WO2012057000A1 - Hard film coated member and method for forming hard coating film - Google Patents

Abstract

The present invention provides a first hard film coated member wherein: layers A having a composition that satisfies Ti_aCr_bAl_cSi_dY_e(B_uC_vN_w) (wherein a, b, c, d, e, u, v and w respectively represent specific atomic ratios) and layers B having a composition that satisfies Ti_fCr_gAl_h(B_xC_yN_z) (wherein f, g, h, x, y and z respectively represent specific atomic ratios) are alternately laminated on a substrate; and when a lamination structure composed of a pair of the layer A and the layer B is considered as one unit, the thickness of the one unit is 10-50 nm and the film thickness of the hard coating film is 1-5 μm. The present invention also provides a second hard film coated member wherein: the layer A is laminated on the layer B with an intermediate layer interposed therebetween and having a thickness of 0.5 μm or less or without an intermediate layer; and the layer A has a thickness of 0.5-5.0 μm and the layer B has a thickness of 0.05-3.0 μm.

Description

Hard film forming member and hard film forming method

The present invention relates to a hard film forming member obtained by coating a hard film on the surface of a cutting tool, a sliding member, a molding die, and the like, and a method for forming the hard film.

Conventionally, to improve the wear resistance of cutting tools such as chips, drills and end mills based on cemented carbide, cermet, high-speed tool steel, etc. and jigs and tools such as presses, forging dies and punching punches. For the purpose, a hard film such as TiN, TiC, TiCN, TiAlN, TiAlCrN, TiAlCrCN, TiAlCrSiBCN, TiCrAlSiBN, CrAlSiBYN, and AlCrN is coated.

For example, Patent Document 1 discloses a hard coating for a cutting tool that is made of TiAlCrCN and defines the atomic ratio of each element. Patent Document 2 discloses a hard coating for a cutting tool that is made of TiAlCrSiBCN and defines the atomic ratio of each element. Further, these documents disclose a technique for forming a film by an arc ion plating method.

Further, Patent Document 3 discloses (M) CrAlSiBYZ [wherein M is at least one element selected from Group 4A elements, Group 5A elements, Group 6A elements (excluding Cr) in the periodic table, and Z Is one of N, CN, NO or CNO] or CrAlSiBYZ [wherein Z is one of N, CN, NO or CNO], and M, Cr, Al, Si, B, A hard coating that defines the atomic ratio of Y is disclosed. In addition, a hard film is disclosed in which these hard films are alternately laminated with different compositions, and the thickness of each layer is defined. Furthermore, a technique for forming a film by an arc ion plating method is disclosed.

Patent Document 4 is composed of AlCrX [where X is any one of N, C, B, CN, BN, CBN, NO, CO, BO, CNO, BNO, or CBNO]. A workpiece having a hard material layer (hard coating) with a defined atomic ratio is disclosed.

Japanese Unexamined Patent Publication No. 2003-71610 Japanese Unexamined Patent Publication No. 2003-71611 Japanese Unexamined Patent Publication No. 2008-7835 Japan Special Table 2006-524748

These hard coatings composed of a single layer or multiple layers improve the oxidation resistance of the coating by defining the atomic ratio of predetermined elements. However, in order to use a member with a hard coating in an environment where higher oxidation resistance is required, such as when applied to a cutting tool that performs dry processing, for example, performance in a member such as wear resistance. Further improvement is desired. Further, with the recent increase in hardness and cutting speed of work materials, there is a demand for hard coatings that have further improved wear resistance compared to conventional hard coatings.

This invention is made | formed in view of this situation, and makes it a subject to provide the formation method of the hard film formation member excellent in abrasion resistance, and a hard film.

As a result of diligent research, the inventors of the present invention combined a layer A having a predetermined component composition and a layer B having a predetermined component composition to form a laminated film, and 1 of the laminated structure of the A layer and the B layer. It has been found that the wear resistance of a hard coating (hereinafter referred to as a coating as appropriate) can be improved by defining the thickness of the unit (that is, the lamination cycle). That is, the wear resistance is not sufficiently improved only by defining the atomic ratio of the predetermined element in each layer of the A layer and the B layer, and the wear resistance is not sufficiently improved only by defining the thickness of one unit. . However, it has been found that the wear resistance is improved by simultaneously controlling the component composition of the film and the thickness of one unit.

That is, the first hard coating member of the present invention is a hard coating formed member having a hard coating on a substrate, said hard coating composition is _{Ti a Cr b Al c Si d} Y e (B u C _v N _w ), and when a, b, c, d, e, u, v, w are atomic ratios, 0.05 ≦ a, 0.05 ≦ b, 0.2 ≦ a + b ≦ 0.55, 0.4 ≦ c ≦ 0.7, 0.02 ≦ d ≦ 0.2, 0 ≦ e ≦ 0.1, 0 ≦ u ≦ 0.1, 0 ≦ v ≦ 0.3, a + b + c + d + e = A layer satisfying 1, u + v + w = 1, and the composition is Ti _f Cr _g Al _h (B _x C _y N _z ), where f, g, h, x, y, z are atomic ratios 0 ≦ f, 0.05 ≦ g, 0.25 ≦ f + g ≦ 0.6, 0.4 ≦ h ≦ 0.75, 0 ≦ x ≦ 0.1, 0 ≦ y ≦ 0.3, f + g + h = 1, x + y B layer satisfying + z = 1, the A layer and the B layer are alternately stacked, and when one set of the stacked structure of the A layer and the B layer is 1 unit, this 1 unit The thickness of the hard coating is 10 to 50 nm, and the thickness of the hard coating is 1 to 5 μm.

According to such a configuration, the layer A has a predetermined component composition in each of the layers A and B, so that the layer A has a high oxidation resistance, high hardness, and excellent wear resistance. Is a film having high toughness and excellent oxidation resistance. And the hardness of a film becomes high and abrasion resistance improves by prescribing | regulating the thickness of 1 unit of the laminated structure of this A layer and B layer. Furthermore, by defining the film thickness of the entire film, the film has excellent wear resistance and is difficult to peel from the substrate.

Further, the first hard film forming member of the present invention has an integral intensity I (200) of diffraction lines from the (200) plane when the hard film is measured by X-ray diffraction of the θ-2θ method ( It is preferably at least twice the integrated intensity I (111) of the diffraction line from the (111) plane. Further, it is preferable that the half width of the diffraction line from the (200) plane when the hard coating described above is measured by the X-ray diffraction of the θ-2θ method is 0.7 or more.
According to such a configuration, the wear resistance of the coating is further improved.

The method for forming a hard film in the first hard film forming member of the present invention is characterized in that the hard film is formed by an arc ion plating method or a sputtering method. Further, as described above, when the relationship between the integrated intensity of the diffraction lines is specified and the half width is a predetermined value, when the hard coating is formed by the arc ion plating method or the sputtering method, The bias voltage applied to the substrate is a negative voltage having an absolute value of 130 V or more.

The composition of the film can be accurately controlled by forming the film by the arc ion plating method or the sputtering method. Also, by setting the bias voltage applied to the base material to a negative voltage having an absolute value of 130 V or more, the integral of the diffraction line from the (200) plane when the film is measured by the X-ray diffraction of the θ-2θ method The intensity I (200) is at least twice the integrated intensity I (111) of the diffraction line from the (111) plane, and the (200) plane when the film is measured by X-ray diffraction using the θ-2θ method. The half-value width of the diffraction line from is 0.7 ° or more.

In addition, as a result of intensive studies, the present inventors have found that the layer A is a film having high oxidation resistance, high hardness, and excellent wear resistance. It has been found that the characteristics can be further improved by controlling. Regarding the crystal structure, it is known that the crystal structure of the A layer is a mixed layer of a cubic structure and a hexagonal structure, and the hardness of the film is lowered and the oxidation resistance is also deteriorated. A layer structure results in a film having high hardness and excellent oxidation resistance and improved wear resistance. In order to improve the wear resistance of the A layer, in addition to the cubic single layer structure, the smaller the crystal grain size, the harder the hardness and the better the wear resistance. Further, it has been found that the cubic structure is generally preferentially oriented in the (111) plane, but the cutting performance is further improved by preferentially orienting in the (200) plane. In addition to the component composition, these A layers with controlled crystal structure, crystal grain size, and crystal orientation are films with high oxidation resistance, high hardness, and excellent wear resistance, but when used as a single layer, There is a problem that peeling occurs due to poor adhesion to the material, resulting in poor wear resistance.

On the other hand, the B layer is a film excellent in oxidation resistance and high toughness, and a cubic single layer structure can be easily obtained, and the crystal orientation can be easily changed by a substrate bias. However, when used alone, there is a problem that the wear resistance is inferior to that of the A layer. The present invention solves these problems, by defining the components of the A layer and the B layer, and by forming a two-layer film that forms the A layer of a predetermined thickness on the B layer of a predetermined thickness, Abrasion resistance could be improved. That is, the adhesion strength with the base material can be improved by using the B layer as a base, and the cutting performance can be dramatically improved as compared with the single layer film of only the A layer or the B layer. . Furthermore, by using the B layer having the same crystal structure as that of the A layer as a base and controlling the crystal orientation of the B layer to (200) orientation, the consistency at the interface between the B layer and the A layer is improved. Utilizing this, it was possible to form the A layer while maintaining the crystal orientation of the B layer.

That second hard coating member of the present invention is a hard coating formed member having a hard coating on a substrate, said hard coating composition is _{Ti a Cr b Al c Si d} Y e (B u C _v N _w ), and when a, b, c, d, e, u, v, w are atomic ratios, 0.05 ≦ a, 0.05 ≦ b, 0.2 ≦ a + b ≦ 0.55, 0.4 ≦ c ≦ 0.7, 0.02 ≦ d ≦ 0.2, 0 ≦ e ≦ 0.1, 0 ≦ u ≦ 0.1, 0 ≦ v ≦ 0.3, a + b + c + d + e = A layer satisfying 1, u + v + w = 1, and the composition is Ti _f Cr _g Al _h (B _x C _y N _z ), where f, g, h, x, y, z are atomic ratios 0 ≦ f, 0.05 ≦ g, 0.25 ≦ f + g ≦ 0.6, 0.4 ≦ h ≦ 0.75, 0 ≦ x ≦ 0.1, 0 ≦ y ≦ 0.3, f + g + h = 1, x + y B layer satisfying + z = 1, and the A layer is laminated on the B layer through an intermediate layer having a thickness of 0.5 μm or less or without an intermediate layer. The thickness is 0.5 to 5.0 μm, and the thickness of the B layer is 0.05 to 3.0 μm.

According to such a configuration, the layer A has a predetermined component composition in each of the layers A and B, so that the layer A has a high oxidation resistance, high hardness, and excellent wear resistance. Is a film having high toughness and excellent oxidation resistance. And by providing A layer of predetermined thickness on B layer of predetermined thickness, the hardness of a film becomes high and abrasion resistance improves.
Further, when an intermediate layer having a thickness of 0.5 μm or less is provided, the crystal matching of the hard coating is enhanced, the adhesion between the A layer and the B layer is improved, and the wear resistance is further improved.

Further, the second hard film forming member of the present invention includes an intermediate layer having a thickness of 0.5 μm or less between the A layer and the B layer, and the intermediate layer has the same composition as the A layer. It is preferable that the layer which consists of, and the layer which consists of the same composition as the said B layer are laminated | stacked alternately.

According to such a configuration, when an intermediate layer having a thickness of 0.5 μm or less is provided, the intermediate layer can be formed by using layers having the same composition as the A layer and the B layer as the two types of layers. It becomes easy.

Further, the second hard film forming member of the present invention has an integral intensity I (200) of diffraction lines from the (200) plane when the hard film is measured by X-ray diffraction of the θ-2θ method. It is preferably at least twice the integrated intensity I (111) of the diffraction line from the (111) plane. Further, it is preferable that the half width of the diffraction line from the (200) plane when the hard coating is measured by X-ray diffraction of the θ-2θ method is 1 ° or more.
According to such a configuration, the wear resistance of the coating is further improved.

The method for forming a hard film in the second hard film forming member of the present invention is characterized in that the hard film is formed by an arc ion plating method or a sputtering method. Further, as described above, when the relationship of the integrated intensity of diffraction lines is specified, the intermediate layer is formed when the A layer and the B layer are formed by the arc ion plating method or the sputtering method. In the case of forming the A layer, the B layer and the intermediate layer by an arc ion plating method or a sputtering method, the bias voltage applied to the substrate is a negative voltage having an absolute value of 70 V or more. Further, when the half width is set to a predetermined value, when the A layer is formed by the arc ion plating method or the sputtering method, the bias voltage applied to the substrate is a negative voltage having an absolute value of 130 V or more. To do.

The film structure can be accurately controlled by forming the film by the arc ion plating method or the sputtering method. When forming the A layer, the B layer and the intermediate layer, the bias voltage applied to the substrate when forming the intermediate layer is set to a negative voltage having an absolute value of 70 V or more, so that the film is The integrated intensity I (200) of the diffraction line from the (200) plane as measured by X-ray diffraction by the 2θ method is at least twice the integrated intensity I (111) of the diffraction line from the (111) plane. . In addition, when the bias voltage applied to the substrate when forming the A layer was a negative voltage having an absolute value of 130 V or more, the film was measured by X-ray diffraction of the θ-2θ method (200) The half width of the diffraction line from the surface is 1 ° or more.

Since the first and second hard film forming members according to the present invention have a hard film having a predetermined composition and structure, they have high hardness and excellent wear resistance.
Moreover, according to the formation method of the hard film in the first and second hard film forming members, a hard film having high hardness and excellent wear resistance can be formed on the substrate.

It is sectional drawing which shows the 1st hard film formation member which concerns on this invention. FIG. 3 is an X-ray diffraction (XRD) pattern when the hard film in the first hard film forming member is measured by the X-ray diffraction of the θ-2θ method. It is the schematic of the composite film-forming apparatus for performing film-forming. (A), (b) It is sectional drawing which shows the 2nd hard film formation member which concerns on this invention. It is a X-ray diffraction (XRD) figure when the hard film in the second hard film forming member is measured by X-ray diffraction of the θ-2θ method.

Next, the hard film forming member and the hard film forming method according to the present invention will be described in detail with reference to the drawings.

≪First hard film forming member≫
As shown in FIG. 1, a first hard film forming member 10 according to the present invention is provided with a hard film (hereinafter referred to as a film as appropriate) 4 on a substrate 1. The coating 4 includes an A layer 2 containing a predetermined amount of a predetermined element and a B layer 3 containing a predetermined amount of the predetermined element. Then, when the A layer 2 and the B layer 3 are alternately laminated, and a set of the laminated structure of the A layer 2 and the B layer 3 is one unit, the thickness (lamination cycle) of this unit is 10 to 50 nm. And the film 4 has a thickness of 1 to 5 μm. In the present embodiment, the B layer 3 is first formed on the substrate 1, and the A layer 2 is formed on the B layer 3 to form a plurality of units. Further, an underlayer (not shown) may be provided between the B layer 3 of the hard coating 4 and the substrate 1. Note that “on the base material 1” means one surface, both surfaces, or the entire surface of the base material 1, and the coated parts differ depending on the type of tool.
This will be specifically described below.

<Base material>
Examples of the substrate 1 include cemented carbide, iron-based alloy having metal carbide, cermet, high-speed tool steel, and the like. However, the substrate 1 is not limited to these, and is applicable to members such as cutting tools such as chips, drills, and end mills, and jigs and tools such as presses, forging dies, molding dies, and punching punches. Anything is possible as long as it is possible.

<A layer>
The A layer 2 is composed of Ti _a Cr _b Al _c Si _d Y _e (B _u C _v N _w ), and when the a, b, c, d, e, u, v, and w are atomic ratios “0.05 ≦ a” (in the metal element, the same shall apply hereinafter), “0.05 ≦ b”, “0.2 ≦ a + b ≦ 0.55”, “0.4 ≦ c ≦ 0.7”, “0.02 ≦ d ≦ 0.2”, “0 ≦ e ≦ 0.1”, “0 ≦ u ≦ 0.1”, “0 ≦ v ≦ 0.3”, “a + b + c + d + e = 1”, “u + v + w” = 1 ”. This A layer 2 is a film having high oxidation resistance, high hardness, and excellent wear resistance.

[Ti: a (0.05 ≦ a, 0.2 ≦ a + b ≦ 0.55, a + b + c + d + e = 1)]
[Cr: b (0.05 ≦ b, 0.2 ≦ a + b ≦ 0.55, a + b + c + d + e = 1)]
Ti and Cr are elements to be added in order to keep the crystal structure of the A layer 2 in a high hardness phase. In order to exert this effect, it is necessary to add Ti and Cr in total in an atomic ratio of 0.2 or more. On the other hand, in order to ensure the addition amount of Al, Si, and Y, the total of Ti and Cr needs to be 0.55 or less. Further, when nitrides having different lattice constants (for example, TiN: 0.424 nm, CrN: 0.414 nm, AlN: 0.412 nm) are combined, the hardness increases. The Cr amount must be 0.05 or more in atomic ratio. Therefore, the atomic ratio a of Ti and the atomic ratio b of Cr are 0.05 ≦ a, 0.05 ≦ b, and 0.2 ≦ a + b ≦ 0.55. A more preferable range is 0.2 ≦ a + b ≦ 0.5.

[Al: c (0.4 ≦ c ≦ 0.7, a + b + c + d + e = 1)]
Al is an element that improves the oxidation resistance of the A layer 2. In order to impart high oxidation resistance to the A layer 2, it is necessary to add Al in an atomic ratio of 0.4 or more. On the other hand, if it exceeds 0.7, the A layer 2 becomes soft and wear resistance decreases. Therefore, the atomic ratio c of Al is set to 0.4 ≦ c ≦ 0.7. A more preferable range is 0.45 ≦ c ≦ 0.6.

[Si: d (0.02 ≦ d ≦ 0.2, a + b + c + d + e = 1)]
Si is an element that improves the oxidation resistance of the A layer 2. In order to impart high oxidation resistance to the A layer 2, it is necessary to add Si in an atomic ratio of 0.02 or more. On the other hand, if it exceeds 0.2, the A layer 2 becomes soft and wear resistance decreases. Therefore, the atomic ratio d of Si is set to 0.02 ≦ d ≦ 0.2. A more preferable range is 0.05 ≦ d ≦ 0.15.

[Y: e (0 ≦ e ≦ 0.1, a + b + c + d + e = 1)]
Y is an element added to further improve oxidation resistance. However, if the atomic ratio exceeds 0.1, the A layer 2 becomes soft and wear resistance decreases. Therefore, the atomic ratio e of Y is set to 0 ≦ e ≦ 0.1. A more preferable range is 0.02 ≦ e ≦ 0.05.

[B: u, C: v, N: w (0 ≦ u ≦ 0.1, 0 ≦ v ≦ 0.3, u + v + w = 1)]
By adding B and C, the hardness of the A layer 2 can be increased. However, when B exceeds 0.1 in atomic ratio, the A layer 2 becomes amorphous and the hardness decreases. On the other hand, when C exceeds 0.3 in atomic ratio, free C is generated in the A layer 2 and the A layer 2 is softened and the oxidation resistance is lowered. Therefore, B and C may be added in an atomic ratio of 0.1 or 0.3, respectively. N is required to be 0.6 or more because N plays a role of forming a nitride forming the skeleton of the film 4 in the present invention by combining with a metal element.

As described above, Ti, Cr, Al, Si, and N are essential components, and Y, B, and C are optional components. Therefore, combinations relating to the composition of the A layer 2 are TiCrAlSiY (BCN), TiCrAlSi ( BCN), TiCrAlSiY (CN), TiCrAlSiY (BN), TiCrAlSi (CN), TiCrAlSi (BN), TiCrAlSiYN, TiCrAlSiN, and the like.

<B layer>
The B layer 3 is composed of Ti _f Cr _g Al _h (B _x C _y N _z ), and when f, g, h, x, y, z are atomic ratios, “0 ≦ f”, “0.05 ≦ g”, “0.25 ≦ f + g ≦ 0.6”, “0.4 ≦ h ≦ 0.75”, “0 ≦ x ≦ 0.1”, “0 ≦ y ≦ 0.3 ”,“ F + g + h = 1 ”, and“ x + y + z = 1 ”. This B layer 3 is a film having high toughness and excellent oxidation resistance.

[Ti: f (0 ≦ f, 0.25 ≦ f + g ≦ 0.6, f + g + h = 1)]
Ti is an element added together with Cr in order to ensure the toughness of the B layer 3. In order to exert this effect, it is necessary to add Ti and Cr in a total atomic ratio of 0.25 or more. On the other hand, when the total exceeds 0.6, Al is relatively decreased and oxidation resistance is lowered. Therefore, 0.25 ≦ f + g ≦ 0.6. A more preferable range is 0.3 ≦ f + g ≦ 0.5. Since the B layer 3 does not need to be as hard as the A layer 2, Ti may be 0. When only Cr is added without adding Ti, that is, when the B layer is Cr _g Al _h (B _x C _y N _z ), the hardness does not change as compared with the case where Ti is included, but Cr is not Ti. Compared with the better oxidation resistance, the wear resistance is improved in dry high-speed cutting.

[Cr: g (0.05 ≦ g, 0.25 ≦ f + g ≦ 0.6, f + g + h = 1)]
Cr is an element added to ensure the oxidation resistance and toughness of the B layer 3. In order to exhibit the effect of ensuring oxidation resistance, it is necessary to add 0.05 or more by atomic ratio. Moreover, in order to exhibit the effect of ensuring toughness, it is necessary to add Ti and Cr in total and 0.25 or more by atomic ratio. On the other hand, when the total exceeds 0.6, Al is relatively decreased and oxidation resistance is lowered. Therefore, the atomic ratio g of Cr is set to 0.05 ≦ g and 0.25 ≦ f + g ≦ 0.6. A more preferable range is 0.3 ≦ f + g ≦ 0.5.

[Al: h (0.4 ≦ h ≦ 0.75, f + g + h = 1)]
In order to impart a certain oxidation resistance to the B layer 3 as well, it is necessary to add Al in an atomic ratio of 0.4 or more. On the other hand, when it exceeds 0.75, the B layer 3 becomes soft and wear resistance decreases. Therefore, the atomic ratio h of Al is set to 0.4 ≦ h ≦ 0.75. A more preferable range is 0.5 ≦ h ≦ 0.7.

[B: x, C: y, N: z (0 ≦ x ≦ 0.1, 0 ≦ y ≦ 0.3, x + y + z = 1)]
By adding B and C, the hardness of the B layer 3 can be increased. However, if B exceeds 0.1 in atomic ratio, the B layer 3 becomes amorphous and the hardness decreases. On the other hand, when C exceeds 0.3 in atomic ratio, free C is generated in the B layer 3 and the B layer 3 is softened, and the oxidation resistance is lowered. Therefore, B and C may be added in an atomic ratio of 0.1 or 0.3, respectively. N is required to be 0.6 or more because N plays a role of forming a nitride forming the skeleton of the film 4 in the present invention by combining with a metal element.

As described above, Cr, Al, and N are essential components, and Ti, B, and C are optional components. Therefore, combinations relating to the composition of the B layer 3 are TiCrAl (BCN), CrAl (BCN), and TiCrAl. (CN), TiCrAl (BN), CrAl (CN), CrAl (BN), TiCrAlN, CrAlN and the like.

<Laminated structure>
[1 unit thickness: 10 to 50 nm]
When the thickness of one unit (that is, the lamination period) of the laminated structure of one A layer 2 and one B layer 3 is 10 to 50 nm, the hardness of the coating 4 increases and the wear resistance increases. improves. As described above, even when the composition of the A layer 2 and the B layer 3 is defined, if the thickness of one unit is less than 10 nm or exceeds 50 nm, the wear resistance of the coating 4 is not improved. Therefore, the thickness of one unit is 10 to 50 nm. More preferably, it is 20 to 40 nm. One unit (lamination period) means, for example, a set of the A layer 2 and the B layer 3 formed in close contact with the A layer 2, and in close contact with the A layer 2. It also refers to a set with the formed B layer 3. Therefore, the thickness of one unit is 10 to 50 nm in combination with any of the B layers 3 above and below the A layer 2.

[Film thickness: 1-5μm]
With respect to the film thickness of the film 4 (that is, the total film thickness), if it is less than 1 μm, the effect of improving the wear resistance is small. On the other hand, when the thickness exceeds 5 μm, the film 4 peels from the substrate 1 due to the residual compressive stress peculiar to the film formed by the PVD (Physical Vapor Deposition (physical vapor deposition or physical vapor deposition)) method. Therefore, the film thickness of the film 4 is 1 to 5 μm.

[Others]
The film thickness ratio of the A layer 2 and the B layer 3 is about 1: 1 as a guide, but there is almost no change in the performance such as hardness and wear resistance even if it changes from about 1: 5 to 5: 1. However, if it exceeds the range of 1: 5 to 5: 1, the performance tends to deteriorate. Therefore, the film thickness ratio between the A layer 2 and the B layer 3 is preferably 1: 5 to 5: 1. More preferably, it is 1: 3 to 3: 1. Here, the first layer on the substrate 1, that is, the layer that adheres to the substrate 1 is the B layer 3, and the A layer 2 is laminated on the B layer 3. And the order of lamination of the B layer 3 are not particularly specified. However, the first layer on the substrate 1 is preferably the B layer 3 having excellent toughness and adhesion. The number of A layers 2 and B layers 3 may be the same or different.

<Preferred orientation of film and half width of diffraction line>
The first hard film forming member 10 has an integral intensity I (200) of diffraction lines from the (200) plane when the hard film 4 is measured by the X-ray diffraction of the θ-2θ method, from the (111) plane. It is preferable that the integrated intensity I (111) of the diffraction lines of the above is at least twice (that is, I (111) × 2 ≦ I (200)). The hard film forming member 10 has a full width half maximum (FWHM) of 0.7 when the hard film 4 is measured by X-ray diffraction of the θ-2θ method. It is preferable that it is more than °.

As described later, these controls can be performed by setting the bias voltage applied to the substrate 1 when the coating 4 is formed to a negative voltage having an absolute value of 130 V or more. That is, by setting the bias voltage to −130 V or less, the integrated intensity of diffraction lines when the film 4 is measured by the X-ray diffraction of the θ-2θ method can have the above relationship, and the half of the diffraction lines can be obtained. The value range can be the above value.

[Preferred orientation (relationship of integral intensity): I (111) × 2 ≦ I (200)]
The intensity ratio of diffraction lines, that is, the preferential orientation depends on the bias voltage applied to the substrate 1 during film formation. As the bias voltage increases, the (200) orientation becomes dominant, but the (200) plane is particularly excellent in wear resistance. And when the relationship becomes more than twice the strength of (111) in the strength ratio as the index, the wear resistance is improved. More preferably, it is 3 times or more.

[Half width: 0.7 ° or more]
Depending on the value of the bias voltage applied to the substrate 1, not only the orientation but also the crystal state of the coating 4 changes. Specifically, the crystal grain size of the film 4 changes, and the half-value width of the (200) plane diffraction line that is observed more strongly can be used as the index. Abrasion resistance is further improved when the half-width of the diffraction line is 0.7 ° or more. More preferably, it is 0.9 ° or more. The half width of the diffraction line tends to increase in a region where the bias voltage is −130 V or less, but the increase saturates in the vicinity of 2 °.

Measurement by X-ray diffraction can be performed under the following conditions as an example.
Equipment used: RINT-ULTIMA PC manufactured by Rigaku Denki, measurement method: θ-2θ, X-ray source: Cuka (using graphite monochromator), excitation voltage-current: 40 kV-40 mA, divergence slit: 1 °, divergence longitudinal limit slit: 10.00 mm, scattering slit: 1 °, light receiving slit: 0.15 mm, monochrome light receiving slit: none

The bias voltage applied to the substrate 1 is -150 V, the A layer 2 is made of (Ti0.2Cr0.2Al0.55Si0.03Y0.02) N, and the B layer 3 is made of (Ti0.25Cr0.1Al0.65) N. When a multilayer film (15 nm each, 1 unit thickness is 30 nm, total film thickness is 3 μm), the X-ray diffraction (XRD) pattern shown in FIG. 2 is obtained. The integrated intensity and half width of each diffraction line can be calculated from the XRD figure (raw data) using, for example, spreadsheet software IgorPro. Specifically, each value is calculated by performing fitting using a Voigt function as a peak shape using the multi-peak fit package of the software. Since the diffraction line of the base material is also detected in the raw data at the time of fitting, separation of the diffraction component from the base material component and the film component is also carried out (the base material component is indicated by a thick line (reference numeral M in the figure) ).

<< Method for Forming Hard Film in First Hard Film Forming Member >>
The hard coating 4 is formed by an arc ion plating method or a sputtering method.

In order to accurately control the composition of a layer containing many elements such as the A layer 2 and the B layer 3, the film is formed by an arc ion plating (AIP) method using a solid evaporation source or A sputtering method is suitable. Among them, the AIP method is particularly recommended because the ionization rate at the time of evaporation of the target atoms is high and a dense film can be formed by a bias voltage applied to the substrate.

However, in the case where the preferential orientation of the film and the half width of the diffraction line are set as the above conditions, the absolute value of the bias voltage applied to the substrate is 130 V when the film is formed by the arc ion plating method or the sputtering method. It is necessary to set the above negative voltage (the bias voltage is −130 V or less). By forming the film with a bias voltage of −130 V or less, as described above, the integral intensity ratio is I (111) × 2 ≦ I (200) when the film is measured by X-ray diffraction using the θ-2θ method. , Half width: 0.7 ° or more. More preferably, it is −140V or less. If the bias voltage is too large and negative, heating of the base material during film formation and a decrease in film formation rate occur. Therefore, the lower limit is preferably −250V.

That is, in order to produce the first hard film forming member 10 by forming the film 4 on the base material 1, first, the base material 1 having a predetermined size is prepared by ultrasonic degreasing and cleaning as necessary (base material). Preparation step). Next, after the base material 1 is introduced into the film forming apparatus, the base material 1 is maintained at a predetermined temperature of 500 to 550 ° C. (base material heating step), and a film is formed on the base material by arc ion plating or sputtering. 4 is formed (film formation step). Thereby, the 1st hard film forming member 10 which has a predetermined composition and structure can be manufactured.

Next, as an example of a film forming method on the substrate 1, a case where a composite film forming apparatus is used will be described with reference to FIG. 3, but the film forming method is not limited to this.
As shown in FIG. 3, the composite film forming apparatus 100 is connected to a chamber 13 having an exhaust port 11 for evacuating, a gas supply port 12 for supplying a film forming gas and a rare gas, and an arc evaporation source 14. Arc power source 15, sputter power source 17 connected to sputter evaporation source 16, a support stage 19 on a substrate stage 18 that supports an object to be processed (not shown), and a support base 19. A bias power source 20 for applying a negative bias voltage to the object to be processed through the support 19 between the chamber 13 and the chamber 13 is provided. In addition, a heater 21, a discharge DC power source 42, a filament heating AC power source 23, and the like are provided.
Note that by using the arc evaporation source 14, unbalanced magnetron sputtering (UBM) evaporation can be performed by using the arc ion plating (AIP) evaporation and the sputtering evaporation source 16.

First, various alloy or metal targets (not shown) are attached to the cathode (not shown) of the composite film forming apparatus 100, and further, a target object (not shown) is placed on a support base 19 on the rotating substrate stage 18. ), The substrate 1 is attached, and the inside of the chamber 13 is evacuated (exhausted to 5 × 10 ³ Pa or less) to be in a vacuum state. Thereafter, the temperature of the object to be processed is heated to about 500 ° C. by the heater 21 in the chamber 13, and etching with Ar ions is performed for 5 minutes by an ion source by thermionic emission from the filament. Thereafter, by using an arc evaporation source 14 with a φ100 mm target, an arc current of 150 A, an N ₂ atmosphere with a total pressure of 4 Pa, and when containing carbon, a gas containing carbon is added to the N ₂ gas. Arc ion plating is performed in a dry atmosphere. When B (boron) is contained, B is contained in the target.

Further, it is possible to form a laminated film by attaching targets having different compositions to a plurality of evaporation sources, placing an object to be processed on a rotating support base 19, and rotating the film during film formation. As the substrate stage 18 rotates, the object to be processed on the support table 19 alternately passes in front of the evaporation source to which the target having a different composition is attached. At that time, the film corresponding to the target composition of each evaporation source. It is possible to form a laminated film by alternately forming. The thickness of each of the A layer 2 and the B layer 3, the thickness of one unit of the laminated structure, and the number of units depend on the input power (evaporation amount) to each evaporation source, the rotational speed and the rotational speed of the support base 19. Control. In addition, when the rotational speed of the support base 19 is faster, the thickness per layer becomes thinner and the thickness of one unit becomes thinner (that is, the stacking cycle becomes shorter).

≪Second hard film forming member≫
As shown in FIG. 4A, the second hard film forming member 10a according to the present invention is provided with a hard film (hereinafter referred to as a film) 4a on the substrate 1a. The coating 4a includes an A layer 2a containing a predetermined amount of a predetermined element and a B layer 3a containing a predetermined amount of the predetermined element. Then, the A layer 2a is laminated on the B layer 3a, the thickness of the A layer 2a is 0.5 to 5.0 μm, and the thickness of the B layer 3a is 0.05 to 3.0 μm. . Moreover, as shown in FIG.4 (b), it is good also as hard film formation member 10a 'provided with the intermediate | middle layer 5 between A layer 2a and B layer 3a. Moreover, you may provide the base layer (illustration omitted) between B layer 3a of the hard film 4a ', and the base material 1a. Note that “on the substrate 1a” refers to one or both surfaces of the substrate 1a, the entire surface, or the like, and the portions that are covered differ depending on the type of tool.
This will be specifically described below.

<Base material, A layer and B layer>
The base material 1a, the A layer 2a, and the B layer 3a are the same as the base material 1, the A layer 2, and the B layer 3 in the first hard film forming member 10, respectively.

<Laminated structure>
[A layer is laminated on B layer]
The first layer on the substrate 1a is the B layer 3a having excellent toughness and adhesion, and the A layer 2a having high hardness and excellent wear resistance is the outermost layer. Further, the interface between the B layer 3a and the A layer 2a is obtained by using the B layer 3a having the same crystal structure as that of the A layer 2a as a base and controlling the crystal orientation of the B layer 3a to (200) orientation. The A layer 2a can be formed in a state in which the crystal orientation of the B layer 3a is maintained by utilizing the consistency in FIG. Thereby, cutting performance can be further improved.

[Thickness of layer A: 0.5 to 5.0 μm]
The A layer 2a, which is the cutting surface, has a thickness of less than 0.5 μm, so that the cutting life is shortened. Preferably it is 0.75 μm or more. On the other hand, if the thickness of the A layer 2a exceeds 5.0 μm, the internal stress of the A layer 2a increases and the A layer 2a is broken (chipped). Preferably it is 3.0 micrometers or less.

[B layer thickness: 0.05 to 3.0 μm]
When the thickness of the B layer 3a used as the underlayer is less than 0.05 μm, it becomes difficult to ensure adhesion with the substrate 1a and to control the orientation. Further, chipping occurs in the film. Therefore, the thickness is set to 0.05 μm or more. Preferably it is 0.1 micrometer or more. On the other hand, if the thickness of the B layer 3a exceeds 3.0 μm, the preferential orientation of the crystal changes from (200) to a more stable (111). Preferably it is 2.5 μm or less.

<Intermediate layer>
As shown in FIG.4 (b), it is good also as hard film formation member 10a 'provided with the intermediate | middle layer 5 whose thickness is 0.5 micrometer or less between A layer 2a and B layer 3a. Although this two-layer film sufficiently improves the wear resistance during cutting even without the intermediate layer 5, an intermediate layer 5 having a thickness of 0.5 μm or less is provided at the interface between the A layer 2a and the B layer 3a. Thus, the crystal matching of the hard coating 4a ′ can be improved, and the adhesion between the A layer 2a and the B layer 3a can be improved. As a result, the wear resistance during cutting is further improved. Here, since the intermediate layer 5 is lower in hardness than the A layer 2a, if the thickness of the intermediate layer 5 exceeds 0.5 μm, the intermediate layer 5 becomes a starting point of cracking, resulting in chipping. . For this reason, when providing the intermediate layer 5, the thickness of the intermediate layer 5 shall be 0.5 micrometer or less. Preferably it is 0.4 micrometer or less, More preferably, it is 0.3 micrometer or less. On the other hand, when the intermediate layer 5 is too thin, the effect of the intermediate layer 5 is not obtained, so that the thickness is preferably 0.05 μm or more. More preferably, it is 0.07 μm or more.

The intermediate layer 5 may be a single layer or a film composed of two or more layers. As shown in FIG. 4B, in the intermediate layer 5, the Aa layer 22 having the same composition as the A layer 2a and the Bb layer 33 having the same composition as the B layer 3a are alternately stacked. preferable. The composition of each layer of the intermediate layer 5 may be different from that of the A layer 2a and the B layer 3a, but it has the same composition from the viewpoint of eliminating the consistency of the crystal grain size and the replacement of the target during film formation. It is preferable to use one. Further, two types of layers having different compositions are alternately stacked, and when one set of the laminated structure of the two types of layers is defined as one unit, the thickness of the one unit is 0.005 to 0.04 μm. It is preferable that the film is composed of two or more units. By setting the intermediate layer 5 to such a configuration, the wear resistance of the coating 4a ′ is further improved. Moreover, the adhesiveness of A layer 2a and B layer 3a further improves by setting it as 2 units or more.

Here, the Aa layer 22 is first formed on the B layer 3a, but the Bb layer 33 may be formed first on the B layer 3a. The number of Aa layers 22 and Bb layers 33 may be the same or different. In addition, one unit (stacking period) means, for example, a set of an Aa layer 22 and a Bb layer 33 formed in close contact with the Aa layer 22, and in close contact with the Aa layer 22. One set with the formed Bb layer 33 is also referred to. Therefore, the thickness of one unit is preferably 0.005 to 0.04 μm in any combination with the upper and lower Bb layers 33 of the Aa layer 22. Further, as the structure of the intermediate layer 5, the Aa layer 22 and the Bb layer 33 may have the same film thickness ratio, but as the Aa layer 22 approaches the A layer 2a, the thickness of the Aa layer 22 becomes Bb. Adhesion can be further increased by employing a structure that is thicker than the thickness of the layer 33. The intermediate layer 5 may be a single layer film having a gradient composition that approaches the composition of the A layer 2a as it goes from the B layer 3a side to the A layer 2a side.

<Preferred orientation of film and half width of diffraction line>
The second hard film forming member 10a (10a ') has an integrated intensity I (200) of diffraction lines from the (200) plane when the hard film 4a (4a') is measured by X-ray diffraction of the θ-2θ method. ) Is preferably at least twice the integrated intensity I (111) of the diffraction line from the (111) plane (that is, I (111) × 2 ≦ I (200)). Further, the hard film forming member 10a (10a ') has a half-width (FWHM: Full) of a diffraction line from the (200) plane when the hard film 4a (4a') is measured by X-ray diffraction of the θ-2θ method. It is preferable that Width Half Maximum) is 1 ° or more.

The preferential orientation of the film 4a (4a ′) is a negative bias having an absolute value of 70 V or more applied to the base material 1a when forming the A layer 2a, the B layer 3a and the intermediate layer 5, as will be described later. This can be achieved by using the following voltage. The half width of the diffraction line can be achieved by making the bias voltage applied when forming the A layer 2a a negative voltage having an absolute value of 130V or more. That is, by setting the bias voltage to −70 V or less, the integrated intensity of diffraction lines when the hard coating 4a (4a ′) is measured by the X-ray diffraction of the θ-2θ method can have the above relationship. Further, by setting the bias voltage to −130 V or less, the half width of the diffraction line when the hard coating 4a (4a ′) is measured by the X-ray diffraction of the θ-2θ method can be set to the above value.

[Preferred orientation (relationship of integral intensity): I (111) × 2 ≦ I (200)]
Cutting characteristics are improved by setting the preferred orientation of the cubic crystal to the (200) plane orientation. The preferential orientation of the surface layer A layer 2a can be controlled by the preferential orientation of the base layer B layer 3a. The preferential orientation of the B layer 3a depends on the composition of the B layer 3a and the base material 1a when the B layer 3a is formed. Depending on the combination of applied bias voltages, a cubic single-layer structure and a (200) orientation can be used instead of the (111) orientation which is inherently stable. The orientation can be controlled by a bias voltage applied to the substrate 1a when the B layer 3a is formed. As the absolute value of the negative bias voltage (hereinafter, appropriately referred to as negative bias) increases, the (111) plane orientation becomes the (200) plane orientation. Furthermore, it is also important that the thickness of the B layer 3a is 3.0 μm or less because it becomes easy to obtain a stable (111) orientation as the thickness of the B layer 3a increases. On the other hand, in order to make the A layer 2a consistent with the B layer 3a, it is necessary not to be a mixed layer of a hexagonal crystal structure and a cubic structure, but to have a cubic structure alone. These structural changes can be controlled by a bias voltage applied to the substrate 1a during film formation. When the absolute value of the negative bias is low, a mixed layer is deposited. In addition, the crystal orientation of the A layer 2a can be controlled by controlling the crystal orientation of the B layer 3a. As an evaluation of the (200) orientation of the two-layer film, the (200) diffraction line is obtained from the X-ray diffraction result of the two-layer film. The wear resistance is improved when the integrated intensity of is more than twice the integrated intensity of the (111) diffraction line. More preferably, it is 2.5 times or more.

[Half width: 1 ° or more]
The A layer 2a has a cubic single layer structure, and the wear resistance improves as the crystal grain size decreases. The crystal grain size of the A layer 2a can be controlled by the value of the bias applied to the substrate 1a. The larger the absolute value of the negative bias, the finer the crystal grains. As a specific index of the crystal grain size of the film, the half width of the (200) plane diffraction line observed from the X-ray diffraction result can be used. If the half-value width of the diffraction line is 1.0 ° or more, the crystal grains are sufficiently refined, and as a result, the wear resistance is improved. More preferably, it is 1.2 ° or more. The half width of the diffraction line tends to increase in a region where the bias voltage is −130 V or less, but the increase saturates in the vicinity of 2.5 °.

The measurement by X-ray diffraction can be performed in the same manner as the X-ray diffraction in the first hard film forming member 10.

The bias voltage applied to the base material 1a when the A layer 2a is formed is -150V, and the bias voltage applied to the base material 1a when the A layer 2a is (Ti0.2Cr0.2Al0.55Si0.05) N and the B layer 3a is formed. Is set to −100V, and when the B layer 3a forms a two-layer film (each 1.5 μm) made of (Ti0.2Cr0.2Al0.6) N, the X-ray diffraction (XRD) pattern shown in FIG. 5 is obtained. . The integrated intensity and half width of each diffraction line can be calculated from the XRD figure (raw data) using, for example, spreadsheet software IgorPro. Specifically, each value is calculated by performing fitting using a Voigt function as a peak shape using the multi-peak fit package of the software. Since the diffraction line of the base material is also detected in the raw data at the time of fitting, separation of the diffraction component from the base material component and the film component is also carried out (the base material component is indicated by a thick line (reference numeral M in the figure) ).

<< Method for Forming Hard Film in Second Hard Film Forming Member >>
The hard coating 4a (4a ′) can be formed in the same manner as the hard coating 4 in the first hard coating forming member 10.

However, regarding the preferential orientation of the film 4a (4a '), in order to control both the orientation of the B layer 3a and the crystal structure of the A layer 2a to desired conditions, the A layer 2a, the B layer 3a, and the intermediate layer When the layer 5 is provided, it is necessary to set the absolute value of the bias voltage applied to the substrate to a negative voltage of 70 V or more (bias voltage of −70 V or less) when forming the intermediate layer 5. By forming the film at a bias voltage of −70 V or less, as described above, when the film 4 is measured by the X-ray diffraction of the θ-2θ method, the integrated intensity ratio is I (111) × 2 ≦ I (200 ) More preferably, it is −90 V or less. If the bias voltage is too large and negative, heating of the substrate 1a during film formation and a decrease in the film formation rate occur. Therefore, the lower limit is preferably −300V.

Regarding the half-value width of the diffraction line, when the A layer 2a is provided, the negative value of the bias voltage applied to the substrate 1a is 130 V or more when the intermediate layer 5 is formed (the bias voltage is −130 V or less). It is necessary to. By forming the film at a bias voltage of −130 V or less, as described above, when the film 4a is measured by the X-ray diffraction of the θ-2θ method, the half-value width is 1.0 ° or more. More preferably, it is −140V or less. If the bias voltage is too large and negative, heating of the substrate 1a during film formation and a decrease in the film formation rate occur. Therefore, the lower limit is preferably −300V.

That is, in order to manufacture the second hard film forming member 10a (10a ') by forming the film 4a on the base material 1a, first, the base material 1a having a predetermined size is prepared by ultrasonic degreasing and cleaning as necessary. (Base material preparation step). Next, after introducing the substrate 1a into the film forming apparatus, the substrate 1a is held at a predetermined temperature of 500 to 550 ° C. (substrate heating step), and a film is formed on the substrate by arc ion plating or sputtering. 4a (4a ') is formed (film formation step). Thereby, the 2nd hard film forming member 10a (10a ') which has a predetermined composition and structure can be manufactured.

In addition, the same thing as what was used for manufacture of a 1st hard film formation member can be used for a film-forming apparatus, and the same operation is performed. However, the thicknesses of the A layer 2a, the B layer 3a, the intermediate layer 5, and the layers 22 and 33 constituting the intermediate layer 5, the thickness of one unit of the laminated structure of the intermediate layer 5, and the number of units are as follows. Is controlled by the input power (evaporation amount), the rotation speed and the rotation speed of the support base 19.

As described above, in the first hard film forming member 10, the A layer 2 and the B layer 3 having a predetermined component composition have a laminated structure, and the thickness of one unit is within a predetermined range. The wear resistance of the hard coating 4 can be improved. In the second hard film forming member 10a (10 '), the A layer 2a having a predetermined component composition is formed on the B layer 3a having a predetermined component composition, and the A layer 2a and the B layer 3a By setting the thickness within a predetermined range, it is possible to improve the wear resistance of the hard coating 4a (4a ′). Furthermore, by providing the intermediate layer 5 having a predetermined thickness between the A layer 2a and the B layer 3a, the wear resistance of the hard coating 4a (4a ') can be further improved.

Accordingly, the first and second hard film forming members coated with such a hard film having excellent wear resistance include, for example, cutting tools such as chips, drills, end mills, presses, forging dies, and molding. Examples include jigs and punching tools. In particular, it is suitable for a tool used for dry cutting.

Examples according to the present invention will be described below. The present invention is not limited to the following examples.
In this example, a film was formed using the composite film forming apparatus shown in FIG.

Example A: First hard film forming member
[First embodiment]
In the first embodiment, the A voltage and the B voltage having different compositions are formed so that the bias voltage during film formation is fixed to −150 V and the thickness of one unit of the multilayer structure (lamination cycle) is 30 nm. The effect of film composition on hardness and cutting performance was examined.

First, a target of various alloys or metals is attached to the cathode of the composite film forming apparatus, and further, a cutting tool (two-blade carbide end mill, φ10 mm) and hardness investigation that are ultrasonically degreased and washed in ethanol. A mirror-finished carbide test piece (length 13 mm × width 13 mm × thickness 5 mm) was mounted on a support stage on a substrate stage. Then, the chamber was evacuated (evacuated to 5 × 10 ⁻³ Pa or less) to be in a vacuum state. Next, after the temperature of the object to be processed was heated to 500 ° C. with a heater, etching with Ar ions was carried out for 5 minutes by an ion source by thermionic emission from the filament. Thereafter, a mixed gas obtained by adding nitrogen gas or a gas containing carbon as necessary to nitrogen gas is introduced to a total pressure of 4 Pa, and the arc evaporation source (target diameter φ100 mm) is operated at a discharge current of 150 A to obtain a predetermined thickness. A film was formed.

In addition, about formation of laminated film, the target of the composition of A layer and B layer was attached to a separate evaporation source, the substrate stage carrying a substrate was rotated in an apparatus, and only the target of B layer was mentioned above first. A single layer was discharged for a short time in a predetermined atmosphere such as nitrogen gas, and a bias voltage of −150 V was applied to the substrate to form a B layer having a predetermined thickness. Thereafter, the target of layer A is discharged, the targets of layer A and layer B are simultaneously discharged, and the substrate stage is rotated while applying a bias voltage of −150 V to the substrate. A film (multilayer film) having a laminated structure laminated in order was formed on the substrate so as to have a total thickness of 3 μm. The thickness of the A layer was about 15 nm, the thickness of the B layer was about 15 nm, and one unit was 30 nm. The thickness of each of the A layer and the B layer, the thickness of one unit of the laminated structure, and the number of units were controlled by the rotational speed and the rotational speed of the support base.

After the film formation was completed, the component composition in the film was measured, and the hardness and abrasion resistance of the film were evaluated.
<Film composition>
The component composition of the metal element in the A layer and the B layer was measured by EPMA (Electron Probe Micro Analyzer).

<Hardness>
The hardness of the film was evaluated by examining the Vickers hardness of the film in a carbide end mill under the conditions of a load of 20 mN and a holding time of 15 seconds using a micro Vickers hardness meter. A sample having a hardness of 25 GPa or more was judged good, and a sample having a hardness of less than 25 GPa was judged defective.

<Abrasion resistance>
Wear resistance was evaluated by conducting a cutting test under the following conditions and measuring the amount of wear at the boundary (flank wear amount (wear width)) after a certain distance. When the amount of wear (wear width) was less than 200 μm, the wear resistance was good, and when it was over 200 μm, the wear resistance was poor.

[Cutting test conditions]
Work material: SKD61 (HRC57)
Cutting speed: 400m / min
Depth cut: 5mm
Radial depth of cut: 0.6mm
Feed: 0.06mm / tooth
Evaluation condition: Flank wear after 100 m cutting (boundary part)
These results are shown in Tables 1 and 2. In the table, those not satisfying the scope of the present invention are indicated by underlining the composition of each layer. However, those that do not contain essential components are not underlined.

As shown in Tables 1 and 2, no. Nos. 1A to 26A had good hardness and wear resistance because the compositions of the films (A layer and B layer) satisfied the scope of the present invention.
On the other hand, no. Since 27A to 49A did not satisfy the scope of the present invention, their hardness and wear resistance were poor. In addition, No. In 50A, the coating peeled off from the substrate during cutting. Specifically, it is as follows.

No. In 27A, the Al amount in the A layer was less than the lower limit. No. In 28A, the total amount of Ti and Cr in the A layer was less than the lower limit, and the amount of Al exceeded the upper limit. No. 29A did not contain Si in the A layer. No. In 30A, the Si amount exceeded the upper limit in the A layer. No. 31A did not contain Ti and Cr in the A layer, and the Al amount exceeded the upper limit. No. 32A did not contain Cr in the A layer, and the Al amount exceeded the upper limit. No. 33A did not contain Ti in the A layer, and the Al amount exceeded the upper limit.

No. In 34A, the total amount of Ti and Cr in the A layer was less than the lower limit. No. In 35A, the total amount of Ti and Cr in the A layer exceeded the upper limit, and the Al amount was less than the lower limit. No. In 36A, the Y amount exceeded the upper limit in the A layer. No. In 37A, the B amount exceeded the upper limit in the A layer. No. As for 38A, C amount exceeded the upper limit in A layer. No. In the case of 39A, the total amount of Ti and Cr in the B layer exceeded the upper limit value, and the Al amount was less than the lower limit value. No. In 40A, the total amount of Ti and Cr in the B layer was less than the lower limit, and the amount of Al exceeded the upper limit. No. 41A and 42A did not contain Cr in the B layer.

No. In 43A, the total amount of Ti and Cr exceeded the upper limit in the A layer and did not contain Cr or Al. No. In 44A, the total amount of Ti and Cr exceeded the upper limit in the B layer, and contained no Cr or Al. No. In 45A, the total amount of Ti and Cr exceeded the upper limit in the B layer and did not contain Al. No. 46A did not contain Cr in the A layer, Al exceeded the upper limit, and the total amount of Ti and Cr exceeded the upper limit in the B layer, and did not contain Cr or Al. No. 47A did not contain Ti in the A layer, Al exceeded the upper limit, and the total amount of Ti and Cr exceeded the upper limit in the B layer, and did not contain Al. No. In 48A, the B amount exceeded the upper limit in the B layer. No. In 49A, the C amount exceeded the upper limit in the B layer. No. 50A contained Si in the B layer. Therefore, the adhesiveness was lowered.

[Second Embodiment]
In the second example, the coating composition was constant, and a coating having a thickness of 1 unit was formed for each sample, and the influence of the thickness of 1 unit on hardness and cutting performance was examined.
The film was formed by the same method as in the first example (conditions other than the thickness were the same as in the first example). At this time, the thickness of one unit was changed for each sample.

After the film formation was completed, the component composition in the film was measured, and the hardness and abrasion resistance of the film were evaluated. The measuring method of the component composition and the evaluation method of hardness and wear resistance are the same as in the first embodiment. In addition, the component composition in a film | membrane was A layer "(Ti0.2Cr0.15Al0.55Si0.1) N" and B layer "(Ti0.2Cr0.2Al0.6) N".
These results are shown in Table 3. In the table, those not satisfying the scope of the present invention are indicated by underlining the numerical values.

As shown in Table 3, No. In each of 51A to 55A, the thickness of one unit of the laminated structure of the A layer and the B layer satisfied the range of the present invention, so that the hardness and wear resistance were good. On the other hand, no. As for 56A, since the thickness of 1 unit was less than a lower limit, hardness and abrasion resistance were unsatisfactory. No. 57A and 58A had poor hardness and wear resistance because the thickness of one unit exceeded the upper limit.

[Third embodiment]
In the third embodiment, the film composition and the thickness of one unit are made constant, the bias voltage at the time of film formation is changed, and the preferential orientation of the film by X-ray diffraction and the half width of the diffraction line on the hardness and cutting performance are affected. The impact was examined.
The film was formed by the same method as in the first example. At this time, the bias voltage was changed for each sample. The thickness of one unit was 30 nm, the ratio of the thicknesses of the A layer and the B layer was 1: 1, and the total film thickness was 3 μm.

After completion of the film formation, the component composition in the film was measured, and the preferential orientation of the film by X-ray diffraction and the half-value width of the diffraction line were examined. In addition, the hardness and abrasion resistance of the film were evaluated. The measuring method of the component composition and the evaluation method of hardness and wear resistance are the same as in the first embodiment. The component composition was A layer “(Ti0.2Cr0.15Al0.55Si0.1) N” and B layer “(Ti0.2Cr0.2Al0.6) N”.

The preferential orientation of the film and the half-value width of the diffraction line are the integrated intensity ratios of diffraction lines from the (111) plane and the (200) plane when the film is measured by X-ray diffraction using the θ-2θ method (in the table, ( 200) / (111)), and the half-value width of the diffraction line from the (200) plane when the film was measured by X-ray diffraction using the θ-2θ method.
The conditions for X-ray diffraction are shown below.
[X-ray diffractometer]
Equipment used: RINT-ULTIMA PC from Rigaku Denki
Measuring method: θ-2θ
X-ray source: Cuka (graphite monochromator used)
Excitation voltage-current: 40 kV-40 mA
Divergence slit: 1 °
Divergence length restriction slit: 10.00mm
Scattering slit: 1 °
Receiving slit: 0.15mm
Monochrome light receiving slit: None

Then, for each sample, the integral intensity of each diffraction line was obtained from the XRD figure (raw data) using the spreadsheet software IgorPro after fitting the diffraction lines of the raw data. Specifically, the value was calculated by performing fitting using the Voigt function as the peak shape using the multi-peak fit package of the software.
These results are shown in Table 4. In the table, those not satisfying the preferred range of the present invention are indicated by underlining the numerical values.

As shown in Table 4, no. In 61A to 63A, since the bias voltage was −130 V or less which is the preferable upper limit value of the present invention, the effect of improving hardness and wear resistance was good.
On the other hand, no. Nos. 59A and 60A were satisfactory in improving the hardness and wear resistance, but the bias voltage exceeded -130 V, which is the preferred upper limit of the present invention. Slightly inferior to 61A-63A.

Example B: Second hard film forming member
[First embodiment]
In the first example, after the B layer is formed to a thickness of 1.5 μm, an intermediate layer in which two types of layers having the same composition as the A layer and the B layer are laminated is formed to a thickness of one unit (lamination cycle). The film was fixed to 20 nm to form a 0.2 μm film, and an A layer was formed to a 1.5 μm film thereon. The bias voltage at the time of film formation was fixed at −150 V when the A layer and the intermediate layer were formed, and was fixed at −100 V when the B layer was formed. In this way, A and B layers having different compositions were formed, and the influence of the coating composition on hardness and cutting performance was examined. The intermediate layer was formed by laminating a layer having the same composition as that of the A layer and a layer having the same composition as that of the B layer in this order so as to be 10 nm each.

First, a target of various alloys or metals is attached to the cathode of the composite film forming apparatus, and further, a cutting tool (two-blade carbide end mill, φ10 mm) and hardness investigation that are ultrasonically degreased and washed in ethanol. A mirror-finished carbide test piece (length 13 mm × width 13 mm × thickness 5 mm) was mounted on a support stage on a substrate stage. Then, the chamber was evacuated (evacuated to 5 × 10 ⁻³ Pa or less) to be in a vacuum state. Next, after the temperature of the object to be processed was heated to 500 ° C. with a heater, etching with Ar ions was carried out for 5 minutes by an ion source by thermionic emission from the filament. Thereafter, a mixed gas obtained by adding nitrogen gas or, if necessary, a gas containing carbon to nitrogen gas is introduced to a total pressure of 4 Pa, the arc evaporation source (target diameter φ100 mm) is operated at a discharge current of 150 A, and the substrate A film having a predetermined thickness was formed at a rotation speed of 3 rpm.

In addition, about formation of laminated film, the target of the composition of A layer and B layer was attached to a separate evaporation source, the substrate stage carrying a substrate was rotated in an apparatus, and only the target of B layer was mentioned above first. A discharge was performed alone in a predetermined atmosphere such as nitrogen gas, and a bias voltage of −100 V was applied to the substrate to form a B layer having a predetermined thickness. Thereafter, the target of layer A is discharged, the targets of layer A and layer B are simultaneously discharged in a predetermined atmosphere, and the substrate stage is rotated while applying a bias voltage of −150 V to the substrate. An intermediate layer having a predetermined thickness and composed of a layer having the same composition and a layer having the same composition as the B layer was formed. Thereafter, only the target of the A layer was discharged alone in a predetermined atmosphere, a bias voltage of −150 V was applied to the substrate, and an A layer having a predetermined thickness was formed on the intermediate layer. The thickness of each of the A layer and the B layer, the thickness of one unit of the laminated structure of the intermediate layer, and the number of units were controlled by the rotational speed and the rotational speed of the support base.

After the film formation was completed, the component composition in the film was measured, and the hardness and abrasion resistance of the film were evaluated.
The film composition, hardness, wear resistance, and cutting test conditions are the same as in Example 1 of Example A.
These results are shown in Tables 5 and 6. In the table, those not satisfying the scope of the present invention are indicated by underlining the composition of each layer. However, those that do not contain essential components are not underlined.

As shown in Tables 5 and 6, no. Nos. 1B to 26B had good hardness and wear resistance because the compositions of the films (A layer and B layer) satisfied the scope of the present invention.
On the other hand, no. Since Nos. 27B to 49B did not satisfy the scope of the present invention, one or more of hardness and wear resistance were poor. In addition, No. For 50B, the amount of flank wear could not be measured due to the occurrence of chipping. Specifically, it is as follows.

No. In 27B, the Al amount in the A layer was less than the lower limit. No. In 28B, the total amount of Ti and Cr in the A layer was less than the lower limit, and the amount of Al exceeded the upper limit. No. 29B did not contain Si in the A layer. No. In 30B, the Si amount exceeded the upper limit in the A layer. No. 31B did not contain Ti and Cr in the A layer, and the Al amount exceeded the upper limit. No. 32B did not contain Cr in the A layer, and the Al amount exceeded the upper limit. No. 33B did not contain Ti in the A layer, and the Al amount exceeded the upper limit.

No. In 34B, the total amount of Ti and Cr in the A layer was less than the lower limit. No. In 35B, the total amount of Ti and Cr in the A layer exceeded the upper limit, and the Al amount was less than the lower limit. No. In 36B, the Y amount exceeded the upper limit in the A layer. No. In 37B, the B amount exceeded the upper limit in the A layer. No. In 38B, the C amount exceeded the upper limit in the A layer. No. In the case of 39B, the total amount of Ti and Cr exceeded the upper limit in the B layer, and the Al amount was less than the lower limit. No. In 40B, the total amount of Ti and Cr in the B layer was less than the lower limit, and the amount of Al exceeded the upper limit. No. 41B and 42B did not contain Cr in the B layer.

No. In 43B, the total amount of Ti and Cr in the A layer exceeded the upper limit, and Cr and Al were not contained. No. In 44B, the total amount of Ti and Cr exceeded the upper limit in the B layer, and contained no Cr or Al. No. In 45B, the total amount of Ti and Cr exceeded the upper limit in the B layer and did not contain Al. No. 46B did not contain Cr in the A layer, Al exceeded the upper limit, and the total amount of Ti and Cr exceeded the upper limit in the B layer, and did not contain Cr or Al. No. 47B did not contain Ti in the A layer, Al exceeded the upper limit, and the total amount of Ti and Cr exceeded the upper limit in the B layer, and did not contain Al. No. For 48B, the B amount exceeded the upper limit in the B layer. No. In 49B, the C amount exceeded the upper limit in the B layer. No. 50B contained Si in the B layer. Therefore, chipping occurred.

[Second Embodiment]
The film composition was fixed, the thicknesses of the A layer and B layer were fixed to 1.5 μm, the thickness of the intermediate layer was changed, and the influence of the thickness of the intermediate layer on hardness and cutting performance was examined.
The film was formed by the same method as in the first example (conditions other than the intermediate layer were the same as in the first example). The intermediate layer was formed by laminating a layer having the same composition as the A layer and a layer having the same composition as the B layer in this order. The ratio of the thickness of each layer of the intermediate layer was 1: 1, and the thickness of one unit was fixed at 20 nm. In addition, No. 51B is not provided with an intermediate layer.

After the film formation was completed, the component composition in the film was measured, and the hardness and abrasion resistance of the film were evaluated. The measuring method of the component composition and the evaluation method of hardness and wear resistance are the same as in the first embodiment. In addition, the component composition in a film | membrane was A layer "(Ti0.2Cr0.15Al0.55Si0.1) N" and B layer "(Ti0.2Cr0.2Al0.6) N".
These results are shown in Table 7. In the table, those not satisfying the scope of the present invention are indicated by underlining the numerical values.

As shown in Table 7, no. Nos. 51B to 55B had good hardness and wear resistance because the thickness of the intermediate layer satisfied the range of the present invention. On the other hand, no. In 56B, since the thickness of the intermediate layer exceeded the upper limit value, chipping occurred, and the flank wear amount could not be measured.

[Third embodiment]
In the third example, the coating composition was kept constant, and coatings having different thicknesses of the A layer and the B layer were formed for each sample, and the influence of the thicknesses of the A layer and the B layer on hardness and cutting performance was examined. The preferential orientation of the film by X-ray diffraction was also examined. Here, an intermediate layer is provided.
The film was formed by the same method as in the first example (conditions other than the film thickness were the same as in the first example). At this time, the thicknesses of the A layer and the B layer were changed for each sample. As a comparative example, a single layer film composed of an A layer or a B layer was also formed.

After film formation, the composition of the components in the film was measured, and the preferential orientation of the film was examined by X-ray diffraction. In addition, the hardness and abrasion resistance of the film were evaluated. The measuring method of the component composition and the evaluation method of hardness and wear resistance are the same as in the first embodiment. In addition, the component composition in a film | membrane was A layer "(Ti0.2Cr0.15Al0.55Si0.1) N" and B layer "(Ti0.2Cr0.2Al0.6) N".

The preferred orientation of the film is the integrated intensity ratio of diffraction lines from the (111) plane and the (200) plane when the film is measured by X-ray diffraction of the θ-2θ method (in the table, (200) / (111) ).
The conditions for X-ray diffraction and the data processing method are the same as in the third example of Example A.
These results are shown in Table 8. In the table, those not satisfying the range of the present invention and those whose integrated intensity ratio does not satisfy the preferable range of the present invention are indicated by underlining the numerical values.

As shown in Table 8, no. In 57B to 66B, the thicknesses of the A layer and the B layer satisfied the range of the present invention, and thus the hardness and wear resistance were good. Further, the integrated intensity ratio satisfied the preferable range of the present invention. On the other hand, no. No. 67B has no B layer and In 69B, since the thickness of the B layer was less than the lower limit, chipping occurred, and the flank wear amount could not be measured. No. 70B is the thickness of layer B, No. In 72B, since the thickness of the A layer exceeded the upper limit value, chipping occurred, and the flank wear amount could not be measured. No. No. 68B is not provided with an A layer, 71B had poor wear resistance because the thickness of the A layer was less than the lower limit. No. In 69B and 70B, the integrated intensity ratio was less than the preferred lower limit of the present invention.

[Fourth embodiment]
In the fourth example, the film composition, the thicknesses of the A layer and the B layer are made constant, the bias voltage at the time of film formation is changed, and the hardness and cutting performance are affected. The effect of the full width at half maximum was examined.
The film was formed by the same method as in the first example. However, the intermediate layer was not provided, and the bias voltage when the A layer was formed was changed. That is, the B layer was formed to a thickness of 1.5 μm with a bias voltage of −100 V, and the A layer was formed to 1.5 μm. At this time, the bias voltage when forming the A layer was changed for each sample.

After completion of the film formation, the component composition in the film was measured, and the preferential orientation of the film by X-ray diffraction and the half-value width of the diffraction line were examined. In addition, the hardness and abrasion resistance of the film were evaluated. The measuring method of the component composition and the evaluation method of hardness and wear resistance are the same as in the first embodiment. The component composition was A layer “(Ti0.2Cr0.15Al0.55Si0.1) N” and B layer “(Ti0.2Cr0.2Al0.6) N”.

The preferential orientation of the film and the half-value width of the diffraction line are the integrated intensity ratios of diffraction lines from the (111) plane and the (200) plane when the film is measured by X-ray diffraction using the θ-2θ method (in the table, ( 200) / (111)), and the half-value width of the diffraction line from the (200) plane when the film was measured by X-ray diffraction using the θ-2θ method.
The X-ray diffraction conditions are the same as in the third example.

Then, after fitting the diffraction lines of the raw data from the XRD figure (raw data) for each sample using the spreadsheet software IgorPro, the integrated intensity and the half width of each diffraction line were obtained. Specifically, the value was calculated by performing fitting using the Voigt function as the peak shape using the multi-peak fit package of the software.
These results are shown in Table 9. In the table, those not satisfying the preferred range of the present invention are indicated by underlining the numerical values.

As shown in Table 9, no. In 77B to 80B, the bias voltage is −75 V or less which is the preferable upper limit value of the present invention, and therefore, the integral intensity ratio satisfies the preferable range of the present invention. In addition, since the bias voltage is −130 V or less which is the preferable upper limit value of the present invention, the half width satisfies the preferable range of the present invention. Therefore, the effect of improving hardness and wear resistance was good.
On the other hand, no. In 73B, since the bias voltage exceeded −130 V and further exceeded −75 V, the integrated intensity ratio and the half-value width were less than the preferred lower limits of the present invention. No. Since the bias voltage of 74B to 76B exceeded −130 V, the half width was less than the preferred lower limit of the present invention. Therefore, these were good in improving the hardness and wear resistance, but No. Slightly inferior to 77B-80B.

The present invention has been described in detail with reference to the embodiments and examples. However, the gist of the present invention is not limited to the above-described contents, and the scope of right is widely interpreted based on the description of the claims. Must. Needless to say, the contents of the present invention can be widely modified and changed based on the above description.

This application is based on a Japanese patent application filed on October 29, 2010 (Japanese Patent Application No. 2010-244767) and a Japanese patent application filed on October 29, 2010 (Japanese Patent Application No. 2010-244768). Incorporated herein by reference.

The hard coating of the present invention is useful for cutting tools such as chips, drills and end mills, and jigs and tools such as presses, forging dies, molding dies and punching punches, and greatly improves their wear resistance.

1, 1a base material
2, 2a A layer
3, 3a B layer
4, 4a, 4a 'Hard coating
10 1st hard film forming member 10a, 10a '2nd hard film forming member 22 Aa layer 33 Bb layer

Claims (14)

1. A hard film forming member having a hard film on a substrate,
   The hard coating is composed of Ti _a Cr _b Al _c Si _d Y _e (B _u C _v N _w ), and the a, b, c, d, e, u, v, and w are atomic ratios. In addition,
   0.05 ≦ a
   0.05 ≦ b
   0.2 ≦ a + b ≦ 0.55
   0.4 ≦ c ≦ 0.7
   0.02 ≦ d ≦ 0.2
   0 ≦ e ≦ 0.1
   0 ≦ u ≦ 0.1
   0 ≦ v ≦ 0.3
   a + b + c + d + e = 1
   u + v + w = 1
   A layer satisfying
   When the composition is composed of Ti _f Cr _g Al _h (B _x C _y N _z ), and the f, g, h, x, y, and z are atomic ratios,
   0 ≦ f
   0.05 ≦ g
   0.25 ≦ f + g ≦ 0.6
   0.4 ≦ h ≦ 0.75
   0 ≦ x ≦ 0.1
   0 ≦ y ≦ 0.3
   f + g + h = 1
   x + y + z = 1
   B layer satisfying
   When the A layer and the B layer are alternately stacked, and a set of the stacked structure of the A layer and the B layer is one unit, the thickness of the one unit is 10 to 50 nm,
   A hard film forming member, wherein the film thickness of the hard film is 1 to 5 μm.
2. The integrated intensity I (200) of the diffraction line from the (200) plane when the hard film is measured by X-ray diffraction of the θ-2θ method is the integrated intensity I (111) of the diffraction line from the (111) plane. The hard film forming member according to claim 1, wherein the hard film forming member is 2 times or more.
3. The half width of the diffraction line from the (200) plane when the hard film is measured by X-ray diffraction of the θ-2θ method is 0.7 ° or more. The hard film forming member as described.
4. A hard film forming member having a hard film on a substrate,
   The hard coating is composed of Ti _a Cr _b Al _c Si _d Y _e (B _u C _v N _w ), and the a, b, c, d, e, u, v, and w are atomic ratios. In addition,
   0.05 ≦ a
   0.05 ≦ b
   0.2 ≦ a + b ≦ 0.55
   0.4 ≦ c ≦ 0.7
   0.02 ≦ d ≦ 0.2
   0 ≦ e ≦ 0.1
   0 ≦ u ≦ 0.1
   0 ≦ v ≦ 0.3
   a + b + c + d + e = 1
   u + v + w = 1
   A layer satisfying
   When the composition is composed of Ti _f Cr _g Al _h (B _x C _y N _z ), and the f, g, h, x, y, and z are atomic ratios,
   0 ≦ f
   0.05 ≦ g
   0.25 ≦ f + g ≦ 0.6
   0.4 ≦ h ≦ 0.75
   0 ≦ x ≦ 0.1
   0 ≦ y ≦ 0.3
   f + g + h = 1
   x + y + z = 1
   B layer satisfying
   The A layer is laminated on the B layer with or without an intermediate layer having a thickness of 0.5 μm or less, and the thickness of the A layer is 0.5 to 5.0 μm, A hard film forming member, wherein the B layer has a thickness of 0.05 to 3.0 μm.
5. An intermediate layer having a thickness of 0.5 μm or less is provided between the A layer and the B layer,
   The hard film forming member according to claim 4, wherein the intermediate layer is formed by alternately stacking layers having the same composition as the A layer and layers having the same composition as the B layer.
6. The integrated intensity I (200) of the diffraction line from the (200) plane when the hard film is measured by X-ray diffraction of the θ-2θ method is the integrated intensity I (111) of the diffraction line from the (111) plane. The hard film forming member according to claim 4, wherein the hard film forming member is 2 times or more.
7. The integrated intensity I (200) of the diffraction line from the (200) plane when the hard film is measured by X-ray diffraction of the θ-2θ method is the integrated intensity I (111) of the diffraction line from the (111) plane. The hard film forming member according to claim 5, wherein the hard film forming member is twice or more of
8. 8. The half width of the diffraction line from the (200) plane when the hard film is measured by X-ray diffraction of the θ-2θ method is 1 ° or more, 8. The hard film forming member according to one item.
9. A method for forming a hard film for producing the hard film forming member according to claim 1, wherein the hard film is formed by an arc ion plating method or a sputtering method.
10. A method of forming a hard film for producing the hard film forming member according to claim 2 or claim 3, wherein the hard film is formed on the base material by an arc ion plating method or a sputtering method. A method for forming a hard coating, characterized in that a bias voltage to be applied is a negative voltage having an absolute value of 130 V or more.
11. A hard film forming method for producing the hard film forming member according to claim 4 or 5, wherein the hard film is formed by an arc ion plating method or a sputtering method. Forming method.
12. A method of forming a hard film for producing the hard film forming member according to claim 6, wherein when the A layer, the B layer, and the intermediate layer are formed, the intermediate layer is further formed by an arc ion plate. A method of forming a hard coating, characterized in that a bias voltage applied to the base material is a negative voltage having an absolute value of 70 V or more when forming by a coating method or a sputtering method.
13. A hard film forming method for producing the hard film forming member according to claim 7, wherein the A layer, the B layer and the intermediate layer are formed by an arc ion plating method or a sputtering method. A method for forming a hard coating, wherein the bias voltage applied to the substrate is a negative voltage having an absolute value of 70 V or more.
14. 9. A method of forming a hard film for producing the hard film forming member according to claim 8, wherein the bias voltage applied to the substrate when the A layer is formed by an arc ion plating method or a sputtering method. Is a negative voltage having an absolute value of 130 V or more.
    

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