JPH0615426B2 - Bonded body of SiC or Si (bottom 3) N (bottom 4) base material and Mo or W base material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for joining ceramics and metal, particularly Si or Si ₃ N ₄ and Mo or W.

[Conventional technology]

A high-strength joint cannot be obtained by directly joining the Mo or W base material and the SiC or Si ₃ N ₄ base material, as well as by joining through the Cu + Co alloy brazing material. This is SiC or S
Bonding reactivity between i ₃ N ₄ and Mo or W, SiC or Si ₃ N ₄ and C
This is because the bonding reactivity with the u + Co alloy brazing is insufficient.

The joint of Mo or W and SiC or Si ₃ N ₄ is often used at high temperature because of the excellent heat resistance of SiC or Si ₃ N ₄ . In that case, in many cases, an oxidizing atmosphere is used, and in such an environment, Mo or W causes severe oxidation and cannot be used. In the conventional method, no consideration has been given to such problems, and in the high temperature oxidizing atmosphere, the obtained joint cannot withstand use and is not in practical use at present.

[Problems to be solved by the invention]

An object of the present invention is to provide a method for firmly joining Mo or W and SiC or Si ₃ N ₄ by using an appropriate insert material, and a method for secondarily providing oxidation resistance of Mo and W. It is a thing.

[Means for solving problems]

A first invention of the present invention is a Mo or W substrate, a first Cr coating layer deposited on the substrate, and at least one of Cr, Ni and Cu deposited on the Cr coating layer. Second metal coating layer, and a SiC or Si ₃ N ₄ base material fixed in contact with the second metal coating layer, and a SiC or Si ₃ N ₄ base material and Mo or W It is a bonded body with a base material, and
Cr coating layer and the second metal coating layer are coated on the entire surface of the Mo or W substrate, and the outermost layer of the second metal coating layer is C
A preferred embodiment is an r-diffused plating layer.

A second invention of the present invention is a Mo or W substrate, a first Cr coating layer deposited on the substrate, and at least one of Cr, Ni and Cu deposited on the Cr coating layer. One kind of second
Metal coating layer, Ni deposited on the second metal coating layer
At least one brazing material, a brazing material, a Cu brazing material, and an Ag brazing material, and a layer to be fixed in contact with the brazing material coating layer
A conjugate of the SiC or Si ₃ N ₄ SiC or Si ₃ N ₄ base material and Mo or W substrate characterized by comprising consisting substrate, first
Cr coating layer and the second metal coating layer are coated on the entire evaluation surface of the Mo or W substrate, and the outermost layer of the second metal coating layer is C.
A preferred embodiment is an r-diffused plating layer.

In addition, in the said 1st, 2nd invention, when the 2nd metal coating layer is Cr, you may be a Cr single-layer coating layer which combined the 1st Cr coating layer and the 2nd Cr coating layer. .

The present invention can be applied to, for example, a method of joining ceramics and a metal of a ceramic gas turbine vane.

[Action]

First invention In the bonding of Mo or W and SiC or Si ₃ N ₄ , Cr that does not form a brittle intermetallic compound on the Mo or W surface and solidifies to obtain a strong metallurgical bond, and insert the very poor SiC or Si ₃ N ₄ surfaces by focusing on free Si present in SiC or Si ₃ N _4, Ni to fulfill the bonding excellent this Si, any one of Cu and Cr As a material, a high-strength joint strength can be obtained by heating and pressurizing in a non-oxidizing atmosphere such as vacuum or Ar gas to perform solid-phase joining. When the above-mentioned insert materials are used, the combination of insert materials is Cr, Ni, C
A joint combination of r, Cu, and Cr-Cr appears, but these are solid-solved with each other and are capable of excellent metallurgical joining, and a good joint can be obtained.

One embodiment of the first invention will be described in detail with reference to FIG.

First, the Cr coating layer 3 is provided on the Mo or W base material 1.
{Step A- (a); In the case of Cr single layer coating layer)
By Cr plating, Cr vapor deposition, Cr thermal spraying, etc.

Alternatively, the Ni coating layer 4 or the Cu coating layer 5 is further disposed on the Cr coating layer 3. (Step A (b)) The method is by Ni or Cu plating, Ni or Cu vapor deposition, Ni or Cu thermal spraying, disposition of Ni or Cu foil, or the like.

After disposing the insert material on the Mo or W base material 1,
The SiC or Si ₃ N ₄ base material 2 is superposed on this, heated in vacuum or Ar to a temperature lower than the melting point of any of Mo or W, SiC or Si ₃ N ₄ and the insert material, and pressurized. Solid phase bonding. (Step B) Second Invention In joining Mo or W and SiC or Si ₃ N ₄ , Cr that does not form a brittle intermetallic compound on the Mo or W surface and forms a solid solution with each other to obtain a strong metallurgical bond, And a brazing filler metal (Ni brazing, Cu brazing, Ag brazing) to be used and Ni or Cu excellent in brazing property laminated on this Cr and bonded, and then free Si existing in SiC or Si ₃ N _4. By brazing SiC or Si ₃ N ₄ with Ni braze, Cu braze, or Ag braze, which enables good brazing, high joint strength can be obtained.

When the above-mentioned insert material is used, a combination of Cr and Ni, Cr and Cu, Cr and the above brazing material, Ni and the above brazing material, and Cu and the above brazing material can be obtained by the combination of the inserts. It is a combination that enables excellent metallurgical bonding without melting or forming a brittle intermetallic compound, and a good joint can be obtained.

One embodiment of the second invention will be described in detail with reference to FIG.

First, the Cr coating layer 3 is provided on the Mo or W base material 1.
{Step A- (a); In the case of Cr single-layer coating layer}
By Cr plating, Cr vapor deposition, Cr thermal spraying, etc.

Alternatively, the Ni coating layer 4 or the Cu coating layer 5 is further disposed on the Cr coating layer 3. (Step A (b)) The method is by Ni or Cu plating, Ni or Cu vapor deposition, Ni or Cu thermal spraying, disposition of Ni or Cu foil, or the like.

The Mo or W base material 1 on which the above-mentioned insert material is arranged is heated in a vacuum or Ar to a temperature lower than the melting point of either Mo or W and the insert material, and pressurized to insert material and Mo or The W base material 1 is solid-phase bonded.

Then, with the Mo or W base material to which the insert material is joined
Ni or Cu braze or Ag with SiC or Si ₃ N ₄ substrate 2
Brazing is performed using a braze 6 in vacuum or in Ar.
(Step B) Preferred Embodiment of First Invention In joining Mo or W with SiC or Si ₃ N ₄ , good metallurgical joining with Mo or W can be obtained on the entire surface including Mo or W and the joining surface. After coating Cr,
Ni, which forms a solid solution with Cr and has excellent bondability,
On the whole surface of the Ni coating layer and then Cr diffusion plating treatment on the entire surface of the Ni coating layer. Then, SiC or Si ₃ N ₄ is heated or pressurized in vacuum or Ar to perform solid-phase bonding to achieve high joint strength. Can be obtained.

The characteristic of this method is that a Ni / Cr alloy layer (obtained by subjecting the Ni coating layer to Cr diffusion plating treatment) is formed on the outermost surface of Mo or W, and it has excellent oxidation resistance as well as various high temperature corrosion resistance, It is to greatly expand the range of application of Mo or W and SiC or Si ₃ N ₄ joints.

One embodiment of the above method will be described in detail with reference to FIG.

First, the Cr coating layer 3 is provided on the entire surface of the Mo or W base material 1. The method is Cr plating, Cr vapor deposition, Cr thermal spraying, or the like. Then, the Ni coating layer 4 is formed on the entire surface of the Cr coating layer 3.
To arrange. The method is Ni plating, Ni deposition, Ni
Due to thermal spraying, etc. Then, Cr diffusion plating 7 treatment is performed on the entire surface of the Ni coating layer 4.

Then, the Mo or W base material 1 and the SiC or Si ₃ N ₄ base material 2 which have been subjected to the above treatment are superposed on each other, and the Mo or W, SiC or Si ₃ N ₄ and insert materials are placed in vacuum or in Ar. It is heated to a temperature lower than either melting point and pressurized to perform solid phase bonding.

Preferred embodiment of the second invention In the bonding of Mo or W and SiC or Si ₃ N ₄ , after applying the coating and Cr diffusion plating treatment explained in the preferred embodiment of the first invention to the entire surface including the bonding surface of Mo or W. , SiC or Si ₃ N ₄ can be used to obtain high strength joint strength by brazing described in the second invention.

The feature of this method is that, as described in the preferred embodiment of the first invention, a Ni / Cr alloy layer excellent in oxidation resistance and various high temperature corrosion resistance is formed on the outermost surface of Mo or W, and Mo or W And to greatly expand the application range of SiC or Si ₃ N ₄ joints.

One embodiment of the above method will be described in detail with reference to FIG.

First, the Cr coating layer 3 is provided on the entire surface of the Mo or W base material 1. The method is Cr plating, Cr vapor deposition, Cr thermal spraying, or the like. Then, the Ni coating layer 4 is provided on the entire surface of the Cr coating layer 3. The method is Ni plating, Ni vapor deposition, N
i By thermal spraying, etc. Then, Cr is formed on the entire surface of the Ni coating layer 4.
Diffusion plating 7 processing is performed.

Thereafter, the Mo or W base material 1 and the SiC or Si ₃ N ₄ base material 2 which have been subjected to the above treatment are brazed in vacuum or in Ar using Ni solder, Cu solder or Ag solder 6.

In the preferred embodiments of the first and second inventions,
C of the insert material on the entire surface including the joint surface of Mo or W
r, Cr and Ni, or Cr and Cu are coated to obtain a high-strength joint, and the presence of this coating layer, which is superior in oxidation resistance to Mo or W,
The application range of SiC or Si ₃ N ₄ joints can also be expanded.

〔The invention's effect〕

(1) Mo or W and SiC or Si ₃ N ₄ can be firmly bonded by using an appropriate insert material.

(2) The joint of Mo or W and SiC or Si ₃ N ₄ is SiC or Si ₃
Due to the excellent heat resistance of N ₄ , it is often used at high temperatures. Moreover, in that case, there are many cases of an oxidizing atmosphere, and in such an environment, Mo or W causes severe oxidation and cannot be used. On the other hand, the bonding insert material of the present invention has excellent corrosion resistance as well as oxidation resistance, and by coating this on the entire surface of Mo or W, Mo or W and SiC or Si ₃ N ₄ joint of The range of application can be expanded.

〔Example〕

(Example 1) Mo of 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
When bonding SiC plates, Cr plating is 20μ on the Mo bonding surface.
And then overlaying with SiC, under 10 ^-4 Torr, 1
Diffusion welding was performed at 100 ° C. × 0.5 kg / mm ² × 30 minutes. As a result, a strong joint was obtained without cracking of SiC.

(Example 2) Mo of 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
In the joining of SiC plates, Cr vapor deposition of 10μ was performed on the Mo joining surface, followed by Ni thermal spraying of 30μ, and then SiC was overlaid and diffused in an Ar atmosphere at 850 ° C. × 100 kg / mm ² × 1 hour. Welded. As a result, a strong joint was obtained without cracking of SiC.

(Example 3) 5 mm (plate thickness) x 50 mm (width) x 100 mm (length) Mo
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
In the joining of SiC plates, Cr is sprayed on the Mo joining surface by 30μ, then Cu plating is done by 40μ, and then SiC is overlaid at 1050 ° C × 0.5kg / mm ² under 10 ^-4 Torr.
Diffusion welding was performed for 30 minutes. As a result, a strong joint was obtained without cracking of SiC.

(Example 4) In joining a 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) W plate and a 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) SiC plate, After making 30μ of Cr plating on the joint surface, insert 50μ of Cu foil and superimpose SiC on it.
Diffusion welding was performed under ^-4 Torr at 1050 ° C x 0.5 kg / mm ² x 30 minutes. As a result, a strong bonded joint was obtained without cracking of Si ₃ N ₄ .

(Example 5) Mo of 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
When bonding Si ₃ N ₄ plates, Cr plating 2 on the Mo bonding surface.
After applying 0μ, overlay Si ₃ N ₄ and 10 ^-4 Torr
Diffusion welding was performed below at 1200 ° C. × 0.5 kg / mm ² × 30 minutes. As a result, a strong bonded joint was obtained without cracking of Si ₃ N ₄ .

(Example 6) 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) W plate and 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) Si ₃ W ₄
In the joining of the plates, Cr plating 20μ is performed on the W joining surface, Ni plating 20μ is subsequently applied, and then Si ₃ N ₄ is superposed and 1200 ° C. × 0.5 kg / m under 10 ⁻⁴ Torr.
Diffusion welding of m ² × 1H was performed. As a result, a strong bonded joint was obtained without cracking of Si ₃ N ₄ .

(Example 7) 5 mm (plate thickness) x 50 mm (width) x 100 mm (length) Mo
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
When joining SiC plates, Cr plating is 30μ on the joining surface of Mo.
After being subjected to 1000 ° C. under 10 ⁻⁴ Torr.
01kg / mm ² × 2 hours of diffusion welding, then using Ni solder (BNi-2) in vacuum, SiC and 1050 ℃ × 1
I brazed in 0 minutes. As a result, a strong joint was obtained without cracking of SiC.

(Example 8) In joining a 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) W plate and a 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) SiC plate, After applying 30μ of Cr plating on the joint surface, apply Ni foil of 50μ under 900 ⁻¹⁰ Torr.
℃ × 2kg / mm ² × 1 hour diffusion welding, then in vacuum, using Ag brazing (BAg-8), SiC and 800 ℃ ×
I brazed in 10 minutes. As a result, a strong joint was obtained without cracking of SiC.

(Example 9) Mo of 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
In joining SiC plates, after depositing 10μ of Cr on the joining face of Mo, Cu foil of 50μ is placed in Ar at 900 ° C × 2kg.
/ mm ² × 1 hour diffusion welding was performed, and then Cu brazing (BCuP-3) was used in Ar for brazing at 800 ° C. for 15 minutes with SiC. As a result, there is no crack in the SiC,
A strong joint was obtained.

(Example 10) 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) W plate and 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) Si ₃ N ₄
In joining the plates, after applying 20μ of Cr plating to the joining surface of W, 1000 ° C × 0.01k under 10 ^-4 Torr
g / mm ² × 2 hours of diffusion welding, then in vacuum
Using Ni solder (BNi-2), Si ₃ N ₄ and 1100 ° C ×
I brazed with 10 beauty. As a result, a strong bonded joint was obtained without cracking of Si ₃ N ₄ .

(Example 11) Mo of 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
When bonding Si ₃ N ₄ plates, Cr plating 2 on the Mo bonding surface.
0μ, followed by Cu plating 20μm, then at 10 ^-4 Torr, 1000 ° C. × 0.01 kg / mm ² ×
Diffusion welding was performed for 2 hours, and then brazing was performed with Cu braze (BCuP-3) in Si at 1100 ° C. for 10 minutes with Si ₃ N ₄ . As a result, a strong joint was obtained without cracking of SiC.

(Example 12) 5 mm (plate thickness) x 50 mm (width) x 100 mm (length) Mo
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
When bonding SiC plates, Cr plating 20 is applied to the entire surface of Mo plates.
After performing μ, Ni plating 50μ is performed on the entire surface, and then Cr diffusion plating (in metal Cr + Al ₂ O ₃ + NH ₄ Cl, 1100 ° C. × 5 hours diffusion plating treatment) is performed on the entire surface of the Ni plating layer. After completing the process, overlay SiC and ^-10 Torr
Diffusion welding was carried out at 900 ° C. × 2 kg / mm ² × 1 hour. As a result, a strong joint was obtained without cracking of SiC.

(Example 13) 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) W plate and 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) Si ₃ N ₄
In the joining of the plates, Cr plating 20 μ is performed on the entire surface of the W plate, Ni deposition 20 μ is performed on the entire surface, and then Cr diffusion plating (metal Cr + Al) is formed on the entire surface of the Ni deposition layer.
Diffusion plating treatment in ₂ O ₃ + NH ₄ Cl for 5 hours at 1100 ° C)
And then Si ₃ N ₄ on top of each other under 10 ⁻⁴ Torr,
Diffusion welding was performed at 1200 ° C. × 0.5 kg / mm ² × 1 hour. As a result, a strong bonded joint was obtained without cracking of Si ₃ N ₄ .

(Example 14) In joining a 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) W plate and a 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) SiC plate, a W plate Cr plating 20μ on the entire surface of, then Ni plating 50μm on the whole surface,
Next, a Cr diffusion plating (metal Cr +
Diffusion plating treatment at 1100 ° C for 5 hours in Al ₂ O ₃ + NH ₄ Cl), and then brazing with Ni braze (BNi-2) in vacuum at 1050 ° C for 10 minutes with SiC. I went.
As a result, a strong joint was obtained without cracking of SiC. In addition, using Ag wax (BAg-8), SiC
And 800 ° C x 10 minutes, using Cu wax (BCuP-3),
The same good joining result was obtained when brazing was performed with SiC at 800 ° C. for 15 minutes.

(Example 15) Mo of 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
In joining Si ₃ N ₄ plates, after Cr plating of 20μ is performed on the entire surface of Mo plate, Ni spraying of 50μ is performed on the entire surface, and then Cr diffusion plating (metal C
After performing diffusion plating treatment at 1100 ° C. for 5 hours in r + Al ₂ O ₃ + NH ₄ Cl, Ni braze (BNi−
Using 2), brazing was performed with Si ₃ N ₄ at 1100 ° C. for 10 minutes. As a result, a strong bonded joint was obtained without cracking of Si ₃ N ₄ . In addition, using Cu brazing (BCuP-3), Si ₃ N ₄ and 1100 ° C. for 10 minutes, Ag brazing (BAg
-8) with, even if the brazing having conducted in Si ₃ N ₄ and 800 ° C. × 10 minutes, similarly good bonding results.

(Example 16) 5 mm (plate thickness) x 50 mm (width) x 100 mm (length) Mo
Plate and 5 mm (plate thickness) x 50 mm (width) x 100 mm (length)
When bonding SiC plates, Cr plating 20 is applied to the entire surface of Mo plates.
After performing μ, Ni alloy (Ni50% + Cr
50%) Spraying 200μ on the entire surface, and then Cr diffusion plating (metal Cr + Al ₂ O ₃ + NH ₄ Cl) on the entire surface of the Ni alloy sprayed surface.
(1100 ° C x 5 hours diffusion plating treatment) in a vacuum, and then, in a vacuum, using Ni solder (BNi-2), SiC and 1
Brazing was performed at 100 ° C. for 10 minutes. As a result, a strong joint was obtained without cracking of SiC. In addition, using Cu solder (BCuP-3), SiC and 1100 ℃
× 10 minutes, using Ag wax (BAg-8), SiC and 800
Even when brazing was performed at 10 ° C. for 10 minutes, similarly good joining results were obtained.

(Example 17) 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) Mo plate and 3 mm (plate thickness) x 25 mm (width) x 25 mm (length) SiC
In the joining of the plates, Cr plating 20μ is performed on the entire surface of Mo, then 200μ of Cu alloy (Cu70% + Ni30%) is sprayed on the entire surface, and then SiC is superposed.
Diffusion welding was carried out at 1000 ° C. × 0.5 kg / mm ² × 30 minutes under ⁻⁴ Torr. As a result, a strong joint was obtained without cracking of SiC.

[Brief description of drawings]

1 to 4 are explanatory views showing the steps of the method for joining Mo or W and SiC or Si ₃ N ₄ according to the present invention.

Claims (4)

[Claims] 1. A Mo or W substrate, a first Cr coating layer deposited on the substrate, Cr deposited on the Cr coating layer,
A second metal coating layer of at least one of Ni and Cu, and SiC fixed in contact with the second metal coating layer
Or SiC or Si ₃ N characterized by comprising a Si ₃ N ₄ base material
A joined body of ₄ base materials and Mo or W base material. 2. The first Cr coating layer and the second metal coating layer are coated on the entire surface of the Mo or W substrate, and the outermost layer of the second metal coating layer is a Cr diffusion plating layer. The joined body according to claim 1, which is characterized by the above. 3. A Mo or W substrate, a first Cr coating layer deposited on the substrate, Cr deposited on the Cr coating layer,
A second metal coating layer of at least one of Ni and Cu, Ni braze deposited on the second metal coating layer, Cu
At least one brazing material coating layer of brazing material and Ag brazing material and SiC or Si ₃ adhered to the brazing material coating layer in contact therewith
SiC or Si ₃ N ₄ base material and Mo or W conjugate with the substrate, characterized by comprising from N ₄ substrate. 4. The first Cr coating layer and the second metal coating layer are coated on the entire surface of the Mo or W substrate, and the outermost layer of the second metal coating layer is a Cr diffusion plating layer. The joined body according to claim 3, which is characterized.