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WO2018164118A1 - Composition de pâte, corps fritté en carbure, son procédé de production, et élément réfractaire - Google Patents

Composition de pâte, corps fritté en carbure, son procédé de production, et élément réfractaire Download PDF

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Publication number
WO2018164118A1
WO2018164118A1 PCT/JP2018/008563 JP2018008563W WO2018164118A1 WO 2018164118 A1 WO2018164118 A1 WO 2018164118A1 JP 2018008563 W JP2018008563 W JP 2018008563W WO 2018164118 A1 WO2018164118 A1 WO 2018164118A1
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WO
WIPO (PCT)
Prior art keywords
carbide
sintered body
paste composition
fluoride
carbide sintered
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2018/008563
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English (en)
Japanese (ja)
Inventor
一成 目黒
哲宗 黒村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Mining and Smelting Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
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Priority to JP2019504600A priority Critical patent/JP6942788B2/ja
Publication of WO2018164118A1 publication Critical patent/WO2018164118A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/36—Carbides

Definitions

  • the present invention relates to a paste composition. More specifically, the present invention relates to a paste composition containing a carbide having a melting point of 3000 ° C. or higher, a carbide sintered body, a manufacturing method thereof, and a refractory member.
  • SiC Silicon carbide
  • SiC silicon carbide
  • the raw material is supplied to a heat-resistant container (crucible) such as graphite and the raw material is heated from the outside of the container by means of high-frequency heating or the like, and SiC single crystal growth is performed at an ultrahigh temperature of about 2500 ° C. Done in the area.
  • a heat-resistant container such as graphite
  • SiC single crystal growth is performed at an ultrahigh temperature of about 2500 ° C. Done in the area.
  • SiC single crystal growth method as described above, sublimation gases such as Si 2 C and SiC 2 sublimated by high-temperature heating, SiH
  • the surface of the graphite container is exposed to a reactive gas derived from a source gas such as 4 . In the presence of such a reactive gas, the heat resistance of graphite is significantly reduced.
  • Patent Document 1 JP 2009-137789 A discloses that tantalum carbide powder is sintered under a high pressure of 20 MPa or higher under vacuum to sinter high-density tantalum carbide. It has been proposed to obtain a molded body consisting of a body.
  • Patent Document 2 discloses a paste in which an auxiliary powder made of transition metal or transition metal carbide is added to carbides such as niobium carbide, hafnium carbide, tantalum carbide, and tungsten carbide.
  • Patent Document 3 a ceramic layer obtained by sintering a mixture containing a metal nitride or metal carbide and a sintering aid such as yttrium oxide is provided on the surface of the carbon material.
  • a carbon material-ceramic material joined body obtained by joining the two has been proposed.
  • the tantalum carbide sintered body proposed in Patent Document 1 needs to be pressurized at the time of sintering, it is not easy to obtain a compact body having a complicated shape and a high density. It was difficult to form a tantalum carbide sintered film on the surface of the material.
  • the paste described in Patent Document 2 and the mixture described in Patent Document 3 contain a sintering aid, a small amount of auxiliary powder is contained in the sintered body when a carbide sintered body is obtained. It tends to remain.
  • the portion where the sintering aid remains in the sintered body is preferentially eroded by the reactive gas, From there, the reactive gas permeates the coating and erodes the graphite, which is the base material, which may deteriorate the high temperature durability of the container.
  • the reactive gas permeates the coating and erodes the graphite, which is the base material, which may deteriorate the high temperature durability of the container.
  • it is considered necessary to fire at a temperature (2500 ° C. or higher) higher than the heat resistance of the base graphite.
  • the object of the present invention is to sinter at a lower temperature than in the prior art, there is little residual amount of sintering aid in the sintered body, and the sintered carbide body has high density and high gas shielding properties. Is to provide a paste composition.
  • Another object of the present invention is to provide a carbide sintered body using the paste composition, a method for producing the same, and a refractory member.
  • the present inventors can sinter the sintered body even when sintered at a temperature lower than 2450 ° C. It was found that a carbide sintered body with a small amount of residual sintering auxiliary agent, a high density and a high gas shielding property can be obtained.
  • the following paste composition, the manufacturing method of the carbide sintered compact using the same, and a refractory member are provided.
  • the paste composition according to the present invention includes a carbide having a melting point of 3000 ° C. or higher, A fluoride of at least one element selected from Group 2 or Group 3 of the Periodic Table; Is included.
  • the carbide sintered body according to another aspect of the present invention is a carbide sintered body of the paste composition described above,
  • the area occupancy of the sintered body obtained from the electron microscope observation of the cross section of the carbide sintered body is D (%),
  • the carbide required condition index S expressed by the following is a sintered carbide body in which S ⁇ 0.69.
  • a fireproof member is a fireproof member comprising a base material and a coating covering at least a part of the surface of the base material,
  • the coating consists of a sintered carbide of the paste composition described above,
  • the carbide sintered body is:
  • the area occupancy of the carbide sintered body obtained from the electron microscope observation of the cross section of the carbide sintered body is D (%),
  • I metal element content other than the carbide obtained by energy dispersive X-ray spectroscopy in the cross section
  • the pure carbide requirement index S expressed by the following is S ⁇ 0.69.
  • the fireproof member according to another aspect of the present invention is a fireproof member formed by bonding the first base material and the second base material via a connecting material
  • the connecting material comprises a carbide sintered body of the paste composition described above,
  • the carbide sintered body is:
  • the area occupancy of the carbide sintered body obtained from the electron microscope observation of the cross section of the carbide sintered body is D (%),
  • I (mol%) the metal element content other than the carbide obtained by energy dispersive X-ray spectroscopy in the cross section
  • I mol%
  • S D ⁇ (1 ⁇ I / 0.6)
  • the pure carbide requirement index S expressed by the following is S ⁇ 0.69.
  • a paste composition in which a specific fluoride is added as a sintering aid to a carbide having a high melting point that is difficult to sinter It is possible to realize a paste composition in which a sintered sintering agent remaining amount in the bonded body is small, and a carbide sintered body having a high density and a high gas shielding property can be obtained.
  • the electron microscope observation photograph of the section of the carbide sintered compact obtained using paste composition 4 of an example The analysis image binarized from the electron microscopic observation photograph of FIG. 1 with the closed region occupied by the pore portion as a black portion and the other as a white portion.
  • the paste composition according to the present invention contains a carbide having a melting point of 3000 ° C. or higher and a fluoride of at least one element selected from Group 2 or Group 3 of the periodic table as essential components. Even when the paste composition according to the present invention is sintered at a temperature lower than that of the prior art, a carbide sintering body having a high density and a high gas shielding property is obtained with a small amount of residual sintering aid in the sintered body. can get. The reason for this is not clear, but is considered as follows. That is, a carbide having a high melting point has low sinterability, and a high-density sintered body cannot be obtained unless a sintering aid is used in combination.
  • the sintering aid one having a melting point lower than the sintering temperature is selected. That is, when the sintering aid melts during sintering, the carbides are easily sintered and a high-density sintered body is obtained. However, usually a small amount of sintering aid remains in the sintered body.
  • a fluoride of an element selected from Group 2 or Group 3 of the periodic table for example, calcium fluoride
  • the sintering aid is melted at the initial stage of sintering.
  • the fluoride is sublimated or vaporized as the sintering proceeds, so that the remaining amount of the sintering aid in the obtained sintered body is considered to be reduced.
  • the carbide used in the present invention is not particularly limited as long as it has a melting point (Tm) of 3000 ° C. or higher, but a known carbide can be suitably used as a metal carbide having a high melting point.
  • a known carbide can be suitably used as a metal carbide having a high melting point.
  • tantalum carbide is preferable from the viewpoint of heat resistance, but two or more kinds may be mixed.
  • the metal carbide as described above can be obtained by a known method.
  • a metal oxide titanium, zirconia, hafnium, niobium, tantalum, tungsten, etc.
  • carbon are mixed, and the mixture is subjected to a hydrogen reduction atmosphere.
  • Metal carbide can be obtained by heating at Alternatively, a metal carbide is obtained by heat-treating, in a non-oxygen atmosphere, a mixed solution in which an organic substance having a functional group capable of coordinating to the metal (for example, OH group or COOH group) is added as a carbon source to a metal alkoxide. Also good.
  • the carbide used in the paste composition according to the present invention is preferably in the form of particles. This is because it is necessary to uniformly disperse the carbide in the paste composition.
  • the average particle size of the carbide is preferably in the range of 0.05 to 20.0 ⁇ m, more preferably in the range of 0.1 to 10.0 ⁇ m. By using carbide particles having an average particle diameter in such a range, the carbide can be uniformly dispersed in the paste composition, and when the paste composition is sintered, a higher-density carbide firing is performed. A ligation can be obtained.
  • the average particle diameter is an average particle diameter (Fischer diameter) measured by an air permeation method using a Fisher sub-sieve sizer model 49 average particle size measuring device manufactured by Fischer, USA.
  • a carbide for example, TaC
  • the average particle diameter of the carbide can be appropriately adjusted depending on the average particle diameter of the raw material (metal oxide) and the pulverization conditions when the obtained carbide is pulverized (pulverized).
  • the particle size of the material to be pulverized is large, and when the pulverization time is long, the particle size tends to be small and the particle size distribution tends to be narrow.
  • the paste composition according to the present invention includes fluoride of at least one element selected from Group 2 or Group 3 of the periodic table in addition to the above-described carbide.
  • Fluoride functions as a sintering aid when sintering carbide. That is, the sintering aid is melted at a temperature equal to or lower than the starting temperature when sintering the carbide (about 1400 ° C.), and the sintered body can be densified when the carbide is sintered.
  • this fluoride as described above has a relatively low boiling point and sublimates or vaporizes at the carbide sintering temperature (2200 to 2600 ° C.), so that the amount of fluoride remaining after sintering can be kept low. . It is considered that a carbide sintered body having a high density and a high gas shielding property can be obtained by using such a fluoride as a sintering aid for the carbide sintered body.
  • the fluoride include beryllium fluoride, magnesium fluoride, calcium fluoride, barium fluoride, lanthanum fluoride, and cerium fluoride.
  • magnesium fluoride and calcium fluoride are used because the carbide can be sufficiently connected by melting of the sintering aid before the carbide is solidified and sintered by sublimation or vaporization of the sintering aid.
  • Barium fluoride, lanthanum fluoride, and cerium fluoride are preferred.
  • calcium fluoride can be preferably used from the viewpoint of obtaining a high-density, high-gas-shielding carbide sintered body.
  • Calcium fluoride has a melting point of about 1400 ° C. and a boiling point of about 2500 ° C.
  • the above-mentioned fluoride is also preferably in a particulate form from the viewpoint of being uniformly dispersed in the paste composition. It is preferable to use a fluoride having an average particle size in the range of 0.1 to 10.0 ⁇ m, and more preferably in the range of 0.5 to 5.0 ⁇ m. The definition of the average particle diameter is the same as described above.
  • the fluoride content in the paste composition is preferably in a ratio of 0.5 to 7 mol with respect to 100 mol of carbide.
  • the paste composition according to the present invention may contain a binder resin in addition to the above-described carbide and fluoride.
  • a binder resin By adding a binder resin, the viscosity adjustment of the paste composition is facilitated and the coating properties and handling properties are improved, so that the moldability when sintering the paste composition to form a carbide sintered body is improved. Can do.
  • the binder resin is not particularly limited as long as the above effects can be obtained.
  • polyvinyl alcohol resin, acrylic resin, polyvinyl butyral resin, methyl cellulose resin, ethyl cellulose resin, acetyl cellulose resin, phenol Resin, urea resin, melamine resin, etc. are mentioned. Two or more of these binder resins may be mixed and used.
  • a particularly preferred binder resin is a polyvinyl butyral resin.
  • the binder resin content in the paste composition affects the viscosity of the paste composition, it is used for the paste composition, that is, for coating the substrates, or for bonding the substrates.
  • the range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of carbide is preferable.
  • the paste composition according to the present invention may contain an additive for improving the dispersibility of carbides and fluorides in addition to the binder resin.
  • an additive for improving the dispersibility of carbides and fluorides for example, a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, a polyallylamine polymer dispersant and the like can be suitably used.
  • the content of the additive is preferably in the range of 0.03 to 0.20 parts by mass with respect to 100 parts by mass of carbide.
  • the paste composition may contain a solvent in addition to the binder resin and additives.
  • the solvent include organic solvents such as ethanol, benzyl alcohol, toluene, dimethylacetamide, and methyl ethyl ketone, and these can be used alone or in combination. Since the solvent content affects the viscosity of the paste composition, it can be appropriately adjusted according to the use of the paste composition, but is generally 5.0 to 30.0 parts by mass with respect to 100 parts by mass of the carbide. The range of is preferable.
  • the carbide sintered body according to the present invention can be obtained by sintering the paste composition described above.
  • the paste composition is poured into a container having a desired shape.
  • the paste composition is dried to remove the solvent. Drying of the paste composition may be natural drying, or may be hot air drying or vacuum drying to shorten the drying time.
  • the temperature at which hot air drying is performed is generally 50 to 150 ° C., although it depends on the type of solvent used. When drying in a heated atmosphere, it is preferably performed in an inert atmosphere to prevent oxidation of the paste composition.
  • the molded body (paste composition) from which the solvent has been removed is sintered to obtain a carbide sintered body.
  • Sintering is performed at a temperature of 2200 to 2600 ° C., preferably at a temperature of 2350 to 2450 ° C.
  • the fluoride in the paste composition is melted below the temperature at the start of sintering (about 1400 ° C.) and the carbide is sintered, the sintered body is densified and the fluoride at the above sintering temperature. Is vaporized or sublimated, so that a sintered carbide with high density and high gas shielding properties can be obtained.
  • the area occupancy D (%) refers to an arbitrary observation region of 15 ⁇ m ⁇ 25 ⁇ m in a cross section of a carbide sintered body, a sintered body portion (matrix region) and a pore portion (non-matrix). It is defined as an area ratio (%) of the sintered body portion. Specifically, in the cross-sectional image of the carbide sintered body, when the closed region occupied by the pore portion is a blackened portion and the other is whitened, the total area of the whitened portion is the observation region. The area occupancy D (%) can be obtained as a ratio of the area.
  • the metal element content I is a mapping of the observation region by energy dispersive X-ray spectroscopic analysis, and the metal elements (for example, titanium, zirconia, It is defined as a ratio (mol%) of a metal element (for example, calcium derived from calcium fluoride) other than metal elements such as hafnium, niobium, tantalum, and tungsten.
  • Typical observation conditions for an electron micrograph are, for example, an acceleration voltage of 15 kV, a movable aperture diameter of 30 ⁇ m, and an emission current of 260 ⁇ A.
  • the value of the pure carbide necessary condition index S of the carbide sintered body is less than 0.69, a carbide sintered body having high density and high gas shielding properties cannot be realized.
  • a preferable range of the pure carbide requirement index S is 0.70 ⁇ S ⁇ 0.90.
  • the carbide sintered body according to the present invention is formed from a carbide sintered body having a desired shape by forming the paste composition into a desired shape as described above and sintering the paste composition.
  • a fireproof member provided as a coating on the surface of a base material made of graphite or the like as described below, or used as a connecting material for joining the base materials together.
  • a coating film is not restricted to application
  • the coating film is sintered at a temperature of 2200 to 2600 ° C. In this way, when the fluoride in the paste composition melts and the carbide is sintered, the sintered body is densified, and the fluoride is vaporized or sublimated by sintering, so it has excellent high temperature durability.
  • a refractory member having a coating made of a carbide sintered body having a high density and a high gas shielding property can be produced.
  • the thickness of the coating made of a carbide sintered body is preferably 30 to 500 ⁇ m, although it depends on the use of the refractory member. If the film thickness is too thin, the fire resistance and high-temperature durability may be insufficient. On the other hand, if the film thickness is too thick, the film may crack or peel due to the difference in thermal expansion coefficient with the substrate. is there.
  • a carbide sintered body that has a thermal expansion coefficient close to that of the base material, or use a base material close to the thermal expansion coefficient of the carbide sintered body. Is preferably used.
  • base materials made of graphite, boron nitride, or the like may be bonded together via a connecting material made of the carbide sintered body of the present invention.
  • a connecting material made of the carbide sintered body of the present invention For example, preparing a plurality of base materials on a flat plate, applying the paste composition described above to the end portions of the flat plate base material, joining the end portions of the substrate to form a container, etc., and then sintering.
  • Sintering is performed at a temperature of 2200 to 2600 ° C. as described above.
  • the thickness of the connecting material is preferably 30 to 500 ⁇ m for the reason described above.
  • Tantalum carbide (Mitsui Metal Mining Co., Ltd., purity 99.5%) having an average particle size of 0.5 to 1.5 ⁇ m was used as a carbide having a melting point of 3000 ° C. or higher.
  • average particle diameter was measured using calcium fluoride (manufactured by Hakuho Chemical Laboratory Co., Ltd.) having an average particle diameter of 10.0 to 15.0 ⁇ m, ethanol as a solvent, and zirconia balls having a diameter of 10 mm. Calcium fluoride ground to a diameter of 1.5 ⁇ m was used.
  • vinyl butyral resin manufactured by Sekisui Chemical Co., Ltd.
  • polyethyleneimine manufactured by Wako Pure Chemical Industries, Ltd.
  • ethanol was used as a solvent. It mix
  • a resin binder is 0.5 mass part with respect to 100 mass parts of carbides
  • an additive is 0.1 mass part.
  • paste compositions 1 to 4 each component was mixed so that the ratio of the solvent was 8.5 parts by mass, and mixed with a hybrid mixer (ARE-310, manufactured by Shinky Co., Ltd.) for 120 seconds to prepare paste compositions 1 to 4. Further, paste composition 5 was prepared in the same manner as paste composition 2 except that 2 mol% of cobalt was added instead of calcium fluoride. Furthermore, paste composition 6 was prepared in the same manner as paste composition 1 except that calcium fluoride was not added.
  • ARE-310 manufactured by Shinky Co., Ltd.
  • An isotropic graphite substrate (manufactured by Shin Nippon Techno Carbon Co., Ltd.) was prepared as a base material.
  • the paste composition obtained as described above was brushed on the surface of the substrate to form a coating film.
  • the coating amount was adjusted so that the coating thickness after drying was 120 ⁇ m.
  • the coating film was dried at a temperature of 50 ° C. to remove the solvent, and then sintered at a temperature of 2400 ° C. in an argon atmosphere to form a carbide sintered body coating on the graphite substrate.
  • the film thickness was 100 ⁇ m.
  • the analysis image binarized by making the closed region which a pore part occupies into a black coating part, and making other than a white coating part is shown in FIG.
  • the area occupation ratio D (%) that is, the ratio of the total area of the white areas other than the pores to the area of the entire observation area of 15 ⁇ m ⁇ 25 ⁇ m was obtained.
  • the carbide sintered bodies (Examples 1 to 4) obtained using the paste compositions 1 to 4 containing fluoride each have an area occupancy ratio D of 70%.
  • the sintered body has a high density and a high theoretical density.
  • the carbide sintered compact (comparative example 1) obtained using the paste composition 5 which uses cobalt as a sintering auxiliary agent is a very high-density sintered compact.
  • the carbide sintered body (Comparative Example 2) obtained using the paste composition 6 containing no sintering aid has an area occupation ratio D of less than 70% and is not a high-density sintered body. Recognize.
  • Example 4 in which the compounding amount of fluoride is contained as much as 6 mol% with respect to the carbide. Even in this case, it can be seen that almost no fluoride remains in the sintered carbide body (the metal element content is less than the detection limit).
  • the carbide sintered body of Comparative Example 1 uses cobalt (Co) as a sintering aid, although it is a very high density sintered body, Co remains in the sintered body. I understand that.
  • the carbide sintered bodies of Examples 1 to 4 had an S value of 0.69 or more, whereas the carbide sintered body of Comparative Example 1 had an S value much lower than these, -0.21. It was.

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  • Ceramic Engineering (AREA)
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Abstract

Le problème décrit par l'invention est de produire une composition de pâte permettant d'obtenir un corps fritté en carbure qui présente une densité élevée et un rendement de protection contre les gaz élevé, tout en contenant moins d'auxiliaire de frittage résiduel dans le corps fritté, même dans des cas où le frittage est effectué à des températures plus basses que jamais auparavant. La solution selon l'invention porte sur une composition de pâte contenant un carbure qui présente un point de fusion supérieur ou égal à 3 000 °C et un fluorure d'au moins un élément qui est choisi parmi des éléments du groupe 2 ou du groupe 3 du tableau périodique.
PCT/JP2018/008563 2017-03-07 2018-03-06 Composition de pâte, corps fritté en carbure, son procédé de production, et élément réfractaire Ceased WO2018164118A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115504791A (zh) * 2022-08-12 2022-12-23 河南好运祥耐材有限公司 一种高抗氧化性能的O’-SiAlON-SiC预制件及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62104002A (ja) * 1985-10-30 1987-05-14 太陽誘電株式会社 抵抗材料
JP2004091241A (ja) * 2002-08-30 2004-03-25 Sumitomo Coal Mining Co Ltd 炭化タングステン系超硬質材料及びその製造方法
JP2010248060A (ja) * 2009-03-23 2010-11-04 Toyota Central R&D Labs Inc 耐高温部材およびその製造方法と耐高温接着剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62104002A (ja) * 1985-10-30 1987-05-14 太陽誘電株式会社 抵抗材料
JP2004091241A (ja) * 2002-08-30 2004-03-25 Sumitomo Coal Mining Co Ltd 炭化タングステン系超硬質材料及びその製造方法
JP2010248060A (ja) * 2009-03-23 2010-11-04 Toyota Central R&D Labs Inc 耐高温部材およびその製造方法と耐高温接着剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115504791A (zh) * 2022-08-12 2022-12-23 河南好运祥耐材有限公司 一种高抗氧化性能的O’-SiAlON-SiC预制件及其制备方法

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TW201838954A (zh) 2018-11-01
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