JPWO2014142190A1 - Hard coating, hard coating covering member, and manufacturing method thereof - Google Patents

Abstract

(AlxTiyMz) aN1-a (M is Cr and / or W, x, y, z and a are atomic ratios of 0.6 ≦ x ≦ 0.9, 0.05 ≦ y ≦ 0.4, 0 ≦ z ≦ 0.2, x + y + z = 1 and 0.2 ≦ a ≦ 0.8.) X-ray diffraction shows a wurtzite single structure, and the (002) plane X-ray diffraction peak of the wurtzite structure is the maximum peak. A certain hard film can be formed by an arc ion plating method in which a bipolar pulse bias voltage is applied to a substrate maintained at a temperature of 560 to 650 ° C. and a rectangular wave pulsed arc current is applied to the target. .

Description

  The present invention relates to an (AlTiM) N film and a hard film-coated member excellent in lubricity, and methods for producing them.

In recent years, high-performance and long-life (AlTiM) N coating coated cutting tools have been demanded for cutting work materials at high feed rates and high speeds. High performance and long life (AlTiM) N coating molds are also desired. Under such circumstances, “Kobe Steel Technical Report Vol. 41, No. 3, July 1991, Vol. 167” is shown in the right column on page 10, and the (Ti _0.3 Al _0.7 ) N film has a B1-type crystal structure. In addition to (also called cubic or rock salt type structure), a phase that can be regarded as a trace amount of wurtzite type (also called hexagonal crystal) was detected, and the (Ti _0.15 Al _0.85 ) N film has a wurtzite type structure. It is described.

Japanese Patent No. 2644710 has a chemical composition represented by (Al _x Ti _1-x ) (N _y C _1-y ) (provided that 0.56 ≦ x ≦ 0.75, 0.6 ≦ y ≦ 1), and is of the NaCl type Discloses a member in which a high-hardness wear-resistant film having a crystal structure of 0.8 to 10 μm and excellent in high-temperature oxidation resistance is formed on the surface of a substrate. FIG. 1 of Japanese Patent No. 2644710 shows that a wurtzite structure is obtained when the AlN ratio is 70 mol% or more.

  JP 2008-533310 A discloses an arc deposition coating apparatus having a configuration in which target electrodes 5 ′ and 20 ′ are connected to a pulse power source 16 in paragraph [0024] and FIG. 3.

  Japanese Patent Laid-Open No. 2003-113463 discloses a member in which a single-layer or multi-layer TiAl compound film is formed on the surface of a substrate having at least one edge ridge line, wherein the TiAl compound film includes nitrides and carbides containing Ti and Al. A first layer having at least one Ti / Al atomic ratio and a small Ti / Al atomic ratio in the vicinity of the edge ridge line, and comprising at least one of carbonitride, carbonate, nitride oxide and carbonitride. A member which is composed of two layers and is a single layer film having a constant Ti / Al atomic ratio in the center is disclosed. Japanese Patent Laid-Open No. 2003-113463 describes in the column of Comparative Example 2 in Table 1 that the arc current during the formation of the (Ti, Al) N film is 50 to 90 A.

  However, in both documents, when forming the (AlTiM) N film by the arc ion plating method, a bipolar pulse bias voltage of a predetermined condition is applied to the substrate, and a pulsed arc current of a predetermined condition is applied to the arc discharge evaporation source. Neither discloses nor suggests the technical idea of energizing and obtaining an (AlTiM) N coating that is preferentially oriented to the (002) plane of the wurtzite structure and has excellent lubricity and long life.

  Accordingly, a first object of the present invention is to provide an (AlTiM) N film having a lubricity superior to that of a conventional (AlTiM) N film and having a long life.

  The second object of the present invention is to provide a member such as a cutting tool, a mold or the like on which such an (AlTiM) N film is formed.

  A third object of the present invention is to provide a method for forming such (AlTiM) N coatings.

  The fourth object of the present invention is to provide a method for producing a member on which such an (AlTiM) N film is formed.

The hard coating of the present invention is (Al _x Ti _y M _z ) _a N _1-a (where M element is Cr and / or W, and x, y, z and a are each an atomic ratio of 0.6 ≦ x ≦ 0.9, 0.05 ≦ y ≦ 0.4, 0 ≦ z ≦ 0.2, x + y + z = 1 and 0.2 ≦ a ≦ 0.8.) And formed by arc ion plating. The X-ray diffraction pattern shows a single structure of wurtzite type, and the X-ray diffraction peak of the (002) plane of the wurtzite type structure is the maximum peak.

  When the equivalent X-ray diffraction intensity ratio TC (002) of the wurtzite structure is 2.5 or more, the hard coating of the present invention has a significantly improved lubricity.

  In the hard coating of the present invention, when the element M does not contain or the element M is mainly W, the X-ray diffraction peak intensity I (002) of the (002) plane and the (100) plane of the wurtzite structure When the ratio of I (100) satisfies the relationship of I (002) / I (100) ≧ 3.0, better lubricity can be obtained. The relational expression means that the X-ray diffraction peak intensity ratio between the (002) plane and the (100) plane oriented perpendicular to the film thickness direction is 3 or more.

  In the hard coating of the present invention, when the M element is mainly Cr, the ratio of the X-ray diffraction peak intensities I (002) and I (103) of the (002) plane and the (103) plane of the wurtzite structure is When satisfying the relationship of I (002) / I (103) ≧ 3.0, more excellent lubricity can be obtained. The relational expression means that the X-ray diffraction peak intensity ratio between the (002) plane and the (103) plane oriented perpendicular to the film thickness direction is 3 or more.

  The hard film-coated member of the present invention is characterized in that the hard film is formed on a substrate. Between the base and the hard coating, by physical vapor deposition, at least one metal element selected from the group consisting of elements 4a, 5a and 6a, Al and Si, and B, O, C and N It is preferable to form an intermediate layer that essentially includes at least one element selected from the group consisting of:

The method of the present invention for forming a hard film having the above composition on a substrate by an arc ion plating method,
When forming the hard coating on the substrate maintained at a temperature of 560 to 650 ° C. in a nitriding gas atmosphere, a bipolar pulse bias voltage is applied to the substrate, and AlTi provided in the arc discharge evaporation source Apply a pulsed arc current to a target made of an alloy or AlTiM alloy,
The bipolar pulse bias voltage has a positive bias voltage of +5 V to +15 V, a negative bias voltage of −60 V to −20 V, and a frequency of 20 to 50 kHz;
The pulsed arc current has a maximum arc current value of 80 to 110 A, a minimum arc current value of 40 to 80 A, and a frequency of 1 to 15 kHz, and a difference between the maximum arc current value and the minimum arc current value Is a substantially rectangular wave shape of 10 A or more.

The method for producing the hard film-coated member of the present invention is as follows.
When forming a hard film having the above composition on the substrate maintained at a temperature of 560 to 650 ° C. in a nitriding gas atmosphere by an arc ion plating method, a bipolar pulse bias voltage is applied to the substrate, Apply a pulsed arc current to a target made of AlTi alloy or AlTiM alloy provided in the discharge evaporation source,
The bipolar pulse bias voltage has a positive bias voltage of +5 V to +15 V, a negative bias voltage of −60 V to −20 V, and a frequency of 20 to 50 kHz;
The pulsed arc current has a maximum arc current value of 80 to 110 A, a minimum arc current value of 40 to 80 A, and a frequency of 1 to 15 kHz, and a difference between the maximum arc current value and the minimum arc current value Is a substantially rectangular wave shape of 10 A or more.

  In order to further improve the performance of the hard coating, it is preferable to perform etching treatment (Ti ion bombardment treatment) using Ti ions on the substrate before forming the hard coating. Further, in order to stably form the (AlTiM) N film, it is preferable to set the duty ratio of the pulse arc current to 20 to 50%.

The hard coating of the present invention has an Al-rich (AlTiM) N composition, the X-ray diffraction pattern shows a single structure of wurtzite type, and the X-ray diffraction peak of the (002) plane of the wurtzite type structure is Since it consists of polycrystalline grains with the maximum peak, it is significantly richer in lubricity than the conventional (AlTiM) N coating. Therefore, members (cutting tools, dies, etc.) on which this film is formed have a significantly long life.
By the production method of the present invention, such a long-life (AlTiM) N film-coated member can be produced efficiently.

It is a schematic sectional drawing which shows an example of the arc ion plating apparatus which can be used for formation of the hard film of this invention. It is a figure which shows an example of the pulse arc current waveform applied to the arc discharge type evaporation source at the time of hard film formation of this invention. 2 is a scanning electron micrograph (magnification: 25,000 times) showing a cross section of the hard film-coated tool of Example 1. FIG. 2 is a graph showing an X-ray diffraction pattern of the (AlTi) N film of Example 1. FIG. 6 is a graph showing an X-ray diffraction pattern of the (AlTi) N film of Conventional Example 1. 2 is a scanning electron micrograph (magnification: 3,000 times) showing the surface of the (AlTi) N film of Example 1. FIG. 2 is a scanning electron micrograph (magnification: 3,000 times) showing the surface of the (AlTi) N film of Conventional Example 1. 2 is a photograph showing a limited field diffraction image of the (AlTi) N film of Example 1. FIG. It is a perspective view which shows an example of the insert base | substrate which comprises the hard film coating | coated member of this invention. It is the schematic which shows an example of the blade-tip-exchange-type rotary tool equipped with the insert. It is a partial section schematic diagram showing an example of a hard coat covering metallic mold. 4 is a scanning electron micrograph (magnification: 25,000 times) showing a cross section of the hard film-coated tool of Example 39. 42 is a graph showing an X-ray diffraction pattern of the (AlTiCr) N film of Example 39. FIG. 40 is a photograph showing a limited field diffraction image of the (AlTiCr) N film of Example 39. FIG. 4 is a scanning electron micrograph (magnification: 25,000 times) showing a cross section of the hard film-coated tool of Example 43. 4 is a graph showing an X-ray diffraction pattern of an (AlTiW) N film of Example 43. FIG. 4 is a photograph showing a limited-field diffraction image of the (AlTiW) N film of Example 43. FIG.

[1] Hard film covering member The hard film covering member of the present invention is formed on a substrate by an arc ion plating method (AI method) (Al _x Ti _y M _z ) _a N _1-a (where M element is Cr and / or W, and x, y, z and a are numbers satisfying the atomic ratios satisfying 0.6 ≦ x ≦ 0.9, 0.05 ≦ y ≦ 0.4, 0 ≦ z ≦ 0.2, x + y + z = 1 and 0.2 ≦ a ≦ 0.8, respectively. A hard film having a composition represented by: There are hard coatings that contain M and those that do not contain, so they can be called (AlTi) N coatings or (AlTiM) N coatings, but unless otherwise specified, both are collectively referred to as `` (AlTiM) N coatings ''. To do. The X-ray diffraction pattern of the (AlTiM) N hard film shows a wurtzite type single structure, and the (002) plane X-ray diffraction peak of the wurtzite type structure is the maximum peak.

(A) Substrate The substrate must be made of a material that can be applied with physical vapor deposition at a temperature close to 600 ° C. Examples of the base material include ceramics represented by cemented carbide, cermet, high speed steel, tool steel, or boron nitride sintered body (cBN sintered body) mainly composed of cubic boron nitride. From the viewpoints of strength, hardness, wear resistance, toughness, thermal stability, and the like, a WC-based cemented carbide substrate is preferred. The WC-based cemented carbide is composed of tungsten carbide (WC) particles and a binder phase of Co or an alloy mainly composed of Co. The content of the binder phase is preferably 1 to 13.5% by mass, and 3 to 13% by mass. More preferred. If the binder phase content is less than 1% by mass, the substrate has insufficient toughness, and if the binder phase exceeds 13.5% by mass, the hardness (wear resistance) becomes insufficient. The (AlTiM) N coating of the present invention can be formed on any of the unprocessed surface, polished surface, and blade edge processed surface of the sintered WC-based cemented carbide.

(B) (AlTiM) N coating
(1) Composition
The (AlTiM) N film of the present invention coated on a substrate by the AI method is made of a nitride containing Al and Ti as essential elements. The composition of the (AlTiM) N film is represented by the general formula: (Al _x Ti _y M _z ) _a N _1-a (atomic ratio). M element is Cr and / or W, x, y, z and a are numbers satisfying 0.6 ≦ x ≦ 0.9, 0.05 ≦ y ≦ 0.4, 0 ≦ z ≦ 0.2, x + y + z = 1 and 0.2 ≦ a ≦ 0.8, respectively. It is. With this composition, an (AlTiM) N film having a single structure of the wurtzite type with the (002) plane oriented can be obtained.

  By containing M element (Cr and / or W), the (AlTiM) N film becomes denser and oxidation resistance is improved. In particular, when Cr is contained, the crystal grains become large and the orientation of the (002) plane of the wurtzite structure is strengthened. Moreover, when it contains W, high temperature stability increases and the film hardness at the time of high temperature improves. In other words, the content of W increases the generation temperature of Ti oxide and Al oxide, so that phase separation is less likely to occur, it is strongly oriented to the (002) plane of the wurtzite structure, and excellent cutting performance and mold performance (AlTiM) N film exhibiting

  When the total of Al, Ti and M elements (x + y + z) is 1, and x indicating the Al ratio is less than 0.6, a rock salt structure is formed, and when it exceeds 0.9, the adhesion between the substrate and the (AlTiM) N film is remarkable. Damaged. A preferred range for x is 0.65 to 0.85.

  When the total of Al, Ti and M elements (x + y + z) is 1, and y indicating the ratio of Ti is less than 0.05, the adhesion between the substrate and the (AlTiM) N film is significantly impaired. Formed and the lubricity is impaired. A preferred range for y is 0.05 to 0.35.

  If the total of Al, Ti and M elements (x + y + z) is 1, z indicating the ratio of M elements is 0.2 or less and may be 0. When z exceeds 0.2, a rock salt structure is formed and the lubricity is impaired. A preferred range for z is 0.05 to 0.2.

  When the total of the metal component and nitrogen in the (AlTiM) N film is 1, and the ratio (a) of the metal component is less than 0.2, impurities are easily taken into the crystal grain boundaries of the (AlTi) N polycrystal. Impurities are derived from the internal residue of the film forming apparatus. In such a case, the bonding strength of the (AlTiM) N film is reduced, and the (AlTiM) N film is easily destroyed by external impact. On the other hand, if a exceeds 0.8, the ratio of the metal component is excessive, the crystal strain increases, the adhesion to the substrate is lowered, and the (AlTiM) N film is easily peeled off.

  The (AlTiM) N film of the present invention may contain at least one of C, B and O. In that case, the total amount of C, B and O is preferably 30 atomic% or less of the N content (1-a). In order to maintain high lubricity, the total amount of C, B and O is more preferably 10 atomic% or less. When containing at least one of C, B and O, the (AlTiM) N coating can be referred to as a nitrocarbide, boronitride, oxynitride, nitrocarbon boride, nitrocarbon oxide or nitrocarbon borate.

(2) Film thickness The average thickness of the (AlTiM) N film of the present invention is preferably 0.5 to 15 µm, more preferably 1 to 12 µm. With a film thickness in this range, peeling between the substrate and the (AlTiM) N film is suppressed, and excellent lubricity is exhibited. When the average thickness is less than 0.5 μm, the effect of the (TiAl) N film cannot be substantially obtained. On the other hand, if the average thickness exceeds 15 μm, the residual stress becomes excessive, and it becomes easy to peel from the substrate. Since the (AlTiM) N film is not completely flat, the term “thickness” simply means the average thickness.

(3) Crystal structure The X-ray diffraction pattern of the (AlTiM) N film of the present invention consists of a wurtzite single structure. In the limited field diffraction pattern of the (AlTiM) N film of the present invention by a transmission electron microscope, it is allowed that the wurtzite structure is the main structure and the other structure (rock salt structure or the like) is the substructure.

(4) Crystal Orientation The (AlTiM) N film of the present invention is composed of (AlTi) N polycrystalline grains strongly oriented on the (002) plane of the wurtzite structure. As will be described later, this crystal orientation is evaluated by calculating an equivalent X-ray diffraction intensity ratio TC (002) from the X-ray diffraction pattern of the (AlTiM) N film. The crystal plane (hkl) of the (AlTiM) N film of the present invention includes (100) plane, (002) plane, (101) plane, (102) plane, (110) plane, (103) plane, (200) Plane, (112) plane, (201) plane, and (004) plane. The orientation of each crystal plane is calculated by assuming the number of crystal planes to be calculated as 10 and the following equivalent X-ray diffraction intensity ratios TC (100), TC (002), TC (101), TC (102), TC (110) , TC (103), TC (200), TC (112), TC (201) and TC (004) can be converted into numerical values.
TC (100) = [I (100) / I ₀ (100)] / Σ [I (hkl) / 10I ₀ (hkl)] ... (1)
TC (002) = [I (002) / I ₀ (002)] / Σ [I (hkl) / 10I ₀ (hkl)] ... (2)
TC (101) = [I (101) / I ₀ (101)] / Σ [I (hkl) / 10I ₀ (hkl)] ... (3)
TC (102) = [I (102) / I ₀ (102)] / Σ [I (hkl) / 10I ₀ (hkl)] ... (4)
TC (110) = [I (110) / I ₀ (110)] / Σ [I (hkl) / 10I ₀ (hkl)] ... (5)
TC (103) = [I (103) / I ₀ (103)] / Σ [I (hkl) / 10I ₀ (hkl)] ... (6)
TC (200) = [I (200) / I ₀ (200)] / Σ [I (hkl) / 10I ₀ (hkl)] (7)
TC (112) = [I (112) / I ₀ (112)] / Σ [I (hkl) / 10I ₀ (hkl)] ... (8)
TC (201) = [I (201) / I ₀ (201)] / Σ [I (hkl) / 10I ₀ (hkl)] ... (9)
TC (004) = [I (004) / I ₀ (004)] / Σ [I (hkl) / 10I ₀ (hkl)] ... (10)
However, (hkl) is (100), (002), (101), (102), (110), (103), (200), (112), (201) and (004).

In TC (hkl), I (hkl) is the measured X-ray diffraction peak intensity from the (hkl) plane, and I ₀ (hkl) is the standard X-ray diffraction peak intensity described in JCPDS file number 251133. TC (hkl) defined by the above formula indicates the relative intensity of the measured X-ray diffraction peak intensity from the (hkl) plane of the wurtzite structure, and the larger TC (hkl), the more the X-ray from the (hkl) plane. The diffraction peak intensity is larger than the peak intensity of other X-ray diffraction surfaces. This indicates that the (hkl) plane is oriented perpendicular to the film thickness direction.

  The (AlTiM) N film of the present invention has the largest TC (002) in the equivalent X-ray diffraction intensity ratio TC. Specifically, TC (002) is preferably 2.5 or more, more preferably 2.5 to 7, and most preferably 3 to 6. When TC (002) is 5 to 6, the orientation to the (002) plane is particularly strong, and the lubricating effect is improved. If TC (002) is less than 2.5, the orientation to the (002) plane is insufficient and the lubricity is insufficient. On the other hand, if TC (002) exceeds 7, the wear resistance is lowered.

  The (002) plane of the wurtzite structure is parallel to the c-axis of the crystal lattice, and TC (002) ≧ 2.5 is the direction in which the polycrystalline grains constituting the (AlTiM) N film are parallel to the substrate surface. Shows a significant growth. The most fragile slip of the wurtzite structure is the (002) plane slip. This is because the bonding force between the (002) planes is weak and easy to break. When the (002) plane of the wurtzite structure satisfies TC (002) ≧ 2.5, the bond between the (002) planes is easily broken with a slight external force, and the (002) plane is broken into layers. As a result, the portion where the work material and the (AlTiM) N film are in contact with each other is remarkably easily slid, so that the amount of wear of the (AlTiM) N coated member that occurs during cutting or mold forming can be kept small. Furthermore, since the (AlTiM) N coating of the wurtzite structure of the present invention has very poor wettability with respect to metal elements (Fe, Ni, etc.) contained in the work material, Welding can be minimized. As described above, the cutting tool or the mold in which the (AlTiM) N film of the present invention strongly oriented on the (002) plane of the wurtzite structure is formed on the substrate has remarkably improved lubricity.

(C) Intermediate layer Between the substrate and the (AlTiM) N film, by physical vapor deposition, at least one element selected from the group consisting of elements 4a, 5a and 6a, Al and Si, and B, O It is practical to form an intermediate layer that essentially contains at least one element selected from the group consisting of C and N. As the intermediate layer, for example, (TiAl) N, (TiAl) NC, (TiAl) NCO, (TiAlCr) N, (TiAlCr) NC, (TiAlCr) NCO, (TiAlNb) N with the main structure of TiN, rock salt structure , (TiAlNb) NC, (TiAlNb) NCO, (TiAlW) N, (TiAlW) NC and (TiAlW) NCO, (TiSi) N, (TiB) N, TiCN, Al ₂ O ₃ , Cr ₂ O ₃ , (AlCr And at least one film selected from the group consisting of ₂ O ₃ , (AlCr) N, (AlCr) NC, and (AlCr) NCO.

[2] Deposition equipment
An arc ion plating device (AI device) can be used to form the (AlTiM) N film, and an AI device or other physical vapor deposition device (such as a sputtering device) can be used to form the intermediate layer. Can do. This film forming apparatus includes arc discharge evaporation sources 12 and 27 attached to a decompression vessel 5 through an insulator 13, targets 10 and 17 attached to the arc discharge evaporation sources 12 and 27, and an arc discharge type. The arc discharge power supplies 11 and 11 connected to the evaporation sources 12 and 27, the support column 6 supported on the rotation axis in the decompression vessel 5 via the bearing portion 4, and the support column 6 to hold the base body 7 A holder 8, a driving unit 1 that rotates the support 6, and a bias power source 3 that applies a bias voltage to the base 7 are provided. The decompression vessel 5 is provided with a gas introduction part 2 and an exhaust port 16. The arc ignition mechanisms 15 and 15 are attached to the decompression vessel 5 via arc ignition mechanism bearing portions 14 and 14. The electrode 19 is attached to the decompression vessel 5 via an insulator 18. Between the targets 10, 17 and the base body 7, a shielding plate 22 attached to the decompression vessel 5 via a shielding plate bearing portion 20 is provided. The shielding plate 22 is movable up and down and left and right, for example, by the shielding plate driving unit 21, and the (AlTiM) N film is formed in a state where the shielding by the shielding plate 22 is released.

(A) Target As a target for film formation of the (AlTiM) N film of the present invention, Al _x Ti _y M _z other than inevitable impurities (provided that M element is Cr and / or W, and x, y, and z are respectively It is preferable to use an AlTi alloy or an AlTiM alloy having a composition represented by the following formula: 0.6 ≦ x ≦ 0.9, 0.05 ≦ y ≦ 0.4, 0 ≦ z ≦ 0.2, and x + y + z = 1. Hereinafter, both alloys are collectively referred to as “AlTiM alloy” unless otherwise specified. If x, y, and z do not satisfy the conditions of 0.6 ≦ x ≦ 0.9, 0.05 ≦ y ≦ 0.4, and z ≦ 0.2, the (AlTiM) N film of the present invention cannot be obtained.

(B) Arc discharge type evaporation source and arc discharge power source As shown in FIG. 1, arc discharge type evaporation sources 12 and 27 are equipped with cathode material targets (AlTiM alloys) 10 and 17, respectively, and arc discharge power source 11 and 11, a pulse arc current is applied to the targets 10 and 17 under the conditions described later. Although not shown in FIG. 1, the arc discharge evaporation sources 12 and 27 are provided with magnetic field generating means (electromagnets and / or permanent magnets), and several tens of meters are provided in the vicinity of the base 7 on which the (AlTiM) N film is formed. A magnetic field distribution with a gap magnetic flux density of G (for example, 10 to 50 G) is formed.

  Since the target made of an AlTiM alloy contains Al, which is a low melting point metal, the arc spot moving on the target tends to stagnate at the Al portion. When the movement of the arc spot is retained, a large dissolved portion is formed in the retained portion, and the droplet (referred to as “droplet”) adheres to the surface of the substrate to roughen the surface of the (AlTiM) N film. The presence of droplets also causes a decrease in grains having a wurtzite structure and an inhibition of growth, and ultimately greatly reduces the orientation rate of the (002) plane of the wurtzite structure. Furthermore, the (AlTiM) N film with many droplets has a form close to amorphous (non-oriented state).

  In forming the (AlTiM) N film of the present invention by the AI method, a bipolar pulse bias voltage to the substrate is used to suppress the generation of droplets and to preferentially orient the (002) plane of the wurtzite structure. Is applied under predetermined conditions, and a pulsed arc current must be applied to the target of the arc discharge evaporation source under predetermined conditions.

(C) Bias power source As shown in FIG. 1, a DC voltage or a bipolar pulse bias voltage is applied to the substrate 7 from the bias power source 3.

[3] Film formation conditions The (AlTiM) N film of the present invention strongly oriented on the (002) plane of the wurtzite structure applies a bipolar pulse bias voltage to the substrate and applies a pulse arc to the target of the arc discharge evaporation source. It can be manufactured by performing the AI method under film formation conditions in which a current is passed. Hereinafter, the film forming conditions of the (AlTiM) N film of the present invention will be described for each step.

(A) Substrate cleaning process After the substrate 7 is set on the holder 8 of the AI apparatus shown in FIG. 1, a heater (not shown) is used while holding the vacuum container 5 at a vacuum of 1.5 × 10 ⁻² Pa. The substrate 7 is heated to a temperature of 250 to 650 ° C. Although shown in FIG. 1 as a cylinder, the substrate 7 can take various shapes such as a solid type end mill or insert. Thereafter, Ar gas is introduced into the decompression vessel 5 to obtain an Ar gas atmosphere of 0.5 to 10 Pa. In this state, a DC power supply voltage or pulse bias voltage of −250 V to −150 V is applied to the substrate 7 from the bias power source 3, and the surface of the substrate 7 is bombarded with Ar gas and cleaned.

  When the substrate temperature is less than 250 ° C., there is no etching effect by Ar gas, and when it exceeds 650 ° C., the etching effect by Ar gas is saturated and industrial productivity decreases. The substrate temperature is measured by a thermocouple embedded in the substrate. If the pressure of Ar gas in the decompression vessel 5 is outside the range of 0.5 to 10 Pa, the bombardment with Ar gas becomes unstable. When the DC bias voltage or pulse bias voltage is less than −250 V, arcing occurs in the substrate, and when it exceeds −150 V, the cleaning effect by etching cannot be sufficiently obtained.

(B) (AlTiM) N Film Formation Process After the substrate cleaning process, an (AlTiM) N film is formed on the substrate 7. At this time, using a nitriding gas, a pulsed arc current is supplied from the arc discharge power supplies 11 and 11 to the surfaces of the targets 10 and 17 attached to the arc discharge evaporation sources 12 and 27 under the conditions described later. At the same time, a bipolar pulse bias voltage is applied from the bias power source 3 to the substrate 7 controlled to a predetermined temperature under the conditions described later.

(1) Substrate temperature
The substrate temperature needs to be 560 to 650 ° C. when the (AlTiM) N film is formed. If the substrate temperature is less than 560 ° C, a wurtzite-type single structure cannot be obtained, and if it exceeds 650 ° C, the rock salt-type structure becomes stable and a wurtzite-type structure cannot be obtained. The substrate temperature is preferably 560 to 630 ° C.

(2) Type and pressure of nitriding gas As the nitriding gas for forming the (AlTiM) N film on the substrate 7, for example, nitrogen gas, a mixed gas of ammonia gas and hydrogen gas, or the like can be used. The pressure of the nitriding gas is preferably 2 to 6 Pa. If it is less than 2 Pa, the formation of nitride is insufficient, and if it exceeds 6 Pa, the effect of adding nitriding gas is saturated.

(3) Bipolar pulse bias voltage applied to the substrate In order to obtain an (AlTiM) N film oriented on the (002) plane of the wurtzite structure, a substantially rectangular bipolar pulse bias voltage consisting of a positive bias voltage and a negative bias voltage is obtained. Must be applied to the substrate. The positive bias voltage (positive peak value excluding a steep portion rising from zero to the positive side) is +5 V to +15 V, preferably +8 V to +15 V. Within this range, the base 7 can be sufficiently prevented from being charged, so that the orientation of the (002) plane of the wurtzite structure can be promoted. When the peak value of the positive bias voltage is less than +5 V, the antistatic effect cannot be obtained, and the wurtzite structure does not align with the (002) plane. On the other hand, if it exceeds +15 V, the deposition rate of the (AlTiM) N film is drastically reduced, which is not practical. The negative bias voltage (negative peak value excluding a portion with a steep fall from zero to the negative side) is −60 V to −20 V, and preferably −50 V to −20 V. When the negative bias voltage is less than −60 V, the (002) plane of the wurtzite structure is not oriented (not the maximum peak), and when it exceeds −20 V, the wurtzite structure becomes unstable.

  The frequency of the bipolar pulse bias voltage is 20 to 50 kHz, preferably 30 to 40 kHz. Outside the range of 20 to 50 kHz, the wurtzite structure becomes unstable or the (002) plane of the wurtzite structure is not oriented.

(4) Pulsed arc current
In order to suppress the generation of droplets during the formation of the (AlTiM) N film, a pulse arc current is applied to each of the targets 10 and 17. The pulse arc current is a substantially rectangular pulse wave having at least two stages, as schematically shown in FIG. 2 (waveform waveform of the pulse arc current of Example 1), for example. Setting the minimum value (Amin) and maximum value (Amax) in the stable region of the pulse arc current is extremely important. In FIG. 2, t _min is the energization time on the minimum value Amin side in the stable region of the pulse arc current in the cycle T, and t _max is the energization time on the maximum value Amax side in the stable region of the pulse arc current in the cycle T.

As shown in FIG. 2, Amax and _tmax are obtained in a stable region excluding a steep rising portion from Amin to Amax. Although not observed steep part falling leading to Amin Figures 2, Amax, if this steep part exists seek Amin and t _min in a stable region excluding this part. In one pulse (period T) of the pulse arc current waveform, the stable region on the maximum value side is in the range of 96 to 100% of the maximum value excluding the steep portion, and the stable region on the minimum value side is excluding the steep portion. The minimum value is in the range of 100 to 104%.

  In order to suppress the generation of droplets during the formation of the (AlTiM) N film, Amin is 40 to 80 A, preferably 40 to 70 A. When Amin is less than 40 A, arc discharge does not occur and film formation is impossible. On the other hand, when Amin exceeds 80 A, the number of droplets increases, and the (002) plane of the (AlTiM) N film having a wurtzite structure is not oriented. Amax is 80 to 110 A, preferably 85 to 100 A. When Amax is outside the range of 80 to 110 A, the wurtzite structure becomes unstable or the (002) plane of the wurtzite structure is not oriented.

  The difference ΔA between Amax and Amin is 10 A or more, preferably 10 to 60 A, and more preferably 20 to 50 A. If ΔA is less than 10 A, the droplets increase and a wurtzite structure cannot be obtained, or even if it is obtained, its (002) plane is not the maximum peak.

The output ratio between t _max and t _min in the pulse arc current is controlled by the duty ratio D. Duty ratio D is the following formula:
D = [t _min / (t _min + t _max )] × 100%
(Where t _min is the energization time in the stable region of the minimum value Amin of the pulse arc current, and t _max is the energization time in the stable region of the maximum value Amax of the pulse arc current).

  The duty ratio D is preferably 20 to 50%, and more preferably 25 to 45%. When the duty ratio D is outside the range of 20 to 50%, the wurtzite structure becomes unstable or the (002) plane of the wurtzite structure tends not to be oriented. However, the waveform of the pulse arc current is not limited to the two stages shown in FIG. 2, and may be three or more stages (for example, 3 to 10 stages) as long as it has a stable region of at least Amax and Amin.

  The frequency of the pulse arc current is 1 to 15 kHz, preferably 1 to 4 kHz. When the frequency of the pulse arc current is outside the range of 1 to 15 kHz, the wurtzite structure becomes unstable or the (002) plane of the wurtzite structure is not oriented.

  In forming the (AlTiM) N film, by setting the pulse bias voltage application condition and the pulse arc current energization condition within the above optimum range, the arc spot moves uniformly on the target without stagnation in the Al part. Therefore, the AlTiM alloy on the target surface melts and evaporates uniformly, and the generation of droplets is greatly reduced. As a result, the wurtzite structure of the (AlTiM) N film formed on the substrate is stabilized, the orientation of the (002) plane of the wurtzite structure is strengthened, and the performance is improved.

  As will be described later, in the (AlTiM) N film of Conventional Example 1, the (100) plane orientation of the wurtzite type structure was obtained, and the (002) plane of the wurtzite type structure was not oriented. In the X-ray diffraction pattern of the (AlTiM) N film of the present invention, the X-ray diffraction peak of the (002) plane of the wurtzite structure becomes the maximum peak, that is, the mechanism by which the (002) plane of the wurtzite structure is oriented. Although not necessarily clear, it is considered as follows. As described above, in forming the (AlTiM) N film of the present invention, by applying a pulse bias voltage under predetermined conditions, micro-arcing on the surface of the substrate 7 is suppressed, and the ionization rate of the gas component introduced into the vacuum vessel 5 Is increased. In addition, the ionization rate of Al, Ti (and M elements) constituting the targets 10 and 17 is changed by energization with a pulsed arc current under predetermined conditions, and thus plasma formed by Al, Ti and N (and M elements). This is considered to be because the amount of ions of Al, Ti and N (and M elements) reaching the substrate 7 becomes suitable for the orientation of the (002) plane of the wurtzite structure by changing the density of .

  The present invention will be described in more detail with reference to the following examples, but the present invention is of course not limited thereto.

Example 1
(1) Cleaning the substrate
High feed milling insert base made of WC-base cemented carbide containing 6.0% by mass of Co and the balance consisting of WC and inevitable impurities (EDNW15T4TN-15 made by Hitachi Tool Co., Ltd. having the shape shown in FIG. 7) ), And an insert base for measuring physical properties (SNMN120408 manufactured by Hitachi Tool Co., Ltd.) were set on the holder 8 of the AI apparatus shown in FIG. 1, and heated to 600 ° C. with a heater (not shown) simultaneously with evacuation. Thereafter, Ar gas was introduced at 500 sccm (cc / min at 1 atm and 25 ° C., the same shall apply hereinafter) to adjust the pressure in the vacuum vessel 5 to 2.0 Pa, and a negative DC bias voltage of −200 V was applied to each substrate. Each substrate was cleaned by etching with Ar ions.

(2) Formation of (AlTi) N film While maintaining the substrate temperature at 600 ° C., 700 sccm of nitrogen gas was introduced to adjust the pressure in the decompression vessel 5 to 3.2 Pa. Targets 10 and 17 made of an AlTi alloy having a composition of Al _0.85 Ti _0.15 (atomic ratio) were placed in arc discharge evaporation sources 12 and 27 to which arc discharge power sources 11 and 11 were connected, respectively.

A bias power supply 3 applied a positive pulse voltage of +10 V, a negative bias voltage of −40 V, and a bipolar pulse bias voltage having a substantially rectangular wave shape having a frequency of 40 kHz to each substrate. Along with the application of the bipolar pulse bias voltage, a (AlTi) N hard coating was formed on the surfaces of the targets 10 and 17 while applying a substantially rectangular wave pulse arc current from the arc discharge power supplies 11 and 11. As shown in Figure 2, the minimum value Amin of the pulse arc current is 50 A, the maximum value Amax is 100 A, the frequency is 4 kHz (period T = 2.5 × 10 ⁻⁴ seconds / pulse), and the duty ratio D was 35%. Under these conditions, an (Al _0.82 Ti _0.18 ) _0.33 N _0.67 film (atomic ratio) having a thickness of 3.0 μm was coated on each substrate. The composition is such that the center position in the thickness direction of the film is measured under the conditions of an acceleration voltage of 10 kV, an irradiation current of 0.05 A, and a beam diameter of 0.5 μm using an electron probe microanalyzer EPMA (JXA-8500F, manufactured by JEOL Ltd.) It was measured by.

  FIG. 3 is a scanning electron microscope (SEM) photograph (magnification: 25,000 times) showing a cross-sectional structure of an insert substrate for measuring physical properties on which an (AlTi) N film is formed. In FIG. 3, 41 is a substrate and 42 is an (AlTi) N film.

(3) X-ray diffraction pattern of (AlTi) N film X-ray diffractometer (EMPYREAN manufactured by Panalytical) was used to measure the crystal structure and crystal orientation of (AlTi) N film on the insert substrate for measuring physical properties. Then, CuKα1 line (wavelength λ: 0.15405 nm) was irradiated to the (AlTi) N film, and an X-ray diffraction pattern [FIG. 4 (a)] was obtained under the following conditions.
Tube voltage: 45 kV
Tube current: 40 mA
Incident angle ω: Fixed at 3 °
2θ: 30-80 °

  In FIG. 4 (a), w- (002), w- (100), w- (101) and w- (112) represent X-ray diffraction peaks of the wurtzite structure, respectively. FIG. 4 (a) shows that all X-ray diffraction peaks have a wurtzite type structure, and it was confirmed that the (AlTi) N film of Example 1 has a wurtzite type single structure.

(4) Measurement of droplet FIG. 5 (a) is an SEM photograph (magnification: 3,000 times) showing the surface of the (AlTi) N film of the physical property measurement insert. As a result of counting droplets with a diameter of 1 μm or more in the field of view of 35 μm length × 40 μm width of this SEM photograph, the surface of the (AlTi) N coating of Example 1 is the surface of the (AlTi) N coating of Conventional Example 1 described later. It can be seen that there are fewer droplets compared to (Figure 5b).

(5) Restricted field diffraction pattern of (AlTi) N film Using transmission electron microscope TEM (JEM-2100, manufactured by JEOL Ltd.), limited field diffraction pattern of (AlTi) N film of insert for physical property measurement (diffraction) Pattern) was observed under the conditions of an acceleration voltage of 200 kV and a camera length of 50 cm. In the obtained limited-field diffraction pattern (FIG. 6), w- (002), w- (100), w- (101) and w- (102) represent diffraction spots of wurtzite structure, and c- ( 200) shows the diffraction spot of rock salt structure. From Fig. 6, most of the diffraction spots have a wurtzite structure, few diffraction spots are attributed to the rock salt structure, and the (AlTi) N film of the physical property measurement insert has a wurtzite structure in the TEM limited field diffraction pattern. It can be seen that the mold structure is the main structure.

Table 1 shows the standard X-ray diffraction intensities I ₀ and 2θ of AlN having a wurtzite structure described in JCPDS file number 251133. Since AlN has the same wurtzite structure as (AlTi) N and has a similar composition, the values in Table 1 are adopted as the standard X-ray diffraction intensity I ₀ (hkl) of the (AlTi) N film of the present invention. did.

  In the hard film-coated member of Example 1, the orientation of the (100) plane, (002) plane, (101) plane, and (112) plane of the wurtzite structure is expressed by their equivalent X-ray diffraction intensity ratio TC (hkl ). TC (hkl) was determined by the formulas (1) to (10) described in paragraphs [1] (B) (4). Table 2 shows the actual measurement values and TC (hkl) values of the X-ray diffraction peak intensity of the (AlTi) N coating. Among the crystal faces of the wurtzite structure where X-ray diffraction peaks were observed, TC (002) was the largest at 6.2.

Note: (1) No X-ray diffraction peak was observed.

(6) Tool life measurement
Four high-feed cutting tool inserts 30 (Fig. 7) coated with (AlTi) N coating are replaced with the tip of the tool body 36 of the blade-changeable rotary tool (Hitachi Tool Co., Ltd., ASR5063-4) 40 shown in Fig. 8. The part 38 was attached with a set screw 37. The blade diameter of the tool 40 was 63 mm. In order to measure the tool life based on the following criteria, cutting was performed under the following rolling conditions, and the rake face of the insert 30 sampled per unit time was observed with an optical microscope with a magnification of 100 times. The processing time when the AlTi) N film was lost and the WC-base cemented carbide of the substrate was exposed on the surface was judged as the tool life.

Cutting conditions Machining method: High feed continuous turning Work material: S50C square material of 130 mm x 250 mm Insert used: EDNW15T4TN-15 (for milling)
Cutting tool: ASR5063-4
Cutting speed: 300 m / min
Feed per tooth: 1.5 mm / tooth Axial cut depth: 1.0 mm
Radial depth of cut: 44.0 mm
Cutting fluid: None (dry machining)

  Table 3 shows the tool life of the (AlTi) N film together with the composition, X-ray diffraction and electron diffraction results, and droplet measurement results. As is apparent from Table 3, the insert 30 for a high feed cutting tool of Example 1 had a long life of 36 minutes.

Examples 2-4 and Comparative Examples 1 and 2
(1) (AlTi) N film composition In terms of atomic ratio, Al _0.90 Ti _0.10 alloy (Example 2), Al _0.71 Ti _0.29 alloy (Example 3), Al _0.62 Ti _0.38 alloy (Example 4), Al _0.05 Ti _0.95 Each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that a target composed of an alloy (Comparative Example 1) and an Al _0.96 Ti _0.04 alloy (Comparative Example 2) was used. Table 3 shows the composition, X-ray diffraction result, electron diffraction result, droplet measurement result, and tool life of each (AlTi) N film.

Note: (1) Single structure.
(2) Main structure.

  As is clear from Table 3, the hard coating tools of Examples 2 to 4 had few droplets and had a long service life of 18 minutes or longer, but the hard coating tools of Comparative Examples 1 and 2 each had a tool life. It was as short as 6 and 9 minutes. The reason for this is that in Comparative Example 1, the (AlTi) N film has a rock-salt structure, so that the lubricity was inferior.In Comparative Example 2, the (AlTi) N film contained excessive Al and contained many droplets. This is because it was formed.

Example 5 and Comparative Examples 3 and 4
In order to clarify the influence of the substrate temperature on the (AlTi) N film of the present invention, the substrate temperature was changed to 560 ° C. in Example 5, 400 ° C. in Comparative Example 3, and 700 ° C. in Comparative Example 4. In the same manner as in Example 1, each cutting tool (insert) was produced and evaluated. Table 4 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTi) N film.

Note: (1) Single structure.
(2) Main structure.

  As is clear from Table 4, the hard coating tool of Example 5 had a long life of 21 minutes, but the hard coating tools of Comparative Examples 3 and 4 had an (AlTi) N coating with a wurtzite structure. However, it was short-lived because it was oriented in the (100) plane.

Examples 6 and 7, and Comparative Examples 5 and 6
Negative Bias Voltage of Bipolar Pulse In order to investigate the influence of the negative peak value of the negative bias voltage of the bipolar pulse on the (AlTi) N film of the present invention, the peak value applied to the substrate was set to −20 in Example 6. V, each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that it was −60 V in Example 7, −10 V in Comparative Example 5, and −80 V in Comparative Example 6. Table 5 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTi) N film.

Note: (1) Single structure.
(2) Main structure.

  As is clear from Table 5, in Examples 6 and 7, the tool life was as long as 21 minutes or more, but in Comparative Examples 5 and 6 that exceeded the upper and lower limits of the negative bias voltage, the (002) plane of the wurtzite structure Was not oriented and the tool life was short.

Examples 8 and 9 and Comparative Examples 7 and 8
In order to investigate the influence of the peak value of the positive bias voltage of the bipolar pulse on the (AlTi) N film, the peak value was 5 V in Example 8, 15 V in Example 9, and 3 V in Comparative Example 7. In Comparative Example 8, each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that the voltage was 20 V. Table 6 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTi) N film.

Note: (1) Single structure.
(2) Main structure.

  As is clear from Table 6, the hard coating tools of Examples 8 and 9 both had a long service life of 30 minutes or more, but the hard coating tools of Comparative Examples 7 and 8 had a (AlTi) N coating on the wurtzite. Since there was no (002) plane orientation of the ore structure, the lifetime was short.

Examples 10 and 11 and Comparative Examples 9 and 10
In order to investigate the influence of the frequency of the bipolar pulse bias voltage on the (AlTi) N film, the frequency of the pulse bias voltage was 20 kHz in Example 10, 50 kHz in Example 11, and 10 kHz in Comparative Example 9. In Comparative Example 10, each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that the frequency was 80 kHz. Table 7 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTi) N film.

Note: (1) Single structure.
(2) Main structure.

  As is apparent from Table 7, the hard coating tools of Examples 10 and 11 all had a long life of 30 minutes or more, but the hard coating tools of Comparative Examples 9 and 10 had a short life. The reason for this is that in Comparative Example 9, charging occurred when the pulse bias frequency was too low, and it was not oriented on the (002) plane of the wurtzite structure, and in Comparative Example 10, charging was caused by the excessive pulse bias frequency. This is because it was not eliminated and it was not oriented in the (002) plane of the wurtzite structure.

Examples 12-15 and Comparative Examples 11 and 12
In order to investigate the influence of the frequency of the pulsed arc current on the (AlTi) N film, the frequency was 1 kHz in Example 12, 8 kHz in Example 13, 12 kHz in Example 14, and Example 15 Each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that the frequency was 15 kHz, the comparative example 11 was 0.5 kHz, and the comparative example 12 was 20 kHz. Table 8 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTi) N film.

Note: (1) Single structure.
(2) Main structure.

  As apparent from Table 8, the hard coating tools of Examples 12 to 15 all had a long life of 27 minutes or more, whereas the hard coating tools of Comparative Examples 11 and 12 had a short life. This is because the droplets of the (AlTi) N film did not decrease and the (002) plane of the wurtzite structure was not oriented.

Examples 16-1 to 16-5, Comparative Example 13, and Conventional Example 1
In order to investigate the influence of Amin, Amax and ΔA (= Amax−Amin) of the pulse arc current on the (AlTi) N film, Example 1 and Example 1 were changed except that Amin, Amax and ΔA were changed as shown in Table 9. Similarly, each cutting tool (insert) was produced and evaluated. Table 10 shows the composition, X-ray diffraction result, electron diffraction result, droplet measurement result, and tool life of each (AlTi) N film.

Note: (1) Duty ratio.
(2) ΔA = Amax−Amin.

Note: (1) Single structure.
(2) Main structure.

  From Tables 9 and 10, the hard coatings of Examples 16-1 to 16-5 formed under film forming conditions within the ranges of Amin = 40 to 80 A, Amax = 80 to 110 A, and ΔA = 10 to 60 A In either case, the (002) plane of the wurtzite structure was strongly oriented, and each tool had a long life. In contrast, the tools of Comparative Example 13 and Conventional Example 1 had a short life. This is because in Comparative Example 13 in which Amin, Amax and ΔA are all outside the scope of the present invention, and in the (AlTi) N film of Conventional Example 1 in which the arc current is not a pulse, droplets are remarkably generated and the wurtzite type This is because the (002) plane of the structure was not oriented.

  In particular, the (AlTi) N film of Conventional Example 1 has the largest orientation of the (100) plane of the wurtzite structure, as is apparent from the X-ray diffraction pattern of FIG. As apparent from the SEM photograph (magnification: 3,000 times), the surface had very many droplets.

Examples 17 and 18, and Comparative Examples 14 and 15
In order to investigate the influence of the duty ratio D of Amin on the pulse arc current on the (AlTi) N film, the duty ratio D was set to 50% in Example 17, 20% in Example 18, and 10% in Comparative Example 14. Each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that the ratio was 65% in Comparative Example 15. Table 11 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTi) N film.

Note: (1) Single structure.
(2) Main structure.

  As apparent from Table 11, the tools of Examples 17 and 18 had a long life of 30 minutes or more, while the tools of Comparative Examples 14 and 15 had a short life. This is because the duty ratio D is excessive in Comparative Example 14 and the duty ratio D is excessive in Comparative Example 15, so that the (002) plane of the wurtzite structure was not oriented.

Examples 19-22
By adjusting the film formation time, the film thickness of the (AlTi) N film was 1.0 μm in Example 19, 6.0 μm in Example 20, 8.0 μm in Example 21, and 10.0 μm in Example 22. Except for the above, each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1. Table 12 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTi) N film. As is clear from Table 12, the hard coating tools of Examples 19 to 22 had a long life of 21 minutes or longer.

Note: (1) Single structure.
(2) Main structure.

Examples 23-34
In order to investigate the influence of the intermediate layer on the hard film coated member of the present invention, each target of Table 13-1 was used between the same substrate and (AlTi) N film as in Example 1, and Table 13-2 A cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that each intermediate layer shown in FIG. Table 13 shows the film forming conditions for each intermediate layer, and Table 14 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTi) N film.

Notes: (1) Arc current of arc discharge evaporation source.
(2) Peak value of negative bias voltage by DC bias power supply.

Note: (3) As a result of X-ray diffraction measurement as in Example 1, it was a rock salt type single structure.

Note: (1) Single structure.
(2) Main structure.

  In Examples 23 to 34, at least one selected from the group consisting of elements 4a, 5a and 6a, Al and Si by physical vapor deposition between the WC-based cemented carbide substrate and the (AlTi) N film An intermediate layer (hard film) having an essential constituent element of at least one selected from the group consisting of B, O, C and N was formed. It had a lifetime of more than 30 minutes.

Example 35
(1) Cleaning the substrate
A WC-based cemented carbide turning insert base (CNMG120408 manufactured by Hitachi Tool Co., Ltd.) containing 6% by mass of Co and the balance consisting of WC and inevitable impurities on the AI equipment holder shown in FIG. The substrate was heated to 600 ° C. with a heater simultaneously with evacuation. Thereafter, 500 sccm of Ar gas was introduced to adjust the pressure in the decompression vessel 5 to 2.0 Pa, a −200 V DC bias voltage was applied to the substrate, and the substrate was cleaned by etching Ar ions.

(2) Ti ion bombardment treatment After that, Ar gas was introduced at 40 sccm, and an arc current of 100 A was applied to an arc discharge evaporation source equipped with a pure Ti target (having a composition of Ti _1.00 except for inevitable impurities). At the same time, a DC bias voltage of −800 V was applied to the insert substrate, and bombardment with Ti ions was performed for 10 minutes.

(3) Formation and analysis of (AlTi) N film
An (AlTi) N film was formed on the insert substrate treated with Ti ion bombardment in the same manner as in Example 1. The (AlTi) N film was subjected to composition analysis, X-ray diffraction and electron diffraction in the same manner as in Example 1. Table 15 shows the composition of the (AlTi) N film, the X-ray diffraction results, and the electron diffraction results.

(4) Tool life evaluation
Turning was performed under the following conditions using a turning tool with an insert formed with an (AlTi) N film, and the peeling state of the (AlTi) N film, wear on the flank, and chipping were investigated. Whether or not the (AlTi) N film is peeled off is checked by observing with an optical microscope (magnification: 100 times) whether or not the (AlTi) N film of the insert sampled at each unit time of turning is peeled off. did. In turning, the tool life was defined as the shortest cutting time until the maximum wear width of the flank surface exceeded 0.30 mm, until the (AlTi) N film peeled, or until the (AlTi) N film chipped. Table 15 shows the tool life.
Cutting conditions Work material: SUS630
Machining method: Continuous turning Tool shape: CNMG120408
Cutting speed: 150 m / min Feed: 0.25 mm / rotation Cutting: 1.5 mm
Cutting fluid: Water-soluble cutting oil

Example 36
A (AlTi) N film-coated cutting tool (insert) was prepared and evaluated in the same manner as in Example 35 except that the bombardment treatment with Ti ions was not performed. Table 15 shows the composition, X-ray diffraction results, electron diffraction results, and tool life of the film obtained.

Comparative Example 16
A (AlTi) N film-coated cutting tool (insert) was prepared and evaluated in the same manner as in Example 35 except that the same (AlTi) N film as in Comparative Example 2 was formed. Table 15 shows the composition, X-ray diffraction results, electron diffraction results, and tool life of the film obtained.

Note: (1) Single structure.
(2) Main structure.

  From Table 15, it can be seen that the (AlTi) N coated insert of Example 35 subjected to Ti ion bombardment has a longer life than the (AlTi) N coated insert of Example 36 not subjected to Ti ion bombardment. In addition, the (AlTi) N-coated inserts of Examples 35 and 36 were subjected to Ti ion bombardment, but had a significantly longer life than the insert of Comparative Example 16 in which the same (AlTi) N coating as in Comparative Example 2 was formed.

Example 37
The same (AlTi) N coating as in Example 1 was formed on the punch 51 of the mold 56 shown in FIG. This die 56 includes a punch 51 for punching, a horizontal member 52 to which the punch 51 is fixed, a pair of guide pins 53 and 53 for moving the horizontal member 52 in the vertical direction with high accuracy, and the tip of the punch 51. An upper die 54 having a central hole 54a (hole diameter: 0.15 mm) through which the portion 51a passes, and a lower die 55 having a central hole 55a (hole diameter: 0.15 mm) into which the tip 51a of the punch 51 enters. . The base of the punch 51 is made of a WC-based cemented carbide (Co content: 6% by mass).

  After punching a thin plate S (made of SUS304, plate thickness 0.2 mm) fixed between the upper die 54 and the lower die 55 with a punch 51 and moving it a predetermined distance in the horizontal direction, the shot was continuously performed 5000 times. The presence or absence of peeling of the (AlTi) N film on the tip 51a of the punch 51 was observed with an optical microscope (magnification: 100 times). The results are shown in Table 16.

Example 38
Except that the base of the punch 51 was made of high speed steel (SKH57), an (AlTi) N film was formed on the base of the punch 51, and punching was continuously performed for 5000 shots. The presence or absence of exfoliation of the (AlTi) N film on the tip 51a was observed. The results are shown in Table 16.

Comparative Example 17
In the same manner as in Example 37 except that the same (AlTi) N film as in Comparative Example 2 was formed, after the (AlTi) N film was formed on the base of the punch 51 and punched continuously for 5000 shots, the punch 51 The presence or absence of exfoliation of the (AlTi) N film on the tip 51a was observed. The results are shown in Table 16.

Comparative Example 18
The base of the punch 51 is made of high speed steel (SKH57), and the same (AlTi) N film as in Comparative Example 2 is formed in the same manner as in Example 37 to form the (AlTi) N film on the base of the punch 51, After continuous punching of 5000 shots, the presence or absence of peeling of the (AlTi) N film on the tip 51a of the punch 51 was observed. The results are shown in Table 16.

  As is clear from Table 16, in the punch 51 of Examples 37 and 38 in which the (AlTi) N film of Example 1 was formed, regardless of whether the substrate is made of cemented carbide or high speed steel, Although there was no peeling of the (AlTi) N film, the (AlTi) N film was peeled off in both punches 51 of Comparative Examples 17 and 18 in which the (AlTi) N film of Comparative Example 2 was formed.

Example 39
(1) Cleaning the substrate
High feed milling insert base made of WC-base cemented carbide containing 6.0% by mass of Co and the balance consisting of WC and inevitable impurities (EDNW15T4TN-15 made by Hitachi Tool Co., Ltd. having the shape shown in Fig. 7) And an insert substrate for measuring physical properties (SNMN120408 manufactured by Hitachi Tool Co., Ltd.) was set on the holder 8 of the AI apparatus shown in FIG. 1, and each substrate was cleaned by etching Ar ions in the same manner as in Example 1. .

(2) Formation of (AlTiCr) N film Thickness on each substrate in the same manner as in Example 1 except that an AlTiCr alloy having a composition represented by Al _0.80 Ti _0.10 Cr _0.10 (atomic ratio) was used for targets 10 and 17 A 3.0 μm thick (Al _0.81 Ti _0.09 Cr _0.10 ) _0.35 N _0.65 film (atomic ratio) was formed. The composition of the (AlTiCr) N film was analyzed by EPMA as in Example 1.

  FIG. 10 is an SEM photograph (magnification: 25,000 times) showing the cross-sectional structure of the insert of Example 39. In FIG. 10, 141 is a substrate and 142 is an (AlTiCr) N film.

(3) X-ray diffraction pattern of (AlTiCr) N film In the same manner as in Example 1, CuKα1 ray (wavelength λ: 0.15405 nm) was irradiated to the (AlTiCr) N film of the physical property measurement insert, and the X-ray shown in FIG. A diffraction pattern was obtained. In FIG. 11, w- (002), w- (102), w- (103) and w- (112) are X-ray diffraction peaks of the wurtzite structure. As is clear from FIG. 11, the diffraction peaks of the (AlTiCr) N film of Example 39 all corresponded to the wurtzite structure. Around 2θ = 36 °, the X-ray diffraction peak corresponding to the (002) plane of the (AlTiCr) N coating wurtzite structure overlaps with the X-ray diffraction peak of the WC-based cemented carbide. A value obtained by subtracting the X-ray diffraction peak intensity of the WC-based cemented carbide from the X-ray diffraction peak intensity is shown in FIG. 11 as the X-ray diffraction peak intensity of the (002) plane of the wurtzite structure.

(4) Restricted-field diffraction pattern of (AlTiCr) N film Using TEM in the same manner as in Example 1, a limited-field diffraction pattern of (AlTiCr) N film (FIG. 12) was obtained. In FIG. 12, all diffraction spots corresponded to the wurtzite structure.

(5) X-ray diffraction peak intensity and TC (hkl)
For the (AlTiCr) N film of the insert of Example 39, as in Example 1, the (100) plane, (002) plane, (101) plane, (112) plane, (102) plane of the wurtzite structure, The orientation of the (103) plane was determined by the formulas (1) to (10) described in the paragraphs [1], (B) and (4). Table 17 shows the actual measurement value of the X-ray diffraction peak intensity of the (AlTiCr) N film and the TC (hkl) value. Among the crystal faces of the wurtzite structure where X-ray diffraction peaks were observed, TC (002) was the largest at 5.2.

Note: (1) No X-ray diffraction peak was observed.

(6) Tool life measurement
The four high-feed cutting tool inserts 30 (FIG. 7) of Example 39 coated with an (AlTiCr) N film were replaced with the cutting edge-replaceable rotary tool (ASR5063 manufactured by Hitachi Tool Co., Ltd.) shown in FIG. -4) A set screw 37 was attached to the tip 38 of 40 tool bodies 36, and the tool life was measured.

  Table 18 shows the composition, X-ray diffraction results, electron diffraction results, and tool life of the (AlTiCr) N film of Example 39. As apparent from Table 18, the life of the blade-tip-exchangeable rotary tool of Example 39 was as long as 40 minutes.

Examples 40-42 and Comparative Examples 19 and 20
In atomic ratio, Al _0.92 Ti _0.04 Cr _0.04 alloy (Example 40), Al _0.74 Ti _0.13 Cr _0.13 alloy (Example 41), Al _0.70 Ti _0.17 Cr _0.13 alloy (Example 42), Al _0.60 Ti _0.35 Cr _0.05 alloy Each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that (Comparative Example 19) and a target made of an Al _0.95 Ti _0.03 Cr _0.02 alloy (Comparative Example 20) were used. Table 18 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTiCr) N film of Examples 40 to 42 and Comparative Examples 19 and 20.

Note: (1) Single structure.
(2) Main structure.

  As is apparent from Table 18, the hard-coated tools of Examples 40 to 42 have a long life of 20 minutes or more, whereas the hard-coated tools of Comparative Examples 19 and 20 have a short time of 7 minutes and 10 minutes, respectively. It was a lifetime. The reason for this is that in Comparative Example 19, the (AlTiCr) N film has a rock-salt structure, so the lubricity is poor, and in Comparative Example 20, the (AlTiCr) N film contains an excessive amount of Al and many droplets are formed. It was because it was done.

Example 43
(1) Cleaning the substrate
High feed milling insert base made of WC-base cemented carbide with a composition containing 6.0% by mass of Co and the balance consisting of WC and inevitable impurities (EDNW15T4TN-15 made by Hitachi Tool Co., Ltd. having the shape shown in FIG. 7) and The insert substrate for measuring physical properties (manufactured by Hitachi Tool Co., Ltd., specification: SNMN120408) was cleaned by etching with Ar ions in the same manner as in Example 1.

(2) Formation of (AlTiW) N film Next, on each substrate in the same manner as in Example 1 except that an AlTiW alloy having a composition represented by Al _0.80 Ti _0.10 W _0.10 (atomic ratio) was used as the targets 10 and 17. (Al _0.80 Ti _0.10 W _0.10 ) _0.38 N _0.62 film (atomic ratio) having a thickness of 3.0 μm was formed on the film. The film composition was analyzed by EPMA as in Example 1. FIG. 13 is an SEM photograph (magnification: 25,000 times) showing the cross-sectional structure of the physical property measurement insert of Example 43. In FIG. 13, 241 is a substrate and 242 is an (AlTiW) N film.

(3) X-ray diffraction pattern of (AlTiW) N film In the same manner as in Example 1, CuKα1 line (wavelength λ: 0.15405 nm) was irradiated to the (AlTiW) N film, and the X-ray diffraction pattern shown in FIG. 14 was obtained. In FIG. 14, w- (002), w- (102), w- (103), w- (110), and w- (112) all indicate X-ray diffraction peaks of the wurtzite structure. From FIG. 14, it was confirmed that any diffraction peak of the (AlTiW) N film of Example 43 had a wurtzite structure. In addition, since the X-ray diffraction peak of the (002) plane of the wurtzite structure of the (AlTiW) N film and the X-ray diffraction peak of the WC-based cemented carbide overlapped in the vicinity of 2θ = 36 °, overlapping X-rays A value obtained by subtracting the X-ray diffraction peak intensity of the WC-based cemented carbide from the diffraction peak intensity is shown in FIG. 14 as the X-ray diffraction peak intensity of the (002) plane of the wurtzite structure.

(4) Restricted field diffraction pattern of (AlTiW) N film
Using a TEM, the limited field diffraction pattern (diffraction pattern) of the (AlTiW) N film of the insert of Example 43 was observed in the same manner as in Example 1 to obtain a limited field diffraction pattern (FIG. 15). All diffraction spots in FIG. 15 had a wurtzite structure.

(5) X-ray diffraction peak intensity and TC (hkl)
Table 19 shows the measured values of the X-ray diffraction peak intensity of the (AlTiW) N film, and the TC (hkl) values obtained by the equations (1) to (10) described in the paragraphs [1] (B) (4). Indicates. Of the crystal planes of the wurtzite structure where X-ray diffraction peaks were observed, TC (002) was the largest at 4.2.

Note: (1) No X-ray diffraction peak was observed.

(6) Tool life measurement
The four high-feed cutting tool inserts 30 (FIG. 7) coated with the (AlTiW) N coating are the same as in Example 1 except that the blade tip replaceable rotary tool (ASR5063-4 manufactured by Hitachi Tool Co., Ltd.) 40 of FIG. A tool screw 36 was attached to the tip 38 of the tool body 36 with a set screw 37, and the tool life was measured. Table 20 shows the composition of the (AlTiW) N film, X-ray diffraction results, electron diffraction results, and tool life.

Examples 44-46 and Comparative Examples 21 and 22
Atomic ratio Al _0.92 Ti _0.04 W _0.04 alloy (Example 44), Al _0.72 Ti _0.14 W _0.14 alloy (Example 45), Al _0.68 Ti _0.20 W _0.12 alloy (Example 46), Al _0.58 Ti _0.37 W _0.05 alloy Each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that a target made of (Comparative Example 21) and an Al _0.94 Ti _0.03 W _0.03 alloy (Comparative Example 22) was used. Table 20 shows the compositions, X-ray diffraction results, electron diffraction results, and tool life of the (AlTiW) N coatings of Examples 44 to 46 and Comparative Examples 21 and 22.

Note: (1) Single structure.
(2) Main structure.

  As is apparent from Table 20, the hard-coated tools of Examples 43 to 46 have a long life of 21 minutes or more, while the hard-coated tools of Comparative Examples 21 and 22 have a short life of 6 minutes and 9 minutes, respectively. there were. The reason for this is that in Comparative Example 21, the (AlTiW) N film has a rock-salt structure, so the lubricity is inferior.In Comparative Example 22, the (AlTiW) N film contains an excessive amount of Al and many droplets are formed. This is because.

Examples 47-49
Atomic ratios from Al _0.72 Ti _0.14 Cr _0.03 W _0.11 alloy (Example 47), Al _0.72 Ti _0.14 Cr _0.07 W _0.07 alloy (Example 48), and Al _0.72 Ti _0.14 Cr _0.11 W _0.03 alloy (Example 49), respectively. Each cutting tool (insert) was prepared and evaluated in the same manner as in Example 1 except that the target was used. Table 21 shows the composition, X-ray diffraction result, electron diffraction result, and tool life of each (AlTiCrW) N film of Examples 47 to 49.

Note: (1) Single structure.
(2) Main structure.
(3) z = z1 + z2.

  As is apparent from Table 21, the hard film coated tools of Examples 47 to 49 had a long life of 39 minutes or more.

1: Drive unit
2: Gas introduction part
3: Bias power supply
4: Bearing part
5: Vacuum container
6: Prop
7: Base
8: Retaining tool
10, 17: Target
11: Power supply for arc discharge
12, 27: Arc discharge evaporation source
13, 18: Insulator
14: Arc ignition mechanism bearing
15: Arc ignition mechanism
16: Exhaust port
19: Electrode
20: Shield plate bearing
21: Shield plate drive
22: Shield plate
30: Insert for milling
35: Main cutting edge of insert
36: Tool body
37: Insert set screw
38: Tip of tool body
40: Blade-changeable rotary tool
41, 141, 241: Cemented carbide substrate
42, 142, 242: (AlTiM) N coating
51: Punching punch
52: Horizontal member
53: Guide pin
54: Upper mold
54a: Upper mold hollow (hole)
55: Lower mold
55a: Lower mold hollow (hole)
56: Mold

Claims (12)

(Al _x Ti _y M _z ) _a N _1-a (where M element is Cr and / or W, and x, y, z and a are atomic ratios of 0.6 ≦ x ≦ 0.9, 0.05 ≦ y ≦ 0.4, respectively. , 0 ≦ z ≦ 0.2, x + y + z = 1 and 0.2 ≦ a ≦ 0.8), and a hard film formed by an arc ion plating method,
A hard film, wherein an X-ray diffraction pattern of the hard film shows a wurtzite type single structure, and an X-ray diffraction peak of the (002) plane of the wurtzite type structure is a maximum peak. 2. The hard film according to claim 1, wherein an equivalent X-ray diffraction intensity ratio TC (002) of the wurtzite structure is 2.5 or more. In the hard coating according to claim 1 or 2, when the element M does not contain or the element M is mainly W, the X-ray diffraction peak intensity of the (002) plane and the (100) plane of the wurtzite structure A hard film characterized in that the ratio of I (002) and I (100) satisfies the relationship of I (002) / I (100) ≧ 3.0. In the hard film according to claim 1 or 2, when the M element is mainly Cr, the (002) plane of the wurtzite structure and the (103) plane X-ray diffraction peak intensity I (002) and I ( A hard film characterized in that the ratio of 103) satisfies the relationship of I (002) / I (103) ≧ 3.0. 5. A hard coating-coated member, wherein the hard coating according to claim 1 is formed on a substrate. 6. The hard film-coated member according to claim 5, wherein at least one selected from the group consisting of elements 4a, 5a and 6a, Al and Si by a physical vapor deposition method between the substrate and the hard film. A hard coating member characterized by forming an intermediate layer that essentially includes a metal element and at least one element selected from the group consisting of B, O, C, and N. (Al _x Ti _y M _z ) _a N _1-a (where M element is Cr and / or W, and x, y, z and a are atomic ratios of 0.6 ≦ x ≦ 0.9 and 0.05 ≦ y ≦ 0.4, respectively. , 0 ≦ z ≦ 0.2, x + y + z = 1 and 0.2 ≦ a ≦ 0.8), a hard film having a composition represented by the following:
When forming the hard coating on the substrate maintained at a temperature of 560 to 650 ° C. in a nitriding gas atmosphere, a bipolar pulse bias voltage is applied to the substrate, and AlTi provided in the arc discharge evaporation source Apply a pulsed arc current to a target made of an alloy or AlTiM alloy,
The bipolar pulse bias voltage has a positive bias voltage of +5 V to +15 V, a negative bias voltage of −60 V to −20 V, and a frequency of 20 to 50 kHz;
The pulsed arc current has a maximum arc current value of 80 to 110 A, a minimum arc current value of 40 to 80 A, and a frequency of 1 to 15 kHz, and a difference between the maximum arc current value and the minimum arc current value Is a substantially rectangular wave shape of 10 A or more. 8. The method of manufacturing a hard film according to claim 7, wherein the substrate before coating with the hard film is etched with Ti ions. 9. The method of manufacturing a hard coating film according to claim 7, wherein a duty ratio of the pulse arc current is set to 20 to 50%. (Al _x Ti _y M _z ) _a N _1-a (where M element is Cr and / or W, and x, y, z and a are atomic ratios of 0.6 ≦ x ≦ 0.9 and 0.05 ≦ y ≦ 0.4, respectively. , 0 ≦ z ≦ 0.2, x + y + z = 1 and 0.2 ≦ a ≦ 0.8.) A method for producing a hard film-coated member having a hard film having a composition represented on a substrate,
When forming the hard film by arc ion plating on the substrate maintained at a temperature of 560 to 650 ° C. in a nitriding gas atmosphere, a bipolar pulse bias voltage is applied to the substrate and arc discharge evaporation is performed. Apply a pulsed arc current to a target made of AlTi alloy or AlTiM alloy provided in the source,
The bipolar pulse bias voltage has a positive bias voltage of +5 V to +15 V, a negative bias voltage of −60 V to −20 V, and a frequency of 20 to 50 kHz;
The pulsed arc current has a maximum arc current value of 80 to 110 A, a minimum arc current value of 40 to 80 A, and a frequency of 1 to 15 kHz, and a difference between the maximum arc current value and the minimum arc current value Is a substantially rectangular wave shape of 10 A or more. 11. The method for producing a hard film-coated member according to claim 10, wherein the substrate is etched using Ti ions before the hard film is formed. 12. The method for manufacturing a hard coating member according to claim 10 or 11, wherein a duty ratio of the pulse arc current is set to 20 to 50%.