JP2010207916A - Surface coated cutting tool - Google Patents

Surface coated cutting tool Download PDF

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JP2010207916A
JP2010207916A JP2009053275A JP2009053275A JP2010207916A JP 2010207916 A JP2010207916 A JP 2010207916A JP 2009053275 A JP2009053275 A JP 2009053275A JP 2009053275 A JP2009053275 A JP 2009053275A JP 2010207916 A JP2010207916 A JP 2010207916A
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layer
ti
surface
cutting tool
si
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Japanese (ja)
Inventor
Daisuke Kazami
Takashi Koyama
Kazunori Sato
Shinichi Shikada
Takahito Tabuchi
Yusuke Tanaka
和則 佐藤
孝 小山
裕介 田中
貴仁 田渕
大介 風見
信一 鹿田
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Mitsubishi Materials Corp
三菱マテリアル株式会社
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface coated cutting tool having a hard coating layer which exhibits excellent wear resistance under high-speed cutting conditions for a heat-resistant alloy such as an Ni-based alloy or a Co-based alloy. <P>SOLUTION: The surface coated cutting tool includes the hard coating layer, formed of a lower layer and an upper layer, and formed by vapor deposition on a surface of its tool base; wherein the lower layer is formed of alternate laminates of a thin layer A and a thin layer B, the upper layer is formed of alternate laminates of the thin layer A and a thin layer C, the thin layer A is either a (Ti, Al) N-layer or a (Ti, Al, Si) N-layer, the thin layer B is either a (Cr, Al) N-layer or a (Cr, Al, Si) N-layer, and the thin layer C is a (Ti, Si) N-layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention provides a surface-coated cutting tool that exhibits excellent wear resistance with a hard coating layer even when heat-resistant alloys such as Ni-base alloys and Co-base alloys are cut under high-speed cutting conditions with high heat generation. (Hereinafter referred to as a coated tool).

  In general, for coated tools, throwaway inserts that can be used detachably attached to the tip of a cutting tool for turning and planing of various steel and cast iron, drilling of the work material, etc. Drills and miniature drills, and solid type end mills used for chamfering, grooving, shouldering, etc. of the work material, etc. A slow-away end mill tool that performs cutting work in the same manner as an end mill is known.

  Further, as a specific coated tool, for example, on the surface of a tool base made of tungsten carbide (hereinafter referred to as WC) based cemented carbide, first, a Ti and Al based composite nitride layer (hereinafter referred to as ( Ti, Al) N layer), and then a Ti and Si-based composite nitride layer (hereinafter referred to as (Ti, Si) N layer) is formed. A coating tool (hereinafter referred to as a conventional coating tool) is known in which a hard coating layer having an alternately laminated structure of the above layers is formed by repeated deposition with the (Ti, Si) N layer. However, it is also known that it exhibits excellent wear resistance in high-speed cutting of alloy steel.

  In the above conventional coated tool, for example, a plurality of cathode electrodes (evaporation sources) made of a Ti—Al alloy and a Ti—Si alloy having a composition according to the type of hard coating layer to be deposited are arranged. In an arc ion plating apparatus, a tool base is inserted into the apparatus, a nitrogen gas reaction atmosphere is formed in the apparatus, and in a heated state, a plurality of cathode electrodes (evaporation sources) and anode electrodes are sequentially placed. Then, arc discharge is generated, and a (Ti, Al) N layer and a (Ti, Si) N layer are alternately deposited on the surface of the tool base under the condition that a bias voltage is applied to the tool base. It is also known that it is manufactured by

JP 2000-334606 A JP 2000-334607 A

  In recent years, the performance of cutting devices has been dramatically improved, while there is a strong demand for labor saving and energy saving and further cost reduction for cutting processing. Although there is a demand for generalization of cutting tools for various work materials, in the above-mentioned conventional coated tools, when this is used for high-speed cutting of alloy steel, no particular problem arises, for example, When used in high-speed cutting with high heat generation of heat-resistant alloys such as Ni-base alloys and Co-base alloys, the heat conductivity of the heat-resistant alloy that is the work material is low, so the surface of the cutting edge of the cutting tool due to the cutting heat As the temperature rises and this heat is transmitted to the substrate and Co, which is a component of the tool substrate, diffuses into the hard coating layer, there are also problems such as deterioration of the properties of the hard coating layer. The wear resistance of the layer is Not exerted on, at present, leading to a relatively short time service life.

  Therefore, from the above viewpoint, the present inventors have excellent resistance to hard coating even when used in high-speed cutting with high heat generation of heat-resistant alloys such as Ni-base alloys and Co-base alloys. As a result of earnest research to develop a coated tool that exhibits wear, the following findings were obtained.

(A) The Al component in the (Ti, Al) N layer that constitutes one layer of the above-described alternately laminated layers of the conventional coated tool improves the high temperature hardness, and the Ti component has high temperature toughness and high temperature strength. In addition, the Ti component in the (Ti, Si) N layer constituting the other layers of the alternately laminated layer has the same effect as described above, and the Si component improves the oxidation resistance and oxidizes. In addition to suppressing the decrease in the hardness of the layer due to the above, and also by increasing the stacking with the (Ti, Al) N layer, the hardness is improved, so that the (Ti, Al) N layer and the (Ti, Si) N layer alternately By providing a hard coating layer having a laminated structure, oxidation resistance and wear resistance are improved under normal cutting conditions.
However, in high-speed cutting of heat-resistant alloys such as Ni-base alloys and Co-base alloys, the cutting blade surface temperature becomes high, and Co diffusion from the base into the hard coating layer occurs, so the characteristics of the hard coating layer also deteriorate. Therefore, sufficient satisfactory wear resistance was not obtained.

(B) Therefore, the present inventors have replaced the (Ti, Si) N layers that are alternately stacked with the (Ti, Al) N layers, and have relatively high hardness and the highest stability at high temperatures ( When alternating layers are formed with the (Cr, Al) N layers, the (Cr, Al) N layers forming the alternately stacked layers are formed in the hard coating layer from the substrate even when the surface of the cutting edge or the tool substrate temperature becomes high. It was found that the Co diffusion to the metal was suppressed, and as a result, the deterioration of the characteristics of the hard coating layer composed of the alternating lamination of the (Ti, Al) N layer and the (Cr, Al) N layer could be prevented.

(C) Furthermore, the present inventors have further improved the hardness of the hard coating layer, although the alternate lamination of the (Ti, Al) N layer and the (Cr, Al) N layer has excellent characteristics, and wear resistance. In order to further improve the property, an alternate lamination of the (Ti, Al) N layer and the (Cr, Al) N layer is deposited on the surface of the tool base as a lower layer, and on the lower layer, When an upper layer composed of alternating layers of (Ti, Al) N layers and (Ti, Si) N layers is formed by vapor deposition, a lower layer composed of the above-mentioned alternate stacked structure is formed, thereby forming alternating layers of upper layers. The (Ti, Si) N layer has a high hardness, and as a result, it exhibits even better wear resistance in high-speed cutting of heat-resistant alloys such as Ni-base alloys and Co-base alloys that generate high heat. I found out that

(D) Further, the present inventors replaced part of the constituent components of the (Ti, Al) N layer and (Cr, Al) N layer with Si, and provided intermediate adhesion between the lower layer and the upper layer. It has been found that by further forming a layer, and by forming an underlying adhesion layer between the tool base surface and the lower layer, the wear resistance is further improved.

This invention has been made based on the above findings,
“(1) A surface-coated cutting tool in which a hard coating layer composed of at least a lower layer and an upper layer is vapor-deposited on the surface of a tool base,
(A) The lower layer is a layer having a total layer thickness of 1 to 5 μm composed of alternating layers of a thin layer A having a thickness of 0.003 to 0.02 μm and a thin layer B having a thickness of 0.003 to 0.02 μm. Because
(B) The upper layer is a layer having a total layer thickness of 1 to 5 μm composed of alternating layers of a thin layer A having a thickness of 0.003 to 0.02 μm and a thin layer C having a thickness of 0.003 to 0.02 μm. Because
(C) The thin layer A is
Composition formula: [Ti 1-X Al X ] N
X represents a composite nitride layer of Ti and Al that satisfies 0.40 to 0.70 (however, the atomic ratio),
(D) The thin layer B is
Composition formula: [Cr 1-P Al P ] N
, P is a composite nitride layer of Cr and Al that satisfies 0.40 to 0.75 (however, atomic ratio),
(E) The thin layer C is
Composition formula: [Ti 1 -U Si U ] N
In this case, U is a composite nitride layer of Ti and Si that satisfies 0.01 to 0.30 (however, the atomic ratio),
A surface-coated cutting tool characterized in that
(2) In the surface-coated cutting tool according to (1),
The thin layer C constituting the alternate lamination of the upper layers is formed such that the layer thickness gradually increases from the lower layer side toward the upper layer surface layer. Surface coated cutting tool.
(3) In the surface-coated cutting tool according to (1) or (2),
Between the lower and upper layers,
Composition formula: [Ti 1-X Al X ] N
, X is 0.40 to 0.70 (provided that the atomic ratio is satisfied), and an intermediate adhesion layer made of a composite nitride of Ti and Al is formed with a thickness of 0.03 to 0.10 μm. The surface-coated cutting tool according to (1) or (2), wherein
(4) In the surface-coated cutting tool according to any one of (1) to (3),
Between the tool base surface and the lower layer,
Composition formula: [Ti 1-X Al X ] N
X is 0.4 to 0.70 (provided that the atomic ratio is satisfied), and an underlying adhesion layer made of a composite nitride of Ti and Al is formed with a thickness of 0.1 to 1 μm. The surface-coated cutting tool according to any one of (1) to (3), wherein:
(5) In the surface-coated cutting tool according to any one of (1) to (4),
The thin layer A is
Composition formula: [Ti 1-XY Al X Si Y ] N
X is 0.40 to 0.70 and Y is a composite nitride layer of Ti, Al, and Si that satisfies 0.01 to 0.1 (where X and Y are both atomic ratios). The surface-coated cutting tool according to any one of (1) to (4), wherein the surface-coated cutting tool is provided.
(6) In the surface-coated cutting tool according to any one of (1) to (5),
The thin layer B is
Composition formula: [Cr 1-P-Q Al P Si Q] N
, P is 0.40 to 0.75 and Q is 0.01 to 0.1 (however, P and Q are both atomic ratios) and a composite nitride layer of Cr, Al, and Si. The surface-coated cutting tool according to any one of (1) to (5), wherein the surface-coated cutting tool is provided.
(7) In the surface-coated cutting tool according to any one of (1) to (6),
Between the lower and upper layers,
Composition formula: [Ti 1-XY Al X Si Y ] N
X is 0.40 to 0.70 and Y is 0.01 to 0.1 (where X and Y are both atomic ratios), and the composite nitride layer of Ti, Al, and Si is used. The surface-coated cutting tool according to any one of (1) to (6), wherein the intermediate adhesion layer is formed with a thickness of 0.03 to 0.10 μm.
(8) In the surface-coated cutting tool according to any one of (1) to (7),
Between the tool base surface and the lower layer,
Composition formula: [Ti 1-XY Al X Si Y ] N
X is 0.40 to 0.70 and Y is 0.01 to 0.1 (where X and Y are both atomic ratios), and the composite nitride layer of Ti, Al, and Si is used. The surface-coated cutting tool according to any one of (1) to (7), wherein the underlying adhesion layer is interposed with a layer thickness of 0.1 to 1 μm. "
It has the characteristics.

  First, the hard coating layer of the coated tool of the invention of claim 1 will be described in detail.

Lower layer A:
Since the (Ti, Al) N layer constituting the alternate layered structure with the thin layer B is excellent in strength and interlayer adhesion, by constructing the alternate layered with the thin layer B, the thin layer B It is a layer for complementing the relatively lacking characteristics and at the same time increasing the strength of the entire lower layer and further improving the interlayer adhesion.
A thin layer A composed of a (Ti, Al) N layer,
Composition formula: [Ti 1-X Al X ] N
X is a composite nitride layer of Ti and Al that satisfies 0.40 to 0.70 (however, the atomic ratio), and the value of X that represents the Al content (however, the atomic ratio) is If the value is less than 0.40, the high-temperature hardness of the thin layer A becomes insufficient. On the other hand, if the value of X exceeds 0.70, the high-temperature toughness and high-temperature strength of the thin layer A will decrease. Therefore, the value of X was set to 0.40 to 0.70 (however, atomic ratio).

Lower layer B:
As described above, the thin layer B composed of the (Cr, Al) N layers constituting the alternating laminated structure with the thin layer A has a relatively high hardness and is the highest temperature stability layer. Therefore, even at high temperatures during high-speed cutting of heat-resistant alloys such as Ni-base alloys and Co-base alloys, the diffusion of Co, which is a base component, into the hard coating layer is suppressed, and the deterioration of the layer characteristics is prevented. .
A thin layer B composed of a (Cr, Al) N layer,
Composition formula: [Cr 1-P Al P ] N
In this case, P is a composite nitride layer of Cr and Al that satisfies 0.40 to 0.75 (however, the atomic ratio), the Al component has high temperature hardness, the Cr component has high temperature toughness, While improving the high temperature strength and improving the oxidation resistance in the coexistence of Al and Cr, the value of P indicating the Al content (however, the atomic ratio) is less than 0.40. And the high-temperature hardness of the thin layer B becomes insufficient. On the other hand, if the value of P exceeds 0.75, the high-temperature toughness and high-temperature strength of the thin layer B will decrease. It was set to 0.40 to 0.75 (however, atomic ratio).

Layer thickness of thin layer A and thin layer B, total layer thickness of lower layer:
When alternating layers of the thin layer A and the thin layer B are configured, each layer is adjacent to each other to form a layer having a different composition, so that the growth of particles in each layer is prevented from being coarsened. Fineness is achieved and the film strength is improved to improve chipping resistance and chipping resistance. However, if the thickness of each of the thin layer A and the thin layer B is less than 0.003 μm, each thin layer Not only can be clearly formed as having a predetermined composition, but the above-mentioned excellent characteristics of each thin layer cannot be exhibited, while when the thickness of each layer exceeds 0.02 μm, Since the chipping resistance and chipping resistance are reduced due to the decrease in film strength due to the coarsening of the particles, the thickness of each of the thin layer A and the thin layer B was determined to be 0.003 to 0.02 μm.
In addition, the lower layer configured as an alternating laminated structure of the thin layer A and the thin layer B has a total layer thickness of less than 1 μm. On the other hand, if the total layer thickness exceeds 5 μm, chipping and chipping are likely to occur. Therefore, the lower layer configured as an alternate laminated structure of the thin layer A and the thin layer B is likely to occur. The total layer thickness was determined to be 1-5 μm.

Upper layer A:
The component / composition, action, and layer thickness of the thin layer A in the upper layer are the same as those of the thin layer A in the lower layer. Moreover, the thin layer A of the upper layer constitutes an alternating laminated structure with the thin layer C, and gives strength and interlayer adhesion to the upper layer while maintaining the high hardness of the thin layer C.

Upper layer thin layer C:
The thin layer C composed of the (Ti, Si) N layer constituting the upper layer by forming the alternate layered structure with the thin layer A is improved in oxidation resistance by the Si component. As a result, the Ni-based alloy, Co Excellent high hardness is maintained even at high temperatures in high-speed cutting of heat-resistant alloys such as base alloys.
A thin layer C composed of a (Ti, Si) N layer,
Composition formula: [Ti 1 -U Si U ] N
In this case, U is composed of a composite nitride layer of Ti and Si that satisfies 0.01 to 0.30 (however, atomic ratio), but U value (however, atomic ratio) indicating the Si content ratio. However, if it is less than 0.01, the high-temperature hardness of the thin layer C becomes insufficient. On the other hand, if the value of U exceeds 0.30, the high-temperature toughness and high-temperature strength of the thin layer C decrease. Therefore, the value of U was set to 0.01 to 0.30 (however, the atomic ratio).

Layer thickness of thin layer A and thin layer C, total layer thickness of upper layer:
When alternating layers of the thin layer A and the thin layer C are configured, as in the case of the alternate stacking of the lower layer, each layer is adjacent to each other to form a layer having a different composition. Growth coarsening is prevented, particles are refined, and film strength is improved to improve chipping resistance and chipping resistance. However, the thickness of each of the thin layer A and the thin layer C is 0. When the thickness is less than 0.003 μm, it is difficult to clearly form each thin layer as having a predetermined composition, and the above-mentioned excellent characteristics of each thin layer cannot be exhibited. If the layer thickness exceeds 0.02 μm, the chip strength and chipping resistance decrease due to the decrease in film strength due to the coarsening of the particles. 003 to 0.02 μm.
In addition, the upper layer configured as an alternate laminated structure of the thin layer A and the thin layer C, when the total layer thickness is less than 1 μm, sufficiently exhibits the high hardness provided by the thin layer C and improves the wear resistance. On the other hand, if the total layer thickness exceeds 5 μm, chipping and defects are likely to occur. Therefore, the total layer thickness of the upper layer configured as an alternately laminated structure of the thin layer A and the thin layer C is set to 1 to 1. It was set to 5 μm.

Next, the hard coating layer of the coated tool of the invention of claim 2 will be described. The thin layer C constituting the alternate lamination of the upper layer has a high residual stress after vapor deposition, and therefore, the residual of the lower layer and the upper layer. Due to the stress difference, the upper layer may peel off during the cutting process.
Therefore, when the thin layer C of the upper layer is formed by vapor deposition, the gap of the residual stress is reduced by forming the thin layer C so that the layer thickness gradually increases from the lower layer side to the upper layer surface layer. In addition, it is possible to prevent separation of the layers due to the difference in residual stress between the lower layer and the upper layer.

Next, the hard coating layer of the coated tool of the invention of claim 3 will be described. Since the lower layer and the upper layer are each formed as an alternate lamination with a thin layer A composed of a (Ti, Al) N layer, Although it has excellent interlayer adhesion strength, it is composed of the same component as the thin layer A between the lower layer and the upper layer, and has a layer thickness (Ti, Al) larger than the layer thickness of the thin layer A ) By interposing the N layer as an intermediate adhesion layer, the interlayer adhesion strength between the lower layer and the upper layer can be made stronger. In addition, as described above, a residual stress difference after vapor deposition occurs between the lower layer and the upper layer, which may cause delamination, but the residual stress difference can be mitigated through the intermediate adhesion layer. And the occurrence of delamination can be prevented.
When the thickness of the intermediate adhesion layer is less than 0.03 μm, the effect of improving the interlayer adhesion strength between the lower layer and the upper layer is small. On the other hand, when the thickness of the intermediate adhesion layer exceeds 0.10 μm, the wear resistance is improved. Since a decreasing tendency is observed, the layer thickness of the intermediate adhesion layer is determined to be 0.03 to 0.10 μm.

Next, the hard coating layer of the coated tool of the invention of claim 4 will be described. As described above, the (Ti, Al) N layer itself has high strength, and the thin layer B or the thin layer C and the laminated layers are alternately laminated. When formed, the interlayer adhesion strength of each thin layer is increased, but the (Ti, Al) N layer also has a high adhesion strength with the tool substrate surface, so the same as the thin layer A between the tool substrate surface and the lower layer. By forming an (Ti, Al) N layer composed of components and having a thickness larger than the thickness of the thin layer A as an underlying adhesion layer, the adhesion strength between the tool base and the lower layer is made stronger. be able to.
If the layer thickness of the base adhesion layer is less than 0.1 μm, the effect of improving the adhesion strength between the tool substrate and the lower layer is small. On the other hand, if the layer thickness of the base adhesion layer exceeds 1 μm, the wear resistance tends to decrease. Therefore, the thickness of the base adhesion layer was determined to be 0.1 to 1 μm.

Next, the hard coating layer of the coated tool of the invention of claim 5 will be described.
The thin layer A composed of the (Ti, Al) N layer is a layer having excellent strength and interlayer adhesion, but a part of Ti as a constituent component of the thin layer A is replaced with Si,
Composition formula: [Ti 1-XY Al X Si Y ] N
X is 0.40 to 0.70 and Y is a composite nitride layer of Ti, Al, and Si that satisfies 0.01 to 0.1 (where X and Y are both atomic ratios). When the thin layer A is configured, the thin layer A has excellent oxidation resistance and high hardness, and thus is superior under high-temperature conditions such as high-speed cutting of heat-resistant alloys such as Ni-base alloys and Co-base alloys. Shows wear resistance.
When the Y value (however, the atomic ratio) indicating the content ratio of Si is less than 0.01, improvement in oxidation resistance cannot be expected. On the other hand, when the Y value exceeds 0.1, Since high temperature hardness falls, Y value which shows the content rate of Si component was defined as 0.01-0.1.

Next, the hard coating layer of the coated tool of the invention of claim 6 will be described.
As described above, the thin layer B made of the (Cr, Al) N layer is a layer having a relatively high hardness and the highest stability at high temperature, but is one of Cr that is a constituent component of the thin layer B. Part is replaced with Si,
Composition formula: [Cr 1-P-Q Al P Si Q] N
, P is 0.40 to 0.75 and Q is 0.01 to 0.1 (however, P and Q are both atomic ratios) and a composite nitride layer of Cr, Al, and Si. When the thin layer B is configured, the Si component has the effect of improving the high temperature hardness and the heat-resistant plastic deformation, so the thin layer B and the lower layer formed by alternately laminating this and the thin layer A are more excellent. Demonstrate wear resistance.
However, if the Q value (atomic ratio) indicating the content ratio of Si is less than 0.01, the effect of improving the wear resistance due to the improvement of high temperature hardness and heat plastic deformation cannot be expected, while the Q value is 0.1. When the value exceeds 1, the wear resistance improving effect tends to decrease, so the Q value was determined to be 0.01 to 0.1.

Next, the hard coating layer of the coated tool of the invention of claim 7 will be described.
Since the lower layer and the upper layer are formed as alternating layers with the thin layer A composed of (Ti, Al) N layers, respectively, the lower layer and the upper layer have excellent interlayer adhesion strength. (Ti, Al, Si) N layer in which a part of the constituents of the thin layer A is replaced by Si between the layers, ie,
Composition formula: [Ti 1-XY Al X Si Y ] N
X is 0.40 to 0.70 and Y is 0.01 to 0.1 (where X and Y are atomic ratios), a composite nitride layer of Ti, Al, and Si,
By interposing and forming as an intermediate adhesion layer, the interlayer adhesion strength between the lower layer and the upper layer can be made stronger. Also, a residual stress difference after vapor deposition occurs between the lower layer and the upper layer, which may cause delamination, but the residual stress difference can be mitigated through the intermediate adhesion layer, and delamination Can be prevented.
If the thickness of the intermediate adhesion layer is less than 0.03 μm as in the case of the intermediate adhesion layer made of (Ti, Al) N layer, the effect of improving the interlayer adhesion strength between the lower layer and the upper layer is small. When the layer thickness exceeds 0.10 μm, a tendency to decrease the wear resistance is observed. Therefore, the layer thickness of the intermediate adhesion layer is determined to be 0.03 to 0.10 μm.

Next, the hard coating layer of the coated tool of the invention of claim 8 will be described.
As described above, by interposing and forming the (Ti, Al) N layer as the base adhesion layer, the adhesion strength between the tool base and the lower layer can be strengthened. However, the configuration of the (Ti, Al) N layer (Ti, Al, Si) N layer in which a part of the components is replaced by Si, that is,
Formula: [Ti 1-X-Y Al X Si Y] N
X is 0.40 to 0.70 and Y is 0.01 to 0.1 (where X and Y are atomic ratios), a composite nitride layer of Ti, Al, and Si,
Is interposed between the tool base surface and the lower layer, whereby the adhesion strength between the tool base and the lower layer can be further strengthened.
If the layer thickness of the base adhesion layer is less than 0.1 μm, the effect of improving the adhesion strength between the tool substrate and the lower layer is small. On the other hand, if the layer thickness of the base adhesion layer exceeds 1 μm, the wear resistance tends to decrease. Therefore, the thickness of the base adhesion layer was determined to be 0.1 to 1 μm.

In the surface-coated cutting tool of the present invention, the hard coating layer is composed of a lower layer composed of an alternating laminate structure of thin layers A and B and an upper layer consisting of an alternating laminate structure of thin layers A and C. (Claim 1) Thus, excellent wear resistance is exhibited in high-speed cutting of heat-resistant alloys such as Ni-base alloys and Co-base alloys.
Further, the (Ti, Si) N layer constituting the thin layer C is formed such that the layer thickness increases toward the surface layer of the upper layer (Claim 2), whereby the lower layer after vapor deposition is formed. -The residual stress difference between the upper layers is relaxed and peeling of the layers is prevented, and an intermediate adhesion layer is formed between the lower layer and the upper layer (Claims 3 and 7), so that Interlayer adhesion strength is ensured, and a base adhesion layer is formed between the surface of the substrate and the lower layer (Claims 4 and 8), thereby ensuring adhesion strength between the substrate and the lower layer. Is replaced with Si (Claim 5), and a part of the constituents of the thin layer B is replaced with Si (Claim 6), whereby high-speed heat-resistant alloys such as Ni-base alloys and Co-base alloys Excellent cutting and chipping, chipping, uneven wear, and no peeling It is intended to exert over the wear resistance in long-term.

The arc ion plating apparatus used for forming the hard coating layer which comprises the coating tool of this invention is shown, (a) is a schematic plan view, (b) is a schematic front view. The arc ion plating apparatus used for forming the hard coating layer which comprises a comparative coating tool is shown, (a) is a schematic plan view, (b) is a schematic front view.

  Next, the coated tool of the present invention will be specifically described with reference to examples.

As raw material powders, WC powder, TaC powder, NbC powder, Cr 3 C 2 powder and Co powder all having an average particle diameter of 1 to 3 μm are prepared, and these raw material powders are blended in the composition shown in Table 1. The mixture is wet mixed in a ball mill for 72 hours, dried, and then pressed into a green compact at a pressure of 100 MPa. The green compact is sintered in a 6 Pa vacuum at a temperature of 1400 ° C. for 1 hour. After sintering, honing of R: 0.02 was applied to the cutting edge portion to form tool bases A-1 to A-5 made of WC-base cemented carbide having ISO standard / CNMG120408 chip shape.

(A) Next, each of the tool bases A-1 to A-5 is ultrasonically cleaned in acetone and dried, and the center on the rotary table in the arc ion plating apparatus shown in FIG. Attached along the outer periphery at a predetermined distance in the radial direction from the shaft, each cathode electrode (evaporation source) has a component composition corresponding to the target composition shown in Table 2 (Ti, Al ) N-layer forming Ti—Al alloy, (Cr, Al) N-layer forming Cr— having a component composition corresponding to the target composition shown in Table 2, respectively, as the opposite cathode electrode (evaporation source) Al alloy, (Ti, Si) N having a component composition corresponding to the target composition shown in Table 2 at an intermediate position between the cathode electrode (evaporation source) on one side and the cathode electrode (evaporation source) on the other side Ti for layer formation The Si alloy disposed across the rotary table.
The cathode electrode (evaporation source) made of a Ti—Al alloy is used for the vapor deposition formation of the thin layer A, the intermediate adhesion layer and the underlying adhesion layer, and the bombard cleaning of the tool base, and the cathode electrode (evaporation) made of a Cr—Al alloy. The source) is used for vapor deposition of the thin layer B, and the cathode electrode (evaporation source) made of a Ti—Si alloy is used for vapor deposition of the thin layer C.
(B) First, the inside of the apparatus is evacuated and kept at a vacuum of 0.5 Pa or less, and the inside of the apparatus is heated to 500 ° C. with a heater, and then the tool substrate that rotates while rotating on the rotary table is −1000 V A direct current bias voltage is applied and, for example, a current of 100 A is passed between a Ti—Al alloy cathode electrode and an anode electrode to generate an arc discharge, whereby the tool base surface is bombarded.
(C) Next, nitrogen gas is introduced as a reaction gas into the apparatus to form a reaction atmosphere of 2 Pa, and a DC bias voltage of −100 V is applied to the tool base that rotates while rotating on the rotary table. An arc discharge is generated by passing a current of 100 A between the Al alloy cathode electrode and the anode electrode, so that a base adhesion layer having a target composition and a target layer thickness shown in Tables 2 and 3 is deposited on the surface of the tool base. To do.
(D) Next, nitrogen gas is introduced as a reaction gas into the apparatus to form a reaction atmosphere of 2 Pa, and a DC bias voltage of −100 V is applied to the tool base that rotates while rotating on the rotary table. A predetermined current within a range of 50 to 200 A is passed between the cathode electrode and the anode electrode of the Cr—Al alloy to generate an arc discharge, and a thin layer having a predetermined layer thickness is formed on the tool base (the underlying adhesion layer). Layer B is formed, and then a predetermined current in the range of 50 to 200 A is passed between the cathode electrode and the anode electrode of Ti—Al alloy to generate arc discharge, thereby forming thin layer A having a predetermined layer thickness. After that, the thin layer B and the thin layer A are alternately and repeatedly formed until the total thickness of the target lower layer is reached.
(E) Next, a nitrogen gas is introduced as a reaction gas into the apparatus and a DC bias voltage of −100 V is applied to a tool base that rotates while rotating on the rotary table while maintaining a reaction atmosphere of 2 Pa. -An arc discharge is generated by passing a current of 100 A between the Al alloy cathode electrode and the anode electrode, so that an intermediate adhesion layer having the target composition and target layer thickness shown in Tables 2 and 3 is deposited on the surface of the tool base. Form.
(F) Next, a DC bias voltage of −100 V was applied to the rotating tool base while rotating on the rotary table while introducing a nitrogen gas as a reaction gas into the apparatus and maintaining a reaction atmosphere of 2 Pa. In this state, a predetermined current in the range of 50 to 200 A is passed between the cathode electrode and the anode electrode of the Cr—Al alloy to generate arc discharge, and a thin layer C having a predetermined layer thickness is formed on the intermediate adhesion layer. After that, a predetermined current in the range of 50 to 200 A is passed between the cathode electrode and the anode electrode of the Ti—Al alloy to generate arc discharge to form a thin layer A having a predetermined layer thickness. Furthermore, the formation of the thin layer C and the thin layer A is repeated alternately until the total thickness of the target upper layer is reached (in addition, each time the thin layer C is repeatedly deposited, the deposition time is lengthened). By In the claims 2, it is possible to layer thickness toward the upper layer surface to form a thin layer C to be large).
By the above steps (a) to (f), the lower layer composed of the alternating lamination of the thin layer A and the thin layer B on the surface of the tool base, the base adhesion layer having the target composition and the target layer thickness shown in Tables 2 and 3 The present invention coated chips 1 to 10 as the present invention coated tool having a throwaway tip shape defined in ISO / CNMG120408 by vapor deposition of an intermediate adhesion layer and an upper layer composed of alternately laminated thin layers A and C. Were manufactured respectively.
In addition, said (c) is a process corresponding to Claim 4, said (e) is a process corresponding to Claim 3, respectively, and in order to form the thin layer of Claims 5-8, Ti-Al alloy is formed. Instead of the cathode electrode, a Ti—Al—Si alloy cathode electrode may be used, and instead of the Cr—Al alloy cathode electrode, a Cr—Al—Si alloy cathode electrode may be used.

For the purpose of comparison, these tool bases A-1 to A-5 were ultrasonically cleaned in acetone and dried, and then charged into the arc ion plating apparatus shown in FIG. As a source), a Ti—Al alloy and a Ti—Si alloy each having a component composition corresponding to the target composition shown in Table 4 are mounted,
First, while evacuating the inside of the apparatus and maintaining the vacuum at 0.5 Pa or less, the inside of the apparatus was heated to 500 ° C. with a heater, a DC bias voltage of −1000 V was applied to the tool base, and the cathode electrode An arc discharge is generated by passing a current of 100 A between the Ti—Al alloy (or Ti—Si alloy) and the anode electrode, and the tool base surface is bombarded with the Ti—Al alloy,
Next, nitrogen gas is introduced into the apparatus as a reaction gas to make a reaction atmosphere of 2 Pa, and the bias voltage applied to the tool base is lowered to −100 V, so that the cathode electrode and the anode electrode of the Ti—Al alloy are placed between them. An arc discharge is generated, and a (Ti, Al) N layer having a target composition and a target layer thickness shown in Table 4 is formed on the surface of the tool base by vapor deposition.
Next, an arc discharge is generated between the cathode electrode and the anode electrode of the Ti—Si alloy, and the (Ti, Si) N layer having the target composition and target layer thickness shown in Table 4 is formed on the surface of the tool base. Vapor-deposited,
By alternately repeating the deposition formation of the above (Ti, Al) N layer and (Ti, Si) N layer, it has a hard coating layer consisting of alternating lamination of the target composition and target layer thickness shown in Table 4, Comparative coated tips 1 to 10 as a comparative coated tool having a throwaway tip shape defined in ISO / CNMG120408 were manufactured.

Next, in the state where each of the above various coated chips is screwed to the tip of the tool steel tool with a fixing jig, the present coated chips 1 to 10 and the comparative coated chips 1 to 10 are as follows.
Work Material: Ni-19% Cr-18.5% Fe-5.2% Cd-5% Ta-3% Mo-0.9% Ti-0.5% Al-0.3% by mass% Four longitudinally-grooved round bars at equal intervals in the length direction of a Ni-based alloy having a composition of Si-0.2% Mn-0.05% Cu-0.04% C,
Cutting speed: 100 m / min. ,
Cutting depth: 1.5 mm,
Feed: 0.2 mm / rev. ,
Cutting time: 5 minutes,
A dry high-speed intermittent cutting test of a Ni-based alloy under the above conditions (cutting condition A) (normal cutting speed is 30 m / min.),
Work material: Equal intervals in the length direction of Co-based alloy having a composition of Co-23% Cr-6% Mo-2% Ni-1% Fe-0.6% Si-0.4% C in mass% 4 fluted round bars,
Cutting speed: 80 m / min. ,
Cutting depth: 1.5 mm,
Feed: 0.15 mm / rev. ,
Cutting time: 5 minutes,
A dry high-speed intermittent cutting test of a Co-based alloy under the conditions (cutting condition B) (normal cutting speed is 25 m / min.),
In each cutting test, the flank wear width of the cutting edge was measured. The measurement results are shown in Table 5.

As raw material powders, WC powder having an average particle size of 0.8 μm, 2.3 μm Cr 3 C 2 powder, 1.5 μm VC powder, and 1.8 μm Co powder were prepared. 6 was added to the composition shown in FIG. 6 and added with wax, mixed in a ball mill for 24 hours in acetone, dried under reduced pressure, and then press-molded into various compacts of a predetermined shape at a pressure of 100 MPa. The body is heated to a predetermined temperature in the range of 1370 to 1470 ° C. at a heating rate of 7 ° C./min in a vacuum atmosphere of 6 Pa, held at this temperature for 1 hour, and then sintered under furnace cooling conditions. Then, a round tool sintered body for forming a tool base is formed, and further, a diameter of the cutting edge portion × length is 10 mm × 22 mm and a twist angle is 45 degrees by grinding from the round bar sintered body. Made of WC-based cemented carbide with a 4-flute square shape Tool substrate (end mill) C-1~C-4 were prepared, respectively.

  Next, the surfaces of these tool bases (end mills) C-1 to C-4 were ultrasonically cleaned in acetone and dried, and then charged into the arc ion plating apparatus shown in FIG. Under the same conditions as in Example 1, along the layer thickness direction, a base adhesive layer having a target composition and target layer thickness shown in Table 7, a lower layer composed of alternating layers of thin layers A and B, an intermediate adhesive layer, and a thin layer The present invention coated end mills 1 to 8 as the present invention coated tools were produced by vapor-depositing an upper layer composed of alternately laminated layers A and thin layers C, respectively.

  For the purpose of comparison, the surfaces of the tool bases (end mills) C-1 to C-4 are ultrasonically cleaned in acetone and dried, and then mounted on the arc ion plating apparatus shown in FIG. Then, under the same conditions as in Example 1, the (Ti, Al) N layer having the target composition and target layer thickness shown in Table 8 is formed on the surface of the tool base (end mill) C-1 to C-4 ( Comparative coating end mills 1 to 8 as comparative coating tools were manufactured by vapor-depositing a hard coating layer composed of alternating layers of Ti, Si) N layers.

Next, for the present invention coated end mills 1-8 and comparative coated end mills 1-8,
Work Material-Plane Dimensions: 100mm x 250mm, Thickness: 50mm, Mass%, Ni-19% Cr-14% Co-4.5% Mo-2.5% Ti-2% Fe-1.2 Ni-base alloy plate material having a composition of% Al-0.7% Mn-0.4% Si,
Cutting speed: 60 m / min. ,
Groove depth (cut): 2.5 mm,
Table feed: 250 mm / min,
Ni-base alloy dry high-speed grooving test under the conditions (normal cutting speed and groove depth are 25 m / min. And 1.2 mm, respectively),
The cutting groove length was measured until the flank wear width of the outer peripheral edge of the cutting edge reached 0.1 mm, which is a guide for the service life. The measurement results are shown in Tables 7 and 8, respectively.

  Using the round bar sintered body manufactured in Example 2 above, from this round bar sintered body, the diameter x length of the groove forming portion is 8 mm x 48 mm and the helix angle is 30 degrees by grinding. WC base cemented carbide tool bases (drills) D-1 to D-4 each having a two-blade shape were manufactured.

  Next, the cutting edges of these tool bases (drills) D-1 to D-4 are subjected to honing, ultrasonically cleaned in acetone, and dried to the arc ion plating apparatus shown in FIG. The lower layer consisting of the alternating lamination of thin layer A and thin layer B under the same conditions as in Example 1 above, with the underlying composition and target layer thickness shown in Table 9 along the layer thickness direction The present invention-coated drills 1 to 8 as the present invention-coated tools were produced by vapor-depositing and forming an intermediate adhesion layer and an upper layer composed of alternately laminated thin layers A and C, respectively.

  For the purpose of comparison, the surface of the tool base (drill) D-1 to D-4 is subjected to honing, ultrasonically cleaned in acetone, and dried, and the arc ions shown in FIG. In the plating apparatus, under the same conditions as in Example 1, the target compositions and target layer thicknesses (Ti, Al) shown in Table 10 are formed on the surfaces of the tool bases (drills) D-1 to D-4. Comparative coating drills 1 to 8 as comparative coating tools were manufactured by vapor-depositing a hard coating layer having an alternately laminated structure of N layers and (Ti, Si) N layers.

Next, for the present invention coated drills 1-8 and comparative coated drills 1-8,
Work Material—Plane Size: 100 mm × 250 mm, Thickness: 50 mm, Mass%, Ni-19% Cr-18.5% Fe-5.2% Cd-5% Ta-3% Mo-0.9 Ni-based alloy plate having a composition of% Ti-0.5% Al-0.3% Si-0.2% Mn-0.05% Cu-0.04% C,
Cutting speed: 50 m / min. ,
Feed: 0.25 mm / rev,
Hole depth: 20 mm,
Wet high-speed drilling test of Ni-based alloy under the following conditions (normal cutting speed and feed are 25 m / min. And 0.12 mm / rev, respectively),
(Using water-soluble cutting oil), and the number of drilling operations was measured until the flank wear width of the cutting edge surface reached 0.3 mm. The measurement results are shown in Tables 9 and 10, respectively.

  As a result of the present invention coated tool as the present coated tool 1-10, the present invention coated end mills 1-8, and the underlying adhesion layer constituting the hard coated layer of the present coated drill 1-8, thin layer A and A lower layer composed of an alternately laminated structure of thin layers B, an intermediate adhesion layer and an upper layer composed of an alternately laminated structure of thin layers A and C, and further, comparative coated chips 1 to 10, comparative coated end mills 1 to 8 and comparative coated The composition of the (Ti, Al) N layer and (Ti, Si) N layer constituting the hard coating layer consisting of the alternating layers of the drills 1 to 8 is measured by energy dispersive X-ray analysis using a transmission electron microscope. As a result, each showed substantially the same composition as the target composition.

  Moreover, when the average layer thickness of said hard coating layer was cross-sectional measured using the scanning electron microscope, all showed the average value (average value of five places) substantially the same as target layer thickness.

From the results shown in Tables 5 and 7 to 10, the coated tool of the present invention is such that the hard coating layer is a lower adhesion layer, an intermediate adhesion layer and a thin layer comprising an underlayer adhesion layer and an alternating laminated structure of thin layers A and B. It is composed of an upper layer composed of an alternating laminated structure of A and thin layers C (Claim 1), and exhibits excellent wear resistance in high-speed cutting of heat-resistant alloys such as Ni-base alloys and Co-base alloys, and is thin. The (Ti, Si) N layer constituting the layer C is formed such that the layer thickness increases toward the surface layer of the upper layer (Claim 2), whereby the lower layer-upper layer after vapor deposition is formed. The residual stress difference between the lower layer and the upper layer is prevented, and the interlayer adhesion is formed between the lower layer and the upper layer, so that the interlayer adhesion strength between the lower layer and the upper layer is ensured. And a base adhesion layer is formed between the substrate surface and the lower layer. According to the present invention, adhesion strength between the substrate and the lower layer is ensured, and a part of Ti as a constituent component of the thin layer A is replaced with Si (Claim 5), or a constituent component of the thin layer B By substituting a part of Cr, which is, with Si (Claim 6), high-speed cutting of heat-resistant alloys such as Ni-base alloys and Co-base alloys can be performed without occurrence of chipping, chipping, uneven wear, and peeling. Demonstrate wear resistance over a long period of time.
On the other hand, in the comparative coated tool in which the hard coating layer is configured by alternately laminating (Ti, Al) N layers and (Ti, Si) N layers, a heat-resistant alloy such as a Ni-based alloy or a Co-based alloy is used. In high-speed cutting, it is apparent that the service life is reached in a relatively short time due to lack of chipping resistance and fracture resistance.

  As described above, the coated tool of the present invention can be used for high-speed cutting of heat-resistant alloys such as Ni-base alloys and Co-base alloys with high heat generation as well as cutting of general steel and ordinary cast iron. Because it exhibits excellent wear resistance over a long period of time and exhibits excellent cutting performance, it is sufficiently satisfied with the FA of cutting equipment, labor saving and energy saving of cutting work, and further cost reduction It can respond.

Claims (8)

  1. A surface-coated cutting tool in which a hard coating layer composed of at least a lower layer and an upper layer is vapor-deposited on the surface of a tool substrate,
    (A) The lower layer is a layer having a total layer thickness of 1 to 5 μm composed of alternating layers of a thin layer A having a thickness of 0.003 to 0.02 μm and a thin layer B having a thickness of 0.003 to 0.02 μm. Because
    (B) The upper layer is a layer having a total layer thickness of 1 to 5 μm composed of alternating layers of a thin layer A having a thickness of 0.003 to 0.02 μm and a thin layer C having a thickness of 0.003 to 0.02 μm. Because
    (C) The thin layer A is
    Composition formula: [Ti 1-X Al X ] N
    X represents a composite nitride layer of Ti and Al that satisfies 0.40 to 0.70 (however, the atomic ratio),
    (D) The thin layer B is
    Composition formula: [Cr 1-P Al P ] N
    , P is a composite nitride layer of Cr and Al that satisfies 0.40 to 0.75 (however, atomic ratio),
    (E) The thin layer C is
    Composition formula: [Ti 1 -U Si U ] N
    In this case, U is a composite nitride layer of Ti and Si that satisfies 0.01 to 0.30 (however, the atomic ratio),
    A surface-coated cutting tool characterized in that
  2. The surface-coated cutting tool according to claim 1,
    The said thin layer C which comprises the alternate lamination | stacking of an upper layer is formed so that the layer thickness may increase gradually as it goes to the upper layer surface layer from the lower layer side. Surface coated cutting tool.
  3. The surface-coated cutting tool according to claim 1 or 2,
    Between the lower and upper layers,
    Composition formula: [Ti 1-X Al X ] N
    , X is 0.40 to 0.70 (provided that the atomic ratio is satisfied), and an intermediate adhesion layer made of a composite nitride of Ti and Al is formed with a thickness of 0.03 to 0.10 μm. The surface-coated cutting tool according to claim 1, wherein the surface-coated cutting tool is provided.
  4. In the surface coating cutting tool as described in any one of Claims 1 thru | or 3,
    Between the tool base surface and the lower layer,
    Composition formula: [Ti 1-X Al X ] N
    X is 0.4 to 0.70 (provided that the atomic ratio is satisfied), and an underlying adhesion layer made of a composite nitride of Ti and Al is formed with a thickness of 0.1 to 1 μm. The surface-coated cutting tool according to any one of claims 1 to 3, wherein the surface-coated cutting tool is provided.
  5. The surface-coated cutting tool according to any one of claims 1 to 4,
    The thin layer A is
    Composition formula: [Ti 1-XY Al X Si Y ] N
    X is 0.40 to 0.70 and Y is a composite nitride layer of Ti, Al, and Si that satisfies 0.01 to 0.1 (where X and Y are both atomic ratios). The surface-coated cutting tool according to claim 1, wherein the surface-coated cutting tool is provided.
  6. The surface-coated cutting tool according to any one of claims 1 to 5,
    The thin layer B is
    Composition formula: [Cr 1-P-Q Al P Si Q] N
    , P is 0.40 to 0.75 and Q is 0.01 to 0.1 (however, P and Q are both atomic ratios) and a composite nitride layer of Cr, Al, and Si. The surface-coated cutting tool according to claim 1, wherein the surface-coated cutting tool is provided.
  7. The surface-coated cutting tool according to any one of claims 1 to 6,
    Between the lower and upper layers,
    Composition formula: [Ti 1-XY Al X Si Y ] N
    X is 0.40 to 0.70 and Y is 0.01 to 0.1 (where X and Y are both atomic ratios), and the composite nitride layer of Ti, Al, and Si is used. The surface-coated cutting tool according to any one of claims 1 to 6, wherein the intermediate adhesion layer is interposed with a layer thickness of 0.03 to 0.10 µm.
  8. The surface-coated cutting tool according to any one of claims 1 to 7,
    Between the tool base surface and the lower layer,
    Composition formula: [Ti 1-XY Al X Si Y ] N
    X is 0.40 to 0.70 and Y is 0.01 to 0.1 (where X and Y are both atomic ratios), and the composite nitride layer of Ti, Al, and Si is used. The surface-coated cutting tool according to any one of claims 1 to 7, wherein the underlying adhesion layer is interposed with a layer thickness of 0.1 to 1 µm.
JP2009053275A 2009-03-06 2009-03-06 Surface coated cutting tool Withdrawn JP2010207916A (en)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN102886552A (en) * 2011-07-22 2013-01-23 三菱综合材料株式会社 Surface-coated drill having excellent lubricating property and abrasion resistance
WO2014025057A1 (en) * 2012-08-10 2014-02-13 株式会社タンガロイ Coated tool
JP2015139868A (en) * 2014-01-30 2015-08-03 三菱マテリアル株式会社 Surface-coated cutting tool exhibiting chipping resistance over a long period in cutting work of high-hardness steel
JP2015530270A (en) * 2012-09-28 2015-10-15 バルター アクチェンゲゼルシャフト Tool with TiAlCrSiN coating by PVD
JP5973001B2 (en) * 2013-02-07 2016-08-17 三菱重工工作機械株式会社 Surface coating material and cutting tool and machine tool using the same
WO2017037956A1 (en) * 2015-09-04 2017-03-09 オーエスジー株式会社 Hard coating and hard coating-covered member
WO2017037955A1 (en) * 2015-09-04 2017-03-09 オーエスジー株式会社 Hard coating and hard coating-covered member

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102886552A (en) * 2011-07-22 2013-01-23 三菱综合材料株式会社 Surface-coated drill having excellent lubricating property and abrasion resistance
CN102886552B (en) * 2011-07-22 2016-01-06 三菱综合材料株式会社 The surface coated drill of lubrication property and excellent in abrasion resistance
US10501842B2 (en) 2012-08-10 2019-12-10 Tungaloy Corporation Coated tool
JP5817932B2 (en) * 2012-08-10 2015-11-18 株式会社タンガロイ Coated tool
WO2014025057A1 (en) * 2012-08-10 2014-02-13 株式会社タンガロイ Coated tool
US10487388B2 (en) 2012-09-28 2019-11-26 Walter Ag Tool with TiAlCrSiN PVD coating
JP2015530270A (en) * 2012-09-28 2015-10-15 バルター アクチェンゲゼルシャフト Tool with TiAlCrSiN coating by PVD
JP5973001B2 (en) * 2013-02-07 2016-08-17 三菱重工工作機械株式会社 Surface coating material and cutting tool and machine tool using the same
US9528186B2 (en) 2013-02-07 2016-12-27 Mitsubishi Heavy Industries Machine Tool Co., Ltd. Surface-coating material, cutting tool in which said material is used, and working machine in which said material is used
JP2015139868A (en) * 2014-01-30 2015-08-03 三菱マテリアル株式会社 Surface-coated cutting tool exhibiting chipping resistance over a long period in cutting work of high-hardness steel
WO2017037955A1 (en) * 2015-09-04 2017-03-09 オーエスジー株式会社 Hard coating and hard coating-covered member
CN108138306A (en) * 2015-09-04 2018-06-08 Osg株式会社 Hard film and hard film coating component
WO2017037956A1 (en) * 2015-09-04 2017-03-09 オーエスジー株式会社 Hard coating and hard coating-covered member
CN108138306B (en) * 2015-09-04 2020-01-03 Osg株式会社 Hard coating and hard coating-coated member

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