Vanadium silicon carbide film-coated member and method for manufacturing the same

Abstract

To provide a vanadium silicon carbide film-coated member that can improve the adhesion between a vanadium silicon carbide film and a substrate and a method for manufacturing the same, and a vanadium silicon carbide film-forming substrate and a method for manufacturing the same.SOLUTION: A vanadium silicon carbide film-coated member 1 comprises a substrate 2b, a nitride layer 2a formed on a surface of the substrate 2b and having a surface roughness Rzjis of 0.2-1.0 μm, and a vanadium silicon carbide film 3 formed on the nitride layer 2a. The vanadium silicon carbide film 3 contains vanadium, silicon, and carbon. In the film, the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration is 90 atom% or more.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a vanadium silicon carbide film-coated member and a method for manufacturing the same. According to the method and.

Background Art

[0002] Conventionally, on the surface of a base material such as a mold used for press working or forging, a cutting tool, a forging tool, or an automobile part, in order to prevent wear of the mold surface and damage to the material to be formed due to contact friction during processing of the material to be formed, it is known to form a hard film having a higher hardness than the base material on the surface of the base material. Patent Document 1 describes a vanadium silicon carbide film-coated member in which a vanadium silicon carbide film (VSiC film) containing vanadium, carbon, and silicon, which is a kind of hard film excellent in adhesion to the base material and wear resistance, is formed on the surface of the base material by an ion plating method.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The vanadium silicon carbide film-coated member is used in a state where a large surface pressure is applied to the surface of the member depending on the application. For example, when the vanadium silicon carbide film-coated member is used as a forging die, a large surface pressure is applied to the surface of the member every time forming is performed. When the vanadium silicon carbide film-coated member is used in such a state, if the adhesion between the base material and the vanadium silicon carbide film is insufficient, peeling of the vanadium silicon carbide film occurs, and the product life is significantly reduced. For this reason, further improvement in the adhesion between vanadium silicon carbide formed on the surface of a mold, cutting tool, tooth cutting tool, forging tool, automobile part, etc. used for press working or forging and the base material has been desired.

[0005] The present invention has been made in view of the above circumstances, and aims to provide a vanadium silicon carbide film-coated member capable of improving the adhesion between the vanadium silicon carbide film and a substrate, and a method for manufacturing the same. According to the method To achieve this object.

Means for Solving the Problems

[0006] The inventors of the present invention have found that by forming a nitride layer having a predetermined surface roughness on the surface of a substrate on which a vanadium silicon carbide film is to be formed, and forming a vanadium silicon carbide film on the nitride layer, a vanadium silicon carbide film-coated member having high adhesion to the substrate can be obtained, and thus the present invention has been completed.

[0007] One aspect of the present invention for solving the above problems is as listed below. [1] A substrate, A nitride layer formed on the surface of the substrate, having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, and A vanadium silicon carbide film formed on the nitride layer, and having, The vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at% or more. , wherein 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% , a vanadium silicon carbide film-coated member. [2] a substrate, a nitride layer formed on the surface of the substrate with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, and a vanadium silicon carbide film formed on the nitride layer, the vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at% or more, a vanadium silicon carbide film-coated member that satisfies the following formula (1). (the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≥ 25 at% ··· (1) [3] a substrate, a nitride layer formed on the surface of the substrate with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, and a vanadium silicon carbide film formed on the nitride layer, the vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at% or more, a vanadium silicon carbide film-coated member that satisfies the following formula (2). (the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≥ 30 at% ··· (2) [4] a substrate, a nitride layer formed on the surface of the substrate with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, and a vanadium silicon carbide film formed on the nitride layer, the vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at% or more, a vanadium silicon carbide film-coated member that satisfies the following formula (3). (the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at% ··· (3) [5] a substrate, a nitride layer formed on the surface of the substrate with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, and a vanadium silicon carbide film formed on the nitride layer, the vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at% or more, a vanadium silicon carbide film-coated member that satisfies the following formula (4). the silicon element concentration / (the vanadium element concentration + the silicon element concentration) > 0.7 ··· (4) 6 The surface roughness Rzjis of the nitride layer is 0.25 μm or more, [1] any one of ~[5] The vanadium silicon carbide film-coated member according to [1]. 7 The surface roughness Rzjis of the nitride layer is 0.4 μm or more, [1] any one of ~[5] The vanadium silicon carbide film-coated member according to [1]. 8 The substrate is a steel material, the vanadium silicon carbide film-coated member according to any one of [1] to [7] [[1]]. 9 A nitriding treatment 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, A vanadium silicon carbide film forming step of forming a vanadium silicon carbide film containing vanadium, silicon, and carbon and having a total of vanadium element concentration, silicon element concentration, and carbon element concentration in the film of 90 at% or more on the nitride layer formed in the nitriding treatment step, and having , 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%. A method for manufacturing a vanadium silicon carbide film-coated member.

[10] A nitriding treatment 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; A vanadium silicon carbide film forming step of forming a vanadium silicon carbide film containing vanadium, silicon, and carbon on the nitride layer formed in the nitriding treatment step, and the total of the vanadium element concentration, silicon element concentration, and carbon element concentration in the film being 90 at% or more. A method for manufacturing a vanadium silicon carbide film-coated member that satisfies the following formula (1). (The carbon element concentration - the vanadium element concentration - the silicon element concentration) ≥ 25 at% ··· (1)

[11] A nitriding treatment 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; A vanadium silicon carbide film forming step of forming a vanadium silicon carbide film containing vanadium, silicon, and carbon on the nitride layer formed in the nitriding treatment step, and the total of the vanadium element concentration, silicon element concentration, and carbon element concentration in the film being 90 at% or more. A method for manufacturing a vanadium silicon carbide film-coated member that satisfies the following formula (2). (The carbon element concentration - the vanadium element concentration - the silicon element concentration) ≥ 30 at% ··· (2) ​​​​

[12] A nitriding treatment 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; A vanadium silicon carbide film forming step of forming a vanadium silicon carbide film containing vanadium, silicon, and carbon on the nitride layer formed in the nitriding treatment step, and the total of the vanadium element concentration, silicon element concentration, and carbon element concentration in the film being 90 at% or more. A method for manufacturing a vanadium silicon carbide film-coated member that satisfies the following formula (3). (The carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at% ··· (3)

[13] A nitriding treatment 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; A vanadium silicon carbide film forming step of forming a vanadium silicon carbide film containing vanadium, silicon, and carbon on the nitride layer formed in the nitriding treatment step, and the total of the vanadium element concentration, silicon element concentration, and carbon element concentration in the film being 90 at% or more. A method for manufacturing a vanadium silicon carbide film-coated member that satisfies the following formula (4). The concentration of the silicon element / (the concentration of the vanadium element + the concentration of the silicon element) > 0.7 ··· (4) 14 The surface roughness Rzjis of the nitride layer is 0.25 μm or more, Any one of [9] to

[13] The manufacturing method of the vanadium silicon carbide film-coated member described in 15 The surface roughness Rzjis of the nitride layer is 0.4 μm or more, Any one of [9] to

[13] The manufacturing method of the vanadium silicon carbide film-coated member described in 16 In the nitriding treatment step, the nitriding treatment of the substrate is performed by plasmaizing hydrogen gas and nitrogen gas, [9] ~

[15] The manufacturing method of the vanadium silicon carbide film-coated member described in any one of 17 The substrate is a steel material, [9] ~

[16] The manufacturing method of the vanadium silicon carbide film-coated member described in any one of 18 In the vanadium silicon carbide film formation step, vanadium chloride gas, a silicon source gas, a hydrocarbon gas, and hydrogen gas are supplied, and the vanadium silicon carbide film is formed by plasma chemical vapor deposition, [9] ~

[17] The manufacturing method of the vanadium silicon carbide film-coated member described in any one of

[19] In the vanadium silicon carbide film formation step, argon gas is further supplied, and the flow rate ratio of the vanadium chloride gas, the silicon source gas, the hydrocarbon gas, the hydrogen gas, and the argon gas is 1:0.25~2:3~20:20~35:0.5~2,

[18] The manufacturing method of the vanadium silicon carbide film-coated member described in

Effect of the Invention

[0008] According to the present invention, a vanadium silicon carbide film-coated member capable of improving the adhesion between a vanadium silicon carbide film and a substrate and a manufacturing method thereof method can be provided.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0010] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In the present specification and the drawings, elements having substantially the same functional configuration are denoted by the same reference numerals, and redundant description is omitted.

[0011] FIG. 1 is a diagram showing a schematic configuration of a vanadium silicon carbide film-coated member according to the present embodiment.

[0012] The vanadium silicon carbide film-coated member 1 is composed of a substrate 2 for forming a vanadium silicon carbide film and a vanadium silicon carbide film 3 formed on the surface of the substrate 2 for forming a vanadium silicon carbide film.

[0013] The substrate 2 for forming a vanadium silicon carbide film is composed of a substrate 2b and a nitride layer 2a formed on the surface of the substrate 2b.

[0014] The material of the base material 2b is not particularly limited, and a material suitable for the use of the vanadium silicon carbide 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 mainly composed of iron, containing 2% or less carbon and other components. Examples of the steel materials used for molds and tools include die steel, high-speed tool steel, and matrix high speed steel, which will be described below.

[0015] Die steel is a type of alloy tool steel for cold molds. It can be quenched to high hardness, has little quenching distortion, and is widely used because of its excellent wear resistance. Die steel contains vanadium, molybdenum, tungsten, chromium, etc. The steel material symbol in JIS (Japanese Industrial Standards) is "SKD", and typical steel grades include SKD-11 and SKD-61.

[0016] High-speed tool steel, also called high speed steel, is a material with better wear resistance, impact resistance, and toughness compared to die steel. The steel material symbol in JIS is "SKH", and JIS summarizes it in JISG4403. Typical steel grades include SKH-51 and SKH-55.

[0017] Matrix high speed steel is designed to reduce eutectic carbides and increase the ratio of alloying elements in the matrix by keeping the carbon content lower than that of high-speed tool steel, thereby obtaining high hardness, high toughness, and high heat resistance. Generally available products on the market include YXR3, YXR7, and YXR33 of Hitachi Metals Tool Steel Co., Ltd. These materials are used for molds that require high dimensional accuracy among tool steels, punches used for shearing, cutting tools, etc. Therefore, in order to strengthen the above-mentioned characteristics of high hardness, high toughness, and high heat resistance, the surface coating as shown in this embodiment plays an important role.

[0018] The nitride layer 2a of the substrate 2 for forming a vanadium silicon carbide film is a layer composed of at least one of a compound layer and a diffusion layer, and is formed by subjecting the substrate 2b to a nitriding treatment. Considering the iron nitride, the nitride layer is composed of a γ' phase (Fe4N), an ε phase (Fe 2-3 N), and a metastable α" phase (Fe 16 N), etc. In the examples of the present application, nitrides containing alloy elements are formed according to these. For example, when die steel, high-speed tool steel, or matrix high-speed steel is used as the steel material, nitrides of vanadium, molybdenum, tungsten, chromium, etc. are precipitated. The presence of the nitride layer 2a on the surface of the substrate 2b improves the chemical compatibility between the substrate 2 for forming a vanadium silicon carbide film and the vanadium silicon carbide film 3, and also eliminates the lattice mismatch. As a result, the adhesion between the substrate 2 for forming a vanadium silicon carbide film and the vanadium silicon carbide film 3 can be further improved. From the viewpoint of further improving the adhesion between the substrate 2 for forming a vanadium silicon carbide film and the vanadium silicon carbide film 3, it is preferable that no compound layer is formed in the nitride layer 2a.

[0019] To confirm that the nitride layer 2a is formed on the surface of the substrate 2b, in accordance with the provisions of "JIS G 0562 Method for Measuring the Depth of Nitride Layer of Steel", the cut surface of the substrate 2 for forming a vanadium silicon carbide film is corroded, and using a metalloscope, the coloring state of the corroded cut surface is observed. 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, so it is possible to visually distinguish the presence or absence of the compound layer in the nitride layer 2a and the boundary between the nitride layer 2a and the substrate 2b.

[0020] The nitriding depth of the nitride layer 2a is not particularly limited, but is preferably 20 to 250 μm. When the nitriding depth of the nitride layer 2a is 20 μm or more, it is possible to suppress a rapid change in characteristics in the depth direction, such as a change in hardness due to nitriding. On the other hand, when the nitriding depth is 250 μm or less, the nitriding treatment time can be shortened, excessive nitriding can be suppressed, and the surface roughness of the nitride layer can be easily controlled. The "nitriding depth" of the nitride layer 2a is the distance from the surface of the nitride layer 2a to the position where the hardness becomes the substrate hardness × 1.15 HV. The "substrate hardness" is measured by the following method. First, according to the provisions of "JIS G 0562 Method for Measuring Nitrided Layer Depth of Steel", the cut surface of the test piece on which the nitride 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, the point at which the hardness value converges in the transition curve is specified, and the hardness value at this point is taken as the substrate hardness.

[0021] The nitride layer 2a formed on the surface of the substrate 2b has a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less. As shown in the examples described later, the substrate 2 for forming a vanadium silicon carbide film has a nitride layer 2a with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less on the surface of the substrate 2b, so that the adhesion between the substrate 2 for forming a vanadium silicon carbide film and the vanadium silicon carbide film 3 can be improved. From the viewpoint of further enhancing this effect, the surface roughness Rzjis of the nitride layer 2a is preferably 0.25 μm or more, and more preferably 0.4 μm or more.

[0022] (Vanadium silicon carbide film) The vanadium silicon carbide film-coated member 1 has a vanadium silicon carbide film 3 on a nitride layer 2a with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less. The vanadium silicon carbide film 3 contains vanadium (V), silicon (Si), and carbon (C), and is a film in which the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration is 90 at% or more. The vanadium silicon carbide film 3 preferably has a total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film of 91 at% or more, more preferably 92 at% or more.

[0023] The vanadium element concentration, the silicon element concentration, and the carbon element concentration in the vanadium silicon 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 silicon carbide film 3 is 1 μm or less, the measurement results of EPMA include the influence of the component composition of the base material. Therefore, when performing the composition analysis of the vanadium silicon carbide film 3 with a thin film thickness, it is necessary to perform EPMA measurement of only the base material 2b in advance and subtract the vanadium element concentration, the silicon element concentration, and the carbon element concentration derived from the base material from the measurement results of EPMA after the formation of the vanadium silicon carbide film 3.

[0024] The vanadium silicon 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%.

[0025] The vanadium element concentration, the silicon element concentration, and the carbon element concentration in the vanadium silicon carbide film 3 preferably satisfy the following formula (1), whereby the adhesion between the base material 2 for forming the vanadium silicon carbide film and the vanadium silicon carbide film 3 can be further improved. (Carbon element concentration - Vanadium element concentration - Silicon element concentration) ≧ 25 at% ··· (1)

[0026] Also, when the following formula (2) is satisfied, the friction coefficient with the mating member in contact with the vanadium silicon carbide film-coated member 1 can be reduced. (Carbon element concentration - Vanadium element concentration - Silicon element concentration) ≥ 30 at% ··· (2)

[0027] When the following formula (3) is satisfied, the hardness of the vanadium silicon carbide film 3 can be increased. (Carbon element concentration - Vanadium element concentration - Silicon element concentration) ≤ 36 at% ··· (3)

[0028] When the following formula (4) is satisfied, the heat resistance of the vanadium silicon carbide film 3 can be improved. Silicon element concentration / (Vanadium element concentration + Silicon element concentration) > 0.7 ··· (4)

[0029] The film thickness of the vanadium silicon carbide film 3 is appropriately set according to the use of the vanadium silicon carbide film-coated member 1. For example, when forming the vanadium silicon carbide film 3 on the base material of the mold, the film thickness is preferably 0.5 to 4 μm.

[0030] In addition, the vanadium silicon carbide film 3 may contain elements other than the vanadium element, the silicon element, and the carbon element as long as the effect of improving the adhesion is not impaired. Examples of the elements other than the vanadium element, the silicon element, and the carbon element include fluorine, chlorine, hydrogen, argon contained in the raw material gas or argon gas supplied in the vanadium silicon carbide film forming process, and oxygen, nitrogen, etc. contained in the gas remaining in the chamber of the vanadium silicon carbide film forming apparatus described later. The elements other than the vanadium element, the silicon element, and the carbon element contained in the vanadium silicon carbide film 3 are preferably limited to 9 at% or less, and more preferably limited to 8 at% or less.

[0031] Next, a method for manufacturing the vanadium silicon carbide film forming substrate 2 and the vanadium silicon carbide film-coated member 1 will be described. In the present embodiment, the vanadium silicon carbide film forming substrate 2 is produced by forming 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. Then, a vanadium silicon carbide film 3 is formed on the nitride layer 2a to produce the vanadium silicon carbide film-coated member 1.

[0032] First, prepare the substrate 2b. The substrate 2b is preferably polished until the surface roughness Rzjis becomes 0.1 μm or less. By having the surface roughness Rzjis of the substrate 2b be 0.1 μm or less, the nitride layer 2a can be uniformly formed on the surface of the substrate 2b, and it is considered that the adhesion is further improved.

[0033] <Nitriding treatment step> Next, perform nitriding treatment on the substrate 2b to produce the substrate 2 for forming the vanadium silicon carbide film. In the nitriding treatment step, a nitride 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 substrate 2b.

[0034] As the nitriding treatment apparatus for forming the nitride layer 2a and the forming apparatus for the vanadium silicon carbide film coating member 1 described later, for example, a plasma treatment apparatus 10 as shown in FIG. 2 is used. The plasma treatment apparatus 10 includes a chamber 11 into which the substrate 2b is carried, an anode 12 and a cathode 13, and a DC pulse power source 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 exhausting the gas in the chamber 11 is connected to the lower part of the chamber 11. A vacuum pump (not shown) is provided on the downstream side of the gas exhaust pipe 16. The cathode 13 also serves as a support base for supporting the substrate 2b, and the substrate 2b 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 ambient temperature in the chamber 11 by the heater.

[0035] Note that the configuration of the plasma treatment 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 raw material gas may be provided and used as the anode 12. Further, the substrate 2b may be heated only by glow current without providing a heater. That is, the plasma treatment apparatus 10 may be configured to be able to plasmaize the raw material gas supplied into the chamber 11 and form the nitride layer 2a on the substrate 2b.

[0036] The nitriding treatment method of the base material 2b is not particularly limited, and for example, plasma nitriding treatment, gas nitriding treatment, etc. are applicable. However, when the vanadium silicon carbide film is formed by plasma chemical vapor deposition and the nitriding treatment is performed by plasma nitriding treatment, it is possible to perform the nitriding treatment of the base material 2b and the formation of the vanadium silicon carbide film 3 in the same plasma treatment apparatus. Therefore, from the viewpoint of manufacturing the vanadium silicon carbide film-coated member 1 efficiently as compared with the case of using separate apparatuses, the nitriding treatment of the base material 2b is preferably performed by plasma nitriding treatment. Further, the nitriding treatment is preferably performed by plasma nitriding treatment in the same plasma treatment apparatus because it is possible to prevent the influence of surface oxidation and the like. Further, since the film can be formed without performing processes such as cooling and cleaning steps of the base material 2b, it is possible to manufacture the vanadium silicon carbide film-coated member 1 efficiently.

[0037] The plasma nitriding treatment is a nitriding treatment in which hydrogen gas and nitrogen gas supplied into the plasma treatment apparatus are made into plasma to form a nitride layer 2a on the surface of the base material 2b. At the time of this plasma nitriding treatment, argon gas may be appropriately supplied in addition to hydrogen gas and nitrogen gas. Argon gas contributes to the stabilization of plasma and the improvement of ion density by argon ions ionizing other molecules. The surface roughness Rzjis of the nitride layer 2a can be controlled by appropriately changing the nitriding treatment time, the partial pressure ratio of the supplied hydrogen gas and nitrogen gas, voltage, current density, Duty ratio, etc.

[0038] From the viewpoint of productivity, the treatment time of the plasma nitriding treatment is preferably 30 to 300 minutes. More preferably, it is 60 to 240 minutes.

[0039] The nitrogen partial pressure / hydrogen partial pressure, which is the ratio of the nitrogen partial pressure to the hydrogen partial pressure in the plasma processing apparatus, is preferably 0.15 to 2.0, whereby the substrate 2b is likely to be nitrided. From the viewpoint of suppressing the formation of the compound layer in the nitride layer 2a, it is preferable to set the nitrogen partial pressure / hydrogen partial pressure to 1.0 or less, and 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 in the chamber 11 during the plasma nitriding treatment is preferably 30 to 200 Pa.

[0040] The power supply voltage during the plasma nitriding treatment is preferably 1000 to 2500 V, and more preferably 1200 to 2000 V. The current density during the plasma nitriding treatment is preferably 0.2 to 0.7 mA / cm 2 and 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)}

[0041] The substrate 2 for forming the vanadium silicon carbide film in the present embodiment is manufactured by the above nitriding treatment.

[0042] <Vanadium silicon carbide film forming step> Next, a vanadium silicon carbide film 3 is formed on the nitride layer 2a of the substrate 2 for forming the vanadium silicon carbide film by plasma chemical vapor deposition.

[0043] As a raw material gas for forming the vanadium silicon carbide film 3, vanadium chloride gas, a silicon source gas, a hydrocarbon gas, and hydrogen gas are supplied into the chamber 11 of the plasma processing apparatus 10, and a pulse voltage is applied between the anode 12 and the cathode 13 using the pulse power supply 14. As a result, the raw material gas supplied into the chamber 11 between the anode 12 and the cathode 13 is turned into plasma, and the vanadium silicon carbide film 3 is formed on the nitride layer 2a. Thereby, the vanadium silicon carbide film-coated member 1 in the present embodiment is manufactured.

[0044] As the vanadium chloride gas, for example, vanadium tetrachloride (VCl4) gas, vanadium oxychloride (VOCl3) gas, etc. are used. From the viewpoint that the number of elements constituting the gas is small and it becomes easy to remove impurities in the vanadium silicon carbide film 3, it is preferable to use vanadium tetrachloride gas. Further, vanadium tetrachloride gas is easy to obtain, is liquid at normal temperature, and is easy to supply as a gas, so it is also preferable to use it from this viewpoint.

[0045] As the silicon source gas, for example, silane-based gases such as monomethylsilane gas, dimethylsilane gas, trimethylsilane gas, tetramethylsilane gas, silicon tetrachloride gas, silicon tetrafluoride gas, etc. are used.

[0046] As the hydrocarbon gas, for example, methane gas, ethane gas, ethylene gas, acetylene gas, etc. are used. The gases exemplified here may be supplied alone or two or more kinds of gases may be mixed and supplied.

[0047] When the raw material gas supplied in the vanadium silicon carbide film forming step contains silicon tetrachloride gas, the vanadium silicon carbide film 3 necessarily contains chlorine as an impurity in the remainder excluding vanadium, silicon, and carbon. Since chlorine easily binds to hydrogen gas, when the raw material gas contains hydrogen gas, chlorine generated from the vanadium chloride gas easily binds to hydrogen and is discharged out of the system. Thereby, the mixing of chlorine into the vanadium silicon carbide film 3 can be suppressed.

[0048] In addition, the remaining portion of the vanadium silicon carbide film 3 may contain inevitable impurities other than chlorine. In the vanadium silicon carbide film forming step, when vanadium chloride gas and silicon tetrachloride gas are supplied into the chamber 11, the volume flow rate of the hydrogen gas supplied into the chamber 11 is preferably 5 to 25 times the total of the volume flow rate of the vanadium chloride gas and the volume flow rate of the silicon tetrachloride gas. In addition, argon gas may be supplied into the chamber 11 as needed because argon ions contribute to the stabilization of the plasma and the improvement of the ion density by ionizing other molecules.

[0049] In the vanadium silicon carbide film forming step, the flow rate ratio of the vanadium chloride gas, the silicon source gas, the hydrocarbon gas, the hydrogen gas, and the argon gas is preferably 1:0.25 to 2:3 to 20:20 to 35:0.5 to 2. Thereby, it becomes easy to obtain the vanadium silicon carbide film 3 in which the total 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, the "flow rate of the vanadium chloride gas", the "flow rate of the silicon source gas", the "flow rate of the hydrocarbon gas", the "flow rate of the hydrogen gas", and the "flow rate of the argon gas" used in calculating the above flow rate ratio are volume flow rates at 0 °C and 1 atm.

[0050] The pressure in the chamber 11 in the vanadium silicon carbide film forming step is preferably, for example, 30 to 200 Pa. Also, the power applied from the DC pulse power supply 14 in the vanadium silicon carbide film forming step is preferably 100 to 1000 W. Further, the voltage applied from the DC pulse power supply 14 is preferably 1000 to 2000 V. The duty ratio is preferably 10% to 60%. The vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film of the vanadium silicon carbide film 3 can be controlled by appropriately setting the flow rate of each raw material gas, the power of the pulse power supply, the voltage of the pulse power supply, and the duty ratio.

[0051] By the vanadium silicon carbide film forming process as described above, a vanadium silicon carbide film 3 with a total concentration of vanadium element, silicon element, and carbon element of 90 at% or more is formed on a nitride layer 2a with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less. The vanadium silicon carbide film coated member 1 manufactured in this way is excellent in the adhesion between the substrate 2 for forming the vanadium silicon carbide film and the vanadium silicon carbide film 3.

[0052] As described above, an embodiment of the present invention has been explained, but the present invention is not limited to such examples. It is obvious that those skilled in the art can conceive of various modification examples or correction examples within the scope of the technical idea described in the claims, and it is naturally understood that they also belong to the technical scope of the present invention.

Example

[0053] After producing a substrate 2 for forming a vanadium silicon carbide film in which a nitride layer 2a was formed on the surface of the substrate 2b by plasma nitriding treatment, a vanadium silicon carbide film coated member 1 in which a vanadium silicon carbide film 3 was formed on the nitride layer 2a of the substrate 2 for forming a vanadium silicon carbide film by plasma chemical vapor deposition treatment was produced, and various evaluations were carried out. As the apparatus for nitriding the substrate 2b and forming the vanadium silicon carbide film 3, a plasma processing apparatus having the structure shown in FIG. 2 was used, and a DC pulse power source was used as the power source.

[0054] The substrate 2b was made by cutting a φ22 mm round bar made of SKH-51, which is a kind of high-speed tool steel, at intervals of 6 to 7 mm, mirror-polishing the film-forming surface of the round bar cut as shown in FIG. 3, and making the surface roughness Rzjis of the film-forming surface 0.085 μm. The nitride layer 2a and the vanadium silicon carbide film 3 are formed on the side surface of the substrate 2b that has been mirror-polished.

[0055] (Example 1) Hereinafter, the nitriding treatment method of the above-mentioned substrate and the method for forming a vanadium silicon carbide film in Example 1 will be described. Note that the nitriding treatment conditions and the formation conditions of the vanadium silicon carbide film are also described in Tables 1 and 2 below. In addition, the volume flow rate of each gas in the following description is the volume flow rate at 0 °C and 1 atm.

[0056] First, place the substrate in the chamber of the plasma processing apparatus, evacuate the chamber for 60 minutes, and reduce the pressure in the chamber to 25 Pa or less. At this time, the heater provided in the chamber is not operated. The ambient temperature in the chamber is measured by a sheath thermocouple. Subsequently, set the heater temperature to 550 °C and perform a baking treatment on the substrate for 60 minutes. Then, turn off the power of the heater and leave the forming apparatus for 120 minutes to cool the inside of the chamber.

[0057] Next, supply hydrogen gas into the chamber at a volume flow rate of 100 ml / min, and adjust the exhaust volume to set the pressure in the chamber to 100 Pa. Then, set the heater temperature to 525 °C and heat the atmosphere in the chamber for 30 minutes.

[0058] <Nitriding treatment step> Thereafter, change the flow rate of hydrogen gas to 80 ml / min and supply nitrogen gas and argon gas into the chamber. In this step, the flow rate of nitrogen gas is set to 20 ml / min and the flow rate of argon gas is set to 3 ml / min. At this time, the total pressure in the chamber is maintained at 58 Pa by adjusting the exhaust volume. 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. Then, set the voltage of the pulse power supply to 1400 V and the duty ratio to 40%, and operate the DC pulse power supply in a unipolar output format. Here, when the voltage of the pulse power supply is increased, hydrogen gas, nitrogen gas, and argon gas are in a plasma state between the electrodes. As a result, nitrogen penetrates from the surface of the substrate, and a nitriding treatment for forming a nitride layer on the surface of the substrate is performed for 120 minutes to obtain a substrate for forming a vanadium silicon carbide film.

[0059] <Vanadium silicon carbide film formation process> Subsequently, the volume flow rate of vanadium tetrachloride gas as vanadium chloride gas is set to 3 ml / min, the volume flow rate of monomethylsilane gas as silicon source gas is set to 4.5 ml / min, the volume flow rate of methane gas as hydrocarbon gas is set to 30 ml / min, the volume flow rate of hydrogen gas is set to 78 ml / min, and the volume flow rate of argon gas is set to 3 ml / min, and each gas is supplied into the chamber of the plasma processing apparatus. In other words, each gas is supplied into the chamber in a state where the flow rate ratio of vanadium chloride gas, silicon source gas, hydrocarbon gas, hydrogen gas, and argon gas is 1:1.5:11.5:26:1. At this time, the exhaust volume is adjusted to make the pressure in the chamber 58 Pa. Then, the voltage of the pulse power supply is set to 1400 V and the Duty ratio is set to 20%. The power of the pulse power supply at this time was 241 W. Thereby, the plasmaized vanadium, silicon, and carbon are adsorbed on the nitride layer, and a vanadium silicon carbide film containing vanadium, silicon, and carbon is formed on the nitride layer. This state is maintained for 180 minutes to obtain a vanadium silicon carbide film-coated member in which a vanadium silicon carbide film is coated on the vanadium silicon carbide film-forming substrate.

[0060] (Example 2) In the nitriding treatment step of Example 1, a vanadium silicon carbide film-forming substrate was obtained under the same conditions as in Example 1, except that the nitriding treatment time was changed to 60 minutes. Also, in the vanadium silicon carbide film formation step, the volume flow rate of methane gas was set to 10 ml / min and the volume flow rate of hydrogen gas was set to 98 ml / min, and each gas was supplied into the chamber in a state where the flow rate ratio of vanadium chloride gas, silicon source gas, hydrocarbon gas, hydrogen gas, and argon gas was 1:1.5:4.8:33:1. A vanadium silicon carbide film was formed under the same conditions as in Example 1 to obtain a vanadium silicon carbide film-coated member, except that the power of the pulse power supply was set to 364 W and the Duty ratio was set to 40%.

[0061] (Example 3) In the nitriding treatment step of Example 1, a vanadium silicon carbide film-coated member was obtained by forming a vanadium silicon carbide film under the same conditions as in Example 1, except that the nitriding treatment time was changed to 240 minutes to obtain a substrate for forming a vanadium silicon carbide film.

[0062] (Example 4) In the vanadium silicon carbide film forming step of Example 1, a vanadium silicon carbide film-coated member was obtained by forming a vanadium silicon carbide film under the same conditions as in Example 1, except that the formation time of the vanadium silicon carbide film was changed to 315 minutes.

[0063] (Example 5) In the vanadium silicon carbide film forming step of Example 1, a vanadium silicon carbide film-coated member 1 was obtained by forming a vanadium silicon carbide film under the same conditions as in Example 1, except that the formation time of the vanadium silicon carbide film was changed to 420 minutes.

[0064] (Example 6) In the vanadium silicon carbide film forming step of Example 1, instead of the monomethylsilane gas supplied as the silicon source gas, silicon tetrachloride gas was supplied at a volume flow rate of 4.5 ml / min, the volume flow rate of methane gas was set to 15 ml / min, the volume flow rate of hydrogen gas was set to 98 ml / min, and each gas was supplied into the chamber in a state where the flow rate ratio of vanadium chloride gas, silicon source gas, hydrocarbon gas, hydrogen gas, and argon gas was 1:1.5:5:33:1. The power of the pulse power supply was set to 364 W and the duty ratio was set to 40%. A vanadium silicon carbide film-coated member was obtained by forming a vanadium silicon carbide film under the same conditions as in Example 1, except that the formation time of the vanadium silicon carbide film was 300 minutes.

[0065] (Comparative Example 1) A vanadium silicon carbide film-coated member was obtained by forming a vanadium silicon carbide film on the substrate under the same conditions as in Example 6 without performing nitriding treatment.

[0066] [Table 1]

[0067] [Table 2]

[0068] Next, for the test pieces of the substrates for forming vanadium silicon carbide films in Examples 1 to 6 and the test pieces of the substrates of the comparative examples that did not undergo nitriding treatment, the formation state of the nitride layer was confirmed and the surface roughness Rzjis of the nitride layer was measured. Further, for the test pieces of the substrates for forming vanadium silicon carbide films in Examples 1, 3 to 6, the nitriding depth was measured.

[0069] <Confirmation of the formation state of the 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 acid alcohol method (Nital method) specified in JIS G 0562, nitric acid and ethanol were mixed, and the test piece was immersed in the obtained corrosion solution containing 3% nitric acid for 5 minutes. Thereafter, the cross-section of the test piece was observed at a magnification of 1000 times using a metal (optical) microscope. For the test piece in which the portion colored black in the microscope image could be visually recognized, it was determined that a diffusion layer was formed in the nitride layer, and it was described as "Yes" in Table 3. When the black portion could not be visually recognized, it was described as "No". Further, for the test piece in which the portion colored white in the microscope image could be visually recognized, it was determined that a compound layer was formed in the nitride layer, and it was described as "Yes" in Table 3. When the white portion could not be visually recognized, it was described as "No".

[0070] <Measurement of nitriding depth> The hardness of the substrate of the test piece was measured, and the nitriding depth (the distance from the surface of the nitride layer to the position where the hardness becomes the hardness of the substrate hardness × 1.15 HV) was measured. The measurement results are described in Table 3. The value of the substrate hardness was determined according to the provisions of JIS G 0562. After polishing and mirror-finishing the cut surface of the test piece on which the nitride layer was formed, a Vickers hardness test was performed with a load of 25 gf using a micro-Vickers hardness tester, and a hardness transition curve was created from the results. The value of the point at which the hardness value converged in the transition curve was used.

[0071] <Measurement of surface roughness> For surface roughness measurement, a 3D laser microscope (VK-X120 manufactured by Keyence Corporation) was used. With the magnification of the objective lens set at 50 times, a laser microscope image of 0.2 mm × 1.2 mm was acquired. Then, 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. Subsequently, 15 line profiles were obtained in the long side direction of the test piece, and the value of the surface roughness Rzjis was obtained by averaging the surface roughness Rzjis obtained from each line profile. Table 3 shows the results of measuring the surface roughness Rzjis of the nitride layer of the test pieces of the substrates for forming vanadium silicon carbide films in Examples 1 to 3 and the surface roughness Rzjis of the test piece of the substrate in Comparative Example 1 where nitriding treatment was not performed.

[0072] Next, for the vanadium silicon carbide film-coated members in Examples 1 to 6 and Comparative Example 1, film thickness measurement of the vanadium silicon carbide film, composition analysis of the vanadium silicon carbide film, scratch test, hardness measurement, heat resistance evaluation, and friction evaluation test (ball-on-disk test) were carried out.

[0073] <Film Thickness Measurement> The film thickness of the vanadium silicon carbide film formed on the substrate was measured by vertically cutting the test piece, mirror-polishing the cut surface, observing the cut surface with the magnification of the metal microscope set at 1000 times, and calculating based on the observed image information. The measurement results are described in Table 3.

[0074] <Composition Analysis> The analysis conditions are as follows. The measurement results are described in Table 3. 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: Circular Beam diameter set value: 50 μm Spectrometer crystal: LDE6H, TAP, LDE5H, PETH, LIFH, LDE1H In addition, when the film thickness of the vanadium silicon carbide film is 1 μm or less, the measurement results of EPMA include the influence of the component composition of the substrate. Therefore, when calculating the composition analysis of a thin vanadium silicon carbide film, it is necessary to first perform an EPMA measurement of only the substrate, and subtract the vanadium element concentration, silicon element concentration, carbon element concentration, and chlorine element concentration derived from the substrate from the EPMA measurement results after the formation of the vanadium silicon carbide film.

[0075] <Scratch Test> The adhesion between the substrate and the vanadium silicon carbide film was evaluated using a scratch tester (Revetest manufactured by CSM). The scratch test was carried out using a conical diamond indenter with a tip curvature of 100 μm, with 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 critical load, which is the load when the vanadium silicon carbide film around the contact point between the indenter and the test piece is broken, that is, the load when the vanadium silicon carbide film peels off from the substrate, was measured, and the adhesion between the substrate and the vanadium silicon carbide film was evaluated based on this critical load. The larger the critical load in the scratch test, the more difficult it is for the vanadium silicon carbide film to peel off from the substrate, indicating higher adhesion between the substrate and the vanadium silicon carbide film. In addition, if the film thickness of the vanadium silicon carbide film is within the range of 0.5 to 5.0 μm, the variation in the scratch test results due to the difference in film thickness becomes negligibly small.

[0076] <Hardness Measurement> It is carried out by the nanoindentation method using the FISCHER SCOPE (registered trademark) H100C manufactured by Fischer Instruments. Specifically, a Berkovich-type diamond indenter is pressed into the test piece with a maximum indentation load of 3 mN, and the indentation depth is continuously measured. From the measured data of the indentation depth obtained, the martensite hardness and the Vickers hardness converted from the martensite hardness are calculated using the software "Product name: WIN-HCU (registered trademark)" manufactured by Fischer Instruments. 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 measurement point. In this example, the Vickers hardness of 20 arbitrary points on the outermost surface of each test piece was obtained, and the average value of the obtained hardness was taken as the Vickers hardness of the film. The measurement results are shown in Table 3.

[0077] <Heat resistance evaluation> First, the surface hardness of the test piece is measured at room temperature (25 °C). Next, the test piece is placed in a heat treatment furnace and heated to the target temperature over 60 minutes. Then, after holding the test piece at the target temperature for another 60 minutes, it is cooled naturally for 120 minutes or more. All of these processes are carried out in an air atmosphere. After natural cooling, the surface hardness of the test piece is measured again at room temperature (25 °C). The target temperature during heat treatment is set in 100 °C increments in the range from room temperature to 1000 °C, and one test piece is prepared for each target temperature to conduct a heat treatment test. Then, the maximum target temperature when the surface hardness after heat treatment / the surface hardness before heat treatment ≥ 0.75 is taken as the heat resistance temperature for that film type and film formation conditions.

[0078] <Friction evaluation test (ball-on-disk test)> The ball-on-disk tester used was the "Tribometer" manufactured by CSM Instruments. The disk was a test piece of the vanadium silicon carbide film-coated member of Examples 1 to 3, 5, and the comparative example. As the ball brought into contact with the disk, a 6-mm diameter ball made of carbon steel S45C was used. In an environment where the temperature was 23 to 24°C and the humidity was 21%, as shown in Figure 4, the ball was brought into contact with the disk, and while applying a load of 5 N to the ball, the disk was rotated so that the sliding speed became 0.167 m / s. The contact point between the ball and the disk was a point 6 mm in radius from the center of the disk. Then, when the sliding distance between the disk and the ball reached 100 m, the friction coefficient between the disk and the ball was taken as the measured value of the friction coefficient of the vanadium silicon carbide film formed on the substrate.

[0079] [Table 3]

[0080] (Summary) In view of the results of Examples 1 to 6 and the comparative example, it was found that the adhesion was improved by forming a vanadium silicon carbide film on a substrate for forming a vanadium silicon carbide film having a nitride layer with a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less. According to the comparison between Examples 1, 3 to 6 and Example 2, it was found that a vanadium silicon carbide film-coated member having higher adhesion could be obtained by the surface roughness Rzjis of the nitride layer being 0.4 μm or more.

[0081] According to the comparison between Examples 1, 3 to 6 and Example 2, it was found that the adhesion was further improved by satisfying the following formula (1). (Carbon element concentration - vanadium element concentration - silicon element concentration) ≥ 25 at% ··· (1)

[0082] According to the comparison between Examples 1, 5 and Examples 2, 3, it was found that the friction coefficient with the mating member in contact with the vanadium silicon carbide film-coated member was reduced by satisfying the following formula (2). (Carbon element concentration - vanadium element concentration - silicon element concentration) ≥ 30 at% ··· (2)

[0083] According to the comparison between Examples 2, 3, 6 and Examples 1, 4, 5, it was found that by satisfying the following formula (3), the hardness of the vanadium silicon carbide film was increased. (Carbon element concentration - vanadium element concentration - silicon element concentration) ≤ 36 at% ··· (3)

[0084] According to the comparison between Examples 1, 4, 5 and Example 6, it was found that by satisfying the following formula (4), the heat resistance of the vanadium silicon carbide film was improved. Silicon element concentration / (Vanadium element concentration + Silicon element concentration) > 0.7 ··· (4)

Industrial Applicability

[0085] The substrate for forming a vanadium silicon carbide film and the vanadium silicon carbide film-coated member according to the present invention can be suitably used as a substrate for forming a vanadium silicon carbide film and a vanadium silicon carbide film-coated member used for molds, cutting tools, tooth cutting tools, forging tools, automobile parts, etc. that are used in a state where a large surface pressure is applied.

Explanation of Symbols

[0086] 1 Vanadium silicon carbide film-coated member 2 Substrate for forming vanadium silicon carbide film 2a Nitride layer 2b Substrate 3 Vanadium silicon carbide film 10 Plasma processing apparatus 11 Chamber 12 Anode 13 Cathode 14 Pulse power supply 15 Gas supply pipe 16 Gas exhaust pipe

Claims

1. a base material, a nitride layer formed on the surface of the base material and having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, and a vanadium silicon carbide film formed on the nitride layer, wherein the vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at% or more, and 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%; a vanadium silicon carbide film-coated member.

2. A base material, a nitride layer formed on the surface of the base material and having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, and a vanadium silicon carbide film formed on the nitride layer, wherein the vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at% or more, a vanadium silicon carbide film-coated member satisfying the following formula (1). (the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≥ 25 at%... (1)

3. A base material, a nitride layer formed on the surface of the base material and having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, and a vanadium silicon carbide film formed on the nitride layer, wherein the vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at% or more, a vanadium silicon carbide film-coated member satisfying the following formula (2). (the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≥ 30 at%... (2)

4. A base material, a nitride layer formed on the surface of the base material and having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, and a vanadium silicon carbide film formed on the nitride layer, wherein the vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, the silicon element concentration, and the carbon element concentration in the film is 90 at% or more, a vanadium silicon carbide film-coated member satisfying the following formula (3). (the carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at%... (3)

5. A base material, a nitride layer formed on the surface of the base material and having a surface roughness Rzjis of 0.2 μm or more and 1.0 μm or less, It has a vanadium silicon carbide film formed on the nitride layer, The vanadium silicon carbide film contains vanadium, silicon, and carbon, and the total of the vanadium element concentration, silicon element concentration, and carbon element concentration in the film is 90 at% or more, A vanadium silicon carbide film coating member that satisfies the following formula (4). The silicon element concentration / (the vanadium element concentration + the silicon element concentration) > 0.7... (4)

6. The vanadium silicon carbide film coating member according to any one of claims 1 to 5, wherein the surface roughness Rzjis of the nitride layer is 0.25 μm or more.

7. The vanadium silicon carbide film coating member according to any one of claims 1 to 5, wherein the surface roughness Rzjis of the nitride layer is 0.4 μm or more.

8. The vanadium silicon carbide film coating member according to any one of claims 1 to 7, wherein the base material is a steel material.

9. A nitriding treatment 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 base material; A vanadium silicon carbide film forming step of forming a vanadium silicon carbide film containing vanadium, silicon, and carbon and having a total of the vanadium element concentration, silicon element concentration, and carbon element concentration in the film of 90 at% or more on the nitride layer formed in the nitriding treatment step; A method for manufacturing a vanadium silicon carbide film coating member, wherein 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%.

10. A nitriding treatment 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 base material; A vanadium silicon carbide film forming step of forming a vanadium silicon carbide film containing vanadium, silicon, and carbon and having a total of the vanadium element concentration, silicon element concentration, and carbon element concentration in the film of 90 at% or more on the nitride layer formed in the nitriding treatment step; A method for manufacturing a vanadium silicon carbide film coating member that satisfies the following formula (1). (The carbon element concentration - the vanadium element concentration - the silicon element concentration) ≧ 25 at%... (1)

11. A nitriding treatment 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 base material; On the nitride layer formed in the nitriding treatment step, a vanadium silicon carbide film containing vanadium, silicon, and carbon and having a total of vanadium element concentration, silicon element concentration, and carbon element concentration in the film of 90 at% or more is formed, and a vanadium silicon carbide film forming step. A method for manufacturing a vanadium silicon carbide film-coated member that satisfies the following formula (2). (The carbon element concentration - the vanadium element concentration - the silicon element concentration) ≥ 30 at%... (2)

12. A nitriding treatment 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 a base material; On the nitride layer formed in the nitriding treatment step, a vanadium silicon carbide film containing vanadium, silicon, and carbon and having a total of vanadium element concentration, silicon element concentration, and carbon element concentration in the film of 90 at% or more is formed, and a vanadium silicon carbide film forming step. A method for manufacturing a vanadium silicon carbide film-coated member that satisfies the following formula (3). (The carbon element concentration - the vanadium element concentration - the silicon element concentration) ≤ 36 at%... (3)

13. A nitriding treatment 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 a base material; On the nitride layer formed in the nitriding treatment step, a vanadium silicon carbide film containing vanadium, silicon, and carbon and having a total of vanadium element concentration, silicon element concentration, and carbon element concentration in the film of 90 at% or more is formed, and a vanadium silicon carbide film forming step. A method for manufacturing a vanadium silicon carbide film-coated member that satisfies the following formula (4). The silicon element concentration / (the vanadium element concentration + the silicon element concentration) > 0.7... (4)

14. The method for manufacturing a vanadium silicon carbide film-coated member according to any one of claims 9 to 13, wherein the surface roughness Rzjis of the nitride layer is 0.25 μm or more.

15. The method for manufacturing a vanadium silicon carbide film-coated member according to any one of claims 9 to 13, wherein the surface roughness Rzjis of the nitride layer is 0.4 μm or more.

16. The method for manufacturing a vanadium silicon carbide film-coated member according to any one of claims 9 to 15, wherein in the nitriding treatment step, the base material is nitrided by plasmaizing hydrogen gas and nitrogen gas.

17. The method for manufacturing a vanadium silicon carbide film-coated member according to any one of claims 9 to 16, wherein the base material is a steel material.

18. In the step of forming the vanadium silicon carbide film, vanadium chloride gas, a silicon source gas, a hydrocarbon gas, and hydrogen gas are supplied, and the vanadium silicon carbide film is formed by plasma chemical vapor deposition. The method for manufacturing a vanadium silicon carbide film-coated member according to any one of claims 9 to 17.

19. In the step of forming the vanadium silicon carbide film, argon gas is further supplied, and the flow rate 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 to 20:20 to 35:0.5 to 2. The method for manufacturing a vanadium silicon carbide film-coated member according to claim 18.

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