JPH08245275A - Production of laminated brazing filler metal and joining method - Google Patents

Abstract

PURPOSE: To produce a laminated brazing filler metal fit to join a ceramic part to a metallic part and capable of improving bonding strength and airtight joinability. CONSTITUTION: This laminated brazing filler metal is produced through a lst process in which a sheet (A) of a principal constituent component selected from among Ag, Cu, AgCu, AgCuIn, AgCuSn, AgCuZn, AgCuCd and CuMn is prepd. in 30-2,000μm thickness, a 2nd process in which a sheet (B) of an active metallic component selected from among Ti, AgTi, CuTi and AgCuTi is prepd. in 1-100μm thickness, a 3rd process in which the sheets A, B are put in a blanking die and a 4th process in which the sheets A, B are blanked and integrated at the same time to form a chip AB of a laminated brazing filler metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to, for example, a vacuum valve,
The present invention relates to a method for producing a composite brazing material for joining a ceramic part [X] and a metal part [Y], which is used for either a thyristor valve or an electron tube. The present invention relates to an improved method for producing a composite brazing material and a joining method for joining a ceramic part [X] and a metal part [Y], and more particularly to a joining method in which an active metal component is used to improve joining strength and airtight joining property.

[0002]

2. Description of the Related Art Ceramics have excellent heat resistance, electrical insulation, airtightness, etc., and are utilized as various electric component materials by taking advantage of their characteristics. For example, in vacuum valves, magnetron tubes, and other electronic tubes for communication and electric power, in order to maintain a vacuum inside the ceramic insulating container, it is necessary to maintain airtightness strictly for a long period of time. In this case, it is indispensable to satisfy both the bonding strength and the airtight bonding property.

Conventionally, when a ceramic insulating container (ceramic part [X]) and a sealing metal (metal part [Y]) are joined via a silver brazing material, a metallized layer (eg, a metallized layer) is previously formed on the end face of the ceramic member. It is general that Mo-Mn) is applied and silver brazing is performed through the metallized layer.

That is, as a method of joining ceramics, a method of first applying Mo--Mn metallizing to a ceramic member and then brazing and joining to a metal is used. The following methods are known as general metallizing methods.

(1): A method in which a powder containing Mo or W as a main component is applied to the surface of a ceramic base material and heated at 1400 to 1700 ° C. in a reducing atmosphere to react with the ceramic base material for metallization. If necessary, Ni or the like is plated on the metallized layer.

(2): A method of arranging Au or Pt on the surface of the ceramic base material and heating them while applying pressure to metallize them. (3): A method in which a transition metal such as Ni or Cu, which is an active metal such as Ti or Zr, is arranged on a ceramic base material, and is heat-treated at a temperature higher than the melting point of those alloys to perform metalizing (Japanese Patent Laid-Open Publication No. Sho. 56-163093).

Conventionally, as a brazing material using an active metal such as Ti, several percent of the brazing material containing Ag and Cu as main components is used.
A brazing material in which Ti is uniformly added is known. However, in such an active metal solder, since Ti is uniformly dispersed, the proportion of reaction with the ceramic is small and the bonding strength is small. Therefore, rolling of an Ag-Cu plate and a Ti foil has been attempted, but it is difficult to uniformly integrate the Ti and Ag-Cu brazing filler metals due to the difference in ductility. In addition, a paste of Ti powder was used as Ag-C.
Methods have also been attempted in which the u solder material is applied to one side and then joined to the ceramic.

[0008]

SUMMARY OF THE INVENTION The above-mentioned conventional (1)
The method (1) has a problem in a complicated process such as requiring treatment at a high temperature during metalizing. Even a slight variation in the processing conditions makes it difficult to obtain sufficient bonding strength, and variations in strength occur. In particular, the problem of variation is the decrease in airtightness,
Due to the decrease in the bonding strength, it will seriously affect the transmission performance, transmission performance, and reception performance of various electron tubes, and the long-term reliability reliability of vacuum valves and thyristor valves.

Further, in the conventional method (2), since an expensive precious metal is used, there is a problem in economic efficiency and high pressure is required for the purpose of enhancing adhesion, which is not preferable. There is also a problem in productivity (a pressurizing part for obtaining pressure occupies a certain space in the brazing furnace).

On the other hand, in the conventional method (3), since the active metal wets the ceramic base material, almost no special pressurization is required, and the effect of the active metal provides a strong adhesion to the ceramic base material. Now you can metallize.

However, when the metal member and the ceramic member are sufficiently overlapped with each other, the silver brazing shows good bonding, but there is a very small gap between the metal member and the ceramic member, and there is a sufficient gap. If there is a non-overlapping portion, the metallization may not be performed well, and there is a problem in airtight bonding.

As described above, the above-mentioned conventional (1),
In any of the methods (2) and (3), after metallizing, the ceramic insulating container (ceramic part [X]) and the sealing metal (metal part [Y]) are brazed. Therefore, the process is complicated, and either one or both of the bonding strength and the airtight bonding property becomes a problem.

Thus, the above-mentioned conventional (1), (2),
In the method (3), the metallizing step, the ceramic insulating container, and the sealing metal (ceramic part [X] and metal part [Y]) need to be performed separately, which is a drawback that the process is complicated. is there. Therefore, it is possible to change the metal to a ceramic (metal part [Y] without performing the above metalizing in advance.
A technique for brazing a ceramic part [X]) has come to be studied.

Therefore, the following one-step joining method has been proposed as a method for joining the ceramic member, the metal member (ceramic portion [X]) and (metal portion [Y] without metalizing in advance. (Japanese Patent Laid-Open No. 59-
No. 32628).

That is, an Ag brazing material containing Ti and / or Zr as an active metal is used (it is inserted between a metal member and a ceramic member and joined). Alternatively,
Ag laminated with the thin plate of the active metal and the Ag brazing material
A brazing material is used (this is inserted between the metal member and the ceramic member and bonded).

Since this one-step joining method does not require metallizing, the process can be simplified. However, even in the case of this one-step joining method, the above (3)
If the Ag brazing material is not sufficiently adhered to the metal member or the ceramic member, especially the ceramic member, the same phenomenon as that observed in (3) may not be obtained in some cases. In order to obtain sufficient adhesion, it is necessary to correct the non-uniformity of the pressing force, and there is a problem that a strong pressurization is required.

As a technique for improving this drawback, in Japanese Patent Laid-Open No. 63-49758, an active metal Ti or / and Zr powder is used as a means for obtaining non-uniformity of pressing force, and this is used as a ceramic member surface. We are proposing a technology to apply to. By pulverizing the active metal, Ti and / or Zr are evenly distributed and closely adhered to the ceramic member, so that a bonding state having both bonding strength and airtight bonding property is obtained.

However, the conventional method has the following serious problems. (A) If there is a very small gap between the metal member and the ceramic member described above, or if there is a portion that does not sufficiently overlap with each other, good metallization cannot be achieved.

(B) When the active metal Ti or / and Zr powder is applied to the surface of the ceramic member coated with a binder such as polyvinyl alcohol or ethyl cellulose, the active metal powder is treated with an organic solvent such as ethanol or tetralin. Since the paste is in a paste state, there are problems such as environmental problems due to these binders and organic solvents.

However, when this paste is used, the organic solvent and the binder, which are the constituent materials of the paste, are decomposed in the heating step for bonding in a vacuum atmosphere, and a good bonding atmosphere cannot be obtained. There is a problem that the solvent and the binder have an adverse effect on the environment.

Further, a method of depositing Ti on one surface of an Ag-Cu brazing material by vapor deposition or the like has been attempted, but it takes a long time to obtain a uniform Ti layer over a wide area, and it is industrially necessary. Does not match.

As described above, in the brazing material using active metal Ti, it is preferable that a large amount of Ti is present on the joint surface with the ceramic. Regarding the method of forming the Ti layer on one surface of the brazing material containing Ag and Cu as the main components, there is room for improvement in terms of reliability, environmental aspects, economical efficiency, and the like.

Therefore, the first object of the present invention is to improve the bonding strength and airtight bonding property, and to form a uniform Ti layer over a wide range without forming all the metal parts in the laminated and roll shapes. It is an object of the present invention to provide a method for producing a composite brazing material for joining a ceramic part [X] and a metal part [Y] that can be obtained at low cost. The second object of the present invention is to
It is an object of the present invention to provide a method for joining a ceramic part [X] and a metal part [Y] capable of improving the bonding strength and airtightness.

[0024]

In order to achieve the above object, the invention corresponding to any one of claims 1 to 18 is configured as follows. That is, claim 1
The invention corresponding to, is a method for manufacturing a composite brazing material for joining a ceramic part [X] and a metal part [Y], wherein Ag, Cu, A having a plate thickness or line thickness of 30 to 2000 μm.
gCu, AgCuln, AgCuSn, AgCuZn,
First step of preparing one main constituent plate or wire [A] selected from AgCuCd, CuMn, and Ti, AgTi, CuT having a plate thickness or wire thickness of 1 to 100 μm
i, a second step of preparing one active metal component plate [B] selected from AgCuTi, and the main component plate or wire [A] and the active metal component plate or wire [B] into a punching mold. A third step of introducing and a fourth step of producing a composite brazing material piece [AB] in which the main constituent component plate or wire [A] and the active metal component plate or wire [B] are punched and integrated at the same time.
And a step for sequentially performing the first to fourth steps, which is a method for producing a composite brazing material.

In the invention corresponding to claim 2, in the third step, a main component plate or wire [A] and an active metal component plate or wire [B] are preliminarily overlapped with each other to form a punching die. The method for producing a composite brazing material according to claim 1, wherein the method is a method for producing a composite brazing material.

In the invention corresponding to claim 3, in the third step, the main constituent plate or wire [A], the active metal component plate or wire [B], and the brazing material plate are preliminarily out of order. 2. The method for producing a composite brazing material according to claim 1, wherein the composite brazing material is introduced into a punching die after being superposed.

In the invention corresponding to claim 4, the main constituent plate or wire [A] is Cu clad Ag, Ag clad Cu, Cu clad AgCu, AgCu clad C.
u, Cu clad AgCuln, Cu clad AgCu
It is one selected from Sn and Cu clad CuMn, It is a manufacturing method of the composite brazing material according to any one of claims 1 to 3 characterized by things.

In the invention corresponding to claim 5, the main constituent component plate or wire [A] is sufficiently softened by heat treatment before the third step with the active metal component plate or wire [B]. It is a thing, It is a manufacturing method of the composite brazing material in any one of Claims 1-4 characterized by the above-mentioned.

In the invention corresponding to claim 6, the surface roughness of the active metal component plate or wire [B] is almost equal to that of the main component plate or wire [A], and 0.1 to 30 μm.
6. The composite according to claim 1, wherein the composite has a surface roughness in the range of m (however, [A] plate thickness μm or line thickness μm> [B] surface roughness μm). It is a method of manufacturing a brazing material.

In the invention corresponding to claim 7, before the third step, a heat treatment is performed to improve the adhesion between the main textural component plate or wire [A] and the active metal component plate or wire [B]. The method for producing a composite brazing material according to any one of claims 1 to 6, wherein:

The invention corresponding to claim 8 is a brazing material,
A method of manufacturing a composite brazing material, characterized in that an active metal foil and a diffusion preventing material are laminated in the same order and then heat-treated to integrate the brazing material and the metal foil.

The invention corresponding to claim 9 is a brazing material,
A method for producing a composite brazing material, characterized in that an active metal foil and a diffusion preventing material are wound in a roll shape and then heat-treated to integrate the brazing material and the metal foil.

In the invention corresponding to claim 10, the brazing material is Cu, Ag--Cu, two layers of Cu and Ag--Cu, and A
10. The method for producing a composite brazing material according to claim 8 or 9, wherein the composite brazing material is g-Cu-In.

The invention corresponding to claim 11 is characterized in that the active metal foil is Ti.
It is a method for manufacturing the described composite brazing material. The invention corresponding to claim 12 is the method for producing a composite brazing material according to claim 8 or 9, wherein the heat treatment temperature is 880 ° C or lower.

The invention according to claim 13 is characterized in that the atmosphere for the heat treatment is a vacuum atmosphere having a pressure of 10 ^-1 Pa or less, and the production of the composite brazing material according to claim 8 or claim 9. Is the way.

The invention corresponding to claim 14 is characterized in that the diffusion preventing material is at least one of Al ₂ O ₃ powder and paper, and the composite brazing material according to claim 8 or 9. Is a manufacturing method.

According to a fifteenth aspect of the present invention, in the method of joining the ceramic portion [X] and the metal portion [Y], Ag, Cu, AgC having a plate thickness or line thickness of 30 to 2000 μm is used.
u, AgCuln, AgCuSn, AgCuZn, Ag
The first step of preparing one main component plate or wire [A] selected from CuCd and CuMn, and Ti, AgTi, CuTi having a plate thickness or wire thickness of 1 to 100 μm,
The second step of preparing one active metal component plate [B] selected from AgCuTi, and introducing the main component plate or wire [A] and the active metal component plate or wire [B] into the punching die. Third step and fourth step of producing a composite brazing material piece [AB] in which the main component plate or wire [A] and the active metal component plate or wire [B] are punched and integrated at the same time
And the active metal component [B] surface of the composite brazing material piece [AB] so as to face and face the surface to be bonded [X] of the ceramic part, and if necessary, to bond the metal part. A ceramic part [X] including a fifth step of placing a brazing material between the surface [Y] and heating and melting the brazing material, and sequentially performing the first to fifth steps. ] And the metal part [Y].

According to a sixteenth aspect of the present invention, in the method of joining the ceramic portion [X] and the metal portion [Y], Ag, Cu, AgC having a plate thickness or a wire thickness of 30 to 2000 μm is used.
u, AgCuln, AgCuSn, AgCuZn, Ag
The first step of preparing one main component plate or wire [A] selected from CuCd and CuMn, and Ti, AgTi, CuTi having a plate thickness or wire thickness of 1 to 100 μm,
The second step of preparing one active metal component plate [B] selected from AgCuTi, and introducing the main component plate or wire [A] and the active metal component plate or wire [B] into the punching die. Third step and fourth step of producing a composite brazing material piece [AB] in which the main component plate or wire [A] and the active metal component plate or wire [B] are punched and integrated at the same time
And the surface of the active metal component [B] of the composite brazing material piece [AB] so as to face the surface of the metal part to be joined [Y], and the surface of the ceramic part to be joined [B]. X]] and a heating and melting step of arranging a brazing material between the first and fifth steps, and the first to fifth steps are sequentially performed.
And a metal part [Y].

The invention according to claim 17 is characterized in that the fifth step is carried out in a vacuum atmosphere or a non-oxidizing atmosphere, and the ceramic portion [X] according to claim 15 or 16. And a metal part [Y].

According to the eighteenth aspect of the present invention, the ceramic portion [X] is an alumina cylindrical tube having a desired electrode inside, and the metal portion [Y] is a Fe—Ni, F sealing material.
It is an e-Co alloy, It is characterized by the above-mentioned.
The method for joining the ceramic part [X] and the metal part [Y] described in any one of 1.

[0041]

According to the invention described in any one of claims 1 to 7, the following effects can be obtained. That is,
In a method of manufacturing a composite brazing material for joining a ceramics part [X] and a metal part [Y], a main component plate or wire [A] and an active metal component plate or wire [B] are punched and simultaneously molded integrally. A composite brazing material piece [AB] is produced.

Therefore, AgC containing a conventional active metal component is used.
Compared with the method using the u alloy as a brazing material, the contact state of the active metal component with the ceramic joint is improved, and the joint strength and airtight joint property are improved. Further, as compared with the method of directly depositing the active metal powder on the ceramic bonded portion, the handling problem of fine powder and solvent is released and the simplicity is improved.

According to the invention described in any one of claims 15 to 18, the following operational effects can be obtained. In the method of joining the ceramic part [X] and the metal part [Y], the surface of the active metal component [B] of the composite brazing material piece [AB] is brought into contact with the surface to be joined [X] of the ceramic part. After interposing and placing a known brazing material between the surface to be joined [Y] of the metal part as necessary, the ceramic part [X] and the metal part [Y] that have been heat-bonded are joined together. There is. Therefore, in the joining of the ceramic part [Y] and the metal part [Y], there is no problem of the active metal component powder falling off from the ceramic part [X].

As described above, in the joining method, this composite brazing material plate is brought into contact with the ceramic portion [X] to perform the heat joining treatment. This is a mere contact placement, and the point that metallizing treatment is not performed in particular, that is, the pre-formed composite brazing material piece [AB] is heated at a high temperature like the conventional Mo-Mn method. In that it is not a metallized layer that requires processing,
The content, function and effect are different from the conventional metal / ceramic bonding technology.

The advantages of the method for producing the composite brazing material of the present invention and the joining method using the same will be described. (1) In the conventional screen printing method, a mesh is placed on the adhered surface of the ceramic part [X], and the active metal powder is printed and adhered onto the mesh by mainly utilizing the adhesive force of the binder. This technology is widely used from the viewpoint of simplicity and economy, but it is still not perfect for products that place importance on not only bonding strength but also airtightness, such as electron tubes, power tubes such as thyristor valves, and vacuum valves. Is not solved by
In particular, the airtightness characteristics vary.

That is, the conventional screen printing method is
(B) Since the original mesh is used, the adhesion state (deposition amount and distribution) of the active metal powder on the adherend surface should be uniform, but on the adherend surface nevertheless In the distribution state of active metal powder in the non-uniformity is recognized,
(B) In the conventional screen method, the adhesive force between the active metal powder and the metal part [Y] uses the adhesive force of the binder and the adhered state, so that the thermal decomposition of the binder is performed. The time and the degree of thermal decomposition affect the extent of the active metal falling out of the ceramic part [X], and the bonding strength and hermetic bonding depend on the distribution of the active metal and the dispersion of the distribution density. I understood.

In the fields of application and products using the conventional metal / ceramic bonding technology by the active metal method, it was sufficient to attach particular importance to the bonding strength. That is, in the conventional active metal method, it is not necessary to recognize that the present invention aims to achieve both the target bonding strength and the airtight bonding property, and no attention has been paid at all. Simply, the active metal powder is simply attached through the mesh. , Printing was enough.

On the other hand, in the case of the application purpose such as the electron tube, the power tube, and the vacuum valve in which the airtightness as well as the bonding strength is important, a large amount of the adhesive substance or the organic solvent as in the conventional screen method is used. It is extremely important to develop a technology that can optimize the state of adhesion between the active metal powder and the metal part [Y] while limiting the use so that the active metal powder does not fall off before the brazing process. I found that.

(2) When a problem occurs in the airtightness, such as the vacuum level immediately after the airtight bonding by the active metal method, a vacuum leak problem, and a decrease in the vacuum level after a long period of time, the cause is the metal part of the active metal. Segregation is observed in the state of adhesion to [Y], that is, the amount of adhesion and the distribution state of adhesion. However, the bonding strength at this time tends to show a sufficient value if the amount of the active metal is a sufficient amount.

That is, when the active metal adhesion state was within the range of the predetermined conditions, a very stable airtight property was exhibited.
As a cause of this, the distribution of the active metal [A] on the adhered surface tended to be extremely uniformly dispersed over the entire adhered surface.
At this time, the bonding strength between the ceramic container and the metal lid body also showed a sufficient value if the amount of the active metal deposited was sufficient.

Even when the coating was carried out through the mesh, the active metal powder was satisfactorily present in the corners of the mesh. For example, in the airtight joining of a ceramic container of a vacuum valve and a metal lid, the strength of the joining can be easily secured by controlling the deposition amount of the active metal. It depends on the segregation state represented by the deposition distribution rather than the deposition amount. In this way, there is a close correlation between the deposition state of the active metal on the metal part [Y] and the airtight property, and the life and electrical characteristics of electron tubes, power tubes such as thyristor valves, vacuum valves, etc. Have an impact.

(3) Ceramic insulating containers (ceramic members) such as electron tubes, power tubes such as thyristor valves, and vacuum circuit breakers vary in size (outer diameter, inner diameter) and their heights are also indefinite. Therefore, there are many technical problems in quality control. Therefore, the conventional active metal bonding method has many disadvantages when it is applied to ceramic members having different sizes and shapes. For example, brazing is performed on the end face of the ceramic insulating container having a thickness of 30 to 1000 mm and a thickness of the ceramic cylinder of 5 mm or less. In this case, workability at the time of depositing an active metal such as Ti, Zr, Cr, and Hf powder on the joined surface of the end face of the ceramic insulating container and nonuniformity of the metalizing layer are problems.

With respect to these problems, in the invention according to any one of claims 1 to 7, in the production of the composite brazing material plate for joining the ceramic part [X] and the metal part [Y], A method for producing a composite brazing material piece [AB] by punching the predetermined main constituent component plate [A] and the predetermined active metal component plate [B] in an overlapping state and simultaneously molding and integrating them. I am collecting. Therefore, as compared with the conventional method of using an AgCu alloy containing an active metal component as a brazing material, the contact state of the active metal component with the portion to be joined to the ceramic is improved, and the joining strength and airtight joining property are improved.
Further, as compared with the method of directly depositing the active metal powder on the ceramic bonded portion, the handling problem of fine powder and solvent is released and the simplicity is improved. By utilizing the active metal component plate [B] as described above, it is possible to obtain a ceramic insulating container (ceramic member) having good airtightness and bonding strength while avoiding the above-mentioned variations and nonuniformities.

(4) In the conventional method of depositing the active metal powder on the adhered portion (ceramics portion [X], metal portion [Y]),
In some cases, the adhesion strength of Ti, Zr, Cr, Hf, etc., is not sufficient just by applying them, and heat treatment for metalizing was inevitably required. On the other hand, in the state where the main component plate [A] and the predetermined active metal component plate [B] are superposed, both are punched and simultaneously molded and integrated to make a composite brazing material piece [AB]. In the fourth step of the production method of the present invention, since the metal part [Y] is uniformly and sufficiently conformed and adheres well, it is characterized in that it is uniformly attached and dispersed on the entire surface to be adhered. As a result, it has a characteristic that good airtightness and bonding strength can be obtained without heat treatment for metallization. If there is a demand to make it even more familiar, the third
Before the step, either or both of the main component plate [A] and the active metal component plate [B] may be softened.

(5) In the manufacturing method of the present invention, the active metal component plate [B] such as Ti has a thickness of 0.001 to 0.1 mm (1 to
It is necessary to have a plate thickness of 100 μm). When the plate thickness is 0.001 mm or less, the main component plate [A] and the active metal component plate [B] are superposed on each other, and the active metal component plate [B] in the third step is introduced into the punching die. ] Not only becomes technically difficult in terms of handling but becomes inefficient, and when the main component plate [A] and the active metal component plate [B] are punched out after the third step. Even in the fourth step of simultaneously forming and integrally forming the composite brazing material piece [AB], the disadvantage that the active metal component plate [B] has many fractured portions is not noticeable.

When the plate thickness is 0.1 mm or more, an excessive amount of active metal is supplied to the joint, which not only contributes to the generation of huge holes near the joint after the joint but also causes the joint to become large. The supply of an excessive amount of active metal to the alloy causes a high melting point due to the progress of alloying with the main component plate [A] during the bonding heat treatment, which also contributes to the occurrence of defective bonding.

Furthermore, the surface roughness of the active metal component plate [B] is preferably equal to or less than that of the main component plate [A], and it is necessary that the surface roughness is in the range of 0.1 to 30 μm. That is, when the surface roughness is 0.1 μm or less, the main component plate [A] and the active metal component plate [B] are separated from each other in the fourth step of forming and integrating the composite brazing material pieces [AB]. With respect to the improvement of the adhesiveness, not only does it show a negative tendency but also the economic efficiency becomes negative, which can be said to be an excessive surface state of the active metal component. On the other hand, the surface roughness is 30
If the thickness is more than μm, the degree of adhesion (adhesion strength, adhesion density, etc.) of the active metal component to the ceramic part [X] will be in a coarse and dense state, and as a result, it will be one of the causes of variations in joining strength and airtight joining property. .

(6) As a representative brazing material, 779 ° C.
Eutectic silver brazing material (72 wt% Ag-Cu)
Alloy) is known. Also in one embodiment of the joining of the method of the present invention, for example, a Ti active metal plate is punched on one surface (both sides are acceptable) of a plate-shaped eutectic silver brazing plate having a thickness of 0.1 mm, and at the same time, a composite is formed. Uses wax material.

According to the invention described in any of claims 8 to 14, the following operational effects can be obtained. As mentioned above, in order to bond ceramics and metal,
It is preferable to use a brazing material having a large amount of Ti at the bonding interface. As a method for forming a Ti layer on one surface of a brazing material containing Ag-Cu as a main component, a paste method, a vapor deposition method, or the like has been studied. However, there were problems such as reliability, environmental aspects, and economical efficiency. However, it has become possible to obtain a uniform Ti layer by thermal diffusion as in the method of the present invention.
Although joining dissimilar metals by thermal diffusion is a known technique, a feature of the present invention is to introduce a diffusion prevention layer. This makes it possible to obtain a uniform Ti layer over a wide range at low cost even if the metal parts are not integrated as a laminated or roll shape, and it is possible to manufacture a brazing material for bonding a ceramic and a metal. is there.

[0060]

Hereinafter, embodiments of the present invention will be described.
First, the evaluation conditions of the composite brazing material obtained by the method of the present invention will be described below. The detachment force of the metal / ceramic bonding portion of the ceramic insulating container after the hermetically sealed bonding was measured by an Instron type universal testing machine. Predetermined dimensions (outer diameter 6.7 cm, inner diameter 5.6 cm, height 10c
The tripping force of 700 kg or more when using the ceramic insulating container of m) was used as a criterion for passing.

The airtightness was evaluated by using a He leak detector, and the leak amount was 5 × 10 ⁻¹⁰ (Torr).
・ L / sec) or less was passed. The withstand voltage characteristic was evaluated by measuring the withstand voltage characteristic when an impulse voltage of 0 to 120 KV was applied 10 times to both ends of the ceramic insulating container after hermetically sealing and joining, and when dielectric breakdown was shown. The voltage value or the number of dielectric breakdowns was shown. Dielectric breakdown voltage value is 9
The case where the number of dielectric breakdowns was zero at 5 KV was used as a criterion for passing.

Also, the breaking performance is evaluated by the contact diameter of 42 m.
Using a vacuum valve equipped with m, 7.2kV, 12k
The rate of occurrence of re-ignition when A was interrupted 1000 times was 0.1% or less as a criterion for passing. The re-ignition occurrence rate (%) at the time of failure is also shown for reference.

<Examples 1 to 3 and Comparative Examples 1 and 2> Ceramics having an outer diameter of 6.7 cm, an inner diameter of 5.6 cm, and a height of 10 cm, which were mechanically polished to a surface roughness of the end face of about 0.5 μm. An experiment is performed in which both ends of an insulating container (main component: AL ₂ O ₃ ) are hermetically sealed with a sealing metal (Cu plating on the surface) made of 42% Ni—Fe alloy having a plate thickness of 2 mm.

As shown in Table 1, Ti was selected as the active metal component plate [B], the plate thickness was 50 μm, and the surface roughness was 0.1 μm.
m Ti plate was prepared. Ti plate is a mesh (Ti wire mesh)
It may be.

As the main constituent plate [A], a surface roughness of 0.5 μm was targeted, and a thickness of 20 to 5000 μm was changed to 72 with an outer diameter of 6.7 cm and an inner diameter of 5.6 cm.
An AgCu plate foil (a ring shape with the inside hollowed out) was prepared. The main component plate [A] may also be a wire mesh instead of a plate.

Next, the active metal plate [B] and the main component plate [A] are inserted and arranged in a punching mold, and then both are punched and integrally molded at the same time while adjusting punching conditions to form a composite brazing material piece. Obtained [AB]. The main advantage of integration is improved handling. Therefore, the strength of contact between the active metal plate [B] and the main component plate [A] may be strong or may be such that they are merely in contact with each other. Also, there is no problem with the airtight sealing function.

After the above-mentioned preparation, the Ti surface of the composite brazing material piece [AB] is located between the end portion (ceramic portion [X]) and the metal portion [Y] of the ceramic insulating container. X]] so that the composite brazing material piece [AB]
And a 72AgCu plate (main component plate [A]) were further arranged, and then assembled in such a structure.

Inside is 50% Cu-for a breaking test.
A Cr contact was mounted. The ceramic container sealed and assembled while being heated and evacuated was evaluated for hermetic bonding property and pressure resistance, and after this evaluation, a tensile test was conducted to investigate the bonding strength.

The cutoff test is performed at 7.2 k as described above.
When the occurrence rate of the re-ignition phenomenon when the V-12 kA was cut off 1000 times was 0.1% or less, it was judged as pass. The Ti plate (active metal plate [B]) reacts with the ceramic part [X] in contact with it, and is alloyed with the melted 72AgCu plate foil [A] to complete airtight adhesion.

As is clear from the experimental conditions shown in Table 1 and the experimental results shown in Table 3, a vacuum having a hermetically sealed portion of a vacuum valve using the composite brazing material piece [AB] obtained by the method of the present invention. The valve has a main component plate [A] with a plate thickness of 5
When the thickness was 0 to 2000 μm (0.05 μm to 2 mm), good bonding strength, airtight bonding and electrical characteristics were exhibited (Examples 1 to 3).

However, as in Comparative Example 1, the Ti plate (active metal plate [B]) has a surface roughness of 50 μm and a surface roughness of 0.1.
μm, and the surface roughness of the main component plate [A] is 0.5 μm
In the case of m, when the plate thickness was 20 μm (Comparative Example 1), problems occurred in all of the bonding strength, airtight bonding, and electrical characteristics. In particular, in the interruption test, two of the planned five vacuum valves could not be tested (Comparative Example 1).

The plate thickness of the main constituent plate [A] is 5000
Even in the case of μm (Comparative Example 2), problems occurred in all of the bonding strength, airtight bonding, and electrical characteristics. In particular, in the interruption test, two of the planned five vacuum valves could not be tested (Comparative Example 2). From these, the plate thickness of the main component plate [A] is preferably in the range of 50 to 2000 μm.

As a result of a cross-sectional examination in the vicinity of the bonded interface, the distribution of Ti deposition was uniform and good in Examples 1 to 3. On the other hand, in Comparative Example 1, the ratio of the amount of AgCu and the amount of Ti in the amount of Ti is too large, and the lack of the total amount of AgCu and Ti causes the active metal from the interface to the depth direction. The existence was hardly seen, the interface was not joined, and vacancies were recognized. On the contrary, in Comparative Example 2, AgCu content and Ti
It was found that the total amount was too large and that there were many segregated portions on the Ti deposition.

In the above description, the Ti surface of the composite brazing material piece [AB] is in contact with the ceramic portion [X] between the end portion (ceramic portion [X]) and the metal portion [Y] of the ceramic insulating container. Although the composite brazing material piece [AB] is arranged as described above, the Ti brazing surface of the composite brazing material piece [AB] may not be in direct contact with the ceramic portion [X].

In the above description, the Ti surface of the composite brazing material piece [AB] is in contact with the ceramic portion [X] between the end portion (ceramic portion [X]) and the metal portion [Y] of the ceramic insulating container. Place the decryption brazing material piece [AB]
Further, a 72AgCu plate (main constituent component plate [A]) is arranged. However, when the 72AgCu plate is selected as the main constituent component plate [A], this main constituent component plate [A] exhibits a bonding function. By adjusting the amount ratio of the constituent component [A] and the active metal plate [B], a known brazing material (known brazing material) [D] described later can be bonded with or without use. That is, as in Examples 15 to 16 to be described later, when Ag and Cu having a low bonding function and a simple substance of Cu are selected as the main component plate [A], a known brazing material [D] is inserted and arranged. Indispensable.

On the other hand, in the prior art of metallizing MoMn on one surface of the ceramic part [X] without using the composite brazing material piece [AB] according to the method of the present invention, metallizing at a high temperature as described above. In addition to requiring complicated steps such as treatment and heating, the bonding strength under the same conditions as the comparative examples is 680 to 1000 kg, which is inferior to the method of the present invention, and variations are observed. Further, the use of the composite brazing material piece [AB], which is the method of the present invention, also shows advantages such as improved workability in joining.

<Examples 4 to 7 and Comparative Examples 3 to 4> In the above Examples 1 to 3 and Comparative Examples 1 and 2, the active metal component plate [B] was used.
As a Ti plate having a thickness of 50 μm and a surface roughness of 5 μm, the bonding strength when the surface roughness of the active metal component plate [B] is changed to 0.01 to 100 μm,
The effects on airtightness and electrical properties were investigated.

Between the end (ceramics part [X]) and the metal part [Y] of the ceramic insulating container, the composite brazing material piece [AB] has a Ti surface in contact with the ceramics part [X]. The material piece [AB] is arranged, and a known brazing material [D] 97AgCd is inserted and arranged between the material piece [AB] and the metal portion [Y].

As is clear from the experimental conditions shown in Table 1 and the experimental results shown in Table 3, a vacuum having a hermetically sealed portion of the vacuum valve using the composite brazing material piece [AB] obtained by the method of the present invention was used. The valve has a plate thickness of the main constituent plate [A] of 20.
When the surface roughness is constant at 0 μm (2 mm), the surface roughness is about 0.
In the range of 1 to 30 μm, good joining strength, airtight joining property and electrical characteristics were exhibited (Examples 4 to 7).

However, as in Comparative Example 3, the active metal component plate [B] had a Ti plate thickness of 100 μm and a surface roughness of 0.1 μm, and the main component plate [A] had a surface roughness of 0 μm. If 0.01 μm, the bonding strength, airtight bonding,
Although it was functionally acceptable in terms of electrical characteristics, there were many economic problems in maintaining and controlling this level of surface roughness industrially, and there were variations in electrical characteristics. There is. Therefore, from the viewpoint of product stability, the case where the surface roughness of the main component plate [A] is 0.01 μm is excluded from the present invention.

On the other hand, the surface roughness of the main component plate [A] 1
When the thickness was set to 00 μm (Comparative Example 4), problems occurred in all of the bonding strength, airtight bonding, and electrical characteristics. Especially, in the shutoff test, one of the planned five vacuum valves could not be tested (Comparative Example 4). From these, the surface roughness of the main component plate [A] is preferably in the range of 0.1 to 30 μm.

Further, as a result of the cross-sectional examination in the vicinity of the bonding interface, in Examples 4 to 7 and Comparative Example 3, the Ti deposition distribution was uniform and good. On the other hand, in Comparative Example 4, the surface roughness of the main component plate [A] is too large, and the recesses are particularly likely to cause the formation of voids, and a large number of segregated portions are observed in the Ti deposition. .

<Examples 8 to 10, Comparative Examples 5 to 6> In Examples 4 to 7 and Comparative Examples 3 to 4 described above, the active metal component plate [B] has a thickness of 50 to 100 μm and a surface thereof. The influence of the plate thickness of the main component plate [A] and the surface roughness when using a Ti plate having a roughness of 0.1 μm was investigated. Here, the plate thickness of the active metal component plate [B] is investigated. 0.1 to
Bond strength, airtight bondability when changed to 1200 μm,
The influence on the electrical characteristics was investigated.

A known brazing material piece [D] 96AgIn is placed between the end (ceramic part [X]) and the metal part [Y] of the ceramic insulating container, and then the main component plate [A] 72AgCu is placed. Arrangement, then piece of composite brazing material [A
B], and a known brazing material [D] 96AgS.
n is inserted and arranged between the metal portion [Y] and the metal portion [Y].

As is clear from the experimental conditions shown in Table 1 and the experimental results shown in Table 3, a vacuum having a hermetically sealed portion of a vacuum valve using the composite brazing material piece [AB] obtained by the method of the present invention. The valve has a plate thickness of the main constituent plate [A] of 20.
The thickness of the active metal component plate [B] is 0.1 to 30 when the surface roughness is kept constant at 0 μm (2 mm) and 0.5 μm.
In μm, good bonding strength, airtight bonding and electrical characteristics were exhibited (Examples 4 to 7).

However, as in Comparative Example 5, when the plate thickness of the main component plate [A] was set to 200 μm (2 mm) and the surface roughness was fixed to 0.5 μm, the main metal component plate [B] ], The plate thickness was 0.1 μm or less (Comparative Example 5), problems occurred in both the bonding strength and the airtight bonding property. In particular, in the shutoff test, a large leak occurred in all of the five planned vacuum valves, and the test was impossible (Comparative Example 5). The plate thickness of the active metal component plate [B] is 1200 μm
In the case of (Comparative Example 6), there were problems in further lowering of bonding strength, airtight bonding, and electrical characteristics. Especially in the breaking test, a large leak occurred in 3 out of the planned 5 vacuum valves and a small leak occurred in 2 of them, and the test was stopped.
(Comparative example 6).

From these, it was found that the plate thickness of the active metal component plate [B] is preferably in the range of 1 to 200 μm. In addition, as a result of the cross-sectional examination in the vicinity of the bonding interface, in Examples 8 to 10, the Ti deposition distribution was uniform and good. On the other hand, in Comparative Example 5, the plate thickness of the active metal component plate [B] was extremely thin at 0.1 μm or less, and the ratio of the Ti amount in the {AgCu amount + Ti amount} was too small. As a cause, the existence of active metal in the depth direction from the interface was hardly seen, the interface was not joined, and vacancies were observed. On the contrary, in Comparative Example 6, since the amount of Ti was too large with respect to the amount of {AgCu + Ti}, the occurrence of non-bonding portions due to the increase in the melting temperature at the bonding interface and the occurrence of large cracks around Ti were observed. There is.

<Examples 11 to 14 and Comparative Examples 7 to 8> In Examples 8 to 10 and Comparative Examples 5 to 6 described above, the plate thickness of the main component plate [A] was 200 μm, and the surface roughness thereof was 0.5μ
The effect of the plate thickness of the active metal component plate [B] was investigated when the value was kept constant at m. Here, when the surface roughness of the active metal component plate [B] was changed to 0.01 to 100 μm. The effects on bonding strength, airtight bonding, and electrical properties were investigated.

Between the end portion (ceramics portion [X]) of the ceramic insulating container and the metal portion [Y], the composite brazing material piece [AB] is placed so that the Ti surface of the composite brazing material piece [AB] is in contact with the ceramics portion [X]. The material piece [AB] is arranged, and the known brazing material [D] 97AgZd is inserted and arranged between the material piece [AB] and the metal portion [Y].

As is clear from the experimental conditions shown in Table 2 and the experimental results shown in Table 4, a vacuum having a hermetically sealed portion of a vacuum valve using the composite brazing material piece [AB] obtained by the method of the present invention. The valve has a plate thickness of the main constituent plate [A] of 10
When the surface roughness is 0 μm (1 mm) and 0.5 μm, the surface roughness of the active metal component plate [B] is 0.1-3.
At 0 μm, good bonding strength, airtight bonding, and electrical characteristics were exhibited (Examples 11 to 14).

However, as in Comparative Example 7, after the plate thickness of the main component plate [A] was set to 100 μm (1 mm) and the surface roughness thereof was kept constant at 0.5 μm, the active metal component plate [B] was prepared. When the plate thickness is less than 0.01, it was functionally acceptable in terms of bonding strength, airtight bonding, and electrical characteristics.
To maintain and control this level of surface roughness industrially,
There are many economic problems, and there are variations in electrical characteristics. Therefore, in the present invention, from the viewpoint of product stabilization, the case where the surface roughness of the active metal component plate [B] is 0.01 μm is excluded from the present invention.

The surface roughness of the active metal component plate [B] is 100.
In the case of μm (Comparative Example 8), problems occurred in both bonding strength and airtight bonding. Especially in the breaking test, a large leak occurred in all of the planned 5 vacuum valves, and the electrical characteristic evaluation was stopped. (Comparative example 8). From these, it was found that the surface roughness of the active metal component plate [B] is preferably in the range of 0.1 to 30 μm.

<Examples 15 to 21> Examples 1 to 1 described above.
In Comparative Examples 1 to 8, 72AgCu was representatively shown as the material of the main component plate [A], but the composite material manufacturing method of the present invention is not limited to this, and Ag, C
u, 67Ag27CuIn, 68Ag27CuSn, 6
5Ag30CuZn, 65Ag30CuCd, 90Cu
Adaptation to other main component plates [A] such as Mn is also effective (Examples 15 to 21).

That is, as is clear from the experimental conditions shown in Table 3 and the experimental results shown in Table 4, the airtightly attached part of the vacuum valve using the composite brazing material piece [AB] obtained by the method of the present invention was The vacuum valve has a main component plate [A] with a plate thickness of 200 μm (2 mm) and a surface roughness of 0.5 μm.
The plate thickness of the active metal component plate [B] is 10
[mu] m and the surface roughness was kept constant at 0.5 [mu] m, good bonding strength, airtight bonding, and electrical characteristics were exhibited (Examples 15 to 21).

Further, as a result of the cross-sectional investigation in the vicinity of the bonding interface, T
The deposition distribution of i was uniform, and the presence of the active metal in the depth direction from the interface was good. In Examples 15 to 16, a known brazing material [D] 64Ag25CuPd was first placed between the end (ceramics part [X]) and the metal part [Y] of the ceramic insulating container, and then the active metal component plate. A composite brazing material piece [ABA] sandwiching [B] from the upper and lower surfaces with a main constituent plate [A] is arranged, and a known brazing material [D] 80AgCu is inserted and arranged between the metal portion [Y]. It was configured. Since Ag and Cu, which are inferior in airtight bonding function, are selected as the main component plate [A] of the composite brazing material piece [ABA], between the composite brazing material piece [ABA] and the ceramic part [X], A known brazing material [D] is inserted both between the metal part [Y] and the metal part [Y].

In Examples 17 to 21, the Ti surface of the composite brazing material piece [AB] was located between the end (ceramic part [X]) and the metal part [Y] of the ceramic insulating container, and the ceramic part [X]. ] The composite brazing material piece [AB] is arranged so as to be in contact with the above], and the known brazing material [D] 97AgZd is inserted and arranged between the metal brazing material [Y] and the known brazing material [D].

<Examples 22 to 28> Examples 1 to 2 described above.
1, Comparative Examples 1 to 8 show examples of a single metal or an alloy as a representative example of the material of the main component plate [A], but the composite material manufacturing method of the present invention is not limited to this. Cu clad Ag plate, Ag clad Cu plate, Cu clad 90AgCu plate, 90AgCu clad Cu plate,
Cu clad AgCuIn, Cu clad 90AgCu
It is also effective to apply to Sn, Cu clad 90CuMn plate and other main constituent plate [A] (Examples 22 to 2).
8).

That is, as is clear from the experimental conditions shown in Table 2 and the experimental results shown in Table 4, the air-sealed joint of the vacuum valve using the composite brazing material piece [AB] obtained by the method of the present invention was The vacuum valve has a main component plate [A] with a plate thickness of 100 μm (1 mm) and a surface roughness of 0.5 μm.
The plate thickness of the active metal component plate [B] is 10
[mu] m and the surface roughness was kept constant at 0.5 [mu] m, good bonding strength, airtight bonding, and electrical characteristics were exhibited (Examples 22 to 28).

Further, as a result of the cross-sectional investigation near the bonding interface, T
The deposition distribution of i was uniform, and the presence of the active metal in the depth direction from the interface was good. In Examples 22 to 28, first, a known brazing material [D] 64Ag25CuPd was disposed between the end (ceramics part [X]) and the metal part [Y] of the ceramic insulating container, and then the active metal component plate. A composite brazing material piece [ABA] sandwiching [B] from the upper and lower surfaces with a main constituent plate [A] is arranged, and a known brazing material [D] 80AgCu is inserted and arranged between the metal portion [Y]. It was configured.

<Examples 29 to 31> Examples 1 to 2 described above.
In Comparative Examples 1 to 8, a Ti plate was shown as a representative example of the material of the active metal component plate [B], but the composite material manufacturing method of the present invention is not limited to this, and 90 AgT
i, 80CuTi, 68Ag27CuTi (Example 29
˜31) and other active metal component plates [B] are also effective (Examples 22 to 28).

That is, as is clear from the experimental conditions shown in Table 2 and the experimental results shown in Table 4, the air-sealed attachment portion of the vacuum valve using the composite brazing material piece [AB] obtained by the method of the present invention was The vacuum valve has a main component plate [A] with a plate thickness of 100 μm (1 mm) and a surface roughness of 0.5 μm.
The plate thickness of the active metal component plate [B] is 20
[mu] m and the surface roughness was kept constant at 0.5 [mu] m, good bonding strength, airtight bonding, and electrical characteristics were exhibited (Examples 22 to 28).

Further, as a result of the cross-sectional examination near the bonding interface, T
The deposition distribution of i was uniform, and the presence of the active metal in the depth direction from the interface was good. In addition, the composite brazing material such that the Ti surface of the composite brazing material piece [AB] is in contact with the ceramics part [X] between the end (ceramics part [X]) and the metal part [Y] of the ceramic insulating container. A piece [AB] is arranged, and a known brazing material [D] 97AgCd is inserted and arranged between the piece [AB] and the metal part [Y].

According to the embodiment corresponding to any of claims 1 to 7 described above, the following operational effects can be obtained. That is, in the manufacturing method of the composite brazing material for joining the ceramic part [X] and the metal part [Y], at the same time as punching the main component plate or wire [A] and the active metal component plate or wire [B]. A composite brazing material piece [AB] which is integrally formed is manufactured.

Therefore, AgC containing a conventional active metal component is used.
Compared with the method using the u alloy as a brazing material, the contact state of the active metal component with the ceramic joint is improved, and the joint strength and airtight joint property are improved. Further, as compared with the method of directly depositing the active metal powder on the ceramic bonded portion, the handling problem of fine powder and solvent is released and the simplicity is improved.

Further, according to the embodiment corresponding to any of claims 15 to 18, the following operational effects can be obtained. In the method of joining the ceramic part [X] and the metal part [Y], the surface of the active metal component [B] of the composite brazing material piece [AB] is brought into contact with the surface to be joined [X] of the ceramic part. After interposing and placing a known brazing material between the surface to be joined [Y] of the metal part as necessary, the ceramic part [X] and the metal part [Y] that have been heat-bonded are joined together. There is. Therefore, in the joining of the ceramic part [Y] and the metal part [Y], there is no problem of the active metal component powder falling off from the ceramic part [X].

As described above, in the joining method, this composite brazing material plate is brought into contact with the ceramics portion [X] to perform the heating joining process. This is a mere contact placement, and the point that metallizing treatment is not performed in particular, that is, the pre-formed composite brazing material piece [AB] is heated at a high temperature like the conventional Mo-Mn method. In that it is not a metallized layer that requires processing,
The content, function and effect are different from the conventional metal / ceramic bonding technology.

The advantages of the method for manufacturing the composite brazing material of the above-described embodiment and the joining method using the composite brazing material made by this manufacturing method will be described. (1) In the conventional screen printing method, a mesh is placed on the adhered surface of the ceramic part [X], and the active metal powder is printed and adhered onto the mesh by mainly utilizing the adhesive force of the binder. This technology is widely used from the viewpoints of simplicity and economy, but it is still not perfect for products that place importance on not only sealing strength but also airtightness, such as electron tubes, power tubes such as thyristor valves, and vacuum valves. Is not solved by
In particular, the airtightness characteristics vary.

That is, the conventional screen printing method is
(B) Since the original mesh is used, the adhesion state (deposition amount and distribution) of the active metal powder on the adherend surface should be uniform, but on the adherend surface nevertheless In the distribution state of active metal powder in the non-uniformity is recognized,
(B) In the conventional screen method, the adhesive force between the active metal powder and the metal part [Y] uses the adhesive force of the binder and the adhered state, so that the thermal decomposition of the binder is performed. The time and the degree of thermal decomposition affect the extent of the active metal falling out of the ceramic part [X], and the bonding strength and hermetic bonding depend on the distribution of the active metal and the dispersion of the distribution density. I understood.

In the fields of application and products utilizing the conventional metal / ceramic bonding technology by the active metal method, it was sufficient to attach particular importance to the bonding strength. That is, in the conventional active metal method, it is not necessary to recognize that the present invention aims to achieve both the target bonding strength and the airtight bonding property, and no attention has been paid at all. Simply, the active metal powder is simply attached through the mesh. , Printing was enough.

On the other hand, in the case of the application purpose such as the electron tube, the power tube, and the vacuum valve in which importance is attached to not only the bonding strength but also the airtightness, a large amount of an adhesive substance or an organic solvent like the conventional screen method is used. It is extremely important to develop a technology that can optimize the state of adhesion between the active metal powder and the metal part [Y] while limiting the use so that the active metal powder does not fall off before the brazing process. I found that.

(2) When a problem occurs in the airtightness such as a vacuum level immediately after airtight bonding by the active metal method, a vacuum leak problem, and a decrease in the vacuum level after a long period of time, the cause is the metal part of the active metal. Segregation is observed in the state of adhesion to [Y], that is, the amount of adhesion and the distribution state of adhesion. However, the bonding strength at this time tends to show a sufficient value if the amount of the active metal is a sufficient amount.

That is, when the active metal adhesion state was within the range of the predetermined conditions, a very stable airtight property was exhibited.
As a cause of this, the distribution of the active metal [A] on the adhered surface tended to be extremely uniformly dispersed over the entire adhered surface.
At this time, the bonding strength between the ceramic container and the metal lid body also showed a sufficient value if the amount of the active metal deposited was sufficient.

Even when adhered through the mesh, the active metal powder was satisfactorily present in the corners of the mesh. For example, in the airtight joining of a ceramic container of a vacuum valve and a metal lid, the strength of the joining can be easily secured by controlling the deposition amount of the active metal. It depends on the segregation state represented by the deposition distribution rather than the deposition amount. In this way, there is a close correlation between the deposition state of the active metal on the metal part [Y] and the airtight property, and the life and electrical characteristics of electron tubes, power tubes such as thyristor valves, vacuum valves, etc. Have an impact.

(3) Ceramic insulating containers (ceramic members) such as electron tubes, power tubes such as thyristor valves, and vacuum circuit breakers vary in size (outer diameter, inner diameter) and their heights are also indefinite. Therefore, there are many technical problems in quality control. Therefore, the conventional active metal bonding method has many disadvantages when it is applied to ceramic members having different sizes and shapes. For example, brazing is performed on the end face of the ceramic insulating container having a thickness of 30 to 1000 mm and a thickness of the ceramic cylinder of 5 mm or less. In this case, workability at the time of depositing an active metal such as Ti, Zr, Cr, and Hf powder on the joined surface of the end face of the ceramic insulating container and nonuniformity of the metalizing layer are problems.

With respect to these problems, in the invention according to any one of claims 1 to 7, in the production of the composite brazing material plate for joining the ceramic part [X] and the metal part [Y], A method for producing a composite brazing material piece [AB] by punching the predetermined main constituent component plate [A] and the predetermined active metal component plate [B] in an overlapping state and simultaneously molding and integrating them. I am collecting. Therefore, as compared with the conventional method of using an AgCu alloy containing an active metal component as a brazing material, the contact state of the active metal component with the portion to be joined to the ceramic is improved, and the joining strength and airtight joining property are improved.
Further, as compared with the method of directly depositing the active metal powder on the ceramic bonded portion, the handling problem of fine powder and solvent is released and the simplicity is improved. By utilizing the active metal component plate [B] as described above, it is possible to obtain a ceramic insulating container (ceramic member) having good airtightness and bonding strength while avoiding the above-mentioned variations and nonuniformities.

(4) In the conventional method of depositing the active metal powder on the adhered portion (ceramics portion [X], metal portion [Y]),
In some cases, the adhesion strength of Ti, Zr, Cr, Hf, etc., is not sufficient just by applying them, and heat treatment for metalizing was inevitably required. On the other hand, in the state where the main component plate [A] and the predetermined active metal component plate [B] are superposed, both are punched and simultaneously molded and integrated to make a composite brazing material piece [AB]. In the fourth step of the production method of the present invention, since the metal part [Y] is uniformly and sufficiently conformed and adheres well, it is characterized in that it is uniformly attached and dispersed on the entire surface to be adhered. As a result, it has a characteristic that good airtightness and bonding strength can be obtained without heat treatment for metallization. If there is a demand to make it even more familiar, the third
Before the step, either or both of the main component plate [A] and the active metal component plate [B] may be softened.

(5) In the manufacturing method of the present invention, the active metal component plate [B] such as Ti has a thickness of 0.001 to 0.1 mm (1 to
It is necessary to have a plate thickness of 100 μm). When the plate thickness is 0.001 mm or less, the main component plate [A] and the active metal component plate [B] are superposed on each other, and the active metal component plate [B] in the third step is introduced into the punching die. ] Not only becomes technically difficult in terms of handling but becomes inefficient, and when the main component plate [A] and the active metal component plate [B] are punched out after the third step. Even in the fourth step of simultaneously forming and integrally forming the composite brazing material piece [AB], the disadvantage that the active metal component plate [B] has many fractured portions is not noticeable.

When the plate thickness is 0.1 mm or more, an excessive amount of active metal is supplied to the joint portion, which not only contributes to the generation of huge holes near the joint portion after the joint but also causes the joint portion to grow. The supply of an excessive amount of active metal to the alloy causes a high melting point due to the progress of alloying with the main component plate [A] during the bonding heat treatment, which also contributes to the occurrence of defective bonding.

Further, the surface roughness of the active metal component plate [B] is preferably equal to or less than that of the main constituent component plate [A], and the surface roughness in the range of 0.1 to 30 μm is required. That is, when the surface roughness is 0.1 μm or less, the main component plate [A] and the active metal component plate [B] are separated from each other in the fourth step of forming and integrating the composite brazing material pieces [AB]. With respect to the improvement of the adhesiveness, not only does it show a negative tendency but also the economic efficiency becomes negative, which can be said to be an excessive surface state of the active metal component. On the other hand, the surface roughness is 30
If the thickness is more than μm, the degree of adhesion (adhesion strength, adhesion density, etc.) of the active metal component to the ceramic part [X] will be in a coarse and dense state, and as a result, it will be one of the causes of variations in joining strength and airtight joining property. .

(6) As a typical brazing material, 779 ° C.
Eutectic silver brazing material (72 wt% Ag-Cu)
Alloy) is known. Also in one embodiment of the joining of the method of the present invention, for example, a Ti active metal plate is punched on one surface (both sides are acceptable) of a plate-shaped eutectic silver brazing plate having a thickness of 0.1 mm, and at the same time, a composite is formed. Uses wax material.

The main constituents of the above-mentioned embodiment are not limited to the above-mentioned embodiment, but the method of separately supplying Ag and Cu which are the constituents of the eutectic silver wax, that is, the Ag thin plate. As the Cu thin plate, the active metal component Ti is superposed on this Ag thin plate (or Cu thin plate), the third step, the fourth step and the final composition ratio is desired (for example, 72 wt% Ag-Cu alloy). It may be.

The brazing material is not limited to the silver brazing material, but the Au brazing material, the Pd brazing material, the Pt brazing material,
It may be a Cu-based brazing material.

In the above-mentioned embodiment, if necessary, the main component plate [A] and the active metal component plate [B] are overlapped, punched and simultaneously molded and integrated to obtain a composite brazing material piece [AB].
Between the metal portion [Y] surface having a plating layer such as Ag and the ceramic portion [X] so that the surface of the active metal component plate [B] contacts the ceramic portion [X]. However, it is to be heat sealed. Therefore, the point is how to integrate the active metal on the [Y] surface of the metal part under what conditions and by what means. In this case, it is more preferable that the surface roughness of the main component plate [A] and the active metal component metal plate portion [Y] be in the range of 0.1 to 30 μm. As described above, it is possible to provide a high-performance airtight sealing method suitable for manufacturing electron tubes, power tubes, and vacuum valves, and a method for manufacturing a composite brazing material required therefor.

[Examples 32 to 40, Comparative Examples 9 to 11]
Next, with reference to Table 5, description will be made on a manufacturing method of a bonding composite brazing material different from the manufacturing method of the bonding composite brazing material described above. In this manufacturing method, a brazing material containing Ag and Cu as a main component, a Ti foil having a thickness of 5 μm, and a diffusion prevention layer are heat-treated in a vacuum to obtain a brazing material containing Ag and Cu as a main component. The Ti foil is bonded to one surface.

<Comparative Example 9, Examples 32 and 33> The brazing material is Cu, the heat treatment temperature is 800 ° C., and the degree of vacuum is 1 × 10 ⁻³ P.
As a, a brazing material having a Ti layer on one surface of the brazing material was manufactured by the conventional method and the method according to the present invention. In the conventional method of Comparative Example 9, when Cu and Ti foils were joined by thermal diffusion without using a diffusion preventive material, Cu and Ti were all integrated, and it was impossible to use as a brazing material.
Using Al ₂ O ₃ powder as a diffusion barrier, Cu and T
In Example 32 in which the laminated structure was formed together with the i-foil and heat-treated, only Cu and Ti were bonded, and Al ₂ O ₃ was added.
Both Cu and Ti did not react, and a plurality of brazing materials having a uniform Ti layer on one surface of Cu could be obtained. In Example 33 in which Cu, Ti foil, and a diffusion barrier layer formed of Al ₂ O ₃ powder were wound in a roll shape a plurality of times and heat-treated, only Cu and Ti were bonded,
Al ₂ O ₃ is unreacted with both Cu and Ti, and C
One long coil-shaped brazing material having a uniform Ti layer on one surface of u could be obtained. The coiled brazing material was rewound to form a single long plate, cut and used for brazing.

<Examples 34 to 37> As a brazing material, C was used.
u, Ag-28 wt% Cu, Cu and Ag-28 wt% C
2 layers of u are used for diffusion bonding with Ti foil, Al ₂
O ₃ powder was sandwiched as a diffusion preventive material to form a roll, and then heat treatment was performed at a temperature of 700 ° C. and a vacuum degree of 1 × 10 ⁻³ Pa. Example 3 using Cu as a brazing material
4. In Example 35 using Ag-28 wt% Cu, it was possible to obtain a brazing material having a uniform Ti layer on one surface of Cu and Ag-28 wt% Cu, respectively. For Example 36 in which two layers of Cu and Ag-28 wt% Cu were used as the brazing material, Cu and Ag-28 wt% Cu were used.
It was possible to obtain a brazing material which was joined and had a uniform Ti layer on the multiple faces of Cu.

As a brazing material, Ag-27 wt% Cu-
Diffusion preventive material Al ₂ with Ti foil using 5 wt% In
A laminated structure was formed with O ₃ at a temperature of 650
Regarding Example 37 which was heat-treated under the conditions of the temperature of 1 ° C. and the degree of vacuum of 1 × 10 ⁻³ Pa, Ag-27 wt% Cu-5 wt% I
A plurality of brazing materials having a uniform Ti layer on one surface of n could be obtained.

Comparative Example 10 and Example 38 The brazing material is C
After winding u, Ti foil, and diffusion preventive agent Al ₂ O ₃ into a coil, the temperature was set to 1 in a vacuum atmosphere of 1 × 10 ⁻³ Pa.
Heat treatment was performed at 000 ° C. and 850 ° C. In Comparative Example 2 in which the heat treatment temperature was 1000 ° C., the metal part was melted during the heat treatment and could not be used as a brazing material. In Example 38 in which the heat treatment temperature was 850 ° C., a brazing material having a uniform Ti layer on one side of the metal brazing material could be obtained.

<Example 39, Comparative Example 11> The brazing material is C
After winding u, Ti foil and diffusion preventive agent Al ₂ O ₃ into a coil, the holding temperature was 800 ° C. and the atmosphere was 1 × 10 ^−1.
The heat treatment was performed in a Pa vacuum or in the atmosphere. 1 x 10
^In Example 39 performed in a vacuum of ^-1 Pa, a brazing material having a uniform Ti layer on one surface of the metal brazing material could be obtained. In Comparative Example 3 in which the heat treatment was performed in the atmosphere, the surface of Ti was oxidized and the performance of the active brazing material was deteriorated.

<Example 40> In Example 40 in which paper was used as the diffusion preventing material, although the paper was deteriorated after the heat treatment, a brazing material having a uniform Ti layer on one surface of the metal brazing material was obtained. I was able to.

[0131]

[Table 1]

[0132]

[Table 2]

[0133]

[Table 3]

[0134]

[Table 4]

[0135]

[Table 5]

According to the embodiment corresponding to any of claims 8 to 14 described above, the following operational effects can be obtained. As described above, in order to bond the ceramics and the metal, it is preferable to use a brazing material having a large amount of Ti at the bonding interface, and a Ti layer is formed on one surface of the brazing material containing Ag-Cu as a main component. Although a paste method, a vapor deposition method, or the like has been studied as a method for forming a film, there are problems such as reliability, environmental aspects, and economical efficiency. However, it has become possible to obtain a uniform Ti layer by thermal diffusion as in the method of the present invention. Although joining dissimilar metals by thermal diffusion is a known technique, a feature of the present invention is to introduce a diffusion prevention layer. This makes it possible to obtain a uniform Ti layer over a wide range at low cost even if the metal parts are not integrated as a laminated or roll shape, and it is possible to manufacture a brazing material for bonding a ceramic and a metal. is there.

According to the embodiments described above, a composite brazing material having a Ti layer on one side of a metal brazing material can be obtained,
The material thus obtained, for example, a vacuum switch container,
It can be used for joining airtightly adhered parts such as a silicon rectifier container and a joining terminal plate.

[0138]

According to the present invention, the following effects can be obtained. That is, the inventions corresponding to claims 1 to 7 can improve the bonding strength and airtight bondability, and the inventions of claims 8 to
The invention corresponding to claim 14 is a ceramic part [X] and a metal part capable of inexpensively obtaining a uniform Ti layer over a wide range without forming all the metal parts in a laminated or roll shape. A method for manufacturing a composite brazing material for joining with [Y] can be provided.

Further, according to the inventions corresponding to claims 15 to 18, it is possible to provide a method of joining the ceramic part [X] and the metal part [Y] capable of improving the joining strength and the airtight joining property.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Atsushi Yamamoto 1st Toshiba Town, Fuchu City, Tokyo Toshiba Corporation Fuchu Factory

Claims (18)

[Claims] 1. A method of manufacturing a composite brazing material for joining a ceramic part [X] and a metal part [Y], wherein Ag, Cu having a plate thickness or a wire thickness of 30 to 2000 μm,
AgCu, AgCuln, AgCuSn, AgCuZ
n, AgCuCd, the first step of preparing one main component plate or wire [A] selected from CuMn, and Ti, AgTi having a plate thickness or line thickness of 1 to 100 μm,
The second step of preparing one active metal component plate [B] selected from CuTi and AgCuTi, and the main component plate or wire [A] and the active metal component plate or wire [B] into a punching die. A third step of introducing and a fourth step of producing a composite brazing material piece [AB] in which the main constituent component plate or wire [A] and the active metal component plate or wire [B] are punched and integrated at the same time. And a step of sequentially performing the first to fourth steps. 2. The third step is characterized in that the main constituent component plate or wire [A] and the active metal component plate or wire [B] are superposed in advance and then introduced into a punching die. A method for manufacturing the composite brazing material according to claim 1. 3. The punching die according to the third step, which comprises preliminarily superimposing the main component plate or wire [A], the active metal component plate or wire [B], and the brazing material plate in any order. 2. The method for producing a composite brazing material according to claim 1, wherein 4. The main component plate or wire [A] is C
u clad Ag, Ag clad Cu, Cu clad Ag
Cu, AgCu clad Cu, Cu clad AgCul
n, Cu clad AgCuSn, Cu clad CuMn
It is one selected from the following.
4. The method for manufacturing the composite brazing material according to any one of 3 above. 5. The main component plate or wire [A] is an active metal component plate or wire [B] which is sufficiently softened by heat treatment before the third step. The method for manufacturing the composite brazing material according to claim 1. 6. The surface roughness of the active metal component plate or line [B] is almost the same as that of the main component plate or line [A], and the surface roughness in the range of 0.1 to 30 μm ( However, [A] plate thickness μm or line thickness μm> [B] surface roughness μ
m) is contained, The manufacturing method of the composite brazing material in any one of Claims 1-5 characterized by the above-mentioned. 7. Before the third step, a heat treatment is applied to improve the adhesion between the main textural component plate or wire [A] and the active metal component plate or wire [B]. A method for manufacturing the composite brazing material according to claim 1. 8. A composite brazing material, wherein the brazing material, the active metal foil, and the diffusion preventing material are laminated in the same order and then heat-treated to integrate the brazing material and the metal foil. Production method. 9. A composite brazing material, characterized in that the brazing material, the active metal foil and the diffusion preventive material are wound in a roll shape and then heat treated to integrate the brazing material and the metal foil. Production method. 10. The brazing material is Cu, Ag—Cu,
10. The method for producing a composite brazing material according to claim 8 or 9, wherein the composite brazing material is one of two layers of Cu and Ag-Cu, and Ag-Cu-In. 11. The method for producing a composite brazing material according to claim 8, wherein the active metal foil is Ti. 12. The method for producing a composite brazing material according to claim 8, wherein the heat treatment temperature is 880 ° C. or lower. 13. The method for producing a composite brazing material according to claim 8, wherein the atmosphere of the heat treatment is a vacuum atmosphere having a pressure of 10 ⁻¹ Pa or less. 14. The method for producing a composite brazing material according to claim 8, wherein the diffusion preventing material is at least one of Al ₂ O ₃ powder and paper. 15. A ceramic part [X] and a metal part [Y].
In the joining method of No. 1, Ag, Cu having a plate thickness or wire thickness of 30 to 2000 μm,
AgCu, AgCuln, AgCuSn, AgCuZ
n, AgCuCd, the first step of preparing one main component plate or wire [A] selected from CuMn, and Ti, AgTi having a plate thickness or line thickness of 1 to 100 μm,
The second step of preparing one active metal component plate [B] selected from CuTi and AgCuTi, and the main component plate or wire [A] and the active metal component plate or wire [B] into a punching die. A third step of introducing and a fourth step of producing a composite brazing material piece [AB] in which the main constituent component plate or wire [A] and the active metal component plate or wire [B] are punched and simultaneously integrated. And the active metal component [B] surface of the composite brazing material piece [AB],
The ceramic part is placed so as to face the surface [X] to be bonded, and if necessary, the surface to be bonded [Y] of the metal part.
And a fifth step of heating and melting the brazing material after the brazing material is disposed between the ceramics part [X] and the metal part. How to join with [Y]. 16. A ceramic part [X] and a metal part [Y].
In the joining method of No. 1, Ag, Cu having a plate thickness or wire thickness of 30 to 2000 μm,
AgCu, AgCuln, AgCuSn, AgCuZ
n, AgCuCd, the first step of preparing one main component plate or wire [A] selected from CuMn, and Ti, AgTi having a plate thickness or line thickness of 1 to 100 μm,
The second step of preparing one active metal component plate [B] selected from CuTi and AgCuTi, and the main component plate or wire [A] and the active metal component plate or wire [B] into a punching die. A third step of introducing and a fourth step of producing a composite brazing material piece [AB] in which the main constituent component plate or wire [A] and the active metal component plate or wire [B] are punched and integrated at the same time. And the active metal component [B] surface of the composite brazing material piece [AB],
A fifth step of placing the brazing material between the joined surface [X] of the ceramic portion and the joined surface [Y] of the ceramic portion, and then heating and melting the brazing material. A method for joining a ceramic part [X] and a metal part [Y], characterized in that the first to fifth steps are sequentially carried out. 17. The ceramic part [X] and the metal part [Y] according to claim 15 or 16, wherein the fifth step is performed in a vacuum atmosphere or a non-oxidizing atmosphere. How to join. 18. The ceramic part [X] is an alumina cylindrical tube having a desired electrode inside, and the metal part [Y] is a Fe—Ni or Fe—Co alloy for sealing. A method for joining the ceramic part [X] and the metal part [Y] according to any one of claims 15 to 17.