JP2001220253A - Metal-ceramic bonded material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-ceramic bonded material having stable bonded state and high bonding strength and provide its production method. SOLUTION: A metallic part 3 and a ceramic part 2 are bonded together at their butt ends interposing a reaction layer 4 being in contact with the ceramic part 2 and a soldering material layer 5 being in contact with the metallic part 3. The ceramic part 2 is made of e.g. an alumina-based ceramic composed mainly of alumina and the metallic part 3 is made of a Ni-containing alloy such as an Fe-Ni-Co alloy The reaction layer 4 contains Ti as a main active metal element and the soldering material layer 5 contains a Ag-Cu alloy as a main component. A Ti-Ni intermetallic compound is scarcely formed between the soldering material layer 5 and the metallic part 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-ceramic joint and a method for manufacturing the same.

[0002]

2. Description of the Related Art Ceramic members have excellent heat resistance, impact resistance and insulation properties, and are being utilized in various fields by utilizing their properties. For example, in a vacuum switch outer tube using a ceramic tube, an opening end of a cylindrical ceramic member is welded and sealed with a cylindrical metal member provided with a lid. Conventionally, when joining such a ceramic member and a metal member,
A method is used in which the butted ends of both members are joined by brazing. As a metal member, an iron alloy containing Ni is often used in order to secure corrosion resistance and high-temperature strength.

[0003]

However, in the conventional brazing connection between a metal member and a ceramic member,
For example, an active metal such as Ti contained in a brazing material may react with Ni metal or the like in a metal member to form an intermetallic compound. In this case, the joining strength is reduced at the portion where the intermetallic compound is formed, or the active metal reacting with the ceramic member is insufficient, and the joining state near the interface between the ceramic member and the brazing material becomes unstable. Has occurred.

[0004] It is an object of the present invention to provide a metal-ceramic joint having a stable joining state and high joining strength, and a method for producing the same.

[0005]

Means for Solving the Problems and Functions / Effects The metal-ceramic joined body of the present invention for solving the above problems is:
A metal member containing Ni and a ceramic member are joined via a brazing material layer, and between the brazing material layer and the ceramic member, a material selected from Ti, Zr, and Hf is used.
A reaction layer containing one or more active metal components is formed, while the amount of the intermetallic compound containing the active metal component and Ni between the brazing material layer and the metal member is increased as much as possible. It is characterized by being made smaller in size.

A method of manufacturing a metal-ceramic joint according to the present invention is a method of manufacturing a metal-ceramic joint in which a metal member containing Ni and a ceramic member are joined via a brazing material layer. , Zr, Hf, a primary brazing material containing one or more active metal components selected from the group consisting of a primary brazing material and a metallizing treatment is performed on the joining surface of the ceramic member. The metal member is secondarily brazed to the metalized end face of the ceramic member by a secondary brazing material having a low melting point and a small content of the active metal component.

That is, as a result of intensive studies conducted by the present inventors in view of the above problems, as described in the above-mentioned manufacturing method, a brazing material for joining a ceramic member and a metal member is replaced with a primary brazing material containing an active metal component, A two-step brazing process in which the brazing material is divided into a secondary brazing material having a lower melting point than the primary brazing material and a small content of the active metal component (preferably not contained), and brazing individually. As described above, to produce a metal-ceramic joined body in which the amount of the intermetallic compound containing Ni and the active metal component formed between the brazing material layer and the metal member is made as small as possible. Became possible.

That is, in the primary brazing, a primary brazing material containing an active metal is metallized on the joining surface on the ceramic member side, so that a reaction layer of the active metal and the ceramic component is formed on the joining surface of the ceramic member. Is formed. The reaction layer has excellent affinity for both the ceramic and the brazing metal component other than the active metal in the brazing material layer, and forms a strong joint structure between the brazing material layer and the ceramic member. Play a central role. At the time of the secondary brazing, the secondary brazing material having a lower melting point than the primary brazing material and having a low content of the active metal component (preferably not containing) has a lower temperature than at the time of the primary brazing. In this case, diffusion of the active metal component from the reaction layer to the brazing material layer side is suppressed, and the Ni component in the metal member joined via the brazing material layer and the reaction layer (ie, the primary brazing material) The reaction with the active metal component from the catalyst becomes extremely unlikely. As a result, an intermetallic compound containing an active metal component and Ni is hardly formed, and as a result, a metal-ceramic bonded body having a high bonding strength with a stable bonding state at a bonding interface can be obtained.

In the above manufacturing method, the primary brazing temperature T1 depends on the type of the brazing material to be used, but it is 840-8.
The temperature is preferably set to 80 ° C. Similarly, the secondary brazing temperature T2
Is preferably 800 to 820 ° C. The difference ΔT≡T1−T2 preferably satisfies 20 to 80 ° C. That is, by setting the secondary brazing temperature T2 to be lower than the primary brazing temperature T1 by about ΔT, the active metal component in the reaction layer formed by the primary brazing is changed to the brazing material layer during the secondary brazing. Through the reaction with the Ni component contained in the metal member can be effectively suppressed.
Ni-based intermetallic compounds are less likely to be formed. T1 and T
When 2 is set in the above range, if ΔT is less than 20 ° C., the above effects will be insufficient. On the other hand, when the temperature exceeds 80 ° C., the secondary brazing temperature becomes too low, so that the formation of the brazing material layer becomes incomplete and the bonding strength is rather lowered. ΔT is desirably about 30 to 70 ° C., and more desirably about 40 to 60 ° C.

[0010] The primary brazing material specifically includes Ti, Zr, and H.
f and 1 to 20% by weight of a simple substance and / or a compound composed of one or more active metal elements selected from f. As the active metal component, Ti can be particularly preferably used because it can exhibit excellent bonding performance with many ceramics and is relatively inexpensive in terms of price. In this case, in order to enhance the reaction activity of the Ti component, the Ti component in the primary brazing material is in the form of titanium hydride (the general composition formula is TiH ₂ , but is not limited to a stoichiometric compound). It is desirable that it be contained. Also, by including TiH ₂ in the primary brazing material, oxidation or nitridation of Ti can be effectively prevented. When the content of the active metal component in the primary brazing material is less than 1% by weight, formation of a reaction layer becomes insufficient, and bonding failure may easily occur. On the other hand, if the content of the active metal component exceeds 20% by weight, poor wetting may occur between the primary brazing material and the secondary brazing material during secondary brazing, and the reaction layer may become excessively thick. Too much, the bonding strength may be reduced, or the airtightness of the bonded portion may be reduced. The content of the active metal component in the primary brazing material is preferably 5 to 10% by weight.

Further, in the above manufacturing method, the primary brazing is preferably performed in a vacuum, and the degree of vacuum is 1.0 × 10
^-3 Torr or less is preferable. Primary brazing 1.
If performed under conditions exceeding 0 × 10 ⁻³ Torr, poor wetting of the primary brazing material may occur, or the active metal component may be oxidized or nitrided, making it difficult to form a stable reaction layer. The atmosphere of the primary brazing is not limited to a vacuum atmosphere, and a stable reaction layer can be formed even if the primary brazing is performed in an inert gas atmosphere such as an Ar gas atmosphere.

For example, in the metallizing process by primary brazing, the active metal component in the primary brazing material reacts with the ceramic member to form a reaction layer, while the remaining metal component is
In some cases, a primary metallized layer that covers the reaction layer in a contact form is formed. For example, as the primary brazing material, components other than the active metal (hereinafter, referred to as base components), in other words, components to constitute the primary metallized layer, are Ag, Cu, A
u, Sn, etc. can be used. The secondary brazing material used for the secondary brazing is a material having excellent wettability or affinity with the primary metallized layer based on the base component, for example, the primary metallized layer. It may be desirable to use brazing materials of similar composition. As such a secondary brazing material,
Specifically, an Ag-Cu alloy can be used.
The Ag-Cu alloy is less likely to react with an active metal component such as Ti to form an intermetallic compound, has a low melting point, and has good bondability with a metal member, and thus is suitable as the secondary brazing material of the present invention. ing. In addition, the content ratio of Ag and Cu in the Ag-Cu-based alloy is such that Cu3
The content is preferably 0 to 50 parts by weight. If Cu is less than 30 parts by weight, the melting point of the brazing material becomes too high, and for example, the bonding strength may decrease due to the formation of the above-mentioned intermetallic compound due to the diffusion of the active metal component from the reaction layer. On the other hand, 50
When the amount exceeds the weight part, in addition to the same problem due to the high melting point of the brazing material, the oxidation resistance of the brazing material layer may be impaired, and the high-temperature bonding strength and the like may be impaired. In addition, as the Ag-Cu-based alloy as described above, for example, JIS-Z3261
Silver wax: BAg-8 or the like can be used.

In the metal-ceramic joint, the thickness of the reaction layer in the joining direction of the metal member and the ceramic member is preferably 50 μm to 300 μm.
When the thickness of the reaction layer is less than 50 μm, the bondability may decrease due to the lack of the reaction layer, and when it exceeds 300 μm, the reaction layer may become too thick and the bonding strength may decrease. By setting the range of the thickness of the reaction layer to desirably 150 μm to 200 μm, the bonding state of the metal-ceramic bonded body is further stabilized, and the bonding strength is further improved.

In the above metal-ceramic joint, the thickness between the end surface of the brazing material layer on the reaction layer side and the joining end surface of the metal member (hereinafter referred to as the brazing material joining thickness) is 30.
It is good that it is set to μm to 100 μm. The thickness is 3
When it is less than 0 μm, an intermetallic compound is easily formed between the active metal component and the metal member, which may cause a decrease in bonding strength. On the other hand, when the thickness exceeds 100 μm, the brazing material layer becomes too thick, and the bonding strength may be reduced. The above range is desirably 50 μm to 80 μm. In this case, the bonding state of the metal-ceramic bonded body is further stabilized, and the bonding strength is further improved.

Next, the ceramic member is preferably used in the present invention because alumina-based ceramics containing alumina as a main component are excellent in high-temperature strength and high-temperature corrosion resistance or chemical resistance and relatively inexpensive. Can be. On the other hand,
The metal member has a relatively small coefficient of linear expansion, and thermal stress between the ceramic member and the ceramic member is relatively unlikely to occur.
When applied to a vacuum switch or the like, the point of selecting materials is to ensure heat resistance and corrosion resistance. Specifically, an Fe-Ni-Co-based alloy containing Fe as a main component and the subcomponent having the highest content being one of Ni and Co and the subcomponent having the second highest content being the other of Ni and Co Alloy, Fe as the main component, the secondary component with the highest content is Ni
And the like can be used. In addition, Fe-
As the Ni—Co alloy, for example, Fe: 54%, N
An alloy containing i: 29% and Co: 17% (trade name: Kovar), and an Fe-Ni-based alloy containing, for example, 58% Fe and 42% Ni (commonly referred to as 42) Alloy) or the like can be used. In the present specification, “main component”, “mainly” or “main component” and the like refer to a component having the highest weight content in a substance of interest unless otherwise specified. .

Next, the flatness of the joining surface of the ceramic member is preferably set to 0.1 mm or less. When the flatness exceeds 0.1 mm, the formation of the reaction layer becomes incomplete or causes brazing failure at the time of secondary brazing, and as a result, the bonding strength of the manufactured joined body is reduced. There is.

Next, as a specific embodiment of the above-mentioned metal-ceramic joined body, for example, a brazing material layer is formed so that a butt portion between the metal member and the ceramic member can be joined with high strength. A mode in which a fillet formed at the butted portion (hereinafter also referred to as a brazing filler material) can be exemplified. For example, as a structure for joining a metal member and a ceramic member, each of which is formed in a cylindrical shape, a metal cylindrical body and a ceramic cylindrical body each having at least one open end surface are open, and the metal cylindrical body and the ceramic cylindrical body are respectively formed. The body may be coaxially butted on the open end face side, and the butted portion may be joined via an annular brazing material layer (brazing material fillet). In this case, both the metal tubular body and the ceramic tubular body are formed in a cylindrical shape, and the joining end face on the metal tubular body side can be positioned substantially at the center of the joining end face on the ceramic tubular body side in the radial direction. . When the tubular members are brazed to each other in this manner, by introducing the joined body of the present invention, the joining layer (consisting of the reaction layer and the brazing material layer) has no joining unevenness, and has a good joining state. And it is possible to provide a highly airtight joint.

Specific examples of the structure for joining the ceramic tubular body and the metal tubular body with higher strength include the following. That is, at the butting portion,
The joining end faces of the metal tubular body and the ceramic tubular body are each formed in a planar shape, and the joining end face of the metal tubular body at an arbitrary cross section including the axis of the metallic tubular body and the ceramic tubular body. The width of the metal-side joining end surface (hereinafter, referred to as a metal-side joining end surface) is made smaller than the width of the joining end surface of the ceramic tubular body (hereinafter, referred to as a ceramic-side joining end surface). A shape in which both sides in the thickness direction of the metal cylindrical body are covered, and the cross-sectional outer shape of the metal cylindrical body at both the inner surface side and the outer surface side is flared from the metal cylindrical body side toward the ceramic cylindrical body side. Shall be presented. Then, by applying the joined structure of the present invention, in the butt joining of the tubular members, a joining structure with little joining unevenness and excellent in joining strength and airtightness can be obtained. For example, the metal-ceramic joint having the above structure is particularly effective for application to a vacuum switch. In this case, the cylindrical ceramic member can be used as an outer tube for a vacuum switch, and the metal member can be used as a metal cover that covers the vacuum switch outer tube. In this case, by applying the present invention, it is possible to provide a vacuum switch outer tube having high airtightness and high bonding strength.

[0019]

Embodiments of the present invention will be described below with reference to the embodiments shown in the drawings. FIG. 1 is an enlarged sectional view showing a joint portion of a metal-ceramic joint body 1 according to one embodiment of the present invention. Metal member 3 and ceramic member 2
Are joined at their butted portions via a reaction layer 4 in contact with the ceramic member 2 and a brazing material fillet (brazing material layer) 5 in contact with the metal member 3. The joining end faces of the members 2 and 3, that is, the ceramic-side joining end face 6 and the metal-side joining end face 7 are each formed in a flat shape, and the flatness of the ceramic-side joining end face 6 is particularly set to 0.1 mm or less. The metal-side joint end face 7 is smaller than the ceramic-side joint end face 6. On the other hand, the brazing filleret 5 covers the entire peripheral edge of the joining end of the metal member 3 so as to be buried in the joining end, and the cross-sectional outer shape of the metal member 3 on both sides of the metal member 3 is changed from the metal member 3 side to the ceramic member 2.
It has a shape that expands toward the side. In this embodiment, the width of the joining end face of the metal member 3 is smaller than the width of the joining end face of the ceramic member.

The ceramic member 2 is made of, for example, an alumina-based ceramic containing alumina as a main component, and the metal member 3 is made of, for example, Fe: 54%, Ni: 29%, Co: 1.
It is composed of an Fe-Ni-Co alloy containing 7%. The reaction layer 4 contains Ti as an active metal component,
The brazing filler material 5 is mainly composed of an Ag-Cu alloy.

In the metal-ceramic joined body 1, the thickness t1 of the reaction layer 4 is, for example, 50 μm to 300 μm (150 μm in this embodiment), and the end face on the reaction layer 4 side in the brazing filler material 5. The thickness between the metal member 3 and the bonding end face 7 of the metal member 3, that is, the thickness t2 of the brazing material bonding layer 5a is, for example, 30 μm to 100 μm (80 μm in the present embodiment).

The thickness t1 of the reaction layer 4 and the thickness t2 of the brazing material joining layer 5a are determined, for example, by an electron probe microanalyzer (EPMA), an energy dispersive X-ray spectroscopy (EDM).
S), and can be measured by a known method such as wavelength dispersive X-ray spectroscopy (WDS). In the present invention, it is defined as follows. As shown in FIG. 5, a cation component having the highest content of the ceramic member (for example, X-ray photoelectron spectroscopy (X
PS) is an elemental component showing a positive valence when analyzed by, for example, Al for alumina and Si for silicon nitride.
Is Q, and the metal component having the highest content of the metal member is M, while the active metal component is A. And
The cross section of the joint was observed with a scanning electron microscope (SEM). Further, in the joining direction of each part, the SE component, the metal component M, and the active metal component A of the SE were examined.
Suppose that a line analysis was performed using the EPMA attached to M. In this case, it is considered that the content of each of the component Q, the component M, and the component A is proportional to the detection intensity of the corresponding characteristic X-ray. At this time, the maximum value of the characteristic X-ray intensity based on the component Q is IQmax (measured at the height from the background with the lowest value on the metal member side as the background), and the characteristic X-ray intensity based on the component M Maximum intensity is IMmax
(Measured at the height from the background with the lowest value on the ceramic member side as the background), and the maximum value of the characteristic X-ray intensity based on the component A is IAmax
(Measured at the height from the background, with the lowest value on the ceramic member side or the metal member side as the background), the position where 0.8 IQmax is reached is defined as the boundary BC between the ceramic member and the reaction layer. As -R,
The position where 0.8IAmax is reached is the boundary B between the reaction layer and the brazing material layer.
RW, and a position at which the value of 0.8 IMmax is determined as a boundary BW-M between the brazing material layer and the metal member. The thickness t1 of the reaction layer 4 is the distance between the boundaries BC-R and BR-W, and the thickness t2 of the brazing material joining layer 5a is the distance between the boundaries BR-W and BW-M. Respectively.

Further, an intermetallic compound containing an active metal component and Ni, for example, a Ti—Ni-based compound is hardly formed between the brazing filler material 5 and the metal member 3. This is, in other words, the Ni component in the metal member,
This means that the reaction with the Ti component forming the reaction layer hardly occurred. As means for specifically confirming this, for example, a crystal structure analysis is performed on the cross section of the joint by micro X-ray diffraction or the like, and for example, Ti ₂ Ni,
If a diffraction peak of a Ti—Ni-based compound such as TiNi or Ni ₃ Ti is not confirmed, it can be considered that a Ti—Ni-based compound is not formed. In FIG. 5, when the line analysis of the active metal component A was performed, the reaction of the peak value I′Amax of the characteristic X-ray intensity of the active metal component A observed at the interface between the brazing filler metal layer and the metal member was observed. The ratio I'Amax / IAm to the peak value IAmax in the layer
ax is desirably 0.01 or less (preferably substantially zero within the range of measurement variation).

Hereinafter, a method of manufacturing the metal-ceramic joined body 1 will be described. First, as shown in FIG. 4A, a paste of a primary brazing material 104 containing Ti as an active metal component is placed on an end surface (joining surface) of the ceramic member 2 and a predetermined atmosphere is set in an atmosphere heating furnace. Then, a metallizing process is performed by heating at a temperature to form a reaction layer 4 as shown in FIG. In some cases, a brazing filler metal component other than the active metal component may form the primary metallized layer 5b that covers the reaction layer 4 in a contact form. The conditions of the primary brazing are as follows: the brazing temperature T1 is 840 to 880 ° C. (860 ° C. in the present embodiment), and the degree of vacuum is 1.0 × 10 ⁻³ Torr or less (in the present embodiment, for example, 1.0 × 10 ⁻³ Torr). ^{- 4} Torr)
Can be performed in a vacuum. The composition of the primary brazing material is
For example, portions other than the active metal can be made of Ag and Cu. As the active metal component, for example, a material containing 1 to 20% by weight (5% by weight in the present embodiment) of Ti in the form of TiH ₂ is used. it can.

Next, as shown in FIG. 4 (c), the melting point of the active metal component is lower than that of the primary brazing material and the content of the active metal component is smaller. The secondary brazing material foil 105 that is not contained in the reaction layer 4
(Or the primary metallized layer 5b), and the end faces (joining surfaces) of the metal members 3 are abutted and heated in an atmosphere heating furnace at a predetermined atmosphere and temperature.
Secondary brazing. Thereby, the secondary brazing material foil 105 is melted to form the brazing material fillet 5 shown in FIG. When the primary metallization layer 5b is formed, a part or all of the primary metallization layer 5b may be melted and integrated with the secondary brazing material foil 105 and taken into the brazing material fillet 5. The condition of the secondary brazing is that the brazing temperature T2 is 800
８820 ° C. (800 ° C. in the present embodiment), and the difference ΔT≡T1−T2 from the primary brazing temperature T1 is 20 to 8
The temperature is set to 0 ° C. (60 ° C. in this embodiment). In addition, silver brazing BAg-8 (Ag: Cu = 18: 7) described in JIS-Z3261 is used as the secondary brazing material.

FIG. 2 is a schematic cross-sectional view of a part of a vacuum switch outer tube using the metal-ceramic composite 1. The vacuum switch outer tube 10 has a form in which a cylindrical ceramic member (ceramic cylindrical body) 12 forming a ceramic tube and a metal member (metal cylindrical body) 13 having a lid member 14 are hermetically bonded. Have. These ceramic tubular body 12 and metal tubular body 13
Are cylindrical bodies each having an open end face, which are coaxially butted on the open end face side, and the butt portion is interposed via an annular bonding layer (consisting of the reaction layer 4 and the brazing filler material 5) 15. To form a metal-ceramic joint according to the present invention. In the abutting portion, the joining end face on the side of the metal tubular body 13 is positioned substantially at the center in the radial direction of the joining end face on the side of the ceramic tubular body 12.

When performing primary brazing on the joining surface of such a ceramic tubular body 12, as shown in FIG. 4E, an annular primary brazing material foil 104 corresponding to the end face shape is used. it can. Also, when performing secondary brazing,
As shown in FIG. 4F, an annular secondary brazing material foil 105 is sandwiched between the end surfaces of the ceramic tubular body 12 and the metal tubular body 13.

In the above-described vacuum switch, the structure of the metal-ceramic bonded body of the present invention allows the ceramic cylindrical body 12 and the metal cylindrical body 13 to be sealed by the bonding layer 15 to achieve high airtightness. By performing the brazing in two steps as described above, since the Ti—Ni-based intermetallic compound is hardly formed between the joining layer 15 (the brazing filler material 5) and the metal cylindrical body 13, the joining is performed. It also has excellent strength. In addition, on the side of the cover member 14 of the metal member 13, a flange-like portion 13 a that bulges outward is formed to maintain the airtightness and the bonding strength between the metal member 13 and the cover member 14.

FIG. 3 shows a more specific configuration example of the vacuum switch. This vacuum valve 50 is connected to the insulating container 5.
Metal end plates 57, 57 (metal members) with lids are hermetically sealed to the openings at both ends of 5 (ceramic member) to form a container. In this vacuum container, contact 6
Numerals 0, 61 are provided such that the contact 61 is fixed, the contact 60 is movable, and the contact 60 is movable.
Are airtightly attached to the end plate 57, and the movable contact 6
The zero movable electrode rod 56 is movably and airtightly attached to the end plate 57 via the bellows 58. The fixed contact 61 and the movable contact 60 are surrounded by the arc shield 54, and the bellows cover 59 of the bellows 58 is attached to the movable electrode rod 56.

In such a vacuum valve 50, the movable electrode rod 56 is operated in the pulling-out direction by an operating mechanism (not shown), and the contacts 60 and 61 are separated. These contacts 60, 6
Even when 1 is separated, an arc is generated between the two contacts while the distance is small, and the current continues to flow. However, when the distance is increased beyond a certain value, the generated arc reaches the zero current point and is diffused into the vacuum. , The current between the contacts is interrupted. Here, the end plate (metal member) 57 and the insulating container (ceramic member) 55 can be brazed and joined as the metal-ceramic joint of the present invention. Thereby, the joint has high airtightness and joint strength, and can exhibit excellent performance as a vacuum valve.

(Example 1) The following experiment was conducted to confirm the effects of the present invention. First, as the ceramic cylindrical body 12 shown in FIG. 2, an inner diameter 5 made of alumina ceramic (alumina content 92% by weight, density 3.6 g / cm ³ ) is used.
1 mm, an outer diameter of 61 mm, and a length of 91 mm were prepared. On the other hand, as the metal cylindrical body 13 shown in FIG.
4 wt% -Ni: 29 wt% -Co: 17 wt% alloy (Kovar) having an inner diameter of 55 mm and an outer diameter of the joint surface side of 57.
5 mm, a flange side outer diameter of 62 mm, and a length of 10 mm were prepared.

As the primary brazing material, an alloy powder containing 72 parts by weight of Ag and 28 parts by weight of Cu (an alloy powder that forms the balance other than the active metal component) is compared with a TiH ₂ powder as an active metal component. Was mixed in various proportions, and a solvent and a dispersant were added to prepare a primary brazing material paste. In addition, as a secondary brazing material, an inner diameter of 51 mm, an outer diameter of 60 mm,
An annular BAg-8 brazing filler metal foil having a thickness of 0.13 mm was prepared. Further, the end surface on the joining side of the ceramic cylindrical body was polished by a grinder and lap polishing so as to have various flatnesses. Further, the end face on the joining side of the metal cylindrical body was cut so that the flatness became 0.1 mm during the lace processing (cutting).

Then, the above-mentioned primary brazing material paste is applied at a thickness of 200 μm to the end face on the joining side of the ceramic cylindrical body, and the temperature T1 = 860 ° C., the degree of vacuum = 1 × 10 ⁻⁴ in an atmosphere heating furnace. Primary brazing was performed at １1 × 10 ⁻² Torr to form a primary metallized layer. Next, the joining-side end face of the ceramic tubular body on which the primary metallized layer is formed and the joining-side end face of the metallic tubular body are abutted with the secondary brazing material foil interposed therebetween, and the temperature T2 = 800. ℃, degree of vacuum =
Secondary brazing was performed at 1.0 × 10 ⁻⁴ Torr.

The joining strength of each joined body thus obtained is
Measured by a tensile test using an autograph, the strength value is 3
2,000 kg or more were evaluated as ◎, 2000 to 3000 kg were evaluated as ○, and 2000 kg or less as Δ. In addition, the airtightness is H using a He leak detector.
e measured by a leak test, the He leak amount was 10 ⁻⁹ P
a · m ³ / sec or less: 、 ^{１０10 −9} to 10 ⁻⁸
○ those of ^{Pa · m 3 / sec, 10} -8 Pa · m 3 /
Those that were not shorter than sec were evaluated as Δ. The above results are shown in Tables 1 to 3.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

Table 1 shows that the flatness of the joining-side end face of the ceramic member was fixed at 0.05 mm, and the degree of vacuum at the time of the primary brazing was fixed at 1.0 × 10 ⁻⁴ Torr, and the primary brazing used. The results in the case where the content of TiH _{2 in} the material is variously changed are shown. It can be seen that by setting the content of TiH ₂ to 1.0 to 20.0% by weight, both a sufficient bonding strength and high airtightness can be achieved. Further, in this case, when a cross section obtained by cutting the joint portion in the axial direction was externally observed with a projector, it was also confirmed that the joint was in a good joining state without uneven joining. On the other hand, the joined bodies (Nos. 1, 6, and 7) in which the content of TiH ₂ is out of the above range are the above joined bodies (No. ₂ to No. ₂ ).
Compared with 5), the bonding strength was low and the airtightness was slightly reduced.

Table 2 shows that the degree of vacuum during primary brazing was 1.0
× 10 ⁻⁴ Torr, the content of TiH ₂ in the primary brazing material was fixed at 12% by weight, and the flatness of the joining-side end face of the ceramic member was adjusted to various values of 0.05 to 0.15 mm. This is the result when the value is changed. 0.1m flatness
It can be understood that a bonding structure excellent in both bonding strength and airtightness is realized by setting the value to m or less. Also, the cross-sectional observation result was good as in Example 1. On the other hand, in the joined bodies (Nos. 3 and 4) having a flatness exceeding 0.1 mm, the joining strength was slightly low and the airtightness was slightly reduced.

Table 3 shows that the flatness of the joining side end face of the ceramic member was fixed at 0.05 mm, the content of TiH ₂ in the primary brazing material was fixed at 12% by weight, and the vacuum at the time of the primary brazing was fixed. The degree is 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻² To
These are the results when changing to various values of rr. The joined bodies (Nos. 12 and 13) produced under the condition that the degree of vacuum at the time of the primary brazing is 1.0 × 10 ⁻³ Torr or less show sufficient joining strength and have high airtightness by a He leak test. And observation of the cross section also showed that the bonding condition was good. On the other hand, if the degree of vacuum is 1.0 × 10
^-3 Torr (No. 3)
No. 14, 15), the bonding strength was slightly low and the airtightness was slightly reduced.

In the above examples, the same tests were performed as in the above examples using an Fe-Ni-based alloy (containing 58% of Fe and 42% of Ni) as the metal member.
As a result, it was confirmed that the same tendency as in the case of using Kovar was exhibited.

[Brief description of the drawings]

FIG. 1 is an enlarged schematic cross-sectional view showing one embodiment of a metal-ceramic joined body of the present invention.

FIG. 2 is a schematic cross-sectional view showing one embodiment using the metal-ceramic joined body of FIG.

FIG. 3 is a cross-sectional view showing one embodiment in which the metal-ceramic joined body of the present invention is used as a vacuum switch outer tube.

FIG. 4 is a diagram illustrating a method for manufacturing a metal-ceramic joined body of the present invention.

FIG. 5 is an explanatory diagram for determining the thicknesses of a reaction layer and a brazing material layer in the metal-ceramic joined body of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 metal-ceramic joined body 2, 12 ceramic member 3, 13 metal member 4 reaction layer 5 brazing material fillet (brazing material layer) 6 ceramic-side joining end face 7 metal-side joining end face 10 vacuum switch outer tube 15 joining layer (reaction layer and Brazing material layer) 50 Vacuum valve

Claims (14)

[Claims] 1. A metal member containing Ni and a ceramic member are joined via a brazing material layer, and Ti, Zr, H is provided between the brazing material layer and the ceramic member.
f, a reaction layer containing one or more active metal components selected from the group consisting of a metal containing the active metal component and Ni between the brazing material layer and the metal member. A metal-ceramic joined body characterized in that the amount of intermetallic compound formed is made as small as possible. 2. The metal-ceramic joined body according to claim 1, wherein the ceramic member is made of an alumina-based ceramic containing alumina as a main component. 3. The metal member contains Fe as a main component, and the sub-component having the highest content is one of Ni and Co, and the sub-component having the second highest content is Ni.
And a Fe-Ni-Co-based alloy which is the other of Co and Co, or a Fe-Ni-based alloy whose main component is Fe and whose secondary component has the highest content of Ni. 3. The metal-ceramic joint according to 2. 4. The metal-ceramic joined body according to claim 1, wherein the brazing material layer is a fillet formed at an abutting portion between the ceramic member and the metal member. 5. The metal member and the ceramic member are a metal cylindrical body and a ceramic cylindrical body each having at least one open end face, and the metal cylindrical body and the ceramic cylindrical body are arranged on the open end face side. The metal-ceramic joint according to any one of claims 1 to 4, wherein the butted portions are coaxially butted and the butted portions are joined via an annular brazing material layer. 6. The metal cylindrical body and the ceramic cylindrical body are both formed in a cylindrical shape, and a joining end surface on the metal cylindrical body side is positioned substantially at a center of a joining end surface on the ceramic cylindrical body side in a radial direction. The metal-ceramic joint according to claim 5, which is formed. 7. A joining end face between the metal tubular body and the ceramic tubular body at the abutting portion is formed in a planar shape, and includes an axis of the metal tubular body and the ceramic tubular body. In an arbitrary cross section, the width of the joining end face of the metal tubular body (hereinafter, referred to as a metal-side joining end face) is made smaller than the width of the joining end face of the ceramic tubular body (hereinafter, referred to as a ceramic-side joining end face). The fillet covers both sides in the thickness direction of the metal cylindrical body so as to bury the end of the metal cylindrical body, and the cross-sectional outer shape of the metal cylindrical body on both the inner surface side and the outer surface side is the metal cylindrical shape. The metal-ceramic joined body according to claim 5 or 6, wherein the joined body has a shape that expands from the body side toward the ceramic tubular body side. 8. The metal-ceramic joined body according to claim 1, wherein the ceramic member is an outer tube for a vacuum switch. 9. A method for manufacturing a metal-ceramic joined body in which a metal member containing Ni and a ceramic member are joined via a brazing material layer, wherein one or more of Ti, Zr, and Hf are selected. Using a primary brazing material containing an active metal component, performing primary brazing for metallizing the bonding surface of the ceramic member, and then having a lower melting point than the primary brazing material, and having a content of the active metal component of A method of manufacturing a metal-ceramic joined body, wherein the metal member is secondarily brazed to a metalized end face of the ceramic member with a small secondary brazing material. 10. The temperature of the primary brazing is T1,
When the temperature of the secondary brazing is T2, T1: 840 to 880 ° C., T2: 800 to 820 ° C., and the difference (T1−T2) is 20 to 80 ° C. Item 10. The method for producing a metal-ceramic joint according to Item 9. 11. The primary brazing material includes Ti, Zr, H
The method for producing a metal-ceramic joined body according to claim 9 or 10, wherein a simple substance and / or a compound composed of one or more active metal elements selected from f is contained in an amount of 1 to 20% by weight. . 12. The primary brazing is performed in a vacuum,
The method for producing a metal-ceramic joined body according to claim 9, wherein the degree of vacuum is 1.0 × 10 ⁻³ Torr or less. 13. The method for manufacturing a metal-ceramic joined body according to claim 9, wherein an Ag—Cu alloy is used as the secondary brazing material. 14. The metal according to claim 13, wherein the content ratio of Ag and Cu in the Ag—Cu alloy is 30 to 50 parts by weight of Cu with respect to 100 parts by weight of Ag.
Manufacturing method of ceramic joined body.