WO2022215651A1 - Vanadium silicon carbide film coated member and method for manufacturing same, and vanadium silicon carbide film-forming substrate and method for manufacturing same - Google Patents
Vanadium silicon carbide film coated member and method for manufacturing same, and vanadium silicon carbide film-forming substrate and method for manufacturing same Download PDFInfo
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- WO2022215651A1 WO2022215651A1 PCT/JP2022/016627 JP2022016627W WO2022215651A1 WO 2022215651 A1 WO2022215651 A1 WO 2022215651A1 JP 2022016627 W JP2022016627 W JP 2022016627W WO 2022215651 A1 WO2022215651 A1 WO 2022215651A1
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- vanadium
- silicide film
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- vanadium silicide
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- 239000000758 substrate Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 26
- MANBDHUBXBMZNV-UHFFFAOYSA-N [V]=[Si] Chemical compound [V]=[Si] MANBDHUBXBMZNV-UHFFFAOYSA-N 0.000 title abstract description 11
- 229910010271 silicon carbide Inorganic materials 0.000 title abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 76
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 76
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 66
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 150000004767 nitrides Chemical class 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 230000003746 surface roughness Effects 0.000 claims abstract description 40
- VKTGMGGBYBQLGR-UHFFFAOYSA-N [Si].[V].[V].[V] Chemical compound [Si].[V].[V].[V] VKTGMGGBYBQLGR-UHFFFAOYSA-N 0.000 claims description 206
- 239000007789 gas Substances 0.000 claims description 106
- 239000000463 material Substances 0.000 claims description 69
- 238000005121 nitriding Methods 0.000 claims description 53
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910000831 Steel Inorganic materials 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 239000010959 steel Substances 0.000 claims description 20
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 15
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 37
- 235000019589 hardness Nutrition 0.000 description 35
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000011282 treatment Methods 0.000 description 20
- 238000012545 processing Methods 0.000 description 13
- 238000005259 measurement Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 238000004453 electron probe microanalysis Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229910001315 Tool steel Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005242 forging Methods 0.000 description 6
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000005049 silicon tetrachloride Substances 0.000 description 5
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910000997 High-speed steel Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000004439 roughness measurement Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 241000428199 Mustelinae Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- -1 argon ions Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 101150031287 petH gene Proteins 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 102200082816 rs34868397 Human genes 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
-
- 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
- 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
- C23C16/42—Silicides
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- 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
- C23C8/36—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 using ionised gases, e.g. ionitriding
- C23C8/38—Treatment of ferrous surfaces
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- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
A vanadium silicon carbide film coated member comprising a substrate, a nitride layer formed on a surface of the substrate, and a vanadium silicon carbide film formed on the nitride layer and having a surface roughness Rzjis of 0.2-1.0 μm, wherein the vanadium silicon carbide film contains vanadium, silicon, and carbon, and, in the film, the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration is 90 at% or more.
Description
本発明は、珪炭化バナジウム膜被覆部材およびその製造方法並びに珪炭化バナジウム膜形成用基材およびその製造方法に関する。
The present invention relates to a vanadium silicide film-coated member and its manufacturing method, as well as a substrate for forming a vanadium silicide film and its manufacturing method.
従来、プレス加工や鍛造加工に用いられる金型や、切削工具、鍛造工具、自動車部品等の基材表面には、被成型材の加工時における接触摩擦に起因した金型表面の摩耗や被成型材の傷つきを防ぐため、基材よりも高硬度の硬質皮膜を基材表面に形成することが知られている。特許文献１には、基材表面に対して、基材密着性と耐摩耗性に優れた硬質皮膜の一種である、バナジウムと、炭素と、珪素を含む珪炭化バナジウム膜（ＶＳｉＣ膜）をイオンプレーティング法により形成した珪炭化バナジウム膜被覆部材が記載されている。
Conventionally, on the surface of base materials such as dies used for press working and forging, cutting tools, forging tools, automobile parts, etc., wear and deposits on the die surface due to contact friction during processing of the material to be molded. In order to prevent the mold material from being damaged, it is known to form a hard coating having higher hardness than the base material on the surface of the base material. Patent Document 1 discloses that a vanadium silicide film (VSiC film) containing vanadium, carbon, and silicon, which is a kind of hard coating excellent in substrate adhesion and wear resistance, is applied to the surface of the substrate by ions. A vanadium silicide film-coated member formed by a plating method is described.
珪炭化バナジウム膜被覆部材は、用途によっては部材表面に大きな面圧がかかった状態で使用される。例えば珪炭化バナジウム膜被覆部材が鍛造用金型として使用される場合には、成形を行う度に部材表面に大きな面圧がかかる。このような状態で珪炭化バナジウム膜被覆部材が使用される場合、基材と珪炭化バナジウム膜との間の密着性が不十分であると、珪炭化バナジウム膜の剥離が生じ、製品寿命が著しく低下する。このため、プレス加工や鍛造加工に用いられる金型や、切削工具、歯切工具、鍛造工具、自動車部品等の表面に形成される珪炭化バナジウムと基材のさらなる密着性向上が望まれていた。
The vanadium silicide film-coated member is used in a state where a large surface pressure is applied to the member surface depending on the application. For example, when a vanadium silicide film-coated member is used as a forging die, a large surface pressure is applied to the surface of the member each time molding is performed. When the vanadium silicide film-coated member is used in such a state, if the adhesion between the substrate and the vanadium silicide film is insufficient, the vanadium silicide film will peel off and the product life will be significantly shortened. descend. For this reason, it has been desired to further improve the adhesion between vanadium silicide formed on the surface of metal molds used in press working and forging, cutting tools, gear cutting tools, forging tools, automobile parts, etc. and the base material. .
本発明は、上記事情に鑑みてなされたものであり、珪炭化バナジウム膜と基材の密着性を向上させることが可能な珪炭化バナジウム膜被覆部材およびその製造方法並びに珪炭化バナジウム膜形成用基材およびその製造方法を提供することを目的とする。
The present invention has been made in view of the above circumstances, and provides a vanadium silicide film-coated member capable of improving the adhesion between the vanadium silicide film and the base material, a method for producing the same, and a substrate for forming a vanadium silicide film. The purpose is to provide a material and its manufacturing method.
本発明者らは、珪炭化バナジウム膜を形成する基材の表面に所定の表面粗さとなる窒化層を形成し、その窒化層上に珪炭化バナジウム膜を形成することで、基材との密着性が高い珪炭化バナジウム膜の被覆部材が得られることを見出し、本発明を完成するに至った。
The present inventors formed a nitride layer having a predetermined surface roughness on the surface of a base material on which a vanadium silicide film is formed, and formed a vanadium silicide film on the nitride layer to achieve adhesion to the base material. The inventors have found that it is possible to obtain a member coated with a vanadium silicide film having high properties, and have completed the present invention.
上記課題を解決する本発明の一態様は、以下に列挙されるものである。
［１］珪炭化バナジウム膜被覆部材であって、基材と、前記基材の表面に形成された、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層と、前記窒化層上に形成された珪炭化バナジウム膜と、を有し、前記珪炭化バナジウム膜は、バナジウムと、珪素と、炭素を含有し、かつ、膜中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計が９０ａｔ％以上である。
［２］上記［１］に記載の珪炭化バナジウム膜被覆部材において、前記窒化層の表面粗さＲｚｊｉｓが０．２５μｍ以上である。
［３］上記［１］に記載の珪炭化バナジウム膜被覆部材において、前記窒化層の表面粗さＲｚｊｉｓが０．４μｍ以上である。
［４］上記［１］に記載の珪炭化バナジウム膜被覆部材において、前記基材が鋼材である。
［５］上記［１］に記載の珪炭化バナジウム膜被覆部材において、前記バナジウム元素濃度が３～１５ａｔ％、前記珪素元素濃度が１５～３０ａｔ％、前記炭素元素濃度が６０～８０ａｔ％である。
［６］上記［１］に記載の珪炭化バナジウム膜被覆部材において、下記（１）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧２５ａｔ％ ・・・（１）
［７］上記［１］に記載の珪炭化バナジウム膜被覆部材において、下記（２）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧３０ａｔ％ ・・・（２）
［８］上記［１］に記載された珪炭化バナジウム膜被覆部材において、下記（３）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≦３６ａｔ％ ・・・（３）
［９］上記［１］に記載の珪炭化バナジウム膜被覆部材において、下記（４）式を満たす。
前記珪素元素濃度／（前記バナジウム元素濃度＋前記珪素元素濃度）＞０．７ ・・・（４）
［１０］珪炭化バナジウム膜形成用基材であって、基材の表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を有する。
［１１］珪炭化バナジウム膜被覆部材の製造方法であって、基材の表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を形成する窒化処理工程と、前記窒化処理工程で形成された窒化層上に、バナジウムと、珪素と、炭素を含有し、かつ、膜中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計が９０ａｔ％以上の珪炭化バナジウム膜を形成する珪炭化バナジウム膜形成工程と、を有する。
［１２］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記窒化層の表面粗さＲｚｊｉｓが０．２５μｍ以上である。
［１３］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記窒化層の表面粗さＲｚｊｉｓが０．４μｍ以上である。
［１４］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記窒化処理工程において、水素ガスおよび窒素ガスをプラズマ化することで前記基材の窒化処理を行う。
［１５］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記基材が鋼材である。
［１６］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記珪炭化バナジウム膜形成工程において、塩化バナジウムガス、珪素源ガス、炭化水素ガスおよび水素ガスを供給し、プラズマ化学蒸着法によって前記珪炭化バナジウム膜を形成する。
［１７］上記［１６］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記珪炭化バナジウム膜形成工程において、アルゴンガスをさらに供給し、前記塩化バナジウムガス、前記珪素源ガス、前記炭化水素ガス、前記水素ガスおよび前記アルゴンガスの流量比が１：０．２５～２：３～２０：２０～３５：０．５～２である。
［１８］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記バナジウム元素濃度が３～１５ａｔ％、前記珪素元素濃度が１５～３０ａｔ％、前記炭素元素濃度が６０～８０ａｔ％である。
［１９］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、下記（１）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧２５ａｔ％ ・・・（１）
［２０］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、下記（２）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧３０ａｔ％ ・・・（２）
［２１］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、下記（３）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≦３６ａｔ％ ・・・（３）
［２２］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、下記（４）式を満たす。
前記珪素元素濃度／（前記バナジウム元素濃度＋前記珪素元素濃度）＞０．７ ・・・（４）
［２３］珪炭化バナジウム膜形成用基材の製造方法であって、基材の表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を形成する窒化処理工程を有する。 One aspect of the present invention for solving the above problems is enumerated below.
[1] A member coated with a vanadium silicide carbide film comprising a base material, a nitride layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less formed on the surface of the base material, and on the nitride layer and a vanadium silicide carbide film formed in the vanadium silicide film containing vanadium, silicon, and carbon, and the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film. is 90 at % or more.
[2] In the vanadium silicide film-coated member described in [1] above, the nitride layer has a surface roughness Rzjis of 0.25 μm or more.
[3] In the vanadium silicide film-coated member described in [1] above, the nitride layer has a surface roughness Rzjis of 0.4 μm or more.
[4] In the vanadium silicide film-coated member according to [1] above, the base material is a steel material.
[5] In the vanadium silicide film-coated member according to [1] above, the vanadium element concentration is 3 to 15 at %, the silicon element concentration is 15 to 30 at %, and the carbon element concentration is 60 to 80 at %.
[6] The vanadium silicide film-coated member described in [1] above satisfies the following formula (1).
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧25 at % (1)
[7] The vanadium silicide film-coated member described in [1] above satisfies the following formula (2).
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧30 at % (2)
[8] The vanadium silicide film-coated member described in [1] above satisfies the following formula (3).
(the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at% (3)
[9] The vanadium silicide film-coated member described in [1] above satisfies the following formula (4).
The silicon element concentration/(the vanadium element concentration+the silicon element concentration)>0.7 (4)
[10] A substrate for forming a vanadium silicide film, having a nitride layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of the substrate.
[11] A method for producing a vanadium silicide film-coated member, comprising a nitriding step of forming a nitrided layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of a substrate; A vanadium silicon carbide film containing vanadium, silicon and carbon and having a sum of the vanadium element concentration, the silicon element concentration and the carbon element concentration in the film being 90 at % or more on the nitride layer formed in the process. and a vanadium silicide film forming step of forming a.
[12] In the method for producing a vanadium silicide film-coated member described in [11] above, the nitride layer has a surface roughness Rzjis of 0.25 μm or more.
[13] In the method for producing a vanadium silicide film-coated member described in [11] above, the nitride layer has a surface roughness Rzjis of 0.4 μm or more.
[14] In the method for producing a vanadium silicide film-coated member described in [11] above, in the nitriding step, the base material is nitrided by converting hydrogen gas and nitrogen gas into plasma.
[15] In the method for manufacturing a vanadium silicide film-coated member described in [11] above, the base material is a steel material.
[16] In the method for producing a vanadium silicide film-coated member described in [11] above, in the vanadium silicide film-forming step, a vanadium chloride gas, a silicon source gas, a hydrocarbon gas and a hydrogen gas are supplied to generate a plasma. The vanadium silicide film is formed by chemical vapor deposition.
[17] In the method for producing a vanadium silicide film-coated member described in [16] above, in the vanadium silicide film-forming step, argon gas is further supplied, and the vanadium chloride gas, the silicon source gas, and the carbonization are further supplied. The flow ratio of hydrogen gas, said hydrogen gas and said argon gas is 1:0.25-2:3-20:20-35:0.5-2.
[18] In the method for producing a vanadium silicide film-coated member described in [11] above, the vanadium element concentration is 3 to 15 at %, the silicon element concentration is 15 to 30 at %, and the carbon element concentration is 60 to 80 at %. %.
[19] In the method for producing a vanadium silicide film-coated member described in [11] above, the following formula (1) is satisfied.
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧25 at % (1)
[20] In the method for producing a vanadium silicide film-coated member described in [11] above, the following formula (2) is satisfied.
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧30 at % (2)
[21] In the method for producing a vanadium silicide film-coated member described in [11] above, the following formula (3) is satisfied.
(the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at% (3)
[22] In the method for manufacturing a vanadium silicide film-coated member described in [11] above, the following formula (4) is satisfied.
The silicon element concentration/(the vanadium element concentration+the silicon element concentration)>0.7 (4)
[23] A method for producing a substrate for forming a vanadium silicide film, comprising a nitriding step of forming a nitride layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of the substrate.
［１］珪炭化バナジウム膜被覆部材であって、基材と、前記基材の表面に形成された、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層と、前記窒化層上に形成された珪炭化バナジウム膜と、を有し、前記珪炭化バナジウム膜は、バナジウムと、珪素と、炭素を含有し、かつ、膜中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計が９０ａｔ％以上である。
［２］上記［１］に記載の珪炭化バナジウム膜被覆部材において、前記窒化層の表面粗さＲｚｊｉｓが０．２５μｍ以上である。
［３］上記［１］に記載の珪炭化バナジウム膜被覆部材において、前記窒化層の表面粗さＲｚｊｉｓが０．４μｍ以上である。
［４］上記［１］に記載の珪炭化バナジウム膜被覆部材において、前記基材が鋼材である。
［５］上記［１］に記載の珪炭化バナジウム膜被覆部材において、前記バナジウム元素濃度が３～１５ａｔ％、前記珪素元素濃度が１５～３０ａｔ％、前記炭素元素濃度が６０～８０ａｔ％である。
［６］上記［１］に記載の珪炭化バナジウム膜被覆部材において、下記（１）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧２５ａｔ％ ・・・（１）
［７］上記［１］に記載の珪炭化バナジウム膜被覆部材において、下記（２）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧３０ａｔ％ ・・・（２）
［８］上記［１］に記載された珪炭化バナジウム膜被覆部材において、下記（３）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≦３６ａｔ％ ・・・（３）
［９］上記［１］に記載の珪炭化バナジウム膜被覆部材において、下記（４）式を満たす。
前記珪素元素濃度／（前記バナジウム元素濃度＋前記珪素元素濃度）＞０．７ ・・・（４）
［１０］珪炭化バナジウム膜形成用基材であって、基材の表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を有する。
［１１］珪炭化バナジウム膜被覆部材の製造方法であって、基材の表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を形成する窒化処理工程と、前記窒化処理工程で形成された窒化層上に、バナジウムと、珪素と、炭素を含有し、かつ、膜中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計が９０ａｔ％以上の珪炭化バナジウム膜を形成する珪炭化バナジウム膜形成工程と、を有する。
［１２］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記窒化層の表面粗さＲｚｊｉｓが０．２５μｍ以上である。
［１３］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記窒化層の表面粗さＲｚｊｉｓが０．４μｍ以上である。
［１４］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記窒化処理工程において、水素ガスおよび窒素ガスをプラズマ化することで前記基材の窒化処理を行う。
［１５］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記基材が鋼材である。
［１６］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記珪炭化バナジウム膜形成工程において、塩化バナジウムガス、珪素源ガス、炭化水素ガスおよび水素ガスを供給し、プラズマ化学蒸着法によって前記珪炭化バナジウム膜を形成する。
［１７］上記［１６］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記珪炭化バナジウム膜形成工程において、アルゴンガスをさらに供給し、前記塩化バナジウムガス、前記珪素源ガス、前記炭化水素ガス、前記水素ガスおよび前記アルゴンガスの流量比が１：０．２５～２：３～２０：２０～３５：０．５～２である。
［１８］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、前記バナジウム元素濃度が３～１５ａｔ％、前記珪素元素濃度が１５～３０ａｔ％、前記炭素元素濃度が６０～８０ａｔ％である。
［１９］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、下記（１）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧２５ａｔ％ ・・・（１）
［２０］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、下記（２）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧３０ａｔ％ ・・・（２）
［２１］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、下記（３）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≦３６ａｔ％ ・・・（３）
［２２］上記［１１］に記載された珪炭化バナジウム膜被覆部材の製造方法において、下記（４）式を満たす。
前記珪素元素濃度／（前記バナジウム元素濃度＋前記珪素元素濃度）＞０．７ ・・・（４）
［２３］珪炭化バナジウム膜形成用基材の製造方法であって、基材の表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を形成する窒化処理工程を有する。 One aspect of the present invention for solving the above problems is enumerated below.
[1] A member coated with a vanadium silicide carbide film comprising a base material, a nitride layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less formed on the surface of the base material, and on the nitride layer and a vanadium silicide carbide film formed in the vanadium silicide film containing vanadium, silicon, and carbon, and the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film. is 90 at % or more.
[2] In the vanadium silicide film-coated member described in [1] above, the nitride layer has a surface roughness Rzjis of 0.25 μm or more.
[3] In the vanadium silicide film-coated member described in [1] above, the nitride layer has a surface roughness Rzjis of 0.4 μm or more.
[4] In the vanadium silicide film-coated member according to [1] above, the base material is a steel material.
[5] In the vanadium silicide film-coated member according to [1] above, the vanadium element concentration is 3 to 15 at %, the silicon element concentration is 15 to 30 at %, and the carbon element concentration is 60 to 80 at %.
[6] The vanadium silicide film-coated member described in [1] above satisfies the following formula (1).
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧25 at % (1)
[7] The vanadium silicide film-coated member described in [1] above satisfies the following formula (2).
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧30 at % (2)
[8] The vanadium silicide film-coated member described in [1] above satisfies the following formula (3).
(the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at% (3)
[9] The vanadium silicide film-coated member described in [1] above satisfies the following formula (4).
The silicon element concentration/(the vanadium element concentration+the silicon element concentration)>0.7 (4)
[10] A substrate for forming a vanadium silicide film, having a nitride layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of the substrate.
[11] A method for producing a vanadium silicide film-coated member, comprising a nitriding step of forming a nitrided layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of a substrate; A vanadium silicon carbide film containing vanadium, silicon and carbon and having a sum of the vanadium element concentration, the silicon element concentration and the carbon element concentration in the film being 90 at % or more on the nitride layer formed in the process. and a vanadium silicide film forming step of forming a.
[12] In the method for producing a vanadium silicide film-coated member described in [11] above, the nitride layer has a surface roughness Rzjis of 0.25 μm or more.
[13] In the method for producing a vanadium silicide film-coated member described in [11] above, the nitride layer has a surface roughness Rzjis of 0.4 μm or more.
[14] In the method for producing a vanadium silicide film-coated member described in [11] above, in the nitriding step, the base material is nitrided by converting hydrogen gas and nitrogen gas into plasma.
[15] In the method for manufacturing a vanadium silicide film-coated member described in [11] above, the base material is a steel material.
[16] In the method for producing a vanadium silicide film-coated member described in [11] above, in the vanadium silicide film-forming step, a vanadium chloride gas, a silicon source gas, a hydrocarbon gas and a hydrogen gas are supplied to generate a plasma. The vanadium silicide film is formed by chemical vapor deposition.
[17] In the method for producing a vanadium silicide film-coated member described in [16] above, in the vanadium silicide film-forming step, argon gas is further supplied, and the vanadium chloride gas, the silicon source gas, and the carbonization are further supplied. The flow ratio of hydrogen gas, said hydrogen gas and said argon gas is 1:0.25-2:3-20:20-35:0.5-2.
[18] In the method for producing a vanadium silicide film-coated member described in [11] above, the vanadium element concentration is 3 to 15 at %, the silicon element concentration is 15 to 30 at %, and the carbon element concentration is 60 to 80 at %. %.
[19] In the method for producing a vanadium silicide film-coated member described in [11] above, the following formula (1) is satisfied.
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧25 at % (1)
[20] In the method for producing a vanadium silicide film-coated member described in [11] above, the following formula (2) is satisfied.
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧30 at % (2)
[21] In the method for producing a vanadium silicide film-coated member described in [11] above, the following formula (3) is satisfied.
(the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at% (3)
[22] In the method for manufacturing a vanadium silicide film-coated member described in [11] above, the following formula (4) is satisfied.
The silicon element concentration/(the vanadium element concentration+the silicon element concentration)>0.7 (4)
[23] A method for producing a substrate for forming a vanadium silicide film, comprising a nitriding step of forming a nitride layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of the substrate.
本発明によれば、珪炭化バナジウム膜と基材の密着性を向上させることが可能な珪炭化バナジウム膜被覆部材およびその製造方法並びに珪炭化バナジウム膜形成用基材およびその製造方法を提供することができる。
According to the present invention, there are provided a vanadium silicide film-coated member capable of improving the adhesion between the vanadium silicide film and the substrate, a manufacturing method thereof, and a base material for forming a vanadium silicide film and a manufacturing method thereof. can be done.
以下、本発明の一実施形態について、図面を参照しながら説明する。なお、本明細書および図面において、実質的に同一の機能構成を有する要素においては、同一の符号を付することにより重複説明を省略する。
An embodiment of the present invention will be described below with reference to the drawings. In the present specification and drawings, elements having substantially the same functional configuration are denoted by the same reference numerals, thereby omitting redundant description.
図１は、本実施形態に係る珪炭化バナジウム膜被覆部材の概略構成を示す図である。
FIG. 1 is a diagram showing a schematic configuration of a vanadium silicide film-coated member according to this embodiment.
珪炭化バナジウム膜被覆部材１は、珪炭化バナジウム膜形成用基材２と、珪炭化バナジウム膜形成用基材２の表面に形成された珪炭化バナジウム膜３で構成されている。
The vanadium silicide film-coated member 1 is composed of a vanadium silicide film-forming substrate 2 and a vanadium silicide film 3 formed on the surface of the vanadium silicide film-forming substrate 2 .
珪炭化バナジウム膜形成用基材２は、基材２ｂと、基材２ｂの表面に形成された窒化層２ａで構成されている。
The base material 2 for vanadium silicide film formation is composed of a base material 2b and a nitride layer 2a formed on the surface of the base material 2b.
基材２ｂの材料は特に限定されず、珪炭化バナジウム膜被覆部材１の用途に応じて適した材料が用いられる。例えば、基材２ｂの材料としては、各種鋼材が用いられる。本明細書における鋼材とは、鉄を主成分とし、２％以下の炭素と、その他の成分からなる材料である。金型や工具などに用いられる鋼材としては、以下に説明するダイス鋼や高速度工具鋼、マトリックスハイスなどがある。
The material of the base material 2b is not particularly limited, and a material suitable for the application of the vanadium silicide film-coated member 1 is used. For example, various steel materials are used as the material of the base material 2b. The steel material in this specification is a material composed mainly of iron, 2% or less carbon, and other components. Steel materials used for dies and tools include die steel, high-speed tool steel, matrix high speed steel, and the like, which will be described below.
ダイス鋼は、冷間金型用の合金工具鋼の一種である。高硬度に焼き入れが可能で、焼き入れ歪みが少なく、耐摩耗性に優れていることから、広く用いられている。ダイス鋼は、バナジウム、モリブデン、タングステン、クロムなどを含有する。JIS（日本工業規格）における鉄鋼系材料記号としては「SKD」が用いられ、代表的な鋼種としてはSKD-11、SKD-61などがある。
Die steel is a type of alloy tool steel for cold working dies. It is widely used because it can be quenched to a high degree of hardness, has little quenching strain, and has excellent wear resistance. Die steel contains vanadium, molybdenum, tungsten, chromium, and the like. "SKD" is used as the steel material symbol in JIS (Japanese Industrial Standards), and representative steel grades include SKD-11 and SKD-61.
高速度工具鋼は、ハイスとも呼ばれ、ダイス鋼と比較して耐摩耗性、耐衝撃性、靭性に優れた材料である。JISにおける鉄鋼系材料記号としては「SKH」が用いられ、JISではJISG4403にまとめられている。代表的な鋼種としてはSKH-51、SKH-55などがある。
High-speed tool steel, also called HSS, is a material with superior wear resistance, impact resistance, and toughness compared to die steel. "SKH" is used as the symbol for iron and steel materials in JIS, and it is summarized in JISG4403 in JIS. Typical steel grades include SKH-51 and SKH-55.
マトリックスハイスは、高速度工具鋼よりも炭素量を低く抑えることで、共晶炭化物を低下させると共にマトリックス中の合金元素比率を高め、これにより高硬度、高靭性、高耐熱性が得られるよう設計された材料である。一般的に市場に供給されている製品としては、日立金属工具鋼株式会社のYXR3、YXR7、YXR33などがある。これらの材料は、工具鋼の中でも高い寸法精度が要求される金型、せん断加工に用いられるパンチ、刃物などに用いられる。このため、上述の高硬度、高靭性、高耐熱性の特徴を強化するためには、本実施形態で示すような表面コーティングが重要な役割を担うこととなる。
Matrix high speed steel is designed to have a lower carbon content than high-speed tool steel, thereby reducing eutectic carbide and increasing the ratio of alloying elements in the matrix, thereby achieving high hardness, toughness, and high heat resistance. It is a material that has been Products commonly supplied to the market include YXR3, YXR7, and YXR33 from Hitachi Metals Tool Steel. Among tool steels, these materials are used for molds that require high dimensional accuracy, punches used for shearing, cutting tools, and the like. Therefore, the surface coating as shown in this embodiment plays an important role in enhancing the above-described features of high hardness, high toughness, and high heat resistance.
珪炭化バナジウム膜形成用基材２の窒化層２ａは、化合物層および拡散層の少なくともいずれか一方からなる層であり、基材２ｂに対し、窒化処理を行うことで形成される。窒化層は、鉄窒化物で考えると、γ’相(Fe4N)、ε相(Fe2-3N)及び準安定相のα”相(Fe16N)などから構成される。本願の例においてはこれらに準じて合金元素も含んだ窒化物が構成されている。例えば鋼材としてダイス鋼や高速度工具鋼、マトリックスハイスが用いられる場合は、バナジウム、モリブデン、タングステン、クロムなどの窒化物が析出される。窒化層２ａが基材２ｂの表面に存在することで、珪炭化バナジウム膜形成用基材２と珪炭化バナジウム膜３の化学的な相性が改善し、格子の不整合も解消される。これによって珪炭化バナジウム膜形成用基材２と珪炭化バナジウム膜３の密着性をより向上させることができる。なお、珪炭化バナジウム膜形成用基材２と珪炭化バナジウム膜３の密着性をより向上させる観点からは、窒化層２ａには化合物層が形成されていないことが好ましい。
The nitrided layer 2a of the base material 2 for vanadium silicide film formation is a layer composed of at least one of a compound layer and a diffusion layer, and is formed by subjecting the base material 2b to a nitriding treatment. Considering iron nitride, the nitrided layer is composed of a γ' phase (Fe 4 N), an ε phase (Fe 2-3 N), a metastable α″ phase (Fe 16 N), and the like. In examples, nitrides containing alloying elements are formed according to these.For example, when die steel, high-speed tool steel, and matrix high speed steel are used as steel materials, nitrides such as vanadium, molybdenum, tungsten, and chromium The presence of the nitride layer 2a on the surface of the substrate 2b improves the chemical compatibility between the vanadium silicide film-forming substrate 2 and the vanadium silicide film 3, and eliminates lattice mismatch. This can further improve the adhesion between the vanadium silicide film-forming substrate 2 and the vanadium silicide film 3. The adhesion between the vanadium silicide film-forming substrate 2 and the vanadium silicide film 3 can be improved. From the viewpoint of further improving the properties, it is preferable that no compound layer is formed on the nitride layer 2a.
基材２ｂの表面に窒化層２ａが形成されていることの確認は、「JIS G 0562 鉄鋼の窒化層深さ測定方法」の規定に従い、珪炭化バナジウム膜形成用基材２の切断面を腐食させ、金属顕微鏡を用いて、腐食させた切断面の着色状態を観察することで行われる。顕微鏡画像では、窒化層２ａの化合物層は白色に着色され、窒化層２ａの拡散層は黒色に着色されるため、窒化層２ａにおける化合物層の有無や、窒化層２ａと基材２ｂとの境界を視覚的に判別することが可能である。
Confirmation that the nitride layer 2a is formed on the surface of the substrate 2b is performed by corroding the cut surface of the vanadium silicide film forming substrate 2 in accordance with the provisions of "JIS G 0562 Steel nitride layer depth measurement method". and observing the coloring state of the corroded cut surface using a metallurgical microscope. In the microscope image, the compound layer of the nitride layer 2a is colored white, and the diffusion layer of the nitride layer 2a is colored black. can be visually determined.
窒化層２ａの窒化深さは特に限定されないが、２０～２５０μｍであることが好ましい。窒化層２ａの窒化深さが２０μｍ以上である場合には、例えば窒化による硬さの変化など、深さ方向における特性の変化が急激に起こることを抑制することができる。一方、窒化深さが２５０μｍ以下である場合には、窒化処理時間を短くすることができ、過剰な窒化を抑制することができ、窒化層の表面粗さを制御しやすい。なお、窒化層２ａの“窒化深さ”とは、窒化層２ａの表面から、基材硬さ×１．１５ＨＶの硬さとなる位置までの距離である。“基材硬さ”は、次の方法で測定される。まず、「JIS G 0562 鉄鋼の窒化層深さ測定方法」の規定に従い、窒化層が形成された試験片の切断面を研磨および鏡面仕上げする。続いて、マイクロビッカース硬さ試験機を用いて２５ｇｆの荷重でビッカース硬さ試験を行い、その結果に基づいて試験片表面からの硬さ推移曲線を作成する。そして、その推移曲線において硬さの値が収束した点を特定し、この点の硬さの値を基材硬さとする。
Although the nitrided depth of the nitrided layer 2a is not particularly limited, it is preferably 20 to 250 μm. When the nitriding depth of the nitrided layer 2a is 20 μm or more, it is possible to suppress sudden changes in characteristics in the depth direction, such as changes in hardness due to nitriding. On the other hand, when the nitriding depth is 250 μm or less, the nitriding time can be shortened, excessive nitriding can be suppressed, and the surface roughness of the nitrided layer can be easily controlled. The "nitriding depth" of the nitrided layer 2a is the distance from the surface of the nitrided layer 2a to the position where the hardness is the substrate hardness×1.15 HV. "Substrate hardness" is measured by the following method. First, according to the provisions of "JIS G 0562 Method for Measuring Nitrided Layer Depth of Iron and Steel", the cut surface of the test piece on which the nitrided layer is formed is polished and mirror-finished. Subsequently, a Vickers hardness test is performed with a load of 25 gf using a micro Vickers hardness tester, and a hardness transition curve from the surface of the test piece is created based on the results. Then, a point where the hardness value converges on the transition curve is specified, and the hardness value at this point is defined as the base material hardness.
基材２ｂの表面に形成される窒化層２ａは、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下である。後述の実施例で示すように、珪炭化バナジウム膜形成用基材２は、基材２ｂの表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層２ａを有することで、珪炭化バナジウム膜形成用基材２と珪炭化バナジウム膜３の密着性を向上させることができる。この効果をより高める観点においては、窒化層２ａの表面粗さＲｚｊｉｓは好ましくは０．２５μｍ以上であり、さらに好ましくは０．４μｍ以上である。
The nitride layer 2a formed on the surface of the base material 2b has a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less. As shown in the examples below, the vanadium silicide film-forming substrate 2 has a nitride layer 2a having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of the substrate 2b. Adhesion between the vanadium silicide film-forming substrate 2 and the vanadium silicide film 3 can be improved. From the viewpoint of enhancing this effect, the surface roughness Rzjis of the nitride layer 2a is preferably 0.25 μm or more, more preferably 0.4 μm or more.
（珪炭化バナジウム膜）
珪炭化バナジウム膜被覆部材１は、表面粗さＲｚｊｉｓが０．２μｍ以上１．０μｍ以下の窒化層２ａ上に、珪炭化バナジウム膜３を有している。珪炭化バナジウム膜３は、バナジウム（V）、珪素（Si）、炭素（Ｃ）を含有し、かつ、バナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計が９０ａｔ％以上の膜である。珪炭化バナジウム膜３は、膜中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計は、より好ましくは９１ａｔ％以上であり、さらに好ましくは、９２ａｔ％以上である。 (vanadium silicon carbide film)
A vanadium silicide film coated member 1 has avanadium silicide film 3 on a nitride layer 2a having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less. The vanadium silicide carbide film 3 contains vanadium (V), silicon (Si), and carbon (C), and the total of vanadium element concentration, silicon element concentration, and carbon element concentration is 90 at % or more. . In the vanadium silicide carbide film 3, the total of vanadium element concentration, silicon element concentration and carbon element concentration in the film is more preferably 91 at % or more, more preferably 92 at % or more.
珪炭化バナジウム膜被覆部材１は、表面粗さＲｚｊｉｓが０．２μｍ以上１．０μｍ以下の窒化層２ａ上に、珪炭化バナジウム膜３を有している。珪炭化バナジウム膜３は、バナジウム（V）、珪素（Si）、炭素（Ｃ）を含有し、かつ、バナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計が９０ａｔ％以上の膜である。珪炭化バナジウム膜３は、膜中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計は、より好ましくは９１ａｔ％以上であり、さらに好ましくは、９２ａｔ％以上である。 (vanadium silicon carbide film)
A vanadium silicide film coated member 1 has a
珪炭化バナジウム膜３中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度は、電子プローブマイクロアナライザー（以下、ＥＰＭＡと称す）による組成分析によって測定することができる。なお、珪炭化バナジウム膜３の膜厚が１μｍ以下の場合には、ＥＰＭＡの測定結果に基材の成分組成の影響が含まれる。このため、膜厚の薄い珪炭化バナジウム膜３の組成分析を行う際には、事前に基材２ｂのみのＥＰＭＡ測定を実施し、珪炭化バナジウム膜３の成膜後のＥＰＭＡの測定結果から基材由来のバナジウム元素濃度、珪素元素濃度、炭素元素濃度を差し引く必要がある。
The vanadium element concentration, silicon element concentration, and carbon element concentration in the vanadium silicide carbide film 3 can be measured by composition analysis using an electron probe microanalyzer (hereinafter referred to as EPMA). When the film thickness of the vanadium silicide film 3 is 1 μm or less, the EPMA measurement results include the influence of the component composition of the base material. Therefore, when the composition analysis of the vanadium silicide film 3 having a small film thickness is performed, the EPMA measurement of only the base material 2b is performed in advance, and the EPMA measurement result after the formation of the vanadium silicide film 3 is used as the basis. It is necessary to subtract the vanadium element concentration, silicon element concentration, and carbon element concentration derived from the material.
珪炭化バナジウム膜３は、バナジウム元素濃度が３～１５ａｔ％、珪素元素濃度が１５～３０ａｔ％、炭素元素濃度が６０～８０ａｔ％であることが好ましい。バナジウム元素濃度は、より好ましくは４～１５ａｔ％である。
The vanadium silicide carbide film 3 preferably has a vanadium element concentration of 3 to 15 at %, a silicon element concentration of 15 to 30 at %, and a carbon element concentration of 60 to 80 at %. The vanadium element concentration is more preferably 4 to 15 at %.
珪炭化バナジウム膜３中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度は、下記（１）式を満たすことが好ましく、これにより、珪炭化バナジウム膜形成用基材２と珪炭化バナジウム膜３の密着性をさらに向上させることができる。
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≧２５ａｔ％・・・（１） The vanadium element concentration, the silicon element concentration, and the carbon element concentration in thevanadium silicide film 3 preferably satisfy the following formula (1). The adhesion of 3 can be further improved.
(carbon element concentration-vanadium element concentration-silicon element concentration)≧25 at % (1)
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≧２５ａｔ％・・・（１） The vanadium element concentration, the silicon element concentration, and the carbon element concentration in the
(carbon element concentration-vanadium element concentration-silicon element concentration)≧25 at % (1)
また、下記（２）式を満たす場合には、珪炭化バナジウム膜被覆部材１に接触する相手部材との摩擦係数を小さくすることができる。
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≧３０ａｔ％ ・・・（２） Moreover, when the following formula (2) is satisfied, the coefficient of friction between the vanadium silicide film-coated member 1 and a mating member in contact can be reduced.
(carbon element concentration-vanadium element concentration-silicon element concentration)≧30 at % (2)
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≧３０ａｔ％ ・・・（２） Moreover, when the following formula (2) is satisfied, the coefficient of friction between the vanadium silicide film-coated member 1 and a mating member in contact can be reduced.
(carbon element concentration-vanadium element concentration-silicon element concentration)≧30 at % (2)
下記（３）式を満たす場合には、珪炭化バナジウム膜３の硬度を高めることができる。
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≦３６ａｔ％ ・・・（３） When the following formula (3) is satisfied, the hardness of thevanadium silicide film 3 can be increased.
(carbon element concentration - vanadium element concentration - silicon element concentration) ≤ 36 at% (3)
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≦３６ａｔ％ ・・・（３） When the following formula (3) is satisfied, the hardness of the
(carbon element concentration - vanadium element concentration - silicon element concentration) ≤ 36 at% (3)
下記（４）式を満たす場合には、珪炭化バナジウム膜３の耐熱性を向上させることができる。
珪素元素濃度／（バナジウム元素濃度＋珪素元素濃度）＞０．７・・・（４） When the following formula (4) is satisfied, the heat resistance ofvanadium silicide film 3 can be improved.
Silicon element concentration/(vanadium element concentration+silicon element concentration)>0.7 (4)
珪素元素濃度／（バナジウム元素濃度＋珪素元素濃度）＞０．７・・・（４） When the following formula (4) is satisfied, the heat resistance of
Silicon element concentration/(vanadium element concentration+silicon element concentration)>0.7 (4)
珪炭化バナジウム膜３の膜厚は、珪炭化バナジウム膜被覆部材１の用途に応じて適宜設定されるが、例えば金型の基材上に珪炭化バナジウム膜３を形成する場合は、膜厚は０．５～４μｍであることが好ましい。
The film thickness of the vanadium silicide film 3 is appropriately set according to the application of the vanadium silicide film-coated member 1. For example, when the vanadium silicide film 3 is formed on a base material of a mold, the film thickness is It is preferably 0.5 to 4 μm.
なお、珪炭化バナジウム膜３は、密着性向上の効果を損なわない範囲でバナジウム元素と、珪素元素と、炭素元素以外の元素を含んでいてもよい。バナジウム元素と、珪素元素と、炭素元素以外の元素としては、例えば珪炭化バナジウム膜形成工程で供給される原料ガスやアルゴンガスに含まれるフッ素、塩素、水素、アルゴンや、後述する珪炭化バナジウム膜の形成装置のチャンバー内に残存するガスに含まれる酸素、窒素などが挙げられる。珪炭化バナジウム膜３に含まれるバナジウム元素と、珪素元素と、炭素元素以外の元素は、９ａｔ％以下に制限されていることが好ましく、８ａｔ％以下に制限されていることがより好ましい。
The vanadium silicide film 3 may contain elements other than the vanadium element, the silicon element, and the carbon element within a range that does not impair the effect of improving adhesion. Elements other than the vanadium element, the silicon element, and the carbon element include, for example, fluorine, chlorine, hydrogen, and argon contained in the raw material gas and argon gas supplied in the vanadium silicide film formation process, and the vanadium silicide film described later. oxygen, nitrogen, etc. contained in the gas remaining in the chamber of the forming apparatus of . Elements other than the vanadium element, the silicon element, and the carbon element contained in the vanadium silicide carbide film 3 are preferably limited to 9 at % or less, more preferably 8 at % or less.
次に、珪炭化バナジウム膜形成用基材２および珪炭化バナジウム膜被覆部材１の製造方法について説明する。本実施形態においては、基材２ｂの表面に表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層２ａを形成することで珪炭化バナジウム膜形成用基材２を作製する。その後、窒化層２ａ上に珪炭化バナジウム膜３を形成して珪炭化バナジウム膜被覆部材１を作製する。
Next, a method for manufacturing the vanadium silicide film-forming substrate 2 and the vanadium silicide film-coated member 1 will be described. In the present embodiment, the substrate 2 for vanadium silicide film formation is produced by forming the nitride layer 2a having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of the substrate 2b. After that, a vanadium silicide film 3 is formed on the nitride layer 2a to fabricate the vanadium silicide film-coated member 1. Next, as shown in FIG.
まず基材２ｂを準備する。基材２ｂは、表面粗さＲｚｊｉｓが０．１μｍ以下となるまで研磨されていることが好ましい。基材２ｂの表面粗さＲｚｊｉｓが０．１μｍ以下であることにより、窒化層２ａを基材２ｂの表面に均一に形成することができ、より密着性が向上すると考えられる。
First, the base material 2b is prepared. The substrate 2b is preferably polished to a surface roughness Rzjis of 0.1 μm or less. When the surface roughness Rzjis of the base material 2b is 0.1 μm or less, the nitride layer 2a can be uniformly formed on the surface of the base material 2b, and it is considered that the adhesion is further improved.
＜窒化処理工程＞
次に、基材２ｂの窒化処理を行い、珪炭化バナジウム膜形成用基材２を作製する。窒化処理工程では、基材２ｂの表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層２ａを形成する。 <Nitriding process>
Next, thebase material 2b is subjected to nitriding treatment to produce the base material 2 for vanadium silicide film formation. In the nitriding step, a nitrided layer 2a having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less is formed on the surface of the base material 2b.
次に、基材２ｂの窒化処理を行い、珪炭化バナジウム膜形成用基材２を作製する。窒化処理工程では、基材２ｂの表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層２ａを形成する。 <Nitriding process>
Next, the
窒化層２ａを形成する為の窒化処理装置および後述する珪炭化バナジウム膜被覆部材１の形成装置としては、例えば図２に示すようなプラズマ処理装置１０が用いられる。プラズマ処理装置１０は、基材２ｂが搬入されるチャンバー１１と、陽極１２および陰極１３と、陽極１２と陰極１３との間にパルス電圧を印加する直流のパルス電源１４とを備えている。チャンバー１１の上部には各原料ガスが供給されるガス供給管１５が接続され、チャンバー１１の下部にはチャンバー１１内のガスを排気するガス排気管１６が接続されている。ガス排気管１６の下流側には真空ポンプ（不図示）が設けられている。陰極１３は基材２ｂを支持する支持台としての役割も有しており、チャンバー１１内に搬入された基材２ｂは陰極１３上に載置される。チャンバー１１の内部にはヒーター（不図示）が設けられており、ヒーターによりチャンバー１１内の雰囲気温度が調節されることで基材２ｂの温度が調節される。
As a nitriding apparatus for forming the nitride layer 2a and a forming apparatus for the vanadium silicon carbide film-coated member 1 described later, for example, a plasma processing apparatus 10 as shown in FIG. 2 is used. The plasma processing apparatus 10 includes a chamber 11 into which the substrate 2b is loaded, an anode 12 and a cathode 13, and a DC pulse power supply 14 that applies a pulse voltage between the anode 12 and the cathode 13. A gas supply pipe 15 for supplying each raw material gas is connected to the upper part of the chamber 11 , and a gas exhaust pipe 16 for discharging the gas in the chamber 11 is connected to the lower part of the chamber 11 . A vacuum pump (not shown) is provided downstream of the gas exhaust pipe 16 . The cathode 13 also has a role as a support base for supporting the substrate 2 b , and the substrate 2 b carried into the chamber 11 is placed on the cathode 13 . A heater (not shown) is provided inside the chamber 11, and the temperature of the substrate 2b is adjusted by adjusting the atmospheric temperature in the chamber 11 with the heater.
なお、プラズマ処理装置１０の構成は本実施形態で説明した構成に限定されない。例えば直流のパルス電源１４に代えて高周波電源を用いてもよいし、原料ガスを供給するシャワーヘッド（不図示）を設け、それを陽極１２として用いてもよい。また、ヒーターを設けずにグロー電流のみで基材２ｂを加熱してもよい。すなわち、プラズマ処理装置１０は、チャンバー１１内に供給される原料ガスをプラズマ化することが可能であって、基材２ｂに窒化層２ａを形成できる構成であればよい。
The configuration of the plasma processing apparatus 10 is not limited to the configuration described in this embodiment. For example, a high-frequency power source may be used instead of the DC pulse power source 14 , or a shower head (not shown) for supplying the source gas may be provided and used as the anode 12 . Alternatively, the substrate 2b may be heated only by a glow current without providing a heater. That is, the plasma processing apparatus 10 may have any configuration as long as it is capable of plasmatizing the raw material gas supplied into the chamber 11 and capable of forming the nitride layer 2a on the substrate 2b.
基材２ｂの窒化処理方法は特に限定されず、例えばプラズマ窒化処理やガス窒化処理などが適用可能である。ただし、珪炭化バナジウム膜をプラズマ化学蒸着法で形成し、窒化処理をプラズマ窒化処理で行う場合は、基材２ｂの窒化処理と珪炭化バナジウム膜３の形成を同一のプラズマ処理装置で行うことが可能となる。したがって、別々の装置を使用する場合と比較して効率良く珪炭化バナジウム膜被覆部材１を製造する観点では、基材２ｂの窒化処理はプラズマ窒化処理によって行うことが好ましい。また、窒化処理はプラズマ窒化処理を同一のプラズマ処理装置で行うことで、表面の酸化などの影響を防ぐことができるため好ましい。また、基材２ｂの冷却や洗浄工程などの処理をせずに成膜できるため、効率良く珪炭化バナジウム膜被覆部材１を製造することが可能となる。
The method of nitriding the substrate 2b is not particularly limited, and for example, plasma nitriding or gas nitriding can be applied. However, when the vanadium silicocarbide film is formed by the plasma chemical vapor deposition method and the nitriding treatment is performed by the plasma nitriding treatment, the nitriding treatment of the substrate 2b and the formation of the vanadium silicocarbide film 3 can be performed in the same plasma treatment apparatus. It becomes possible. Therefore, from the viewpoint of producing the vanadium silicon carbide film-coated member 1 more efficiently than when using separate apparatuses, the nitriding treatment of the substrate 2b is preferably performed by the plasma nitriding treatment. Further, the nitriding treatment is preferably performed by performing the plasma nitriding treatment in the same plasma treatment apparatus because the influence of surface oxidation or the like can be prevented. In addition, since the film can be formed without cooling the base material 2b or performing a cleaning process, etc., the vanadium silicide film-coated member 1 can be manufactured efficiently.
プラズマ窒化処理は、プラズマ処理装置内に供給した水素ガスおよび窒素ガスをプラズマ化し、基材２ｂの表面に窒化層２ａを形成する窒化処理である。このプラズマ窒化処理時には、水素ガスおよび窒素ガス以外にアルゴンガスを適宜供給してもよい。アルゴンガスは、アルゴンイオンが他の分子をイオン化させることによってプラズマの安定化やイオン密度の向上に寄与する。窒化層２ａの表面粗さＲｚｊｉｓは、窒化処理時間、供給する水素ガスと窒素ガスの分圧比、電圧、電流密度やＤｕｔｙ比などを適宜変更することによって制御することができる。
The plasma nitriding process is a nitriding process in which the hydrogen gas and nitrogen gas supplied into the plasma processing apparatus are plasmatized to form the nitride layer 2a on the surface of the base material 2b. During this plasma nitriding treatment, argon gas may be appropriately supplied in addition to hydrogen gas and nitrogen gas. Argon gas contributes to stabilization of plasma and improvement of ion density by causing argon ions to ionize other molecules. The surface roughness Rzjis of the nitrided layer 2a can be controlled by appropriately changing the nitriding treatment time, the partial pressure ratio of the supplied hydrogen gas and nitrogen gas, the voltage, the current density, the duty ratio, and the like.
プラズマ窒化処理の処理時間は、生産性の観点から３０～３００分にすることが好ましい。より好ましくは、６０～２４０分である。
The processing time of the plasma nitriding treatment is preferably 30 to 300 minutes from the viewpoint of productivity. More preferably, it is 60 to 240 minutes.
プラズマ処理装置内の窒素分圧と水素分圧との比である窒素分圧／水素分圧は、０．１５～２．０であることが好ましく、これにより基材２ｂが窒化しやすくなる。窒化層２ａ中の化合物層の形成を抑制する観点からは、窒素分圧／水素分圧を１．０以下にすることが好ましく、０．７０以下にすることがより好ましい。一方、窒素分圧／水素分圧の下限は、０．２５以上にすることが好ましい。プラズマ窒化処理時におけるチャンバー１１内の圧力は、３０～２００Ｐａであることが好ましい。
The nitrogen partial pressure/hydrogen partial pressure, which is the ratio of the nitrogen partial pressure and the hydrogen partial pressure in the plasma processing apparatus, is preferably 0.15 to 2.0, which facilitates nitridation of the substrate 2b. From the viewpoint of suppressing the formation of a compound layer in the nitride layer 2a, the nitrogen partial pressure/hydrogen partial pressure is preferably 1.0 or less, more preferably 0.70 or less. On the other hand, the lower limit of the nitrogen partial pressure/hydrogen partial pressure is preferably 0.25 or more. The pressure inside the chamber 11 during plasma nitriding is preferably 30 to 200 Pa.
プラズマ窒化処理時の電源電圧は、１０００～２５００Ｖであることが好ましく、より好ましくは１２００～２０００Ｖである。プラズマ窒化処理時の電流密度は、０．２～０．７ｍＡ／ｃｍ2であることが好ましく、より好ましくは０．３～０．６ｍＡ／ｃｍ2である。１周期あたりの電圧印加時間で定義される以下の式で算出されるＤｕｔｙ比は、５～６０％であることが好ましい。
Ｄｕｔｙ比（％）＝１００×印加時間（ＯＮ ｔｉｍｅ）／｛印加時間（ＯＮ ｔｉｍｅ）＋印加停止時間（ＯＦＦ ｔｉｍｅ）｝ The power supply voltage during plasma nitridation is preferably 1000-2500V, more preferably 1200-2000V. The current density during plasma nitriding treatment is preferably 0.2 to 0.7 mA/cm 2 , more preferably 0.3 to 0.6 mA/cm 2 . The duty ratio calculated by the following formula defined by the voltage application time per cycle is preferably 5 to 60%.
Duty ratio (%)=100×application time (ON time)/{application time (ON time)+application stop time (OFF time)}
Ｄｕｔｙ比（％）＝１００×印加時間（ＯＮ ｔｉｍｅ）／｛印加時間（ＯＮ ｔｉｍｅ）＋印加停止時間（ＯＦＦ ｔｉｍｅ）｝ The power supply voltage during plasma nitridation is preferably 1000-2500V, more preferably 1200-2000V. The current density during plasma nitriding treatment is preferably 0.2 to 0.7 mA/cm 2 , more preferably 0.3 to 0.6 mA/cm 2 . The duty ratio calculated by the following formula defined by the voltage application time per cycle is preferably 5 to 60%.
Duty ratio (%)=100×application time (ON time)/{application time (ON time)+application stop time (OFF time)}
本実施形態における珪炭化バナジウム膜形成用基材２は、以上の窒化処理によって製造される。
The base material 2 for vanadium silicide film formation in the present embodiment is manufactured by the nitriding treatment described above.
＜珪炭化バナジウム膜形成工程＞
次に、プラズマ化学蒸着法によって珪炭化バナジウム膜形成用基材２の窒化層２ａの上に珪炭化バナジウム膜３を形成する。 <Vanadium silicide film formation step>
Next, avanadium silicide film 3 is formed on the nitride layer 2a of the substrate 2 for vanadium silicide film formation by plasma chemical vapor deposition.
次に、プラズマ化学蒸着法によって珪炭化バナジウム膜形成用基材２の窒化層２ａの上に珪炭化バナジウム膜３を形成する。 <Vanadium silicide film formation step>
Next, a
珪炭化バナジウム膜３を形成するための原料ガスとして、プラズマ処理装置１０のチャンバー１１内に塩化バナジウムガス、珪素源ガス、炭化水素ガスおよび水素ガスを供給し、パルス電源１４を用いて陽極１２と陰極１３の間にパルス電圧を印加する。これにより、陽極１２と陰極１３の間においてチャンバー１１内に供給した原料ガスがプラズマ化し、窒化層２ａ上に珪炭化バナジウム膜３が形成される。これにより、本実施形態における珪炭化バナジウム膜被覆部材１が製造される。
As raw material gases for forming the vanadium silicide film 3, a vanadium chloride gas, a silicon source gas, a hydrocarbon gas, and a hydrogen gas are supplied into the chamber 11 of the plasma processing apparatus 10. A pulse voltage is applied between the cathodes 13 . As a result, the raw material gas supplied into the chamber 11 is turned into plasma between the anode 12 and the cathode 13, and the vanadium silicocarbide film 3 is formed on the nitride layer 2a. Thus, the vanadium silicide film-coated member 1 in this embodiment is manufactured.
塩化バナジウムガスとしては、例えば四塩化バナジウム（ＶＣｌ４）ガス、三塩化酸化バナジウム（ＶＯＣｌ３）ガスなどが用いられる。なお、ガスを構成する元素の数が少なく、かつ、珪炭化バナジウム膜３中の不純物を取り除くことが容易になるという観点では、四塩化バナジウムガスを用いることが好ましい。また、四塩化バナジウムガスは、入手が容易で、常温において液体であり、ガスとしての供給が容易であるため、この観点からも用いることが好ましい。
As the vanadium chloride gas, for example, vanadium tetrachloride (VCl 4 ) gas, vanadium trichloride oxide (VOCl 3 ) gas, or the like is used. It is preferable to use vanadium tetrachloride gas from the viewpoint that the number of elements constituting the gas is small and that impurities in the vanadium silicide film 3 can be easily removed. In addition, vanadium tetrachloride gas is easily available, is liquid at room temperature, and can be easily supplied as a gas.
珪素源ガスとしては、例えばモノメチルシランガス、ジメチルシランガス、トリメチルシランガス、テトラメチルシランガス、四塩化珪素ガス、四フッ化珪素ガス等のシラン系ガスなどが用いられる。
Silane-based gases such as monomethylsilane gas, dimethylsilane gas, trimethylsilane gas, tetramethylsilane gas, silicon tetrachloride gas, and silicon tetrafluoride gas are used as the silicon source gas.
炭化水素ガスとしては、例えばメタンガス、エタンガス、エチレンガス、アセチレンガスなどが用いられる。ここで例示されるガスは単独で供給されてもよいし、２種以上のガスが混合されて供給されてもよい。
As the hydrocarbon gas, for example, methane gas, ethane gas, ethylene gas, acetylene gas, etc. are used. The gases exemplified here may be supplied singly, or two or more kinds of gases may be mixed and supplied.
珪炭化バナジウム膜形成工程で供給される原料ガスに四塩化珪素ガスが含まれる場合、珪炭化バナジウム膜３には、バナジウム、珪素および炭素を除いた残部に必然的に不純物としての塩素が含まれる。塩素は水素ガスと結合しやすいことから、原料ガスに水素ガスが含まれる場合には、塩化バナジウムガスから発生する塩素が水素と結合して系外に排出されやすくなる。これにより、珪炭化バナジウム膜３中への塩素の混入を抑えることができる。
When the raw material gas supplied in the vanadium silicide film forming step contains silicon tetrachloride gas, the vanadium silicide film 3 inevitably contains chlorine as an impurity in the remainder excluding vanadium, silicon and carbon. . Since chlorine easily bonds with hydrogen gas, when hydrogen gas is contained in the raw material gas, chlorine generated from vanadium chloride gas is easily combined with hydrogen and discharged out of the system. This can prevent chlorine from entering the vanadium silicide film 3 .
なお、珪炭化バナジウム膜３の残部には、塩素以外にも不可避的不純物が含まれ得る。珪炭化バナジウム膜形成工程において、チャンバー１１内に塩化バナジウムガスおよび四塩化珪素ガスが供給される場合、チャンバー１１内に供給される水素ガスの体積流量は、塩化バナジウムガスの体積流量と四塩化珪素ガスの体積流量の合計に対して５倍～２５倍であることが好ましい。なお、アルゴンガスは、アルゴンイオンが他の分子をイオン化させることによってプラズマの安定化やイオン密度の向上に寄与するため、必要に応じてチャンバー１１内に供給されてもよい。
The remainder of the vanadium silicide film 3 may contain unavoidable impurities other than chlorine. When vanadium chloride gas and silicon tetrachloride gas are supplied into chamber 11 in the vanadium silicide film forming step, the volumetric flow rate of hydrogen gas supplied into chamber 11 is the same as that of vanadium chloride gas and that of silicon tetrachloride. It is preferably 5 to 25 times the total gas volumetric flow rate. Note that argon gas may be supplied into the chamber 11 as necessary, since argon ions ionize other molecules, thereby contributing to stabilization of plasma and improvement of ion density.
珪炭化バナジウム膜形成工程においては、塩化バナジウムガスと、珪素源ガスと、炭化水素ガスと、水素ガスと、アルゴンガスの流量の比が１：０．２５～２：３～２０：２０～３５：０．５～２であることが好ましい。これにより、膜中のバナジウム元素濃度、珪素元素濃度、炭素元素濃度の合計が９０ａｔ％以上となる珪炭化バナジウム膜３が得られやすくなる。なお、本明細書において、上記流量比の算出の際に用いられる“塩化バナジウムガスの流量”、“珪素源ガスの流量”、“炭化水素ガスの流量”、“水素ガスの流量”、“アルゴンガスの流量”とは、０℃、１atmにおける体積流量である。
In the vanadium silicide film forming step, the flow rate ratio of vanadium chloride gas, silicon source gas, hydrocarbon gas, hydrogen gas, and argon gas is 1:0.25-2:3-20:20-35. : preferably 0.5 to 2. This makes it easier to obtain the vanadium silicide film 3 in which the sum of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at % or more. In this specification, "flow rate of vanadium chloride gas", "flow rate of silicon source gas", "flow rate of hydrocarbon gas", "flow rate of hydrogen gas", "flow rate of hydrogen gas", and "argon "Gas flow rate" is the volumetric flow rate at 0°C and 1 atm.
珪炭化バナジウム膜形成工程におけるチャンバー１１内の圧力は、例えば３０～２００Ｐａであることが好ましい。また、珪炭化バナジウム膜形成工程において直流のパルス電源１４から印加される電力は、１００～１０００Ｗであることが好ましい。また、直流のパルス電源１４から印加される電圧は、１０００～２０００Ｖであることが好ましい。Ｄｕｔｙ比は、１０％～６０％であることが好ましい。珪炭化バナジウム膜３の膜中のバナジウム元素濃度、珪素元素濃度、炭素元素濃度は、各原料ガスの流量、パルス電源の電力、パルス電源の電圧、Ｄｕｔｙ比を適宜設定することで制御することができる。
The pressure inside the chamber 11 in the vanadium silicide film forming step is preferably 30 to 200 Pa, for example. Further, the power applied from the DC pulse power supply 14 in the vanadium silicide film forming step is preferably 100 to 1000W. The voltage applied from the DC pulse power source 14 is preferably 1000-2000V. The duty ratio is preferably 10% to 60%. The vanadium element concentration, silicon element concentration, and carbon element concentration in the vanadium silicide film 3 can be controlled by appropriately setting the flow rate of each source gas, the power of the pulse power source, the voltage of the pulse power source, and the duty ratio. can.
以上のような珪炭化バナジウム膜形成工程によって、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層２ａ上に、バナジウム元素濃度、珪素元素濃度、炭素元素濃度の合計が９０ａｔ％以上となる珪炭化バナジウム膜３が形成される。このようにして製造された珪炭化バナジウム膜被覆部材１は、珪炭化バナジウム膜形成用基材２と珪炭化バナジウム膜３の密着性に優れている。
By the vanadium silicide carbide film formation process as described above, the sum of the vanadium element concentration, the silicon element concentration, and the carbon element concentration is 90 at % or more on the nitride layer 2a having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less. A vanadium silicide film 3 is formed. The vanadium silicide film-coated member 1 manufactured in this manner has excellent adhesion between the vanadium silicide film-forming substrate 2 and the vanadium silicide film 3 .
以上、本発明の一実施形態について説明したが、本発明はかかる例に限定されない。当業者であれば、請求の範囲に記載された技術的思想の範疇内において、各種の変更例または修正例に想到しうることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。
Although one embodiment of the present invention has been described above, the present invention is not limited to such an example. It is obvious that a person skilled in the art can conceive of various modifications or modifications within the scope of the technical idea described in the claims. be understood to belong to
基材２ｂの表面にプラズマ窒化処理により窒化層２ａを形成した珪炭化バナジウム膜形成用基材２を作製した後、珪炭化バナジウム膜形成用基材２の窒化層２ａの上に、プラズマ化学蒸着処理により珪炭化バナジウム膜３を形成した珪炭化バナジウム膜被覆部材１を作製し、各種評価を実施した。基材２ｂの窒化処理および珪炭化バナジウム膜３の形成を行う装置は、図２に示される構造のプラズマ処理装置を用い、電源としては直流のパルス電源を使用した。
After manufacturing the vanadium silicide film-forming substrate 2 in which the nitride layer 2a is formed on the surface of the substrate 2b by plasma nitriding treatment, plasma chemical vapor deposition is performed on the nitride layer 2a of the vanadium silicide film-forming substrate 2. A vanadium silicide film-coated member 1 in which a vanadium silicide film 3 was formed by treatment was produced, and various evaluations were carried out. The apparatus for nitriding the substrate 2b and forming the vanadium silicide film 3 was the plasma processing apparatus having the structure shown in FIG. 2, and the power source used was a DC pulse power source.
基材２ｂは、高速度工具鋼の一種であるSKH-51から成るφ２２ｍｍの丸棒を６～７ｍｍ間隔で切断し、図３のように切断された丸棒の成膜面を鏡面研磨し、成膜面の表面粗さＲｚｊｉｓを０．０８５μｍにしたものを使用した。なお、窒化層２ａおよび珪炭化バナジウム膜３は、基材２ｂの鏡面研磨した側の面に形成される。
The substrate 2b is made of SKH-51, a type of high-speed tool steel, by cutting a round bar of φ22 mm at intervals of 6 to 7 mm, and mirror-polishing the film-forming surface of the cut round bar as shown in FIG. A film having a surface roughness Rzjis of 0.085 μm was used. Nitride layer 2a and vanadium silicide film 3 are formed on the mirror-polished surface of substrate 2b.
（実施例１）
以下、実施例１における上記基材の窒化処理方法および珪炭化バナジウム膜の形成方法について説明する。なお、窒化処理条件および珪炭化バナジウム膜の形成条件については、後述の表１、表２にも記載している。また、以下の説明における各ガスの体積流量は、それぞれ０℃、１ａｔｍにおける体積流量である。 (Example 1)
Hereinafter, the method for nitriding the base material and the method for forming the vanadium silicon carbide film in Example 1 will be described. Nitriding conditions and vanadium silicide film formation conditions are also described in Tables 1 and 2 below. Also, the volumetric flow rate of each gas in the following description is the volumetric flow rate at 0° C. and 1 atm.
以下、実施例１における上記基材の窒化処理方法および珪炭化バナジウム膜の形成方法について説明する。なお、窒化処理条件および珪炭化バナジウム膜の形成条件については、後述の表１、表２にも記載している。また、以下の説明における各ガスの体積流量は、それぞれ０℃、１ａｔｍにおける体積流量である。 (Example 1)
Hereinafter, the method for nitriding the base material and the method for forming the vanadium silicon carbide film in Example 1 will be described. Nitriding conditions and vanadium silicide film formation conditions are also described in Tables 1 and 2 below. Also, the volumetric flow rate of each gas in the following description is the volumetric flow rate at 0° C. and 1 atm.
まず、プラズマ処理装置のチャンバー内に基材をセットし、６０分間チャンバー内を真空引きし、チャンバー内の圧力を２５Ｐａ以下まで小さくする。このとき、チャンバー内に設けられたヒーターは作動させない。なお、チャンバー内の雰囲気温度はシース熱電対で測定している。続いて、ヒーターの設定温度を５５０℃とし、基材のベーキング処理を６０分間行う。その後、ヒーターの電源を切り、１２０分間形成装置を放置してチャンバー内を冷却する。
First, the substrate is set in the chamber of the plasma processing apparatus, the chamber is evacuated for 60 minutes, and the pressure in the chamber is reduced to 25 Pa or less. At this time, the heater provided in the chamber is not activated. The ambient temperature in the chamber is measured with a sheathed thermocouple. Subsequently, the set temperature of the heater is set to 550° C., and the substrate is baked for 60 minutes. After that, the heater is turned off and the forming apparatus is left for 120 minutes to cool the inside of the chamber.
次に、チャンバー内に１００ｍｌ／ｍｉｎの体積流量で水素ガスを供給し、排気量を調節してチャンバー内の圧力を１００Ｐａとする。そして、ヒーターの設定温度を５２５℃とし、３０分間チャンバー内の雰囲気を加熱する。
Next, hydrogen gas is supplied into the chamber at a volumetric flow rate of 100 ml/min, and the pressure in the chamber is adjusted to 100 Pa by adjusting the exhaust amount. Then, the temperature of the heater is set to 525° C., and the atmosphere in the chamber is heated for 30 minutes.
＜窒化処理工程＞
その後、水素ガスの流量を８０ｍｌ／ｍｉｎにすると共にチャンバー内に窒素ガスおよびアルゴンガスを供給する。本工程においては、窒素ガスの流量を２０ｍｌ／ｍｉｎとし、アルゴンガスの流量を３ｍｌ／ｍｉｎとする。このとき、チャンバー内の全圧は排気量が調節されることで５８Ｐａに維持される。実施例１における窒素分圧と水素分圧の分圧比である窒素分圧／水素分圧は０．２５であった。その後、パルス電源の電圧を１４００Ｖ、Ｄｕｔｙ比を４０％に設定し、ユニポーラ出力形式で直流パルス電源を作動させる。ここでパルス電源の電圧が上げられることによって電極間では水素ガス、窒素ガスおよびアルゴンガスがプラズマ化した状態となる。これにより、基材の表面から窒素が侵入し、基材の表面に窒化層が形成される窒化処理を１２０分行い、珪炭化バナジウム膜形成用基材を得た。 <Nitriding process>
After that, the flow rate of hydrogen gas is set to 80 ml/min, and nitrogen gas and argon gas are supplied into the chamber. In this step, the flow rate of nitrogen gas is set at 20 ml/min and the flow rate of argon gas is set at 3 ml/min. At this time, the total pressure in the chamber is maintained at 58 Pa by adjusting the exhaust amount. The nitrogen partial pressure/hydrogen partial pressure, which is the partial pressure ratio of the nitrogen partial pressure and the hydrogen partial pressure in Example 1, was 0.25. After that, the voltage of the pulse power source is set to 1400 V and the duty ratio is set to 40%, and the DC pulse power source is operated in a unipolar output format. Here, by increasing the voltage of the pulse power source, hydrogen gas, nitrogen gas and argon gas are brought into a plasma state between the electrodes. As a result, nitrogen penetrated from the surface of the base material, nitriding treatment was performed for 120 minutes to form a nitride layer on the surface of the base material, and a base material for forming a vanadium silicocarbide film was obtained.
その後、水素ガスの流量を８０ｍｌ／ｍｉｎにすると共にチャンバー内に窒素ガスおよびアルゴンガスを供給する。本工程においては、窒素ガスの流量を２０ｍｌ／ｍｉｎとし、アルゴンガスの流量を３ｍｌ／ｍｉｎとする。このとき、チャンバー内の全圧は排気量が調節されることで５８Ｐａに維持される。実施例１における窒素分圧と水素分圧の分圧比である窒素分圧／水素分圧は０．２５であった。その後、パルス電源の電圧を１４００Ｖ、Ｄｕｔｙ比を４０％に設定し、ユニポーラ出力形式で直流パルス電源を作動させる。ここでパルス電源の電圧が上げられることによって電極間では水素ガス、窒素ガスおよびアルゴンガスがプラズマ化した状態となる。これにより、基材の表面から窒素が侵入し、基材の表面に窒化層が形成される窒化処理を１２０分行い、珪炭化バナジウム膜形成用基材を得た。 <Nitriding process>
After that, the flow rate of hydrogen gas is set to 80 ml/min, and nitrogen gas and argon gas are supplied into the chamber. In this step, the flow rate of nitrogen gas is set at 20 ml/min and the flow rate of argon gas is set at 3 ml/min. At this time, the total pressure in the chamber is maintained at 58 Pa by adjusting the exhaust amount. The nitrogen partial pressure/hydrogen partial pressure, which is the partial pressure ratio of the nitrogen partial pressure and the hydrogen partial pressure in Example 1, was 0.25. After that, the voltage of the pulse power source is set to 1400 V and the duty ratio is set to 40%, and the DC pulse power source is operated in a unipolar output format. Here, by increasing the voltage of the pulse power source, hydrogen gas, nitrogen gas and argon gas are brought into a plasma state between the electrodes. As a result, nitrogen penetrated from the surface of the base material, nitriding treatment was performed for 120 minutes to form a nitride layer on the surface of the base material, and a base material for forming a vanadium silicocarbide film was obtained.
＜珪炭化バナジウム膜形成工程＞
続いて、塩化バナジウムガスとしての四塩化バナジウムガスの体積流量を３ｍｌ／ｍｉｎ、珪素源ガスとしてモノメチルシランガスの体積流量を４．５ｍｌ／ｍｉｎ、炭水素ガスとしてのメタンガスの体積流量を３０ｍｌ／ｍｉｎ、水素ガスの体積流量を７８ｍｌ／ｍｉｎ、アルゴンガスの体積流量を３ｍｌ／ｍｉｎに設定してプラズマ処理装置のチャンバー内に各ガスを供給する。換言すると、塩化バナジウムガス、珪素源ガス、炭化水素ガス、水素ガスおよびアルゴンガスの流量比が１：１．５：１１．５：２６：１となる状態で各ガスをチャンバー内に供給する。このとき、排気量を調節してチャンバー内の圧力を５８Ｐａとする。そして、パルス電源の電圧を１４００Ｖ、Ｄｕｔｙ比を２０％に設定した。このときのパルス電源の電力は２４１Ｗであった。これにより、プラズマ化したバナジウム、珪素、炭素が窒化層に吸着し、窒化層上にバナジウム、珪素、炭素を含有する珪炭化バナジウム膜が形成される。この状態を１８０分間維持し、珪炭化バナジウム膜形成用基材上に珪炭化バナジウム膜が被覆された珪炭化バナジウム膜被覆部材を得た。 <Vanadium silicide film forming step>
Subsequently, the volume flow rate of vanadium tetrachloride gas as vanadium chloride gas is 3 ml/min, the volume flow rate of monomethylsilane gas as silicon source gas is 4.5 ml/min, the volume flow rate of methane gas as hydrocarbon gas is 30 ml/min, The volume flow rate of hydrogen gas is set at 78 ml/min, and the volume flow rate of argon gas is set at 3 ml/min, and each gas is supplied into the chamber of the plasma processing apparatus. In other words, the vanadium chloride gas, the silicon source gas, the hydrocarbon gas, the hydrogen gas and the argon gas are supplied into the chamber at a flow ratio of 1:1.5:11.5:26:1. At this time, the pressure in the chamber is adjusted to 58 Pa by adjusting the exhaust amount. Then, the voltage of the pulse power supply was set to 1400 V, and the duty ratio was set to 20%. The power of the pulse power supply at this time was 241W. As a result, vanadium, silicon, and carbon converted into plasma are adsorbed on the nitride layer, and a vanadium silicocarbide film containing vanadium, silicon, and carbon is formed on the nitride layer. This state was maintained for 180 minutes to obtain a vanadium silicide film-coated member in which a base material for vanadium silicide film formation was coated with a vanadium silicide film.
続いて、塩化バナジウムガスとしての四塩化バナジウムガスの体積流量を３ｍｌ／ｍｉｎ、珪素源ガスとしてモノメチルシランガスの体積流量を４．５ｍｌ／ｍｉｎ、炭水素ガスとしてのメタンガスの体積流量を３０ｍｌ／ｍｉｎ、水素ガスの体積流量を７８ｍｌ／ｍｉｎ、アルゴンガスの体積流量を３ｍｌ／ｍｉｎに設定してプラズマ処理装置のチャンバー内に各ガスを供給する。換言すると、塩化バナジウムガス、珪素源ガス、炭化水素ガス、水素ガスおよびアルゴンガスの流量比が１：１．５：１１．５：２６：１となる状態で各ガスをチャンバー内に供給する。このとき、排気量を調節してチャンバー内の圧力を５８Ｐａとする。そして、パルス電源の電圧を１４００Ｖ、Ｄｕｔｙ比を２０％に設定した。このときのパルス電源の電力は２４１Ｗであった。これにより、プラズマ化したバナジウム、珪素、炭素が窒化層に吸着し、窒化層上にバナジウム、珪素、炭素を含有する珪炭化バナジウム膜が形成される。この状態を１８０分間維持し、珪炭化バナジウム膜形成用基材上に珪炭化バナジウム膜が被覆された珪炭化バナジウム膜被覆部材を得た。 <Vanadium silicide film forming step>
Subsequently, the volume flow rate of vanadium tetrachloride gas as vanadium chloride gas is 3 ml/min, the volume flow rate of monomethylsilane gas as silicon source gas is 4.5 ml/min, the volume flow rate of methane gas as hydrocarbon gas is 30 ml/min, The volume flow rate of hydrogen gas is set at 78 ml/min, and the volume flow rate of argon gas is set at 3 ml/min, and each gas is supplied into the chamber of the plasma processing apparatus. In other words, the vanadium chloride gas, the silicon source gas, the hydrocarbon gas, the hydrogen gas and the argon gas are supplied into the chamber at a flow ratio of 1:1.5:11.5:26:1. At this time, the pressure in the chamber is adjusted to 58 Pa by adjusting the exhaust amount. Then, the voltage of the pulse power supply was set to 1400 V, and the duty ratio was set to 20%. The power of the pulse power supply at this time was 241W. As a result, vanadium, silicon, and carbon converted into plasma are adsorbed on the nitride layer, and a vanadium silicocarbide film containing vanadium, silicon, and carbon is formed on the nitride layer. This state was maintained for 180 minutes to obtain a vanadium silicide film-coated member in which a base material for vanadium silicide film formation was coated with a vanadium silicide film.
（実施例２）
実施例１の窒化処理工程において、窒化処理時間を６０分に変更したことを除き、実施例１と同様の条件で珪炭化バナジウム膜形成用基材を得た。また、珪炭化バナジウム膜形成工程において、メタンガスの体積流量を１０ｍｌ／ｍｉｎ、水素ガスの体積流量を９８ｍｌ／ｍｉｎに設定し、塩化バナジウムガス、珪素源ガス、炭化水素ガス、水素ガスおよびアルゴンガスの流量比を１：１．５：４．８：３３：１となる状態で各ガスをチャンバー内に供給したこと、パルス電源の電力を３６４Ｗに、Ｄｕｔｙ比を４０％に設定したことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Example 2)
A base material for forming a vanadium silicocarbide film was obtained under the same conditions as in Example 1, except that the nitriding time in the nitriding process of Example 1 was changed to 60 minutes. Further, in the vanadium silicocarbide film forming step, the volume flow rate of methane gas was set at 10 ml/min and the volume flow rate of hydrogen gas was set at 98 ml/min, and vanadium chloride gas, silicon source gas, hydrocarbon gas, hydrogen gas and argon gas were mixed. Except that each gas was supplied into the chamber with a flow rate ratio of 1: 1.5: 4.8: 33: 1, the power of the pulse power supply was set to 364 W, and the duty ratio was set to 40%. A vanadium silicide film was formed under the same conditions as in Example 1 to obtain a vanadium silicide film-coated member.
実施例１の窒化処理工程において、窒化処理時間を６０分に変更したことを除き、実施例１と同様の条件で珪炭化バナジウム膜形成用基材を得た。また、珪炭化バナジウム膜形成工程において、メタンガスの体積流量を１０ｍｌ／ｍｉｎ、水素ガスの体積流量を９８ｍｌ／ｍｉｎに設定し、塩化バナジウムガス、珪素源ガス、炭化水素ガス、水素ガスおよびアルゴンガスの流量比を１：１．５：４．８：３３：１となる状態で各ガスをチャンバー内に供給したこと、パルス電源の電力を３６４Ｗに、Ｄｕｔｙ比を４０％に設定したことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Example 2)
A base material for forming a vanadium silicocarbide film was obtained under the same conditions as in Example 1, except that the nitriding time in the nitriding process of Example 1 was changed to 60 minutes. Further, in the vanadium silicocarbide film forming step, the volume flow rate of methane gas was set at 10 ml/min and the volume flow rate of hydrogen gas was set at 98 ml/min, and vanadium chloride gas, silicon source gas, hydrocarbon gas, hydrogen gas and argon gas were mixed. Except that each gas was supplied into the chamber with a flow rate ratio of 1: 1.5: 4.8: 33: 1, the power of the pulse power supply was set to 364 W, and the duty ratio was set to 40%. A vanadium silicide film was formed under the same conditions as in Example 1 to obtain a vanadium silicide film-coated member.
（実施例３）
実施例１の窒化処理工程において、窒化処理時間を２４０分に変更して珪炭化バナジウム膜形成用基材を得たことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Example 3)
A vanadium silicide film was formed under the same conditions as in Example 1, except that in the nitriding step of Example 1, the nitriding time was changed to 240 minutes to obtain a substrate for forming a vanadium silicide film. A vanadium silicide film-coated member was obtained.
実施例１の窒化処理工程において、窒化処理時間を２４０分に変更して珪炭化バナジウム膜形成用基材を得たことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Example 3)
A vanadium silicide film was formed under the same conditions as in Example 1, except that in the nitriding step of Example 1, the nitriding time was changed to 240 minutes to obtain a substrate for forming a vanadium silicide film. A vanadium silicide film-coated member was obtained.
（実施例４）
実施例１の珪炭化バナジウム膜形成工程において、珪炭化バナジウム膜の形成時間を３１５分に変更したことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Example 4)
In the vanadium silicide film forming step of Example 1, except that the formation time of the vanadium silicide film was changed to 315 minutes, a vanadium silicide film was formed under the same conditions as in Example 1 to coat the vanadium silicide film. got the parts.
実施例１の珪炭化バナジウム膜形成工程において、珪炭化バナジウム膜の形成時間を３１５分に変更したことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Example 4)
In the vanadium silicide film forming step of Example 1, except that the formation time of the vanadium silicide film was changed to 315 minutes, a vanadium silicide film was formed under the same conditions as in Example 1 to coat the vanadium silicide film. got the parts.
（実施例５）
実施例１の珪炭化バナジウム膜形成工程において、珪炭化バナジウム膜の形成時間を４２０分に変更したことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材１を得た。 (Example 5)
In the vanadium silicide film forming step of Example 1, except that the formation time of the vanadium silicide film was changed to 420 minutes, a vanadium silicide film was formed under the same conditions as in Example 1 to coat the vanadium silicide film. A member 1 was obtained.
実施例１の珪炭化バナジウム膜形成工程において、珪炭化バナジウム膜の形成時間を４２０分に変更したことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材１を得た。 (Example 5)
In the vanadium silicide film forming step of Example 1, except that the formation time of the vanadium silicide film was changed to 420 minutes, a vanadium silicide film was formed under the same conditions as in Example 1 to coat the vanadium silicide film. A member 1 was obtained.
（実施例６）
実施例１の珪炭化バナジウム膜形成工程において、珪素源ガスとして供給していたモノメチルシランガスの代わりに四塩化珪素ガスを体積流量４．５ｍｌ／ｍｉｎで供給し、メタンガスの体積流量を１５ｍｌ／ｍｉｎ、水素ガスの体積流量を９８ｍｌ／ｍｉｎに設定し、塩化バナジウムガス、珪素源ガス、炭化水素ガス、水素ガスおよびアルゴンガスの流量比が１：１．５：５：３３：１となる状態で各ガスをチャンバー内に供給し、パルス電源の電を３６４Ｗに、Ｄｕｔｙ比を４０％に設定し、珪炭化バナジウム膜の形成時間を３００分にしたことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Example 6)
In the vanadium silicide film forming step of Example 1, silicon tetrachloride gas was supplied at a volume flow rate of 4.5 ml/min instead of monomethylsilane gas supplied as the silicon source gas, and the volume flow rate of methane gas was set at 15 ml/min. The volume flow rate of hydrogen gas was set to 98 ml/min, and the flow ratio of vanadium chloride gas, silicon source gas, hydrocarbon gas, hydrogen gas and argon gas was 1:1.5:5:33:1. Gas was supplied into the chamber, the power of the pulse power source was set to 364 W, the duty ratio was set to 40%, and the formation time of the vanadium silicide film was set to 300 minutes. A vanadium silicide film-coated member was obtained by forming a vanadium carbide film.
実施例１の珪炭化バナジウム膜形成工程において、珪素源ガスとして供給していたモノメチルシランガスの代わりに四塩化珪素ガスを体積流量４．５ｍｌ／ｍｉｎで供給し、メタンガスの体積流量を１５ｍｌ／ｍｉｎ、水素ガスの体積流量を９８ｍｌ／ｍｉｎに設定し、塩化バナジウムガス、珪素源ガス、炭化水素ガス、水素ガスおよびアルゴンガスの流量比が１：１．５：５：３３：１となる状態で各ガスをチャンバー内に供給し、パルス電源の電を３６４Ｗに、Ｄｕｔｙ比を４０％に設定し、珪炭化バナジウム膜の形成時間を３００分にしたことを除き、実施例１と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Example 6)
In the vanadium silicide film forming step of Example 1, silicon tetrachloride gas was supplied at a volume flow rate of 4.5 ml/min instead of monomethylsilane gas supplied as the silicon source gas, and the volume flow rate of methane gas was set at 15 ml/min. The volume flow rate of hydrogen gas was set to 98 ml/min, and the flow ratio of vanadium chloride gas, silicon source gas, hydrocarbon gas, hydrogen gas and argon gas was 1:1.5:5:33:1. Gas was supplied into the chamber, the power of the pulse power source was set to 364 W, the duty ratio was set to 40%, and the formation time of the vanadium silicide film was set to 300 minutes. A vanadium silicide film-coated member was obtained by forming a vanadium carbide film.
（比較例１）
基材に対し、窒化処理を実施せずに実施例６と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Comparative example 1)
A vanadium silicide film-coated member was obtained by forming a vanadium silicide film on the substrate under the same conditions as in Example 6 without nitriding.
基材に対し、窒化処理を実施せずに実施例６と同様の条件で珪炭化バナジウム膜を形成して珪炭化バナジウム膜被覆部材を得た。 (Comparative example 1)
A vanadium silicide film-coated member was obtained by forming a vanadium silicide film on the substrate under the same conditions as in Example 6 without nitriding.
次に、実施例１～６の珪炭化バナジウム膜形成用基材の試験片と、窒化処理を実施していない比較例の基材の試験片に対し、窒化層の形成状態の確認と、窒化層の表面粗さRzjisの測定を行った。また、実施例１、３～６の珪炭化バナジウム膜形成用基材の試験片に対し、窒化深さの測定を行った。
Next, the formation state of the nitride layer was confirmed for the test pieces of the vanadium silicide film forming substrates of Examples 1 to 6 and the test pieces of the substrate of the comparative example that was not subjected to the nitriding treatment, and the nitriding was performed. The layer surface roughness Rzjis was measured. Further, the nitriding depth was measured for the test pieces of the vanadium silicide film-forming substrates of Examples 1 and 3 to 6.
＜窒化層の形成状態の確認＞
試験片を表面に対し垂直方向に切断し、エメリー紙で断面を研磨し、バフで研磨面を鏡面仕上げした。そして、JIS G 0562に規定された硝酸アルコール法（ナイタール法）に基づき、硝酸とエタノールとを混合し、得られた硝酸３％の腐食液に試験片を５分間浸漬させた。その後、金属（光学）顕微鏡を用いて試験片の断面を倍率１０００倍で観察し、顕微鏡画像で黒色に着色された部分を視認することができた試験片については、窒化層に拡散層が形成されたと判断し、表３に「有」と記載し、黒色部分を視認できなかった場合は「無」と記載した。また、顕微鏡画像で白色に着色された部分を視認することができた試験片については、窒化層に化合物層が形成されたと判断し、表３に「有」と記載し、白色部分を視認できなかった場合は「無」と記載した。 <Confirmation of formation state of nitride layer>
The test piece was cut perpendicular to the surface, the cross section was polished with emery paper, and the polished surface was mirror-finished with a buff. Then, based on the nitric alcohol method (nital method) specified in JIS G 0562, nitric acid and ethanol were mixed, and the test piece was immersed in the resulting 3% nitric acid corrosive solution for 5 minutes. After that, the cross section of the test piece was observed at a magnification of 1000 times using a metallographic (optical) microscope, and for the test piece in which the black colored portion was visible in the microscope image, a diffusion layer was formed in the nitride layer. It was judged that it was done, and it was described as "yes" in Table 3, and when the black part could not be visually recognized, it was described as "no". In addition, for test pieces in which a white colored portion could be visually recognized in the microscope image, it was judged that a compound layer was formed on the nitride layer, and described as "present" in Table 3, and the white portion could be visually recognized. If not, write "none".
試験片を表面に対し垂直方向に切断し、エメリー紙で断面を研磨し、バフで研磨面を鏡面仕上げした。そして、JIS G 0562に規定された硝酸アルコール法（ナイタール法）に基づき、硝酸とエタノールとを混合し、得られた硝酸３％の腐食液に試験片を５分間浸漬させた。その後、金属（光学）顕微鏡を用いて試験片の断面を倍率１０００倍で観察し、顕微鏡画像で黒色に着色された部分を視認することができた試験片については、窒化層に拡散層が形成されたと判断し、表３に「有」と記載し、黒色部分を視認できなかった場合は「無」と記載した。また、顕微鏡画像で白色に着色された部分を視認することができた試験片については、窒化層に化合物層が形成されたと判断し、表３に「有」と記載し、白色部分を視認できなかった場合は「無」と記載した。 <Confirmation of formation state of nitride layer>
The test piece was cut perpendicular to the surface, the cross section was polished with emery paper, and the polished surface was mirror-finished with a buff. Then, based on the nitric alcohol method (nital method) specified in JIS G 0562, nitric acid and ethanol were mixed, and the test piece was immersed in the resulting 3% nitric acid corrosive solution for 5 minutes. After that, the cross section of the test piece was observed at a magnification of 1000 times using a metallographic (optical) microscope, and for the test piece in which the black colored portion was visible in the microscope image, a diffusion layer was formed in the nitride layer. It was judged that it was done, and it was described as "yes" in Table 3, and when the black part could not be visually recognized, it was described as "no". In addition, for test pieces in which a white colored portion could be visually recognized in the microscope image, it was judged that a compound layer was formed on the nitride layer, and described as "present" in Table 3, and the white portion could be visually recognized. If not, write "none".
＜窒化深さ測定＞
試験片の基材硬さを測定し、窒化深さ（窒化層の表面から、基材硬さ×１．１５ＨＶの硬さとなる位置までの距離）を測定した。測定した結果を表３に記載する。なお、基材硬さの値は、JIS G 0562の規定に従い、窒化層が形成された試験片の切断面を研磨および鏡面仕上げした後、マイクロビッカース硬さ試験機を用いて２５ｇｆの荷重でビッカース硬さ試験を行い、その結果から硬さ推移曲線を作成し、その推移曲線において硬さの値が収束した点の値を用いた。 <Nitriding depth measurement>
The substrate hardness of the test piece was measured, and the nitriding depth (the distance from the surface of the nitrided layer to the position where the hardness is the substrate hardness×1.15 HV) was measured. Table 3 shows the measured results. In addition, the value of the substrate hardness was determined by polishing and mirror-finishing the cut surface of the test piece on which the nitride layer was formed, according to the provisions of JIS G 0562, and then using a micro Vickers hardness tester with a load of 25 gf. A hardness test was conducted, a hardness transition curve was created from the results, and the value at the point where the hardness values converged on the transition curve was used.
試験片の基材硬さを測定し、窒化深さ（窒化層の表面から、基材硬さ×１．１５ＨＶの硬さとなる位置までの距離）を測定した。測定した結果を表３に記載する。なお、基材硬さの値は、JIS G 0562の規定に従い、窒化層が形成された試験片の切断面を研磨および鏡面仕上げした後、マイクロビッカース硬さ試験機を用いて２５ｇｆの荷重でビッカース硬さ試験を行い、その結果から硬さ推移曲線を作成し、その推移曲線において硬さの値が収束した点の値を用いた。 <Nitriding depth measurement>
The substrate hardness of the test piece was measured, and the nitriding depth (the distance from the surface of the nitrided layer to the position where the hardness is the substrate hardness×1.15 HV) was measured. Table 3 shows the measured results. In addition, the value of the substrate hardness was determined by polishing and mirror-finishing the cut surface of the test piece on which the nitride layer was formed, according to the provisions of JIS G 0562, and then using a micro Vickers hardness tester with a load of 25 gf. A hardness test was conducted, a hardness transition curve was created from the results, and the value at the point where the hardness values converged on the transition curve was used.
＜表面粗さ測定＞
表面粗さ測定には、３Ｄレーザー顕微鏡（キーエンス社製VK-X120）を用いた。対物レンズの倍率を５０倍として、０．２ｍｍ×１．２ｍｍのレーザー顕微鏡像を取得したのち、顕微鏡付属のマルチファイル解析アプリケーションの複数線粗さ計測機能により窒化層の表面粗さＲｚｊｉｓを測定した。そして、試験片の長辺方向に１５本のラインプロファイルを取得し、それぞれのラインプロファイルから得られた表面粗さＲｚｊｉｓを平均することで、表面粗さＲｚｊｉｓの値を得た。実施例１～３の珪炭化バナジウム膜形成用基材の試験片の窒化層の表面粗さＲｚｊｉｓおよび窒化処理を実施していない比較例１の基材の試験片に対し表面粗さＲｚｊｉｓを測定した結果を表３に記載する。 <Surface roughness measurement>
A 3D laser microscope (VK-X120 manufactured by Keyence Corporation) was used for surface roughness measurement. After obtaining a 0.2 mm × 1.2 mm laser microscope image with an objective lens magnification of 50, the surface roughness Rzjis of the nitride layer was measured using the multi-line roughness measurement function of the multi-file analysis application attached to the microscope. . Then, 15 line profiles were obtained in the longitudinal direction of the test piece, and the surface roughness Rzjis obtained from each line profile was averaged to obtain the value of the surface roughness Rzjis. The surface roughness Rzjis of the nitride layer of the test piece of the vanadium silicide film forming substrate of Examples 1 to 3 and the surface roughness Rzjis of the test piece of the substrate of Comparative Example 1 not subjected to nitriding treatment were measured. Table 3 shows the results obtained.
表面粗さ測定には、３Ｄレーザー顕微鏡（キーエンス社製VK-X120）を用いた。対物レンズの倍率を５０倍として、０．２ｍｍ×１．２ｍｍのレーザー顕微鏡像を取得したのち、顕微鏡付属のマルチファイル解析アプリケーションの複数線粗さ計測機能により窒化層の表面粗さＲｚｊｉｓを測定した。そして、試験片の長辺方向に１５本のラインプロファイルを取得し、それぞれのラインプロファイルから得られた表面粗さＲｚｊｉｓを平均することで、表面粗さＲｚｊｉｓの値を得た。実施例１～３の珪炭化バナジウム膜形成用基材の試験片の窒化層の表面粗さＲｚｊｉｓおよび窒化処理を実施していない比較例１の基材の試験片に対し表面粗さＲｚｊｉｓを測定した結果を表３に記載する。 <Surface roughness measurement>
A 3D laser microscope (VK-X120 manufactured by Keyence Corporation) was used for surface roughness measurement. After obtaining a 0.2 mm × 1.2 mm laser microscope image with an objective lens magnification of 50, the surface roughness Rzjis of the nitride layer was measured using the multi-line roughness measurement function of the multi-file analysis application attached to the microscope. . Then, 15 line profiles were obtained in the longitudinal direction of the test piece, and the surface roughness Rzjis obtained from each line profile was averaged to obtain the value of the surface roughness Rzjis. The surface roughness Rzjis of the nitride layer of the test piece of the vanadium silicide film forming substrate of Examples 1 to 3 and the surface roughness Rzjis of the test piece of the substrate of Comparative Example 1 not subjected to nitriding treatment were measured. Table 3 shows the results obtained.
次に、実施例１～６、比較例１の珪炭化バナジウム膜被覆部材に対し、珪炭化バナジウム膜の膜厚測定、珪炭化バナジウム膜の組成分析、スクラッチ試験、硬さ測定、耐熱性評価および摩擦評価試験（ボールオンディスク試験）を実施した。
Next, for the vanadium silicide film-coated members of Examples 1 to 6 and Comparative Example 1, the film thickness measurement of the vanadium silicide film, the composition analysis of the vanadium silicide film, the scratch test, the hardness measurement, the heat resistance evaluation, and the A friction evaluation test (ball-on-disk test) was performed.
＜膜厚測定＞
基材上に形成された珪炭化バナジウム膜の膜厚は、試験片を垂直に切断して切断面を鏡面研磨した後、金属顕微鏡の倍率を１０００倍として切断面を観察し、観察した画像情報に基づいて算出することで測定した。測定した結果を表３に記載する。 <Film thickness measurement>
The film thickness of the vanadium silicide film formed on the substrate was obtained by cutting the test piece vertically, mirror-polishing the cut surface, and then observing the cut surface with a metallurgical microscope at a magnification of 1000 times. It was measured by calculating based on. Table 3 shows the measured results.
基材上に形成された珪炭化バナジウム膜の膜厚は、試験片を垂直に切断して切断面を鏡面研磨した後、金属顕微鏡の倍率を１０００倍として切断面を観察し、観察した画像情報に基づいて算出することで測定した。測定した結果を表３に記載する。 <Film thickness measurement>
The film thickness of the vanadium silicide film formed on the substrate was obtained by cutting the test piece vertically, mirror-polishing the cut surface, and then observing the cut surface with a metallurgical microscope at a magnification of 1000 times. It was measured by calculating based on. Table 3 shows the measured results.
＜組成分析＞
分析条件は次の通りである。測定した結果を表３に記載する。
測定装置：ＥＰＭＡ（日本電子株式会社製JXA-8530F）
測定モード：半定量分析
加速電圧：１５ｋＶ
照射電流：１．０×１０-7Ａ
ビーム形状：円
ビーム径設定値：５０μｍ
分光結晶：LDE6H, TAP, LDE5H, PETH, LIFH, LDE1H
なお、珪炭化バナジウム膜の膜厚が１μｍ以下の場合には、ＥＰＭＡの測定結果に基材の成分組成の影響が含まれる。このため、膜厚の薄い珪炭化バナジウム膜の組成分析を算出する場合には、事前に基材のみのＥＰＭＡ測定を実施しておき、珪炭化バナジウム膜の形成後のＥＰＭＡの測定結果から基材由来のバナジウム元素濃度、珪素元素濃度、炭素元素濃度および塩素元素濃度を差し引く必要がある。 <Composition analysis>
Analysis conditions are as follows. Table 3 shows the measured results.
Measuring device: EPMA (JXA-8530F manufactured by JEOL Ltd.)
Measurement mode: Semi-quantitative analysis Acceleration voltage: 15 kV
Irradiation current: 1.0×10 −7 A
Beam shape: circle Beam diameter setting value: 50 μm
Analysis crystal: LDE6H, TAP, LDE5H, PETH, LIFH, LDE1H
When the film thickness of the vanadium silicide film is 1 μm or less, the EPMA measurement results include the influence of the component composition of the base material. Therefore, when calculating the composition analysis of a thin vanadium silicide film, the EPMA measurement of only the substrate is performed in advance, and the EPMA measurement result after the formation of the vanadium silicide film is used to calculate the It is necessary to subtract the original vanadium element concentration, silicon element concentration, carbon element concentration and chlorine element concentration.
分析条件は次の通りである。測定した結果を表３に記載する。
測定装置：ＥＰＭＡ（日本電子株式会社製JXA-8530F）
測定モード：半定量分析
加速電圧：１５ｋＶ
照射電流：１．０×１０-7Ａ
ビーム形状：円
ビーム径設定値：５０μｍ
分光結晶：LDE6H, TAP, LDE5H, PETH, LIFH, LDE1H
なお、珪炭化バナジウム膜の膜厚が１μｍ以下の場合には、ＥＰＭＡの測定結果に基材の成分組成の影響が含まれる。このため、膜厚の薄い珪炭化バナジウム膜の組成分析を算出する場合には、事前に基材のみのＥＰＭＡ測定を実施しておき、珪炭化バナジウム膜の形成後のＥＰＭＡの測定結果から基材由来のバナジウム元素濃度、珪素元素濃度、炭素元素濃度および塩素元素濃度を差し引く必要がある。 <Composition analysis>
Analysis conditions are as follows. Table 3 shows the measured results.
Measuring device: EPMA (JXA-8530F manufactured by JEOL Ltd.)
Measurement mode: Semi-quantitative analysis Acceleration voltage: 15 kV
Irradiation current: 1.0×10 −7 A
Beam shape: circle Beam diameter setting value: 50 μm
Analysis crystal: LDE6H, TAP, LDE5H, PETH, LIFH, LDE1H
When the film thickness of the vanadium silicide film is 1 μm or less, the EPMA measurement results include the influence of the component composition of the base material. Therefore, when calculating the composition analysis of a thin vanadium silicide film, the EPMA measurement of only the substrate is performed in advance, and the EPMA measurement result after the formation of the vanadium silicide film is used to calculate the It is necessary to subtract the original vanadium element concentration, silicon element concentration, carbon element concentration and chlorine element concentration.
＜スクラッチ試験＞
スクラッチ試験機（csm社製Revetest）を用い、基材と珪炭化バナジウム膜の密着性を評価した。スクラッチ試験は、先端曲率１００μｍの円錐形ダイヤモンド圧子を用い、最小荷重１Ｎ、最大荷重１００Ｎ、荷重速度１００Ｎ／分、スクラッチ速度５ｍｍ／分、スクラッチ距離５ｍｍにて実施された。そして、圧子と試験片の接触箇所周辺の珪炭化バナジウム膜が破壊されたときの荷重、すなわち基材から珪炭化バナジウム膜が剥離したときの荷重である臨界荷重を測定し、この臨界荷重に基づいて基材と珪炭化バナジウム膜の密着性を評価した。スクラッチ試験における臨界荷重が大きいほど、基材から珪炭化バナジウム膜が剥離しにくく、基材と珪炭化バナジウム膜の密着性が高いことを示す。なお、珪炭化バナジウム膜の膜厚が０．５～５．０μｍの範囲内であれば、膜厚の違いに起因するスクラッチ試験結果のばらつきが無視できるほどに小さくなる。 <Scratch test>
Using a scratch tester (Revetest manufactured by csm), the adhesion between the substrate and the vanadium silicide film was evaluated. The scratch test was performed using a conical diamond indenter with a tip curvature of 100 μm, a minimum load of 1 N, a maximum load of 100 N, a load rate of 100 N/min, a scratch speed of 5 mm/min, and a scratch distance of 5 mm. Then, the load when the vanadium silicide film around the contact point between the indenter and the test piece is destroyed, that is, the critical load, which is the load when the vanadium silicide film is peeled off from the base material, is measured. The adhesiveness between the base material and the vanadium silicide film was evaluated using The greater the critical load in the scratch test, the more difficult it was for the vanadium silicide film to separate from the substrate, indicating that the adhesiveness between the substrate and the vanadium silicide film was high. If the film thickness of the vanadium silicide film is within the range of 0.5 to 5.0 μm, the variation in the scratch test results due to the difference in the film thickness becomes negligible.
スクラッチ試験機（csm社製Revetest）を用い、基材と珪炭化バナジウム膜の密着性を評価した。スクラッチ試験は、先端曲率１００μｍの円錐形ダイヤモンド圧子を用い、最小荷重１Ｎ、最大荷重１００Ｎ、荷重速度１００Ｎ／分、スクラッチ速度５ｍｍ／分、スクラッチ距離５ｍｍにて実施された。そして、圧子と試験片の接触箇所周辺の珪炭化バナジウム膜が破壊されたときの荷重、すなわち基材から珪炭化バナジウム膜が剥離したときの荷重である臨界荷重を測定し、この臨界荷重に基づいて基材と珪炭化バナジウム膜の密着性を評価した。スクラッチ試験における臨界荷重が大きいほど、基材から珪炭化バナジウム膜が剥離しにくく、基材と珪炭化バナジウム膜の密着性が高いことを示す。なお、珪炭化バナジウム膜の膜厚が０．５～５．０μｍの範囲内であれば、膜厚の違いに起因するスクラッチ試験結果のばらつきが無視できるほどに小さくなる。 <Scratch test>
Using a scratch tester (Revetest manufactured by csm), the adhesion between the substrate and the vanadium silicide film was evaluated. The scratch test was performed using a conical diamond indenter with a tip curvature of 100 μm, a minimum load of 1 N, a maximum load of 100 N, a load rate of 100 N/min, a scratch speed of 5 mm/min, and a scratch distance of 5 mm. Then, the load when the vanadium silicide film around the contact point between the indenter and the test piece is destroyed, that is, the critical load, which is the load when the vanadium silicide film is peeled off from the base material, is measured. The adhesiveness between the base material and the vanadium silicide film was evaluated using The greater the critical load in the scratch test, the more difficult it was for the vanadium silicide film to separate from the substrate, indicating that the adhesiveness between the substrate and the vanadium silicide film was high. If the film thickness of the vanadium silicide film is within the range of 0.5 to 5.0 μm, the variation in the scratch test results due to the difference in the film thickness becomes negligible.
＜硬さ測定＞
Fischer Instruments製のFISCHER SCOPE（登録商標）H100Cを用いたナノインデンテーション法により実施する。具体的には、最大押し込み荷重を３ｍＮとして試験片にバーコビッチ型のダイヤモンド圧子を押し込み、連続的に押し込み深さを計測する。得られた押し込み深さの計測データからフィッシャー・インストルメンツ社製のソフトウエアである「商品名：WIN-HCU（登録商標）」を用いて、マルテンス硬さと、そのマルテンス硬さから換算されるビッカース硬さを算出する。算出されたビッカース硬さは測定装置の画面に表示され、この数値を測定点における膜の硬度として扱う。本実施例では、各試験片の最表面の任意の２０点のビッカース硬さを求め、得られた硬度の平均値を膜のビッカース硬さとした。測定した結果を表３に記載する。 <Hardness measurement>
It is carried out by the nanoindentation method using a FISCHER SCOPE® H100C manufactured by Fischer Instruments. Specifically, the maximum indentation load is 3 mN, and a Berkovich type diamond indenter is indented into the test piece, and the indentation depth is continuously measured. From the measurement data of the indentation depth obtained, using the software "Product name: WIN-HCU (registered trademark)" manufactured by Fisher Instruments, Martens hardness and Vickers converted from the Martens hardness Calculate hardness. The calculated Vickers hardness is displayed on the screen of the measuring device, and this numerical value is treated as the hardness of the film at the measuring point. In this example, the Vickers hardness of 20 arbitrary points on the outermost surface of each test piece was determined, and the average value of the obtained hardnesses was taken as the Vickers hardness of the film. Table 3 shows the measured results.
Fischer Instruments製のFISCHER SCOPE（登録商標）H100Cを用いたナノインデンテーション法により実施する。具体的には、最大押し込み荷重を３ｍＮとして試験片にバーコビッチ型のダイヤモンド圧子を押し込み、連続的に押し込み深さを計測する。得られた押し込み深さの計測データからフィッシャー・インストルメンツ社製のソフトウエアである「商品名：WIN-HCU（登録商標）」を用いて、マルテンス硬さと、そのマルテンス硬さから換算されるビッカース硬さを算出する。算出されたビッカース硬さは測定装置の画面に表示され、この数値を測定点における膜の硬度として扱う。本実施例では、各試験片の最表面の任意の２０点のビッカース硬さを求め、得られた硬度の平均値を膜のビッカース硬さとした。測定した結果を表３に記載する。 <Hardness measurement>
It is carried out by the nanoindentation method using a FISCHER SCOPE® H100C manufactured by Fischer Instruments. Specifically, the maximum indentation load is 3 mN, and a Berkovich type diamond indenter is indented into the test piece, and the indentation depth is continuously measured. From the measurement data of the indentation depth obtained, using the software "Product name: WIN-HCU (registered trademark)" manufactured by Fisher Instruments, Martens hardness and Vickers converted from the Martens hardness Calculate hardness. The calculated Vickers hardness is displayed on the screen of the measuring device, and this numerical value is treated as the hardness of the film at the measuring point. In this example, the Vickers hardness of 20 arbitrary points on the outermost surface of each test piece was determined, and the average value of the obtained hardnesses was taken as the Vickers hardness of the film. Table 3 shows the measured results.
＜耐熱性評価＞
まず、常温（２５℃）にて試験片の表面硬さを測定する。次に、試験片を熱処理炉に収容し、目標温度まで６０分かけて加熱する。そして、試験片を目標温度でさらに６０分間保持した後に１２０分以上、放冷する。これらの処理はすべて大気雰囲気下で行う。放冷後、常温（２５℃）にて再び試験片の表面硬さを測定する。熱処理時の目標温度は、常温から１０００℃までの範囲において１００℃刻みで設定され、目標温度毎に１つの試験片を準備して熱処理試験を実施した。そして、熱処理後の表面硬さ／熱処理前の表面硬さ≧０．７５となった時の最大目標温度を、その膜種、成膜条件での耐熱温度とした。 <Heat resistance evaluation>
First, the surface hardness of the test piece is measured at room temperature (25°C). The specimen is then placed in a heat treatment furnace and heated to the target temperature over 60 minutes. After holding the test piece at the target temperature for an additional 60 minutes, it is allowed to cool for 120 minutes or more. All of these treatments are performed in an air atmosphere. After standing to cool, the surface hardness of the test piece is measured again at room temperature (25°C). The target temperature during the heat treatment was set in increments of 100° C. in the range from room temperature to 1000° C., and one test piece was prepared for each target temperature and the heat treatment test was performed. The maximum target temperature when the surface hardness after heat treatment/surface hardness before heat treatment satisfies ≧0.75 was taken as the heat resistant temperature for that film type and film formation conditions.
まず、常温（２５℃）にて試験片の表面硬さを測定する。次に、試験片を熱処理炉に収容し、目標温度まで６０分かけて加熱する。そして、試験片を目標温度でさらに６０分間保持した後に１２０分以上、放冷する。これらの処理はすべて大気雰囲気下で行う。放冷後、常温（２５℃）にて再び試験片の表面硬さを測定する。熱処理時の目標温度は、常温から１０００℃までの範囲において１００℃刻みで設定され、目標温度毎に１つの試験片を準備して熱処理試験を実施した。そして、熱処理後の表面硬さ／熱処理前の表面硬さ≧０．７５となった時の最大目標温度を、その膜種、成膜条件での耐熱温度とした。 <Heat resistance evaluation>
First, the surface hardness of the test piece is measured at room temperature (25°C). The specimen is then placed in a heat treatment furnace and heated to the target temperature over 60 minutes. After holding the test piece at the target temperature for an additional 60 minutes, it is allowed to cool for 120 minutes or more. All of these treatments are performed in an air atmosphere. After standing to cool, the surface hardness of the test piece is measured again at room temperature (25°C). The target temperature during the heat treatment was set in increments of 100° C. in the range from room temperature to 1000° C., and one test piece was prepared for each target temperature and the heat treatment test was performed. The maximum target temperature when the surface hardness after heat treatment/surface hardness before heat treatment satisfies ≧0.75 was taken as the heat resistant temperature for that film type and film formation conditions.
＜摩擦評価試験（ボールオンディスク試験）＞
ボールオンディスクス試験機は、CSM Instruments社製の「Tribometer」を用いた。ディスクは、実施例１～３、５および比較例の珪炭化バナジウム膜被覆部材の試験片である。ディスクに接触させるボールとして、炭素鋼のＳ４５Ｃからなる直径が６ｍｍのボールを使用した。温度が２３～２４℃、湿度が２１％の環境下で、図４に示すように、ボールをディスクに接触させ、ボールに５Ｎの荷重を加えながら、摺動速度が０．１６７ｍ／ｓとなるようにディスクを回転させた。ボールとディスクの接触点はディスクの中心から半径６ｍｍの点である。そして、ディスクとボールの摺動距離が１００ｍに達した際のディスクとボールとの摩擦係数を、基材上に形成された珪炭化バナジウム膜の摩擦係数の測定値とした。 <Friction evaluation test (ball-on-disk test)>
As the ball-on-disc tester, "Tribometer" manufactured by CSM Instruments was used. The disks are test pieces of vanadium silicide film-coated members of Examples 1 to 3, 5 and Comparative Example. A ball made of carbon steel S45C and having a diameter of 6 mm was used as a ball to be brought into contact with the disk. In an environment where the temperature is 23 to 24° C. and the humidity is 21%, as shown in FIG. The disk was rotated like this. The point of contact between the ball and the disc is a point with a radius of 6 mm from the center of the disc. The coefficient of friction between the disc and the ball when the sliding distance between the disc and the ball reached 100 m was used as the measured value of the coefficient of friction of the vanadium silicide film formed on the substrate.
ボールオンディスクス試験機は、CSM Instruments社製の「Tribometer」を用いた。ディスクは、実施例１～３、５および比較例の珪炭化バナジウム膜被覆部材の試験片である。ディスクに接触させるボールとして、炭素鋼のＳ４５Ｃからなる直径が６ｍｍのボールを使用した。温度が２３～２４℃、湿度が２１％の環境下で、図４に示すように、ボールをディスクに接触させ、ボールに５Ｎの荷重を加えながら、摺動速度が０．１６７ｍ／ｓとなるようにディスクを回転させた。ボールとディスクの接触点はディスクの中心から半径６ｍｍの点である。そして、ディスクとボールの摺動距離が１００ｍに達した際のディスクとボールとの摩擦係数を、基材上に形成された珪炭化バナジウム膜の摩擦係数の測定値とした。 <Friction evaluation test (ball-on-disk test)>
As the ball-on-disc tester, "Tribometer" manufactured by CSM Instruments was used. The disks are test pieces of vanadium silicide film-coated members of Examples 1 to 3, 5 and Comparative Example. A ball made of carbon steel S45C and having a diameter of 6 mm was used as a ball to be brought into contact with the disk. In an environment where the temperature is 23 to 24° C. and the humidity is 21%, as shown in FIG. The disk was rotated like this. The point of contact between the ball and the disc is a point with a radius of 6 mm from the center of the disc. The coefficient of friction between the disc and the ball when the sliding distance between the disc and the ball reached 100 m was used as the measured value of the coefficient of friction of the vanadium silicide film formed on the substrate.
（まとめ）
実施例１～６と比較例の結果に鑑みると、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を有する珪炭化バナジウム膜形成用基材上に珪炭化バナジウム膜を形成することで、密着性が向上することがわかった。実施例１、３～６と実施例２の比較によれば、窒化層の表面粗さＲｚｊｉｓが０．４μｍ以上であることで、より高い密着性を備える珪炭化バナジウム膜被覆部材を得られることがわかった。 (summary)
In view of the results of Examples 1 to 6 and Comparative Example, a vanadium silicide film was formed on a substrate for vanadium silicide film formation having a nitride layer with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less. It was found that the adhesion was improved by doing so. According to a comparison between Examples 1, 3 to 6 and Example 2, it was found that a vanadium silicon carbide film-coated member having higher adhesion can be obtained by setting the surface roughness Rzjis of the nitride layer to 0.4 μm or more. I found out.
実施例１～６と比較例の結果に鑑みると、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を有する珪炭化バナジウム膜形成用基材上に珪炭化バナジウム膜を形成することで、密着性が向上することがわかった。実施例１、３～６と実施例２の比較によれば、窒化層の表面粗さＲｚｊｉｓが０．４μｍ以上であることで、より高い密着性を備える珪炭化バナジウム膜被覆部材を得られることがわかった。 (summary)
In view of the results of Examples 1 to 6 and Comparative Example, a vanadium silicide film was formed on a substrate for vanadium silicide film formation having a nitride layer with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less. It was found that the adhesion was improved by doing so. According to a comparison between Examples 1, 3 to 6 and Example 2, it was found that a vanadium silicon carbide film-coated member having higher adhesion can be obtained by setting the surface roughness Rzjis of the nitride layer to 0.4 μm or more. I found out.
実施例１、３～６と実施例２の比較によれば、下記（１）式を満たすことで、より密着性が向上することがわかった。
（炭素元素濃度－バナジウム元素濃度-珪素元素濃度）≧２５ａｔ％ ・・・（１） A comparison between Examples 1 and 3 to 6 and Example 2 revealed that the adhesion was further improved by satisfying the following formula (1).
(carbon element concentration-vanadium element concentration-silicon element concentration)≧25 at % (1)
（炭素元素濃度－バナジウム元素濃度-珪素元素濃度）≧２５ａｔ％ ・・・（１） A comparison between Examples 1 and 3 to 6 and Example 2 revealed that the adhesion was further improved by satisfying the following formula (1).
(carbon element concentration-vanadium element concentration-silicon element concentration)≧25 at % (1)
実施例１、５と実施例２、３の比較によれば、下記（２）式を満たすことで、珪炭化バナジウム膜被覆部材に接触する相手部材との摩擦係数が小さくなることがわかった。
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≧３０ａｔ％ ・・・（２） According to the comparison between Examples 1 and 5 and Examples 2 and 3, it was found that the coefficient of friction between the vanadium silicide film-coated member and the counterpart member in contact with the vanadium silicide film-coated member was reduced by satisfying the following expression (2).
(carbon element concentration-vanadium element concentration-silicon element concentration)≧30 at % (2)
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≧３０ａｔ％ ・・・（２） According to the comparison between Examples 1 and 5 and Examples 2 and 3, it was found that the coefficient of friction between the vanadium silicide film-coated member and the counterpart member in contact with the vanadium silicide film-coated member was reduced by satisfying the following expression (2).
(carbon element concentration-vanadium element concentration-silicon element concentration)≧30 at % (2)
実施例２、３、６と実施例１、４、５の比較によれば、下記（３）式を満たすことで、珪炭化バナジウム膜の硬度が高まることがわかった。
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≦３６ａｔ％ ・・・（３） A comparison of Examples 2, 3 and 6 with Examples 1, 4 and 5 revealed that the hardness of the vanadium silicide film increased by satisfying the following formula (3).
(carbon element concentration - vanadium element concentration - silicon element concentration) ≤ 36 at% (3)
（炭素元素濃度－バナジウム元素濃度－珪素元素濃度）≦３６ａｔ％ ・・・（３） A comparison of Examples 2, 3 and 6 with Examples 1, 4 and 5 revealed that the hardness of the vanadium silicide film increased by satisfying the following formula (3).
(carbon element concentration - vanadium element concentration - silicon element concentration) ≤ 36 at% (3)
実施例１、４、５と実施例６の比較によれば、下記（４）式を満たすことで、珪炭化バナジウム膜の耐熱性が向上することがわかった。
珪素元素濃度／（バナジウム元素濃度＋珪素元素濃度）＞０．７・・・（４） A comparison between Examples 1, 4 and 5 and Example 6 revealed that the heat resistance of the vanadium silicide film was improved by satisfying the following formula (4).
Silicon element concentration/(vanadium element concentration+silicon element concentration)>0.7 (4)
珪素元素濃度／（バナジウム元素濃度＋珪素元素濃度）＞０．７・・・（４） A comparison between Examples 1, 4 and 5 and Example 6 revealed that the heat resistance of the vanadium silicide film was improved by satisfying the following formula (4).
Silicon element concentration/(vanadium element concentration+silicon element concentration)>0.7 (4)
本発明に係る珪炭化バナジウム膜形成用基材および珪炭化バナジウム膜被覆部材は、大きな面圧がかかった状態で使用される金型や切削工具、歯切工具、鍛造工具、自動車部品等に用いられる珪炭化バナジウム膜を形成るための基材および珪炭化バナジウム膜被覆部材として好適に利用することできる。
The base material for forming a vanadium silicide film and the vanadium silicide film-coated member according to the present invention are used in molds, cutting tools, gear cutting tools, forging tools, automobile parts, etc., which are used under high surface pressure. It can be suitably used as a substrate for forming a vanadium silicide film and a member covered with a vanadium silicide film.
１ 珪炭化バナジウム膜被覆部材
２ 珪炭化バナジウム膜形成用基材
２ａ 窒化層
２ｂ 基材
３ 珪炭化バナジウム膜
１０ プラズマ処理装置
１１ チャンバー
１２ 陽極
１３ 陰極
１４ パルス電源
１５ ガス供給管
１６ ガス排気管 1 vanadium silicidefilm coating member 2 base material for vanadium silicide film formation 2a nitride layer 2b base material 3 vanadium silicide film 10 plasma processing device 11 chamber 12 anode 13 cathode 14 pulse power supply 15 gas supply pipe 16 gas exhaust pipe
２ 珪炭化バナジウム膜形成用基材
２ａ 窒化層
２ｂ 基材
３ 珪炭化バナジウム膜
１０ プラズマ処理装置
１１ チャンバー
１２ 陽極
１３ 陰極
１４ パルス電源
１５ ガス供給管
１６ ガス排気管 1 vanadium silicide
Claims (23)
- 珪炭化バナジウム膜被覆部材であって、
基材と、
前記基材の表面に形成された、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層と、
前記窒化層上に形成された珪炭化バナジウム膜と、を有し、
前記珪炭化バナジウム膜は、バナジウムと、珪素と、炭素を含有し、かつ、膜中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計が９０ａｔ％以上である。 A vanadium silicide film coated member,
a substrate;
a nitride layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less formed on the surface of the substrate;
a vanadium silicocarbide film formed on the nitride layer;
The vanadium silicide film contains vanadium, silicon, and carbon, and the sum of vanadium element concentration, silicon element concentration, and carbon element concentration in the film is 90 at % or more. - 請求項１に記載の珪炭化バナジウム膜被覆部材において、
前記窒化層の表面粗さＲｚｊｉｓが０．２５μｍ以上である。 The vanadium silicide film-coated member according to claim 1,
The nitride layer has a surface roughness Rzjis of 0.25 μm or more. - 請求項１に記載の珪炭化バナジウム膜被覆部材において、
前記窒化層の表面粗さＲｚｊｉｓが０．４μｍ以上である。 In the vanadium silicide film-coated member according to claim 1,
The nitride layer has a surface roughness Rzjis of 0.4 μm or more. - 請求項１に記載の珪炭化バナジウム膜被覆部材において、
前記基材が鋼材である。 In the vanadium silicide film-coated member according to claim 1,
The base material is steel. - 請求項１に記載の珪炭化バナジウム膜被覆部材において、
前記バナジウム元素濃度が３～１５ａｔ％、前記珪素元素濃度が１５～３０ａｔ％、前記炭素元素濃度が６０～８０ａｔ％である。 In the vanadium silicide film-coated member according to claim 1,
The vanadium element concentration is 3 to 15 at %, the silicon element concentration is 15 to 30 at %, and the carbon element concentration is 60 to 80 at %. - 請求項１に記載の珪炭化バナジウム膜被覆部材において、
下記（１）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧２５ａｔ％ ・・・（１） In the vanadium silicide film-coated member according to claim 1,
The following formula (1) is satisfied.
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧25 at % (1) - 請求項１に記載の珪炭化バナジウム膜被覆部材において、
下記（２）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧３０ａｔ％ ・・・（２） In the vanadium silicide film-coated member according to claim 1,
It satisfies the following expression (2).
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧30 at % (2) - 請求項１に記載された珪炭化バナジウム膜被覆部材において、
下記（３）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≦３６ａｔ％ ・・・（３） In the vanadium silicide film-coated member according to claim 1,
The following formula (3) is satisfied.
(the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at% (3) - 請求項１に記載の珪炭化バナジウム膜被覆部材において、
下記（４）式を満たす。
前記珪素元素濃度／（前記バナジウム元素濃度＋前記珪素元素濃度）＞０．７ ・・・（４） In the vanadium silicide film-coated member according to claim 1,
The following formula (4) is satisfied.
The silicon element concentration/(the vanadium element concentration+the silicon element concentration)>0.7 (4) - 珪炭化バナジウム膜形成用基材であって、
基材の表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を有する。 A base material for forming a vanadium silicide film,
A nitride layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less is provided on the surface of the substrate. - 珪炭化バナジウム膜被覆部材の製造方法であって、
基材の表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を形成する窒化処理工程と、
前記窒化処理工程で形成された窒化層上に、バナジウムと、珪素と、炭素を含有し、かつ、膜中のバナジウム元素濃度と、珪素元素濃度と、炭素元素濃度の合計が９０ａｔ％以上の珪炭化バナジウム膜を形成する珪炭化バナジウム膜形成工程と、を有する。 A method for producing a vanadium silicide film-coated member, comprising:
a nitriding step of forming a nitrided layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of the substrate;
Silicon containing vanadium, silicon, and carbon and having a sum of vanadium element concentration, silicon element concentration, and carbon element concentration of 90 at % or more on the nitride layer formed in the nitriding process and a vanadium silicide carbide film forming step of forming a vanadium carbide film. - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
前記窒化層の表面粗さＲｚｊｉｓが０．２５μｍ以上である。 In the method for producing a vanadium silicide film-coated member according to claim 11,
The nitride layer has a surface roughness Rzjis of 0.25 μm or more. - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
前記窒化層の表面粗さＲｚｊｉｓが０．４μｍ以上である。 In the method for producing a vanadium silicide film-coated member according to claim 11,
The nitride layer has a surface roughness Rzjis of 0.4 μm or more. - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
前記窒化処理工程において、水素ガスおよび窒素ガスをプラズマ化することで前記基材の窒化処理を行う。 In the method for producing a vanadium silicide film-coated member according to claim 11,
In the nitriding step, the base material is nitrided by converting hydrogen gas and nitrogen gas into plasma. - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
前記基材が鋼材である。 In the method for producing a vanadium silicide film-coated member according to claim 11,
The base material is steel. - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
前記珪炭化バナジウム膜形成工程において、塩化バナジウムガス、珪素源ガス、炭化水素ガスおよび水素ガスを供給し、プラズマ化学蒸着法によって前記珪炭化バナジウム膜を形成する。 In the method for producing a vanadium silicide film-coated member according to claim 11,
In the vanadium silicide film forming step, vanadium chloride gas, silicon source gas, hydrocarbon gas and hydrogen gas are supplied to form the vanadium silicide film by plasma chemical vapor deposition. - 請求項１６に記載された珪炭化バナジウム膜被覆部材の製造方法において、
前記珪炭化バナジウム膜形成工程において、アルゴンガスをさらに供給し、前記塩化バナジウムガス、前記珪素源ガス、前記炭化水素ガス、前記水素ガスおよび前記アルゴンガスの流量比が１：０．２５～２：３～２０：２０～３５：０．５～２である。 In the method for producing a vanadium silicide film-coated member according to claim 16,
In the vanadium silicide film forming step, argon gas is further supplied, and the flow ratio of the vanadium chloride gas, the silicon source gas, the hydrocarbon gas, the hydrogen gas and the argon gas is 1:0.25 to 2: 3-20: 20-35: 0.5-2. - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
前記バナジウム元素濃度が３～１５ａｔ％、前記珪素元素濃度が１５～３０ａｔ％、前記炭素元素濃度が６０～８０ａｔ％である。 In the method for producing a vanadium silicide film-coated member according to claim 11,
The vanadium element concentration is 3 to 15 at %, the silicon element concentration is 15 to 30 at %, and the carbon element concentration is 60 to 80 at %. - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
下記（１）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧２５ａｔ％ ・・・（１） In the method for producing a vanadium silicide film-coated member according to claim 11,
The following formula (1) is satisfied.
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧25 at % (1) - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
下記（２）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≧３０ａｔ％ ・・・（２） In the method for producing a vanadium silicide film-coated member according to claim 11,
It satisfies the following expression (2).
(the carbon element concentration-the vanadium element concentration-the silicon element concentration)≧30 at % (2) - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
下記（３）式を満たす。
（前記炭素元素濃度－前記バナジウム元素濃度－前記珪素元素濃度）≦３６ａｔ％ ・・・（３） In the method for producing a vanadium silicide film-coated member according to claim 11,
The following formula (3) is satisfied.
(the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at% (3) - 請求項１１に記載された珪炭化バナジウム膜被覆部材の製造方法において、
下記（４）式を満たす。
前記珪素元素濃度／（前記バナジウム元素濃度＋前記珪素元素濃度）＞０．７ ・・・（４） In the method for producing a vanadium silicide film-coated member according to claim 11,
The following formula (4) is satisfied.
The silicon element concentration/(the vanadium element concentration+the silicon element concentration)>0.7 (4) - 珪炭化バナジウム膜形成用基材の製造方法であって、
基材の表面に、表面粗さＲｚｊｉｓが０．２μｍ以上、１．０μｍ以下の窒化層を形成する窒化処理工程を有する。
A method for producing a substrate for forming a vanadium silicide film, comprising:
The method includes a nitriding step of forming a nitrided layer having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of the substrate.
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| JP2021065970A JP2022161284A (en) | 2021-04-08 | 2021-04-08 | Vanadium silicon carbide film-coated member and method for manufacturing the same, and vanadium silicon carbide film-forming substrate and method for manufacturing the same |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0598422A (en) * | 1991-04-04 | 1993-04-20 | Sumitomo Electric Ind Ltd | Continuous treatment for ion nitriding-ceramic coating |
| JPH07300649A (en) * | 1994-04-27 | 1995-11-14 | Kobe Steel Ltd | Hard film excellent in wear resistance and oxidation resistance and high hardness member |
| JP2004084014A (en) * | 2002-08-27 | 2004-03-18 | Tokyo Metropolis | Coating method with diamond-like carbon film and die for plastic working |
| JP2004283995A (en) * | 2003-03-25 | 2004-10-14 | Nachi Fujikoshi Corp | Advanced high-speed steel tool |
| JP2005153126A (en) * | 2003-11-28 | 2005-06-16 | Nachi Fujikoshi Corp | Tool coated with plasma nitriding ceramic hard film |
| JP2019035108A (en) * | 2017-08-14 | 2019-03-07 | Ｄｏｗａサーモテック株式会社 | Vanadium silicide carbide nitride film, member covering vanadium silicide carbide nitride film and method for manufacturing the same |
| JP2021025063A (en) * | 2019-07-31 | 2021-02-22 | Ｄｏｗａサーモテック株式会社 | Method for manufacturing vanadium silicon nitride film coated member, and vanadium silicon nitride film coated member |
| JP2021055189A (en) * | 2019-09-30 | 2021-04-08 | Ｄｏｗａサーモテック株式会社 | Silica vanadium carbide membrane, silica vanadium carbide membrane coating member, and production method of silica vanadium carbide membrane coating member |
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- 2021-04-08 JP JP2021065970A patent/JP2022161284A/en active Pending
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0598422A (en) * | 1991-04-04 | 1993-04-20 | Sumitomo Electric Ind Ltd | Continuous treatment for ion nitriding-ceramic coating |
| JPH07300649A (en) * | 1994-04-27 | 1995-11-14 | Kobe Steel Ltd | Hard film excellent in wear resistance and oxidation resistance and high hardness member |
| JP2004084014A (en) * | 2002-08-27 | 2004-03-18 | Tokyo Metropolis | Coating method with diamond-like carbon film and die for plastic working |
| JP2004283995A (en) * | 2003-03-25 | 2004-10-14 | Nachi Fujikoshi Corp | Advanced high-speed steel tool |
| JP2005153126A (en) * | 2003-11-28 | 2005-06-16 | Nachi Fujikoshi Corp | Tool coated with plasma nitriding ceramic hard film |
| JP2019035108A (en) * | 2017-08-14 | 2019-03-07 | Ｄｏｗａサーモテック株式会社 | Vanadium silicide carbide nitride film, member covering vanadium silicide carbide nitride film and method for manufacturing the same |
| JP2021025063A (en) * | 2019-07-31 | 2021-02-22 | Ｄｏｗａサーモテック株式会社 | Method for manufacturing vanadium silicon nitride film coated member, and vanadium silicon nitride film coated member |
| JP2021055189A (en) * | 2019-09-30 | 2021-04-08 | Ｄｏｗａサーモテック株式会社 | Silica vanadium carbide membrane, silica vanadium carbide membrane coating member, and production method of silica vanadium carbide membrane coating member |
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