Surface-coated cutting tool in which hard coating layer exhibits excellent chipping resistance and peeling resistance
11278967 · 2022-03-22
Assignee
Inventors
Cpc classification
B23C5/16
PERFORMING OPERATIONS; TRANSPORTING
C23C16/0272
CHEMISTRY; METALLURGY
C23C28/044
CHEMISTRY; METALLURGY
B23B2224/32
PERFORMING OPERATIONS; TRANSPORTING
B23B27/14
PERFORMING OPERATIONS; TRANSPORTING
C23C28/048
CHEMISTRY; METALLURGY
International classification
B23B27/14
PERFORMING OPERATIONS; TRANSPORTING
B23C5/16
PERFORMING OPERATIONS; TRANSPORTING
C23C16/30
CHEMISTRY; METALLURGY
C23C28/04
CHEMISTRY; METALLURGY
Abstract
A surface-coated cutting tool has a hard coating layer including an upper layer α, an adhesion layer β, and a lower layer γ. The upper layer α is formed of an α-Al.sub.2O.sub.3 layer formed under low temperature conditions. The adhesion layer β includes a TiCN layer having a thickness of 0.5 μm or more in an outermost layer and contains 0.5 to 3 μm to a maximum depth of 0.5 μm toward the inside in a layer thickness direction of the TiCN layer from the interface between the TiCN layer and the upper layer α. The lower layer γ is formed of (Ti.sub.1-XAl.sub.X)(C.sub.YN.sub.1-Y) of a single phase of a NaCl type face-centered cubic structure, in which an average content ratio X.sub.avg of Al and an average content ratio Y.sub.avg of C in this composition formula satisfy 0.60≤X.sub.avg≤0.95 and 0≤Y.sub.avg≤0.005.
Claims
1. A surface-coated cutting tool comprising: a hard coating layer including at least three layers of an upper layer α, an adhesion layer β, and a lower layer γ; and a tool body, wherein the hard coating layer is formed on a surface of the tool body which is made of any of a cemented carbide containing tungsten carbide, a cermet containing titanium carbonitride, or a cubic boron nitride ultrahigh-pressure sintered body, (a) the upper layer α is formed of an Al.sub.2O.sub.3 layer having an α-type crystal structure with an average layer thickness of 1.0 to 10 μm, (b) the adhesion layer β has a total average layer thickness of 0.5 to 10.0 μm, and contains an outermost layer that is in contact with an interface with the upper layer α and includes at least a TiCN layer having a layer thickness of at least 0.5 μm or more, (c) oxygen is contained to a maximum depth of 0.5 μm toward the inside in a layer thickness direction of the TiCN layer from the interface with the upper layer α, and an average oxygen content in the depth area is 0.5 to 3 at % of a total content of Ti, C, N, and O contained in the depth area, (d) the lower layer γ is formed of a layer of a complex nitride or complex carbonitride of Ti and Al having an average layer thickness of 1.0 to 20 μm, (e) the layer of a complex nitride or complex carbonitride of Ti and Al is formed of a single phase of a NaCl type face-centered cubic structure, (f) in a case where an average composition of the layer of a complex nitride or complex carbonitride of Ti and Al is expressed by (Ti.sub.1-XAl.sub.X)(C.sub.YN.sub.1-Y), an average content ratio X.sub.avg of Al to a total amount of Ti and Al and an average content ratio Y.sub.avg of C to a total amount of C and N (here, each of X.sub.avg and Y.sub.avg is in atomic ratio) respectively satisfy 0.60≤X.sub.avg≤0.95 and 0≤Y.sub.avg≤0.005, and (g) the adhesion layer β further includes a layer of a complex nitride or complex carbonitride of Ti and Al whose average layer thickness L.sub.avg (μm) satisfies 0.30≤L.sub.avg5.0, and when X.sub.βavg is an average content ratio of Al to a total amount of Ti and Al in each section obtained by dividing the layer of a complex nitride or complex carbonitride of Ti and Al by [L.sub.avg]+2, X.sub.βavg<X.sub.avg is satisfied in each of the sections, and X.sub.βavg of a section closer to a surface side is equal to or smaller than X.sub.βavg of a section closer to a body side.
2. The surface-coated cutting tool according to claim 1, wherein the upper layer a contains 0.05 to 0.5 at % of chlorine.
3. The surface-coated cutting tool according to claim 1, wherein the average content ratio X.sub.avg of Al to the total amount of Ti and Al of the layer of a complex nitride or complex carbonitride of Ti and Al in the lower layer γ is 0.70≤X.sub.avg≤0.95.
4. The surface-coated cutting tool according to claim 1, wherein the adhesion layer β further includes one or two or more layers selected from a Ti carbide layer, a Ti nitride layer, a Ti carbonitride layer, a Ti oxycarbide layer, and a Ti oxycarbonitride layer.
5. The surface-coated cutting tool according to claim 1, wherein, in a case where the layer of a complex nitride or complex carbonitride of Ti and Al in the lower layer γ is analyzed in an arbitrary section perpendicular to the surface of the tool body, crystal grains having a NaCl type face-centered cubic structure, which has a periodic composition variation of Ti and Al, are present, and at least the crystal grains, in which an angle between a direction in which a period of the periodic composition variation of Ti and Al is minimized and a surface perpendicular to the surface of the tool body is 30 degrees or less, are present.
6. The surface-coated cutting tool according to claim 1, wherein a lowermost layer δ is present between the tool body and the lower layer γ, and the lowermost layer δ is formed of one or two or more layers selected from a layer of a complex nitride or complex carbonitride of Ti and Al with a different composition from the lower layer γ, a Ti carbide layer, a Ti nitride layer, a Ti carbonitride layer, a Ti oxycarbide layer, and a Ti oxycarbonitride layer and has a total average layer thickness of 0.1 to 10 μm.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) These and other features and advantages of the present invention will become more readily appreciated when considered in connection with the following detailed description and appended drawing(s), wherein like designations denote like elements in the various views, and wherein:
(2)
(3)
(4)
(5)
(6)
DETAILED DESCRIPTION OF THE INVENTION
(7) Next, examples of a coated tool of the present invention will be described in detail.
(8) Although a case of using tungsten carbide-based cemented carbide (hereinafter, referred to as “WC-based cemented carbide”) or titanium carbonitride-based cermet (hereinafter, referred to as “TiCN-based cermet”) as a tool body is described in the following examples, this can also be applied to a case of using a cubic boron nitride-based ultrahigh-pressure sintered body as the tool body.
Example 1
(9) As raw material powders, a WC powder, a TiC powder, a TaC powder, a NbC powder, a Cr.sub.3C.sub.2 powder, and a Co powder, all of which had an average grain size of 1 to 3 μm, were prepared, and the raw material powders were mixed in mixing compositions shown in Table 1. Wax was further added thereto, and the mixture was blended in acetone by a ball mill for 24 hours and was decompressed and dried. Thereafter, the resultant was press-formed into green compacts having predetermined shapes at a pressure of 98 MPa, and the green compacts were sintered in a vacuum at 5 Pa under the condition that the green compacts were held at a predetermined temperature in a range of 1370° C. to 1470° C. for one hour. After the sintering, tool bodies A to C made of WC-based cemented carbide with insert shapes according to ISO standard SEEN1203AFSN were produced.
(10) In addition, as raw material powders, a TiCN (TiC/TiN=50/50 in terms of mass ratio) powder, an Mo.sub.2C powder, a ZrC powder, a NbC powder, a WC powder, a Co powder, and a Ni powder, all of which had an average grain size of 0.5 to 2 μm, were prepared, and the raw material powders were mixed in mixing compositions shown in Table 2, were subjected to wet mixing by a ball mill for 24 hours, and were dried. Thereafter, the resultant was press-formed into a green compact at a pressure of 98 MPa, and the green compact was sintered in a nitrogen atmosphere at 1.3 kPa under the condition that the green compact was held at a temperature of 1500° C. for one hour. After the sintering, a tool body D made of TiCN-based cermet with insert shapes according to ISO standard SEEN1203AFSN was produced.
(11) Next, on the surfaces of the tool bodies A to D, any one or both of a Ti compound layer and a (Ti,Al)(C,N) layer were formed as a lowermost layer δ using a typical chemical vapor deposition apparatus.
(12) Specifically, as the lowermost layer δ as the Ti compound layer, the Ti compound layer shown in Table 6 was formed under conditions shown in Table 3, and as the lowermost layer δ as the (Ti,Al)(C,N) layer, the (Ti,Al)(C,N) layer shown in Table 6 was formed under gas conditions shown in Table 4 and forming conditions shown in Table 5.
(13) For some of the tool bodies, both the Ti compound layer and the (Ti,Al)(C,N) layer were formed as the lowermost layer S.
(14) Under film forming conditions Aδ to Eδ for the lowermost layer δ formed of the (Ti,Al)(C,N) layer, by changing the gas conditions and forming conditions Aγ to Eγ shown in Tables 4 and 5 between the initial stage of film formation and the final stage of film formation, the (Ti,Al)(C,N) layer in which the content ratio of Al in the (Ti,Al)(C,N) layer was gradually increased continuously or in stages from the surface of the tool body toward a lower layer γ was formed.
(15) Next, the lower layer γ formed of a (Ti,Al)(C,N) layer having a single phase of a NaCl type face-centered cubic structure was formed on the surface of the lowermost layer δ using the chemical vapor deposition apparatus under gas conditions Aγ to Eγ shown in Table 7 and under forming conditions Aγ to Eγ shown in Table 8.
(16) That is, by performing a thermal CVD method for a predetermined time according to the forming conditions Aγ to Eγ shown in Tables 8 and 9, in which a gas group A of NH.sub.3 and H.sub.2 and a gas group B of TiCl.sub.4, AlCl.sub.3, N.sub.2, C.sub.2H.sub.4, and H.sub.2 were used, in each gas supply method, a reaction gas composition (vol % with respect to the total amount of the gas group A and the gas group B) included a gas group A of NH.sub.3: 2.0% to 3.0% and H.sub.2: 65% to 75% and a gas group B of AlCl.sub.3: 0.6% to 0.9%, TiCl.sub.4: 0.1% to 0.4%, N.sub.2: 0.0% to 12.0%, C.sub.2H.sub.4: 0% to 0.5%, H.sub.2: the remainder, a reaction atmosphere pressure was 4.5 kPa to 5.0 kPa, a reaction atmosphere temperature was 700° C. to 900° C., a supply period was 1 to 5 seconds, a gas supply time per one period was 0.15 to 0.25 seconds, and a phase difference between the supply of the gas group A and the supply of the gas group B was 0.10 to 0.20 seconds, the lower layer γ formed of the (Ti,Al)(C,N) layer shown in Table 14 was formed.
(17) Next, an adhesion layer β was formed on the surface of the lower layer γ.
(18) As the adhesion layer β, any one or both of a Ti compound layer and a (Ti,Al)(C,N) layer can be formed.
(19) However, regardless of whether the adhesion layer β is formed of the Ti compound layer, the (Ti,Al)(C,N) layer, or both the Ti compound layer and the (Ti,Al)(C,N) layer, an oxygen-containing TiCN layer having a layer thickness of at least 0.5 μm or more is formed on the outermost surface of the adhesion layer β (the outermost layer of the adhesion layer β being in contact with the interface with an upper layer α).
(20) Film forming conditions under which the adhesion layer β formed of the Ti compound layer is formed are shown in Table 9, film forming conditions Aβ to Eβ under which the adhesion layer β formed of the (Ti,Al)(C,N) layer is formed are shown in Tables 10 and 11, and film forming conditions A to D under which the adhesion layer β formed of a TiCN layer, which is one layer in the Ti compound layer, and the oxygen-containing TiCN layer is formed are shown in Table 12.
(21) The adhesion layer β shown in Table 14 was formed under the film forming conditions shown in Tables 9 to 12.
(22) Under the film forming conditions Aβ to Eβ for the adhesion layer β formed of the (Ti,Al)(C,N) layer, by changing the gas conditions and forming conditions shown in Tables 10 and 11 between the initial stage of film formation and the final stage of film formation, the (Ti,Al)(C,N) layer in which the content ratio of Al in the (Ti,Al)(C,N) layer was gradually decreased continuously or in stages from the lower layer γ toward the upper layer α was formed.
(23) Subsequently, the upper layer α shown in Table 14 was formed on the surface of the adhesion layer β including at least the TiCN layer and the oxygen-containing TiCN layer in the outermost layer under film forming condition shown in Table 13.
(24) In addition, for the upper layer α, two stages of film forming treatment including nucleation of α-Al.sub.2O.sub.3 in the initial stage of film formation, and film formation of α-Al.sub.2O.sub.3 were performed.
(25) By the film forming processes described above, the hard coating layer including the lower layer γ, the adhesion layer β, and the upper layer α was formed on the surface of the tool body made of WC-based cemented carbide or TiCN-based cermet, whereby coated tools of present invention 1 to 15 shown in Table 14 were produced.
(26) In addition, for the purpose of comparison, a lower layer γ formed of a (Ti,Al)(C,N) layer of a NaCl type face-centered cubic structure single phase was formed on the surfaces of the tool bodies A to D under the gas conditions Aγ to Eγ shown in Table 7 and under the forming conditions Aγ to Eγ shown in Table 8 using the chemical vapor deposition apparatus.
(27) Next, an adhesion layer β formed of a Ti compound layer, an adhesion layer β formed of a (Ti,Al)(C,N) layer, or an adhesion layer β formed of both the layers was formed on the surface of the lower layer γ.
(28) The adhesion layer β formed of the Ti compound layer was formed under conditions shown in Table 15, and the adhesion layer β formed of the (Ti,Al)(C,N) layer was formed under the same conditions as the conditions of the present invention shown in Tables 10 and 11.
(29) The adhesion layer β formed of the (Ti,Al)(C,N) layer was formed so that as in the present invention, the content ratio of Al in the (Ti,Al)(C,N) layer gradually decreased continuously or in stages from the lower layer γ toward the upper layer α.
(30) Next, an oxygen-containing TiCN layer was formed on the outermost surface of the adhesion layer β (the outermost layer of the adhesion layer (3 being in contact with the interface with the upper layer α) under conditions shown in Table 16.
(31) In addition, the film forming temperature of the Ti compound layer shown in Table 15 is higher than the film forming temperature of the Ti compound layer of the present invention shown in Table 9, and the film forming temperature of the oxygen-containing TiCN layer shown in Table 16 is also higher than the film forming temperature of the TiCN layer and the oxygen-containing TiCN layer of the present invention shown in Table 12.
(32) Next, an upper layer α was formed on the surface of the adhesion layer β in which the oxygen-containing TiCN layer was formed under film forming conditions shown in Table 17.
(33) In addition, for the upper layer α, two stages of film forming treatment including nucleation of α-Al.sub.2O.sub.3 in the initial stage of film formation, and film formation of α-Al.sub.2O.sub.3 were performed.
(34) The film forming temperature of the upper layer α shown in Table 17 is a temperature higher than the film forming temperature of the upper layer α of the present invention shown in Table 13.
(35) By the film forming processes described above, the hard coating layer including the lower layer γ, the adhesion layer β, and the upper layer α was formed on the surface of the tool body made of WC-based cemented carbide or TiCN-based cermet, whereby comparative example coated tools 1 to 15 shown in Table 18 were produced.
(36) The section of each of constituent layers of the coated tools of present invention 1 to 15 and the comparative example coated tools 1 to 15 in the direction perpendicular to the tool body was measured using a scanning electron microscope (at a magnification of 5,000 times). An average layer thickness was obtained by measuring and averaging the layer thicknesses of five points in an observation visual field. All of the results showed substantially the same average layer thicknesses as the target layer thicknesses shown in Tables 14 and 18.
(37) In addition, regarding the average content ratio X.sub.avg of Al in the (Ti,Al) (C,N) layer forming the lower layer γ, a sample, of which the surface was polished, was irradiated with electron beams from the sample surface side, and the average content ratio X.sub.avg of Al was obtained by averaging 10 points of the analytic result of obtained characteristic X-rays, using an electron probe micro-analyzer (EPMA). The average content ratio Y.sub.avg of C was obtained by secondary ion mass spectroscopy (SIMS). Ion beams were emitted toward a range of 70 μm X 70 μm from the sample surface side, and the concentration of components emitted by a sputtering action was measured in a depth direction. The average content ratio Y.sub.avg of C represents the average value of the (Ti,Al)(C,N) layer in the depth direction.
(38) The crystal structure of the (Ti,Al)(C,N) layer forming the lower layer γ was identified from diffraction peaks measured by X-ray diffraction, and whether the crystal structure was a single phase of a NaCl type cubic structure or included (Ti,Al)(C,N) crystal grains of a hexagonal crystal structure was examined. In addition, the X-ray diffraction measurement was performed by a 2θ-θ method using CuKα radiation with an X-ray diffractometer PANalytical Empyrean manufactured by Spectris, and the measurement was performed under measurement conditions of a measurement range (2θ) of 30 to 130 degrees, an X-ray output of 45 kV, 40 mA, a divergence slit of 0.5 degrees, a scan step of 0.013 degrees, and a measurement time per one step of 0.48 sec/step.
(39) Regarding the (Ti,Al)(C,N) layer forming the lower layer γ, a small area of the layer was observed by using the transmission electron microscope under the condition of an acceleration voltage of 200 kV, and area analysis from the section side was performed using energy-dispersive X-ray spectroscopy (EDS), whereby the presence or absence of a periodic composition variation of Ti and Al in the composition formula: (Ti.sub.1-XAl.sub.X)(C.sub.YN.sub.1-Y) in the crystal grains having the NaCl type face-centered cubic structure was examined, and the presence or absence of crystal grains having a direction of the composition variation of the present invention in the crystal grains in which the composition variation was present was examined.
(40) In addition, the “crystal grains having a direction of the composition variation of the present invention” refers to crystal grains in which the angle between the direction in which the period of the periodic composition variation of Ti and Al is minimized and the direction perpendicular to the surface of the tool body is 30 degrees or less.
(41) The angle of the surface perpendicular to the surface of the tool body with respect to the direction of the periodic composition variation was measured as follows.
(42) The angle can be obtained by observing an arbitrary area of 1 μm X 1 μm from an arbitrary section perpendicular to the body in the crystal grains having a NaCl type face-centered cubic structure using the transmission electron microscope and measuring the angle between the direction in which the periodic composition variation of Ti and Al is present and the period of the periodic composition variation of Ti and Al in the section is minimized and the surface of the tool body.
(43) Tables 14 and 18 show the results.
(44) Next, regarding the adhesion layer β, the average content ratio of oxygen in the oxygen-containing TiCN layer forming the outermost surface of the layer, that is, the average content ratio (=O/(Ti+C+N+O)×100) of oxygen in a depth area up to 0.5 μm in the layer thickness direction of the layer and the average content ratio (═O/(Ti+C+N+O)×100) of oxygen in a depth area exceeding 0.5 μm were calculated in terms of at % by measuring the intensities of the Auger peaks of Ti, C, N, and O by irradiating a polished surface of a longitudinal section of the adhesion layer β with an electron beam having a diameter of 10 nm using an Auger electron spectrometer and obtaining the ratio of the Auger peak of O to the sum of the peak intensities.
(45) Tables 14 and 18 show such values.
(46) Regarding the case where the adhesion layer β included the (Ti,Al)(C,N) layer, the average content ratio X.sub.βavg of Al to the total amount of Ti and Al in each of sections obtained by dividing the (Ti,Al)(C,N) layer by [L.sub.avg]+2 in the layer thickness direction was obtained by performing area analysis using energy-dispersive X-ray spectroscopy (EDS). Here, [L.sub.avg] represents the Gaussian symbol. [x] is a mathematical symbol representing the largest integer that does not exceed x, and when [x]=n, x is defined as n≤x<n+1 (here, n is an integer).
(47) Tables 14 and 18 show such values.
(48) In addition, regarding the chlorine content in the upper layer α, a section of a sample was polished and irradiated with an electron beam at an acceleration voltage of 10 kV from the sample section side, and the average chlorine content Cl.sub.avg was calculated by averaging points of the analytic result of obtained characteristic X-rays, using the electron probe micro-analyzer (EPMA).
(49) Tables 14 and 18 show such values.
(50) TABLE-US-00001 TABLE 1 Mixing composition (mass %) Type Co TiC TaC NbC Cr.sub.3C.sub.2 WC Tool body A 8.0 1.5 — 3.0 0.4 Remainder B 8.5 — 1.8 0.2 — Remainder C 7.0 — — — — Remainder
(51) TABLE-US-00002 TABLE 2 Mixing composition (mass %) Type Co Ni ZrC NbC Mo.sub.2C WC TiCN Tool body D 8 5 1 6 6 10 Remainder
(52) TABLE-US-00003 TABLE 3 Forming conditions (pressure of reaction Ti compound layer of atmosphere is expressed as kPa and lowermost layer δ temperature is expressed as ° C.) Formation Reaction gas Reaction atmosphere Type symbol composition (vol %) Pressure Temperature Ti TiC TiC TiCl.sub.4: 4.2%, CH.sub.4: 8.5%, 7 850 compound H.sub.2: remainder layer TiN TiN TiCl.sub.4: 4.2%, N.sub.2: 35%, 7 800 H.sub.2: remainder TiCN TiCN TiCl.sub.4: 3%, C.sub.2H.sub.4: 2.5%, 7 850 NH.sub.3: 0.8%, N.sub.2: 20%, H.sub.2: remainder TiCO TiCO TiCl.sub.4: 2%, CO.sub.2: 3%, H.sub.2: 7 900 remainder TiCNO TiCNO TiCl.sub.4: 4%, C.sub.2H.sub.4: 2%, 7 900 NH.sub.3: 0.6%, N.sub.2: 10%, CO.sub.2: 3%, H.sub.2: remainder
(53) TABLE-US-00004 TABLE 4 Formation of Gas conditions (reaction gas composition indicates proportion lowermost layer in total amount of gas group A and gas group B) δ Reaction gas group A Reaction gas group B Formation symbol composition (vol %) composition (vol %) Present Aδ Initial stage of film formation TiCl.sub.4: 0.30%, AlCl.sub.3: 0.10%, N.sub.2: invention NH.sub.3: 2.2%, H.sub.2: 75% 8%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder film Final stage of film formation TiCl.sub.4: 0.10%, AlCl.sub.3: 0.90%, N.sub.2: forming NH.sub.3: 2.2%, H.sub.2: 75% 8%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder process Bδ Initial stage of film formation TiCl.sub.4: 0.50%, AlCl.sub.3: 0.15%, N.sub.2: NH.sub.3: 2.0%, H.sub.2: 75% 12%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.15%, AlCl.sub.3: 0.85%, N.sub.2: NH.sub.3: 2.0%, H.sub.2: 75% 12%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder Cδ Initial stage of film formation TiCl.sub.4: 0.40%, AlCl.sub.3: 0.10%, N.sub.2: NH.sub.3: 2.8%, H.sub.2: 70% 0%, C.sub.2H.sub.4: 0.5%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.30%, AlCl.sub.3: 0.65%, N.sub.2: NH.sub.3: 2.8%, H.sub.2: 70% 0%, C.sub.2H.sub.4: 0.5%, H.sub.2 as remainder Dδ Initial stage of film formation TiCl.sub.4: 0.45%, AlCl.sub.3: 0.00%, N.sub.2: NH.sub.3: 2.0%, H.sub.2: 68% 0%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.35%, AlCl.sub.3: 0.60%, N.sub.2: NH.sub.3: 2.5%, H.sub.2: 68% 0%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder Eδ Initial stage of film formation TiCl.sub.4: 0.35%, AlCl.sub.3: 0.10%, N.sub.2: NH.sub.3: 2.5%, H.sub.2: 66% 0%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.40%, AlCl.sub.3: 0.60%, N.sub.2: NH.sub.3: 3.0%, H.sub.2: 65% 0%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder
(54) TABLE-US-00005 TABLE 5 Forming conditions (pressure of reaction atmosphere is expressed as kPa and temperature is expressed as ° C.) Gas group A Gas group B Phase difference in Supply time Supply time supply between gas Supply per one Supply per one group A and gas Formation of lowermost layer δ period period period period group B Reaction atmosphere Formation symbol (sec) (sec) (sec) (sec) (sec) Pressure Temperature Present Aδ Initial stage of 2 0.20 2 0.20 0.10 4.5 800 invention film formation film Final stage of 2 0.20 2 0.20 0.10 4.5 800 forming film formation process Bδ Initial stage of 1 0.17 1 0.17 0.15 5.0 700 film formation Final stage of 1 0.17 1 0.17 0.15 5.0 700 film formation Cδ Initial stage of 5 0.25 5 0.25 0.20 4.7 720 film formation Final stage of 5 0.25 5 0.25 0.20 4.7 720 film formation Dδ Initial stage of 3 0.23 3 0.23 0.10 4.7 850 film formation Final stage of 3 0.23 3 0.23 0.10 4.7 850 film formation Eδ Initial stage of 4 0.15 4 0.15 0.20 5.0 900 film formation Final stage of 4 0.15 4 0.15 0.20 5.0 900 film formation
(55) TABLE-US-00006 TABLE 6 Lowermost layer δ (numerical value at the bottom indicates the average target layer thickness of the layer (μm)) Tool (Ti, Al) (C, N) layer body First Second Third Formation X.sub.δavg of X.sub.δavg of Type symbol layer layer layer symbol section 1 section 2 Coated 1 A TiN — — Aδ 0.28 0.45 tools (0.3) of present 2 B TiC TiCN — Bδ 0.25 0.41 invention (0.2) (0.5) 3 C TiC — — Cδ 0.21 0.36 (0.3) 4 A TiN TiCO — Dδ 0.1 0.28 (0.3) (0.5) 5 B TiC TiCN TiCNO Eδ 0.24 0.33 (0.2) (0.5) (0.5) 6 C — — — — — — 7 D — — — Bδ 0.22 0.43 8 A TiC TiCN — Cδ 0.23 0.32 (0.3) (0.4) 9 B — — — — — — 10 C — — — — — — 11 D — — — — — — 12 A — — — — — — 13 B — — — — — — 14 C — — — — — — 15 D — — — — — — Lowermost layer δ (numerical value at the bottom indicates the average targetlayer thickness of the layer (μm)) (Ti, Al) (C, N) layer Average target layer X.sub.δavg of X.sub.δavg of X.sub.δavg of X.sub.δavg of X.sub.δavg of thickness Type section 3 section 4 section 5 section 6 section 7 Y.sub.avg (μm) Coated 1 0.75 — — — — 0.0001 1.0 tools or less of present 2 0.66 — — — — 0.0001 1.5 invention or less 3 0.47 — — — — 0.0048 1.2 4 0.45 — — — — 0.0033 1.0 5 0.41 — — — — 0.0033 1.0 6 — — — — — — — 7 0.62 — — — — 0.0001 1.1 or less 8 0.42 — — — — 0.0046 1.5 9 — — — — — — — 10 — — — — — — — 11 — — — — — — — 12 — — — — — — — 13 — — — — — — — 14 — — — — — — — 15 — — — — — — —
(56) TABLE-US-00007 TABLE 7 Formation of lower Gas conditions (reaction gas composition indicates proportion layer γ in total amount of gas group A and gas group B) Formation Reaction gas group A Reaction gas group B symbol composition (vol %) composition (vol %) Present Aγ NH.sub.3: 2.2%, H.sub.2: 75% TiCl.sub.4: 0.10%, AlCl.sub.3: 0.90%, N.sub.2: invention 8%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder film Bγ NH.sub.3: 2.0%, H.sub.2: 75% TiCl.sub.4: 0.15%, AlCl.sub.3: 0.85%, N.sub.2: forming 12%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder process Cγ NH.sub.3: 2.8%, H.sub.2: 70% TiCl.sub.4: 0.30%, AlCl.sub.3: 0.65%, N.sub.2: 0%, C.sub.2H.sub.4: 0.5%, H.sub.2 as remainder Dγ NH.sub.3: 2.5%, H.sub.2: 68% TiCl.sub.4: 0.35%, AlCl.sub.3: 0.60%, N.sub.2: 0%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder Eγ NH.sub.3: 3.0%, H.sub.2: 65% TiCl.sub.4: 0.40%, AlCl.sub.3: 0.60%, N.sub.2: 0%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder
(57) TABLE-US-00008 TABLE 8 Forming conditions (pressure of reaction atmosphere is expressed as kPa and temperature is expressed as ° C.) Phase difference Gas group A Gas group B in supply Formation of lower Supply time Supply time between gas layer γ Supply per one Supply per one group A and Process Formation period period period period gas group B Reaction atmosphere type symbol (sec) (sec) (sec) (sec) (sec) Pressure Temperature Present Aγ 2 0.20 2 0.20 0.10 4.5 800 invention Bγ 1 0.17 1 0.17 0.15 5.0 700 film Cγ 5 0.25 5 0.25 0.20 4.7 720 forming Dγ 3 0.23 3 0.23 0.10 4.7 850 process Eγ 4 0.15 4 0.15 0.20 5.0 900
(58) TABLE-US-00009 TABLE 9 Ti compound layer of Forming conditions (pressure of reaction atmosphere is expressed adhesion layer β as kPa and temperature is expressed as ° C.) Formation Reaction atmosphere Type symbol Reaction gas composition (vol %) Pressure Temperature Ti TiC TiC TiCl.sub.4: 4.2%, CH.sub.4: 8.5%, H.sub.2: remainder 7 850 compound TiN TiN TiCl.sub.4: 4.2%, N.sub.2: 35%, H.sub.2: remainder 7 800 layer TiCN TiCN TiCl.sub.4: 3%, C.sub.2H.sub.4: 2.5%, NH.sub.3: 0.8%, N.sub.2: 7 850 20%, H.sub.2: remainder TiCO TiCO TiCl.sub.4: 2%, CO.sub.2: 3%, H.sub.2: remainder 7 900 TiCNO TiCNO TiCl.sub.4: 4%, C.sub.2H.sub.4: 2%, NH.sub.3: 0.6%, N.sub.2: 7 900 10%, CO.sub.2: 3%, H.sub.2: remainder
(59) TABLE-US-00010 TABLE 10 Formation of adhesion Gas conditions (reaction gas composition indicates proportion layer β in total amount of gas group A and gas group B) Formation Reaction gas group A Reaction gas group B symbol composition (vol %) composition (vol %) Present Aβ Initial stage of film formation TiCl.sub.4: 0.10%, AlCl.sub.3: 0.90%, N.sub.2: invention NH.sub.3: 2.2%, H.sub.2: 75% 1%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder film Final stage of film formation TiCl.sub.4: 0.30%, AlCl.sub.3: 0.10%, N.sub.2: forming NH.sub.3: 2.2%, H.sub.2: 75% 1%, C.sub.2H.sub.4: 0.5%, H.sub.2 as remainder process Bβ Initial stage of film formation TiCl.sub.4: 0.15%, AlCl.sub.3: 0.85%, N.sub.2: NH.sub.3: 2.0%, H.sub.2: 75% 12%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.50%, AlCl.sub.3: 0.15%, N.sub.2: NH.sub.3: 2.0%, H.sub.2: 75% 6%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder Cβ Initial stage of film formation TiCl.sub.4: 0.30%, AlCl.sub.3: 0.65%, N.sub.2: NH.sub.3: 2.8%, H.sub.2: 70% 0%, C.sub.2H.sub.4: 0.5%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.40%, AlCl.sub.3: 0.10%, N.sub.2: NH.sub.3: 2.8%, H.sub.2: 70% 0%, C.sub.2H.sub.4: 0.5%, H.sub.2 as remainder Dβ Initial stage of film formation TiCl.sub.4: 0.35%, AlCl.sub.3: 0.60%, N.sub.2: NH.sub.3: 2.5%, H.sub.2: 68% 3%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.45%, AlCl.sub.3: 0.15%, N.sub.2: NH.sub.3: 2.0%, H.sub.2: 68% 3%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder Eβ Initial stage of film formation TiCl.sub.4: 0.40%, AlCl.sub.3: 0.60%, N.sub.2: NH.sub.3: 3.0%, H.sub.2: 65% 8%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.35%, AlCl.sub.3: 0.10%, N.sub.2: NH.sub.3: 2.5%, H.sub.2: 66% 8%, C.sub.2H.sub.4: 0.4%, H.sub.2 as remainder
(60) TABLE-US-00011 TABLE 11 Forming conditions (pressure of reaction atmosphere is expressed as kPa and temperature is expressed as ° C.) Phase difference Gas group A Gas group B in supply Supply time Supply time between gas Supply per one Supply per one group A and gas Formation of adhesion layer β period period period period group B Reaction atmosphere Formation symbol (sec) (sec) (sec) (sec) (sec) Pressure Temperature Present Aβ Initial stage of 2 0.20 2 0.20 0.10 4.5 800 invention film formation film Final stage of 2 0.20 2 0.20 0.10 4.5 800 forming film formation process Bβ Initial stage of 1 0.17 1 0.17 0.15 5.0 700 film formation Final stage of 1 0.17 1 0.17 0.15 5.0 700 film formation Cβ Initial stage of 5 0.25 5 0.25 0.20 4.7 720 film formation Final stage of 5 0.25 5 0.25 0.20 4.7 720 film formation Dβ Initial stage of 3 0.23 3 0.23 0.10 4.7 850 film formation Final stage of 3 0.23 3 0.23 0.10 4.7 850 film formation Eβ Initial stage of 4 0.15 4 0.15 0.20 5.0 900 film formation Final stage of 4 0.15 4 0.15 0.20 5.0 900 film formation
(61) TABLE-US-00012 TABLE 12 “TiCN layer” and “oxygen- containing TiCN layer” Forming conditions (pressure of reaction atmosphere is expressed as kPa and temperature is expressed as ° C.) of adhesion Amount of CO.sub.2 added layer β during film formation Formation Reaction atmosphere of oxygen-containing symbol Reaction gas composition (vol %) Pressure Temperature TiCN layer (vol %) A TiCN: TiCl.sub.4: 2%, C.sub.2H.sub.4: 2.0%, NH.sub.3: 0.5%, N.sub.2: 10%, H.sub.2: remainder 6 800 5 B TiCN: TiCl.sub.4: 3%, C.sub.2H.sub.4: 2.2%, NH.sub.3: 0.6%, N.sub.2: 12%, H.sub.2: remainder 10 900 3 C TiCN: TiCl.sub.4: 4%, C.sub.2H.sub.4: 3.0%, NH.sub.3: 1.0%, N.sub.2: 17%, H.sub.2: remainder 7 870 4 D TiCN: TiCl.sub.4: 6%, C.sub.2H.sub.4: 2.8%, NH.sub.3: 0.8%, N.sub.2: 20%, H.sub.2: remainder 9 830 1
(62) TABLE-US-00013 TABLE 13 Upper layer α Forming conditions (pressure of reaction atmosphere is expressed (α-Al.sub.2O.sub.3) as kPa and temperature is expressed as ° C.) Formation Reaction gas group A Reaction atmosphere symbol composition (vol %) Pressure Temperature A Initial nucleation conditions: AlCl.sub.3: 5 850 3.0%, CO.sub.2: 5%, HCl: 1.0%, H.sub.2: remainder Growth conditions: AlCl.sub.3: 2.0%, CO.sub.2: 5 850 8%, HCl: 3.0%, H.sub.2S: 0.7%, H.sub.2: remainder B Initial nucleation conditions: AlCl.sub.3: 15 900 2.0%, CO.sub.2: 1%, HCl: 0.3%, H.sub.2: remainder Growth conditions: AlCl.sub.3: 1.5%, CO.sub.2: 10 900 6%, HCl: 4.0%, H.sub.2S: 0.5%, H.sub.2: remainder C Initial nucleation conditions: AlCl.sub.3: 7.5 800 1.0%, CO.sub.2: 2%, HCl: 0.5%, H.sub.2: remainder Growth conditions: AlCl.sub.3: 4.0%, CO.sub.2: 15 800 4%, HCl: 6.0%, H.sub.2S: 0.9%, H.sub.2: remainder D Initial nucleation conditions: AlCl.sub.3: 10 850 2.5%, CO.sub.2: 4%, HCl: 0.8%, H.sub.2: remainder Growth conditions: AlCl.sub.3: 5.0%, CO.sub.2: 12.5 850 2%, HCl: 8.0%, H.sub.2S: 1.0%, H.sub.2: remainder
(63) TABLE-US-00014 TABLE 14 Hard coating layer Lower layer γ Presence or absence of Average Presence or composition Adhesion layer β Tool layer absence of variation (Ti, Al) (C, N) layer body Formation thickness hexagonal of present Formation X.sub.avg of X.sub.avg of X.sub.avg of X.sub.avg of X.sub.avg of X.sub.avg of Type symbol symbol (μm) X.sub.avg Y.sub.avg structure invention symbol section 1 section 2 section 3 section 4 section 5 section 6 Coated 1 A Aγ 3.4 0.93 0.0001 AB AB Aβ 0.68 0.3 — — — — tools or less of present 2 B Bγ 4.0 0.83 0.0001 AB PR Bβ 0.7 0.5 0.25 — — — invention or less 3 C Cγ 1.8 0.68 0.0050 AB AB Cβ 0.73 0.24 — — — — 4 A Dγ 2.6 0.62 0.0035 AB AB Dβ 0.57 0.54 0.36 0.24 — — 5 B Eγ 1.5 0.60 0.0030 AB AB Eβ 0.4 0.23 — — — — 6 C Aγ 1.0 0.95 0.0001 AB AB Aβ 0.78 0.61 0.37 — — — or less 7 A Bγ 5.9 0.83 0.0001 AB PR Bβ 0.61 0.42 0.25 — — — or less 8 B Cγ 3.5 0.68 0.0047 AB AB — — — — — — — 9 C Dγ 1.2 0.63 0.0033 AB AB — — — — — — — 10 A Eγ 3.9 0.60 0.0037 AB AB — — — — — — — 11 B Aγ 3.5 0.91 0.0001 AB AB — — — — — — — or less 12 C Bγ 2.4 0.85 0.0001 AB PR — — — — — — — or less 13 A Cγ 3.3 0.69 0.0048 AB AB — — — — — — — 14 B Dγ 4.6 0.63 0.0033 AB AB — — — — — — — 15 C Eγ 1.0 0.60 0.0036 AB AB — — — — — — — Hard coating layer Adhesion layer β Formation symbol of Ti compound TiCN layer and layer (numerical oxygen-containing value at the TiCN layer bottom indicates Average Average the average oxygen oxygen (Ti, Al) (C, N) layer target layer content content Total Upper layer α Average thickness of the at depth at depth average Average layer layer (μm)) up to exceeding layer Chlorine layer X.sub.avg of thickness First Second Third Formation 0.5 μm 0.5 μm thickness Formation content thickness Type section 7 (μm) layer layer layer symbol (at %) (at %) (μm) symbol (at %) (μm) Coated 1 — 0.3 TiN — — A 2.9 0.0* 1.5 A 0.06 1.8 tools (0.2) of present 2 — 1.5 TiC — — B 1.6 0.0* 3.5 B 0.09 1.4 invention (0.5) 3 — 0.5 TiC TiCO — A 2.9 0.0* 2.2 C 0.41 2.6 (0.3) (0.4) 4 — 2.0 TiN TiC — B 1.8 0.0* 5.0 D 0.50 2.3 (0.3) (0.5) 5 — 0.5 TiC TiCN — A 3.0 0.0* 4.0 A 0.06 2.0 (0.2) (0.5) 6 — 1.0 — — — C 2.1 0.0* 3.4 B 0.07 1.4 7 — 1.2 — — — D 0.5 0.0* 3.0 C 0.34 1.5 8 — — TiC TiCNO TiCO C 2.0 0.0* 2.3 D 0.47 1.3 (0.3) (0.2) (0.5) 9 — — — — D 0.5 0.0* 2.4 A 0.05 5.0 10 — — — — C 2.1 0.0* 3.0 B 0.04 3.5 11 — — — — B 1.5 0.0* 5.0 D 0.51 2.3 12 — — — — A 3.0 0.0* 0.5 D 0.52 1.2 13 — — — — B 1.8 0.0* 0.7 A 0.04 1.0 14 — — — — A 2.8 0.0* 2.1 A 0.03 2.2 15 — — — — B 1.4 0.0* 1.0 D 0.52 1.2 (Note 1) Any of Xavg and Yavg in boxes indicates atomic ratio. (Note 2) “Presence or absence of hexagonal structure” in boxes indicates “PR (Present)” in a case where crystal grains having a hexagonal structure are contained from diffraction peaks measured by X-ray diffraction, and indicates “AB (Absent)” in a case of a single phase of a cubic structure. (Note 3) “Presence or absence of composition variation of present invention” in boxes indicates ““PR (Present)” in a case where crystal grains having a NaCl type face-centered cubic structure in which the angle between the direction in which the period of a periodic composition variation of Ti and Al and the surface perpendicular to the surface of the tool body is 30 degrees or less are present, and indicates “AB (Absent)” in a case where such crystal grains are not present. (Note4) *in boxes indicates that an average oxygen content of 0 at % means that only unavoidable oxygen is determined.
(64) TABLE-US-00015 TABLE 15 Ti compound layer of Forming conditions (pressure of reaction atmosphere is expressed adhesion layer β as kPa and temperature is expressed as ° C.) Formation Reaction atmosphere Type symbol Reaction gas composition (vol %) Pressure Temperature Ti TiC TiC TiCl.sub.4: 4.2%, CH.sub.4: 8.5%, H.sub.2: remainder 7 1020 compound TiN TiN TiCl.sub.4: 4.2%, N.sub.2: 35%, H.sub.2: remainder 7 1000 layer TiCN TiCN TiCl.sub.4: 4%, CH.sub.4: 1%, N.sub.2: 25%, H.sub.2: remainder 7 1000 TiCO TiCO TiCl.sub.4: 2%, CO.sub.2: 2%, H.sub.2: remainder 7 1020 TiCNO TiCNO TiCl.sub.4: 4%, CH.sub.4: 2%, N.sub.2: 15%, CO.sub.2: 6%, H.sub.2: remainder 7 1020
(65) TABLE-US-00016 TABLE 16 “Oxygen- containing HT- TiCN layer” of adhesion layer Forming conditions (pressure of reaction atmosphere is expressed β as kPa and temperature is expressed as ° C.) Formation Reaction atmosphere symbol Reaction gas composition (vol %) Pressure Temperature a HT-TiCN: TiCl.sub.4: 2%, CH.sub.4: 1%, CO.sub.2: 2%, N.sub.2: 6 1000 10%, H.sub.2: remainder b HT-TiCN: TiCl.sub.4: 2.5%, CH.sub.4: 2%, CO.sub.2: 6%, N.sub.2: 10 1000 20%, H.sub.2: remainder c HT-TiCN: TiCl.sub.4: 7%, CH.sub.4: 3%, CO.sub.2: 4%, N.sub.2: 7 1000 20%, H.sub.2: remainder d HT-TiCN: TiCl.sub.4: 4%, CH.sub.4: 2.6%, CO.sub.2: 2%, N.sub.2: 9 1000 25%, H.sub.2: remainder
(66) TABLE-US-00017 TABLE 17 Upper layer α Forming conditions (pressure of reaction atmosphere is expressed (α-Al.sub.2O.sub.3) as kPa and temperature is expressed as ° C.) Formation Reaction atmosphere symbol Reaction gas composition (vol %) Pressure Temperature a Initial nucleation conditions: AlCl.sub.3: 3.0%, 5 1000 CO.sub.2: 5%, HCl: 1.0%, H.sub.2: remainder Growth conditions: AlCl.sub.3: 2.0%, CO.sub.2: 8%, 5 1000 HCl: 3.0%, H.sub.2S: 0.7%, H.sub.2: remainder b Initial nucleation conditions: AlCl.sub.3: 2.0%, 15 960 CO.sub.2: 1%, HCl: 0.3%, H.sub.2: remainder Growth conditions: AlCl.sub.3: 1.5%, CO.sub.2: 6%, 10 960 HCl: 4.0%, H.sub.2S: 0.5%, H.sub.2: remainder c Initial nucleation conditions: AlCl.sub.3: 1.0%, 7.5 1040 CO.sub.2: 2%, HCl: 0.5%, H.sub.2: remainder Growth conditions: AlCl.sub.3: 4.0%, CO.sub.2: 4%, 15 1040 HCl: 6.0%, H.sub.2S: 0.9%, H.sub.2: remainder d Initial nucleation conditions: AlCl.sub.3: 2.5%, 10 1020 CO.sub.2: 4%, HCl: 0.8%, H.sub.2: remainder Growth conditions: AlCl.sub.3: 5.0%, CO.sub.2: 2%, 12.5 1020 HCl: 8.0%, H.sub.2S: 1.0%, H.sub.2: remainder
(67) TABLE-US-00018 TABLE 18 Hard coating layer Lower layer γ Presence or absence of Average Presence or composition adhesion layer β Tool layer absence of variation of (Ti, Al) (C, N) layer body Formation thickness hexagonal present Formation X.sub.avg of X.sub.avg of X.sub.avg of X.sub.avg of X.sub.avg of Type symbol symbol (μm) X.sub.avg Y.sub.avg structure invention symbol section 1 section 2 section 3 section 4 section 5 Comparative 1 A Aγ 3.5 0.93 0.0001 PR AB Aβ 0.66 0.29 — — — example or less coated 2 B Bγ 4.0 0.83 0.0001 PR AB Bβ 0.6 0.4 0.21 — — tool or less 3 C Cγ 2.5 0.90 0.0050 PR AB Cβ 0.69 0.2 — — — 4 A Dγ 2.6 0.66 0.0035 PR AB Dβ 0.5 0.36 0.21 — — 5 B Eγ 1.5 0.60 0.0034 PR AB Eβ 0.4 0.23 — — — 6 C Aγ 1.0 0.94 0.0001 PR AB Aβ 0.69 0.41 0.19 — — or less 7 A Bγ 1.2 0.83 0.0001 PR AB Bβ 0.6 0.39 — — — or less 8 B Cγ 3.5 0.88 0.0047 PR AB Cβ 0.55 0.35 0.28 — — 9 C Dγ 2.5 0.64 0.0033 PR AB Dβ 0.41 0.3 0.21 — — 10 A Eγ 4.5 0.60 0.0037 PR AB Eβ 0.5 0.42 0.31 0.2 — 11 B Aγ 5.0 0.94 0.0001 PR AB — — — — — — or less 12 C Bγ 3.0 0.82 0.0001 PR AB — — — — — — or less 13 A Cγ 3.5 0.89 0.0048 PR AB — — — — — — 14 B Dγ 4.0 0.67 0.0033 PR AB — — — — — — 15 C Eγ 2.0 0.61 0.0036 PR AB — — — — — — Hard coating layer adhesion layer β Formation symbol of Ti compound layer (numerical Oxygen-containing value at the TiCN layer bottom indicates Average the average Average oxygen (Ti, Al) (C, N) layer target layer oxygen content at Total Upper layer α Average thickness of the content depth average Average layer layer (μm)) at depth exceeding layer Chlorine layer X.sub.avg of X.sub.avg of thickness First Second Third Formation up to 0.5 0.5 μm thickness Formation content thickness Type section 6 section 7 (μm) layer layer layer symbol μm (at %) (at %) (μm) symbol (at %) (μm) Comparative 1 — — 0.5 TiN — — a 2.2 2.2 1.7 a 0.03 1.9 example (0.2) coated 2 — — 1.0 TiC — — b 3.6 3.6 3 b 0.04 1.4 tool (0.5) 3 — — 0.5 TiC TiCO — a 2.3 2.3 2 c 0.04 1.5 (0.3) (0.4) 4 — — 1.4 TiN TiC — b 3.4 3.4 3 d 0.04 1.4 (0.3) (0.5) 5 — — 0.5 TiC TiCN TiCO a 2.1 2.2 2.90 a 0.03 1.6 (0.2) (0.5) (0.5) 6 — — 1.0 TiN — — c 2.0 2.0 2.3 b 0.02 1.7 (0.3) 7 — — 0.5 TiC — — d 1.5 1.5 3.1 c 0.04 1.4 (0.3) 8 — — 1.5 TiC TiCNO TiCO c 2.1 2.2 3.5 d 0.04 1.3 (0.3) (0.2) (0.5) 9 — — 1.0 TiN — — d 1.5 1.5 3.5 a 0.03 2.1 (0.2) 10 — — 2.5 TiC — — c 2.1 2.0 5.20 b 0.04 1.3 (0.2) 11 — — — TiC — — b 3.5 3.4 1.2 c 0.03 2.1 (0.3) 12 — — — — — — a 2.1 2.0 1 d 0.04 2.1 13 — — — TiN — — b 3.4 3.4 1.4 a 0.02 1.6 (0.2) 14 — — — TiN TiCNO TiC a 2.2 2.2 2 b 0.02 1.8 (0.3) (0.3) (0.3) 15 — — — — — — b 3.7 3.6 1.5 c 0.04 2.0 (Note 1) Any of Xavg and Yavg in boxes indicates atomic ratio. (Note 2) “Presence or absence of hexagonal structure” in boxes indicates “PR (Present)” in a case where crystal grains having a hexagonal structure are contained from diffraction peaks measured by X-ray diffraction, and indicates “AB (Absent)” in a case of a single phase of a cubic structure. (Note 3) “Presence or absence of composition variation of present invention” in boxes indicates “PR (Present)” in a case where crystal grains having a NaCl type face-centered cubic structure in which the angle between the direction in which the period of a periodic composition variation of Ti and Al and the surface perpendicular to the surface of the tool body is 30 degrees or less are present, and indicates “AB (Absent)” in a case where such crystal grains are not present.
(68) Next, in a state in which each of the various coated tools was clamped to a cutter tip end portion made of tool steel with a cutter diameter of 125 mm by a fixing tool, the coated tools of present invention 1 to 15 and the comparative example coated tools 1 to 15 were subjected to wet high-speed face milling, which is a type of high-speed intermittent cutting of cast iron, and a center-cut cutting test, which will be described below, and the flank wear width of a cutting edge was measured.
(69) Table 19 shows the results.
(70) Cutting test: wet high-speed face milling, center-cut cutting
(71) Cutter diameter: 125 mm
(72) Work material: a block material of JIS FCD700 with a width of 100 mm and a length of 400 mm
(73) Rotational speed: 891 min.sup.−1
(74) Cutting speed: 350 m/min
(75) Depth of cut: 1.5 mm
(76) Feed per tooth: 0.3 mm/tooth
(77) Cutting time: 5 minutes
(78) (a typical cutting speed is 200 m/min)
(79) TABLE-US-00019 TABLE 19 Flank wear Cutting test width results Type (mm) Type (min) Coated tools of 1 0.10 Comparative 1 3.1 present invention 2 0.08 coated tool 2 3.2 3 0.12 3 3.4 4 0.13 4 2.8 5 0.12 5 3.6 6 0.11 6 4.2 7 0.09 7 3.4 8 0.14 8 3.3 9 0.16 9 3.1 10 0.16 10 2.4 11 0.15 11 3.3 12 0.15 12 2.9 13 0.16 13 2.5 14 0.17 14 2.2 15 0.18 15 3.0 Numerical values in boxes of comparative coated tools indicate cutting times (min) until the end of a service life caused by the occurrence of chipping.
(80) From the results shown in Table 19, in the coated tools of present invention, since the lower layer γ has a single phase of a NaCl type cubic structure and thus has high hardness, and furthermore, the oxygen-containing TiCN layer having excellent adhesion to the upper layer α is formed between the upper layer α and the adhesion layer β, which are formed under low temperature conditions, the occurrence of chipping and the occurrence of peeling are suppressed, whereby excellent wear resistance is exhibited during long-term use in high-speed intermittent cutting during which intermittent and impact loads are exerted on a cutting edge.
(81) Contrary to this, the comparative example coated tools reach the end of the service life within a short period of time due to the occurrence of abnormal damage such as chipping and peeling.
Example 2
(82) On the surfaces of the tool bodies A to C made of WC-based cemented carbide shown in Table 1 and the surface of the tool body D made of TiCN-based cermet shown in Table 2, any one or both of a Ti compound layer and a (Ti,Al)(C,N) layer were formed as a lowermost layer δ using a typical chemical vapor deposition apparatus.
(83) Specifically, as the lowermost layer δ as the Ti compound layer, the Ti compound layer shown in Table 22 was formed under the conditions shown in Table 3, and as the lowermost layer δ as the (Ti,Al)(C,N) layer, the (Ti,Al)(C,N) layer shown in Table 22 was formed under gas conditions shown in Table 20 and forming conditions shown in Table 21.
(84) For some of the tool bodies, both the Ti compound layer and the (Ti,Al)(C,N) layer were formed as the lowermost layer δ.
(85) Under film forming conditions Aδ to Eδ for the lowermost layer δ formed of the (Ti,Al)(C,N) layer, by changing the gas conditions and forming conditions shown in Tables 20 and 21 between the initial stage of film formation and the final stage of film formation, the (Ti,Al)(C,N) layer in which the content ratio of Al in the (Ti,Al)(C,N) layer was gradually increased continuously or in stages from the surface of the tool body toward a lower layer γ was formed.
(86) Here, when the average content ratio of X.sub.δavg of Al to the total amount of Ti and Al in each of sections obtained by dividing the (Ti,Al)(C,N) layer as the lowermost layer δ by [L.sub.avg]+2 was obtained, X.sub.δavg<X.sub.avg was satisfied in each of the sections, and X.sub.δavg of the section closer to the surface side being equal to or greater than X.sub.βavg of the section closer to the body side was satisfied.
(87) Next, the lower layer γ formed of a (Ti,Al)(C,N) layer having a single phase of a NaCl type face-centered cubic structure, shown in Table 23, was formed on the surface of the lowermost layer δ formed on the surfaces of the tool bodies A to D using the chemical vapor deposition apparatus under the gas conditions Aγ to Eγ shown in Table 7 and under the forming conditions Aγ to Eγ shown in Table 8.
(88) Next, an adhesion layer β was formed on the surface of the lower layer γ.
(89) As the adhesion layer β, any one or both of a Ti compound layer and a (Ti,Al)(C,N) layer were formed.
(90) However, regardless of whether the adhesion layer β was formed of the Ti compound layer, the (Ti,Al)(C,N) layer, or both the Ti compound layer and the (Ti,Al)(C,N) layer, an oxygen-containing TiCN layer having a layer thickness of at least 0.5 μm or more was formed on the outermost surface of the adhesion layer β (the outermost layer of the adhesion layer β being in contact with the interface with an upper layer α).
(91) Film forming conditions under which the adhesion layer β formed of the Ti compound layer was formed are shown in Table 9, film forming conditions Aβ to Eβ under which the adhesion layer β formed of the (Ti,Al)(C,N) layer was formed are shown in Tables 10 and 11, and film forming conditions A to D under which the adhesion layer β formed of a TiCN layer, which is one layer in the Ti compound layer, and the oxygen-containing TiCN layer was formed are shown in Table 12.
(92) The adhesion layer β shown in Table 23 was formed under the film forming conditions shown in Tables 9 to 12.
(93) Under the film forming conditions Aβ to Eβ for the adhesion layer β formed of the (Ti,Al)(C,N) layer, by changing the gas conditions and forming conditions shown in Tables 10 and 11 between the initial stage of film formation and the final stage of film formation as in the case of Example 1, the (Ti,Al)(C,N) layer in which the content ratio of Al in the (Ti,Al)(C,N) layer was gradually decreased continuously or in stages from the lower layer γ toward the upper layer α was formed.
(94) However, the average layer thickness L.sub.avg (μm) of the (Ti,Al)(C,N) layer of the adhesion layer β satisfied 0.30≤L.sub.avg≤5.0, and when an average content ratio X.sub.βavg of Al to the total amount of Ti and Al was obtained in each of sections obtained by dividing the layer of a complex nitride or complex carbonitride of Ti and Al by [L.sub.avg]+2, X.sub.βavg<X.sub.avg was satisfied in each of the sections, and X.sub.βavg of the section closer to the surface side being equal to or smaller than X.sub.βavg of the section closer to the body side was satisfied.
(95) Subsequently, the upper layer α shown in Table 23 was formed on the surface of the adhesion layer β including at least the TiCN layer and the oxygen-containing TiCN layer in the outermost layer under the film forming condition shown in Table 13.
(96) In addition, for the upper layer α, two stages of film forming treatment including nucleation of α-Al.sub.2O.sub.3 in the initial stage of film formation, and film formation of α-Al.sub.2O.sub.3 were performed.
(97) By the processes described above, the hard coating layer including the lowermost layer δ, the lower layer γ, the adhesion layer β, and the upper layer α was formed on the surface of the tool bodies A to C and D, whereby coated tools of present invention 16 to 25 were produced.
(98) For the coated tools of present invention 16 to 25, each of the following measurements was performed in the same manner as in the case of Example 1.
(99) First, the average layer thickness of each layer was obtained, and all of the results showed substantially the same average layer thicknesses as the target layer thicknesses shown in Tables 22 and 23.
(100) In addition, the average content ratio X.sub.avg of Al and the average content ratio Y.sub.avg of C in the (Ti,Al)(C,N) layer forming the lower layer γ were obtained, and Table 23 shows the results.
(101) In addition, whether the (Ti,Al)(C,N) layer forming the lower layer γ had a single phase of a NaCl type cubic structure or contained (Ti,Al)(C,N) crystal grains having a hexagonal crystal structure was examined, and Table 23 shows the results.
(102) Furthermore, regarding the (Ti,Al)(C,N) layer forming the lower layer γ, the presence or absence of a periodic composition variation of Ti and Al in the crystal grains having the NaCl type face-centered cubic structure was examined, and the presence or absence of crystal grains (crystal grains in which the angle between the direction in which the period of the periodic composition variation of Ti and Al was minimized and the direction perpendicular to the surface of the tool body was 30 degrees or less) having a direction of the composition variation of the present invention in the crystal grains in which the composition variation was present was examined.
(103) Table 23 shows the results.
(104) In addition, regarding the adhesion layer β, the average content ratio (=O/(Ti+C+N+O)×100) of oxygen in the oxygen-containing TiCN layer forming the outermost surface of the layer in a depth area up to 0.5 μm in the layer thickness direction of the layer and the average content ratio (=O/(Ti+C+N+O)×100) of oxygen in a depth area exceeding 0.5 μm were obtained by Auger electron spectrometry in the same manner as in the case of Example 1.
(105) Table 23 shows the results.
(106) Regarding the case where the adhesion layer β included the (Ti,Al)(C,N) layer, the average content ratio X.sub.βavg of Al to the total amount of Ti and Al in each of sections obtained by dividing the (Ti,Al)(C,N) layer by [L.sub.avg]+2 in the layer thickness direction was obtained by performing area analysis using energy-dispersive X-ray spectroscopy (EDS). Here, [L.sub.avg] represents the Gaussian symbol. [x] is a mathematical symbol representing the largest integer that does not exceed x, and when [x]=n, x is defined as n≤x<n+1 (here, n is an integer).
(107) Tables 22 and 23 show the results.
(108) In addition, regarding the chlorine content in the upper layer α, a section of a sample was polished and irradiated with an electron beam at an acceleration voltage of 10 kV from the sample section side, and the average chlorine content Cl.sub.avg was calculated by averaging points of the analytic result of obtained characteristic X-rays, using the electron probe micro-analyzer (EPMA).
(109) Table 23 shows the results.
(110) TABLE-US-00020 TABLE 20 Gas conditions (reaction gas composition indicates proportion Formation of in total amount of gas group A and gas group B) lowermost layer δ Reaction gas group A Reaction gas group B Formation symbol composition (vol %) composition (vol %) Present Aδ Initial stage of film formation TiCl.sub.4: 0.36%, AlCl.sub.3: 0.10%, N.sub.2: invention NH.sub.3: 2.2%, H.sub.2: 75% 0%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder film Final stage of film formation TiCl.sub.4: 0.10%, AlCl.sub.3: 0.60%, N.sub.2: forming NH.sub.3: 2.2%, H.sub.2: 75% 8%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder process Bδ Initial stage of film formation TiCl.sub.4: 0.52%, AlCl.sub.3: 0.12%, N.sub.2: NH.sub.3: 2.0%, H.sub.2: 75% 6%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder Cδ Final stage of film formation TiCl.sub.4: 0.15%, AlCl.sub.3: 0.85%, N.sub.2: NH.sub.3: 2.0%, H.sub.2: 75% 12%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder Initial stage of film formation TiCl.sub.4: 0.44%, AlCl.sub.3: 0.12%, N.sub.2: NH.sub.3: 2.8%, H.sub.2: 70% 0%, C.sub.2H.sub.4: 0%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.30%, AlCl.sub.3: 0.50%, N.sub.2: NH.sub.3: 2.8%, H.sub.2: 70% 0%, C.sub.2H.sub.4: 0.5%, H.sub.2 as remainder Dδ Initial stage of film formation TiCl.sub.4: 0.42%, AlCl.sub.3: 0.10%, N.sub.2: NH.sub.3: 2.5%, H.sub.2: 68% 0%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.35%, AlCl.sub.3: 0.60%, N.sub.2: NH.sub.3: 2.5%, H.sub.2: 68% 0%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder Eδ Initial stage of film formation TiCl.sub.4: 0.38%, AlCl.sub.3: 0.10%, N.sub.2: NH.sub.3: 2.5%, H.sub.2: 66% 0%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder Final stage of film formation TiCl.sub.4: 0.40%, AlCl.sub.3: 0.60%, N.sub.2: NH.sub.3: 2.5%, H.sub.2: 65% 0%, C.sub.2H.sub.4: 0.2%, H.sub.2 as remainder
(111) TABLE-US-00021 TABLE 21 Forming conditions (pressure of reaction atmosphere is expressed as kPa and temperature is expressed as ° C.) Gas group A Gas group B Phase difference Supply Supply in supply between Supply time per Supply time per gas group A and Formation of lowermost layer δ period one period period one period gas group B Reaction atmosphere Formation symbol (sec) (sec) (sec) (sec) (sec) Pressure Temperature Present Aδ Initial stage of 1 0.15 1 0.15 0.10 4.5 800 invention film formation film Final stage of 1 0.15 1 0.15 0.10 4.5 800 forming film formation process Bδ Initial stage of 2 0.2 2 0.2 0.15 4.7 700 film formation Final stage of 2 0.2 2 0.2 0.15 4.7 700 film formation Cδ Initial stage of 3 0.25 3 0.25 0.20 4.7 720 film formation Final stage of 3 0.25 3 0.25 0.20 4.7 720 film formation Dδ Initial stage of 5 0.25 5 0.25 0.10 4.7 850 film formation Final stage of 5 0.25 5 0.25 0.10 4.7 850 film formation Eδ Initial stage of 4 0.15 4 0.15 0.20 5.0 900 film formation Final stage of 4 0.15 4 0.15 0.20 5.0 900 film formation
(112) TABLE-US-00022 TABLE 22 Lowermost layer δ (numerical value at the bottom indicates the average target layer thickness of the layer (μm)) Tool (Ti, Al) (C, N) layer body First Second Third Formation X.sub.δavg of X.sub.δavg of Type symbol layer layer layer symbol section 1 section 2 Coated 16 A TiN — — Aδ 0.29 0.52 tools of (0.3) present 17 B TiC TiCN — Bδ 0.24 0.52 invention (0.3) (2.3) 18 C TiCO — — Cδ 0.2 0.31 (0.5) 19 A TiC TiCN TiCNO Dδ 0.22 0.28 (0.2) (2.8) (2.0) 20 B — — — Eδ 0.21 0.28 21 C — — — — — — 22 A — — — — — — 23 B — — — — — — 24 C — — — — — — 25 D — — — — — — Lowermost layer δ (numerical value at the bottom indicates the average targetlayer thickness of the layer (μm)) (Ti, Al) (C, N) layer Average target layer X.sub.δavg of X.sub.δavg of X.sub.δavg of X.sub.δavg of X.sub.δavg of thickness Type section 3 section 4 section 5 section 6 section 7 Y.sub.avg (μm) Coated 16 0.71 — — — — 0.0001 1.0 tools of or less present 17 0.56 0.68 — — — 0.0001 2.0 invention or less 18 0.42 — — — — 0.0048 1.2 19 0.33 0.34 0.35 0.42 0.44 0.0033 5.0 20 0.34 0.38 0.40 — — 0.0033 3.5 21 — — — — — — — 22 — — — — — — — 23 — — — — — — — 24 — — — — — — — 25 — — — — — — —
(113) TABLE-US-00023 TABLE 23 Hard coating layer Lower layer γ Presence or absence of Average Presence or composition Adhesion layer β Tool layer absence of variation (Ti, Al) (C, N) layer body Formation thickness hexagonal of present Formation X.sub.avg of X.sub.avg of X.sub.avg of X.sub.avg of X.sub.avg of X.sub.avg of Type symbol symbol (μm) X.sub.avg Y.sub.avg structure invention symbol section 1 section 2 section 3 section 4 section 5 section 6 Coated 16 A Aγ 20.0 0.94 0.0001 AB AB Aβ 0.8 0.75 0.6 0.57 0.27 — tools of or less present 17 B Bγ 10.0 0.84 0.0001 AB PR Bβ 0.7 0.57 0.54 0.41 0.37 0.23 invention or less 18 C Cγ 7.5 0.67 0.0050 AB AB Cβ 0.75 0.72 0.5 0.44 0.28 0.22 19 A Dγ 10.1 0.63 0.0035 AB AB Dβ 0.6 0.51 0.41 0.3 0.25 20 B Bγ 9.0 0.60 0.0034 AB AB Eβ 0.5 0.35 0.22 — — — 21 C Aγ 7.6 0.92 0.0001 AB AB Aβ 0.74 0.5 0.28 — — — or less 22 A Bγ 5.0 0.83 0.0001 AB PR Bβ 0.63 0.44 0.32 0.24 — — or less 23 B Cγ 4.1 0.68 0.0047 AB AB — — — — — — — 24 C Dγ 4.0 0.63 0.0033 AB AB — — — — — — — 26 A Eγ 6.0 0.60 0.0030 AB AB — — — — — — — Hard coating layer Adhesion layer β Formation symbol of Ti compound TiCN layer and layer (numerical oxygen-containing value at the TiCN layer bottom indicates Average Average the average oxygen oxygen (Ti, Al) (C, N) layer target layer content content Total Upper layer α Average thickness of the at depth at depth average Average layer layer (μm)) up to exceeding layer Chlorine layer X.sub.avg of thickness First Second Third Formation 0.5 μm 0.5 μm thickness Formation content thickness Type section 7 (μm) layer layer layer symbol (at %) (at %) (μm) symbol (at %) (μm) Coated 16 — 3.0 TiN — — A 3.0 0.0* 4.5 A 0.06 3.0 tools of (0.2) present 17 0.22 5.0 TiC — — B 1.6 0.0* 10.0 B 0.07 5.0 invention (0.5) 18 — 4.0 TiC TiCO — A 2.9 0.0* 5.3 C 0.42 10.0 (0.3) (0.4) 19 — 3.0 TiN TiC — B 1.7 0.0* 5.0 D 0.51 2.3 (0.3) (0.5) 20 — 1.8 TiC TiCN TiCO A 2.8 0.0* 4.0 A 0.04 2.0 (0.2) (0.5) (0.5) 21 — 1.0 TiN — — C 2.4 0.0* 3.4 B 0.07 4.0 (0.3) 22 — 2.4 — — — D 0.5 0.0* 5.0 C 0.34 5.0 23 — — — — — C 2.0 0.0* 3.9 D 0.52 3.5 24 — — — — — D 0.7 0.0* 6.9 A 0.04 9.0 26 — — — — — C 2.4 0.0* 3.2 B 0.05 3.5 (Note 1) Any of Xavg and Yavg in boxes indicates atomic ratio. (Note 2) “Presence or absence of hexagonal structure” in boxes indicates “PR (Present)” in a case where crystal grains having a hexagonal structure are contained from diffraction peaks measured by X-ray diffraction, and indicates “AB (Absent)” in a case of a single phase of a cubic structure. (Note 3) “Presence or absence of composition variation of present invention” in boxes indicates “PR (Present)” in a case where crystal grains having a NaCl type face-centered cubic structure in which the angle between the direction in which the period of a periodic composition variation of Ti and Al and the surface perpendicular to the surface of the tool body is 30 degrees or less are present, and indicates “AB (Absent)” in a case where such crystal grains are not present. (Note4) *in boxes indicates that an average oxygen content of 0 at % means that only unavoidable oxygen is determined.
(114) Next, in a state in which each of the coated tools of present invention 16 to 25 was screwed to a tip end portion of an insert holder made of tool steel by a fixing tool, a wet high-speed intermittent cutting test for stainless steel, which will be described below, was conducted thereon, and the flank wear width of a cutting edge was measured.
(115) Work material: a round bar of JIS SUS304 with four longitudinal grooves formed at equal intervals in the longitudinal direction
(116) Cutting speed: 300 m/min
(117) Depth of cut: 1.0 mm
(118) Feed: 0.2 mm/rev
(119) Cutting time: 5 minutes
(120) (a typical cutting speed is 150 m/min)
(121) The results of the cutting test are shown in Table 24.
(122) TABLE-US-00024 TABLE 24 Flank wear width Type (mm) Coated tools of 16 0.13 present invention 17 0.11 18 0.13 19 0.16 20 0.15 21 0.15 22 0.14 23 0.19 24 0.18 25 0.17
(123) From the results shown in Table 24, in the coated tools of present invention, since the lower layer γ has a single phase of a NaCl type cubic structure and thus has high hardness, and furthermore, the oxygen-containing TiCN layer having excellent adhesion to the upper layer α is formed between the upper layer α and the adhesion layer β, which are formed under low temperature conditions, the occurrence of chipping and the occurrence of peeling are suppressed.
(124) Therefore, the coated tools of present invention exhibit excellent wear resistance during long-term use in high-speed intermittent cutting during which intermittent and impact loads are exerted on a cutting edge.
INDUSTRIAL APPLICABILITY
(125) As described above, the coated tool of the present invention exhibits excellent wear resistance during long-term use in high-speed intermittent cutting during which intermittent and impact loads are exerted on a cutting edge and thus sufficiently satisfy an improvement in performance of a cutting device, power saving and energy saving during cutting, and a further reduction in costs.