy coated, and 1050
℃ in a dry hydrogen atmosphere for 20 minutes to bond. A steel bar with a diameter of 10 mm was attached with a silver roll to the surface of the Cu plate of this bonded body, and a tensile test was conducted. As shown in Table 1, both samples No. 1 and 1.2 were firmly bonded. .

A bonding strength of 9J10n'' and 9.5kg/nu'' was obtained.

In addition, sample No. 3 (50Ca-30Si-
When SiAlON and Cu were bonded using 20Ti in the same manner as above, a bonding strength of 10 kg/nu2 was obtained.

As a comparative example, bonding was attempted under the same conditions as above using a Ca--Si alloy containing 10% Ca as shown in Sample No. 4 in Table 1, but no bonded body was obtained.

In addition, CaO, which has been known as an insert material,
(Sample No. 5), CuS (Sample No. 6)
After mixing with a powder of 150 mesh or less and applying it to the surface of a Sialon board, hold it in the atmosphere at 1250°C for 30 minutes,
Next, a Cu plate (thickness: 5 nu) was placed on the coated surface and held at 1000° C. for 20 minutes in a hydrogen atmosphere, but no bonded body was obtained.

Ta.

Table 1 Example 2 Sample No. 7 in Table 1 Ca- containing 50% Ca
After crushing the Si alloy to 150 mesh or less and making it into a paste with isopropyl alcohol, 30
Further, a Ni plate (thickness: 1 mm) was placed on the coated surface and held at 1200° C. for 30 minutes in a hydrogen atmosphere to obtain a bonded body. This joined body was firmly joined, and as a result of performing a tensile test in the same manner as in Example 1,
The bond strength was 9.3 kg/nn+''.

In the present invention, it may be possible to obtain a good bonded body by applying a slight pressure during bonding. An example is shown below.

Ca- containing 50% Ca of Sample No. 6 in Table 1
After crushing the 3i alloy to 150 mesh or less and making it into a paste with isopropyl alcohol, apply the 3i alloy to a sialon plate.
It was applied at a rate of mg/nm2, and a Ni plate (
It was ground to a thickness of 150 mesh or less and made into a paste with isopropyl alcohol. Apply 30mg10w of this paste-like alloy to the surface of the Sialon plate.
Coat at a ratio of I + 2, and on top of this a Cu plate (thickness l ah
) was placed thereon, a pressure of 20,./cot was applied, and the temperature was maintained at 1050° C. for 20 minutes in an argon atmosphere. The obtained bonded body was subjected to a tensile test in the same manner as in Example 1, and as a result, as shown in Table 1, a bond strength of 10 kg/mm2 was obtained.

〔Effect of the invention〕

As explained above, according to the present invention, non-oxide ceramics and metal can be firmly joined to each other, which has been difficult to join using conventional insert materials.

This will expand the uses of ceramics.

Claims (1)

[Claims] 1 The non-oxide ceramic and the metal are in weight percent, Ca
15 to 80%, the balance being Si and unavoidable impurities, which are integrated through a layer containing the constituent elements of the insert material, the constituent elements of the non-oxide ceramic, and the constituent elements of the metal. A bonded body of oxide ceramics and metal. 2 Non-oxide ceramics and metals are Ca1 in weight%
5 to 80% Ti, 15% or less Ti, the balance Si and unavoidable impurities, which are integrated through a layer containing the constituent elements of the non-oxide ceramic and the metal. A bonded body of non-oxide ceramics and metal. 3. A joined body of non-oxide ceramic and metal according to claim 1 or 2, wherein the non-oxide ceramic is Sialon. 4. An insert material consisting of 15 to 80% Ca, the balance Si and unavoidable impurities is sandwiched between the non-oxide ceramic and the metal to be joined, and the above-mentioned joining is carried out at 900°C or higher in a non-oxidizing atmosphere. A method for joining non-oxide ceramics and metals, characterized by heat treatment at a temperature below the melting point of the metal to be bonded. 5 An insert material consisting of 15 to 80% Ca, 15% or less Ti, the balance Si and unavoidable impurities is sandwiched between the non-oxide ceramic and the metal to be joined, and heated at 900°C in a non-oxidizing atmosphere. As described above, the method for joining non-oxide ceramics and metals is characterized in that heat treatment is performed at a temperature below the melting point of the metals to be joined. 6. The method of joining a non-oxide ceramic and a metal according to claim 3 or 4, wherein the non-oxide ceramic is Sialon.