Surface-coated cutting tool with hard coating layer that exhibits excellent chipping resistance and manufacturing method thereof

Information

  • Patent Grant
  • 10625347
  • Patent Number
    10,625,347
  • Date Filed
    Monday, October 31, 2016
    8 years ago
  • Date Issued
    Tuesday, April 21, 2020
    4 years ago
Abstract
In a hard coating layer that contains at least any of a layer of a complex nitride or a complex carbonitride (composition formula: (Ti1-xAlx)(CyN1-y)) of chemically-vapor-deposited Ti and Al, a layer of a complex nitride or a complex carbonitride (composition formula: (Ti1-α-βAlαMrβ)(CγNi1-γ)) of Ti, Al, and Me, and a layer of a complex nitride or a complex carbonitride (composition formula: (Cr1-pAlp)(CqN1-q) of Cr and Al in a surface-coated cutting tool, some crystal grains that form the layer of a complex nitride or a complex carbonitride have cubic structures, and a predetermined average crystal grain misorientation and inclined angle frequency distribution are present in the crystal grains that have cubic structures.
Description
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This application is a U.S. National Phase Application under 35 U.S.C. § 371 of International Patent Application No. PCT/JP2016/082353 filed on Oct. 31, 2016 and claims the benefit of Japanese Patent Applications No. 2015-214520, filed Oct. 30, 2015, No. 2015-214524, filed Oct. 30, 2015, No. 2015-214527, filed Oct. 30, 2015, and No. 2016-211414, filed Oct. 28, 2016, all of which are incorporated herein by reference in their entireties. The International Application was published in Japanese on May 4, 2017 as International Publication No. WO/2017/073789 under PCT Article 21(2).


FIELD OF THE INVENTION

The present invention relates to a surface-coated cutting tool (hereinafter, referred to as “coated tool”) with a hard coating layer that has excellent chipping resistance and exhibits excellent cutting performance in use over a long period of time in a high-speed intermittent cutting of alloy steel or the like during which high temperature is generated and impact loads are exerted on a cutting edge.


BACKGROUND OF THE INVENTION

In the related art, a coated tool in which a Ti—Al-based or Cr—Al-based complex nitride layer is coated as a hard coating layer on a surface of a tool body that is formed of a tungsten carbide (hereinafter, referred to as WC)-based cemented carbide, titanium carbonitride (hereinafter, referred to as TiCN)-based cermet, or a cubic crystal boron nitride (hereinafter, referred to as cBN)-based ultra-high-pressure sintered body (hereinafter, collectively referred to as a tool body) by a physical vapor deposition method is typically known, and it is known that this exhibits excellent wear resistance.


However, since the coated tool in the related art, in which the Ti—Al-based or Cr—Al-based complex nitride layer is coated, has relatively excellent wear resistance while abnormal wear such as chipping tends to occur in a case in which the coated tool is used under high-speed intermittent cutting conditions, various suggestions have been made to improve the hard coating layer.


For example, Japanese Unexamined Publication No. 2012-20391 discloses a surface-coated cutting tool that can obtain excellent wear resistance and fracture resistance by a configuration in which a hard coating layer is formed on a surface of a tool body, in which the hard coating layer is formed of one layer or a plurality of layers, T1<T2 is satisfied where T1 represents the thickness of the thinnest portion of the hard coating layer at a ridge line portion of a cutting edge, and T2 represents the thickness at a location of 1 mm away from the ridge line of the cutting edge in a rake face direction, Da and Db are inside specific numerical ranges where a represents a location that is a distance Da in the rake face direction from the ridge line of the cutting edge on the surface of the hard coating layer, and b represents a location that is a distance Db in a flank face direction therefrom, and unevenness in a crystal orientation of crystal grains that form the hard coating layer is equal to or greater than 5 degrees and less than 10 degrees in a region corresponding to 10% or more of a region E that occupies the thickness 0.1T1 to 0.9T1 from the surface of the hard coating layer from the location a to the location b.


In addition, Japanese Unexamined Publication No. 2000-144376 discloses that a film with excellent wear resistance, seizure resistance, and oxidation resistance, with a low friction coefficient, and excellent sliding properties is obtained by forming a complex hard film that is formed of at least two kinds of metal nitride from among nitrides of Cr, Ti, Al, and V on the surface of a tool body and setting an intensity ratio I(111)/I(200) between X-ray diffraction peaks I(111) and I(200) of a (111) plane and a (200) plane that are obtained by X-ray diffraction for the hard film to be a value from 3 to 6.


However, there is a disclosure that TiAlN is deposited as the hard coating layer in the aforementioned coated tool while there is neither disclosure nor indication that the content ratio x of Al is set to be equal to or greater than 0.65.


From such a viewpoint, a technology of increasing the content ratio x of Al to about 0.9 by forming the hard coating layer by a chemical vapor deposition method has also been proposed.


For example, Japanese Unexamined Publication No. 2011-516722 describes that it is possible to deposit a (Ti1-xAlx)N layer in which the value of the content ratio x of Al ranges from 0.65 to 0.95 by performing chemical vapor deposition within a temperature range of 650 to 900° C. in mixed reaction gas of TiCl4, AlCl3, and NH3. However, since an Al2O3 layer is further applied onto the (Ti1-xAlx)N layer for the purpose of enhancing a thermal insulation effect, it is not obvious in this document how the formation of the (Ti1-xAlx)N layer in which the value of the content ratio x of Al is increased up to 0.65 to 0.95 affects cutting performance.


In addition, Japanese Unexamined Publication No. 2011-513594, for example, proposes that heat resistance and fatigue strength of a coated tool are improved by coating, as an outer layer, a (Ti1-xAlx)N layer (where an atomic ratio of x ranges from 0.65 to 0.90) with a cubic structure or a hexagonal structure by a chemical vapor deposition method on a TiCN layer and an Al2O3 layer that are inner layers and applying compressive stress of 100 to 1100 MPa to the outer layer.


For example, Japanese Unexamined Publication No. 2006-82207 discloses a surface-coated cutting tool that includes a tool body and a hard coating layer formed on the body thereof, in which wear resistance and oxidation resistance of the hard coating layer are significantly improved due to either or both Al and Cr elements, at least one kind of element selected from a group consisting of Group 4a elements, Group 5a elements, and Group 6a elements in the periodic table and Si, a compound that is formed from at least one kind of element selected from a group consisting of carbon, nitrogen, oxygen, and boron, and chlorine being contained.


For example, Japanese Unexamined Publication No. 2014-208394 proposes that the adhesion strength between a lower layer and an upper layer may be improved, and chipping resistance and wear resistance may thus be improved by providing a hard coating layer that is formed of the lower layer, an intermediate layer, and an upper layer on a surface of a tool body such that the lower layer has a predetermined average layer thickness and is formed of a TiAl compound that has a cubic structure formed of one layer or two or more layers from among a Ti1-xAlxN layer, a Ti1-xAlxC layer, and a Ti1-xAlxCN layer (X is the content ratio (atomic ratio) of Al and satisfies 0.65≤X≤0.95), the intermediate layer has a predetermined average layer thickness and is formed of a CrAl compound that has a cubic structure formed of one layer or two or more layers from among a Cr1-YAlYN layer, a Cr1-YAlYC layer, and a Cr1-YAlYCN layer (Y is the content ratio (atomic ratio) of Al and satisfies 0.60≤Y≤0.90), and upper layer is formed of Al2O3 that has a predetermined average layer thickness, in order to improve the chipping resistance and the wear resistance in a high-speed intermittent cutting of stainless steel, a Ti alloy, or the like.


In addition, Japanese Unexamined Publication No. 2014-198362 proposes that the adhesion strength between a lower layer and an upper layer may be improved, and the upper layer be formed of an Al2O3 layer that has fine pores with a predetermined pore diameter and pore density to alleviate mechanical and thermal impacts, thereby improving chipping resistance and wear resistance, by providing a hard coating layer that is formed of the lower layer, an intermediate layer, and the upper layer on a surface of a tool body such that the lower layer is formed of a Ti compound that has a cubic crystal structure formed of one layer or two or more layers from among a Ti1-xAlxN layer, a Ti1-xAlxC layer, and a Ti1-xAlxCN layer (X is an atomic ratio that indicates a content portion of Al and satisfies 0.65≤X≤0.95) with a predetermined average layer thickness per layer, the intermediate layer is formed of a Cr compound that has a cubic crystal structure formed of one layer or two or more layers from among a Cr1-YAlYN layer, a Cr1-YAlYC layer, and a Cr1-YAlYCN layer (Y is an atomic ratio that indicates the content ratio of Al and satisfies 0.60≤Y≤0.90), and the upper layer is formed of Al2O3 that has fine pores with a predetermined pore diameter and pore density and an average layer thickness, in order to improve the chipping resistance and the wear resistance in a high-speed intermittent cutting of a heat-resistant alloy such as precipitation hardening stainless steel and an Inconel alloy.


Further, Japanese Unexamined Publication No. 2009-56539 proposes that the high-temperature strength of an (Al1-XCrX)N layer may be improved, and fracture resistance of a hard coating layer in a heavy-duty cutting may thus be improved by providing the hard coating layer formed of the (Al1-XCrX)N layer (where X is an atomic ratio and satisfies X=0.3 to 0.6) on the surface of the tool body, and forming a crystal orientation and a constituent atom shared lattice point distribution form such that in an inclined angle frequency distribution graph created by measuring inclined angles formed by normal lines of {100} planes with respect to a normal line of a polished surface as a surface of the tool body, the highest peak is present in an inclined angle section from 30 to 40 degrees and the total frequencies thereof accounts for equal to or greater than 60% with respect to the entire frequencies, and in a constituent atom shared lattice point distribution graph created by measuring inclined angles formed by normal lines of {112} planes with respect to the normal line of the polished surface as a surface, the highest peak is present at Σ3, and the distribution ratio thereof is equal to or greater than 50% with respect to the entire frequencies, in order to enhance fracture resistance of the hard coating layer in heavy-duty cutting of steel or cast iron, in which a large load acts on the cutting edge.


Problems to be Solved by the Invention

Requirements for saving power and energy in a cutting have increased in recent years, which has been accompanied by trends to a higher speed and efficiency in the cutting, and a coated tool has been required to have higher abnormal damage resistance such as chipping resistance, fracture resistance, and peeling resistance and also to have excellent wear resistance for use over a long period of time.


However, since the coated tools described in Japanese Unexamined Publications No. 2012-20391 and No. 2000-144376 described above do not take an increase in the content ratio x of Al in the hard coating layer formed of the (Ti1-xAlx)N layer into consideration, there is a problem that it is not possible to state that the wear resistance and the chipping resistance are sufficient in a case in which the coated tool is used in high-speed intermittent cutting of alloy steel.


Meanwhile, since in the (Ti1-xAlx)N layer deposited by the chemical vapor deposition method described in Japanese Unexamined Publication No. 2011-516722 described above, the content ratio x of Al can be increased and cubic structures are formed, it is possible to obtain a hard coating layer with predetermined hardness and excellent wear resistance. However, there is a problem that toughness is poor.


Furthermore, since the coated tool described in Japanese Unexamined Publication No. 2011-513594 described above has poor toughness although it has predetermined hardness and excellent wear resistance, there is a problem that abnormal damages, such as chipping, fracture, and peeling tend to occur and it is not possible to state that the coated tool exhibits satisfactory cutting performance in a case in which the coated tool is used in a high-speed intermittent cutting or the like of alloy steel.


In addition, although the coated tool described in Japanese Unexamined Publication No. 2006-82207 described above is intended to improve wear resistance and oxidation resistant properties, there is a problem that chipping resistance is not sufficient under cutting conditions with impacts, such as high-speed intermittent cutting.


In addition, since the coated tools described in Japanese Unexamined Publications No. 2014-208394 and No. 2014-198362 described above do not have sufficient strength and hardness for a CrAl compound and Cr compound themselves although the adhesion strength between the lower layer and the upper layer is improved and chipping resistance is enhanced by causing the CrAl compound and the Cr compound to be interposed as the intermediate layer in the hard coating layer, it is not possible to state that chipping resistance and wear resistance are sufficient in a case in which the coated tool is used in a high-speed intermittent cutting.


In addition, since the coated tool described in Japanese Unexamined Publication No. 2009-56539 described above also do not have sufficient strength and hardness for the (Ti1-xAlx)N layer although it is possible to improve the strength of the hard coating layer, and as a result, it is possible to improve chipping resistance and fracture resistance by adjusting the content ratio of Cr in the hard coating layer formed of (Ti1-xAlx) N and controlling a crystal orientation and a constituent atom shared lattice point distribution form, there is a problem that the coated tool may not exhibit excellent chipping resistance and wear resistance in use over a long period of time and a tool life for high-speed intermittent cutting of alloy steel may be short.


Thus, a technical problem to be solved by the present invention, namely an object of the present invention is to provide a coated tool that has excellent toughness and exhibits excellent chipping resistance and wear resistance in use over a long period of time even in a case in which the coated tool is used in high-speed intermittent cutting of carbon steel, alloy steel, cast iron, or the like.


SUMMARY OF THE INVENTION
Means for Solving the Problems

Thus, the present inventors has gained the following knowledge as a result of extensive research to improve chipping resistance and wear resistance of a coated tool in which a hard coating layer that contains at least a complex nitride or a complex carbonitride of Ti and Al (hereinafter, also referred to as “(Ti, Al)(C, N)” or “(Ti1-xAlx)(CyN1-y)” in some cases) and a complex nitride or a complex carbonitride of Cr and Al (hereinafter, also referred to as “(Cr, Al)(C, N) or (Cr1-pAlp)(CqN1-q)” in some cases) is deposited, from the aforementioned viewpoint.


That is, a hard coating layer that includes at least one (Ti1-xAlx)(CyN1-y) layer and one (Cr1-pAlp)(CqN1-q) layer and has a predetermined average layer thickness has high wear resistance in a case in which the (Ti1-xAlx)(CyN1-y) layer and the (Cr1-pAlp)(CqN1-q) layer are formed into columnar shapes in a direction perpendicular to the tool body. On the other hand, toughness of the (Ti1-xAlx)(CyN1-y) layer and the (Cr1-pAlp)(CqN1-q) layer decreases as anisotropy of the (Ti1-xAlx)(CyN1-y) layer and the (Cr1-pAlp)(CqN1-q) layer increases. As a result, chipping resistance and fracture resistance decrease, sufficient wear resistance cannot be exhibited in use over a long period of time, and it is not possible to state that the tool life is satisfactory.


Thus, the present inventors have found new knowledge that it is possible to successfully improve both hardness and toughness by causing strain in crystal grains that have NaCl-type face-centered cubic structures (hereinafter, also simply referred to as “cubic structures”) and to improve chipping resistance and fracture resistance of the hard coating layer as a result on the basis of the following completely new ideas (1) to (3), as a result of intensive studies regarding the (Ti1-xAlx)(CyN1-y) layer and the (Cr1-pAlp)(CqN1-q) layer that form the hard coating layer.


(1) An idea that the (Ti1-xAlx)(CyN1-y) layer that is a complex nitride or a complex carbonitride of Ti and Al contains crystal grains that have NaCl-type face-centered cubic structures and average crystal grain misorientations of the crystal grains that have cubic structures are set to be equal to or greater than 2 degrees.


(2) An idea that the hard coating layer is caused to contain one kind of element (hereinafter, referred to as “Me” selected from Si, Zr, B, V, and Cr, the (Ti1-α-βAlα)(CγN1-γ) layer which is a complex nitride or a complex carbonitride of Ti, Al, and Me contains crystal grains that have NaCl-type face-centered cubic structures, and the average crystal grain misorientations of the crystal grains that have a cubic structure are set to be equal to or greater than 2 degrees.


(3) An idea that the (Cr1-pAlp)(CqN1-q) layer that is a complex nitride or a complex carbonitride of Cr and Al contains crystal grains that have NaCl-type face-centered cubic structure, and the average crystal grain misorientations of the crystal grains that have a cubic structures are set to be equal to or greater than 2 degrees.


Further, the present inventors have found new knowledge that a higher ratio of the {111} orientation on the side of the film surface than on the side of the surface of the tool body in the columnar-shaped crystal grain causes further improvement in toughness.


Specifically, the present inventors have found that in a case in which the hard coating layer:


(1) contains at least a layer of a complex nitride or a complex carbonitride of Ti and Al and is represented by a composition formula: (Ti1-xAlx)(CyN1-y), particularly, and the average content ratio xavg of Al with respect to the total amount of Ti and Al and the average content ratio of C with respect to the total amount of C and N (where both xavg and yavg are atomic ratios) satisfy 0.60≤xavg≤0.95 and 0≤yavg≤0.005, respectively, it is possible to cause strain in crystal grains that have a cubic structures when some crystal grains that form the layer of a complex nitride or a complex carbonitride have cubic structure, and crystal grains with average crystal grain misorientations of equal to or greater than 2 degrees are present at an area ratio of 20% or greater in the layer of a complex nitride or a complex carbonitride in a case in which the crystal orientations of the crystal grains are analyzed in a vertical sectional direction by using an electron backscatter diffraction apparatus, and the average crystal grain misorientations of the individual crystal grains are obtained;


(2) contains at least a layer of a complex nitride or a complex carbonitride of Ti, Al, and Me (where Me is one kind of element selected from Si, Zr, B, V, and Cr) and is represented by a composition formula: (Ti1-α-βAlαMeβ)(CγN1-γ), particularly, when an average content ratio αavg of Al with respect to the total amount of Ti, Al, and Me, an average content ratio βavg of Me with respect to the total amount of Ti, Al and Me, and an average content ratio γavg of C with respect to the total amount of C and N (where all of αavg, βavg and γavg are atomic ratios) satisfy 0.60≤αavg, 0.005≤βavg≤0.10, 0≤γavg≤0.005, and 0.605≤αavgavg≤0.95, respectively, it is possible to cause strain in crystal grains that have cubic structures when some crystal grains that form the layer of a complex nitride or a complex carbonitride have cubic structures and crystal grains with average crystal grain misorientations of equal to or greater than 2 degrees are present at an area ratio of 20% or greater in the layer of a complex nitride or a complex carbonitride in a case in which the crystal orientations of the crystal grains are analyzed in the vertical sectional direction by using an electron backscatter diffraction apparatus, and the average crystal grain misorientations of the individual crystal grains are obtained; and


(3) contains at least a layer of a complex nitride or a complex carbonitride of Cr and Al and is represented by a composition formula: (Cr1-pAlp)(CqN1-q), particularly, when an average content ratio pavg of Al with respect to the total amount of Cr and Al and an average content ratio qavg of C with respect to the total amount of C and N (where both pavg and qavg are atomic ratios) satisfy 0.70≤pavg≤0.95 and 0≤qavg≤0.005, respectively, it is possible to cause strain in crystal grains that have cubic structures when some crystal grains that form the layer of a complex nitride or a complex carbonitride have cubic structures, and crystal grains with average crystal grain misorientations of equal to or greater than 2 degrees are present at an area ratio of 20% or greater in the layer of a complex nitride or a complex carbonitride in a case in which the crystal orientations of the crystal grains are analyzed in the vertical sectional direction by using an electron backscatter diffraction apparatus and the average crystal grain misorientations of the individual crystal grains are obtained, and


(4) further, in any of (1) to (3) described above, toughness is improved by setting a higher ratio of the {111} orientation of the crystal grains on the side of the film surface than on the side of the surface of the tool body.


As a result, the present inventors have found that a cutting tool with such a hard coating layer formed thereon has improved chipping resistance and fracture resistance and exhibits excellent wear resistance over a long period of time.


Further, the (Ti1-xAlx)(CyN1-y) layer, the (Ti1-α-βAlαMeβ)(CγN1-γ) layer, and the (Cr1-pAlp)(CqN1-q) layer with the aforementioned configurations can be formed by the following chemical vapor deposition methods, in which a reaction gas composition is periodically changed on the surface of the tool body, for example.


(1) Concerning (Ti1-xAlx)(CyN1-y) Layer


A gas group A consisting of NH3, N2, and H2 and a gas group B consisting of TiCl4, Al(CH3)3, AlCl3, N2, and H2 are supplied to a reactor of a chemical vapor deposition reaction apparatus which is to beused from separate gas supply tubes. The gas group A and the gas group B are supplied into the reaction apparatus such that the gas flows over time intervals with a specific cycle for a shorter time than the cycle and a phase difference in a shorter time than the gas supply time occurs in the gas supply of the gas group A and the gas group B, thereby temporarily changing the reaction gas composition on the surface of the tool body among the gas group A, mixed gas of the gas group A and the gas group B, and the gas group B. Incidentally, there is no need to introduce a gas discharge process over a long time intended to strictly substitute the gas in the present invention. Therefore, it is also possible to realize a gas supply method by rotating a gas supply port, rotating a tool body, or reciprocating the tool body to temporarily change the reaction gas composition on the surface of the tool body among mixed gas mainly containing the gas group A (first reaction gas), mixed gas of the gas group A and the gas group B (second reaction gas), and mixed gas mainly containing the gas group B (third reaction gas).


The (Ti1-xAlx)(CyN1-y) layer with a predetermined target layer thickness is formed by performing a thermal CVD method on the surface of the tool body for a predetermined time by setting the reaction gas composition (% by volume with respect to the total of the gas group A and the gas group B) to NH3: 1.0 to 1.5%, N2: 1.0 to 2.0%, and H2: 55 to 60% as the gas group A, AlCl3: 0.6 to 0.9%, TiCl4: 0.2 to 0.3%, Al(CH3)3: 0 to 0.5%, N2: 12.5 to 15.0%, and H2: the remaining amount as the gas group B, for example, under conditions of a reaction atmosphere pressure: 4.5 to 5.0 kPa, a reaction atmosphere temperature: 700 to 900° C., a supply cycle: 1 to 5 seconds, a gas supply time per cycle: 0.15 to 0.25 seconds, and a supply phase difference between the gas group A and the gas group B: 0.10 to 0.20 seconds.


Then, local strain in crystal lattice is formed in the crystal grains due to introduction of local unevenness in composition, dislocation, and point defect, and it is possible to change degrees of {111} orientation of the crystal grains on the side of the surface of the tool body and on the side of the film surface, by supplying the gas group A and the gas group B such that a difference occurs between a time at which the gas group A reaches the surface of the tool body and a time at which the gas group B reaches the surface of the tool body, setting NH3: 1.0 to 1.5% as a nitrogen raw material gas in the gas group A, and setting AlCl3: 0.6 to 0.9%, TiCl4: 0.2 to 0.3%, and Al(CH3)3: 0 to 0.5% as metal chloride raw materials or carbon raw materials in the gas group B as described above. It has been found that as toughness is significantly improved while wear resistance is maintained as a result. The present inventors have found that as a result, fracture resistance and chipping resistance, in particular, are improved while wear resistance is maintained, and the hard coating layer can exhibit an excellent cutting performance in use for a long period of time even in a case in which the coated tool is used in a high-speed intermittent cutting of alloy steel or the like in which an intermittent and impact load are exterted on the cutting edge.


(2) Concerning (Ti1-α-βAlαMeβ)(CγN1-γ)


A gas group A consisting of NH3, N2, and H2 and a gas group B consisting of TiCl4, Al(CH3)3, AlCl3, MeCln (chloride of Me), N2, and H2 are supplied to a reactor of a chemical vapor deposition reaction apparatus which is to be used from separate gas supply tubes. The gas group A and the gas group B are supplied into the reaction apparatus such that the gas flows over time intervals with a specific cycle for a shorter time than the cycle and a phase difference in a shorter time than the gas supply time occurs in the gas supply of the gas group A and the gas group B, thereby temporarily changing the reaction gas composition on the surface of the tool body among the gas group A, mixed gas of the gas group A and the gas group B, and the gas group B. Incidentally, there is no need to introduce a gas discharge process over a long time intended to strictly substitute the gas in the present invention. Therefore, it is also possible to realize a gas supply method by rotating a gas supply port, rotating a tool body, or reciprocating the tool body to temporarily change the reaction gas composition on the surface of the tool body among mixed gas mainly containing the gas group A (first reaction gas), mixed gas of the gas group A and the gas group B (second reaction gas), and mixed gas mainly containing the gas group B (third reaction gas).


The (Ti1-α-βAlαMeβ)(CγN1-γ) layer with a predetermined target layer thickness is formed by performing a thermal CVD method on the surface of the tool body for a predetermined time by setting the reaction gas composition (% by volume with respect to the total of the gas group A and the gas group B) to NH3: 1.0 to 1.5%, N2: 1.0 to 2.0%, and H2: 55 to 60% as the gas group A, AlCl3: 0.6 to 0.9%, TiCl4: 0.2 to 0.3%, MeCln (chloride of Me): 0.1 to 0.2%, Al(CH3)3: 0 to 0.5%, N2: 12.5 to 15.0%, and H2: the remaining amount as the gas group B, for example, under conditions of a reaction atmosphere pressure: 4.5 to 5.0 kPa, a reaction atmosphere temperature: 700 to 900° C., a supply cycle: 1 to 5 seconds, a gas supply time per cycle: 0.15 to 0.25 seconds, and a supply phase difference between the gas group A and the gas group B: 0.10 to 0.20 seconds.


Thus, local strain in crystal lattice is formed in the crystal grains due to introduction of local unevenness in composition, dislocation, and point defect, and it is possible to change degrees of {111} orientation of the crystal grains on the side of the surface of the tool body and on the side of the film surface, by supplying the gas group A and the gas group B such that a difference occurs between a time at which the gas group A reaches the surface of the tool body and a time at which the gas group B reaches the surface of the tool body, setting NH3: 1.0 to 1.5% as a nitrogen raw material gas in the gas group A, and setting AlCl3: 0.6 to 0.9%, TiCl4: 0.2 to 0.3%, MeCln (chloride of Me): 0.1 to 0.2%, and Al(CH3)3: 0 to 0.5% as metal chloride raw materials or carbon raw materials in the gas group B as described above. The present inventors have found that as a result, toughness is significantly improved. The present inventors have found that as a result, the hard coating layer can exhibit an excellent cutting performance in use for a long period of time even in a case in which the coated tool is used in a high-speed intermittent cutting of alloy steel or the like in which an intermittent and impact load are exterted on the cutting edge.


(3) Concerning (Cr1-pAlp)(CqN1-q) Layer


A gas group A consisting of NH3, N2, and H2 and a gas group B consisting of CrCl3, AlCl3, Al(CH3)3, N2, and H2 are supplied to a reactor of a chemical vapor deposition reaction apparatus used from separate gas supply tubes. The gas group A and the gas group B are supplied into the reaction apparatus such that the gas flows over time intervals with a specific cycle for a shorter time than the cycle and a phase difference in a shorter time than the gas supply time occurs in the gas supply of the gas group A and the gas group B, thereby temporarily changing the reaction gas composition on the surface of the tool body among the gas group A, mixed gas of the gas group A and the gas group B, and the gas group B. Incidentally, there is no need to introduce a gas discharge process over a long time intended to strictly substitute the gas in the present invention. Therefore, it is also possible to realize a gas supply method by rotating a gas supply port, rotating a tool body, or reciprocating the tool body to temporarily change the reaction gas composition on the surface of the tool body among mixed gas mainly containing the gas group A (first reaction gas), mixed gas of the gas group A and the gas group B (second reaction gas), and mixed gas mainly containing the gas group B (third reaction gas).


The (Cr1-pAlp)(CqN1-q) layer with a predetermined target layer thickness is formed by performing a thermal CVD method on the surface of the tool body for a predetermined time by setting the reaction gas composition (% by volume with respect to the total of the gas group A and the gas group B) to NH3: 1.0 to 1.5%, N2: 1.0 to 2.0%, and H2: 55 to 60% as the gas group A, AlCl3: 0.6 to 0.9%, CrCl3: 0.2 to 0.3%, Al(CH3)3: 0 to 0.5%, N2: 12.5 to 15.0%, and H2: the remaining amount as the gas group B, for example, under conditions of a reaction atmosphere pressure: 4.5 to 5.0 kP, a reaction atmosphere temperature: 750 to 900° C., a supply cycle: 1 to 5 seconds, a gas supply time per cycle: 0.15 to 0.25 seconds, and a supply phase difference between the gas group A and the gas group B: 0.10 to 0.20 seconds.


Thus, local strain in crystal lattice is formed in the crystal grains due to introduction of local unevenness in composition, dislocation, and point defect, and it is possible to change degrees of {111} orientation of the crystal grains on the side of the surface of the tool body and on the side of the film surface, by supplying the gas group A and the gas group B such that a difference occurs between a time at which the gas group A reaches the surface of the tool body and a time at which the gas group B reaches the surface of the tool body, setting NH3: 1.0 to 1.5% as a nitrogen raw material gas in the gas group A, and setting AlCl3: 0.6 to 0.9%, CrCl3: 0.2 to 0.3%, and Al(CH3)3: 0 to 0.5% as metal chloride raw materials or carbon raw materials in the gas group B as described above. The present inventors have found that as a result, toughness is significantly improved while wear resistance is maintained. The present inventors have found that as a result, fracture resistance and chipping resistance, in particular, are improved, and the hard coating layer can exhibit an excellent cutting performance in use for a long period of time even in a case in which the coated tool is used in a high-speed intermittent cutting of alloy steel or the like in which an intermittent and impact load are exterted on the cutting edge.


The present invention has been made on the basis of the aforementioned knowledge and has aspects described below.


(1) A surface-coated cutting tool in which a hard coating layer is formed on a surface of a tool body that is formed of any of tungsten-carbide-based cemented carbide, titanium-carbonitride-based cermet, and a cubic boron-nitride-based ultra-high-pressure sintered body, wherein


(a) the hard coating layer contains at least any of a layer of a complex nitride or a complex carbonitride of Ti and Al or a layer of a complex nitride or a complex carbonitride of Ti, Al, and Me (where Me is one kind of element selected from Si, Zr, B, V, and Cr), or a layer of a complex nitride or a complex carbonitride of Cr and Al, with an average layer thickness of 2 to 20 μm,


(b) the layer of a complex nitride or a complex carbonitride contains at least a phase of a complex nitride or a complex carbonitride that has an NaCl-type face-centered cubic structure,


(c) in a case in which crystal orientations of crystal grains that have NaCl-type face-centered cubic structures from among crystal grains that form the layer of a complex nitride or a complex carbonitride are analyzed in a vertical sectional direction by using an electron backscatter diffraction apparatus, and average crystal grain misorientations in the individual crystal grains are obtained, crystal grains with average crystal grain misorientations of 2 degrees or more are present at an area ratio of 20% with respect to the entire area of the layer of a complex nitride or a complex carbonitride,


(d) further, in a case in which inclined angles formed by normal lines of {111} planes, which are crystal plane, with respect to a normal line direction of a surface of a tool body of the crystal grains are measured in a region on a side of the tool body and a region on a side of the surface obtained by equally dividing the layer of a complex nitride or a complex carbonitride into two regions in a layer thickness direction, and frequencies at which measured inclined angles within a range of 0 to 45 degrees with respect to the normal line direction are present from among the measured inclined angles in the respective sections obtained by dividing the inclined angles into each pitch of 0.25 degrees are aggregated,

    • in a case where a ratio of total frequencies of the presence in a range of 0 to 12 degrees with respect to the entire frequencies in inclined angle frequency distribution is set as be Mdeg, Mdeg ranges from 10 to 40% in the region on the side of the tool body, and
    • in a case where a highest peak is present in an inclined angle section within a range of 0 to 12 degrees in a region on the side of the surface, a ratio of total frequencies of the presence in the range of 0 to 12 degrees with respect to the entire frequencies in inclined angle frequency distribution is set as be Ndeg, Ndeg is Mdeg+10 to Mdeg+30%.


(2) The surface-coated cutting tool according to (1), in which the layer of a complex nitride or a complex carbonitride is a layer of a complex nitride or a complex carbonitride of Ti and Al, and in a case in which a composition thereof is represented by a composition formula: (Ti1-xAlx)(CyN1-y), an average content ratio xavg of Al with respect to the total amount of Ti and Al and an average content ratio yavg of C with respect to the total amount of C and N (where both xavg and yavg are atomic ratios) in the layer of a complex nitride or a complex carbonitride satisfy 0.60≤xavg≤0.95 and 0≤yavg≤0.005, respectively.


(3) The surface-coated cutting tool according to (1), in which the layer of a complex nitride or a complex carbonitride is a layer of a complex nitride or a complex carbonitride of Ti, Al, and Me (where Me is one kind of element selected from Si, Zr, B, V, and Cr), and in a case in which a composition thereof is represented by a composition formula: (Ti1-α-βAlαMeβ)(CγN1-γ), an average content ratio αavg of Al with respect to the total amount of Ti, Al, and Me, an average content ratio βavg of Me with respect to the total amount of Ti, Al, and Me, and an average content ratio γavg of C with respect to the total amount of C and N (where all of αavg, βavg and γavg are atomic ratios) in the layer of a complex nitride or a complex carbonitride satisfy 0.60≤αavg, 0.005≤βavg≤0.10, 0≤γavg≤0.005, and 0.605≤αavgavg≤0.95, respectively.


(4) The surface-coated cutting tool according to (1), in which the layer of a complex nitride or a complex carbonitride is a layer of a complex nitride or a complex carbonitride of Cr and Al, and in a case in which a composition thereof is represented by a composition formula: (Cr1-pAlp)(CqN1-q), an average content ratio pavg of Al with respect to the total amount of Cr and Al and an average content ratio qavg of C with respect to the total amount of C and N (where both pavg and qavg are atomic ratios) in the layer of a complex nitride or a complex carbonitride satisfy 0.70≤pavg≤0.95 and 0≤qavg≤0.005, respectively.


(5) The surface-coated cutting tool according to any one of (1) to (4), in which the layer of a complex nitride or a complex carbonitride contains at least 70% by area or more of a phase of a complex nitride or a complex carbonitride that has an NaCl-type face-centered cubic structure.


(6) The surface-coated cutting tool according to any one of (1) to (5), in which in a case where the layer of a complex nitride or a complex carbonitride is observed in a vertical sectional direction of the layer, the layer of a complex nitride or a complex carbonitride has a columnar structure in which an average crystal grain width W ranges from 0.1 to 2 μm and an average aspect ratio A ranges from 2 to 10 of the individual crystal grains that have NaCl-type face-centered cubic structures.


(7) The surface-coated cutting tool according to any one of (1) to (6), in which a lower layer that is formed of a Ti compound layer including one layer or two or more layers from among a carbide layer, a nitride layer, a carbonitride layer, a oxycarbide layer, and a oxycarbonitride layer of Ti and that has a total average layer thickness of 0.1 to 20 μm is present between the tool body and the layer of a complex nitride or a complex carbonitride.


(8) The surface-coated cutting tool according to any one of (1) to (7), in which an upper layer that contains at least an aluminum oxide layer and has a total average layer thickness of 1 to 25 μm is formed above the layer of a complex nitride or a complex carbonitride.


(9) A manufacturing method of the surface-coated cutting tool according to any one of (1) to (8), comprising: forming the layer of a complex nitride or a complex carbonitride by a chemical vapor deposition method in which at least trimethyl aluminum is contained as a reaction gas component.


Note that the “average crystal grain misorientation” means a value of grain orientation spread (GOS), which will be described later.


Effects of the Invention

By configuring a surface-coated cutting tool in which a hard coating layer is formed on a surface of a tool body according to an aspect of the present invention (hereinafter, referred to as “the surface-coated cutting tool according to the present invention” or “the cutting tool according to the present invention”) such that the hard coating layer contains at least any of a layer of a complex nitride or a complex carbonitride of Ti and Al or a layer of a complex nitride or a complex carbonitride of Ti, Al, and Me (where Me is one kind of element selected from Si, Zr, B, V, and Cr), or a layer of a complex nitride or a complex carbonitride of Cr and Al, with an average layer thickness of 2 to 20 μm, and in a case in which some crystal grains that form the layer of a complex nitride or a complex carbonitride have cubic structures, crystal orientations of crystal grains that have cubic structures from among crystal grains that form the layer of a complex nitride or a complex carbonitride are analyzed in a vertical sectional direction by using an electron backscatter diffraction apparatus, and average crystal grain misorientations in the individual crystal grains are obtained, crystal grains with average crystal grain misorientations of 2 degrees or more are present at an area ratio of 20% with respect to the entire area of the layer of a complex nitride or a complex carbonitride, further, in a case in which inclined angles formed by normal lines of {111} planes, which are crystal planes, with respect to a normal line direction of a surface of a tool body of the crystal grains are measured in a region on a side of the tool body and a region on a side of the surface obtained by equally dividing the layer of a complex nitride or a complex carbonitride into two regions in a layer thickness direction, and frequencies at which measured inclined angles within a range of 0 to 45 degrees with respect to the normal line direction are present from among the measured inclined angles in the respective sections obtained by dividing the inclined angles into each pitch of 0.25 degrees are aggregated, a) Mdeg ranges from 10 to 40% when a ratio of total frequencies of the presence in a range of 0 to 12 degrees with respect to the entire frequencies in inclined angle frequency distribution is set as be Mdeg, and b) Ndeg is Mdeg+10 to Mdeg+30% when a highest peak is present in an inclined angle section within a range of 0 to 12 degrees in a region on the side of the surface, and a ratio of total frequencies of the presence in the range of 0 to 12 degrees with respect to the entire frequencies in inclined angle frequency distribution is set as be Ndeg, and in a case in which the layer of a complex nitride or a complex carbonitride is observed from the side of the film section, the layer of a complex nitride or a complex carbonitride has a columnar structure in which an average crystal grain width W ranges from 0.1 to 2 μm and an average aspect ratio A ranges from 2 to 10 of the individual crystal grains that have NaCl-type face-centered cubic structures, strain occurs in the crystal grains that have cubic structures, and grain boundary slipping of the crystal grains is suppressed due to an increase in degrees of the {111) orientation. Therefore, the hardness and toughness of the crystal gains are improved. As a result, an effect that chipping resistance is improved without degrading wear resistance is achieved, the hard coating layer exhibits a superior cutting performance in use over a long period of time, and a long life of the coated tool is achieved, as compared with the hard coating layer in the related art.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is an explanatory outline diagram showing a method of measuring an average crystal grain misorientation of a crystal grain that has an NaCl-type face-centered cubic structure (cubic crystal) in a layer of a complex nitride or a complex carbonitride of Ti and Al, Ti, Al and Me, or Cr and Al in a coated tool according to the present invention.



FIG. 2 is a film configuration diagram schematically showing a section of a layer of a complex nitride or a complex carbonitride of Ti and Al, Ti, Al and Me, or Cr and Al, which forms a hard coating layer in a surface-coated cutting tool according to the present invention.



FIG. 3 shows an example of histogram regarding an area ratio of average crystal grain misorientations (GOS values) of the individual crystal grains that have cubic structures in a section of the layer of the complex nitride or the complex carbonitride of Ti and Al, which forms a hard coating layer in the coated tool according to the present invention. The dotted line in the vertical direction in the histogram represents a boundary at which the average crystal grain misorientation is 2°, and the bars on the right side of the dotted line in the vertical direction in FIG. 3 represent those with an average crystal grain misorientation of equal to or greater than 2°.



FIG. 4 shows an example of histogram regarding an area ratio of average crystal grain misorientations (GOS values) of the individual crystal grains that have cubic structures in a section of a layer of a complex nitride or a layer of a complex carbonitride of Ti and Al that forms a hard coating layer in a coated tool according to a comparative example. The dotted line in the vertical direction in the histogram represents a boundary at which the average crystal grain misorientation is 2°, and the bars on the right side of the dotted line in the vertical direction in FIG. 4 represent those with the average crystal grain misorientation of equal to or greater than 2°.



FIG. 5 shows an example of an inclined angle frequency distribution graph of a created {111} plane in a region on a side of a tool body of a layer of a complex nitride or a complex carbonitride of Ti and Al, which forms a hard coating layer in the coated tool according to the present invention. An aggregation frequency is represented by a relative value standardized on the assumption that the maximum aggregation frequency is 100.



FIG. 6 shows an inclined angle frequency distribution graph of a created {111} plane in a region on a side of a surface of a layer of a complex nitride or a complex carbonitride of Ti and Al, which forms a hard coating layer in the coated tool according to the present invention. The aggregation frequency is represented by a relative value standardized on the assumption that the maximum aggregation frequency is 100.



FIG. 7 shows an example of histogram regarding an area ratio of average crystal grain misorientations (GOS values) of the individual crystal grains that have cubic structures in a section of a layer of a complex nitride or a layer of a complex carbonitride of Ti, Al, and Me, which forms a hard coating layer in the coated tool according to the present invention. The dotted line in the vertical direction in the histogram represents a boundary at which the average crystal grain misorientation is 2°, and the bars on the right side of the dotted line in the vertical direction in FIG. 7 represent those with the average crystal grain misorientation of equal to or greater than 2°.



FIG. 8 shows an example of histogram regarding an area ratio of average crystal grain misorientations (GOS values) of the individual crystal grains that have cubic structures in a section of a layer of a complex nitride or a layer of a complex carbonitride of Ti, Al and Me, which forms a hard coating layer in a coated tool according to a comparative example. The dotted line in the vertical direction in the histogram represents a boundary at which the average crystal grain misorientation is 2°, and the bars on the right side of the dotted line in the vertical direction in FIG. 8 represent those with the average crystal grain misorientation of equal to or greater than 2°.



FIG. 9 shows an example of an inclined angle frequency distribution graph of a created {111} plane in a region on a side of a tool body of a layer of a complex nitride or a complex carbonitride of Ti and Al, which forms a hard coating layer in the coated tool according to the present invention. The aggregation frequency is represented by a relative value standardized on the assumption that the maximum aggregation frequency is 100.



FIG. 10 shows an example of an inclined angle frequency distribution graph of a created {111} plane in a region on a side of a surface of a layer of a complex nitride or a complex carbonitride of Ti, Al, and Me, which forms a hard coating layer in the coated tool according to the present invention. The aggregation frequency is represented by a relative value standardized on the assumption that the maximum aggregation frequency is 100.



FIG. 11 shows an example of histogram regarding an area ratio of average crystal grain misorientations (GOS values) of the individual crystal grains that have cubic structures in a section of a layer of a complex nitride or a layer of a complex carbonitride of Cr and Al, which forms a hard coating layer in the coated tool according to the present invention. The dotted line in the vertical direction in the histogram represents a boundary at which the average crystal grain misorientation is 2°, and the bars on the right side of the dotted line in the vertical direction in FIG. 11 represent those with the average crystal grain misorientation of equal to or greater than 2°.



FIG. 12 shows an example of histogram regarding an area ratio of average crystal grain misorientations (GOS values) of the individual crystal grains that have cubic structures in a section of a layer of a complex nitride or a layer of a complex carbonitride of Cr and Al, which forms a hard coating layer in a coated tool according to a comparative example. The dotted line in the vertical direction in the histogram represents a boundary at which the average crystal grain misorientation is 2°, and the bars on the right side of the dotted line in the vertical direction in FIG. 12 represent those with the average crystal grain misorientation of equal to or greater than 2°.



FIG. 13 shows an example of an inclined angle frequency distribution graph of a created {111} plane in a region on a side of a tool body of a layer of a complex nitride or a complex carbonitride of Cr and Al, which forms a hard coating layer in the coated tool according to the present invention. The aggregation frequency is represented by a relative value standardized on the assumption that the maximum aggregation frequency is 100.



FIG. 14 shows an example of an inclined angle frequency distribution graph of a created {111} plane in a region on a side of a surface of a layer of a complex nitride or a complex carbonitride of Cr and Al, which forms a hard coating layer in the coated tool according to the present invention. The aggregation frequency is represented by a relative value standardized on the assumption that the maximum aggregation frequency is 100.





DETAILED DESCRIPTION OF THE INVENTION

Embodiments to implement the present invention will be described below.


Average Layer Thickness of Layer of a Complex Nitride or a Complex Carbonitride that Forms Hard Coating Layer:


A hard coating layer that has a surface-coated cutting tool according to the present invention contains at least any of a layer of a complex nitride or a complex carbonitride of chemically-vapor-deposited Ti and Al (composition formula: (Ti1-xAlx)(CyN1-y)), a layer of a complex nitride or a complex carbonitride of Ti, Al, and Me (composition formula: (Ti1-α-βAlαMeβ)(CγN1-γ)), or a layer of a complex nitride or a complex carbonitride of Cr and Al (composition formula: (Cr1-pAlp)(CqN1-q)). This layer of a complex nitride or a complex carbonitride has high hardness and excellent wear resistance, and effects are significantly exhibited especially when an average layer thickness ranges from 2 to 20 μm. This is because it is not possible to sufficiently secure wear resistance in use over a long period of time when the average layer thickness is less than 2 μm that is thin, and meanwhile, the crystal grains in the layer of a complex nitride or a complex carbonitride tend to become coarse and chipping tends to occur when the average layer thickness exceeds 20 μm. Therefore, the average layer thickness is defined as 2 to 20 μm.


Composition of layer of a complex nitride or a complex carbonitride that forms hard coating layer:


(1) Concerning Complex Nitride or Complex Carbonitride of Ti and Al According to the Present Invention


In a case in which the composition is represented by a composition formula: (Ti1-xAlx)(CyN1-y), it is preferable that an average content ratio xavg of Al with respect to the total amount of Ti and Al and an average content ratio yavg of C with respect to the total amount of C and N (where both xavg and yavg are atomic ratios) satisfy 0.60≤xavg≤0.95 and 0≤yavg≤0.005, respectively.


This is because wear resistance is not sufficient in a case in which the coated tool is used in high-speed intermittent cutting of alloy steel or the like since the layer of a complex nitride or a complex carbonitride of Ti and Al has poor hardness when the average content ratio xavg of Al is less than 0.60. Meanwhile, the average content ratio xavg of Al exceeding 0.95 brings about a relative decrease in the content ratio of Ti, thus leads to embrittlement, and degrades chipping resistance. Therefore, the average content ratio xavg of Al is defined as 0.60≤xavg≤0.95.


In addition, when the content ratio (atomic ratio) yavg of the C component included in the layer of a complex nitride or a complex carbonitride is low and within a range of 0≤yavg≤0.005, adhesion between the layer of a complex nitride or a complex carbonitride and a tool body or a lower layer is increased, and lubricity is increased, thereby alleviating impacts at the time of cutting, and improving fracture resistance and chipping resistance of the layer of a complex nitride or a complex carbonitride as a result. Meanwhile, it is not preferable that the average content ratio yavg of the C component deviate from the range of 0≤yavg≤0.005 since toughness of the layer of a complex nitride or a complex carbonitride is then degraded, and fracture resistance and chipping resistance are thus degraded in an opposite manner Therefore, the average content ratio yavg of the C component is defined as 0≤yavg≤0.005.


(2) Concerning Complex Nitride or Complex Carbonitride of Ti, Al, and Me According to the Present Invention


In a case in which the composition is represented by a composition formula: (Ti1-α-βAlαMeβ)(CγN1-γ) (where Me is one kind of element selected from Si, Zr, B, V, and Cr), it is preferable to control average content ratios such that an average content ratio αavg of Al with respect to the total amount of Ti, Al, and Me, an average content ratio βavg of Me with respect to the total amount of Ti, Al, and Me, and an average content ratio γavg of C with respect to the total amount of C and N (where all of a αavg, βavg and γavg are atomic ratios) satisfy 0.60≤αavg, 0.005≤βavg≤0.10, 0≤γavg≤0.005, and 0.605≤αavgavg≤0.95.


This is because hardness of the layer of a complex nitride or a complex carbonitride of Ti, Al and Me is degraded when the average content ratio αavg of Al is less than 0.60, and wear resistance is thus not sufficient in a case in which the coated tool is used in high-speed intermittent cutting of alloy steel or the like.


Since hardness of the layer of a complex nitride or a complex carbonitride of Ti, Al, and Me is degraded when the average content ratio βavg of Me is less than 0.005, wear resistance is not sufficient in a case in which the coated tool is used in high-speed intermittent cutting of alloy steel or the like. Meanwhile, when the average content ratio βavg of Me exceeds 0.10, toughness of the layer of a complex nitride or a complex carbonitride of Ti, Al, and Me is degraded due to segregation or the like of Me at the grain boundaries, and chipping resistance is not sufficient in a case in which the coated tool is used in high-speed intermittent cutting of alloy steel or the like. Therefore, the average content ratio βavg of Me is defined as 0.005≤βavg≤0.10.


Meanwhile, when the sum αavgavg of the average content ratio αavg of Al and the average content ratio βavg of Me is less than 0.605, hardness of the layer of a complex nitride or a complex carbonitride of Ti, Al and Me is degraded, and wear resistance is thus not sufficient in a case in which the coated tool is used in high-speed intermittent cutting of alloy steel or the like. When the sum αxvgavg exceeds 0.95, the content ratio of Ti relatively decreases, which leads to embrittlement and degradation of chipping resistance. Therefore, the sum αavgavg of the average content ratio αavg of Al and the average content ratio βavg of Me is defined as 0.605≤αavgavg≤0.95.


Here, one kind of element selected from Si, Zr, B, V, and Cr is used as a specific component for Me.


Since in a case in which an Si component or a B component is used as Me such that βavg is equal to or greater than 0.005, hardness of the layer of a complex nitride or a complex carbonitride is improved, and wear resistance is thus improved, a Zr component has an effect of reinforcing the crystal grain boundaries, a V component improves toughness, thus further improving chipping resistance, and the Cr component improves oxidation resistance, a longer tool life can then be expected. However, since the average content ratios of the Al component and the Ti component relatively decrease when the average content ratio βavg of any of these components exceeds 0.10, and wear resistance or chipping resistance exhibits decrease trends, the average content ratio βavg that exceeds 0.10 has to be avoided.


In addition, when the average content ratio (atomic ratio) γavg of C contained in the layer of a complex nitride or a complex carbonitride is low and within a range of 0≤γavg≤0.005, adhesion between the layer of a complex nitride or a complex carbonitride and the tool body or the lower layer is improved, and lubricity is improved, impacts at the time of cutting are thus alleviated, and as a result, fracture resistance and chipping resistance of the layer of a complex nitride or a complex carbonitride are improved. In contrast, when the average content ratio γavg of C is outside the range of 0≤γavg≤0.005, toughness of the layer of a complex nitride or a complex carbonitride is degraded, and fracture resistance and chipping resistance are thus degraded in an opposite manner, which is unfavorable. Therefore, the average content ratio γavg of C is defined as 0≤γavg≤0.005.


(3) Concerning Complex Nitride or Complex Carbonitride of Cr and Al


In a case in which the composition is represented by a composition formula (Cr1-pAlp)(CqN1-q), it is preferable to control average content ratios such that an average content ratio pavg of Al with respect to the total amount of Cr and Al and an average content ratio qavg of C with respect to the total amount of C and N (where both pavg and qavg are atomic ratios) satisfy 0.70≤pavg≤0.95 and 0≤qavg≤0.005.


This is because high-temperature hardness of the layer of a complex nitride or a complex carbonitride of Cr and Al is degraded, and oxidation resistance thereof is also degraded when the average content ratio pavg of Al is less than 0.70, and wear resistance is thus not sufficient in a case in which the coated tool is used in high-speed intermittent cutting of alloy steel or the like. Meanwhile, the average content ratio pavg of Al exceeding 0.95 relatively decreases the content ratio of Cr, thus leads to embrittlement, and degrades chipping resistance. Therefore, the average content ratio pavg of Al is defined as 0.70≤pavg≤0.95.


In addition, when the content ratio (atomic ratio) qavg of the C component contained in the layer of a complex nitride or a complex carbonitride is low and within a range of 0≤qavg≤0.005, adhesion between the layer of a complex nitride or a complex carbonitride and the tool body or the lower layer is improved, lubricity is improved, impacts at the time of cutting are thus alleviated, and as a result, fracture resistance and chipping resistance of the layer of a complex nitride or a complex carbonitride are improved. Meanwhile, when the average content ratio of the C component is outside the range of 0≤qavg≤0.005, toughness of the layer of a complex nitride or a complex carbonitride is degraded, and fracture resistance and chipping resistance are thus degraded in an opposite manner, which is unfavorable. Therefore, the average content ratio qavg of the C component is defined as 0≤qavg≤0.005.


Average Crystal Grain Misorientations (GOS Values) of Individual Crystal Grains that Form Layer of a Complex Nitride or a Complex Carbonitride and have Cubic Structures:


First, an electron backscatter diffraction apparatus is used to analyze the coated tool at intervals of 0.1 μm in the vertical sectional direction, and in a case in which there is a misorientation of 5 degrees or greater between adjacent measurement points P (hereinafter, referred to as pixels) as shown in FIG. 1, the point is defined as a grain boundary B in the present invention. The vertical sectional direction means a direction perpendicular to a vertical section. The vertical section means a section of a tool perpendicular to the surface of the tool body. In addition, a region surrounded by a grain boundary B is defined as one crystal grain. However, a pixel P that has misorientations of 5 degrees or greater with respect to all adjacent pixels P and is present alone is not regarded as a crystal grain, and a crystal grain to which two or more pixels are coupled is handled as a crystal grain.


Further, a value obtained by calculating misorientations between a certain pixel P in a crystal grain and all the other pixels in the same crystal grain and averaging the misorientations is defined as a grain orientation spread (GOS) value. An outline diagram is shown in FIG. 1. The GOS value is described in the literature “Transactions of the Japan Society of Mechanical Engineers, Series A, Vol. 71, No. 712 (2005-12), Article No. 05-0367 1722 to 1728”, for example. Note that the “average crystal grain misorientation” in the present invention means this GOS value. In a case in which a GOS value is represented by an equation, the GOS value can be expressed by the following equation, where n represents the number of pixels in the same crystal grain, i and j represents numbers applied to different pixels in the crystal grain (here, 1≤i and j≤n), and αij(i*j) represents a crystal misorientation obtained from a crystal orientation at a pixel i and a crystal orientation at a pixel j.










G





O





S

=





i
,

j
=
1


n



α

ij


(

i
*
j

)





n


(

n
-
1

)







[

Expression
.




1

]







Note that it is possible to state in other words that the average crystal grain misorientation, namely the GOS value is a numerical value acquired by obtaining misorientations between pixels P in a crystal grain and all the other pixels in the same crystal grain and averaging the values thereof, and becomes a larger numerical value as a continuous change in orientations in the crystal grain becomes larger.


An electron backscatter diffraction apparatus was used


(1) to analyze a layer of a complex nitride or a complex carbonitride of Ti and Al or a layer of a complex nitride or a complex carbonitride of Cr and Al at intervals of 0.1 μm in the vertical sectional direction thereof and perform measurement in the vertical sectional direction within a measurement range in five fields of view with a width of 10 μm and a longitudinal length of the film thickness,


(2) to measure a polished surface as a surface as a surface within a measurement range of 25×25 μm at intervals of 0.1 μm in a direction perpendicular to the surface of a layer of a complex nitride or a complex carbonitride of Ti, Al and Me in five fields of view,


the total numbers of pixels that belonged to crystal grains that had cubic structures and formed the layer of a complex nitride or a complex carbonitride were thus obtained, the average crystal grain misorientations were divided at intervals of 1 degree, and the pixels P of the crystal grains with the average crystal grain misorientations within a range of these values were aggregated and divided according to the total numbers of pixels, thereby enabling creation of a histogram that represented an area ratio of the average crystal grain misorientations. As a result, it was found that the crystal orientations in crystal grains varied, and that the crystal grains with the average crystal grain misorientations of 2 degrees or greater were present at an area ratio of 20% or greater with respect to the entire layer of a complex nitride or a complex carbonitride of Al and Ti in the obtained histogram (see FIG. 3 of the measurement in accordance with (1) described above for one example).


Since the crystal grains that form the layer of a complex nitride or a complex carbonitride of Al and Ti, the complex nitride or the complex carbonitride of Ti, Al, and Me, or the complex nitride or the complex carbonitride of Al and Cr included in the surface coated cutting tool according to the present invention include greater variation of crystal orientations in the crystal grains, that is, the crystal grains include strain as compared with crystal grains in the related art that form a TiAlN layer or a CrAlN layer as described above, this contributes to improvement in hardness and toughness.


A preferable area ratio of the crystal grains with the average crystal grain misorientations of 2 degrees or greater with respect to the area of the layer of a complex nitride or a complex carbonitride ranges from 30 to 60%. A more preferable area ratio of the crystal grains with the average crystal grain misorientations of 2 degrees or greater with respect to the area of the layer of a complex nitride or a complex carbonitride ranges from 35 to 55%. In addition, a further preferable area ratio of the crystal grains with the average crystal grain misorientations of 2 degrees or greater with respect to the area of the layer of a complex nitride or a complex carbonitride ranges from 40 to 50% in a case of the complex nitride or the complex carbonitride of Al and Ti or a complex nitride or a complex carbonitride of Al and Cr.


Crystal orientation in a region on side of tool body and region on side of surface, which is obtained by equally dividing layer of a complex nitride or a complex carbonitride into two regions in the layer thickness direction


Since crystal grains that form the layer of a complex nitride or a complex carbonitride are orientated in a greater degree in a normal line direction of the surface of the tool body, that is, toward the {111} plane on the side of the surface than on the side of the surface (boundary surface) of the tool body, effects specific to the present invention that grain boundary slipping of the crystal grains is suppressed and that toughness is improved are exhibited.


However, when a ratio of an increase in the degree of {111} plane orientation on the side of the surface is less than 10% as compared with the side of the tool body, the ratio of the increase in the degree of {111} plane orientation is low, and the effect of improving toughness while maintaining wear resistance expected in the present invention is not sufficiently exhibited. Meanwhile, when the ratio exceeds 30%, epitaxial growth of the crystals is inhibited due to a rapid change in the orientation, and toughness is rather degraded. In addition, it has been found that the ratio of the increase in the degree of the {111} plane orientation becomes equal to or greater than 30% when the degree of the {111} plane orientation on the side of the tool body is less than 10%, and that the ratio of the increase in the degree of the {111} plane orientation on the surface becomes less than 10% when the degree of the {111} plane orientation on the side of the tool body exceeds 40%. Therefore, in a case in which inclined angles formed by the normal lines of the {111} planes, which are crystal planes of the crystal grains, with respect to the normal line direction of the surface of the tool body are measured in the region on the side of the tool body and the region on the side of the surface, which are obtained by equally dividing the layer of a complex nitride or a complex carbonitride into two regions in the layer thickness direction, and frequencies at which the measured inclined angles are present in each section obtained by dividing the measured inclined within a range of 0 to 45 degrees with respect to the normal line direction into each pitch of 0.25 degrees are aggregated, a) Mdeg ranges from 10 to 40% when a ratio of the total of the frequencies at which the measured inclined angles are present within a range of 0 to 12 degrees with respect to the total frequencies in the inclined angle frequency distribution in the region on the side of the tool body is set as be Mdeg, and b) Ndeg is defined to be Mdeg+10 to Mdeg to 30% when the highest peak is present in the inclined angle sections in the range of 0 to 12 degrees and a ratio of the total frequencies at which the measured inclined angles are present within the range of 0 to 12 degrees with respect to the total frequencies in the inclined angle frequency distribution in the region on the side of the surface is set as Ndeg.


Area Ratio of Layer of a Complex Nitride or a Complex Carbonitride:


The layer of a complex nitride or a complex carbonitride of Ti and Al, Ti, Al and Me, or Cr and Al exhibits excellent wear resistance by at least a phase of a complex nitride or a complex carbonitride that has an NaCl-type face-centered cubic structure being contained, and exhibits especially excellent wear resistance by the area ratio thereof exceeding 70%.


Average crystal grain width W and average aspect ratio A of individual crystal grains that have cubic structures in layer of a complex nitride or a complex carbonitride:


The aforementioned effects that toughness and wear resistance are improved can be further exhibited by employing such a configuration in which the individual crystal grains that have cubic structures in the layer of a complex nitride or a complex carbonitride of Ti and Al, Ti, Al and Me, or Cr and Al have columnar structures with an average crystal grain width W of 0.1 to 2 μm and an average aspect ratio A of 2 to 10.


That is, the average crystal grain width W is set to 0.1 to 2 μm because when the average crystal grain width W is less than 0.1 μm, a ratio of atoms that belong to TiAlCN crystal grain boundaries, TiAlMeCN crystal grain boundaries, or CrAlCN crystal grain boundaries with respect to atoms exposed to the surface of the coated layer relatively increases, reactivity with a work material to be cut thus increases, and as a result, wear resistance cannot sufficiently be exhibited, and when the average crystal grain width W exceeds 2 μm, the ratio of the atoms that belong to the TiAlCN crystal grain boundaries, the TiAlMeCN crystal grain boundaries, or the CrAlCN crystal grain boundaries with respect to the entire coated layer relatively decreases, toughness is thus degraded, and chipping resistance cannot sufficiently be exhibited. Therefore, it is preferable to set the average crystal grain width W to 0.1 to 2 μm.


In addition, in a case in which the average aspect ratio A is less than 2, sufficient columnar structures are not achieved, this leads to dropping out of equiaxial crystals with low aspect ratios, and as a result, wear resistance cannot sufficiently be exhibited. Meanwhile, when the average aspect ratio A exceeds 10, the strength of the crystal grains themselves cannot be maintained, and chipping resistance is rather degraded, which is unfavorable. Therefore, it is preferable to set the average aspect ratio A to 2 to 10.


Note that for the average aspect ratio A in the present invention, an aspect ratio a (=1/w) of each crystal grain is calculated by observing the hard coating layer on a side of a film section perpendicular to the surface of the tool body in vertical section observation of the hard coating layer within a range including the width of 100μ and the height of the entire hard coating layer by using a scanning electron microscope, and measuring the crystal grain width w in a direction parallel to the surface of the body and the crystal grain length L in a direction perpendicular to the surface of the body, and the average value of the aspect ratios a obtained for the individual crystal grains is calculated for the average aspect ratio A. In addition, an average value of the crystal grain widths w obtained for the individual crystal grains is calculated for the average crystal grain width W.


Lower Layer and Upper Layer:


In addition, the layer of a complex nitride or a complex carbonitride of Ti and Al, Ti, Al and Me, or Cr and Al that the surface-coated cutting tool according to the present invention has exhibits sufficient effects alone. However, in a case in which a lower layer that is made of a Ti compound layer including one layer or two or more layers from among a carbide layer, a nitride layer, a carbonitride layer, a oxycarbide layer, and a oxycarbonitride layer of Ti and has a total average layer thickness of 0.1 to 20 μm is provided and/or in a case in which an upper layer that includes an aluminum oxide layer that has an average layer thickness of 1 to 25 μm is provided, superior properties can be produced along with the effects that these layers exhibit. In a case in which a lower layer that is formed of a Ti compound layer including one layer or two or more layers from among a carbide layer, a nitride layer, a carbonitride layer, a oxycarbide layer, and a oxycarbonitride layer of Ti, and the total average layer thickness of the lower layer is less than 0.1 μm, the effects of the lower layer are not sufficiently exhibited. Meanwhile, when the total average layer thickness of the lower layer exceeds 20 μm, the crystal grains tend to be coarse, and chipping tends to occur. In addition, when the total average layer thickness of the upper layer that includes an aluminum oxide layer is less than 1 μm, the effects of the upper layer are not sufficiently exhibited. Meanwhile, when the total average layer thickness of the upper layer exceeds 25 μm, the crystal grain tends to be coarse, and chipping tends to occur.


Note that a diagram schematically showing a section of the layer of a complex nitride or a complex carbonitride of Ti and Al, Ti, Al and Me, or Cr and Al that forms the hard coating layer according to the present invention is shown in FIG. 2.


EXAMPLES

Next, the coated tool according to the present invention will be more specifically described in examples. Note that although a coated tool that contains WC-based cemented carbide or TiCN-based cermet in a tool body will be described in examples, the same is applied for a case in which a cubic boron-nitride-based ultra-high-pressure sintered body is used for a tool body.


Example 1

WC powder, TiC powder, TaC powder, NbC powder, Cr3C2 powder, and Co powder with average grain sizes of 1 to 3 μm were prepared as raw material powder, the raw material powder was mixed together in the mixing compositions shown in Table 1, wax was further added thereto, the mixture was mixed with acetone in a ball mill for 24 hours, was dried in a reduced pressure, and was press-molded into a green compact at a pressure of 98 MPa, the green compact is vacuum-sintered under conditions in which it was held in vacuum of 5 Pa at a predetermined temperature within a range of 1370 to 1470° C. for 1 hour, and after the sintering, tool bodies A to C made of WC-based cemented carbide with an insert shape of ISO standard SEEN1203AFSN were respectively manufactured.


In addition, TiCN (at a mass ratio TiC/TiN=50/50) powder, Mo2C powder, ZrC powder, NbC powder, WC powder, Co powder, and Ni powder with average grain sizes of 0.5 to 2 μm were prepared as raw material powder, the powder was mixed together in the mixing compositions shown in Table 2, the mixture was wet-mixed by ball mill for 24 hours, was dried, and was press-molded into a green compact at a pressure of 98 MPa, the green compact was sintered under conditions in which it was held in a nitrogen atmosphere of 1.3 kPa at a temperature of 1500° C. for 1 hour, and after the sintering, a tool body D made of TiCN-based cermet with an insert shape of ISO standard SEEN1203AFSN was manufactured.


Next, a chemical vapor deposition apparatus was used on the surfaces of these tool bodies A to D.


(a) to manufacture coated tools 1 to 15 according to the present invention under the forming conditions A to J shown in Tables 4 and 5, that is, by using a gas group A consisting of NH2, N2, and H2 and a gas group B consisting of TiCl4, Al(CH3)3, AlCl3, N2, and H2 and performing a thermal CVD method for a predetermined period of time using a gas supply method in which a reaction gas composition was set to satisfy NH3: 1.0 to 1.5%, N2: 1.0 to 2.0%, and H2: 55 to 60% as the gas group A and AlCl3: 0.6 to 0.9%, TiCl4: 0.2 to 0.3%, Al(CH3)3: 0 to 0.5%, N2: 12.5 to 15.0%, and H2 as the gas group B under conditions of a reaction atmosphere pressure: 4.5 to 5.0 kPa, a reaction atmosphere temperature: 700 to 900° C., a supply cycle: 1 to 5 seconds, a gas supply time per cycle: 0.15 to 0.25 seconds, and a supply phase difference between the gas group A and the gas group B: 0.10 to 0.20 seconds to form hard coating layers of (Ti1-xAlx)(CyN1-y) layers, in which crystal grains that had cubic structures with average crystal grain misorientations of 2 degrees or greater as shown in Table 7 were present at area ratios shown in Table 7, which had target layer thicknesses shown in Table 7.


Note that for coated tools 6 to 13 according to the present invention, lower layers shown in Table 6 and/or upper layers shown in Table 7 were formed under forming conditions shown in Table 3.


For the purpose of comparison, hard coating layers that contained at least layer of a complex nitride or a complex carbonitrides of Ti and Al were deposited on surfaces of tool bodies A to D under the conditions shown in Tables 4 and 5 with the target layer thicknesses (μm) shown in Table 8 in a manner similar to those of coated tools 1 to 15 according to the present invention. At this time, Comparative coated tools 1 to 13 were manufactured by forming the hard coating layers such that the reaction gas composition on the surface of the tool bodies did not change temporarily in a process of forming the (Ti1-xAlx)(CyN1-y) layer.


Note that the lower layers shown in Table 6 and/or the upper layers shown in Table 8 were formed under the forming conditions shown in Table 3 for Comparative coated tools 6 to 13 in a manner similar to those of coated tools 6 to 13 according to the present invention.


For reference, Reference coated tools 14 and 15 shown in Table 8 were manufactured by depositing (Ti1-xAlx)(CyN1-y) layers in reference examples with target layer thicknesses by arc ion plating using a physical vapor deposition apparatus in the related art on the surfaces of the tool body B and the tool body C.


Note that conditions of the arc ion plating used for the vapor deposition in the reference examples were as follows:


(a) Aforementioned tool bodies B and C were ultrasonically washed in acetone and were attached to a rotation table in an arc ion plating apparatus along an outer circumferential portion at a position away from the center axis by a predetermined distance in a radial direction in a dried state, and an Al—Ti alloy with a predetermined composition was deployed for a cathode electrode (evaporation source).


(b) First, the inside of the apparatus was evacuated and was heated to 500° C. with a heater while being maintained at a vacuum of 10−2 Pa or lower, a DC bias voltage of −1000V was then applied to the tool bodies that rotated while revolving on the aforementioned rotation table, a current of 200 A was caused to flow between the cathode electrode made of the Al—Ti alloy and an anode electrode to cause arc discharge and generate Al ions and Ti ions in the apparatus, and thereafter, the surfaces of the tool bodies were treated by bombard cleaning.


(c) Then, nitrogen gas was introduced as reaction gas into the apparatus to obtain a reaction atmosphere at 4 Pa, a DC bias voltage at −50 V was applied to the tool bodies that rotated while revolving on the rotation table, and a current of 120 A was caused to flow between the cathode electrode (evaporation source) made of the Al—Ti alloy and the anode electrode to cause arc discharge.


In addition, a scanning electron microscope (magnification: 5000 times) was used to measure sections of the respective constituent layers of coated tools 1 to 15 according to the present invention, Comparative coated tools 1 to 13 and Reference coated tools 14 and 15 in directions perpendicular to the tool bodies, and layer thicknesses at five points in an observation field of view were measured and averaged to obtain average layer thicknesses. All the layers had average layer thicknesses that were substantially the same as the target layer thicknesses shown in Tables 6 to 8.


In addition, for the average content ratio xavg of Al in the layer of a complex nitride or a complex carbonitride, the average content ratio xavg of Al was obtained from averages of obtained analysis results of characteristic X-rays at ten points by irradiating polished surface as a surfaces of the samples with electron beams from the side of the surfaces of the samples by using an electron microanalyzer (electron-probe-micro-analyzer: EPMA). The average content ratio yavg of C was obtained by secondary ion mass analysis (secondary-ion-mass-spectroscopy: SIMS). The ranges of 70 μm×70 μm from the side of the surfaces of the samples were irradiated with ion beams, and concentrations of the components discharged by a sputtering effect were measured in a depth direction. The average content ratio yavg of C represents an average value in the depth direction of the layer of a complex nitride or a complex carbonitride of Ti and Al. However, the content ratio of C excludes the content ratio of inevitable C contained even when gas containing C is intentionally not used as a gas raw material. Specifically, the content ratio (atomic ratio) of the C component contained in the layer of a complex nitride or a complex carbonitride in a case in which the supply amount of Al(CH3)3 is assumed to be 0 was obtained as the content ratio of inevitable C, and a value obtained by subtracting the content ratio of inevitable C from a content ratio (atomic ratio) of the C component contained in the layer of a complex nitride or a complex carbonitride obtained in a case in which Al(CH3)3 was intentionally supplied was obtained as yavg.


Furthermore, crystal orientations of the individual crystal grains that formed the layer of a complex nitride or a complex carbonitride of Ti and Al and had cubic structures were analyzed in the vertical sectional direction by using an electron backscatter diffraction apparatus, and in a case in which there were misorientations of 5 degrees or greater between adjacent pixels, that parts were regarded as grain boundaries, a region surrounded by grain boundaries was regarded as one crystal grain, crystal grain misorientations were obtained between a certain pixel in a crystal grain and all the other pixels in the same crystal grain, and the crystal grain misorientations were mapped by dividing a range of 0 to 10 degrees into sections of each 1 degree, that is, a section of equal to or greater than 0 degrees and less than 1 degree, a section of equal to or greater than 1 degree and less than 2 degrees, a section of equal to or greater than 2 degrees and less than 3 degrees, a section of equal to or greater than 3 degrees and less than 4 degrees, and the like. The area ratio of the crystal grains with the average crystal grain misorientations of 2 degrees or greater with respect to the entire layer of a complex nitride or a complex carbonitride of Ti and Al was obtained from the mapping diagram. The results are shown in Tables 7 and 8.



FIG. 3 shows an example of histogram of the average crystal grain misorientations (that is, GOS values) measured in the coated tool 8 according to the present invention, and FIG. 4 shows an example of histogram of the average crystal grain misorientations measured in the comparative coated tool 12.


In addition, for inclined angle frequency distribution of the hard coating layer, a section of the hard coating layer formed of the layer of complex carbonitride of Ti and Al that had cubic structures was placed in a body tube of a field emission-type scanning electron microscope in a state in which the section was polished, the polished surface as a surface was analyzed in a region on the side of the surface (boundary surface) of the tool body and a region on the side of the surface, which were obtained by equally dividing the polished surface as a surface into two regions in the layer thickness direction, the individual crystal grains that had cubic crystal grain lattice that was present within the measurement ranges were irradiated with electron beams at an acceleration voltage of 10 kV at an incident angle of 70 degrees with an irradiation current of 1 nA, within the measurement ranges of the region on the side of the tool body and the region on the side of the surface in the direction perpendicular to the tool body, and for the width of 10 μm for five fields of view at intervals of 0.1 μm/step in the horizontal direction of the tool body, inclined angles of normal lines of {111} planes, which were crystal planes of the crystal grains, with respect to a normal line of the surface of the tool body (a direction perpendicular to the surface of the tool body in the polished section) were measured by using an electron backscatter diffraction image apparatus, measured inclined angles within a range of 0 to 45 degrees from among the measured inclined angles were divided into sections at a pitch of 0.25 degrees on the basis of the measurement results, and frequencies at which the measured inclined angles were present in the respective sections were aggregated, thereby a ratio of frequencies at which the measured inclined angles were present within a range of 0 to 12 degrees being obtained. The results are shown in Tables 7 and 8.



FIG. 5 shows an example of the inclined angle frequency distribution measured in the region on the side of the tool body of the hard coating layer that is formed of the layer of complex carbonitride of Ti and Al of the coated tool according to the present invention, and FIG. 6 shows an example of the inclined angle frequency distribution measured in the region on the side of the surface of the hard coating layer that is formed of the layer of complex carbonitride of Ti and Al of the coated tool according to the present invention.


Further, analysis was performed at intervals of 0.1 μm in the vertical sectional direction by using an electron backscatter diffraction apparatus, measurement within a measurement range with a width of 10 μm and a vertical length of the film thickness in the vertical sectional direction was performed in five fields of view, the total number of pixels that belonged to the crystal grains that formed the layer of a complex nitride or a complex carbonitride and had cubic structures was obtained, and the area ratio of the crystal grains that had the layer of a complex nitride or a complex carbonitride and had the cubic structures was obtained from a ratio with respect to the total number of measured pixels in the measurement performed on the hard coating layer in the aforementioned five fields of view.











TABLE 1









Mixing composition (% by mass)













Type
Co
TiC
TaC
NbC
Cr3C2
WC

















Tool
A
8.5
1.5

3.0
0.4
Remainder


body
B
9.0

1.8
0.2

Remainder



C
7.5




Remainder


















TABLE 2









Mixing composition (% by mass)














Type
Co
Ni
ZrC
NbC
Mo2C
WC
TiCN


















Tool
D
8
5
1
6
6
10
Remainder


body

















TABLE 3








Forming conditions (pressure of reaction atmosphere indicates


Constituent layer of hard coating layer
kPa and temperature indicates ° C.)Forming conditions










Formation
Reaction atmosphere











Type
symbol
Reaction gas composition (% by volume)
Pressure
Temperature















(Ti1−XAlx)(CYN1−Y)
TiAlCN
TiAlCN
See Table 4
See Table 5
See Table 5


layer


Ti component
TiC
TiC
TiCl4: 4.2%, CH4: 8.5%, H2: remainder
7
900


layer
TiN
TiN-1
TiCl4: 4.2%, N2: 30%, H2: remainder
30
850




TiN-2
TiCl4: 4.2%, Ng: 35%, H2: remainder
50
900



1-TiCN
1-TiCN
TiCl4: 2%, CH3CN: 0.7%, N2: 10%, H2: remainder
7
900



TiCN
TiCN
TiCl4: 2%, CH4: 1%, N2: 15%, H2: remainder
13
900



TiCO
TiCO
TiCl4: 4.2%, CO: 4%, H2: remainder
7
900



TiCNO
TiCNO
TiCl4: 2%, CO: 1%, CH4: 1%, N2: 5%, H2: remainder
13
900


Al2O3 layer
Al2O3
Al2O3
AlCl3: 2.2%, CO2: 5.5%, HCl: 2.2%, H2S: 0.2%, H2: remainder
7
900

















TABLE 4








Forming conditions


Formation of hard
(Reaction gas composition is represented by ratios with respect to a total for the gas group A and the gas group B.)









coating layer
Reaction gas group A











Process type
Formation symbol
composition (% by volume)
Reaction gas group B composition (% by volume)



















Film
A
NH3: 1.5%
N2: 2.0%
H2: 55%
AlCl3: 0.6%
TiCl4: 0.2%
N2: 12.5%
Al(CH3)3: 0%
H2: remainder


forming
B
NH3: 1.5%
N2: 1.0%
H2: 55%
AlCl3: 0.7%
TiCl4: 0.2%
N2: 13%
Al(CH3)3: 0%
H2: remainder


process
C
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.8%
TiCl4: 0.3%
N2: 14%
Al(CH3)3: 0%
H2: remainder


according to
D
NH3: 1.0%
N2: 2.0%
H2: 60%
AlCl3: 0.6%
TiCl4: 0.2%
N2: 13.5%
Al(CH3)3: 0%
H2: remainder


the present
E
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.8%
TiCl4: 0.3%
N2: 13%
Al(CH3)3: 0%
H2: remainder


invention
F
NH3: 1.0%
N2: 1.0%
H2: 55%
AlCl3: 0.6%
TiCl4: 0.3%
N2: 13.5%
Al(CH3)3: 0.4%
H2: remainder



G
NH3: 1.5%
N2: 1.0%
H2: 55%
AlCl3: 0.7%
TiCl4: 0.3%
N2: 14.5%
Al(CH3)3: 0.2%
H2: remainder



H
NH3: 1.5%
N2: 2.0%
H2: 60%
AlCl3: 0.7%
TiCl4: 0.3%
N2: 15%
Al(CH3)3: 0%
H2: remainder



I
NH3: 1.0%
N2: 1.0%
H2: 55%
AlCl3: 0.9%
TiCl4: 0.3%
N2: 14%
Al(CH3)3: 0.5%
H2: remainder



J
NH3: 1.5%
N2: 2.0%
H2: 60%
AlCl3: 0.9%
TiCl4: 0.2%
N2: 12.8%
Al(CH3)3: 0%
H2: remainder


Comparative
A′
NH3: 1.5%
N2: 2.0%
H2: 55%
AlCl3: 0.6%
TiCl4: 0.2%
N2: 12.5%
Al(CH3)3: 0%
H2: remainder


film forming
B′
NH3: 1.5%
N2: 1.0%
H2: 55%
AlCl3: 0.7%
TiCl4: 0.2%
N2: 13%
Al(CH3)3: 0%
H2: remainder


process
C′
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.8%
TiCl4: 0.3%
N2: 14%
Al(CH3)3: 0%
H2: remainder



D′
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.8%
TiCl4: 0.2%
N2: 13.5%
Al(CH3)3: 0%
H2: remainder



E′
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.8%
TiCl4: 0.3%
N2: 13%
Al(CH3)3: 0%
H2: remainder



F′
NH3: 1.0%
N2: 1.0%
H2: 55%
AlCl3: 0.6%
TiCl4: 0.3%
N2: 13.5%
Al(CH3)3: 0.4%
H2: remainder



G′
NH3: 1.5%
N2: 1.0%
H2: 55%
AlCl3: 0.7%
TiCl4: 0.3%
N2: 14.5%
Al(CH3)3: 0.2%
H2: remainder



H′
NH3: 1.5%
N2: 2.0%
H2: 60%
AlCl3: 0.7%
TiCl4: 0.3%
N2: 15%
Al(CH3)3: 0%
H2: remainder



I′
NH3: 1.0%
N2: 1.0%
H2: 55%
AlCl3: 0.9%
TiCl4: 0.3%
N2: 14%
Al(CH3)3: 0.5%
H2: remainder



J′
NH3: 1.5%
N2: 2.0%
H2: 60%
AlCl3: 0.9%
TiCl4: 0.2%
N2: 12.8%
Al(CH3)3: 0%
H2: remainder


















TABLE 5









Forming conditions (pressure of reaction atmosphere indicates kPa and temperature



indicates ° C.) Forming conditions














Phase






difference





in supply



Gas group A
Gas group B
between













Formation of hard

Supply

Supply
gas group



coating layer
Supply
time per
Supply
time per
A and gas















Formation
cycle
cycle
cycle
cycle
group B
Reaction atmosphere















Process type
symbol
(seconds)
(seconds)
(seconds)
(seconds)
(seconds)
Pressure
Temperature


















Film
A
5
0.2
5
0.2
0.15
4.7
800


forming
B
1
0.2
1
0.2
0.15
4.7
800


process
C
2.5
0.2
2.5
0.2
0.1
4.7
750


according to
D
1.5
0.15
1.5
0.15
0.1
4.7
700


the present
E
4
0.2
4
0.2
0.1
5
850


invention
F
4.5
0.2
4.5
0.2
0.1
4.7
800



G
2.5
0.2
2.5
0.2
0.15
4.5
800



H
3
0.15
3
0.15
0.1
4.5
800



I
2
0.25
2
0.25
0.15
5
700



J
1.2
0.25
1.2
0.25
0.2
4.7
900


Comparative
A′





4.7
800


film forming
B′





4.7
800


process
C′





4.7
750



D′





4.7
700



E′





5
850



F′





4.7
800



G′





4.5
800



H′





4.5
800



I′





5
700



J′





4.7
900


















TABLE 6









Hard coating layer (Numerical values



in the lower sections represent



target average layer thickness



(μm) of the layer.)



Lower layer












Tool body
First
Second
Third











Type
symbol
layer
layer
layer















Coated tools
1
A





of the
2
B





present
3
C





invention/
4
D





Comparative
5
A





coated
6
B
TiC




tools/


(0.5)


Reference
7
C
TiN-1




coated tools


(0.3)



8
D
TiN-1
1-TiCN






(0.5)
(4)



9
A
TiN-1
1-TiCN
TiCN





(0.3)
(2)
(0.7)



10
B






11
C
TiN-1







(0.5)



12
D
TiC







(1)  



13
A
TiN-1







(0.1)



14
B






15
C





















TABLE 7









Hard coating layer



TiAl complex carbide, carbonitride layer (Ti1−xAlx)(CyN1−y)




















Area ratio of







Formation


crystal grains




symbol of


having




process of


average




forming


crystal grain

Average




TiAlCN


misorientation

crystal grain
Average




film (See
Content

equal to or
Area ratio
width w of
aspect ratio



Tool body
Tables 4
ratio xavg of
Content ratio
greater than 2
of cubic
crystal
A of crystal


Type
symbol
and 5)
Al
of yavg of C
degrees (%)
crystal (%)
grains (μm)
grains



















Coated tools
1
A
A
0.78
0.0001 or less
51
100
0.7
2.0


according to
2
B
B
0.93
0.0001 or less
46
100
0.8
5.0


the present
3
C
C
0.75
0.0001 or less
41
94
0.8
2.2


invention



4
D
D
0.73
0.0001 or less
30
100
0.4
10.0



5
A
E
0.67
0.0001 or less
41
100
1.1
1.5



6
B
F
0.89
0.0038
20
100
0.2
3.2



7
C
G
0.81
0.0041
63
100
0.3
2.3



8
D
H
0.80
0.0001 or less
54
100
0.1
2.3



9
A
I
0.95
0.0022
37
65
0.1
3.1



10
B
J
0.93
0.0001 or less
35
70
0.60
2.6



11
C
A
0.74
0.0001 or less
53
98
1.1
3.5



12
D
B
0.92
0.0001 or less
47
100
0.9
4.7



13
A
C
0.72
0.0001 or less
36
93
0.7
1.8



14
B
D
0.71
0.0001 or less
30
98
0.4
9.5



15
C
E
0.68
0.0001 or less
42
100
0.8
1.4












Hard coating layer










TiAl complex carbide, carbonitride layer




(Ti1−xAlx)(CyN1−y)













Distribution
Distribution






ratio of
ratio of



frequencies
frequencies



at which
at which



inclined
inclined



angles of
angles of



normal lines
normal lines
Inclined



of {111}
of {111}
angle



planes are
planes are
section in



present in a
present in a
which the



range of 0
range of 0
highest peak



to 12
to 12
is observed



degrees in
degrees in
in the region

Upper layer



the region
the region
on the side

(Numerical values in the lower



on the side
on the side
of the
Target layer
sections represent target average layer



of the tool
of the
surface
thickness
thickness (μm) of the layers.















Type
body Mdeg
surface Ndeg
(degrees)
(μm)
First layer
Second layer




















Coated tools
1
29
59
4.75 to 5.00
4





according to
2
15
30
5.25 to 5.50
5





the present
3
16
39
11.75 to 12.00
3.5





invention




4
10
38
8.00 to 8.25
7






5
32
51
2.75 to 3.00
6






6
21
40
4.00 to 4.25
2






7
27
45
4.50 to 4.75
6






8
40
70
3.75 to 4.00
4






9
35
61
2.00 to 2.25
8






10
26
48
3.00 to 3.25
4.5
Al2O3










(2.5)




11
28
58
4.25 to 4.50
5
TiCN
Al2O3









(0.5)
(3)




12
17
35
4.25 to 4.50
6
TiCO
Al2O3









(1)  
(2)




13
12
38
9.00 to 9.25
2.5
TiCNO
Al2O3









(0.3)
(1)




14
14
42
7.25 to 7.50
5






15
34
56
4.50 to 4.75
3





















TABLE 8









Hard coating layer



TiAl complex carbide, carbonitride layer (Ti1−xAlx)(CyN1−y)

















Formation




Average





symbol of


Area ratio of crystal

crystal




process of


grains having average

grain
Average




forming


crystal grain

width w of
aspect



Tool
TiAlCN (See


misorientation equal to
Area ratio of
crystal
ratio A of



body
Tables 4 and
Content ratio
Content ratio
or greater than 2
cubic crystal
grains
crystal


Type
symbol
5)
xavg of Al
of yavg of C
degrees (%)
(%)
(μm)
grains



















Comparative
1
A
A′
0.67
0.0001 or less
5
93
0.6
1.5


Coated tool
2
B
B′
0.91
0.0001 or less
7
100
0.7
4.5



3
C
C′
0.72
0.0001 or less
6
94
0.5
1.5



4
D
D′
0.69
0.0001 or less
12
100
0.4
2.1



5
A
E′
0.66
0.0001 or less
4
100
0.9
2.5



6
B
F′
0.84
0.0023
8
96
0.2
3.1



7
C
G′
0.78
0.0033
4
100
1.0
1.8



8
D
H′
0.62
0.0001 or less
5
100
0.4
0.8



9
A
I′
0.92
0.0041
6
71
0.2
1.2



10
B
J′
0.94
0.0001 or less
5
73
0.40
1.5



11
C
A′
0.69
0.0001 or less
4
95
0.8
3.2



12
D
B′
0.90
0.0001 or less
8
100
0.8
4.2



13
A
C′
0.69
0.0001 or less
4
95
0.8
1.3


Reference
14
B
AIP
0.50
0.0001 or less
15
100
1.5
3.3


coated tool
15
C
AIP
0.59
0.0001 or less
14
100
0.6
2.2












Hard coating layer










TiAl complex carbide, carbonitride layer




(Ti1−xAlx)(CyN1−y)













Distribution
Distribution






ratio of
ratio of



frequencies at
frequencies at



which inclined
which inclined



angles of
angles of
Inclined angle



normal lines of
normal lines of
section in

Upper layer



{111} planes
{111} planes
which the

(Numerical values in the



are present in a
are present in a
highest peak

lower sections represent



range of 0 to 12
range of 0 to 12
is observed in

target average layer



degrees in the
degrees in the
the region on

thickness (μm) of the



region on the
region on the
the side of the
Target layer
layers.
















side of the tool
side of the
surface
thickness
First
Second



Type
body Mdeg
surface Ndeg
(degrees)
(μm)
layer
layer




















Comparative
1
33
37
14.25 to 14.50
4





Coated tool
2
25
31
32.00 to 32.25
5






3
19
23
28.25 to 28.50
3.5






4
24
19
26.75 to 27.00
7






5
34
43
14.50 to 14.75
6






6
27
22
32.75 to 33.00
2






7
21
24
24.25 to 24.50
6






8
24
28
23.25 to 24.50
4






9
34
28
16.25 to 16.50
8






10
22
17
41.50 to 41.75
4.5
Al2O3










(2.5)




11
31
41
31.25 to 31.50
5
TiCN
Al2O3









(0.5)
(3)




12
26
32
31.25 to 31.50
6
TiCO
Al2O3









(1)  
(2)




13
21
23
32.25 to 32.50
2.5
TiCNO
Al2O3









(0.3)
(1)



Reference
14
25
31
31.25 to 31.50
5





coated tool
15
19
24
32.25 to 32.50
3









(Note)



“AIP” indicates a film formed through arc ion plating.






Next, all the aforementioned variety of coated tools, namely coated tools 1 to 15 according to the present invention, Comparative coated tools 1 to 13, and Reference coated tools 14 and 15 were subjected to the following dry high-speed intermittent cutting test and a center cutting machining test, which are types of high-speed intermittent cutting of alloy steel, in a state in which the coated tools were clamped with fixing jigs at tip ends of cutters made of tool steel with a cutter diameter of 125 mm, and wear width of a flank faces at all the cutting edges were measured. The results are shown in Table 9.


Tool body: tungsten-carbide-based cemented carbide, titanium-carbonitride-based cermet Cutting test: dry high-speed face milling, center cutting machining Work material: block material of JIS-SCM440 with a width of 100 mm and a length of 400 mm


Rotation speed: 892 min−1


Cutting speed: 350 m/min


Depth of cut: 2.5 mm


Feed rate per tooth: 0.25 mm/tooth


Cutting time: 8 minutes












TABLE 9






Wear width

Results of



of a flank

cutting test


Type
face (mm)
Type
(minutes)




















Coated tools
1
0.07
Comparative
1
2.2*


according to
2
0.08
coated
2
3.5*


the present
3
0.09
tools
3
2.1*


invention
4
0.11

4
4.0*



5
0.12

5
4.6*



6
0.09

6
3.9*



7
0.07

7
3.4*



8
0.10

8
2.3*



9
0.14

9
1.8*



10
0.10

10
1.9*



11
0.09

11
4.6*



12
0.08

12
4.2*



13
0.13

13
2.3*



14
0.11
Reference
14
4.4*



15
0.12
coated tools
15
4.2*





The * marks in the sections of the comparative coated tools and the reference coated tools denote cutting times (minutes) at which the life end was reached due to the occurrence of chipping.






Example 2

WC powder, TiC powder, TaC powder, NbC powder, Cr3C2 powder, TiN powder, and Co powder with average grain sizes of 1 to 3 μm were prepared as raw material powder, the raw material powder was mixed together in the mixing compositions shown in Table 10, wax was further added thereto, the mixture was mixed with acetone in a ball mill for 24 hours, was dried in a reduced pressure, and was press-molded into a green compact with a predetermined shape under a pressure of 98 MPa, the green compact is vacuum-sintered under conditions in which it was held in vacuum of 5 Pa at a predetermined temperature within a range of 1370 to 1470° C. for 1 hour, and after the sintering, tool bodies α to γ made of WC-based cemented carbide with an insert shape of ISO standard CNMG120412 were respectively manufactured by performing honing machining at R: 0.07 mm on cutting edge portions.


TiCN (mass ratio TiC/TiN=50/50) powder, NbC powder, WC powder, Co powder, and Ni powder with average grain sizes of 0.5 to 2 μm were prepared as raw material powder, the raw material powder was mixed together in the mixing compositions shown in Table 11, the mixture was wet mixed in a ball mill for 24 hours, was dried, and was press-molded into a green compact under a pressure of 98 MPa, the green compact is sintered under conditions in which it was held in nitrogen atmosphere at 1.3 kPa at a temperature of 1500° C. for 1 hour, and after the sintering, a tool body δ made of TiCN-based cermet with an insert shape of ISO standard CNMG120412 was manufactured by performing honing machining at R: 0.09 mm on a cutting edge portion.


Next, coated tools 16 to 30 according to the present invention shown in Table 13 were manufactured by using a chemical vapor deposition apparatus on the surfaces of these tool bodies α to γ and the tool body δ to deposit hard coating layers with target layer thicknesses, which included at least (Ti1-xAlx)(CyN1-y), under the conditions shown in Tables 4 and 5 by a method similar to that in Example 1.


Note that the lower layers shown in Table 12 and/or the upper layers shown in Table 13 were formed for coated tools 19 to 28 according to the present invention under the forming conditions shown in Table 3.


In addition, for the purpose of comparison, Comparative coated tools 16 to 28 shown in Table 14 were manufactured by using a chemical vapor deposition apparatus on the surfaces of these tool bodies α to γ and the tool body δ to deposit hard coating layers with target layer thicknesses shown in Table 14 under the conditions shown in Tables 4 and 5 by a method similar to that for the coated tools according to the present invention.


Note that the lower layers shown in Table 12 and/or the upper layers shown in Table 14 were formed for Comparative coated tools 19 to 28 under the forming conditions shown in Table 3 in a manner similar to that for coated tools 19 to 28 according to the present invention.


For reference, Reference coated tools 29 and 30 shown in Table 14 were manufactured by depositing (Ti1-xAlx)(CyN1-y) layers in the reference examples with target layer thicknesses on the surfaces of the tool body β and the tool body γ by arc ion plating using a physical vapor deposition apparatus in the related art.


Note that conditions similar to the conditions shown in Example 1 were used as conditions for the arc ion plating.


In addition, a scanning electron microscope (magnification: 5000 times) was used to measure sections of the respective constituent layers of coated tools 16 to 30 according to the present invention, Comparative coated tools 16 to 28, and Reference coated tools 29 and 30, and layer thicknesses at five points in an observation field of view were measured and averaged to obtain average layer thicknesses. All the layers had average layer thicknesses that were substantially the same as the target layer thicknesses shown in Tables 12 to 14.


Furthermore, crystal orientations of the individual crystal grains that formed the layer of a complex nitride or a complex carbonitride of Ti and Al and had cubic structures were analyzed in the vertical sectional direction by using an electron backscatter diffraction apparatus, and crystal grain misorientations were mapped by dividing a range of 0 to 10 degrees into sections of each 1 degree, that is, a section of equal to or greater than 0 degrees and less than 1 degree, a section of equal to or greater than 1 degree and less than 2 degrees, a section of equal to or greater than 2 degrees and less than 3 degrees, a section of equal to or greater than 3 degrees and less than 4 degrees, and the like. Average crystal grain misorientations and an area ratio of the crystal grains with the average crystal grain misorientations of 2 degrees or greater with respect to the entire layer of a complex nitride or a complex carbonitride of Ti and Al were obtained from the mapping diagram. The results are shown in Tables 13 and 14.


In addition, for inclined angle frequency distribution of the hard coating layer, a section of the hard coating layer formed of the layer of complex carbonitride of Ti and Al that had cubic structures was placed in a body tube of a field emission-type scanning electron microscope in a state in which the section was polished, the polished surface as a surface was analyzed in a region on the side of the surface (boundary surface) of the tool body and a region on the side of the surface, which were obtained by equally dividing the polished surface as a surface into two regions in the layer thickness direction, the individual crystal grains that had cubic crystal grain lattice that was present within measurement ranges in the region on the side of the tool body and in the region on the side of the surface were irradiated with electron beams at an acceleration voltage of 10 kV at an incident angle of 70 degrees with an irradiation current of 1 nA, inclined angles of normal lines of {111} planes, which were crystal planes of the crystal grains, with respect to a normal line of the surface of the tool body (a direction perpendicular to the surface of the tool body in the polished section) were measured for the width of 10 μm for five fields of view at intervals of 0.1 μm/step in the horizontal direction of the tool body by using an electron backscatter diffraction image apparatus, measured inclined angles within a range of 0 to 45 degrees from among the measured inclined angles were divided into sections at a pitch of 0.25 degrees on the basis of the measurement results, and frequencies at which the measured inclined angles were present in the respective sections were aggregated, thereby a ratio of frequencies at which the measured inclined angles were present within a range of 0 to 12 degrees being obtained. The results are shown in Tables 13 and 14.











TABLE 10









Mixing composition (% by mass)















Type
Co
TiC
ZrC
TaC
NbC
Cr3C2
TiN
WC



















Tool
α
7.0

1.5

2.9
0.1
1.5
Remainder


body
β
8.1
2.6

4.0
0.5

1.1
Remainder



γ
6.5






Remainder


















TABLE 11









Mixing composition (% by mass)














Type
Co
Ni
NbC
WC
TiCN



















Tool body
δ
11
4
6
15
Remainder




















TABLE 12










Hard coating layer (The numerical




values in the lower sections represent




target average layer thicknesses




(μm) of the layers.)



Tool
Lower layer













body
First
Second
Third
Fourth


Type
symbol
layer
layer
layer
layer
















Coated tools
16
α






according to the
17
β






present invention/
18
γ






Comparative coated
19
δ
TiC





tools/Reference


(0.5)


coated tools
20
α
TiN-1








(0.1)



21
β
TiN-1
1-TiCN







(0.5)
(7)



22
γ
TiN-1
1-TiCN
TiN-2






(0.3)
(10) 
(0.7)



23
δ
TiN-1
1-TiCN
TiCN
TiN-2





(0.3)
(4)
(0.4)
(0.3)



24
α







25
β
TiN-1







(0.5)



26
γ
TiC







(1)  



27
δ
TiN-1







(0.1)



28
α
TiN-1







(0.1)



29
β






30
γ





















TABLE 13









Hard coating layer



TiAl complex carbide, carbonitride layer (Ti1−xAlx)(CyN1−y)

















Formation




Average





symbol of


Area ratio of crystal

crystal




process of


grains having average

grain
Average




forming


crystal grain

width W
aspect



Tool
TiAlCN (See
Content
Content
misorientation equal
Area ratio of
of crystal
ratio A of



body
Tables 4 and
ratio xavg
ratio of yavg
to or greater than 2
cubic crystal
grains
crystal


Type
symbol
5)
of Al
of C
degrees (%)
(%)
(μm)
grains



















Coated
16
α
A
0.71
0.0001 or
56
90
1.3
5.0


tools




less


according
17
β
B
0.94
0.0001 or
45
100
0.4
3.0


to the




less


present
18
γ
C
0.69
0.0001 or
39
93
0.9
3.2


invention




less



19
δ
D
0.78
0.0001 or
48
98
0.5
2.2







less



20
α
E
0.69
0.0001 or
45
100
0.8
4.5







less



21
β
F
0.83
0.0038
55
95
0.7
2.1



22
γ
G
0.76
0.0023
33
100
2.0
3.1



23
δ
H
0.63
0.0001 or
32
100
1.1
2.0







less



24
α
I
0.93
0.0031
22
63
0.4
5.1



25
β
J
0.92
0.0001 or
39
68
0.8
2.2







less



26
γ
A
0.72
0.0001 or
58
93
0.8
7.0







less



27
δ
B
0.93
0.0001 or
43
100
0.2
2.5







less



28
α
C
0.69
0.0001 or
39
92
1.1
3.5







less



29
β
D
0.81
0.0001 or
48
100
0.6
2.5







less



30
γ
E
0.68
0.0001 or
51
100
0.6
2.0







less












Hard coating layer










TiAl complex carbide, carbonitride layer




(Ti1−xAlx)(CyN1−y)













Distribution
Distribution






ratio of
ratio of



frequencies at
frequencies at



which inclined
which inclined



angles of
angles of
Inclined



normal lines
normal lines
angle section



of {111}
of {111}
in which the



planes are
planes are
highest peak



present in a
present in a
is observed

Upper layer (Numerical values



range of 0 to
range of 0 to
in the region

in the lower sections



12 degrees in
12 degrees in
on the side
Target
represent target average layer



the region on
the region on
of the
layer
thickness (μm) of the layer.)


















the side of the
the side of the
surface
thickness
First
Second
Third
Fourth



Type
tool body Mdeg
surface Ndeg
(degrees)
(μm)
layer
layer
layer
layer






















Coated
16
15
30
5.25 to 5.50
12







tools



according
17
21
40
3.00 to 3.25
6







to the



present
18
24
44
2.50 to 2.75
7







invention




19
34
53
4.25 to 4.50
20








20
1
41
3.50 to 3.75
16








21
29
56
2.75 to 3.00
3








22
17
29
4.50 to 4.75
8
TiN-2












(0.7)




23
35
59
4.75 to 5.00
4
TiCN
TiN-2











(0.4)
(0.3)




24
37
52
6.00 to 6.55
7
Al2O3












(2)  




25
16
39
10.00 to 10.25
15
TiCN
Al2O3











(0.5)
(2.5)




26
15
30
4.75 to 5.00
16
TiCO
Al2O3











(1)  
(2)  




27
21
42
3.25 to 3.50
4
TiCNO
Al2O3











(0.3)
(1)  




28
25
47
3.50 to 3.75
9
TiN-2
TiCN
TiCNO
Al2O3









(0.3)
(0.8)
(0.3)
(3)




29
32
49
4.75 to 5.00
11








30
26
47
2.75 to 3.00
5























TABLE 14









Hard coating layer



TiAl complex carbide, carbonitride layer (Ti1−xAlx)(CyN1−y)
















Formation









symbol of


Area ratio of crystal




process of


grains having average

Average




forming


crystal grain

crystal grain




TiAlCN (See


misorientation equal
Area ratio of
width w of



Tool body
Tables 4 and
Content ratio
Content ratio of
to or greater than 2
cubic crystal
crystal


Type
symbol
5)
xavg of Al
yavg of C
degrees (%)
(%)
grains (μm)


















Comparative
16
α
A′
0.68
0.0001 or less
6
97
0.8


coated


tools
17
β
B′
0.93
0.0001 or less
9
100
1.1



18
γ
C′
0.70
0.0001 or less
5
98
0.4



19
δ
D′
0.75
0.0001 or less
6
95
0.4



20
α
E′
0.67
0.0001 or less
7
100
0.8



21
β
F′
0.84
0.0045
10
94
0.4



22
γ
G′
0.79
0.0028
5
100
1.0



23
δ
H′
0.60
0.0001 or less
6
100
0.7



24
α
I′
0.91
0.0029
1
75
1.0



25
β
J′
0.91
0.0001 or less
4
66
0.2



26
γ
A′
0.66
0.0001 or less
5
95
0.2



27
δ
B′
0.92
0.0001 or less
6
100
0.9



28
α
C′
0.70
0.0001 or less
8
96
0.7


Reference
29
β
AIP
0.49
0.0001 or less
13
100
1.4


coated tool



30
γ
AIP
0.60
0.0001 or less
16
100
0.6












Hard coating layer










TiAl complex carbide, carbonitride layer




(Ti1−xAlx)(CyN1−y)















Distribution
Distribution







ratio of
ratio of




frequencies at
frequencies at




which inclined
which inclined
Inclined




angles of
angles of
angle section




normal lines of
normal lines of
in which the




{111} planes
{111} planes
highest peak




are present in a
are present in a
is observed



Average
range of 0 to 12
range of 0 to 12
in the region

TiAl complex carbide,



aspect
degrees in the
degrees in the
on the side
Target
carbonitride layer



ratio A of
region on the
region on the
of the
layer
(Ti1−xAlx)(CyN1−y)

















crystal
side of the tool
side of the
surface
thickness
First
Second
Third
Fourth


Type
grains
body Mdeg
surface Ndeg
(degrees)
(μm)
layer
layer
layer
layer




















Comparative
16
5.2
27
29
33.75 to
12






coated




34.00


tools
17
2.7
34
43
14.50 to
6











14.75



18
0.8
15
18
33.25 to
7











33.50



19
1.5
22
17
41.50 to
20











41.75



20
5.2
19
23
28.25 to
16











28.50



21
2.1
24
19
26.75 to
3











27.00



22
3.0
21
24
34.25 to
8
TiN-2










34.50

(0.7)



23
5.0
25
1
32.00 to
4
TiCN
TiN-2









32.25

(0.4)
(0.5)



24
1.6
26
22
15.25 to
7
Al2O3










15.50

(2)  



25
1.2
34
28
36.25 to
15
TiCN
Al2O3









36.50

(0.5)
(2.5)



26
5.5
1
34
32.75 to
16
TiCO
Al2O3









33.00

(1)  
(2)  



27
2.5
33
41
16.50 to
4
TiCNO
Al2O3









16.75

(0.3)
(1)  



28
1.2
19
18
31.50 to
9
TiN-2
TiCN
TiCNO
Al2O3







31.75

(0.3)
(0.8)
(0.3)
(3)


Reference
29
1
24
32
29.25 to
11






coated tool




29.50



30
2.1
18
26
31.25 to
5











31.50





(Note)


“AIP” indicates a film formed through arc ion plating.






Next, all the aforementioned variety of coated tools, namely coated tools 16 to 30 according to the present invention, Comparative coated tools 16 to 28, and Reference coated tools 29 and 30 were subjected to the following dry high-speed intermittent cutting test of carbon steel and a wet high-speed intermittent cutting test of ductile cast iron in a state in which the coated tools were screw-fixed with fixing jigs at tip ends of cutting tools made of tool steel, and wear width of a flank faces at all the cutting edges were measured.


Cutting condition 1:


Work material: round bar of JIS⋅S45C with four longitudinal grooves at an equal interval in a length direction


Cutting speed: 330 m/min


Depth of cut: 2.0 mm


Feed: 0.3 mm/rev


Cutting time: 5 minutes


(The ordinary cutting speed is 220 m/min)


Cutting condition 2:


Work material: round bar of JIS⋅FCD700 with four longitudinal grooves at an equal interval in a length direction


Cutting speed: 280 m/min


Depth of cut: 2.0 mm


Feed: 0.3 mm/rev


Cutting time: 5 minutes


(The ordinary cutting speed is 200 m/min)


Table 15 shows results of the cutting test.













TABLE 15









Wear width of a flank face

Result of cutting



(mm)

test (minutes)













Cutting
Cutting

Cutting
Cutting


Type
condition 1
condition 2
Type
condition 1
condition 2

















Coated
16
0.21
0.21
Comparative
16
4.3*
2.5*


tools
17
0.21
0.22
coated tools
17
4.7*
4.3*


according
18
0.16
0.10

18
2.2*
2.4*


to the
19
0.14
0.14

19
2.3*
2.3*


present
20
0.22
0.22

20
3.8*
3.9*


invention
21
0.10
0.11

21
4.3*
2.8*



22
0.22
0.23

22
4.8*
4.2*



23
0.18
0.13

23
4.3*
4.2*



24
0.23
0.24

24
2.9*
1.9*



25
0.22
0.23

25
2.2*
1.7*



26
0.20
0.19

26
3.6*
4.4*



27
0.19
0.17

27
4.8*
3.8*



28
0.19
0.16

28
3.1*
2.3*



29
0.13
0.14
Reference
29
4.3*
2.5*



30
0.20
0.20
coated tools
30
3.4*
3.6*





The * marks in the sections of the comparative coated tools and the reference coated tools denote cutting times (minutes) at which the life end was reached due to the occurrence of chipping.






From the results shown in Tables 9 and 15, hardness is improved due to strain of the crystal grains, and toughness is improved while high wear resistance is maintained in the coated tools according to the present invention, by the predetermined average crystal grain misorientations being present in the crystal grains which have cubic structures which form the layer of a complex nitride or a complex carbonitride of Al and Ti that forms the hard coating layer, and by the inclined angles of the normal lines of the {111} planes having the predetermined inclined angle frequency distribution in the region on the side of the tool body and in the region on the side of the surface of the crystal grains. Further, it is obvious that excellent chipping resistance and fracture resistance are achieved even in a case in which the coated tools are used in a high-speed intermittent cutting in which an intermittent and impact, high load exerts on cutting edges, and as a result, excellent wear resistance is exhibited in use over a long period of time.


In contrast, it is obvious that Comparative coated tools 1 to 13 and 16 to 28 and Reference coated tools 14, 15, 29, and 30 in which the predetermined average crystal grain misorientations are not present in the crystal grains which have cubic structures which form the layer of a complex nitride or a complex carbonitrides of Al and Ti that forms the hard coating layers or in which the inclined angles of the normal lines of the {111} planes do not have the predetermined inclined angle frequency distribution in the region on the side of the tool body and in the region on the side of the surface of the crystal grains end the lifes thereof in short periods of time due to the occurrence of chipping, fracture, and the like in a case in which the coated tools are used in the high-speed intermittent cutting, which is accompanied with high heat generation, in which an intermittent and impact, high load exerts on the cutting edges.


Example 3

WC powder, TiC powder, TaC powder, NbC powder, Cr3C2 powder, and Co powder with average grain sizes of 1 to 3 μm were prepared as raw material powder, the raw material powder was mixed together in the mixing compositions shown in Table 16, wax was further added thereto, the mixture was mixed with acetone in a ball mill for 24 hours, was dried in a reduced pressure, and was press-molded into a green compact with a predetermined shape under a pressure of 98 MPa, the green compact is vacuum-sintered under conditions in which it was held in vacuum of 5 Pa at a predetermined temperature within a range of 1370 to 1470° C. for 1 hour, and after the sintering, tool bodies E to G made of WC-based cemented carbide with an insert shape of ISO standard SEEN1203AFSN were respectively manufactured.


TiCN (mass ratio TiC/TiN=50/50) powder, Mo2C powder, ZrC powder, NbC powder, WC powder, Co powder, and Ni powder with average grain sizes of 0.5 to 2 μm were prepared as raw material powder, the raw material powder was mixed together in the mixing compositions shown in Table 17, the mixture was wet mixed in a ball mill for 24 hours, was dried, and was press-molded into a green compact under a pressure of 98 MPa, the green compact is sintered under conditions in which it was held in nitrogen atmosphere at 1.3 kPa at a temperature of 1500° C. for 1 hour, and after the sintering, a tool body H made of TiCN-based cermet with an insert shape of ISO standard SEEN1203AFSN was manufactured.


Next, a thermal CVD method was performed for on the surfaces of the tool bodies E to H for a predetermined time by using a chemical vapor deposition apparatus under the forming conditions shown in Tables 19 and 20, that is, by using the gas group A consisting of NH3, N2, and H2, the gas group B consisting of TiCl4, Al(CH3)3, AlCl3, MeCln (where any of SiCl4, ZrCl4, BCl3, VCl4, and CrCl2), N2, and H2, and the gas supply method of setting the reaction gas composition (% by volume with respect to the total of the gas group A and the gas group B) to NH3: 1.0 to 1.5%, N2: 1.0 to 2.0%, and H2: 55 to 60% as the gas group A, AlCl3: 0.6 to 0.9%, TiCl4: 0.2 to 0.3%, Al(CH3)3: 0 to 0.5%, MeCln (where any of SiCl4, ZrCl4, BCl3, VCl4, and CrCl2): 0.1 to 0.2%, N2: 12.5 to 15.0%, and H2: the remaining amount as the gas group B, for example, under conditions of a reaction atmosphere pressure: 4.5 to 5.0 kPa, a reaction atmosphere temperature: 700 to 900° C., a supply cycle: 1 to 5 seconds, a gas supply time per cycle: 0.15 to 0.25 seconds, and a supply phase difference between the gas group A and the gas group B: 0.10 to 0.20 seconds, and the hard coating layers, in which the crystal grains which have cubic structures with the average crystal grain misorientations of 2 degrees or greater as shown in Table 22 were present at the area ratios shown in Table 22, which were made of (Ti1-x-yAlxMey)(CzN1-z) layers with the target layer thicknesses shown in Table 22, thereby coated tools 31 to 45 according to the present invention were manufactured.


Note that the lower layers shown in Table 21 and/or the upper layers shown in Table 22 were formed for coated tools 36 to 43 according to the present invention under the forming conditions shown in Table 18.


In addition, for the purpose of comparison, hard coating layers that contained at least layer of a complex nitride or a complex carbonitrides of Ti and Al with the target layer thicknesses (μm) shown in Table 23 were deposited on the surfaces of the tool bodies E to H under the conditions shown in Tables 19 and 20 in a manner similar to that for coated tools 31 to 45 according to the present invention. At this time, Comparative coated tools 31 to 45 were manufactured by forming the hard coating layers such that the reaction gas composition on the surface of the tool bodies did not temporarily change in a process of forming the (Ti1-α-βAlαMeβ)(CγN1-γ) layers.


Note that the lower layers shown in Table 21 and/or the upper layers shown in Table 23 were formed for Comparative coated tools 36 to 43 under the forming conditions shown in Table 18 in a manner similar to that for coated tools 36 to 43 according to the present invention.


In addition, a scanning electron microscope (magnification: 5000 times) was used to measure sections in a direction perpendicular to the tool bodies of the respective constituent layers of coated tools 31 to 45 according to the present invention and Comparative coated tools 31 to 45, and layer thicknesses at five points in an observation field of view were measured and averaged to obtain average layer thicknesses. All the layers had average layer thicknesses that were substantially the same as the target layer thicknesses shown in Tables 21 to 23.


In addition, for the average content ratio of Al and an average content ratio of Me in the layer of a complex nitride or a complex carbonitride, the average content ratio αavg of Al and the average content ratio βavg of Me were obtained from averages of obtained analysis results of characteristic X-rays at ten points by irradiating polished surface as a surfaces of the samples with electron beams from the side of the surfaces of the samples by using an electron microanalyzer (EPMA). The average content ratio γavg of C was obtained by secondary ion mass analysis (SIMS). The ranges of 70 μm×70 μm from the side of the surfaces of the samples were irradiated with ion beams, and concentrations of the components discharged by a sputtering effect were measured in a depth direction. The average content ratio γavg of C represents an average value in the depth direction of the layer of a complex nitride or a complex carbonitride of Ti, Al, and Me. However, the content ratio of C excludes the content ratio of inevitable C contained even when gas containing C is intentionally not used as a gas raw material. Specifically, the content ratio (atomic ratio) of the C component contained in the layer of a complex nitride or a complex carbonitride in a case in which the supply amount of Al(CH3)3 is assumed to be 0 was obtained as the content ratio of inevitable C, and a value obtained by subtracting the content ratio of inevitable C from a content ratio (atomic ratio) of the C component contained in the layer of a complex nitride or a complex carbonitride obtained in a case in which Al(CH3)3 was intentionally supplied was obtained as γavg. The results thereof are shown in Tables 22 and 23.


Furthermore, crystal orientations of the individual crystal grains that formed the layer of a complex nitride or a complex carbonitride of Ti, Al, and Me and had cubic structures were analyzed in the vertical sectional direction by using an electron backscatter diffraction apparatus, and in a case in which there were misorientations of 5 degrees or greater between adjacent pixels, the parts were regarded as grain boundaries, a region surrounded by grain boundaries was regarded as one crystal grain, crystal grain misorientations were obtained between a certain pixel in a crystal grain and all the other pixels in the same crystal grain, and the crystal grain misorientations were mapped by dividing a range of 0 to 10 degrees into sections of each 1 degree, that is, a section of equal to or greater than 0 degrees and less than 1 degree, a section of equal to or greater than 1 degree and less than 2 degrees, a section of equal to or greater than 2 degrees and less than 3 degrees, a section of equal to or greater than 3 degrees and less than 4 degrees, and the like. The area ratio of the crystal grains with the average crystal grain misorientations of 2 degrees or greater with respect to the entire layer of a complex nitride or a complex carbonitride of Ti, Al, and Me was obtained from the mapping diagram. The results are shown in Tables 22 and 23.



FIG. 7 shows an example of histogram of the average crystal grain misorientations measured in the coated tool according to the present invention, and FIG. 8 shows an example of histogram of the average crystal grain misorientations measured in the comparative coated tool.


In addition, for inclined angle frequency distribution of the hard coating layer, a section of the hard coating layer formed of the layer of complex carbonitride of Ti, Al, and Me that had cubic structures was placed in a body tube of a field emission-type scanning electron microscope in a state in which the section was polished, the polished surface as a surface was analyzed in a region on the side of the surface of the tool body (tool body) and a region on the side of the surface, which were obtained by equally dividing the polished surface as a surface into two regions in the layer thickness direction, the individual crystal grains that had cubic crystal grain lattice that was present within the measurement ranges were irradiated with electron beams at an acceleration voltage of 10 kV at an incident angle of 70 degrees with an irradiation current of 1 nA, within the measurement ranges of the region on the side of the boundary surface and the region on the side of the surface in the direction perpendicular to the tool body, and for the width of 10 μm for five fields of view at intervals of 0.1 μm/step in the horizontal direction of the tool body, inclined angles of normal lines of {111} planes, which were crystal planes of the crystal grains, with respect to a normal line of the surface of the tool body (a direction perpendicular to the surface of the tool body in the polished section) were measured by using an electron backscatter diffraction image apparatus, measured inclined angles within a range of 0 to 45 degrees from among the measured inclined angles were divided into sections at a pitch of 0.25 degrees on the basis of the measurement results, and frequencies at which the measured inclined angles were present in the respective sections were aggregated, thereby ratio Mdeg and Ndeg of frequencies at which the measured inclined angles were present within an angular range in which the highest peak was present in inclined angle sections in the region on the side of the surface and within a range of 0 to 12 degrees were obtained. The results are shown in Tables 22 and 23.



FIG. 9 shows an example of the inclined angle frequency distribution measured in the region on the side of the tool body of the hard coating layer that is formed of the layer of a complex nitride or a complex carbonitride of Ti, Al, and Me of the coated tool according to the present invention, and FIG. 10 shows an example of the inclined angle frequency distribution measured in the region on the side of the surface of the hard coating layer that is formed of the layer of a complex nitride or a complex carbonitride of Ti, Al, and Me of the coated tool according to the present invention.


Further, analysis was performed at intervals of 0.1 μm in the vertical sectional direction by using an electron backscatter diffraction apparatus, measurement within a measurement range with a width of 10 μm and a vertical length of the film thickness in the vertical sectional direction was performed in five fields of view, the total number of pixels that belonged to the crystal grains which had cubic structures that formed the layer of a complex nitride or a complex carbonitride was obtained, and the area ratio of the crystal grains which had cubic structures that had the layer of a complex nitride or a complex carbonitride was obtained from a ratio with respect to the total number of measured pixels in the measurement performed on the hard coating layer in the aforementioned five fields of view. The results are shown in Tables 22 and 23.


Further, the individual crystal grains in the (Ti1-x-yAlxMey)(CzN1-z) layers that were present within a range at the length of 10 μm in the horizontal direction of the surface of the tool bodies and that formed the layer of a complex nitride or a complex carbonitrides of Ti, Al, and Me in coated tools 31 to 45 according to the present invention and Comparative coated tools 31 to 45 were observed from the side of the film sections perpendicular to the surfaces of the tool bodies by using a scanning electron microscope (magnitude of 5000 times or 20000 times) in the section direction perpendicular to the tool bodies, the crystal grain widths w in the direction parallel to the surfaces of the bodies and the crystal grain lengths l in the direction perpendicular to the surfaces of the bodies were measured, aspect ratios a (=l/w) of the respective crystal grains were calculated, an average value of the aspect ratios a obtained for the individual crystal grains was calculated as an average aspect ratio A, and an average value of the crystal grain widths w obtained for the individual crystal grains was calculated as an average crystal grain width W. The results are shown in Tables 22 and 23.











TABLE 16









Mixing composition (% by mass)













Type
Co
TiC
TaC
NbC
Cr3C2
WC

















Tool
E
8.0
1.5

3.0
0.4
Remainder


body
F
8.5

1.8
0.2

Remainder



G
7.0




Remainder


















TABLE 17









Mixing composition (% by mass)














Type
Co
Ni
ZrC
NbC
Mo2C
WC
TiCN


















Tool
H
8
5
1
6
6
10
Remainder


body

















TABLE 18








Forming conditions (pressure of reaction atmosphere indicates


Constituent layer of hard coating layer
kPa and temperature indicates ° C.)Forming conditions










Formation
Reaction atmosphere











Type
symbol
Reaction gas composition (% by volume)
Pressure
Temperature











(Ti1−α−βAlαMeβ)(CγN1-γ) layer
See Tables 19 and 20












Ti compound
TiC
TiC
TiCl4: 2%, CH4: 10%, H2: remainder
7
850


layer
TiN
TiN
TiCl4: 4.2%, N2: 30%, H2: remainder
30
780



TiCN
TiCN
TiCl4: 2%, CH3CN: 0.7%, N2: 10%, H2: remainder
7
780



TiCO
TiCO
TiCl4: 4.2%, CO: 4%, H2: remainder
7
850



TiCNO
TiCNO
TiCl4: 2%, CH3CN: 0.7%, N2: 10%, CO2: 0.3%, H2: remainder
13
780


Al2O3 layer
Al2O3
Al2O3
AlCl3: 2.2%, CO2: 5.5%, HCl: 2.2%, H2S: 0.8%, H2: remainder
7
800

















TABLE 19







Formation of



hard coating layer
Forming conditions (reaction gas composition is










For-
represented as ratio with respect to a total for the gas group A and the gas group B.)










Process
mation
Reaction gas group A



type
symbol
composition (% by volume)
Reaction gas group B composition (% by volume)




















Film
Si-A
NH3: 1.4%
N2: 1.3%
H2: 58%
AlCl3: 0.7%
TiCl4: 0.3%
SiCl4: 0.1%
N2: 13.0%
Al(CH3)3: 0.5%
H2: remainder


forming
Si-B
NH3: 1.0%
N2: 1.7%
H2: 55%
AlCl3: 0.8%
TiCl4: 0.2%
SiCl4: 0.1%
N2: 14.5%
Al(CH3)3: 0%
H2: remainder


process
Si-C
NH3: 1.3%
N2: 1.5%
H2: 60%
AlCl3: 0.9%
TiCl4: 0.3%
SiCl4: 0.2%
N2: 12.5%
Al(CH3)3: 0%
H2: remainder


according
Zr-A
NH3: 1.2%
N2: 1.8%
H2: 56%
AlCl3: 0.8%
TiCl4: 0.2%
ZrCl4: 0.2%
N2: 14.0%
Al(CH3)3: 0%
H2: remainder


to the
Zr-B
NH3: 1.5%
N2: 1.0%
H2: 57%
AlCl3: 0.9%
TiCl4: 0.2%
ZrCl4: 0.1%
N2: 13.0%
Al(CH3)3: 0%
H2: remainder


present
Zr-C
NH3: 1.3%
N2: 1.9%
H2: 55%
AlCl3: 0.6%
TiCl4: 0.3%
ZrCl4: 0.1%
N2: 15.0%
Al(CH3)3: 0.2%
H2: remainder


invention
B-A
NH3: 1.1%
N2: 1.6%
H2: 59%
AlCl3: 0.7%
TiCl4: 0.2%
BCl3: 0.1%
N2: 13.5%
Al(CH3)3: 0%
H2: remainder



B-B
NH3: 1.3%
N2: 2.0%
H2: 57%
AlCl3: 0.8%
TiCl4: 0.3%
BCl3: 0.2%
N2: 14.0%
Al(CH3)3: 0.2%
H2: remainder



B-C
NH3: 1.4%
N2: 1.5%
H2: 58%
AlCl3: 0.7%
TiCl4: 0.3%
BCl3: 0.1%
N2: 12.5%
Al(CH3)3: 0%
H2: remainder



V-A
NH3: 1.5%
N2: 1.2%
H2: 56%
AlCl3: 0.8%
TiCl4: 0.2%
VCl4: 0.1%
N2: 13.5%
Al(CH3)3: 0%
H2: remainder



V-B
NH3: 1.2%
N2: 1.7%
H2: 60%
AlCl3: 0.9%
TiCl4: 0.3%
VCl4: 0.1%
N2: 13.0%
Al(CH3)3: 0.5%
H2: remainder



V-C
NH3: 1.0%
N2: 1.1%
H2: 58%
AlCl3: 0.7%
TiCl4: 0.3%
VCl4: 0.2%
N2: 15.0%
Al(CH3)3: 0%
H2: remainder



Cr-A
NH3: 1.4%
N2: 1.4%
H2: 59%
AlCl3: 0.6%
TiCl4: 0.3%
CrCl2: 0.2%
N2: 14.0%
Al(CH3)3: 0%
H2: remainder



Cr-B
NH3: 1.3%
N2: 1.0%
H2: 56%
AlCl3: 0.8%
TiCl4: 0.3%
CrCl2: 0.1%
N2: 14.5%
Al(CH3)3: 0%
H2: remainder



Cr-C
NH3: 1.3%
N2: 1.8%
H2: 57%
AlCl3: 0.7%
TiCl4: 0.2%
CrCl2: 0.1%
N2: 13.5%
Al(CH3)3: 0%
H2: remainder


Compar-
Si-a
NH3: 1.2%
N2: 3.0%
H2: 58%
AlCl3: 0.8%
TiCl4: 0.3%
SiCl4: 0.4%
N2: 13.0%
Al(CH3)3: 0%
H2: remainder


ative
Si-b
NH3: 1.5%
N2: 1.5%
H2: 65%
AlCl3: 0.4%
TiCl4: 0.3%
SiCl4: 0.1%
N2: 15.0%
Al(CH3)3: 0.2%
H2: remainder


film
Si-c
NH3: 0.6%
N2: 2.0%
H2: 55%
AlCl3: 0.7%
TiCl4: 0.2%
SiCl4: 0.2%
N2: 11.0%
Al(CH3)3: 0%
H2: remainder


forming
Zr-a
NH3: 1.4%
N2: 1.2%
H2: 59%
AlCl3: 0.9%
TiCl4: 0.1%
ZrCl4:
N2: 14.5%
Al(CH3)3: 0%
H2: remainder


process






0.05%



Zr-b
NH3: 1.0%
N2: 0.7%
H2: 57%
AlCl3: 0.5%
TiCl4: 0.4%
ZrCl4: 0.2%
N2: 12.5%
Al(CH3)3: 0%
H2: remainder



Zr-c
NH3: 1.3%
N2: 1.7%
H2: 47%
AlCl3: 0.6%
TiCl4: 0.3%
ZrCl4: 0.1%
N2: 14.0%
Al(CH3)3: 0.7%
H2: remainder



B-a
NH3: 1.3%
N2: 1.8%
H2: 58%
AlCl3: 0.7%
TiCl4: 0.2%
BCl3: 0.3%
N2: 17.5%
Al(CH3)3: 0%
H2: remainder



B-b
NH3: 2.0%
N2: 1.3%
H2: 60%
AlCl3: 0.8%
TiCl4: 0.1%
BCl3: 0.1%
N2: 13.0%
Al(CH3)3: 0%
H2: remainder



B-c
NH3: 1.1%
N2: 1.1%
H2: 56%
AlCl3: 1.2%
TiCl4: 0.2%
BCl3: 0.2%
N2: 14.0%
Al(CH3)3: 0.5%
H2: remainder



V-a
NH3: 1.8%
N2: 2.5%
H2: 50%
AlCl3: 0.9%
TiCl4: 0.3%
VCl4: 0.1%
N2: 13.5%
Al(CH3)3: 0%
H2: remainder



V-b
NH3: 1.4%
N2: 1.4%
H2: 59%
AlCl3: 0.8%
TiCl4: 0.2%
VCl4: 0.03%
N2: 20.0%
Al(CH3)3: 0%
H2: remainder



V-c
NH3: 1.2%
N2: 1.0%
H2: 60%
AlCl3: 0.6%
TiCl4: 0.5%
VCl4: 0.1%
N2: 15.0%
Al(CH3)3: 1.0%
H2: remainder



Cr-a
NH3: 1.5%
N2: 2.0%
H2: 70%
AlCl3: 0.7%
TiCl4: 0.3%
CrCl2: 0.2%
N2: 10.0%
Al(CH3)3: 0%
H2: remainder



Cr-b
NH3: 0.8%
N2: 1.6%
H2: 55%
AlCl3: 1.4%
TiCl4: 0.2%
CrCl2: 0.1%
N2: 13.5%
Al(CH3)3: 0%
H2: remainder



Cr-c
NH3: 1.0%
N2: 0.3%
H2: 57%
AlCl3: 0.7%
TiCl4: 0.2%
CrCl2: 0.3%
N2: 14.5%
Al(CH3)3: 0%
H2: remainder


















TABLE 20









Forming conditions (pressure of reaction atmosphere indicates kPa and temperature



indicates ° C.)














Phase






difference



Gas group A
Gas group B
in supply













Formation of hard

Supply

Supply
between



coating layer
Supply
time per
Supply
time per
gas group















Formation
cycle
cycle
cycle
cycle
A and gas
Reaction Atmosphere















Process type
symbol
(seconds)
(seconds)
(seconds)
(seconds)
group B
Pressure
Temperature


















Film
Si-A
3
0.20
3
0.20
0.15
4.7
800


forming
Si-B
4
0.25
4
0.25
0.20
5.0
900


process
Si-C
5
0.25
5
0.25
0.20
4.7
750


according to
Zr-A
2
0.15
2
0.15
0.10
4.5
800


the present
Zr-B
4
0.20
4
0.20
0.15
4.5
850


invention
Zr-C
1
0.15
1
0.15
0.10
5.0
700



B-A
3
0.20
3
0.20
0.15
4.5
900



B-B
1
0.15
1
0.15
0.10
4.7
750



B-C
5
0.25
5
0.25
0.20
5.0
800



V-A
3
0.20
3
0.20
0.15
4.7
800



V-B
4
0.20
4
0.20
0.15
4.7
750



V-C
5
0.25
5
0.25
0.20
4.5
700



Cr-A
2
0.15
2
0.15
0.10
5.0
850



Cr-B
4
0.20
4
0.20
0.15
4.7
800



Cr-C
3
0.20
3
0.20
0.15
4.5
800


Comparative
Si-a





6.0
600


film forming
Si-b





5.0
900


process
Si-c





4.5
850



Zr-a





4.7
750



Zr-b





4.7
650



Zr-c





4.0
800



B-a





4.5
700



B-b





5.0
800



B-c





4.7
950



V-a





3.5
800



V-b





4.7
850



V-c





4.5
750



Cr-a





5.5
700



Cr-b





4.7
800



Cr-c





5.0
950


















TABLE 21









Hard coating layer (Numerical values



in the lower sections represent



target average layer thicknesses



(μm) of the layer.)



Lower layer











First
Second
Third










Type
layer
layer
layer














Coated tools according
31





to the present
32





invention/Comparative
33





coated tools
34






35






35
TiC






(0.3)



37
TiN






(0.5)



38
TiN
TiCN





(0.1)
(1)



39
TiN
TiCN





(0.1)
(3)



40
TiN






(0.3)



41
TiN
TiCN





(0.5)
(2)



42
TiN
TiCN





(0.3)
(1)



43
TiN






(0.5)



44






45




















TABLE 22








Hard coating layer



TiAlMe complex carbonitride layer (T1−α−βAlαMeβ)(CγN1−γ)
















Formation









symbol of




Area ratio of crystal




process of


Sum of

grains having




forming


average

average crystal grain



Tool
TiAlMeCN
Content
Content
content ratios
Average
misorientation equal



body
(See Tables 4
ratio Xavg of
ratio of Yavg
of Al and Me
content
to or greater than 2


Type
symbol
and 5)
Al
of Me
Xavg + Yavg
ratio Zavg of C
degrees (%)


















Coated tool
31
E
Si-A
0.67
0.031
0.701
0.0048
48


according
32
F
Si-B
0.77
0.054
0.824
0.0001 or
69


to the






less



present
33
G
Si-C
0.79
0.076
0.866
0.0001 or
42


invention






less




34
H
Zr-A
0.86
0.089
0.949
0.0001 or
45









less




35
E
Zr-B
0.92
0.018
0.938
0.0001 or
62









less




38
F
Zr-C
0.61
0.046
0.656
0.0019
22



37
G
B-A
0.84
0.049
0.889
0.0001 or
58









less




38
H
B-B
0.75
0.082
0.832
0.0011
26



39
E
B-C
0.69
0.020
0.710
0.0001 or
64









less




40
F
V-A
0.89
0.023
0.913
0.0001 or
49









less




41
G
V-B
0.80
0.008
0.808
0.0036
38



42
H
V-C
0.65
0.085
0.735
0.0001 or
36









less




43
E
Cr-A
0.63
0.097
0.727
0.0001 or
43









less




44
F
Cr-B
0.74
0.013
0.753
0.0001 or
47









less




45
G
Cr-C
0.86
0.045
0.905
0.0001 or
40









less












Hard coating layer










TiAlMe complex carbonitride layer (T1−α−βAlαMeβ)(CγN1−γ)

















Distribution










ratio of
Distribution









frequencies at
ratio of









which
frequencies at









inclined
which









angles of
inclined
Inclined








normal lines
angles of
angle








of {111}
normal lines
section in




Upper layer



planes are
of {111}
which the

Average


(Numerical values in



present in a
planes are
highest peak

crystal


the lower sections



range of 0 to
present in a
is observed
Area
grain
Average

represent target



12 degrees in
range of 0 to
in the region
ratio
width W
aspect

average layer



the region on
12 degrees in
on the side
of
of cubic
ratio A
Target
thickness (μm) of the



the side of the
the region on
of the
cubic
crystal
of cubic
layer
layer.)

















tool body
the side of the
surface
crystal
grains
crystal
thickness
First
Second


Type
Mdeg
surface Ndeg
(degrees)
(%)
(μm)
grains
(μm)
layer
layer




















Coated tool
31
24
41
9.75 to 10.0 
91
0.8
4.8
4




according
32
19
48
7.5 to 7.75
94
1.1
4.3
5




to the












present
33
39
53
4.5 to 4.75
83
1.6
3.0
5




invention













34
34
50
4.0 to 4.25
62
0.3
5.7
3





35
11
36
10.0 to 10.25
59
0.08
15.8
4





38
39
56
3.25 to 3.5 
96
2.3
2.6
6





37
23
46
8.0 to 8.25
96
0.4
9.3
4





38
39
51
3.75 to 4.0 
92
1.7
1.5
3





39
21
47
6.25 to 6.5 
100
0.7
5.3
4





40
27
44
8.5 to 8.75
80
0.05
12.9
2
TiCN
Al2O3











(0.5)
(2)



41
38
62
0.75 to 1.0 
78
2.1
1.3
3
TiCNO
Al2O3











(0.2)
(1)



42
35
58
2.75 to 3.0 
88
1.4
1.2
2
TiCO
Al2O3











(0.3)
(2)



43
16
34
11.5 to 11.75
77
0.5
1.9
2
TiCNO
Al2O3











(0.3)
(3)



44
25
45
7.0 to 7.25
100
1.2
2.3
3





45
33
48
5.0 to 5.25
85
0.9
5.0
5



















TABLE 23








Hard coating layer



TiAlMe complex carbonitride layer (T1 − α − βAlαMeβ)(CγN1 − γ)























Distribution









Area
ratio of









ratio of
frequencies at









crystal
which









grains
inclined









having
angles of









average
normal lines




Formation




crystal
of {111}




symbol




grain
planes are




of process




misorientation
present in a




of


Sum of

equal to
range of 0 to




forming


average

or
12 degrees in




TiAlMeCN

Content
content

greater
the region on



Tool
(See

ratio of
ratios of Al
Average
than 2
the side of the



body
Tables 4
Content ratio
Yavg of
and Me Xavg +
content ratio
degrees
tool body


Type
symbol
and 5)
Xavg of Al
Me
Yavg
Zavg of C
(%)
Mdeg



















Comparative
31
E
Si-a
0.73
0.137
0.867
0.0001 or
9
54


coated






less




tools
32
F
Si-b
0.56
0.056
0.616
0.0017
2
37



33
G
Si-c
0.86
0.097
0.957
0.0001 or
0
24









less





34
H
Zr-a
0.99
0.003
0.993
0.0001 or











less





35
E
Zr-b
0.52
0.089
0.609
0.0001 or
1
67









less





36
F
Zr-c
0.61
0.047
0.657
0.0077
3
47



37
G
B-a
0.84
0.113
0.953
0.0001 or
0
29









less





38
H
B-b
0.98
0.019
0.999
0.0001 or











less





39
E
B-c
0.96
0.038
0.998
0.0045





40
F
V-a
0.79
0.007
0.797
0.0001 or
0
31









less





41
G
V-b
0.89
0.002
0.892
0.0001 or
3
39









less





42
H
V-c
0.53
0.013
0.543
0.0111
4
59



43
E
Cr-a
0.66
0.086
0.746
0.0001 or
1
49









less





44
F
Cr-b
0.98
0.004
0.984
0.0001 or
0
25









less





45
G
Cr-c
0.83
0.106
0.936
0.0001 or
0
 7









less












Hard coating layer










TiAlMe complex carbonitride layer (T1 − α − βAlαMeβ)(CγN1 − γ)
















Distribution









ratio of









frequencies at









which









inclined
Inclined








angles of
angle








normal lines
section in








of {111}
which the

Average






planes are
highest peak

crystal


Upper layer (Numerical



present in a
is observed

grain
Average

values in the lower



range of 0 to
in the region

width W
aspect

sections represent



12 degrees in
on the side

of cubic
ratio A of
Target
target average



the region on
of the
Area ratio
crystal
cubic
layer
layer thickness



the side of the
surface
of cubic
grains
crystal
thickness
(μm) of the layer.)

















Type
surface Ndeg
(degrees)
crystal (%)
(μm)
grains
(μm)
First layer
Second layer





















Comparative
31
62
2.5 to 2.75
89
1.7
2.3
4





coated












tools
32
37
11.0 to 11.25
97
0.2
19.6
5






33
24
16.75 to 17.0 
68
0.07
1.8
5






34


0


3






35
68
1.5 to 1.75
100
1.5
2.5
4






36
50
5.0 to 5.25
81
1.0
3.3
6






37
28
27.25 to 27.5 
43
0.8
2.3
4






38


0


3






39


0


4






40
30
19.75 to 20.0 
100
0.05
9.8
0.5
TiCN
Al2O3











(0.5)
(2)




41
44
8.5 to 8.75
96
0.3
6.1
3
TiCNO
Al2O3











(0.2)
(1)




42
65
2.75 to 3.0 
73
2.4
0.7
2
TiCO
Al2O3











(0.3)
(2)




43
51
6.0 to 6.25
99
1.2
0.8
2
TiCNO
Al2O3











(0.3)
(3)




44
21
22.5 to 22.75
17
0.1
1.5
3






45
13
31.5 to 31.75
40
0.06
22.4
5







(Note)


Only hexagonal crystals were observed and no cubic crystals were observed in Comparative coated tools 34, 38, and 39.






Next, all the aforementioned variety of coated tools, namely coated tools 31 to 45 according to the present invention and Comparative coated tools 31 to 45 were subjected to the following dry high-speed face milling and a center cutting machining test, which are types of high-speed intermittent cutting of alloy steel, in a state in which the coated tools were clamped with fixing jigs at tip ends of cutters made of tool steel with a cutter diameter of 125 mm, and wear width of a flank faces at all the cutting edges were measured. The results are shown in Table 24.


Tool body: tungsten-carbide-based cemented carbide, titanium-carbonitride-based cermet Cutting test: dry-type high-speed face milling, center cutting machining


Work material: block material of JIS⋅S55C with a width of 100 mm and a length of 400 mm


Rotation speed: 713 min−1


Cutting speed: 280 m/min


Depth of cut: 2.5 mm


Feed rate per tooth: 0.30 mm/tooth


Cutting time: 8 minutes












TABLE 24






Wear width

Cutting



of a flank

test result


Type
face (mm)
Type
(minutes)




















Coated tools
31
0.17
Comparative
31
3.8*


according to
32
0.13
coated
32
5.9*


the present
33
0.14
tools
33
4.1*


invention
34
0.15

34
1.7*



35
0.16

35
3.3*



36
0.12

36
4.4*



37
0.13

37
1.9*



38
0.08

38
2.0*



39
0.11

39
1.6*



40
0.10

40
7.2*



41
0.07

41
6.8*



42
0.10

42
5.2*



43
0.12

43
6.4*



44
0.14

44
4.8*



45
0.15

45
3.7*





The * marks in the sections of the comparative coated tools denote cutting times (minutes) at which life end was reached due to the occurrence of chipping.






Example 4

WC powder, TiC powder, ZrC powder, TaC powder, NbC powder, Cr3C2 powder, TiN powder, and Co powder with average grain sizes of 1 to 3 μm were prepared as raw material powder, the raw material powder was mixed together in the mixing compositions shown in Table 25, wax was further added thereto, the mixture was mixed with acetone in a ball mill for 24 hours, was dried in a reduced pressure, and was press-molded into a green compact with a predetermined shape under a pressure of 98 MPa, the green compact is vacuum-sintered under conditions in which it was held in vacuum of 5 Pa at a predetermined temperature within a range of 1370 to 1470° C. for 1 hour, and after the sintering, tool bodies ε to η made of WC-based cemented carbide with an insert shape of ISO standard CNMG120412 were respectively manufactured by performing honing machining at R: 0.07 mm on cutting edge portions.


TiCN (mass ratio TiC/TiN=50/50) powder, NbC powder, WC powder, Co powder, and Ni powder with average grain sizes of 0.5 to 2 μm were prepared as raw material powder, the raw material powder was mixed together in the mixing compositions shown in Table 26, the mixture was wet mixed in a ball mill for 24 hours, was dried, and was press-molded into a green compact under a pressure of 98 MPa, the green compact is sintered under conditions in which it was held in nitrogen atmosphere at 1.3 kPa at a temperature of 1500° C. for 1 hour, and after the sintering, a tool body θ made of TiCN-based cermet with an insert shape of ISO standard CNMG120412 was manufactured by performing honing machining at R: 0.09 mm on a cutting edge portion.


Next, coated tools 46 to 60 according to the present invention shown in Table 28 were manufactured by using a chemical vapor deposition apparatus on the surfaces of these tool bodies ε to η and the tool body θ to deposit hard coating layers with target layer thicknesses, which included at least (Ti1-x-yAlxMey)(CzN1-z), under the conditions shown in Tables 19 and 20 by a method similar to that in Example 1.


Note that the lower layers shown in Table 27 and/or the upper layers shown in Table 28 were formed for coated tools 49 to 58 according to the present invention under the forming conditions shown in Table 18.


In addition, for the purpose of comparison, Comparative coated tools 46 to 60 shown in Table 29 were manufactured by using a chemical vapor deposition apparatus on the surfaces of these tool bodies E to and the tool body θ to deposit hard coating layers with target layer thicknesses shown in Table 29 under the conditions shown in Tables 19 and 20 by a method similar to that for the coated tools according to the present invention.


Note that the lower layers shown in Table 27 and/or the upper layers shown in Table 29 were formed for Comparative coated tools 49 to 58 under the forming conditions shown in Table 18 in a manner similar to that for coated tools 49 to 58 according to the present invention.


In addition, a scanning electron microscope (magnification: 5000 times) was used to measure sections of the respective constituent layers of coated tools 46 to 60 according to the present invention and Comparative coated tools 46 to 60, and layer thicknesses at five points in an observation field of view were measured and averaged to obtain average layer thicknesses. All the layers had average layer thicknesses that were substantially the same as the target layer thicknesses shown in Tables 27 to 29.


In addition, average content ratios αavg of Al, average content ratios βavg of Me, average content ratios γavg of C, inclined angle frequency distributions Mdeg on the side of the tool bodies, inclined angle frequency distributions Ndeg on the side of the front, angular ranges in which the highest peaks were present in inclined angle sections in the regions on the side of the front, average crystal grain widths W and average aspect ratios A of the crystal grains, and area ratios of cubic crystal phases in the crystal grains in the hard coating layers of coated tools 46 to 60 according to the present invention and Comparative coated tools 46 to 60 were obtained by a method similar to that shown in Example 3. The results are shown in Tables 28 and 29.


Furthermore, crystal orientations of the individual crystal grains which had cubic structures that formed the layer of a complex nitride or a complex carbonitride of Ti and Al were analyzed in the vertical sectional direction by using an electron backscatter diffraction apparatus, and crystal grain misorientations were mapped by dividing a range of 0 to 10 degrees into sections of each 1 degree, that is, a section of equal to or greater than 0 degrees and less than 1 degree, a section of equal to or greater than 1 degree and less than 2 degrees, a section of equal to or greater than 2 degrees and less than 3 degrees, a section of equal to or greater than 3 degrees and less than 4 degrees, and the like. Average crystal grain misorientations and an area ratio of the crystal grains with the average crystal grain misorientations of 2 degrees or greater with respect to the entire layer of a complex nitride or a complex carbonitride of Ti, Al, and Me was obtained from the mapping diagram. The results are shown in Tables 28 and 29.










TABLE 25








Mixing composition (% by mass)















Type
Co
TiC
ZrC
TaC
NbC
Cr3C2
TiN
WC



















Tool
ε
6.5

1.5

2.9
0.1
1.5
Remainder


body
ξ
7.6
2.6

4.0
0.5

1.1
Remainder



η
6.0






Remainder


















TABLE 26








Mixing composition (% by mass)













Type
Co
Ni
NbC
WC
TiCN
















Tool
θ
11
4
6
15
Remainder


body



















TABLE 27









Lower layer (Numerical values




in the lower sections represent



target average layer thickness



(μm) of the layer.)












First
Second
Third
Fourth














Type

layer
layer
layer
layer


















Coated tools
46







according to
47







the present
48







invention/
49
TiC






Comparative

(0.5)



coated tools
50
TiN








(0.3)




51
TiN
TiCN







(0.5)
(7)




52
TiN
TiCN
TiN






(0.1)
(8)
(0.7)




53
TiN
TiCN







(0.3)
(10) 




54








55
TiN
TiCN







(0.5)
(6)




56
TiC
TiN







(0.5)
  (0.5)




57
TiN
TiCN







(0.3)
(8)




58
TiN
TiCN







(0.1)
(4)




59








60






















TABLE 28








Hard coating layer



TiAlMe complex carbonitride layer (Ti1−α−βAlαMeβ)(CγN1−γ)
























Distribution











ratio of
Distribution










frequencies
ratio of










at which
frequencies










inclined
at which










angles of
inclined










normal
angles of










lines of
normal lines










{111}
of {111}









Area ratio of
planes are
planes are




Formation




crystal grains
present in a
present in a




symbol of




having
range of 0
range of 0




process of




average
to 12
to 12




forming


Sum of

crystal grain
degrees in
degrees in




TiAlMeCN

Content
average
Average
misorientation
the region
the region



Tool
(See
Content
ratio of
content ratios
content
equal to or
on the side
on the side



body
Tables 4
ratio Xavg
Yavg of
of Al and Me
ratio Zavg
greater than 2
of the tool
of the


Type
symbol
and 5)
of Al
Me
Xavg + Yavg
of C
degrees (%)
body Mdeg
surface Ndeg




















Coated
46
ε
Si-A
0.68
0.027
0.707
0.0046
52
22
42


tools
47
ξ
Si-B
0.79
0.051
0.841
0.0001 or
66
17
45


according






less





to the
48
η
Si-C
0.77
0.072
0.842
0.0001 or
45
36
50


present






less





invention
49
θ
Zr-A
0.85
0.085
0.935
0.0001 or
41
37
50









less






50
ε
Zr-B
0.93
0.013
0.943
0.0001 or
58
10
34









less






51
ξ
Zr-C
0.62
0.044
0.664
0.0023
21
38
54



52
η
B-A
0.86
0.047
0.907
0.0001 or
55
20
42









less






53
θ
B-B
0.77
0.080
0.850
0.0017
29
37
52



54
ε
B-C
0.67
0.017
0.687
0.0001 or
61
22
49









less






55
ξ
V-A
0.91
0.026
0.936
0.0001 or
52
24
43









less






56
η
V-B
0.79
0.006
0.796
0.0039
36
35
64



57
θ
V-C
0.67
0.082
0.752
0.0001 or
41
33
56









less






58
ε
Cr-A
0.60
0.094
0.694
0.0001 or
47
14
36









less






59
ξ
Cr-B
0.77
0.011
0.781
0.0001 or
46
27
43









less






60
η
Cr-C
0.87
0.042
0.912
0.0001 or
37
35
46









less












Hard coating layer










TiAlMe complex carbonitride layer (Ti1−α−βAlαMeβ)(CγN1−γ)















Inclined








angle








section in








which the








highest

Average






peak is

crystal






observed

grain
Average





in the
Area
width W
aspect

Upper layer (Numerical values in the



region on
ratio of
of cubic
ratio A of
Target
lower sections represent target average



the side of
cubic
crystal
cubic
layer
layer thicknesses (μm) of the layer.)



















the surface
crystal
grains
crystal
thickness
First
Second
Third
Fourth



Type
(degrees)
(%)
(μm)
grains
(μm)
layer
layer
layer
layer






















Coated
46
9.25 to 9.5 
93
0.7
13.5
19







tools
47
8.0 to 8.25
95
1.3
6.6
14







according













to the
48
4.25 to 4.5 
80
1.4
8.6
16







present













invention
49
3.75 to 4.0 
64
0.2
6.3
12








50
10.5 to 10.75
61
0.09
14.9
10








51
3.5 to 3.75
98
2.5
1
8








52
8.75 to 9.0 
94
0.3
17.4
9
TiN













(0.5)







53
3.75 to 4.0 
91
1.5
6.0
10
TiN
TiCN
TiN











(0.3)
(0.4)
(0.3)





54
5.5 to 5.75
100
0.8
7.4
7
TiCNO
Al2O3












(0.3)
(3)






55
8.0 to 8.25
82
0.06
11.7
6
TiCN
Al2O3












(0.5)
(3)






56
1.0 to 1.25
75
2.0
1.8
7
TiCO
Al2O3












(0.5)
(4)






57
2.25 to 2.5 
86
1.6
4.3
9
TiCNO
Al2O3












(0.3)
(5)






58
11.0 to 11.25
79
0.6
9.6
10
TiN
TiCN
TiCNO
Al2O3










(0.3)
(0.5)
(0.3)
(3)




59
7.5 to 7.75
100
1.1
5.2
13








60
5.5 to 5.75
84
0.7
16.8
17





















TABLE 29








Hard coating layer



TiAlMe complex carbonitride layer (Ti1−α−βAlαMeβ)(CγN1−γ)
























Distribution
Distribution










ratio of
ratio of










frequencies
frequencies










at which
at which










inclined
inclined










angles of
angles of










normal
normal










lines of
lines of










{111}
{111}










planes are
planes are









Area ratio of
present in a
present in a




Formation


Sum of

crystal grains
range of 0
range of 0




symbol of


average

having average
to 12
to 12




process of


content

crystal grain
degrees in
degrees in




forming

Content
ratios of
Average
misorientation
the region
the region



Tool
TiAlMeCN
Content
ratio of
Al and Me
content
equal to or
on the side
on the side



body
(See Tables
ratio Xavg
Yavg of
Xavg +
ratio Zavg
greater than 2
of the tool
of the


Type
symbol
4 and 5)
of Al
Me
Yavg
of C
degrees (%)
body Mdeg
surface Ndeg




















Comparative
46
ε
Si-a
0.76
0.129
0.889
0.0001 or
8
55
60


coated tools






less






47
ξ
Si-b
0.54
0.062
0.602
0.0023
4
35
36



48
η
Si-c
0.87
0.093
0.963
0.0001 or
0
22
22









less






49
θ
Zr-a
0.99
0.005
0.995
0.0001 or












less






50
ε
Zr-b
0.53
0.092
0.622
0.0001 or
2
65
66









less






51
ξ
Zr-c
0.63
0.041
0.671
0
2
48
48



52
η
B-a
0.85
0.118
0.968
0.0001 or
0
24
21









less






53
θ
B-b
0.99
0.008
0.998
0.0001 or












less






54
ε
B-c
0.97
0.027
0.997
0.0041






55
ξ
V-a
0.78
0.006
0.786
0.0001 or
0
28
28









less






56
η
V-b
0.91
0.001
0.911
0.0001 or
5
41
43









less






57
θ
V-c
0.54
0.019
0.559
0
6
55
57



58
ε
Cr-a
0.67
0.080
0.750
0.0001 or
2
50
51









less






59
ξ
Cr-b
0.97
0.003
0.973
0.0001 or
0
20
27









less






60
η
Cr-c
0.85
0.109
0.959
0.0001 or
0
 5
 8









less












Hard coating layer










TiAlMe complex carbonitride layer (Ti1−α−βAlαMeβ)(CγN1−γ)















Inclined








angle








section in








which the








highest

Average






peak is

crystal






observed

grain






in the

width
Average





region on
Area
W of
aspect

Upper layer (Numerical values in the



the side of
ratio of
cubic
ratio A
Target
lower sections represent target average



the
cubic
crystal
of cubic
layer
layer thicknesses (μm) of the layer.)



















surface
crystal
grains
crystal
thickness
First
Second
Third
Fourth



Type
(degrees)
(%)
(μm)
grains
(μm)
layer
layer
layer
layer






















Comparative
46
2.0 to 2.25
85
1.5
7.7
22







coated tools














47
11.5 to 11.75
94
0.3
17.4 
14








48
17.25 to 17.5 
58
 0.05
1.5
16








49

0


12








50
0.75 to 1.0 
100
1.8
5.4
10








51
5.5 to 5.75
84
1.4
2.7
8








52
21.25 to 21.5 
37
0.9
1.9
9
TiN













(0.5)







53

0


10
TiN
TiCN
TiN











(0.3)
(0.4)
(0.3)





54

0


7
TiCNO
Al2O3












(0.3)
(3)






55
23.0 to 23.25
100
 0.08
21.1 
6
TiCN
Al2O3












(0.5)
(3)






56
8.75 to 9.0 
88
0.5
5.2
7
TiCO
Al2O3












(0.5)
(4)






57
2.5 to 2.75
69
2.2
1.7
9
TiCNO
Al2O3












(0.3)
(5)






58
4.75 to 5.0 
97
1.1
6.8
10
TiN
TiCN
TiCNO
Al2O3










(0.3)
(0.5)
(0.3)
(3)




59
25.25 to 25.5 
26
0.1
1.3
13








60
28.5 to 28.75
37
 0.05
25.0 
17









(Note)


Only hexagonal crystals were observed and no cubic crystals were observed in Comparative coated tools 49, 53, and 54.






Next, all the aforementioned variety of coated tools, namely coated tools 46 to 60 according to the present invention and Comparative coated tools 46 to 60 were subjected to the following dry high-speed intermittent cutting test of carbon steel and a wet high-speed intermittent cutting test of ductile cast iron in a state in which the coated tools were screw-fixed with fixing jigs at tip ends of cutting tools made of tool steel, and wear width of a flank faces at all the cutting edges were measured.


Cutting condition 1:


Work material: round bar of JIS⋅S15C with four longitudinal grooves at an equal interval in a length direction


Cutting speed: 300 m/min


Depth of cut: 2.5 mm


Feed: 0.30 mm/rev


Cutting time: 5 minutes


(The ordinary cutting speed is 220 m/min)


Cutting condition 2:


Work material: round bar of JIS⋅FCD450 with four longitudinal grooves at an equal interval in a length direction


Cutting speed: 280 m/min


Depth of cut: 2.0 mm


Feed: 0.30 mm/rev


Cutting time: 5 minutes


(The ordinary cutting speed is 250 m/min)


Table 30 shows results of the cutting test.












TABLE 30








Wear width of a flank

Cutting test result



face (mm)

(minutes)













Cutting
Cutting

Cutting
Cutting


Type
condition 1
condition 2
Type
condition 1
condition 2

















Coated
46
0.18
0.15
Comparative
46
2.3*
2.5*


tools
47
0.14
0.11
coated tools
47
3.7*
3.9*


according
48
0.16
0.12

48
3.0*
3.2*


to the
49
0.17
0.13

49
1.2*
1.4*


present
50
0.17
0.15

50
2.7*
2.5*


invention
51
0.13
0.10

51
3.2*
3.3*



52
0.15
0.12

52
1.4*
1.5*



53
0.08
0.07

53
1.5*
1.3*



54
0.10
0.08

54
1.3*
1.5*



55
0.11
0.09

55
4.5*
4.7*



56
0.07
0.05

56
4.1*
4.2*



57
0.09
0.09

57
3.3*
3.5*



58
0.13
0.11

58
3.9*
4.0*



59
0.16
0.12

59
2.9*
2.8*



60
0.17
0.14

60
2.4*
2.6*





The * marks in the sections of the comparative coated tools and the reference coated tools denote cutting times (minutes) at which the life end was reached due to the occurrence of chipping.






From the results shown in Tables 24 and 30, toughness is improved due to strain of the crystal grains and suppression of grain boundary slipping of the crystal grains in the coated tools according to the present invention, by the predetermined average crystal grain misorientations being present in the crystal grains which have cubic structures which form the layer of a complex nitride or a complex carbonitride of Al and Ti that forms the hard coating layer, and by the inclined angles of the normal lines of the {111} planes having the predetermined inclined angle frequency distribution in the region on the side of the tool body and in the region on the side of the surface of the crystal grains. Further, it is obvious that excellent chipping resistance and fracture resistance are achieved even in a case in which the coated tools are used in a high-speed intermittent cutting in which an intermittent and impact, high load exerts on cutting edges, and as a result, excellent wear resistance is exhibited in use over a long period of time.


In contrast, it is obvious that Comparative coated tools 31 to 45 and 46 to 60 in which the predetermined average crystal grain misorientations are not present in the crystal grains which have cubic structures which formed the layer of a complex nitride or a complex carbonitrides of Al, Ti, and Me that form the hard coating layers end the life thereof in short periods of time due to the occurrence of chipping, fracture, and the like in a case in which the coated tools are used in the high-speed intermittent cutting, which is accompanied with high heat generation, in which an intermittent and impact, high load exerts on the cutting edges.


Example 5

Tool bodies A to C made of WC-based cemented carbide and a tool body D made of TiCN-based cermet with insert shapes of ISO standard SEEN1203AFSN, which was similar to that in Example 1, were respectively manufactured.


Next, a chemical vapor deposition apparatus is used on the surfaces of these tool bodies A to D

    • (a) to manufacture coated tools 61 to 75 according to the present invention under the forming conditions A to J shown in Tables 32 and 33, that is, by using a gas group A consisting of NH3, N2, and H2 a gas group B consisting of CrCl3, AlCl3, Al(CH3)3, N2, and H2 and the respective gas supply methods of performing a thermal CVD method for a predetermined period of time using a gas supply method in which in which a reaction gas composition (% by volume with respect to the total for the gas group A and the gas group B) was set to satisfy NH3: 1.0 to 1.5%, N2: 1.0 to 2.0%, and H2: 55 to 60% as the gas group A and AlCl3: 0.6 to 0.9%, CrCl3: 0.2 to 0.3%, Al(CH3)3: 0 to 0.5%, N2: 12.5 to 15.0%, and H2: remainder under conditions of a reaction atmosphere pressure: 4.5 to 5.0 kPa, a reaction atmosphere temperature: 750 to 900° C., a supply cycle: 1 to 5 seconds, a gas supply time per cycle: 0.15 to 0.25 seconds, and a supply phase difference between the gas group A and the gas group B of 0.10 to 0.20 seconds to form hard coating layers of (Cr1-pAlp)(CqN1-q) layers, in which crystal grains that had cubic structures with average crystal grain misorientations of 2 degrees or greater as shown in Table 35 were present at area ratios shown in Table 35, which had target layer thicknesses shown in Table 35.


Note that for coated tools 66 to 73 according to the present invention, lower layers shown in Table 34 and/or upper layers shown in Table 35 were formed under forming conditions shown in Table 31.


In addition, for the purpose of comparison, hard coating layers that contained at least layer of a complex nitride or a complex carbonitrides of Cr and Al with the target layer thicknesses (μm) shown in Table 36 were deposited on the surfaces of tool bodies A to D under the conditions shown in Tables 32 and 33 in a manner similar to that for coated tools 61 to 75 according to the present invention. At this time, Comparative coated tools 61 to 73 were manufactured by forming the hard coating layers such that the reaction gas composition on the surface of the tool bodies did not temporarily change in a process of forming the (Cr1-pAlp)(CqN1-q) layers.


Note that the lower layers shown in Table 34 and/or the upper layers shown in Table 36 were formed for Comparative coated tools 66 to 73 in a manner similar to those for coated tools 66 to 73 according to the present invention under the forming conditions shown in Table 31.


For reference, Reference coated tools 74 and 75 shown in Table 36 were manufactured by depositing (Cr1-pAlp)(CqN1-q) layers in the reference examples with target layer thicknesses on the surfaces of the tool body B and the tool body C by arc ion plating using a physical vapor deposition apparatus in the related art.


Note that conditions for the arc ion plating used in the vapor deposition in the reference examples were as follows.


(a) Aforementioned tool bodies B and C were ultrasonically washed in acetone and were attached to a rotation table in an arc ion plating apparatus along an outer circumferential portion at a position away from the center axis by a predetermined distance in a radial direction in a dried state, and an Al—Cr alloy with a predetermined composition was deployed for a cathode electrode (evaporation source).


(b) First, the inside of the apparatus was evacuated and was heated to 500° C. with a heater while being maintained at a vacuum of 10−2 Pa or lower, a DC bias voltage of −1000V was then applied to the tool bodies that rotated while revolving on the aforementioned rotation table, a current of 200 A was caused to flow between the cathode electrode made of the Al—Cr alloy and an anode electrode to cause arc discharge and generate Al ions and Cr ions in the apparatus, and thereafter, the surfaces of the tool bodies were treated by bombard cleaning.


(c) Then, nitrogen gas was introduced as reaction gas into the apparatus to obtain a reaction atmosphere at 4 Pa, a DC bias voltage at −50 V was applied to the tool bodies that rotated while revolving on the rotation table, and a current of 120 A was caused to flow between the cathode electrode (evaporation source) made of the Al—Cr alloy and the anode electrode to cause arc discharge.


In addition, a scanning electron microscope (magnification: 5000 times) was used to measure sections in a direction perpendicular to the tool bodies of the respective constituent layers of coated tools 61 to 75 according to the present invention, Comparative coated tools 61 to 73, and Reference coated tools 74 and 75, and layer thicknesses at five points in an observation field of view were measured and averaged to obtain average layer thicknesses. All the layers had average layer thicknesses that were substantially the same as the target layer thicknesses shown in Tables 34 to 36.


In addition, for the average content ratio pavg of Al in the layer of a complex nitride or a complex carbonitride, the average content ratio pavg of Al was obtained from averages of obtained analysis results of characteristic X-rays at ten points by irradiating polished surface as a surfaces of the samples with electron beams from the side of the surfaces of the samples by using an electron microanalyzer (EPMA). The average content ratio qavg of C was obtained by secondary ion mass analysis (SIMS). The ranges of 70 μm×70 μm from the side of the surfaces of the samples were irradiated with ion beams, and concentrations of the components discharged by a sputtering effect were measured in a depth direction. The average content ratio qavg of C represents an average value in the depth direction of the layer of a complex nitride or a complex carbonitride of Cr and Al. However, the content ratio of C excludes a content ratio of inevitable C contained even when gas containing C is intentionally not used as a gas raw material. Specifically, the content ratio (atomic ratio) of the C component contained in the layer of a complex nitride or a complex carbonitride in a case in which the supply amount of Al(CH3)3 is assumed to be 0 was obtained as the content ratio of inevitable C, and a value obtained by subtracting the content ratio of inevitable C from a content ratio (atomic ratio) of the C component contained in the layer of a complex nitride or a complex carbonitride obtained in a case in which Al(CH3)3 was intentionally supplied was obtained as qavg.


Furthermore, crystal orientations of the individual crystal grains which had cubic structures that formed the layer of a complex nitride or a complex carbonitride of Cr and Al were analyzed in the vertical sectional direction by using an electron backscatter diffraction apparatus, and in a case in which there were misorientations of 5 degrees or greater between adjacent pixels, the parts were regarded as grain boundaries, a region surrounded by grain boundaries was regarded as one crystal grain, crystal grain misorientations were obtained between a certain pixel in a crystal grain and all the other pixels in the same crystal grain, and the crystal grain misorientations were mapped by dividing a range of 0 to 10 degrees into sections of each 1 degree, that is, a section of equal to or greater than 0 degrees and less than 1 degree, a section of equal to or greater than 1 degree and less than 2 degrees, a section of equal to or greater than 2 degrees and less than 3 degrees, a section of equal to or greater than 3 degrees and less than 4 degrees, and the like. The area ratio of the crystal grains with the average crystal grain misorientations of 2 degrees or greater with respect to the entire layer of a complex nitride or a complex carbonitride of Cr and Al was obtained from the mapping diagram. The results are shown in Tables 35 and 36.



FIG. 11 shows an example of histogram of the average crystal grain misorientations (that is, GOS values) measured in the coated tool 18 according to the present invention, and FIG. 12 shows an example of histogram of the average crystal grain misorientations measured in the comparative coated tool 9.


In addition, for inclined angle frequency distribution of the hard coating layer, a section of the hard coating layer formed of the layer of the complex carbonitride of Cr and Al that had cubic structures was placed in a body tube of a field emission-type scanning electron microscope in a state in which the section was polished, the polished surface as a surface was analyzed in a region on the side of the surface (boundary surface) of the tool body and a region on the side of the surface, which were obtained by equally dividing the polished surface as a surface into two regions in the layer thickness direction, the individual crystal grains that had cubic crystal grain lattice that was present within the measurement ranges were irradiated with electron beams at an acceleration voltage of 10 kV at an incident angle of 70 degrees with an irradiation current of 1 nA, within the measurement ranges of the region on the side of the tool body and the region on the side of the surface in the direction perpendicular to the tool body, and for the width of 10 μm for five fields of view at intervals of 0.1 μm/step in the horizontal direction of the tool body, inclined angles of normal lines of {111} planes, which were crystal planes of the crystal grains, with respect to a normal line of the surface of the tool body (a direction perpendicular to the surface of the tool body in the polished section) were measured by using an electron backscatter diffraction image apparatus, measured inclined angles within a range of 0 to 45 degrees from among the measured inclined angles were divided into sections at a pitch of 0.25 degrees on the basis of the measurement results, and a ratio of the frequencies at which the measured inclined angles were present within a range of 0 to 12 degrees being obtained by aggregating the frequencies at which the measured inclined angles were present. The results are shown in Tables 35 and 36.



FIG. 13 shows an example of the inclined angle frequency distribution measured in the region on the side of the tool body of the hard coating layer that is formed of the layer of the complex carbonitride of Cr and Al of the coated tool according to the present invention, and FIG. 14 shows an example of the inclined angle frequency distribution measured in the region on the side of the surface of the hard coating layer that is formed of the layer of complex carbonitride of Cr and Al of the coated tool according to the present invention.


Further, analysis was performed at intervals of 0.1 μm in the vertical sectional direction by using an electron backscatter diffraction apparatus, measurement within a measurement range with a width of 10 μm and a vertical length of the film thickness in the vertical sectional direction was performed in five fields of view, the total number of pixels that belonged to the crystal grains that formed the layer of a complex nitride or a complex carbonitride was obtained, and the area ratio of the crystal grains which had cubic structures that had the layer of a complex nitride or a complex carbonitride and had the cubic structures was obtained from a ratio with respect to the total number of measured pixels in the measurement performed on the hard coating layer in the aforementioned five fields of view.










TABLE 31








Forming conditions (pressure of reaction atmosphere indicates


Constituent layer of hard coating layer
kPa and temperature indicates ° C.)Forming conditions










Formation
Reaction atmosphere











Type
symbol
Reaction gas composition (% by volume)
Pressure
Temperature















(Cr1−pAlp)(CqN1−q)
CrAlCN
CrAlCN
See Table 32.
See Table 33.
See Table 33.


layer


Ti compound
TiC
TiC
TiCl4: 4.2%, CH4: 8.5%, H2: remainder
7
900


layer
TiN
TiN-1
TiCl4: 4.2%, N2: 30%, H2: remainder
30
850




TiN-2
TiCl4: 4.2%, N2: 35%, H2: remainder
50
900



1-TiCN
1-TiCN
TiCl4: 2%, CH3CN: 0.7%, N2: 10%, H2: remainder
7
900



TiCN
TiCN
TiCl4: 2%, CH4: 1%, N2: 15%, H2: remainder
13
900



TiCO
TiCO
TiCl4: 4.2%, CO: 4%, H2: remainder
7
900



TiCNO
TiCNO
TiCl4: 2%, CO: 1%, CH4: 1%, N2: 5%, H2: remainder
13
900


Al2O3 layer
Al2O3
Al2O3
AlCl3: 2.2%, CO2: 5.5%, HCl: 2.2%, H2S: 0.2%, H2: remainder
7
900

















TABLE 32







Formation of hard
Forming conditions (reaction gas composition is represented as


coating layer
ratio with respect to a total for the gas group A and the gas group B.)










Process
Formation
Reaction gas group A
Reaction gas group B


type
symbol
composition (% by volume)
composition (% by volume)



















Film
A
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.8%
CrCl3: 0.3%
N2: 13%
Al(CH3)3: 0%
H2: remainder


forming
B
NH3: 1.5%
N2: 2.0%
H2: 55%
AlCl3: 0.6%
CrCl3: 0.2%
N2: 12.5%
Al(CH3)3: 0%
H2: remainder


process
C
NH3: 1.5%
N2: 2.0%
H2: 60%
AlCl3: 0.9%
CrCl3: 0.2%
N2: 12.8%
Al(CH3)3: 0%
H2: remainder


according
D
NH3: 1.0%
N2: 1.0%
H2: 55%
AlCl3: 0.9%
CrCl3: 0.3%
N2: 14%
Al(CH3)3: 0.5%
H2: remainder


to the
E
NH3: 1.5%
N2: 1.0%
H2: 55%
AlCl3: 0.7%
CrCl3: 0.2%
N2: 13%
Al(CH3)3: 0%
H2: remainder


present
F
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.8%
CrCl3: 0.3%
N2: 14%
Al(CH3)3: 0%
H2: remainder


invention
G
NH3: 1.0%
N2: 1.0%
H2: 55%
AlCl3: 0.6%
CrCl3: 0.3%
N2: 13.5%
Al(CH3)3: 0.4%
H2: remainder



H
NH3: 1.5%
N2: 1.0%
H2: 55%
AlCl3: 0.7%
CrCl3: 0.3%
N2: 14.5%
Al(CH3)3: 0.2%
H2: remainder



I
NH3: 1.0%
N2: 2.0%
H2: 60%
AlCl3: 0.6%
CrCl3: 0.2%
N2: 13.5%
Al(CH3)3: 0%
H2: remainder



J
NH3: 1.5%
N2: 2.0%
H2: 60%
AlCl3: 0.7%
CrCl3: 0.3%
N2: 15%
Al(CH3)3: 0%
H2: remainder


Compar-
A′
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.8%
CrCl3: 0.3%
N2: 13%
Al(CH3)3: 0%
H2: remainder


ative
B′
NH3: 1.5%
N2: 2.0%
H2: 55%
AlCl3: 0.6%
CrCl3: 0.2%
N2: 12.5%
Al(CH3)3: 0%
H2: remainder


film
C′
NH3: 1.5%
N2: 2.0%
H2: 60%
AlCl3: 0.9%
CrCl3: 0.2%
N2: 12.8%
Al(CH3)3: 0%
H2: remainder


forming
D′
NH3: 1.0%
N2: 1.0%
H2: 55%
AlCl3: 0.9%
CrCl3: 0.3%
N2: 14%
Al(CH3)3: 0.5%
H2: remainder


process
E′
NH3: 1.5%
N2: 1.0%
H2: 55%
AlCl3: 0.7%
CrCl3: 0.2%
N2: 13%
Al(CH3)3: 0%
H2: remainder



F′
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.8%
CrCl3: 0.3%
N2: 14%
Al(CH3)3: 0%
H2: remainder



G′
NH3: 1.0%
N2: 1.0%
H2: 55%
AlCl3: 0.6%
CrCl3: 0.3%
N2: 13.5%
Al(CH3)3: 0.4%
H2: remainder



H′
NH3: 1.5%
N2: 1.0%
H2: 55%
AlCl3: 0.7%
CrCl3: 0.3%
N2: 14.5%
Al(CH3)3: 0.2%
H2: remainder



I′
NH3: 1.0%
N2: 1.0%
H2: 60%
AlCl3: 0.6%
CrCl3: 0.2%
N2: 13.5%
Al(CH3)3: 0%
H2: remainder



J′
NH3: 1.5%
N2: 2.0%
H2: 60%
AlCl3: 0.7%
CrCl3: 0.3%
N2: 15%
Al(CH3)3: 0%
H2: remainder

















TABLE 33








Forming conditions (pressure of reaction atmosphere indicates kPa and temperature



indicates ° C.) Forming conditions














Phase






difference






in supply




Gas group A
Gas group B
between














Formation of hard

Supply

Supply
gas group



coating layer
Supply
time per
Supply
time per
A and gas
















Formation
cycle
cycle
cycle
cycle
group B
Reaction atmosphere















Process type
symbol
(seconds)
(seconds)
(seconds)
(seconds)
(seconds)
Pressure
Temperature


















Film
A
4
0.2
4
0.2
0.1
5
850


forming
B
5
0.2
5
0.2
0.15
4.7
800


process
C
1.2
0.25
1.2
0.25
0.2
4.7
900


according to
D
2
0.25
2
0.25
0.15
5
750


the present
E
1
0.2
1
0.2
0.15
4.7
800


invention
F
2.5
0.2
2.5
0.2
0.1
4.7
750



G
4.5
0.2
4.5
0.2
0.1
4.7
800



H
2.5
0.2
2.5
0.2
0.15
4.5
800



I
1.5
0.15
1.5
0.15
0.1
4.7
750



J
3
0.15
3
0.15
0.1
4.5
800


Comparative
A′





5
850


film forming
B′





4.7
800


process
C′





4.7
900



D′





5
750



E′





4.7
800



F′





4.7
750



G′





4.7
800



H′





4.5
800



I′





4.7
750



J′





4.5
800


















TABLE 34









Hard coating layer (Numerical values



in the lower sections represent



target average layer thickness



(μm) of the layer.



Lower layer












Tool body
First
Second
Third











Type
symbol
layer
layer
layer















Coated tools
61
A





according to
62
B





the present
63
C





invention/
64
D





Comparative
65
A





coated tools/
66
B
TiC




Reference


(0.5)


coated tools
67
C
TiN-1







(0.3)



68
D
TiN-1
1-TiCN






(0.5)
(4)



69
A
TiN-1
1-TiCN
TiCN





(0.3)
(2)
(0.7)



70
B






71
C
TiN-1







(0.5)



72
D
TiC







(1)  



73
A
TiN-1







(0.1)



74
B






75
C




















TABLE 35








Hard coating layer



CrAl complex carbide or carbonitride layer (Cr1−pAlp)(CqN1−q)



















Area ratio of









crystal grains






Formation


having






symbol of


average






process of


crystal grain

Average




forming


misorientation

crystal grain



Tool
CrAlCN
Content

equal to or
Area ratio
width W of



body
(See Tables
ratio xavg of
Content ratio
greater than 2
of cubic
crystal


Type
symbol
4 and 5)
Al
of yavg of C
degrees (%)
crystal (%)
grains (μm)


















Coated tools
61
A
A
0.74
0.0001 or less
41
100
1.1


according to
62
B
B
0.82
0.0001 or less
51
100
1.1


the present
63
C
C
0.93
0.0001 or less
35
89
0.6


invention
64
D
D
0.95
0.0042
35
65
0.1



65
A
E
0.93
0.0001 or less
42
99
0.8



66
B
F
0.74
0.0001 or less
36
100
0.8



67
C
G
0.89
0.0035
20
100
0.2



68
D
H
0.83
0.0013
63
100
0.5



69
A
I
0.79
0.0001 or less
30
100
0.4



70
B
J
0.70
0.0001 or less
54
100
0.30



71
C
A
0.75
0.0001 or less
39
100
0.9



72
D
B
0.81
0.0001 or less
58
100
1.3



73
A
C
0.92
0.0001 or less
38
92
1.2



74
B
D
0.94
0.0041
39
72
0.5



75
C
E
0.92
0.0001 or less
38
96
1.1












Hard coating layer










CrAl complex carbide or carbonitride layer (Cr1−pAlp)(CqN1−q)














Distribution
Distribution






ratio of
ratio of






frequencies
frequencies






at which
at which






inclined
inclined






angles of
angles of






normal lines
normal lines
Inclined





of {111}
of {111}
angle





planes are
planes are
section in





present in a
present in a
which the

















range of 0
range of 0
highest peak

Upper layer




to 12
to 12
is observed

(Numerical values in the




degrees in
degrees in
in the region

lower sections represent



Average
the region
the region
on the side

target average layer



aspect ratio
on the side
on the side
of the
Target layer
thicknesses (μm) of the



A of crystal
of the tool
of the
surface
thickness
layers.)














Type
grains
body Mdeg
surface Ndeg
(degrees)
(μm)
First layer
Second layer


















Coated tools
61
1.5
32
54
7.75 to 8.00
6




according to
62
2.1
28
56
4.75 to 5.00
4




the present
63
2.6
25
48
3.00 to 3.25
4.5




invention
64
3.1
40
61
4.25 to 4.50
2.5





65
4.7
15
30
5.25 to 5.50
5





66
2.3
16
39
9.00 to 9.25
3.5





67
3.2
21
40
6.00 to 6.25
2





68
2.2
28
45
4.50 to 4.75
3





69
8.5
10
39
8.50 to 8.75
7





70
1.5
31
52
6.75 to 7.00
4
Al2O3










(2.5)




71
2.4
25
44
5.50 to 5.75
3
TiCN
Al2O3









(0.5)
(3)



72
2.8
29
59
4.25 to 4.50
5
TiCO
Al2O3









(1)
(2)



73
3.8
31
45
3.50 to 3.75
6
TiCNO
Al2O3









(0.3)
(1)



74
4.2
40
63
5.00 to 5.25
7





75
3.1
17
29
4.50 to 4.75
8



















TABLE 36








Hard coating layer



CrAl complex carbide or carbonitride layer (Cr1−pAlp)(CqN1−q)



















Area ratio of









crystal grains






Formation


having






symbol of


average

Average




process of


crystal grain

crystal




forming


misorientation

grain width



Tool
CrAlCN
Content

equal to or
Area ratio
W of



body
(See Tables
ratio xavg of
Content ratio
greater than 2
of cubic
crystal


Type
symbol
4 and 5)
Al
of yavg of C
degrees (%)
crystal (%)
grains (μm)


















Comparative
61
A
A′
0.76
0.0001 or
4
98
0.9


coated tools




less






62
B
B′
0.83
0.0001 or
9
93
0.8







less






63
C
C′
0.91
0.0001 or
6
91
0.4







less






64
D
D′
0.94
0.0039
6
81
0.2



65
A
E′
0.91
0.0001 or
7
97
0.7







less






66
B
F′
0.73
0.0001 or
4
100
0.8







less






67
C
G′
0.88
0.0023
0
96
0.2



68
D
H′
0.81
0.0022
4
100
0.4



69
A
I′
0.77
0.0001 or
13
100
0.4







less






70
B
J′
0.71
0.0001 or
5
100
0.40







less






71
C
A′
0.78
0.0001 or
8
98
0.8







less






72
D
B′
0.81
0.0001 or
6
92
0.7







less






73
A
C′
0.94
0.0001 or
5
93
1.1







less





Reference coated
74
B
AIP
0.69
0.0001 or
14
100
1.4


tools




less






75
C
AIP
0.59
0.0001 or
11
100
0.7







less












Hard coating layer










CrAl complex carbide or carbonitride layer (Cr1−pAlp)(CqN1−q)














Distribution
Distribution






ratio of
ratio of






frequencies
frequencies






at which
at which






inclined
inclined






angles of
angles of






normal
normal






lines of
lines of






{111}
{111}


















planes are
planes are


Upper layer




present in a
present in a


(Numerical values




range of 0
range of 0
Inclined angle

in the lower




to 12
to 12
section in which

sections represent




degrees in
degrees in
the highest peak

target average



Average
the region
the region
is observed in
Target
layer thicknesses



aspect ratio
on the side
on the side
the region on the
layer
(μm) of the layers.)















A of crystal
of the tool
of the
side of the
thickness
First



Type
grains
body Mdeg
surface Ndeg
surface (degrees)
(μm)
layer
Second layer


















Comparative
61
2.5
34
43
23.25 to 23.50
6




coated tools











62
1.5
33
37
21.25 to 21.50
4





63
2.2
26
32
28.25 to 28.50
4.5





64
2.6
34
28
18.25 to 18.50
2.5





65
4.8
25
32
35.00 to 35.25
5





66
2.6
19
22
28.25 to 28.50
3.5





67
3.1
27
22
32.75 to 33.00
2





68
1.9
22
25
31.00 to 31.25
3





69
7.6
24
21
26.75 to 27.00
7





70
2.1
24
28
23.25 to 23.50
4
Al2O3










(2.5)




71
1.9
32
41
25.50 to 25.75
3
TiCN
Al2O3









(0.5)
(3)



72
2.4
26
34
17.25 to 17.50
5
TiCO
Al2O3









(1)
(2)



73
3.5
35
28
41.50 to 41.75
6
TiCNO
Al2O3









(0.3)
(1)


Reference coated
74
3.3
27
32
28.25 to 28.50
7




tools











75
2.8
25
31
30.25 to 30.50
6







(Note)


“AIP” indicates a film formed through arc ion plating.






Next, all the aforementioned variety of coated tools, namely coated tools 61 to 75 according to the present invention, Comparative coated tools 61 to 73, and Reference coated tools 74 and 75 were subjected to the following dry high-speed face milling and a center cutting machining test, which are types of high-speed intermittent cutting of carbon steel, in a state in which the coated tools were clamped with fixing jigs at tip ends of cutters made of tool steel with a cutter diameter of 125 mm, and wear width of a flank faces at all the cutting edges were measured. The results are shown in Table 37.


Tool body: tungsten-carbide-based cemented carbide, titanium-carbonitride-based cermet Cutting test: dry high-speed face milling, center cutting machining


Work material: block material of JIS⋅S55C with a width of 100 mm and a length of 400 mm


Rotation speed: 713 min−1


Cutting speed: 280 m/min


Depth of cut: 2.5 mm


Feed rate per tooth: 0.25 mm/tooth


Cutting time: 8 minutes












TABLE 37






Wear width

Cutting



of a flank

test result


Type
face (mm)
Type
(minutes)




















Coated tools
61
0.13
Comparative
61
2.3*


according to
62
0.07
coated
62
3.7*


the present
63
0.08
tools
63
3.1*


invention
64
0.14

64
2.0*



65
0.09

65
4.2*



66
0.08

66
4.2*



67
0.10

67
4.0*



68
0.11

68
1.9*



69
0.08

69
4.4*



70
0.13

70
2.5*



71
0.12

71
2.1*



72
0.07

72
4.4*



73
0.10

73
4.3*



74
0.09
Reference
74
3.8*



75
0.12
coated tools
75
2.8*





The * marks in the sections of the comparative coated tools and the reference coated tools denote cutting times (minutes) at which life end was reached due to the occurrence of chipping.






Example 6

Tool bodies α to γ made of WC-based cemented carbide and a tool body δ made of TiCN-based cermet with insert shapes of ISO standard SEEN1203AFSN, which was similar to that in Example 2, were respectively manufactured.


Next, coated tools 76 to 90 according to the present invention shown in Table 39 were manufactured by using a chemical vapor deposition apparatus on the surfaces of these tool bodies α to γ and the tool body δ to deposit hard coating layers with target layer thicknesses, which included at least (Cr1-pAlp)(CqN1-q), under the conditions shown in Tables 32 and 33 by a method similar to that in Example 5.


Note that the lower layers shown in Table 38 and/or the upper layers shown in Table 39 were formed for coated tools 79 to 88 according to the present invention under the forming conditions shown in Table 31.


In addition, for the purpose of comparison, Comparative coated tools 76 to 88 shown in Table 40 were similarly manufactured by using an ordinary chemical vapor deposition apparatus on the surfaces of these tool bodies α to γ and the tool body δ to deposit hard coating layers with target layer thicknesses shown in Table 40 under the conditions shown in Tables 32 and 33 in a manner similar to that for the coated tools according to the present invention.


Note that the lower layers shown in Table 38 and/or the upper layers shown in Table 40 were formed for Comparative coated tools 79 to 88 under the forming conditions shown in Table 31 in a manner similar to that for coated tools 79 to 88 according to the present invention.


For reference, Reference coated tools 89 and 90 shown in Table 40 were manufactured by depositing (Cr1-pAlp)(CqN1-q) layers in the reference examples with target layer thicknesses on the surfaces of the tool body β and the tool body γ by arc ion plating using a physical vapor deposition apparatus in the related art.


Note that conditions similar to the conditions shown in Example 5 were used as conditions for the arc ion plating.


In addition, a scanning electron microscope (magnification: 5000 times) was used to measure sections of the respective constituent layers of coated tools 76 to 90 according to the present invention, Comparative coated tools 76 to 88, and Reference coated tools 89 and 90, and layer thicknesses at five points in an observation field of view were measured and averaged to obtain average layer thicknesses. All the layers had average layer thicknesses that were substantially the same as the target layer thicknesses shown in Tables 39 to 40.


Furthermore, crystal orientations of the individual crystal grains which had cubic structures that formed the layer of a complex nitride or a complex carbonitride of Cr and Al were analyzed in the vertical sectional direction by using an electron backscatter diffraction apparatus, and crystal grain misorientations were mapped by dividing a range of 0 to 10 degrees into sections of each 1 degree, that is, a section of equal to or greater than 0 degrees and less than 1 degree, a section of equal to or greater than 1 degree and less than 2 degrees, a section of equal to or greater than 2 degrees and less than 3 degrees, a section of equal to or greater than 3 degrees and less than 4 degrees, and the like. Average crystal grain misorientations and an area ratio of the crystal grains with the average crystal grain misorientations of 2 degrees or greater with respect to the entire layer of a complex nitride or a complex carbonitride of Cr and Al were obtained from the mapping diagram. The results are shown in Tables 39 and 40.


In addition, for inclined angle frequency distribution of the hard coating layer, a section of the hard coating layer formed of the layer of the complex carbonitride of Cr and Al that had cubic structures was placed in a body tube of a field emission-type scanning electron microscope in a state in which the section was polished, the polished surface as a surface was analyzed in a region on the side of the surface (boundary surface) of the tool body and a region on the side of the surface, which were obtained by equally dividing the polished surface as a surface into two regions in the layer thickness direction, the individual crystal grains that had cubic crystal grain lattice that was present within measurement ranges in the region on the side of the tool body and in the region on the side of the surface were irradiated with electron beams at an acceleration voltage of 10 kV at an incident angle of 70 degrees with an irradiation current of 1 nA, inclined angles of normal lines of {111} planes, which were crystal planes of the crystal grains, with respect to a normal line of the surface of the tool body (a direction perpendicular to the surface of the tool body in the polished section) were measured for the width of 10 μm for five fields of view at intervals of 0.1 μm/step in the horizontal direction of the tool body by using an electron backscatter diffraction image apparatus, measured inclined angles within a range of 0 to 45 degrees from among the measured inclined angles were divided into sections at a pitch of 0.25 degrees on the basis of the measurement results, and frequencies at which the measured inclined angles were present in the respective sections were aggregated, thereby a ratio of frequencies at which the measured inclined angles were present within a range of 0 to 12 degrees being obtained. The results are shown in Tables 39 and 40.










TABLE 38








Hard coating layer (Numerical values in the lower



sections represent target average layer



thickness (μm) of the layer.)



Lower layer













Tool body



Fourth


Type
symbol
First layer
Second layer
Third layer
layer
















Coated tools according
76
α






to the present
77
β






invention/Comparative
78
γ






coated tools/Reference
79
δ
TiC





coated tools


(0.5)






80
α
TiN-1








(0.1)






81
β
TiN-1
1-TiCN







(0.5)
(7)





82
γ
TiN-1
1-TiCN
TiN-2






(0.3)
(10) 
(0.7)




83
δ
TiN-1
1-TiCN
TiCN
TiN-2





(0.3)
(4)
(0.4)
(0.3)



84
α







85
β
TiN-1








(0.5)






86
γ
TiC








(1)






87
δ
TiN-1








(0.1)






88
α
TiN-1








(0.1)






89
β







90
γ




















TABLE 39








Hard coating layer



CrAl complex carbide, carbonitride layer (Cr1−pAlp)(CqN1−q)

















Formation










symbol










of










process










of




Average





forming


Area ratio of crystal

crystal





CrAlCN


grains having average

grain
Average




(See


crystal grain

width W
aspect



Tool
Tables 4


misorientation equal to
Area ratio of
of crystal
ratio A of



body
and
Content ratio
Content ratio
or greater than 2
cubic crystal
grains
crystal


Type
symbol
5)
xavg of Al
of yavg of C
degrees (%)
(%)
(μm)
grains



















Coated
76
α
A
0.75
0.0001 or
28
97
2.0
5.6


tools




less






according
77
β
B
0.80
0.0001 or
59
98
1.8
5.8


to the




less






present
78
γ
C
0.94
0.0001 or
46
96
1.8
5.9


invention




less







79
δ
D
0.93
0.0041
44
79
0.6
4.8



80
α
E
0.91
0.0001 or
24
93
0.4
10.0







less







81
β
F
0.75
0.0001 or
39
100
0.9
3.2







less







82
γ
G
0.87
0.0033
55
95
0.7
2.1



83
δ
H
0.82
0.0021
33
100
1.2
4.2



84
α
I
0.77
0.0001 or
48
98
1.4
10.0







less







85
β
J
0.72
0.0001 or
51
100
0.5
2.0







less







86
γ
A
0.78
0.0001 or
31
97
1.2
3.2







less







87
δ
B
0.82
0.0001 or
61
96
1.7
8.2







less







88
α
C
0.93
0.0001 or
42
95
1.2
2.1







less







89
β
D
0.95
0.0037
42
81
0.5
5.3



90
γ
E
0.90
0.0001 or
22
96
0.7
8.6







less












Hard coating layer










CrAl complex carbide, carbonitride layer (Cr1−pAlp)(CqN1−q)














Distribution
Distribution






ratio of
ratio of






frequencies at
frequencies at






which inclined
which inclined






angles of
angles of
Inclined





normal lines of
normal lines of
angle section





{111} planes
{111} planes
in which the





are present in a
are present in a
highest peak

Upper layer (Numerical



range of 0 to
range of 0 to
is observed in

values in the lower sections represent



12 degrees in
12 degrees in
the region on

target average layer thicknesses



the region on
the region on
the side of
Target layer
(μm) of the layer.)


















the side of the
the side of the
the surface
thickness
First
Second
Third
Fourth



Type
tool body Mdeg
surface Ndeg
(degrees)
(μm)
layer
layer
layer
layer





















Coated
76
38
49
11.75 to
16







tools



12.00








according
77
38
67
5.25 to 5.50
12







to the












present
78
33
55
4.75 to 5.00
15







invention













79
40
61
3.75 to 4.00
7








80
10
38
10.00 to
6











10.25









81
24
44
3.50 to 3.75
7








82
29
56
2.75 to 3.00
3
TiN-2












(0.7)







83
16
30
3.75 to 4.00
8
TiCN
TiN-2











(0.4)
(0.3)






84
21
49
7.25 to 7.50
20
Al2O3












(2)







85
29
59
5.75 to 6.00
4
TiCN
Al2O3











(0.5)
(2.5)






86
36
52
8.75 to 9.00
5
TiCO
Al2O3











(1)
(2)






87
40
70
4.50 to 4.75
16
TiCNO
Al2O3











(0.3)
(1)






88
36
52
6.00 to 6.25
4
TiN-2
TiCN
TiCNO
Al2O3









(0.3)
(0.8)
(0.3)
(3)




89
38
59
2.00 to 2.25
9








90
15
42
6.00 to 6.25
11





















TABLE 40








Hard coating layer



CrAl complex carbide, carbonitride layer (Cr1−pAlp)(CqN1−q)

















Formation










symbol










of










process










of




Average





forming


Area ratio of crystal

crystal





CrAlCN


grains having average

grain
Average




(See


crystal grain

width W
aspect



Tool
Tables 4


misorientation equal to
Area ratio of
of crystal
ratio A of



body
and
Content ratio
Content ratio
or greater than 2
cubic crystal
grains
crystal


Type
symbol
5)
xavg of Al
of yavg of C
degrees (%)
(%)
(μm)
grains



















Comparative
76
α
A′
0.76
0.0001 or
3
100
2.0
4.8


coated




less






tools
77
β
B′
0.83
0.0001 or
6
100
1.6
6.8







less







78
γ
C′
0.92
0.0001 or
4
96
1.7
5.4







less







79
δ
D′
0.95
0.0038
1
78
0.7
3.9



80
α
E′
0.90
0.0001 or
6
99
0.6
7.3







less







81
β
F′
0.74
0.0001 or
4
100
0.8
4.2







less







82
γ
G′
0.90
0.0029
10
94
0.4
2.2



83
δ
H′
0.83
0.0017
5
100
1.3
3.8



84
α
I′
0.79
0.0001 or
5
95
1.3
8.9







less







85
β
J′
0.69
0.0001 or
6
100
0.3
1.9







less







86
γ
A′
0.74
0.0001 or
6
100
1.1
2.8







less







87
δ
B′
0.79
0.0001 or
7
98
1.5
7.3







less







88
α
C′
0.91
0.0001 or
7
91
0.80
2.6







less






Reference
89
β
AIP
0.70
0.0001 or
12
100
1.5
3.3


coated




less






tools
90
γ
AIP
0.60
0.0001 or
13
100
1.6
5.1







less












Hard coating layer










CrAl complex carbide, carbonitride layer (Cr1−pAlp)(CqN1−q)














Distribution
Distribution






ratio of
ratio of






frequencies at
frequencies at






which inclined
which inclined






angles of
angles of
Inclined





normal lines of
normal lines of
angle section





{111} planes
{111} planes
in which the





are present in a
are present in a
highest peak

Upper layer (Numerical values



range of 0 to
range of 0 to
is observed in

in the lower sections represent



12 degrees in
12 degrees in
the region on

target average layer thicknesses



the region on
the region on
the side of
Target layer
(μm) of the layer.)


















the side of the
the side of the
the surface
thickness
First
Second
Third
Fourth



Type
tool body Mdeg
surface Ndeg
(degrees)
(μm)
layer
layer
layer
layer





















Comparative
76
18
23
32.00 to
16







coated



32.25








tools
77
29
36
32.25 to
12











32.50









78
27
22
33.25 to
15











33.50









79
26
22
15.25 to
7











15.50









80
34
43
24.50 to
6











24.75









81
15
18
33.25 to
7











33.50









82
24
19
26.75 to
3
TiN-2










27.00

(0.7)







83
31
28
34.25 to
8
TiCN
TiN-2









34.50

(0.4)
(0.3)






84
23
18
42.50 to
20
Al2O3










42.75

(2)







85
26
31
32.00 to
4
TiCN
Al2O3









32.25

(0.5)
(2.5)






86
21
25
29.25 to
5
TiCO
Al2O3









29.50

(1)
(2)






87
25
31
27.25 to
16
TiCNO
Al2O3









27.50

(0.3)
(1)






88
31
27
36.75 to
4
TiN-2
TiCN
TiCNO
Al2O3







37.00

(0.3)
(0.8)
(0.3)
(3)



Reference
89
26
33
31.75 to
9







coated



32.00








tools
90
28
36
29.25 to
11











29.50





(Note)


“AIP” indicates a film formed through arc ion plating.






Next, all the aforementioned variety of coated tools, namely coated tools 76 to 90 according to the present invention, Comparative coated tools 76 to 88, and Reference coated tools 89 and 90 were subjected to the following dry high-speed intermittent cutting test of carbon steel and a wet high-speed intermittent cutting test of ductile cast iron in a state in which the coated tools were screw-fixed with fixing jigs at tip ends of cutting tools made of tool steel, and wear width of a flank faces at all the cutting edges were measured.


Cutting condition 1:


Work material: round bar of JIS⋅S15C with four longitudinal grooves at an equal interval in a length direction


Cutting speed: 290 m/min


Depth of cut: 2.5 mm


Feed: 0.32 mm/rev


Cutting time: 5 minutes


(The ordinary cutting speed is 220 m/min)


Cutting condition 2:


Work material: round bar of JIS⋅FCD450 with four longitudinal grooves at an equal interval in a length direction


Cutting speed: 270 m/min


Depth of cut: 2.0 mm


Feed: 0.32 mm/rev


Cutting time: 5 minutes


(The ordinary cutting speed is 200 m/min)


Table 41 shows results of the cutting test.












TABLE 41








Wear width of a

Cutting test result



flank face (mm)

(minutes)













Cutting
Cutting

Cutting
Cutting


Type
condition 1
condition 2
Type
condition 1
condition 2

















Coated tools
76
0.21
0.23
Comparative coated
76
4.0*
2.4*


according to
77
0.10
0.12
tools
77
4.7*
3.5*


the present
78
0.19
0.10

78
2.3*
4.3*


invention
79
0.22
0.14

79
2.4*
3.9*



80
0.18
0.20

80
4.4*
2.7*



81
0.13
0.11

81
4.5*
3.0*



82
0.19
0.22

82
4.2*
1.8*



83
0.21
0.13

83
3.2*
4.4*



84
0.15
0.21

84
3.9*
2.4*



85
0.23
0.23

85
2.5*
1.9*



86
0.22
0.16

86
2.9*
4.1*



87
0.12
0.20

87
4.8*
4.2*



88
0.20
0.17

88
3.6*
2.5*



89
0.16
0.22
Reference coated
89
4.3*
2.3*



90
0.22
0.18
tools
90
3.4*
3.7*





The * marks in sections of the comparative coated tools and the reference coated tools denote cutting times (minutes) at which life end was reached due to the occurrence of chipping.






From the results shown in Tables 37 and 41, hardness was improved due to strain of the crystal grains, and toughness is improved while high wear resistance is maintained in the coated tools according to the present invention, by the predetermined average crystal grain misorientations being present in the crystal grains which formed the layer of a complex nitride or a complex carbonitride of Al and Cr that formed the hard coating layer and which had cubic structures, and by the inclined angles of the normal lines of the {111} planes having the predetermined inclined angle frequency distribution in the region on the side of the tool body and in the region on the side of the surface of the crystal grains. Further, it was obvious that excellent chipping resistance and fracture resistance were achieved even in a case in which the coated tools were used in a high-speed intermittent cutting in which an intermittent and impact, high load exerted on cutting edges, and as a result, excellent wear resistance was exhibited in use over a long period of time.


In contrast, it was obvious that Comparative coated tools 61 to 73 and 76 to 88 and Reference coated tools 74, 75, 89, and 90 in which the predetermined average crystal grain misorientations were not present in the crystal grains which had cubic structures which formed the layer of a complex nitride or a complex carbonitrides of Al and Cr that formed the hard coating layers or in which the inclined angles of the normal lines of the {111} planes did not have the predetermined inclined angle frequency distribution in the region on the side of the tool body and in the region on the side of the surface of the crystal grains ended the life thereof in short periods of time due to the occurrence of chipping, fracture, and the like in a case in which the coated tools were used in the high-speed intermittent cutting, which was accompanied with high heat generation, in which an intermittent and impact, high load exerted on the cutting edges.


INDUSTRIAL APPLICABILITY

As described above, since the coated tool according to the present invention can be used not only in a high-speed intermittent cutting of alloy steel but also as a coated tool for a variety of work materials to be cut, and further, the coated tool exhibits excellent chipping resistance and wear resistance in use over a long period of time, the coated tool can sufficiently satisfactorily address an improvement in a performance of a cutting apparatus, and power saving, energy saving, and cost reduction for a cutting.


REFERENCE SIGNS LIST



  • P Measurement point (pixel)

  • B Grain boundary


  • 1 Tool body


  • 2 Hard coating layer


  • 3 Layer of a complex nitride or a complex carbonitride


Claims
  • 1. A surface-coated cutting tool comprising: a hard coating layer; anda tool body that is formed of any of tungsten-carbide-based cemented carbide, titanium-carbonitride-based cermet, and cubic boron-nitride-based ultra-high-pressure sintered body, whereinthe hard coating layer is formed on a surface of the tool body,(a) the hard coating layer contains at least any of a layer of a complex nitride or a complex carbonitride of Ti and Al or a layer of a complex nitride or a complex carbonitride of Ti, Al, and Me (where Me is one kind of element selected from Si, Zr, B, V, and Cr), or a layer of a complex nitride or a complex carbonitride of Cr and Al, with an average layer thickness of 2 to 20 μm,(b) the layer of a complex nitride or a complex carbonitride contains at least a phase of a complex nitride or a complex carbonitride that has an NaCl-type face-centered cubic structure,(c) in a case in which crystal orientations of crystal grains that have NaCl-type face-centered cubic structures from among crystal grains that form the layer of a complex nitride or a complex carbonitride are analyzed in a vertical sectional direction by using an electron backscatter diffraction apparatus, and average crystal grain misorientations in the individual crystal grains are obtained, crystal grains with average crystal grain misorientations of 2 degrees or more are present at an area ratio of 20% with respect to the entire area of the layer of a complex nitride or a complex carbonitride,(d) further, in a case in which inclined angles formed by normal lines of {111} planes, which are crystal planes, with respect to a normal line direction of a surface of a tool body of the crystal grains are measured in a region on a side of the tool body and a region on a side of the surface obtained by equally dividing the layer of a complex nitride or a complex carbonitride into two regions in a layer thickness direction, and frequencies at which measured inclined angles within a range of 0 to 45 degrees with respect to the normal line direction are present from among the measured inclined angles in the respective sections obtained by dividing the inclined angles into each pitch of 0.25 degrees are aggregated, in a case where a ratio of total frequencies of the presence in a range of 0 to 12 degrees with respect to the entire frequencies in inclined angle frequency distribution is set as be Mdeg, Mdeg ranges from 10 to 40%, andin a case where a highest peak is present in an inclined angle section within a range of 0 to 12 degrees in a region on the side of the surface, and a ratio of total frequencies of the presence in the range of 0 to 12 degrees with respect to the entire frequencies in inclined angle frequency distribution is set as be Ndeg, Ndeg is Mdeg+10 to Mdeg+30%.
  • 2. The surface-coated cutting tool according to claim 1, wherein the layer of a complex nitride or a complex carbonitride is a layer of a complex nitride or a complex carbonitride of Ti and Al, and in a case in which a composition is represented by a composition formula: (Ti1-xAlx)(CyN1-y), andan average content ratio xavg of Al with respect to the total amount of Ti and Al and an average content ratio yavg of C with respect to the total amount of C and N (where both xavg and yavg are atomic ratios) in the layer of a complex nitride or a complex carbonitride satisfy 0.60≤xavg≤0.95 and 0≤yavg≤0.005, respectively.
  • 3. The surface-coated cutting tool according to claim 1, wherein the layer of a complex nitride or a complex carbonitride is layer of a complex nitride or a complex carbonitride of Ti, Al, and Me (where Me is one kind of element selected from Si, Zr, B, V, and Cr), and in a case in which a composition thereof is represented by a composition formula: (Ti1-α-βAlαMeβ)(CγNi1-γ), andan average content ratio αavg of Al with respect to the total amount of Ti, Al, and Me, an average content ratio βavg of Me with respect to the total amount of Ti, Al, and Me, and an average content ratio γavg of C with respect to the total amount of C and N (where all of αavg, βavg, and γavg are atomic ratios) in the layer of a complex nitride or a complex carbonitride satisfy 0.60≤αavg, 0.005≤βavg≤0.10, 0≤γavg≤0.05, and 0.605≤αavg+βavg≤0.95, respectively.
  • 4. The surface-coated cutting tool according to claim 1, wherein the layer of a complex nitride or a complex carbonitride is a layer of a complex nitride or a complex carbonitride of Cr and Al, and in a case in which a composition thereof is represented by a composition formula: (Cr1-pAlp)(CqN1-q), andan average content ratio pavg of Al with respect to the total amount of Cr and Al and an average content ratio qavg of C with respect to the total amount of C and N (where both pavg and qavg are atomic ratios) in the layer of a complex nitride or a complex carbonitride satisfy 0.70≤pavg≤0.95 and 0≤qavg≤0.005, respectively.
  • 5. The surface-coated cutting tool according to claim 1, wherein the layer of a complex nitride or a complex carbonitride contains at least 70% by area or more of a phase of a complex nitride or a complex carbonitride that has an NaCl-type face-centered cubic structure.
  • 6. The surface-coated cutting tool according to claim 1, wherein in a case in which the layer of a complex nitride or a complex carbonitride is observed in a vertical sectional direction of the layer, the layer of a complex nitride or a complex carbonitride has a columnar structure in which an average crystal grain width W of the individual crystal grains that have NaCl-type face-centered cubic structures ranges from 0.1 to 2 μm and an average aspect ratio A ranges from 2 to 10.
  • 7. The surface-coated cutting tool according to claim 1, wherein a lower layer that is formed of a Ti compound layer including one layer or two or more layers from among a carbide layer, a nitride layer, a carbonitride layer, a oxycarbide layer, and a oxycarbonitride layer of Ti and that has a total average layer thickness of 0.1 to 20 μm is present between the tool body and the layer of a complex nitride or a complex carbonitride.
  • 8. The surface-coated cutting tool according to claim 1, wherein an upper layer that contains at least an aluminum oxide layer and has a total average layer thickness of 1 to 25 μm is formed above the layer of a complex nitride or a complex carbonitride.
  • 9. A method for manufacturing the surface-coated cutting tool according to claim 1, comprising a step of: forming the layer of a complex nitride or a complex carbonitride by a chemical vapor deposition method in which at least trimethyl aluminum is contained as a reaction gas component.
Priority Claims (4)
Number Date Country Kind
2015-214520 Oct 2015 JP national
2015-214524 Oct 2015 JP national
2015-214527 Oct 2015 JP national
2016-211414 Oct 2016 JP national
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2016/082353 10/31/2016 WO 00
Publishing Document Publishing Date Country Kind
WO2017/073789 5/4/2017 WO A
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Related Publications (1)
Number Date Country
20180311742 A1 Nov 2018 US