JP6851033B2 - Method of manufacturing the joint and the joint - Google Patents

Description

The present invention relates to a method for manufacturing a bonded body in which an aluminum member and a ceramic member are joined, and such a bonded body.

There is a great demand for technology 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 an alumina and an aluminum member.

It is considered that this is because an oxide film (alumina layer) that interferes with the bonding with the ceramic member exists on the surface of the aluminum member. That is, in the bonding process, the oxide film existing on the surface of the aluminum member does not provide good affinity between the aluminum member and the ceramic member, and further, good adhesion cannot be obtained, whereby good bonding between the two is not obtained. It is considered that the state cannot be formed.

Against this background, a new method for joining an aluminum member and a ceramic member has recently been proposed (Patent Document 1).

Japanese Unexamined Patent Publication No. 2014-196233

In the method described in Patent Document 1, the aluminum member and the ceramic member can be joined by heating both of them in a state where the siloxane-based polymer is installed between the aluminum member and the ceramic member.

However, originally, there is a problem that the difference in the coefficient of thermal expansion is relatively large between the aluminum member and the ceramic member. Therefore, even if the aluminum member and the ceramic member can be joined by the above-mentioned method, such a joined body may be damaged when subjected to thermal stress, for example, during use.

The present invention has been made in view of such a background, and an object of the present invention is to provide a method for manufacturing a bonded body of an aluminum member and a ceramic member, which is relatively unlikely to be damaged even when subjected to thermal stress. And. Another object of the present invention is to provide a bonded body of an aluminum member and a ceramic member, which is relatively resistant to breakage even when subjected to thermal stress.

The present invention is a method for manufacturing a bonded body having an aluminum member and a ceramic member.
(A) A step of preparing an aluminum member, a ceramic member containing aluminum and / or silicon, and a first alloy member containing aluminum.
The first alloy member has first and second surfaces.
The coefficient of thermal expansion of the first alloy member is smaller than that of the aluminum member and larger than that of the ceramic member.
(B) The first bonding material is installed on at least one of the bonded surface of the aluminum member and the first surface of the first alloy member, and the bonded surface of the ceramic member and the first alloy. A step of installing a second bonding material on at least one of the second surfaces of the member.
The first and second joint materials are independently
(I) An organosilicon polymer having a main chain having at least one Si—C—Si group and a Si—N—Si group.
(Ii) An organosilicon polymer having a Si—O—Si group in the main chain,
(Iii) Carbon powder-containing silica sol, and (iv) Organosilicon polymer having a Si—Si group in the main chain,
With at least one compound of
(C) A step of laminating the aluminum member, the first alloy member, and the ceramic member in this order to form an assembly.
The first alloy member is arranged so that the side of the first surface faces the surface to be joined of the aluminum member and the side of the second surface faces the surface to be joined of the ceramic member. When,
(D) A step of heating the assembly at a temperature of 400 ° C. to 800 ° C. under an inert gas atmosphere or a vacuum atmosphere.
A manufacturing method having the above is provided.

Further, the present invention is a method for manufacturing a bonded body having an aluminum member and a ceramic member.
(A) A step of preparing an aluminum member, a ceramic member containing aluminum and / or silicon, a first alloy member containing aluminum, and a second alloy member containing aluminum.
The first alloy member has first and second surfaces.
The second alloy member has third and fourth surfaces and has
The coefficient of thermal expansion of the first and second alloy members is smaller than that of the aluminum member and larger than that of the ceramic member, respectively.
The coefficient of thermal expansion of the second alloy member is smaller than the coefficient of thermal expansion of the first alloy member.
(B) A first bonding material is installed on at least one of the bonded surface of the aluminum member and the first surface of the first alloy member, and the bonded surface of the ceramic member and the second alloy member. A second bonding material is installed on at least one of the fourth surfaces of the first alloy member, and a third surface is provided on at least one of the second surface of the first alloy member and the third surface of the second alloy member. It is a step to install the joint material,
The first, second, and third joint materials are independently
(I) An organosilicon polymer having a main chain having at least one Si—C—Si group and a Si—N—Si group.
(Ii) An organosilicon polymer having a Si—O—Si group in the main chain,
(Iii) Carbon powder-containing silica sol, and (iv) Organosilicon polymer having a Si—Si group in the main chain,
With at least one of the steps,
(C) A step of laminating the aluminum member, the first alloy member, the second alloy member, and the ceramic member in this order to form an assembly.
The first alloy member is arranged so that the side of the first surface faces the surface to be joined of the aluminum member, and the second alloy member has the fourth surface to be joined to the ceramic member. Steps and steps that are placed face-to-face
(D) A step of heating the assembly at a temperature of 400 ° C. to 800 ° C. under an inert gas atmosphere or a vacuum atmosphere.
A manufacturing method having the above is provided.

Further, in the present invention, it is a joint including an aluminum member and a ceramic member containing aluminum and / or silicon.
Further, a first alloy member is provided between the aluminum member and the ceramic member.
The first alloy member has a first side and a second side, and the first side is closer to the aluminum member than the second side.
The first alloy member contains aluminum and contains aluminum.
The coefficient of thermal expansion of the first alloy member is smaller than that of the aluminum member and larger than that of the ceramic member.
A first bonding layer is present on the first side of the first alloy member.
A second bonding layer is present on the second side of the first alloy member.
The first and second bonding layers are, respectively.
(I) Amorphous phase containing carbon and silicon, having a carbon content of 8% by weight or more and an oxygen content of less than 30% by weight, and / or (II) aluminosilicate.
Bonds are provided, including.

In the present invention, it is possible to provide a method for manufacturing a bonded body of an aluminum member and a ceramic member, which is relatively unlikely to be damaged even when subjected to thermal stress. Further, in the present invention, it is possible to provide a bonded body of an aluminum member and a ceramic member, which is relatively unlikely to be damaged even when subjected to thermal stress.

It is a figure which showed schematic flow of the manufacturing method of the joint body including the aluminum member and the ceramics member by one Example of this invention. It is a figure which showed the flow of another manufacturing method of the joint containing the aluminum member and the ceramics member according to one Example of this invention schematically. It is a figure which showed the flow of still another manufacturing method of the joined body including the aluminum member and the ceramics member according to one Example of this invention schematically. It is sectional drawing which showed the schematic structure of the joint body by one Example of this invention. It is sectional drawing which showed the schematic structure of another joint by one Example of this invention. It is a figure which shows the result of the X-ray diffraction (XRD) analysis of the bonding layer between a silumin plate and a ceramic member in the bonding body which concerns on Example 1. FIG.

Hereinafter, the present invention will be described in detail.

As described above, since an oxide film (alumina layer) that interferes with the bonding with the ceramic member exists on the surface of the aluminum member, there is a problem that it is difficult to properly bond the ceramic member and the aluminum member.

In relation to this problem, the inventors of the present application have been able to bond the ceramic member and the ceramic member by heating both of them in a state where the siloxane-based polymer is installed between the aluminum member and the ceramic member. (For example, Patent Document 1).

However, originally, there is a problem that the difference in the coefficient of thermal expansion is relatively large between the aluminum member and the ceramic member. Therefore, even if the aluminum member and the ceramic member can be joined by the above-mentioned method, such a joined body may be damaged when subjected to thermal stress, for example, during use. ..

With this awareness in mind, the inventors of the present application have further promoted research on a method for joining an aluminum member and a ceramic member. As a result, we have found a measure that can significantly improve the resistance of the joint body of the aluminum member and the ceramic member to thermal stress, and have reached the present invention.

That is, in one embodiment of the present invention, it is a method for manufacturing a bonded body having an aluminum member and a ceramic member.
(A) A step of preparing an aluminum member, a ceramic member containing aluminum and / or silicon, and a first alloy member containing silicon and aluminum.
The first alloy member has first and second surfaces.
The coefficient of thermal expansion of the first alloy member is smaller than that of the aluminum member and larger than that of the ceramic member.
(B) The first bonding material is installed on at least one of the bonded surface of the aluminum member and the first surface of the first alloy member, and the bonded surface of the ceramic member and the first alloy. A step of installing a second bonding material on at least one of the second surfaces of the member.
The first and second joint materials are independently
(I) An organosilicon polymer having a main chain having at least one Si—C—Si group and a Si—N—Si group.
(Ii) An organosilicon polymer having a Si—O—Si group in the main chain,
(Iii) Carbon powder-containing silica sol, and (iv) Organosilicon polymer having a Si—Si group in the main chain,
With at least one compound of
(C) A step of laminating the aluminum member, the first alloy member, and the ceramic member in this order to form an assembly.
The first alloy member is arranged so that the side of the first surface faces the surface to be joined of the aluminum member and the side of the second surface faces the surface to be joined of the ceramic member. When,
(D) A step of heating the assembly at a temperature of 400 ° C. to 800 ° C. under an inert gas atmosphere or a vacuum atmosphere.
A manufacturing method having the above is provided.

In one embodiment of the present invention, when a bonded body having an aluminum member and a ceramic member is manufactured, an alloy member is interposed between the two. This alloy member has a smaller coefficient of thermal expansion than the aluminum member and a larger coefficient of thermal expansion than the ceramic member. Such an alloy member can function as a stress relaxation layer when the joint body is subjected to thermal stress.

Therefore, the joint body produced by the production method according to the embodiment of the present invention can significantly suppress the breakage of the joint body even if it receives thermal stress.

However, in one embodiment of the present invention, the alloy member comprises silicon and aluminum. Therefore, this alloy member behaves like an aluminum member during the joining process. Therefore, if such an alloy member is simply arranged between the aluminum member and the ceramic member, even if the heat treatment is performed, the presence of the oxide film as described above on the surface of the alloy member causes each member. It is difficult to obtain a well-bonded alloy.

On the other hand, in one embodiment of the present invention, a joining material selected from a specific material group is installed on both sides of the alloy member during the joining treatment. When heated in this state, as will be described later, the joining material exerts a function as an adhesive for joining the aluminum member and the alloy member, and the alloy member and the ceramic member. As a result, in the method for manufacturing a bonded body according to the embodiment of the present invention, the aluminum member and the ceramic member can be appropriately bonded with the alloy member interposed therebetween.

As described above, in one embodiment of the present invention, the aluminum member and the ceramic member can be properly joined, and the heat-resistant stress characteristics of the obtained joined body can be improved.

In the present application, the aluminum member and the alloy member may be collectively referred to as a "metal member".

Here, in one embodiment of the present invention, the bonding material includes at least one of the following materials (i) to (iv):
(I) An organosilicon polymer having a main chain having at least one Si—C—Si group and a Si—N—Si group.
(Ii) An organosilicon polymer having a Si—O—Si group in the main chain,
(Iii) A carbon powder-containing silica sol, and (iv) an organosilicon polymer having a Si—Si group in the main chain.

Of these, the organosilicon polymer of (i) contains a carbon atom. This carbon atom plays a role of reducing the oxide film formed on the surface of the metal member or destabilizing the oxide film in a high temperature state. Therefore, when a bonding material containing (i) is used, the action of carbon atoms reduces the barrier property of the oxide film covering the surface of the metal member, and activates the metal member, that is, makes the metal member easy to react. it can.

Further, the organosilicon polymer of (i) has at least one Si—C—Si group and Si—N—Si group in the main chain. Therefore, an organosilicon polymer having a main chain as in (i) changes into a compound containing silicon and carbon when heated in an inert atmosphere. This silicon-carbon-containing compound can react in high temperature environments with so-called "active" metal members with reduced barrier function of the oxide film.

Further, in one embodiment of the present invention, a ceramic member containing aluminum and / or silicon is used as the ceramic member. Such ceramic members have an affinity for the above-mentioned compounds containing silicon and carbon.

Therefore, when the heat treatment is performed in a low oxygen atmosphere by interposing the above-mentioned joining material between the aluminum member and the alloy member and between the alloy member and the ceramic member, the carbon contained in the joining material is contained. Atoms reduce a portion of the oxide film present on the surface of the metal member. Alternatively, the oxide film existing on the surface of the metal member becomes incomplete. As a result, the metal member is activated.

Further, the reaction component generated when the bonding material is heated, that is, the compound containing silicon and carbon as described above reacts with the activated metal member, and as a result, the bonding material is transformed into a bonding layer. Usually, the resulting bonding layer contains a silicon carbide compound.

Here, the silicon carbide-based compound includes, for example, SiC, SiOC, SiCN, SiOCN, AlSiC, AlSiOC, AlSiCN, and / or AlSiOCN and the like. Silicon carbide compounds are often formed as an amorphous (glass) phase.

Due to the presence of such a bonding layer, the ceramic member is firmly adhered to the bonding layer, and the aluminum member and the alloy member are also firmly adhered to the bonding layer. As a result, the aluminum member, the alloy member, and the ceramic member are joined via the joining layer.

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

On the other hand, the case where the bonding material contains (ii) to (iv) is also considered in the same manner.

However, when the bonding material contains (ii) or (iii), when the bonding material is heated in an inert atmosphere by the silicon (Si) and oxygen (O) contained in the bonding material, a compound containing silicon and oxygen. Is generated. Then, as a result of this compound reacting with the metal member, an aluminosilicate-based compound is formed as a bonding layer between the aluminum member and the alloy member and between the alloy member and the ceramic member.

Aluminosilicate-based compound, general formula is represented by _Al x _Si y _{O z,} where a 0 <x <3,0 <y < 51,0 <z <104. The aluminosilicate compound may be a mixture of alumina and silica.

The ceramic member used in the present application also has an affinity for compounds containing silicon and oxygen.

Therefore, even when the bonding material contains (iii) or (iii), the ceramic member is firmly adhered to the bonding layer due to the presence of the bonding layer. Therefore, in this case as well, good bonding can be obtained between the aluminum portion, the alloy member, and the ceramic member.

In the above description, the features of one embodiment of the present invention have been described by taking as an example the case where the alloy member is composed of a material containing both silicon and aluminum. However, this is only an example, and the alloy member may be composed of a material containing aluminum and not silicon.

(Method for manufacturing a bonded body according to an embodiment of the present invention)
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

FIG. 1 schematically shows a flow of a method for manufacturing a bonded body including an aluminum member and a ceramic member (hereinafter, referred to as “first manufacturing method”) according to an embodiment of the present invention.

As shown in FIG. 1, the first manufacturing method is
(A) A step (step S110) of preparing an aluminum member, a ceramic member containing aluminum and / or silicon, and an alloy member containing silicon and aluminum.
(B) The first bonding material is installed on at least one of the bonded surface of the aluminum member and the first surface of the alloy member, and the bonded surface of the ceramic member and the second surface of the alloy member. Step (step S120) of installing the second bonding material on at least one of the above.
(C) A step (step S130) of laminating the aluminum member, the alloy member, and the ceramic member in this order to form an assembly.
(D) A step of heating the assembly at a temperature of 400 ° C. to 800 ° C. under an inert gas atmosphere or a vacuum atmosphere (step S140).
Have.

Each step will be described in detail below.

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

The shape of the aluminum member is not particularly limited, and the aluminum member may have the shape of a block, a plate, a rod, a foil, a disk, or the like.

In the present application, the term "aluminum member" refers to a member substantially made of aluminum metal, a member containing 50 wt% or more of aluminum metal by weight, and a member substantially made of aluminum alloy. And a member containing an aluminum alloy having a weight ratio of 80 wt% or more is included.

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

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, examples of alumina include 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 of aluminum nitride by weight. Examples of the silicon nitride include high-purity silicon nitride containing 80 wt% or more of silicon nitride by weight.

Although the crystal form of the ceramics is not particularly limited, α-alumina can be preferably used as the alumina.

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

On the other hand, the alloy member is selected from alloy materials containing silicon and aluminum. The weight ratio of silicon may be 0.3 to 99%. Further, the weight ratio of aluminum may be in the range of 1% to 99%.

Since silicon has a small coefficient of thermal expansion, the coefficient of thermal expansion of the alloy member can be reduced by adding silicon to the alloy member. Further, when aluminum melts and then solidifies during the joining process, silicon solidifies and expands. Therefore, by adding aluminum and silicon to the alloy member, it is possible to mitigate the volume change of the alloy member that may occur during the joining process.

The composition of the alloy member is not particularly limited as long as it has a coefficient of thermal expansion smaller than that of the prepared aluminum member and a coefficient of thermal expansion larger than that of the ceramic member.

The alloy member is, for example, an alloy containing aluminum (Al) as a main component and silicon (Si) (Al—Si alloy), an alloy mainly composed of Al containing Si and magnesium (Mg) (Al—Si—Mg alloy), or an alloy member. It may be an alloy containing Si as a main component and Al (Si—Al alloy) or the like. Here, "mainly composed of element A" means that element A is contained in an amount of 50% by weight or more.

When the alloy member is an Al—Si alloy or an Al—Si—Mg alloy, the weight ratio of Al may be in the range of 50% to 99%. Further, in this case, the weight ratio of Si may be in the range of 0.3% to 50%. Further, the weight ratio of Mg may be in the range of 0.1% to 5.0%.

On the other hand, when the alloy member is a Si—Al alloy, the weight ratio of Si may be in the range of 50% to 99%. Further, in this case, the weight ratio of Al may be in the range of 1% to 50%.

When the above-mentioned aluminum member is not silumin (Al-12% Si alloy), the alloy member may be silumin.

Further, the alloy member may contain Cu, Ni, Mn, Fe and Zn as additional elements. The weight ratio of Cu is in the range of 0 to 6.0 wt%, the weight ratio of Ni is in the range of 0 to 1.5 wt%, the weight ratio of Mn is in the range of 0 to 1.5 wt%, and the weight ratio of Fe is 0 to 1. The range of .3 wt% and the weight ratio of Zn may be in the range of 0 to 1.5 wt%.

Further, the alloy member may contain particles having a coefficient of thermal expansion smaller than that of the alloy member.

Such particles may include at least one of metal particles, alloy particles, and ceramic particles.

Examples of the metal particles include silicon, molybdenum, and tungsten. Examples of the ceramic particles include alumina (Al ₂ O ₃ ), silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), and diamond.

When an alloy member containing such particles is used, the coefficient of thermal expansion of the alloy member can be finely adjusted within a desired range.

The form of the alloy member is not particularly limited as long as it has two opposing surfaces (referred to as "first surface" and "second surface", respectively). For example, the alloy member may be plate-shaped or block-shaped.

(Step S120)
Next, the first bonding material is installed on at least one of the surface to be bonded of the aluminum member and the first surface of the alloy member. Further, the second bonding material is installed on at least one of the surface to be bonded of the ceramic member and the second surface of the alloy member.

The first joining material and the second joining material may be the same or different.

Here, the first and second bonding materials (hereinafter, also simply referred to as “bonding materials”) are selected from those containing carbon (C) and silicon (Si), respectively.

The bonding material may contain at least one of the following (i) to (iv):
(I) An organosilicon polymer having a main chain having at least one Si—C—Si group and a Si—N—Si group.
(Ii) An organosilicon polymer having a Si—O—Si group in the main chain,
(Iii) A carbon powder-containing silica sol, and (iv) an organosilicon polymer having a Si—Si group in the main chain.

An example of the chemical formula of the organosilicon polymer of (i) having a Si—C—Si group in the main chain (hereinafter referred to as “Si—C—Si polymer”) is shown in the following formula (1). Shown in:

Here, the sum of p and q is in the range of 500 to 5000. Further, R ¹ , R ² , R ³ , and R ⁴ are independently one of H, CH ₃ , C ₂ H ₃ , C ₆ H ₅ , and OMCH ₃ (C _m H _{2m + 1} ) ₂ , respectively. .. At ^{least two of R 1} , R ² , R ³ , and R ⁴ may be the same. In addition, m represents an integer of 1 or more, and M represents one or more kinds of Ti, Zr, and / or Cr.

Examples of the first organosilicon polymer having the chemical structure represented by the formula (1) include polycarbosilane represented by the following formula (2) and polytitanocarbo represented by the formula (3). Silane and the like are included.

Further, an example of the chemical formula of the above-mentioned organosilicon polymer (i) having a main chain having a Si—N—Si group (hereinafter referred to as “Si—N—Si polymer”) is as follows. Shown in equation (4):

Here, the sum of p and q is in the range of 1 to 5000. Further, R ¹ , R ² , R ³ , and R ⁴ are independently one of H, CH ₃ , C ₂ H ₃ , and C ₆ H ₅ , respectively. At ^{least two of R 1} , R ² , R ³ , and R ⁴ may be the same.

The Si—N—Si based polymer having the chemical structure represented by the formula (4) is represented by, for example, polymethyldisilazane (PMDS) represented by the following formula (5) and the formula (6). Polydimethylmethylsilazane (PDMMS) and the like are included.

Further, the Si—C—Si based polymer may have the following chemical structural formula.

In formula (7), the sum of p and q is in the range of 1 to 5000. Further, R ¹ , R ² , R ³ , and R ⁴ are independently one of H, CH ₃ , C ₂ H ₃ , and C ₆ H ₅ , respectively. At ^{least two of R 1} , R ² , R ³ , and R ⁴ may be the same.

Here, the Si—C—Si based polymer represented by the formula (7) has a Si—N—Si group in a part of the main chain. Therefore, this polymer can also be referred to as a Si—C—Si based polymer.

In addition, the above-mentioned organosilicon polymer (i) is not limited to, for example, polycarbosilazan, allylhydride polycarbosilane, polysilmethylene, polysilazane, polyhydropolysilazane, and polyorgano. Includes silazane and the like.

On the other hand, as the organosilicon polymer of (ii), a siloxane-based polymer (hereinafter, referred to as “Si—O—Si-based polymer”) can be mentioned.

For example, Si—O—Si based polymers include siloxane-based polymers having a linear Si—O—Si group as the main chain, such as polymethylhydrosiloxane (PMHS) and polymethylphenylsiloxane (PMPHS). ..

Alternatively, the Si—O—Si based polymer is, for example, a silsesquioxane polymer having a three-dimensional structure having a Si—O—Si group as a main skeleton, for example, polymethylsilsesquioxane (PMSQ) and polyphenylsiloxane. It may be (PPSQ).

The following formula (8) shows the chemical structural formula of PMPhS. Further, the following formula (9) shows the chemical structural formula of PMSQ.

一方、前述の（ｉｖ）の有機ケイ素系ポリマーは、以下の化学構造式を有しても良い。

On the other hand, the above-mentioned organosilicon polymer (iv) may have the following chemical structural formula.

ここで、Ｒ^１およびＲ^２は、それぞれ独立に、水素、ＣＨ_３、またはＣ_６Ｈ_５などである。また、nは、１０〜１０００の間の任意の整数である。

Here, R ¹ and R ² are independently hydrogen, CH ₃ , C ₆ H ₅ , and the like. Also, n is any integer between 10 and 1000.

The organosilicon polymer of (iv) includes, but is not limited to, polyhydrosilane, polymethylsilane, polyphenylsilane, and the like.

The bonding material may include two or all of the above-mentioned (i) to (iv).

The method of installing such a bonding material is not particularly limited.

The joining material may be installed on the joining 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 as evenly as possible, it is desirable to apply it by a dipping method having a pulling speed of 1 mm / sec or less or a spin coater method having a rotation speed of 100 rpm or more.

The thickness of the finally obtained bonding layer changes depending on the thickness of the bonding material. Therefore, it is preferable to adjust the type and thickness of the bonding material according to the purpose.

Further, the organosilicon-based polymer as shown in the above-mentioned (i) and (ii) has a relatively high viscosity. Therefore, when these are applied by the dipping method, it is preferable to dilute them with a solvent and adjust the viscosity appropriately. In this case, from the viewpoint of compatibility, it is preferable to use an aromatic organic solvent such as benzene or toluene. The solvent concentration may be in the range of 0.001 mol / L to 1 mol / L.

If the amount of the bonding material installed on the surface to be bonded of the aluminum member and / or the ceramic member is too small, the bonding material does not spread uniformly over the entire surface to be bonded, and the oxide layer is sufficiently provided on the surface to be bonded of the aluminum member. There is a risk that it cannot be returned. Therefore, the thickness of the bonding material is preferably 0.1 μm (after solvent volatilization) or more. On the other hand, even if the bonding material is too thick, bonding 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 shrinkage of the bonding material portion due to ceramicization. Therefore, the thickness of the bonding material is preferably 1 mm (after solvent volatilization) or less.

Further, when the amount of the bonding material installed is excessive, the silicon contained in the bonding material is reduced by the aluminum member, so that metallic silicon is likely to be deposited near the interface between the bonding layer and the aluminum member. Therefore, the silicon content in the bonding material is preferably selected in the range of 10 wt% to 45 wt%.

(Step S130)
Next, the aluminum member, the alloy member, and the ceramic member are laminated in this order to form an assembly.

Here, the alloy member is arranged so that the side of the first surface faces the surface to be joined of the aluminum member and the second surface faces the surface to be joined of the ceramic member.

In the assembly, the aluminum member, the alloy member, and the ceramic member may be laminated on each other in a substantially non-pressurized state (however, a load due to their own weight is applied). Alternatively, a certain load may be applied between the aluminum member and the ceramic member.

(Step S140)
The assembly is then heat treated for joining. As a result, a bonded body in which the aluminum member, the alloy member, and the ceramic member are bonded to each other via the bonding layer is manufactured.

The heat treatment is performed in an atmosphere that is substantially free of oxygen, such as an inert gas atmosphere or a vacuum atmosphere. When the heat treatment is carried out in an environment containing oxygen such as an atmospheric atmosphere, the oxide on the surface of the aluminum member or the like is not sufficiently reduced, and between the aluminum member and the alloy member and between the alloy member and the ceramic member. Therefore, it becomes difficult to obtain a good bond.

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

The temperature of the heat treatment is 400 ° C. or higher, preferably 450 ° C. or higher. The temperature of the heat treatment is preferably 800 ° C. or lower, for example. In particular, the heat treatment temperature is preferably in the range of 540 ° C to 660 ° C.

Heat treatment of the assembly changes the first and second joints. As a result, a first bonding layer is formed between the aluminum member and the alloy member, and a second bonding layer is formed between the alloy member and the ceramic member.

The first bonding material and / or the second bonding material may be melted during the heat treatment of the assembly. In this case, the first bonding layer is a layer that is solidified after the first bonding material is melted, and the second bonding layer is a layer that is solidified after the second bonding material is melted.

As described above, the composition of the first and second bonding layers (hereinafter, simply referred to as “bonding layer”) varies depending on the type of bonding material.

For example, when a bonding material containing the above-mentioned (i) and (iv) is used, a bonding layer containing a silicon carbide-based compound can be obtained. The silicon carbide-based compound may have an amorphous phase.

As described above, the silicon carbide-based compound may include, for example, SiC, SiOC, SiCN, SiOCN, AlSiC, AlSiOC, AlSiCN, and / or AlSiOCN and the like. The silicon carbide compound contained in the bonding layer also changes depending on the type of bonding material used, the material of the ceramic member, and the like.

In addition to the silicon carbide compound, the bonding layer may contain a small amount of other substances such as carbon lumps, metallic silicon lumps, and / or aluminosilicates.

On the other hand, when a material containing the above-mentioned (ii) or (iii) is used as the bonding material, a bonding layer containing an aluminosilicate-based compound can be obtained.

As described above, aluminosilicate compounds have the general formula is represented by _Al x _Si y _{O z,} where a 0 <x <3,0 <y < 51,0 <z <104. The aluminosilicate compound may be a mixture of alumina and silica.

In this case as well, the bonding layer may contain a small amount of other substances such as carbon lumps and metallic silicon lumps in addition to the aluminosilicate-based compound.

Through the above steps, a joint having an aluminum member, an alloy member, and a ceramic member is manufactured.

In the first manufacturing method, an alloy member having a coefficient of thermal expansion between the aluminum member and the ceramic member is installed between the aluminum member and the ceramic member. Therefore, even if thermal stress is applied to the manufactured joint body, the alloy member functions as a stress relaxation layer, and damage to the joint body can be significantly suppressed.

Further, in the first manufacturing method, the above-mentioned type of joining material is installed between the aluminum member and the alloy member, and between the alloy member and the ceramic member during the joining process. Due to the presence of these joining materials, the aluminum member and the alloy member, and the alloy member and the ceramic member are properly joined after the joining treatment.

Therefore, in the first manufacturing method, the aluminum member and the ceramic member can be properly joined, and the heat-resistant stress characteristics of the obtained joined body can be improved.

(Method for manufacturing another bonded body according to one embodiment of the present invention)
Next, another method for producing a bonded body according to an embodiment of the present invention will be described.

FIG. 2 schematically shows a flow of a method for manufacturing a bonded body having an aluminum member and a ceramic member (hereinafter, referred to as a “second manufacturing method”) according to an embodiment of the present invention.

As shown in FIG. 2, the second manufacturing method is
(A) A step (step S210) of preparing an aluminum member, a ceramic member containing aluminum and / or silicon, a first alloy member containing silicon and aluminum, and a second alloy member containing silicon and aluminum.
(B) A first bonding material is installed on at least one of the bonded surface of the aluminum member and the first surface of the first alloy member, and the bonded surface of the ceramic member and the second alloy member. A second bonding material is installed on at least one of the fourth surfaces of the first alloy member, and a third surface is provided on at least one of the second surface of the first alloy member and the third surface of the second alloy member. Step (step S220) to install the joint material,
(C) A step (step S230) of laminating the aluminum member, the first alloy member, the second alloy member, and the ceramic member in this order to form an assembly.
(D) A step of heating the assembly at a temperature of 400 ° C. to 800 ° C. under an inert gas atmosphere or a vacuum atmosphere (step S240).
Have.

Each step will be described in detail below.

(Step S210)
First, an aluminum member, a ceramic member, and first and second alloy members are prepared.

Here, with respect to the aluminum member, the ceramic member, and the first alloy member, the description of each in step S110 of the first manufacturing method described above can be referred to. Therefore, detailed description is omitted here.

On the other hand, the second alloy member is selected from alloy materials containing silicon and aluminum. The weight ratio of silicon may be 0.3 to 99%. Further, the weight ratio of aluminum may be in the range of 1% to 99%.

The composition of the second alloy member is not particularly limited as long as it has a coefficient of thermal expansion smaller than that of the first alloy member and a coefficient of thermal expansion larger than that of the ceramic member.

The second alloy member is, for example, an alloy containing aluminum (Al) as a main component and silicon (Si) (Al-Si alloy), and an alloy containing Al as a main component and containing Si and magnesium (Mg) (Al-Si-Mg alloy). ), Or an alloy containing Si as a main component and Al (Si—Al alloy) or the like.

When the second alloy member is an Al—Si alloy or an Al—Si—Mg alloy, the weight ratio of Al may be in the range of 50% to 99%. Further, in this case, the weight ratio of Si may be in the range of 0.3% to 50%. Further, the weight ratio of Mg may be in the range of 0.1% to 5.6%.

On the other hand, when the second alloy member is a Si—Al alloy, the weight ratio of Si may be in the range of 50% to 99%. Further, in this case, the weight ratio of Al may be in the range of 1% to 50%.

Further, the second alloy member may contain Cu, Ni, Mn, Fe and Zn as additional elements. The weight ratio of Cu is in the range of 0 to 6.0 wt%, the weight ratio of Ni is in the range of 0 to 1.5 wt%, the weight ratio of Mn is in the range of 0 to 1.5 wt%, and the weight ratio of Fe is 0 to 1. The range of .3 wt% and the weight ratio of Zn may be in the range of 0 to 1.5 wt%.

The form of the second alloy member is not particularly limited as long as it has two opposing surfaces (referred to as "third surface" and "fourth surface", respectively). For example, the second alloy member may be plate-shaped or block-shaped.

(Step S220)
Next, the first bonding material is installed on at least one of the surface to be bonded of the aluminum member and the first surface of the first alloy member. Further, the second bonding material is installed on at least one of the surface to be bonded of the ceramic member and the fourth surface of the second alloy member. Further, a third bonding material is installed on at least one of the second surface of the first alloy member and the third surface of the second alloy member.

At least two of the first joining material, the second joining material, and the third joining material may be the same. Further, the first joining material, the second joining material, and the third joining material may all be the same.

The first to third bonding materials (hereinafter, also simply referred to as “bonding materials”) are selected from those containing carbon (C) and silicon (Si), respectively.

Each of the bonding materials may contain at least one of the following (i) to (iv):
(I) An organosilicon polymer having a main chain having at least one Si—C—Si group and a Si—N—Si group.
(Ii) An organosilicon polymer having a Si—O—Si group in the main chain,
(Iii) A carbon powder-containing silica sol, and (iv) an organosilicon polymer having a Si—Si group in the main chain.

The bonding material may include, for example, two or all three of (i) to (iv). The details of (i) to (iv) are as described above, and will not be described further here.

The joining material may be installed, for example, by a coating method or the like as described above. Examples of the coating method include a dipping method, a spin coater method, and a spray method.

The thickness of the finally obtained bonding layer changes depending on the thickness of the bonding material. Therefore, it is preferable to adjust the type and thickness of the bonding material according to the purpose.

(Step S230)
Next, the aluminum member, the first alloy member, the second alloy member, and the ceramic member are laminated in this order to form an assembly.

Here, the first alloy member is arranged so that the side of the first surface faces the surface to be joined of the aluminum member and the second surface faces the third surface of the second alloy member. Further, the second alloy member is arranged so that the side of the fourth surface faces the surface to be joined of the ceramic member.

In the assembly, the aluminum member, the first alloy member, the second alloy member, and the ceramic member may be laminated on each other in a substantially non-pressurized state (however, a load due to their own weight is applied). .. Alternatively, a certain load may be applied between the aluminum member and the ceramic member.

(Step S240)
The assembly is then heat treated for joining. As a result, a joined body in which the aluminum member, the first alloy member, the second alloy member, and the ceramic member are joined to each other via a joining layer is manufactured.

As described above, the heat treatment is carried out in an atmosphere in which there is substantially no oxygen, such as an inert gas atmosphere or a vacuum atmosphere.

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

The temperature of the heat treatment is 400 ° C. or higher, preferably 450 ° C. or higher. The temperature of the heat treatment is preferably 800 ° C. or lower, for example. The heat treatment temperature is more preferably in the range of 540 ° C to 660 ° C.

By heat-treating the assembly, the first to third bonding materials are changed, a first bonding layer is formed between the aluminum member and the first alloy member, and the second alloy member and the ceramic member are formed. A second bonding layer is formed between the and. Further, a third bonding layer is formed between the first alloy member and the second alloy member.

As described above, the composition of the first to third bonding layers (hereinafter, simply referred to as “bonding layer”) varies depending on the type of bonding material.

For example, when a bonding material containing the above-mentioned (i) and (iv) is used, a bonding layer containing a silicon carbide-based compound can be obtained. The silicon carbide-based compound may have an amorphous phase. In addition to the silicon carbide compound, the bonding layer may contain a small amount of other substances such as carbon lumps, metallic silicon lumps, and / or aluminosilicates.

On the other hand, when a material containing the above-mentioned (ii) or (iii) is used as the bonding material, a bonding layer containing an aluminosilicate-based compound can be obtained.

As described above, aluminosilicate compounds have the general formula is represented by _Al x _Si y _{O z,} where a 0 <x <3,0 <y < 51,0 <z <104. The aluminosilicate compound may be a mixture of alumina and silica.

In this case as well, the bonding layer may contain a small amount of other substances such as carbon lumps and metallic silicon lumps in addition to the aluminosilicate-based compound.

Through the above steps, a bonded body having an aluminum member, a first alloy member, a second alloy member, and a ceramic member in this order is manufactured.

The joint produced by such a second manufacturing method has first and second alloy members between the aluminum member and the ceramic member, and the first alloy is located closer to the aluminum member. The coefficient of thermal expansion of the member is between the coefficient of thermal expansion of the aluminum member and the coefficient of thermal expansion of the second alloy member. Further, in the second alloy member located closer to the ceramic member, the coefficient of thermal expansion is between the coefficient of thermal expansion of the ceramic member and the coefficient of thermal expansion of the first alloy member.

Therefore, the present joint can further enhance the resistance to thermal stress as compared with the joint produced by the above-mentioned first manufacturing method.

(Another method for producing a bonded body according to an embodiment of the present invention)
Next, with reference to FIG. 2A, another method for producing a bonded body according to the embodiment of the present invention will be described.

FIG. 2A schematically shows a flow of still another manufacturing method (hereinafter, referred to as “third manufacturing method”) of a bonded body including an aluminum member and a ceramic member according to an embodiment of the present invention.

As shown in FIG. 2A, the third manufacturing method is
(A) A step (step S310) of preparing an aluminum member, a ceramic member containing aluminum and / or silicon, and an alloy member containing aluminum.
(B) The first bonding material is installed on at least one of the bonded surface of the aluminum member and the first surface of the alloy member, and the bonded surface of the ceramic member and the second surface of the alloy member. Step (step S320) of installing the second bonding material on at least one of the above,
(C) A step (step S330) of laminating the aluminum member, the alloy member, and the ceramic member in this order to form an assembly.
(D) The step of heating the assembly at a temperature of 400 ° C. to 800 ° C. under an inert gas atmosphere or a vacuum atmosphere (step S340).
Have.

Here, in the third manufacturing method, each step S310 to step 340 is substantially equal to steps S110 to step 140 in the first manufacturing method described above. However, in this third manufacturing method, an alloy member containing aluminum is used as the alloy member.
It is different from the first manufacturing method.

Therefore, the alloy member used in the third manufacturing method will be described in detail below.

In the third manufacturing method, the alloy member is selected from alloy materials containing aluminum. The weight ratio of aluminum may be in the range of 1% to 99%.

The alloy member is, for example, either an Al-Zn alloy, an Al-Sn alloy, an Al-Mg-Sn alloy, an Al-Mg-Zn alloy, an Al-Si-Sn alloy, or an Al-Sn-Zn alloy. Is also good.

The composition of these alloy members is not particularly limited as long as they have a coefficient of thermal expansion smaller than that of the prepared aluminum member and a coefficient of thermal expansion larger than that of the ceramic member.

As described above, the alloy member may contain particles having a coefficient of thermal expansion smaller than that of the alloy member.

Such particles may include at least one of metal particles, alloy particles, and ceramic particles.

Examples of the metal particles include silicon, molybdenum, and tungsten. Examples of the ceramic particles include alumina (Al ₂ O ₃ ), silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), and diamond.

The form of the alloy member is not particularly limited as long as it has two opposing surfaces (referred to as "first surface" and "second surface", respectively). For example, the alloy member may be plate-shaped or block-shaped.

Also in the third manufacturing method, the aluminum member and the ceramic member can be properly joined, and the heat-resistant stress characteristics of the obtained joined body can be improved.

As described above, the manufacturing method of the bonded body according to the embodiment of the present invention has been described by taking the first to third manufacturing methods as an example. However, the above description is merely an example, and it is clear to those skilled in the art that a part of the above-mentioned method may be modified or combined with other steps.

For example, in the second manufacturing method, two alloy members are arranged between the aluminum member and the ceramic member. However, as another aspect, three or more alloy members may be arranged between the aluminum member and the ceramic member. In this case, the alloy members are arranged in order from the aluminum member to the ceramic member in descending order of the coefficient of thermal expansion.

Further, in the second manufacturing method, an alloy material containing both silicon and aluminum is used as the first and second alloy members. However, at least one of the first and second alloy members may be an alloy member as used in the third manufacturing method. That is, at least one of the first and second alloy members is an Al—Zn alloy, an Al—Sn alloy, an Al—Mg—Sn alloy, an Al—Mg—Zn alloy, an Al—Si—Sn alloy, or Al. It may be any of −Sn—Zn alloys.

It will be apparent to those skilled in the art that various other changes and combinations are possible.

(Joint body according to one embodiment of the present invention)
Next, with reference to FIG. 3, a bonded body according to an embodiment of the present invention will be described.

FIG. 3 shows a schematic cross-sectional view of a joint according to an embodiment of the present invention (hereinafter, referred to as “first joint”).

As shown in FIG. 3, the first joint body 100 has an aluminum member 110, an alloy member 120, and a ceramic member 130. A first bonding layer 140 is installed between the aluminum member 110 and the alloy member 120, and a second bonding layer 150 is installed between the alloy member 120 and the ceramic member 130.

The aluminum member 110 includes a member substantially made of aluminum metal, a member containing 50% or more of aluminum metal by weight, a member substantially made of aluminum alloy, and 50% or more of aluminum by weight. It may be an alloy member including.

The shape of the aluminum member 110 is not particularly limited, and the aluminum member 110 may have the shape of a block, a plate, a rod, a foil, a disk, or the like.

The alloy member 120 contains silicon and aluminum. The weight ratio of silicon may be 0.3 to 99%. Further, the weight ratio of aluminum may be in the range of 1% to 99%.

The composition of the alloy member 120 is not particularly limited as long as it has a coefficient of thermal expansion smaller than that of the aluminum member 110 and a coefficient of thermal expansion larger than that of the ceramic member 130.

The alloy member 120 includes, for example, an alloy containing aluminum (Al) as a main component and silicon (Si) (Al—Si alloy), an alloy containing Al as a main component and containing Si and magnesium (Mg) (Al—Si—Mg alloy), and the like. Alternatively, it may be an alloy containing Si as a main component and Al (Si—Al alloy) or the like.

When the alloy member 120 is an Al—Si alloy or an Al—Si—Mg alloy, the weight ratio of Al may be in the range of 50% to 99%. Further, in this case, the weight ratio of Si may be in the range of 0.3% to 50%. Further, the weight ratio of Mg may be in the range of 0.1% to 45%.

On the other hand, when the alloy member 120 is a Si—Al alloy, the weight ratio of Si may be in the range of 50% to 99%. Further, in this case, the weight ratio of Al may be in the range of 1% to 50%.

When the aluminum member 110 is not silumin (Al-12% Si alloy), the alloy member 120 may be silumin.

Alternatively, the alloy member 120 may be made of an alloy containing aluminum. For example, the alloy member 120 is either an Al—Zn alloy, an Al—Sn alloy, an Al—Mg—Sn alloy, an Al—Mg—Zn alloy, an Al—Si—Sn alloy, or an Al—Sn—Zn alloy. You may. In these alloys, the weight ratio of Mg may be in the range of 0.1 to 95%. The weight ratio of Zn may be 0.1 to 99%. The weight ratio of Sn may be 0.1 to 99%.

Further, the alloy member 120 may contain Cu, Ni, Mn, Fe, and Zn as additional elements. The weight ratio of Cu is in the range of 0 to 6.0 wt%, the weight ratio of Ni is in the range of 0 to 1.5 wt%, the weight ratio of Mn is in the range of 0 to 1.5 wt%, and the weight ratio of Fe is 0 to 1. The range of .3 wt% and the weight ratio of Zn may be in the range of 0 to 1.5 wt%.

The form of the alloy member 120 is not particularly limited. For example, the alloy member 120 may have a plate shape or a block shape.

The alloy member 120 may be one that is once melted and then solidified.

Further, the alloy member 120 may contain particles inside. Such particles may be at least one of metal particles, alloy particles, and ceramic particles.

Examples of the metal particles include silicon, molybdenum, and tungsten. Examples of the ceramic particles include alumina (Al ₂ O ₃ ), silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), and diamond.

The ceramic member 130 is made of ceramics containing an aluminum component and / or a silicon component. For example, the ceramic member 130 contains at least one of alumina, aluminum nitride, silicon nitride, and aluminosilicate.

The crystal form of the ceramic member 130 is not particularly limited, but α-alumina can be preferably used as the alumina.

The shape of the ceramic member 130 is not particularly limited, and the ceramic member 130 may have the shape of a block, a plate, a rod, a disk, or the like.

On the other hand, the first bonding layer 140 may have the following configuration.
(I) Layer containing a silicon carbide compound:
The first bonding layer 140 may mainly contain an amorphous phase containing carbon and silicon, that is, an amorphous phase of a silicon carbide compound. The amorphous phase may include, for example, SiC, SiOC, SiCN, SiOCN, AlSiC, AlSiOC, AlSiCN, and / or AlSiOCN and the like.

The first bonding layer 140 may further contain a small amount of carbon lumps, metallic silicon lumps, and / or aluminosilicates and the like. The aluminosilicate may be crystalline or amorphous.

The amount of carbon in the amorphous phase of the first bonding layer 140 is 8% by weight or more, and the amount of oxygen in the same region is less than 30% by weight.
(II) Layer containing an aluminosilicate compound:
The first bonding layer 140 may contain an aluminosilicate-based compound as a main component. Aluminosilicate-based compound, general formula is represented by _Al x _Si y _{O z,} where a 0 <x <3,0 <y < 51,0 <z <104. The aluminosilicate compound may be a mixture of alumina and silica.

The first bonding layer 140 may further contain a small amount of carbon lumps and / or metallic silicon lumps.

On the other hand, the same can be said for the second bonding layer 150 as for the first bonding layer 140. However, the second bonding layer 150 may be the same as or different from the first bonding layer 140.

In the first joint body 100 having such a configuration, the aluminum member 110 and the alloy member 120 can be suitably joined by the presence of the first joint layer 140. Further, the presence of the second bonding layer 150 makes it possible to suitably bond the alloy member 120 and the ceramic member 130.

Further, in the first bonded body 100, the heat resistant stress characteristics can be significantly enhanced by the presence of the first alloy member 120 having a coefficient of thermal expansion between the aluminum member 110 and the ceramic member 130.

As described above, in one embodiment of the present invention, it is possible to provide a bonded body that is relatively resistant to breakage even when subjected to thermal stress.

(Another conjugate according to one embodiment of the present invention)
Next, another junction according to the embodiment of the present invention will be described with reference to FIG.

FIG. 4 shows a schematic cross-sectional view of another joint according to an embodiment of the present invention (hereinafter, referred to as “second joint”).

As shown in FIG. 4, the second joint body 200 has an aluminum member 210, a first alloy member 220, a second alloy member 225, and a ceramic member 230 in this order.

A first bonding layer 240 is arranged between the aluminum member 210 and the first alloy member 220, and a second bonding layer 250 is arranged between the second alloy member 225 and the ceramic member 230. .. Further, a third bonding layer 260 is arranged between the first alloy member 220 and the second alloy member 225.

As described above, the aluminum member 210 includes a member substantially made of aluminum metal, a member containing aluminum metal having a weight ratio of 50% or more, a member substantially made of an aluminum alloy, and a weight ratio of 50. It may be an alloy member containing% or more of aluminum.

The shape of the aluminum member 210 is not particularly limited, and the aluminum member 210 may have the shape of a block, a plate, a rod, a foil, a disk, or the like.

The first alloy member 220 and the second alloy member 225 may contain silicon and aluminum. The weight ratio of silicon may be 0.3 to 99%. Further, the weight ratio of aluminum may be in the range of 1% to 99%.

The composition of the first alloy member 220 is not particularly limited as long as it has a coefficient of thermal expansion smaller than that of the aluminum member 210 and a coefficient of thermal expansion larger than that of the second alloy member 225.

The first alloy member 220 is, for example, an alloy containing aluminum (Al) as a main component and silicon (Si) (Al—Si alloy), and an alloy containing Al as a main component and containing Si and magnesium (Mg) (Al—Si—Mg). It may be an alloy) or an alloy containing Si as a main component and Al (Si—Al alloy).

When the first alloy member 220 is an Al—Si alloy or an Al—Si—Mg alloy, the weight ratio of Al may be in the range of 50% to 99%. Further, in this case, the weight ratio of Si may be in the range of 0.3% to 50%. Further, the weight ratio of Mg may be in the range of 0.1% to 45%.

On the other hand, when the first alloy member 220 is a Si—Al alloy, the weight ratio of Si may be in the range of 50% to 99%. Further, in this case, the weight ratio of Al may be in the range of 1% to 50%.

When the aluminum member 110 is not silumin (Al-12% Si alloy), the first alloy member 220 may be silumin.

Further, the first alloy member 220 may contain Cu, Ni, Mn, Fe and Zn as additional elements. The weight ratio of Cu is in the range of 0 to 6.0 wt%, the weight ratio of Ni is in the range of 0 to 1.5 wt%, the weight ratio of Mn is in the range of 0 to 1.5 wt%, and the weight ratio of Fe is 0 to 1. The range of .3 wt% and the weight ratio of Zn may be in the range of 0 to 1.5 wt%.

Alternatively, the first alloy member 220 may be an alloy containing aluminum. For example, the first alloy member 220 may be any of Al—Zn alloy, Al—Sn alloy, Al—Mg—Sn alloy, Al—Mg—Zn alloy, Al—Si—Sn alloy, or Al—Sn—Zn alloy. It may be. In these alloys, the weight ratio of Mg may be in the range of 0.1 to 95%. The weight ratio of Zn may be 0.1 to 99%. The weight ratio of Sn may be 0.1 to 99%.

The form of the first alloy member 220 is not particularly limited. For example, the first alloy member 220 may have a plate shape or a block shape.

On the other hand, the composition of the second alloy member 225 is not particularly limited as long as it has a coefficient of thermal expansion smaller than that of the first alloy member 220 and a coefficient of thermal expansion larger than that of the ceramic member 230.

The second alloy member 225 is, for example, an alloy containing aluminum (Al) as a main component and silicon (Si) (Al-Si alloy), and an alloy containing Al as a main component and containing Si and magnesium (Mg) (Al-Si-Mg). It may be an alloy) or an alloy containing Si as a main component and Al (Si—Al alloy).

When the second alloy member 225 is an Al—Si alloy or an Al—Si—Mg alloy, the weight ratio of Al may be in the range of 50% to 99%. Further, in this case, the weight ratio of Si may be in the range of 0.3% to 50%. Further, the weight ratio of Mg may be in the range of 0.1% to 45%.

On the other hand, when the second alloy member 225 is a Si—Al alloy, the weight ratio of Si may be in the range of 50% to 99%. Further, in this case, the weight ratio of Al may be in the range of 1% to 50%.

Further, the second alloy member 225 may contain Cu, Ni, Mn, Fe and Zn as additional elements. The weight ratio of Cu is in the range of 0 to 6.0 wt%, the weight ratio of Ni is in the range of 0 to 1.5 wt%, the weight ratio of Mn is in the range of 0 to 1.5 wt%, and the weight ratio of Fe is 0 to 1. The range of .3 wt% and the weight ratio of Zn may be in the range of 0 to 1.5 wt%.

Alternatively, the second alloy member 225 is, for example, an Al—Zn alloy, an Al—Sn alloy, an Al—Mg—Sn alloy, an Al—Mg—Zn alloy, an Al—Si—Sn alloy, or an Al—Sn—Zn alloy. It may be any of. In these alloys, the weight ratio of Mg may be in the range of 0.1 to 95%. The weight ratio of Zn may be 0.1 to 99%. The weight ratio of Sn may be 0.1 to 99%.

The first alloy member 220 and / or the second alloy member 225 may be one that is once melted and then solidified.

The ceramic member 230 is made of ceramics containing an aluminum component and / or a silicon component. For example, the ceramic member 230 contains at least one of alumina, aluminum nitride, silicon nitride, and aluminosilicate.

The crystal form of the ceramic member 230 is not particularly limited, but α-alumina can be preferably used as the alumina.

The shape of the ceramic member 230 is not particularly limited, and the ceramic member 230 may have the shape of a block, a plate, a rod, a disk, or the like.

The first bonding layer 240 may have the following configuration.
(I) Layer containing a silicon carbide compound:
The first bonding layer 240 may mainly contain an amorphous phase containing carbon and silicon, that is, an amorphous phase of a silicon carbide compound. The amorphous phase may include, for example, SiC, SiOC, SiCN, SiOCN, AlSiC, AlSiOC, AlSiCN, and / or AlSiOCN and the like.

The first bonding layer 240 may further contain a small amount of carbon lumps, metallic silicon lumps, and / or aluminosilicates and the like. The aluminosilicate may be crystalline or amorphous.

The amount of carbon in the amorphous phase of the first bonding layer 240 is 8% by weight or more, and the amount of oxygen in the same region is less than 30% by weight.
(II) Layer containing an aluminosilicate compound:
The first bonding layer 240 may contain an aluminosilicate-based compound as a main component.

As described above, aluminosilicate compounds have the general formula is represented by _Al x _Si y _{O z,} where a 0 <x <3,0 <y < 51,0 <z <104. The aluminosilicate compound may be a mixture of alumina and silica.

In addition to the aluminosilicate-based compound, the first bonding layer 240 may contain a small amount of other substances such as carbon lumps and / or metallic silicon lumps.

The same can be said for the second bonding layer 250 and the third bonding layer 260 as in the first bonding layer 240. However, the second bonding layer 250 may be the same as or different from the first bonding layer 240. Similarly, the third bonding layer 260 may be the same as or different from the first bonding layer 240. Further, the third bonding layer 260 may be the same as or different from the second bonding layer 250.

In the second joint body 200 having such a configuration, the aluminum member 210 and the first alloy member 220 can be suitably joined by the presence of the first joint layer 240. Further, due to the presence of the second bonding layer 250, the second alloy member 225 and the ceramic member 230 can be suitably bonded. Further, the presence of the third bonding layer 260 allows the first gold member 220 and the second alloy member 225 to be suitably bonded.

Further, in the second joint body 200, the heat-resistant stress characteristics can be significantly enhanced by the presence of the first alloy member 220 and the second alloy member 225.

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

In the following description, Examples 1, 3 and 5 to 15 are Examples, and Examples 2 and 4 are Comparative Examples.

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

First, as a ceramic member, a silicon nitride plate (purity 90% or more, manufactured by JFC) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was less than 1 wt%.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, a silumin (Al-12 wt% Si alloy) plate having a length of 20 mm, a width of 20 mm, and a thickness of 0.2 mm was prepared. Hereinafter, both surfaces of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, a commercially available polycarbosilane (NIPUSI Type-A, manufactured by Nippon Carbon Co., Ltd.) was diluted to 0.1 mol / L with a toluene solvent to prepare a coating liquid (hereinafter referred to as "coating liquid A").

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the spin coating method. The conditions for spin coating were a rotation speed of 3000 rps and a rotation time of 30 seconds.

Further, the silumin plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, a silumin plate was installed on the surface to be joined. The silumin plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was installed on the silumin plate. Further, an alumina plate (weight 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 600 ° C. for 1 hour under an argon atmosphere. During the treatment, it was observed that the silumin plate was melted.

As a result, a bonded body in which a silicon nitride plate, a silumin plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 1".

(Evaluation)
The following evaluation was performed using the conjugate according to Example 1 produced by the above method.

(Evaluation of joint condition)
Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the silumin plate and between the silumin plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

(Evaluation of joint layer)
FIG. 5 shows the results of X-ray diffraction analysis in the portion of the bonding layer formed between the silumin plate and the ceramic member. In the analysis result, a continuous peak exists from 20 ° to 40 °, which indicates that the bonding layer has an amorphous phase.

In addition, as a result of detailed analysis of the bonding layer, it was found that the bonding layer contained a small amount of carbon lumps and metallic silicon lumps in addition to the silicon carbide-based compounds constituting the amorphous phase. In particular, it was found that the silicon carbide compound contains AlSiC, AlSiOC, AlSiCN, and AlSiOCN in addition to SiC.

Further, as a result of EDX analysis in the region of the amorphous phase of the bonding layer, it was found that the amount of carbon in the region was 8% by weight or more and the amount of oxygen was less than 30% by weight.

(Heat resistance test)
A heat resistance property test was carried out using the bonded body according to Example 1.

The heat resistance property test was carried out by repeatedly exposing the bonded body to the environment of 150 ° C. and −40 ° C. Specifically, the operation of holding the bonded product in an environment of 150 ° C. for 10 seconds and then holding it in an environment of −40 ° C. for 10 seconds was repeated 100 times.

After the test, the state of the joined body according to Example 1 was observed. As a result, no peeling or breakage was observed, and the joint according to Example 1 was in a healthy state.

(Example 2)
A bonded body was produced by the same method as in Example 1.

However, in this example 2, the silumin plate was not installed between the silicon nitride plate and the aluminum plate. That is, the heat treatment was performed in a state where the silicon nitride plate in which the coating liquid A was applied to the surface to be bonded and the aluminum plate were laminated. The coating conditions, heat treatment conditions, and the like are the same as in Example 1.

As a result, the conjugate according to Example 2 was obtained.

The above-mentioned heat resistance property test was carried out using the bonded body according to Example 2. When the bonded body was observed after the test, peeling was observed between the silicon nitride plate and the aluminum plate.

(Example 3)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, an aluminum nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.6 mm in thickness was prepared.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, a Si—Al alloy (Si-1 wt% Al alloy) plate having a length of 20 mm, a width of 20 mm, and a thickness of 0.5 mm was prepared. Hereinafter, both surfaces of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the aluminum nitride plate by the spin coating method. The conditions for spin coating were a rotation speed of 1000 rps and a rotation time of 30 seconds.

Further, the Si—Al alloy plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the aluminum nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, a Si—Al alloy plate was installed on the surface to be joined. The Si—Al alloy plate was installed so that the second surface faced the surface to be joined of the aluminum nitride plate.

Next, an aluminum plate was placed on the Si—Al alloy plate. Further, an alumina plate (weight 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 600 ° C. for 1 hour under an argon atmosphere. As a result, an aluminum nitride plate, a Si—Al alloy plate, and a bonded body to which the aluminum plate was joined were obtained. Hereinafter, this joint will be referred to as "the joint according to Example 3".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the Si-Al alloy plate and between the Si-Al alloy plate and the aluminum nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 3. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 3 was in a healthy state.

(Example 4)
A bonded body was produced by the same method as in Example 3.

However, in this Example 3, the Si—Al alloy plate was not installed between the aluminum nitride plate and the aluminum plate. That is, the heat treatment was performed in a state where the aluminum nitride plate coated with the coating liquid A on the surface to be joined and the aluminum plate were laminated. The coating conditions, heat treatment conditions, and the like are the same as in Example 1.

As a result, the conjugate according to Example 4 was obtained.

The above-mentioned heat resistance property test was carried out using the bonded body according to Example 4. When the joint was observed after the test, peeling was observed between the aluminum nitride plate and the aluminum plate.

(Example 5)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, a silicon nitride plate (purity 80% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was 3 wt% or more.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, a silumin (Al-12 wt% Si alloy) plate having a length of 20 mm, a width of 20 mm, and a thickness of 0.2 mm was prepared. Hereinafter, both surfaces of the silumin plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, a commercially available polymethylphenylsiloxane (KF-54: manufactured by Shin-Etsu Chemical Co., Ltd.) is diluted to 0.1 mol / L with a toluene solvent, and the coating solution (hereinafter referred to as "coating solution B") is used. Was prepared.

Next, the above-mentioned coating liquid B was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the spin coating method. The conditions for spin coating were a rotation speed of 3000 rps and a rotation time of 30 seconds.

Further, the silumin plate was immersed in the coating liquid B, and the coating liquid B was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, a silumin plate was installed on the surface to be joined. The silumin plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was installed on the silumin plate. Further, an alumina plate (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 500 ° C. for 8 hours under an argon atmosphere. As a result, a bonded body in which a silicon nitride plate, a silumin plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 5".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the silumin plate and between the silumin plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 5. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 5 was in a healthy state.

(Example 6)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, a silicon nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was 3 wt% or more.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, a silumin (Al-12 wt% Si alloy) plate having a length of 20 mm, a width of 20 mm, and a thickness of 0.2 mm was prepared. Hereinafter, both surfaces of the silumin plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid B was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the spin coating method. The conditions for spin coating were a rotation speed of 3000 rps and a rotation time of 30 seconds.

Further, the silumin plate was immersed in the coating liquid B, and the coating liquid B was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, a silumin plate was installed on the surface to be joined. The silumin plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was installed on the silumin plate. Further, an alumina plate (weight of about 35 g) having a length of 30 mm, a width of 30 mm, and a thickness of 10 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 620 ° C. for 1 hour under an argon atmosphere. The heat treatment temperature is a temperature exceeding the melting point of the silumin plate.

After the heat treatment, a bonded body in which a silicon nitride plate, a silumin plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 6".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the silumin plate and between the silumin plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 6. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 6 was in a healthy state.

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

First, as a ceramic member, a silicon nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was less than 1 wt%.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, a silumin (Al-12 wt% Si alloy) plate having a length of 20 mm, a width of 20 mm, and a thickness of 0.5 mm was prepared. Hereinafter, both surfaces of the silumin plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the spin coating method. The conditions for spin coating were a rotation speed of 3000 rps and a rotation time of 30 seconds.

Further, the silumin plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, a silumin plate was installed on the surface to be joined. The Al—Si alloy plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was installed on the silumin plate. Further, an alumina block (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 550 ° C. for 8 hours under an argon atmosphere. As a result, a bonded body in which a silicon nitride plate, a silumin plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 7".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the silumin plate and between the silumin plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 7. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 7 was in a healthy state.

(Example 8)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, an alumina plate (purity 99% or more) having dimensions of 20 mm in length × 20 mm in width × 1 mm in thickness was prepared.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, an Al-Si-Mg (0.3 wt% Si, 4.9 wt% Mg) plate having a length of 20 mm, a width of 20 mm and a thickness of 2 mm was prepared. Hereinafter, both surfaces of the Al—Si—Mg plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the alumina plate by the spin coating method. The conditions for spin coating were a rotation speed of 500 rpm and a rotation time of 30 seconds.

Further, the Al—Si—Mg alloy plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the alumina plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, an Al—Si—Mg alloy plate was installed on the surface to be joined. The Al—Si alloy plate was installed so that the second surface faced the surface to be joined of the alumina plate.

Next, an aluminum plate was placed on the Al—Si—Mg alloy plate. Further, an alumina block (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 600 ° C. for 8 hours under an argon atmosphere. As a result, a bonded body in which an alumina plate, an Al-Si-Mg plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 8".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the Al-Si-Mg plate and between the Al-Si-Mg plate and the alumina plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 8. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 8 was in a healthy state.

(Example 9)
v A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, a silicon nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was less than 1 wt%.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, a silumin (Al-12 wt% Si alloy) plate having a length of 20 mm, a width of 20 mm, and a thickness of 0.08 mm was prepared. Hereinafter, both surfaces of the silumin plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, a commercially available polysilane (SI-20-10, manufactured by Osaka Gas Chemical Co., Ltd.) was diluted to 0.1 mol / L with a toluene solvent to prepare a coating liquid (hereinafter referred to as “coating liquid C”).

Next, the above-mentioned coating liquid C was applied to the bonded surface (one surface of 20 mm × 20 mm) of the silicon nitride plate by the spin coating method. The conditions for spin coating were a rotation speed of 1000 rps and a rotation time of 30 seconds.

Further, the silumin plate was immersed in the coating liquid C, and the coating liquid C was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, a silumin plate was installed on the surface to be joined. The silumin plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was installed on the silumin plate. Further, an alumina block (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 350 ° C. for 4 hours under an argon atmosphere. As a result, a bonded body in which a silicon nitride plate, a silumin plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 9".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the silumin plate and between the silumin plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 9. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 9 was in a healthy state.

(Example 10)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, a silicon nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was less than 1 wt%.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, a silumin (Al-12 wt% Si alloy) plate having a length of 20 mm, a width of 20 mm, and a thickness of 0.2 mm was prepared. Hereinafter, both surfaces of the silumin plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the dipping method. Then, alumina powder (AS-40, manufactured by Showa Denko) was thinly sprayed on the surface of the coating liquid surface.

Further, the silumin plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, a silumin plate was installed on the surface to be joined. The silumin plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was installed on the silumin plate. Further, an alumina block (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 620 ° C. for 1 hour under an argon atmosphere. As a result, a bonded body in which a silicon nitride plate, a silumin plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 10".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the silumin plate and between the silumin plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 10. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 10 was in a healthy state.

(Example 11)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, a silicon nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was less than 1 wt%.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, a silumin (Al-12 wt% Si alloy) plate having a length of 20 mm, a width of 20 mm, and a thickness of 0.2 mm was prepared. Hereinafter, both surfaces of the silumin plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the dipping method. Then, silicon carbide powder (GC # 1000, manufactured by Fujimi Incorporated) was thinly sprayed on the surface of the coating liquid surface.

Further, the silumin plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, a silumin plate was installed on the surface to be joined. The silumin plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was installed on the silumin plate. Further, an alumina block (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 620 ° C. for 4 hours under an argon atmosphere. As a result, a bonded body in which a silicon nitride plate, a silumin plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 11".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the silumin plate and between the silumin plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 11. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 11 was in a healthy state.

(Example 12)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, a silicon nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was less than 1 wt%.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, a silumin (Al-12 wt% Si alloy) plate having a length of 20 mm, a width of 20 mm, and a thickness of 0.2 mm was prepared. Hereinafter, both surfaces of the silumin plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the dipping method. Then, a metallic silicon powder prepared by crushing a silicon wafer (SI-500443, manufactured by Niraco) was thinly sprayed on the surface of the coating liquid surface.

Further, the silumin plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, a silumin plate was installed on the surface to be joined. The silumin plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was installed on the silumin plate. Further, an alumina block (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 620 ° C. for 4 hours under an argon atmosphere. As a result, a bonded body in which a silicon nitride plate, a silumin plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 12".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the silumin plate and between the silumin plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 12. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 12 was in a healthy state.

(Example 13)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, a silicon nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was less than 1 wt%.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, an Al—Zn alloy plate (RZ-203, manufactured by Shin-Fuji Burner) rolled into a length of 20 mm × width of 20 mm × thickness of 0.2 mm was prepared. Hereinafter, both surfaces of the Al—Zn alloy plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the dipping method. Then, a metallic silicon powder prepared by crushing a silicon wafer (SI-500443, manufactured by Niraco) was thinly sprayed on the surface of the coating liquid surface.

Further, the Al—Zn alloy plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, an Al—Zn alloy plate was installed on the surface to be joined. The Al—Zn alloy plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was placed on the Al—Zn alloy plate. Further, an alumina block (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 550 ° C. for 1 hour under an argon atmosphere. As a result, a bonded body in which a silicon nitride plate, an Al—Zn alloy plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 13".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the Al—Zn alloy plate and between the Al—Zn alloy plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 13. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 13 was in a healthy state.

(Example 14)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, a silicon nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was less than 1 wt%.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, an Al—Sn alloy plate produced by a known method, which was rolled into a length of 20 mm, a width of 20 mm, and a thickness of 0.2 mm, was prepared. Hereinafter, both surfaces of the Al—Sn alloy plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the dipping method. Then, a metallic silicon powder prepared by crushing a silicon wafer (SI-500443, manufactured by Niraco) was thinly sprayed on the surface of the coating liquid surface.

Further, the Al—Sn alloy plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. In addition, an Al—Sn alloy plate was installed on the surface to be joined. The Al—Sn alloy plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was placed on the Al—Sn alloy plate. Further, an alumina block (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 620 ° C. for 4 hours under an argon atmosphere. As a result, a bonded body in which a silicon nitride plate, an Al—Sn alloy plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 14".

Using a scanning electron microscope, the bonding layer formed between the aluminum plate and the Al—Sn alloy plate and between the Al—Sn alloy plate and the silicon nitride plate was observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 14. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 14 was in a healthy state.

(Example 15)
A joint body of a ceramic member and an aluminum member was manufactured by the following method.

First, as a ceramic member, a silicon nitride plate (purity 90% or more) having dimensions of 20 mm in length × 20 mm in width × 0.32 mm in thickness was prepared. As a result of measuring the aluminum content in the silicon nitride plate by the EDS method, the content was less than 1 wt%.

Further, as an aluminum member, a commercially available aluminum plate (purity 99% or more, manufactured by 3S Co., Ltd.) having dimensions of 20 mm in length × 20 mm in width × 5 mm in thickness was prepared. Further, as an alloy member, an Al—Si—Sn alloy plate produced by a known method, which was rolled into a length of 20 mm × a width of 20 mm × a thickness of 0.2 mm, was prepared. Hereinafter, both surfaces of the Al—Si—Sn alloy plate having a size of 20 mm × 20 mm will be referred to as a first surface and a second surface, respectively.

Next, the above-mentioned coating liquid A was applied to the surface to be joined (one surface of 20 mm × 20 mm) of the silicon nitride plate by the dipping method. Then, a metallic silicon powder prepared by crushing a silicon wafer (SI-500443, manufactured by Niraco) was thinly sprayed on the surface of the coating liquid surface.

Further, the Al—Si—Sn alloy plate was immersed in the coating liquid A, and the coating liquid A was placed on the entire surface.

Next, the silicon nitride plate was placed horizontally on the table so that the surface to be joined was facing upward. Further, an Al—Si—Sn alloy plate was installed on the surface to be joined. The Al—Si—Sn alloy plate was installed so that the second surface faced the surface to be joined of the silicon nitride plate.

Next, an aluminum plate was placed on the Al—Si—Sn alloy plate. Further, an alumina block (weight of about 70 g) having a length of 40 mm, a width of 40 mm, and a thickness of 11 mm was arranged on the aluminum plate as a weight.

Next, the obtained assembly was heat-treated at 620 ° C. for 4 hours under an argon atmosphere. As a result, a bonded body in which a silicon nitride plate, an Al—Si—Sn alloy plate, and an aluminum plate were joined was obtained. Hereinafter, this joint will be referred to as "the joint according to Example 15".

Using a scanning electron microscope, the bonding layers formed between the aluminum plate and the Al—Si—Sn alloy plate and between the Al—Si—Sn alloy plate and the silicon nitride plate were observed. As a result, no defects such as cracks and voids were observed in any of the bonding layers.

Further, the above-mentioned heat resistance property test was carried out using the bonded body according to Example 15. When the joint was observed after the test, no abnormality such as peeling or damage was observed at any of the portions, and the joint according to Example 15 was in a healthy state.

This application claims priority based on Japanese Patent Application No. 2016-115124 filed on June 9, 2016, and the entire contents of the Japanese application are incorporated herein by reference.

100 First joint body 110 Aluminum member 120 Alloy member 130 Ceramic member 140 First joint layer 150 Second joint layer 200 Second joint 210 Aluminum member 220 First alloy member 225 Second alloy member 230 Ceramics Member 240 First bonding layer 250 Second bonding layer 260 Third bonding layer

Claims (13)

A method for manufacturing a bonded body having an aluminum member, a ceramic member, and one or two alloy members between them.
It has a preparation step, an installation step, an assembly step, and a heating step.
When there is one alloy member,
The preparation step
Prepare the first alloy member having (a) (1) the aluminum member, (2) the ceramic member containing aluminum and / or silicon, and (3) the first and second surfaces and containing aluminum. The first alloy member is selected from the group consisting of Al—Si alloy, Si—Al alloy, Al—Sn alloy, and Al—Si—Sn alloy (however, the first alloy member is selected. unless alloy member, comprise only alloy components of the ceramic component and the aluminum member of the ceramic member, and comprising a ceramic component of the ceramic member)
The installation step
(B) The first bonding material is installed on at least one of the bonded surface of the aluminum member and the first surface of the first alloy member, and the bonded surface of the ceramic member and the first alloy. An installation step in which a second bonding material is installed on at least one of the second surfaces of the member.
The assembly step
(C) The aluminum member, the first alloy member, and the ceramic member, the first surface of the first alloy member faces the bonded surface of the aluminum member, and the second surface faces the bonded surface of the aluminum member. It is an assembly step in which the ceramic members are laminated so as to face the surface to be joined to form an assembly.
When there are two alloy members,
The preparation step
(A) (1) the aluminum member, (2) the ceramic member containing aluminum and / or silicon, (3) a first alloy member having first and second surfaces and containing aluminum, and ( 4) This is a preparatory step of preparing a second alloy member having a third and fourth surface and containing aluminum, and the first and second alloy members are Al—Si alloy and Si−, respectively. Selected from the group consisting of Al alloys, Al—Sn alloys, and Al—Si—Sn alloys (however, the first and second alloy members are the ceramic component of the ceramic member and the alloy component of the aluminum member, respectively. (Except when it is composed of only aluminum and when it contains the ceramic component of the ceramic member),
The installation step
(B) A first bonding material is installed on at least one of the bonded surface of the aluminum member and the first surface of the first alloy member, and the bonded surface of the ceramic member and the second alloy member. A second bonding material is installed on at least one of the fourth surfaces of the first alloy member, and a third surface is provided on at least one of the second surface of the first alloy member and the third surface of the second alloy member. It is an installation step to install the joint material,
The assembly step
(C) The aluminum member, the first alloy member, the second alloy member, and the ceramic member, the first surface of the first alloy member faces the surface to be joined of the aluminum member. The second surface of the first alloy member and the third surface of the second alloy member face each other, and the fourth surface of the second alloy member is the surface to be joined of the ceramic member. It is an assembly step that is laminated so as to face each other to form an assembly.
Regardless of the number of alloy members, the heating step
(D) A heating step in which the assembly is heated at a temperature of 400 ° C. to 800 ° C. under an inert gas atmosphere or a vacuum atmosphere.
The coefficient of thermal expansion of the first and second alloy members is smaller than the coefficient of thermal expansion of the aluminum member and larger than the coefficient of thermal expansion of the ceramic member, respectively.
The coefficient of thermal expansion of the second alloy member is smaller than the coefficient of thermal expansion of the first alloy member.
The first, second, and third joint materials are independently
(I) An organosilicon polymer having a main chain having at least one Si—C—Si group and a Si—N—Si group.
(Ii) An organosilicon polymer having a Si—O—Si group in the main chain,
(Iii) Carbon powder-containing silica sol, and (iv) Organosilicon polymer having a Si—Si group in the main chain,
Have at least one of
A method for manufacturing a bonded body, wherein the aluminum member is an aluminum metal or an Al—Si alloy. The manufacturing method according to claim 1, wherein the first alloy member contains particles having a coefficient of thermal expansion smaller than that of the first alloy member. The production method according to claim 2, wherein the particles include at least one of metal particles and alloy particles. The organosilicon polymer of (i) is selected from the group consisting of polycarbosilane, polycarbosilazane, allylhydride polycarbosilane, polytitanocarbosilane, polysilmethylene, polysilazane, polyhydropolysilazane, and polyorganosilazane. The production method according to claim 1, wherein the production method comprises at least one of the above. The organosilicon polymer of (ii) is selected from the group consisting of polymethylhydrosiloxane (PMHS), polymethylphenylsiloxane (PMPHS), polymethylsilsesquioxane (PMSQ), and polyphenylsiloxane (PPSQ). The production method according to claim 1, which comprises at least one of the above. The production method according to claim 1, wherein the organosilicon polymer of (iv) contains at least one selected from the group consisting of polyhydrosilane, polymethylsilane, and polyphenylsilane. The production 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. A bonded body containing an aluminum member and a ceramic member containing aluminum and / or silicon.
A first bonding layer, a first alloy member, and a second bonding layer exist between the aluminum member and the ceramic member in this order.
It said first alloy member comprises aluminum (however, the first alloy member, comprise only alloy components of the ceramic component and the aluminum member of the ceramic member, and the ceramic component of the ceramic member (Except when included),
The coefficient of thermal expansion of the first alloy member is smaller than the coefficient of thermal expansion of the aluminum member and larger than the coefficient of thermal expansion of the ceramic member.
The aluminum member is an aluminum metal or an Al—Si alloy.
The first alloy member is selected from the group consisting of Al—Si alloys, Si—Al alloys, Al—Sn alloys, and Al—Si—Sn alloys.
The first and second bonding layers are, respectively.
(I) Amorphous phase and / or (II) aluminosilicate, which contains carbon and silicon, has a carbon content of 8% by mass or more and an oxygen content of less than 30% by mass.
Containing, including. Further, a second alloy member and a third bonding layer are provided between the second bonding layer and the ceramic member in this order.
The second alloy member is selected from the group consisting of Al—Si alloy, Si—Al alloy, Al—Sn alloy, and Al—Si—Sn alloy (however, the second alloy member is the ceramic member. ( Except when it is composed only of the ceramic component of the above and the alloy component of the aluminum member, and when it contains the ceramic component of the ceramic member),
The coefficient of thermal expansion of the second alloy member is smaller than the coefficient of thermal expansion of the first alloy member and larger than the coefficient of thermal expansion of the ceramic member.
The third bonding layer is
(I) Amorphous phase and / or (II) aluminosilicate, which contains carbon and silicon, has a carbon content of 8% by mass or more and an oxygen content of less than 30% by mass.
The joined body according to claim 8. The bonded body according to claim 8, wherein the first alloy member contains particles having a coefficient of thermal expansion smaller than that of the first alloy member. The bonded body according to claim 9, wherein the second alloy member contains particles having a coefficient of thermal expansion smaller than that of the second alloy member. The conjugate according to claim 10 or 11, wherein the particles include at least one of metal particles and alloy particles. The junction according to claim 8, wherein the aluminum and / or silicon-containing ceramic member comprises at least one material selected from the group consisting of alumina, aluminum nitride, silicon nitride, mullite and aluminosilicate.

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