JP3288440B2 - Joining method and joined body of heat-resistant alloy containing Al - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant alloy, and more particularly to a method for joining a heat-resistant alloy containing Al, which will be described later. The present invention relates to a joining method and a joined body of a heat-resistant alloy which is required to have extremely severe heat resistance, heat cycle resistance, and electric insulation, such as a carrier.

[0002]

2. Description of the Related Art As a method for joining heat-resistant alloys in the form of a plate or a foil, a method using various organic or inorganic adhesives, a method by brazing, a method by welding, and the like are generally known.

On the other hand, as a technique for forming an oxide layer on a metal surface to obtain electrical insulation between the metal substrate and the surface, for example, JP-A-2-97686, JP-A-2-97687, and JP-A-1-141834. JP-A-63-312985,
It is also well known that there is an enamel technique disclosed in JP-A-63-203779.

[0004] However, it is impossible to impart electrical insulation to the joints by the above-mentioned brazing and welding methods. As a method of obtaining only electric insulation, for example, there is a method of sandwiching an electric insulating material between heat-resistant alloys and joining the insulating material and the heat-resistant alloy foil with an organic adhesive. Alternatively, a method is also conceivable in which a heat-resistant alloy is directly joined with an organic adhesive by utilizing the electrical insulating properties of the organic adhesive. However, any of these methods is not suitable for use in a high-temperature environment, which is the object of the present invention, because the organic adhesive has poor heat resistance.

A method of sandwiching an insulating material between heat-resistant alloys and joining the insulating material and the heat-resistant alloy foil with an inorganic adhesive, or
In the method of joining the heat-resistant alloy directly with the inorganic adhesive using the electrical insulation properties of the inorganic adhesive, although heat resistance is obtained,
When a heat cycle load is applied, cracks occur in the adhesive and eventually break, and the problem of heat cycle resistance cannot be solved. That is, the method of using an organic or inorganic adhesive could not solve the object of the present invention.

[0006] On the other hand, the above-mentioned enamel technique has a technical idea of obtaining electrical insulation and heat cycle resistance, but is only concerned with metal surface treatment techniques and cannot be directly applied to the present invention for joining metals. Absent.

[0007]

SUMMARY OF THE INVENTION In the present invention, when joining heat-resistant alloys containing Al in the form of a plate or a foil, the joining portion has a heat resistance capable of withstanding a high temperature of 800.degree. To provide a joining method and a joined body that simultaneously satisfy the three characteristics of heat cycle resistance that can withstand the heat cycle at high temperatures and electrical insulation between the joined heat-resistant alloys and that have a particularly high joint strength. Is the main issue.

[0008]

The present invention for solving the above-mentioned problems is to oxidize the surface of a heat-resistant alloy containing Al to form an oxide film mainly composed of alumina, and to form a Ti or Zr metal on the surface layer. Contacting and heating in a non-oxidizing atmosphere to perform a process of diffusing into the heat-resistant alloy, then removing the Ti or Zr metal, and bringing any surfaces of the pair of heat-resistant alloys subjected to the diffusion process together. An oxide having a melting point of 800 ° C. or more and 1400 ° C. or less and a thickness of 1 mm or less is interposed between the facing surfaces, and the heat-resistant alloy is joined by heating to 9/10 or more of the melting point of the oxide. It is a feature.

Further, the surface of the heat-resistant alloy containing Al is oxidized to form an oxide film mainly composed of alumina, and Ti or Zr metal is disposed on one surface layer thereof and heated in a non-oxidizing atmosphere. In this way, a process of diffusing into the heat-resistant alloy is performed, and then the surfaces of the pair of heat-resistant alloys subjected to the diffusion process, which are opposite to the surfaces on which the Ti or Zr is arranged, face each other. Another feature is that the heat-resistant alloy is joined by interposing an oxide having a temperature of 1 ° C. or more and 1400 ° C. or less and a thickness of 1 mm or less and heating to 9/10 or more of the melting point of the oxide.

Further, the surface of the heat-resistant alloy containing Al is oxidized to form an oxide film mainly composed of alumina, and a Ti or Zr metal, a brazing material and a metal plate are sequentially laminated on one surface layer. Then, brazing treatment is performed in a non-oxidizing atmosphere to form a joined body. Then, the opposite surfaces of the pair of joined bodies subjected to the brazing treatment on which the Ti or Zr are arranged face each other. Melting point 800 ° C or higher 1400 on the facing surface
Another feature is that the heat-resistant alloy is bonded by interposing an oxide having a thickness of 1 ° C. or less and a temperature of 9/10 or more of the melting point of the oxide.

The surface of the heat-resistant alloy containing Al is oxidized to form an oxide film mainly composed of alumina, and a Ti or Zr metal, a brazing material, and a metal plate are sequentially laminated on one surface layer. Then, with respect to the two sets of the stacked arrangement bodies, the opposite surfaces on which the heat-resistant alloy Ti or Zr is arranged face each other,
A melting point of 800 ° C. or more and 1400 ° C. or less and a thickness of 1
mm or less of the melting point of this oxide.
Another feature is that the heat-resistant alloy is joined by heating to 0 or more.

[0012] Further, since the joint body of the heat-resistant alloy has an oxide film mainly composed of alumina on the surface and diffuses Ti or Zr into the surface layer on one side thereof, the interface between the oxide film and the heat-resistant alloy substrate is formed at the interface. Or A having a segregated part of Zr
1 interposed between a pair of plates or foils of a heat-resistant alloy containing
An oxide intermediate bonding layer formed by heating at a temperature of 400 ° C. or less and a thickness of 1 mm or less to 9/10 or more of the melting point.

[0013]

According to the present invention, a heat-resistant alloy containing Al is oxidized in advance to form an oxide film mainly composed of alumina, and the oxide film reacts with an intervening oxide to join.
In addition to joining the heat-resistant alloys more efficiently,
By diffusing i or Zr from the outside, the adhesive strength between the oxide film and the heat-resistant alloy substrate is improved. Therefore, it is indispensable that Al is added to the heat-resistant alloy. Preferably, if about 1% by weight or more is added, a sufficiently dense oxide film is formed.

After forming an oxide film mainly composed of alumina on the surface of the heat-resistant alloy containing Al, Ti or Z
When r is diffused into the heat-resistant alloy, these elements become
As shown in FIG. 5, segregation occurs at the interface between the oxide film 11 mainly composed of alumina and the heat-resistant alloy base material 12 and the oxide film 11 of the heat-resistant alloy is formed.
And Ti or Zr are oxide film 11 and heat-resistant alloy base 1
The composite oxide 13 is formed at the interface of No. 2. The oxide film 11 mainly composed of alumina and the composite oxide 13 are joined, and thus the interface 13a between the oxide film 11 of the heat-resistant alloy and the heat-resistant alloy base 12 in the absence of Ti or Zr is flat, When the composite oxide 13 of Ti or Zr is formed, a region where the interface 13a is stuck in the heat-resistant alloy base is formed, and the adhesion between the oxide film 11 and the heat-resistant alloy base 12 is improved by the anchoring effect.

The following method can be considered as a method for diffusing Ti or Zr metal. First, the heat-resistant alloy is oxidized to form an oxide film mainly composed of alumina on the surface, and as shown in FIG.
The Ti or Zr metal 20 is brought into direct contact and heated and diffused using any of vacuum, inert, and reducing atmospheres. As the Ti or Zr metal 20, powder, foil, plate or vapor-deposited can be used. In addition to the method of contacting only one side shown in FIG. A method of coating the entire surface with Ti or Zr metal, or a method of burying in Ti or Zr metal powder may be used. As soon as the diffusion process is completed, Ti
Alternatively, the Zr metal is removed. Thereafter, as shown in FIG. 3, the heat-resistant alloy 14 in which Ti or Zr is diffused (hereinafter, referred to as “heat-resistant alloy”).
Oxide 1 on any two surfaces (referred to as diffused alloy)
5 and then fired to join.

As shown in FIG. 2, a Ti or Zr metal 20 is added to a heat-resistant alloy 10 having an oxide film formed thereon.
When the diffusion treatment is performed by a method of contacting one surface of the heat-resistant alloy 10 with the oxide film formed thereon, and when the oxide 15 is interposed on the surface opposite to the surface on which Ti or Zr is arranged, after the diffusion treatment is completed, Ti Alternatively, there is no need to remove the Zr metal.

Further, when joining a heat-resistant alloy with an intervening oxide and joining another metal to both sides thereof,
Brazing treatment of another metal and heat-resistant alloy, Ti or Z
It is advantageous to perform the diffusion process of r at the same time.

In this case, the surface of the heat-resistant alloy is oxidized to form a heat-resistant alloy 10 having an oxide film mainly composed of alumina. Thereafter, as shown in FIG. The brazing material 30 is arranged on the outside, the metal plate 40 is arranged on the outside, and the brazing is performed to produce the brazed body 2 (see FIG. 5). At that time brazing and T
The diffusion process of i or Zr proceeds simultaneously. Thereafter, as shown in FIG. 5, the oxide 15 is interposed between the opposite surfaces of the heat-resistant alloy 10 on which the oxide film is formed and the Ti or Zr metal 20 is arranged in the brazing body 2, and thereafter, sintering is performed.
Braze and join.

Furthermore, if the conditions for firing for joining the heat-resistant alloy and the brazing process for another metal and the heat-resistant alloy are the same, the brazing process for another metal and the heat-resistant alloy, Diffusion treatment and sintering of heat-resistant alloy 3
It is advantageous to perform the steps simultaneously.

In this case, the surface of the heat-resistant alloy is oxidized to form an oxide film mainly composed of alumina.
Then, as shown in FIG. 6, an oxide 15, a heat-resistant alloy 10 having an oxide film formed thereon, a Ti or Zr metal 2
0, a brazing material 30, and a metal plate 40 are arranged, and then fired and joined. At this time, the brazing, the diffusion treatment of Ti or Zr, and the joining of the heat-resistant alloy proceed simultaneously.

FIG. 7 is a sectional structural view showing one embodiment of the joined body 1 according to the present invention. In the figure, reference numeral 120 denotes a heat-resistant alloy substrate containing Al.
Has an oxide film 110 formed on at least one side thereof. At the interface between the oxide film 110 and the heat-resistant alloy substrate 120, the composite oxide 1 formed by segregation of Ti or Zr is formed.
There are 30. The heat-resistant alloy having such an oxide film is disposed such that the oxide films 110 face each other, and an intermediate bonding layer 16 made of oxide is interposed between the facing surfaces. The joined body 1 configured as described above has a complicated structure in which the joined portion is used as an insulator, the joined body 1 is used alone, or another member such as a metal plate is joined to the outside of the joined body 1. It is possible to configure a simple structure.

Next, with respect to the firing temperature after the oxide is interposed between the facing surfaces in order to join the heat-resistant alloys, the present inventors consider that the melting point of the oxide 15 (absolute temperature) It has been found that sufficient bonding strength can be obtained by heating to 9/10 or more of ()). The reason is that it is necessary to cause the intervening oxide 15 to react with the oxide film 11 over the entire surface of the oxide film by sufficiently flowing the intervening oxide. If it is lower than this, the oxide does not flow sufficiently and high strength cannot be obtained. In the case of many oxides, the softening point exists at a temperature lower than the melting point.
If the heating is less than / 10, the heating temperature is insufficient from the viewpoint of the fluidity of the oxide, and heating at least 9/10 or more of the melting point is indispensable. An oxidizing atmosphere cannot be used when the sintering atmosphere involves the diffusion treatment of Ti or Zr. However, in the case of joining using the brazing body 2 or the diffused alloy 10, that is, the diffusion treatment of Ti or Zr. Is completed, reducing atmosphere, inert atmosphere,
Either a vacuum atmosphere or an oxidizing atmosphere may be used.

The use environment to which the present invention is directed is at least 8 environments such as a metal carrier for purifying automobile exhaust gas.
Because of the high temperature environment of 00 ° C., an oxide having a low melting point, for example, a low melting point glass containing a large amount of lead cannot be used as an intervening oxide. The present inventors have found that heat resistance can be obtained by using an oxide having a melting point of 800 ° C. or higher. If it is lower than that, the strength of the oxide decreases, and it is not possible to obtain sufficient bonding strength.

Further, in the case of a metal carrier for purifying automobile exhaust gas,
A thermal cycle occurs as the engine runs and stops.
In order to obtain heat cycle resistance, it is necessary to reduce the thickness of the intervening oxide itself. The value of this upper limit is 1 mm. In order to withstand a thermal cycle at room temperature and 800 ° C., the melting point of the oxide needs to be 1400 ° C. or less. If the thickness exceeds the upper limit, breakage tends to occur due to the difference in thermal expansion between the oxide and the heat-resistant alloy base. Further, when the melting point is 1400 ° C. or less, the oxide can be deformed at a relatively low temperature, so that thermal shock can be absorbed. Melting point 1400 ° C
If it exceeds 300, the heat deformability of the oxide is insufficient, so that the heat cycle resistance deteriorates.

In the present invention, electrical insulation, heat resistance,
With the aim of simultaneously satisfying the three properties of heat cycle resistance, and by diffusing Ti or Zr,
The purpose is to improve the adhesive strength between the oxide film and the heat-resistant alloy. The three properties aimed at by the present invention can be satisfied only by optimizing the properties of the metal substrate, the properties of the intervening oxide, and the firing conditions, and the adhesive strength between the oxide film and the heat-resistant alloy can be satisfied. Also improve.

[0026]

【Example】

Example 1 The following test was performed to grasp the effects of the present invention.
First, a heat-resistant alloy foil (Fe-20Cr-5Al alloy) having a thickness of 60 μm, a length of 100 mm, and a width of 17 mm was kept in the air at 1100 ° C. for 60 minutes to form an oxide film of about 1 μm. Then, the heat-resistant alloy foil 10 on which the oxide film was formed 10
As shown in FIG. 8, an oxide paste 150 having a composition shown in Table 1 and having various melting points was applied to the surface of No. 0. The oxide is a heat-resistant alloy foil 1 having an oxide film formed by screen-printing a powdery material having an average particle size of 10 μm and kneading with an organic vehicle to form a paste.
00 was coated so that half of its surface was coated. Then, as shown in FIG. 9, the application surfaces face each other, and a SUS430 plate 41 having a length of 100 mm and a thickness of 3 mm, a Ti foil 21 having a thickness of 5 μm, and a BNi-5 brazing material foil 31 having a thickness of 25 μm are arranged. did. Then, it is fixed with a jig and baked at a predetermined temperature in a vacuum atmosphere.
S430 plate 41a, heat-resistant alloy foil 10 with oxide film formed
0a, a joined body 1a made of an intervening oxide 150a was produced.

Thereafter, the joined body 1a is heated at a temperature of 20.degree.
A thermal cycle test was performed up to 1000 cycles at a temperature of 0 ° C. Table 1 shows the results of this test. High heat cycle resistance was obtained when the firing temperature at an oxide melting point of 800 to 1400 ° C. was 9/10 or more of the melting point. In addition,
The determination as to whether or not bonding was possible was made based on whether or not the fired bonded body was broken during handling.

[0028]

[Table 1]

Example 2 In order to evaluate the heat resistance of the joined body, the joined body 1a
The bondability when exposed to a temperature of 00 ° C. was evaluated. In this test, as shown in FIG. 11, a load of 10 kg was applied to the joined body 1a in the direction of the arrow at a temperature of 800 ° C. to examine whether or not the joined body was broken. Table 2 shows the results
Shown in It was found that the oxide having a melting point of 800 ° C. or higher did not break.

[0030]

[Table 2]

Example 3 Next, using the same sample as in Example 1, Ti or Z
The effect of the presence of r on the joint strength was tested. First, heat-resistant alloy foil (Fe-20Cr-5Al) was placed in air 11
As shown in FIG. 8, the heat-resistant alloy foil 100 having been oxidized at 00 ° C. for 60 minutes to form an oxide film of about 1 μm has a melting point of 12 μm.
00 ° C (10Al ₂ O ₃ -45MnO-45SiO
After applying the ₂ ) oxide 150 with a thickness of 10 μm,
The application surfaces face each other, and as shown in FIG.
30 plate 41, Ti foil 21 and BNi-5 brazing material foil 31 were arranged, and baked at 1200 ° C. for 10 minutes in a sintering condition vacuum,
The joined body 1a was produced.

As shown in FIG. 12, a heat-resistant alloy foil 100 having an oxide film coated with an oxide 150 and SUS
The 430 plate 41, the Zr foil 22, and the BNi-5 brazing material foil 31 were arranged, and fired in a vacuum at 1200 ° C. for 10 minutes in a firing condition to produce a joined body 1b. Also, as shown in FIG.
Heat-resistant alloy foil 100 having an oxide film coated with oxide 150, SUS430 plate 41, BNi-5 brazing material foil 31
And sintering was carried out in a vacuum at 1200 ° C. for 10 minutes in vacuum to produce a joined body 1c. Then, the joined bodies 1a, 1
As shown in FIG. 11, a load was applied to b and 1c in the direction of the arrow, and the strength when the joint was broken was examined. Table 3 shows an example of the results. In each case, there was no breakage at the brazing portion. However, due to the presence of Ti or Zr, the bonding strength around the insulating material, particularly the bonding between the oxide film and the stainless steel substrate interface. It was confirmed that the strength was significantly improved.

[0033]

[Table 3]

Example 4 Next, in addition to the Fe-20Cr-5Al alloy shown in Example 1, a heat-resistant alloy foil Fe-12Al alloy having a thickness of 60 μm, a length of 100 mm, and a width of 17 mm was used as a heat-resistant alloy to be joined. , Fe-15Cr-3Al alloy, Inconel 700, Nimonic 100 which are Ni-base super heat resistant alloys
Then, they were oxidized in the air at 1100 ° C. for 60 minutes to form a heat-resistant alloy foil 100 having an oxide film of about 1 μm on the heat-resistant alloy foil 100 at a melting point of 1200 ° C. (10Al ₂ O ₃ −45, as shown in FIG. 8).
(MnO-45SiO ₂ based) oxide 150 having a thickness of 10
After coating with a thickness of μm, as shown in FIG.
1, the Ti foil 21 and the BNi-5 brazing material foil 31 were arranged and fired at 1200 ° C. for 10 minutes in a vacuum to produce a joined body 1a shown in FIG. 10, and the strength at room temperature was measured. Strength is Fe
As in the case of the -20Cr-5Al alloy, the main fracture site was in the insulating material in each case, and the fracture at the interface between the heat-resistant alloy base and the oxide film was small.

Example 5 Next, the influence of the thickness of the oxide and the heat cycle resistance were evaluated. First heat-resistant alloy foil (Fe-20Cr-5Al) was oxidized under the conditions of 1100 ° C. 60 minutes in the air, the heat-resistant alloy foil 100 to form an oxide film of about 1 [mu] m, the melting point of 1200 ° C. As shown in FIG. 8 (10Al ₂ O ₃ -45MnO-45Si
The oxide 150 of the O ₂ system) was applied at various thicknesses,
The application surfaces face each other, and as shown in FIG.
30 plates 41, a Ti foil 21, and a BNi-5 brazing material foil 31 were arranged. Next, firing conditions were sintering in vacuum at 1200 ° C. for 10 minutes to produce a joined body 1a shown in FIG. In this test, a heat cycle test was performed up to 1000 cycles at a temperature of 20 to 800 ° C. as in the test of Table 1 described above.
The electrical insulation was determined based on whether or not there was conduction between the two SUS430 plates 41a in the joined body 1a shown in FIG. Specifically, when the resistance was 1000 ohms or less, conduction was determined. Table 4 shows the results. Although the electrical insulation was good in all the joined bodies, when the thickness of the intervening oxide exceeded 1 mm, the thermal cycling property was deteriorated.

[0036]

[Table 4]

Example 6 The effect of an oxide film on bonding strength was investigated. Two kinds of heat-resistant alloy foils 100, each of which is formed by oxidizing an Fe-20Cr-5Al alloy at 1100 ° C. for 60 minutes in the air at 1100 ° C. for 60 minutes, and forming an oxide film of about 1 μm, and a heat-resistant alloy foil 101 not subjected to oxidation are prepared. 8 or 14
As shown in the figure, the melting point is 1200 ° C. (10 Al ₂ O ₃ -45M
After coating an oxide of (nO-45SiO ₂ ) with a thickness of 10 μm, the coated surfaces face each other, and as shown in FIG. 9 or FIG.
The Ni-5 brazing material foil 31 was arranged. Next, firing conditions were baked in vacuum at 1200 ° C. for 10 minutes to produce a joined body, and the strength at room temperature was measured. Strength is 10 when there is no oxide film
Only about MPa was obtained, confirming the effectiveness of the oxide film.

Example 7 A heat-resistant alloy foil having a thickness of 60 μm, a length of 100 mm and a width of 17 mm (F
e-20Cr-5Al alloy) in air at 1100 ° C.
By holding for 0 minutes, an oxide film of about 1 μm is formed, and then a Ti film having a length of 100 mm, a width of 17 mm and a thickness of 1 mm is formed.
As shown in FIG. 16, the plate 23 is arranged so as to be in contact with one side of the heat-resistant alloy foil 100 on which the oxide film has been formed, and
The diffusion treatment was performed at 0 ° C. for 100 minutes. Then, the Ti plate was removed, and pastes of oxides 150 having various melting points shown in Table 1 were applied to a surface 140a of the diffused alloy foil 140 where no Ti was arranged, as shown in FIG. The oxide is a heat-resistant alloy foil 100 having an oxide film formed by screen-printing a paste having a mean particle size of 10 μm by kneading with an organic vehicle.
Was applied so as to cover half of the surface. Thereafter, as shown in FIG. 18, the joining surfaces face each other and closely adhered to each other, fixed with a jig, and baked at a predetermined temperature in a vacuum atmosphere to produce a joined body 1 d shown in FIG. 19. afterwards,
When a heat cycle test was performed up to 1000 cycles at 20 to 800 ° C., exactly the same results as in Example 1 were obtained. In the same manner, the same result is obtained when the heat-resistant alloy foil 100 on which the oxide film is formed is placed so as to be in contact with both sides, and diffusion processing is performed at 1200 ° C. for 100 minutes to remove the Ti plate, and similar bonding is performed. was gotten.

Example 8 Next, as shown in FIG. 8, a bonded body 1d produced in the same manner as in Example 7 and a heat-resistant alloy foil 100 on which an oxide film was formed were melted at 1200 ° C. (10Al ₂ O ₃ -45MnO ₂ ). −45
After applying an oxide of SiO ₂ ) with a thickness of 10 μm,
The coated surfaces were faced to each other without performing the Ti or Zr diffusion treatment, and then fired at 1200 ° C. for 10 minutes in vacuum under the sintering conditions to produce a joined body.
A load was applied in the direction of the arrow shown in FIG. As a result, similarly to the result of Example 3, it was recognized that the strength was improved by performing the Ti diffusion treatment.

Example 9 A heat-resistant alloy foil (F) having a thickness of 60 μm, a length of 100 mm and a width of 17 mm
e-20Cr-5Al alloy) in air at 1100 ° C.
By holding it for 0 minutes, a heat-resistant alloy foil 100 having an oxide film of about 1 μm was prepared, and then 100 mm long,
Ti foil 21 of 17 mm width and 5 μm thickness, BN of 25 μm thickness
An i-5 brazing material foil 31, a 3 mm thick SUS430 plate 41 is arranged as shown in FIG. 20, and brazed at 1200 ° C. for 10 minutes in a vacuum to produce a brazed body 2e. As shown in FIG. 21, on the surface on which no Ti was arranged, as shown in FIG.
A powdery oxide of μm is kneaded with an organic vehicle and screen-printed to form an oxide paste 150, so that half of the surface of the heat-resistant alloy foil 100e having an oxide film is coated. Then, the coated surfaces were brought into close contact with each other, fixed with a jig, and fired at a predetermined temperature in a vacuum atmosphere to produce a bonded body 1f shown in FIG. Thereafter, 100-200 ° C.
When a heat cycle test was performed up to 0 cycles, the same results as in Example 1 were obtained.

[0041]

As described above, according to the present invention, electrical insulation, heat resistance, and heat cycle resistance, which were previously impossible, are simultaneously satisfied, and the adhesion between the heat-resistant alloy substrate and the oxide film is remarkably improved. Therefore, a joined body of a heat-resistant alloy having particularly high joining strength can be obtained. In particular, this bonding method can be applied to an insulating material such as a preheated metal carrier for purifying automobile exhaust gas which requires this property.

[Brief description of the drawings]

FIG. 1 Ti or Zr on the interface between heat-resistant alloy and oxide film
FIG. 4 is a schematic cross-sectional view showing that a composite oxide of FIG.

FIG. 2 shows a heat-resistant alloy with an oxide film formed on Ti or Z
The side view which shows the state which r metal is contacting.

FIG. 3 is a side view showing that an oxide is interposed between diffused alloys.

FIG. 4 is a side view showing an arrangement of a metal plate, a brazing material, a Ti or Zr metal, and a heat-resistant alloy foil having an oxide film formed thereon.

FIG. 5 is a side view showing that an oxide is interposed between brazing bodies.

FIG. 6 is a side view showing the arrangement of a metal plate, a brazing material, a Ti or Zr metal, a heat-resistant alloy foil having an oxide film formed thereon, and an intervening oxide.

FIG. 7 is a sectional view showing the structure of a joined body of a heat-resistant alloy.

FIG. 8 is a side view showing a state in which an oxide paste is applied to a heat-resistant alloy foil having an oxide film formed thereon.

FIG. 9 is a side view showing the arrangement of a SUS430 plate, a brazing filler metal foil, a Ti foil, and a heat-resistant alloy foil having an oxide film coated with an oxide.

FIG. 10: SUS430 plate, brazing filler metal foil, Ti
The side view which shows the joined body which baked the foil and the heat-resistant alloy foil which formed the oxide film to which the oxide was applied.

FIG. 11: SUS430 plate, brazing filler metal foil, Ti
The side view which shows the joined body which baked the foil and the heat-resistant alloy foil which formed the oxide film to which the oxide was applied.

FIG. 12 is a side view showing an arrangement of a SUS430 plate, a brazing material foil, a Zr foil, a heat-resistant alloy foil having an oxide film coated with an oxide, and a side view showing a joined body obtained by firing the same.

FIG. 13 is a side view showing the arrangement of a SUS430 plate, a brazing filler metal foil, and a heat-resistant alloy foil having an oxide film coated with an oxide, and a side view showing a joined body obtained by firing the same.

FIG. 14 is a side view showing a state in which an oxide paste is applied to a heat-resistant alloy foil having no oxide film formed thereon.

FIG. 15 is a side view showing an arrangement of a SUS430 plate, a brazing material foil, a Ti foil, and a heat-resistant alloy foil having no oxide film coated with an oxide.

FIG. 16 is a side view showing a state in which Ti or Zr metal is in contact with a heat-resistant alloy foil having an oxide film formed thereon.

FIG. 17 is a side view showing a state in which an oxide paste is applied to a diffused alloy foil.

FIG. 18 is a side view showing a state where the application surfaces of the diffused alloy foil on which the oxide is applied face each other.

FIG. 19 is a side view showing a joined body formed by sintering the coated surfaces of the diffused alloy foil coated with the oxide face to face.

FIG. 20 is a side view showing an arrangement of a SUS430 plate, a brazing filler metal foil, a Ti foil, a heat-resistant alloy foil having an oxide film coated with an oxide, and a brazing body formed by brazing the same.

FIG. 21 is a side view showing a state in which the application surfaces of the brazing body to which the oxide has been applied face each other;

FIG. 22 is a side view showing a joined body formed by sintering the brazed bodies to which oxides have been applied with their applied surfaces facing each other.

[Explanation of symbols]

1,1a, 1b, 1c, 1d, 1f Joined body 2,2e Brazing body 10 Heat-resistant alloy with oxide film formed 100,100a, 100b, 100c, 100d, 1
00e Heat-resistant alloy foil with oxide film formed 101 Heat-resistant alloy foil without oxide film formed 11,110 Oxide film 12,120 Heat-resistant alloy substrate 13,130 Complex oxide 14 Diffusion alloy 140,140d Diffusion alloy foil oxide Paste-coated heat-resistant alloy foil 140a Surface of diffused alloy foil opposite to the surface on which Ti is arranged 15 Interposed oxide 150 In the state where oxide paste is applied 150a, 150b, 150c, 150d, 150f
20 Ti or Zr metal 21 Ti foil 22 Zr foil 23 Ti plate 30 brazing material 31 BNi-5 brazing material foil 40 Metal plate 41, 41 a, 41 b , 41c, 41e, 41f SU
S430 board

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 29/00 B23K 1/19 B23K 20/00 310

Claims (5)

(57) [Claims] 1. A method of oxidizing the surface of a heat-resistant alloy containing Al to form an oxide film mainly composed of alumina, bringing a Ti or Zr metal into contact with the surface layer, and heating in a non-oxidizing atmosphere. A process of diffusing into the heat-resistant alloy is performed, after which the Ti or Zr metal is removed, and any surface of the pair of heat-resistant alloys subjected to the diffusion process faces each other. Below, thickness 1mm
The following oxide is interposed, and 9/10 of the melting point of this oxide
A method for joining heat-resistant alloys, comprising joining the heat-resistant alloy by heating as described above. 2. A surface of a heat-resistant alloy containing Al is oxidized to form an oxide film mainly composed of alumina, and a Ti or Zr metal is disposed on one surface layer thereof and heated in a non-oxidizing atmosphere. In this way, a process of diffusing into the heat-resistant alloy is performed, and then the surfaces of the pair of heat-resistant alloys subjected to the diffusion process, which are opposite to the surfaces on which the Ti or Zr is arranged, face each other. ℃ to 1400 ℃,
A method for joining a heat-resistant alloy, comprising: interposing an oxide having a thickness of 1 mm or less, and heating the oxide to 9/10 or more of a melting point of the oxide to join the heat-resistant alloy. 3. A surface of a heat-resistant alloy containing Al is oxidized to form an oxide film mainly composed of alumina, and a Ti or Zr metal, a brazing material, and a metal plate are sequentially laminated on one surface layer. Then, brazing treatment is performed in a non-oxidizing atmosphere to form a joined body. Then, the opposite surfaces of the pair of joined bodies subjected to the brazing treatment on which the Ti or Zr are arranged face each other. An oxide having a melting point of 800 ° C. or more and 1400 ° C. or less and a thickness of 1 mm or less is interposed on the opposing surface, and the heat-resistant alloy is joined by heating to 9/10 or more of the melting point of the oxide. Alloy joining method. 4. A surface of a heat-resistant alloy containing Al is oxidized to form an oxide film mainly composed of alumina, and a Ti or Zr metal, a brazing material, and a metal plate are sequentially laminated on one surface layer. Then, with respect to the two sets of the stacked arrangement bodies, the opposite surfaces on which the heat-resistant alloy Ti or Zr is arranged face each other, and an oxide having a melting point of 800 ° C. or more and 1400 ° C. or less and a thickness of 1 mm or less is interposed on the facing surfaces, A method for joining heat-resistant alloys, wherein the heat-resistant alloy is joined by heating to 9/10 or more of the melting point of the oxide. 5. A segregated portion of Ti or Zr is present at the interface between the oxide film and the heat-resistant alloy substrate due to having an oxide film mainly composed of alumina on the surface and diffusing Ti or Zr into one surface layer of the oxide film. A pair of plates or foils of a heat-resistant alloy containing Al and a surface of the pair of plates or foils having a melting point of 800 ° C. or more and 1400 ° C. or less, and a thickness of 1 mm or less and 9/9 of the melting point. A bonded body of a heat-resistant alloy having excellent heat resistance, heat cycle resistance, electrical insulation and bonding strength, comprising an oxide intermediate bonding layer formed by heating to 10 or more.