JP3215701B2 - Method for producing high heat load resistant C / C material and first wall material of fusion reactor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a C / C material (carbon fiber reinforced carbon composite material) having high heat load resistance and a nucleus composed of the C / C material. The present invention relates to a first wall material of a fusion reactor.

[Conventional technology]

Fusion reactor power generation has advantages such as less environmental pollution than conventional nuclear power generation by nuclear fission, so development research is being promoted on a national scale.

Fusion reactor types include tokamak type, mirror type, laser type, etc. Among them, the first wall material of tokamak type, which is considered to be the mainstream, is exposed to severe heat load conditions, causing damage. It must be made of a material that can withstand thermal shock and erosion.

Since the carbon material inherently has heat resistance that can withstand a high temperature of 3000 ° C., it has been studied as a promising candidate for the first wall material.

In particular, the C / C material has a tissue composed of a fiber skeleton,
Because of its excellent resistance to thermal shock, it is expected to be a great material for the first wall.

However, the C / C material, on the other hand, has a drawback of poor erosion resistance due to low thermal conductivity. So, C /
Attempts have also been made to improve the erosion resistance by forming and coating pyrolytic graphite having excellent thermal conductivity on the surface of the C material by the CVD method.

[Problems to be solved by the invention]

In consideration of the situation at the execution stage as the first wall material of the fusion reactor, it is easy to manufacture a large-sized material having high heat load resistance, and it is possible to supply the material at low cost; An important manufacturing condition is that a portion consumed by a phenomenon such as erosion can be repaired in a short time.

In this respect, in the method of forming a pyrolytic graphite film on the surface of the C / C material described above, it is difficult to manufacture a large-sized material at low cost, and the above-described manufacturing conditions are satisfied because local repair cannot be performed. Not.

An object of the present invention is to provide a method for producing a high heat load resistant C / C material that satisfies the above-mentioned production conditions based on the C / C material, and a first method for a fusion reactor composed of the obtained C / C material. The wall material is provided.

[Means for solving the problem]

In order to achieve the above object, the method for producing a high heat load resistant C / C material according to the present invention comprises, on a surface of a carbon fiber reinforced carbon composite substrate, spreading a high-density graphite film via a resin-based adhesive. Then, the structure is characterized by performing a firing carbonization treatment.

The carbon fiber reinforced carbon composite base material used in the present invention is not particularly limited in terms of production history, texture, shape and the like, but usually the one produced as follows is applied.

For the carbon fiber, woven fabric such as plain weave, twill weave, felt or tow manufactured from various raw materials such as polyacrylonitrile, rayon, and pitch is used, and phenol, furan, and other good carbonizable matrix resins are used. Liquid thermosetting resin is used. Carbon fiber is
Immersion, impregnation, fully wet with the matrix resin using means such as coating and then semi-cured to form a prepreg,
Subsequently, lamination pressure molding is performed. The molded body is heated to completely cure the resin component, and then calcined or carbonized or further graphitized according to a conventional method to obtain a base material. The base material is impregnated with the matrix resin as necessary, cured, and repeatedly carbonized,
The organization can be refined.

A high-density graphite film is spread on the surface of the carbon fiber reinforced carbon composite base material thus obtained via a resin-based adhesive.

As the high-density graphite film, a film produced by a method of carbonizing a polymer film selected from aromatic polyimide, polyoxydiazole or polyparaphenylene vinylene is effectively applied. At this time, as a condition of the carbonization treatment, a polymer film was sandwiched between carbonaceous holding plates and 10 to 100 g.
It is preferable that the treatment is carried out in a heating furnace maintained in an inert atmosphere while applying a pressing pressure of about f / cm ² , and the treatment temperature is set to 2000 ° C. or higher, preferably 2000 to 2500 ° C.

The high-density graphite film obtained by the method is a flexible, glassy thin graphite sheet having a highly oriented layered crystal structure in which the graphite layer surface is arranged in parallel with the film, and has a thickness of 0.02.
It can be manufactured to a desired thickness in the range of 22 mm.

Resin-based adhesives include a resin solution composed of at least one component of a resin having a relatively high residual carbon ratio such as a phenol-based, furan-based, or polyimide-based resin, or a fine resin such as graphite, coke, glassy carbon, etc. A paste obtained by mixing powder or carbon black is preferably used.

For spreading, apply a resin-based adhesive evenly to the surface of the carbon fiber reinforced carbon composite base material and attach a high-density graphite film,
The method can be carried out by heating and curing at a temperature of 50 to 300 ° C. while gently pressing.

The carbon fiber reinforced carbon composite base material on which the high-density graphite film is spread is then subjected to a calcination treatment in a temperature range of 700 ° C. or more in an inert atmosphere to produce a high heat load resistant C / C material.

The first wall material of the fusion reactor composed of the high heat load resistant C / C material obtained by the above manufacturing method is the second invention.

(Operation)

The high-density graphite film spread on the substrate surface in the production method of the present invention has good thermal conductivity because of the property that the graphite crystal layer is oriented along the film surface, and therefore has very low resistance to erosion. high. This feature
In combination with the high thermal shock resistance of the carbon fiber reinforced carbon composite base material, high heat load resistance as a material is effectively improved.

Therefore, the first wall material of the fusion reactor according to the present invention constituted by the manufactured C / C material is guaranteed to be stably used for a long period of time. In addition, when the surface portion is worn out by the erosion phenomenon, it can be repaired in a short time by replacing or supplementing the high-density graphite film.

Further, according to the production method of the present invention, since the high-density graphite film has appropriate flexibility, it can be easily spread even if the substrate has a curved surface or other complicated shape, and the operation is simple. Therefore, production of large materials is possible.

〔Example〕

 Hereinafter, examples of the present invention will be described in comparison with comparative examples.

Examples (1) Preparation of Carbon Fiber Reinforced Carbon Composite Substrate Polyacrylonitrile-based high elasticity type plain woven carbon fiber cloth [W6101 manufactured by Toho Rayon Co., Ltd.] was converted to a phenol resin initial condensate [Sumitomo Durez Co., Ltd., PR940]. And immersion in a matrix resin solution consisting of This is laminated and put into a mold, heating temperature 110 ° C, applied pressure 20kg /
Composite molding was performed under the condition of cm ² .

After the molded article was heated to a temperature of 250 ° C. to be completely cured, it was transferred to a firing furnace maintained in a nitrogen atmosphere, and was fired and carbonized at a temperature of 2500 ° C. for 5 hours.

The obtained carbon fiber reinforced carbon composite base material is a 10-mm-thick two-dimensional laminated plate-shaped body, with a bulk density of 1.53 g / cc and bending strength.
It had characteristics of 15.8 kgf / cm ² .

(2) Preparation of high-density graphite film An aromatic polyimide resin film ("Kapton H" manufactured by Du Pont-Toray Co., Ltd.) was sandwiched between graphite pressing plates having a smooth surface, and a pressing pressure of 60 gf / cm ² was applied. In this state, it was put into a nitrogen gas atmosphere furnace and carbonized at a temperature of 2200 ° C.

The obtained graphite film was a 0.05 mm thick flexible thin film sheet having a high density structure with a bulk density of 2.25 g / cc.

(3) Production of high heat load resistant C / C material The carbon fiber reinforced carbon composite base material prepared in the above (1) is cut into 100 mm in length and width, and a polyimide resin-based precursor varnish [Ube Industries ( U-varnish A)
Was uniformly applied, and then the high-density graphite film of the above (2) was attached. Subsequently, while applying a load of about 100 gf / cm ² to the application surface, the adhesive was heated to a temperature of 120 ° C. to cure the adhesive component, thereby completing the spreading.

The substrate on which the high-density graphite film was spread was then transferred to a heating furnace maintained in a nitrogen atmosphere, and calcined and carbonized at a temperature of 2000 ° C. to produce a high heat load resistant C / C material.

(4) Performance evaluation as the first wall material of fusion reactor The thermal shock resistance and the thermal shock resistance when the high heat load resistant C / C material produced in (3) above was used as the first wall material tile of a tokamak fusion reactor C / C material (10
The sample was irradiated with an electron beam on the high-density graphite film-deposited surface. Lighting conditions, heat flux 100 MW / m ^2, the irradiation time 0.1s
ec., the irradiation area was 10 mm square, and irradiation was repeated 10 times.

The occurrence of cracks due to thermal shock after the irradiation treatment and the weight loss (average) due to erosion were measured, and the results are shown in Table 1.

Example 2 A paste prepared by kneading a graphite fine powder having an average particle diameter of 8 μm at a weight ratio of 2: 1 to a polyimide resin-based precursor varnish [U-Varnish A, manufactured by Ube Industries, Ltd.] as an adhesive was used. Other than that, a high heat load resistant C / C material was manufactured using the same material and process as in Example 1.

The obtained high heat load resistant C / C material (10 samples) was evaluated as a first wall material of a fusion reactor by the same method as in Example 1, and the results are shown in Table 1.

Comparative Example 1 An electron beam irradiation test was performed on the carbon fiber reinforced carbon composite base material itself (10 samples) produced in (1) of Example 1 by the same method as in Example 1, and the results are also shown in Table 1.

Comparative Example 2 An isotropic high-density graphite material (G347, manufactured by Tokai Carbon Co., Ltd.) having characteristics of a bulk density of 1.83 g / cc and a bending strength of 500 kgf / cm ² was cut into a length and width of 100 mm and a thickness of 10 mm. An electron beam irradiation test was performed on the test pieces (10 samples) in the same manner as in Example 1, and the results are also shown in Table 1.

From the results shown in Table 1, it is recognized that the high heat load resistant C / C material produced according to the present invention exhibits excellent thermal shock resistance and erosion resistance when used as the first wall material of a fusion reactor. In contrast, C / C materials that do not have a high-density graphite film spread on the surface have poor erosion resistance, and ordinary isotropic high-density graphite materials do not satisfy the required performance in terms of thermal shock resistance. I understand.

〔The invention's effect〕

As described above, according to the present invention, a large high heat load resistant C / C material can be produced at a low cost by spreading a high-density graphite film on the surface of a carbon fiber reinforced carbon composite substrate and integrally firing and carbonizing. Can be manufactured. Further, the present invention provides a first wall material of a fusion reactor having both high thermal shock resistance and erosion resistance and exhibiting stable performance over a long period of time, and the erosion portion can be easily repaired. .

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08G 73/10 G21B 1/00 D C09J 179/08 C04B 35/52 E G21B 1/00 G (58) Investigated field (Int. Cl. ^7, DB name) C04B 41/87 C04B 35/52 C04B 35/83 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A high heat load resistant C / C, wherein a high-density graphite film is spread on a surface of a carbon fiber reinforced carbon composite base material via a resin-based adhesive, and then calcined and carbonized.
The method of manufacturing the material. 2. The high-temperature graphite film according to claim 1, wherein the high-density graphite film is obtained by carbonizing a polymer film selected from aromatic polyimide, polyoxydiazole or polyparaphenylene vinylene at a temperature of 2000 ° C. or higher. Load resistance
Manufacturing method of C / C material. 3. The high heat load according to claim 1, wherein the resin-based adhesive is a resin liquid comprising at least one component of a phenolic resin, a furan-based resin, or a polyimide resin, or a paste obtained by mixing a carbonaceous powder with these resin liquids. Manufacturing method of resistant C / C material. 4. A first wall material of a fusion reactor comprising the high heat load resistant C / C material according to claim 1.