WO2015025612A1 - Carbon material and heat treatment jig using said carbon material - Google Patents

Carbon material and heat treatment jig using said carbon material Download PDF

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WO2015025612A1
WO2015025612A1 PCT/JP2014/066804 JP2014066804W WO2015025612A1 WO 2015025612 A1 WO2015025612 A1 WO 2015025612A1 JP 2014066804 W JP2014066804 W JP 2014066804W WO 2015025612 A1 WO2015025612 A1 WO 2015025612A1
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carbon material
boron
heat treatment
carbon
less
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PCT/JP2014/066804
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French (fr)
Japanese (ja)
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裕治 瀧本
井上　崇
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東洋炭素株式会社
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Priority to JP2015532752A priority Critical patent/JP6309526B2/en
Priority to DE112014003877.6T priority patent/DE112014003877T5/en
Publication of WO2015025612A1 publication Critical patent/WO2015025612A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5057—Carbides
    • C04B41/5059—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
    • C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3821—Boron carbides
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase

Definitions

  • the present invention relates to a carbon material and a jig for heat treatment using the carbon material.
  • Carbon materials have excellent properties such as heat resistance, chemical resistance, good electrical conductivity, low coefficient of thermal expansion, and light weight, so they are used in a wide range of industries.
  • the carbon material has a drawback that it is susceptible to oxidation consumption in high-temperature air.
  • Si—B—C ternary carbon materials have been proposed (see Patent Document 1, Non-Patent Documents 1 and 2). It is known that the carbon material maintains a state in which the oxidation consumption rate at 1200 ° C. in the atmosphere is several percent or less for a long time, that is, has a high oxidation resistance. This is because a glass layer is formed inside and on the surface of the carbon material at the same time as the oxidation of the carbon material by dispersing the component to be vitrified by oxidation inside the carbon material, so that the progress of the oxidation can be prevented. Because.
  • the Si—B—C ternary carbon material exhibits oxidation resistance when a borosilicate glass layer having a low softening point is formed inside and on the surface, but the glass layer serves as an adhesive component,
  • the Si—B—C ternary carbon material can lower the softening point of silicate glass with boron and protect the oxidation progress of the carbon material with the borosilicate glass layer, while the glass layer having a low softening point.
  • the phenomenon of adhering to other materials occurs due to the presence of.
  • this invention aims at providing the jig
  • the carbon material of the present invention is a carbonaceous substrate comprising a carbon-boron carbide-silicon carbide sintered body (hereinafter sometimes referred to as a Si—B—C ternary sintered body).
  • a protective layer made of silicon carbide is formed on the surface of the substrate.
  • the oxidation resistance is excellent, and when used as an in-furnace jig or the like, there is an excellent effect that adhesion to a counterpart material such as a processed product hardly occurs.
  • the carbon material of the present invention is characterized in that a protective layer made of silicon carbide is formed on the surface of a carbonaceous substrate made of a Si—B—C ternary sintered body. Since a protective layer made of silicon carbide is formed on the surface of the carbonaceous substrate, the carbonaceous substrate and oxygen come into contact with each other even when the carbon material of the present invention is used in an oxidizing atmosphere. Can be suppressed. Therefore, the carbon material of the present invention exhibits high oxidation wear resistance.
  • the carbonaceous base material and the protective layer may be cracked or peeled off in part of the protective layer due to different thermal expansion coefficients, etc., and the carbonaceous base material may be exposed.
  • the use of Si-BC ternary sintered body with excellent resistance to oxidation and consumption as the carbonaceous substrate causes problems due to oxidation and consumption. Can be suppressed over a long period of time.
  • the Si—B—C ternary sintered body forms a low softening point (about 800 ° C.) borosilicate glass when exposed to high temperature (about 800 ° C. to about 1200 ° C.) air.
  • the protective layer formed forms a silicate glass layer having a high softening point (about 1500 to 1700 ° C.) when exposed to air at a high temperature (about 800 ° C. to about 1200 ° C.). Therefore, if the carbon material has a protective layer made of silicon carbide, a protective layer with a high softening point is formed on the surface of the carbon material even when the carbon material is exposed to a high temperature state. Even if it contacts with another member, it can prevent that a carbon material and another member adhere.
  • the softening point of the glass is a temperature at which the glass begins to be significantly softened and deformed by its own weight, and is a temperature corresponding to a viscosity of about 107.6 dPa ⁇ s, and is a method defined in JIS R 3103-1: 2001. Can be measured.
  • silicon carbide penetrates into the pores of the carbonaceous substrate. If silicon carbide penetrates into the pores of the carbonaceous substrate as in the above configuration, the anchor effect is exerted, so that the adhesion strength between the carbonaceous substrate and the protective layer is increased.
  • the thickness of the protective layer is desirably 5.3 ⁇ m or more. If the thickness of the protective layer is 5.3 ⁇ m or more, the above-described effects are further exhibited.
  • the carbon material described above can be suitably used as a heat treatment jig.
  • heat treatment jigs When carbon materials are used as heat treatment jigs, they are not always used in a reducing atmosphere, but for use in oxidizing atmospheres (atmospheres exposed to high temperatures in the presence of oxygen) for the following reasons. There are also many.
  • a carbon material such as graphite may not be used as a heat treatment jig, and even if it can be used, there is a problem that the heat treatment jig has a short life.
  • the carbon material composed of the above-mentioned Si—B—C ternary sintered body is used as a heat treatment jig, oxidation of the heat treatment jig can be suppressed, but it can adhere to the counterpart material. is there. Therefore, these problems can be solved by using the carbon material of the present invention as a heat treatment jig.
  • the carbon material of the present invention can be used even in an environment where there is a high risk of oxidation exhaustion (for example, an environment exposed to a high temperature of 1200 ° C. in the presence of oxygen). Because of its excellent oxidation resistance, it can be used for a long time. Moreover, even if it contacts the target object of heat processing at the time of heat processing, the adhesion resulting from the borosilicate glass which arises on a carbonaceous base material can be prevented with a protective layer. For these reasons, the carbon material of the present invention can be suitably used as a jig for heat treatment.
  • the carbon material of the present invention is used only for the portion that comes into contact with the counterpart material, and the carbon that consists only of the Si—B—C ternary sintered body is used for the portion that does not come into contact with the counterpart material.
  • a structure using a material may be used. With such a structure, the manufacturing cost of the jig for heat treatment can be reduced.
  • a carbon material characterized in that a borosilicate glass layer having a boron / silicon mass ratio of 0.16 or less is formed on the surface of a carbonaceous substrate comprising a carbon-boron carbide-silicon carbide sintered body.
  • the borosilicate glass layer is desirably obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.50 or less at a temperature of 1200 ° C. or higher in an oxygen-existing atmosphere.
  • the borosilicate glass layer is preferably obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.40 or less at a temperature of 1100 ° C. or more and less than 1200 ° C. in an oxygen-existing atmosphere. . In this way, a borosilicate glass layer having a boron / silicon mass ratio of 0.16 or less can be formed.
  • the upper limit of the heat treatment temperature is preferably 1880 ° C. or lower, more preferably 1800 ° C. or lower, which is the boiling point of silicon monoxide.
  • a jig for heat treatment wherein a borosilicate glass layer having a boron / silicon mass ratio of 0.16 or less is formed on the surface of a carbonaceous substrate made of a carbon-boron carbide-silicon carbide sintered body. It is characterized by.
  • the borosilicate glass layer is desirably obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.50 or less at a temperature of 1200 ° C. or higher in an oxygen-existing atmosphere.
  • the borosilicate glass layer is preferably obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.40 or less at a temperature of 1100 ° C. or more and less than 1200 ° C. in an oxygen-existing atmosphere. .
  • the borosilicate glass layer is preferably used at a high temperature of 1000 ° C., and the boron / silicon mass ratio of the borosilicate glass layer is preferably 0.16 or less.
  • the borosilicate glass layer is used at a high temperature of 1100 ° C.
  • the boron / silicon mass ratio is desirably 0.095 or less, and is used at a high temperature of 1200 ° C., and the boron / silicon mass ratio of the borosilicate glass layer is 0.05 or less. desirable.
  • Example 1 First, 67% by mass of artificial graphite powder and 33% by mass of a resin binder (phenol resin) were mixed and pulverized to obtain a carbonaceous powder (particle size 5 to 100 ⁇ m). Next, a mixed powder containing boron carbide powder (average particle size 15 ⁇ m) and silicon carbide powder (average particle size 3 ⁇ m) in a weight ratio of 1: 4 is added to the carbonaceous powder. For 1 hour. Next, the mixed powder is molded at a pressure of 400 MPa, and further, this molded body is heat-treated at 900 ° C. for 1 hour in a non-oxidizing atmosphere to thereby sinter the Si—B—C ternary system. A carbonaceous substrate consisting of body was obtained. The composition of the obtained carbonaceous substrate was 71.2% by mass of carbon, 26.85% by mass of silicon, and 1.95% by mass of boron.
  • a resin binder phenol resin
  • a slurry was prepared by mixing and dispersing silicon powder (average particle size 40 ⁇ m) and a 10 wt% aqueous solution of polyvinyl alcohol (PVA) resin in a weight ratio of 8:10.
  • PVA polyvinyl alcohol
  • this slurry is applied to the surface of the carbonaceous substrate so as to have a thickness of about 0.1 mm, dried in a dryer at 100 ° C. for 1 hour, and further 1600 in a non-oxidizing atmosphere. Heat treatment was performed at 0 ° C. for 1 hour. Then, it cooled and took out.
  • a carbon material was obtained in which a protective layer (thickness 1.7 ⁇ m) made of silicon carbide was formed on the surface of a carbonaceous substrate made of a Si—B—C ternary sintered body.
  • FIG. 1 A cross-sectional SEM photograph of this carbon material is shown in FIG.
  • a whitish portion extending in the lateral direction is a protective layer 1 made of silicon carbide, and a carbonaceous substrate 2 is present below the protective layer 1.
  • some of the silicon carbide in the protective layer 1 penetrates into the pores of the carbonaceous substrate 2.
  • the white vertical and horizontal straight lines in FIG. 1 are scale lines, and the distance between the lines is 10 ⁇ m.
  • the carbon material produced in this way is hereinafter referred to as material A1.
  • Example 2 A carbon material was prepared in the same manner as in Example 1 except that the thickness of the protective layer was changed as shown in Table 1 below by changing the coating thickness of the slurry (about 0.4 to 10 mm). did.
  • the carbon materials thus produced are hereinafter referred to as materials A2 to A6.
  • Comparative Example 2 As the carbon material, an isotropic graphite material (IG-11 manufactured by Toyo Tanso Co., Ltd.) having a protective layer formed by the same method as in Example 1 was used. However, since the coating thickness of the slurry is different from that in Example 1, the thickness of the protective layer is different from that of the material A1.
  • the carbon material thus produced is hereinafter referred to as material Z2.
  • Example 3 A carbon material was produced in the same manner as in Example 1 except that the protective layer was not formed (that is, the carbon material was composed only of a Si—B—C ternary sintered body).
  • the carbon material thus produced is hereinafter referred to as material Z3.
  • Oxidation tests of the above materials A1 to A6 and Z1 to Z3 are performed under the following conditions.
  • the reason why the alumina dish is used in the adhesion test is that the alumina dish has a large surface irregularity and is easily surface-attached.
  • Oxidation test conditions The muffle furnace was heated to 1200 ° C in advance, and the alumina pan on which the materials A1 to A6 and Z1 to Z3 were placed was placed in the muffle furnace and left in the atmosphere at 1200 ° C for 1 hour. Then, the condition is that the alumina dish is cooled. The weights of the materials A1 to A6 and Z1 to Z3 were measured before and after the oxidation test.
  • Oxidation consumption rate [(weight of material after oxidation test ⁇ weight of material before oxidation test) / weight of material before oxidation test] ⁇ 100 (1)
  • the materials A1 to A6 in which the carbonaceous substrate is made of a Si—B—C ternary sintered body and a protective layer made of SiC is formed on the surface of the carbonaceous substrate are very low even if oxidation consumption is not recognized or there is oxidation consumption. Further, there is no adhesion to the alumina dish, or slight adhesion even if there is adhesion to the alumina dish.
  • the oxidation consumption rate is higher than the materials A1 to A6.
  • the material Z3 in which the carbonaceous base material is made of a Si—B—C ternary sintered body and the protective layer is not formed on the surface of the carbonaceous base material has a higher oxidation consumption rate than the materials Z1 and Z2. Although it was lower, the oxidation consumption rate was higher than that of the materials A1 to A6, and adhesion to the alumina dish was observed.
  • the carbonaceous substrate is made of a Si—B—C ternary sintered body
  • the protective layer made of SiC is made of a carbonaceous substrate. It can be seen that it is preferable to use a carbon material formed on the surface.
  • the SiC film thickness is preferably 5.3 ⁇ m or more, and particularly preferably 15.7 ⁇ m or more.
  • the manufacturing cost of a carbon material will become high if a SiC film thickness becomes large too much, it is preferable to regulate to 30 micrometers or less.
  • Example 1 Self-sintering carbon pulverized powder having an average particle size of 10 ⁇ m obtained by kneading and finely pulverizing coke powder and pitch, SiC powder having an average particle size of 3 ⁇ m, and B 4 C powder having an average particle size of 15 ⁇ m,
  • the mixing ratio was set to the mixing ratio (a) shown in Table 2 below, and these were mixed for 5 minutes with a stirring mixer in an air stream.
  • the obtained mixed powder was molded into a shape of 30 ⁇ 45 ⁇ 160 mm at 100 MPa, and then fired at 1100 ° C. in a reducing atmosphere to obtain a Si—B—C ternary oxidation resistant carbon composite material. It was.
  • the oxidation-resistant carbon composite material was processed into a 10 ⁇ 10 ⁇ 10 mm test piece, and then placed on an alumina cloth and heat-treated at 1200 ° C. for 1 hour in an air flow of 2 L / min.
  • a carbon composite material having a glass film formed on the material surface was obtained.
  • the carbon composite material thus produced is hereinafter referred to as material B1.
  • Examples 2 to 5 The carbon composite material was prepared in the same manner as in Example 1 except that the blending ratios of the carbon pulverized powder, SiC powder, and B 4 C powder were blends (b) to (e) shown in Table 2 below. Obtained.
  • the carbon composite materials thus produced are hereinafter referred to as materials B2 to B5, respectively.
  • Example 6 Carbon composite materials were obtained in the same manner as in Examples 2 to 5 except that the temperature during heat treatment in the air flow was 1100 ° C.
  • the carbon composite materials thus produced are hereinafter referred to as materials B6 to B9.
  • Example 2 A carbon composite material was obtained in the same manner as in Example 1 except that the temperature during heat treatment in the air flow was set to 1100 ° C.
  • the carbon composite material thus produced is hereinafter referred to as material Y.
  • B / Si ratio the ratio of carbon, SiC, and B 4 C, and the mass element concentration ratio of B and Si (hereinafter sometimes referred to as B / Si ratio) are shown in Table 2 below.
  • Example 1 Since the adhesion test of the materials B1 to B9 and Y was conducted, the results are shown in Table 3. The experiment was conducted at a predetermined test temperature (800 ° C., 1000 ° C., 1100 ° C., 1200 ° C. in the state where materials B1 to B9, Y and alumina cloth were in contact with each other in an air flow of 2 L / min. B9 and Y were allowed to stand at 1000 ° C. and 1100 ° C. only for 1 hour. After cooling, the presence or absence of adhesion between the materials B1 to B9 and Y and the alumina cloth was examined. The results are shown in Table 3. Table 3 also shows the B / Si mass concentration ratio before and after film formation.
  • the materials B1 to B9 have less adhesion between the test piece and the alumina cloth during the heat treatment after the film formation than the material Y. Specifically, material Y adheres during heat treatment at 1000 ° C., whereas materials B1 to B9 do not adhere at all during heat treatment at 1000 ° C. In particular, the materials B2 to B5 and B9 did not adhere even during the heat treatment at 1100 ° C. Among them, the material B5 did not adhere even during the heat treatment at 1200 ° C. This is thought to be due to the following reasons.
  • the Si—B—O glass film with less boron component approaches a high melting point SiO 2 composition, and thus has a higher softening point. As a result, it is considered that adhesion between the test piece and the alumina cloth hardly occurs.
  • material B has a B / Si ratio of 0.172 after film formation
  • materials B1 to B9 have a B / Si ratio of 0.042 to 0.137 after film formation. It is.
  • the materials B2 to B5 and B9 are 0.042 to 0.089, and among them, the materials B5 and B9 are 0.042 to 0.044.
  • FIG. 2 shows the relationship between the B / Si ratio, the use temperature, and the presence or absence of adhesion. As is clear from the figure, the smaller the B / Si ratio after film formation, the smaller the test piece and alumina during high temperature treatment. It can be seen that adhesion to the cloth is difficult to occur.
  • Example 2 The oxidation consumption rates of the materials B1 to B9, Z1, and Z2 were examined in the same manner as in the experiment of the first example, and the results are shown in Table 4.
  • the oxidation consumption rate after film formation shows the experimental result of 1 time
  • the oxidation consumption rate at the time of film formation is the number of times of the adhesion test under each condition (2 times for 1100 ° C film formation, 1200 ° C film formation) In the formation, the average value of 4 times) is described.
  • Table 4 also describes the B / Si ratio.
  • Table 5 shows the results of measurement of the film thickness of the glass film in the materials B1 to B9 and Y. In addition, the film thickness of the glass film was calculated
  • the present invention can be used as a jig for heat treatment.

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Abstract

The purpose of the present invention is to provide: a carbon material which exhibits excellent oxidation resistance and which is inhibited from adhering to a mating member such as an article to be treated; and a heat treatment jig. This carbon material is characterized by comprising: a carbonaceous substrate which consists of a carbon/boron carbide/silicon carbide sintered body; and a protective layer which is made of silicon carbide and which is formed on the carbonaceous substrate. It is preferable that a part of the silicon carbide constituting the protective layer permeates into the pores of the carbonaceous substrate. Further, it is preferable that the thickness of the protective layer is 5.3μm or more.

Description

炭素材料及びこの炭素材料を用いた熱処理用治具Carbon material and jig for heat treatment using the carbon material
　本発明は炭素材料及びこの炭素材料を用いた熱処理用治具に関するものである。 The present invention relates to a carbon material and a jig for heat treatment using the carbon material.
　炭素材料は耐熱性、耐薬品性、良電気伝導性、低熱膨張率、軽量であるなど優れた性質を有するため、産業界の広い分野で使用されている。ところが、炭素材料は、高温の空気中では酸化消耗を受け易いという欠点を有する。 Carbon materials have excellent properties such as heat resistance, chemical resistance, good electrical conductivity, low coefficient of thermal expansion, and light weight, so they are used in a wide range of industries. However, the carbon material has a drawback that it is susceptible to oxidation consumption in high-temperature air.
　そこで、Ｓｉ－Ｂ－Ｃ三元系の炭素材料が提案されている（特許文献１、非特許文献１、２参照）。当該炭素材料では、大気中１２００℃での酸化消耗率が数％以下である状態が長時間にわたって維持される、即ち、高い耐酸化特性を有することが知られている。これは、酸化によってガラス化する成分を炭素材料の内部に分散化しておくことで、炭素材料の酸化と同時にその内部および表面にガラス層が形成されるため、酸化の進行を阻止することができるからである。 Therefore, Si—B—C ternary carbon materials have been proposed (see Patent Document 1, Non-Patent Documents 1 and 2). It is known that the carbon material maintains a state in which the oxidation consumption rate at 1200 ° C. in the atmosphere is several percent or less for a long time, that is, has a high oxidation resistance. This is because a glass layer is formed inside and on the surface of the carbon material at the same time as the oxidation of the carbon material by dispersing the component to be vitrified by oxidation inside the carbon material, so that the progress of the oxidation can be prevented. Because.
特開平０８－１１９７４１号公報JP-A-08-119741
　しかしながら、Ｓｉ－Ｂ－Ｃ三元系の炭素材料は、その内部及び表面において低軟化点の硼珪酸ガラス層が形成されることで耐酸化性が発現するが、そのガラス層が粘着成分となり、炭素材料が他の材料と接触している場合に、炭素材料と他の材料とが付着する問題がある。即ち、Ｓｉ－Ｂ－Ｃ三元系の炭素材料は、硼素によって珪酸ガラスの軟化点を下げ、硼珪酸ガラス層で炭素材料の酸化進行を保護することができる一方、その軟化点の低いガラス層の存在によって他の材料と付着するという現象が生じる。このため、Ｓｉ－Ｂ－Ｃ三元系の炭素材料を炉内治具等に用いた場合には、炭素製品（炉内治具等）と接触する処理製品とが付着するという課題を有していた。 However, the Si—B—C ternary carbon material exhibits oxidation resistance when a borosilicate glass layer having a low softening point is formed inside and on the surface, but the glass layer serves as an adhesive component, When the carbon material is in contact with another material, there is a problem that the carbon material and the other material adhere to each other. That is, the Si—B—C ternary carbon material can lower the softening point of silicate glass with boron and protect the oxidation progress of the carbon material with the borosilicate glass layer, while the glass layer having a low softening point. The phenomenon of adhering to other materials occurs due to the presence of. For this reason, when a Si—B—C ternary carbon material is used for an in-furnace jig or the like, there is a problem that a carbon product (in-furnace jig or the like) and a treated product coming into contact with the carbon product are attached. It was.
　そこで本発明は、耐酸化性に優れるとともに、接触する処理製品等の相手材への付着を抑制することができる炭素材料及びこの炭素材料を用いた熱処理用治具を提供することを目的としている。 Then, this invention aims at providing the jig | tool for heat processing using this carbon material which can suppress adhesion to the other materials, such as a processed product which is excellent in oxidation resistance, and this carbon material. .
　上記目的を達成するために本発明の炭素材料は、炭素－炭化ホウ素－炭化ケイ素焼結体（以下、Ｓｉ－Ｂ－Ｃ三元系焼結体と称することがある）から成る炭素質基材の表面に、炭化ケイ素から成る保護層が形成されていることを特徴とする。 In order to achieve the above object, the carbon material of the present invention is a carbonaceous substrate comprising a carbon-boron carbide-silicon carbide sintered body (hereinafter sometimes referred to as a Si—B—C ternary sintered body). A protective layer made of silicon carbide is formed on the surface of the substrate.
　本発明によれば、耐酸化性に優れるとともに、炉内治具等として使用したときに処理製品等の相手材への付着が生じ難いといった優れた効果を奏する。 According to the present invention, the oxidation resistance is excellent, and when used as an in-furnace jig or the like, there is an excellent effect that adhesion to a counterpart material such as a processed product hardly occurs.
材料Ａ１の断面ＳＥＭ写真である。It is a cross-sectional SEM photograph of material A1. Ｂ／Ｓｉ比、使用温度と付着の有無との関係を示すグラフである。It is a graph which shows the relationship between B / Si ratio, use temperature, and the presence or absence of adhesion.
　本発明の炭素材料は、Ｓｉ－Ｂ－Ｃ三元系焼結体から成る炭素質基材の表面に、炭化ケイ素から成る保護層が形成されていることを特徴とする。
　炭素質基材の表面には炭化ケイ素から成る保護層が形成されているので、酸化性雰囲気中で本発明の炭素材料を用いた場合であっても、炭素質基材と酸素とが接触するのを抑制できる。したがって、本発明の炭素材料は高い耐酸化消耗性を発揮する。 The carbon material of the present invention is characterized in that a protective layer made of silicon carbide is formed on the surface of a carbonaceous substrate made of a Si—B—C ternary sintered body.
Since a protective layer made of silicon carbide is formed on the surface of the carbonaceous substrate, the carbonaceous substrate and oxygen come into contact with each other even when the carbon material of the present invention is used in an oxidizing atmosphere. Can be suppressed. Therefore, the carbon material of the present invention exhibits high oxidation wear resistance.
　また、炭素質基材と保護層とは熱膨張率が異なる等といった理由により、保護層の一部にクラックや剥離が生じて、炭素質基材が露出する場合がある。しかしながら、当該クラック等が生じた場合であっても、炭素質基材として耐酸化消耗性に優れたＳｉ－Ｂ－Ｃ三元系焼結体が用いられているので、酸化消耗による不具合の発生を長期にわたって抑制することが可能となる。 Also, the carbonaceous base material and the protective layer may be cracked or peeled off in part of the protective layer due to different thermal expansion coefficients, etc., and the carbonaceous base material may be exposed. However, even when such cracks occur, the use of Si-BC ternary sintered body with excellent resistance to oxidation and consumption as the carbonaceous substrate causes problems due to oxidation and consumption. Can be suppressed over a long period of time.
　加えて、Ｓｉ－Ｂ－Ｃ三元系焼結体は高温（約８００℃～約１２００℃）の空気に触れると低軟化点（約８００℃）の硼珪酸ガラスを形成するが、炭化ケイ素から成る保護層は高温（約８００℃～約１２００℃）の空気に触れると高軟化点（約１５００～１７００℃）の珪酸ガラス層を形成する。したがって、炭化ケイ素から成る保護層を有すれば炭素材料が高温状態に曝された場合であっても、炭素材料の表面に高軟化点の保護層が形成されるので、高温状態で炭素材料が他の部材と接触しても、炭素材料と他の部材とが付着するのを防止できる。
　ここで、ガラスの軟化点とはガラスが自重で顕著に軟化変形しはじめる温度で、約１０７．６ｄＰａ・ｓの粘度に相当する温度のことでありＪＩＳ　Ｒ　３１０３－１：２００１に規定される方法により測定することができる。 In addition, the Si—B—C ternary sintered body forms a low softening point (about 800 ° C.) borosilicate glass when exposed to high temperature (about 800 ° C. to about 1200 ° C.) air. The protective layer formed forms a silicate glass layer having a high softening point (about 1500 to 1700 ° C.) when exposed to air at a high temperature (about 800 ° C. to about 1200 ° C.). Therefore, if the carbon material has a protective layer made of silicon carbide, a protective layer with a high softening point is formed on the surface of the carbon material even when the carbon material is exposed to a high temperature state. Even if it contacts with another member, it can prevent that a carbon material and another member adhere.
Here, the softening point of the glass is a temperature at which the glass begins to be significantly softened and deformed by its own weight, and is a temperature corresponding to a viscosity of about 107.6 dPa · s, and is a method defined in JIS R 3103-1: 2001. Can be measured.
　上記炭化ケイ素のうち一部の炭化ケイ素は、上記炭素質基材の気孔中に浸透していることが望ましい。
　上記構成の如く、炭化ケイ素が炭素質基材の気孔中に浸透していれば、アンカー効果が発揮されるので、炭素質基材と保護層との密着強度が高くなる。 It is desirable that a part of the silicon carbide penetrates into the pores of the carbonaceous substrate.
If silicon carbide penetrates into the pores of the carbonaceous substrate as in the above configuration, the anchor effect is exerted, so that the adhesion strength between the carbonaceous substrate and the protective layer is increased.
　上記保護層の厚みが５．３μｍ以上であることが望ましい。
　保護層の厚みが５．３μｍ以上であれば、上述の作用効果が一層発揮される。 The thickness of the protective layer is desirably 5.3 μm or more.
If the thickness of the protective layer is 5.3 μm or more, the above-described effects are further exhibited.
　上述した炭素材料は、熱処理用治具として好適に用いることができる。炭素材料を熱処理用治具として用いる場合、常に還元雰囲気中で用いられるわけではなく、下記に示す理由等により、酸化性雰囲気（酸素の存在下で高温に曝される雰囲気）中で用いられる場合も多い。 The carbon material described above can be suitably used as a heat treatment jig. When carbon materials are used as heat treatment jigs, they are not always used in a reducing atmosphere, but for use in oxidizing atmospheres (atmospheres exposed to high temperatures in the presence of oxygen) for the following reasons. There are also many.
（１）金属製品やセラミックス製品の焼結工程、接着工程、或いは脱脂工程に用いられる熱処理炉では、製造工程サイクルの向上（短縮）のために、より高温で炉扉が開放される場合が多い。
（２）炉の気密性を高めるには設備コストが高くなる問題があるため、低い気密性での操炉が実施される場合も多い。
（３）高温での処理中に、製品から酸素成分が発生する場合がある。 (1) In heat treatment furnaces used in the sintering process, bonding process, or degreasing process of metal products and ceramic products, the furnace door is often opened at a higher temperature in order to improve (shorten) the manufacturing process cycle. .
(2) Since there is a problem that the equipment cost becomes high in order to increase the airtightness of the furnace, the operation with low airtightness is often performed.
(3) Oxygen components may be generated from the product during processing at high temperatures.
　このような条件下では、黒鉛等の炭素材料を熱処理用治具として用いることができない場合があり、また、用いることができたとしても、熱処理用治具が短寿命となるといった問題がある。
　この場合、前述のＳｉ－Ｂ－Ｃ三元系焼結体から成る炭素材料を熱処理用治具として用いれば、熱処理用治具の酸化を抑制することができるが、相手材に付着することがある。そこで、本発明の炭素材料を熱処理用治具として用いれば、これらの問題を解消できる。 Under such conditions, a carbon material such as graphite may not be used as a heat treatment jig, and even if it can be used, there is a problem that the heat treatment jig has a short life.
In this case, if the carbon material composed of the above-mentioned Si—B—C ternary sintered body is used as a heat treatment jig, oxidation of the heat treatment jig can be suppressed, but it can adhere to the counterpart material. is there. Therefore, these problems can be solved by using the carbon material of the present invention as a heat treatment jig.
　即ち、本発明の炭素材料を熱処理用治具として用いれば、酸化消耗の恐れが高い環境（例えば、酸素の存在下で１２００℃の高温に曝される環境）下で使用されても、炭素材料の耐酸化消耗性に優れるため長期間にわたる使用が可能となる。また、熱処理時に、熱処理の対象物と接触していても、炭素質基材で生じる硼珪酸ガラスに起因する付着を、保護層によって防ぐことができる。これらのことから、本発明の炭素材料は熱処理用治具として好適に使用可能となる。 That is, if the carbon material of the present invention is used as a jig for heat treatment, the carbon material can be used even in an environment where there is a high risk of oxidation exhaustion (for example, an environment exposed to a high temperature of 1200 ° C. in the presence of oxygen). Because of its excellent oxidation resistance, it can be used for a long time. Moreover, even if it contacts the target object of heat processing at the time of heat processing, the adhesion resulting from the borosilicate glass which arises on a carbonaceous base material can be prevented with a protective layer. For these reasons, the carbon material of the present invention can be suitably used as a jig for heat treatment.
　尚、熱処理用治具として用いる場合、相手材と接触する部分にのみ本発明の炭素材料を用い、相手材と接触しない部分については、Ｓｉ－Ｂ－Ｃ三元系焼結体のみから成る炭素材料（保護層が形成されていない炭素材料）を用いる構造であっても良い。このような構造であれば、熱処理用治具の製造コストを低減できる。 When used as a jig for heat treatment, the carbon material of the present invention is used only for the portion that comes into contact with the counterpart material, and the carbon that consists only of the Si—B—C ternary sintered body is used for the portion that does not come into contact with the counterpart material. A structure using a material (a carbon material on which a protective layer is not formed) may be used. With such a structure, the manufacturing cost of the jig for heat treatment can be reduced.
　炭素材料であって、炭素－炭化ホウ素－炭化ケイ素焼結体から成る炭素質基材の表面に、ホウ素／ケイ素の質量比が０．１６以下のホウ珪酸ガラス層が形成されていることを特徴とする。 A carbon material, characterized in that a borosilicate glass layer having a boron / silicon mass ratio of 0.16 or less is formed on the surface of a carbonaceous substrate comprising a carbon-boron carbide-silicon carbide sintered body. And
　上記ホウ珪酸ガラス層は、ホウ素／ケイ素の質量比が０．５０以下の炭素質基材を酸素存在雰囲気中で１２００℃以上の温度で熱処理して得られたものであることが望ましく、また、上記ホウ珪酸ガラス層は、ホウ素／ケイ素の質量比が０．４０以下の炭素質基材を酸素存在雰囲気中で１１００℃以上１２００℃未満の温度で熱処理して得られたものであることが望ましい。
　このようにして、ホウ素／ケイ素の質量比が０．１６以下のホウ珪酸ガラス層を形成することができる。
　尚、上記酸素存在雰囲気中での熱処理は、温度が高すぎるとホウ珪酸ガラス層が蒸発して失われる恐れがある。したがって、熱処理温度の上限は、一酸化ケイ素の沸点である１８８０℃以下が好ましく、より好ましくは１８００℃以下である。 The borosilicate glass layer is desirably obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.50 or less at a temperature of 1200 ° C. or higher in an oxygen-existing atmosphere. The borosilicate glass layer is preferably obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.40 or less at a temperature of 1100 ° C. or more and less than 1200 ° C. in an oxygen-existing atmosphere. .
In this way, a borosilicate glass layer having a boron / silicon mass ratio of 0.16 or less can be formed.
In the heat treatment in the oxygen-existing atmosphere, if the temperature is too high, the borosilicate glass layer may be evaporated and lost. Therefore, the upper limit of the heat treatment temperature is preferably 1880 ° C. or lower, more preferably 1800 ° C. or lower, which is the boiling point of silicon monoxide.
　熱処理用治具であって、炭素－炭化ホウ素－炭化ケイ素焼結体から成る炭素質基材の表面に、ホウ素／ケイ素の質量比が０．１６以下のホウ珪酸ガラス層が形成されていることを特徴とする。 A jig for heat treatment, wherein a borosilicate glass layer having a boron / silicon mass ratio of 0.16 or less is formed on the surface of a carbonaceous substrate made of a carbon-boron carbide-silicon carbide sintered body. It is characterized by.
　上記ホウ珪酸ガラス層は、ホウ素／ケイ素の質量比が０．５０以下の炭素質基材を酸素存在雰囲気中で１２００℃以上の温度で熱処理して得られたものであることが望ましく、また、上記ホウ珪酸ガラス層は、ホウ素／ケイ素の質量比が０．４０以下の炭素質基材を酸素存在雰囲気中で１１００℃以上１２００℃未満の温度で熱処理して得られたものであることが望ましい。 The borosilicate glass layer is desirably obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.50 or less at a temperature of 1200 ° C. or higher in an oxygen-existing atmosphere. The borosilicate glass layer is preferably obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.40 or less at a temperature of 1100 ° C. or more and less than 1200 ° C. in an oxygen-existing atmosphere. .
　また、１０００℃の高温下で用いられ、上記ホウ珪酸ガラス層のホウ素／ケイ素の質量比が０．１６以下であることが望ましく、また、１１００℃の高温下で用いられ、上記ホウ珪酸ガラス層のホウ素／ケイ素の質量比が０．０９５以下であることが望ましく、更に、１２００℃の高温下で用いられ、上記ホウ珪酸ガラス層のホウ素／ケイ素の質量比が０．０５以下であることが望ましい。 Further, the borosilicate glass layer is preferably used at a high temperature of 1000 ° C., and the boron / silicon mass ratio of the borosilicate glass layer is preferably 0.16 or less. The borosilicate glass layer is used at a high temperature of 1100 ° C. The boron / silicon mass ratio is desirably 0.095 or less, and is used at a high temperature of 1200 ° C., and the boron / silicon mass ratio of the borosilicate glass layer is 0.05 or less. desirable.
　　　　　　　　　　　　〔第１実施例〕
（実施例１）
　先ず、人造黒鉛粉６７質量％と樹脂バインダー（フェノール樹脂）３３質量％とを混捏し、粉砕することで炭素質粉末（粒子径５～１００μｍ）を得た。次に、この炭素質粉末に、炭化ホウ素粉（平均粒径１５μｍ）と炭化ケイ素粉（平均粒径３μｍ）とが重量比で１：４の割合で含まれた混合粉を加え、らいかい機で１時間混合した。次いで、当該混合した粉体を４００ＭＰａの圧力で金型成形し、更に、この成形体を非酸化性雰囲気下にて９００℃で１時間熱処理することによって、Ｓｉ－Ｂ－Ｃ三元系焼結体から成る炭素質基材を得た。得られた炭素質基材の組成は、炭素が７１．２質量％、ケイ素が２６．８５質量％、ホウ素が１．９５質量％であった。 [First embodiment]
Example 1
First, 67% by mass of artificial graphite powder and 33% by mass of a resin binder (phenol resin) were mixed and pulverized to obtain a carbonaceous powder (particle size 5 to 100 μm). Next, a mixed powder containing boron carbide powder (average particle size 15 μm) and silicon carbide powder (average particle size 3 μm) in a weight ratio of 1: 4 is added to the carbonaceous powder. For 1 hour. Next, the mixed powder is molded at a pressure of 400 MPa, and further, this molded body is heat-treated at 900 ° C. for 1 hour in a non-oxidizing atmosphere to thereby sinter the Si—B—C ternary system. A carbonaceous substrate consisting of body was obtained. The composition of the obtained carbonaceous substrate was 71.2% by mass of carbon, 26.85% by mass of silicon, and 1.95% by mass of boron.
　次に、ケイ素粉末（平均粒度４０μｍ）と、ポリビニルアルコール（ＰＶＡ）樹脂の１０重量％水溶液とを、重量比で８：１０の割合で混合分散させてスラリーを調製した。次いで、このスラリーを、上記炭素質基材の表面に厚みが約０．１ｍｍとなるように塗布し、乾燥機の中で１００℃、１時間で乾燥させ、さらに非酸化性雰囲気下にて１６００℃で１時間熱処理した。その後、冷却して取り出した。この一連の処理により、Ｓｉ－Ｂ－Ｃ三元系焼結体から成る炭素質基材の表面に、炭化ケイ素から成る保護層（厚さ１．７μｍ）が形成された炭素材料を得た。 Next, a slurry was prepared by mixing and dispersing silicon powder (average particle size 40 μm) and a 10 wt% aqueous solution of polyvinyl alcohol (PVA) resin in a weight ratio of 8:10. Next, this slurry is applied to the surface of the carbonaceous substrate so as to have a thickness of about 0.1 mm, dried in a dryer at 100 ° C. for 1 hour, and further 1600 in a non-oxidizing atmosphere. Heat treatment was performed at 0 ° C. for 1 hour. Then, it cooled and took out. By this series of treatments, a carbon material was obtained in which a protective layer (thickness 1.7 μm) made of silicon carbide was formed on the surface of a carbonaceous substrate made of a Si—B—C ternary sintered body.
　この炭素材料の断面ＳＥＭ写真を図１に示す。図１において、横方向に延びる白っぽい部位が炭化ケイ素から成る保護層１であり、この保護層１の下側に存在するのが、炭素質基材２である。図１から明らかなように、保護層１の炭化ケイ素のうち一部の炭化ケイ素は、上記炭素質基材２の気孔中に浸透していることがわかる。尚、図１における白い縦横の直線はスケール線であり、線間距離は１０μｍである。
　このようにして作製した炭素材料を、以下、材料Ａ１と称する。 A cross-sectional SEM photograph of this carbon material is shown in FIG. In FIG. 1, a whitish portion extending in the lateral direction is a protective layer 1 made of silicon carbide, and a carbonaceous substrate 2 is present below the protective layer 1. As can be seen from FIG. 1, some of the silicon carbide in the protective layer 1 penetrates into the pores of the carbonaceous substrate 2. The white vertical and horizontal straight lines in FIG. 1 are scale lines, and the distance between the lines is 10 μm.
The carbon material produced in this way is hereinafter referred to as material A1.
（実施例２～６）
　上記スラリーの塗布厚みを変える（約０．４～１０ｍｍ）ことにより、下記表１に示すように保護層の膜厚を変化させたこと以外は、上記実施例１と同様にして炭素材料を作製した。
　このようにして作製した炭素材料を、以下それぞれ、材料Ａ２～Ａ６と称する。 (Examples 2 to 6)
A carbon material was prepared in the same manner as in Example 1 except that the thickness of the protective layer was changed as shown in Table 1 below by changing the coating thickness of the slurry (about 0.4 to 10 mm). did.
The carbon materials thus produced are hereinafter referred to as materials A2 to A6.
（比較例１）
　炭素材料として、等方性黒鉛材（東洋炭素社製のＩＧ－１１であって、保護層が形成されていないもの）を用いた。
　このようにして作製した炭素材料を、以下、材料Ｚ１と称する。 (Comparative Example 1)
As the carbon material, an isotropic graphite material (IG-11 manufactured by Toyo Tanso Co., Ltd., with no protective layer formed) was used.
The carbon material thus produced is hereinafter referred to as material Z1.
（比較例２）
　炭素材料として、等方性黒鉛材（東洋炭素社製のＩＧ－１１）の表面に、上記実施例１と同様の方法で保護層を形成したものを用いた。但し、上記実施例１とはスラリーの塗布厚みが異なるので、保護層の膜厚は材料Ａ１と異なっている。
　このようにして作製した炭素材料を、以下、材料Ｚ２と称する。 (Comparative Example 2)
As the carbon material, an isotropic graphite material (IG-11 manufactured by Toyo Tanso Co., Ltd.) having a protective layer formed by the same method as in Example 1 was used. However, since the coating thickness of the slurry is different from that in Example 1, the thickness of the protective layer is different from that of the material A1.
The carbon material thus produced is hereinafter referred to as material Z2.
（比較例３）
　保護層を形成しなかったこと以外は、上記実施例１と同様にして炭素材料を作製した（即ち、炭素材料はＳｉ－Ｂ－Ｃ三元系焼結体のみから構成されている）。
　このようにして作製した炭素材料を、以下、材料Ｚ３と称する。 (Comparative Example 3)
A carbon material was produced in the same manner as in Example 1 except that the protective layer was not formed (that is, the carbon material was composed only of a Si—B—C ternary sintered body).
The carbon material thus produced is hereinafter referred to as material Z3.
（実験）
　上記材料Ａ１～Ａ６、Ｚ１～Ｚ３の酸化試験を下記の条件で行い、下記（１）式で示す酸化消耗率と、アルミナ製蒸発皿（以下、アルミナ皿と称することがある）への付着の有無について調べたので、それらの結果を表１に示す。尚、付着試験においてアルミナ皿を使用するのは、当該アルミナ皿は表面の凹凸が大きく、付着が起こり易い表面形状だからである。 (Experiment)
Oxidation tests of the above materials A1 to A6 and Z1 to Z3 are performed under the following conditions. The oxidation consumption rate represented by the following formula (1) and adhesion to an alumina evaporating dish (hereinafter sometimes referred to as an alumina dish) Since the presence or absence was examined, the results are shown in Table 1. The reason why the alumina dish is used in the adhesion test is that the alumina dish has a large surface irregularity and is easily surface-attached.
・酸化試験の条件
　マッフル炉を予め１２００℃まで加熱しておき、材料Ａ１～Ａ６、Ｚ１～Ｚ３が載置されたアルミナ皿を上記マッフル炉内に配置して、大気中１２００℃で１時間放置し、その後、アルミナ皿を冷却するという条件である。尚、酸化試験の前後で、材料Ａ１～Ａ６、Ｚ１～Ｚ３の重量を測定した。 Oxidation test conditions The muffle furnace was heated to 1200 ° C in advance, and the alumina pan on which the materials A1 to A6 and Z1 to Z3 were placed was placed in the muffle furnace and left in the atmosphere at 1200 ° C for 1 hour. Then, the condition is that the alumina dish is cooled. The weights of the materials A1 to A6 and Z1 to Z3 were measured before and after the oxidation test.
・酸化消耗率の算出
　酸化消耗率＝〔（酸化試験後の材料の重量―酸化試験前の材料の重量）／酸化試験前の材料の重量〕×１００・・・（１） ・ Calculation of oxidation consumption rate Oxidation consumption rate = [(weight of material after oxidation test−weight of material before oxidation test) / weight of material before oxidation test] × 100 (1)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記表１から明らかなように、炭素質基材がＳｉ－Ｂ－Ｃ三元系焼結体からなり、この炭素質基材の表面にＳｉＣから成る保護層が形成された材料Ａ１～Ａ６では、酸化消耗が認められないか、又は、酸化消耗があっても酸化消耗率は極めて低くなっている。更に、アルミナ皿への付着は無いか、又は、アルミナ皿への付着があっても若干の付着となっている。 As is clear from Table 1 above, the materials A1 to A6 in which the carbonaceous substrate is made of a Si—B—C ternary sintered body and a protective layer made of SiC is formed on the surface of the carbonaceous substrate. The oxidation consumption rate is very low even if oxidation consumption is not recognized or there is oxidation consumption. Further, there is no adhesion to the alumina dish, or slight adhesion even if there is adhesion to the alumina dish.
　これに対して、炭素質基材が黒鉛であり、この炭素質基材の表面に保護層が形成されていない材料Ｚ１では、アルミナ皿への付着は無いが、酸化消耗率が極めて高くなっている。また、炭素質基材が黒鉛であり、この炭素質基材の表面に保護層が形成されている材料Ｚ２では、アルミナ皿への付着は無く、材料Ｚ１よりも酸化消耗率が低くなっている。但し、材料Ａ１～Ａ６に比べると酸化消耗率が高くなっている。更に、炭素質基材がＳｉ－Ｂ－Ｃ三元系焼結体からなり、この炭素質基材の表面に保護層が形成されていない材料Ｚ３では、材料Ｚ１、Ｚ２よりも酸化消耗率が低くなっているものの、材料Ａ１～Ａ６に比べると酸化消耗率は高く、しかも、アルミナ皿への付着が認められた。 On the other hand, in the material Z1 in which the carbonaceous substrate is graphite and the protective layer is not formed on the surface of the carbonaceous substrate, there is no adhesion to the alumina dish, but the oxidation consumption rate is extremely high. Yes. Further, in the material Z2 in which the carbonaceous substrate is graphite and the protective layer is formed on the surface of the carbonaceous substrate, there is no adhesion to the alumina dish, and the oxidation consumption rate is lower than that of the material Z1. . However, the oxidation consumption rate is higher than the materials A1 to A6. Further, the material Z3 in which the carbonaceous base material is made of a Si—B—C ternary sintered body and the protective layer is not formed on the surface of the carbonaceous base material has a higher oxidation consumption rate than the materials Z1 and Z2. Although it was lower, the oxidation consumption rate was higher than that of the materials A1 to A6, and adhesion to the alumina dish was observed.
　以上の実験結果から、酸化性雰囲気で熱処理用治具等の材料としては、炭素質基材がＳｉ－Ｂ－Ｃ三元系焼結体からなり、ＳｉＣから成る保護層が炭素質基材の表面に形成されている炭素材料を用いるのが好ましいことが分かる。 From the above experimental results, as materials for heat treatment jigs and the like in an oxidizing atmosphere, the carbonaceous substrate is made of a Si—B—C ternary sintered body, and the protective layer made of SiC is made of a carbonaceous substrate. It can be seen that it is preferable to use a carbon material formed on the surface.
　また、材料Ａ１～Ａ６を比較した場合、材料Ａ１ではアルミナ皿への若干付着しているが、材料Ａ２～Ａ６ではアルミナ皿への付着は認められなかった。更に、材料Ａ１、Ａ２では酸化消耗が若干生じているが、材料Ａ３～Ａ６では酸化消耗が全く生じていなかった。これらのことから、ＳｉＣ膜厚は５．３μｍ以上であることが好ましく、特に、１５．７μｍ以上であることが好ましいことが分かる。尚、ＳｉＣ膜厚が大きくなり過ぎると、炭素材料の製造コストが高くなるので、３０μｍ以下に規制するのが好ましい。 Further, when the materials A1 to A6 were compared, the material A1 slightly adhered to the alumina dish, but the materials A2 to A6 did not adhere to the alumina dish. Further, although the materials A1 and A2 were slightly oxidized, the materials A3 to A6 were not oxidized at all. From these, it can be seen that the SiC film thickness is preferably 5.3 μm or more, and particularly preferably 15.7 μm or more. In addition, since the manufacturing cost of a carbon material will become high if a SiC film thickness becomes large too much, it is preferable to regulate to 30 micrometers or less.
　　　　　　　　　　　　〔第２実施例〕
（実施例１）
　先ず、コークス粉末とピッチを混練し微粉砕して得られた平均粒子径１０μｍの自己焼結性のカーボン粉砕粉と、平均粒子径３μｍのＳｉＣ粉末と、平均粒子径１５μｍのＢ４Ｃ粉末との配合比率を下記表２の配合（ａ）とし、これらを気流中撹拌混合機で５分間混合した。次に、得られた混合粉末を、ｌ００ＭＰａで３０×４５×１６０ｍｍの形状に成形した後、還元雰囲気中１１００℃で焼成し、Ｓｉ－Ｂ－Ｃ三元系の耐酸化性炭素複合材料を得た。次いで、該耐酸化性炭素複合材料を１０×１０×１０ｍｍの試験片に加工した後、アルミナクロスの上に載せて２Ｌ／ｍｉｎの空気フロー中、１２００℃で１時間熱処理した。これによって、素材表面にガラス被膜が形成された炭素複合材料を得た。
　このようにして作製した炭素複合材料を、以下、材料Ｂ１と称する。 [Second Embodiment]
Example 1
First, self-sintering carbon pulverized powder having an average particle size of 10 μm obtained by kneading and finely pulverizing coke powder and pitch, SiC powder having an average particle size of 3 μm, and B 4 C powder having an average particle size of 15 μm, The mixing ratio was set to the mixing ratio (a) shown in Table 2 below, and these were mixed for 5 minutes with a stirring mixer in an air stream. Next, the obtained mixed powder was molded into a shape of 30 × 45 × 160 mm at 100 MPa, and then fired at 1100 ° C. in a reducing atmosphere to obtain a Si—B—C ternary oxidation resistant carbon composite material. It was. Next, the oxidation-resistant carbon composite material was processed into a 10 × 10 × 10 mm test piece, and then placed on an alumina cloth and heat-treated at 1200 ° C. for 1 hour in an air flow of 2 L / min. Thus, a carbon composite material having a glass film formed on the material surface was obtained.
The carbon composite material thus produced is hereinafter referred to as material B1.
（実施例２～５）
　カーボン粉砕粉と、ＳｉＣ粉末と、Ｂ４Ｃ粉末との配合比率を、それぞれ、下記表２の配合（ｂ）～（ｅ）とした他は、上記実施例１と同様にして炭素複合材料を得た。
　このようにして作製した炭素複合材料を、以下それぞれ、材料Ｂ２～Ｂ５と称する。 (Examples 2 to 5)
The carbon composite material was prepared in the same manner as in Example 1 except that the blending ratios of the carbon pulverized powder, SiC powder, and B 4 C powder were blends (b) to (e) shown in Table 2 below. Obtained.
The carbon composite materials thus produced are hereinafter referred to as materials B2 to B5, respectively.
（実施例６～９）
　空気フロー中で熱処理する際の温度を１１００℃とした他は、それぞれ、上記実施例２～５と同様にして炭素複合材料を得た。
　このようにして作製した炭素複合材料を、以下それぞれ、材料Ｂ６～Ｂ９と称する。 (Examples 6 to 9)
Carbon composite materials were obtained in the same manner as in Examples 2 to 5 except that the temperature during heat treatment in the air flow was 1100 ° C.
The carbon composite materials thus produced are hereinafter referred to as materials B6 to B9.
（比較例）    
　空気フロー中で熱処理する際の温度を１１００℃とした他は、上記実施例１と同様にして炭素複合材料を得た。
　このようにして作製した炭素複合材料を、以下、材料Ｙと称する。 (Comparative example)
A carbon composite material was obtained in the same manner as in Example 1 except that the temperature during heat treatment in the air flow was set to 1100 ° C.
The carbon composite material thus produced is hereinafter referred to as material Y.
　ここで、カーボンとＳｉＣとＢ４Ｃとの割合、及び、ＢとＳｉとの質量元素濃度比（以下、Ｂ／Ｓｉ比と称することがある)を下記表２に示す。 Here, the ratio of carbon, SiC, and B 4 C, and the mass element concentration ratio of B and Si (hereinafter sometimes referred to as B / Si ratio) are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（実験１）
　材料Ｂ１～Ｂ９、Ｙの付着試験を行ったので、その結果を表３に示す。実験は、材料Ｂ１～Ｂ９、Ｙとアルミナクロスとが接した状態で、２Ｌ／ｍｉｎの空気フロー中で、所定の試験温度（８００℃、１０００℃、１１００℃、１２００℃。但し、材料Ｂ６～Ｂ９、Ｙでは、１０００℃、１１００℃のみ。）で１時間静置して、冷却後に材料Ｂ１～Ｂ９、Ｙとアルミナクロスとの付着の有無を調査したので、その結果を表３に示す。表３には、被膜形成前後のＢ／Ｓｉ質量濃度比も併せて示している。
　尚、表３から明らかなように、多くの場合、ガラス被膜形成時に試験片とアルミナクロスとが付着していた。そこで、付着試験では、ガラス被膜形成時に付着のなかった上面を下面として、アルミナクロスと接触させ、この状態で上記実験を行った。
  (Experiment 1)
Since the adhesion test of the materials B1 to B9 and Y was conducted, the results are shown in Table 3. The experiment was conducted at a predetermined test temperature (800 ° C., 1000 ° C., 1100 ° C., 1200 ° C. in the state where materials B1 to B9, Y and alumina cloth were in contact with each other in an air flow of 2 L / min. B9 and Y were allowed to stand at 1000 ° C. and 1100 ° C. only for 1 hour. After cooling, the presence or absence of adhesion between the materials B1 to B9 and Y and the alumina cloth was examined. The results are shown in Table 3. Table 3 also shows the B / Si mass concentration ratio before and after film formation.
As apparent from Table 3, in many cases, the test piece and the alumina cloth adhered to each other when the glass film was formed. Therefore, in the adhesion test, the above experiment was performed in this state by bringing the upper surface, which was not adhered when the glass coating was formed, into contact with the alumina cloth.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３から明らかなように、材料Ｂ１～Ｂ９は材料Ｙに比べて、被膜形成後の熱処理時において、試験片とアルミナクロスとの付着が抑制されているのがわかる。具体的には、材料Ｙでは、１０００℃での熱処理時に付着しているのに対して、材料Ｂ１～Ｂ９では、１０００℃での熱処理時には全て付着していない。特に、材料Ｂ２～Ｂ５、Ｂ９では、１１００℃での熱処理時でも付着しておらず、その中でも、材料Ｂ５では、１２００℃での熱処理時でも付着していなかった。これは、以下に示す理由によるものと考えられる As is apparent from Table 3, it can be seen that the materials B1 to B9 have less adhesion between the test piece and the alumina cloth during the heat treatment after the film formation than the material Y. Specifically, material Y adheres during heat treatment at 1000 ° C., whereas materials B1 to B9 do not adhere at all during heat treatment at 1000 ° C. In particular, the materials B2 to B5 and B9 did not adhere even during the heat treatment at 1100 ° C. Among them, the material B5 did not adhere even during the heat treatment at 1200 ° C. This is thought to be due to the following reasons.
　ホウ素化合物を大気中(酸素存在下)で加熱すると、５００℃以上で揮発性の酸化ホウ素（Ｂ２Ｏ３）を生成し、ホウ素成分濃度が低下する。この現象を利用し、Ｓｉ－Ｂ－Ｃ三元系の耐酸化炭素複合材料を大気中で熱処理して、基板（材料）表面にホウ素成分の少ないＳｉ－Ｂ－Ｏガラス被膜を形成する。その場合、当該被膜を形成するための熱処理温度が高いほど、Ｂ２Ｏ３の蒸発が速く進む。このため、同じ１時間の熱処理時間でも、熱処理温度が高いほど、ホウ素成分がより少ないＳｉ－Ｂ－Ｏガラス被膜が生成する。加えて、熱処理前のホウ素の量が少ないほど、ホウ素成分がより少ないＳｉ－Ｂ－Ｏガラス被膜が生成する。そして、当該ホウ素成分がより少ないＳｉ－Ｂ－Ｏガラス被膜は、高融点のＳｉＯ２組成に近づくため、軟化点が高くなる。この結果、試験片とアルミナクロスとの付着が生じ難くなるものと考えられる。 When the boron compound is heated in the atmosphere (in the presence of oxygen), volatile boron oxide (B 2 O 3 ) is generated at 500 ° C. or higher, and the boron component concentration decreases. Utilizing this phenomenon, a Si—B—C ternary oxidation resistant carbon composite material is heat-treated in the atmosphere to form a Si—B—O glass film having a small boron component on the surface of the substrate (material). In that case, the higher the heat treatment temperature for forming the film, the faster the evaporation of B 2 O 3 . For this reason, even with the same heat treatment time of 1 hour, the higher the heat treatment temperature is, the more Si—B—O glass film with fewer boron components is produced. In addition, the smaller the amount of boron before heat treatment, the more Si—B—O glass coatings with fewer boron components are produced. The Si—B—O glass film with less boron component approaches a high melting point SiO 2 composition, and thus has a higher softening point. As a result, it is considered that adhesion between the test piece and the alumina cloth hardly occurs.
　具体的には、材料Ｙでは、被膜形成後のＢ／Ｓｉ比が０．１７２であるのに対して、材料Ｂ１～Ｂ９では、被膜形成後のＢ／Ｓｉ比が０．０４２～０．１３７である。特に、材料Ｂ２～Ｂ５、Ｂ９では、０．０４２～０．０８９であり、その中でも、材料Ｂ５、Ｂ９では０．０４２～０．０４４となっている。
　Ｂ／Ｓｉ比、使用温度と付着の有無との関係を図２に示したが、同図から明らかなように、被膜形成後のＢ／Ｓｉ比が小さくなるほど、高温処理時における試験片とアルミナクロスとの付着が生じ難くなっていることがわかる。 Specifically, material B has a B / Si ratio of 0.172 after film formation, whereas materials B1 to B9 have a B / Si ratio of 0.042 to 0.137 after film formation. It is. In particular, the materials B2 to B5 and B9 are 0.042 to 0.089, and among them, the materials B5 and B9 are 0.042 to 0.044.
FIG. 2 shows the relationship between the B / Si ratio, the use temperature, and the presence or absence of adhesion. As is clear from the figure, the smaller the B / Si ratio after film formation, the smaller the test piece and alumina during high temperature treatment. It can be seen that adhesion to the cloth is difficult to occur.
（実験２）
　材料Ｂ１～Ｂ９、Ｚ１、Ｚ２の酸化消耗率を、上記第１実施例の実験と同様にして調べたので、その結果を表４に示す。尚、被膜形成後の酸化消耗率は、１回の実験結果を示しているが、被膜形成時の酸化消耗率は、各条件での付着試験回数（１１００℃被膜形成では２回、１２００℃被膜形成では４回）の平均値を記載している。また、表４には、Ｂ／Ｓｉ比についても記載している。 (Experiment 2)
The oxidation consumption rates of the materials B1 to B9, Z1, and Z2 were examined in the same manner as in the experiment of the first example, and the results are shown in Table 4. In addition, although the oxidation consumption rate after film formation shows the experimental result of 1 time, the oxidation consumption rate at the time of film formation is the number of times of the adhesion test under each condition (2 times for 1100 ° C film formation, 1200 ° C film formation) In the formation, the average value of 4 times) is described. Table 4 also describes the B / Si ratio.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　被膜形成後の酸化消耗率試験において、材料Ｂ１～Ｂ９は材料Ｚ１、Ｚ２に比べて、高い耐酸化消耗性を示すことがわかる。 In the oxidation consumption rate test after film formation, it can be seen that the materials B1 to B9 exhibit higher oxidation consumption resistance than the materials Z1 and Z2.
（実験３）
　材料Ｂ１～Ｂ９、Ｙにおけるガラス被膜の膜厚を測定したので、その結果を表５に示す。尚、ガラス被膜の膜厚は各材料のＳＥＭ写真から求めた。 (Experiment 3)
Table 5 shows the results of measurement of the film thickness of the glass film in the materials B1 to B9 and Y. In addition, the film thickness of the glass film was calculated | required from the SEM photograph of each material.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表５から明らかなように、ガラス被膜（ホウケイ酸ガラス被膜）の膜厚が１５μｍの材料Ｂ１、Ｂ２、Ｂ６であっても、上記実験２に示したように、酸化消耗は十分に抑制されている。したがって、ガラス被膜の膜厚は１５μｍ以上あれば十分であることがわかる。尚、材料Ｂ８、Ｂ９で特に膜厚が大きくなっているのは、被膜形成時に酸化消耗が大きく、カーボンが焼失する過程で取り残されたＳｉＣとＢ４Ｃが多いため考えられる As is clear from Table 5, even in the case of materials B1, B2, and B6 having a glass film (borosilicate glass film) thickness of 15 μm, as shown in Experiment 2, the oxidation consumption was sufficiently suppressed. Yes. Therefore, it can be seen that it is sufficient if the film thickness of the glass coating is 15 μm or more. Note that the film thicknesses of the materials B8 and B9 are particularly large because the oxidation consumption is large during the formation of the film, and there are a lot of SiC and B 4 C left behind in the process of carbon burning.
　本発明は熱処理用治具等として用いることができる。 The present invention can be used as a jig for heat treatment.
　　１　保護層
　　２　炭素質基材 1 Protective layer 2 Carbonaceous substrate

Claims (13)

  1. 　炭素－炭化ホウ素－炭化ケイ素焼結体から成る炭素質基材の表面に、炭化ケイ素から成る保護層が形成されていることを特徴とする炭素材料。 A carbon material characterized in that a protective layer made of silicon carbide is formed on the surface of a carbonaceous substrate made of a sintered body of carbon-boron carbide-silicon carbide.
  2. 　上記炭化ケイ素のうち一部の炭化ケイ素は、上記炭素質基材の気孔中に浸透している、請求項１に記載の炭素材料。 2. The carbon material according to claim 1, wherein a part of the silicon carbide penetrates into pores of the carbonaceous substrate.
  3. 　上記保護層の厚みが５．３μｍ以上である、請求項１又は２に記載の炭素材料。 The carbon material according to claim 1 or 2, wherein the protective layer has a thickness of 5.3 µm or more.
  4. 　請求項１～３の何れか1項に記載の炭素材料が用いられることを特徴とする熱処理用治具。 A heat treatment jig characterized in that the carbon material according to any one of claims 1 to 3 is used.
  5. 　炭素－炭化ホウ素－炭化ケイ素焼結体から成る炭素質基材の表面に、ホウ素／ケイ素の質量比が０．１６以下のホウ珪酸ガラス層が形成されていることを特徴とする炭素材料。 A carbon material characterized in that a borosilicate glass layer having a boron / silicon mass ratio of 0.16 or less is formed on the surface of a carbonaceous substrate made of a carbon-boron carbide-silicon carbide sintered body.
  6. 　上記ホウ珪酸ガラス層は、ホウ素／ケイ素の質量比が０．５０以下の炭素質基材を酸素存在雰囲気中で１２００℃以上の温度で熱処理して得られたものである、請求項５に記載の炭素材料。 The said borosilicate glass layer is a thing obtained by heat-treating the carbonaceous base material whose mass ratio of boron / silicon is 0.50 or less at the temperature of 1200 degreeC or more in oxygen presence atmosphere. Carbon material.
  7. 　上記ホウ珪酸ガラス層は、ホウ素／ケイ素の質量比が０．４０以下の炭素質基材を酸素存在雰囲気中で１１００℃以上１２００℃未満の温度で熱処理して得られたものである、請求項５に記載の炭素材料。 The borosilicate glass layer is obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.40 or less at a temperature of 1100 ° C or more and less than 1200 ° C in an oxygen-existing atmosphere. 5. The carbon material according to 5.
  8. 　炭素－炭化ホウ素－炭化ケイ素焼結体から成る炭素質基材の表面に、ホウ素／ケイ素の質量比が０．１６以下のホウ珪酸ガラス層が形成されていることを特徴とする熱処理用治具。 A heat treatment jig, characterized in that a borosilicate glass layer having a boron / silicon mass ratio of 0.16 or less is formed on the surface of a carbonaceous substrate made of a carbon-boron carbide-silicon carbide sintered body. .
  9. 　上記ホウ珪酸ガラス層は、ホウ素／ケイ素の質量比が０．５０以下の炭素質基材を酸素存在雰囲気中で１２００℃以上の温度で熱処理して得られたものである、請求項８に記載の熱処理用治具。 The said borosilicate glass layer is a thing obtained by heat-processing the carbonaceous base material whose mass ratio of boron / silicon is 0.50 or less at the temperature of 1200 degreeC or more in oxygen presence atmosphere. Heat treatment jig.
  10. 　上記ホウ珪酸ガラス層は、ホウ素／ケイ素の質量比が０．４０以下の炭素質基材を酸素存在雰囲気中で１１００℃以上１２００℃未満の温度で熱処理して得られたものである、請求項８に記載の熱処理用治具。 The borosilicate glass layer is obtained by heat-treating a carbonaceous substrate having a boron / silicon mass ratio of 0.40 or less at a temperature of 1100 ° C or more and less than 1200 ° C in an oxygen-existing atmosphere. The jig for heat treatment as described in 8.
  11. 　１０００℃の高温下で用いられ、上記ホウ珪酸ガラス層のホウ素／ケイ素の質量比が０．１６以下である、請求項８～１０の何れか１項に記載の熱処理用治具。 The heat treatment jig according to any one of claims 8 to 10, wherein the jig is used at a high temperature of 1000 ° C, and the boron / silicon mass ratio of the borosilicate glass layer is 0.16 or less.
  12. 　１１００℃の高温下で用いられ、上記ホウ珪酸ガラス層のホウ素／ケイ素の質量比が０．０９５以下である、請求項８～１０の何れか１項に記載の熱処理用治具。 The heat treatment jig according to any one of claims 8 to 10, wherein the jig is used at a high temperature of 1100 ° C, and the boron / silicon mass ratio of the borosilicate glass layer is 0.095 or less.
  13. 　１２００℃の高温下で用いられ、上記ホウ珪酸ガラス層のホウ素／ケイ素の質量比が０．０５以下である、請求項８～１０の何れか１項に記載の熱処理用治具。 The jig for heat treatment according to any one of claims 8 to 10, which is used at a high temperature of 1200 ° C and has a boron / silicon mass ratio of 0.05 or less in the borosilicate glass layer.
PCT/JP2014/066804 2013-08-23 2014-06-25 Carbon material and heat treatment jig using said carbon material WO2015025612A1 (en)

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JPH08119741A (en) * 1994-10-17 1996-05-14 Toyo Tanso Kk Carbon-boron carbide sintered compact and carbon-boron carbide-silicon carbide sintered compact
JPH11180788A (en) * 1997-12-18 1999-07-06 Toyo Tanso Kk Oxidation resistant carbon-silicon carbide composite material and heating part using the same
JP2000119081A (en) * 1998-10-15 2000-04-25 Kurosaki Refract Co Ltd Carbon material having multilayer structure and its production
JP2006514912A (en) * 2003-03-26 2006-05-18 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド Silicon carbide ceramic member having an oxide layer

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JPS59131576A (en) * 1983-01-19 1984-07-28 工業技術院長 Acid-resistant high strength carbon material
JPH08119741A (en) * 1994-10-17 1996-05-14 Toyo Tanso Kk Carbon-boron carbide sintered compact and carbon-boron carbide-silicon carbide sintered compact
JPH11180788A (en) * 1997-12-18 1999-07-06 Toyo Tanso Kk Oxidation resistant carbon-silicon carbide composite material and heating part using the same
JP2000119081A (en) * 1998-10-15 2000-04-25 Kurosaki Refract Co Ltd Carbon material having multilayer structure and its production
JP2006514912A (en) * 2003-03-26 2006-05-18 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド Silicon carbide ceramic member having an oxide layer

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