JPH09208335A - Carbon-composite member and its composite method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily bond large-size carbonaceous member(s) of complicated shape without containing Ag at the joint, by metallically bonding carbonaceous members to each other or a carbonaceous member to another member through a composition essentially comprising Cu and Mn. SOLUTION: A composition consisting mainly of Cu and Mn and serving as an adhesive is pref. composed of 15-45wt.% Mn and the rest of Cu. If the Mn content of the composition falls within the above range, the melting point of the composition (alloy) stands at 870-950 deg.C, a range being enough to be applicable to Cu or Cu alloy bonding. Besides, incorporation of 1-10wt.% Ti in the above composition facilitates bonding operation. The composition may be of any form: i.e., Cu-Mn-Ti alloy or powder, or brazing material with the surface of a Cu-Mn alloy foil provided with Ti-film. The bonding is conducted as follows: the above composition or alloy foil with the surface of Cu-Mn alloy foil provided with Ti-film is put between carbonaceous members or between a carbonaceous member and metallic member followed by heating in a nonoxidative atmosphere at a temperature higher than the melting point of the composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial product using a carbon member, including a furnace wall for aerospace equipment, a nuclear fusion device and a high temperature gas reactor.

[0002]

2. Description of the Related Art Conventionally, a method of joining carbon members to each other or other materials is an Ag-Cu alloy or an active metal method in which Ti is added to Cu (USA Patent No. 2739375), Fe-N.
i-Ti alloy wax (Japanese Patent Publication No. 290561), Ti-
Zr-Be alloy solder (Wel. J., Vol 41, No. 68),
Ni-Cr-Pd-Si alloy braze (JP-A-1-178399)
No.), Mo-Ni-Cr-Fe alloy brazing alloy (JP-A-62-1176).
No. 8), V-Ti alloy foil (JP-A-2-23499), and other methods for directly joining a carbon member to another member with a brazing material or foil are disclosed.

On the other hand, as a method of brazing after forming a metallized layer on the surface of a carbon member, Japanese Patent Laid-Open No. 3-54182 discloses a method of:
A method is disclosed in which a eutectic alloy of Mo or W and Zr is placed on the surface of graphite and heated in a non-oxidizing atmosphere.

[0004]

The method of joining the carbon members to each other or the carbon member to another member by the above-mentioned conventional method has the following problems.

When joining a carbon member to copper or a copper alloy, a method of joining with a brazing material containing Ag and Cu as the main components is known. However, when this method is adopted for joining the fusion reactor members, if Ag is contained in the joint, the neutron irradiation during the operation of the fusion reactor causes
g is converted to Cd. Since Cd has a low melting point and a high vapor pressure, it diffuses into the plasma during the operation of the fusion reactor and reduces the purity of the plasma. For this reason, the plasma temperature is lowered and it becomes impossible to operate the fusion reactor. Therefore, in order to join the members applied in the fusion reactor, a joining method that does not contain Ag at the joint is necessary.

On the other hand, as a joining method in which Ag is not contained in the joint, for example, a Ni-Cr brazing material or Cu-T is used.
A method of joining with an i-based brazing material or the like is known. But,
When the carbon member is bonded to Cu or Cu alloy with the brazing material, there are the following problems.

(1) Since the brazing material is close to or higher than the melting point of Cu, it is difficult to bond Cu or Cu alloy. (2) It is difficult to make a brazing foil because the brazing material has high rigidity. (3) Since the brazing filler metal generally has high rigidity, the residual stress in the joint becomes high, and a highly reliable joint cannot be obtained. (4) As described above, in the case of a brazing material having high rigidity, when the carbon member has a complicated shape, the brazing material cannot adhere to the joining surface of the carbon member. For this reason,
A healthy joint cannot be obtained. There are problems such as.

An object of the present invention is to obtain a highly reliable composite member between isotropic carbon members or carbon fiber carbon composite members and between the carbon member and another member such as a metal, and the composite member. It is to provide a joining method for this.

[0009]

As described above, in order to join the fusion reactor members, it is necessary to use a joining method that does not contain Ag at the joint. The present invention provides a compounding method for obtaining a bonded body of carbon members that do not contain Ag at their joints or a carbon member and a metal. Further, in the present invention, C does not contain Ag in the joint and has a relatively low melting point.
A joining method for easily joining a carbon member to u and Cu alloys is provided.

It has been invented that an alloy containing Cu and Mn as main components or a powdery mixture is preferable as a composition for bonding that does not contain Ag in the joint.

The composition containing Cu and Mn as main components is 15
A composition of ˜45 wt% Mn and the balance Cu is desirable. In the composition in which the amount of Mn is in the range of 15 to 45 wt%, the melting point (liquidus line) of this alloy is 870 to 950 ° C., which is the temperature range applicable to the bonding of Cu or Cu alloy. Desirably, the melting point can be lowered to 870 ° C. in the composition of Cu-35 wt% Mn. Therefore, since the melting point of Cu is lower by 200 ° C., Cu or a Cu alloy and the carbon member can be easily bonded.

Further, by adding 1 to 10 wt% of Ti to the composition containing Cu and Mn as main components, it is possible to easily bond the carbon parts or the carbon member to another member. The composition is Cu-M containing Cu and Mn as main components.
This object can be achieved either in the state of n-Ti alloy or in the state of Cu-Mn-Ti powder. Further, the present object can be achieved even with a brazing material having a Ti film formed on the surface of an alloy foil made of Cu-Mn.

On the other hand, a method for joining the carbon members and the carbon member and the metal with the composition will be described below.

(1) A composition containing Cu and Mn as main components between the carbon members or between the carbon member and the metal member or Cu
An alloy foil having a Ti film formed on the surface of the alloy foil of and Mn is placed and heated in a non-oxidizing atmosphere to a temperature equal to or higher than the melting point of the composition.

(2) After forming a Ti film on the surface of the carbon member in advance, a composition consisting of Cu and Mn is arranged thereon, and a carbon member or a metal member is arranged thereon, and the composition is made non-oxidizing. Heating above the melting point of the composition in an atmosphere.

(3) A composition containing Cu and Mn or Cu-Mn-Ti as main components is printed or applied on the surface of the carbon member. By heating this above the melting point of the composition in a non-oxidizing atmosphere, a metallized layer is formed in advance on the surface of the carbon member. The carbon member on which the metallized layer is formed is bonded to a metal or the like with a Cu-P alloy brazing material containing no Ag.

On the other hand, this object can also be achieved by a composition comprising Cu-P-Ti. The composition has P of 4 to 6 wt.
%, Ti is 1 to 10 wt%, and a composition in which the balance is Cu is desirable. That is, the melting point (solidus point) of this composition becomes about 710 ° C. by adding 4 to 6 wt% of P to Cu. By adding 1 to 10 wt% of Ti to this, the carbon member can be bonded to Cu and the Cu alloy at the melting point of the Cu or the Cu alloy or less.

The composition can achieve this object even in the form of an alloy of Cu-P-Ti or in the form of powder. Furthermore, an alloy foil in which a Ti film is formed on the surface of an alloy foil composed of 4 to 6 wt% P and the balance Cu is more desirable in terms of workability.

The method of joining the carbon members or the carbon member and the metal using the composition is the same as in (1) to (3).

When a composition containing Cu and Mn as main components is placed between a carbon member and a metal and heated above the melting point of the composition in a non-oxidizing atmosphere, Mn in the composition reacts with carbon. , Manganese carbide is generated at the joint, forming a joint layer. In addition, T in Cu-Mn alloy or powder
In the case of the composition to which i is added, titanium carbide is generated in addition to manganese carbide at the joint, and a more desirable joining layer is formed. Further, Mn not only forms carbide, but also lowers the melting point of the Cu-Mn composition.

On the other hand, in the case of Cu-P-Ti, P lowers the melting point in the alloy. Ti reacts with carbon to produce titanium carbide at the joint, forming a joint layer.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION

(Example 1) Isotropic graphite and carbon fiber-carbon composite material and Cu
An example of joining a member with a brazing alloy of Cu and Mn will be described. In this example, an alloy brazing foil made of 35 wt% Mn and the balance Cu having a thickness of 100 μm is arranged between the carbon member and the Cu member, and this is higher than the melting point of the brazing foil by 50 ° C. in a non-oxidizing atmosphere 920. Heat at ℃ for 3 minutes.

As a result of the shear test of the joined body joined by the above-mentioned method, a high shear strength equivalent to the shear strength of the graphite member or the carbon fiber-carbon composite material was obtained, and a highly reliable carbon composite member was obtained. Was obtained.

(Embodiment 2) Ti powder is mixed with an organic solvent on the surface of the joint surface of isotropic graphite and carbon fiber-carbon composite member of 30 mm square having a circular arc shape with a radius of 15 mm and paste is mixed with an organic solvent. The shaped product is applied to a thickness of 10 to 30 μm. On top of this, an alloy brazing foil consisting of 35 wt% Mn and the balance Cu and having a thickness of 100 μm, and having a diameter of 14.8 mm
Place the copper pipe. This is heated in a non-oxidizing atmosphere at 900 ° C., which is 30 ° C. higher than the melting point of the wax foil, for 3 minutes.

As a result of a shear test of the joined body joined by the above-mentioned method, a shear strength equivalent to that of the graphite member or the carbon fiber-carbon composite material was obtained, and a highly reliable carbon composite member was obtained. Was given. Similar results were obtained when a Ti film having a thickness of 5 μm was formed on the surface of the joining surface of the isotropic graphite and the carbon fiber-carbon composite material by the vapor deposition method and the Ti film was joined by the same method as described above.

(Embodiment 3) Ti powder is mixed with an organic solvent and pasted on the surface of the joint surface of isotropic graphite and carbon fiber-carbon composite member of 30 mm square having a circular arc shape with a radius of 15 mm. The shaped product is applied to a thickness of 10 to 50 μm. On this, an alloy brazing foil having a thickness of 100 μm and composed of 35 wt% Mn and the balance Cu, and a copper foil having a thickness of 1 mm are arranged. This is heated in a non-oxidizing atmosphere at a temperature of 910 ° C., which is 40 ° C. higher than the melting point of the wax foil, for 3 minutes. This forms a Cu metallization layer having a thickness of about 1 mm on the bonding surface of the carbon member.

On the joint surface of the carbon member on which the metallized layer is formed, a copper copper braze made of Cu-5 wt% P having a thickness of 100 μm and a copper pipe having a diameter of 14.8 mm are arranged thereon. This is heated in air at a temperature of 800 ° C., which is 50 ° C. higher than the solidus point of the wax foil, for 3 minutes.

As a result of a shear test of the joined body joined by the above-mentioned method, a shear strength equivalent to that of the graphite member or the carbon fiber-carbon composite material was obtained, and a highly reliable carbon composite member was obtained. Was given.

(Example 4) 35 wt% Mn and the balance Cu
A Ti film having a thickness of 5 μm is formed on the surface of an alloy foil having a thickness of 150 μm, which is made of, by physical vapor deposition. Alloy foil Ti
The surface side on which the film is formed is arranged between the Cu member and the carbon fiber-carbon composite member of the material to be bonded. This is heated in a non-oxidizing atmosphere at a temperature of 920 ° C., which is 50 ° C. higher than the melting point of the alloy foil, for 3 minutes.

As a result of a shear test of the joined body joined by the above-mentioned method, a shear strength equivalent to that of the graphite member or the carbon fiber-carbon composite material was obtained, and a highly reliable carbon composite member was obtained. Was given.

(Embodiment 5) On one surface of isotropic graphite and carbon fiber-carbon composite member, Ti powder is mixed with an organic solvent to form a paste, which is applied to a thickness of 10 to 20 μm. On top of this, a thickness of 5 wt% P and the balance of Cu is 10
A 0 μm alloy braze foil is placed with a copper block on it. This is 10% from the solidus line of the wax foil in a non-oxidizing atmosphere.
Heat at 0 ° C to 800 ° C for 3 minutes.

As a result of a shear test of the joined body joined by the above-mentioned method, a shear strength equivalent to that of the graphite member or the carbon fiber-carbon composite material was obtained, and a highly reliable carbon composite member was obtained. Was given.

(Embodiment 6) A paste-like Ti is formed on the surface of an alloy foil having a thickness of 150 m, which is composed of 5 wt% P and the balance Cu.
To a thickness of 20 μm. The alloy foil is arranged between the carbon fiber-carbon composite member of the material to be joined and the Cu member. 80% higher than the melting point of the alloy foil in a non-oxidizing atmosphere
Heat at 0 ° C for 3 min. As a result of a shear test of the joined body joined by the above-described method, a shear strength equivalent to that of the graphite member or the carbon fiber-carbon composite material was obtained, and a highly reliable carbon composite member was obtained.

Example 7 One side of a carbon fiber-carbon composite material having a thickness of 20 mm and a size of 30 mm is processed into an arc shape having a radius of 10.5 mm. A carbon composite material processed in the shape of an arc is coated with a paste-like Ti powder having a thickness of 20 μm to obtain 20
Make one.

Next, an outer diameter of 20 mm and an inner diameter of 16 are formed on the arc-shaped portion of the carbon composite member coated with the pasty Ti powder.
mm with a length of 1000 mm and a thickness of 100 μ between them
A 65 wt% Cu-35 wt% Mn alloy foil of m is placed. Next, from the melting point of the brazing filler metal in a non-oxidizing atmosphere,
Heat to 920 ° C, 50 ° C higher for 3 minutes. As a result, at the joint between the carbon fiber-carbon composite member and the copper pipe, Ti
And titanium carbide and manganese carbide formed by the reaction between Mn and carbon to form a strong bond. The joined body joined by the above method was used as a heat receiving plate for a nuclear fusion device. While the inner surface of the copper pipe of the heat receiving plate was being cooled with cooling water having a flow rate of 2 m / s, the heat receiving plate was sound as a result of being circumferentially irradiated with a hydrogen ion beam having a heat flux of 20 MW / m ² . The carbon fiber composite material was Al ₂
Similar results were obtained in the case of a heat receiving plate for a fusion reactor joined to a Cu alloy dispersion-strengthened with O ₃ .

[0036]

EFFECTS OF THE INVENTION According to the present invention, since it is possible to easily join a carbon member having a complicated shape and a large size, it is possible to easily manufacture a large structure such as a reactor wall for a nuclear fusion device.

Claims (11)

[Claims] 1. A carbon composite member, wherein carbon members are metallically bonded to each other or a carbon member and another member are metallically joined by a composition containing Cu and Mn as main components. 2. Main components of Cu and Mn, in which 1 to 10 are added.
A carbon composite member, wherein the carbon members are metallically bonded to each other or the carbon member and another member are metallically bonded by a composition containing wt% Ti. 3. The composition containing Cu and Mn as main components according to claim 1 or 2, wherein the Mn content is 15 to 45 wt% and the balance is Cu.
A carbon composite member made of. 4. A carbon composite member in which a metallized layer is formed on the surface of a carbon member by the composition according to claim 1, 2, or 3. 5. A carbon composite member, wherein the carbon members are metallically bonded to each other or the carbon member and another member are metallically bonded with each other by a composition comprising Cu-P-Ti. 6. The composition according to claim 5, wherein P is 4 to 6 w.
The carbon composite member is a composition in which t% and Ti are 1 to 5 wt% and the balance is Cu. 7. The carbon composite member according to claim 1, 2, 3, 4, 5 or 6, wherein the carbon composite member is isotropic graphite and a carbon fiber carbon composite member. 8. A step of forming a Ti film on the surface of a carbon member in advance, and then Cu and Mn or Cu and P on the surface of the Ti film.
A carbon member or a carbon member by a step of disposing a composition containing as a main component, a step of disposing a carbon member or a metal member, and a step of heating this to a melting point of the composition or higher in a non-oxidizing atmosphere. A method for compounding a carbon member, which is characterized by compounding with another member metallically. 9. A step of forming a Ti film on the surface of a carbon member in advance, and then Cu and Mn or Cu and P on the surface of the Ti film.
Forming a metallized layer on the surface of the carbon member by a step of disposing a composition containing as a main component and then a step of heating the composition above the melting point of the composition in a non-oxidizing atmosphere. Composite method of carbon member. 10. A brazing material for joining carbon members, wherein a Ti film having a thickness of 1 to 10 μm is formed on the surface of an alloy foil containing Cu and Mn or Cu and P as main components. 11. The method of claim 1, 2, 3, 4, 5, 6, 7,
A reactor wall for a nuclear fusion device, wherein a plurality of carbon members are metallically joined in a tile shape to a metal member having a cooling function by the method described in 8, 9, or 10.