WO2005099944A1

WO2005099944A1 - Coated member and method for manufacture thereof

Info

Publication number: WO2005099944A1
Application number: PCT/JP2005/007091
Authority: WO
Inventors: Tetsuo Nakai; Nobuo Omae; Masahito Tagawa; Hiroshi Kinoshita
Original assignee: National University Corporation Kobe University
Priority date: 2004-04-15
Filing date: 2005-04-12
Publication date: 2005-10-27

Abstract

A coated member having a substrate (1) and a thin film (2) formed on the surface of the substrate, wherein the substrate (1) comprises cermet, cemented carbides or diamond, and the thin film (2) comprises at least one of a carbide, a nitride and a carbonitride of an element of 4a Group element, fluorine and oxygen, and wherein the thin film (2) has a thickness of 1 to 100 atoms in terms of the number of the atoms constituting the film; and a method for manufacturing the above coated member. The formation of the above thin film (2) allows the effective inhibition of the deposition of a material to be cut on the surface of a tool, and thus the above member can provide a cutting tool exhibiting a markedly enhanced working accuracy.

Description

Specification

Coating member and manufacturing method thereof

Technical field

The present invention relates to a coated member in which a thin film is formed on a substrate such as a cemented carbide, diamond, or cermet, and a method for producing the same. In particular, it relates to a covering member having an extremely thin thin film.

Background art

[0002] In recent years, in the field of optical products such as optical communication components and small digital cameras, smaller

'High precision lenses are required. Usually, a mold is used for manufacturing such a lens, and an iron-based material having high strength and high abrasion resistance is often used for the mold material. Then, in order to manufacture a mold using such an iron-based material, high-precision mirror finishing is required.

[0003] For high-precision processing of such an iron-based material, a tool using a cemented carbide or a cermet as a base material is used. In particular, in order to respond to the demand for higher precision machining and longer tool life, technologies for forming various hard coatings on the base material of cutting tools using CVD and PVD methods have been developed. I have.

[0004] Patent Document 1 provides a cutting tool for long-life high-precision machining by controlling the film thickness of a coated cutting tool coated by a CVD method or a PVD method. That is, in this document, the thickness of the rake face and 0.5~2.0 / ζ πι, Nyori that the thickness of the flank and 1.0 to 4.0 _i um, suppressing Chippi ring of thin, substantially tool life Is described.

[0005] Other new technologies that have recently attracted attention are disclosed in Patent Documents 2 and 3. Each of these documents discloses a technique of generating an atom having no charge by a laser beam and utilizing the atom.

[0006] Patent Document 2 relates to a high-energy atomic source, and discloses a method of concentrating a carbon dioxide gas laser on a raw material inlet using a convex lens.

[0007] Patent Document 3 describes a further improvement of the technique applied to a semiconductor manufacturing apparatus.

Use of dangerous fluorine gas is increasing in semiconductor cleaning and etching processes. Yes. This Patent Document 3 discloses that a safe SF gas is formed by forming atomic fluorine.

6

Discloses a technique using.

[0008] On the other hand, for high-precision cutting such as mirror finishing of non-ferrous materials, a tool using a single crystal diamond as a cutting edge is used (for example, Patent Document 4).

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-347403

Patent Document 2: U.S. Pat.No. 4,894,511

Patent Document 3: JP 2004-79704 A

Patent Document 4: JP-A-10-43903

Disclosure of the invention

Problems to be solved by the invention

[0010] However, a thin film formed by a conventional CVD method or PVD method grows preferentially at a sharp portion, so that the film surface formed on a sharp portion of a substrate becomes round. When a cutting tool made of such a covering member is used under conditions in which the cutting tool is operated at a low processing feed or a small depth of cut, chipping of a thin film is likely to occur. When chipping occurs, the surface roughness of the work material becomes rough, and the machining accuracy deteriorates. Therefore, the tool cannot be used as a high-precision machining tool.

[0011] In addition, a tool having a rounded edge has a large cutting resistance and increases the surface temperature of the tool. As a result, there is a problem that the work material is welded to the surface of the tool, the surface roughness of the tool is increased, and the surface roughness of the work material is increased. In particular, in the case of a thin film formed by the PVD method, the material constituting the thin film may adhere to the substrate as a lump of several microns, so that the film thickness becomes uneven and the surface roughness increases. When such a member is used as a cutting tool, since the surface roughness is large, the surface roughness of the work material becomes large, and the work material is easily welded to the surface of the tool.

[0012] Furthermore, the techniques described in Patent Documents 2 and 3 make specific proposals as to under what conditions a film is formed and in what field it can be used as a practical technique. Not.

[0013] On the other hand, diamond has a drawback that it cannot be used for iron-based materials. Diamond is suitable as a cutting tool material for hardness and thermal conductivity, but is composed of carbon nuclear.Since carbon atoms easily dissolve in the iron-based material, which is the main raw material of the mold, diamond is used. The tool wears so much that it cannot be used for cutting ferrous materials.

[0014] For this reason, conventionally, after rough cutting of an iron-based mold material using a cemented carbide tool, the surface of the die is plated with Ni-P or the like, and the surface of the metal die having a sharp edge is formed. It is finished by a single crystal diamond tool or by polishing after the rough cutting. As a result, the cost and delivery time of the production of molds are high, and there has been a strong demand for a technique for directly adding iron-based materials with high precision.

The present invention has been made in view of the above circumstances, and a main object of the present invention is to provide a covering member that can be used for a cutting tool in which a work material is not easily welded to the surface of the tool, and a method for manufacturing the same. And there.

[0016] Another object of the present invention is to provide a coating member capable of suppressing reaction with an iron-based material while using diamond as a base material and reducing cutting resistance, and a method of manufacturing the same. Means for solving the problem

[0017] The coated member of the present invention is a coated member in which a thin film is formed on a substrate surface. The substrate is made of diamond, cemented carbide or cermet. The thin film is composed of at least one selected from the group consisting of carbides, nitrides, carbonitrides, fluorine, and oxygen of Group 4a elements of the periodic table. The thickness of the thin film is characterized by the number of atoms constituting the thin film being 1 to 100 atoms.

[0018] By forming a very thin thin film having the above-described specific composition power, a covering member suitable for a tool in which a work material is unlikely to be welded to the surface of the tool can be obtained.

Further, according to the method for producing a coated member of the present invention, a raw material gas for a thin film is supplied into a vacuum chamber maintained at a predetermined degree of vacuum, and the raw material gas is irradiated with a laser to emit an atomic beam having no charge. A group consisting of carbides, nitrides, carbonitrides, fluorine and oxygen of Group 4a elements of the periodic table is generated by irradiating the atomic beam onto a diamond, cemented carbide or cermet substrate. A thin film composed of at least one selected from the group consisting of:

[0020] By irradiating an atomic beam having no charge to the surface of the base material to form an extremely thin thin film, it is possible to obtain a tool in which the work material does not easily adhere to the surface of the tool.

Hereinafter, the case of a sintered member having a cemented carbide or cermet as a base material and the case of The present invention will be described separately for the case of a diamond member as a material.

[0022] <Sintered member>

The present inventors have obtained the knowledge that by forming a very thin thin film having a predetermined component force on the surface of a cemented carbide or cermet, welding to a work material can be suppressed and cutting resistance can be reduced. Thus, the coated member of the present invention was completed.

[0023] The coated member of the present invention is a coated member in which a thin film is formed on the surface of a hard metal or cermet as a base material. The thin film is composed of at least one selected from the group consisting of carbides, nitrides, carbonitrides, fluorine, and oxygen of Group 4a elements of the periodic table. The thickness of the thin film is 1 to 100 atoms in terms of the number of atoms constituting the thin film.

[0024] The base material is a cemented carbide or cermet. A cemented carbide is usually composed of a hard phase composed of WC and the like, and a binder phase also composed of an iron group metal such as Co. In addition, the cermet is composed of a hard phase having a strong property such as carbides, nitrides and WC of Ti and a binder phase formed of an iron group metal such as Co and Ni. A thin film of 1 to 100 atoms is formed on these substrates. Since the thin film is formed under a high vacuum as described later, the thin film is free from foreign matter. Therefore, the surface state of the substrate appears on the thin film surface as it is.

[0025] The thin film is composed of at least one member selected from the group consisting of carbides, nitrides, carbonitrides, fluorine and oxygen of Group 4a elements of the periodic table. It is a force that becomes a thin film with excellent welding resistance. It can be confirmed by QCM described later that fluorine and oxygen can be coated on the cemented carbide or cermet. Fluorine is also present on the substrate surface, possibly as a fluorine compound bonded to fluorine atoms, fluorine molecules, and constituent materials of the base material.Oxygen is formed as an oxygen compound bonded to oxygen atoms, oxygen molecules, and the constituent materials of the base material. It is presumed that also exists on the substrate surface. Therefore, the fluorine or oxygen referred to in the present invention includes the substances presumed as described above.

[0026] It is preferable that this thin film is an extremely high-purity film. For example, in the conventional CVD method or the film formation by the PVD method, various impurities are contained in a film obtained with a low degree of vacuum (high pressure) at the time of film formation. On the other hand, since the thin film of the coated member of the present invention is formed in an extremely high vacuum as described later, it has a very high purity and substantially no film defects. Can be obtained. More specifically, when the thin film is analyzed by XPS (X-ray Photo-electron Spectroscopy), it is preferable that 0, H, Ar, and the like are not detected from the thin film. More specifically, (1) when the thin film has a layer composed of oxygen, at least one of H and Ar is not practically detected from the oxygen layer, and (2) the thin film is formed of a substance other than oxygen. In the case of having a non-oxygen layer composed of the following, it is desirable that at least one of the non-oxygen layer forces 0, H, and Ar is not substantially detected.

[0028] The thin film is preferably composed of at least one selected from the group consisting of carbides, nitrides, carbonitrides, fluorine and oxygen of Ti. This is because a thin film having more excellent wear resistance is obtained.

[0029] Furthermore, it is more preferable that the thin film be a carbide, nitride or carbonitride of Ti as a first layer on a cemented carbide or cermet and fluorine as an uppermost layer. By coating fluorine or a fluorine compound on the carbide, nitride or carbonitride of Ti, welding resistance can be further improved. At the same time, the coefficient of friction of the thin film can be reduced.

[0030] The surface roughness of the thin film is preferably Rmax (maximum height: JIS B 0601 1982) of 0.2 m or more and 1 m or less. For example, when this covering member is used for a cutting tool or the like, a smooth cutting edge can be obtained, and surface properties excellent in wear resistance and welding resistance can be obtained. The surface roughness of such a thin film is controlled by controlling the surface roughness of the base material before film formation to 0.2 μm or more and 1 μm or less by Rmax, and performing film formation by an atomic beam according to the method of the present invention described later. This can be achieved.

[0031] The sintered member of the present invention can be suitably used as a cutting tool. For example, Neut, Endmill

, Drills and the like. By using such a cutting tool, the wear resistance and welding resistance of the tool can be improved, and the tool life can be extended.

[0032] <Diamond member>

The present inventors have obtained the knowledge that by forming a very thin thin film composed of a predetermined component on the diamond surface, it is possible to suppress the direct contact with the work material and reduce the cutting resistance and complete the present invention member. I came to.

[0033] The diamond member of the present invention is a diamond member having a thin film formed on a diamond surface. This thin film is made of carbide, nitride, carbonitride, fluorine and A group power consisting of oxygen and oxygen. The thin film is characterized in that the thickness of the thin film is 1 to 100 atoms.

[0034] As the diamond used here, either polycrystal or single crystal can be used. In particular, it is preferable to use a single crystal diamond. Single crystal diamond can provide a smooth and sharp cutting edge with a grain boundary.

The thin film is composed of at least one force selected from the group consisting of carbides, nitrides, carbonitrides, fluorine and oxygen of Group 4a elements of the periodic table. When a diamond is used as the base material, the thin film made of these materials suppresses the reaction between the diamond and the iron-based material, and becomes a thin film having excellent wear resistance and welding resistance.

[0036] It can be confirmed by QCM described later that fluorine and oxygen can be coated on the diamond. Fluorine is also present on the substrate surface, possibly as a fluorine compound bonded to fluorine atoms, fluorine molecules, constituent materials of the base material, etc., and oxygen is an oxygen compound bonded to oxygen atoms, oxygen molecules, constituent materials of the base material, etc. Is presumed to be present on the substrate surface. Therefore, the fluorine or oxygen referred to in the present invention includes the substances presumed as described above.

[0037] It is preferable that this thin film be an extremely high-purity film. For example, in the conventional CVD method or the film formation by the PVD method, various impurities are contained in a film obtained with a low degree of vacuum (high pressure) at the time of film formation. On the other hand, since the thin film of the diamond member of the present invention is formed in an extremely high vacuum as described later, the purity is extremely high, and film defects are substantially V. , Strength can be obtained.

[0038] More specifically, when the thin film is analyzed by XPS (X-ray Photo-electron Spectroscopy), it is preferable that 0, H, Ar, and the like are not detected from the thin film. More specifically, (1) when the thin film has an oxygen layer composed of oxygen, at least one of H and Ar is not practically detected from the oxygen layer, and (2) the thin film is made of a substance other than oxygen. In the case of having a non-oxygen layer composed of the following, it is desirable that at least one of the non-oxygen layer forces 0, H, and Ar is not substantially detected.

[0039] Further, it is more preferable that the thin film be made of a carbide, nitride or carbonitride of Ti as the first layer on the diamond and fluorine or oxygen as the uppermost layer. By coating the carbide, nitride or carbonitride of Ti with fluorine or oxygen, the welding resistance can be further improved. Wear. At the same time, the coefficient of friction of the thin film can be reduced.

[0040] The surface roughness of the thin film is preferably Rmax (maximum height: JIS B 0601 1982) of 10 nm or less. By setting the surface roughness of the thin film to the specified value or less, a smooth cutting edge can be obtained, and a surface property excellent in wear resistance and welding resistance can be obtained. The surface roughness of such a thin film is controlled, for example, by controlling the surface roughness of the diamond before film formation to 1 Onm or less at Rmax, and if the film is formed by an atomic beam described later, the surface roughness of the diamond is substantially reduced. This can be achieved by maintaining the surface roughness of the thin film as it is.

[0041] The diamond member of the present invention can be suitably used as a cutting tool. For example, it can be used for cutting tools, end mills, drills, and the like. By using such a cutting tool, the wear resistance and welding resistance of the tool can be improved, and the tool life can be extended. In particular, it is suitable for cutting iron-based materials. By forming the above-described thin film on the diamond surface, direct contact between the diamond and the iron-based material can be suppressed, and wear of the diamond due to the reaction with the iron-based material can be reduced.

When the diamond member of the present invention is used as a cutting tool, the cutting method is not particularly limited, but it is preferable to perform cutting by an elliptical vibration cutting method. In the elliptical vibration cutting method, vibrations in the cutting direction and the chip outflow direction are superimposed on the cutting edge of a cutting tool by a piezoelectric element, and the cutting edge is moved in an elliptical vibration trajectory. This is a technology that presses against the work material to perform cutting. The elliptical vibration of the cutting blades allows the machining to be performed while lifting the chips, thereby reducing the cutting force and enabling high-precision machining. In particular, when cutting an iron-based material, the cutting edge does not always contact the work material, so that the reaction between the diamond and the work material can be further reduced, and the tool life can be extended.

In addition, the present inventors have conducted various studies on a technique for forming a film on a cemented carbide, cermet, or diamond surface, and have found that film formation using an atomic beam is suitable for forming an extremely thin film. Thus, the method of the present invention has been completed.

That is, according to the method for producing a coated member of the present invention, a raw material gas for a thin film is supplied into a vacuum chamber maintained at a predetermined degree of vacuum. Subsequently, the material gas is irradiated with a laser to generate an atomic beam having no charge. Then, the atomic beam is irradiated with cemented carbide, cermet or diamond. By irradiating the surface of the mond, a thin film having at least one force selected from the group consisting of carbides, nitrides, carbonitrides, fluorine and oxygen of the Group 4a element of the periodic table is formed.

[0045] Among the base materials used in the present invention, diamond is a stable material except that it reacts with a metal that forms oxygen or a carbide at a high temperature at which corrosion resistance is high. For the surface modification of diamond, ion beam irradiation can be considered. However, since diamond is an insulator, it is charged and it becomes difficult to irradiate with an ion beam, and it is difficult to maintain uniformity of surface modification. On the other hand, it was found that if the film was formed by irradiation with a neutral atomic beam, the irradiated atoms were uniformly bonded to the diamond surface and an extremely thin thin film could be formed with high precision.

In the method of the present invention, for example, when a pulse laser of carbon dioxide gas is irradiated on the raw material gas of the thin film, the raw material gas is turned into plasma, and then the plasma is electrically neutralized to become a neutral atomic beam. it is conceivable that. As will be described later in the embodiments, as a result of analyzing a gas in a vacuum with a mass spectrometer or the like, only neutral atoms are detected. The detailed reason why this gas becomes neutral is unclear, but it is presumed that electrons are transferred during the flight of the source gas ions, and the gas becomes neutral.

[0047] The source gas is appropriately selected according to the type of the thin film to be formed. For example, TiCl, N, CO

4 2 2

, SF, CF etc. can be used. In addition, the introduction of the source gas into the vacuum vessel is performed intermittently.

6 4

Is desirable. In that case, it is more preferable to match the timing of gas introduction with the timing of laser irradiation. Since the source gas is intermittently introduced, a decrease in the degree of vacuum can be suppressed, and a predetermined degree of vacuum can be easily obtained. Furthermore, by adjusting the laser irradiation timing to the introduction timing of the raw material gas, it is possible to more reliably generate an atomic beam. More specifically, it is preferable to supply the source gas in a pulse form from the nozzle, and irradiate the nozzle with a laser synchronized with the supply of the source gas to generate an atomic beam.

[0048] In order to generate an atomic beam, a laser is applied to the source gas. This laser is preferably a pulsed laser. Typically, a carbon dioxide laser can be used. More specifically, it is preferable to irradiate a pulsed carbon dioxide gas laser under conditions of about 5 to 7 J / pulse.

[0049] The atomic beam is applied to the base material with the same energy as the binding energy of the thin film constituent material. Irradiation is preferred. For example, assume that the energy of the atomic beam is 3 to 20 eV. By irradiating an atomic beam with such energy, the irradiated atoms can be deposited almost uniformly on the surface of the cemented carbide, cermet or diamond.

The atomic beam is generated by controlling the inside of the vacuum chamber to a predetermined vacuum state. The preferred pressure of the vacuum chamber is about ^{^{1 X 10- 4 ~1 X 10- 8}} Pa. More preferred pressure 1 X 10- ⁵ Pa, more preferably not more than 1 X 10- ⁶ Pa. When neutral atoms collide with other atoms, they return to the original molecule or form new conjugates. In order to prevent such collision, in the method of the present invention, the space in the vacuum chamber where the source gas is atomized is maintained at a high degree of vacuum, and a long mean free path is maintained. The high degree of vacuum not only maintains the surface cleanliness of the thin film and the substrate, but also reduces the amount of impurity elements in the thin film.

[0051] Furthermore, the temperature of the substrate is preferably from room temperature to 800 ° C! In this temperature range, the cemented carbide, cermet or diamond substrate is not damaged.

[0052] The thin film is formed by atoms that directly collide with the base material in the atomic beam generated as described above. At this time, specific neutral atoms constituting the atomic beam are selected and coated on the base material. Because this atom is neutral, it cannot accelerate electrically or bend its orbit. Therefore, the speed at which atoms collide with the substrate can be said to be the speed based on the energy of the atoms. Since the kinetic energies of the atomic beams in the same system are almost equal, light elements fly faster and heavy atoms fly at a slower speed.

[0053] In the vacuum chamber, atoms unnecessary for forming a thin film are also flying. Since the flight speed of an atom depends on the amount of an atom, it passes through the atom only when the atom necessary for forming a thin film arrives in synchronization with the pulse of the carbon dioxide laser, and does not pass through the rest of the time. By setting up the chives, atoms can be selected.

The invention's effect

[0054] The sintered member of the present invention has a very thin thin film in which atoms are aligned. Therefore, the surface roughness of the thin film is equivalent to the surface roughness of the substrate of cemented carbide or cermet, and the surface roughness of the thin film can be reduced by reducing the surface roughness of the substrate. . Therefore, it is possible to effectively suppress the welding of the work material and obtain a cutting tool with extremely high processing accuracy. [0055] The diamond member of the present invention can avoid or suppress direct contact between diamond and a work material by forming a very thin film of a specific type on the diamond surface. Therefore, when the member of the present invention is applied to a cutting tool, a ferrous material can be machined with diamond with high accuracy. Along with this, direct cutting of iron-based materials with diamond, which was impossible in the past, is now possible, and it can be expected that the cost and delivery time, especially for molds for optical parts, will be significantly improved.

According to the method of the present invention, since a thin film is formed under a high vacuum, the number of neutral atoms supplied to the substrate per unit time is smaller than that of the conventional method. Neutral atoms arriving at the substrate accumulate and transfer electrons on the substrate, and the thin film grows slowly. As a result, a uniform thin film having 1 to 100 atoms deposited therein is formed, and the thin film is not rounded at the tip of the base material. Therefore, it is possible to provide a cutting tool with less chipping at the tip of the cutting edge!

When a film is formed on a substrate surface by a general thin film forming technique such as a CVD method or a PVD method, it is difficult to obtain a sharp cutting edge. However, in the method of the present invention using atomic beam irradiation, An extremely thin film can be formed on the surface, and a sharp cutting edge can be obtained.

[0058] The method of the present invention using atomic beam irradiation has almost no various effects on the cutting edge of the substrate. For example, a good diamond member can be obtained by avoiding problems such as a decrease in the surface roughness of the diamond surface, generation of defects inside the diamond, and a decrease in the surface roughness of the thin film.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described.

[0060] <Example>

FIG. 1 shows a schematic cross-sectional view of the coated member of the present invention.

[0061] This covering member is composed of a substrate 1 and a thin film 2 coated on its surface. The substrate is a cemented carbide, cermet or diamond. For example, WC-based cemented carbide, TiC-based cermet, and single crystal diamond are used as the base material. The thin film 2 is formed of at least one of carbides, nitrides, carbonitrides, fluorine and oxygen of a Group 4a element in the periodic table, such as TiC, TiN, TiCN, or F or O. This thin film 2 is a constituent element of the thin film 2 The number of children should be 1 to 100. In FIG. 1, each of the circles constituting the thin film 2 represents a constituent atom, but in this figure, the size of the constituent atoms is exaggerated and is larger than the actual size.

Next, the configuration of the atomic beam generator used for manufacturing the coated member of the present invention will be described with reference to FIG.

[0063] In this apparatus, a molecular beam valve 101, a nozzle 102, a laser entrance window 103, a mirror 104, a base material holder 105, a quartz oscillator, are provided in a vacuum vessel 10 partitioned into a first area 10A and a third area 10C. It is equipped with a microbalance (QCM) 106 and a quadrupole mass spectrometer (QMS) 107. Each of the shift regions of the vacuum vessel 10 can be maintained at a predetermined vacuum by a turbo molecular pump (TMP). Further, in this apparatus, an X-ray analyzer 20 is provided in the vacuum vessel 10, and a transfer chamber 30 for transferring a sample between the vacuum vessel 10 and the X-ray analyzer 20 is also provided.

A molecular beam valve 101 for introducing a predetermined source gas is disposed on the end face of the vacuum vessel 10 in the first region 10A, and a nozzle 102 for irradiating an atomic beam to the inside of the vacuum vessel of the valve 101 is disposed. ing. An entrance window 103 for the laser beam L is also formed on the end face where the molecular beam valve 101 is provided. The laser beam L applied to the source gas enters the vacuum vessel 10 through the entrance window 103.

The laser L incident on the vacuum vessel 10 is reflected by a mirror 104 (made of Au) similarly arranged in the first area 10 A and irradiated near the nozzle 102. Since a raw material gas supplied through the molecular beam valve 101 is introduced into the vicinity of the nozzle 102, the raw material gas is irradiated with the laser L, thereby generating an atomic beam having no charge. The generated atom beam is irradiated from the nozzle 102 to the second and third regions 10B and 10C. The QCM 106 is arranged in the irradiation locus of the atomic beam in the first region 10A, and the irradiation amount (the number of atoms) per unit time and unit area of the atomic beam can be measured by the QCM 106.

[0066] Further, a base material holder 105 for setting the sample S is provided in the second region 10B of the vacuum container. The substrate holder 105 includes a heater, and can control the heating of the sample S set on the holder 105 to 800 ° C. at room temperature. Then, the generated atomic beam is applied to the sample S set in the substrate holder.

[0067] Further, on the irradiation locus of the atomic beam in the third region 10C, the energy of the atomic beam is displayed. QMS107 for measuring energy is provided. The energy of the atomic beam is measured by the QMS 107, and the energy of the laser is adjusted so that irradiation is performed at a predetermined energy.

On the other hand, the transfer chamber 30 is connected to the second area 10B. The transfer chamber 30 is provided with a pair of transfer rods 301 arranged in an orthogonal direction so that the sample can be transferred between the vacuum vessel 10 and the X-ray analyzer 20.

[0069] The X-ray analysis unit 20 is also connected to the transfer chamber 30. The X-ray analysis unit 20 has an X-ray source 201 and a DP-CMA (Double Path Cylindrical Mirror Analyzer) 202, and is configured to be able to analyze a sample by XPS (X-ray Photo-electron Spectroscopy). I have.

WC-Positive tip made of cemented carbide of 6 mass% Co and having model number TCGW110300 was prepared. The surface and rake face of this sample were further polished to a surface roughness of 0.2 μm at Rmax to obtain a substrate. Next, based on the same principle as the atomic beam generator shown in FIG. 2, the prepared substrate was attached to a substrate holder in an apparatus having three atomic beam generation forces S3. The raw material gas to be used is appropriately selected according to the type of the thin film to be formed. The source gas of this embodiment is TiCl

Four

, N, C〇, SF.

2 2 6

[0071] Next, adjust the vacuum vessel to a high vacuum of 1 X 10- ⁸ torr (about 1.33 X 10 ^"6 Pa), also setting the temperature of the substrate Holder to 100 ° C. Table 1 The material in the column of thin film material was formed on the substrate surface using the source gas described in the column of beam 1 to beam 3. At this time, the introduction of the source gas into the vacuum vessel was synchronized with the irradiation timing of the laser. The pulse laser was a carbon dioxide gas laser with a wavelength of 10.6 m, the energy of which was 7 J / pulse. Opening for microseconds, closing for 1 to 2 seconds, and repeating this opening and closing were performed, whereby the raw material gas introduced into the vacuum vessel was immediately turned into plasma, and then electrically neutralized and charged. Without it, it is possible to efficiently generate an atomic beam And reduced the degree of vacuum.

[Table 1] Specimen beam 1 Beam 2 Beam 3 Thin film material Film thickness Rmax Welding number Source gas Source gas Source gas Number of atoms (pieces)

1-1 TiCl ₄ N ₂ ― TiN 20 0.5 slightly

1-2 TiCl ₄ ― co ₂ TiC 50 0.5 a little

1-3 TiCl ₄ co ₂ TiCN 100 0.9 slightly

1-4 TiCl ₄ N ₂ SF ₆ TiN + F 50 + 10 0.7 None

1-5 TiCl ₄ co ₂ SF ₆ TiC + F 50 + 10 0.7 None

1-6 SF ₆ ― 1 F 20 0.5 None

1-7 TiCl ₄ C0 ₂ ― TiC 500 4 Yes

1-8 TiCl ₄ co ₂ ― TiC 1000 9 Yes

[0073] A chopper was arranged in front of the sample in accordance with the number of beams, so that only a specific atomic beam reached the substrate. The bigleaf was produced by providing a notch or the like at the outer periphery of the rotating disk. If the thin film is composed of two or more elements, arrange the same number of chambers in front of the sample as the number of beams, and adjust the rotation number of the chamber so that only the required atoms reach the sample at the same time. I made it. Because the element that reaches the sample is in the atomic state, the two elements combine on the substrate to form a compound. In Table 1, Sample Nos. 1-4 coated ΉΝ with TiCl and N as raw materials using Beams 1 and 2, and Sample Nos. 1-5 used Beams 1 and 2

4 2

After coating TiC using TiCl and CO as raw materials, the SF of beam 3 is

The material is further coated with fluorine as a material. Sample Nos. 1-6 are samples coated with fluorine only. When SF is used as a raw material, fluorine or the like can be used without using

6

A thin film is formed.

[0074] The covering member produced in this manner was taken out of a vacuum vessel, and its performance was evaluated.

First, the film thickness was calculated by the following method based on various data during and after the preparation of the thin film. The thin film material was analyzed by XRD (X-ray diffraction) and XPS at the X-ray analysis unit. As a result of analysis by XPS, 0, H, and Ar were not observed in Sample Nos. Ll to l-8. The film thickness was checked using QCM. QCM is a device that measures the resonance frequency. When a substance is adsorbed on the surface of the crystal unit, the weight of the crystal unit increases and the resonance frequency changes. QCM is a means to calculate the weight increase of a crystal unit by utilizing the fact that the change in the resonance frequency of the crystal unit and the change in the weight are in a proportional relationship. The increased weight of the crystal oscillator obtained by QCM and the material strength of the thin film specified by XRD are known, and the number of atoms in the thickness direction can be obtained by calculation. In Table 1, the sample numbers 1-4 and 1-5 have the film thicknesses of TiN and TiC. This shows that each of the atoms is 50 atoms, and that there is an additional 10 atoms of fluorine coated thereon.

Further, when the surface roughness of the thin film surface was measured, it was confirmed as shown in Table 1 that all of the samples No. 1-1 to 1-6 had an Rmax of 1 μm or less.

Next, the performance as a tool was evaluated. The cutting conditions were as follows: Ato Si alloy was used as a work material, and cutting was performed for 10 minutes using an ultra-precision lathe under cutting conditions of a cutting speed of 100 m / min, a depth of cut of 0.1 mm and a feed of 0.3 mm. The performance evaluation was performed by examining the situation where the work material welded to the tool. As a result, Sample Nos. 1 to 3 had slight traces of welded work material. Sample numbers 1-4, 1-5 and 1-6 proved that the uppermost layer was fluorine and thus had high welding resistance because welding was not performed. In sample Nos. 7 and 1-8, the cutting edge with the thicker thin film was rounded and the work material was welded.

Next, using the same principle as the atomic beam generator shown in Fig. 2, a substance shown in Table 2 was attached to the surface of single-crystal diamond using a device with three atomic beam generators to form a thin film. The sample used was a single-crystal diamond processed to have a radius of curvature of 10 nm or less at the edge and a surface roughness Rmax force of nm or less. The deposition conditions were as follows: 1 x 10 " ⁹ torr (approximately 133 x 10" ⁹ Pa) in the vacuum vessel, and then various source gases were intermittently introduced from the molecular beam valve, and the wavelength was adjusted in accordance with the gas introduction timing. Irradiate a 10.6 μm carbon dioxide laser with 7JZ pulses. The introduction of the raw material gas was performed by opening the molecular beam valve made of piezoelectric ceramic for about 100 microseconds, closing it for 1-2 seconds, and repeating this opening and closing. By doing so, the raw material gas introduced into the vacuum vessel is immediately converted into plasma, and then it is possible to efficiently generate an atomic beam that is electrically neutralized and has no charge, thereby suppressing a reduction in the degree of vacuum. Was. The surface of the single crystal diamond was irradiated with an atomic beam generated by irradiating the source gas with a laser to form a thin film.

[0078] [Table 2] Soot max: nmnm

,

, O) 〇

,

Less ο々, 〇〇

There are a few

There is shaving,

When a compound gas was used as the source gas, a chopper was arranged in front of the sample in accordance with the number of beams, so that only a specific atomic beam reached the base material. The chopper was manufactured by providing a notch or the like at the outer periphery of the rotating disk. If the thin film is composed of two or more elements, the attached atoms are identified by QMS, The atoms were allowed to reach the sample simultaneously. Since the elements that reach the sample are in the atomic state, the two elements combine on the substrate to form a compound. When the energy of the atomic beam was measured by the time-flight method, it was 5 to 10 eV.

[0080] Sample numbers 2-4 and 2-5 in Table 2 were obtained by first coating TiN and TiC and then further coating fluorine using CF of beam 3 as a raw material. Sample numbers 2-6 and 2-7 are

Four

This is a sample coated only with fluorine. Coating only fluorine using CF or SF as raw material

4 6

In this case, the chives may not be used.

[0081] The type of the adhered substance was analyzed by XRD (X-ray diffraction) and XPS, and the amount of the adhered substance was examined using QCM. As a result of analysis using XPS, 0, H, and Ar were not observed in sample Nos. 2-1, 2-2, 2-3, 2-4, 2-5, 2-6, and 2-7. Helped. In addition, QCM is a mass measurement method that uses the fact that the frequency changes when a substance is adsorbed on the surface of the crystal unit, and that the change in frequency is proportional to the mass. Mass measurement result by QCM Force Unit time ・ The amount of irradiation per unit area is determined, and the atomic radius is determined by the substance. Desired. Furthermore, when the surface roughness of the thin film surface was evaluated by Rmax (maximum height: JIS B 0601 1982), it was confirmed that all samples had an Rmax of 10 nm or less.

Next, a SUS440C ball having a radius of 5 mm was pressed against the surface of the sample on which the thin film was formed at 5 N, a friction test was performed at a speed of 2 mm / sec, and a friction coefficient was measured. Furthermore, a diamond tool with a nose radius of 0.8 mm was fabricated using the obtained sample, and ultra-precision cutting of alloy tool steel SKT4 with a Vickers hardness of 450 was performed at a cutting speed of 50 m / min, a cutting depth of 50 m, and a feed of 10 m. Cutting was performed for 5 minutes using a lathe. Then, the surface roughness of the work material, the radius of curvature of the edge portion after atom attachment, and the state of the cutting edge after steel cutting were examined. For comparison, a friction test and a cutting test were similarly performed on a single crystal diamond without a thin film. Table 2 also shows the above test results along with the identification results of the attached substances and the thickness of the thin film.

As is clear from Table 2, abrasion was substantially observed in each of the samples in which a thin film was formed on the surface of a single crystal diamond and the thickness of the thin film was 1 to 100 in terms of the number of atoms constituting the thin film. It can be seen that the reaction with the work material due to the coating of the thin film was suppressed. In particular, fluorine It can be seen that a sample having a strong thin film on its surface has excellent welding resistance.

Next, a diamond tool with a nose radius of 0.8 mm was prepared using a sample in which a thin film was formed on the surface of a single crystal diamond, and SUS420J2 with a Rockwell hardness of HRC40 was cut at a cutting speed of 500 mm / min, a depth of cut of 5 μm, and a pick feed of 5 μm. Cutting was performed using an ultra-precision lathe under dry conditions of 2 m and a cutting distance of 2 m. More specifically, a cutting test was performed by cutting 2 mm in length in the cutting direction and repeating this cutting 1000 times sequentially in the feed direction orthogonal to the cutting direction. Here, in addition to sample No. 2-7 (adhered substance F) in Table 2 above, sample No. 2-9 was prepared in which the adhering substance of the thin film was 0 (oxygen), and each sample was tested. Was served. The source gases of sample No. 2-9 were beam 1: oxygen, beam 2: none, and beam 3: none. The thin film of sample No. 2-9 was analyzed by XPS, and the maximum flank wear width of each sample after cutting was determined. As a result of XPS analysis, neither H nor Ar was detected in the thin film of Sample No. 2-9. For comparison, a single crystal diamond without a thin film (sample No. 2-8 in Table 2) was also subjected to a cutting test.

[0085] The maximum flank wear width is shown in the graph of Fig. 3, and the micrograph of the cutting edge of each sample after the cutting test is shown in Fig. 4. As is clear from this graph, Sample No. 2-7 (F) and Sample No. 2-9 (0) with the thin film were both compared to Sample No. 2-8 (Normal) without the thin film. It can be seen that the maximum flank wear width is small. In addition, as can be seen from the photomicroscopic power, the sample No. 2-8 (Normal) without a thin film showed a large abrasion on the flank as shown in FIG. ) And sample No. 2-9 (0) shown in Fig. 4 (B) show that the flank wear is small.

Industrial applicability

[0086] The present invention can be suitably used for a cutting tool. In particular, since tools with little welding can be provided, they can be used as cutting tools in the field of precision machining with small cutting and feed. Further, it can be suitably used for a steel cutting tool.

Brief Description of Drawings

FIG. 1 is a schematic sectional view of a coated member of the present invention.

FIG. 2 is a schematic view of an atomic beam generator used in the method for producing a coated member of the present invention. FIG. 3 is a graph showing the maximum flank wear width of each sample after a cutting test.

[Figure 4] Photomicrographs of the cutting edge of each sample after the cutting test are shown, (A) without a thin film, (B) with a thin film formed with oxygen, and (C) with a thin film formed with fluorine. Things.

Explanation of symbols

1 Substrate 2 Thin film

10 Vacuum container 10A First area 10B Second area 10C Third area

101 molecular beam valve 102 nozzle 103 entrance window 104 mirror

105 Base material Honoreda 106 QCM 107 QMS

20 X-ray analyzer 201 X-ray source 202 DP-CMA

30 Transfer chamber 301 Transfer rod

Claims

The scope of the claims

[1] A coated member having a thin film formed on a substrate surface,

The substrate is made of diamond, cemented carbide or cermet,

The thin film is constituted by at least one kind of force selected from the group consisting of carbides, nitrides, carbonitrides, fluorine and oxygen of group 4a elements in the periodic table,

The coating material is characterized in that the thickness of the thin film is 1100 atoms in the number of atoms constituting the thin film.

2. The thin film according to claim 1, wherein the thin film has at least one kind of force selected from a group force consisting of carbides, nitrides, carbonitrides, fluorine, and oxygen of Ti. Covering member.

3. The thin film according to claim 1, wherein the thin film includes a first layer on a substrate made of carbide, nitride or carbonitride of Ti, and an uppermost layer made of fluorine or oxygen. 14. The covering member according to any one of the above.

[4] the thin film has a layer composed of oxygen,

2. The covering member according to claim 1, wherein at least one type of H Ar is not substantially detected in the oxygen layer when analyzed by XPS.

[5] the thin film has a layer composed of a material other than oxygen,

2. The covering member according to claim 1, wherein at least one kind of 0 H Ar is not substantially detected in the non-oxygen layer when analyzed by XPS.

[6] The base material is diamond,

2. The coating member according to claim 1, wherein the surface roughness of the thin film is 10 or less in Rmax.

[7] The base material is a cemented carbide or cermet,

2. The covering member according to claim 1, wherein the surface roughness of the thin film is not less than 0.2 μm and not more than 1 μm in Rmax.

[8] The coated member according to claim 1, wherein the base material is diamond, and the diamond is a single crystal.

[9] Supply the raw material gas of the thin film into a vacuum chamber maintained at a predetermined degree of vacuum, This raw material gas is irradiated with a laser to generate an atomic beam having no charge, and the atomic beam is irradiated onto a diamond, cemented carbide or cermet base material, thereby forming carbides and nitrides of Group 4a elements of the periodic table. A method for producing a covering member, comprising: forming a thin film composed of at least one member selected from the group consisting of materials, carbonitrides, fluorine, and oxygen.

[10] Supply of raw material gas into the vacuum chamber is performed intermittently.

The production of a coated member according to claim 9, wherein a laser beam synchronized with the supply of the source gas is applied to the source gas supplied into the vacuum chamber to generate an atom beam having no charge. Method.

[11] The method according to claim 9 or 10, wherein the energy of the atomic beam is 3 to 20 eV.

[12] The claims ninth Koma other, characterized in that a ^{^{1 X 10- 4 ~1 X 10- 8}} Pa the pressure in the vacuum chamber producing method of the covering member according to Section 10.