JPS63190769A - Ceramic-metal bonded body - 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 applications The present invention relates to a joined body of ceramics and metal.

More specifically, the present invention provides oxides, carbides, borides,
The present invention relates to an improvement in a joined body of a ceramic ceramic member and a metal member, which is constructed by metallizing the surface of a ceramic such as a nitride or a composite thereof, and joining a metal member to the metallized surface via a brazing material.

Conventional ceramics have excellent heat resistance, wear resistance, light weight, etc., but their use is limited because they are difficult to bond with metals. In general, a joined body of a ceramic member and a metal member is
This is done by metallizing the surface of the ceramic and joining it to another metal member on this metallized surface. When such a bond between a ceramic member and a metal member is achieved with sufficient strength, it can be used to bond a metal element or heat dissipation fin to a ceramic substrate in an electronic component, or to bond a ceramic member and a metal member in a structural or engine component. The applications of ceramics, such as bodies, are expected to expand.

Typical ceramic metallization methods used to obtain such a joined body of a ceramic member and a metal member include a molybdenum-manganese method, an active metal method, and an oxide solder method. Among these, the active metal method uses Ti,
This method uses active metals such as Zr, which become active at high temperatures and easily react with ceramics. That is, this is a method in which a plate or foil-shaped active metal is inserted between the ceramic and the sealing metal, and the ceramics and the sealing metal are heated and sealed in a vacuum or an inert gas.

Nikkei Mechanical (NIKKEI MECH 8 old C to L)
On January 13, 1986, a method for using active metal brazing materials is described. This active metal brazing method is a method using a brazing material and an active metal, and either a foil of the brazing material is used together with the active metal, or the active metal is mixed into the brazing material. Also disclosed is a method in which powder of an active metal such as Ni is sprinkled on the surface of a ceramic such as Si, N, and the like is heated under vacuum to metallize the surface.

As mentioned above, conventional methods of metallizing ceramics using active metals for joining ceramic members and metal members include methods using alloy brazing fillers mixed with active metals; Additionally, methods have been proposed in which the metal is bonded in the form of foil or plate. However, these methods do not allow the use of highly pure activated metals, and furthermore, the activity decreases due to the inclusion of impurities.On the other hand, Due to their high activity, active metals have the property of being susceptible to corrosion such as oxidation, so there is a problem that the high activity of active metals cannot be utilized.

In addition, in order to solve these problems, a method has been proposed in which highly purified Ti is deposited on the surface of ceramics using an ion blating method. However, since TiN deposited by this method is bonded in a solid state, it has poor wettability with respect to ceramics, and there are problems in that the reaction with ceramics does not proceed and the interfacial strength is low. For this reason, a homogeneous bonded body with sufficiently high bonding strength between ceramic and metal has not yet been developed.

Therefore, an object of the present invention is to solve the problems of the prior art described above and to provide a joined body of a ceramic member and a metal member having a clean, homogeneous and strong joint surface.

In order to solve the problems, the inventors of the present invention have completed the present invention as a result of repeated various experiments and studies in view of the above-mentioned problems of bonding ceramics and metals in the prior art.

According to the present invention, a joined body of a ceramic member and a metal member, the ceramic member and the metal member are
The A layer is bonded to the ceramic member side and the metal member side via BJil, and the above A layer is formed by vapor depositing two or more metals including an active metal by physical vapor deposition, and depositing the vapor deposited metal layer above its melting point. The layer is formed by heating to a temperature of , and is interdiffused with the ceramic member, the BN is a brazing material, and the layer is bonded to the metal member and the AN. A joined body of a ceramic member and a metal member is provided.

The ceramic-metal bonded body of the present invention will be explained with reference to the attached FIG. 1. One surface of the ceramic member l is metallized to form an A layer 2.

On the other hand, 8M3 is present on the surfaces of the A layer 2 and the metal member 4. Here, AM2 is a metallized layer formed by depositing two or more metals including an active metal by a physical vapor deposition method and heating the metal layer to a temperature higher than its melting point. It is interdiffused with the BH3 on the side of the ceramic member 1 and the metal member 4 to be joined. On the other hand, BIi 13 is a brazing material and is bonded to the metal member 4 and A12.

The brazing material forming the layer 3 is preferably Au--Cu brazing material.

The melting point of the vapor deposited metal of the A layer 2 is preferably 1600°C or less, and by setting the melting point to such a low temperature, it is possible to heat the vapor deposited metal and join the ceramic member 1 to the metal member 4. The heating temperature can be lowered. Therefore, damage to the ceramic member 1 can be prevented and a strong bonded member can be obtained.

Furthermore, according to an aspect of the present invention, the ceramic member 1 is
Ceramics such as oxides, carbides, borides, nitrides or composites thereof, while active metals include Ti,
Preferably, it is NiXZr, Fe, Nb, W, Mo, T1 or A1.

Further, the two types of metals constituting the A layer 2 are formed by laminated deposition or composite deposition using a physical vapor deposition method such as an ion blasting method or a sputtering method, and the heat treatment is preferably performed under vacuum. Here, composite deposition refers to simultaneously depositing different metals or depositing an alloy of different metals.

Furthermore, when joining metallized JiA ceramic members via a brazing material, it is preferable to perform the joining under vacuum.

(2) The characteristics of the joined body of the ceramic member and metal member of the present invention will be explained in more detail.

First, in order to produce a joined body of a ceramic member and a metal member of the present invention, two or more metals including an active metal are vapor-deposited on the surface of the ceramic member by a physical vapor deposition method such as an ion blasting method or a sputtering method. The active metal is brought into contact with the ceramic in a highly active state. This increases the reactivity as much as possible by bringing the active metal into contact with the ceramic in a pure state (that is, in a state of high purity and free from corrosion such as oxidation), while at the same time having an adverse effect on the interface between the ceramic member and the A layer. This is to suppress the generation of oxides etc. that cause

For example, when using Ti as the active metal, Ti01
The generation of TiO□ is a major cause of a decrease in the strength of the interface, but the physical vapor deposition method suppresses their generation and allows the active metal to be vapor-deposited in a highly active state in a clean and homogeneous state.

Further, in the present invention, two or more metals including an active metal are deposited to form the AM. This forms a layer of two or more metals, and when heated, these metals form a eutectic alloy,
This is because the melting point is significantly lowered. In other words, as in the prior art, the active metal alone has a very high melting point, and when heated and melted, the temperature becomes high and there is a risk of damaging the ceramic, but in the case of the present invention, the A layer, which is the vapor deposited layer, can be heated even at a low temperature. Since it can be melted, there is no damage to the ceramics.

Therefore, in a preferred embodiment of the present invention, the melting point of the entire metal constituting AJi is set to 1600°C or less. Two or more types of metals may be laminated one after another, or may be compositely deposited at the same time.

Composite deposition refers to simultaneously depositing different metals or alloys of different metals.

Next, the vapor-deposited AlW made of two or more metals is heat-treated at a temperature higher than its melting point, and reacts with the ceramic member in a molten state. This is because by bringing the metal layer into contact with the ceramic in a molten state, the wettability of the metal improves, the contact area between the ceramic and the active metal increases, and the activity of the active metal can be utilized to the maximum. This is because a strong reaction layer can be formed on ceramics. In this way, wettability with respect to ceramics is improved compared to reacting in a solid state, and the reactivity of the active metal can be maximized due to the synergistic effect of forming a metal layer by physical vapor deposition. In addition, since the deposited metal is melted and heated, it becomes a molten liquid and reacts uniformly with the ceramic, making it possible to obtain a stable interfacial strength without variation.

Furthermore, it is preferable to carry out the heating and melting treatment under vacuum because the activity of the active metal is not impaired and a bonding interface with even higher strength can be obtained.

The heat treatment temperature for these metal layers is preferably 1600'C or less in order to control excessive reaction of the active metal and to prevent deterioration of the ceramic itself. The metal group to be deposited is selected so that the temperature is 1600°C or less.

Next, the brazing material forming the B layer will be explained. The brazing material of the B layer is preferably a soft brazing material having plastic deformability. By interposing the wax material in this manner, the thermal stress caused by the difference in thermal expansion coefficient between the ceramic member and the metal member during bonding is alleviated and absorbed, and the bonding strength is significantly improved. Moreover, since it is a brazing material, it is soft and compatible with metals, making it easy to join with metals and having high strength and reliability.

Furthermore, it is preferable to bond the metallized layer A of the ceramic member to the metal member via the brazing material under vacuum.

This is because the interface with the ceramic produced by the active metal is less likely to be corroded by the atmosphere, resulting in a bond with even higher strength.

As explained above, highly reactive metal layers and ceramics can be strongly bonded, and metals can also be bonded with almost no influence of thermal stress, so the bonding process is easy and a bond with high bonding strength can be achieved. You get a body.

Hereinafter, the present invention will be explained with reference to Examples, but these Examples are merely illustrative of the present invention, and of course do not limit the technical scope of the present invention.

Scrap open earth with dimensions of 10 x 10 x 20 dragons, purity 99%
The surface of the I202 ceramic was cleaned, and Nb and Ni were deposited in layers of 1 μm each using an ion blating device. The evaporation conditions at this time were a degree of vacuum of 5 x 1
It was 0-'Torr. The melting point of these laminated metal layers was 1280°C.

Regarding the obtained specimen, the temperature is higher than the melting point from 500'C.
The metallized A layer was formed by heat treatment at various temperatures up to 600°C. Next, it was bonded to 345C steel at 850'C using a Heg-Cu brazing material (BAg-80 material). Process the joined body into a 3 x 4 x 40m shape, and
The joint strength was evaluated using the point bending method. The results are shown in Table 1.

As shown in Table 1, the melting point of AJli's vapor deposited metal is 1.
When heat treated at a temperature below 280°C, the bonding strength is extremely low. On the other hand, when heat-treated at a temperature higher than the melting point of layer A according to the present invention, layer A is firmly bonded to the ceramic member, resulting in a high strength bonded body as a whole. However, when the heat treatment temperature of layer A becomes high, the quality of the ceramic changes and the strength rapidly decreases.

A ZrO2 ceramic member having dimensions of 110×10×20 and partially stabilized by adding Y z O:I was cleaned, and Zr5Cu was deposited in a layer of 0.5 μm each using an ion blasting device. The evaporation conditions at this time were a vacuum level of 5 x 10-'Torr and a substrate temperature of 500°C.
℃1 Zr vapor deposition intensity was 5.0 people/sec, Cu vapor deposition intensity was 20 people/sec, and ionization was performed by high frequency. The melting point of the metal layer thus laminated was 990°C.

Regarding the obtained specimen, the temperature is higher than the melting point from 500'C.
Heat treatments were carried out at various temperatures ranging up to 600°C.

After treatment, some of the specimens were heated to 345 Cf by holding them at 1000°C for 10 minutes through Ag-Cu brazing material and the other parts as they were.
! It was joined with I. Each specimen obtained was divided into 3 x 4
It was processed into a shape of x40mm, and the bonding strength was evaluated by a four-point bending method. The results are shown in Table 2.

Table 2 As shown in Table 2, the melting point of AJil's vapor deposited metal is 9
If the heat treatment is performed at a temperature below 90°C, the bonding strength will be extremely low regardless of whether or not a brazing material is used.

On the other hand, when heat treated at a temperature equal to or higher than the melting point of layer A according to the present invention, AJil is firmly bonded to the ceramic member, and when a brazing material is interposed, a high-strength bonded body is obtained as a whole. However, when the heat treatment temperature of layer A becomes high, the quality of the ceramic changes and the strength rapidly decreases. In addition, when no brazing material was used, the ZrO2 side broke during cooling due to thermal stress.

A pressureless sintered SiC ceramic containing Chisel Kaiyu B is cleaned, and Mo is removed by a magnetron sputtering device.
1. czm and sic were each deposited in layers to a thickness of 2.0 μm. After that, it was heat-treated at 1500° C. under vacuum and then joined to heat-resistant 5US310S under vacuum with or without intervening Cu-Ag brazing material. The resulting joined body was processed into a size of 3 x 4 x 4 (ha) and evaluated for bending strength (4-point bending).The bending strength of the joined body using Ag-Cu brazing material was 22 g/mm. On the other hand, those joined without using the Ag-Cu brazing material showed a strength of only 2.5 Kg/mm''.

Composite vapor deposition of Fe:Si=1:1 (weight ratio) alloy with a film thickness of 1.0 μm was performed on the surface of a Tsinhu Yan clay AIN ceramic substrate using an ion-blating device.

The melting point of these vapor deposited metal layers was measured to be 1250'c.
Therefore, heat treatment was performed at 1350°C for 10 minutes under vacuum.

Thereafter, when the Cu radiation fins were bonded using Ag-Cu brazing material, a strong bonded body was obtained, and the bonded portion remained good even after a long heat cycle.

Furthermore, as explained above, the ceramic-metal bonded body of the present invention exhibits significantly higher strength and a more homogeneous bonded state than those of the prior art.

Therefore, the ceramic-metal bonded body of the present invention is an excellent composite member that has both the properties of ceramic itself, which is excellent in heat resistance and abrasion resistance, and the excellent properties such as lightness of metal, and its uses are as follows. It spans a wide range of fields including ceramic electronic parts, structural parts, and engine parts (turbochargers, engine piston heads, lock arms, engine cylinders), etc.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a ceramic-metal bonded body according to the present invention. (Main reference numbers) 1...Ceramics member, 2...AF! (metallized surface), 3... B layer (brazing material), 4... metal member

Claims (5)

[Claims] (1) A joined body of a ceramic member and a metal member,
These ceramic members and metal members are bonded through layer A on the ceramic member side and layer B on the metal member side, and the above layer A is coated with two or more metals including active metals by physical vapor deposition. It is a layer that is formed by vapor depositing and heating the vapor deposited metal layer to a temperature above its melting point, and is interdiffused with the ceramic member, and the layer B is a brazing material, and the metal member and the A A joined body of a ceramic member and a metal member, characterized in that the layer is bonded to another layer. (2) The joined body of a ceramic member and a metal member according to claim 1, wherein the brazing material of the B layer is an Ag-Cu brazing material. (3) Claim 1 or 2, characterized in that the vapor-deposited metal of layer A has a melting point of 1600°C or less.
A joined body of a ceramic member and a metal member as described in 2. (4) Claims 1 to 5, characterized in that the layer A is formed by laminated vapor deposition of two or more metals.
A joined body of a ceramic member and a metal member according to any one of the above items. (5) Claims 1 to 5, characterized in that the layer A is formed by composite vapor deposition of two or more metals.
A joined body of a ceramic member and a metal member according to any one of the above items.