WO2022230363A1 - 切削工具及びその製造方法 - Google Patents
切削工具及びその製造方法 Download PDFInfo
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- WO2022230363A1 WO2022230363A1 PCT/JP2022/009464 JP2022009464W WO2022230363A1 WO 2022230363 A1 WO2022230363 A1 WO 2022230363A1 JP 2022009464 W JP2022009464 W JP 2022009464W WO 2022230363 A1 WO2022230363 A1 WO 2022230363A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
- B23B27/148—Composition of the cutting inserts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
- B23P15/28—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass cutting tools
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- C23C16/403—Oxides of aluminium, magnesium or beryllium
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/048—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with layers graded in composition or physical properties
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
- C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2226/00—Materials of tools or workpieces not comprising a metal
- B23B2226/12—Boron nitride
- B23B2226/125—Boron nitride cubic [CBN]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2226/00—Materials of tools or workpieces not comprising a metal
- B23B2226/27—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2226/00—Materials of tools or workpieces not comprising a metal
- B23B2226/72—Silicon carbide
Definitions
- US Pat. No. 5,300,001 discloses a nanocomposite coating comprising a nanocrystalline layer of TiC x N 1-x and a second phase of amorphous SiC x N y produced by thermal CVD.
- Patent Document 2 discloses at least a first nanocrystalline phase made of cubic titanium oxycarbonitride produced by a thermal CVD method and a second amorphous phase made of silicon oxycarbonitride or silicon oxycarbide.
- One nanocomposite layer is disclosed.
- Non-Patent Document 1 discloses a TiSiCN film having a nanocomposite structure formed by the PVD method.
- the cutting tools of the present disclosure are A cutting tool comprising a substrate and a coating disposed on the substrate,
- the coating comprises a hard particle layer made of hard particles,
- the hard particles have a multilayer structure in which first unit layers and second unit layers are alternately laminated,
- the first unit layer is made of a first compound having a cubic crystal structure
- the second unit layer is made of a second compound having a cubic crystal structure,
- Each of the first compound and the second compound is one or more metal elements selected from the group consisting of Group 4 elements, Group 5 elements, and Group 6 elements of the periodic table; Silicon and and one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen,
- the percentage of the number of silicon atoms relative to the total number of atoms of the metal element and silicon in the first unit layer is the number of silicon atoms relative to the total number of atoms of the metal element and silicon in the second unit layer.
- the manufacturing method of the cutting tool of the present disclosure comprises: A method for manufacturing the above cutting tool, a first step of preparing a substrate; A second step of forming a coating on the base material to obtain a cutting tool,
- the second step includes a step 2a of forming a hard particle layer made of hard particles by a CVD method,
- the 2a step includes a 2a-1 step of ejecting the first raw material gas, the second raw material gas, and the third raw material gas toward the surface of the base material
- the first raw material gas contains one or more elements selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table
- the second source gas is SiCl 4
- the third source gas contains one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen,
- the first raw material gas is jetted from a plurality of first injection holes provided in a nozzle
- the second raw material gas is jetted from a plurality of second injection holes provided in the nozzle
- FIG. 1 is a schematic diagram showing an example of a cross section of a cutting tool according to Embodiment 1.
- FIG. FIG. 2 is a schematic diagram showing another example of the cross section of the cutting tool according to Embodiment 1.
- FIG. 3 is a schematic diagram showing another example of the cross section of the cutting tool according to Embodiment 1.
- FIG. 4 is a schematic diagram showing another example of the cross section of the cutting tool according to Embodiment 1.
- FIG. 5 is a bright field scanning electron microscope (BF-SEM) image of a cross section of the hard phase particle layer of the cutting tool according to Embodiment 1.
- FIG. FIG. 6 is an electron diffraction image taken within the area A shown in FIG.
- BF-SEM bright field scanning electron microscope
- FIG. 7 shows the percentage ⁇ A Si / (A Si +A M ) ⁇ 100.
- FIG. 8 is a Fourier transform image obtained by Fourier transforming the area A shown in FIG.
- FIG. 9 is a graph showing the intensity profile within the rectangular frame of the Fourier transform image of FIG.
- FIG. 10 is a schematic cross-sectional view of an example of a CVD apparatus used for manufacturing a cutting tool according to Embodiment 2.
- the cutting tool of the present disclosure is A cutting tool comprising a substrate and a coating disposed on the substrate,
- the coating comprises a hard particle layer made of hard particles,
- the hard particles have a multilayer structure in which first unit layers and second unit layers are alternately laminated,
- the first unit layer is made of a first compound having a cubic crystal structure
- the second unit layer is made of a second compound having a cubic crystal structure,
- Each of the first compound and the second compound is one or more metal elements selected from the group consisting of Group 4 elements, Group 5 elements, and Group 6 elements of the periodic table; Silicon and and one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen,
- the percentage of the number of silicon atoms relative to the total number of atoms of the metal element and silicon in the first unit layer is the number of silicon atoms relative to the total number of atoms of the metal element and silicon in the second unit layer.
- the first unit layer and the second unit layer preferably have the same crystal orientation. According to this, it is possible to minimize the interfacial energy, and the hardness is less likely to decrease even when exposed to a high-temperature environment.
- the percentage of the number of silicon atoms with respect to the total number of atoms of the metal element and the silicon is 0.5% or more and 10% or less. is preferred. According to this, the thermal crack resistance of the coating and the adhesion between the hard particle layer and the adjacent layer are improved in a well-balanced manner.
- the hard particle layer has a thickness of 3 ⁇ m or more and 15 ⁇ m or less;
- the thickness of the coating is preferably 3 ⁇ m or more and 30 ⁇ m or less.
- the wear resistance and chipping resistance of the coating are improved in a well-balanced manner.
- the coating comprises an underlayer disposed between the substrate and the hard particle layer;
- the underlayer is made of a third compound,
- the third compound is one or more elements selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements of the periodic table and aluminum; and one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen.
- the adhesion between the coating and the substrate is improved, and the wear resistance is also improved.
- the coating includes an underlying layer disposed immediately above the substrate;
- the underlying layer is preferably made of at least one selected from the group consisting of a TiN layer, a TiC layer, a TiCN layer, a TiBN layer and an Al2O3 layer.
- the adhesion between the substrate and the coating can be enhanced. Also, by using an Al 2 O 3 layer as the underlayer, the oxidation resistance of the coating can be enhanced.
- the coating comprises a surface layer disposed on its outermost surface,
- the surface layer is made of a fourth compound,
- the fourth compound is one or more elements selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements of the periodic table and aluminum; and one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen.
- the thermal crack resistance and wear resistance of the coating are improved.
- the coating preferably has an intermediate layer arranged between the underlayer and the hard particles. According to this, the abrasion resistance of the coating is improved.
- the method for manufacturing a cutting tool of the present disclosure includes: A method for manufacturing the above cutting tool, a first step of preparing a substrate; A second step of forming a coating on the base material to obtain a cutting tool, The second step includes a step 2a of forming a hard particle layer made of hard particles by a CVD method, The 2a step includes a 2a-1 step of ejecting the first raw material gas, the second raw material gas, and the third raw material gas toward the surface of the base material,
- the first raw material gas contains one or more elements selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table, the second source gas is SiCl 4 ,
- the third source gas contains one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen,
- the first raw material gas is jetted from a plurality of first injection holes provided in a nozzle,
- the second raw material gas is jetted from a plurality of second injection holes provided in the nozzle,
- a compound or the like when represented by a chemical formula, it shall include any conventionally known atomic ratio unless the atomic ratio is particularly limited, and should not necessarily be limited only to those within the stoichiometric range.
- TiSiCN the ratio of the number of atoms constituting TiSiCN includes all conventionally known atomic ratios.
- any one numerical value described in the lower limit and any one numerical value described in the upper limit shall also be disclosed.
- a1 or more, b1 or more, c1 or more is described as the lower limit, and a2 or less, b2 or less, or c2 or less is described as the upper limit, a1 or more and a2 or less, a1 or more and b2 or less, a1 or more and c2 or less, b1 to a2, b1 to b2, b1 to c2, c1 to a2, c1 to b2, and c1 to c2.
- a cutting tool of one embodiment of the present disclosure (hereinafter also referred to as "this embodiment") is A cutting tool comprising a substrate and a coating disposed on the substrate,
- the coating comprises a hard particle layer made of hard particles,
- the hard particles comprise a multilayer structure in which first unit layers and second unit layers are alternately laminated,
- the first unit layer is made of a first compound having a cubic crystal structure
- the second unit layer is made of a second compound having a cubic crystal structure,
- Each of the first compound and the second compound is one or more metal elements selected from the group consisting of Group 4 elements, Group 5 elements, and Group 6 elements of the periodic table; Silicon and and one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen,
- the percentage of the number of atoms of the silicon relative to the total number of atoms of the metal element and the silicon in the first unit layer is the number of atoms of the silicon relative to the total number of atoms of the metal element and the silicon in the second unit layer.
- Group 4 elements of the periodic table include titanium (Ti), zirconium (Zr) and hafnium (Hf), and Group 5 elements include vanadium (V), niobium (Nb) and tantalum (Ta). Group 6 elements include chromium (Cr), molybdenum (Mo) and tungsten (W).
- the cutting tool of this embodiment can have a long tool life even in milling of high-hardness heat-resistant stainless steel. The reason for this is not clear, but is presumed to be as described in (i) to (iii) below.
- the coating has a hard particle layer made of hard particles.
- the hard particle layer can have a region of grain structure in its thickness direction. This improves the toughness of the hard particle layer, and even if thermal cracks occur on the surface of the coating due to cutting, the cracks are effectively suppressed from progressing to the base material.
- the coating contains layers other than the hard particle layer, the difference in crystallinity between the hard particle layer and the other layers can be reduced. Propagation of cracks at the interface is suppressed, and film peeling is suppressed. Therefore, the cutting tool can have a long tool life.
- the hard particles include a multilayer structure in which first unit layers and second unit layers having different compositions are alternately laminated. According to this, even if strain occurs in the hard particles and cracks are generated on the surface of the coating due to cutting, the propagation of the cracks to the base material is effectively suppressed. Moreover, the hardness of the hard particles and the hard particle layer is increased, and the wear resistance of the cutting tool is improved. Also, the cutting tool can thus have a long tool life.
- each of the first compound and the second compound has a cubic crystal structure; one or more metal elements selected from the group consisting of Group 4 elements, Group 5 elements, and Group 6 elements of the periodic table; Silicon and and one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen.
- the above first compound and second compound have high hardness. Therefore, the hard particle layer containing the first compound and the second compound has high hardness and excellent wear resistance. Therefore, the cutting tool can have a long tool life.
- the cutting tool 1 of this embodiment includes a substrate 10 and a coating 15 placed on the substrate 10 .
- FIG. 1 shows the case where the coating 15 is composed only of the hard particle layer 11 .
- the film 15 preferably covers at least a portion of the substrate involved in cutting, and more preferably covers the entire surface of the substrate.
- the portion involved in cutting of the substrate means a region within 500 ⁇ m from the ridgeline of the cutting edge on the surface of the substrate. It would not depart from the scope of the present disclosure if portions of the substrate were not coated with this coating or if the composition of the coating varied.
- Cutting tools of the present disclosure include, for example, drills, end mills (e.g., ball end mills), indexable cutting inserts for drills, indexable cutting inserts for end mills, indexable cutting inserts for milling, indexable cutting inserts for turning. It can be a cutting tip, metal saw, gear cutting tool, reamer, tap, or the like.
- the substrate 10 includes a rake face and a flank, and any conventionally known substrate of this type can be used.
- cemented carbide for example, WC-based cemented carbide containing tungsten carbide and cobalt, the cemented carbide may contain carbonitrides such as Ti, Ta, Nb), cermet (TiC, TiN, TiCN etc.), high speed steel, ceramics (titanium carbide, silicon carbide, silicon nitride, aluminum nitride, aluminum oxide, etc.), cubic boron nitride sintered body or diamond sintered body is preferred.
- a substrate made of a cemented carbide containing tungsten carbide and cobalt, in which the content of cobalt in the cemented carbide is 6% by mass or more and 11% by mass or less, is preferable. According to this, it has an excellent balance of hardness and strength at high temperatures, and has excellent properties as a base material for cutting tools for the above applications.
- a WC-based cemented carbide When a WC-based cemented carbide is used as the substrate, its structure may contain free carbon, an abnormal layer called ⁇ phase or ⁇ phase, and the like.
- the base material may have its surface modified.
- a ⁇ -free layer may be formed on the surface, and in the case of cermet, a hardened surface layer may be formed.
- the substrate exhibits the desired effect even if its surface has been modified.
- the substrate may or may not have a chip breaker.
- the shape of the cutting edge ridgeline is sharp edge (the ridge where the rake face and the flank face intersect), honing (sharp edge with radius), negative land (chamfering), or a combination of honing and negative land. Any of them, such as a combination thereof, can be employed.
- the coating of this embodiment includes a hard particle layer.
- the coating of this embodiment may contain other layers as long as it contains the hard particle layer.
- the coating 35 can include the surface layer 13 disposed on the hard particle layer 11 in addition to the hard particle layer 11 and the base layer 12 .
- the coating 45 includes the hard particle layer 11, the base layer 12, the surface layer 13, as well as the intermediate layer 14 disposed between the base layer 12 and the hard particle layer 11.
- hard particle layer Details of the hard particle layer, base layer, intermediate layer and surface layer will be described later.
- the thickness of the coating in this embodiment is preferably 3 ⁇ m or more and 30 ⁇ m or less.
- the thickness of the coating means the thickness of the entire coating.
- the thickness of the entire coating is 3 ⁇ m or more, excellent abrasion resistance can be obtained.
- the thickness of the entire coating is 30 ⁇ m or less, it is possible to suppress the occurrence of peeling or breakage of the coating when a large stress is applied between the coating and the substrate during cutting.
- the lower limit of the thickness of the entire coating is more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more.
- the upper limit of the thickness of the entire coating is more preferably 25 ⁇ m or less, still more preferably 20 ⁇ m or less, from the viewpoint of suppressing the occurrence of peeling or breakage of the coating.
- the thickness of the entire coating is more preferably 5 ⁇ m or more and 25 ⁇ m or less, and still more preferably 10 ⁇ m or more and 20 ⁇ m or less.
- the thickness of the coating is measured, for example, by obtaining a cross-sectional sample parallel to the normal direction of the surface of the base material and observing this sample with a scanning transmission electron microscope (STEM).
- the cross-sectional sample is a thin section sample processed using an ion slicer or the like.
- Scanning transmission electron microscopes include JEM-2100F (trademark) manufactured by JEOL Ltd., for example.
- the measurement conditions are an acceleration voltage of 200 kV and a current of 0.3 nA.
- the thickness means the average thickness.
- the observation magnification of the cross-sectional sample is set to 10000 times, and a rectangular measurement field of (100 ⁇ m in the direction parallel to the substrate surface) ⁇ (distance including the entire thickness of the coating) is set in the electron microscope image, Ten thickness widths are measured in the field of view, and the average value is defined as "thickness”.
- the thickness (average thickness) of each layer described below is similarly measured and calculated.
- the hard particle layer of the present embodiment is composed of hard particles, and the hard particles include a multilayer structure in which first unit layers and second unit layers are alternately laminated.
- the hard particle layer of the present embodiment exhibits the effects of the present disclosure even if it contains components other than hard particles as inevitable impurities, such as amorphous phases and intermetallic compounds (such as TiSi 2 and Co 2 Si). without departing from the scope of this disclosure in any way.
- the thickness of the hard particle layer of the present embodiment is preferably 3 ⁇ m or more and 15 ⁇ m or less.
- the thickness of the hard particle layer is 3 ⁇ m or more, it can have excellent wear resistance.
- the thickness of the hard particle layer is 15 ⁇ m or less, it is possible to suppress peeling or breakage of the coating when a large stress is applied between the coating and the substrate during cutting.
- the lower limit of the thickness of the hard particle layer is more preferably 4 ⁇ m or more, and even more preferably 5 ⁇ m or more.
- the upper limit of the thickness of the hard particle layer is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, from the viewpoint of suppressing the occurrence of peeling or breakage of the coating.
- the thickness of the hard particle layer is more preferably 4 ⁇ m or more and 15 ⁇ m or less, and even more preferably 5 ⁇ m or more and 10 ⁇ m or less.
- the first unit layer is made of a first compound having a cubic crystal structure.
- the second unit layer is made of a second compound having a cubic crystal structure.
- both excellent wear resistance and high toughness can be achieved.
- the fact that the first compound and the second compound have a cubic crystal structure can be confirmed by pattern analysis of electron beam diffraction using a selected area.
- Each of the first compound and the second compound is one or more metal elements selected from the group consisting of Group 4 elements, Group 5 elements, and Group 6 elements of the periodic table; Silicon and and one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen.
- the composition of the first compound is different from the composition of the second compound. More specifically, the percentage of the number of silicon atoms with respect to the total number of metal elements and silicon atoms in the first compound is different from the percentage of the number of silicon atoms with respect to the total number of metal elements and silicon atoms in the second compound. .
- first compound and the second compound of the present embodiment contain unavoidable impurities, they do not deviate from the scope of the present disclosure as long as the effects of the present disclosure are exhibited.
- Each of the first compound and the second compound is, for example, TiSiC, TiSiN, TiSiCN, TiSiNO, TiSiCNO, TiSiBN, TiSiBNO, TiSiCBN, ZrSiC, ZrSiO 2 , HfSiC, HfSiN, TiCrSiN, TiZrSiN, CrSiN, VSiN, N, ZrSiCN, ZrSiCNO, ZrSiN, NbSiC, NbSiN, NbSiCN and the like can be mentioned.
- the first compound and the second compound contain unavoidable impurities, they do not depart from the scope of the present disclosure.
- the hard particles include a multilayer structure in which the first unit layers and the second unit layers are alternately laminated.
- a cutting tool is cut out with a diamond wire along the normal line of the base material to expose the cross section of the hard particle layer.
- Focused ion beam processing (hereinafter also referred to as “FIB processing”) is performed on the exposed cross section to make the cross section into a mirror surface state.
- FIG. 5 is a diagram showing an example of a BF-STEM image of one hard particle in the cutting tool of this embodiment.
- (A3) Set a measurement area (size: 100 nm ⁇ 100 nm) so as to include an area in which 10 or more layers shown in white and 10 or more layers shown in black are laminated in the BF-STEM image. .
- a square area surrounded by a white frame corresponds to the measurement area.
- the layers shown in black are regions with a high silicon content, and the layers shown in white are regions with a low silicon content.
- a layer shown in white hereinafter also referred to as a “white layer” and a layer shown in black (hereinafter also referred to as a “black layer”) in the measurement region in the BF-STEM image.
- FIG. 6 shows an electron diffraction image taken within the area A shown in FIG. In FIG. 5, the stacking direction is indicated by a white arrow.
- line analysis is performed along the stacking direction by SEM-attached EDX (Energy Dispersive X-ray Spectroscopy) to measure the composition. .
- the beam diameter for line analysis is 0.5 nm or less, the scan interval is 0.5 nm, and the length of line analysis is 50 nm.
- (a1) from the group consisting of one or more metal elements selected from the group consisting of group 4 elements, group 5 elements, and group 6 elements of the periodic table, silicon, and carbon, nitrogen, boron, and oxygen in the measurement region and one or more selected elements.
- the X axis is the distance from the measurement start point
- the Y axis is the percentage of the number of silicon atoms A Si with respect to the sum of the number of metal element atoms AM and the number of silicon atoms A Si .
- FIG. 7 shows the percentage ⁇ A Si /(A Si +A M ) of the number of silicon atoms A Si with respect to the sum of the number of metal element (titanium) atoms A M and the number of silicon atoms A Si along the direction of the arrow. ⁇ 100 change.
- the X-axis indicates the distance along the direction of the arrow from the measurement starting point, and the Y-axis indicates ⁇ A Si /(A Si +A M ) ⁇ 100.
- the average of ⁇ A Si /(A Si +A M ) ⁇ 100 in the measurement area is indicated by dotted line L1.
- the hard particles shown in FIG. 5 include a multilayer structure in which the first unit layers and the second unit layers are alternately laminated.
- the hard particles include a multilayer structure in which the first unit layers and second unit layers are alternately laminated.
- ⁇ A Si / (A Si + A M ) ⁇ x A region where 100 is large is also referred to as a “first unit layer”
- ⁇ A Si /(A Si +A M ) ⁇ ⁇ 100 than the average of ⁇ A Si /(A Si +A M ) ⁇ ⁇ 100 small region is also referred to as a “second unit layer”.
- the percentage of the number of silicon atoms A Si to the sum of the number of metal element atoms A M and the number of silicon atoms A Si ⁇ A Si /(A Si +A M ) ⁇ 100 is preferably 0.5% or more and 10% or less. According to this, the thermal crack resistance of the hard particle layer and the adhesion between the hard particle layer and the adjacent layer are improved in a well-balanced manner.
- the lower limit of ⁇ A Si /(A Si +A M ) ⁇ 100 in each of the first unit layer and the second unit layer is preferably 0.5% or more, preferably 0.7% or more, and 1.0% or more. is preferred, and 1.2% or more is preferred.
- the upper limit of ⁇ A Si /(A Si +A M ) ⁇ 100 in each of the first unit layer and the second unit layer is preferably 10.0% or less, preferably 8.0% or less, and 7.2% or less. is preferred, 7% or less is preferred, and 5% or less is preferred.
- ⁇ A Si /(A Si +A M ) ⁇ 100 in each of the first unit layer and the second unit layer is preferably 0.5% or more and 8.0% or less, and 0.5% or more and 7.2% or less. is preferred, 0.7% or more and 7% or less is preferred, and 1.0% or more and 5.0% or less is preferred.
- the lower limit of the percentage ⁇ A Si /(A Si +A M ) ⁇ 100 of the number of silicon atoms A Si with respect to the sum of the number of metal element atoms A M and the number of silicon atoms A Si in the first unit layer is 1% or more is preferable, 1.5% or more is preferable, 2.0% or more is preferable, 5.3% or more is preferable, 6.0% or more is preferable.
- the upper limit of the percentage ⁇ A Si /(A Si +A M ) ⁇ 100 of the number of silicon atoms A Si with respect to the sum of the number of metal element atoms A M and the number of silicon atoms A Si in the first unit layer is 10.0% or less is preferable, 9.0% or less is preferable, and 8.0% or less is preferable.
- the percentage ⁇ A Si /(A Si +A M ) ⁇ 100 of the number of silicon atoms A Si with respect to the sum of the number of metal element atoms A M and the number A Si of silicon atoms in the first unit layer is the heat resistance.
- the first unit layer has a structure in which the composition changes in the thickness direction, the above ⁇ A Si /(A Si +A M ) ⁇ 100 means the average value in the first unit layer.
- the lower limit of the percentage ⁇ A Si /(A Si +A M ) ⁇ 100 of the number of silicon atoms A Si with respect to the sum of the number of metal element atoms A M and the number of silicon atoms A Si in the second unit layer is 0.1% or more is preferable, 0.2% or more is preferable, and 0.5% or more is preferable.
- the upper limit of the percentage ⁇ A Si /(A Si +A M ) ⁇ 100 of the number of silicon atoms A Si with respect to the sum of the number of metal element atoms A M and the number of silicon atoms A Si in the second unit layer is 2.0% or less is preferable, 1.5% or less is preferable, 1.2% or less is preferable, and 1.0% or less is preferable.
- the percentage ⁇ A Si /(A Si +A M ) ⁇ 100 of the number of silicon atoms A Si with respect to the sum of the number of metal element atoms A M and the number A Si of silicon atoms in the second unit layer is the adhesion From the viewpoint of improvement, 0.1% or more and 2.0% or less is preferable, 0.5% or more and 2.0% or less is preferable, 0.2% or more and 1.5% or less is preferable, 0.5% or more and 1 0.5% or less is preferable, and 0.5% or more and 1.0% or less is more preferable.
- the above ⁇ A Si /(A Si +A M ) ⁇ 100 means the average value in the second unit layer.
- the difference between ⁇ A Si /(A Si +A M ) ⁇ 100 in the first unit layer and ⁇ A Si /(A Si +A M ) ⁇ 100 in the second unit layer is 0 from the viewpoint of improving hardness. 5% or more and 10% or less are preferable, 1% or more and 9% or less are preferable, 2% or more and 8% or less are preferable, and 4% or more and 8% or less are preferable.
- Each of the first unit layer and the second unit layer may have a single composition in the thickness direction, or may have a composition that varies.
- ⁇ A Si /(A Si +A M ) ⁇ 100 in the first unit layer is ⁇ A Si /(A Si +A M ) ⁇ in the first unit layer in the region where the line analysis was performed.
- x100 mean.
- ⁇ A Si /(A Si +A M ) ⁇ 100 in the second unit layer means ⁇ A Si /(A Si +A M ) ⁇ 100 in the second unit layer in the region where the line analysis was performed. Mean of 100.
- the average composition of the laminated structure can be obtained by calculating the average composition of the region subjected to the line analysis based on the result of the line analysis in (A5) above.
- the average of ⁇ A Si /(A Si +A M ) ⁇ 100 in the region where the line analysis was performed is preferably 1% or more and 8% or less, and 1.5% or more and 7.5% or less, from the viewpoint of improving heat resistance. is more preferable, and 2% or more and 5% or less is more preferable.
- the average of ⁇ A Si /(A Si +A M ) ⁇ 100 means the average of the values obtained by performing line analysis on three adjacent hard particles.
- the first unit layer and the second unit layer preferably have the same crystal orientation. According to this, the interfacial energy can be suppressed.
- the crystal orientation include ⁇ 311 ⁇ , ⁇ 211 ⁇ , ⁇ 110 ⁇ , ⁇ 100 ⁇ , and ⁇ 111 ⁇ . In the crystallographic descriptions herein, ⁇ ⁇ indicate aggregate planes.
- the following procedure confirms that the first unit layer and the second unit layer have the same crystal orientation.
- An electron diffraction image as shown in FIG. 6 is obtained by the same method as (A1) to (A4) above.
- the electron diffraction image is a diffraction image from a single crystal, it is determined that the first unit layer and the second unit layer have the same crystal orientation.
- the average periodic width of the laminated structure in the present embodiment is preferably 2 nm or more and 20 nm or less, preferably 4.1 nm or more and 17.7 nm or less, and 3 nm or more and 15 nm from the viewpoint of maintaining the strain between the unit layers and improving the fracture resistance. The following is preferable, and 5 nm or more and 10 nm or less is preferable.
- the periodic width of the laminated structure refers to the distance from one first unit layer to another adjacent first unit layer with a second unit layer adjacent to the one first unit layer interposed therebetween. Note that this distance is a distance connecting the midpoints in the thickness direction of each layer of the first unit layer and other first unit layers.
- the average periodic width of the laminated structure means the average periodic width of all laminated structures measured within the measurement area set in (A3) above.
- the method for measuring the period width of the silicon concentration is as follows.
- a measurement area is set by the same method as (A1) to (A3) above.
- a Fourier transform is performed on the measurement area to obtain a Fourier transform image.
- FIG. 8 shows a Fourier transform image obtained by Fourier transforming the area A shown in FIG.
- the period width is calculated by calculating the reciprocal of the distance between the spot and the center of the image showing maximum intensity in the Fourier transform image.
- the number of laminations (total number of laminations) of the first unit layer and the second unit layer that constitute the multilayer structure layer is not particularly limited, it is preferably 10 layers or more and 1000 layers or less, for example.
- the number of laminated layers is 10 or more, coarsening of crystal grains in each unit layer is suppressed, and the hardness of the hard particles can be maintained.
- the number of laminated layers is 1000 or less, the thickness of each unit layer can be sufficiently secured, and mixing of unit layers can be suppressed.
- the coating comprises an underlayer disposed between the substrate and the hard particle layer, the underlayer comprising a third compound, the third compound comprising: one or more elements selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements of the periodic table and aluminum; and one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen. According to this, the adhesion between the coating and the substrate is improved, and the abrasion resistance is also improved.
- the adhesion between the substrate and the coating can be enhanced.
- the Al 2 O 3 layer as the underlayer, the oxidation resistance of the coating can be enhanced.
- the underlayer preferably has an average thickness of 0.1 ⁇ m or more and 20 ⁇ m or less. According to this, the coating can have excellent wear resistance and chipping resistance.
- the coating comprises a surface layer disposed on its outermost surface, said surface layer comprising a fourth compound, said fourth compound comprising one or more elements selected from the group consisting of Group 4 elements, Group 5 elements, Group 6 elements of the periodic table and aluminum; and one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen. According to this, the thermal crack resistance and wear resistance of the coating are improved.
- the surface layer is the layer located closest to the surface side of the coating. However, it may not be formed at the cutting edge ridge.
- the surface layer is arranged directly above the hard particle layer when no other layer is formed on the hard particle layer.
- the surface layer includes a TiN layer or an Al2O3 layer. Since the TiN layer has a clear color (exhibits gold color), its use as a surface layer has the advantage of facilitating identification of the corners of the cutting tip after use for cutting (identification of used portions). By using the Al 2 O 3 layer as the surface layer, the oxidation resistance of the coating can be enhanced.
- the surface layer preferably has an average thickness of 0.05 ⁇ m or more and 1 ⁇ m or less. According to this, the adhesion between the surface layer and the adjacent layer is improved.
- the intermediate layer is a layer located between the underlayer and the hard particle layer. If the underlying layer is a TiN layer, the intermediate layer is preferably a TiCN layer. Since the TiCN layer has excellent wear resistance, it can impart more suitable wear resistance to the coating.
- the intermediate layer preferably has an average thickness of 1 ⁇ m or more and 20 ⁇ m or less.
- FIG. 10 is a schematic cross-sectional view of an example of a CVD apparatus used for manufacturing the cutting tool of this embodiment.
- the cutting tool manufacturing method of the present embodiment is the cutting tool manufacturing method according to the first embodiment, a first step of preparing a substrate; a second step of forming a coating on the base material to obtain a cutting tool,
- the second step includes a step 2a of forming a hard particle layer made of hard particles by a CVD method,
- the 2a step includes a 2a-1 step of ejecting the first raw material gas, the second raw material gas, and the third raw material gas toward the surface of the base material,
- the first source gas contains one or more elements selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table, the second source gas is SiCl4 ;
- the third source gas contains one or more elements selected from the group consisting of carbon, nitrogen, boron and oxygen;
- the first raw material gas is jetted from a plurality of first injection holes provided in the nozzle,
- the second raw material gas is jetted from a plurality of second injection holes provided in the nozzle,
- a coating is formed on the substrate to obtain a cutting tool.
- the coating is formed using, for example, the CVD apparatus shown in FIG.
- a plurality of substrate setting jigs 52 holding substrates 10 can be installed in the CVD apparatus 50, and these are covered with a reaction vessel 53 made of heat-resistant alloy steel.
- a temperature control device 54 is arranged around the reaction container 53 , and the temperature inside the reaction container 53 can be controlled by the temperature control device 54 .
- a nozzle 56 having three inlets 55 and 57 is arranged in the CVD apparatus 50 .
- the nozzle 56 is arranged so as to penetrate the area where the substrate setting jig 52 is arranged.
- a plurality of injection holes (first injection hole 61, second injection hole 62, third injection hole (not shown)) are formed in a portion of the nozzle 56 near the substrate setting jig 52.
- the gases introduced into the nozzle 56 from the inlets 55, 57 and another inlet (not shown) are not mixed in the nozzle 56, and are injected through different injection holes.
- An exhaust pipe 59 is arranged in the CVD apparatus 50 , and the exhaust gas can be discharged to the outside from an exhaust port 60 of the exhaust pipe 59 .
- the jigs and the like in the reaction vessel 53 are generally made of graphite.
- the coating includes a base layer, an intermediate layer and/or a surface layer
- these layers can be formed by conventionally known methods.
- the second step includes a step 2a of forming a hard particle layer composed of hard particles by a CVD method. Including the 2a-1 step of jetting toward.
- the first raw material gas contains one or more elements selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table.
- the first raw material gas is, for example, a chloride gas of a group 4 element, a group 5 element, or a group 6 element of the periodic table. More specifically, TiCl 4 , ZrCl 4 , VCl 4 , CrCl 3 , and mixed gases containing two or more of these may be mentioned.
- the second source gas is SiCl4 .
- the third source gas is, for example, CH 3 CN, CH 4 , N 2 , NH 3 , BCl 3 , H 2 O, or a mixed gas containing two or more of these.
- the first source gas is jetted from a plurality of first injection holes provided in the nozzle
- the second source gas is jetted from a plurality of second injection holes provided in the nozzle
- the third source gas is jetted from the nozzle. is jetted from a plurality of third injection holes provided in the .
- the first raw material gas is introduced into the nozzle 56 from the inlet port 55 of the nozzle and ejected from the plurality of first injection holes 61 .
- the second raw material gas is introduced into the nozzle 56 from the inlet port 57 of the nozzle and ejected from the plurality of second injection holes 62 .
- the third raw material gas is introduced into the nozzle 56 through an inlet port (not shown) of the nozzle and ejected from a plurality of third injection holes (not shown).
- the nozzle rotates, the plurality of second injection holes includes a 2-1 injection hole and a 2-2 injection hole, and the diameter of the 2-1 injection hole r1 is different from the diameter r2 of the 2-2 injection hole.
- the hard particles have a multilayer structure including a first unit layer and a second unit layer, and the percentage of the number of silicon atoms with respect to the total number of metal elements and silicon atoms in the first unit layer, A multilayer structure can be included in which the percentage of the number of silicon atoms to the total number of metal elements and silicon atoms in the two unit layers is different.
- r1 ⁇ r2 is assumed to facilitate understanding.
- the diameter r1 of the 2-1 injection hole is preferably 0.5 mm or more and 3 mm or less, more preferably 1 mm or more and 2.5 mm or less, and even more preferably 1.5 mm or more and 2 mm or less.
- the diameter r2 of the 2-2 injection hole is preferably 1 mm or more and 4 mm or less, more preferably 1.5 mm or more and 3.5 mm or less, and even more preferably 2 mm or more and 3 mm or less.
- the lower limit of the ratio r1/r2 between the diameter r1 of the 2-1 injection hole and the diameter r2 of the 2-2 injection hole is preferably 0.125 or more, more preferably 0.2 or more, and 0.5 or more. More preferred.
- the upper limit of r1/r2 is preferably less than 1, preferably 0.8 or less, and preferably 0.6 or less.
- r1/r2 is preferably 0.125 or more and less than 1, preferably 0.2 or more and 0.8 or less, and preferably 0.5 or more and 0.6 or less.
- the substrate temperature in the reaction vessel is preferably in the range of 700 to 900° C.
- the pressure in the reaction vessel is preferably in the range of 0.1 to 13 kPa.
- H 2 gas, N 2 gas, Ar gas, or the like can be used as a carrier gas.
- the compositions of the first unit layer and the second unit layer are controlled by the mixing ratio of the raw material gas and the ratio r1/r2 between the diameter r1 of the 2-1 injection hole and the diameter r2 of the 2-2 injection hole. can be done.
- the thickness of the hard particle layer can be controlled by adjusting the flow rate of the raw material gas and the film formation time.
- the thickness of each of the first unit layer and the second unit layer, the lamination period, and the number of lamination can be controlled by adjusting the rotation speed of the nozzle and the film formation time.
- the total gas flow rate of the reaction gas during formation of the hard particle layer can be, for example, 70-90 L/min.
- the “total gas flow rate” indicates the total volumetric flow rate introduced into the CVD furnace per unit time, assuming that the gas under standard conditions (0° C., 1 atm) is an ideal gas.
- the base material 10 with the film formed thereon is cooled.
- the cooling rate does not exceed, for example, 5° C./min, and the cooling rate slows as the temperature of the substrate 10 decreases.
- a heat treatment step such as annealing and a surface treatment step such as surface grinding and shot blasting can be performed.
- the cutting tool of Embodiment 1 can be obtained by the manufacturing method described above.
- a substrate A described in Table 1 below was prepared. Specifically, first, raw material powders having the composition (% by mass) shown in Table 1 were uniformly mixed to obtain a mixed powder. "Remainder” in Table 1 indicates that WC accounts for the remainder of the composition (% by mass). Next, after pressure molding the mixed powder into the shape of SEMT13T3AGSR-G (exchangeable cutting tip manufactured by Sumitomo Electric Hardmetal Co., Ltd.), it is sintered at 1300 to 1500 ° C. for 1 to 2 hours to form a cemented carbide. A base material A was obtained. The shape of substrate A is SEMT13T3AGSR-G.
- a coating was formed on the surface of the substrate A obtained above. Specifically, using the CVD apparatus shown in FIG. 10, the substrate was set in a substrate setting jig, and a thermal CVD method was performed to form a film on the substrate. Table 2 shows the composition of the coating of each sample. Columns marked with "-" in Table 2 mean that no layer is present.
- the underlying layer (TiN layer), the intermediate layer (TiCN layer) and the surface layer (Al 2 O 3 layer) shown in Table 2 are layers formed by a conventionally known CVD method.
- the row of "TiN (underlying layer)" in Table 3 shows the deposition conditions for the TiN layer as the underlying layer.
- the description of the TiN layer (underlying layer) in Table 3 is based on the fact that the substrate is placed in the reaction vessel of the CVD apparatus (reaction vessel internal pressure 6.7 kPa, substrate temperature 915 ° C.), and 2.0% by volume is placed in the reaction vessel.
- a TiN layer was formed by ejecting a mixed gas consisting of 39.7 vol% of TiCl4 gas, 39.7 vol% of N2 gas and the rest (58.3 vol %) of H2 gas at a flow rate of 63.8 L/min. means that Note that the thickness of each layer formed under each film forming condition was controlled by the time during which each reaction gas was ejected.
- the film forming conditions A to G, X and Y in the hard particle layer column of Table 2 correspond to the film forming conditions A to G of Table 4 and the film forming conditions X and Y of Table 5.
- the hard particle layer of sample 1 indicates that it is a layer formed under film formation condition A in Table 4, and the numbers in parentheses mean that the thickness of the hard particle layer is 4.5 ⁇ m.
- the hard particle layer is formed using the CVD apparatus shown in FIG.
- the nozzle of the CVD apparatus is provided with a first injection hole, a second injection hole (2-1 injection hole and 2-2 injection hole) and a third injection hole.
- the diameter ⁇ r1 of the 2-1 injection hole and the diameter ⁇ r2 of the 2-2 injection hole in the nozzle of the CVD apparatus used under each film forming condition are calculated in the column "diameter ⁇ (mm) r1/r2 of the injection hole" in Table 4. shown in For example, under film formation condition A, the diameter ⁇ r1 of the 2-1 injection hole is 1.5 mm, and the diameter ⁇ r2 of the 2-2 injection hole is 2.5 mm.
- the nozzle rotates during deposition.
- the pressure in the reaction vessel of the CVD apparatus is the pressure described in the "pressure (kPa)” column of Table 4, and the substrate temperature is the “temperature (° C.) )” column.
- the pressure inside the reaction vessel of the CVD apparatus is set to 9.0 kPa, and the substrate temperature is set to 800.degree.
- reaction gas containing the components listed in the "Reaction gas composition (% by volume)" column of Table 4 is introduced into the reaction vessel to form a hard particle layer on the substrate.
- "Remainder” in Table 4 indicates that H2 gas accounts for the remainder of the reactant gas composition (% by volume).
- the reaction gases TiCl 4 , ZrCl 4 , VCl 4 and CrCl 3 are the first source gases, SiCl 4 is the second source gas, and CH 3 CN and BCl 3 are the third source gases.
- H2 is mixed with the third source gas to adjust the total gas flow rate.
- the total gas flow rate of the reaction gas is 80 L/min.
- Total gas flow rate indicates the total volumetric flow rate introduced into the CVD furnace per unit time, assuming that the gas under standard conditions (0° C., 1 atm) is an ideal gas.
- the reaction gas used in film formation condition A is 1 vol% SiCl4 gas, 1 vol% TiCl4 gas, 0.5 vol % CH3CH gas and H2 gas (remainder, 97.5 vol%).
- the rotational speed of the nozzle during film formation is as shown in the "rotational speed (rpm)" column of Table 4.
- the rotation speed of the nozzle is 2.0 rpm.
- Deposition condition X Under film forming conditions X, a conventional CVD apparatus is used to form a hard particle layer. All the injection holes of the nozzles of the CVD apparatus have the same diameter ⁇ of 10 mm. The nozzle does not rotate during deposition.
- the pressure inside the reaction vessel of the CVD apparatus is set to 6 kPa, and the substrate temperature is set to 800°C.
- reaction gas SiCl 4 : 0.84% by volume, TiCl 4 : 0.17% by volume, CH 3 CN : 0.32% by volume, H 2 : balance
- TiSiCN layer hard particle layer
- Film formation condition Y a hard particle layer is formed by a conventional PVD method. Specific conditions of the film-forming condition Y are as shown in the column of "film-forming condition Y" in Table 5.
- the multilayer structure of the hard particle layer obtained under film forming conditions A to G includes a layer (first unit layer) having a large percentage of silicon atoms with respect to the total number of metal element and silicon atoms, and a metal element and a layer (second unit layer) having a small percentage of the number of silicon atoms with respect to the total number of silicon atoms.
- Samples 1 to 10 (Example) have a longer cutting distance and a longer tool life in milling (dry machining) of high-hardness heat-resistant stainless steel. was confirmed. This is presumably because the hard particles of Samples 1 to 10 have a multi-layered structure, so that the thermal crack growth resistance and the peeling resistance are improved.
- Samples 11 to 16 (Examples) have a longer cutting distance and a longer tool life in milling (wet machining) of high-hardness heat-resistant stainless steel. was confirmed. This is presumably because the hard particles of Samples 11 to 16 had a multi-layered structure, which improved the thermal crack growth resistance and peeling resistance.
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Abstract
Description
基材と、前記基材上に配置された被膜とを含む切削工具であって、
前記被膜は、硬質粒子からなる硬質粒子層を備え、
前記硬質粒子は、第1単位層と第2単位層とが交互に積層された多層構造を含み、
前記第1単位層は、立方晶構造を有する第1化合物からなり、
前記第2単位層は、立方晶構造を有する第2化合物からなり、
前記第1化合物及び前記第2化合物のそれぞれは、
周期表の4族元素、5族元素、及び6族元素からなる群より選ばれる1種以上の金属元素と、
珪素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなり、
前記第1単位層における前記金属元素及び前記珪素の原子数の合計に対する前記珪素の原子数の百分率は、前記第2単位層における前記金属元素及び前記珪素の原子数の合計に対する前記珪素の原子数の百分率と異なる、切削工具である。
上記の切削工具の製造方法であって、
基材を準備する第1工程と、
前記基材上に被膜を形成して切削工具を得る第2工程と、を備え、
前記第2工程は、CVD法により硬質粒子からなる硬質粒子層を形成する第2a工程を含み、
前記第2a工程は、第1原料ガス、第2原料ガス及び第3原料ガスを前記基材の表面に向かって噴出する第2a-1工程を含み、
前記第1原料ガスは、周期表の4族元素、5族元素及び6族元素からなる群より選ばれる1種以上の元素を含み、
前記第2原料ガスは、SiCl4であり、
前記第3原料ガスは、炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素を含み、
前記第1原料ガスは、ノズルに設けられた複数の第1噴射孔から噴出され、
前記第2原料ガスは、前記ノズルに設けられた複数の第2噴射孔から噴出され、
前記第3原料ガスは、前記ノズルに設けられた複数の第3噴射孔から噴出され、
前記第2a-1工程において、前記ノズルは回転し、
前記複数の第2噴射孔は、第2-1噴射孔と、第2-2噴射孔と、を含み、
前記第2-1噴射孔の径r1は、前記第2-2噴射孔の径r2と異なる、切削工具の製造方法である。
近年、工具寿命の向上への要求が益々高まり、特に、高硬度耐熱ステンレスのフライス加工においても、工具寿命の更なる向上が求められている。
[本開示の効果]
最初に本開示の実施態様を列記して説明する。
(1)本開示の切削工具は、
基材と、前記基材上に配置された被膜とを含む切削工具であって、
前記被膜は、硬質粒子からなる硬質粒子層を備え、
前記硬質粒子は、第1単位層と第2単位層とが交互に積層された多層構造を含み、
前記第1単位層は、立方晶構造を有する第1化合物からなり、
前記第2単位層は、立方晶構造を有する第2化合物からなり、
前記第1化合物及び前記第2化合物のそれぞれは、
周期表の4族元素、5族元素、及び6族元素からなる群より選ばれる1種以上の金属元素と、
珪素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなり、
前記第1単位層における前記金属元素及び前記珪素の原子数の合計に対する前記珪素の原子数の百分率は、前記第2単位層における前記金属元素及び前記珪素の原子数の合計に対する前記珪素の原子数の百分率と異なる、切削工具である。
前記被膜の厚さは、3μm以上30μm以下であることが好ましい。
前記下地層は、第3化合物からなり、
前記第3化合物は、
周期表の4族元素、5族元素、6族元素及びアルミニウムからなる群より選ばれる1種以上の元素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなる、ことが好ましい。
前記下地層は、TiN層、TiC層、TiCN層、TiBN層及びAl2O3層からなる群より選択される少なくとも1種からなることが好ましい。
前記表面層は、第4化合物からなり、
前記第4化合物は、
周期表の4族元素、5族元素、6族元素及びアルミニウムからなる群より選ばれる1種以上の元素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなる、ことが好ましい。
上記の切削工具の製造方法であって、
基材を準備する第1工程と、
前記基材上に被膜を形成して切削工具を得る第2工程と、を備え、
前記第2工程は、CVD法により硬質粒子からなる硬質粒子層を形成する第2a工程を含み、
前記第2a工程は、第1原料ガス、第2原料ガス及び第3原料ガスを前記基材の表面に向かって噴出する第2a-1工程を含み、
前記第1原料ガスは、周期表の4族元素、5族元素及び6族元素からなる群より選ばれる1種以上の元素を含み、
前記第2原料ガスは、SiCl4であり、
前記第3原料ガスは、炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素を含み、
前記第1原料ガスは、ノズルに設けられた複数の第1噴射孔から噴出され、
前記第2原料ガスは、前記ノズルに設けられた複数の第2噴射孔から噴出され、
前記第3原料ガスは、前記ノズルに設けられた複数の第3噴射孔から噴出され、
前記第2a-1工程において、前記ノズルは回転し、
前記複数の第2噴射孔は、第2-1噴射孔と、第2-2噴射孔と、を含み、
前記第2-1噴射孔の径r1は、前記第2-2噴射孔の径r2と異なる、切削工具の製造方法である。
本発明者らは、高硬度耐熱ステンレスのフライス加工においても長い工具寿命を有する切削工具を開発するにあたり、従来の切削工具で高硬度耐熱ステンレスのフライス加工を行い、工具の損傷状態を観察した。
本開示の一実施形態(以下、「本実施形態」とも記す。)の切削工具は、
基材と、該基材上に配置された被膜とを含む切削工具であって、
該被膜は、硬質粒子からなる硬質粒子層を備え、
該硬質粒子は、第1単位層と第2単位層とが交互に積層された多層構造を含み、
該第1単位層は、立方晶構造を有する第1化合物からなり、
該第2単位層は、立方晶構造を有する第2化合物からなり、
該第1化合物及び該第2化合物のそれぞれは、
周期表の4族元素、5族元素、及び6族元素からなる群より選ばれる1種以上の金属元素と、
珪素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなり、
該第1単位層における該金属元素及び該珪素の原子数の合計に対する該珪素の原子数の百分率は、該第2単位層における該金属元素及び該珪素の原子数の合計に対する該珪素の原子数の百分率と異なる、切削工具である。
周期表の4族元素、5族元素、及び6族元素からなる群より選ばれる1種以上の金属元素と、
珪素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなる。
上記の第1化合物及び第2化合物は硬度が高い。よって、第1化合物及び第2化合物を含む硬質粒子層は硬度が高く、優れた耐摩耗性を有する。よって、切削工具は長い工具寿命を有することができる。
図1に示されるように、本実施形態の切削工具1は、基材10と、該基材10上に配置された被膜15とを備える。図1では、該被膜15が硬質粒子層11のみから構成される場合を示している。被膜15は、基材の切削に関与する部分の少なくとも一部を被覆することが好ましく、基材の全面を被覆することが更に好ましい。基材の切削に関与する部分とは、基材表面において、刃先稜線からの距離が500μm以内の領域を意味する。基材の一部がこの被膜で被覆されていなかったり被膜の構成が部分的に異なっていたりしていたとしても、本開示の範囲を逸脱するものではない。
本開示の切削工具は、例えば、ドリル、エンドミル(例えば、ボールエンドミル)、ドリル用刃先交換型切削チップ、エンドミル用刃先交換型切削チップ、フライス加工用刃先交換型切削チップ、旋削加工用刃先交換型切削チップ、メタルソー、歯切工具、リーマ、タップ等であり得る。
基材10は、すくい面と逃げ面とを含み、この種の基材として従来公知のものであればいずれも使用することができる。例えば、超硬合金(例えば、炭化タングステンとコバルトとを含むWC基超硬合金、該超硬合金はTi、Ta、Nbなどの炭窒化物を含むことができる)、サーメット(TiC、TiN、TiCNなどを主成分とするもの)、高速度鋼、セラミックス(炭化チタン、炭化ケイ素、窒化ケイ素、窒化アルミニウム、酸化アルミニウムなど)、立方晶型窒化ホウ素焼結体またはダイヤモンド焼結体のいずれかであることが好ましい。
(被膜の構成)
本実施形態の被膜は、硬質粒子層を含む。本実施形態の被膜は、硬質粒子層を含む限り、他の層を含んでいてもよい。
本実施形態の被膜の厚さは、3μm以上30μm以下が好ましい。ここで、被膜の厚さとは、被膜全体の厚さを意味する。被膜全体の厚さが3μm以上であると、優れた耐摩耗性を有することができる。一方、被膜全体の厚さが30μm以下であると、切削加工時に、被膜と基材との間に大きな応力が加わった際の被膜の剥離または破壊の発生を抑制することができる。被膜全体の厚さの下限は、耐摩耗性向上の観点から、5μm以上がより好ましく、10μm以上が更に好ましい。被膜全体の厚さの上限は、被膜の剥離または破壊の発生を抑制する観点から、25μm以下がより好ましく、20μm以下が更に好ましい。被膜全体の厚さは、5μm以上25μm以下がより好ましく、10μm以上20μm以下が更に好ましい。
(硬質粒子層の構成)
本実施形態の硬質粒子層は硬質粒子からなり、該硬質粒子は、第1単位層と第2単位層とが交互に積層された多層構造を含む。
本実施形態の硬質粒子層の厚さは、3μm以上15μm以下が好ましい。硬質粒子層の厚さが3μm以上であると、優れた耐摩耗性を有することができる。一方、硬質粒子層の厚さが15μm以下であると、切削加工時に、被膜と基材との間に大きな応力が加わった際の被膜の剥離または破壊の発生を抑制することができる。硬質粒子層の厚さの下限は、耐摩耗性向上の観点から、4μm以上がより好ましく、5μm以上が更に好ましい。硬質粒子層の厚さの上限は、被膜の剥離または破壊の発生を抑制する観点から、15μm以下が好ましく、10μm以下がより好ましい。硬質粒子層の厚さは、4μm以上15μm以下がより好ましく、5μm以上10μm以下が更に好ましい。
周期表の4族元素、5族元素、及び6族元素からなる群より選ばれる1種以上の金属元素と、
珪素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなる。
ここで、第1化合物の組成と、第2化合物の組成とは異なる。より具体的には、第1化合物における金属元素及び珪素の原子数の合計に対する珪素の原子数の百分率は、第2化合物における金属元素及び珪素の原子数の合計に対する珪素の原子数の百分率と異なる。
第1単位層及び第2単位層のそれぞれにおいて、金属元素の原子数AMと、珪素の原子数ASiとの合計に対する、珪素の原子数ASiの百分率{ASi/(ASi+AM)}×100は、0.5%以上10%以下であることが好ましい。これによると、硬質粒子層の耐熱亀裂性、及び、硬質粒子層と隣接する層との密着性がバランス良く向上する。第1単位層及び第2単位層のそれぞれにおける{ASi/(ASi+AM)}×100の下限は、0.5%以上が好ましく、0.7%以上が好ましく、1.0%以上が好ましく、1.2%以上が好ましい。第1単位層及び第2単位層のそれぞれにおける{ASi/(ASi+AM)}×100の上限は、10.0%以下が好ましく、8.0%以下が好ましく、7.2%以下が好ましく、7%以下が好ましく、5%以下が好ましい。第1単位層及び第2単位層のそれぞれにおける{ASi/(ASi+AM)}×100は、0.5%以上8.0%以下が好ましく、0.5%以上7.2%以下が好ましく、0.7%以上7%以下が好ましく、1.0%以上5.0%以下が好ましい。
積層構造の平均組成は、上記(A5)のライン分析の結果に基づき、ライン分析を行った領域の平均組成を算出することにより得られる。
第1単位層と第2単位層とは、同一の結晶方位を有することが好ましい。これによると、界面エネルギーが抑えられる。該結晶方位は、例えば、{311}、{211}、{110}、{100}、{111}などが挙げられる。本明細書中の結晶学的記載においては、{}は集合面を示している。
本実施形態における積層構造の周期幅の平均は、単位層間の歪みを維持し、耐欠損を向上させる観点から、2nm以上20nm以下が好ましく、4.1nm以上17.7nm以下が好ましく、3nm以上15nm以下が好ましく、5nm以上10nm以下が好ましい。ここで、積層構造の周期幅とは、1つの第1単位層から、該1つの第1単位層に隣接する第2単位層を挟んで隣接する他の第1単位層までの距離をいう。なお、この距離は、第1単位層および他の第1単位層の各層の厚み方向の中点を結ぶ距離とする。積層構造の周期幅の平均とは、上記(A3)で設定した測定領域内で測定された全ての積層構造の周期幅の平均を意味する。
被膜は、前記基材と前記硬質粒子層との間に配置される下地層を備え、該下地層は、第3化合物からなり、該第3化合物は、
周期表の4族元素、5族元素、6族元素及びアルミニウムからなる群より選ばれる1種以上の元素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなることが好ましい。
これによると、被膜と基材との密着性が向上し、耐摩耗性も向上する。
被膜は、その最表面に配置される表面層を備え、該表面層は、第4化合物からなり、該第4化合物は、
周期表の4族元素、5族元素、6族元素及びアルミニウムからなる群より選ばれる1種以上の元素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなることが好ましい。これによると、被膜の耐熱亀裂性及び耐摩耗性が向上する。
中間層は、下地層と硬質粒子層との間に配置される層である。下地層がTiN層の場合、中間層はTiCN層であることが好ましい。TiCN層は耐摩耗性に優れるため、被膜により好適な耐摩耗性を付与することができる。中間層は、平均厚さが1μm以上20μm以下であることが好ましい。
本実施形態の切削工具の製造方法について図10を用いて説明する。図10は、本実施形態の切削工具の製造に用いられるCVD装置の一例の概略的な断面図である。
基材を準備する第1工程と、
該基材上に被膜を形成して切削工具を得る第2工程と、を備え、
該第2工程は、CVD法により硬質粒子からなる硬質粒子層を形成する第2a工程を含み、
該第2a工程は、第1原料ガス、第2原料ガス及び第3原料ガスを該基材の表面に向かって噴出する第2a-1工程を含み、
該第1原料ガスは、周期表の4族元素、5族元素及び6族元素からなる群より選ばれる1種以上の元素を含み、
該第2原料ガスは、SiCl4であり、
該第3原料ガスは、炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素を含み、
該第1原料ガスは、ノズルに設けられた複数の第1噴射孔から噴出され、
該第2原料ガスは、該ノズルに設けられた複数の第2噴射孔から噴出され、
該第3原料ガスは、該ノズルに設けられた複数の第3噴射孔から噴出され、
該第2a-1工程において、該ノズルは回転し、
該複数の第2噴射孔は、第2-1噴射孔と、第2-2噴射孔と、を含み、
該第2-1噴射孔の径r1は、該第2-2噴射孔の径r2と異なる、切削工具の製造方法である。
第1工程において、基材を準備する。基材の詳細は、実施形態1に記載されているため、その説明は繰り返さない。
次に、第2工程において、上記基材上に被膜を形成して切削工具を得る。被膜の形成は、例えば図10に示されるCVD装置を用いて行う。CVD装置50内には、基材10を保持した基材セット治具52を複数設置することができ、これらは耐熱合金鋼製の反応容器53でカバーされる。また、反応容器53の周囲には調温装置54が配置されており、この調温装置54により、反応容器53内の温度を制御することができる。
第2工程は、CVD法により硬質粒子からなる硬質粒子層を形成する第2a工程を含み、該第2a工程は、第1原料ガス、第2原料ガス及び第3原料ガスを該基材の表面に向かって噴出する第2a-1工程を含む。
次に、被膜が形成された基材10を冷却する。冷却速度は、例えば、5℃/minを超えることはなく、また、その冷却速度は基材10の温度が低下するにつれて遅くなる。
以下の表1に記載の基材Aを準備した。具体的には、まず、表1に記載の配合組成(質量%)からなる原料粉末を均一に混合して混合粉末を得た。表1中の「残り」とは、WCが配合組成(質量%)の残部を占めることを示している。次に、混合粉末をSEMT13T3AGSR-G(住友電工ハードメタル社製の刃先交換型切削チップ)の形状に加圧成形した後、1300~1500℃で1~2時間焼結することにより、超硬合金製の基材Aを得た。基材Aの形状はSEMT13T3AGSR-Gである。
上記で得られた基材Aに対してその表面に被膜を形成した。具体的には、図10に示されるCVD装置を用い、基材を基材セット治具にセットし、熱CVD法を行うことにより、基材上に被膜を形成した。各試料の被膜の構成を表2に示す。表2の「-」で示される欄は、層が存在しないことを意味する。
成膜条件A~成膜条件Gでは、図10に示されるCVD装置を用いて硬質粒子層を形成する。CVD装置のノズルには、第1噴射孔、第2噴射孔(第2-1噴射孔及び第2-2噴射孔)及び第3噴射孔が設けられている。各成膜条件で用いられるCVD装置のノズルにおける第2-1噴射孔の径φr1及び第2-2噴射孔の径φr2を、表4の「噴射孔の径φ(mm)r1/r2」欄に示す。たとえば、成膜条件Aでは、第2-1噴射孔の径φr1は1.5mmであり、第2-2噴射孔の径φr2は2.5mmである。該ノズルは、成膜中に回転する。
成膜条件Xでは、従来のCVD装置を用いて硬質粒子層を形成する。CVD装置のノズルの噴射孔の径φは全て同一で、10mmである。該ノズルは、成膜中に回転しない。
成膜条件Yでは、従来のPVD法により硬質粒子層を形成する。成膜条件Yの具体的な条件は、表5の「成膜条件Y」の列に示す通りである。
(硬質粒子層の構造)
成膜条件A~成膜条件Gにより得られた被膜の硬質粒子層を明視野走査電子顕微鏡(BF-SEM)で観察したところ、硬質粒子層は複数の硬質粒子からなり、該硬質粒子内に多層構造が確認された。成膜条件A~成膜条件Gにより得られた硬質粒子層の多層構造は、金属元素及び珪素の原子数の合計に対する珪素の原子数の百分率の大きい層(第1単位層)と、金属元素及び珪素の原子数の合計に対する珪素の原子数の百分率の小さい層(第2単位層)とが交互に積層されて形成されていることが確認された。
各成膜条件により得られた硬質粒子層について、積層構造の平均組成、第1単位層における金属元素及び珪素の原子数の合計に対する珪素の原子数の百分率(Si/Me+Si(%))、及び、第2単位層における金属元素及び珪素の原子数の合計に対する珪素の原子数の百分率({ASi/(ASi+AM)}×100(%))を測定した。具体的な測定方法は実施形態1に記載の通りであるため、その説明は繰り返さない。結果を表6の「平均組成」、「第1単位層{ASi/(ASi+AM)}×100(%)」及び「第2単位層{ASi/(ASi+AM)}×100(%)」欄に示す。なお、「-」の表記は、測定を行わなかったことを示す。
各成膜条件により得られた硬質粒子層において、多層構造の周期幅の平均を測定した。具体的な測定方法は実施形態1に記載の通りであるため、その説明は繰り返さない。結果を表6の「周期幅平均(nm)」欄に示す。なお、「-」の表記は、測定を行わなかったことを示す。
試料1~試料10及び試料1-1及び試料1-3の切削工具を用いて、以下の切削条件にて切削を行い、工具刃先が欠損状態となるまでの切削距離を測定した。以下の切削条件は、高硬度耐熱ステンレスのフライス加工(ドライ加工)に該当する。切削距離が長いもの程、工具寿命が長いことを示す。結果を表7に示す。
被削材:SUS630/H900 ブロック材(寸法:300mm×150mm×50mm)
カッター:WGX13100RS(住友電工ハードメタル社製)
インサート:SEMT13T3AGSR-G
切削速度Vc:300m/min
1刃当たりの送りFz:0.1mm/t
切込み深さAp:1.0mm
切削幅Ae:75mm
切削液:なし(Dry)
試料1~試料10(実施例)は、試料1-1及び試料1-3(比較例)に比べて、高硬度耐熱ステンレスのフライス加工(ドライ加工)において、切削距離が長く、工具寿命が長いことが確認された。これは、試料1~試料10では、硬質粒子が多層構造を含むため、耐熱亀裂進展性及び耐剥離性が向上したためと推察される。
試料11~試料16及び試料1-2及び試料1-4の切削工具を用いて、以下の切削条件にて切削を行い、工具刃先が欠損状態となるまでの切削距離を測定した。以下の切削条件は、高硬度耐熱ステンレスのフライス加工(ウェット加工)に該当する。切削距離が長いもの程、耐熱性に優れ、工具寿命が長いことを示す。結果を表8に示す。
被削材:SUS640/H900 ブロック材(寸法:300mm×150mm×50mm)
カッター:WGX13100RS(住友電工ハードメタル社製)
インサート:SEMT13T3AGSR-G
切削速度Vc:150m/min
1刃当たりの送りfz:0.3mm/t
切込み深さap:1.0mm
切削幅ae:75mm
切削液:WET
試料11~試料16(実施例)は、試料1-2及び試料1-4(比較例)に比べて、高硬度耐熱ステンレスのフライス加工(ウェット加工)において、切削距離が長く、工具寿命が長いことが確認された。これは、試料11~試料16では、硬質粒子が多層構造を含むため、耐熱亀裂進展性及び耐剥離性が向上したためと推察される。
今回開示された実施の形態および実施例はすべての点で例示であって、制限的なものではないと考えられるべきである。本発明の範囲は上記した実施の形態および実施例ではなく請求の範囲によって示され、請求の範囲と均等の意味、および範囲内でのすべての変更が含まれることが意図される。
Claims (10)
- 基材と、前記基材上に配置された被膜とを含む切削工具であって、
前記被膜は、硬質粒子からなる硬質粒子層を備え、
前記硬質粒子は、第1単位層と第2単位層とが交互に積層された多層構造を含み、
前記第1単位層は、立方晶構造を有する第1化合物からなり、
前記第2単位層は、立方晶構造を有する第2化合物からなり、
前記第1化合物及び前記第2化合物のそれぞれは、
周期表の4族元素、5族元素、及び6族元素からなる群より選ばれる1種以上の金属元素と、
珪素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなり、
前記第1単位層における前記金属元素及び前記珪素の原子数の合計に対する前記珪素の原子数の百分率は、前記第2単位層における前記金属元素及び前記珪素の原子数の合計に対する前記珪素の原子数の百分率と異なる、切削工具。 - 前記第1単位層及び前記第2単位層は、同一の結晶方位を有する、請求項1に記載の切削工具。
- 前記第1単位層及び前記第2単位層のそれぞれにおいて、前記金属元素及び前記珪素の原子数の合計に対する前記珪素の原子数の百分率は、0.5%以上10%以下である、請求項1又は請求項2に記載の切削工具。
- 前記硬質粒子層の厚さは、3μm以上15μm以下であり、
前記被膜の厚さは、3μm以上30μm以下である、請求項1から請求項3のいずれか1項に記載の切削工具。 - 前記第1単位層における金属元素の原子数AMと、珪素の原子数ASiとの合計に対する、珪素の原子数ASiの百分率{ASi/(ASi+AM)}×100と、前記第2単位層における金属元素の原子数AMと、珪素の原子数ASiとの合計に対する、珪素の原子数ASiの百分率{ASi/(ASi+AM)}×100との差は、0.5%以上10%以下である、請求項1から請求項4のいずれか1項に記載の切削工具。
- 前記被膜は、前記基材と前記硬質粒子層との間に配置される下地層を備え、
前記下地層は、第3化合物からなり、
前記第3化合物は、
周期表の4族元素、5族元素、6族元素及びアルミニウムからなる群より選ばれる1種以上の元素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなる、請求項1から請求項4のいずれか1項に記載の切削工具。 - 前記被膜は、前記基材の直上に配置される下地層を含み、
前記下地層は、TiN層、TiC層、TiCN層、TiBN層及びAl2O3層からなる群より選択される少なくとも1種からなる、請求項1から請求項5のいずれか1項に記載の切削工具。 - 前記被膜は、その最表面に配置される表面層を備え、
前記表面層は、第4化合物からなり、
前記第4化合物は、
周期表の4族元素、5族元素、6族元素及びアルミニウムからなる群より選ばれる1種以上の元素と、
炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素と、からなる、請求項1から請求項7のいずれか1項に記載の切削工具。 - 前記被膜は、前記下地層と前記硬質粒子との間に配置される中間層を有する、請求項6又は請求項7に記載の切削工具。
- 請求項1から請求項9のいずれか1項に記載の切削工具の製造方法であって、
基材を準備する第1工程と、
前記基材上に被膜を形成して切削工具を得る第2工程と、を備え、
前記第2工程は、CVD法により硬質粒子からなる硬質粒子層を形成する第2a工程を含み、
前記第2a工程は、第1原料ガス、第2原料ガス及び第3原料ガスを前記基材の表面に向かって噴出する第2a-1工程を含み、
前記第1原料ガスは、周期表の4族元素、5族元素及び6族元素からなる群より選ばれる1種以上の元素を含み、
前記第2原料ガスは、SiCl4であり、
前記第3原料ガスは、炭素、窒素、硼素及び酸素からなる群より選ばれる1種以上の元素を含み、
前記第1原料ガスは、ノズルに設けられた複数の第1噴射孔から噴出され、
前記第2原料ガスは、前記ノズルに設けられた複数の第2噴射孔から噴出され、
前記第3原料ガスは、前記ノズルに設けられた複数の第3噴射孔から噴出され、
前記第2a-1工程において、前記ノズルは回転し、
前記複数の第2噴射孔は、第2-1噴射孔と、第2-2噴射孔と、を含み、
前記第2-1噴射孔の径r1は、前記第2-2噴射孔の径r2と異なる、切削工具の製造方法。
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