WO2011081210A1 - 炭化タンタル被覆炭素材料及びその製造方法 - Google Patents
炭化タンタル被覆炭素材料及びその製造方法 Download PDFInfo
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- WO2011081210A1 WO2011081210A1 PCT/JP2010/073810 JP2010073810W WO2011081210A1 WO 2011081210 A1 WO2011081210 A1 WO 2011081210A1 JP 2010073810 W JP2010073810 W JP 2010073810W WO 2011081210 A1 WO2011081210 A1 WO 2011081210A1
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
- C23C16/14—Deposition of only one other metal element
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
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- 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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/0025—Compositions or ingredients of the compositions characterised by the crystal structure
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00405—Materials with a gradually increasing or decreasing concentration of ingredients or property from one layer to another
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Definitions
- the present invention relates to a tantalum carbide-coated carbon material having a carbon substrate and a tantalum carbide coating film formed on the carbon substrate, and a method for producing the same.
- tantalum carbide has heat resistance and gas etching resistance
- a tantalum carbide-coated carbon material in which a tantalum carbide coating film is coated on a carbon material is used as a member of a single crystal manufacturing apparatus for semiconductors such as Si, SiC, and GaN. It is used.
- Patent Document 1 by making the tantalum carbide layer amorphous, the anisotropy of the tantalum carbide crystal is reduced, and the chemically or physically weak portion is reduced on the surface of the tantalum carbide layer.
- the tantalum carbide coating film in Patent Document 2 is a tantalum carbide-coated carbon material by specifically developing the (220) plane of a diffraction peak corresponding to tantalum carbide with respect to another mirror surface by X-ray diffraction. To improve the corrosion resistance and thermal shock resistance.
- the tantalum carbide layer disclosed in Patent Document 1 is amorphous. Further, in the tantalum carbide coating film disclosed in Patent Document 2, although the crystal grains have departed from the amorphous state and shifted to the crystalline state, fine crystal grains are in a dense state. Therefore, the tantalum carbide layers described in Patent Documents 1 and 2 have very many crystal grain boundaries.
- the tantalum carbide coating film having a large number of crystal grain boundaries described in Patent Documents 1 and 2 is a tantalum carbide-coated carbon material having a short lifetime.
- the tantalum carbide coating film when the tantalum carbide coating film is formed on the surface of the carbon base material, it is common to form the tantalum carbide coating film while supporting the carbon base material from below with a jig.
- the tantalum carbide coating film since the tantalum carbide coating film is not formed at the contact portion of the carbon base material with the jig, the tantalum carbide coated carbon material does not exhibit heat resistance and gas etching resistance. Therefore, when performing each tantalum carbide coating film forming step, the tantalum carbide coating film can be formed on the entire surface of the carbon substrate by changing the support position of the jig.
- the present invention has a carbon base material and a tantalum carbide coating film coated on the carbon base material, and the tantalum carbide coating film has a diffraction peak corresponding to tantalum carbide by X-ray diffraction ( 311)
- the tantalum carbide coating film has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- Mainly include crystal grains having a (311) plane parallel to the surface of the carbon base material forming the tantalum carbide coating film. Therefore, since the crystal grains constituting the tantalum carbide coating film are likely to grow, the crystal grain boundary of the tantalum carbide coating film can be drastically reduced as compared with the prior art. Therefore, a dense and high-strength tantalum carbide coating film can be obtained, and the lifetime of the tantalum carbide-coated carbon material can be extended.
- the present invention is a tantalum carbide-coated carbon material having a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction of the tantalum carbide coating film.
- the tantalum carbide coating film there are mainly crystal grains having a (220) plane parallel to the surface of the carbon substrate forming the tantalum carbide coating film. Therefore, since the crystal grains constituting the tantalum carbide coating film are likely to grow, the crystal grain boundary of the tantalum carbide coating film can be drastically reduced as compared with the prior art.
- the sum of the intensities of diffraction lines corresponding to the (311) plane and the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is the total of tantalum carbide in the X-ray diffraction pattern of the tantalum carbide coating film. It is preferably 0.5 or more and 0.9 or less with respect to the total intensity of diffraction lines corresponding to the crystal plane.
- the intensity of diffraction lines on the (311) plane or the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is maximized.
- the crystal grain boundary of a tantalum carbide coating film can be reduced compared with a prior art.
- the half width of the diffraction line on the (311) plane or the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is 0 mm. It is preferable that it is 2 ° or less.
- the tantalum carbide coating film is composed of tantalum carbide crystal grains with high crystallinity and sufficiently developed, so the crystal grain boundary of the tantalum carbide coating film is dramatically reduced compared to the prior art. Can be made.
- the present invention has a carbon substrate and a tantalum carbide coating film coated on the carbon substrate, and the crystal grains forming the tantalum carbide coating film are coated with tantalum carbide coating from the surface of the carbon substrate. It is a tantalum carbide-coated carbon material that increases in a gradient toward the outer surface of the coating. As a result, the tantalum carbide coating film has improved adhesion to the carbon base material and can greatly reduce crystal grain boundaries.
- the present invention is a method for producing a tantalum carbide coated carbon material for forming a tantalum carbide coating film on a carbon substrate, a crystal nucleation step of forming a tantalum carbide crystal nucleus on the surface of the carbon substrate, A crystal growth step of growing the tantalum carbide crystal nuclei after the crystal nucleation step, wherein the crystal growth step is a method for producing a tantalum carbide-coated carbon material having a temperature raising step for gradually increasing the production temperature.
- tantalum carbide crystal nuclei are formed inside the recesses on the surface of the carbon base material, and the crystallinity of the tantalum carbide coating film is gradually improved by gradually increasing the manufacturing temperature in the crystal growth step. I can. Therefore, since a tantalum carbide coating film adapted to the uneven shape on the surface of the carbon substrate can be formed, the tantalum carbide coating film is difficult to peel off from the carbon substrate, and the vicinity of the surface of the tantalum carbide coating film is crystalline. Therefore, a tantalum carbide coating film having fewer crystal grain boundaries than the conventional one can be obtained.
- the temperature for forming the tantalum carbide crystal nucleus is preferably 850 to 950 ° C.
- sufficient tantalum carbide crystal nuclei can be formed inside the recesses on the surface of the carbon substrate, and a tantalum carbide coating film adapted to the uneven shape on the surface of the carbon substrate can be obtained.
- the adhesion of the film to the carbon substrate can be improved.
- the temperature raising step preferably has a temperature difference of 50 ° C. or more.
- a tantalum carbide coating film adapted to the concavo-convex shape of the carbon substrate surface is obtained near the surface of the carbon substrate, and crystal grains develop and crystal grain boundaries are formed near the outer surface of the tantalum carbide coating film.
- a tantalum carbide coating film with a low content can be obtained.
- the tantalum carbide coating film in which crystal grains are developed can be laminated. For this reason, a tantalum carbide coating film having fewer crystal grain boundaries than the conventional one can be obtained with a desired thickness.
- the temperature raising step it is preferable to increase the manufacturing temperature at a constant rate. Thereby, the crystallinity improvement of the tantalum carbide crystal grains can be prevented, and the tantalum carbide coating film can be prevented from peeling off. As a result, the crystallinity of the tantalum carbide coating film can be improved in a gradient manner.
- the present invention is a method for producing a tantalum carbide coated carbon material, wherein a tantalum carbide coated film is formed on a carbon substrate by a tantalum carbide coated film forming step, wherein the tantalum carbide coated film forming step includes the carbon A first forming step of forming a first tantalum carbide coating film on the surface of the substrate; and a second forming step of forming at least one tantalum carbide coating film on the first tantalum carbide coating film.
- the first tantalum carbide coating film is a method for producing a tantalum carbide-coated carbon material having a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction. is there.
- the crystal grain boundary of the tantalum carbide coating film formed by the tantalum carbide coating film forming step is remarkably smaller than that of the conventional tantalum carbide coating film, and the tantalum carbide coating film is formed during the new tantalum carbide coating film forming step. Impurities are not released from Therefore, no impurity gas is interposed between the tantalum carbide coating film as a base and the new tantalum carbide coating film. Further, the crystallinity of the tantalum carbide coating film as the base is hardly changed by the heat treatment, and the crystallinity of the new tantalum carbide coating film is equivalent to that of the new tantalum carbide coating film.
- the tantalum carbide coating film has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the crystal grains having a (311) plane parallel to the surface of the carbon substrate forming the tantalum carbide coating film are mainly crystal grains having a (311) plane parallel to the surface of the carbon substrate forming the tantalum carbide coating film. Therefore, since the crystal grains constituting the tantalum carbide coating film are likely to grow, the crystal grain boundary of the tantalum carbide coating film can be drastically reduced as compared with the prior art. Therefore, a dense and high-strength tantalum carbide coating film can be obtained, and the lifetime of the tantalum carbide-coated carbon material can be extended.
- the first forming step and the second forming step are performed while supporting the object to be covered by a support tool, and a second portion is formed on the missing portion of the coating film generated by the support tool in the first forming step. It is preferable to coat in the process. Thereby, a tantalum carbide coating film can be formed on the entire surface of the carbon substrate.
- the first forming step includes a crystal nucleation step for forming tantalum carbide crystal nuclei on the surface of the carbon substrate, and a crystal growth step for crystal growth of the tantalum carbide crystal nuclei after the crystal nucleation step.
- the crystal growth step includes a temperature raising step for gradually increasing the manufacturing temperature.
- the crystallinity of the tantalum carbide coating film can be improved in a gradient manner by gradually increasing the manufacturing temperature in the crystal growth step. Accordingly, crystallinity develops near the surface of the tantalum carbide coating film, and a tantalum carbide coating film with fewer crystal grain boundaries than in the prior art can be obtained.
- the tantalum carbide coating film preferably has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the tantalum carbide coating film there are mainly crystal grains having a (220) plane parallel to the surface of the carbon substrate forming the tantalum carbide coating film. Therefore, since the crystal grains constituting the tantalum carbide coating film are likely to grow, the crystal grain boundary of the tantalum carbide coating film can be drastically reduced as compared with the prior art.
- the sum of the intensity of diffraction lines corresponding to the (311) plane and the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is the same as that of tantalum carbide in the X-ray diffraction pattern of the tantalum carbide coating film. It is preferably 0.5 or more and 0.9 or less with respect to the sum of the intensities of diffraction lines corresponding to all crystal planes.
- the intensity of the diffraction line corresponding to the (311) plane or the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is maximized.
- the crystal grain boundary of a tantalum carbide coating film can be reduced compared with a prior art.
- the half width of the diffraction line on the (311) plane or the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is 0 mm. It is preferable that it is 12 degrees C or less.
- the tantalum carbide coating film is composed of tantalum carbide crystal grains with high crystallinity and sufficiently developed, so the crystal grain boundary of the tantalum carbide coating film is dramatically reduced compared to the prior art. Can be made.
- the present invention is a method for producing a tantalum carbide-coated carbon material for forming a tantalum carbide coating film on a carbon substrate, and a tantalum coating film forming step for forming a tantalum coating film on the surface of the carbon substrate. And a carburizing treatment step of carburizing the tantalum coating film.
- a tantalum coating film is formed on the surface of a carbon substrate, and this tantalum coating film is converted into a tantalum carbide coating film, so that the crystal grain boundary of tantalum carbide is dramatically improved compared to the prior art. Can be reduced.
- the tantalum coating film softens under high temperature and is adapted to the unevenness of the carbon substrate surface to form a tantalum carbide coating film. be able to. Accordingly, a tantalum carbide-coated carbon material having a dense and high-strength tantalum carbide coating film having a high degree of adhesion to the carbon substrate can be obtained.
- the tantalum coating film forming step and the carburizing treatment step a plurality of times in order. Thereby, the film thickness of the tantalum carbide coating film can be easily changed.
- the tantalum coating film forming step it is preferable to repeat the tantalum coating film forming step a plurality of times. Thereby, the film thickness of the tantalum coating film can be changed.
- the carburizing process is performed at 1700 ° C. to 2500 ° C. in the carburizing process. Thereby, a tantalum carbide-coated carbon material that is not easily consumed in a high-temperature environment can be obtained.
- the carbon base material preferably has a thermal expansion coefficient of 6.5 to 8.0 ⁇ 10 ⁇ 6 / K.
- the tantalum coating step is performed while the object to be coated is supported by a support, and in the first tantalum coating film forming step, the defective portion generated by the support is formed for the second and subsequent tantalum coating films. It is preferable to coat in the process. Thereby, a tantalum carbide coating film can be formed on the entire surface of the carbon substrate.
- the present invention is a method for producing a tantalum carbide-coated carbon material that forms a tantalum carbide coating film on a carbon substrate by a tantalum carbide coating formation step, and the tantalum coating film that forms a tantalum coating film on the surface of the carbon substrate.
- a first tantalum carbide coating film forming step for forming a first tantalum carbide coating film through a coating film forming process and a carburizing process for carburizing the tantalum coating film; and on the first tantalum carbide coating film.
- a tantalum coating film is formed on the surface of a carbon substrate, and a first tantalum carbide coating film is formed by converting the tantalum coating film into a tantalum carbide coating film.
- a new second tantalum carbide coating film is formed on the film, it is possible to easily form a second tantalum carbide coating film that inherits the crystal orientation of the first tantalum carbide coating film. It is possible to obtain a tantalum carbide-coated carbon material having a drastic reduction in the amount of the material compared with the prior art. Therefore, a tantalum carbide-coated carbon material having a dense and high-strength tantalum carbide coating film can be obtained.
- the first tantalum carbide coating film that requires a tantalum coating film forming step and a carburizing treatment step. Succeeded in reducing the manufacturing process to only the tantalum carbide coating film forming process.
- the tantalum film is preferably carburized at 1700 ° C. to 2500 ° C. Thereby, a tantalum carbide-coated carbon material that is not easily consumed in a high-temperature environment can be obtained.
- the carbon base material preferably has a thermal expansion coefficient of 6.5 to 8.0 ⁇ 10 ⁇ 6 / K.
- the thermal expansion coefficient of a carbon base material is close to the thermal expansion coefficient of a tantalum carbide, the thermal stress concerning a tantalum carbide coating film can be reduced. Therefore, a tantalum carbide-coated carbon material having a tantalum carbide coating film that is difficult to peel from the carbon substrate can be obtained.
- the tantalum carbide coating film preferably has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the tantalum carbide coating film preferably has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the tantalum carbide coating film preferably has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction. Thereby, there are mainly crystal grains having a (220) plane parallel to the surface of the carbon base material forming the first tantalum carbide coating film. Therefore, a dense and high strength tantalum carbide film with few crystal grain boundaries can be obtained.
- the sum of diffraction intensities in the (311) plane and the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film corresponds to the entire crystal plane of tantalum carbide in the X-ray diffraction pattern of the tantalum carbide coating film. It is preferable that it is 0.5 or more and 0.9 or less with respect to the sum total of the intensity
- the intensity of diffraction lines on the (311) plane in the X-ray diffraction pattern of the tantalum carbide coating film is maximized. Thereby, a dense and high strength tantalum carbide film with few crystal grain boundaries can be obtained.
- the half width of the diffraction line on the (311) plane in the X-ray diffraction pattern of the tantalum carbide coating film is 0 mm. It is preferable that it is 12 degrees C or less. As a result, a tantalum carbide coating film composed of tantalum carbide crystal grains having high crystallinity and sufficiently developed can be obtained, so that a dense and high-strength tantalum carbide film with few crystal grain boundaries can be obtained.
- the tantalum carbide coated film has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the tantalum carbide coating film there are mainly crystal grains having a (311) plane parallel to the surface of the carbon base material forming the tantalum carbide coating film. Therefore, since the crystal grains constituting the tantalum carbide coating film are likely to grow, the crystal grain boundary of the tantalum carbide coating film can be drastically reduced as compared with the prior art. Therefore, a dense and high-strength tantalum carbide coating film can be obtained, and the lifetime of the tantalum carbide-coated carbon material can be extended.
- the tantalum carbide crystal nucleus is formed inside the recess on the surface of the carbon substrate, and in the crystal growth step
- the crystallinity of the tantalum carbide coating film can be improved in a gradient manner. Therefore, since a tantalum carbide coating film adapted to the uneven shape on the surface of the carbon substrate can be formed, the tantalum carbide coating film is difficult to peel off from the carbon substrate, and the vicinity of the surface of the tantalum carbide coating film is crystalline. Therefore, a tantalum carbide coating film having fewer crystal grain boundaries than the conventional one can be obtained.
- the crystal grain boundary of the tantalum carbide coating film formed by the tantalum carbide coating film forming step is conventionally known.
- the impurities are not released. Therefore, no impurity gas is interposed between the tantalum carbide coating film as a base and the new tantalum carbide coating film.
- the tantalum carbide coating film serving as the base is hardly changed in crystallinity during the new tantalum carbide coating film forming process, and the crystallinity of the new tantalum carbide coating film is equivalent to that of the new tantalum carbide coating film. Therefore, the difference in crystallinity hardly occurs between the tantalum carbide coating film as a base and the new tantalum carbide coating film, and the adhesion is good.
- the tantalum coating film is formed on the surface of the carbon base material. Is converted into a tantalum carbide coating film, the crystal grain boundaries of tantalum carbide can be drastically reduced as compared with the prior art.
- the tantalum coating film softens under high temperature and is adapted to the unevenness of the carbon substrate surface to form a tantalum carbide coating film. be able to. Accordingly, a tantalum carbide-coated carbon material having a dense and high-strength tantalum carbide coating film having a high degree of adhesion to the carbon substrate can be obtained.
- the tantalum coating film is formed on the surface of the carbon substrate.
- the second tantalum carbide coating film which inherits the crystal orientation of the first tantalum carbide coating film, can be easily formed, and the crystal grain boundaries of the tantalum carbide coating film are drastically reduced compared to the prior art. Can be made.
- a tantalum carbide-coated carbon material having a dense and high-strength tantalum carbide coating film can be obtained. Furthermore, by changing the manufacturing method of the second tantalum carbide coating film with respect to the first tantalum carbide coating film, the first tantalum carbide coating film that requires a tantalum coating film forming step and a carburizing treatment step. Succeeded in reducing the manufacturing process to only the tantalum carbide coating film forming process.
- FIG. 6 is a diagram showing the results of Examples 1 to 4.
- FIG. 6 is a diagram showing the results of Examples 1 to 4. It is a figure which shows the result of Example 3.
- Example 5 It is a figure which shows the result of Example 5, 6. It is a figure which shows the result of Example 5, 6. It is a figure which shows the result of Example 6, It is a figure which shows the result of Example 6. It is a figure which shows the result of Example 7,8. It is a figure which shows the result of Example 7,8. It is a figure which shows the result of Example 7. It is a figure which shows the result of the tantalum coating film of Example 9. It is a figure which shows the result of Example 9. It is a figure which shows the result of Example 9. It is a figure which shows the result of Example 9. It is a figure which shows the result of Example 9. It is a figure which shows the result of Example 9. It is a figure which shows the result of the tantalum carbide coating film used as the foundation
- Example 10 It is a figure which shows the result of Example 10. It is a figure which shows the result of Example 10. It is a figure which shows the result of Example 10. It is a figure which shows the result of Example 10. It is a figure which shows the result of the comparative example 1. It is a figure which shows the result of the comparative example 1. It is a figure which shows the result of the comparative example 3. It is a figure which shows the result of the comparative example 3.
- Method for producing tantalum carbide-coated carbon material (Method for producing tantalum carbide-coated carbon material] (Method for forming tantalum carbide coating film by CVD process (1))
- a process for forming a tantalum carbide coating film by a CVD process will be described.
- the method for forming the tantalum carbide coating film is not limited to the CVD method, and a conversion (CVR) method, a thermal spraying method, a physical vapor deposition (PVD) method, or the like may be used.
- CVR conversion
- PVD physical vapor deposition
- the high frequency induction heating apparatus has a CVD reaction chamber.
- the CVD reaction chamber refers to the inside of a graphite furnace wall (not shown) serving as an inductive load wrapped in a heat insulating material (not shown) installed inside a quartz tube having a double tube structure.
- a heating device having a high frequency coil (induction coil) is disposed outside the quartz tube.
- the space in the CVD reaction chamber is heated by a high frequency coil.
- a gas introduction pipe into which a source gas is introduced is disposed at one end of the CVD reaction chamber.
- An exhaust port is formed at the other end of the CVD reaction chamber.
- An exhaust pipe for exhausting the gas in the CVD reaction chamber is disposed at the exhaust port.
- a variable valve is installed near the exhaust port of the exhaust pipe.
- the pressure in the CVD reaction chamber can be adjusted by a variable valve.
- a gas flow controller is provided upstream of the CVD reaction chamber.
- the gas flow rate of the source gas introduced into the CVD reaction chamber is adjusted by a gas flow controller.
- the CVD reaction chamber is evacuated, and then degassing processing and CVD processing are sequentially performed.
- One or a plurality of carbon base materials 1 are installed in the CVD reaction chamber (see FIG. 2A), and the CVD reaction chamber is evacuated to about 0.1 to 0.01 Torr (13.33 Pa to 1.333 Pa). To do.
- degassing is performed by heating the inside of the CVD reaction chamber. Specifically, after introducing hydrogen gas into the CVD reaction chamber at 7000 cc / min, the inside of the CVD reaction chamber is heated to about 1100 ° C. to degas the CVD reaction chamber.
- a process for forming a tantalum carbide coating film by a CVD process will be described. While keeping the CVD reaction chamber shown in FIG. 1 at 850 to 1100 ° C., the pressure inside the CVD reaction chamber is reduced to 10 Torr (1333 Pa) or less by operating the variable valve. Thereafter, a halogen gas of tantalum such as tantalum pentachloride (TaCl 5 ) and a hydrocarbon gas such as methane (CH 4 ) are supplied as source gases into the CVD reaction chamber.
- a carrier gas for example, argon gas, hydrogen gas, or a mixed gas thereof is supplied.
- a tantalum carbide coating film 2 is formed on the surface of the carbon substrate (see FIG. 2B).
- the C / Ta ratio in the tantalum carbide coating film 2 is preferably 1.0 to 2.0.
- the carbon source in the source gas supplied into the CVD reaction chamber is preferably 2 to 25 times the tantalum source.
- reaction of following Reaction formula (1) advances by thermal decomposition reaction of the mixed gas of tantalum pentachloride, methane gas, and hydrogen gas.
- the tantalum carbide produced by this reaction is laminated on the surface of the carbon material to form a tantalum carbide coating film.
- the reaction of reaction formula (1) proceeds, impurities are present at the crystal grain boundaries of the tantalum carbide coating film.
- chloride used as a raw material
- chlorine-based impurities are mainly present.
- the impurities mainly chlorine impurities
- the CVD process deposition process of the tantalum carbide coating film
- the CVD process is performed at 850 to 1100 ° C., so that the impurities are released from the coating film at the same time as the film formation, and the tantalum carbide coating is formed.
- the impurity concentration of the covering film can be reduced.
- This method is a method for producing a tantalum carbide-coated carbon material for forming a tantalum carbide coating film on a carbon substrate, a crystal nucleation step for forming tantalum carbide crystal nuclei on the surface of the carbon substrate, and crystal nucleation
- a crystal growth step of growing tantalum carbide crystal nuclei after the step, and the crystal growth step includes a temperature raising step for gradually increasing the manufacturing temperature (hereinafter referred to as a temperature rise).
- the higher the CVD processing temperature the larger the tantalum carbide crystal grains, and the crystal grain boundaries of the tantalum carbide coating film can be reduced.
- the tantalum carbide coating film has many crystal grains larger than the pore diameter on the surface of the carbon substrate. Furthermore, the higher the CVD processing temperature, the shorter the transition from crystal nucleation to nucleus growth, so the crystal growth process proceeds from the crystal nuclei formed on the protrusions on the carbon substrate surface, and the recesses on the carbon substrate surface. However, crystal nucleation is inadequate. For this reason, the contact area between the tantalum carbide coating film and the carbon substrate is reduced, and the degree of adhesion is lowered. In addition, since the tantalum carbide coating film does not have the property of softening under high temperature environment and conforming to the unevenness of the carbon substrate surface like the tantalum coating film, it is suitable to improve the contact area by heat treatment. Absent.
- tantalum carbide-coated carbon material with high adhesion can be obtained.
- tantalum carbide crystal nuclei are formed in the concave portions and convex portions of the surface of the carbon base material by performing a CVD process at a temperature lower than about 950 ° C., preferably lower than 930 ° C. (crystal nucleation step).
- the CVD process temperature is gradually increased (temperature raising step) to promote the nucleus growth of the crystal nucleus (crystal growth step).
- the temperature for forming the tantalum carbide crystal nuclei is preferably 850 to 950 ° C.
- the manufacturing temperature after the temperature raising step it is preferable not to change the manufacturing temperature after the temperature raising step.
- tantalum carbide coating films with developed crystal grains can be laminated, and a tantalum carbide coating film with fewer crystal grain boundaries than the conventional one can be obtained with a desired thickness. Therefore, a desired tantalum carbide coating film thickness can be obtained by raising the manufacturing temperature and then maintaining the processing temperature at 950 ° C. or higher.
- the temperature difference of the production temperature that is gradually increased is preferably 50 ° C. or more, and more preferably 100 ° C. or more.
- a tantalum carbide coating film adapted to the concavo-convex shape of the carbon substrate surface is obtained near the surface of the carbon substrate, and crystal grains develop and crystal grain boundaries are formed near the outer surface of the tantalum carbide coating film.
- a tantalum carbide coating film with a low content can be obtained.
- the crystal grains grown by the above method are gradually increased from the vicinity of the surface of the carbon substrate toward the outer surface of the tantalum carbide coating film, and polygonal pyramid-shaped crystal grains are imagined. This is obtained by increasing the crystallinity of the tantalum carbide coating film in a gradient manner by gradually raising the furnace temperature by CVD treatment.
- the temperature raising step for gradually raising the furnace temperature when the thickness of the tantalum carbide coating film is preferably 5 ⁇ m, more preferably 3 ⁇ m or less.
- the rate of temperature increase is too high, crystal nuclei are not sufficiently formed in the recesses on the surface of the carbon base material, so that the adhesion of the tantalum carbide coating film cannot be improved.
- the rate of temperature increase is too slow, the coating film has many crystal grain boundaries.
- This method is a method of forming a tantalum carbide-coated carbon material subjected to multiple coating by performing the above-described method (1) of forming a tantalum carbide coating film by CVD treatment twice or more.
- the contact surface between the carbon substrate and the jig is coated with tantalum carbide. A film is not formed.
- the support position is changed so that the defect portion generated by the support is covered in the second and subsequent tantalum carbide coating film forming steps.
- the whole surface of a carbon base material can be coat
- the carbon base material 21 is disposed in a reaction chamber (not shown) in a state of being supported from below by a support rod 25 (jig). Then, a first tantalum carbide coating film 22 is formed on the surface of the carbon base material 21 by performing a CVD process on the carbon base material 21 (first film formation step, FIG. 3B). At this time, the tantalum carbide coating film 22 is not formed at the contact portion of the carbon base material 21 with the support rod 25.
- the support position of the carbon base material 21 by the support rod 25 is changed to the surface of the tantalum carbide coating film 22.
- a CVD process is performed under the same conditions as in the first film formation step, so that the second tantalum carbide coating film 23 is formed on the surface of the tantalum carbide coating film 22 as shown in FIG. (Second film formation step).
- the tantalum carbide coating film 23 is laminated on the surface of the tantalum carbide coating film 22, and the tantalum carbide coating film can be formed on the entire surface of the carbon substrate 21.
- the tantalum carbide coating film 22 preferably has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction. Moreover, it is preferable that the half width of the diffraction line on the (311) plane is 0.12 ° or less. If a new tantalum carbide coating film is formed on such a tantalum carbide coating film, the new tantalum carbide coating film 23 is crystal-grown with the crystal grains of the underlying tantalum carbide coating film 22. The tantalum carbide coating film 22 and the tantalum carbide coating film 23 are continuous.
- the new tantalum carbide coating film 23 it is possible to prevent the new tantalum carbide coating film 23 from being peeled off from the underlying tantalum carbide coating film 22. Further, since the crystal grain boundaries of the tantalum carbide coating film 22 are dramatically smaller than before, impurities are not released from the tantalum carbide coating films 22 and 23 formed by the respective tantalum carbide coating film forming steps. Therefore, no impurity gas is interposed between the tantalum carbide coating film 22 as the base and the new tantalum carbide coating film 23.
- the crystallinity of the tantalum carbide coating film 22 which is the base is hardly changed when a new tantalum carbide coating film is formed (during the CVD process), and the crystallinity with the new tantalum carbide coating film 23 is changed.
- the difference in crystallinity hardly occurs between the tantalum carbide coating film 22 and the new tantalum carbide coating film 23 serving as a base, and the adhesion is good.
- the tantalum carbide coating film 22 preferably has the following characteristics.
- the tantalum carbide coating film 22 preferably has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the sum of the intensities of diffraction lines corresponding to the (311) plane and the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film 22 is the total of tantalum carbide in the X-ray diffraction pattern of the tantalum carbide coating film 22. It is preferably 0.5 or more and 0.9 or less with respect to the total intensity of diffraction lines corresponding to the crystal plane.
- the intensity of diffraction lines corresponding to the (311) plane or the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film 22 is maximized.
- the half width of the diffraction line on the (311) plane or the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is 0 mm. It is preferable that it is 12 degrees C or less.
- the tantalum carbide coating film 22 is composed of tantalum carbide crystal grains having high crystallinity and sufficiently developed. Therefore, the crystal grain boundary of the tantalum carbide coating film 23 is drastically compared with the prior art. Can be reduced.
- the CVD conditions such as temperature, pressure, each gas flow rate and processing time, or by appropriately combining these conditions, The growth rate, crystallinity and film thickness, the size of crystal grains constituting the coating film, crystal orientation, and the like can be changed.
- the CVD process conditions can be freely changed by those skilled in the art, and these do not limit the present invention in any way.
- This method includes a tantalum coating film forming method for forming a tantalum coating film on a carbon substrate and a carburizing process for carburizing the tantalum coating film.
- a tantalum coating film forming method for forming a tantalum coating film on a carbon substrate
- a carburizing process for carburizing the tantalum coating film.
- the tantalum coating film can be formed by, for example, a chemical vapor deposition (CVD) method using the apparatus shown in FIG.
- a chemical vapor deposition (CVD) method using the apparatus shown in FIG. 1
- CVD chemical vapor deposition
- CVD chemical vapor deposition
- the method for forming the tantalum coating film is not limited to the CVD method, and a conversion (CVR) method, a thermal spraying method, a physical vapor deposition (PVD) method, or the like may be used.
- CVR conversion
- PVD physical vapor deposition
- ⁇ Pretreatment in tantalum coating film forming method> One or a plurality of carbon base materials 1 are installed in the CVD reaction chamber (see FIG. 4A), and the CVD reaction chamber is evacuated to about 0.1 to 0.01 Torr (13.33 Pa to 1.333 Pa). To do. Next, degassing is performed by heating the inside of the CVD reaction chamber. Specifically, after introducing hydrogen gas into the CVD reaction chamber at 7000 cc / min, the inside of the CVD reaction chamber is heated to about 1100 ° C. to degas the CVD reaction chamber.
- a process for forming a tantalum coating film using high-frequency induction heating device will be described. While keeping the inside of the CVD reaction chamber at about 800 ° C. or more, the inside of the CVD reaction chamber is depressurized to 10 Torr (1333 Pa) or less by operating the variable valve. Then, a tantalum halogen compound such as tantalum pentachloride (TaCl 5 ) is supplied as a source gas into the CVD reaction chamber at a flow rate of 10 to 20 sccm.
- the carrier gas for example, argon gas, hydrogen gas, or a mixed gas thereof is supplied.
- the unit [sccm] indicates the amount of gas (cm 3 ) flowing per minute in the standard state.
- a tantalum coating film is formed on the surface of the carbon substrate 1 under the above conditions (see FIG. 4B).
- the growth of the coating film can be performed by changing the CVD conditions such as temperature, pressure, gas flow rate and processing time, or by appropriately combining these conditions.
- the speed, crystallinity and film thickness, size of crystal grains constituting the coating film, crystal orientation, and the like can be changed.
- the CVD process conditions can be freely changed by those skilled in the art, and these do not limit the present invention in any way.
- the tantalum coating film obtained by the above-described method is composed of tantalum crystal grains.
- the tantalum coating film has diffraction peaks corresponding to the (100) plane, (200) plane, (211) plane, and (220) plane of the tantalum crystal in X-ray diffraction.
- the diffraction peak of the (200) plane shows the maximum diffraction intensity, and the half width of the (200) plane is 0.2 ° or less.
- the thermal expansion coefficient of the carbon base material 31 is 6.5 ⁇ 10 ⁇ 6 to 8.0 ⁇ 10 ⁇ 6 / K, there is a difference in the thermal expansion coefficient between the carbon base material 31 and the tantalum coating film.
- the tantalum coating film has internal stress, and peak shift and peak splitting are observed in the X-ray diffraction pattern.
- the tantalum coating film is softened at about 1100 ° C. or more, and changes to a shape suitable for the unevenness of the surface of the carbon substrate 31. For this reason, it becomes possible for a tantalum coating film to enter inside the open pores on the surface of the carbon base material 31, and it is considered that the adhesion between the carbon base material 31 and the tantalum coating film is improved.
- a carbon substrate 31 on which a tantalum coating film is formed is placed in a carburizing furnace (not shown) (FIG. 4B).
- the temperature in the carburizing furnace is set to 1700 to 2500 ° C.
- the inside of the carburizing furnace is set to a vacuum atmosphere of 10 ⁇ 2 to 10 Pa.
- the carbon source for carburizing carbon contained in a graphite material for a carbon source installed in advance or graphite jigs of a carburizing furnace is used. These carbons convert the tantalum coating film to a tantalum carbide coating film (FIG. 4C).
- a tantalum carbide coating film having a shape adapted to the unevenness of the surface of the carbon base material 1 is carburized to maintain adhesion with the carbon base material and is not easily consumed in a high temperature environment. Can be obtained.
- the film thickness of the tantalum carbide coating film can be easily changed by repeating the tantalum coating film forming step and the carburizing process step a plurality of times in order. Moreover, it becomes possible to change the film thickness of a tantalum coating film by repeating a tantalum coating film formation process in multiple times before performing a carburizing process.
- the tantalum coating film forming step and the carburizing treatment step are repeated a plurality of times in sequence, and when the tantalum coating film forming step is repeated a plurality of times, the tantalum coating step is performed by supporting the object to be coated by the support. While done. Therefore, in the first tantalum coating film forming step, the tantalum carbide coating film is coated on the entire surface of the carbon base material by coating the defect portion generated by the support in the second and subsequent tantalum coating film forming steps. Can be formed.
- the tantalum carbide coating film obtained by the above-described tantalum carbide coating film forming method (4) has a diffraction intensity with the maximum diffraction line on the (311) plane of tantalum carbide in the X-ray diffraction pattern.
- the diffraction line on the (311) plane or the (220) plane of tantalum carbide shows the maximum diffraction intensity in the X-ray diffraction pattern.
- the present inventors have succeeded in taking over the crystal orientation of the tantalum carbide coating film as a base when forming a new tantalum carbide coating film on the tantalum carbide coating film. I found. This also applies to the crystal orientation of the tantalum carbide coating film prepared by different manufacturing processes. With this characteristic, for example, multiple coating can be performed in which a tantalum carbide coating film subjected to a carburizing process is formed on a tantalum carbide coating film by a CVD process.
- the tantalum carbide coating film preferably has the largest diffraction line on the (311) plane of tantalum carbide in the X-ray diffraction pattern. The reason for this will be described later.
- the tantalum carbide coating film obtained by the above-described tantalum carbide coating film forming method (4) having the maximum diffraction line on the (311) plane is the first tantalum carbide coating film.
- the multi-coating coating film has a (311) plane of tantalum carbide in the outermost X-ray diffraction pattern. It becomes easy to obtain a coating film in which the diffraction line shows the maximum diffraction intensity.
- the number of steps can be reduced as compared with the case where the tantalum carbide coating film obtained by the tantalum carbide coating film forming method (4) described above is repeated.
- the half width of the diffraction line on the (311) plane or the (220) plane in the X-ray diffraction pattern in each coating film is preferably 0.12 ° or less.
- the first tantalum carbide coating film preferably has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the first tantalum carbide coating film preferably has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the first tantalum carbide coating film preferably has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the first tantalum carbide coating film preferably has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the sum of the intensity of diffraction lines in the (311) plane and the (220) plane in the X-ray diffraction pattern of the first tantalum carbide coating film is the X-ray diffraction pattern in the X-ray diffraction pattern of the first tantalum carbide coating film. Therefore, it is preferable that it is 0.5 or more and 0.9 or less with respect to the total intensity of diffraction lines in all crystal planes corresponding to tantalum carbide.
- the first tantalum carbide coating film is composed of sufficiently developed tantalum carbide crystal grains.
- tantalum carbide coating film by forming a new tantalum carbide coating film on the first tantalum carbide coating film, it is possible to obtain at least two layers of tantalum carbide coating film having inherited characteristics. As a result, a tantalum carbide coating film having two or more layers with a small grain boundary and a high density can be obtained.
- the carbon base material 41 corresponds to the carbon base materials 1, 21, 31 described above
- the tantalum carbide coating film 42 corresponds to the tantalum carbide coating films 2, 22, 23, 32 described above.
- the tantalum carbide-coated carbon material 400 includes a carbon base material 41 and a tantalum carbide coating film 42 formed on the surface of the carbon base material 41.
- tantalum carbide coating film 42 is composed of tantalum carbide crystal grains.
- tantalum carbide means a compound of a tantalum atom and a carbon atom, for example, a compound represented by a chemical formula such as TaC or Ta 2 C.
- the tantalum carbide coating film 42 has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the tantalum carbide coating film 42 has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the orientation angle is measured by the following method. As shown in FIG. 6, while rotating the tantalum carbide-coated carbon material 400, X-rays are irradiated to measure the angle (orientation angle) at which diffraction peaks of the (220) plane and the (311) plane of tantalum carbide appear. The results are shown in FIGS. 9, 12, 15, 19, 21, 21, and 26. In the graphs shown in FIGS. 9, 12, 15, 19, 21, 24, and 26, the horizontal axis represents the orientation angle ( ⁇ ) shown in FIG. The vertical axis is intensity.
- the crystals constituting the tantalum carbide coating film have the above-mentioned orientation, the crystal grains can be easily grown, so that the crystal grain boundaries of the tantalum carbide coating film can be greatly reduced. The reason for this will be described below.
- the crystal planes confirmed by the X-ray diffraction pattern of the tantalum carbide coating film are mainly (111) plane, (200) plane, (220) plane, (311) plane, (222) plane and (400) plane. It is. Of these crystal planes, the (111) plane and the (222) plane, and the (200) plane and the (400) plane are parallel planes. Consider the relationship of four surfaces: the surface, (200) surface, (220) surface, and (311) surface.
- the plane index and the orientation index are always perpendicular.
- the inclination angle between each plane is always 54.7 ° for (111) plane and (200) plane
- the (111) and (220) planes are 35.3 °
- the (111) and (311) planes are 29.5 °
- the (200) and (220) planes are 45.0 °
- the (200) plane is
- the (311) plane is 25.2 °
- the (220) and (311) planes are 31.5 °.
- Table 1 shows the tilt angles formed by other crystal planes with respect to the reference crystal plane, assuming that the orientation index of the reference crystal plane is perpendicular to the surface of the carbon substrate.
- the density of tantalum and tantalum carbide are each 16.65 g / cm 3 and 13.90 g / cm 3.
- carburizing treatment is performed on the tantalum film to convert it into a tantalum carbide film, volume expansion occurs, and the lattice spacing of each crystal plane is increased.
- the internal stress of the tantalum carbide coating decreases as the orientation index of each crystal plane becomes perpendicular to the surface of the carbon substrate, resulting in a decrease in grain boundaries.
- tantalum carbide crystal nuclei are generated and the crystal nuclei grow.
- Each crystal plane of the tantalum carbide crystal grows with respect to the orientation index.
- the tantalum carbide crystal grains collide with other adjacent crystal grains, thereby inhibiting the growth. It is presumed that as the orientation index of each crystal plane in the tantalum carbide crystal is closer to the carbon substrate surface, the internal stress produced by the adjacent crystal grains becomes smaller and the growth is less likely to be inhibited. As a result, crystal grains develop and crystal grain boundaries decrease.
- the (220) plane in the tantalum carbide coating film 42 is mainly parallel to the carbon substrate surface, and the (311) plane is mainly parallel to the carbon substrate 41 surface. More preferably. Further, crystal grains whose (311) plane is parallel to the surface of the carbon substrate 41 and crystal grains whose (220) plane is parallel to the surface of the carbon substrate 41 may mainly be mixed. This can be judged from the difference between the (311) plane and the orientation angle showing the maximum peak value in the (220) plane orientation angle being within 31.5 °. Thereby, the crystal grain boundary of the tantalum carbide coating film 42 can be reduced, and the dense and high-strength tantalum carbide coating film 42 can be formed.
- the diffraction intensity means a peak value appearing at a diffraction angle peculiar to each crystal plane.
- the sum of I (220) and I (311) is preferably in the range of 0.5 or more and 0.9 or less with respect to the total X-ray diffraction intensity corresponding to each crystal plane.
- the sum of the X-ray diffraction intensities corresponding to the crystal planes is the X-ray diffraction intensity corresponding to the (111) plane determined in the X-ray diffraction pattern (hereinafter referred to as I (111)), (200) X-ray diffraction intensity corresponding to the plane (hereinafter referred to as I (200)), I (220), I (311), X-ray diffraction intensity corresponding to the plane (hereinafter referred to as I (222)) , And the sum of X-ray diffraction line intensities (hereinafter referred to as I (400)) corresponding to the (400) plane (I (111) + I (200) + I (220) + I (311) + I (222) + I (400) )).
- Ip the intensities of X-ray diffraction and the sum thereof are all compared by integral intensity.
- the sum of I (220) and I (311) of tantalum carbide is in the range of 0.5 or more and 0.9 or less with respect to the total Ip of X-ray diffraction intensity corresponding to each crystal plane. Less tantalum carbide coating film.
- the half width of the diffraction line of the (220) plane or (311) plane of tantalum carbide is preferably 0.2 ° or less, more preferably 0.12 ° or less. preferable.
- the diffraction line of (220) plane of tantalum carbide appears at a diffraction angle of about 58.6 °, and the (311) plane at about 70.0 °.
- the high diffraction intensity means the maximum peak height.
- the half width of the diffraction line means a peak width at an intensity that is 1 ⁇ 2 of the maximum height, and is an index of crystallinity.
- the crystal grain boundaries of the tantalum carbide coating film can be reduced by greatly developing the crystal grains.
- the X-ray diffraction pattern of the tantalum carbide coating film 42 can be measured by using, for example, Ultima manufactured by Rigaku Corporation as an X-ray analyzer.
- the gas permeability is preferably 10 ⁇ 7 cm 2 / s or less, and more preferably 10 ⁇ 8 to 10 ⁇ 11 cm 2 / sec. When the gas permeability is within the above range, a dense tantalum carbide coating film 42 is obtained. In general, since a carbon substrate usually has a nitrogen gas permeability of 10 ⁇ 2 to 10 ⁇ 3 cm 2 / sec, the nitrogen gas permeability of the tantalum carbide coating film 42 is 10 ⁇ 7 cm 2 / s or less.
- the nitrogen gas permeability of the tantalum carbide coating film 42 is about 10 ⁇ 5 to 10 ⁇ 4 times the nitrogen gas permeability of the carbon base material.
- the tantalum carbide coating film is a dense film, heat resistance and gas etching resistance can be obtained.
- the nitrogen gas permeability of the tantalum carbide coating film 42 can be measured using, for example, the apparatus shown in FIG. Below, the measuring method of the nitrogen gas permeability
- a measurement sample is formed into a disk shape having a diameter of about 30 mm or more, and is sufficiently dried before measurement of nitrogen gas permeability. Then, the dried measurement sample is placed in the permeation cell shown in FIG. 7, and the pressure is reduced by the rotary pump (rotary vacuum pump) and the turbo molecular pump until the primary side and the secondary side of the permeation cell reach a certain vacuum value. To do. Next, the operation of the rotary pump is stopped, and the valve (V1 shown in FIG. 7) is closed. Then, nitrogen gas is supplied to the primary side of the permeation cell at a constant gas pressure. Nitrogen gas permeates the measurement sample from the primary side and moves to the secondary side, whereby the pressure on the secondary side starts to rise. Measure the rate of pressure rise.
- K (QL) / ( ⁇ PA) (2)
- Q ⁇ (p 2 ⁇ p 1 ) V 0 ⁇ / t (3)
- K is the nitrogen gas permeability
- Q is the air flow rate
- ⁇ P is the pressure difference between the primary side and the secondary side
- A is the permeation area
- L is the thickness of the measurement sample
- p 1 is the initial pressure on the secondary side
- p 2 is the final pressure on the secondary side
- V 0 is the volume on the secondary side
- t is the measurement time.
- the film thickness of the tantalum carbide coating film 42 is preferably 10 to 100 ⁇ m.
- the tantalum carbide coating thickness is less than 10 ⁇ m, the gas permeability is increased and sufficient heat resistance and gas etching resistance cannot be obtained.
- a carbon base material is obtained by adding a binder (pitch or the like) to the raw material powder, mixing, molding, and firing.
- a binder pitch or the like
- each element contained as an impurity in the carbon base material is 0.3 ppm or less of aluminum, 1.0 ppm or less of iron, 0.1 ppm or less of magnesium, and 0.1 ppm or less of silicon. It is preferable that Furthermore, the total ash content of the carbon base material (which may be simply referred to as ash content in this specification) is preferably 10 ppm or less. Ash content can be measured by an ash content analysis method defined in JIS-R-7223.
- the gas release pressure on the basis of 1000 ° C. of the carbon substrate is preferably 10 ⁇ 4 Pa / g or less.
- the gas discharge pressure based on 1000 ° C. means the amount of pressure change by which gas molecules adsorbed on the surface and pores of the carbon substrate are desorbed at a temperature of 1000 ° C., and the desorbed gas increases the pressure in the atmosphere. Specifically, it can be measured by a temperature-programmed desorption spectrum (TDS) disclosed in Japanese Patent No. 2684106.
- TDS temperature-programmed desorption spectrum
- the thermal expansion coefficient of the tantalum carbide coating film is in the range of 6.5 to 8.0 ⁇ 10 ⁇ 6 / K. Therefore, it is preferable that the carbon base material has a thermal expansion coefficient of 6.5 to 8.0 ⁇ 10 ⁇ 6 / K.
- a tantalum carbide-coated carbon material having a small difference in thermal expansion coefficient between the carbon substrate and the tantalum carbide coating film can be formed. Therefore, when the tantalum carbide-coated carbon material is expanded or contracted due to a temperature change, the tantalum carbide-coated film hardly generates thermal stress, and therefore the tantalum carbide-coated film is difficult to peel off.
- the coefficient of thermal expansion of the carbon base material is measured by, for example, a thermal mechanical analysis apparatus (Thermo Plus 2 TMA8310) manufactured by Sakai Rigaku Corporation, but the measuring apparatus is not limited to this apparatus.
- the density of the carbon substrate is preferably 1.65 to 1.90 g / cm 3 , more preferably 1.73 to 1.83 g / cm 3 .
- the mechanical strength of a carbon base material becomes high.
- the average pore radius of the carbon substrate is preferably 0.01 to 5 ⁇ m. Thereby, the anchor effect is sufficiently exhibited, and the tantalum carbide coating film is hardly peeled off from the carbon substrate.
- the “average pore radius” can be determined using a mercury porosimeter measured by a mercury intrusion method, and the cumulative pore volume when the maximum pressure is 98 MPa and the contact angle between the sample and mercury is 141.3 °. It is a pore radius corresponding to a volume of 1/2. When the average pore radius is less than 0.01 ⁇ m, the anchor effect is not sufficiently exhibited, so that the tantalum carbide coating film is easily peeled from the carbon substrate.
- the size and form of the carbon base material are not limited to the forms shown in FIGS. 2 to 5 and can be changed to various sizes and forms.
- the convex part may be provided in the upper surface of the carbon base material.
- the reason for using the carbon base material as the base material will be described.
- a carbon substrate or a tantalum substrate is desirable. Carbon substrates are preferred because they are easy to process.
- carbon in the tantalum carbide coating film diffuses into the tantalum base material depending on the use environment, and the whole including the base material becomes ceramic and loses toughness and becomes brittle.
- a void is a general term for holes having a diameter of several tens to several hundreds of nanometers generated on the surface of a tantalum carbide coating film. It is presumed that a void is generated when a residue existing at a crystal grain boundary is released along the crystal grain boundary. There are two possible reasons for this. The first reason is that undeveloped tantalum carbide crystals and impurities remain in the crystal grain boundaries. The second reason is that the crystal grain boundary has a lower strength than the crystal grain, and therefore tends to be a starting point of fracture.
- the crack spreads or reaches the surface of the tantalum carbide coating film. Can be suppressed.
- produces by the stress which generate
- the tantalum carbide-coated carbon material is used, for example, as a component member and jig of a compound semiconductor single crystal growth apparatus and epitaxial growth apparatus.
- an etching gas such as ammonia gas or hydrogen chloride gas having a high temperature of 1000 ° C. or higher is used.
- the etching gas consumes the carbon substrate.
- impurities released from the carbon base material consumed by the etching gas may permeate the tantalum carbide coating film and contaminate the product.
- the tantalum carbide coating film 42 has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the coating film 42 mainly includes crystal grains having a (311) plane parallel to the surface of the carbon base material 41 forming the tantalum carbide coating film 42. Accordingly, since the crystal grains constituting the tantalum carbide coating film 42 are likely to grow, the crystal grain boundaries of the tantalum carbide coating film 42 can be drastically reduced as compared with the prior art. Therefore, a dense and high-strength tantalum carbide coating film 42 is obtained, and the lifetime of the tantalum carbide-coated carbon material 400 can be extended.
- the tantalum carbide coating film has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the sum of the intensities of diffraction lines corresponding to the (311) plane and the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film 42 is the total of tantalum carbide in the X-ray diffraction pattern of the tantalum carbide coating film 42.
- Tantalum carbide coating with tantalum carbide crystal grains sufficiently developed and crystal grain boundaries greatly reduced by being 0.5 or more and 0.9 or less with respect to the total intensity of diffraction lines corresponding to crystal planes The film 42 is formed.
- the crystal grain boundary of the tantalum carbide coating film 42 is compared with the prior art. It can be reduced in comparison.
- the half width of the diffraction line on the (311) plane or the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film 42 is 0 mm. Since the tantalum carbide coating film 42 is composed of tantalum carbide crystal grains having high crystallinity and sufficiently developed by being 2 ° C. or less, the crystal grain boundary of the tantalum carbide coating film 42 is the conventional technology. In comparison, it can be drastically reduced.
- the crystal grains forming the tantalum carbide coating film 42 are directed from the surface of the carbon base material 41 toward the outer surface of the tantalum carbide coating film 42. Increasingly inclined. Thereby, the tantalum carbide coating film 42 has improved adhesion to the carbon base material 41 and can greatly reduce crystal grain boundaries that lead to the generation of voids.
- tantalum carbide crystal nuclei are formed inside the recesses on the surface of the carbon substrate, and the manufacturing temperature is increased in the crystal growth step.
- the crystallinity of the tantalum carbide coating film can be improved in a gradient manner. Therefore, since a tantalum carbide coating film adapted to the uneven shape on the surface of the carbon substrate can be formed, the tantalum carbide coating film is difficult to peel off from the carbon substrate, and the vicinity of the outer surface of the tantalum carbide coating film is crystalline. Therefore, a tantalum carbide coating film having fewer crystal grain boundaries than the conventional one can be obtained.
- the temperature for forming the tantalum carbide crystal nuclei is 850 to 950 ° C., so that sufficient tantalum carbide crystal nuclei can be formed inside the recesses on the surface of the carbon substrate. Therefore, the adhesion of the tantalum carbide coating film to the carbon substrate can be improved.
- the temperature raising step has a temperature difference of 50 ° C. or more, a tantalum carbide coating film adapted to the uneven shape on the surface of the carbon base material is obtained near the surface of the carbon base material. In the vicinity of the outer surface, a tantalum carbide coating film in which crystal grains are developed and crystal grain boundaries are small is obtained.
- the tantalum carbide coating film having developed crystal grains can be laminated by not changing the manufacturing temperature after the temperature raising step. For this reason, a tantalum carbide coating film having fewer crystal grain boundaries than the conventional one can be obtained with a desired thickness.
- the temperature raising step by increasing the manufacturing temperature at a constant rate, it is possible to prevent the crystallinity of the tantalum carbide crystal grains from being sharply improved and to prevent the tantalum carbide coating film from peeling off. As a result, the crystallinity of the tantalum carbide coating film can be improved in a gradient manner.
- the crystal grain boundaries of the tantalum carbide coating film 22 formed by the tantalum carbide coating film forming step are remarkably smaller than conventional, and new carbonization is performed. Impurities are not released from the tantalum carbide coating film 22 during the tantalum coating film formation process (second formation process). Therefore, no impurity gas is interposed between the tantalum carbide coating film 22 as the base and the new tantalum carbide coating film 23.
- the tantalum carbide coating film 22 as the base has almost no change in crystallinity when a new tantalum carbide coating film 23 is formed, and has the same crystallinity as the new tantalum carbide coating film 23. It becomes.
- the tantalum carbide coating film has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction, thereby forming the tantalum carbide coating film.
- the first forming step and the second forming step are performed while supporting the carbon base material 21 with the support rod 25 (support), and the tantalum carbide coating film 22 generated by the support rod 25 in the first forming step.
- a tantalum carbide coating film can be formed on the entire surface of the carbon base material 21 by coating the defect portion in the second forming step.
- the above-mentioned “method for forming a tantalum carbide coating film by CVD process (2)” is used in the “first formation step”, and “the method for forming a tantalum carbide coating film by CVD processing ( By using “1)”, tantalum carbide crystal nuclei are formed inside the recesses on the surface of the carbon substrate, so that a tantalum carbide coating film adapted to the uneven shape on the surface of the carbon substrate can be formed. Therefore, it is possible to obtain a tantalum carbide coating film that does not easily peel from the carbon substrate. Further, the crystallinity of the tantalum carbide coating film can be improved in a gradient manner by gradually increasing the manufacturing temperature in the crystal growth step. Accordingly, crystallinity develops near the surface of the tantalum carbide coating film, and a tantalum carbide coating film with fewer crystal grain boundaries than in the prior art can be obtained.
- the tantalum carbide coating film has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the sum of the intensities of diffraction lines corresponding to the (311) plane and the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is the total crystal of tantalum carbide in the X-ray diffraction pattern of the tantalum carbide coating film. Since the total intensity of diffraction lines corresponding to the surface is 0.5 or more and 0.9 or less, a tantalum carbide coating film composed of sufficiently developed tantalum carbide crystal grains is obtained. The crystal grain boundary of the tantalum coating film can be drastically reduced as compared with the prior art.
- the intensity of the diffraction line corresponding to the (311) plane or the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is maximized, so that the crystal grain boundary of the tantalum carbide coating film is compared with the prior art. Can be reduced.
- the half width of the diffraction line on the (311) plane or the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is 0 mm. Since the first tantalum carbide coating film is composed of tantalum carbide crystal grains having high crystallinity and sufficiently developed by being 12 ° C. or less, the crystal grain boundary of the tantalum carbide coating film is defined as the prior art. In comparison, it can be drastically reduced.
- a tantalum coating film is formed on the surface of the carbon substrate 1, and this tantalum coating film is converted into the tantalum carbide coating film 2.
- the crystal grain boundary of tantalum carbide can be drastically reduced as compared with the prior art.
- the tantalum coating film is softened in a high temperature environment, and the tantalum carbide coating film is adapted to the unevenness of the carbon base material 1 surface. 2 can be used. Therefore, a tantalum carbide-coated carbon material having a dense and high-strength tantalum carbide coating film with high adhesion to the carbon substrate 1 can be obtained.
- the thermal expansion coefficient of the carbon base material 1 is 6.5 to 8.0 ⁇ 10 ⁇ 6 / K
- the thermal expansion coefficient of the carbon base material 1 is close to the thermal expansion coefficient of tantalum carbide.
- the thermal stress applied to the tantalum coating film 2 can be reduced. Therefore, a tantalum carbide-coated carbon material having the tantalum carbide coating film 2 that is difficult to peel from the carbon substrate 1 is obtained.
- the tantalum coating process is performed while the object to be coated is supported by the support, and in the first tantalum coating film forming process, the defective part generated by the support tool is removed in the second and subsequent tantalum coating film forming processes.
- a tantalum carbide coating film can be formed on the entire surface of the carbon substrate.
- the tantalum coating film is formed on the surface of the carbon substrate, and the tantalum coating film is converted into a tantalum carbide coating film.
- a tantalum carbide coating film is formed, and a new second tantalum carbide coating film is formed on the first tantalum carbide coating film, so that the crystal orientation of the first tantalum carbide coating film is inherited.
- the covering film can be easily formed, and the crystal grain boundary can be drastically reduced as compared with the prior art. Therefore, a tantalum carbide-coated carbon material having a dense and high-strength tantalum carbide coating film can be obtained.
- the first tantalum carbide coating film that requires a tantalum coating film forming step and a carburizing treatment step. Succeeded in reducing the manufacturing process to only the tantalum carbide coating film forming process.
- the thermal expansion coefficient of the carbon base material is 6.5 to 8.0 ⁇ 10 ⁇ 6 / K
- the thermal expansion coefficient of the carbon base material is close to that of tantalum carbide. Thermal stress applied to the coating can be reduced. Therefore, a tantalum carbide-coated carbon material having a tantalum carbide coating film that is difficult to peel from the carbon substrate can be obtained.
- the tantalum carbide coating film has a maximum peak value of 80 ° or more in the orientation angle of the (311) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction, whereby the tantalum carbide coating film is There are mainly crystal grains having a (311) plane parallel to the surface of the carbon substrate to be formed. Therefore, a dense and high strength tantalum carbide film with few crystal grain boundaries can be obtained.
- the tantalum carbide coating film has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction, thereby forming the tantalum carbide coating film.
- the sum of the diffraction intensities in the (311) plane and the (220) plane in the X-ray diffraction pattern of the tantalum carbide coating film is the diffraction corresponding to the entire crystal plane of tantalum carbide in the X-ray diffraction pattern of the tantalum carbide coating film. Since the tantalum carbide coating film composed of sufficiently developed tantalum carbide crystal grains is obtained when the total strength of the wires is 0.5 or more and 0.9 or less, there are few crystal grain boundaries. A dense and high strength tantalum carbide film can be obtained.
- the half width of the diffraction line on the (311) plane in the X-ray diffraction pattern of the tantalum carbide coating film is 0 mm.
- it is 12 ° C. or less, crystallinity is high and crystal grains are sufficiently developed.
- a dense and high-strength tantalum carbide coating film with few crystal grain boundaries can be obtained.
- the tantalum carbide coating film was formed using the method (1) for forming a tantalum carbide coating film by the CVD process described above.
- a CVD process was performed under the CVD process conditions shown to form a tantalum carbide coating film on the carbon substrate. At this time, the C / Ta composition ratio of the tantalum carbide coating film was adjusted to 1.0 to 2.0.
- FIG. 8A An image obtained by photographing the surface of the tantalum carbide coating film obtained in Examples 1 to 4 with an electron microscope is shown in FIG. 8A, and an X-ray diffraction pattern is shown in FIG. 8B.
- Table 3 shows the evaluation results of the sum of I (220) and I (311) with respect to Ip of Examples 1 to 4 and the half width of the (311) plane of tantalum carbide in each coating film.
- FIG. 9 shows the results of the orientation angles of the (220) plane and (311) plane of tantalum carbide observed by X-ray diffraction of the surface layer of Example 3.
- FIG. 9 shows the results of the orientation angles of the (220) plane and (311) plane of tantalum carbide observed by X-ray diffraction of the surface layer of Example 3.
- the tantalum carbide coating film of Example 3 has a maximum peak value of 80 ° or more in the orientation angles of the (220) plane and the (311) plane of diffraction peaks corresponding to tantalum carbide by X-ray diffraction. . At this time, crystal grains of tantalum carbide are developed, and crystal grain boundaries are reduced in the tantalum carbide coating film.
- the tantalum carbide coating film was formed using the above-described tantalum carbide coating film forming method (2) by the CVD process.
- a graphite substrate having a diameter of 60 mm and a thickness of 10 mm having a coefficient of thermal expansion of 7.8 ⁇ 10 ⁇ 6 / K, a gas discharge pressure based on 1000 ° C. of 10 ⁇ 6 Pa / g, and an ash content of 2 ppm is shown in the table below.
- a CVD process was performed under the CVD process temperature condition shown in 4 to form a tantalum carbide coating film on the graphite substrate. At this time, the C / Ta composition ratio of the tantalum carbide coating film was adjusted to 1.0 to 2.0.
- the pressure in the furnace and the gas flow rate in the CVD process were the same as those in Examples 1 to 4, respectively.
- the CVD process temperature is gradually increased at 100 ° C./Hr, and when the process temperature reaches 1000 ° C., the temperature rise is stopped and the desired temperature is maintained while maintaining the process temperature at 1000 ° C.
- a tantalum carbide coating film was produced until the thickness was reached.
- photographed the cross section of the obtained tantalum carbide coating film with the electron microscope is shown in FIG.
- a tantalum carbide coating film was formed in the pores and recesses on the surface of the carbon substrate.
- the tantalum carbide crystals constituting the tantalum carbide coating film increase in a gradient from the vicinity of the surface of the graphite substrate toward the outer surface of the coating film.
- crystal grains grew near the outer surface of the tantalum carbide coating film, and the crystal grain boundaries were greatly reduced.
- Table 5 shows the evaluation results of the sum of I (220) and I (311) with respect to Ip of Examples 5 and 6, and the half width of the (311) plane of tantalum carbide in each coating film.
- the tantalum carbide coating film of Example 6 has a maximum peak value of 80 ° or more in the orientation angles of the (220) plane and the (311) plane of diffraction peaks corresponding to tantalum carbide by X-ray diffraction. .
- crystal grains of tantalum carbide are developed, and crystal grain boundaries are reduced in the tantalum carbide coating film.
- the tantalum carbide coating film was formed using the above-described methods (2) and (3) of forming the tantalum carbide coating film by the CVD process.
- Example 7 A CVD treatment temperature is applied to a graphite substrate having a diameter of 60 mm and a thickness of 10 mm, having a thermal expansion coefficient of 7.8 ⁇ 10 ⁇ 6 / K, a gas release pressure of 1000 ° C. based on 10 ⁇ 6 Pa / g and an ash content of 2 ppm.
- a CVD process was performed at 1000 ° C. to form a tantalum carbide coating film as a base on the graphite substrate.
- the C / Ta composition ratio of the tantalum carbide coating film was adjusted to 1.0 to 2.0.
- the conditions for the CVD process pressure, source gas, and the like were the same as in Examples 1 to 4.
- the obtained tantalum carbide-coated carbon material was subjected to a CVD process under the same CVD conditions as described above to form a new tantalum carbide-coated film.
- Example 8 Gas discharge pressure of the thermal expansion coefficient of 7.8 ⁇ 10 -6 / K, 1000 °C standards 10 -6 Pa / g, and ash content is 2 ppm, the graphite substrate with a diameter of 60mm and a thickness of 10 mm, CVD treatment temperature was subjected to a CVD treatment at 900 ° C. to form a tantalum carbide coating film on the graphite substrate. Then, the CVD process temperature is gradually increased at 100 ° C./Hr, and when the process temperature reaches 1000 ° C., the temperature rise is stopped and the C / Ta composition of the coating film is maintained while maintaining the process temperature at 1000 ° C.
- the underlying tantalum carbide coating film was produced to a desired thickness.
- the CVD treatment temperature was set to 1000 ° C. again on the underlying coating film, and a new tantalum carbide coating film was produced.
- Conditions such as pressure and raw material gas at this time were the same as those in Examples 1 to 4.
- FIG. 13 shows an image (SEM image) obtained by photographing the cross section of the obtained tantalum carbide coating film with an electron microscope. From FIG. 13, in Examples 7 and 8, it was found that the crystal grains of the new tantalum carbide coating film when the double coating was performed inherited the crystal grains of the underlying tantalum carbide coating film. . For this reason, peeling from the boundary surface of the multiple coating coating film (the boundary surface between the tantalum carbide coating film serving as the base and the new tantalum carbide coating film) did not occur.
- Table 6 shows the evaluation results of the sum of I (220) and I (311) with respect to Ip of Examples 7 and 8, and the half width of the (311) plane of tantalum carbide in each coating film.
- FIG. 15 shows the results of the orientation angles of the (220) plane and (311) plane of tantalum carbide observed by X-ray diffraction of the surface layer of Example 7.
- the tantalum carbide coating film of Example 7 has a maximum peak value of 80 ° or more in the orientation angles of the (220) plane and the (311) plane of diffraction peaks corresponding to tantalum carbide by X-ray diffraction. .
- crystal grains of tantalum carbide are developed, and crystal grain boundaries are reduced in the tantalum carbide coating film.
- Example 9 the tantalum carbide coating film was formed using the tantalum carbide coating film forming method (4) described above.
- a graphite substrate having a diameter of 60 mm and a thickness of 10 mm having a thermal expansion coefficient of 7.8 ⁇ 10 ⁇ 6 / K, a gas discharge pressure based on 1000 ° C. of 10 ⁇ 6 Pa / g and an ash content of 2 ppm is shown in Table 7 below.
- the tantalum coating film was formed on the graphite substrate by performing the CVD process under the CVD process conditions shown in FIG.
- FIG. 16 shows an image (SEM image) obtained by photographing the surface of the formed tantalum coating film with an electron microscope and an X-ray diffraction pattern.
- FIG. 16A shows an SEM image
- FIG. 16B shows an X-ray diffraction pattern. From FIG. 16, in the X-ray diffraction pattern of the tantalum coating film, diffraction lines on the (110) plane, (200) plane, (211) plane and (220) plane can be confirmed, and the diffraction line on the (200) plane is the most. Strong diffraction intensity was shown. Further, the half width of the (200) plane was 0.2 ° or less.
- the tantalum coating film was carburized under the following conditions.
- the graphite base material on which the tantalum coating film is formed is placed in a carburizing furnace together with a carbon source, the carburizing furnace temperature is set to 2200 ° C., and the carburizing furnace is maintained at a vacuum atmosphere of 2.0 Pa and carburized for 1 hour.
- the tantalum carbide-coated carbon material of Example 9 was obtained.
- FIG. 17 shows an image obtained by photographing the surface of the tantalum carbide coating film of the tantalum carbide coating carbon material obtained in Example 9 with an electron microscope.
- FIG. 17A shows a surface SEM image
- FIG. 17B shows a cross-sectional SEM image.
- the tantalum carbide coating film obtained by carburizing the tantalum coating film has a significantly reduced crystal grain boundary. It was also confirmed that the tantalum carbide coating film was compatible with the irregularities on the surface of the graphite substrate.
- Example 9 the result of the X-ray diffraction pattern of Example 9 is shown in FIG. From FIG. 18, in the X-ray diffraction pattern of Example 9, the (111) plane, (200) plane, (220) plane, (311) plane, (222) plane and (400) plane can be observed, and (311) The diffraction lines on the surface showed the strongest diffraction intensity.
- Table 8 shows the evaluation results of the sum of I (220) and I (311) with respect to Ip of Example 9 and the half width of the (311) plane of tantalum carbide in each coating film.
- Example 9 the sum of I (220) and I (311) with respect to Ip is in the range of 0.5 or more and 0.90 or less, and the half width of the (311) plane is 0.20. It was the following.
- FIG. 19 shows the results of the orientation angles of the (220) plane and (311) plane of tantalum carbide observed by X-ray diffraction of the surface layer of Example 9.
- the tantalum carbide coating film of Example 9 has a maximum peak value of 80 ° or more at the orientation angles of the (220) plane and the (311) plane of diffraction peaks corresponding to tantalum carbide by X-ray diffraction. .
- crystal grains of tantalum carbide are developed, and crystal grain boundaries of the tantalum carbide coating film are reduced.
- Example 10 the tantalum carbide coating film was formed using the method (4) for forming a tantalum carbide coating film by carburization described above.
- FIG. 20 shows an image (SEM image) and an X-ray diffraction pattern obtained by photographing the surface of the tantalum carbide coating film serving as the base with an electron microscope.
- FIG. 20A shows an SEM image
- FIG. 20B shows an X-ray diffraction pattern. From FIG. 20, in the X-ray diffraction pattern of the underlying tantalum carbide coating film, the (111) plane, (200) plane, (220) plane, (311) plane, (222) plane and (400) plane are observed. The diffraction line on the (311) plane showed the strongest diffraction intensity.
- the sum of I (220) and I (311) (I (220) + I (311)) / Ip) with respect to Ip of the tantalum carbide coating film as the base is 0.53, and (311 of tantalum carbide) )
- the half width of the surface was 0.10 °.
- FIG. 21 shows the results of the orientation angles of the (220) plane and (311) plane of tantalum carbide observed by X-ray diffraction of the surface layer of Example 10. From FIG. 21, the tantalum carbide coating film of Example 10 has a maximum peak value of 80 ° or more in the orientation angles of the (220) plane and the (311) plane of diffraction peaks corresponding to tantalum carbide by X-ray diffraction. .
- the graphite substrate on which the tantalum carbide coating film as the base was formed was subjected to CVD treatment under the conditions shown in Table 9 below to form a new tantalum carbide coating film.
- FIG. 22 shows an image obtained by photographing the surface of a new tantalum carbide coating film obtained by the above-described CVD treatment with an electron microscope.
- FIG. 22A shows a surface SEM image
- FIG. 22B shows a cross-sectional SEM image.
- the new tantalum carbide coating film was attracted to the crystal grains of the underlying tantalum carbide coating film, two different types of tantalum carbide in the cross-sectional SEM image of FIG. It can be seen that the coating films are laminated.
- Example 10 the result of the X-ray diffraction pattern of the new tantalum carbide coating film obtained under the conditions of Example 10 is shown in FIG. From FIG. 23, in the X-ray diffraction pattern of Example 10, (111) plane, (200) plane, (220) plane, (311) plane, (222) plane and (400) plane can be observed, and (311) The diffraction lines on the surface showed the strongest diffraction intensity. This is presumably because a new tantalum carbide coating film was formed by taking over the crystal orientation of the tantalum carbide coating film as a base.
- Table 10 shows the evaluation result of the sum of I (220) and I (311) with respect to Ip of Example 10 and the half width of the (311) plane of tantalum carbide in each coating film.
- Example 10 From Table 10, in Example 10, the sum of I (220) and I (311) with respect to Ip is in the range of 0.5 or more and 0.90 or less, and the half width of the (311) plane is 0.20. It was the following.
- FIG. 24 shows the results of the orientation angles of the (220) plane and (311) plane of tantalum carbide observed by X-ray diffraction of the surface layer of Example 10.
- the tantalum carbide coating film of Example 10 has a maximum peak value of 80 ° or more in the orientation angles of the (220) plane and the (311) plane of diffraction peaks corresponding to tantalum carbide by X-ray diffraction. .
- crystal grains of tantalum carbide are developed, and crystal grain boundaries are reduced in the tantalum carbide coating film.
- FIG. 25 shows an image (SEM image) obtained by photographing the surface of the tantalum carbide coating film of the tantalum carbide-coated carbon material obtained in Comparative Example 1 with an electron microscope, and an X-ray diffraction pattern.
- FIG. 25A shows an SEM image
- FIG. 25B shows an X-ray diffraction pattern. From FIG. 25, in the SEM image of Comparative Example 1, many fine crystal grains existed on the surface of the tantalum carbide coating film. In the X-ray diffraction pattern of Comparative Example 1, the (111) plane, the (200) plane, the (220) plane, the (311) plane, the (222) plane, and the (400) plane can be observed. The diffraction line showed the strongest diffraction intensity. Further, the half width of the tantalum carbide (220) surface was 0.15 °.
- the tantalum carbide coating film of Comparative Example 1 has a maximum peak value of 80 ° or more in the orientation angle of the (220) plane of the diffraction peak corresponding to tantalum carbide by X-ray diffraction.
- the peak value of the (311) plane corresponding to the (220) plane showing the maximum peak value was confirmed at a position where the orientation angle was shifted by about 31.5 °.
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Abstract
Description
(CVD処理による炭化タンタル被覆膜の形成方法(1))
ここでは、CVD処理による炭化タンタル被覆膜の形成工程を説明する。本実施形態では、図1に示す装置を用いた方法を説明する。なお、炭化タンタル被覆膜の形成方法は、CVD法に限定されず、コンバージョン(CVR)法、溶射法、物理蒸着(PVD)法等を用いてもよい。最初に、図1に示す高周波誘導加熱装置について説明する。
図1に示すように、高周波誘導加熱装置はCVD反応室を有する。CVD反応室は、二重管構造からなる石英管内部に設置された断熱材(図示せず)に包まれた誘導負荷となる黒鉛炉壁(図示せず)内部を指す。また、石英管の外側には、高周波コイル(誘導コイル)を備えた加熱装置が配設されている。CVD反応室内の空間は高周波コイルにより加熱される。CVD反応室の一端には、原料ガスが導入されるガス導入管が配置されている。また、CVD反応室の他端には、排気口が形成されている。排気口にはCVD反応室内のガスを排気する排気管が配置されている。また、排気管の排気口に近い部分には可変バルブが設置されている。CVD反応室内の圧力は、可変バルブにより調整可能である。CVD反応室の上流にはガスフローコントローラーが設けられている。CVD反応室内へ導入される原料ガスのガス流量は、ガスフローコントローラーにより調整される。
最初に、CVD反応室内を真空引きし、その後、脱ガス処理、CVD処理を順に行う。CVD反応室内に1個又は複数個の炭素基材1を設置し(図2(a)参照)、CVD反応室内を約0.1~0.01Torr(13.33Pa~1.333Pa)まで真空引きする。次に、CVD反応室内部を加熱することにより、脱ガス処理を行う。詳細には、CVD反応室内に水素ガスを7000cc/min導入した後、CVD反応室内部を約1100℃まで加熱し、CVD反応室の脱ガスを行う。
続いて、CVD処理による炭化タンタル被覆膜の形成工程を説明する。図1に示すCVD反応室内を850~1100℃に保つとともに、可変バルブを操作することによりCVD反応室内を10Torr(1333Pa)以下に減圧する。その後、CVD反応室内に原料ガスとして五塩化タンタル(TaCl5)等のタンタルのハロゲン化合物とメタン(CH4)等の炭化水素ガスを供給する。また、キャリアガスとして、例えば、アルゴンガス、水素ガス又はそれらの混合ガスを供給する。
本方法は、炭素基材上に炭化タンタル被覆膜を形成する炭化タンタル被覆炭素材料の製造方法であり、炭素基材の表面に炭化タンタル結晶核を形成する結晶核生成工程と、結晶核生成工程後に炭化タンタル結晶核を結晶成長させる結晶成長工程とを含み、前記結晶成長工程は、製造温度を漸次上昇させる(以下、昇温という。)昇温工程を有する。CVD処理温度が高いほど、炭化タンタル結晶粒が大きくなり、炭化タンタル被覆膜の結晶粒界を低減できる。しかし、CVD処理を950℃以上で行った場合、炭化タンタル被覆膜は炭素基材表面の気孔の径より大きな結晶粒を多く持つ。さらに、CVD処理温度が高いほど、短時間で結晶核形成から核成長に移行するため、炭素基材表面の凸部に形成された結晶核から結晶成長工程が進行し、炭素基材表面の凹部に結晶核形成が行き届かない。このため、炭化タンタル被覆膜と炭素基材との接触面積が減少し、密着度が低下する。また、炭化タンタル被覆膜は、タンタル被覆膜のように高温環境下で軟化して炭素基材表面の凹凸に適合するという性質を有さないため、接触面積を熱処理によって改善することは適わない。
本方法は、上述したCVD処理による炭化タンタル被覆膜の形成方法(1)を2回以上行うことにより、多重コーティングを施した炭化タンタル被覆炭素材料を形成する方法であり、炭素基材の表面に第1炭化タンタル被覆膜を形成する第1形成工程と、第1炭化タンタル被覆膜上に1回以上新たな炭化タンタル被覆膜を形成する第2形成工程とを有する。CVD処理を用いた方法では、炭素基材を治具(支持具)によって支持した状態で炭化タンタル被覆膜の形成を行うことから、炭素基材と治具との接触面に炭化タンタル被覆膜が形成されない。したがって、初回の炭化タンタル被覆膜形成工程において、前記支持具により生じた欠損部分を、2回目以降の炭化タンタル被覆膜形成工程において被覆するように、支持位置を変更する。これにより、炭素基材の全表面を炭化タンタル被覆膜により被覆できる。
本方法は、炭素基材にタンタル被覆膜を形成するタンタル被覆膜形成方法と、タンタル被覆膜を浸炭処理する浸炭処理工程とを有する。以下に、図4を用いて本方法を詳細に説明する。図4(a)に示す炭素基材31を配置する。次に、図4(b)に示すように、炭素基材31の表面にタンタル被覆膜を形成する(タンタル被覆膜形成工程)。そして、タンタル被覆膜を浸炭処理する(浸炭処理工程)。これにより、図4(c)に示すように、タンタル被覆膜は炭化タンタル被覆膜32に転化する。
タンタル被覆膜の形成は、例えば、図1に示す装置を用いた化学蒸着(CVD)法により行うことができる。タンタル源には、例えば、五塩化タンタル(TaCl5)等のタンタルのハロゲン化合物を使用することができる。ここでは、図1に示す高周波誘導加熱装置を用いた化学蒸着(CVD)法について説明する。なお、タンタル被覆膜の形成方法は、CVD法に限定されずコンバージョン(CVR)法、溶射法、物理蒸着(PVD)法等を用いてもよい。また、以下の説明において、図1に示す装置の使用方法は上述した方法と重複するため、説明を省略することがある。
CVD反応室内に1個又は複数個の炭素基材1を設置し(図4(a)参照)、CVD反応室内を約0.1~0.01Torr(13.33Pa~1.333Pa)まで真空引きする。次に、CVD反応室内部を加熱することにより、脱ガス処理を行う。詳細には、CVD反応室内に水素ガスを7000cc/min導入した後、CVD反応室内部を約1100℃まで加熱し、CVD反応室の脱ガスを行う。
CVD処理によるタンタル被覆膜の形成工程を説明する。CVD反応室内を約800℃以上に保つとともに、可変バルブを操作することによりCVD反応室内を10Torr(1333Pa)以下に減圧する。そして、CVD反応室内に原料ガスとして五塩化タンタル(TaCl5)等のタンタルハロゲン化合物を10~20sccmの流量で供給する。また、キャリアガスとして、例えば、アルゴンガス、水素ガス又はそれらの混合ガスを供給する。なお、上記の単位[sccm]は、標準状態において一分間当りに流れる気体の量(cm3)を示す。上記条件下で炭素基材1の表面にタンタル被覆膜を形成する(図4(b)参照)。
上述した方法により得られたタンタル被覆膜は、タンタル結晶粒により構成されている。タンタル被覆膜は、X線回折において、タンタル結晶の(100)面、(200)面、(211)面及び(220)面に対応した回折ピークを有する。また、前記(200)面の回折ピークが最大の回折強度を示し且つ、当該(200)面の半価幅が0.2°以下となる。炭素基材31の熱膨張係数が6.5×10-6~8.0×10-6/Kである場合、炭素基材31とタンタル被覆膜とでは、熱膨張係数に差が生じる。この時、タンタル被覆膜は内部応力を有しており、X線回折図形において、ピークシフトやピークの分裂が観測される。
図示しない浸炭炉内に、タンタル被覆膜が形成された炭素基材31を配置する(図4(b))。浸炭処理では、前記浸炭炉内温度を1700~2500℃とし且つ浸炭炉内を真空雰囲気10-2~10Paとする。浸炭の炭素源には、予め設置した炭素源用黒鉛材や浸炭炉の黒鉛冶具類に含まれる炭素が用いられる。これらの炭素によりタンタル被覆膜が炭化タンタル被覆膜に転化する(図4(c))。
上述した炭化タンタル被覆膜の形成方法(4)により得られた炭化タンタル被覆膜はX線回折図形において炭化タンタルの(311)面の回折線が最大の回折強度をしめす。CVD処理によって得られた炭化タンタル被覆膜はX線回折図形において炭化タンタルの(311)面若しくは、(220)面の回折線が最大の回折強度をしめす。
炭化タンタル被覆膜42は、炭化タンタル結晶粒により構成されている。ここで、炭化タンタルとは、タンタル原子と炭素原子との化合物を意味しており、例えば、TaC,Ta2C等の化学式で表される化合物である。
炭化タンタル被覆膜42は、X線回折により炭化タンタルに対応した回折ピークの(311)面の配向角度において80°以上に最大のピーク値を有する。また、炭化タンタル被覆膜42は、X線回折により炭化タンタルに対応した回折ピークの(220)面の配向角度において80°以上に最大のピーク値を有する。
タンタルと炭化タンタルの密度はそれぞれ16.65g/cm3と13.90g/cm3である。このため、タンタル被膜に浸炭処理を施して炭化タンタル被膜に転化する場合に体積膨張が生じ、各結晶面の格子面間隔が広がる。この際に、各結晶面の方位指数が炭素基材表面に対して垂直に近づくほど、炭化タンタル被膜の内部応力が小さくなり、結果結晶粒界が減少すると推測される。
上記(1),(2),(3)で形成した炭化タンタル被覆膜では、炭化タンタル結晶核が生成し、その結晶核が結晶成長する。炭化タンタル結晶の各結晶面は方位指数に対して成長する。炭化タンタル結晶粒は成長する過程で、隣り合う他の結晶粒とぶつかり合うことで成長が阻害される。炭化タンタル結晶における各結晶面の方位指数が炭素基材表面に対して垂直に近づくほど、隣り合う結晶粒によって生じる内部応力が小さくなり成長が阻害されにくくなると推測される。結果、結晶粒が発達し結晶粒界が減少する。
炭化タンタル被覆膜42のX線回折図形によって求められる炭化タンタルの(220)面に相当する回折強度(以下、I(220)と示す)及び(311)面に相当する回折強度(以下、I(311)と示す)のうちいずれか一方の回折強度が最大となることが好ましい。ここで、回折強度とは、各結晶面に特有の回折角に現れるピーク値を意味する。また、I(220)とI(311)の和が各結晶面に相当するX線回折強度の総和に対して0.5以上且つ0.9以下の範囲であることが好ましい。
また、総和Ipに対して0.9を超える場合、炭化タンタルにおける他の結晶面の成長が弱いことを意味し、結果結晶粒の小さな炭化タンタル被覆膜になると推測される。
炭化タンタル被覆膜42において、ガス透過率は10-7cm2/s以下であることが好ましく、10-8~10-11cm2/secであることがさらに好ましい。ガス透過率が上記範囲内にある場合、緻密な炭化タンタル被覆膜42となる。一般的に炭素基材は通常窒素ガス透過率10-2~10-3cm2/secの値を有するため、当該炭化タンタル被覆膜42の窒素ガス透過率が10-7cm2/s以下である場合、炭化タンタル被覆膜42の窒素ガス透過率は、炭素基材の窒素ガス透過率の約10-5~10-4倍となる。当該炭化タンタル被覆膜が緻密な膜である場合、耐熱性と耐ガスエッチング性が得られる。
K=(QL)/(ΔPA)・・・(2)
Q={(p2-p1)V0}/t・・・(3)
ここで、Kは窒素ガス透過率、Qは通気量、ΔPは一次側と二次側の圧力差、Aは透過面積、Lは測定試料の厚さ、p1は二次側の初期圧力、p2は二次側の最終圧力、V0は二次側の容積、tは測定時間である。
(L1+L2)/K0=L1/K1+L2/K2・・・(4)
ここで、L1は炭素基材の厚さ、L2は炭化タンタルの被覆膜の厚さである。
炭化タンタル被覆膜42の膜厚は、10~100μmであることが好ましい。炭化タンタル被覆膜厚が10μm未満である場合、ガス透過率が大きくなり十分な耐熱性と耐ガスエッチング性が得られない。
原料粉末に結合材(ピッチ等)を添加して混合し、成形し、焼成することにより炭素基材が得られる。なお、必要に応じて、公知の方法により黒鉛化処理及び高純度化処理を施してもよい。また、炭素基材に表面加工処理を施してもよい。これにより、炭素基材の表面が粗面化され、炭素基材と炭化タンタル被覆膜との密着性を向上させることができる。
<炭素基材の灰分>
炭素基材は、不純物をできる限り含まないことが好ましい。具体的には、炭素基材に不純物として含まれる各元素は、アルミニウムが0.3ppm以下であり、鉄が1.0ppm以下であり、マグネシウムが0.1ppm以下であり且つケイ素が0.1ppm以下であることが好ましい。さらに、炭素基材の総灰分(本明細書では、単に灰分と示すことがある)は10ppm以下であることが好ましい。灰分は、JIS-R-7223で規定される灰分の分析方法などにより測定することができる。
炭素基材の1000℃基準のガス放出圧力が10-4Pa/g以下であることが好ましい。1000℃基準のガス放出圧力とは、炭素基材の表面および細孔に吸着したガス分子が1000℃の温度下で脱離し、脱離したガスが雰囲気中の圧力を上昇させる圧力変化量を意味し、具体的には、特許第2684106号に開示される昇温脱離スペクトル(TDS)などにより測定することができる。ガス放出圧力が高いと、脱ガス処理時にCVD炉内汚染が高くなり、炭化タンタル被膜に不純物の混入する危険がある。
炭化タンタル被覆膜の熱膨張係数は、6.5~8.0×10-6/Kの範囲内にある。したがって、炭素基材の熱膨張係数を6.5~8.0×10-6/Kとすることが好ましい。上記炭素基材を用いることにより、炭素基材と炭化タンタル被覆膜との熱膨張係数差が小さな炭化タンタル被覆炭素材料を形成することができる。したがって、炭化タンタル被覆炭素材料の温度変化による膨張や収縮を生じた時、炭化タンタル被覆膜に熱応力が発生しにくいため、炭化タンタル被覆膜が剥離しにくい。
炭素基材の密度は、1.65~1.90g/cm3であることが好ましく、1.73~1.83g/cm3であることがさらに好ましい。炭素基材の密度が上記範囲内にある場合、炭素基材の機械的強度が高くなる。
ボイドとは、炭化タンタル被覆膜の表面に発生する直径数十から数百nmの穴の総称である。ボイドは、結晶粒界に存在する残留物が結晶粒界に沿って放出する際に発生すると推測される。これは、以下の2つの理由が考えられる。1つ目の理由として、結晶粒界には、未発達な炭化タンタルの結晶及び不純物等が残留している。2つ目の理由として結晶粒界は結晶粒に比べて強度が低いため破壊の起点となりやすい。したがって、上記2つの理由から、炭化タンタル被覆膜を熱処理する際、強度の弱い結晶粒界が破壊され、結晶粒界に存在する残留物が結晶粒界に沿って放出し、ボイドが発生すると推測される。よって、結晶粒界の少ない被覆膜ほどボイドの発生を抑えることできる。
ここでは、上述したCVD処理による炭化タンタル被覆膜の形成方法(1)を用いて炭化タンタル被覆膜を形成した。
ここでは、上述したCVD処理による炭化タンタル被覆膜の形成方法(2)を用いて炭化タンタル被覆膜を形成した。
ここでは、上述したCVD処理による炭化タンタル被覆膜の形成方法(2),(3)を用いて炭化タンタル被覆膜を形成した。
熱膨張係数が7.8×10-6/K、1000℃基準のガス放出圧力が10-6Pa/g且つ灰分が2ppmである、直径60mm及び厚さ10mmの黒鉛基板に、CVD処理温度を1000℃としてCVD処理を施し、黒鉛基板上に下地となる炭化タンタル被覆膜を形成した。このとき、炭化タンタル被覆膜のC/Taの組成比が1.0~2.0となるように調整した。CVD処理の圧力、原料ガス等の条件は、実施例1~4と同等の条件とした。そして、得られた炭化タンタル被覆炭素材料に、上記と同じCVD条件でCVD処理を施し、新たな炭化タンタル被覆膜を形成した。
熱膨張係数が7.8×10-6/K、1000℃基準のガス放出圧力が10-6Pa/g、且つ灰分が2ppmである、直径60mm及び厚さ10mmの黒鉛基板に、CVD処理温度を900℃としてCVD処理を施し、黒鉛基板上に炭化タンタル被覆膜を形成した。そして、CVD処理温度を100℃/Hrで漸次上昇させ、処理温度が1000℃に達したときに、昇温を停止し、処理温度を1000℃に維持しながら被覆膜のC/Taの組成比が1.0~2.0となるように調整しながら、下地の炭化タンタル被覆膜を所望の厚みになるまで作製した。次に、当該下地の被覆膜上にCVD処理温度を1000℃として再度CVD処理を施し、新たな炭化タンタル被覆膜を作製した。このときの圧力、原料ガス等の条件は、実施例1~4と同等の条件とした。
ここでは、上述した炭化タンタル被覆膜の形成方法(4)を用いて炭化タンタル被覆膜を形成した。
ここでは、上述した浸炭処理による炭化タンタル被覆膜の形成方法(4)を用いて炭化タンタル被覆膜を形成した。
熱膨張係数が7.8×10-6/K、1000℃基準のガス放出圧力が10-6Pa/g且つ灰分が2ppmである、直径60mm及び厚さ10mmの黒鉛基板に、下記表11に示すCVD処理条件でCVD処理を施し、黒鉛基板上に炭化タンタル被覆膜を形成した。このとき、炭化タンタル被覆膜のC/Taの組成比が1.0~2.0となるように調整した。
比較例1と同様の方法で、黒鉛基材に下地となる炭化タンタル被覆膜を形成した。得られた炭化タンタル被覆炭素材料に比較例1(表11)と同等のCVD条件下でCVD処理を施すことにより、当該下地となる炭化タンタル被覆膜の上に新たな炭化タンタル被覆膜を形成した。得られた炭化タンタル被覆炭素材料の断面を電子顕微鏡によって撮影した像(SEM像)を図28に示す。
2,22,23,32,42 被覆膜
400 炭化タンタル被覆炭素材料
Claims (32)
- 炭素基材と、前記炭素基材上に被覆した炭化タンタル被覆膜とを有しており、
前記炭化タンタル被覆膜は、X線回折により炭化タンタルに対応した回折ピークの(311)面の配向角度において80°以上に最大のピーク値を有することを特徴とする炭化タンタル被覆炭素材料。 - 前記炭化タンタル被覆膜は、X線回折により炭化タンタルに対応した回折ピークの(220)面の配向角度において80°以上に最大のピーク値を有することを特徴とする請求項1に記載の炭化タンタル被覆炭素材料。
- X線回折により炭化タンタル結晶の(311)面及び(220)面における回折強度の和は、X線回折により炭化タンタル結晶に対応した全結晶面における回折強度の総和に対して0.5以上且つ0.9以下であることを特徴とする請求項1または2に記載の炭化タンタル被覆炭素材料。
- 前記炭化タンタル被覆膜のX線回折図形における(311)面又は(220)面の回折線の強度が最大となることを特徴とする請求項1~3のいずれか1項に記載の炭化タンタル被覆炭素材料。
- 前記炭化タンタル被覆膜のX線回折図形における(311)面又は(220)面の回折線の半価幅が0 . 2 ° 以下であることを特徴とする請求項1~4のいずれか1項に記載の炭化タンタル被覆炭素材料。
- 炭素基材と、前記炭素基材上に被覆した炭化タンタル被覆膜とを有しており、
前記炭化タンタル被覆膜を形成する結晶粒は、炭素基材表面から炭化タンタル被覆膜外面に向けて傾斜的に大きくなっていることを特徴とする炭化タンタル被覆炭素材料。 - 炭素基材上に炭化タンタル被覆膜を形成する炭化タンタル被覆炭素材料の製造方法であり、
前記炭素基材の表面に炭化タンタル結晶核を形成する結晶核生成工程と、
前記結晶核生成工程後に前記炭化タンタル結晶核を結晶成長させる結晶成長工程とを含み、
前記結晶成長工程は、製造温度を漸次上昇させる昇温工程を有することを特徴とする炭化タンタル被覆炭素材料の製造方法。 - 前記結晶核生成工程において、
前記炭化タンタル結晶核を形成する温度は850~950℃であることを特徴とする請求項7に記載の炭化タンタル被覆炭素材料の製造方法。 - 前記昇温工程は50℃以上の温度差を有することを特徴とする請求項7又は8に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記昇温工程後に、
前記昇温工程終了時の製造温度を保持することを特徴とする請求項7~9のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。 - 前記昇温工程において、
前記製造温度を一定の速度で上昇させることを特徴とする請求項7~10のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。 - 炭素基材上に炭化タンタル被覆膜形成工程により炭化タンタル被覆膜を形成する炭化タンタル被覆炭素材料の製造方法であり、
前記炭化タンタル被覆膜形成工程は、
前記炭素基材の表面に第1炭化タンタル被覆膜を形成する第1形成工程と、
第1炭化タンタル被覆膜上に少なくとも1層の炭化タンタル被覆膜を形成する第2形成工程とを有し、
前記第1炭化タンタル被覆膜は、X線回折により炭化タンタルに対応した回折ピークの(311)面の配向角度において80°以上に最大のピーク値を有することを特徴とする炭化タンタル被覆炭素材料の製造方法。 - 前記第1形成工程及び前記第2形成工程は、被覆対象物を支持具により支持しながら行われ、前記第1形成工程において支持具により生じた被覆膜の欠損部分を、第2形成工程において被覆することを特徴とする請求項12に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記第1形成工程は、
前記炭素基材の表面に炭化タンタル結晶核を形成する結晶核生成工程と、
前記結晶核生成工程後に前記炭化タンタル結晶核を結晶成長させる結晶成長工程とを含み、
前記結晶成長工程は、
製造温度を漸次上昇させる昇温工程を有していることを特徴とする請求項12又は13に記載の炭化タンタル被覆炭素材料の製造方法。 - 前記炭化タンタル被覆膜は、X線回折により炭化タンタルに対応した回折ピークの(220)面の配向角度において80°以上に最大のピーク値を有することを特徴とする請求項12~14のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記炭化タンタル被覆膜のX線回折図形における(311)面及び(220)面に対応する回折線の強度の和は、前記炭化タンタル被覆膜のX線回折図形における炭化タンタルの全結晶面に対応する回折線の強度の総和に対して0.5以上且つ0.9以下であることを特徴とする請求項12~15のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記炭化タンタル被覆膜のX線回折図形における(311)面または(220)面に対応する回折線の強度が最大となることを特徴とする請求項12~16のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記炭化タンタル被覆膜のX線回折図形における前記(311)面または(220)面の回折線の半価幅が0 .12 ° 以下であることを特徴とする請求項12~17のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
- 炭素基材上に炭化タンタル被覆膜を形成する炭化タンタル被覆炭素材料の製造方法であり、
前記炭素基材の表面にタンタル被覆膜を形成するタンタル被覆膜形成工程と、
前記タンタル被覆膜を浸炭処理する浸炭処理工程とを含むことを特徴とする炭化タンタル被覆炭素材料の製造方法。 - 前記タンタル被覆膜形成工程と、前記浸炭処理工程とを順に複数回繰返すことを特徴とする請求項19に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記タンタル被覆膜形成工程を複数回繰返すことを特徴とする請求項19または20に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記浸炭処理工程において、
1700℃~2500℃で浸炭処理を行うことを特徴とする請求項19~21のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。 - 前記炭素基材の熱膨張係数は6.5~8.0×10-6/Kであることを特徴とする請求項19~22のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記タンタル被覆工程は、被覆対象物が支持具により支持されながら行われ、
初回のタンタル被覆膜形成工程において、前記支持具により生じた欠損部分を、2回目以降のタンタル被覆膜形成工程において被覆することを特徴とする請求項20又は21に記載の炭化タンタル被覆炭素材料の製造方法。 - 炭素基材上に炭化タンタル被覆形成工程により炭化タンタル被覆膜を形成する炭化タンタル被覆炭素材料の製造方法であり、
前記炭素基材の表面にタンタル被覆膜を形成するタンタル被覆膜形成工程と前記タンタル被覆膜を浸炭処理する浸炭処理工程とを経て第1炭化タンタル被覆膜を形成する第1炭化タンタル被覆膜形成工程と、
前記第1炭化タンタル被覆膜上に新たな第2炭化タンタル被覆膜を形成する第2炭化タンタル被覆膜形成工程を有することを特徴とする炭化タンタル被覆炭素材料の製造方法。 - 前記浸炭処理工程において、
1700℃~2500℃で浸炭処理を行うことを特徴とする請求項25に記載の炭化タンタル被覆炭素材料の製造方法。 - 前記炭素基材の熱膨張係数は6.5~8.0×10-6/Kであることを特徴とする請求項25又は26に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記炭化タンタル被覆膜は、X線回折により炭化タンタルに対応した回折ピークの(311)面の配向角度において80°以上に最大のピーク値を有することを特徴とする請求項25~27のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記炭化タンタル被覆膜は、X線回折により炭化タンタルに対応した回折ピークの(220)面の配向角度において80°以上に最大のピーク値を有することを特徴とする請求項25~28のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記炭化タンタル被覆膜のX線回折図形における(311)面及び(220)面における回折線の強度の和は、前記炭化タンタル被覆膜のX線回折図形におけるX線回折により炭化タンタルに対応した全結晶面における回折線の強度の総和に対して0.5以上且つ0.9以下であることを特徴とする請求項25~29のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記炭化タンタル被覆膜のX線回折図形における(311)面の回折線の強度が最大となることを特徴とする請求項25~30のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
- 前記炭化タンタル被覆膜のX線回折図形における(311)面の回折線の半価幅が0 .12 ° 以下であることを特徴とする請求項25~31のいずれか1項に記載の炭化タンタル被覆炭素材料の製造方法。
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JP5502721B2 (ja) | 2014-05-28 |
JP2011153376A (ja) | 2011-08-11 |
CN102770582A (zh) | 2012-11-07 |
US20120301723A1 (en) | 2012-11-29 |
CN103922797B (zh) | 2016-03-16 |
JP5703017B2 (ja) | 2015-04-15 |
JP5762735B2 (ja) | 2015-08-12 |
JP2011153070A (ja) | 2011-08-11 |
JP2011153377A (ja) | 2011-08-11 |
US9322113B2 (en) | 2016-04-26 |
RU2576406C2 (ru) | 2016-03-10 |
KR20120104260A (ko) | 2012-09-20 |
RU2012132436A (ru) | 2014-02-10 |
TW201139717A (en) | 2011-11-16 |
EP2520691A4 (en) | 2014-01-15 |
JP2011153378A (ja) | 2011-08-11 |
JP2011153375A (ja) | 2011-08-11 |
TWI534289B (zh) | 2016-05-21 |
EP2520691B1 (en) | 2022-08-10 |
KR101766500B1 (ko) | 2017-08-08 |
CN103922797A (zh) | 2014-07-16 |
CN102770582B (zh) | 2015-06-17 |
EP2520691A1 (en) | 2012-11-07 |
JP5666899B2 (ja) | 2015-02-12 |
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