WO2005073149A1

WO2005073149A1 - Process for producing joined member and produced joined member

Info

Publication number: WO2005073149A1
Application number: PCT/JP2004/001303
Authority: WO
Inventors: Toshikatsu Miki; Takuya Murata
Original assignee: Yamaguchi Technology Licensing Organization Ltd.
Priority date: 2004-01-29
Filing date: 2004-02-06
Publication date: 2005-08-11
Also published as: JPWO2005073149A1; JP4538579B2

Abstract

A process for producing a joined member, which process is easily applicable to joining of combinations among a wide variety of members, especially joining of members having been difficult in the prior art, for example, joining of a ceramic member with a metal member and three-layer joining for a so-called sandwich structure comprising a metal member and, arranged on both side surfaces thereof, metal members or ceramic or semiconductor members, in particular, being easily applicable to joining of members to be joined without the need of any intervening matter used only for joining purposes; and a thus provided joined member. Specifically, a process comprising pressing two members to be joined, at least one of which is a hydrogen occluding member wherein hydrogen is occluded in at least surface layer portion thereof, in contact with each other so that the hydrogen occluding surface constitutes an interface of the two members and, while maintaining the pressed contact, heating the members to thereby release the occluded hydrogen, wherein the maximum characteristic resides in causing the hydrogen occluding member to function as a joining means for the joining of the two members. Accordingly, the process is also characterized in that it can be carried out without need to employ any intervening matter used only for joining purposes, such as a special joining material or a flux, besides the members to be joined.

Description

Description Method for manufacturing joining member, and joining member

The present invention relates to a method for manufacturing a joining member, and the joining member. More specifically, a method of manufacturing joining members by joining multiple members such as metals, semiconductors, ceramics, plastics, etc., for example, mounting of metal plates, metallized substrates, mounting of electronic components on substrates, wiring, and electrodes The present invention relates to a method for manufacturing a joining member that is a composite body in which different members are joined, such as joining a lead wire and the like, and to the joining member. Background art

Conventionally, solid materials have been joined by liquid phase joining such as welding, brazing, soldering, etc., or diffusion joining, anchor joining, ultrasonic joining, etc., when two members to be joined are directly joined. It is performed by solid phase bonding. As an indirect joining method of providing an intermediate material between two members, there is a method using an organic adhesive or an inorganic adhesive, in addition to the method using the direct joining described above.

As a matter of course, common to such conventional techniques is that there is a limit to the combination of components that can be suitably joined, and it cannot be easily applied to a wide variety of members. There's a problem. For example, diffusion bonding, in which the molecules, atoms, or crystal structures are disturbed between the two members to form a solid solution of the two members and the interface becomes unclear, is a bonding method in which bonding strength is large and separation at the interface is unlikely to occur. However, the difficulty in diffusibility between the materials constituting the two members to be joined becomes a problem, and it becomes difficult to join members that are difficult to diffuse. Also, even if both are of the same kind, it cannot be said that they are easily diffused into each other. In some cases, heating to the sintering temperature of both is necessary, so that many members can be easily spread. It is not an applicable technology. For example, roughening the surface of a member, pressing both members strongly, and pushing the other member into the rough surface In the case of anchor joints that are joined by the anchor effect, at least one joint member can easily roughen its joint surface, and the other joint member has a specific relationship that it is relatively malleable. However, it cannot be easily applied to many parts, and there is also a problem that the product is easily separated due to slight differences in processing conditions, and the product lacks stability. For example, in the case of adhesive bonding using an adhesive, the presence or absence of a suitable adhesive is a problem. At present, there is almost no effective adhesive especially for metal members and highly crystalline members. is there.

The brazing method and the soldering method are widely used because, when a joining member is manufactured by combining a ceramic member and a metal member, a highly precise joining process is not required and a relatively high joining strength can be obtained. Although this method has been adopted, there are problems such as the need for a bonding material. That is, ceramics is a material having excellent properties such as electrical insulation, strength at high temperatures, and abrasion resistance. Such a ceramic member is combined with a metal member excellent in workability to form a composite. As a result, composites that make use of the excellent properties of ceramics and are suitable as components for electronic components and structural components have been manufactured.In the case of such composites, brazing and soldering methods have been widely used. Patent Literature 1 and Patent Literature 2 are examples of such conventional techniques.

Patent Document 1 discloses that, as a brazing material for joining an aluminum nitride member and a metal member, an active metal having a reactivity with aluminum nitride, for example, titanium, zirconium, hafnium, or a powder of a hydride thereof is specified. A metal powder brazing material containing at least one of the following is disclosed as a method for joining the aluminum nitride member and the metal member: for example, screen printing, roll coating, or spraying on the joining surface of at least one of the members. A method is disclosed in which after applying by a method such as transfer, transfer and the like, these are bonded, and then heated and joined. In particular, it has been shown that by using titanium hydride, a suitable bonding state can be obtained because the titanium oxide is not oxidized and loses its activity before the bonding step, and becomes an active metal titanium by the heat treatment in the bonding step. ing.

Patent Document 2 discloses an activity comprising platinum and manganese in which the manganese content is within a predetermined range. Disclosed is a method of joining a ceramic member and a metal member after coating titanium hydride by spraying or pasting the joint surface on the ceramic side using a conductive metal brazing material and baking it. It was shown that hydrogen generated by decomposition of titanium hydride at the time of joining reduces manganese in the brazing material and improves the activity for ceramics, and that titanium after decomposition acts as an active metal for ceramics. ing.

However, the conventional technology for joining these ceramic members and metal members is a liquid-phase joining method that requires a joining material such as a brazing material, and requires a process of applying the joining material and removing residues thereof. In addition, the combination between members that can be suitably bonded to each other is limited in relation to the melting temperature of the bonding material. Furthermore, the working temperature of the manufactured product is naturally higher than the bonding temperature. Limited significantly lower. Also, for example, when joining semiconductor members and the like, the metal of the joining material that has become a liquid phase at the time of joining tends to diffuse into the inside of the semiconductor members and the like, causing deterioration in the performance of the semiconductor members and the like. There were also problems.

Patent Literature 1 and Patent Literature 2 relate to the joining of the two members, and use a hydride of an active metal. Hydrogen generated by the decomposition of the active metal at the time of joining acts as a reducing agent. Although it is intended to obtain a suitable bond by acting as an active metal to the metal, the joining of the two members is performed using a brazing material as described above, and the brazing material is melted. This is a technology for liquid phase bonding.

In addition to the hydride of the active metal, a conventional technology using a hydrogen storage material has been disclosed in connection with the joining of the two members. The conventional technology will be described below. First, Patent Document 3 discloses that when soldering a metal such as copper, tin, lead, and nickel, which easily forms an oxide film, hydrogen is occluded in the metal member having the hydrogen absorbing property, and heat during the soldering is used. A method is disclosed in which hydrogen is released by the above method, and an oxide film is destroyed by utilizing its reducing action to ensure soldering. In the examples, as a method of storing hydrogen in a metal member in this method, hydrogen storage by a cathodic electrolysis hydrogen storage method using a metal member as a cathode (hereinafter sometimes abbreviated as “cathode electrolysis method”) is used. Is illustrated. According to this prior art, the hydrogen absorbed is released by heating the hydrogen-absorbing member that has absorbed the hydrogen at the time of joining. Element is to be used to remove the oxide film on the surface of the metal member. The joining of the two members is performed by soldering using a solder material, as described above. This is a technology for liquid-phase joining. That is, this conventional technique has the same problems as Patent Documents 1 and 2.

Patent Document 4 discloses that a hydrogen absorbing metal, such as Ni, Mo, Fe, Cr, Nb, Ti, Zr, or the like, for the purpose of firmly and integrally joining different kinds of aluminum alloy members by laser spot welding. Shot blasting of an alloy powder containing V as the main component on the joining surface creates a hydrogen absorbing layer inside the joining member, and when the welding is heated, moisture in the atmosphere reacts with magnesium and aluminum. There is disclosed a technique for controlling the sensitivity of the solidification rate of a molten aluminum alloy by absorbing generated hydrogen in a hydrogen absorbing layer. In this conventional technique, a hydrogen absorbing metal is used to absorb hydrogen generated at the time of welding, and the two members are joined by laser-spot welding as described above. This is a technique of melting both members and joining them by liquid phase. In this conventional technique using welding, the combination between members that can be suitably joined is limited in relation to the melting temperature of the two members. Also, since both members are fused and joined, it is necessary to join semiconductor members and the like. It is not suitable for the production of fine electronic components or structural components, such as the mounting and wiring of electronic components on boards and the joining of electrodes and lead wires.

In addition, a technology has been disclosed in which a hydrogen-absorbing metal is used to facilitate the separation of the joint, increase the possibility of reuse, and reduce the burden of disposing and disposing of the composite. For example, Patent Document 5 discloses that a material that is embrittled by hydrogen, such as a material that expands due to a reaction with hydrogen to cause powdering or separation, particularly hydrogen storage, between members to be joined An intermediate material made of a conductive alloy is arranged, for example, in the form of a thin plate or a thin film, and the members are joined through this intermediate material, for example, at room temperature by soldering, anchor bonding, ultrasonic bonding, bonding, and surface activation. A separable joining structure that is joined by a joining method or the like is disclosed, and a separation method in which hydrogen is absorbed by an intermediate material made of the hydrogen absorbing alloy at the time of separation is disclosed.

Similarly, Patent Document 6 discloses that a hydrogen absorbing metal, particularly, substantially hydrogen is contained in a solder material. Disclosed is a joining material in which a powder of a hydrogen-storing metal that is not occluded is mixed and dispersed, and electronic components are mounted and joined to a substrate by soldering using the joining material. However, there is disclosed a method in which hydrogen is stored (or released) in the hydrogen-absorbing metal powder, and separation is performed by expansion (or shrinkage) caused by the storage and release.

As described above, the prior arts disclosed in Patent Documents 5 and 6 facilitate the separation of the hydrogen absorbing metal, increase the possibility of reuse, and dispose and dispose of the composite. This is a technology that we intend to use in order to reduce the burden on the members. When joining members, another joining technology such as soldering is required. That is, it does not provide a new method capable of suitably performing joining.

Patent Document 1 Japanese Patent Application Laid-Open No. 2000-2802

Patent Document 2 Japanese Patent Application Laid-Open No. 2000-2003

Patent Document 3 Japanese Patent Application Laid-Open No. 05-0-0691122

Patent Literature 4 Japanese Patent Application Laid-Open No. 2000-191980

Patent Document 5 Japanese Patent Application Laid-Open No. Hei 10-26 1886

Patent Document 6 Japanese Patent Application Laid-Open No. 2000-2001 _ 3 3 4 3 8 3

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described circumstances relating to a joined member formed by joining a plurality of members. For joining of members, for example, joining of a ceramic member and a metal member, so-called three-layer joining of a sandwich structure in which a metal member, a ceramic member, or a semiconductor member is disposed on both sides with a metal member interposed therebetween. It is an object of the present invention to provide a method for manufacturing a joining member and a joining member which can be easily applied, in particular, can be easily applied without an inclusion used only for the purpose of joining other than a member to be joined. Aim.

As means for achieving the above object, a method for manufacturing a joining member having the following configuration and the joining member are employed. That is, the invention of claim 1 is a joining member in which a plurality of members are joined. Wherein at least one of the two members to be joined is a hydrogen-absorbing member having at least a surface layer absorbing hydrogen, and the hydrogen-absorbing surfaces of the two members are both members. A method for manufacturing a joining member, characterized in that the storage hydrogen is released by press-contacting so as to constitute an interface of the above, and heating while pressing.

According to a second aspect of the present invention, in the method for manufacturing a joining member according to the first aspect, when joining the two members, an interposer used only for the purpose of the joining is not used in addition to the two members. The invention according to claim 3 is the method according to claim 1 or claim 2, wherein the hydrogen-absorbing member that has absorbed hydrogen is a thin section of a hydrogen-absorbing member whose both surface layers have absorbed hydrogen. A separate member is pressed against the surface, and the stored hydrogen is released by heating while pressing.

The invention according to claims 4 and 5 relates to the form of the material of the member. The invention according to claim 4 is the method according to claims 1 to 3, wherein the hydrogen storage member is a hydrogen storage metal member. According to a fifth aspect of the present invention, in the manufacturing method of the first to fourth aspects, the other member to be bonded to the hydrogen storage member is a ceramic. The invention according to claim 6 relates to an embodiment of a method of causing a hydrogen storage member to store hydrogen, and in the production method according to any one of claims 1 to 5, wherein the hydrogen storage member is a cathode electrolysis using a hydrogen storage conductor member as a cathode. This is a method for producing a joining member, which is a hydrogen-storing conductor member that has absorbed hydrogen by a hydrogen-storing method.

The inventions of claims 7 and 8 are the joining member of the present invention. That is, the invention of claim 7 is a joining member manufactured by joining a plurality of members, and characterized in that the joining member is manufactured by joining the plurality of members by the manufacturing method of claims 1 to 6. The invention according to claim 8 is a member, characterized in that the joint does not have any inclusions used only for the purpose of the joining, except for the elements that substantially constitute the plurality of members.

As described in detail below, the present invention provides at least one of the two members to be joined. By using a hydrogen-absorbing member in which at least the surface layer has absorbed hydrogen, and making this hydrogen-absorbing member function as a joining material for joining both members, joining of a wide variety of combinations of many members is possible. In particular, joining of members that were not easy to join in the prior art, for example, joining of a ceramic member and a metal member, a metal member, a ceramic member, or a semiconductor member on both sides with the metal member interposed therebetween. It can be easily applied to the so-called sandwich structure three-layer joining, which is provided with, in particular, it can be easily applied without the need for inclusions used only for joining purpose other than the members to be joined. There is an effect that a member manufacturing method and a joining member thereof can be provided. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, preferred embodiments of the present invention will be described. The surface layer for storing hydrogen in the present invention means the surface of the joining surface of the member and / or the inside of the member near the joining surface (hereinafter, may be referred to as a “near layer”). Further, the hydrogen-absorbing member for storing hydrogen according to the present invention is not limited to a homogeneous member made of a metal or an alloy having a hydrogen-absorbing property. It includes various forms such as a form in which a metal having an occluding property is doped, a hydrogen occluding layer is formed inside the member near the joining surface, and the hydrogen occluding layer is used as a hydrogen occluding member.

As described above, the method for manufacturing a joining member according to the present invention includes, as described above, at least one of the two members to be joined is a hydrogen-absorbing member in which at least the surface layer of the member absorbs hydrogen. A method in which the hydrogen-absorbing surface is pressed so as to form an interface between the two members, and the stored hydrogen is released by heating while being pressed, whereby the hydrogen-absorbing member functions as a joining material for joining the two members. The biggest feature is that. Therefore, the present invention is also characterized in that it can be carried out without using a special bonding material, flux or the like, that is, an inclusion used only for the purpose of bonding, in addition to a member to be bonded.

By heating while press-contacting in this manner, hydrogen is released from the hydrogen-absorbing member, and the generation of active elements in the hydrogen-absorbing member is promoted, or at least the surface of the joint surface or Not only activates the adjacent layer, but also acts as active hydrogen at the nascent stage on the joining surface of the member to be joined, and reduces and activates the surface of the joining surface and the adjacent layer to reduce the crystal structure. Disturbing or facilitating the movement of atoms to cause diffusion of atoms or ions at the interface between both members, or forming a chemical bond between the two, or at least forming an interatomic interaction such as a hydrogen bond Thereby, it can be joined in a combination of various members.

As is apparent from such an embodiment, any mechanism such as reaction, adsorption, and absorption can be used for hydrogen storage as referred to in the present invention, as long as a predetermined bonding can be obtained by heating and releasing the stored hydrogen. May occur. For example, a form in which hydrogen is stored as a hydride that can be stoichiometrically represented as a certain compound, or a crystal lattice of the original material that cannot be defined as a hydrogen compound such as a so-called “hydrogen storage alloy” It can be implemented in various forms, such as a form in which hydrogen expands and occludes hydrogen.

For example, when implemented in the form of absorbing hydrogen as a metal hydride, the metal hydride begins to rapidly dehydrogenate at a certain temperature or higher, and the metal that has been hydrogenated until now has a high free energy, that is, In the active state, a reaction layer mainly composed of dehydrogenated metal is formed at the bonding interface, and is easily combined with nearby elements to form a stable alloy phase. A strong bond results. The temperature at which this dehydrogenation starts is much lower than the melting point of the alloy itself, and this feature is used to perform solid-state bonding, which is easier to handle and has a simpler manufacturing process than liquid-phase bonding. be able to.

According to the above-described embodiment, the method for manufacturing a joining member according to the present invention can be easily applied to joining of various combinations of many members. In other words, a very simple manufacturing process in which at least one of the members to be joined is a hydrogen-absorbing member that absorbs hydrogen and heated while pressing the hydrogen-absorbing surface so as to form an interface between the two members. In addition, it can be easily applied by the solid-phase joining method without using special joining materials, fluxes, etc., ie, inclusions used only for joining purposes, in addition to the members to be joined. it can. As described above, the method for manufacturing a joining member according to the present invention can be applied to a wide variety of combinations between many members. Although it is unavoidable, preferred embodiments of the present invention will be described in more detail below.

First, the combination between members to be joined will be described. That is, the two members to be joined according to the present invention are a combination in which at least the surface layer of at least one member is a hydrogen-absorbing member that has absorbed hydrogen, and at least one member has at least the surface layer. If the surface, particularly the surface layer of the bonding surface, is a member made of a hydrogen storage member that stores hydrogen, the other may be a hydrogen storage member that stores hydrogen or may not be a hydrogen storage member. . That is, joining of the hydrogen-storing members that have absorbed hydrogen, joining of the hydrogen-storing member that has absorbed hydrogen with a member that has hydrogen-storing but not storing hydrogen, and joining of the hydrogen-storing member that has absorbed hydrogen. Bonding with a member having no hydrogen storage property can be performed in any form.

In addition, not only can two members be joined, but also three or more members can be laminated in a multilayer and integrally joined. That is, the shape of the member does not limit the present invention in any way. For example, the shape of the member may be plate-like or flake-like, and the plate-like or flake-like hydrogen-absorbing property in which both surface layers absorb hydrogen. It is also possible to adopt a mode in which a member is used, and separate members are pressed into contact with both sides thereof, and these are integrally joined. For example, a so-called sandwich-structured three-layer joining member in which a metal member is sandwiched between metal members, a ceramic member, or a semiconductor member on both sides, which has conventionally been difficult to join, can be integrally joined. . Further, a multilayer joining member having four or more layers can be manufactured by alternately stacking the hydrogen storage member and another member.

Next, a member that can be joined by the present invention, that is, a member that can constitute the joining member of the present invention will be described. The members that can be joined in the present invention cover a wide variety of materials, for example, Cu, A1, Sn, Zn, Ag, Au, Ni, Ti, Zr, Fe, Cr, Nb, Mo, SUS, bronze, brass, Gin蠟, metals gold _{_{蠟等, BaTi0 3, B i 2 Te}} 3, CoSb 3, CoSbYb etc., and semiconductors doped with various metals to _{_{these, A1 2 0 3, A1N,}} BN, ZnO, BaTi0 3 , S i0 _2, ZrO, glass, ceramic sialon, etc. And plastics such as polyesters, polyesters, polyimides, polyamides, polycarbonates, polyurethanes, polysulfones, acrylic resins, polypropylene, bakelites, ebonites, and melamine resins.

Of these, the invention is not particularly limited, but can be particularly effectively applied to the connection between a ceramic member and a metal member. That is, the present invention can be suitably implemented by using a hydrogen storage metal member as the hydrogen storage member and using ceramic as the other member to be joined thereto.

Usually, as the hydrogen storage member, a metal or an alloy having a hydrogen storage property, for example, a lanthanide-based alloy such as La-Mg, La-Pb, La-Sin, La-Ni, or Ce-Ni is used. Force using iron-based alloys such as cerium-based alloys and Fe-Ni ^ Not limited to this, as described above, for example, doping a non-hydrogen-absorbing metal such as ceramics with a hydrogen-absorbing metal, A hydrogen storage layer may be formed inside the member near the joint surface, and this may be implemented as a hydrogen storage member for storing hydrogen.

The shape of the member is not particularly limited, and may be a shape that allows the members to be joined to be pressed against each other. Therefore, a joint between flat plate members, for example, a clad plate, a semiconductor laminate, a multilayer substrate, Suitable for the manufacture of products such as metallized substrates for printed wiring boards, etc., but also for the mounting of electronic components on boards, wiring, bonding of electrodes and lead wires, and application of many other bonding members. Is possible.

Next, the form of a hydrogen storage layer formed by storing hydrogen in a member having hydrogen storage properties will be described. That is, in the present invention, at least one of the two members to be joined is a member having at least a surface layer, particularly a surface layer of the joining surface, made of a hydrogen-absorbing member absorbing hydrogen. Is a mandatory requirement. Therefore, a member that has absorbed hydrogen may be in a form in which hydrogen is occluded only in the surface layer of the joint surface, in a form in which hydrogen is occluded in the surface layer over the entire surface, or in a deep portion inside the member. May be stored.

However, in general, as shown in the above-mentioned literature, a metal that has absorbed hydrogen tends to be brittle and tends to be powdered in some cases. For example, it is preferable to use a sheet-and-foil member that absorbs a large amount of hydrogen in the surface layer, reduces the depth toward the depth, and easily maintains the strength as a metal. That is, it is preferable that the hydrogen-absorbing metal member is configured to absorb hydrogen only to the minimum necessary range. The thickness of the hydrogen-absorbing layer is appropriately determined depending on the combination of the members to be joined and the like. It is to be determined, and not to limit the invention in any way, but a thickness of at least several hundred Angstroms, typically tens of microns, or more is generally preferred.

Next, a mode in which hydrogen is stored in a member having hydrogen storage properties will be described. The method of absorbing hydrogen does not limit the invention as long as the object of the present invention is achieved.For example, cathodic electrolysis, room temperature to 100 ° C. under a hydrogen pressure of 0.01 to 50 MPa It can be used without limitation including conventional techniques such as high-pressure hydrogenation method or hydrogen plasma irradiation method.

. In other words, when the member is a conductor, the cathodic electrolysis method can usually be suitably used, but this does not exclude the use of other hydrogen storage methods, particularly when the hydrogen storage member is a non-conductor. For this, a hydrogen storage method other than the cathodic electrolysis method is used.

When the member is a conductor, this hydrogen storage can be easily performed, particularly by subjecting water to electrolysis by a cathodic electrolysis method using the hydrogen storage conductor member as a cathode. That is, as is well known, the cathodic electrolysis hydrogen storage method is a method in which a member to be subjected to hydrogen storage is used as a cathode, and water is electrolyzed in an aqueous electrolyte solution by applying an appropriately selected voltage equal to or higher than the electrolysis voltage of water. During electrolysis, the nascent hydrogen is adsorbed on the cathode surface in a very short time, then diffuses gradually and spreads inside the cathode, so that the hydrogen absorption depth and occlusion in the cathode depend on the electrolysis time. This is a method that can control the amount and can be suitably used in the present invention. The cathode electrolysis hydrogen storage method is not limited to metals, for example, the graph eye preparative plate Ya Poriasechi conductor Ren like, or that metal is doped ceramic box, such as ZnO and BaTi0 _3, the other semiconductor element or the like If so, the same processing can be performed.

More specifically, the invention does not limit the invention. For example, in consideration of the equilibrium potential of hydrogen and overvoltage, a voltage which is appropriately selected depending on the pH of the electrolyte solution is generally applied at about several tens of volts. At this time, if the current density is too high, the generation of hydrogen gas is promoted, which not only wastes energy but also suppresses the absorption of hydrogen into the cathode, so that in general, several centimeters per square centimeter It is preferable to set it to about 1 to 1 ampere, particularly about tens to hundreds of amperees. The time for the electrolytic treatment is usually such that the hydrogen-absorbing conductive member is made of a metal such as Cu, Fe, Ni, Ag, Ti, Al, Nb, Mo, and an alloy containing these as main components, La-Mg, La Absorbs hydrogen, such as lanthanide alloys such as -Pb, La-Sra, and La-Ni, cerium alloys such as Ce-Ni, iron alloys such as Fe-Ni, gold, silver, etc. In the case of easy metals, the purpose can be generally achieved in minutes to hours. In particular, when a thin member with high hydrogen diffusivity is used, it should be treated for a short time to occlude hydrogen only to the minimum necessary range. Further, ZnO, a semiconductor such as Se and Rami click de one-flop with a transition metal such as the BAT i0 _3, for example 0.5 as 5-5 hours, for a relatively long time treatment results in successful. Incidentally, in the these cathodic hydrogen occlusion treatment, generally can Rukoto to reach a sufficient purpose 10 one ^4-10_ ² Faraday / cm ² of about processing as an electrical quantity.

Next, a description will be given of the process conditions of heating while pressing. In the joining of the members according to the present invention, the members to be joined are pressed against each other so that the hydrogen storage surface forms an interface between the two members, and the hydrogen is released from the hydrogen storage member while being pressed. Heat to a temperature above the specified temperature. In this case, the pressure for the contact should be such that the two members to be joined can be in close contact with each other, and usually about 0.01 to 10 MPa is sufficient.

In general, in order to obtain uniform adhesion at the interface between the two members, relatively high malleability, for example, aluminum, copper, lead, zinc, gold, silver, silver, silver, etc. For example, the pressure may be about 0.01 to 1 MPa, but in the case of tin, iron, nickel, titanium, molybdenum, stainless steel, etc., the deformation caused at the interface by pressing at a relatively high pressure, for example, about 1 to 10 MPa, The unevenness can be corrected to obtain a uniform close contact.

The heating temperature for releasing hydrogen from the hydrogen storage member is different for the members used. It can be checked in advance by heat absorption measurement or other methods, and it is preferable to check and execute it. Generally, about 100 to 700 ° C is sufficient. Note that heating is preferably performed in an atmosphere of an inert gas such as nitrogen, under reduced pressure, or under vacuum.

Next, an embodiment of the joining member of the present invention will be described. That is, the bonding member of the present invention is a composite manufactured by the above-described manufacturing method, and as described above, a two-layer bonding member in which metals are bonded to each other, and a metal and ceramics or plastics in which metal is bonded. Layer-joining members, so-called three-layer joining members with a so-called sandwich structure in which metal members, ceramic members, or semiconductor members are arranged on both sides with a metal member sandwiched between them, and alternately, metal members and ceramic members, etc. It can be easily applied and implemented for joining of a wide variety of combinations between many members, such as multilayer joining members joined together.

In addition, as described above, the joining member of the present invention includes, at the joint thereof, an inclusion used only for the purpose of the joining, such as a brazing material or a flux, except for elements constituting substantially the plurality of members. It can be implemented as a form without. That is, the joining member of the present invention has a form substantially having only elements of the joined members and having a hydrogen storage layer made of a substance having a hydrogen storage property at least in the vicinity of the bonding surface. Can be implemented.

In addition, the bonding member of the present invention uses a hydrogen storage layer made of a substance having a hydrogen storage property in the same manner as in Patent Document 5 and Patent Document 6, and By repeating the absorption and desorption of hydrogen from the hydrogen storage layer, bonding can be easily separated, the possibility of reuse can be increased, and the burden of disposal and treatment of the bonding member of the present invention can be reduced. .

As is clear from the manufacturing method, the joining member of the present invention can be used up to a use temperature much higher than a joining temperature at the time of joining and manufacturing, that is, it can be used up to a heat resistance temperature of the joined member. There is a feature that there is.

According to the embodiments described above, the present invention uses a hydrogen storage member in which at least the surface layer of at least one of the two members to be joined stores hydrogen. By functioning as a joining material for joining members, a wide variety of Combination joining, especially joining of members that were not easy to join with the conventional technology, such as joining of ceramic members and metal members, metal members or ceramic members on both sides with the metal members sandwiched It can be easily applied to the so-called sandwich structure three-layer bonding in which semiconductor members are arranged. In particular, it can be easily applied without the need for inclusion other than the member to be bonded and the inclusion used only for the purpose of bonding. Thus, it is possible to provide a method for manufacturing a joining member and the joining member.

Example

Hereinafter, the present invention will be described more specifically with reference to examples. First, a description will be given of an embodiment in which various combinations of members are joined under various conditions shown in Table 1. As shown in Table 1, the structure of the joining member is composed of member A, hydrogen storage member, and member B, and `` one '' in the column of `` member B '' means the case where member B is not used. This means that two-layer joining between the member A and the hydrogen storage member was performed. In other cases, a three-layered sandwich structure in which a member A and a member B are arranged on both sides of the hydrogen storage member is sandwiched.

"table 1"

Bonding member configuration Hydrogen storage conditions

Run Junction temperature No. Hydrogen storage member Current density Processing time

(Member A member B C)

Thickness (mA / cm ² ) (time)

1 ZnO silver ¾ 1 0.1 one 36 2.0 600 〇

2 A1N A1 1 0.5 A1N 37 0.5 640 〇

3 A1N Cu 1 0.1 A1N 36 2.0 600 〇

4 A1N Ti 1 0.02 A1N 30 0.5 550 〇

5 BaTi0 ₃ Cu 1 0.1 BaTiO, 36 2.0 604 〇

6 Bi ₂ ie ₃ -n Ti 1 0.04 Cu 37 3.0 550 〇

7 Bi ₂ Te ₃ -p Ti 1 0.04 Cu 36 1.0 550 〇

8 Cu Ti 1 0.02 Bi ₂ Te type 36 0.5 530 〇

9 CoSb-n Ti 1 0.04 Cu 33 2.0 600 〇

10 CoSb-p Ti 1 0.04 Cu 34 2.0 600 〇

11 CoSb-Yb-p Ti 1 0.04 Cu 36 1.0 600 〇

12 CoSb π-type Ti 1 0.1 CoSb π-type 34 2.0 600 〇

13 Cu Cu 1 0.1 1 36 2.0 604 〇

14 Cu Ti 1 0.04 Al 35 0.1 640 〇

15 Ag BaTiOj Ag 36 1.0 550 〇

16 Al (H) ZnO Al (H) 36 1.0 550 〇

17 Ni Ag 1 0.1 Ni 36 2.0 510 O

18 Ni Ti 1 0.04 Ni 35 2.0 640 〇

19 ZnO Ag 1 0.1 Cu 30 0.5 560 〇

20 ZnO Ni 1 0.1 Cu 36 2.0 593 〇

21 BaTi0 ₃麵 1 0.1 Cu 36 2.0 600 〇

22 Cu SUS 1 0.1 1 37 0.5 600 〇

23 Al Ni 1 0.1 ― 37 2.0 600 〇

24 Si0 ₂ Cu 1 0.1 Si0 ₂ 36 2.0 520 〇

25 Ag 1 0.1 Si-n 30 0.5 550 〇

26 ¾i-p Ag 1 0.1 Si-p 30 0.5 550 〇

27 A1 ₂ 0 ₃ Cu 1 0.1 ZrO 36 2.0 600 〇

* 28 A1N Cu 1 0.1 A1N one-600 o

29 Ni Ti 1 0.1 Ni ― 1 640 X

30 ZnO Ag 1 0.1 ― 1 1 600 X

31 ZnO Ni 1 0.1 Cu one 550 X

32 Si0 ₂ Ni 1 0.1 Si0 ₂ 1 ― 600 X

33 Al ₂ 0 ₃ Cu 1 0.1 ZrO 11 600 X The hydrogen storage member is a thin piece of 10 mm x 10 mm, and its thickness is as shown in Table 1. Except for some cases (“1” in the “Hydrogen storage conditions” column in Table 1), hydrogen storage was performed for this hydrogen storage member or for members A and B in Run No. 16. Using a member as a cathode and platinum as an anode, hydrogen storage treatment was performed in a 1N aqueous sulfuric acid solution under the electrolysis conditions shown in Table 1 ("hydrogen storage conditions" in Table 1). However, in Table 1, the case marked with * (Run No. 28) was obtained by performing hydrogen storage at a pressure of 3 MPa for 10 minutes in a high-pressure vessel by the high-pressure hydrogenation method.

That is, in Table 1, from Run No. 1 to Run No. 28, a case which is occluded hydrogen, an embodiment of the present invention, from the R _un No. 29 to Run No. 33, the hydrogen This is a comparative example in which ozone is not absorbed. Note that “(H)” in the “member A” column and the “member B” column in Table 1 means that the member has absorbed hydrogen.

In this joining member configuration, using a hot press, the members were laminated as a member AZ hydrogen absorbing member member B, and pressed and pressed to 0.01 to 100 MPa, and heated to the temperature shown in Table 1 while pressing. Then, after the temperature reached the predetermined temperature, the heat treatment was carried out so as to be rapidly cooled. In other words, this embodiment was carried out without providing a step of maintaining the temperature at the heated temperature, and the present invention can be joined by such a simple method. These bonding processes were performed in a nitrogen atmosphere at normal pressure, except for Run No. 9 to Run No. 12 under reduced pressure. For the joint member manufactured as described above, as a judgment of the jointability, an adhesive tape (trade name) was formed so that it could be peeled off from one side on the entire surface (approximately 1 cm ² ) of one of the joints. : Adhesive tape), and when the adhesive tape is rapidly pulled off, if at least a part of the adhesive is separated from the joining surface of the member, it is regarded as “X”, which means that normal joining has not been made. A sample in which the adhesive tape was pulled off without any separation was regarded as having a normal joint, and was measured as “とする”. The results are shown in Table 1. As shown in Table 1, as shown in Table 1, Run No. 1 to Run No. 28, which are examples of the present invention, all had normal joints, but were comparative examples. From Run No. 29 to Run No. 33, all of them are not properly joined. Next, examples of the present invention performed under the conditions shown in Table 2 will be described. The “joining member configuration” and “hydrogen storage conditions” in Table 1 are the same as in Table 1. The members A and B in Table 2 are each obtained by cutting a 5 mra tip of a circular rod having a diameter of 6 to 9 mm and a length of 20 into a diameter of 3 mm.

In the joining member configuration shown in Table 2, a hydrogen absorbing member was interposed between the three-diameter parts of member A and member B and joined together. Heat treatment released hydrogen. The heat treatment was performed by a process of heating to 560 ° C. and immediately quenching after reaching the temperature, as in the above-described example.

The tensile test speed of the embodiment of the joint member of the present invention manufactured as described above was measured using Minebea's Technograph TG-5kN (trade name) (Nichidosel: N MB TU3D-5kN). Tensile tests were performed at 1-3 mm / min.

`` Table 2 '' Bonding member configuration Hydrogen storage conditions

Run tensile strength

No. Hydrogen storage member / Current density Processing time

Part A Part B (kN / mra ² )

Thickness, marauder) (mA / cm ² ) (time)

1 SUS304 Ti 1 0.02 SUS304 30 0.5 0.108

2 SUS304 Ti 1 0.02 SUS304 37 0.5 0.147

3 SUS304 Silver Tad / 0.1 SUS304 30 1.0 0.144

4 SUS304 Silver Tad / 0.1 SUS304 36 0.5 0.145

5 SUS304 silver moth / 0.1 SUS304 37 1.0 0.160

6 Cu Ti 1 0.02 Cu 30 0.5 0.079

7 Cu silver 蠟 / 0.1 Cu 30 0.5 0.058

8 Cu silver / 0.1 Cu 30 1.0 0.095

9 Cu silver / 0.1 Cu 37 0.5 0.078 The results are shown collectively in Table 2, tensile strength 0.058 to 0.160 in the range of kN / mm ^2, as the bonding member, practically in bonding strength is obtained which can be used sufficiently It demonstrates that

In the above embodiments, the present invention is applied to the joining of various combinations of many members, in particular, joining of members that were not easy to join with the conventional technology, for example, joining of ceramic members and metal members, It has been demonstrated that the present invention can be easily applied to a three-layer bonding of a sandwich structure in which a metal member, a ceramic member, or a semiconductor member is disposed on both sides with a metal member interposed therebetween. In particular, it demonstrated that there is no need for inclusions used only for joining purposes other than the members to be joined, and that it can be easily applied by the solid-state joining method.

Although the embodiments of the present invention have been described above, it is apparent that various changes can be made in the form and details without departing from the spirit and scope of the present invention defined in the appended claims. is there. For example, the configuration of the joining member, its shape and dimensions, hydrogen storage conditions, joining conditions, and the like are examples, and do not limit the present invention in any way. can do.

Claims

Claims A method for manufacturing a joined member by joining a plurality of members, wherein at least one of the two members to be joined is a hydrogen absorbing member in which at least the surface layer has absorbed hydrogen. A method for manufacturing a joined member, comprising: pressing the member so that its hydrogen storage surface forms an interface between the two members; and heating the member while pressing the member to release the stored hydrogen.

2. The method for manufacturing a joined member according to claim 1, wherein, when joining the two members, an inclusion used only for the purpose of joining is not used in addition to the two members.

The hydrogen-absorbing member that has absorbed hydrogen is a thin piece of a hydrogen-absorbing member whose surface layers on both sides are occluded with hydrogen. 3. The method for producing a joining member according to claim 1, wherein hydrogen is released.

4. The method according to claim 1, wherein the hydrogen storage member is a hydrogen storage metal member.

5. The method for manufacturing a joined member according to claim 1, wherein the other member to be joined to the hydrogen storage member is a ceramic.

The hydrogen storage member according to claim 1, wherein the hydrogen storage member is a hydrogen storage conductor member that stores hydrogen by a cathodic electrolytic hydrogen storage method using the hydrogen storage conductor member as a cathode. A method for manufacturing a joining member.

A joining member manufactured by joining a plurality of members, wherein the joining member is produced by joining the plurality of members by the manufacturing method according to claim 1.

8. The joining member according to claim 7, wherein the joining portion does not have any inclusions used only for the purpose of the joining, except for elements substantially constituting the plurality of members.