WO2011027756A1 - 炭化ケイ素被覆炭素基材の製造方法及び炭化ケイ素被覆炭素基材並びに炭化ケイ素炭素複合焼結体、セラミックス被覆炭化ケイ素炭素複合焼結体及び炭化ケイ素炭素複合焼結体の製造方法 - Google Patents

炭化ケイ素被覆炭素基材の製造方法及び炭化ケイ素被覆炭素基材並びに炭化ケイ素炭素複合焼結体、セラミックス被覆炭化ケイ素炭素複合焼結体及び炭化ケイ素炭素複合焼結体の製造方法 Download PDF

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WO2011027756A1
WO2011027756A1 PCT/JP2010/064871 JP2010064871W WO2011027756A1 WO 2011027756 A1 WO2011027756 A1 WO 2011027756A1 JP 2010064871 W JP2010064871 W JP 2010064871W WO 2011027756 A1 WO2011027756 A1 WO 2011027756A1
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Prior art keywords
silicon carbide
carbon
coated
base material
sintered body
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PCT/JP2010/064871
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English (en)
French (fr)
Japanese (ja)
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中村　正治
宮本　欽生
東城　哲朗
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Toyo Tanso Co Ltd
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Toyo Tanso Co Ltd
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Priority to EP20100813705 priority Critical patent/EP2474514A4/en
Priority to US13/392,593 priority patent/US9085493B2/en
Priority to RU2012112935/03A priority patent/RU2012112935A/ru
Priority to CN201080039227.7A priority patent/CN102482165B/zh
Publication of WO2011027756A1 publication Critical patent/WO2011027756A1/ja
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Definitions

  • the present invention relates to a method for producing a silicon carbide-coated carbon substrate in which the surface of a carbon substrate such as graphite is coated with silicon carbide, a silicon carbide-coated carbon substrate, a silicon carbide-carbon composite sintered body, and a ceramic-coated silicon carbide-carbon composite firing. Concerning union.
  • carbon materials have low specific gravity, excellent heat resistance, corrosion resistance, slidability, electrical conductivity, thermal conductivity, and workability, and are used in a wide range of fields such as semiconductors, metallurgy, machinery, electricity, and nuclear power. ing.
  • Patent Documents 1 to 3 disclose methods for improving oxidation resistance by forming a silicon carbide film on the surface of a carbon-based material.
  • a chemical vapor deposition method (hereinafter referred to as a CVD method) for depositing silicon carbide generated by a gas phase reaction, or a reaction with a silicon component using carbon of a substrate as a reaction source.
  • a conversion method for forming silicon carbide (hereinafter referred to as CVR method) is used.
  • Patent Document 4 As a composite material of silicon carbide and a carbon material, a silicon carbide carbon sintered body in which silicon carbide fine powder and graphite particles are mixed and sintered at high density by plasma discharge sintering has been proposed (Patent Document 4). ).
  • Patent Document 5 it is proposed to coat the surface of a carbon nanotube with silicon carbide by a CVD method or a CVR method.
  • Patent Document 6 it is proposed to coat the surface of diamond with a silicon carbide film by a CVD method or a CVR method.
  • An object of the present invention is to provide a method for producing a silicon carbide-coated carbon base material capable of densely and uniformly coating a silicon carbide coating on the surface of a carbon base material such as graphite, and a carbonization produced by the production method.
  • An object of the present invention is to provide a silicon-coated carbon base material, and a silicon carbide-carbon composite sintered body that can be produced using the silicon carbide-coated carbon base material.
  • the silicon carbide was coated by forming a silicon carbide by reacting the surface of the carbon substrate with SiO gas in an atmosphere of a temperature of 1400 to 1600 ° C. and a pressure of 1 to 150 Pa to prepare a material. And a step of manufacturing a carbon substrate.
  • Carbon base material in the present invention includes a base portion made of SP 2 carbon structure having no dangling bonds, and an edge portion consisting of SP 2 carbon structure having a dangling bond on the surface.
  • a silicon carbide coating cannot be formed uniformly when a silicon carbide coating is formed on the surface of a carbon substrate such as graphite by a CVD method or a CVR method, on the surface of, there are an edge portion consisting of SP 2 carbon structure having a dangling bond.
  • reaction activity of the edge portion is high, the case of forming the silicon carbide by the CVD method and the CVR method, the reaction activity It was found that a uniform coating cannot be formed because the silicon carbide coating is preferentially formed at the high edge portion.
  • the SP 2 carbon structure has three bonds, and all three bonds are involved in the bond at the base, but one or two of the three bonds are bonded at the edge. It is not in a state. For this reason, it is considered that the reaction activity is high in the edge portion.
  • a silicon carbide film is likely to be preferentially formed at the edge portion, and a uniform film is not formed. Further, when a silicon carbide film is formed by the CVD method, a porous film having a large amount of precipitated particles and a large number of voids is formed, making it difficult to form a dense silicon carbide film uniformly.
  • silicon carbide is formed by reacting the surface of the carbon substrate with SiO gas in an atmosphere at a temperature of 1400 to 1600 ° C. and a pressure of 1 to 150 Pa. Therefore, the silicon carbide film of the present invention is formed by the CVR method.
  • a silicon carbide coating is formed on the surface of a carbon substrate having a base portion and an edge portion by forming a silicon carbide coating by a CVR method in an atmosphere at a temperature of 1400 to 1600 ° C. and a pressure of 1 to 150 Pa. And can be formed uniformly.
  • the pressure is less than 1 Pa, the formation rate of the silicon carbide film by the CVR method is slow, which is not preferable.
  • the pressure exceeds 150 Pa, a silicon carbide film is easily formed by the CVD method, and a dense and uniform film cannot be formed.
  • Examples of the carbon substrate in the present invention include a graphite substrate. Since graphite has an SP 2 carbon structure, a base portion and an edge portion are present on the surface thereof.
  • the carbon substrate in the present invention may be in a block form or a particulate form. Accordingly, the carbon substrate may be carbon particles. In the case of carbon particles, carbon particles having an average particle diameter in the range of 50 nm to 500 ⁇ m are preferably used.
  • the SiO gas can be generated from a SiO source disposed together with the carbon substrate.
  • a SiO source include SiO particles.
  • the carbon substrate and the SiO source are placed in a crucible as a reaction vessel, and the crucible is placed in a firing furnace, whereby the inside of the crucible can be heated and the inside of the crucible can be exhausted.
  • a silicon carbide coated carbon substrate of the present invention includes: a base portion made of SP 2 carbon structure having no dangling bonds, the surface of the carbon substrate having an edge portion consisting of SP 2 carbon structure having a dangling bond on the surface Is a carbon substrate whose surface is coated with a silicon carbide layer by reacting with a silicon component to form silicon carbide, wherein the thickness of the silicon carbide layer is 20 ⁇ m or less.
  • the thickness of the silicon carbide layer is 20 ⁇ m or less. Even if the thickness of the silicon carbide layer is 20 ⁇ m or less, silicon carbide is uniformly and densely formed.
  • Such a silicon carbide-coated carbon substrate of the present invention can be produced by the production method of the present invention.
  • the thickness of the silicon carbide layer is more preferably in the range of 1 nm to 20 ⁇ m, and further preferably in the range of 5 nm to 20 ⁇ m.
  • Examples of the carbon substrate in the silicon carbide-coated carbon substrate of the present invention include a graphite substrate. Further, the carbon substrate may be carbon particles as described above. In this case, the average particle diameter of the carbon particles is preferably in the range of 50 nm to 500 ⁇ m.
  • the silicon carbide-coated carbon substrate of the present invention has a weight loss of less than 5% by heating in air at 650 ° C. for 1 hour. Since the silicon carbide layer is densely and uniformly formed on the surface, the weight loss under the above conditions can be less than 5% by weight.
  • the silicon carbide-carbon composite sintered body of the present invention is a silicon carbide-carbon composite sintered body obtained by sintering carbon substrate particles coated with silicon carbide, and has a relative density of 90 to 100%.
  • the total content of Al, Be, B and Se is less than 0.1% by weight.
  • the silicon carbide carbon composite sintered body of the present invention can be obtained by sintering the silicon carbide-coated carbon base material of the present invention. Since the silicon carbide-coated carbon substrate of the present invention has a dense silicon carbide film uniformly formed on the surface thereof, it can be sintered at a low temperature of 2200 ° C. or less without using a sintering aid. . For this reason, the relative density can be 90 to 100%. Further, the total content of Al, Be, B and Se, which are components of the sintering aid, can be made less than 0.1% by weight.
  • Examples of the carbon substrate particles used in the silicon carbide carbon composite sintered body of the present invention include graphite particles.
  • the average particle size of the carbon base particles is preferably in the range of 50 nm to 500 ⁇ m.
  • the thickness of the silicon carbide layer on the surface of the carbon base particle is preferably in the range of 1 nm to 20 ⁇ m, more preferably in the range of 200 nm to 10 ⁇ m, and further preferably in the range of 500 nm to 5 ⁇ m.
  • the ceramic-coated silicon carbide carbon composite sintered body of the present invention is characterized in that a ceramic coating layer is formed on at least part of the surface of the silicon carbide carbon composite fired body.
  • the method for producing a silicon carbide carbon composite sintered body of the present invention is a method for producing the silicon carbide carbon composite sintered body of the present invention, and is characterized by sintering at a temperature of 2200 ° C. or lower.
  • the silicon carbide-coated carbon base material of the present invention since the silicon carbide-coated carbon base material of the present invention has a dense silicon carbide film uniformly formed on the surface, it can be sintered at a low temperature of 2200 ° C. or lower. As the sintering temperature, a temperature of 1600 to 2200 ° C. is generally mentioned.
  • sintering can be performed at a temperature of 2200 ° C. or less without using a sintering aid. Since sintering can be performed without using a sintering aid, a dense silicon carbide carbon composite sintered body having high purity and low total content of Al, Be, B and Se can be produced.
  • a carbon silicon coating can be formed densely and uniformly on the surface of a carbon substrate such as graphite.
  • the silicon carbide coated carbon substrate of the present invention has a silicon carbide layer thickness of 20 ⁇ m or less. Therefore, a dense silicon carbide carbon composite sintered body having a high relative density can be produced.
  • the silicon carbide carbon composite sintered body of the present invention has a relative density of 90 to 100%, and the total content of Al, Be, B and Se is less than 0.1% by weight. For this reason, it can be set as the precise
  • the ceramic coating layer is formed on at least a part of the surface of the silicon carbide carbon composite fired body. It is possible to easily sinter silicon carbide contained therein to form a ceramic coating layer with extremely high adhesion.
  • the silicon carbide carbon composite sintered body of the present invention can be produced efficiently.
  • FIG. 1 is a schematic cross-sectional view showing an arrangement state in a crucible in an embodiment according to the present invention.
  • FIG. 2 is a cross-sectional view showing a carbon substrate.
  • FIG. 3 is a cross-sectional view showing a silicon carbide-coated carbon substrate.
  • FIG. 4 is a scanning electron micrograph (magnification 2500 times) showing silicon carbide-coated graphite particles in an example according to the present invention.
  • FIG. 5 is a scanning electron micrograph (magnification 25000 times) showing silicon carbide on the surface of silicon carbide-coated graphite particles in an example according to the present invention.
  • FIG. 6 is a scanning electron micrograph (magnification 2500 times) showing silicon carbide-coated graphite particles of a comparative example.
  • FIG. 1 is a schematic cross-sectional view showing an arrangement state in a crucible in an embodiment according to the present invention.
  • FIG. 2 is a cross-sectional view showing a carbon substrate.
  • FIG. 7 is a scanning electron micrograph (magnification 25000 times) showing silicon carbide on the surface of silicon carbide-coated graphite particles in a comparative example.
  • FIG. 8 is a scanning electron micrograph (magnification 25000 times) showing silicon carbide on the surface of silicon carbide-coated graphite particles in an example according to the present invention.
  • FIG. 9 is a scanning electron micrograph (magnification 25000 times) showing silicon carbide on the surface of silicon carbide-coated graphite particles in a comparative example.
  • FIG. 10 is a scanning electron micrograph (magnification 5000 times) showing the uncoated graphite particles used in the examples according to the present invention.
  • FIG. 11 is a scanning electron micrograph (magnification 2500 times) showing silicon carbide-coated graphite particles in an example according to the present invention.
  • FIG. 12 is a scanning electron micrograph (magnification 2500 times) showing silicon carbide-coated graphite particles in a comparative example.
  • FIG. 13 is a scanning electron micrograph (magnification 5000 times) showing silicon carbide-coated graphite particles in a comparative example.
  • FIG. 14 is a diagram showing a weight reduction rate with respect to a heating temperature of silicon carbide-coated graphite particles in an example according to the present invention.
  • FIG. 15 is a schematic cross-sectional view showing a silicon carbide carbon composite sintered body according to the present invention.
  • FIG. 16 is a schematic cross-sectional view showing a ceramic-coated silicon carbide carbon composite sintered body according to the present invention.
  • FIG. 1 is a schematic cross-sectional view showing an arrangement state in a crucible used for silicon carbide coating treatment.
  • the carbon sheet 2 was arrange
  • SiO powder 3 was arrange
  • a carbon felt 4 was disposed on the SiO powder 3, and graphite particles 5 were disposed on the carbon felt 4 as a carbon substrate.
  • a carbon felt 6 was disposed on the graphite particles 5, and a carbon sheet 7 was disposed thereon.
  • the graphite crucible 1 is used, but an alumina crucible may be used.
  • the graphite crucible 1 arranged as shown in FIG. 1 is placed in a firing furnace, and the inside of the firing furnace is evacuated and heated to heat and exhaust the interior of the graphite crucible 1 to a predetermined temperature and a predetermined pressure. did.
  • SiO gas is generated from the SiO powder, and this SiO gas reacts with the surface of the graphite particles as follows.
  • the surface of the graphite particles is converted to silicon carbide, and a silicon carbide film is formed by the CVR method.
  • Example 1 Formation of silicon carbide coating by CVR method
  • SiO powder having an average particle diameter of 300 ⁇ m
  • a particle having an average particle diameter of 20 ⁇ m is used as the graphite particle
  • a silicon carbide film is formed on the surface of the graphite particle in the arrangement state in the crucible shown in Table 1, and carbonized. Silicon-coated graphite particles were obtained.
  • the heating temperature was 1500 ° C. and the heating time was 2 hours.
  • the pressure was controlled to 20 Pa.
  • FIG. 4 is a scanning electron micrograph showing the obtained silicon carbide-coated graphite particles.
  • FIG. 5 is a scanning electron micrograph showing the silicon carbide coating on the surface of the obtained silicon carbide-coated graphite particles.
  • the SiC conversion rate is 55% by weight, and the thickness of the silicon carbide (SiC) coating is 1 ⁇ m.
  • FIG. 2 and 3 are cross-sectional views for explaining the formation of a silicon carbide film by the CVR method.
  • FIG. 2 shows the graphite particles 10.
  • the SiO gas comes into contact with the surface of the graphite particles 10 shown in FIG. 2, the carbon on the surface of the graphite particles 10 reacts with the SiO gas as shown in the above reaction formulas (1) to (3). Converted to silicon carbide.
  • FIG. 3 is a view showing graphite particles on which a silicon carbide film is formed by the CVR method. As shown in FIG. 3, silicon carbide coating 11 is formed on the surface of graphite particles 10 by the reaction of carbon and SiO gas, and silicon carbide-coated graphite particles 12 are formed.
  • FIG. 8 is a scanning electron micrograph (magnification 25000 times) showing an initial silicon carbide film formed by the CVR method. As shown in FIG. 8, it can be seen that the silicon carbide film is densely and uniformly formed.
  • FIG. 6 is a scanning electron micrograph (magnification 2500 times) showing the obtained silicon carbide-coated graphite particles.
  • FIG. 7 is a scanning electron micrograph (magnification 25000 times) showing the surface of the obtained silicon carbide-coated graphite particles.
  • the silicon carbide film is formed by a CVD method, and as shown in FIGS. 6 and 7, the silicon carbide film is formed of relatively large particles and has a lot of voids.
  • the SiC conversion rate is 60% by weight, and the thickness of the silicon carbide (SiC) coating is 2 ⁇ m.
  • FIG. 9 is a scanning electron micrograph (magnification 25000 times) showing an initial silicon carbide film formed by the CVD method. As shown in FIG. 9, it can be seen that silicon carbide is preferentially formed at the edge of the graphite particles.
  • the heating temperature was changed to 1200 ° C., 1300 ° C., 1400 ° C., 1450 ° C., 1500 ° C., 1550 ° C., 1600 ° C., 1700 ° C., and 1800 ° C., and the influence of the heating temperature was examined.
  • the pressure was 20 Pa.
  • Other conditions were the same as in Example 1, and a silicon carbide coating was formed on the surface of the graphite particles.
  • the obtained silicon carbide-coated graphite particles were observed with a scanning electron micrograph (SEM), and the state of the silicon carbide coating on the surface was evaluated.
  • SEM scanning electron micrograph
  • the heating temperature when the heating temperature is in the range of 1400 ° C. to 1600 ° C., the silicon carbide film can be formed densely and uniformly.
  • the heating temperature is less than 1400 ° C., the film is not sufficiently formed.
  • the heating temperature exceeds 1600 ° C., the thin film formation by the CVD method is preferential, so that a porous and rough film is formed.
  • FIG. 10 is a scanning electron micrograph (magnification 5000 times) showing the graphite particles before forming the silicon carbide coating.
  • FIG. 11 is a scanning electron micrograph (magnification 2500 times) showing silicon carbide-coated graphite particles in which silicon carbide-coated silicon is formed at a heating temperature of 1500 ° C.
  • FIG. 12 is a scanning electron micrograph (magnification 2500 times) showing silicon carbide-coated graphite particles having a silicon carbide film formed at a heating temperature of 1800 ° C.
  • FIG. 13 is a scanning electron micrograph (magnification 5000 times) showing silicon carbide-coated graphite particles having a silicon carbide film formed at a heating temperature of 1200 ° C.
  • Silicon carbide-coated graphite particles were produced by changing the pressure at the time of forming the silicon carbide film to 20 Pa, 50 Pa, 100 Pa, 150 Pa, and 200 Pa at a heating temperature of 1500 ° C.
  • Table 2 shows the evaluation results of the properties of the silicon carbide coating on the surface of the produced silicon carbide graphite particles.
  • the silicon carbide coating can be formed densely and uniformly by setting the pressure to 150 Pa or less.
  • the formation of the silicon carbide film by the CVD method is preferential, so that the silicon carbide film is formed as a porous and rough film.
  • FIG. 14 is a diagram showing the heating temperature and the weight reduction rate.
  • the silicon carbide-coated graphite particles of Example 1 according to the present invention had an oxidation start temperature of 750 ° C. or higher.
  • the oxidation start temperature of the silicon carbide-coated graphite particles of Comparative Example 1 was 700 ° C.
  • the oxidation start temperature of the uncoated graphite particles was about 550 ° C.
  • the silicon carbide-coated graphite particles of Example 1 were confirmed to have a weight reduction of less than 5% by heating in air at 650 ° C. for 1 hour.
  • a silicon carbide-carbon composite sintered body was produced using the silicon carbide-coated graphite particles of Example 1. Silicon carbide-coated graphite particles were sintered by pressure-sintering the silicon carbide-coated graphite particles using a high-current discharge bonding apparatus (“SPS-1050” manufactured by Sumitomo Co., Ltd.) to produce a silicon carbide-carbon composite sintered body. By using this apparatus, sintering was performed by spark plasma sintering. In the discharge plasma sintering, in addition to direct heating by electric current, a current impact by pulse energization is generated, and powder can be sintered at a temperature lower than usual.
  • SPS-1050 high-current discharge bonding apparatus
  • a sintered body was manufactured by heating at a temperature of 2000 ° C. for 20 minutes in a state where the pressure was 40 MPa.
  • FIG. 15 is a schematic cross-sectional view showing a silicon carbide carbon composite sintered body.
  • the silicon carbide carbon composite sintered body 22 has a silicon carbide interface layer 21 around the graphite particles 20.
  • the silicon carbide interface layer 21 is provided in the silicon carbide carbon composite sintered body 22 continuously in a three-dimensional network. Since the silicon carbide-coated graphite particles of the present invention have a silicon carbide coating formed densely and uniformly on the surface thereof, by producing a sintered body using the silicon carbide-coated graphite particles, A silicon carbide interface layer 21 having a uniform thickness is formed around it.
  • a sintered body can be produced at a low temperature of 2200 ° C. or less without using a sintering aid.
  • the obtained sintered body had a bending strength of 150 MPa and a bulk density of 2.52 g / cm 3 . Since the SiC conversion rate of the silicon carbide-coated graphite particles of Example 1 is 55% by weight, the theoretical density is 2.62 g / cm 3 and the relative density is 96%.
  • the total content of Al, Be, B and Sa is less than 0.1% by weight.
  • FIG. 16 is a schematic cross-sectional view showing a ceramic-coated silicon carbide carbon composite sintered body according to an embodiment of the present invention.
  • the ceramic-coated silicon carbide / carbon composite sintered body 24 of the present embodiment is configured by providing a ceramic coating layer 23 on the surface of the silicon carbide / carbon composite sintered body 22.
  • the ceramic coating layer 23 is provided on the entire surface of the silicon carbide carbon composite sintered body 22, but in the present invention, the ceramic coating layer 23 is not necessarily provided on the entire surface.
  • the silicon carbide carbon composite sintered body 22 may be provided on at least a part of the surface.
  • the silicon carbide carbon composite sintered body 22 may be provided only on one of the upper surface, the lower surface, and the side surface.
  • the ceramic coating layer 23 can be formed from ceramics such as oxide, carbide, and nitride.
  • the ceramic material forming the ceramic coating layer 23 may be silicon carbide or a different kind.
  • the composition of the ceramic coating layer 23 may be changed from the inside toward the outside. In this case, the composition inside the ceramic coating layer 23 may be a composition close to that of silicon carbide, and the composition may gradually differ from the inside toward the outside.
  • a molded body of the silicon carbide carbon composite sintered body 22 before firing is molded, and the ceramic coating layer 23 is formed on at least a part of the surface of the molded body.
  • a layer of ceramic powder is provided and the silicon carbide carbon composite sintered body 22 and the ceramic coating layer 23 are integrally sintered in this state.
  • the ceramic coating layer 23 may be formed from a plurality of layers, and the composition may be changed in the thickness direction of the ceramic coating layer 23.
  • the adhesiveness of the silicon carbide carbon composite sintered compact 22 and the ceramic coating layer 23 can be improved, and characteristics, such as the whole intensity
  • the ceramic powder for forming the ceramic coating layer 23 a mixture of silicon carbide powder and another powder may be used. Thereby, the adhesiveness of the ceramic coating layer 23 and the silicon carbide carbon composite sintered compact 22 can be improved, and characteristics, such as an intensity
  • a sintered body of the silicon carbide carbon composite sintered body 22 is manufactured, and a ceramic sintered plate or a ceramic is formed on at least a part of the surface of the sintered body.
  • Specific methods for joining include hot pressing, discharge plasma sintering, and pressure heating.
  • the ceramic coating layer 23 by using a silicon carbide carbon composite sintered body as a substrate and coating the ceramic by a normal CVD method or reactive sputtering method.

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PCT/JP2010/064871 2009-09-04 2010-09-01 炭化ケイ素被覆炭素基材の製造方法及び炭化ケイ素被覆炭素基材並びに炭化ケイ素炭素複合焼結体、セラミックス被覆炭化ケイ素炭素複合焼結体及び炭化ケイ素炭素複合焼結体の製造方法 Ceased WO2011027756A1 (ja)

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EP20100813705 EP2474514A4 (en) 2009-09-04 2010-09-01 PROCESS FOR PRODUCING A SILICIUMCARBIDBESCHICHTETEN CARBON BASED MATERIALS, SILICIUMCARBIDBESCHICHTETES CARBON BASE MATERIAL SINTERED (silicon carbide) CARBON COMPLEX, CERAMIC COATED SINTERED (silicon carbide) CARBON COMPLEX AND METHOD FOR PRODUCING THE SINTERED (silicon carbide) CARBON COMPLEX
US13/392,593 US9085493B2 (en) 2009-09-04 2010-09-01 Process for production of silicon-carbide-coated carbon base material, silicon-carbide-coated carbon base material, sintered (silicon carbide)-carbon complex, ceramic-coated sintered (silicon carbide)-carbon complex, and process for production of sintered (silicon carbide)-carbon complex
RU2012112935/03A RU2012112935A (ru) 2009-09-04 2010-09-01 Способ получения углеродного материала с карбидокремниевым покрытием, углеродный материал с карбидокремниевым покрытием, спеченный комплекс карбид кремния/углерод, спеченный комплекс карбид кремния/углерод с керамическим покрытием и способ получения спеченного комплекса карбид кремния/углерод
CN201080039227.7A CN102482165B (zh) 2009-09-04 2010-09-01 碳化硅包覆碳基材的制造方法、碳化硅包覆碳基材、碳化硅碳复合烧结体、陶瓷包覆碳化硅碳复合烧结体以及碳化硅碳复合烧结体的制造方法

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JP5737547B2 (ja) 2015-06-17
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