JP2020172026A - Method of manufacturing joined body and joined body - Google Patents

Abstract

To join a plurality of members more easily.SOLUTION: A method of manufacturing a joined body includes a joining step of joining a first member and a second member in such a manner that a laminated body including an inorganic structural cloth with a self-standing structure, in which fiber bodies containing metal and/or a metallic compound and/or shell are three-dimensionally connected, arranged between the first member and the second member is subjected to a heat treatment at the Tammann temperature or more that is a half of a temperature of a melting point of the metal and/or the metallic compound included in the inorganic structural cloth and the inorganic structural cloth is used as a joining part.SELECTED DRAWING: Figure 1

Description

In the present specification, a method for producing a bonded body and a bonded body are disclosed.

Conventionally, as a method for manufacturing a bonded body, a carbon fiber is interposed between a metal member and a resin member, and a force is applied from one of the metal member and the resin member to the other, and the carbon fiber is changed to the resin member. A method of melting the resin member by the transferred heat and joining the resin member to the metal member has been proposed (see, for example, Patent Document 1). In this joining method, since heat is transferred to the end face of the resin member using carbon fibers, heat can be efficiently transferred to the resin member, the flowability of the resin member can be improved, and the joining time can be shortened. , And.

Japanese Unexamined Patent Publication No. 2018-161781

However, in Patent Document 1, although it is stated that efficient bonding can be performed by utilizing the heat transfer property of carbon fibers, a resin member is indispensable for the bonded body, and for example, a metal member and a metal member are bonded. That was not taken into account. Further, although it is conceivable to use a member forming a joint portion when producing a joined body, it has been required to join a plurality of members more easily, such as joining at a lower temperature.

The present disclosure has been made in view of such a problem, and an object of the present disclosure is to provide a method for manufacturing a bonded body and a bonded body capable of joining a plurality of members more easily.

As a result of diligent research to achieve the above-mentioned object, the present inventors have made a temperature of 1/2 of the melting point when a plurality of members are joined by using an inorganic structural cloth having a nanostructure containing a metal and a metal compound. It has been found that the inorganic structural cloth can be melted by heating at about the Tanman temperature to obtain a bonded body, and the method for producing the bonded body and the bonded body of the present disclosure have been completed.

That is, the method for producing a bonded body of the present disclosure is as follows.
The inorganic structure is obtained by arranging an inorganic structure cloth having a self-supporting structure in which a fiber body containing a metal and / or a metal compound and / or a shell is three-dimensionally connected between the first member and the second member. Heat treatment is performed at a temperature equal to or higher than the Tanman temperature, which is half the melting point of the metal and / or metal compound constituting the structural cloth, and the inorganic structural cloth is used as a joint to join the first member and the second member. It includes a joining step to be performed.

The conjugate of the present disclosure is
With the first member
The second member and
The fiber body containing a metal and / or a metal compound and / or a shell has an inorganic structure cloth structure having a self-supporting structure in which the shell is three-dimensionally connected, and is formed between the first member and the second member. A joint portion that joins the first member and the second member,
It is equipped with.

In the present disclosure, a plurality of members can be joined more easily. The reason for this can be inferred as follows, for example. Generally, in joining a metal member and a metal member, it is necessary to form a joint portion by heating to a temperature equal to or higher than the melting point of the metal. On the other hand, an inorganic structural cloth containing a metal and / or a metal compound has a nanostructure, has a higher chemical potential, and can be melted at a Tanman temperature lower than the melting point, so that a plurality of members can be formed at a lower temperature. It is presumed that they can be fused.

The explanatory view which shows an example of the manufacturing method of the joint body 10. Explanatory drawing which shows an outline example of the structure of the inorganic structure cloth 20. The schematic diagram of the manufacturing process of an inorganic structure cloth (nonwoven fabric structure). The explanatory view which shows the manufacturing procedure of the IrO ₂ nanowire non-woven fabric of Experimental Example 3. Observation results of Experimental Examples 1 to 3. Observation results of Experimental Examples 3 and 4. Photographs of the non-woven fabric of the base material and the inorganic structure cloth of Experimental Examples 5 to 11 before removing the non-woven fabric. Photograph of an inorganic structure cloth having a non-woven fabric structure of Experimental Examples 5 to 11 in water. Photograph of an inorganic structure cloth having a non-woven fabric structure of Experimental Example 12. Photograph of the joined body of Example 1. Photograph of the joined body of Example 2.

[Manufacturing method of joint]
Hereinafter, one embodiment of the present disclosure will be described in detail with reference to the drawings. FIG. 1 is an explanatory diagram showing an example of a method for manufacturing the bonded body 10. FIG. 2 is an explanatory view showing an outline example of the configuration of the inorganic structural cloth 20. FIG. 3 is a schematic view of a manufacturing process of an inorganic structural cloth (nonwoven fabric structure). The method for producing a bonded body of the present disclosure includes a joining step of joining a first member and a second member using an inorganic structural cloth. Further, the manufacturing step of manufacturing the inorganic structural cloth used in the joining step may be further included before the joining step. The inorganic structural cloth may be prepared in advance and this manufacturing step may be omitted. In this manufacturing method, as shown in FIG. 1, after arranging the inorganic structural cloth 20 between the first member 11 and the second member 12, heat treatment is performed to melt the inorganic structural cloth to form a joint portion 15. By doing so, the bonded body 10 is produced. As shown in FIG. 2, the inorganic structure cloth 20 has a self-supporting structure in which the fiber bodies 21 are three-dimensionally connected. A base material space 22 is formed in the fiber body 21 after the fibers of the base material have been removed. Further, when the fibrous body 21 is enlarged, a protrusion structure 23 having a diameter of 3 nm or more and 10 nm or less is formed on the surface thereof. The fibrous body 21 and the protrusion structure 23 are composed of aggregates of nanoparticles 24 containing at least one of a noble metal, a main group metal, and a transition metal. The inorganic structure cloth 20 having such a structure has flexibility, is easy to handle, has a large surface area, and is easily melted.

Here, the "self-supporting structure" refers to a structure having a strength that allows handling. “Nanoparticles” refer to particles having a particle size of 1 nm or more and 10 nm or less. The “fibrous body” refers to, for example, a fiber that is formed on the surface of a fiber as a base material and has a shape based on the fiber. The "shell" refers to a sheet-like (shell-like) structure having a larger horizontal direction (x-axis direction and / or y-axis direction) than the thickness direction (z-axis direction). "Shell containing agglomerates of nanoparticles" means that the dimensions of the shell in the thickness direction (z-axis direction) have a finite value, and a plurality of nanoparticles are necessarily laminated in the thickness direction. Doesn't mean that. That is, the shell includes a case where the nanoparticles include one nanoparticle layer arranged on the xy plane and a case where the shell includes a laminate of two or more nanoparticles layers. The "protrusion structure" refers to a protrusion having a weight-like outer shape such as a pyramid or a cone. The "diameter of the protrusion structure" refers to the maximum diameter of the protrusion (for example, in the case of a cone, the diameter of the bottom surface). The diameter and number of protrusion structures can be controlled by vapor deposition conditions. In general, the larger the number of small diameter protrusions, the larger the specific surface area of the inorganic fabric. By optimizing the vapor deposition conditions, it is possible to form a protrusion structure composed of nanoparticles and having a diameter of 3 nm or more and 10 nm or less on the surface of the fiber body or the shell.

(Manufacturing process)
In this step, an inorganic structural cloth for joining the first member and the second member is produced. In this manufacturing step, for example, a forming treatment for forming a metal and / or a metal compound on the surface of the base material and a removing treatment for removing a part or all of the base material may be performed. In the forming treatment, the metal and / or the metal compound is formed on the surface of the base material containing the polymer, so that the fiber and / or the shell containing the metal and / or the metal compound is three-dimensionally connected to the surface of the base material. Form a self-supporting structure. Here, it is assumed that the metal includes a metal alloy as well as a single element metal. Further, the metal compound is a compound containing a metal element, and includes, for example, a metal salt, a metal oxide, a metal sulfide, a metal nitride, a metal carbide, a metal phosphoride, a metal iodide, and the like. In this forming treatment, a metal and / or a metal compound may be physically vapor-deposited on the surface of the base material. A polymer can be used as the base material. When a polymer is used as the substrate, nucleation and grain growth of nanoparticles proceed relatively easily on the surface of the substrate during the formation of fibrous bodies and / or shells. The composition of the polymer used for the base material is not particularly limited. However, in order to facilitate the removal of the base material, the base material is preferably a solvent-soluble polymer. Examples of the solvent-soluble polymer include polyether sulfone (PES), polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), polyethylene (PE), polypropylene (PP), polyester, polyvinyl alcohol (PVA), and polyacrylonitrile (polyacrylonitrile). PAN), polyethylene oxide (PEO), polyacrylate, polypropylene oxide and the like. The structure of the base material is not particularly limited, and the optimum structure can be selected according to the purpose. The inorganic structure cloth has a structure in which the surface shape of the base material is transferred. Therefore, when a polymer having a nano-sized structure is used as a base material, a self-supporting film having a nano-sized structure can be produced. Examples of the base material include (a) a nanowire non-woven fabric produced by electrospinning and the like, (b) a porous membrane having pores having a radius of curvature of 20 nm or more and 200 nm or less (so-called “Membrane filter”), ( c) Examples thereof include a porous membrane having an opal structure such as polystyrene particles. The non-woven fabric made of polymer used for the base material (base material non-woven fabric) can be produced by electrospinning. The fiber diameter of the base material non-woven fabric can be, for example, the range of the diameter of the base material space described above, and specifically, the range of 500 nm or less, 200 nm or less, and the like. The fiber diameter of the base non-woven fabric can be adjusted by, for example, the polymer concentration of the solution used for electrospinning, the electric field, the supply rate of the solution, and the like.

In this forming process, the method for forming the fibrous body and / or the shell is not particularly limited, but physical vapor deposition may be used. Examples of the physical vapor deposition method include a sputtering method and a pulse laser deposition (PLD) method. When physical vapor deposition of a metal and / or a metal compound is performed on the surface of the base material, the physical vapor deposition may be performed from one side of the base material or from both sides. For example, when a polymer nanowire non-woven fabric is used as a base material, physical vapor deposition is performed from only one side of the nanowire non-woven fabric to obtain a non-woven fabric structure made of a metal or a metal compound of a half-tube type nanowire. Semi-tube type nanowires have a larger specific surface area than tube-type nanowires or rod-type nanowires. Therefore, for example, when this is applied to the catalyst layer of the catalytic reaction device, the utilization rate of the metal and / or the metal compound can be increased. The conditions for physical vapor deposition are not particularly limited, and the optimum conditions can be selected according to the purpose. In general, the longer the deposition time, the thicker the fiber and / or shell can be. Further, in the physical vapor deposition method, the amount of vapor deposition can be controlled at the atomic level. Therefore, if the vapor deposition conditions are optimized, a protrusion structure having a diameter of 3 nm or more and 10 nm or less can be formed on the surface of the shell.

The average diameter of the fibrous bodies formed on the base material is, for example, preferably 10 nm or more, more preferably 50 nm or more, and may be 100 nm or more. The average diameter of the fibrous body is, for example, preferably 500 nm or less, more preferably 200 nm or less, and may be 100 nm or less. At this time, the average diameter of the base fiber (see the diameter d in FIG. 2) is preferably, for example, 5 nm or more, more preferably 40 nm or more, and may be 80 nm or more. The average diameter of the base fiber is, for example, preferably 180 nm or less, more preferably 120 nm or less, and may be 80 nm or less. The average diameter of the base fibers is a major factor in determining the average diameter of the fibers, and the finer the average diameter, the more the surface area of the inorganic structural cloth can be increased. The average diameter of the base fiber and the average diameter of the fiber body can be appropriately selected depending on the intended use. Assuming that the size of the nanoparticles constituting the fiber body is 3 nm to 4 nm, the fiber body can have an average diameter obtained by adding 6 nm or more to the base fiber. When the cross section of the fibrous body has a partially chipped shape such as a crescent shape, the diameter of the fibrous body means the diameter of a pseudo-circle having a circular shape including the chipped portion (diameter in FIG. 2). See D). This average diameter is determined by observing a predetermined visual field (for example, 5 visual fields) with an SEM, determining the diameter of each fiber, and obtaining the average value.

In this forming process, for example, one or more of noble metals, main group metals, transition metals and alloys thereof can be used as metals in the self-supporting structure constituting the inorganic structural cloth. Further, in this forming treatment, one or more of metal salts, metal oxides, metal sulfides, metal nitrides, metal carbides, metal phosphates, and metal iodides can be used for the self-supporting structure as the metal compound. .. Examples of the noble metal include one or more of Au, Ag, Pt, Pd, Rh, Ir, Ru and Os. Further, as a typical metal, for example, one or more of Sn, Al, Mg, Ti, V, and Zn can be mentioned. Further, examples of the transition metal include one or more of Cu, Fe, Co, Ni, Mn, and Mo. Examples of alloys containing metals include Pt-Fe alloys, Pt-Ni alloys, Pt-Co alloys, Ir-Fe alloys, Ir-Co alloys, Ir-Ni alloys and the like. Examples of the metal oxide include iridium oxide, copper oxide, iron oxide, nickel oxide, manganese oxide, cobalt oxide and the like. Examples of the metal sulfide include iridium sulfide, copper sulfide, iron sulfide, nickel sulfide, cobalt sulfide, molybdenum sulfide and the like. Examples of the metal nitride include copper nitride, iron nitride, nickel nitride, manganese nitride, cobalt nitride and the like. Examples of the metal carbide include iridium carbide, silicon carbide, iron carbide, copper carbide, cobalt carbide, manganese carbide and the like. Examples of the metal phosphide include iridium phosphide, iron phosphide, copper phosphide, cobalt phosphide, and manganese phosphide. Examples of the metal iodide include iridium iodide, iron iodide, copper iodide, cobalt iodide, manganese iodide and the like. The inorganic structure cloth may contain nanoparticles of any one of these, or may contain two or more of them. It is preferable that the melting point is low because it is used for the joint portion of the bonded body. Further, when the joint body requires conductivity, the resistance of the joint portion is preferably low.

In the removal treatment, after forming a self-supporting structure on the surface of the base material, all or part of the base material is removed. The base material may be completely removed or a part thereof may be removed. For use in the joint, it is preferable to remove all of the substrate. The method for removing the base material is not particularly limited, and the optimum method can be selected according to the type of the base material. For example, when a solvent-soluble polymer is used as the base material, it is preferable to remove the base material using a solvent. Examples of the solvent capable of dissolving various polymers include dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), NaBH ₄ solution (solvent: 1: 1 mixture of water and ethanol), chloroform, acetone, and the like. Examples thereof include alcohols such as methanol and ethanol, water, 2-methyl tetrahydrofuran, dioxane, dimethyl sulfoxide, sulfolane, and nitromethane.

FIG. 3 is a schematic diagram of a manufacturing process of an inorganic structural cloth (nonwoven fabric structure), and FIG. 3A is a schematic diagram of a non-woven fabric of PVP nanowires having a diameter of 100 to 200 nm. When such a non-woven fabric is used as a base material and, for example, a metal or a metal compound (hereinafter, also referred to as “metal material”) is physically vapor-deposited on the surface of the base material, as shown in FIG. 3B, the metal material is formed on the surface of the base material. The complex in which the shell of is formed is obtained. Further, when the PVP nanowires are removed from the obtained composite, as shown in FIG. 3C, a non-woven fabric (pure metal non-woven fabric) in which the nanowires containing substantially only the metal material are three-dimensionally connected is obtained. Be done. At this time, if the physical vapor deposition conditions are optimized, protrusions having a size of several nanometers are formed on the surface of the nanowire.

When a metal or a metal compound is physically vapor-deposited on the surface of a polymer substrate, a large number of nanoparticles are formed on the surface of the substrate and the particles grow. As a result, fibrous bodies and shells containing agglomerates of nanoparticles are formed on the surface of the base material. When physical vapor deposition is further continued, nucleation and grain growth of nanoparticles are further repeated on the surface of the fiber or shell. As a result, a protruding structure of nanoparticles having a diameter of 1 to 10 nm is formed on the surface of the fiber or shell. Since the obtained fibers and shells are three-dimensionally connected, the self-supporting structure is maintained even if the base material is removed. The inorganic structural cloth thus obtained has substantially no substrate / nanoparticle interface. Further, by using a polymer membrane having a radius of curvature of 20 to 200 nm or a nanowire having a diameter of 20 to 200 nm as a template, an inorganic structural cloth to which such a structure is transferred can be obtained. .. Further, in a physical film forming process such as sputtering, since the amount of vapor deposition can be controlled at the atomic level, a protruding structure having a diameter of about 3 to 10 nm can be formed on the outermost surface. Furthermore, the obtained inorganic structural cloth has high homogeneity, and its manufacturing process is much simpler than that of the ink process. Then, by producing a fiber or shell containing the target metal and / or metal compound by using a physical vapor deposition method such as a sputtering method on the surface of the self-supporting base material, the self-supporting structure imitates the structure of the base material. A film is obtained. Removing the polymer removes the polymer that inhibits the reaction and reveals the surface of the metal and / or the metal compound. Therefore, a high specific surface area can be obtained, the chemical potential is higher, and melting can be performed at a Tanman temperature lower than the melting point.

The obtained inorganic structural cloth has a self-supporting structure in which fibrous bodies and / or shells containing a metal and / or a metal compound are three-dimensionally connected. In this inorganic structural cloth, the fibrous body and the shell may contain an aggregate of nanoparticles containing a metal and / or a metal compound. The nanoparticles may be crystalline or amorphous. The material of the nanoparticles is not particularly limited, and the optimum material can be selected according to the purpose. The metal nanoparticles may contain, for example, any of a noble metal, a main group element and a transition metal, or may contain an alloy containing at least one of the noble metal, the main group element and the transition metal. Further, the inorganic structure cloth may have a protrusion structure of a metal and / or a metal compound having a diameter of 3 nm or more and 10 nm or less on the surface. Examples of the fiber body include tube-type and semi-tube-type nanowires. The fiber body may have, for example, a thickness (diameter) of 500 nm or less, more preferably 200 nm. Further, the fiber body may have a thickness of 1 μm or less from the viewpoint of realizing the protruding structure of the particles. The inorganic structure cloth may have flexibility. For example, if the inorganic structural cloth is made of a metal or an alloy, it can be made flexible like a metal or an alloy, and can be handled more easily.

(Joining process)
In this step, the first member and the second member are joined by using an inorganic structural cloth as a joining portion. As the inorganic structure cloth, the one produced above can be used. Specifically, a laminating treatment in which the inorganic structural cloth is arranged between the first member and the second member to form a laminated body, and 1/2 of the melting point of the metal and / or the metal compound constituting the inorganic structural cloth. The heat treatment is performed by heating at a temperature equal to or higher than the Tanman temperature, which is the temperature of the above. In the laminating process, the first member and the second member are arranged in a state where they are desired to be joined, and an inorganic structural cloth is arranged between them. At this time, the inorganic structural cloth may be transferred to the first member and / or the second member. In the heat treatment, it is preferable to heat while pressurizing in the direction of pressing the first member and the second member. For this heat treatment, for example, a simple device such as a hot plate or an iron may be used, or a burner or the like may be used. The heat treatment temperature may be equal to or higher than the Tanman temperature, but is preferably lower, preferably lower than the melting point, from the viewpoint of energy consumption. From the viewpoint of bonding strength, it is preferable to set the temperature higher. The heat treatment time may be appropriately set to a time during which sufficient bonding strength can be obtained, depending on the member to be used.

Examples of the first member include one or more of metals and resins. Examples of the metal as the first member include the metal and alloy described in the inorganic structural cloth, and examples thereof include Al metal, Cu metal, and stainless metal. As the resin, a heat-resistant resin or the like is mainly preferable, and for example, polycarbonate (PC), polyamide (PA), polyacetylene (POM), polybutylene terephthalate (PBT), fluororesin (PTFE), phenol resin (PF), One or more of melamine resin (MF), urea resin (UF), polyurethane (PUR), epoxy resin (EP), unsaturated polyester resin (UP) and the like can be mentioned. Examples of the resin include one or more of polyethylene (PE), polypropylene (PP), vinyl chloride (PVC), polystyrene (PS), polyethylene terephthalate (PET) and the like. The shape of the first member may be any shape such as a columnar shape or a plate shape. The second member may be the same as or different from the first member, or may be one or more members of metal and resin.

[Joint]
The joint body of the present disclosure includes a first member, a second member, and a joint portion. The first member and the second member may be any of the above. The joint portion is a portion for joining the first member and the second member, and is formed on an inorganic structural cloth having a self-supporting structure in which fibrous bodies and / or shells containing a metal and / or a metal compound are three-dimensionally connected. It has a structure based on it. For example, when the inorganic structure cloth has a structure in which half-tube type nanowires are three-dimensionally connected, a joint portion is formed by the nanowire-shaped molten metal.

In the method for producing a joined body and the joined body described in detail above, a plurality of members can be joined more easily. The reason for this can be inferred as follows, for example. Generally, in joining a metal member and a metal member, it is necessary to form a joint portion by heating to a temperature equal to or higher than the melting point of the metal. Further, when a plurality of members are joined via an alloy such as solder, it is necessary to heat the alloy above the melting point. On the other hand, the inorganic structural cloth containing a metal and / or a metal compound has a nanostructure, has a higher chemical potential, and can be melted at a Tanman temperature lower than the melting point. Therefore, in the present disclosure of joining members using an inorganic structural cloth, it is presumed that a plurality of members can be fused at a lower temperature.

It goes without saying that the present disclosure is not limited to the above-described embodiment, and can be implemented in various embodiments as long as it belongs to the technical scope of the present disclosure.

In the following, first, an example in which an inorganic structural cloth having a self-supporting structure is specifically produced will be described as an experimental example.

[Experimental Examples 1 and 2]
A PES membrane filter (trade name: Millipore PES) was cut into 4 cm squares, and a Pt film was formed on the surface thereof by a sputtering method (forming step). Sputtering was performed in an Ar atmosphere using an MC1000 ion sputtering apparatus manufactured by Hitachi, Ltd. Then, PES was removed using DMF and NMP (removal step) to obtain an inorganic structural cloth having a self-supporting structure containing only Pt. This was designated as Experimental Example 1. Further, an inorganic structural cloth having a self-supporting structure containing only Pt was obtained in the same manner as in Experimental Example 1 except that a PVDF membrane filter was used as a base material. This was designated as Experimental Example 2.

[Experimental Example 3]
FIG. 4 is an explanatory diagram showing a procedure for producing an IrO ₂ nanowire non-woven fabric (Experimental Example 3). First, a non-woven fabric of PVP polymer nanowires having a diameter of 100 to 200 nm was produced by electrospinning an 8 mass% methanol solution of PVP at 1 kV / cm. FIG. 3A is a photograph of the prepared PVP nanowire non-woven fabric. Next, an IrO ₂ film was formed on the surface of this PVP nanowire non-woven fabric by a sputtering method. The IrO ₂ film was formed by sputtering Ir in an atmosphere of 5% oxygen-95% argon. FIG. 3B is a photograph of a PVP nanowire non-woven fabric sputtered with IrO ₂ . In addition, FIGS. 3C and 3D are SEM photographs and schematic views of PVP nanowires forming an IrO ₂ film, respectively.

Next, the obtained non-woven fabric was placed in a 0.5 M NaBH ₄ solution (solvent: a 1: 1 mixture of water and ethanol), and the mixture was stirred at 80 ° C. for 30 minutes to remove PVP, and the IrO ₂ nanowire non-woven fabric was removed. Got FIG. 3E is a photograph of the stirring process for the de-PVP treatment. FIG. 3F is a photograph of the IrO ₂ nanowire non-woven fabric after the de-PVP treatment floating in an aqueous solution. FIG. 3G is a schematic diagram of IrO ₂ nanowires after the de-PVP treatment. After the de-PVP treatment, the IrO ₂ nanowire non-woven fabric was scooped up from the water surface using a Ti plate. FIG. 3H is a photograph of the IrO ₂ / Ti plate thus obtained.

[Experimental Example 4]
A non-woven fabric of PVP polymer nanowires having a diameter of 10 to 20 nm was produced by electrospinning a 4 mass% methanol solution of PVP at 1 kV / cm. Hereinafter, IrO ₂ nanowire non-woven fabric was obtained in the same manner as in Experimental Example 3 except that this PVP nanowire non-woven fabric was used as a base material. This was designated as Experimental Example 4.

[Evaluation]
The fine structure of the prepared inorganic structure cloths of Experimental Examples 1 to 4 was observed using a scanning electron microscope (SEM, FE5500 manufactured by HITACHI). 5A and 5B are observation results of Experimental Examples 1 to 3, FIG. 5A is a low-magnification SEM image of Experimental Example 1, and FIG. 5B is a high-magnification SEM image of Experimental Example 1. Further, FIG. 5C is a low-magnification SEM image of Experimental Example 2, and FIG. 5D is a high-magnification SEM image of Experimental Example 2. Further, FIG. 5E is a low-magnification SEM image of Experimental Example 3, and FIG. 5F is a high-magnification SEM image of Experimental Example 3. From FIGS. 5A to 5D, the following was found. According to the above-mentioned production method, the pore structure of the polymer membrane filter was transferred as it was, and an inorganic structure cloth having a self-supporting structure containing flexible Pt was obtained. It was found that this inorganic structural cloth consisted of agglomerates of Pt nanoparticles having a diameter of 3 to 10 nm. Further, as shown in FIGS. 5E and 5F, it was found that according to the above-mentioned production method, the nanostructure of the non-woven fabric made of polymer was transferred as it was, and a flexible IrO ₂ nanowire non-woven fabric was obtained. It was also found that this IrO ₂ nanowire non-woven fabric structure contained aggregates of IrO ₂ nanoparticles having a diameter of 3 to ₁₀ nm.

FIG. 6 shows the observation results of Experimental Examples 3 and 4, FIG. 6A is an SEM image of the sputtered surface of the IrO ₂ nanowire non-woven fabric (Experimental Example 3), and FIG. 6B shows the back surface of the sputtered surface of Experimental Example 3. It is an SEM image. Further, FIG. 6C is a low-magnification STEM image of Experimental Example 3, and FIG. 6D is a high-magnification STEM image (enlarged view) of Experimental Example 3. Further, FIG. 6E shows an SEM image of the cross section of Experimental Example 3. Further, FIG. 6F is a STEM image of Experimental Example 2, FIG. 6G is an STEM image of Experimental Example 4, and FIG. 6H is a TEM image taken by taking out a part of FIG. 6F. From FIGS. 6A to 6E, the following was found. In Experimental Example 3, since IrO ₂ was sputtered from one surface of the polymer non-woven fabric, the IrO ₂ nanowires had a semi-tube shape (see FIGS. 6A, 6B, 6E). Further, on the surface of the IrO ₂ nanowires, protrusions in which nanoparticles having a diameter of 3 to 10 nm were connected were formed (see FIGS. 6C and 6D). Further, as shown in FIG. 6G, even when an ultrafine polymer nanowire having a diameter of about 10 to 20 nm is used as a mold, an inorganic structural cloth having a non-woven fabric structure can be produced according to the above production method. I found that I could do it. In addition, the following was found from FIGS. 6F and 6H. According to the above-mentioned production method, it was found that an inorganic structure cloth having a porous membrane structure containing Pt nanoparticles having a diameter of 3 to 10 nm was obtained by directly transferring the nanostructure of the polymer membrane filter.

[Experimental Examples 5 to 11]
A polymer non-woven fabric is produced using a small electrospinning device, and a self-supporting structure of metal is formed on the surface of the polymer non-woven fabric using a small tabletop sputtering device (MC1000 ion sputtering device manufactured by Hitachi), and then the polymer non-woven fabric is formed. It was removed to obtain an inorganic structural cloth. Metal targets of Pt, Au, Ag, Cu, Sn, Ru, and Ir were used for sputtering, and the obtained inorganic structural cloths were designated as Experimental Examples 5 to 11 respectively. Sputtering was carried out in an inert atmosphere (Ar gas).

FIG. 7 is a photograph of the non-woven fabric of the base material and the inorganic structural cloth of Experimental Examples 5 to 11 before removing the non-woven fabric. FIG. 8 is a photograph of an inorganic structural cloth having a non-woven fabric structure of Experimental Examples 5 to 11 in water. FIG. 8 is a photograph of the inorganic structural cloth after removing the non-woven fabric in water, and a part of the cloth is turned up in water. As shown in FIGS. 7 and 8, even if each metal such as Pt, Au, Ag, Ru, Ir as a noble metal, Cu as a transition metal, and Sn as a typical metal is used, the non-woven fabric is flexible. It was found that an inorganic structural cloth having a self-supporting structure can be produced. In particular, a metal having high conductivity (for example, Cu or Sn) is suitable for joining an electrode member, a current collector member, or a conductive member of a power storage device or a drive device. In particular, the inorganic structural cloth has an advantage that it is easy to handle because it is extremely thin and has flexibility.

[Experimental Example 12]
Similar to Experimental Example 5, a Ni film was sputter-deposited with a thickness of 100 nm on the surface of a PVP nanofiber non-woven fabric having a diameter of 100 to 200 nm using a Ni target. By immersing this vapor-deposited body in an aqueous solution, a nanowire non-woven fabric-like Ni structure (Ni nanostructured cloth) was obtained. 9A and 9B are photographs of an inorganic structure having a non-woven fabric structure of Example 12, FIG. 9A is a photograph of a 10 mm square Ni nanostructured cloth floating in pure water, and FIG. 9B is an SEM photograph of the Ni nanostructured cloth. Is. As shown in FIG. 9, it was found that even if Ni is used, an inorganic structure that is flexible and has a self-supporting structure of a non-woven fabric can be produced.

(Examples 1 and 2)
Next, a study was conducted to prepare a bonded body using the above-mentioned prepared inorganic structural cloth. An Al metal plate was used as the first member, a polyamide resin plate was used as the second member, and the Ni metal non-woven fabric of Experimental Example 12 was used as the inorganic structural cloth. The inorganic structural cloth was floated in pure water in the same manner as in Experimental Example 12, and then scooped onto the Al metal plate of the first member to transfer the inorganic structural cloth onto the first member. After the transfer, it was heated to 550 ° C. to fuse the inorganic structural cloth on the first member to form a nanostructure on the first member. A polyamide resin plate was pressed against the surface of the first member to which the nanostructure was transferred while heating at 120 ° C. using a heating press jig, and the second member was fused to prepare a bonded body. Example 1 was formed by arranging and joining flat plates of the first member and the second member in parallel, and Example 2 was formed by vertically joining the flat plates. FIG. 10 is a photograph of the joined body of Example 1. FIG. 11 is a photograph of the joined body of Example 2. As shown in FIGS. 10 and 11, it was found that when an inorganic structural cloth is used, a plurality of members can be joined at the Tanman temperature, which is 1/2 the melting point of the metal. Further, since the metal inorganic structural cloth is used as the joint portion, the first member and the second member can be joined in a state of having conductivity.

Although the examples of the present disclosure have been described in detail above, the present disclosure is not limited to the above-mentioned examples, and various modifications can be made without departing from the gist of the present disclosure.

The method for producing a bonded body and the bonded body of the present disclosure can be used in a technical field for joining a plurality of members.

10 Joined body, 11 First member, 12 Second member, 15 Jointed part, 20 Inorganic structure cloth, 21 Fibrous body, 22 Base material space, 23 Projection structure, 24 Nanoparticles.

Claims (7)

The inorganic structure is obtained by arranging an inorganic structural cloth having a self-supporting structure in which a fibrous body containing a metal and / or a metal compound and / or a shell is three-dimensionally connected between the first member and the second member. Heat treatment is performed at a temperature equal to or higher than the Tanman temperature, which is half the melting point of the metal and / or metal compound constituting the structural cloth, and the inorganic structural cloth is used as a joint to join the first member and the second member. A method for manufacturing a bonded body, which includes a joining step. The method for producing a bonded body according to claim 1, wherein in the bonding step, the inorganic structural cloth having a flexible non-woven fabric structure in which half-tube type nanowires are three-dimensionally connected is used. The method for producing a bonded body according to claim 1 or 2, wherein in the bonding step, an inorganic structural cloth having one or more of the characteristics of (1) to (3) is used.
(1) Includes metal nanoparticles containing any of precious metals, main group elements and transition metals.
(2) Includes metal nanoparticles of an alloy containing at least one of a noble metal, a main group metal and a transition metal.
(3) The surface contains a protruding structure of the metal and / or metal compound having a diameter of 3 nm or more and 10 nm or less. The method for producing a bonded body according to any one of claims 1 to 3, wherein in the bonding step, the inorganic structural cloth containing one or more of Cu, Sn, Ni, Cr and Zn is used. A claim that the joining step uses one or more of the first members of the metal and resin and one or more of the second members of the metal and resin that may be the same as or different from the first member. The method for producing a bonded body according to any one of 1 to 4. By forming a metal and / or a metal compound on the surface of a base material containing a polymer, the metal and / or a fibrous body containing the metal compound and / or a shell are three-dimensionally connected to the surface of the base material. Any one of claims 1 to 5, further comprising a manufacturing step of producing the inorganic structural cloth by performing a forming treatment for forming the structure and then performing a removing treatment for removing all or a part of the base material. The method for producing a bonded body according to. With the first member
The second member and
The fiber body containing a metal and / or a metal compound and / or a shell has an inorganic structure cloth structure having a self-supporting structure in which the shell is three-dimensionally connected, and is formed between the first member and the second member. A joint portion that joins the first member and the second member,
Joined body with.