WO2022075290A1 - Sisic member, heating appliance, and method for producing sisic member - Google Patents

Sisic member, heating appliance, and method for producing sisic member Download PDF

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Publication number
WO2022075290A1
WO2022075290A1 PCT/JP2021/036718 JP2021036718W WO2022075290A1 WO 2022075290 A1 WO2022075290 A1 WO 2022075290A1 JP 2021036718 W JP2021036718 W JP 2021036718W WO 2022075290 A1 WO2022075290 A1 WO 2022075290A1
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Prior art keywords
sic
less
molded body
tubular region
elongated hole
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PCT/JP2021/036718
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French (fr)
Japanese (ja)
Inventor
修平 小川
瑠衣 林
直通 宮川
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Agc株式会社
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Priority to JP2022555485A priority Critical patent/JPWO2022075290A1/ja
Publication of WO2022075290A1 publication Critical patent/WO2022075290A1/en

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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/56Shaped 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 carbides or oxycarbides
    • C04B35/565Shaped 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 carbides or oxycarbides based on silicon carbide
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B6/00Heating by electric, magnetic or electromagnetic fields
    • H05B6/02Induction heating
    • H05B6/10Induction heating apparatus, other than furnaces, for specific applications
    • H05B6/12Cooking devices

Definitions

  • the present invention relates to a SiCIC member, a heating appliance, and a method for manufacturing a SiCIC member.
  • Patent Document 1 a SiCIC member which is a composite material containing silicon carbide (SiC) and silicon (Si) is known.
  • the SiC SiC member is excellent in properties such as thermal conductivity, it is expected to be used for various purposes, and the development of a new SiC SiC member is also desired. For example, even if an attempt is made to make a long hole having an inner diameter of 2 mm or less and a length of 100 mm or more in a SiC member by processing with a drill, the SiC member is so hard that the drill bends and cannot be achieved. Even in processing using a laser, it is not possible to reach a depth of 100 mm while maintaining an inner diameter of 2 mm or less.
  • the present invention has been made in view of the above points, and an object of the present invention is to provide a novel SiCIC member which has never existed in the past.
  • the present invention provides the following [1] to [12].
  • a heating appliance comprising the SiCIC member according to any one of the above [1] to [10], into which a rod-shaped member is inserted into the elongated hole.
  • a method for manufacturing a SiC member which comprises impregnating a SiC molded body in which a filler contained therein is contained and the filler is contained in the groove with a single unit of Si that has been heated and melted.
  • FIG. 1 is a perspective view showing a SiCIC member.
  • FIG. 2 is a schematic cross-sectional view showing the tubular region A.
  • FIG. 3 is a schematic cross-sectional view showing the longitudinal direction of the tubular region A.
  • FIG. 4 is a schematic cross-sectional view showing a tubular region A divided into a plurality of regions.
  • FIG. 5 is a cross-sectional view showing a SiC molded body.
  • FIG. 6 is a cross-sectional view showing a state in which a pipe is arranged in a groove of a SiC molded body.
  • FIG. 7 is a cross-sectional view showing a state in which the groove of the SiC molded body is filled with the filler.
  • FIG. 1 is a perspective view showing a SiCIC member.
  • FIG. 2 is a schematic cross-sectional view showing the tubular region A.
  • FIG. 3 is a schematic cross-sectional view showing the longitudinal direction of the tubular region A.
  • FIG. 8 is a schematic cross-sectional view showing a state in which the Si ejection is present in the elongated hole.
  • FIG. 9 is a cross-sectional view showing a SiCIC member having a joint surface.
  • FIG. 10 is a schematic cross-sectional view for explaining the region C.
  • FIG. 1 is a perspective view showing a SiCIC member 1.
  • the SiSiC member 1 is a composite material containing silicon (Si) and silicon carbide (SiC). For example, it has a low coefficient of thermal expansion and is excellent in heat resistance, abrasion resistance, thermal conductivity, strength and the like. Inside the SiC member 1, a long hole 2 long in one direction is provided.
  • the SiC member 1 may have a plurality of elongated holes 2.
  • the elongated holes 2 may be parallel to each other or intersect with each other, and are appropriately set according to the use of the SiC member 1.
  • the elongated hole 2 may be bent.
  • the upper limit of the number of long holes 2 is not particularly limited, but from the viewpoint of increasing the thermal conductivity of the SiC member 1 to improve the heating efficiency, for example, the cross-sectional area of the portion corresponding to the long holes 2 (long hole portion) is SiCIC.
  • the ratio of the member 1 to the total cross-sectional area is preferably 20% or less, more preferably 13% or less, further preferably 8% or less, particularly preferably 4% or less, still more preferably 1% or less, and 0.5%. % Or less is the most preferable.
  • One end of the elongated hole 2 may be sealed, or the long hole 2 may penetrate from one end to the other end of the SiC member 1.
  • the elongated hole 2 is appropriately set according to the application of the SiCIC member 1.
  • the shape and dimensions of the SiC member 1 are appropriately set according to the use of the SiC member 1.
  • the SiC SiC member 1 shown in FIG. 1 has a rectangular parallelepiped shape, but may have another shape such as a disk shape.
  • the SiC SiC member 1 preferably has at least one surface (for example, the upper surface of the SiC SiC member 1 shown in FIG. 1). From the viewpoint of practical convenience, the area of this surface is, for example, 100 cm 2 or more, preferably 300 cm 2 or more, more preferably 500 cm 2 or more, further preferably 700 cm 2 or more, and particularly preferably 800 cm 2 or more.
  • the upper limit of the above area is not particularly limited, but from the viewpoint of cost effectiveness, for example, it is 10000 cm 2 or less, preferably 5000 cm 2 or less, more preferably 2000 cm 2 or less, further preferably 1500 cm 2 or less, and 1000 cm 2 or less. Is particularly preferable.
  • the thickness of the SiC member 1 is, for example, 2.0 to 15.0 mm, preferably 3.0 to 13.0 mm, from the viewpoint of cost effectiveness and from the viewpoint of preventing cracking due to physical impact. 4.0 to 12.0 mm is more preferable, 5.0 to 10.0 mm is further preferable, 6.0 to 9.0 mm is particularly preferable, and 7.0 to 8.0 mm is most preferable.
  • the SiC member 1 has a tubular region A which is an outer peripheral region of the elongated hole 2 and an extratube region B which is an outer region of the tubular region A.
  • the tubular region A preferably contains at least one selected from the group consisting of elemental C, SiC and SiC.
  • SiCSiC is a composite material of SiC and Si alone.
  • the tubular region A contains C alone or SiC. In this case, it is more preferable that the content of C simple substance or SiC in the tubular region A (unit: volume%) is larger than the content of C simple substance or SiC in the extratube region B (unit: volume%).
  • the tubular region A is formed by using a pipe (carbon tube or SiC tube) as described later when the SiC member 1 having the tubular region A and the out-of-tube region B is manufactured, the tubular region A and the out-tube region A are formed. B preferably meets these requirements.
  • FIG. 2 is a schematic cross-sectional view showing the tubular region A.
  • the diameter a of the elongated hole 2 is 2.0 mm or less, preferably 1.8 mm or less, more preferably 1.5 mm or less, still more preferably 1.2 mm or less, from the viewpoint of increasing the thermal conductivity of the SiC member 1. 0.8 mm or less is even more preferable, 0.7 mm or less is particularly preferable, and 0.4 mm or less is most preferable.
  • the diameter a of the elongated hole 2 is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more.
  • the thickness d of the tubular region A is preferably 0.05 mm or more, more preferably 0.07 mm or more, further preferably 0.10 mm or more, particularly preferably 0.12 mm or more, and 0.15 mm or more. Is the most preferable.
  • the thickness d is, for example, 2.0 mm or less, preferably 1.5 mm or less, from the viewpoint of giving flexibility to the pipe at the time of manufacturing and facilitating handling. 0 mm or less is more preferable, 0.8 mm or less is further preferable, 0.6 mm or less is further preferable, 0.4 mm or less is particularly preferable, and 0.25 mm or less is most preferable.
  • FIG. 3 is a schematic cross-sectional view showing the longitudinal direction of the tubular region A.
  • the length b of the elongated hole 2 is 100 mm or more, preferably 125 mm or more, more preferably 150 mm or more, further preferably 180 mm or more, further preferably 210 mm or more, and even more preferably 240 mm or more, from the viewpoint of practical convenience. Particularly preferably, 270 mm or more is more preferable, and 290 mm or more is most preferable.
  • the length b is, for example, 800 mm or less, preferably 600 mm or less, more preferably 400 mm or less, further preferably 350 mm or less, and particularly preferably 300 mm or less, from the viewpoint of cost effectiveness.
  • the diameter a of the elongated hole 2, the length b of the elongated hole 2, and the thickness d of the tubular region A are based on the inner diameter, length, and thickness of the pipe (carbon tube or SiC tube) described later, respectively.
  • the diameter a of the elongated hole 2, the length b of the elongated hole 2, and the thickness d of the tubular region A are each tubular. It is assumed that the region A is not divided.
  • the length b of the long hole 2 is, that is, the distance of the center line L1 of the long hole 2 .
  • the center line of the elongated hole 2 may be a curved center line L2 instead of the original center line L1. This is called axis misalignment.
  • P be the position farthest from the original center line L 1 on the curved center line L 2 .
  • the shortest distance to the center line L1 of the position P is defined as the amount of misalignment c.
  • the value of the amount of misalignment c is preferably small.
  • the amount of misalignment c is preferably 0.5 mm or less, more preferably less than 0.4 mm, further preferably less than 0.3 mm, further preferably less than 0.2 mm, and particularly preferably 0.1 mm or less. , 0.05 mm or less is most preferable.
  • FIG. 4 is a schematic cross-sectional view showing a tubular region A divided into a plurality of regions.
  • the tubular region A may be divided into a plurality of regions when the ring shape is viewed in cross section from a direction in which the ring shape can be visually recognized.
  • the number of divisions of the tubular region A (hereinafter, also referred to as “division number h”) is two in FIG. 4, but may be three or more.
  • the upper limit is not particularly limited, and for example, the number of divisions h is 8 or less, preferably 6 or less.
  • the tubular region A is evenly divided, but may not be even.
  • ⁇ Position deviation amount e and division interval f> As shown in FIG. 4, when the tubular region A is divided, the divided regions may be displaced (hereinafter, also referred to as “positional deviation”), or a gap may be generated between the divided regions. do.
  • the misalignment amount e is preferably 0.30 mm or less, more preferably 0.20 mm or less, from the viewpoint of manufacturing the diameter of the elongated hole 2 as designed and reducing the value of the Si ejection amount g described later. 0.15 mm or less is further preferable, 0.10 mm or less is further preferable, 0.05 m or less is particularly preferable, and 0.02 mm or less is most preferable.
  • the lower limit of the misalignment amount e is preferably 0 mm.
  • the ratio (e / d) of the displacement amount e of the tubular region A to the thickness d of the tubular region A is preferably 2/3 (0.666 ...) or less, and 1/3 (0) for the same reason. .333 7) Is more preferred, less than 1/4 (0.25) is even more preferred, less than 1/10 (0.1) is even more preferred, and less than 1/20 (0.05) is particularly preferred. Less than / 30 (0.033 ...) Is more particularly preferred, and less than 1/50 (0.02) is most preferred.
  • the misalignment amount e is the distance between the ends (ends on the same side) of the divided regions.
  • the division interval f of the divided tubular regions A is small.
  • SiC which is a material containing no carbon
  • the division interval f of the divided tubular region A is preferably 0.15 mm or less, more preferably 0.14 mm or less, still more preferably 0.10 mm or less, from the viewpoint of reducing the value of the Si ejection amount g described later.
  • the lower limit is not particularly limited, and the division interval f is, for example, 0.000 mm or more, preferably 0.005 mm or more, and more preferably 0.010 mm or more. As shown in FIG. 4, the division interval f is the distance between adjacent end faces (cut surfaces) of the divided regions.
  • the thermal conductivity i of the SiC member is preferably 170 W / (m ⁇ K) or more, more preferably 180 W / (m ⁇ K) or more, and further preferably 190 W / (m ⁇ K) or more from the viewpoint of increasing the heating efficiency.
  • 200 W / (m ⁇ K) or more is more preferable
  • 210 W / (m ⁇ K) or more is particularly preferable
  • 220 W / (m ⁇ K) or more is particularly preferable
  • 230 W / (m ⁇ K) or more is most preferable. ..
  • the thermal conductivity i is determined at room temperature (23 ° C.) by a laser flash method using LFA457 MicroFlash (manufactured by NETZSCH). More specifically, the thermal conductivity in the range of 25.4 mm in diameter including the tubular region A of the SiC member is defined as the thermal conductivity i (thermal conductivity i1). The measured thickness is 6 mm.
  • the thermal conductivity i can also be obtained by the improved unsteady plane measurement method (ASTMD7984) using the thermal conductivity measuring device TCi (manufactured by C-thermtechnologies). More specifically, the thermal conductivity in the range of 17.8 mm in diameter including the tubular region A of the SiC member in the center is defined as the thermal conductivity i (i2).
  • the measured thickness is the same as that of the SiC member. However, in order to eliminate the influence of the air layer, a mirror-finished SiC member is laminated and measured to a total thickness of 15 mm or more. In this case, the measurement accuracy can be measured with an accuracy of about ⁇ 5%.
  • the thermal conductivity of only the out-of-tube region B is defined as the thermal conductivity j.
  • the amount of impurities k of the SiCIC member is preferably 100 mass ppm or less, more preferably 80 mass ppm or less, further preferably 60 mass ppm or less, particularly preferably 40 mass ppm or less, and most preferably 20 mass ppm or less.
  • Impurities include, for example, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Sb, Sn, Sr, Ti, V. , Zn and Zr, at least one element selected from the group.
  • the amount of impurities k is the total amount of these elements.
  • the amount of impurities k is likely to be large.
  • the value of the impurity amount k can be reduced by producing the SiCIC member without providing such a joint surface.
  • the amount of impurities k is determined using an ICP (inductively coupled plasma) emission spectroscopic analyzer (SPS5520, manufactured by Hitachi High-Tech Science Corporation).
  • SiC particles for example, ⁇ -SiC particles
  • SiC particles used as a raw material are crushed so as to have a predetermined particle size before use.
  • impurities such as Fe existing in the voids formed inside the SiC crystals are exposed on the particle surface and can be removed by washing.
  • ⁇ -SiC particles synthesized by the Athison method are pulverized and classified to have a maximum particle diameter of 44 ⁇ m or less and an average particle diameter of 2 to 25 ⁇ m, and then a mixed acid of hydrofluoric acid and nitric acid and pure water. Wash with.
  • the average particle size means the particle size at an integrated value of 50% in the particle size distribution (integrated mass distribution) obtained by the laser diffraction / scattering method (hereinafter, the same applies).
  • FIG. 5 is a cross-sectional view showing the SiC molded body 3.
  • the SiC molded body 3 is a molded body containing SiC particles (not shown) and has a U-shaped groove 4.
  • the shape of the groove 4 is not particularly limited as long as it is a shape into which the pipe 5 (see FIGS. 6 and 7) described later is fitted.
  • the SiC molded body is also a porous body having a large number of pores. Therefore, as will be described later, the SiC molded body is impregnated with the molten Si simple substance.
  • the porosity of the SiC molded product is preferably 10 to 60% by volume, more preferably 12 to 50% by volume, further preferably 14 to 40% by volume, particularly preferably 16 to 30% by volume, and most preferably 18 to 25% by volume. preferable. Porosity is determined by the Archimedes method.
  • the dimensions and shape of the SiC molded body are not particularly limited, and are appropriately set according to the dimensions and shape of the finally obtained SiC member.
  • the method for producing the SiC molded product is not particularly limited.
  • a mixture of SiC particles and a binder (raw material for a SiC molded product) is poured into a mold and dried to prepare a SiC molded product.
  • the solid content concentration of the raw material of the SiC molded body can be appropriately changed in the range of, for example, 5 to 100% by mass.
  • the SiC molded product may be sintered by heating at a high temperature (for example, 1500 to 2300 ° C.) in an inert atmosphere.
  • a method such as a mud waste casting molding method, an isostatic pressing method, or an extrusion molding method can be adopted.
  • the width of the particle size distribution of the SiC particles is wide because the moldability is good and the density of the obtained SiC molded product can be increased.
  • the method described in Japanese Patent Application Laid-Open No. 5-32458 can be mentioned.
  • the binder include an organic binder. Phenol resin, polyvinyl acetate emulsion, acrylic resin emulsion and the like are preferably used as the organic binder.
  • a phenol resin is used as a binder, carbon remains in the obtained SiC molded product. When this carbon is impregnated with Si, which will be described later, it reacts with the molten Si simple substance to become ⁇ -SiC.
  • grooves may be formed using a known cutting tool such as an NC (Numerical Control) milling machine. After forming the groove, the SiC molded body having the groove may be sintered by heating.
  • NC Genetic Control
  • the method for producing the SiC molded product is not limited to the above method.
  • a method such as an extrusion molding method; an injection molding method; a laser irradiation molding method, a 3D (three-dimensional) printing method such as a binder jet molding method; may be used.
  • ⁇ -SiC particles are preferable.
  • the range of the average particle size of the ⁇ -SiC particles is preferably 2 to 25 ⁇ m, more preferably 3 to 15 ⁇ m, for the following reasons. If the average particle size of the ⁇ -SiC particles is too small, Fe, which is an impurity, can be reduced to 5 mass ppm or less by the above-mentioned cleaning, but the impurities mixed in during the pulverization process may increase and the cleaning may take time and effort. be. In addition, the pore structure of the obtained SiC molded product may become too fine, making it difficult to impregnate Si, which will be described later.
  • the average particle size of the ⁇ -SiC particles is too large, many particles that do not pass through the sieve remain in the classification before use (for example, the classification to make the maximum particle size 44 ⁇ m or less), and the usable ratio decreases. There is. Further, the smoothness of the SiC molded body is lowered, which may result in insufficient material properties such as bending strength of the obtained SiC member.
  • FIG. 6 is a cross-sectional view showing a state in which the pipe 5 is arranged in the groove 4 of the SiC molded body 3.
  • the pipe 5 is a tubular member, for example, a carbon pipe containing carbon (C) or a SiC pipe containing silicon carbide (SiC).
  • the pipe 5 is a tubular region A in the obtained SiC member 1 (see FIG. 1).
  • the pipe is preferably not a porous body (it is a dense body). This makes it difficult for the molten Si to impregnate the pipe, as will be described later.
  • the carbon content in the carbon tube is preferably 60% by volume or more, more preferably 70% by volume or more, further preferably 75% by volume or more, particularly preferably 80% by volume or more, and more than 80% by volume. Most preferred.
  • the upper limit is not particularly limited, but for example, a carbon tube having a carbon content of 100% by volume has low flexibility and tends to have a low degree of freedom when placed in a SiC molded body.
  • the carbon content of the carbon tube is 95% by volume or less, the molten Si permeates a part or the whole of the carbon tube and becomes SiC by the reaction with the carbon tube.
  • the tubular region A becomes a complex containing carbon and SiC, and as a result, the difference in expansion coefficient from the out-of-tube region B becomes small, so that cracks due to thermal stress during manufacturing and use are less likely to occur.
  • the carbon content in the carbon tube is preferably 98% by volume or less, more preferably 95% by volume or less, further preferably 92% by volume or less, and particularly preferably 90% by volume or less.
  • the SiC content in the SiC pipe is preferably as follows from the viewpoint of reducing the difference in expansion coefficient during Si impregnation, which will be described later.
  • the content of SiC in the SiC tube is preferably 40% by volume or more, more preferably 43% by volume or more, further preferably 47% by volume or more, and particularly preferably 50% by volume or more.
  • the content of SiC in the SiC tube is preferably 95% by volume or less, more preferably 85% by volume or less, further preferably 70% by volume or less, and particularly preferably 60% by volume or less.
  • the pipe is not limited to a straight pipe and may be bent.
  • the pipe may have one end closed. Pipes with vacant ends may be used and one end may be sealed. Sealing is performed, for example, by adhering end materials of the same material as the pipe to one end of the pipe using an adhesive.
  • the adhesive used include adhesives containing resins such as epoxy resin, polycarbosilane, phenol resin, and methyl cellulose. In addition to these resins, the adhesive may contain particles such as carbon particles, SiC particles, and Si particles.
  • the adhesive may be a filler containing SiC particles, a mixture of Si particles and SiC particles, or the like. The content of each component in the adhesive is appropriately adjusted according to the composition of the pipe (for example, carbon pipe or SiC pipe).
  • the carbon tube produced by winding a carbon sheet or the like in a pipe shape may be cracked and Si ejection, which will be described later, may easily occur.
  • the divided pipe for example, a pipe cut along the longitudinal direction
  • a columnar carbon rod or a SiC rod is cut along the longitudinal direction and divided (for example, divided into two), and then the inside of the obtained divided piece is scraped.
  • a method (method 1) of obtaining a divided pipe can be mentioned.
  • a method (method 2) of obtaining a divided pipe by forming an elongated hole in a carbon rod or a SiC rod using a drill of a machining center or the like and then dividing the hole can be mentioned.
  • the method 1 is preferable from the viewpoint of reducing the amount of misalignment c.
  • the divided pipes are fixed and arranged in the groove so that the misalignment amount e and the division interval f (see FIG. 4) are desired values.
  • the divided pipe pieces may be adhered to each other with the above-mentioned adhesive to fill the gap.
  • FIG. 7 is a cross-sectional view showing a state in which the groove 4 of the SiC molded body 3 is filled with the filler 8.
  • a mixture of SiC particles and a binder is placed in a groove, and then the mixture is dried or heated.
  • the inside of the groove is filled with a filler having the same composition as the SiC molded body.
  • the binder jet molding method for example, a mixture of SiC particles and a curing agent is placed in a groove, and then the binder is sprayed onto the mixture from an inkjet nozzle. As a result, the inside of the groove is filled with a filler having the same composition as the SiC molded body. At this time, if the groove is deep, the groove may be gradually filled with the filler by repeating the binder injection with the mixture. Grooves may be filled with filler by manual application.
  • the filler is also treated as a part of the SiC molded body.
  • the SiC molded product (including the filler) may be sintered by heating in an inert atmosphere after drying.
  • the SiC molded body becomes denser than immediately after drying, and the strength is improved.
  • the impurities are volatilized by heating, and the purity is improved.
  • the heating temperature is preferably 1500 ° C. or higher.
  • the strength of the SiC molded product sufficient strength that can withstand handling with Si impregnation, which will be described later, can be obtained.
  • the heating temperature can be set to about 1000 ° C.
  • the heating temperature is set to, for example, 2100 ° C. or higher, crystal growth called recrystallization proceeds and the structure changes.
  • the heating temperature is preferably 2300 ° C. or lower.
  • Si impregnation the SiC molded body is impregnated with silicon (Si).
  • Si impregnation Specifically, for example, in a state where the SiC molded body and the Si simple substance are in contact with each other, these (SiC molded body and the Si simple substance) are heated to melt the Si simple substance. As a result, the molten Si simple substance is impregnated into the SiC molded body, which is a porous body, by the capillary phenomenon.
  • the environment for melting Si alone is preferably a reduced pressure environment.
  • the heating temperature may be equal to or higher than the melting point of Si.
  • the melting point of Si varies slightly depending on the measuring method, but is approximately 1410 to 1414 ° C.
  • the heating temperature is preferably 1430 to 1800 ° C.
  • SiC SiC member which is a composite material containing SiC and free Si can be obtained.
  • the region that was a pipe becomes a tubular region A (see FIG. 1), and the other region (SiC molded body and filler) is an extrapipe region B (FIG. 1). See).
  • the space created between the adjacent divided pipes is the area C (see FIG. 10).
  • the amount of Si to be introduced into the SiC molded body is appropriately set according to the content of Si alone in the finally obtained SiC member. If the porosity of the SiC molded product is small (there are few pores), the number of closed pores increases, which may make Si impregnation difficult. For example, it is preferable that the SiC molded product is impregnated with 7% by mass or more of Si.
  • the content of Si alone in the obtained SiC member is preferably 35% by mass or less, more preferably 25% by mass or less. As a result, suitable physical properties such as high bending strength can be obtained.
  • the obtained SiC member is sintered by heating when melting Si alone. That is, SiC (including newly generated SiC) and SiC and Si are bonded to each other to obtain a dense sintered body. Therefore, the obtained SiC member is a composite material containing Si and SiC, and is also a sintered body.
  • FIG. 8 is a schematic cross-sectional view showing a state in which the Si ejection 9 exists in the elongated hole 2.
  • the density of silicon (Si) is 2.560 g / cm 3 in the liquid state, whereas it is 2.293 g / cm 3 in the solid state. That is, when the free Si is cooled from the heated melt state to the solid state, the volume increases by 12% and expands.
  • the free Si expands in volume, passes through the gap of the tubular region A, and becomes a ejection (Si ejection 9) into the elongated hole 2.
  • a ejection Si ejection 9
  • the value of the Si ejection amount g is large
  • the values of the division interval f and / or the misalignment amount e are reduced. This makes it difficult for Si to pass through the gaps in the tubular region A. For example, even if the volume-expanded Si enters the gap of the tubular region A, it may stop in the middle of the gap or at the exit. In this way, the Si ejection 9 is suppressed, and it becomes easy to insert a thermocouple or the like into the elongated hole 2.
  • the Si ejection amount g is preferably less than 1 mm, more preferably less than 0.7 mm, further preferably less than 0.4 mm, still more preferably less than 0.2 mm, because it is easy to insert a thermocouple or the like into the elongated hole 2.
  • Less than 0.1 mm is particularly preferable, less than 0.05 mm is more particularly preferable, and less than 0.01 mm is most preferable.
  • the ratio (g / d) of the Si ejection amount g and the thickness d (see FIG. 2) of the tubular region A described above is preferably 3/4 (0.75) or less, preferably 2/4. (0.5) or less is more preferable, less than 1/4 (0.25) is further preferable, less than 1/5 (0.2) is particularly preferable, and less than 1/10 (0.1) is most preferable.
  • the SiC member having a long hole is not particularly limited in its use, but is suitable as a heating appliance because it is excellent in thermal conductivity, strength and the like.
  • a heating appliance for example, the SiC member itself and / or the object to be heated placed on the SiC member is heated.
  • a heating appliance for example, a top plate provided in a heating cooker such as an IH (induction heating) cooker is preferably mentioned.
  • the top plate of a cooking device is a member on which a heated body such as a pot is placed. Conventionally, ceramics and the like have been used as the material of the top plate.
  • the top plate is required to be able to raise and lower the temperature at high speed and have high impact resistance.
  • the SiCIC member can be suitably used as the top plate of the cooking device.
  • a thermocouple (not shown) is inserted into the elongated hole of the SiC member for temperature control. This makes it possible to grasp the temperature of the SiCIC member and, by extension, the heated body arranged on the SiCIC member.
  • the cooker may be used as part of the system kitchen.
  • the system kitchen has equipment such as a workbench and a cooker, and these equipments are connected by a worktop.
  • As the material of the worktop stainless steel, artificial marble, ceramics and the like are used.
  • the cooker is used, for example, by incorporating it into an opening provided in the worktop. In this case, the top plate of the cooker may form part of the worktop of the system kitchen.
  • FIG. 9 is a cross-sectional view showing a SiCIC member 21 having a joint surface.
  • a SiC molded body 3 having a groove 4 and a SiC molded body 3 without a groove are manufactured. After that, as shown in FIG. 9, the SiC molded body 3 having no groove is arranged on the SiC molded body 3 having the groove 4. At this time, the interface between the two is joined using the adhesive 22.
  • the SiC member 21 shown in FIG. 9 is used as a top plate of a cooking cooker.
  • a body to be heated (not shown) is placed on the upper surface of the SiCIC member 21 and heated from the lower surface side.
  • heat is blocked at the joint surface, so that heat may not be easily transferred to the object to be heated (that is, the thermal conductivity is inferior).
  • the SiC member 1 does not have such a joint surface, it is relatively easy to heat the object to be heated. That is, the thermal conductivity is good.
  • the SiCIC member is not limited to the above-mentioned top plate of the cooking device, and other examples thereof include a heater member of an electric furnace for a heating experiment; a member for a semiconductor device manufacturing apparatus; and the like.
  • the SiC member may be used by inserting a rod-shaped member such as an electrode into the elongated hole thereof.
  • Example 1 to 5 Example 7 to Example 16, Example 18, Example 20 to Example 81 are examples, and Examples 6, 17, and 19 are comparative examples.
  • Example 1 to Example 73 Pure water and a water-soluble phenol resin were added to ⁇ -SiC particles having a maximum particle diameter of 44 ⁇ m and an average particle diameter of 8 ⁇ m, which were separated by a 325 mesh sieve, and mixed to obtain a raw material for an SiC molded body.
  • the solid content concentration of the raw material of the SiC molded body is shown in the table below.
  • a rectangular parallelepiped molded product is formed by a method (mud casting molding method) in which the raw material of the SiC molded body is poured into a gypsum mold to be fleshed, and then the raw material of the SiC molded body (slurry) remaining inside is discharged.
  • the thickness of the SiC molded product was adjusted to the thickness shown in Table 1 below after the Si impregnation described later.
  • the length of one side other than the thickness of the SiC molded body was appropriately selected in the range of 100 to 520 mm according to the length of the pipe to be used and the like.
  • the area of the upper surface of the SiC molded body (in the table below, simply referred to as "the area of the SiC molded body") is also described in the table below.
  • the diameter (inner diameter a), length b and thickness d of the pipe used are shown in the table below.
  • a carbon pipe or a SiC pipe which was evenly divided (cut along the longitudinal direction) by the number of divisions shown in the table below was used.
  • SiC having a SiC content of 48% by volume is described as "C81”.
  • Examples 16 to 19 first, a columnar carbon rod or a SiC rod is cut along the longitudinal direction and divided (for example, divided into two), and then the inside of the obtained divided pieces. By scraping, a split pipe was obtained. In Examples 16 to 19, first, an elongated hole was formed in the carbon rod using a drill of a machining center, and then the pipe was divided to obtain a divided pipe.
  • allylhydride polycarbosilane (SMP-10, manufactured by Starfire) was used. After impregnation with Si, which will be described later, the SiC content of the region corresponding to the adhesive 1 was 72% by volume.
  • an epoxy resin (SMC-7030H, manufactured by Shin-Etsu Chemical Co., Ltd.) mixed with carbon particles (SGP-25, manufactured by SEC Carbon Co., Ltd.) having an average particle diameter of 25 ⁇ m was used in an amount of 15% by mass. After impregnation with Si, which will be described later, the SiC content of the region corresponding to the adhesive 2 was 31% by volume.
  • Example 28 the divided pipe pieces were adhered to each other using the adhesive used for sealing the ends.
  • the region C when the content of C alone or SiC in the region C (see FIG. 10) is 20% by volume or more, the region C is regarded as one with the tubular region A, and the division interval f is set to 0 mm. In Examples 28 to 29, this content could be achieved by using the above-mentioned adhesive.
  • the tubular region A was SiC with a SiC content of 71% by volume, whereas the region C was SiC with a SiC content of 72% by volume, and was integrated with SiC having almost the same composition.
  • the SiC molded body in which the groove after arranging the pipe was filled with the filler was dried and then heated at 1800 ° C. for 5 hours in an inert atmosphere using an electric furnace. In this way, a rectangular parallelepiped SiC molded body was obtained.
  • Si impregnation was carried out. More specifically, in the reaction furnace, Si alone was placed on the SiC molded body and heated to 1450 ° C. in a reduced pressure environment. As a result, the Si simple substance was melted and impregnated into the SiC molded body. At this time, all the pores of the SiC molded body are filled with high-purity Si, and at least a part of the carbon existing as a component of the pipe and / or the adhesive reacts with Si to be silicon carbide. In this way, a SiCIC member was obtained.
  • a cross section of the obtained SiSiC member was cut out at an arbitrary location, and the amount of Si ejected g was measured from an optical micrograph of the cross section. The results are shown in the table below. At this time, it was confirmed from the optical micrograph that the diameter a of the long hole, the length b of the long hole, the thickness d of the tubular region A, the amount of misalignment e, and the division interval f were maintained.
  • the thermal conductivity i (i1 and i2) and the thermal conductivity j were measured by the above-mentioned method. The results are shown in the table below.
  • Impurities include Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Sb, Sn, Sr, Ti, V, Zn and Zr were targeted.
  • the SiC members of Examples 74 to 78 were produced as follows, and the thermal conductivity K was calculated based on the following formula.
  • K ⁇ [L- (M ⁇ N)] / L ⁇ ⁇ O
  • K Overall thermal conductivity of SiC member
  • L Overall cross-sectional area of SiC member
  • M Maximum cross-sectional area of tubular region
  • A Number of elongated holes
  • O Thermal conductivity of extratube region B is shown.
  • Example 74 A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (350 mm ⁇ 350 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). : 0.7 mm, thickness: 0.6 mm, length: 330 mm) were arranged at equal intervals. Other conditions were the same as in Example 1 to produce a SiC SiC member. At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 5.1%. The thermal conductivity of the produced SiC member was 218 W / (m ⁇ K) when calculated based on the above formula.
  • Example 75 A carbon tube (outer diameter: 4.1 mm, inner diameter) divided into two in a SiC molded body (300 mm ⁇ 300 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). : 2.0 mm, thickness: 1.0 mm, length: 280 mm) were arranged at equal intervals. Other conditions were the same as in Example 6 to produce a SiC SiC member. At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 12.8%. The thermal conductivity of the produced SiC member was 201 W / (m ⁇ K) when calculated based on the above formula.
  • Example 76 A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (360 mm ⁇ 300 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 49% by mass). : 0.7 mm, thickness: 0.6 mm, length: 330 mm) were arranged at equal intervals. Other conditions were the same as in Example 71, and a SiC SiC member was produced. At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 5.8%. The thermal conductivity of the produced SiC member was 171 W / (m ⁇ K) when calculated based on the above formula.
  • Example 77 A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (350 mm ⁇ 280 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 58% by mass). : 0.7 mm, thickness: 0.6 mm, length: 330 mm) were arranged at equal intervals. Other conditions were the same as in Example 72, and a SiC SiC member was produced. At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 6.4%. The thermal conductivity of the produced SiC member was 189 W / (m ⁇ K) when calculated based on the above formula.
  • Example 78 A carbon tube (outer diameter: 3.1 mm, inner diameter) divided into two in a SiC molded body (350 mm ⁇ 280 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 84% by mass). : 1.3 mm, thickness: 0.9 mm, length: 330 mm) were arranged at equal intervals. Other conditions were the same as in Example 73, and a SiC SiC member was produced. At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 10.4%. The thermal conductivity of the produced SiC member was 208 W / (m ⁇ K) when calculated based on the above formula.
  • Example 79 A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (350 mm ⁇ 350 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). : 0.7 mm, thickness: 0.6 mm, length: 280 mm) was arranged. Other conditions were the same as in Example 1 to produce a SiC SiC member. At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 0.4%. The thermal conductivity of the produced SiC member was 229 W / (m ⁇ K) when calculated based on the above formula.
  • Example 80 A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (350 mm ⁇ 350 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). : 0.7 mm, thickness: 0.6 mm, length: 280 mm) were arranged. Other conditions were the same as in Example 1 to produce a SiC SiC member. At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 2.2%. The thermal conductivity of the produced SiC member was 225 W / (m ⁇ K) when calculated based on the above formula.
  • Example 81 A carbon tube (outer diameter: 4.1 mm, inner diameter) divided into two in a SiC molded body (300 mm ⁇ 300 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). (1.8 mm, thickness: 1.0 mm, length: 280 mm) were arranged at equal intervals of 15 pieces. Other conditions were the same as in Example 6 to produce a SiC SiC member. At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 19%. The thermal conductivity of the produced SiC member was 186 W / (m ⁇ K) when calculated based on the above formula.
  • SiC SiC member 2 Long hole 3: SiC molded body 4: groove 5: pipe 8: filler 9: Si ejection 21: SiC member 22: adhesive A: tubular region B: out-of-tube region C: region a: length Hole diameter b: Long hole length c: Axial deviation d: Tubular region thickness e: Positional deviation f: Division interval g: Si ejection amount L 1 , L 2 : Long hole center line

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Abstract

The present invention relates to an SiSiC member provided with at least one long hole on the inside, wherein the long hole has a diameter a of 2.0 mm or less, a length b of 100 mm or more, and a tubular region A, which is the outer peripheral region of the long hole, and the tubular region A includes at least one selected from the group consisting of C alone, SiC, and SiSiC.

Description

SiSiC部材、加熱器具、およびSiSiC部材の製造方法SiSiC member, heating appliance, and method for manufacturing SiCIC member
 本発明は、SiSiC部材、加熱器具、およびSiSiC部材の製造方法に関する。 The present invention relates to a SiCIC member, a heating appliance, and a method for manufacturing a SiCIC member.
 従来、炭化ケイ素(SiC)とケイ素(Si)とを含有する複合材料であるSiSiC部材が知られている(特許文献1)。 Conventionally, a SiCIC member which is a composite material containing silicon carbide (SiC) and silicon (Si) is known (Patent Document 1).
国際公開第2019/194137号International Publication No. 2019/194137
 SiSiC部材は、熱伝導性などの特性に優れることから、種々の用途に用いられることが期待されており、新たなSiSiC部材の開発も望まれている。
 例えば、ドリルを用いた加工によって、SiSiC部材に、内径2mm以下かつ100mm以上の長さの長孔を空けようとしても、SiSiC部材は非常に硬いためドリルが折れ曲がり、達成できない。レーザーを用いた加工でも、内径2mm以下を維持したまま、100mm深さまでレーザーを到達させることはできない。
Since the SiC SiC member is excellent in properties such as thermal conductivity, it is expected to be used for various purposes, and the development of a new SiC SiC member is also desired.
For example, even if an attempt is made to make a long hole having an inner diameter of 2 mm or less and a length of 100 mm or more in a SiC member by processing with a drill, the SiC member is so hard that the drill bends and cannot be achieved. Even in processing using a laser, it is not possible to reach a depth of 100 mm while maintaining an inner diameter of 2 mm or less.
 本発明は、以上の点を鑑みてなされたものであり、従来には無い新規なSiSiC部材を提供することを目的とする。 The present invention has been made in view of the above points, and an object of the present invention is to provide a novel SiCIC member which has never existed in the past.
 本発明者らは、鋭意検討した結果、下記構成を採用することにより、上記目的が達成されることを見出し、本発明を完成させた。 As a result of diligent studies, the present inventors have found that the above object can be achieved by adopting the following configuration, and have completed the present invention.
 すなわち、本発明は、以下の[1]~[12]を提供する。
[1]少なくとも1本の長孔が内部に設けられたSiSiC部材であって、上記長孔は、径aが2.0mm以下であり、長さbが100mm以上であり、上記長孔の外周の領域である管状領域Aを有し、上記管状領域Aが、C単体、SiCおよびSiSiCからなる群から選ばれる少なくとも1種を含む、SiSiC部材。
[2]熱伝導率iが、170W/(m・K)以上である、上記[1]に記載のSiSiC部材。
[3]上記管状領域Aが、複数の領域に分割されている、上記[1]または[2]に記載のSiSiC部材。
[4]分割されている上記管状領域Aの分割間隔fが、0.15mm以下である、上記[3]に記載のSiSiC部材。
[5]上記長孔におけるSi噴き出し量gが、1mm未満である、上記[1]~[4]のいずれかに記載のSiSiC部材。
[6]上記長孔におけるSi噴き出し量gと、上記管状領域Aの厚さdとの比g/dが、3/4以下である、上記[1]~[5]のいずれかに記載のSiSiC部材。
[7]上記管状領域Aの位置ずれ量eと、上記管状領域Aの厚さdとの比e/dが、1/3未満である、上記[1]~[6]のいずれかに記載のSiSiC部材。
[8]上記長孔の軸ずれ量cが、0.3mm未満である、上記[1]~[7]のいずれかに記載のSiSiC部材。
[9]不純物量kが、100質量ppm以下である、上記[1]~[8]のいずれかに記載のSiSiC部材。
[10]厚さが2.0~15.0mmであり、少なくとも一つの面を有し、上記面の面積が100cm以上である、上記[1]~[9]のいずれかに記載のSiSiC部材。
[11]上記[1]~[10]のいずれかに記載のSiSiC部材を備え、上記長孔に、棒状部材が差し込まれる、加熱器具。
[12]上記[1]~[10]のいずれかに記載のSiSiC部材を製造する方法であって、溝を有するSiC成形体を準備し、上記溝に、パイプを配置し、その後、SiCを含有する充填材を入れ、上記充填材が上記溝に入った上記SiC成形体に、加熱溶融したSi単体を含浸させる、SiSiC部材の製造方法。
That is, the present invention provides the following [1] to [12].
[1] A SiC member having at least one elongated hole provided inside, wherein the elongated hole has a diameter a of 2.0 mm or less, a length b of 100 mm or more, and an outer circumference of the elongated hole. A SiC member having a tubular region A which is a region of the above, wherein the tubular region A contains at least one selected from the group consisting of C alone, SiC and SiC.
[2] The SiC member according to the above [1], wherein the thermal conductivity i is 170 W / (m · K) or more.
[3] The SiC member according to the above [1] or [2], wherein the tubular region A is divided into a plurality of regions.
[4] The SiCIC member according to the above [3], wherein the divided tubular region A has a division interval f of 0.15 mm or less.
[5] The SiC member according to any one of [1] to [4] above, wherein the Si ejection amount g in the elongated hole is less than 1 mm.
[6] The above-mentioned [1] to [5], wherein the ratio g / d of the Si ejection amount g in the elongated hole to the thickness d of the tubular region A is 3/4 or less. SiC SiC member.
[7] Described in any one of the above [1] to [6], wherein the ratio e / d of the misalignment amount e of the tubular region A and the thickness d of the tubular region A is less than 1/3. SiC SiC member.
[8] The SiC member according to any one of [1] to [7] above, wherein the amount c of the long hole is less than 0.3 mm.
[9] The SiC member according to any one of [1] to [8] above, wherein the amount of impurities k is 100 mass ppm or less.
[10] The SiC according to any one of the above [1] to [9], which has a thickness of 2.0 to 15.0 mm, has at least one surface, and has an area of 100 cm 2 or more. Element.
[11] A heating appliance comprising the SiCIC member according to any one of the above [1] to [10], into which a rod-shaped member is inserted into the elongated hole.
[12] The method for manufacturing a SiC member according to any one of the above [1] to [10], wherein a SiC molded body having a groove is prepared, a pipe is arranged in the groove, and then SiC is added. A method for manufacturing a SiC member, which comprises impregnating a SiC molded body in which a filler contained therein is contained and the filler is contained in the groove with a single unit of Si that has been heated and melted.
 本発明によれば、従来には無い新規なSiSiC部材を提供できる。 According to the present invention, it is possible to provide a novel SiCIC member which has never existed in the past.
図1はSiSiC部材を示す斜視図である。FIG. 1 is a perspective view showing a SiCIC member. 図2は管状領域Aを示す断面模式図である。FIG. 2 is a schematic cross-sectional view showing the tubular region A. 図3は管状領域Aの長手方向を示す断面模式図である。FIG. 3 is a schematic cross-sectional view showing the longitudinal direction of the tubular region A. 図4は複数の領域に分割されている管状領域Aを示す断面模式図である。FIG. 4 is a schematic cross-sectional view showing a tubular region A divided into a plurality of regions. 図5はSiC成形体を示す断面図である。FIG. 5 is a cross-sectional view showing a SiC molded body. 図6はSiC成形体の溝にパイプを配置した状態を示す断面図である。FIG. 6 is a cross-sectional view showing a state in which a pipe is arranged in a groove of a SiC molded body. 図7はSiC成形体の溝を充填材で埋めた状態を示す断面図である。FIG. 7 is a cross-sectional view showing a state in which the groove of the SiC molded body is filled with the filler. 図8はSi噴き出しが長孔に存在する状態を示す断面模式図である。FIG. 8 is a schematic cross-sectional view showing a state in which the Si ejection is present in the elongated hole. 図9は接合面を有するSiSiC部材を示す断面図である。FIG. 9 is a cross-sectional view showing a SiCIC member having a joint surface. 図10は領域Cを説明するための断面模式図である。FIG. 10 is a schematic cross-sectional view for explaining the region C.
 図1は、SiSiC部材1を示す斜視図である。
 SiSiC部材1は、ケイ素(Si)と炭化ケイ素(SiC)とを含有する複合材料であり、例えば、熱膨張率が低く、耐熱性、耐摩耗性、熱伝導性、強度などに優れる。
 SiSiC部材1の内部には、一方向に長い長孔2が設けられている。
FIG. 1 is a perspective view showing a SiCIC member 1.
The SiSiC member 1 is a composite material containing silicon (Si) and silicon carbide (SiC). For example, it has a low coefficient of thermal expansion and is excellent in heat resistance, abrasion resistance, thermal conductivity, strength and the like.
Inside the SiC member 1, a long hole 2 long in one direction is provided.
 図1では、長孔2を1本のみ図示しているが、SiSiC部材1は、複数本の長孔2を有していてもよい。複数本の長孔2が存在する場合、それぞれの長孔2は、互いに並行であっても、交差していてもよく、SiSiC部材1の用途に応じて適宜設定される。長孔2は、屈曲していてもよい。
 長孔2の本数の上限は特に限定されないが、SiSiC部材1の熱伝導率を高くして加熱効率を高める観点から、例えば、長孔2に相当する部分(長孔部)の断面積がSiSiC部材1の全体の断面積に占める割合は、20%以下が好ましく、13%以下がより好ましく、8%以下が更に好ましく、4%以下が特に好ましく、1%以下がより特に好ましく、0.5%以下が最も好ましい。
 長孔2は、一方の端部が封止されていてもよいし、SiSiC部材1の一端から他端まで貫通していてもよい。長孔2はSiSiC部材1の用途に応じて適宜設定される。
Although only one elongated hole 2 is shown in FIG. 1, the SiC member 1 may have a plurality of elongated holes 2. When a plurality of elongated holes 2 are present, the elongated holes 2 may be parallel to each other or intersect with each other, and are appropriately set according to the use of the SiC member 1. The elongated hole 2 may be bent.
The upper limit of the number of long holes 2 is not particularly limited, but from the viewpoint of increasing the thermal conductivity of the SiC member 1 to improve the heating efficiency, for example, the cross-sectional area of the portion corresponding to the long holes 2 (long hole portion) is SiCIC. The ratio of the member 1 to the total cross-sectional area is preferably 20% or less, more preferably 13% or less, further preferably 8% or less, particularly preferably 4% or less, still more preferably 1% or less, and 0.5%. % Or less is the most preferable.
One end of the elongated hole 2 may be sealed, or the long hole 2 may penetrate from one end to the other end of the SiC member 1. The elongated hole 2 is appropriately set according to the application of the SiCIC member 1.
 SiSiC部材1の形状および寸法は、SiSiC部材1の用途に応じて、適宜設定される。図1に示すSiSiC部材1は、直方体状であるが、円板状など他の形状であってもよい。
 SiSiC部材1は、少なくとも一つの面(例えば、図1に示すSiSiC部材1の上面)を有することが好ましい。この面の面積は、実用上の利便性の観点から、例えば、100cm以上であり、300cm以上が好ましく、500cm以上がより好ましく、700cm以上が更に好ましく、800cm以上が特に好ましい。
 一方、上記面積の上限は特に限定されないが、費用対効果の観点から、例えば、10000cm以下であり、5000cm以下が好ましく、2000cm以下がより好ましく、1500cm以下が更に好ましく、1000cm以下が特に好ましい。
The shape and dimensions of the SiC member 1 are appropriately set according to the use of the SiC member 1. The SiC SiC member 1 shown in FIG. 1 has a rectangular parallelepiped shape, but may have another shape such as a disk shape.
The SiC SiC member 1 preferably has at least one surface (for example, the upper surface of the SiC SiC member 1 shown in FIG. 1). From the viewpoint of practical convenience, the area of this surface is, for example, 100 cm 2 or more, preferably 300 cm 2 or more, more preferably 500 cm 2 or more, further preferably 700 cm 2 or more, and particularly preferably 800 cm 2 or more.
On the other hand, the upper limit of the above area is not particularly limited, but from the viewpoint of cost effectiveness, for example, it is 10000 cm 2 or less, preferably 5000 cm 2 or less, more preferably 2000 cm 2 or less, further preferably 1500 cm 2 or less, and 1000 cm 2 or less. Is particularly preferable.
 SiSiC部材1の厚さは、費用対効果の観点、および、物理的な衝撃で割れることを防止する観点から、例えば、2.0~15.0mmであり、3.0~13.0mmが好ましく、4.0~12.0mmがより好ましく、5.0~10.0mmが更に好ましく、6.0~9.0mmが特に好ましく、7.0~8.0mmが最も好ましい。 The thickness of the SiC member 1 is, for example, 2.0 to 15.0 mm, preferably 3.0 to 13.0 mm, from the viewpoint of cost effectiveness and from the viewpoint of preventing cracking due to physical impact. 4.0 to 12.0 mm is more preferable, 5.0 to 10.0 mm is further preferable, 6.0 to 9.0 mm is particularly preferable, and 7.0 to 8.0 mm is most preferable.
 図1に示すように、SiSiC部材1は、長孔2の外周の領域である管状領域Aと、管状領域Aの外側の領域である管外領域Bと、を有する。
 管状領域Aは、C単体、SiCおよびSiSiCからなる群から選ばれる少なくとも1種を含むことが好ましい。SiSiCは、SiCとSi単体との複合材料である。
As shown in FIG. 1, the SiC member 1 has a tubular region A which is an outer peripheral region of the elongated hole 2 and an extratube region B which is an outer region of the tubular region A.
The tubular region A preferably contains at least one selected from the group consisting of elemental C, SiC and SiC. SiCSiC is a composite material of SiC and Si alone.
 管状領域Aは、C単体またはSiCを含むことがより好ましい。
 この場合、管外領域BにおけるC単体またはSiCの含有量(単位:体積%)よりも、管状領域AにおけるC単体またはSiCの含有量(単位:体積%)の方が多いことが更に好ましい。管状領域Aおよび管外領域Bを有するSiSiC部材1を製造する際に、後述するように、パイプ(カーボン管またはSiC管)を用いて管状領域Aを形成する場合、管状領域Aおよび管外領域Bは、これらの要件を満たすことが好ましい。
It is more preferable that the tubular region A contains C alone or SiC.
In this case, it is more preferable that the content of C simple substance or SiC in the tubular region A (unit: volume%) is larger than the content of C simple substance or SiC in the extratube region B (unit: volume%). When the tubular region A is formed by using a pipe (carbon tube or SiC tube) as described later when the SiC member 1 having the tubular region A and the out-of-tube region B is manufactured, the tubular region A and the out-tube region A are formed. B preferably meets these requirements.
 〈長孔の径a〉
 図2は、管状領域Aを示す断面模式図である。
 長孔2の径aは、SiSiC部材1の熱伝導率を高める観点から、2.0mm以下であり、1.8mm以下が好ましく、1.5mm以下がより好ましく、1.2mm以下が更に好ましく、0.8mm以下がより更に好ましく、0.7mm以下が特に好ましく、0.4mm以下が最も好ましい。
 一方、長孔2の径aが小さすぎると、後述するSi噴き出しが少量だけ発生した場合にも長孔2が閉塞しやすい。このような閉塞を抑制する観点から、長孔2の径aは、0.1mm以上が好ましく、0.2mm以上がより好ましく、0.3mm以上が更に好ましい。
<Diameter of long hole a>
FIG. 2 is a schematic cross-sectional view showing the tubular region A.
The diameter a of the elongated hole 2 is 2.0 mm or less, preferably 1.8 mm or less, more preferably 1.5 mm or less, still more preferably 1.2 mm or less, from the viewpoint of increasing the thermal conductivity of the SiC member 1. 0.8 mm or less is even more preferable, 0.7 mm or less is particularly preferable, and 0.4 mm or less is most preferable.
On the other hand, if the diameter a of the elongated hole 2 is too small, the elongated hole 2 is likely to be blocked even when a small amount of Si ejection, which will be described later, is generated. From the viewpoint of suppressing such blockage, the diameter a of the elongated hole 2 is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more.
 〈管状領域Aの厚さd〉
 引き続き図2を参照されたい。
 管状領域Aの厚さdは、薄すぎると、割れが生じて不具合が発生する場合がある。このような割れを抑制する観点から、厚さdは、0.05mm以上が好ましく、0.07mm以上がより好ましく、0.10mm以上が更に好ましく、0.12mm以上が特に好ましく、0.15mm以上が最も好ましい。
 一方、上限は特に限定されないが、製造時にパイプに柔軟性を持たせ、取り扱いを簡便にする観点から、厚さdは、例えば、2.0mm以下であり、1.5mm以下が好ましく、1.0mm以下がより好ましく、0.8mm以下が更に好ましく、0.6mm以下がより更に好ましく、0.4mm以下が特に好ましく、0.25mm以下が最も好ましい。
<Thickness d of tubular region A>
Please continue to refer to FIG.
If the thickness d of the tubular region A is too thin, cracks may occur and problems may occur. From the viewpoint of suppressing such cracking, the thickness d is preferably 0.05 mm or more, more preferably 0.07 mm or more, further preferably 0.10 mm or more, particularly preferably 0.12 mm or more, and 0.15 mm or more. Is the most preferable.
On the other hand, although the upper limit is not particularly limited, the thickness d is, for example, 2.0 mm or less, preferably 1.5 mm or less, from the viewpoint of giving flexibility to the pipe at the time of manufacturing and facilitating handling. 0 mm or less is more preferable, 0.8 mm or less is further preferable, 0.6 mm or less is further preferable, 0.4 mm or less is particularly preferable, and 0.25 mm or less is most preferable.
 〈長孔の長さb〉
 図3は、管状領域Aの長手方向を示す断面模式図である。
 長孔2の長さbは、実用状の利便性の観点から、100mm以上であり、125mm以上が好ましく、150mm以上がより好ましく、180mm以上が更に好ましく、210mm以上がより更に好ましく、240mm以上が特に好ましく、270mm以上がより特に好ましく、290mm以上が最も好ましい。
 一方、長さbは、費用対効果の観点から、例えば、800mm以下であり、600mm以下が好ましく、400mm以下がより好ましく、350mm以下が更に好ましく、300mm以下が特に好ましい。
<Length of long hole b>
FIG. 3 is a schematic cross-sectional view showing the longitudinal direction of the tubular region A.
The length b of the elongated hole 2 is 100 mm or more, preferably 125 mm or more, more preferably 150 mm or more, further preferably 180 mm or more, further preferably 210 mm or more, and even more preferably 240 mm or more, from the viewpoint of practical convenience. Particularly preferably, 270 mm or more is more preferable, and 290 mm or more is most preferable.
On the other hand, the length b is, for example, 800 mm or less, preferably 600 mm or less, more preferably 400 mm or less, further preferably 350 mm or less, and particularly preferably 300 mm or less, from the viewpoint of cost effectiveness.
 長孔2の径a、長孔2の長さb、および、管状領域Aの厚さdは、それぞれ、後述するパイプ(カーボン管またはSiC管)の内径、長さおよび厚さに準拠する。 The diameter a of the elongated hole 2, the length b of the elongated hole 2, and the thickness d of the tubular region A are based on the inner diameter, length, and thickness of the pipe (carbon tube or SiC tube) described later, respectively.
 後述するように、管状領域Aが分割されている場合(図4を参照)、長孔2の径a、長孔2の長さb、および、管状領域Aの厚さdは、それぞれ、管状領域Aが分割されていないと仮定した場合の値とする。 As will be described later, when the tubular region A is divided (see FIG. 4), the diameter a of the elongated hole 2, the length b of the elongated hole 2, and the thickness d of the tubular region A are each tubular. It is assumed that the region A is not divided.
 〈軸ずれ量c〉
 引き続き、図3を参照されたい。
 長孔2の長さbは、すなわち、長孔2の中心線Lの距離である。
 例えば、SiSiC部材を製造する過程において、長孔2の中心線が、本来の中心線Lではなく、反り返った中心線Lになる場合がある。これを軸ずれと称する。
 反り返った中心線Lにおいて、本来の中心線Lから最も離れた位置をPとする。位置Pの中心線Lまでの最短距離を、軸ずれ量cとする。
 軸ずれ量cの値は、小さい方が好ましい。具体的には、軸ずれ量cは、0.5mm以下が好ましく、0.4mm未満がより好ましく、0.3mm未満が更に好ましく、0.2mm未満がより更に好ましく、0.1mm以下が特に好ましく、0.05mm以下が最も好ましい。
<Amount of misalignment c>
Please continue to refer to FIG.
The length b of the long hole 2 is, that is, the distance of the center line L1 of the long hole 2 .
For example, in the process of manufacturing a SiC member, the center line of the elongated hole 2 may be a curved center line L2 instead of the original center line L1. This is called axis misalignment.
Let P be the position farthest from the original center line L 1 on the curved center line L 2 . The shortest distance to the center line L1 of the position P is defined as the amount of misalignment c.
The value of the amount of misalignment c is preferably small. Specifically, the amount of misalignment c is preferably 0.5 mm or less, more preferably less than 0.4 mm, further preferably less than 0.3 mm, further preferably less than 0.2 mm, and particularly preferably 0.1 mm or less. , 0.05 mm or less is most preferable.
 〈分割数h〉
 図4は、複数の領域に分割されている管状領域Aを示す断面模式図である。
 管状領域Aは、その環形状が視認できる方向から断面視したときに、図4に示すように、複数の領域に分割されていてもよい。
 管状領域Aの分割数(以下、「分割数h」ともいう)は、図4では2個であるが、3個以上であってもよい。上限は特に限定されず、例えば、分割数hは、8個以下であり、6個以下が好ましい。
 図4では、管状領域Aは、均等に分割されているが、均等でなくてもよい。
<Number of divisions h>
FIG. 4 is a schematic cross-sectional view showing a tubular region A divided into a plurality of regions.
As shown in FIG. 4, the tubular region A may be divided into a plurality of regions when the ring shape is viewed in cross section from a direction in which the ring shape can be visually recognized.
The number of divisions of the tubular region A (hereinafter, also referred to as “division number h”) is two in FIG. 4, but may be three or more. The upper limit is not particularly limited, and for example, the number of divisions h is 8 or less, preferably 6 or less.
In FIG. 4, the tubular region A is evenly divided, but may not be even.
 〈位置ずれ量eおよび分割間隔f〉
 図4に示すように、管状領域Aが分割されることにより、分割された領域どうしにずれ(以下、「位置ずれ」ともいう)が生じたり、分割された領域どうしの間に隙間が生じたりする。
 位置ずれ量eは、長孔2の径を設計通りに製造する観点、および、後述するSi噴き出し量gの値を小さくする観点から、0.30mm以下が好ましく、0.20mm以下がより好ましく、0.15mm以下が更に好ましく、0.10mm以下がより更に好ましく、0.05m以下が特に好ましく、0.02mm以下が最も好ましい。位置ずれ量eの下限は0mmが好ましい。
 管状領域Aの位置ずれ量eと、管状領域Aの厚さdとの比(e/d)は、同様の理由から、2/3(0.666…)以下が好ましく、1/3(0.333…)未満がより好ましく、1/4(0.25)未満が更に好ましく、1/10(0.1)未満がより更に好ましく、1/20(0.05)未満が特に好ましく、1/30(0.033…)未満がより特に好ましく、1/50(0.02)未満が最も好ましい。
 位置ずれ量eは、図4に示すように、分割された領域の端部(同じ側の端部)どうしの距離である。
<Position deviation amount e and division interval f>
As shown in FIG. 4, when the tubular region A is divided, the divided regions may be displaced (hereinafter, also referred to as “positional deviation”), or a gap may be generated between the divided regions. do.
The misalignment amount e is preferably 0.30 mm or less, more preferably 0.20 mm or less, from the viewpoint of manufacturing the diameter of the elongated hole 2 as designed and reducing the value of the Si ejection amount g described later. 0.15 mm or less is further preferable, 0.10 mm or less is further preferable, 0.05 m or less is particularly preferable, and 0.02 mm or less is most preferable. The lower limit of the misalignment amount e is preferably 0 mm.
The ratio (e / d) of the displacement amount e of the tubular region A to the thickness d of the tubular region A is preferably 2/3 (0.666 ...) or less, and 1/3 (0) for the same reason. .333 ...) Is more preferred, less than 1/4 (0.25) is even more preferred, less than 1/10 (0.1) is even more preferred, and less than 1/20 (0.05) is particularly preferred. Less than / 30 (0.033 ...) Is more particularly preferred, and less than 1/50 (0.02) is most preferred.
As shown in FIG. 4, the misalignment amount e is the distance between the ends (ends on the same side) of the divided regions.
 ところで、炭素(C)は、ケイ素(Si)と反応して炭化ケイ素(SiC)になる場合、下記式に示すように、体積が膨張する。
C(52.1cm)+Si(96.8cm)→SiC(100.0cm
 このため、管状領域Aにカーボンを含む材料を用いた場合において、導入されたSiがカーボンと反応してSiCが生成される際に、体積膨張が生じて、パイプ間の隙間に緻密層が形成される。これにより、導入されたSiは、パイプ間を通過しにくくなる。こうして、後述するSi噴き出しが抑制され、長孔に熱電対などを差し込みしやすくなる。
 パイプ間の緻密層の形成によってSiを通過しにくくするためには、分割されている管状領域Aの分割間隔fは小さい方が好ましい。
 管状領域Aにカーボンを含まない材料であるSiCを用いた場合には、このような緻密層の形成は起こらないが、分割されている管状領域Aの分割間隔fは狭い方が、Siが通過しにくく、後述するSi噴き出し量gは小さくなる。
 分割されている管状領域Aの分割間隔fは、後述するSi噴き出し量gの値を小さくする観点から、0.15mm以下が好ましく、0.14mm以下がより好ましく、0.10mm以下が更に好ましく、0.07mm以下がより更に好ましく、0.05mm以下が特に好ましく、0.03mm以下がより特に好ましく、0.02mm以下が最も好ましい。
 一方、下限は特に限定されず、分割間隔fは、例えば、0.000mm以上であり、0.005mm以上が好ましく、0.010mm以上がより好ましい。
 分割間隔fは、図4に示すように、分割された領域の隣り合う端面(切断面)どうしの距離である。
By the way, when carbon (C) reacts with silicon (Si) to become silicon carbide (SiC), its volume expands as shown in the following formula.
C (52.1 cm 3 ) + Si (96.8 cm 3 ) → SiC (100.0 cm 3 )
Therefore, when a material containing carbon is used for the tubular region A, volume expansion occurs when the introduced Si reacts with carbon to generate SiC, and a dense layer is formed in the gap between the pipes. Will be done. This makes it difficult for the introduced Si to pass between the pipes. In this way, the Si ejection described later is suppressed, and it becomes easy to insert a thermocouple or the like into the elongated hole.
In order to make it difficult for Si to pass through by forming a dense layer between the pipes, it is preferable that the division interval f of the divided tubular regions A is small.
When SiC, which is a material containing no carbon, is used in the tubular region A, such formation of a dense layer does not occur, but the narrower the division interval f of the divided tubular regions A, the more Si passes through. It is difficult to do so, and the Si ejection amount g, which will be described later, becomes small.
The division interval f of the divided tubular region A is preferably 0.15 mm or less, more preferably 0.14 mm or less, still more preferably 0.10 mm or less, from the viewpoint of reducing the value of the Si ejection amount g described later. 0.07 mm or less is more preferable, 0.05 mm or less is particularly preferable, 0.03 mm or less is more particularly preferable, and 0.02 mm or less is most preferable.
On the other hand, the lower limit is not particularly limited, and the division interval f is, for example, 0.000 mm or more, preferably 0.005 mm or more, and more preferably 0.010 mm or more.
As shown in FIG. 4, the division interval f is the distance between adjacent end faces (cut surfaces) of the divided regions.
 〈熱伝導率i〉
 SiSiC部材の熱伝導率iは、加熱効率を高める観点から、170W/(m・K)以上が好ましく、180W/(m・K)以上がより好ましく、190W/(m・K)以上が更に好ましく、200W/(m・K)以上がより更に好ましく、210W/(m・K)以上が特に好ましく、220W/(m・K)以上がより特に好ましく、230W/(m・K)以上が最も好ましい。
 熱伝導率iは、LFA457 MicroFlash(NETZSCH社製)を用いて、レーザーフラッシュ法によって、室温(23℃)にて求める。より詳細には、SiSiC部材の管状領域Aを中央に含む、直径が25.4mmの範囲の熱伝導率を、熱伝導率i(熱伝導率i1)とする。測定厚さは6mmとする。
<Thermal conductivity i>
The thermal conductivity i of the SiC member is preferably 170 W / (m · K) or more, more preferably 180 W / (m · K) or more, and further preferably 190 W / (m · K) or more from the viewpoint of increasing the heating efficiency. , 200 W / (m · K) or more is more preferable, 210 W / (m · K) or more is particularly preferable, 220 W / (m · K) or more is particularly preferable, and 230 W / (m · K) or more is most preferable. ..
The thermal conductivity i is determined at room temperature (23 ° C.) by a laser flash method using LFA457 MicroFlash (manufactured by NETZSCH). More specifically, the thermal conductivity in the range of 25.4 mm in diameter including the tubular region A of the SiC member is defined as the thermal conductivity i (thermal conductivity i1). The measured thickness is 6 mm.
 熱伝導率iは、熱伝導率測定装置TCi(C-thermtechnologies社製)を用いて、改良非定常平面測定法(ASTMD7984)によって求めることもできる。より詳細には、SiSiC部材の管状領域Aを中央に含む、直径が17.8mmの範囲の熱伝導率を、熱伝導率i(i2)とする。測定厚さは、SiSiC部材と同じ厚さとする。ただし空気層の影響を無くすため、鏡面仕上げをしたSiSiC部材を積層し計15mm以上の厚さにして測定する。この場合、測定精度は±5%程度の精度で測定できる。 The thermal conductivity i can also be obtained by the improved unsteady plane measurement method (ASTMD7984) using the thermal conductivity measuring device TCi (manufactured by C-thermtechnologies). More specifically, the thermal conductivity in the range of 17.8 mm in diameter including the tubular region A of the SiC member in the center is defined as the thermal conductivity i (i2). The measured thickness is the same as that of the SiC member. However, in order to eliminate the influence of the air layer, a mirror-finished SiC member is laminated and measured to a total thickness of 15 mm or more. In this case, the measurement accuracy can be measured with an accuracy of about ± 5%.
 管外領域Bのみの熱伝導率を、熱伝導率jとする。 The thermal conductivity of only the out-of-tube region B is defined as the thermal conductivity j.
 〈不純物量k〉
 SiSiC部材の不純物量kは、100質量ppm以下が好ましく、80質量ppm以下がより好ましく、60質量ppm以下が更に好ましく、40質量ppm以下が特に好ましく、20質量ppm以下が最も好ましい。
 不純物は、例えば、Al、Ba、Ca、Cd、Co、Cr、Cu、Fe、K、Li、Mg、Mn、Mo、Na、Nb、Ni、P、Pb、Sb、Sn、Sr、Ti、V、ZnおよびZrからなる群から選ばれる少なくとも1種の元素である。不純物量kは、これらの元素の合計量である。
 後述するように、長孔を有するSiSiC部材に接合面が設けられている場合において(図9参照)、この接合面にCuなどの不純物を含有する接着剤が使用されていると、不純物量kの値は大きくなりやすい。
 一方、このような接合面を設けないでSiSiC部材を作製することにより、不純物量kの値を小さくできる。
 不純物量kは、ICP(誘導結合プラズマ)発光分光分析装置(SPS5520、日立ハイテクサイエンス社製)を用いて求める。
<Amount of impurities k>
The amount of impurities k of the SiCIC member is preferably 100 mass ppm or less, more preferably 80 mass ppm or less, further preferably 60 mass ppm or less, particularly preferably 40 mass ppm or less, and most preferably 20 mass ppm or less.
Impurities include, for example, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Sb, Sn, Sr, Ti, V. , Zn and Zr, at least one element selected from the group. The amount of impurities k is the total amount of these elements.
As will be described later, when a joint surface is provided on a SiCIC member having elongated holes (see FIG. 9), if an adhesive containing impurities such as Cu is used on the joint surface, the amount of impurities k The value of is likely to be large.
On the other hand, the value of the impurity amount k can be reduced by producing the SiCIC member without providing such a joint surface.
The amount of impurities k is determined using an ICP (inductively coupled plasma) emission spectroscopic analyzer (SPS5520, manufactured by Hitachi High-Tech Science Corporation).
 なお、不純物の多くは、SiC結晶の内部に形成された空隙に付着している。
 そこで、原料として用いるSiC粒子(例えばα-SiC粒子)を使用前に所定の粒子径となるように破砕する。これにより、SiC粒子において、そのSiC結晶の内部に形成された空隙に存在するFeなどの不純物は、粒子表面に剥き出しとなり、洗浄によって除去できる。
 例えば、アチソン法によって合成されたα-SiC粒子を、粉砕して分級し、最大粒子径を44μm以下、平均粒子径を2~25μmの範囲にしてから、フッ酸と硝酸との混酸および純水を用いて洗浄する。これにより、α-SiC粒子中に存在する不純物であるFeを5質量ppm以下にできる。
 平均粒子径は、レーザー回折・散乱法によって求めた粒度分布(積算質量分布)における積算値50%での粒径を意味する(以下、同様)。
Most of the impurities are attached to the voids formed inside the SiC crystal.
Therefore, SiC particles (for example, α-SiC particles) used as a raw material are crushed so as to have a predetermined particle size before use. As a result, in the SiC particles, impurities such as Fe existing in the voids formed inside the SiC crystals are exposed on the particle surface and can be removed by washing.
For example, α-SiC particles synthesized by the Athison method are pulverized and classified to have a maximum particle diameter of 44 μm or less and an average particle diameter of 2 to 25 μm, and then a mixed acid of hydrofluoric acid and nitric acid and pure water. Wash with. As a result, Fe, which is an impurity present in the α-SiC particles, can be reduced to 5% by mass or less.
The average particle size means the particle size at an integrated value of 50% in the particle size distribution (integrated mass distribution) obtained by the laser diffraction / scattering method (hereinafter, the same applies).
 〈製造方法〉
 SiSiC部材を製造する方法について、図5、図6および図7に基づいて説明する。
<Production method>
A method for manufacturing a SiC member will be described with reference to FIGS. 5, 6 and 7.
 《SiC成形体の作製》
 図5は、SiC成形体3を示す断面図である。
 まず、SiC成形体3を形成する。SiC成形体3は、SiC粒子(図示せず)を含有する成形体であって、U字状の溝4を有する。溝4の形状は、後述するパイプ5(図6および図7を参照)が嵌まり込む形状であれば、特に限定されない。
<< Fabrication of SiC molded product >>
FIG. 5 is a cross-sectional view showing the SiC molded body 3.
First, the SiC molded body 3 is formed. The SiC molded body 3 is a molded body containing SiC particles (not shown) and has a U-shaped groove 4. The shape of the groove 4 is not particularly limited as long as it is a shape into which the pipe 5 (see FIGS. 6 and 7) described later is fitted.
 SiC成形体は、多数の細孔を有する多孔質体でもある。このため、後述するように、SiC成形体に対して、溶融したSi単体が含浸される。
 SiC成形体の空隙率は、10~60体積%が好ましく、12~50体積%がより好ましく、14~40体積%が更に好ましく、16~30体積%が特に好ましく、18~25体積%が最も好ましい。空隙率は、アルキメデス法によって求める。
The SiC molded body is also a porous body having a large number of pores. Therefore, as will be described later, the SiC molded body is impregnated with the molten Si simple substance.
The porosity of the SiC molded product is preferably 10 to 60% by volume, more preferably 12 to 50% by volume, further preferably 14 to 40% by volume, particularly preferably 16 to 30% by volume, and most preferably 18 to 25% by volume. preferable. Porosity is determined by the Archimedes method.
 SiC成形体の寸法および形状は、特に限られず、最終的に得られるSiSiC部材の寸法および形状に応じて、適宜設定される。 The dimensions and shape of the SiC molded body are not particularly limited, and are appropriately set according to the dimensions and shape of the finally obtained SiC member.
 SiC成形体を作製する方法は、特に限定されない。
 例えば、SiC粒子およびバインダの混合物(SiC成形体原料)を、型に流し込み、乾燥することにより、SiC成形体を作製する。SiC成形体原料の固形分濃度は、例えば、5~100質量%の範囲で適宜変更できる。乾燥後、不活性雰囲気にて、高温(例えば1500~2300℃)で加熱して、SiC成形体を焼結させてもよい。
 このような方法として、排泥鋳込成形法、アイソスタチックプレス法、押出成形法などの方法を採用できる。いずれの方法においても、SiC粒子の粒度分布の幅が広い方が、成形性が良好となり、得られるSiC成形体の密度も高くできることから、好ましい。具体的には、日本国特開平5-32458号公報に記載された方法が挙げられる。
 バインダとしては、例えば、有機質の結合剤が挙げられる。有機質の結合剤としては、フェノール樹脂、ポリ酢酸ビニルエマルジョン、アクリル樹脂エマルジョンなどが好適に挙げられる。フェノール樹脂を結合剤として用いる場合、得られるSiC成形体中にカーボンが残留する。このカーボンは、後述するSi含浸の際に、溶融したSi単体と反応してβ-SiCとなる。
The method for producing the SiC molded product is not particularly limited.
For example, a mixture of SiC particles and a binder (raw material for a SiC molded product) is poured into a mold and dried to prepare a SiC molded product. The solid content concentration of the raw material of the SiC molded body can be appropriately changed in the range of, for example, 5 to 100% by mass. After drying, the SiC molded product may be sintered by heating at a high temperature (for example, 1500 to 2300 ° C.) in an inert atmosphere.
As such a method, a method such as a mud waste casting molding method, an isostatic pressing method, or an extrusion molding method can be adopted. In either method, it is preferable that the width of the particle size distribution of the SiC particles is wide because the moldability is good and the density of the obtained SiC molded product can be increased. Specifically, the method described in Japanese Patent Application Laid-Open No. 5-32458 can be mentioned.
Examples of the binder include an organic binder. Phenol resin, polyvinyl acetate emulsion, acrylic resin emulsion and the like are preferably used as the organic binder. When a phenol resin is used as a binder, carbon remains in the obtained SiC molded product. When this carbon is impregnated with Si, which will be described later, it reacts with the molten Si simple substance to become β-SiC.
 溝の無いSiC成形体を作製した後、それを加熱する前に、NC(NumericalControl)フライス盤などの公知の切削工具を用いて溝を形成してもよい。溝の形成後、加熱することにより、溝を有するSiC成形体を焼結させてもよい。 After producing a SiC molded body without grooves, before heating it, grooves may be formed using a known cutting tool such as an NC (Numerical Control) milling machine. After forming the groove, the SiC molded body having the groove may be sintered by heating.
 SiC成形体を作製する方法は、上記方法に限定されない。
 例えば、押出成形法;射出成形法;レーザー照射造形法、バインダジェット造形法などの3D(3次元)印刷法;などの方法を用いてもよい。
The method for producing the SiC molded product is not limited to the above method.
For example, a method such as an extrusion molding method; an injection molding method; a laser irradiation molding method, a 3D (three-dimensional) printing method such as a binder jet molding method; may be used.
 SiC成形体原料に用いるSiC粒子としては、α-SiC粒子が好ましい。
 α-SiC粒子の平均粒子径の範囲は、以下の理由から、2~25μmが好ましく、3~15μmがより好ましい。
 α-SiC粒子の平均粒子径が小さすぎる場合、上述した洗浄によって不純物であるFeを5質量ppm以下にできるが、粉砕過程で混入する不純物が多くなったり、洗浄に手間がかかったりすることがある。また、得られるSiC成形体の気孔組織が細かくなりすぎて、後述するSi含浸が困難になることもある。
 一方、α-SiC粒子の平均粒子径が大きすぎる場合、使用前の分級(例えば、最大粒子径を44μm以下にする分級)において、篩を通過しない粒子が多く残り、使用できる割合が低下することがある。更に、SiC成形体の平滑度が低下し、これによって、得られるSiSiC部材の曲げ強度などの材料物性が不十分となる場合がある。
As the SiC particles used as the raw material for the SiC molded body, α-SiC particles are preferable.
The range of the average particle size of the α-SiC particles is preferably 2 to 25 μm, more preferably 3 to 15 μm, for the following reasons.
If the average particle size of the α-SiC particles is too small, Fe, which is an impurity, can be reduced to 5 mass ppm or less by the above-mentioned cleaning, but the impurities mixed in during the pulverization process may increase and the cleaning may take time and effort. be. In addition, the pore structure of the obtained SiC molded product may become too fine, making it difficult to impregnate Si, which will be described later.
On the other hand, if the average particle size of the α-SiC particles is too large, many particles that do not pass through the sieve remain in the classification before use (for example, the classification to make the maximum particle size 44 μm or less), and the usable ratio decreases. There is. Further, the smoothness of the SiC molded body is lowered, which may result in insufficient material properties such as bending strength of the obtained SiC member.
 《パイプの配置》
 次に、図6に示すように、SiC成形体3の溝4に、パイプ5を配置する。
 図6は、SiC成形体3の溝4にパイプ5を配置した状態を示す断面図である。
 パイプ5は、管状の部材であって、例えば、炭素(C)を含有するカーボン管、または、炭化ケイ素(SiC)を含有するSiC管である。パイプ5は、得られるSiSiC部材1(図1参照)において、管状領域Aとなる。
《Pipe placement》
Next, as shown in FIG. 6, the pipe 5 is arranged in the groove 4 of the SiC molded body 3.
FIG. 6 is a cross-sectional view showing a state in which the pipe 5 is arranged in the groove 4 of the SiC molded body 3.
The pipe 5 is a tubular member, for example, a carbon pipe containing carbon (C) or a SiC pipe containing silicon carbide (SiC). The pipe 5 is a tubular region A in the obtained SiC member 1 (see FIG. 1).
 パイプは、SiC成形体とは異なり、多孔質体ではないこと(緻密体であること)が好ましい。これにより、後述するように、溶融したSiがパイプに含浸しにくい。 Unlike the SiC molded body, the pipe is preferably not a porous body (it is a dense body). This makes it difficult for the molten Si to impregnate the pipe, as will be described later.
 パイプとしてカーボン管を使用する場合、カーボンは強度が低いため、SiSiC部材を製造する際の割れを防ぐためには、カーボン管におけるカーボン含有量をある程度大きくすることが好ましい。
 具体的には、カーボン管におけるカーボンの含有量は、60体積%以上が好ましく、70体積%以上がより好ましく、75体積%以上が更に好ましく、80体積%以上が特に好ましく、80体積%超が最も好ましい。
 上限は特に限定されないが、例えばカーボンの含有量が100体積%であるカーボン管は、柔軟性が低く、SiC成形体に配置する際の自由度が低下しやすい。また、カーボン管のカーボン含有量が95体積%以下であると、溶融したSiがカーボン管の一部または全体に染み込み、カーボン管との反応によりSiC化する。これにより、管状領域Aは、カーボンとSiCとを含む複合体となり、その結果、管外領域Bとの膨張係数差が小さくなることにより、製造時や使用中の熱応力に関する割れが生じにくくなる。このため、カーボン管におけるカーボンの含有量は、98体積%以下が好ましく、95体積%以下がより好ましく、92体積%以下が更に好ましく、90体積%以下が特に好ましい。
When a carbon tube is used as the pipe, the strength of the carbon is low. Therefore, in order to prevent cracking when the SiC member is manufactured, it is preferable to increase the carbon content in the carbon tube to some extent.
Specifically, the carbon content in the carbon tube is preferably 60% by volume or more, more preferably 70% by volume or more, further preferably 75% by volume or more, particularly preferably 80% by volume or more, and more than 80% by volume. Most preferred.
The upper limit is not particularly limited, but for example, a carbon tube having a carbon content of 100% by volume has low flexibility and tends to have a low degree of freedom when placed in a SiC molded body. When the carbon content of the carbon tube is 95% by volume or less, the molten Si permeates a part or the whole of the carbon tube and becomes SiC by the reaction with the carbon tube. As a result, the tubular region A becomes a complex containing carbon and SiC, and as a result, the difference in expansion coefficient from the out-of-tube region B becomes small, so that cracks due to thermal stress during manufacturing and use are less likely to occur. .. Therefore, the carbon content in the carbon tube is preferably 98% by volume or less, more preferably 95% by volume or less, further preferably 92% by volume or less, and particularly preferably 90% by volume or less.
 パイプにSiC管を使用する場合、後述するSi含浸の際の膨張係数差を小さくする観点から、SiC管におけるSiCの含有量は下記が好適である。
 SiC管におけるSiCの含有量は、40体積%以上が好ましく、43体積%以上がより好ましく、47体積%以上が更に好ましく、50体積%以上が特に好ましい。
 一方、SiC管におけるSiCの含有量は、95体積%以下が好ましく、85体積%以下がより好ましく、70体積%以下が更に好ましく、60体積%以下が特に好ましい。
When a SiC pipe is used for the pipe, the SiC content in the SiC pipe is preferably as follows from the viewpoint of reducing the difference in expansion coefficient during Si impregnation, which will be described later.
The content of SiC in the SiC tube is preferably 40% by volume or more, more preferably 43% by volume or more, further preferably 47% by volume or more, and particularly preferably 50% by volume or more.
On the other hand, the content of SiC in the SiC tube is preferably 95% by volume or less, more preferably 85% by volume or less, further preferably 70% by volume or less, and particularly preferably 60% by volume or less.
 パイプは、直線状の管に限定されず、屈曲していてもよい。
 パイプは、一方の端部が閉じていてもよい。
 両端の空いたパイプを使用したうえで、一方の端部を封止してもよい。封止は、例えば、パイプと同じ素材の端材を、接着剤を用いて、パイプの一方の端部に接着させることにより行なう。
 使用する接着剤としては、エポキシ樹脂、ポリカルボシラン、フェノール樹脂、メチルセルロースなどの樹脂を含有する接着剤が挙げられる。接着剤は、これらの樹脂のほかに、炭素粒子、SiC粒子、Si粒子などの粒子を含有してもよい。
 接着剤は、SiC粒子を含有する充填材、Si粒子およびSiC粒子の混合物などであってもよい。
 接着剤における各成分の含有量は、パイプ(例えばカーボン管またはSiC管)の組成等に応じて適宜調整する。
The pipe is not limited to a straight pipe and may be bent.
The pipe may have one end closed.
Pipes with vacant ends may be used and one end may be sealed. Sealing is performed, for example, by adhering end materials of the same material as the pipe to one end of the pipe using an adhesive.
Examples of the adhesive used include adhesives containing resins such as epoxy resin, polycarbosilane, phenol resin, and methyl cellulose. In addition to these resins, the adhesive may contain particles such as carbon particles, SiC particles, and Si particles.
The adhesive may be a filler containing SiC particles, a mixture of Si particles and SiC particles, or the like.
The content of each component in the adhesive is appropriately adjusted according to the composition of the pipe (for example, carbon pipe or SiC pipe).
 なお、カーボンシート等をパイプ形状に巻いて作製したカーボン管は、割れが発生して後述するSi噴き出しが生じやすい場合がある。 It should be noted that the carbon tube produced by winding a carbon sheet or the like in a pipe shape may be cracked and Si ejection, which will be described later, may easily occur.
 管状領域Aを分割させる場合(図4を参照)、分割されたパイプ(例えば、長手方向に沿って切断されたパイプ)を溝に配置する。 When the tubular region A is divided (see FIG. 4), the divided pipe (for example, a pipe cut along the longitudinal direction) is placed in the groove.
 分割されたパイプを得る方法としては、例えば、まず、円柱状のカーボン棒またはSiC棒を長手方向に沿って切断して分割(例えば2分割)し、その後、得られた分割片の内側を削ることにより、分割されたパイプを得る方法(方法1)が挙げられる。
 更に、カーボン棒またはSiC棒に、マシニングセンタのドリル等を用いて長孔を形成し、その後に分割することによって、分割されたパイプを得る方法(方法2)も挙げられる。
 もっとも、方法1と比較して、方法2では、使用するカーボン棒またはSiC棒が直線状であっても、上述した軸ずれが生じやすい場合がある。したがって、軸ずれ量cを低減する観点からは、方法1が好ましい。
As a method for obtaining a divided pipe, for example, first, a columnar carbon rod or a SiC rod is cut along the longitudinal direction and divided (for example, divided into two), and then the inside of the obtained divided piece is scraped. Thereby, a method (method 1) of obtaining a divided pipe can be mentioned.
Further, a method (method 2) of obtaining a divided pipe by forming an elongated hole in a carbon rod or a SiC rod using a drill of a machining center or the like and then dividing the hole can be mentioned.
However, as compared with the method 1, in the method 2, even if the carbon rod or the SiC rod used is linear, the above-mentioned axial deviation may easily occur. Therefore, the method 1 is preferable from the viewpoint of reducing the amount of misalignment c.
 位置ずれ量eおよび分割間隔f(図4を参照)が所望の値となるように、分割されたパイプを固定した状態にして溝に配置する。
 分割されたパイプ片どうしを、上述した接着剤で接着して、隙間を埋めてもよい。
The divided pipes are fixed and arranged in the groove so that the misalignment amount e and the division interval f (see FIG. 4) are desired values.
The divided pipe pieces may be adhered to each other with the above-mentioned adhesive to fill the gap.
 《充填》
 次に、図7に示すように、SiC成形体3の溝4の内部であって、パイプ5の上を、SiC粒子を含有する充填材8で埋める。
 図7は、SiC成形体3の溝4を充填材8で埋めた状態を示す断面図である。
"filling"
Next, as shown in FIG. 7, the inside of the groove 4 of the SiC molded body 3 and the top of the pipe 5 are filled with the filler 8 containing the SiC particles.
FIG. 7 is a cross-sectional view showing a state in which the groove 4 of the SiC molded body 3 is filled with the filler 8.
 例えば、SiC粒子およびバインダの混合物を溝に入れ、その後、この混合物を乾燥したり加熱したりする。これにより、溝の内部が、SiC成形体と同様の組成を有する充填材で埋められる。 For example, a mixture of SiC particles and a binder is placed in a groove, and then the mixture is dried or heated. As a result, the inside of the groove is filled with a filler having the same composition as the SiC molded body.
 上述したバインダジェット造形法を用いる場合、例えば、SiC粒子および硬化剤の混合物を溝に入れ、その後、この混合物にインクジェットノズルからバインダを噴射する。これにより、溝の内部がSiC成形体と同様の組成を有する充填材で埋められる。
 このとき、溝が深い場合は、混合物を入れてバインダ噴射することを繰り返すことにより、溝を段階的に充填材で埋めてもよい。手作業での塗布により、溝を充填材で埋めてもよい。
When the above-mentioned binder jet molding method is used, for example, a mixture of SiC particles and a curing agent is placed in a groove, and then the binder is sprayed onto the mixture from an inkjet nozzle. As a result, the inside of the groove is filled with a filler having the same composition as the SiC molded body.
At this time, if the groove is deep, the groove may be gradually filled with the filler by repeating the binder injection with the mixture. Grooves may be filled with filler by manual application.
 以下、特に断らない限り、充填材もSiC成形体の一部として扱う。 Hereinafter, unless otherwise specified, the filler is also treated as a part of the SiC molded body.
 上述したように、SiC成形体(充填材も含む)は、乾燥後、不活性雰囲気で加熱することにより、焼結させてもよい。これにより、SiC成形体は、乾燥直後よりも緻密化して、強度が向上する。更に、加熱により不純物が揮発して、純度が向上する。
 加熱温度は、1500℃以上が好ましい。これにより、SiC成形体の強度として、後述するSi含浸でのハンドリングに耐えられる十分な強度が得られる。なお、SiC成形体原料のバインダ(結合剤)として、SiC成形体中にカーボンが残留するフェノール樹脂などを使用する場合は、加熱温度を1000℃程度にすることもできる。
 一方、加熱温度を例えば2100℃以上にすると、再結晶と呼ばれる結晶成長が進行し、組織が変化する。もっとも、加熱温度が高すぎると(例えば2300℃超)、結晶成長が顕著になり、更に、SiCの揮発による減量によって、強度や破壊靭性が低下する場合がある。このため、加熱温度は、2300℃以下が好ましい。
As described above, the SiC molded product (including the filler) may be sintered by heating in an inert atmosphere after drying. As a result, the SiC molded body becomes denser than immediately after drying, and the strength is improved. Further, the impurities are volatilized by heating, and the purity is improved.
The heating temperature is preferably 1500 ° C. or higher. As a result, as the strength of the SiC molded product, sufficient strength that can withstand handling with Si impregnation, which will be described later, can be obtained. When a phenol resin or the like in which carbon remains in the SiC molded body is used as the binder (binder) of the raw material of the SiC molded body, the heating temperature can be set to about 1000 ° C.
On the other hand, when the heating temperature is set to, for example, 2100 ° C. or higher, crystal growth called recrystallization proceeds and the structure changes. However, if the heating temperature is too high (for example, over 2300 ° C.), crystal growth becomes remarkable, and further, the strength and fracture toughness may decrease due to the weight loss due to the volatilization of SiC. Therefore, the heating temperature is preferably 2300 ° C. or lower.
 《Si含浸》
 次に、SiC成形体に、ケイ素(Si)を含浸させる。以下、これを「Si含浸」ともいう。
 具体的には、例えば、SiC成形体とSi単体とを相互に接触させた状態で、これら(SiC成形体およびSi単体)を加熱して、Si単体を溶融させる。これにより、溶融したSi単体が、毛細管現象により、多孔質体であるSiC成形体に含浸される。
 このとき、Si単体を、SiC成形体の上面に配置した状態で溶融させることにより、重力を利用して、溶融したSi単体をSiC成形体により含浸させやすくなる。
 Si単体を溶融させる環境は、減圧環境が好ましい。
《Si impregnation》
Next, the SiC molded body is impregnated with silicon (Si). Hereinafter, this is also referred to as "Si impregnation".
Specifically, for example, in a state where the SiC molded body and the Si simple substance are in contact with each other, these (SiC molded body and the Si simple substance) are heated to melt the Si simple substance. As a result, the molten Si simple substance is impregnated into the SiC molded body, which is a porous body, by the capillary phenomenon.
At this time, by melting the Si simple substance in a state of being arranged on the upper surface of the SiC molded body, it becomes easy to impregnate the melted Si simple substance with the SiC molded body by utilizing gravity.
The environment for melting Si alone is preferably a reduced pressure environment.
 加熱温度は、Siの融点以上であればよい。Siの融点は、測定方法により若干異なるが、概ね1410~1414℃である。加熱温度は、1430~1800℃が好ましい。 The heating temperature may be equal to or higher than the melting point of Si. The melting point of Si varies slightly depending on the measuring method, but is approximately 1410 to 1414 ° C. The heating temperature is preferably 1430 to 1800 ° C.
 SiC成形体に含浸されたSiの一部は、パイプにも到達する。しかし、上述したようにパイプが緻密体である場合、パイプにはSiは導入されにくい。
 SiC成形体に導入されたSiのうち、炭素(C)などと反応しなかった分は、そのまま残留する。以下、このようなSiを「遊離Si」ともいう。こうして、SiCと遊離Siとを含有する複合材料であるSiSiC部材が得られる。
 得られるSiSiC部材においては、パイプ(カーボン管またはSiC管)であった領域が管状領域A(図1参照)となり、それ以外の領域(SiC成形体および充填材)が管外領域B(図1参照)となる。
 分割されたパイプを使用する場合、隣り合う分割パイプどうしの間に生じる空間が領域C(図10参照)となる。
A part of Si impregnated in the SiC molded body also reaches the pipe. However, as described above, when the pipe is a dense body, it is difficult to introduce Si into the pipe.
Of the Si introduced into the SiC molded body, the portion that does not react with carbon (C) or the like remains as it is. Hereinafter, such Si is also referred to as "free Si". In this way, a SiC SiC member which is a composite material containing SiC and free Si can be obtained.
In the obtained SiC member, the region that was a pipe (carbon pipe or SiC pipe) becomes a tubular region A (see FIG. 1), and the other region (SiC molded body and filler) is an extrapipe region B (FIG. 1). See).
When a divided pipe is used, the space created between the adjacent divided pipes is the area C (see FIG. 10).
 SiC成形体に導入するSiの量は、最終的に得られるSiSiC部材におけるSi単体の含有量などに応じて、適宜設定される。
 なお、SiC成形体の空隙率が小さい(細孔が少ない)場合は、閉じた細孔が増えてSi含浸が困難となり得る。例えば、SiC成形体には、7質量%以上のSiが含浸されるようにするのが好ましい。
 得られるSiSiC部材におけるSi単体の含有量は、35質量%以下が好ましく、25質量%以下がより好ましい。これにより、高い曲げ強度などの好適な物性が得られる。
The amount of Si to be introduced into the SiC molded body is appropriately set according to the content of Si alone in the finally obtained SiC member.
If the porosity of the SiC molded product is small (there are few pores), the number of closed pores increases, which may make Si impregnation difficult. For example, it is preferable that the SiC molded product is impregnated with 7% by mass or more of Si.
The content of Si alone in the obtained SiC member is preferably 35% by mass or less, more preferably 25% by mass or less. As a result, suitable physical properties such as high bending strength can be obtained.
 得られるSiSiC部材は、Si単体を溶融させる際の加熱によって、焼結される。
 すなわち、SiC(新たに生成したSiCを含む)どうし、および、SiCとSiとが結合して、緻密な焼結体が得られる。
 したがって、得られるSiSiC部材は、SiおよびSiCを含有する複合材料であって、かつ、焼結体でもある。
The obtained SiC member is sintered by heating when melting Si alone.
That is, SiC (including newly generated SiC) and SiC and Si are bonded to each other to obtain a dense sintered body.
Therefore, the obtained SiC member is a composite material containing Si and SiC, and is also a sintered body.
 〈Si噴き出し量g〉
 ここで、図8に基づいて、Si噴き出しの抑制について説明する。
 図8は、Si噴き出し9が長孔2に存在する状態を示す断面模式図である。
<Si ejection amount g>
Here, the suppression of Si ejection will be described with reference to FIG.
FIG. 8 is a schematic cross-sectional view showing a state in which the Si ejection 9 exists in the elongated hole 2.
 ケイ素(Si)の密度は、液体状態では2.560g/cmであるのに対して、固体状態では2.293g/cmである。
 すなわち、遊離Siは、加熱された融液の状態から、冷却されて固体状態に戻ると、体積が12%増えて膨張する。
The density of silicon (Si) is 2.560 g / cm 3 in the liquid state, whereas it is 2.293 g / cm 3 in the solid state.
That is, when the free Si is cooled from the heated melt state to the solid state, the volume increases by 12% and expands.
 このため、図8に示すように、管状領域Aが分割されている場合、遊離Siが体積膨張し、管状領域Aの隙間を通過して、噴き出し(Si噴き出し9)となって長孔2に突出し得る。
 長孔2に大きなSi噴き出し9が存在する(図8中、Si噴き出し量gの値が大きい)場合は、長孔2に熱電対などの棒状部材を差し込みにくい(または、差し込みができない)。
Therefore, as shown in FIG. 8, when the tubular region A is divided, the free Si expands in volume, passes through the gap of the tubular region A, and becomes a ejection (Si ejection 9) into the elongated hole 2. Can protrude.
When a large Si ejection 9 is present in the elongated hole 2 (in FIG. 8, the value of the Si ejection amount g is large), it is difficult (or impossible) to insert a rod-shaped member such as a thermocouple into the elongated hole 2.
 このとき、上述した分割間隔fおよび/または位置ずれ量e(図4を参照)の値を小さくする。これにより、Siは管状領域Aの隙間を通りにくくなる。例えば、体積膨張したSiは、管状領域Aの隙間に侵入しても、隙間の途中や出口で止まったりする。
 こうして、Si噴き出し9が抑制され、長孔2に熱電対などを差し込みしやすくなる。
At this time, the values of the division interval f and / or the misalignment amount e (see FIG. 4) described above are reduced. This makes it difficult for Si to pass through the gaps in the tubular region A. For example, even if the volume-expanded Si enters the gap of the tubular region A, it may stop in the middle of the gap or at the exit.
In this way, the Si ejection 9 is suppressed, and it becomes easy to insert a thermocouple or the like into the elongated hole 2.
 長孔2に熱電対などを差し込みしやすいという理由から、Si噴き出し量gは、1mm未満が好ましく、0.7mm未満がより好ましく、0.4mm未満が更に好ましく、0.2mm未満がより更に好ましく、0.1mm未満が特に好ましく、0.05mm未満がより特に好ましく、0.01mm未満が最も好ましい。
 同様の理由から、Si噴き出し量gと、上述した管状領域Aの厚さd(図2参照)との比(g/d)は、3/4(0.75)以下が好ましく、2/4(0.5)以下がより好ましく、1/4(0.25)未満が更に好ましく、1/5(0.2)未満が特に好ましく、1/10(0.1)未満が最も好ましい。
The Si ejection amount g is preferably less than 1 mm, more preferably less than 0.7 mm, further preferably less than 0.4 mm, still more preferably less than 0.2 mm, because it is easy to insert a thermocouple or the like into the elongated hole 2. , Less than 0.1 mm is particularly preferable, less than 0.05 mm is more particularly preferable, and less than 0.01 mm is most preferable.
For the same reason, the ratio (g / d) of the Si ejection amount g and the thickness d (see FIG. 2) of the tubular region A described above is preferably 3/4 (0.75) or less, preferably 2/4. (0.5) or less is more preferable, less than 1/4 (0.25) is further preferable, less than 1/5 (0.2) is particularly preferable, and less than 1/10 (0.1) is most preferable.
 〈用途〉
 長孔を有するSiSiC部材は、その用途は特に限定されないが、熱伝導性、強度などに優れることから、加熱器具として好適である。SiSiC部材が加熱器具である場合、例えば、SiSiC部材自身および/またはSiSiC部材に載置される被加熱体が加熱される。
 このような加熱器具としては、例えば、IH(誘導加熱)調理器などの加熱調理器が備えるトッププレートが好適に挙げられる。
 加熱調理器のトッププレートは、鍋などの被加熱体が載置される部材である。
 トッププレートの素材としては、従来、セラミックス等が使用されている。トッププレートには、高速で昇降温でき、耐衝撃性が高いことが求められる。このため、加熱調理器のトッププレートとして、SiSiC部材を好適に使用できる。
 温度制御のために、SiSiC部材が有する長孔に熱電対(図示せず)を差し込む。これにより、SiSiC部材、ひいては、SiSiC部材の上に配置された被加熱体の温度を把握できる。
<Use>
The SiC member having a long hole is not particularly limited in its use, but is suitable as a heating appliance because it is excellent in thermal conductivity, strength and the like. When the SiC member is a heating appliance, for example, the SiC member itself and / or the object to be heated placed on the SiC member is heated.
As such a heating appliance, for example, a top plate provided in a heating cooker such as an IH (induction heating) cooker is preferably mentioned.
The top plate of a cooking device is a member on which a heated body such as a pot is placed.
Conventionally, ceramics and the like have been used as the material of the top plate. The top plate is required to be able to raise and lower the temperature at high speed and have high impact resistance. Therefore, the SiCIC member can be suitably used as the top plate of the cooking device.
A thermocouple (not shown) is inserted into the elongated hole of the SiC member for temperature control. This makes it possible to grasp the temperature of the SiCIC member and, by extension, the heated body arranged on the SiCIC member.
 加熱調理器は、システムキッチンの一部として使用されてもよい。
 システムキッチンは、作業台、加熱調理器などの機器を有し、これらの機器がワークトップで繋がっている。ワークトップの素材としては、ステンレス、人工大理石、セラミックス等が用いられる。
 加熱調理器は、例えば、ワークトップに設けられた開口に組み込まれて使用される。この場合、加熱調理器のトッププレートが、システムキッチンのワークトップの一部を構成してもよい。
The cooker may be used as part of the system kitchen.
The system kitchen has equipment such as a workbench and a cooker, and these equipments are connected by a worktop. As the material of the worktop, stainless steel, artificial marble, ceramics and the like are used.
The cooker is used, for example, by incorporating it into an opening provided in the worktop. In this case, the top plate of the cooker may form part of the worktop of the system kitchen.
 ここで、加熱調理器に用いる、長孔を有するSiSiC部材の別態様について、図9に基づいて検討する。 Here, another aspect of the SiCIC member having a long hole used in a cooking device will be examined based on FIG.
 図9は、接合面を有するSiSiC部材21を示す断面図である。
 まず、図5に基づいて説明した方法と同様にして、溝4を有するSiC成形体3と、溝の無いSiC成形体3とを作製する。
 その後、図9に示すように、溝4を有するSiC成形体3の上に、溝の無いSiC成形体3を配置する。このとき、両者の界面を、接着剤22を用いて接合する。
FIG. 9 is a cross-sectional view showing a SiCIC member 21 having a joint surface.
First, in the same manner as the method described with reference to FIG. 5, a SiC molded body 3 having a groove 4 and a SiC molded body 3 without a groove are manufactured.
After that, as shown in FIG. 9, the SiC molded body 3 having no groove is arranged on the SiC molded body 3 having the groove 4. At this time, the interface between the two is joined using the adhesive 22.
 図9に示すSiSiC部材21を、加熱調理器のトッププレートとして使用する場合を考える。この場合、SiSiC部材21の上面に被加熱体(図示せず)を載せ、下面側から加熱する。しかし、使用する接着剤22によっては、接合面において熱が遮られるため、被加熱体に熱が伝わりにくい(すなわち、熱伝導性が劣る)ことがある。 Consider a case where the SiC member 21 shown in FIG. 9 is used as a top plate of a cooking cooker. In this case, a body to be heated (not shown) is placed on the upper surface of the SiCIC member 21 and heated from the lower surface side. However, depending on the adhesive 22 used, heat is blocked at the joint surface, so that heat may not be easily transferred to the object to be heated (that is, the thermal conductivity is inferior).
 これに対して、SiSiC部材1(図1参照)は、このような接合面が無いため、相対的に、被加熱体を加熱しやすい。すなわち、熱伝導性が良好である。 On the other hand, since the SiC member 1 (see FIG. 1) does not have such a joint surface, it is relatively easy to heat the object to be heated. That is, the thermal conductivity is good.
 SiSiC部材の用途は、上述した加熱調理器のトッププレートに限定されず、そのほかに、加熱実験用電気炉のヒーター部材;半導体デバイス製造装置用部材;等が挙げられる。
 SiSiC部材の用途によっては、SiSiC部材は、その長孔に電極などの棒状部材が差し込まれて使用されてもよい。
The use of the SiCIC member is not limited to the above-mentioned top plate of the cooking device, and other examples thereof include a heater member of an electric furnace for a heating experiment; a member for a semiconductor device manufacturing apparatus; and the like.
Depending on the use of the SiC member, the SiC member may be used by inserting a rod-shaped member such as an electrode into the elongated hole thereof.
 以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明は、以下に説明する実施例に限定されない。
 以下、例1~例5、例7~例16、例18、例20~例81が実施例であり、例6、例17および例19が比較例である。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples described below.
Hereinafter, Examples 1 to 5, Example 7 to Example 16, Example 18, Example 20 to Example 81 are examples, and Examples 6, 17, and 19 are comparative examples.
 〈例1~例73〉
 325メッシュの篩で分球された、最大粒子径44μm、平均粒子径8μmのα-SiC粒子に、純水および水溶性のフェノール樹脂を加えて混合し、SiC成形体原料を得た。SiC成形体原料の固形分濃度は、下記表に示す。
 このSiC成形体原料を、石膏型に流し込んで着肉させた後、内部に残留しているSiC成形体原料(泥漿)を排出する方法(排泥鋳込成形法)により、直方体状の成形物を得た。SiC成形物の厚さは、後述するSi含浸の後に、下記表1に示す厚みになるように調整した。SiC成形体の厚さ以外の1辺の長さは、100~520mmの範囲で、使用するパイプの長さ等に応じて、適宜選択した。
 SiC成形体の上面の面積(下記表では、単に「SiC成形体の面積」と表記)も、下記表に記載した。
<Example 1 to Example 73>
Pure water and a water-soluble phenol resin were added to α-SiC particles having a maximum particle diameter of 44 μm and an average particle diameter of 8 μm, which were separated by a 325 mesh sieve, and mixed to obtain a raw material for an SiC molded body. The solid content concentration of the raw material of the SiC molded body is shown in the table below.
A rectangular parallelepiped molded product is formed by a method (mud casting molding method) in which the raw material of the SiC molded body is poured into a gypsum mold to be fleshed, and then the raw material of the SiC molded body (slurry) remaining inside is discharged. Got The thickness of the SiC molded product was adjusted to the thickness shown in Table 1 below after the Si impregnation described later. The length of one side other than the thickness of the SiC molded body was appropriately selected in the range of 100 to 520 mm according to the length of the pipe to be used and the like.
The area of the upper surface of the SiC molded body (in the table below, simply referred to as "the area of the SiC molded body") is also described in the table below.
 次に、SiC成形体に、NCフライス盤を用いて、後述するパイプが嵌まり込む形状の溝を形成した。 Next, using an NC milling machine, a groove having a shape into which a pipe described later was fitted was formed in the SiC molded body.
 次に、SiC成形体の溝に、1本のパイプを配置した。用いたパイプの径(内径a)、長さbおよび厚さdは、下記表に示す。
 パイプは、下記表に示す分割数hで均等に分割された(長手方向に沿って切断された)カーボン管またはSiC管を用いた。下記表の「パイプの素材」の欄には、例えば、カーボンの含有量が81体積%であるカーボン管を用いた場合は「C81」と記載し、SiCの含有量が48体積%であるSiC管を用いた場合は「SiC48」と記載した。
 より具体的には、例16~例19以外では、まず、円柱状のカーボン棒またはSiC棒を長手方向に沿って切断して分割(例えば2分割)し、その後、得られた分割片の内側を削ることにより、分割されたパイプを得た。
 例16~例19では、まず、カーボン棒に、マシニングセンタのドリルを用いて長孔を形成し、その後に分割することによって、分割されたパイプを得た。
Next, one pipe was placed in the groove of the SiC molded body. The diameter (inner diameter a), length b and thickness d of the pipe used are shown in the table below.
As the pipe, a carbon pipe or a SiC pipe which was evenly divided (cut along the longitudinal direction) by the number of divisions shown in the table below was used. In the column of "Pipe material" in the table below, for example, when a carbon tube having a carbon content of 81% by volume is used, it is described as "C81", and SiC having a SiC content of 48% by volume is described as "C81". When a tube was used, it was described as "SiC48".
More specifically, except for Examples 16 to 19, first, a columnar carbon rod or a SiC rod is cut along the longitudinal direction and divided (for example, divided into two), and then the inside of the obtained divided pieces. By scraping, a split pipe was obtained.
In Examples 16 to 19, first, an elongated hole was formed in the carbon rod using a drill of a machining center, and then the pipe was divided to obtain a divided pipe.
 次に、パイプ配置後の溝に、上述したSiC成形体原料を入れ、室温にて12時間乾燥させた。これにより、パイプの上を、SiC成形体と同様の組成を有する充填材で埋めた。この作業は、下記表に示す位置ずれ量eおよび分割間隔fとなるように、分割されたパイプを固定した状態で行なった。 Next, the above-mentioned SiC molded material was placed in the groove after the pipe was placed and dried at room temperature for 12 hours. As a result, the top of the pipe was filled with a filler having the same composition as the SiC molded body. This work was performed in a state where the divided pipes were fixed so as to have the position shift amount e and the division interval f shown in the table below.
 例69~例70以外では、両端の空いたパイプを、一方の端部を封止したうえで使用した。封止は、パイプの端部に、パイプと同じ素材の端材を、接着剤(以下の接着剤1または接着剤2)を用いて接着させることにより行なった。用いた接着剤を下記表に示す。
 例69~例70では、両端の空いたパイプを、端部を封止することなく使用した。この場合、下記表の「接着剤」の欄には「-」を記載した。
Except for Examples 69 to 70, pipes with vacant ends were used after sealing one end. The sealing was performed by adhering the end material of the same material as the pipe to the end portion of the pipe using an adhesive (hereinafter, adhesive 1 or adhesive 2). The adhesive used is shown in the table below.
In Examples 69 to 70, pipes with vacant ends were used without sealing the ends. In this case, "-" is entered in the "Adhesive" column of the table below.
 接着剤1としては、アリルヒドリドポリカルボシラン(SMP-10、Starfire社製)を用いた。後述するSi含浸後において、接着剤1に対応する領域のSiC含有量は、72体積%であった。
 接着剤2としては、エポキシ樹脂(SMC-7030H、信越化学工業社製)に平均粒子径が25μmのカーボン粒子(SGP-25、SECカーボン社製)を15質量%で混合したものを用いた。後述するSi含浸後において、接着剤2に対応する領域のSiC含有量は、31体積%であった。
As the adhesive 1, allylhydride polycarbosilane (SMP-10, manufactured by Starfire) was used. After impregnation with Si, which will be described later, the SiC content of the region corresponding to the adhesive 1 was 72% by volume.
As the adhesive 2, an epoxy resin (SMC-7030H, manufactured by Shin-Etsu Chemical Co., Ltd.) mixed with carbon particles (SGP-25, manufactured by SEC Carbon Co., Ltd.) having an average particle diameter of 25 μm was used in an amount of 15% by mass. After impregnation with Si, which will be described later, the SiC content of the region corresponding to the adhesive 2 was 31% by volume.
 例28~例29では、分割されたパイプ片どうしを、端部の封止に用いた接着剤を用いて接着させた。
 ここで、領域C(図10参照)におけるC単体またはSiCの含有量が20体積%以上であるとき、領域Cを管状領域Aと一体と見なし、分割間隔fを0mmとした。
 例28~例29では、上述した接着剤を用いることで、この含有量を達成できた。
 特に、例28では、管状領域AはSiC含有量が71体積%のSiSiCであるのに対し、領域CはSiC含有量が72体積%のSiSiCとなり、ほぼ同組成のSiSiCで一体化していた。
In Examples 28 to 29, the divided pipe pieces were adhered to each other using the adhesive used for sealing the ends.
Here, when the content of C alone or SiC in the region C (see FIG. 10) is 20% by volume or more, the region C is regarded as one with the tubular region A, and the division interval f is set to 0 mm.
In Examples 28 to 29, this content could be achieved by using the above-mentioned adhesive.
In particular, in Example 28, the tubular region A was SiC with a SiC content of 71% by volume, whereas the region C was SiC with a SiC content of 72% by volume, and was integrated with SiC having almost the same composition.
 次に、パイプを配置した後の溝を充填材で埋めたSiC成形体を、乾燥後、不活性雰囲気にて、電気炉を用いて、1800℃で5時間加熱した。こうして、直方体状のSiC成形体を得た。 Next, the SiC molded body in which the groove after arranging the pipe was filled with the filler was dried and then heated at 1800 ° C. for 5 hours in an inert atmosphere using an electric furnace. In this way, a rectangular parallelepiped SiC molded body was obtained.
 次に、Si含浸を実施した。より詳細には、反応炉内にて、SiC成形体の上にSi単体を配置し、減圧環境にした状態で、1450℃まで加熱した。これにより、Si単体を溶融させて、SiC成形体の中に含浸させた。このとき、SiC成形体のすべての気孔は高純度Siで満たされ、また、パイプおよび/または接着剤の成分として存在しているカーボンは、少なくとも一部がSiと反応し炭化ケイ素化する。こうして、SiSiC部材を得た。 Next, Si impregnation was carried out. More specifically, in the reaction furnace, Si alone was placed on the SiC molded body and heated to 1450 ° C. in a reduced pressure environment. As a result, the Si simple substance was melted and impregnated into the SiC molded body. At this time, all the pores of the SiC molded body are filled with high-purity Si, and at least a part of the carbon existing as a component of the pipe and / or the adhesive reacts with Si to be silicon carbide. In this way, a SiCIC member was obtained.
 得られたSiSiC部材について、任意の場所で断面を切り出し、その断面の光学顕微鏡写真から、Si噴き出し量gを測定した。結果を下記表に示す。
 このとき、光学顕微鏡写真から、長孔の径a、長孔の長さb、管状領域Aの厚さd、位置ずれ量eおよび分割間隔fが維持されていることを確認した。
A cross section of the obtained SiSiC member was cut out at an arbitrary location, and the amount of Si ejected g was measured from an optical micrograph of the cross section. The results are shown in the table below.
At this time, it was confirmed from the optical micrograph that the diameter a of the long hole, the length b of the long hole, the thickness d of the tubular region A, the amount of misalignment e, and the division interval f were maintained.
 得られたSiSiC部材について、上述した方法によって、熱伝導率i(i1およびi2)ならびに熱伝導率jを測定した。結果を下記表に示す。 For the obtained SiC member, the thermal conductivity i (i1 and i2) and the thermal conductivity j were measured by the above-mentioned method. The results are shown in the table below.
 得られたSiSiC部材について、上述した方法によって、不純物量kを測定した。結果を下記表に示す。不純物としては、Al、Ba、Ca、Cd、Co、Cr、Cu、Fe、K、Li、Mg、Mn、Mo、Na、Nb、Ni、P、Pb、Sb、Sn、Sr、Ti、V、ZnおよびZrを対象とした。 For the obtained SiC member, the amount of impurities k was measured by the method described above. The results are shown in the table below. Impurities include Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Sb, Sn, Sr, Ti, V, Zn and Zr were targeted.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
 〈評価結果まとめ〉
 上記表を見ると、例えば、分割間隔fが0.15mmを超えている例42~例49および例63では、Si噴き出し量gが0.2mm以上であった。
 これに対して、分割間隔fが0.15mm以下である例では、Si噴き出し量gが0.2mm未満であった(ただし、位置ずれ量eの値が大きい例23、例41および例61を除く)。
<Summary of evaluation results>
Looking at the above table, for example, in Examples 42 to 49 and Example 63 in which the division interval f exceeds 0.15 mm, the Si ejection amount g was 0.2 mm or more.
On the other hand, in the example where the division interval f is 0.15 mm or less, the Si ejection amount g is less than 0.2 mm (however, Examples 23, 41 and 61 have a large value of the misalignment amount e. except).
 ところで、パイプの本数などを多くすると、得られるSiSiC部材の熱伝導率が低下する懸念がある。そこで、次のように、例74~例78のSiSiC部材を作製し、下記式に基づいて、熱伝導率Kを算出した。 By the way, if the number of pipes is increased, there is a concern that the thermal conductivity of the obtained SiC member will decrease. Therefore, the SiC members of Examples 74 to 78 were produced as follows, and the thermal conductivity K was calculated based on the following formula.
 K={[L-(M×N)]/L}×O
 上記式中、
 K:SiSiC部材の全体の熱伝導率
 L:SiSiC部材の全体の断面積
 M:管状領域Aの最大の断面積
 N:長孔の本数
 O:管外領域Bの熱伝導率を示す。
K = {[L- (M × N)] / L} × O
In the above formula,
K: Overall thermal conductivity of SiC member L: Overall cross-sectional area of SiC member M: Maximum cross-sectional area of tubular region A N: Number of elongated holes O: Thermal conductivity of extratube region B is shown.
 SiC成形体原料の固形分濃度が76質量%である場合のOは230W/(m・K)、同濃度が42質量%である場合のOは182W/(m・K)、同濃度が58質量%である場合のOは202W/(m・K)、同濃度が84質量%である場合のOは232W/(m・K)であった。
 いずれの例においても、管状領域Aと管外領域Bとの密着性は十分に良好であり、境界面の温度差ΔTはゼロとみなした。
When the solid content concentration of the SiC molded body raw material is 76% by mass, O is 230 W / (m · K), when the same concentration is 42% by mass, O is 182 W / (m · K), and the same concentration is 58. When the mass was%, O was 202 W / (m · K), and when the concentration was 84 mass%, O was 232 W / (m · K).
In each example, the adhesion between the tubular region A and the extratube region B was sufficiently good, and the temperature difference ΔT at the interface was regarded as zero.
 〈例74〉
 SiC成形体原料(固形分濃度:76質量%)を用いて作製したSiC成形体(350mm×350mm、厚さ:6.5mm)に、2分割されたカーボン管(外径:1.9mm、内径:0.7mm、厚さ:0.6mm、長さ:330mm)を等間隔で10本配置した。その他の条件は、例1と同様にして、SiSiC部材を作製した。
 このとき、長孔部の断面積がSiSiC部材全体の断面積に占める割合は、5.1%であった。作製したSiSiC部材の熱伝導率は、上記式に基づいて算出したところ、218W/(m・K)であった。
<Example 74>
A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (350 mm × 350 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). : 0.7 mm, thickness: 0.6 mm, length: 330 mm) were arranged at equal intervals. Other conditions were the same as in Example 1 to produce a SiC SiC member.
At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 5.1%. The thermal conductivity of the produced SiC member was 218 W / (m · K) when calculated based on the above formula.
 〈例75〉
 SiC成形体原料(固形分濃度:76質量%)を用いて作製したSiC成形体(300mm×300mm、厚さ:6.5mm)に、2分割されたカーボン管(外径:4.1mm、内径:2.0mm、厚さ:1.0mm、長さ:280mm)を等間隔で10本配置した。その他の条件は、例6と同様にして、SiSiC部材を作製した。
 このとき、長孔部の断面積がSiSiC部材全体の断面積に占める割合は、12.8%であった。作製したSiSiC部材の熱伝導率は、上記式に基づいて算出したところ、201W/(m・K)であった。
<Example 75>
A carbon tube (outer diameter: 4.1 mm, inner diameter) divided into two in a SiC molded body (300 mm × 300 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). : 2.0 mm, thickness: 1.0 mm, length: 280 mm) were arranged at equal intervals. Other conditions were the same as in Example 6 to produce a SiC SiC member.
At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 12.8%. The thermal conductivity of the produced SiC member was 201 W / (m · K) when calculated based on the above formula.
 〈例76〉
 SiC成形体原料(固形分濃度:49質量%)を用いて作製したSiC成形体(360mm×300mm、厚さ:6.5mm)に、2分割されたカーボン管(外径:1.9mm、内径:0.7mm、厚さ:0.6mm、長さ:330mm)を等間隔で10本配置した。その他の条件は、例71と同様にして、SiSiC部材を作製した。
 このとき、長孔部の断面積がSiSiC部材全体の断面積に占める割合は、5.8%であった。作製したSiSiC部材の熱伝導率は、上記式に基づいて算出したところ、171W/(m・K)であった。
<Example 76>
A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (360 mm × 300 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 49% by mass). : 0.7 mm, thickness: 0.6 mm, length: 330 mm) were arranged at equal intervals. Other conditions were the same as in Example 71, and a SiC SiC member was produced.
At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 5.8%. The thermal conductivity of the produced SiC member was 171 W / (m · K) when calculated based on the above formula.
 〈例77〉
 SiC成形体原料(固形分濃度:58質量%)を用いて作製したSiC成形体(350mm×280mm、厚さ:6.5mm)に、2分割されたカーボン管(外径:1.9mm、内径:0.7mm、厚さ:0.6mm、長さ:330mm)を等間隔で10本配置した。その他の条件は、例72と同様にして、SiSiC部材を作製した。
 このとき、長孔部の断面積がSiSiC部材全体の断面積に占める割合は、6.4%であった。作製したSiSiC部材の熱伝導率は、上記式に基づいて算出したところ、189W/(m・K)であった。
<Example 77>
A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (350 mm × 280 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 58% by mass). : 0.7 mm, thickness: 0.6 mm, length: 330 mm) were arranged at equal intervals. Other conditions were the same as in Example 72, and a SiC SiC member was produced.
At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 6.4%. The thermal conductivity of the produced SiC member was 189 W / (m · K) when calculated based on the above formula.
 〈例78〉
 SiC成形体原料(固形分濃度:84質量%)を用いて作製したSiC成形体(350mm×280mm、厚さ:6.5mm)に、2分割されたカーボン管(外径:3.1mm、内径:1.3mm、厚さ:0.9mm、長さ:330mm)を等間隔で10本配置した。その他の条件は、例73と同様にして、SiSiC部材を作製した。
 このとき、長孔部の断面積がSiSiC部材全体の断面積に占める割合は、10.4%であった。作製したSiSiC部材の熱伝導率は、上記式に基づいて算出したところ、208W/(m・K)であった。
<Example 78>
A carbon tube (outer diameter: 3.1 mm, inner diameter) divided into two in a SiC molded body (350 mm × 280 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 84% by mass). : 1.3 mm, thickness: 0.9 mm, length: 330 mm) were arranged at equal intervals. Other conditions were the same as in Example 73, and a SiC SiC member was produced.
At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 10.4%. The thermal conductivity of the produced SiC member was 208 W / (m · K) when calculated based on the above formula.
 〈例79〉
 SiC成形体原料(固形分濃度:76質量%)を用いて作製したSiC成形体(350mm×350mm、厚さ:6.5mm)に、2分割されたカーボン管(外径:1.9mm、内径:0.7mm、厚さ:0.6mm、長さ:280mm)を1本配置した。その他の条件は、例1と同様にして、SiSiC部材を作製した。
 このとき、長孔部の断面積がSiSiC部材全体の断面積に占める割合は、0.4%であった。作製したSiSiC部材の熱伝導率は、上記式に基づいて算出したところ、229W/(m・K)であった。
<Example 79>
A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (350 mm × 350 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). : 0.7 mm, thickness: 0.6 mm, length: 280 mm) was arranged. Other conditions were the same as in Example 1 to produce a SiC SiC member.
At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 0.4%. The thermal conductivity of the produced SiC member was 229 W / (m · K) when calculated based on the above formula.
 〈例80〉
 SiC成形体原料(固形分濃度:76質量%)を用いて作製したSiC成形体(350mm×350mm、厚さ:6.5mm)に、2分割されたカーボン管(外径:1.9mm、内径:0.7mm、厚さ:0.6mm、長さ:280mm)を5本配置した。その他の条件は、例1と同様にして、SiSiC部材を作製した。
 このとき、長孔部の断面積がSiSiC部材全体の断面積に占める割合は、2.2%であった。作製したSiSiC部材の熱伝導率は、上記式に基づいて算出したところ、225W/(m・K)であった。
<Example 80>
A carbon tube (outer diameter: 1.9 mm, inner diameter) divided into two in a SiC molded body (350 mm × 350 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). : 0.7 mm, thickness: 0.6 mm, length: 280 mm) were arranged. Other conditions were the same as in Example 1 to produce a SiC SiC member.
At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 2.2%. The thermal conductivity of the produced SiC member was 225 W / (m · K) when calculated based on the above formula.
 〈例81〉
 SiC成形体原料(固形分濃度:76質量%)を用いて作製したSiC成形体(300mm×300mm、厚さ:6.5mm)に、2分割されたカーボン管(外径:4.1mm、内径:1.8mm、厚さ:1.0mm、長さ:280mm)を等間隔で15本配置した。その他の条件は、例6と同様にして、SiSiC部材を作製した。
 このとき、長孔部の断面積がSiSiC部材全体の断面積に占める割合は、19%であった。作製したSiSiC部材の熱伝導率は、上記式に基づいて算出したところ、186W/(m・K)であった。
<Example 81>
A carbon tube (outer diameter: 4.1 mm, inner diameter) divided into two in a SiC molded body (300 mm × 300 mm, thickness: 6.5 mm) manufactured using a SiC molded body raw material (solid content concentration: 76% by mass). (1.8 mm, thickness: 1.0 mm, length: 280 mm) were arranged at equal intervals of 15 pieces. Other conditions were the same as in Example 6 to produce a SiC SiC member.
At this time, the ratio of the cross-sectional area of the elongated hole portion to the cross-sectional area of the entire SiC member was 19%. The thermal conductivity of the produced SiC member was 186 W / (m · K) when calculated based on the above formula.
 以上、本発明の好適な実施形態について説明したが、本発明は上述の実施の形態に限られるものではなく、特許請求の範囲に記載した限りにおいて、様々な設計変更を行うことが可能なものである。本出願は、2020年10月9日出願の日本国特許出願2020-171478号に基づくものであり、その内容はここに参照として取り込まれる。 Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above-described embodiment, and various design changes can be made as long as it is described in the claims. Is. This application is based on Japanese Patent Application No. 2020-171478 filed on October 9, 2020, the contents of which are incorporated herein by reference.
1:SiSiC部材
2:長孔
3:SiC成形体
4:溝
5:パイプ
8:充填材
9:Si噴き出し
21:SiSiC部材
22:接着剤
A:管状領域
B:管外領域
C:領域
a:長孔の径
b:長孔の長さ
c:軸ずれ量
d:管状領域の厚さ
e:位置ずれ量
f:分割間隔
g:Si噴き出し量
、L:長孔の中心線
1: SiC SiC member 2: Long hole 3: SiC molded body 4: groove 5: pipe 8: filler 9: Si ejection 21: SiC member 22: adhesive A: tubular region B: out-of-tube region C: region a: length Hole diameter b: Long hole length c: Axial deviation d: Tubular region thickness e: Positional deviation f: Division interval g: Si ejection amount L 1 , L 2 : Long hole center line

Claims (12)

  1.  少なくとも1本の長孔が内部に設けられたSiSiC部材であって、
     前記長孔は、径aが2.0mm以下であり、長さbが100mm以上であり、
     前記長孔の外周の領域である管状領域Aを有し、
     前記管状領域Aが、C単体、SiCおよびSiSiCからなる群から選ばれる少なくとも1種を含む、SiSiC部材。
    A SiC member having at least one elongated hole inside.
    The elongated hole has a diameter a of 2.0 mm or less and a length b of 100 mm or more.
    It has a tubular region A, which is an outer peripheral region of the elongated hole, and has a tubular region A.
    A SiC member in which the tubular region A contains at least one selected from the group consisting of elemental C, SiC and SiC.
  2.  熱伝導率iが、170W/(m・K)以上である、請求項1に記載のSiSiC部材。 The SiCIC member according to claim 1, wherein the thermal conductivity i is 170 W / (m · K) or more.
  3.  前記管状領域Aが、複数の領域に分割されている、請求項1または2に記載のSiSiC部材。 The SiCIC member according to claim 1 or 2, wherein the tubular region A is divided into a plurality of regions.
  4.  分割されている前記管状領域Aの分割間隔fが、0.15mm以下である、請求項3に記載のSiSiC部材。 The SiCIC member according to claim 3, wherein the divided tubular region A has a division interval f of 0.15 mm or less.
  5.  前記長孔におけるSi噴き出し量gが、1mm未満である、請求項1~4のいずれか1項に記載のSiSiC部材。 The SiC SiC member according to any one of claims 1 to 4, wherein the Si ejection amount g in the elongated hole is less than 1 mm.
  6.  前記長孔におけるSi噴き出し量gと、前記管状領域Aの厚さdとの比g/dが、3/4以下である、請求項1~5のいずれか1項に記載のSiSiC部材。 The SiC SiC member according to any one of claims 1 to 5, wherein the ratio g / d of the Si ejection amount g in the elongated hole to the thickness d of the tubular region A is 3/4 or less.
  7.  前記管状領域Aの位置ずれ量eと、前記管状領域Aの厚さdとの比e/dが、1/3未満である、請求項1~6のいずれか1項に記載のSiSiC部材。 The SiC member according to any one of claims 1 to 6, wherein the ratio e / d of the displacement amount e of the tubular region A and the thickness d of the tubular region A is less than 1/3.
  8.  前記長孔の軸ずれ量cが、0.3mm未満である、請求項1~7のいずれか1項に記載のSiSiC部材。 The SiCIC member according to any one of claims 1 to 7, wherein the amount c of the long hole is less than 0.3 mm.
  9.  不純物量kが、100質量ppm以下である、請求項1~8のいずれか1項に記載のSiSiC部材。 The SiCIC member according to any one of claims 1 to 8, wherein the amount of impurities k is 100 mass ppm or less.
  10.  厚さが2.0~15.0mmであり、
     少なくとも一つの面を有し、前記面の面積が100cm以上である、請求項1~9のいずれか1項に記載のSiSiC部材。
    It has a thickness of 2.0 to 15.0 mm and has a thickness of 2.0 to 15.0 mm.
    The SiC SiC member according to any one of claims 1 to 9, which has at least one surface and has an area of 100 cm 2 or more.
  11.  請求項1~10のいずれか1項に記載のSiSiC部材と、棒状部材とを備え、
     前記長孔に、前記棒状部材が差し込まれる、加熱器具。
    The SiC SiC member according to any one of claims 1 to 10 and a rod-shaped member are provided.
    A heating appliance in which the rod-shaped member is inserted into the elongated hole.
  12.  請求項1~10のいずれか1項に記載のSiSiC部材を製造する方法であって、
     溝を有するSiC成形体を準備し、
     前記溝に、パイプを配置し、その後、SiCを含有する充填材を入れ、
     前記充填材が前記溝に入った前記SiC成形体に、加熱溶融したSi単体を含浸させる、SiSiC部材の製造方法。
    The method for manufacturing a SiC member according to any one of claims 1 to 10.
    Prepare a SiC molded body with a groove,
    A pipe is placed in the groove, and then a filler containing SiC is put in the groove.
    A method for manufacturing a SiC member, which impregnates the SiC molded body in which the filler is contained in the groove with a simple substance of Si that has been heated and melted.
PCT/JP2021/036718 2020-10-09 2021-10-04 Sisic member, heating appliance, and method for producing sisic member WO2022075290A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000007423A (en) * 1998-06-22 2000-01-11 Ngk Insulators Ltd Composite material and its production
WO2017213089A1 (en) * 2016-06-06 2017-12-14 イビデン 株式会社 Honeycomb structure production method
WO2019176898A1 (en) * 2018-03-13 2019-09-19 イビデン株式会社 Heat exchanger production method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000007423A (en) * 1998-06-22 2000-01-11 Ngk Insulators Ltd Composite material and its production
WO2017213089A1 (en) * 2016-06-06 2017-12-14 イビデン 株式会社 Honeycomb structure production method
WO2019176898A1 (en) * 2018-03-13 2019-09-19 イビデン株式会社 Heat exchanger production method

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