JP2018090488A - Method for joining ceramic member and aluminum member, and joined body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply joining a ceramic member and an aluminum member.SOLUTION: The method for joining a ceramic member and an aluminum member comprises: (a) a step of preparing a ceramic member containing aluminum and/or silicon and an aluminum member; (b) a step of disposing a joining material on at least one of the ceramic member and the aluminum member in which the joining material includes a siloxane-based polymer or a carbon powder-containing silica sol; (c) a step of laminating the ceramic member and the aluminum member in a state that the joining material is interposed therebetween to constitute an assembly; and (d) a step of heating the assembly at a temperature of 600°C to 1,400°C in an inert gas atmosphere or a vacuum atmosphere.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for bonding a ceramic member and an aluminum member, and a bonded body.

  There is a great demand for techniques for joining ceramic members and metal members. However, it is known that joining may be difficult depending on the combination of the ceramic member and the metal member.

  For example, it is well known to those skilled in the art that it is difficult to properly join alumina and an aluminum member.

  This is presumably because an oxide film (alumina layer) that hinders bonding with the ceramic member is present on the surface of the aluminum member. That is, in the joining process, the oxide film present on the surface of the aluminum member does not provide good affinity and good adhesion between the ceramic member and the aluminum member. It is considered that the state cannot be formed.

  In order to cope with such a problem, for example, use of a brazing material of copper, nickel, or titanium has been studied (Patent Documents 1 and 2). That is, when these brazing materials are brazed to the joint surface of the ceramic member, the affinity between the brazing material and the aluminum member is increased, so that the ceramic member and the aluminum member are joined via the brazing material. It has been reported that

JP 11-228245 A Japanese Patent No. 4367675

  As described above, Patent Documents 1 and 2 describe that a ceramic member and an aluminum member, which are difficult to join, can be joined by using a copper, nickel, or titanium brazing material.

  However, this method requires many processing steps such as surface treatment with a flux on the joint surface of the ceramic member and brazing of the ceramic member to the joint surface. For this reason, this method has a problem that it is difficult to simplify the joining process.

  In this method, the flux used includes chloride and fluoride. For this reason, there is a high possibility that chlorides and fluorides remain in the finally obtained product. Such residual compounds can cause a reduction in product quality, such as bonding strength.

  For this reason, there is a demand for a technique for appropriately joining a ceramic member and an aluminum member by a simpler and lower cost method.

  This invention is made | formed in view of such a background, and an object of this invention is to provide the method of joining a ceramic member and an aluminum member more simply. Another object of the present invention is to provide a joined body in which a ceramic member and an aluminum member are joined with good strength.

In the present invention, a method of joining a ceramic member and an aluminum member,
(A) preparing a ceramic member containing aluminum and / or silicon, and an aluminum member;
(B) installing a bonding material on at least one of the ceramic member and the aluminum member, the bonding material including a siloxane polymer or a carbon powder-containing silica sol;
(C) laminating the ceramic member and the aluminum member with the bonding material interposed therebetween, and constituting an assembly;
(D) heating the assembly at a temperature of 600 ° C. to 1400 ° C. in an inert gas atmosphere or a vacuum atmosphere;
Is provided.

Further, in the present invention, a method of joining a ceramic member and an aluminum member,
(A) preparing a ceramic member containing aluminum and / or silicon, and an aluminum member;
(B) installing a bonding material on at least one of the ceramic member and the aluminum member, the bonding material including a siloxane polymer or a carbon powder-containing silica sol;
(C) laminating the ceramic member and the aluminum member with the bonding material interposed therebetween, and constituting an assembly;
(D) heating the assembly at a temperature of 660 ° C. to 1400 ° C. in an inert gas atmosphere or a vacuum atmosphere;
Is provided.

  Here, in the method according to the present invention, the ceramic member may include at least one material selected from the group consisting of alumina, aluminum nitride, silicon nitride, mullite, and aluminosilicate.

  In the method according to the present invention, a carbon lump, a carbide lump or a metal silicon lump may be formed in the aluminum member after the step (d).

  Furthermore, in the present invention, there is provided a joined body in which a ceramic member containing aluminum and / or silicon and an aluminum member are joined via a joining layer containing an aluminosilicate.

Furthermore, in the present invention, a joined body in which a ceramic member containing aluminum and / or silicon and an aluminum member are joined,
There is provided a joined body characterized in that there is a region where the amount of silicon is higher than the ceramic member and the aluminum member.

  Here, in the joined body according to the present invention, the ceramic member containing aluminum and / or silicon may include at least one material selected from the group consisting of alumina, aluminum nitride, silicon nitride, mullite, and aluminosilicate. good.

  In the joined body according to the present invention, the aluminum member may include a carbon lump, a carbide lump, or a metal silicon lump.

  In the joined body according to the present invention, a second ceramic member may be disposed on the opposite side of the aluminum member from the ceramic member via a second joining layer containing an aluminosilicate.

Alternatively, in the joined body according to the present invention, a second ceramic member is disposed on a side of the aluminum member opposite to the ceramic member,
There may be a region where the amount of silicon is higher between the second ceramic member and the aluminum member than the second ceramic member and the aluminum member.

  In the present invention, a method of joining a ceramic member and an aluminum member more simply can be provided. In the present invention, it is possible to provide a joined body in which the ceramic member and the aluminum member are joined with good strength.

It is the graph which showed the result at the time of performing a differential thermal-thermogravimetric (TG-DTA) simultaneous analysis about the sample which apply | coated the siloxane type polymer on the aluminum member. It is the figure which showed roughly the flow of the method (1st joining method) of joining the ceramic member and aluminum member by one Example of this invention. It is a chemical structural formula of PMPhS which is a kind of siloxane polymer. It is a chemical structural formula of PMSQ which is a kind of siloxane polymer. It is the figure which showed schematically the flow of another method (2nd joining method) which joins the ceramic member and aluminum member by one Example of this invention. It is sectional drawing which showed the schematic structure of the conjugate | zygote by one Example of this invention. It is sectional drawing which showed the schematic structure of another conjugate | zygote by one Example of this invention. 2 is a scanning electron microscope (SEM) image of a bonded portion in the bonded body according to Example 1. FIG. It is a figure which shows the energy dispersive X-ray-spectral-analysis (EDS) result of the junction part in the conjugate | zygote which concerns on Example 1. FIG. 3 is a diagram illustrating an X-ray pattern of X-ray diffraction (XRD) analysis of a bonded interface in the bonded body according to Example 1. FIG. It is the figure which showed the result of having observed the joined body based on Example 6 using TEM. It is the figure which showed the top view (photograph) of the conjugate | zygote produced in Example 7. FIG. It is the figure which showed the top view (photograph) of the conjugate | zygote produced in Example 8. FIG. It is the figure which showed the top view (photograph) of the conjugate | zygote produced in Example 9. FIG. It is the figure which showed the top view (photograph) of the conjugate | zygote produced in Example 10. FIG. It is the figure which showed the top view (photograph) of the conjugate | zygote produced in Example 14. FIG.

  The present invention will be described in detail below.

  As described above, since an oxide film (alumina layer) that hinders bonding with the ceramic member exists on the surface of the aluminum member, it is difficult to appropriately bond the ceramic member and the aluminum member. Moreover, it is difficult to say that the joining method of the ceramic member and the aluminum member proposed so far is a simple method. Further, in the conventional method, even if the ceramic member and the aluminum member can be bonded, there is a high possibility that impurities such as chloride and fluoride remain in the bonded portion. For this reason, a problem may arise in terms of product quality, for example, bonding strength. In addition, if such residual compounds are to be removed by washing, an increase in cost due to washing and environmental problems may occur.

  From such a background, the inventors of the present application have been diligently promoting research and development on a technique for appropriately joining a ceramic member and an aluminum member by a simpler method. As a result, the inventors of the present application have found that the ceramic member and the aluminum member can be appropriately bonded by installing a specific type of bonding material between the ceramic member and the aluminum member, leading to the present invention. It was.

That is, in the present invention, a method of joining a ceramic member and an aluminum member,
(A) preparing a ceramic member containing aluminum and / or silicon, and an aluminum member;
(B) installing a bonding material on at least one of the ceramic member and the aluminum member, the bonding material including a siloxane polymer or a carbon powder-containing silica sol;
(C) laminating the ceramic member and the aluminum member with the bonding material interposed therebetween, and constituting an assembly;
(D) heating the assembly at a temperature of 600 ° C. to 1400 ° C. in an inert gas atmosphere or a vacuum atmosphere;
Is provided.

  In the present invention, a bonding material containing a siloxane polymer (hereinafter also referred to as “bonding material 1”) or a bonding material containing a carbon powder-containing silica sol (hereinafter referred to as “bonding material 2”) between the ceramic member and the aluminum member. (Also called).

  Both of these bonding materials 1 and 2 contain carbon (carbon) atoms. These carbon atoms play a role of reducing the oxide film formed on the surface of the aluminum member or making the oxide film unstable in a high temperature state. Therefore, when the bonding materials 1 and 2 are used, the barrier property of the oxide film covering the aluminum metal can be lowered by the action of the carbon atoms, and the aluminum member can be activated, that is, can easily react.

  Further, the bonding material 1 has a Si—O—Si group, and this reactive group can react with a so-called “active” aluminum member having a reduced barrier function of an oxide film in a high temperature environment. Similarly, the bonding material 2 has a silica sol that can react with an “active” aluminum member.

  Accordingly, when the bonding material 1 or the bonding material 2 as described above is interposed between the ceramic member and the aluminum member, and the heat treatment is performed in a low oxygen atmosphere, the carbon member contained in the bonding material causes the aluminum member to A part of the oxide film present on the surface is reduced. Or the oxide film which exists on the surface of an aluminum member will be in an incomplete state. Thereby, the aluminum member is activated.

  The activated aluminum member reacts with reaction components contained in the bonding material, that is, Si—O—Si groups or silica particles. Thereby, at the interface between the aluminum member and the bonding material, the Si—O—Si group or the silica particles in the bonding material is changed to a substance containing silicon and oxygen, for example, aluminosilicate, and a bonding layer is formed.

  Here, in the present invention, a ceramic member containing aluminum and / or silicon is used as the ceramic member. Such a ceramic member has an affinity for the bonding layer containing silicon and oxygen. The aluminum member also has an affinity for the bonding layer containing silicon and oxygen.

  For this reason, the ceramic member is firmly adhered to the bonding layer due to the presence of the bonding layer, and the aluminum member is also firmly adhered to the bonding layer. As a result, the ceramic member and the aluminum member are bonded via the bonding layer containing silicon and oxygen.

  In the joining method according to the present invention, good joining can be obtained between the ceramic member and the aluminum portion due to the above phenomenon.

  By the way, in the joining method by this invention, the heat processing temperature of an assembly, ie, the joining temperature of a ceramic member and an aluminum member, is the range of 600 to 1400 degreeC. This is based on the following experimental results.

  FIG. 1 shows the results of simultaneous differential thermal-thermogravimetric (TG-DTA) analysis of a sample in which a siloxane polymer is applied on an aluminum member. The analysis was performed under an inert gas atmosphere.

  In FIG. 1, the horizontal axis represents temperature, the left vertical axis represents the amount of change (%) with respect to the initial weight of the sample, and the right vertical axis represents the heat flow (W / g). Moreover, in FIG. 1, the broken line has shown the weight change (left vertical axis | shaft) of the sample, and the continuous line represents the heat flow (right vertical axis) of the sample.

  From this analysis result, it can be seen that when the sample is heated in an inert atmosphere, the decomposition of the siloxane-based polymer is completed at about 500 ° C., and the weight of the sample becomes almost constant. Further, when the sample is further heated, it is observed that two endothermic peaks are generated. The first endothermic peak is observed in the temperature range of about 580 ° C. to 600 ° C., and the second absorption peak is observed in the vicinity of the temperature of about 660 ° C.

  Among these, the first endothermic peak is considered to correspond to a chemical reaction on the surface of the aluminum member, that is, a reaction in which the surface oxide of alumina is reduced by a product generated by decomposition of the siloxane polymer. The second endothermic peak is considered to correspond to a phase change due to melting of aluminum.

  From this result, since the surface oxide film of aluminum is reduced in a temperature range that reliably exceeds the temperature of the first endothermic peak, that is, a temperature of 600 ° C. or higher, the aluminum member can be activated. Therefore, by setting the bonding temperature to 600 ° C. or higher, the aluminum member and the ceramic member can be bonded.

  In the temperature range exceeding the second endothermic peak, that is, the temperature range of 660 ° C. or higher, the aluminum member is melted, so that the activity of the aluminum member is further increased. Therefore, when the joining temperature is set to 660 ° C. or higher, the aluminum member and the ceramic member can be joined more easily.

  On the other hand, if the bonding temperature exceeds 1400 ° C., the dissipation due to the vaporization of the aluminum member cannot be ignored.

  In the present invention, from such a viewpoint, the bonding temperature between the ceramic member and the aluminum member is set in a range of 600 ° C to 1400 ° C.

  In addition, the above description has only described the phenomenon which may occur based on one mechanism currently considered. That is, in the joining method according to the present invention, a good joint may be formed between the ceramic member and the aluminum portion by another mechanism.

(Joining method according to one embodiment of the present invention)
Next, a method for joining a ceramic member and an aluminum member (first joining method) according to an embodiment of the present invention will be described in more detail with reference to the drawings.

  FIG. 2 schematically shows a flow of the first joining method.

As shown in FIG. 2, the first joining method is:
Preparing a ceramic member containing aluminum and / or silicon, and an aluminum member (step S110);
A step of installing a bonding material on at least one of the ceramic member and the aluminum member, the bonding material including a siloxane-based polymer (step S120);
Laminating the ceramic member and the aluminum member with the bonding material interposed therebetween to form an assembly (step S130);
Heating the assembly at a temperature of 600 ° C. to 1400 ° C. in an inert gas atmosphere or a vacuum atmosphere (step S140);
Have

  Hereinafter, each step will be described in detail.

(Step S110)
First, a ceramic member and an aluminum member are prepared.

  The ceramic member is not particularly limited as long as it contains aluminum and / or silicon. The ceramic member may include, for example, alumina, aluminum nitride, silicon nitride, mullite, and / or aluminosilicate.

  For example, the alumina includes high-purity alumina containing 90 wt% or more of alumina by weight. Examples of the aluminum nitride include high-purity alumina nitride containing 90 wt% or more aluminum nitride by weight. Examples of silicon nitride include high-purity silicon nitride containing 90 wt% or more of silicon nitride by weight.

  In addition, although there is no restriction | limiting in particular in the crystal form of ceramics, (alpha) -alumina can be used conveniently as an alumina.

  The shape of the ceramic member is not particularly limited, and the ceramic member may have a shape such as a block, a plate, a rod, or a disk.

  Similarly, the shape of the aluminum member is not particularly limited, and the aluminum member may have a shape such as a block, a plate, a bar, a foil, or a disk.

  In the present application, the term “aluminum member” means a member substantially composed of an aluminum metal, a member containing 50 wt% or more aluminum metal by weight, a member substantially composed of an aluminum alloy, And a member containing an aluminum alloy having a weight ratio of 50 wt% or more.

  The aluminum alloy may be, for example, an Al—Si alloy or the like, for example, sirmine containing about 12 wt% silicon.

(Step S120)
Next, a bonding material is placed on at least the bonding surface of the ceramic member and / or the aluminum member. As the bonding material, a bonding material containing a siloxane polymer (that is, the bonding material 1) is used.

  Here, the specification of the bonding material 1 will be briefly described.

(Bonding material 1)
In the bonding material 1 including the siloxane polymer, the type of the siloxane polymer is not particularly limited.

  The siloxane-based polymer may be, for example, a siloxane-based polymer having a linear Si—O—Si group as a main chain, such as polymethylhydrosiloxane (PMHS) and / or polymethylphenylsiloxane (PMPhS). Alternatively, the siloxane-based polymer is, for example, a silsesquioxane-based polymer having a three-dimensional structure having a Si—O—Si group as a main skeleton, such as polymethylsilsesquioxane (PMSQ) and / or polyphenylsiloxane (PPSQ). ).

  3 and 4 show chemical structural formulas of PMPhS (FIG. 3) and PMSQ (FIG. 4) for reference.

  The method of installing the bonding material 1 on the bonding surface (hereinafter simply referred to as “bonding surface”) of the ceramic member and / or the aluminum member is not particularly limited.

  The bonding material 1 may be installed on the bonding surface by, for example, a coating method. Examples of the coating method include a dipping method, a spin coater method, and a spray method. Since it is desirable to apply the bonding material 1 as evenly as possible, it is preferable to apply the dipping method with a pulling speed of 1 mm / second or less, or the spin coater method with a rotation speed of 1500 rpm or more.

  Note that the thickness of the finally obtained bonding layer varies depending on the thickness of the bonding material 1. Therefore, it is preferable to adjust the type and thickness of the bonding material 1 according to the purpose.

  Further, since the siloxane polymer has high viscosity, it is preferable to adjust the viscosity appropriately by diluting with a solvent when applied to the joint surface by a dipping method or the like. In this case, it is preferable to use an aromatic organic solvent such as benzene or toluene from the viewpoint of compatibility. The solvent concentration may be in the range of 0.001 mol / L to 1 mol / L.

  As described above, the carbon atom contained in the siloxane-based polymer has a role of, for example, reducing the oxide layer covering the surface of the aluminum member and increasing the reaction activity of the aluminum member. Further, it is considered that carbon atoms also function as an anchor that bonds the ceramic member and / or the aluminum member and the bonding layer in the vicinity of the interface between the bonding layer and the bonding surface. For this reason, it is desirable that the siloxane-based polymer contains 1 wt% or more, preferably 5 wt% or more, more preferably 10 wt% to 30 wt% of carbon by weight ratio.

  If the amount of the bonding material installed on the bonding surface of the ceramic member is too small, the bonding material does not spread uniformly over the entire bonding surface, and the oxide layer may not be sufficiently reduced on the bonding surface of the aluminum member. Therefore, the thickness of the bonding material is preferably 0.1 μm (after solvent volatilization) or more. On the other hand, even if the joining material is too thick, joining is possible. However, if the thickness of the bonding material is too thick, cracks are likely to occur at the interface between the ceramic member and the bonding layer due to the shrinkage accompanying the ceramicization of the bonding material portion. For this reason, it is preferable that the thickness of the bonding material is 1 mm (after solvent volatilization) or less.

  Moreover, when the installation amount of the bonding material is excessive, metal silicon is likely to be deposited in the vicinity of the interface between the bonding layer and the aluminum member due to the reduction of siloxane by the aluminum member. The same applies when a siloxane polymer having a high silicon content is used. Therefore, the silicon content in the siloxane polymer is preferably selected in the range of 10 wt% to 45 wt%.

  In particular, cage-like siloxane (silsesquioxane) has a high content of silicon and oxygen, and metal silicon tends to precipitate. Therefore, when it is desired to suppress the deposition of metallic silicon in the bonding layer, it is preferable to use linear siloxane (silicone oil). However, when metal silicon is formed in the aluminum member, the strength of the joining member is improved. Therefore, when importance is attached to the strength, a siloxane polymer having a high silicon content may be used.

  Further, when siloxane containing a lot of phenyl groups is used, a carbon lump or carbide lump is easily formed on the bonding layer side of the aluminum member. Therefore, when it is desired to suppress the formation of carbon mass or carbide mass, it is preferable not to use a siloxane-based polymer having a phenyl group in the side chain. However, when a carbon lump or carbide lump is formed in the aluminum member, the strength may be improved.

(Step S130)
Next, the ceramic member and the aluminum member are laminated with the bonding material 1 interposed therebetween to form an assembly. That is, the ceramic member and the aluminum member are arranged such that the bonding surface of the ceramic member and the bonding surface of the aluminum member face each other with the bonding material 1 interposed therebetween.

  In the assembly, the ceramic member and the aluminum member may be stacked on each other in a substantially non-pressurized state. However, a certain amount of load may be applied between the two.

(Step S140)
Next, the assembly is heat treated for the bonding process. Thereby, a joined body in which the ceramic member and the aluminum member are joined via the joining layer is manufactured.

  The heat treatment is performed in an atmosphere substantially free of oxygen, such as an inert gas atmosphere or a vacuum atmosphere. When heat treatment is carried out in an oxygen-containing environment such as an air atmosphere, the oxide on the surface of the aluminum member is not sufficiently reduced, making it difficult to obtain good bonding between the ceramic member and the aluminum member. .

  The inert gas atmosphere may be an atmosphere of argon, helium, and / or nitrogen, for example. The degree of vacuum in the vacuum atmosphere is, for example, −0.08 MPa or less when the atmospheric pressure is set to 0 MPa.

  The temperature of heat processing is the range of 600 to 1400 degreeC. The temperature of heat processing is the range of 660 degreeC-1400 degreeC, for example. Incidentally, in this temperature range, aluminum becomes a liquid. When the temperature of heat processing exceeds 1400 degreeC, there exists a possibility that an aluminum member may vaporize.

In particular, the temperature of the heat treatment is preferably 900 ° C. or higher. At 900 ° C. or higher, it is expected that the oxide present on the surface of the aluminum member is activated and changed to Al ₂ O vapor. Moreover, it is preferable that the temperature of heat processing is the range of 900 to 1300 degreeC from the point of the energy fall of the oxide of the surface of an aluminum member.

  By heat-treating the assembly, the bonding material 1 changes, and a bonding layer is formed at the interface between the ceramic member and the aluminum member.

  The bonding layer may be a “silicon-rich” layer. Here, the term “silicon-rich” means that the amount of silicon is significantly increased compared to aluminum and ceramic members.

  In particular, the bonding layer may include aluminosilicate. The aluminosilicate may be crystalline or amorphous.

The aluminosilicate is represented by a general formula of Al _X Si _Y O _Z (0 <X <3, 0 <Y <51, 0 <Z <104). The aluminosilicate may be a mixture of alumina and silica.

  In addition to the aluminosilicate, other materials such as aluminum, alumina, and / or silica may be present in the bonding layer. Depending on conditions, the bonding layer may include an oxide in which silicon and aluminum are mixed, such as mullite.

  Here, when siloxane with a high carbon content is used as the bonding material 1, massive carbon may be formed in the aluminum member. The outside of the carbon block is aluminum carbide. This carbon block is expected to contribute to improving the strength of the joining member. In addition, a carbide containing silicon carbide, aluminum, and silicon at the same time may be generated.

  On the other hand, when a siloxane having a low carbon content is used as the bonding material 1, almost no carbon lump or carbide lump is generated in the aluminum member. Therefore, in this case, a high purity aluminum member can be obtained.

  Further, when the bonding material 1 having a high silicon content is used, a metal silicon lump may be formed in the aluminum member. This metal silicon mass is considered to be the one in which unreacted Si—O—Si groups are reduced and diffused and entered into the aluminum member when the bonding layer is generated by the reaction between the aluminum member and the bonding material. It is done. Such a metal silicon lump is expected to contribute to improving the strength of the joining member, like the carbon lump or carbide lump.

  Through the above steps, a joined body in which the ceramic member and the aluminum member are favorably joined via the joining layer is manufactured.

(Another joining method according to an embodiment of the present invention)
Next, another method (second joining method) for joining the ceramic member and the aluminum member according to one embodiment of the present invention will be described with reference to FIG.

  FIG. 5 schematically shows a flow of the second joining method.

As shown in FIG. 5, the second joining method is as follows.
Preparing a ceramic member containing aluminum and / or silicon, and an aluminum member (step S210);
Installing a bonding material on at least one of the ceramic member and the aluminum member, the bonding material including a carbon powder-containing silica sol (step S220);
Laminating the ceramic member and the aluminum member with the bonding material interposed therebetween to form an assembly (step S230);
Heating the assembly at a temperature of 600 ° C. to 1400 ° C. in an inert gas atmosphere or a vacuum atmosphere (step S240);
Have

  Here, step S210 and steps S230 to S240 are substantially the same as step S110 and steps S130 to S140 in the first joining method described above, respectively. Therefore, step S220 will be described here.

(Step S220)
In the second bonding method, a bonding material containing carbon powder-containing silica sol (that is, the bonding material 2) is used as the bonding material.

  Here, the specification of the bonding material 2 will be briefly described.

(Bonding material 2)
In the bonding material 2 including the carbon powder-containing silica sol, the form of the silica sol used is not particularly limited. However, in order to avoid uneven distribution of carbon particles, it is preferable to use carbon powder as fine as possible, for example, powder finer than # 2000. For example, a colloidal silica sol having a small silica particle diameter (20 nm or less) may be used. Examples of such silica sol include Snowtex N and Snowtex N-40 (manufactured by Nissan Chemical Co., Ltd.).

  In order to prepare the bonding material 2, it is necessary to add carbon powder to the silica sol. Examples of the carbon powder to be added include carbon black (manufactured by Mitsubishi Chemical Corporation) or ketjen black (manufactured by Lion Corporation).

  The carbon content is 1 wt% or more, preferably 5 wt% or more, more preferably 10 wt% to 30 wt% in terms of mass ratio to the silica particles. This is a value equivalent to the amount of carbon contained in the siloxane polymer in the bonding material 1 described above.

  Since the bonding material 2 is prepared by adding carbon powder to the silica sol, the bonding material 2 has an advantage that the mixing ratio of the carbon powder and the silica sol can be freely adjusted as compared with the bonding material 1.

  As a solvent for mixing silica sol and carbon powder, for example, ethanol and isopropyl alcohol are used. These solvents are preferable because they do not adversely affect the silica sol and the carbon powder and are quick-drying.

  Such a bonding material 2 is placed on at least the bonding surface of the ceramic member and / or the aluminum member.

  The method for installing the bonding material 2 on the bonding surface is not particularly limited, and for example, the method for setting the bonding material 1 on the bonding surface as described in Step S120 described above can be similarly applied.

  Thereafter, a joined body in which the ceramic member and the aluminum member are satisfactorily joined via the joining layer is manufactured through steps S230 to S240.

  The method for joining the ceramic member and the aluminum member according to one embodiment of the present invention has been described above by taking the first joining method and the second joining method as examples. However, the above description is merely an example, and it will be apparent to those skilled in the art that some of the methods described above may be modified or other steps may be combined.

  For example, in the two examples described above, the joined body has a structure in which a ceramic member, a joining layer, and an aluminum member are laminated in this order. However, the joined body may have a structure in which, for example, a first ceramic member, a first joining layer, an aluminum member, a second joining layer, and a second ceramic member are laminated in this order.

  Such a bonded body is formed, for example, by placing a bonding material on each bonding surface of two ceramic members in the process of manufacturing the above-described assembly (step S130, step S230), and further, aluminum between the two ceramic members. An assembly in which members are interposed is formed, and this assembly can be manufactured by heat treatment as in steps S140 and S240.

(Joint body according to one embodiment of the present invention)
Next, a joined body according to an embodiment of the present invention will be described with reference to FIGS.

  FIG. 6 is a schematic cross-sectional view of a joined body according to an embodiment of the present invention.

  As shown in FIG. 6, this joined body 100 includes a ceramic member 110, an aluminum member 130, and a joining layer 150 disposed between the two.

  The ceramic member 110 is made of a ceramic containing an aluminum component and / or a silicon component. For example, the ceramic member 110 includes at least one of alumina, aluminum nitride, silicon nitride, mullite, and aluminosilicate.

  As described above, the aluminum member 130 is a member substantially made of aluminum metal, a member containing 50 wt% or more aluminum metal by weight, a member substantially made of aluminum alloy, or 50 wt% by weight. % Or more of an aluminum alloy-containing member may be used. Further, a carbon lump, a carbide lump, or metal silicon may be present inside the aluminum member 130.

  The bonding layer 150 may be a layer containing aluminosilicate.

  Or, more generally, the bonding layer 150 is comprised of a “silicon-rich” layer. Here, the term “silicon-rich” means that the amount of silicon is significantly increased as compared to the aluminum member 130 and the ceramic member 110.

  Due to the mechanism as described above, a good bonding state is obtained between the ceramic member 110 and the aluminum member 130 due to the presence of the bonding layer 150 including an aluminosilicate or “silicon-rich” layer. Therefore, the bonded body 100 having such a configuration has good bonding strength.

  FIG. 7 shows a schematic cross-sectional view of another joined body according to an embodiment of the present invention.

  As shown in FIG. 7, the joined body 200 further includes a second ceramic member 260 and a second joining layer 290 in addition to the members constituting the joined body 100 shown in FIG. 6. That is, the bonded body 200 is configured by arranging the first ceramic member 210, the first bonding layer 250, the aluminum member 230, the second bonding layer 290, and the second ceramic member 260 in this order. .

  Here, the second ceramic member 260 is made of a ceramic containing an aluminum component and / or a silicon component. For example, the second ceramic member 260 includes at least one of alumina, aluminum nitride, silicon nitride, mullite, and aluminosilicate. Further, the second bonding layer 290 may be a layer containing aluminosilicate, or more generally, the second bonding layer 290 may be a “silicon-rich” layer.

  Even in the second bonded body 200 having such a configuration, it will be easily expected that good bonding strength can be obtained by the presence of the first and second bonding layers 250 and 290.

  Examples of the present invention will be described in detail below. However, the present invention is not limited to these examples.

Example 1
A joined body of a ceramic member and an aluminum member was manufactured by the following method.

  First, two alumina blocks having a size of 20 × 30 × 20 mm (α-alumina having a purity of 99.5%) were prepared. In addition, a toluene solution containing a commercially available polymethylphenylsiloxane (KF-54: manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as “PMPhS”) at a concentration of 0.1 mol / L was prepared.

  Next, after the two alumina blocks were completely immersed in the toluene solution, they were pulled up at a speed of 1 mm / second. Thereafter, each alumina block was sufficiently dried under an air atmosphere. As a result, PMPhS was uniformly applied to at least the bonding surface (one surface of 20 × 30 mm) of each alumina block.

  The carbon content contained in the coating material is 61.8 wt%, the silicon content is 20.6 wt%, and the oxygen content is 11.8 wt%.

  Next, after placing a commercially available aluminum foil (My Foil: made by Sumi Light Aluminum) having a thickness of 22 μm so as to be in contact with the joining surface of one alumina block, another alumina block was placed on this aluminum foil. . At this time, another alumina block was disposed such that the joining surface of the other alumina block was in contact with the aluminum foil.

  The assembly thus obtained was fired at 900 ° C. for 1 hour in an argon atmosphere. As a result, a joined body in which the two alumina blocks were joined via the aluminum foil was obtained. Hereinafter, this joined body is referred to as “joined body according to Example 1”.

  The joining cross section of the joined body according to Example 1 was observed using a scanning electron microscope (SEM) (JEM-5600: manufactured by JEOL). FIG. 8 shows the measurement result (SEM image).

  As shown in FIG. 8, it can be seen that there is a continuous and relatively uniform aluminum layer between the alumina blocks. It can also be seen that a plurality of carbon blocks (black particles) having a size of about 5 μm are present inside the aluminum layer.

  In addition, in the magnification of this FIG. 8, the joining layer between an alumina block and an aluminum layer cannot be visually recognized. However, no gaps or voids are observed at the interface between the alumina block and the aluminum layer, and the bonding layer is expected to exist in a healthy state.

  In FIG. 9, an example of the EDS analysis result of the conjugate | zygote which concerns on Example 1 is shown. For this analysis, an energy dispersive X-ray spectrometer (JEM-2300: manufactured by JEOL) was used. In addition, this analysis was performed near the interface between the alumina block and the aluminum layer of the joined body according to Example 1 (see the region surrounded by the frame in FIG. 8).

  FIG. 9 shows that a silicon-rich layer having a thickness of about 4 μm is formed as a bonding layer between the alumina block and the aluminum layer.

  When the silicon-rich bonding layer was analyzed with an X-ray diffractometer (RINT2500: manufactured by Rigaku), the result shown in FIG. 10 was obtained.

From the results shown in FIG. 10, this silicon-rich bonding layer contains aluminosilicates (Al ₂ Si ₅₀ O ₁₀₃ , Al _1.9 Si _0.05 O _2.95 , and Al ₂ Si ₄ O ₁₀ ). It was confirmed that

  The joined body according to Example 1 was cut out to prepare a test piece, and a four-point bending test was performed on the test piece. The preparation of the test piece and the four-point bending test were performed by a method according to JIS R 1601: 2008. The number of tests was 6.

  As a result of the 4-point bending test of the test piece, the bending strength was an average of 255 MPa, and the maximum strength was 304 MPa. Moreover, when each sample piece after the test was observed, it was confirmed that more than half of the test pieces were broken in the alumina block. From this, the bonding layer containing aluminosilicate is expected to have a bonding strength comparable to that of the alumina block.

  In the column of “Example 1” in Table 1 below, the bonding material used in manufacturing the bonded body according to Example 1, the carbon, silicon and oxygen contents in the bonding material, and the four-point bending test The results are summarized.

(Example 2)
A joined body of a ceramic member and an aluminum member was manufactured in the same manner as in Example 1. However, in Example 2, a commercially available polymethylhydrosiloxane (KF-99: manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as “PMHS”) was used as the siloxane polymer instead of PMPhS. PMHS was added to a toluene solution so as to have a concentration of 0.1 mol / L.

  The carbon content in the coating material was 26.9 wt%, the silicon content was 41.8 wt%, and the oxygen content was 23.9 wt%.

  Other conditions are the same as in the first embodiment.

  As a result, a joined body in which the two alumina blocks were joined via the aluminum foil was obtained. Hereinafter, this joined body is referred to as “joined body according to Example 2”.

  Evaluation similar to Example 1 was performed with respect to the joined body which concerns on Example 2. FIG. As a result, also in the joined body according to Example 2, it was confirmed that an aluminum layer having a continuous and relatively uniform thickness was present between the alumina blocks. In addition, the carbon lump was not recognized inside the aluminum layer.

Further, no gaps or voids were observed at the interface between the alumina block and the aluminum layer, and it was confirmed that the bonding layer was in a healthy state. The bonding layer was about 1 μm thick. Further, the bonding layer, it was confirmed to contain the aluminosilicate _{(Al 2 Si 50 O 103,} Al 1.9 Si 0.05 O 2.95, and _Al 2 _Si 4 _{O 10).}

  When the joined body according to Example 2 was cut out to produce a test piece and a four-point bending test was performed on the test piece, the bending strength was an average of 176 MPa and the maximum strength was 277 MPa. It was confirmed that more than half of the sample pieces after the test were broken at the alumina block portion. From this, the bonding layer containing aluminosilicate is expected to have a bonding strength comparable to that of the alumina block.

  In addition, the bending strength of the joined body according to Example 2 is somewhat lower than that of the joined body according to Example 1. This is considered to be due to the presence or absence of carbon blocks formed in the aluminum layer. That is, in the joined body according to Example 2, since the amount of carbon contained in the joining material is relatively small, no carbon lump is formed in the aluminum layer after the heat treatment, and the joined body according to Example 1 has higher strength. It is expected that there was not.

  In the column of “Example 2” in Table 1 above, the bonding material used when manufacturing the bonded body according to Example 2, the carbon, silicon and oxygen contents in the bonding material, and the four-point bending test The results are summarized.

(Example 3)
A joined body of a ceramic member and an aluminum member was manufactured in the same manner as in Example 1. However, in this Example 3, instead of PMPhS, a commercially available polymethylsilsesquioxane (YR-33707: manufactured by Momentive Performance Materials, Inc., hereinafter referred to as “PMSQ”) was used as the siloxane polymer. PMSQ was added to a toluene solution so that the concentration was 0.1 mol / L.

  The carbon content contained in the coating material was 10.2 wt%, the silicon content was 47.6 wt%, and the oxygen content was 40.7 wt%.

  Other conditions are the same as in the first embodiment.

  As a result, a joined body in which the two alumina blocks were joined via the aluminum foil was obtained. Hereinafter, this joined body is referred to as “joined body according to Example 3.”

  Evaluation similar to Example 1 was performed with respect to the joined body which concerns on Example 3. FIG. As a result, also in the joined body according to Example 3, it was confirmed that an aluminum layer having a continuous and relatively uniform thickness was present between the alumina blocks. It was confirmed that a plurality of metal silicon blocks having dimensions of about 3 μm × 3 μm × 30 μm were present inside the aluminum layer.

Further, no gaps or voids were observed at the interface between the alumina block and the aluminum layer, and it was confirmed that the bonding layer was in a healthy state. The bonding layer was about 2 μm thick. Further, the bonding layer, it was confirmed to contain the aluminosilicate _{(Al 2 Si 50 O 103,} Al 1.9 Si 0.05 O 2.95, and _Al 2 _Si 4 _{O 10).}

  When the joined body according to Example 3 was cut out to produce a test piece and a four-point bending test was performed on the test piece, the bending strength was an average of 225 MPa and the maximum strength was 278 MPa. It was confirmed that more than half of the sample pieces after the test were broken at the alumina block portion. From this, the bonding layer containing aluminosilicate is expected to have a bonding strength comparable to that of the alumina block.

  In the column of “Example 3” in Table 1 described above, the bonding material used in manufacturing the bonded body according to Example 3, the carbon, silicon and oxygen contents in the bonding material, and the four-point bending test The results are summarized.

Example 4
A joined body of a ceramic member and an aluminum member was manufactured in the same manner as in Example 1. However, in Example 4, silica sol containing carbon powder was used as the bonding material.

  For this purpose, first, carbon powder (# 2700, manufactured by Mitsubishi Chemical Corporation) is added to a commercially available silica sol diluted with ethanol (Snowtex N: manufactured by Nissan Chemical Co., Ltd.), and a mixed solution having a carbon powder amount of 10 wt% is added. Prepared.

  Next, after the two alumina blocks were completely immersed in the mixed solution, they were pulled up at a speed of 1 mm / second. Thereafter, each alumina block was sufficiently dried under an air atmosphere.

  Thereby, the silica sol containing carbon powder was uniformly apply | coated to the joining surface (one surface of 20x30 mm) of at least each alumina block.

  The content of carbon contained in the coating material was 30.3% by weight, the content of silicon was 32.6% by weight, and the content of oxygen was 37.1% by weight.

  Other conditions are the same as in the first embodiment.

  As a result, a joined body in which the two alumina blocks were joined via the aluminum foil was obtained. Hereinafter, this joined body is referred to as “joined body according to Example 4”.

  Evaluation similar to Example 1 was performed with respect to the joined body which concerns on Example 4. FIG. As a result, also in the joined body according to Example 4, it was confirmed that an aluminum layer having a continuous and relatively uniform thickness was present between the alumina blocks. A metallic silicon lump was observed inside the aluminum layer.

Further, no gaps or voids were observed at the interface between the alumina block and the aluminum layer, and it was confirmed that the bonding layer was in a healthy state. The bonding layer was about 5 μm thick. Further, the bonding layer, it was confirmed to contain the aluminosilicate _{(Al 2 Si 50 O 103,} Al 1.9 Si 0.05 O 2.95, and _Al 2 _Si 4 _{O 10).}

  When the joined body according to Example 4 was cut out to prepare a test piece and a four-point bending test was performed on the test piece, the bending strength was an average of 212 MPa and the maximum strength was 272 MPa. It was confirmed that more than half of the sample pieces after the test were broken at the alumina block portion. From this, the bonding layer containing aluminosilicate is expected to have a bonding strength comparable to that of the alumina block.

  In the column of “Example 4” in Table 1 above, the bonding material used when manufacturing the bonded body according to Example 4, the carbon, silicon and oxygen contents in the bonding material, and the four-point bending test The results are summarized.

  As an application example of the present technology, aluminum wiring formation by a screen printing method or an ink jet method on a ceramic member can be considered. For this reason, in order to confirm these feasibility, the following experiment was conducted.

(Example 5)
A slurry (solvent: ethanol) containing about 85 wt% of aluminum powder (manufactured by Wako Pure Chemical Industries) having a purity of 99% or more was prepared, and the slurry was screen-printed on the alumina substrate whose surface was coated in the same manner as in Example 1. And baked at 900 ° C. for 1 hour in an argon atmosphere. As a result, a wiring-like aluminum metal having the same pattern as the screen was bonded onto the alumina substrate. This aluminum metal was confirmed not to peel off even when scratched with a finger and to have a good bonding force.

(Example 6)
Except that the firing temperature was changed from 900 ° C. to 950 ° C., a joined body in which two alumina blocks were joined via an aluminum foil was produced in the same manner as in Example 1. Hereinafter, this joined body is referred to as “joined body according to Example 6”.

  Evaluation similar to Example 1 was performed with respect to the joined body which concerns on Example 6. FIG. As a result, also in the joined body according to Example 6, it was confirmed that an aluminum layer having a continuous and relatively uniform thickness was present between the alumina blocks. In addition, it was confirmed that a plurality of carbide lumps exist inside the aluminum layer.

  Further, no gaps or voids were observed at the interface between the alumina block and the aluminum layer, and it was confirmed that the bonding layer was in a healthy state.

  In FIG. 11, the result of having observed the joined_body | zygote which concerns on Example 6 using the transmission electron microscope (TEM) (JEM-2010: The product made by JEOL, S-5000: The product made from Hitachi) is shown. In addition to the TEM image in the vicinity of the joint, FIG. 11 shows the results of elemental analysis at three locations (points A, B, and C) near the joint at the same time.

  As shown in FIG. 11, only the aluminum peak was detected at point A corresponding to the region of the aluminum layer. Also, aluminum and oxygen peaks were observed at point C corresponding to the area of the alumina block.

  In contrast, at point B corresponding to the interface between the two, a large peak indicating the presence of silicon that was not observed at points A and C was observed. At point B, large peaks of oxygen and carbon were also observed.

  From this result, it was confirmed that there is a bonding layer at the interface between the aluminum layer and the alumina block, and this bonding layer has a significantly higher silicon content than the aluminum layer and the alumina block. It was.

  When the joined body according to Example 6 was cut out to prepare a test piece and a four-point bending test was performed on the test piece, the bending strength was an average of 242 MPa and the maximum strength was 289 MPa. It was confirmed that more than half of the sample pieces after the test were broken at the alumina block portion. From this, the bonding layer containing aluminosilicate is expected to have a bonding strength comparable to that of the alumina block.

  In the column of “Example 6” in Table 1 above, the bonding material used when manufacturing the bonded body according to Example 6, the carbon, silicon and oxygen contents in the bonding material, and the four-point bending test The results are summarized.

(Comparative Example 1)
The ceramic member and the aluminum member were tried to be joined by the same method as in Example 1. However, in this comparative example 1, PMPhS was not applied to the joint surface of each aluminum block.

  After the assembly was fired at 900 ° C. for 1 hour in an argon atmosphere, the assembly was observed. As a result, both alumina blocks were not joined. When the portion between the two alumina blocks was observed, aluminum oxide was present at this location, but no aluminum layer was observed. At the same location, the presence of aluminosilicate was not observed.

  In Comparative Example 1, since a joined body of a ceramic member and an aluminum member could not be obtained, a four-point bending test was not performed.

(Comparative Example 2)
The ceramic member and the aluminum member were tried to be joined by the same method as in Example 1. However, in Comparative Example 2, polycarbosilane (Nippi Type-A: manufactured by Nippon Carbon Co., Ltd., hereinafter referred to as “PCS”) was used as the bonding material. PCS was added to a toluene solution so that the concentration was 0.1 mol / L.

  Then, after completely immersing two alumina blocks in this toluene solution, they were pulled up at a speed of 1 mm / second. Thereafter, each alumina block was sufficiently dried under an air atmosphere.

  As a result, PCS was uniformly applied to at least the bonding surface (one surface of 20 × 30 mm) of each alumina block.

  Next, at 200 ° C. in the atmosphere, each alumina block was held for 22.5 hours to perform oxidation infusibilization treatment. Then, each alumina block was heat-treated at 1200 ° C. for 1 hour under an argon gas flow. As a result, a bonding material made of SiC was formed on the surface (bonding surface) of the ceramic member.

  In calculation, the carbon content in the bonding material is 49.8 wt%, the silicon content is 37.6 wt%, and the oxygen content is 12.5 wt%. is expected.

  Next, after placing a commercially available aluminum foil (My foil: made by Sumi Light Aluminum) having a thickness of 24 μm so as to be in contact with the joining surface of one alumina block, another alumina block was placed on this aluminum foil. . At this time, another alumina block was disposed such that the joining surface of the other alumina block was in contact with the aluminum foil.

  The assembly thus obtained was fired at 800 ° C. for 1 hour in an argon atmosphere. As a result, a joined body in which two alumina blocks were joined was obtained. Hereinafter, this joined body is referred to as “joined body according to Comparative Example 2”.

  Evaluation similar to Example 1 was performed with respect to the joined body which concerns on the comparative example 2. FIG. As a result, in the case of the joined body according to Comparative Example 2, it was found that a ceramic joining layer having a thickness of about 40 μm was formed between the two alumina blocks. However, it was confirmed that no aluminum member remained between the two alumina blocks. From this, it was found that in the method of Comparative Example 2, most of the aluminum member disappeared during the treatment.

  In Comparative Example 2, since a joined body of a ceramic member and an aluminum member could not be obtained, a four-point bending test was not performed.

  In the column of “Comparative Example 2” in Table 1 described above, the bonding material used when manufacturing the bonded body according to Comparative Example 2 and the contents of carbon, silicon, and oxygen in the bonding material are collectively shown. .

(Example 7)
A joined body of a ceramic member and an aluminum member was manufactured by the following method.

  First, an alumina plate (α-alumina with a purity of 99.5%) having a size of 30 mm × 30 mm × thickness of 2.5 mm was prepared. In addition, a toluene solution containing PMPhS was prepared in the same manner as in Example 1.

  Next, 5 drops of a toluene solution was dropped on the alumina plate, and then the alumina plate was rotated at 3000 rpm to perform spin coating.

  Next, a commercially available aluminum wire (purity 99% or more: manufactured by Nilaco) was placed on the alumina plate. The thickness of the aluminum wire was three types with diameters of 100 μmφ, 500 μmφ, and 1000 μmφ. Thereafter, the alumina plate was fired at 900 ° C. for 1 hour in an argon atmosphere.

  Thereby, the joined body with which the aluminum wire of various thickness was joined on the alumina board was obtained.

  FIG. 12 shows a plan view (photograph) of the obtained joined body. In addition, none of the aluminum wires peeled at all to the extent that they were scratched with a finger. From this, it was found that each aluminum wire was well bonded to the alumina plate.

(Example 8)
A joined body of a ceramic member and an aluminum member was manufactured in the same procedure as in Example 7.

  However, in Example 8, an aluminum plate (α-alumina having a purity of 99.5%) having dimensions of 20 mm × 20 mm × thickness 300 μm was used instead of the aluminum wire. Moreover, the heat treatment (joining with the aluminum member) conditions of the alumina plate were 650 ° C. and 1 hour in an argon atmosphere.

  Thereby, the joined body with which the aluminum plate was joined on the alumina plate was obtained.

  FIG. 13 shows a plan view (photograph) of the obtained joined body. The aluminum plate did not peel at all as long as it was scratched with a finger. From this, it was found that the aluminum plate was well bonded to the alumina plate.

Example 9
A joined body of a ceramic member and an aluminum member was manufactured by the same procedure as in Example 8.

  However, in this Example 9, the same aluminum foil (20 mm × 20 mm × thickness 22 μm) used in Example 1 was used instead of the aluminum plate. Moreover, the heat processing (joining with an aluminum member) conditions of an alumina board were 600 degreeC and 1 hour in argon atmosphere.

  Thereby, the joined body with which the aluminum foil was joined on the alumina plate was obtained.

  FIG. 14 shows a plan view (photograph) of the obtained joined body. The aluminum foil did not peel at all as long as it was scratched with a finger. From this, it was found that the aluminum foil was well bonded to the alumina plate.

  In addition, the residue of the carbon block derived from the bonding agent was observed on the substrate.

(Example 10)
A joined body of a ceramic member and an aluminum alloy member was manufactured in the same procedure as in Example 7. However, in Example 10, an Al—Si alloy (silmine: silicon content 12 wt%) wire having a diameter of 2000 μmφ was used instead of the aluminum wire. Moreover, the heat processing (joining with an aluminum alloy member) conditions of an alumina plate were 650 degreeC and 1 hour in argon atmosphere.

  As a result, a joined body in which an Al—Si alloy wire was joined on the alumina plate was obtained.

  FIG. 15 shows a plan view (photograph) of the obtained joined body. In addition, the Al—Si alloy wire did not peel at all as long as it was scratched with a finger. From this, it was found that the Al—Si alloy wire was well bonded to the alumina plate.

(Example 11)
A joined body of a ceramic member and an aluminum member was manufactured in the same manner as in Example 1. However, in Example 11, a silicon nitride block (20 mm × 4 mm × 4 mm) was used as the ceramic member instead of the alumina block. That is, the two silicon nitride blocks coated with PMPhS were joined to each other at the joining surfaces (one surface of 20 mm × 4 mm) via an aluminum foil to produce a joined body.

  Evaluation similar to Example 1 was performed with respect to the joined body which concerns on Example 11. FIG. As a result, also in the joined body according to Example 11, it was confirmed that an aluminum layer having a continuous and relatively uniform thickness was present between the silicon nitride blocks. In addition, it was confirmed that a plurality of carbide (silicon carbide) lumps exist inside the aluminum layer.

  Further, no gaps or voids were observed at the interface between the silicon nitride block and the aluminum layer, and it was confirmed that the bonding layer was in a healthy state.

(Example 12)
A joined body of a ceramic member and an aluminum member was manufactured in the same procedure as in Example 7.

  However, in Example 12, a silicon nitride plate having dimensions of 20 mm × 20 mm × thickness 1 mm was used instead of the alumina plate.

  As a result, a joined body in which an aluminum wire was joined on the silicon nitride plate was obtained.

  In addition, none of the aluminum wires peeled at all to the extent that they were scratched with a finger. From this, it was found that each aluminum wire was well bonded to the silicon nitride plate.

(Example 13)
A joined body of a ceramic member and an aluminum member was manufactured in the same procedure as in Example 7.

  However, in Example 13, an aluminum nitride plate having dimensions of 25 mm × 25 mm × thickness 400 μm was used instead of the alumina plate.

  Thereby, a joined body in which an aluminum wire was joined on the aluminum nitride plate was obtained.

  In addition, none of the aluminum wires peeled at all to the extent that they were scratched with a finger. From this, it was found that each aluminum wire was well bonded to the aluminum nitride plate.

(Example 14)
A joined body of a ceramic member and an aluminum member was manufactured in the same procedure as in Example 13. However, in Example 14, the heat treatment (joining with aluminum member) conditions were set to 600 ° C. for 1 hour in an argon atmosphere.

  Thereby, a joined body in which an aluminum wire was joined on the aluminum nitride plate was obtained.

  FIG. 16 shows a plan view (photograph) of the obtained joined body. In addition, none of the aluminum wires peeled at all to the extent that they were scratched with a finger. From this, it was found that each aluminum wire was well bonded to the aluminum nitride plate.

(Example 15)
A joined body of a ceramic member and an aluminum member was manufactured in the same procedure as in Example 12. However, in Example 15, the heat treatment (joining with aluminum member) conditions were set to 600 ° C. for 1 hour in an argon atmosphere.

  As a result, a joined body in which an aluminum wire was joined on the silicon nitride plate was obtained.

  In addition, none of the aluminum wires peeled at all to the extent that they were scratched with a finger. From this, it was found that each aluminum wire was well bonded to the silicon nitride plate.

(Comparative Example 3)
The ceramic member and the aluminum member were tried to be joined by the same procedure as in Example 7. However, in Comparative Example 3, the heat treatment (joining with the aluminum member) conditions of the alumina plate were 580 ° C. and 1 hour in an argon atmosphere. Other conditions are the same as those in the seventh embodiment.

  When it confirmed after heat processing, it turned out that neither aluminum wire is joined to the alumina board.

(Comparative Example 4)
A ceramic member and an aluminum member were tried to be joined in the same procedure as in Example 12. However, in Comparative Example 4, the heat treatment (bonding with the aluminum member) condition of the silicon nitride plate was 580 ° C. for 1 hour in an argon atmosphere. Other conditions are the same as in the case of Example 12.

  When confirmed after the heat treatment, it was found that none of the aluminum wires were bonded to the silicon nitride plate.

(Comparative Example 5)
A ceramic member and an aluminum member were tried to join in the same procedure as in Example 13. However, in Comparative Example 5, the heat treatment conditions (joining with the aluminum member) of the aluminum nitride plate were 580 ° C. and 1 hour in an argon atmosphere. Other conditions are the same as in the case of Example 13.

  When it confirmed after heat processing, it turned out that neither aluminum wire is joined to the aluminum nitride board.

  Table 2 below collectively shows the manufacturing conditions and bonding states of the bonded bodies according to Examples 7 to 15 and Comparative Examples 3 to 5.

  The present invention can be used, for example, for ceramic bonding technology, heteromaterial (metal-ceramics) manufacturing technology, wiring technology for ceramic substrates, and the like.

DESCRIPTION OF SYMBOLS 100 Bonded body 110 Ceramic member 130 Aluminum member 150 Bonding layer 200 Bonded body 210 First ceramic member 230 Aluminum member 250 First bonding layer 260 Second ceramic member 290 Second bonding layer

Claims (10)

A method of joining a ceramic member and an aluminum member,
(A) preparing a ceramic member containing aluminum and / or silicon, and an aluminum member;
(B) installing a bonding material on at least one of the ceramic member and the aluminum member, the bonding material including a siloxane polymer or a carbon powder-containing silica sol;
(C) laminating the ceramic member and the aluminum member with the bonding material interposed therebetween, and constituting an assembly;
(D) heating the assembly at a temperature of 600 ° C. to 1400 ° C. in an inert gas atmosphere or a vacuum atmosphere;
Having a method. A method of joining a ceramic member and an aluminum member,
(A) preparing a ceramic member containing aluminum and / or silicon, and an aluminum member;
(B) installing a bonding material on at least one of the ceramic member and the aluminum member, the bonding material including a siloxane polymer or a carbon powder-containing silica sol;
(C) laminating the ceramic member and the aluminum member with the bonding material interposed therebetween, and constituting an assembly;
(D) heating the assembly at a temperature of 660 ° C. to 1400 ° C. in an inert gas atmosphere or a vacuum atmosphere;
Having a method.   The method according to claim 1, wherein the ceramic member includes at least one material selected from the group consisting of alumina, aluminum nitride, silicon nitride, mullite, and aluminosilicate.   4. The method according to claim 1, wherein a carbon lump, a carbide lump or a metal silicon lump is formed in the aluminum member after the step (d). 5.   A joined body in which a ceramic member containing aluminum and / or silicon and an aluminum member are joined via a joining layer containing an aluminosilicate. A joined body in which a ceramic member containing aluminum and / or silicon and an aluminum member are joined,
Between the two, there is a region where the amount of silicon is higher than that of the ceramic member and the aluminum member.   The ceramic member containing aluminum and / or silicon includes at least one material selected from the group consisting of alumina, aluminum nitride, silicon nitride, mullite, and aluminosilicate. The joined body described.   The joined body according to any one of claims 5 to 7, wherein the aluminum member includes a carbon lump, a carbide lump, or a metal silicon lump.   Furthermore, the 2nd ceramic member is arrange | positioned through the 2nd joining layer containing an aluminosilicate on the opposite side to the said ceramic member of the said aluminum member. The joined body according to any one of 8. Furthermore, a second ceramic member is disposed on the side of the aluminum member opposite to the ceramic member,
9. The region according to claim 5, wherein there is a region where the amount of silicon is higher than that of the second ceramic member and the aluminum member between the second ceramic member and the aluminum member. The joined body according to any one of the above.