(19)
(11)EP 3 318 660 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
26.06.2019 Bulletin 2019/26

(21)Application number: 17199280.3

(22)Date of filing:  30.10.2017
(51)International Patent Classification (IPC): 
C23C 28/04(2006.01)
C23C 16/36(2006.01)
B23B 27/14(2006.01)
C23C 16/34(2006.01)
C23C 16/40(2006.01)

(54)

COATED CUTTING TOOL

BESCHICHTETES SCHNEIDWERKZEUG

OUTIL DE COUPE RECOUVERT


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 02.11.2016 JP 2016215100

(43)Date of publication of application:
09.05.2018 Bulletin 2018/19

(73)Proprietor: Tungaloy Corporation
Iwaki-shi Fukushima 970-1144 (JP)

(72)Inventor:
  • SATOH, Hiroyuki
    Fukushima, 970-1144 (JP)

(74)Representative: Vossius & Partner Patentanwälte Rechtsanwälte mbB 
Siebertstrasse 3
81675 München
81675 München (DE)


(56)References cited: : 
EP-A1- 2 251 122
EP-A1- 3 034 653
EP-A1- 2 604 720
EP-A1- 3 067 133
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention relates to a coated cutting tool.

    Background Art



    [0002] It has been conventionally well known to employ, for the cutting of steel, cast iron, etc., a coated cutting tool which is obtained by depositing, via chemical vapor deposition, a coating layer with a total thickness of from 3 µm or more to 20 µm or less on a surface of a substrate consisting of a cemented carbide. A known example of the above coating layer is a coating layer consisting of a single layer of one kind selected from the group consisting of a Ti carbide, a Ti nitride, a Ti carbonitride, a Ti carbonate, a Ti carboxynitride, and aluminum oxide, or consisting of multiple layers of two or more kinds selected therefrom.

    [0003] As to techniques for improving the fracture resistance of a coated cutting tool, JPH09-507528 T discloses that wear and toughness properties are enhanced by controlling the particle size and thickness of an aluminum oxide layer and also by setting a texture coefficient of a (104) plane so as to be greater than 1.5.

    [0004] JP5902865 B discloses a coating tool in which at least a titanium carbonitride layer and an aluminum oxide layer having an α-type crystalline structure are located, on a substrate surface, in order from the substrate side, wherein, in X-ray diffraction analysis of an aluminum oxide layer, with regard to a texture coefficient (116) represented by Tc (hkl) of the aluminum oxide layer, a surface-side Tc (116) in a surface-side peak is greater than a substrate-side Tc (116) in a substrate-side peak, where the substrate side Tc (116) is from 0.3 or more to 0.7 or less.
    EP 3 034 653 A1 discloses a coated cutting tool comprising a substrate coated with a coating comprising a layer of α-Al2O3, wherein the α-Al2O3layer exhibits a texture coefficient TC(0 0 12) ≥ 7.2.

    Summary


    Technical Problem



    [0005] An increase in speed, feed and depth of cut have become more conspicuous in cutting in recent times, and the thermal shock resistance of a tool is required to be further improved compared to that involved in the prior art. In particular, in recent times, when using coolant in high-speed cutting of steel, the cutting temperature rapidly varies. Under such severe cutting conditions, a conventional cutting tool is likely to involve the occurrence of cracking in a coating layer thereof. This triggers a problem in that fracturing of a coating cutting tool does not allow the tool life to be extended.

    [0006] Based on such background, when only the crystal orientation of an α-type aluminum oxide layer is controlled to achieve preferential orientation of a (104) plane or a (116) plane, as in the tools disclosed in JPH09-507528 T and JP5902865 B mentioned above, sufficient thermal shock resistance cannot be achieved under cutting conditions which place a large load on a coated cutting tool.

    [0007] The present invention has been made in order to solve this problem, and an object of the present invention is to provide a coated cutting tool which has excellent wear resistance and thermal shock resistance and thereby allows the tool life to be extended.

    Solution to Problem



    [0008] A coated cutting tool as recited in the independent claim is provided. The dependent claims define embodiments.

    [0009] The present inventor has conducted studies regarding extending the tool life of a coated cutting tool from the above-described perspective and has then found that the following configurations, including optimizing the crystal orientation in a predetermined plane of an α-type aluminum oxide layer, allow the wear resistance to be improved as the progress of chemical reaction wear is suppressed, and also allow the thermal shock resistance to be improved, and found that, as a result, the tool life of the coated cutting tool can be extended, and this has led to the completion of the present invention.

    [0010] Namely, the present invention is as set forth below:
    1. (1) A coated cutting tool comprising a substrate and a coating layer formed on a surface of the substrate, the coating layer including at least one α-type aluminum oxide layer, wherein, in the α-type aluminum oxide layer, a texture coefficient TC (2,1,10) of a (2,1,10) plane represented by formula (1) below is 1.4 or more.

      (In formula (1), l (h,k,l) denotes a peak intensity for an (h,k,l) plane in X-ray diffraction of the α-type aluminum oxide layer, l0 (h,k,l) denotes a standard diffraction intensity for an (h,k,l) plane which is indicated on a JCPDS Card No. 10-0173 for α-type aluminum oxide, and (h,k,l) refers to eight crystal planes of (0,1,2), (1,0,4), (1,1,0), (1,1,3), (0,2,4), (1,1,6), (2,1,4) and (2,1,10).)


    [0011] An average thickness of the α-type aluminum oxide layer is from 1.0 µm or more to 15.0 µm or less.

    [0012] The coating layer comprises a TiCN layer between the substrate and the α-type aluminum oxide layer.

    [0013] The coating layer comprises, between the TiCN layer and the α-type aluminum oxide layer, an intermediate layer comprised of a compound of at least one kind selected from the group consisting of a Ti carbonate, a Ti oxynitride and a Ti carboxynitride.

    (2) The coated cutting tool of (1), wherein, in the α-type aluminum oxide layer, the texture coefficient TC (2,1,10) is from 2.0 or more to 6.9 or less.

    (3) The coated cutting tool of (1) or (2), wherein a residual stress value in a (1,1,6) plane of the α-type aluminum oxide layer is, in at least part thereof, from -300 MPa or higher to 300 MPa or lower.

    (4) The coated cutting tool of any one of (1) to (3), wherein an average particle size of the TiCN layer is from 0.3 µm or more to 1.5 µm or less.

    (5) The coated cutting tool of any one of (1) to (4), wherein an average thickness of the TiCN layer is from 2.0 µm or more to 20.0 µm or less.

    (6) The coated cutting tool of any one of (1) to (5), wherein an average thickness of the coating layer is from 3.0 µm or more to 30.0 µm or less.

    (7) The coated cutting tool of any one of (1) to (6), wherein the coating layer comprises a TiN layer as an outermost layer on a side opposite to the substrate.

    (8) The coated cutting tool of any one of (1) to (7), wherein the substrate is comprised of any of a cemented carbide, cermet, ceramics and a sintered body containing cubic boron nitride.



    [0014] The present invention can provide a coated cutting tool which has excellent wear resistance and thermal shock resistance and thereby allows the tool life to be extended.

    Description of Embodiments



    [0015] An embodiment for carrying out the present invention (hereinafter simply referred to as the "present embodiment") will hereinafter be described in detail. However, the present invention is not limited to the present embodiment below.

    [0016] A coated cutting tool according to the present embodiment comprises a substrate and a coating layer formed on a surface of the substrate. Specific examples of types of the coated cutting tool include an indexable cutting insert for milling or turning, a drill and an end mill.

    [0017] The substrate in the present embodiment is not particularly limited, as long as it may be used as a substrate for the coated cutting tool. Examples of such substrate include a cemented carbide, cermet, ceramic, a sintered body containing cubic boron nitride, a diamond sintered body and high-speed steel. From among the above examples, the substrate is preferably comprised of any of a cemented carbide, cermet, ceramics and a sintered body containing cubic boron nitride, as this provides excellent wear resistance and fracture resistance, and, from the same perspective, the substrate is more preferably comprised of a cemented carbide.

    [0018] It should be noted that the surface of the substrate may be modified. For instance, when the substrate is comprised of a cemented carbide, a β-free layer may be formed on the surface thereof, and when the substrate is comprised of cermet, a hardened layer may be formed on the surface thereof. The operation and effects of the present invention are still provided, even if the substrate surface has been modified in this way.

    [0019] As to the coating layer in the present embodiment, the average thickness thereof is preferably from 3.0 µm or more to 30.0 µm or less. If the average thickness is 3.0 µm or more, this indicates the tendency of the wear resistance to be further improved, and if such average thickness is 30.0 µm or less, this indicates the tendency of the adhesion with the substrate of the coating layer and the fracture resistance to be further increased. From the same perspective, the average thickness of the coating layer is more preferably from 5.0 µm or more to 27.0 µm or less. It should be noted that, as to the average thickness of each layer and the average thickness of the entire coating layer in the coated cutting tool of the present embodiment, each of such average thicknesses can be obtained by: measuring the thickness of each layer or the thickness of the entire coating layer from each of the cross-sectional surfaces at three or more locations in each layer or in the entire coating layer; and calculating the arithmetic mean of the resulting measurements.

    [0020] The coating layer in the present embodiment includes at least one α-type aluminum oxide layer. In the α-type aluminum oxide layer, a texture coefficient TC (2,1,10) of a (2,1,10) plane represented by formula (1) below is 1.4 or more. When the texture coefficient TC (2,1,10) is 1.4 or more, the ratio of a peak intensity I (2,1,10) for the (2,1,10) plane is high, resulting in excellent thermal shock resistance. From the same perspective, the texture coefficient TC (2,1,10) in the α-type aluminum oxide layer is preferably 1.5 or more, is more preferably 2.0 or more, is further preferably 3.0 or more, and is particularly preferably 4.0 or more. Further, the texture coefficient TC (2,1,10) is preferably 6.9 or less.



    [0021] Herein, in formula (1), l (h,k,l) denotes a peak intensity for an (h,k,l) plane in X-ray diffraction of the α-type aluminum oxide layer, l0 (h,k,l) denotes a standard diffraction intensity for the (h,k,l) plane which is indicated on a JCPDS Card No. 10-0173 for α-type aluminum oxide, and (h,k,l) refers to eight crystal planes of (0,1,2), (1,0,4), (1,1,0), (1,1,3), (0,2,4), (1,1,6), (2,1,4) and (2,1,10). Accordingly, I (2,1,10) denotes a peak intensity for the (2,1,10) plane in X-ray diffraction of the α-type aluminum oxide layer, and l0 (2,1,10) denotes a standard diffraction intensity for the (2,1,10) plane which is indicated on a JCPDS Card No. 10-0173 for α-type aluminum oxide. It should be noted that the standard diffraction intensities for the respective crystal planes are 75.0 for a (0,1,2) plane, 90.0 for a (1,0,4) plane, 40.0 for a (1,1,0) plane, 100.0 for a (1,1,3) plane, 45.0 for a (0,2,4) plane, 80.0 for a (1,1,6) plane, 30.0 for a (2,1,4) plane and 12.0 for a (2,1,10) plane. In the present embodiment, if the texture coefficient TC (2,1,10) is 1.4 or more, this indicates the tendency of the α-type aluminum oxide layer to have preferential orientation of the (2,1,10) plane. In particular, if the texture coefficient TC (2,1,10) is 4.0 or more, the texture coefficient of the (2,1,10) plane is greater than the TC of any of the other crystal planes in light of the point that the total of the TCs of the respective crystal planes is 8.0 or more. In other words, if the texture coefficient TC (2,1,10) is 4.0 or more, the α-type aluminum oxide layer has the most preferential orientation of the (2,1,10) plane. In light of the above, the coated cutting tool of the present embodiment brings about the suppression of the progress of chemical reaction wear and the enhancement of wear resistance and further brings about the enhancement of thermal shock resistance, and, as a result, the tool life of the coated cutting tool can be extended.

    [0022] The average thickness of the α-type aluminum oxide layer of the present embodiment is from 1.0 µm or more to 15.0 µm or less. If the average thickness of the α-type aluminum oxide layer is 1.0 µm or more, this indicates the tendency of the crater wear resistance in the rake surface of the coated cutting tool to be further improved, and if such average thickness is 15.0 µm or less, this indicates the tendency of the fracture resistance of the coated cutting tool to be further improved as the peeling of the coating layer is further suppressed. From the same perspective, the average thickness of the α-type aluminum oxide layer is preferably from 1.5 µm or more to 12.0 µm or less, and is further preferably from 3.0 µm or more to 10.0 µm or less.

    [0023] In the present embodiment, the residual stress value in a (1,1,6) plane of the α-type aluminum oxide layer is, at least in part thereof, preferably from -300 MPa or higher to 300 MPa or lower. If the residual stress value is -300 MPa or higher, this indicates the tendency of the wear resistance to be improved because the progress of wear - which starts from the time when particles fall off from the α-type aluminum oxide layer - can be further suppressed. Further, if the residual stress value is 300 MPa or lower, this indicates the tendency of the fracture resistance of the coated cutting tool to be further improved because the generation of cracking in the α-type aluminum oxide layer can be further suppressed. From the same perspective, the residual stress value in the (1,1,6) plane of the α-type aluminum oxide layer is more preferably from -250 MPa or higher to 250 MPa or lower.

    [0024] Herein, the term "at least in part thereof" indicates that, it is not necessary to satisfy, in the entire α-type aluminum oxide layer, the above residual stress value range in the (1,1,6) plane of the α-type aluminum oxide layer, and such term also indicates that it is only required to satisfy the above residual stress value range in the (1,1,6) plane of the α-type aluminum oxide layer in a specific area such as a rake surface.

    [0025] The residual stress value of the α-type aluminum oxide layer can be measured by a sin2ϕ method using an X-ray stress measuring apparatus. It is preferable to measure, via the sin2ϕ method, the residual stresses at any three points included in the coating layer and to obtain the arithmetic mean of the residual stresses at such three points. Any three points, serving as measurement locations, in the α-type aluminum oxide layer are preferably selected in such a way as to be 0.1 mm or more apart from one another.

    [0026] In order to measure the residual stress value in the (1,1,6) plane of the α-type aluminum oxide layer, the (1,1,6) plane of the α-type aluminum oxide layer which serves as a measurement subject is selected for measurement. More specifically, a sample in which an α-type aluminum oxide layer is formed is subjected to analysis with an X-ray diffractometer. Then, an examination is conducted regarding variations in the diffraction angle of the (1,1,6) plane when a change is made to an angle ϕ formed by a sample plane normal and a lattice plane normal.

    [0027] The α-type aluminum oxide layer is a layer comprised of α-type aluminum oxide. However, such α-type aluminum oxide layer may contain a very small amount of components other than α-type aluminum oxide, as long as it comprises the configuration of the present embodiment and provides the operation and effects of the present invention.

    [0028] The coating layer of the present embodiment comprises a TiCN layer between the substrate and the α-type aluminum oxide layer, as this improves wear resistance. The average particle size of the TiCN layer is preferably from 0.3 µm or more to 1.5 µm or less. This is preferable in that: if the average particle size of the TiCN layer is 0.3 µm or more, the fracture resistance is further enhanced; and, if such average particle size is 1.5 µm or less, the wear resistance is further improved because the progress of wear due to the falling of particles is suppressed. Further, the average particle size of the TiCN layer is preferably from 0.3 µm or more to 1.5 µm or less, because this indicates the tendency of the texture coefficient (2,1,10) in the α-type aluminum oxide layer to have a greater value. From the same perspective, the average particle size of the TiCN layer is more preferably from 0.4 µm or more to 1.3 µm or less.

    [0029] The average particle size of the TiCN layer can be obtained by observing a cross-sectional structure of the TiCN layer using a commercially available electron backscatter diffraction pattern apparatus (EBSD) attached to a field emission scanning electron microscope (FE-SEM) or to a transmission electron microscope (TEM). More specifically, mirror polishing is performed on a cross-section in a direction parallel or substantially parallel to a surface of the substrate of the coated cutting tool, and the resulting mirror-polished surface is regarded as a cross-sectional structure. Examples of a method of mirror-polishing a TiCN layer include: a polishing method with the use of diamond paste or colloidal silica; and ion milling. A sample of a coated cutting tool is set on an FE-SEM such that a cross-sectional structure of a TiCN layer can be irradiated with an electron beam, and the sample is then irradiated with an electron beam under the conditions of an angle of incidence of 70 degrees, an acceleration voltage of 15 kV, and an irradiation current of 0.5 nA. Measurement is desirably performed under the EBSD settings of a measurement range of 30 µm x 50 µm and a step size of 0.1 µm. A particle is defined as an area surrounded by a structure boundary with a misorientation of 5 degrees or more. The diameter of a circle whose area is equal to the area of a particle is regarded as a particle size of such particle. Image analysis software may be used when obtaining a particle size of the cross-sectional structure of the TiCN layer. The particle sizes in the TiCN layer are measured with regard to a range of 30 µm x 50 µm, and the average value (arithmetic mean) of all the obtained particle sizes is regarded as an average particle size.

    [0030] The average thickness of the TiCN layer of the present embodiment is preferably from 2.0 µm or more to 20.0 µm or less. If the average thickness of the TiCN layer is 2.0 µm or more, this indicates the tendency of the wear resistance of the coated cutting tool to be further improved, and, if such average thickness is 20.0 µm or less, this indicates the tendency of the fracture resistance of the coated cutting tool to be further improved as the peeling of the coating layer is further suppressed. From the same perspective, the average thickness of the TiCN layer is more preferably from 5.0 µm or more to 15.0 µm or less.

    [0031] The TiCN layer is a layer comprised of TiCN. However, such TiCN layer may contain a very small amount of components other than TiCN, as long as it comprises the above-described configuration and provides the operation and effects of the TiCN layer.

    [0032] The coating layer of the present embodiment includes, between the TiCN layer and the α-type aluminum oxide layer, an intermediate layer comprised of a compound of at least one kind selected from the group consisting of a Ti carbonate, a Ti oxynitride and a Ti carboxynitride as the adhesion is further improved. The average thickness of such intermediate layer is preferably from 0.2 µm or more to 1.5 µm or less. This is preferable in that: if the average thickness of the intermediate layer is 0.2 µm or more, this indicates the tendency of the adhesion to be further improved; and, if such average thickness is 1.5 µm or less, this indicates the tendency of the texture coefficient TC (2,1,10) of the (2,1,10) plane in the α-type aluminum oxide layer to have a greater value.

    [0033] The intermediate layer is a layer comprised of a compound of at least one kind selected from the group consisting of a Ti carbonate, a Ti oxynitride and a Ti carboxynitride. However, such intermediate layer may contain a very small amount of components other than the above compound, as long as it comprises the above-described configuration and provides the operation and effects of the intermediate layer.

    [0034] The coating layer of the present embodiment preferably comprises a TiN layer as an outermost layer on a side opposite to the substrate as this makes it possible to confirm the usage state, such as whether or not the coated cutting tool has been used, thereby leading to excellent visibility. The average thickness of the TiN layer is preferably from 0.2 µm or more to 1.0 µm or less. This is preferable in that: if the average thickness of the TiN layer is 0.2 µm or more, this provides the effect of further suppressing the falling of particles from the α-type aluminum oxide layer; and, if such average thickness is 1.0 µm or less, the fracture resistance of the coated cutting tool is improved.

    [0035] The coating layer of the present embodiment preferably comprises, between the substrate and the TiCN layer, a TiN layer serving as a lowermost layer in the coating layer, as this leads to adhesion being improved. The average thickness of this TiN layer is preferably from 0.1 µm or more to 0.5 µm or less. If the average thickness of the TiN layer is 0.1 µm or more, this indicates the tendency of the adhesion to be further improved as the TiN layer has a more uniform structure. Meanwhile, if the average thickness of the TiN layer is 0.5 µm or less, this indicates the tendency of the fracture resistance to be further enhanced as the TiN layer, being the lowermost layer, is further prevented from serving as a starting point of peeling.

    [0036] The TiN layers respectively serving as the outermost layer and the lowermost layer are each a layer comprised of TiN. However, such TiN layers may each contain a very small amount of components other than TiN, as long as they respectively comprise the above-described configurations and provide the operation and effects of the outermost layer and the lowermost layer.

    [0037] Examples of a method of forming layers that constitute a coating layer in a coated cutting tool according to the present invention include the method set forth below. However, such method of forming layers is not limited thereto.

    [0038] For instance, a TiN layer can be formed by chemical vapor deposition with a raw material gas composition of TiCl4: from 5.0 mol% or more to 10.0 mol% or less, N2: from 20 mol% or more to 60 mol% or less, and H2: the balance, a temperature of from 850°C or higher to 920°C or lower, and a pressure of from 100 hPa or higher to 400 hPa or lower.

    [0039] A TiCN layer can be formed by chemical vapor deposition with a raw material gas composition of TiCl4: from 1.0 mol% or more to 8.0 mol% or less, CH3CN: from 0.5 mol% or more to 2.0 mol% or less, and H2: the balance, a temperature of from 850°C or higher to 930°C or lower, and a pressure of from 100 hPa or higher to 150 hPa or lower. At this time, the average particle size of the TiCN layer is easily adjusted so as to fall within a range of from 0.3 µm or more to 1.5 µm or less by, for example, controlling the molar ratio of TiCl4 to CH3CN, i.e., TiCl4/CH3CN, so as to be from 4.0 or more to 8.0 or less, and controlling the temperature so as to fall within a range of from 850°C or higher to 920°C or lower.

    [0040] A TiCNO layer, being a layer comprised of a Ti carboxynitride, can be formed by chemical vapor deposition with a raw material gas composition of TiCl4: from 3.0 mol% or more to 5.0 mol% or less, CO: from 0.4 mol% or more to 1.0 mol% or less, N2: from 30 mol% or more to 40 mol% or less, and H2: the balance, a temperature of from 975°C or higher to 1,025°C or lower, and a pressure of from 90 hPa or higher to 110 hPa or lower.

    [0041] A TiCO layer, being a layer comprised of a Ti carbonate, can be formed by chemical vapor deposition with a raw material gas composition of TiCl4: from 0.5 mol% or more to 1.5 mol% or less, CO: from 2.0 mol% or more to 4.0 mol% or less, and H2: the balance, a temperature of from 975°C or higher to 1,025°C or lower, and a pressure of from 60 hPa or higher to 100 hPa or lower.

    [0042] In the present embodiment, a coated cutting tool which involves the controlled orientation (orientation relationship) of an α-type aluminum oxide layer can be obtained by, for example, the method set forth below.

    [0043] Firstly, one or more layers selected from the group consisting of a TiCN layer, if necessary, a TiN layer, also if necessary, and the intermediate layer is(are) formed on a surface of a substrate. Next, from among the above layers, a surface of a layer which is most distant from the substrate is oxidized. Thereafter, a nucleus of an α-type aluminum oxide layer is formed on the surface of the layer which is most distant from the substrate, and an α-type aluminum oxide layer is then formed in the state in which such nucleus has been formed. Further, as needed, a TiN layer may be formed on a surface of the α-type aluminum oxide layer.

    [0044] More specifically, the oxidation of the surface of the layer which is most distant from the substrate is performed under the conditions of a raw material gas composition of CO2: from 0.1 mol% or more to 1.0 mol% or less, C3H6: from 0.05 mol% or more to 0.2 mol% or less, and H2: the balance, a temperature of from 970°C or higher to 1,020°C or lower, and a pressure of from 50 hPa or higher to 70 hPa or lower. Here, the oxidation time is preferably from 5 minutes or more to 10 minutes or less.

    [0045] Thereafter, the nucleus of the α-type aluminum oxide layer is formed by chemical vapor deposition with a raw material gas composition of AlCl3: from 2.0 mol% or more to 5.0 mol% or less, CO2: from 2.5 mol% or more to 4.0 mol% or less, HCl: from 2.0 mol% or more to 3.5 mol% or less, C3H6: from 0.05 mol% or more to 0.2 mol% or less, and H2: the balance, a temperature of from 970°C or higher to 1,030°C or lower, and a pressure of from 60 hPa or higher to 80 hPa or lower.

    [0046] The α-type aluminum oxide layer is then formed by chemical vapor deposition with a raw material gas composition of AlCl3: from 2.0 mol% or more to 5.0 mol% or less, CO2: from 2.5 mol% or more to 4.0 mol% or less, HCl: from 2.0 mol% or more to 3.0 mol% or less, H2S: from 0.15 mol% or more to 0.25 mol% or less, and H2: the balance, a temperature of from 970°C or higher to 1,030°C or lower, and a pressure of from 60 hPa or higher to 80 hPa or lower.

    [0047] As described above, a surface of the TiN layer, the TiCN layer or the intermediate layer is oxidized, the nucleus of the α-type aluminum oxide layer is then formed, and the α-type aluminum oxide layer is then formed with normal conditions, thereby making it possible to obtain an α-type aluminum oxide layer with a texture coefficient TC (2,1,10) of 1.4 or more. At this time, it is preferable that a surface of a TiCN layer with an average particle size of from 0.3 µm or more to 1.5 µm or less is oxidized, and that a nucleus of an α-type aluminum oxide layer is then formed thereon, because this indicates the tendency of the texture coefficient TC (2,1,10) of the α-type aluminum oxide layer to be increased.

    [0048] After the formation of the coating layer, dry shot blasting, wet shot blasting or shot peening is performed thereon, and the conditions are adjusted, thereby making it possible to control the residual stress value in a (4,2,2) plane of the TiCN layer. For instance, as to the conditions for dry shot blasting, a shot material may be shot onto a surface of the coating layer at a shot velocity of from 50 m/sec or more to 80 m/sec or less and for a shot time of from 0.5 minutes or more to 3 minutes or less so as to achieve a shot angle of from 30° or more to 70° or less. From the perspective of easily controlling the residual stress value so as to fall within the above range, the shot material (medium) in dry shot blasting is preferably a material(s) of one or more kinds, each of which has an average particle size of from 100 µm or more to 150 µm or less and is(are) selected from the group consisting of Al2O3 and ZrO2.

    [0049] The thickness of each layer in the coating layer of the coated cutting tool of the present embodiment can be measured by observing a cross-sectional structure of the coated cutting tool, using an optical microscope, a scanning electron microscope (SEM), an FE-SEM, or the like. It should be noted that, as to the average thickness of each layer in the coated cutting tool of the present embodiment, such average thickness can be obtained by: measuring the thickness of each layer at three or more locations near the position 50 µm from the edge, toward the center of the rake surface of the coated cutting tool; and calculating the arithmetic mean of the resulting measurements. Further, the composition of each layer can be measured from a cross-sectional structure of the coated cutting tool of the present embodiment, using an energy-dispersive X-ray spectroscope (EDS), a wavelength-dispersive X-ray spectroscope (WDS) or the like.

    (Examples)



    [0050] Although the present invention will be described in further detail below, with examples, the present invention is not limited to such examples.

    [0051] A cemented carbide cutting insert with a shape of JIS certified CNMA120412 and a composition of 93.1WC-6.4Co-0.5Cr3C2 (mass%) was prepared as a substrate. The edge of such substrate was subjected to round honing by means of an SiC brush, and a surface of the substrate was then washed.

    [0052] After the substrate surface was washed, a coating layer was formed by chemical vapor deposition. As to invention samples 1 to 17, firstly, the substrate was inserted into an external heating chemical vapor deposition apparatus, and a lowermost layer, whose composition is shown in Table 6, was formed on the substrate surface so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions shown in Table 1. Then, a TiCN layer, whose composition is shown in Table 6, was formed on the surface of the lowermost layer so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions shown in Table 2. Next, an intermediate layer, whose composition is shown in Table 6, was formed on the surface of the TiCN layer so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions shown in Table 1. Thereafter, a surface of the intermediate layer was oxidized for the time shown in Table 3, under the raw material gas composition, temperature and pressure conditions shown in Table 3. Then, a nucleus of α-type aluminum oxide was formed on the oxidized surface of the intermediate layer under the raw material gas composition, temperature and pressure conditions concerning the "nucleus formation conditions" shown in Table 4. Further, an α-type aluminum oxide layer, whose composition is shown in Table 6, was formed on the surface of the intermediate layer and the surface of the nucleus of α-type aluminum oxide so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions concerning the "deposition conditions" shown in Table 4. Lastly, an outermost layer, whose composition is shown in Table 6, was formed on the surface of the α-type aluminum oxide layer so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions shown in Table 1. As a result, the coated cutting tools of invention samples 1 to 17 were obtained.

    [0053] Meanwhile, as to comparative samples 1 to 14, firstly, the substrate was inserted into an external heating chemical vapor deposition apparatus, and a lowermost layer, whose composition is shown in Table 6, was formed on the substrate surface so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions shown in Table 1. Then, a TiCN layer, whose composition is shown in Table 6, was formed on the surface of the lowermost layer so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions shown in Table 2. Next, an intermediate layer, whose composition is shown in Table 6, was formed on the surface of the TiCN layer so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions shown in Table 1. Thereafter, the surface of the intermediate layer was oxidized for the time shown in Table 3, under the raw material gas composition, temperature and pressure conditions shown in Table 3. Then, a nucleus of α-type aluminum oxide was formed on the oxidized surface of the intermediate layer under the raw material gas composition, temperature and pressure conditions concerning the "nucleus formation conditions" shown in Table 5. Further, an α-type aluminum oxide layer, whose composition is shown in Table 6, was formed on the surface of the intermediate layer and the surface of the nucleus of α-type aluminum oxide so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions concerning the "deposition conditions" shown in Table 5. Lastly, an outermost layer, whose composition is shown in Table 6, was formed on the surface of the α-type aluminum oxide layer so as to have the average thickness shown in Table 6 under the raw material gas composition, temperature and pressure conditions shown in Table 1. As a result, the coated cutting tools of comparative samples 1 to 14 were obtained.

    [0054] The thickness of each layer of each of the samples was obtained as set forth below. That is, using an FE-SEM, the average thickness was obtained by: measuring the thickness of each layer, from each of the cross-sectional surfaces at three locations near the position 50 µm from the edge of the coated cutting tool, toward the center of the rake surface thereof; and calculating the arithmetic mean of the resulting measurements. Using an EDS, the composition of each layer of the obtained sample was measured from the cross-sectional surface near the position at most 50 µm from the edge of the coated cutting tool, toward the center of the rake surface thereof.
    [Table 1]
    Each layer compositionTemperature (°C)Pressure (hPa)Raw material gas composition (mol%)
    TiN 900 400 TiCl4:7.5%, N2:40.0%, H2:52.5%
    TiC 1,000 75 TiCl4:2.4%, CH4:4.6%, H2:93.0%
    TiCNO 1,000 100 TiCl4:3.5%, CO:0.7%, N2:35.5%, H2:60.3%
    TiCO 1,000 80 TiCl4:1.3%, CO:2.7%, H2:96.0%
    [Table 2]
    Sample No.Temperature (°C)Pressure (hPa)Raw material gas composition (mol%)
    Invention sample 1 880 100 TiCl4:4.0%, CH3CN:1.0%, H2:95.0%
    Invention sample 2 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Invention sample 3 850 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Invention sample 4 880 150 TiCl4:8.0%, CH3CN:1.0%, H2:91.0%
    Invention sample 5 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Invention sample 6 930 150 TiCl4:8.0%, CH3CN:2.0%, H2:90.0%
    Invention sample 7 880 130 TiCl4:3.5%, CH3CN:0.8%, H2:95.7%
    Invention sample 8 880 130 TiCl4:6.0%, CH3CN:1.5%, H2:92.5%
    Invention sample 9 920 130 TiCl4:8.0%, CH3CN:1.0%, H2:91.0%
    Invention sample 10 880 130 TiCl4:4.5%, CH3CN:1.5%, H2:94.0%
    Invention sample 11 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Invention sample 12 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Invention sample 13 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Invention sample 14 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Invention sample 15 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Invention sample 16 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Invention sample 17 880 130 TiCl4:4.5%, CH3CN:1.5%, H2:94.0%
    Comparative sample 1 880 130 TiCl4:4.0%, CH3CN:1.0%, H2:95.0%
    Comparative sample 2 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Comparative sample 3 850 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Comparative sample 4 920 130 TiCl4:8.0%, CH3CN:1.0%, H2:91.0%
    Comparative sample 5 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Comparative sample 6 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Comparative sample 7 880 130 TiCl4:4.0%, CH3CN:1.0%, H2:95.0%
    Comparative sample 8 880 130 TiCl4:4.0%, CH3CN:1.0%, H2:95.0%
    Comparative sample 9 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Comparative sample 10 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Comparative sample 11 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Comparative sample 12 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Comparative sample 13 880 130 TiCl4:6.0%, CH3CN:1.0%, H2:93.0%
    Comparative sample 14 880 130 TiCl4:4.5%, CH3CN:1.5%, H2:94.0%
    [Table 3]
    Sample No.Temperature (°C)Pressure (hPa)Raw material gas composition (mol%)Hour (min)
    Invention sample 1 990 60 CO2:0.4%, C3H6:0.1%, H2:99.5% 5
    Invention sample 2 990 70 CO2:0.8%, C3H6:0.1%, H2:99.1% 6
    Invention sample 3 990 70 CO2:0.4%, C3H6:0.15%, H2:99.45% 8
    Invention sample 4 1,020 70 CO2:0.4%, C3H6:0.1%, H2:99.5% 9
    Invention sample 5 990 60 CO2:0.8%, C3H6:0.1%, H2:99.1% 7
    Invention sample 6 970 50 CO2:1.0%, C3H6:0.1%, H2:98.9% 6
    Invention sample 7 990 50 CO2:0.4%, C3H6:0.1%, H2:99.5% 6
    Invention sample 8 970 60 CO2:0.1%, C3H6:0.1 %, H2:99.8% 5
    Invention sample 9 990 70 CO2:0.8%, C3H6:0.1%, H2:99.1% 6
    Invention sample 10 990 60 CO2:0.8%, C3H6:0.1%, H2:99.1% 8
    Invention sample 11 1,020 60 CO2:0.4%, C3H6:0.2%, H2:99.4% 10
    Invention sample 12 990 60 CO2:0.4%, C3H6:0.1%, H2:99.5% 5
    Invention sample 13 990 70 CO2:0.4%, C3H6:0.15%, H2:99.45% 8
    Invention sample 14 1,020 60 CO2:0.4%, C3H6:0.2%, H2:99.4% 10
    Invention sample 15 990 70 CO2:0.4%, C3H6:0.15%, H2:99.45% 8
    Invention sample 16 990 70 CO2:0.4%, C3H6:0.15%, H2:99.45% 8
    Invention sample 17 990 70 CO2:0.4%, C3H6:0.15%, H2:99.45% 8
    Comparative sample 1 990 60 CO2:0.8%, H2:99.2% 5
    Comparative sample 2 990 50 CO2:0.8%, H2:99.2% 7
    Comparative sample 3 990 60 CO2:0.9%, H2:99.1% 5
    Comparative sample 4 990 60 CO2:0.1%, H2:99.9% 10
    Comparative sample 5 990 70 CO2:0.4%, H2:99.6% 5
    Comparative sample 6 990 60 CO2:0.3%, C3H6:0.05%, H2:99.65% 2
    Comparative sample 7 970 60 CO2:0.4%, H2:99.6% 5
    Comparative sample 8 990 60 CO2:0.8%, H2:99.2% 6
    Comparative sample 9 990 60 CO2:0.8%, H2:99.2% 5
    Comparative sample 10 1,020 60 CO2:0.4%, H2:99.6% 8
    Comparative sample 11 990 50 CO2:0.8%, H2:99.2% 7
    Comparative sample 12 990 50 CO2:0.8%, H2:99.2% 7
    Comparative sample 13 990 50 CO2:0.8%, H2:99.2% 7
    Comparative sample 14 990 50 CO2:0.8%, H2:99.2% 7
    [Table 4]
    Sample No.Nucleus formation conditionsDeposition conditions
    Temperature (°C)Pressure (hPa)Raw material gas composition (mol%)Temperature (°C)Pressure (hPa)Raw material gas composition (mol%)
    Invention sample 1 990 60 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, C3H6:0.1%, H2:90.9% 990 60 AlCl3:3.1%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:91.7%
    Invention sample 2 990 70 AlCl3:4.0%, CO2:3.5%, HCl:2.5%, C3H6:0.15%, H2:89.85% 990 70 AlCl3:3.5%, CO2:2.6%, HCl:2.3%, H2S:0.2%, H2:91.4%
    Invention sample 3 990 70 AlCl3:4.0%, CO2:3.5%, HCl:2.5%, C3H6:0.15%, H2:89.85% 990 70 AlCl3:3.5%, CO2:2.6%, HCl:2.3%, H2S:0.2%, H2:91.4%
    Invention sample 4 1,030 70 AlCl3:2.5%, CO2:3.3%, HCl:2.2%, C3H6:0.2%, H2:91.8% 1,030 70 AlCl3:4.8%, CO2:2.9%, HCl:2.0%, H2S:0.15%, H2:90.15%
    Invention sample 5 990 70 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, C3H6:0.1%, H2:90.9% 990 70 AlCl3:3.5%, CO2:2.6%, HCl:2.3%, H2S:0.2%, H2:91.4%
    Invention sample 6 970 70 AlCl3:5.0%, CO2:2.5%, HCl:3.4%, C3H6:0.1%, H2:89.0% 970 70 AlCl3:2.0%, CO2:3.7%, HCl:2.5%, H2S:0.25%, H2:91.55%
    Invention sample 7 990 80 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, C3H6:0.1%, H2:90.9% 990 80 AlCl3:3.1%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:91.7%
    Invention sample 8 970 60 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, C3H6:0.1%, H2:90.9% 970 60 AlCl3:3.1%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:91.7%
    Invention sample 9 990 60 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, C3H6:0.1%, H2:90.9% 990 60 AlCl3:3.5%, CO2:2.6%, HCl:2.3%, H2S:0.2%, H2:91.4%
    Invention sample 10 990 70 AlCl3:2.0%, CO2:3.6%, HCl:2.3%, C3H6:0.1%, H2:92.0% 990 70 AlCl3:3.5%, CO2:2.6%, HCl:2.3%, H2S:0.2%, H2:91.4%
    Invention sample 11 1,030 70 AlCl3:2.5%, CO2:3.5%, HCl:2.0%, C3H6:0.2%, H2:91.8% 1,030 70 AlCl3:4.8%, CO2:2.9%, HCl:2.5%, H2S:0.15%, H2:89.65%
    Invention sample 12 990 60 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, C3H6:0.1%, H2:90.9% 990 60 AlCl3:3.1%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:91.7%
    Invention sample 13 990 70 AlCl3:4.0%, CO2:3.5%, HCl:2.5%, C3H6:0.15%, H2:89.85% 990 70 AlCl3:3.5%, CO2:2.6%, HCl:2.3%, H2S:0.2%, H2:91.4%
    Invention sample 14 1,030 70 AlCl3:2.5%, CO2:3.5%, HCl:2.0%, C3H6:0.2%, H2:91.8% 1,030 70 AlCl3:4.8%, CO2:2.9%, HCl:2.5%, H2S:0.15%, H2:89.65%
    Invention sample 15 990 70 AlCl3:4.0%, CO2:3.5%, HCl:2.5%, C3H6:0.15%, H2:89.85% 990 70 AlCl3:3.5%, CO2:2.6%, HCl:2.3%, H2S:0.2%, H2:91.4%
    Invention sample 16 990 70 AlCl3:4.0%, CO2:3.5%, HCl:2.5%, C3H6:0.15%, H2:89.85% 990 70 AlCl3:3.5%, CO2:2.6%, HCl:2.3%, H2S:0.2%, H2:91.4%
    Invention sample 17 990 70 AlCl3:4.0%, CO2:3.5%, HCl:2.5%, C3H6:0.15%, H2:89.85% 990 70 AlCl3:3.5%, CO2:2.6%, HCl:2.3%, H2S:0.2%, H2:91.4%
    [Table 5]
    Sample No.Nucleus formation conditionsDeposition conditions
    Temperature (°C)Pressure (hPa)Raw material gas composition (mol%)Temperature (°C)Pressure (hPa)Raw material gas composition (mol%)
    Comparative sample 1 990 60 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 990 60 AlCl3:2.6%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:92.2%
    Comparative sample 2 990 70 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 990 70 AlCl3:2.6%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:92.2%
    Comparative sample 3 990 70 AlCl3:4.0%, CO2:3.5%, HCl:2.5%, C3H6:0.15%, H2:89.85% 990 70 AlCl3:2.6%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:92.2%
    Comparative sample 4 1,030 70 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 1,030 70 AlCl3:4.8%, CO2:2.5%, HCl:2.7%, H2S:0.15%, H2:89.85%
    Comparative sample 5 990 70 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 990 70 AlCl3:3.0%, CO2:3.0%, HCl:2.7%, H2S:0.2%, H2:91.1 %
    Comparative sample 6 990 70 AlCl3:2.5%, CO2:3.5%, HCl:2.5%, C3H6:0.1%, H2:91.4% 990 70 AlCl3:3.0%, CO2:3.0%, HCl:2.7%, H2S:0.2%, H2:91.1%
    Comparative sample 7 990 80 AlCl3:5.0%, CO2:2.5%, HCl:2.5%, H2:90.0% 990 80 AlCl3:2.0%, CO2:4.0%, HCl:2.5%, H2S:0.25%, H2:91.25%
    Comparative sample 8 970 60 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 970 60 AlCl3:3.0%, CO2:3.0%, HCl:2.7%, H2S:0.2%, H2:91.1 %
    Comparative sample 9 990 60 AlCl3:2.0%, CO2:3.5%, HCl:3.0%,H2:91.5% 990 60 AlCl3:3.0%, CO2:3.0%, HCl:2.7%, H2S:0.2%, H2:91.1%
    Comparative sample 10 990 70 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 990 70 AlCl3:2.6%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:92.2%
    Comparative sample 11 990 70 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 990 70 AlCl3:2.6%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:92.2%
    Comparative sample 12 990 70 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 990 70 AlCl3:2.6%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:92.2%
    Comparative sample 13 990 70 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 990 70 AlCl3:2.6%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:92.2%
    Comparative sample 14 990 70 AlCl3:2.5%, CO2:3.0%, HCl:3.5%, H2:91.0% 990 70 AlCl3:2.6%, CO2:2.6%, HCl:2.4%, H2S:0.2%, H2:92.2%
    [Table 6]
    Sample No.Coating layer
    Lowermost layerTiCN layerIntermediate layerα-type aluminum oxide layerOutermost layerTotal thickness (µm)
    CompositionAverage thickness (µm)Compositio nAverage thickness (µm)CompositionAverage thickness (µm)Crystal systemAverage thickness (µm)CompositionAverage thickness (µm)
    Invention sample 1 TiN 0.2 TiCN 6.0 TiCO 0.4 α 4.2 TiN 0.2 11.0
    Invention sample 2 TiN 0.2 TiCN 2.4 TiCNO 0.4 α 12.4 TiN 0.2 15.6
    Invention sample 3 TiN 0.4 TiCN 15.0 TiCO 0.2 α 2.4 TiN 0.4 18.4
    Invention sample 4 TiN 0.4 TiCN 20.0 TiCNO 0.1 α 6.2 TiN 0.4 27.1
    Invention sample 5 TiN 0.7 TiCN 10.4 TiCNO 0.6 α 7.4 TiN 0.4 19.5
    Invention sample 6 TiN 0.7 TiCN 7.2 TiCNO 0.6 α 7.4 TiN 0.6 16.5
    Invention sample 7 TiN 1.2 TiCN 7.2 TiCO 0.3 α 10.5 TiN 0.2 19.4
    Invention sample 8 TiC 1.2 TiCN 9.8 TiCNO 0.8 α 9.6 TiN 0.4 21.8
    Invention sample 9 TiC 0.3 TiCN 5.0 TiCNO 0.8 α 5.5 TiN 0.2 11.8
    Invention sample 10 TiN 0.8 TiCN 5.0 TiCNO 1.0 α 14.0 TiN 0.2 21.0
    Invention sample 11 TiN 0.5 TiCN 3.0 TiCO 0.5 α 3.8 TiN 0.2 8.0
    Invention sample 12 TiN 0.2 TiCN 5.8 TiCNO 0.3 α 9.0 TiN 0.5 15.8
    Invention sample 13 TiN 0.2 TiCN 5.8 TiCNO 0.3 α 9.0 TiN 0.5 15.8
    Invention sample 14 TiN 0.2 TiCN 5.8 TiCNO 0.3 α 9.0 TiN 0.5 15.8
    Invention sample 15 TiN 0.2 TiCN 11.2 TiCNO 0.3 α 3.8 TiN 0.5 16.0
    Invention sample 16 TiN 0.2 TiCN 5.8 TiCNO 0.3 α 9.0 TiN 0.5 15.8
    Invention sample 17 TiN 0.2 TiCN 5.8 TiCNO 0.3 α 9.0 TiN 0.5 15.8
    Comparative sample 1 TiN 0.2 TiCN 6.0 TiCNO 0.4 α 4.4 TiN 0.2 11.2
    Comparative sample 2 TiN 0.2 TiCN 5.0 TiCNO 0.4 α 10.4 TiN 0.2 16.2
    Comparative sample 3 TiC 0.4 TiCN 20.0 TiCNO 0.2 α 2.5 TiN 0.4 23.5
    Comparative sample 4 TiC 0.4 TiCN 2.4 TiCNO 0.1 α 5.5 TiN 0.4 8.8
    Comparative sample 5 TiN 0.7 TiCN 5.5 TiCNO 0.2 α 7.2 TiN 0.2 13.8
    Comparative sample 6 TiN 0.7 TiCN 14.8 TiCNO 0.2 α 6.2 TiN 0.2 22.1
    Comparative sample 7 TiN 0.3 TiCN 7.0 TiCNO 0.4 α 15.0 TiN 0.6 23.3
    Comparative sample 8 TiN 0.8 TiCN 9.8 TiCO 0.6 α 9.6 TiN 0.6 21.4
    Comparative sample 9 TiN 1.2 TiCN 9.6 TiCNO 0.6 α 4.0 TiN 0.4 15.8
    Comparative sample 10 TiN 1.2 TiCN 5.0 TiCNO 1.0 α 10.0 TiN 0.4 17.6
    Comparative sample 11 TiN 0.2 TiCN 5.8 TiCNO 0.3 α 9.0 TiN 0.5 15.8
    Comparative sample 12 TiN 0.2 TiCN 11.2 TiCNO 0.3 α 3.8 TiN 0.5 16.0
    Comparative sample 13 TiN 0.2 TiCN 5.8 TiCNO 0.3 α 9.0 TiN 0.5 15.8
    Comparative sample 14 TiN 0.2 TiCN 5.8 TiCNO 0.3 α 9.0 TiN 0.5 15.8


    [0055] As to invention samples 1 to 17 and comparative samples 1 to 14, after the formation of the coating layer on the surface of the substrate, dry shot blasting was performed on a surface of the coating layer under the shot conditions shown in Table 7, using the shot material shown in Table 7.
    [Table 7]
    Sample No.Shot materialShot conditions
    MaterialAverage particle size (µm)Shot angle (°)Shot velocity (m/sec)Shot time (min)
    Invention sample 1 Al2O3 130 50 70 2.5
    Invention sample 2 Al2O3 130 50 70 2.5
    Invention sample 3 ZrO2 120 50 70 3.0
    Invention sample 4 ZrO2 120 70 70 2.0
    Invention sample 5 ZrO2 120 70 70 2.0
    Invention sample 6 Al2O3 120 50 65 1.0
    Invention sample 7 Al2O3 120 50 65 1.0
    Invention sample 8 Al2O3 120 50 60 1.0
    Invention sample 9 Al2O3 100 45 50 1.0
    Invention sample 10 Al2O3 150 70 70 3.0
    Invention sample 11 Al2O3 150 60 80 1.5
    Invention sample 12 Al2O3 130 50 70 2.5
    Invention sample 13 Al2O3 130 50 70 2.5
    Invention sample 14 Al2O3 130 50 70 2.5
    Invention sample 15 Al2O3 130 50 70 2.5
    Invention sample 16 Al2O3 120 50 65 1.0
    Invention sample 17 Al2O3 130 50 70 2.5
    Comparative sample 1 Al2O3 120 45 70 2.5
    Comparative sample 2 Al2O3 120 45 70 2.5
    Comparative sample 3 ZrO2 120 50 70 3.0
    Comparative sample 4 ZrO2 120 70 70 2.0
    Comparative sample 5 ZrO2 120 70 70 2.0
    Comparative sample 6 Al2O3 120 50 50 1.0
    Comparative sample 7 Al2O3 120 50 50 1.0
    Comparative sample 8 Al2O3 100 45 50 1.0
    Comparative sample 9 Al2O3 100 40 50 1.0
    Comparative sample 10 Al2O3 80 40 50 1.0
    Comparative sample 11 Al2O3 130 50 70 2.5
    Comparative sample 12 Al2O3 130 50 70 2.5
    Comparative sample 13 Al2O3 120 50 65 1.0
    Comparative sample 14 Al2O3 130 50 70 2.5


    [0056] As to the obtained samples, an X-ray diffraction measurement by means of a 2θ/θ focusing optical system with Cu-Kα radiation was performed under the following conditions: an output: 50 kV, 250 mA; an incident-side solar slit: 5°; a divergence longitudinal slit: 2/3°; a divergence longitudinal limit slit: 5 mm; a scattering slit: 2/3°; a light-receiving side solar slit: 5°; a light-receiving slit: 0.3 mm; a BENT monochromator; a light-receiving monochrome slit: 0.8 mm; a sampling width: 0.01°; a scan speed: 4°/min; and a 2θ measurement range: 20°-155°. As to the apparatus, an X-ray diffractometer (model "RINT TTR III") manufactured by Rigaku Corporation was used. The peak intensity for each crystal plane of the α-type aluminum oxide layer was obtained from an X-ray diffraction pattern. A texture coefficient TC (2,1,10) in the α-type aluminum oxide layer was obtained from the resulting peak intensity for each crystal plane. Further, as to the obtained samples, the average particle size of the TiCN layer was obtained via observation of a cross-sectional structure of the TiCN layer. More specifically, mirror polishing was performed on a cross-section in a direction parallel to the surface of the substrate of the sample, and the resulting mirror-polished surface was regarded as a cross-sectional structure. When mirror-polishing the TiCN layer, colloidal silica was used for polishing. Then, the sample was set on an FE-SEM such that a cross-sectional structure of the TiCN layer was able to be irradiated with an electron beam, and the sample was irradiated with an electron beam under the conditions of an angle of incidence of 70 degrees, an acceleration voltage of 15 kV, and an irradiation current of 0.5 nA. At this time, measurement was performed under the EBSD settings of a measurement range of 30 µm x 50 µm and a step size of 0.1 µm. An area surrounded by a structure boundary with a misorientation of 5 degrees or more was regarded as a particle, and the diameter of a circle whose area was equal to the area of a particle was regarded as a particle size of such particle. At this time, a particle size was obtained from the cross-sectional structure of the TiCN layer, using image analysis software. The particle sizes in the TiCN layer in the above measurement were measured, and the average value (arithmetic mean) of all the obtained particle sizes was regarded as an average particle size. The results are shown in Table 8.
    [Table 8]
    Sample No.α-type aluminum oxide layerTiCN layer
    TC (2,1,10)Average particle size (µm)
    Invention sample 1 4.2 1.0
    Invention sample 2 5.1 0.8
    Invention sample 3 5.2 0.5
    Invention sample 4 6.0 0.6
    Invention sample 5 5.2 0.8
    Invention sample 6 2.8 1.6
    Invention sample 7 4.4 0.9
    Invention sample 8 1.6 1.1
    Invention sample 9 5.2 1.4
    Invention sample 10 5.3 1.5
    Invention sample 11 7.0 0.8
    Invention sample 12 4.2 0.8
    Invention sample 13 5.2 0.8
    Invention sample 14 7.0 0.8
    Invention sample 15 5.2 0.8
    Invention sample 16 5.2 0.8
    Invention sample 17 5.2 1.5
    Comparative sample 1 0.2 1.0
    Comparative sample 2 0.2 0.8
    Comparative sample 3 0.7 0.5
    Comparative sample 4 0.4 1.4
    Comparative sample 5 0.3 0.8
    Comparative sample 6 1.1 0.8
    Comparative sample 7 0.1 1.0
    Comparative sample 8 0.4 1.0
    Comparative sample 9 0.2 0.8
    Comparative sample 10 0.5 0.8
    Comparative sample 11 0.2 0.8
    Comparative sample 12 0.2 0.8
    Comparative sample 13 0.2 0.8
    Comparative sample 14 0.2 1.5


    [0057] The residual stress value of the α-type aluminum oxide layer in each of the obtained samples was measured by a sin2ϕ method using an X-ray stress measuring apparatus (model "RINT TTR III" manufactured by Rigaku Corporation). The measurement results are shown in Table 9.
    [Table 9]
    Sample No.α-type aluminum oxide layer
    Residual stress value when measurement was performed with the selection of a (1,1,6) plane (MPa)
    Invention sample 1 -246
    Invention sample 2 -235
    Invention sample 3 -298
    Invention sample 4 -102
    Invention sample 5 -96
    Invention sample 6 165
    Invention sample 7 174
    Invention sample 8 288
    Invention sample 9 292
    Invention sample 10 -408
    Invention sample 11 55
    Invention sample 12 -240
    Invention sample 13 -240
    Invention sample 14 -240
    Invention sample 15 -240
    Invention sample 16 165
    Invention sample 17 -240
    Comparative sample 1 -233
    Comparative sample 2 -238
    Comparative sample 3 -306
    Comparative sample 4 -108
    Comparative sample 5 -92
    Comparative sample 6 144
    Comparative sample 7 152
    Comparative sample 8 300
    Comparative sample 9 288
    Comparative sample 10 360
    Comparative sample 11 -240
    Comparative sample 12 -240
    Comparative sample 13 165
    Comparative sample 14 -240


    [0058] Cutting tests 1 and 2 were conducted using the obtained samples under the following conditions. Cutting test 1 is a wear test for evaluating wear resistance, and cutting test 2 is a fracture test for evaluating fracture resistance. The results of the respective cutting tests are shown in Table 10.

    [Cutting test 1]



    [0059] Workpiece material: S45C round bar
    Cutting speed: 320 m/min
    Feed: 0.25 mm/rev
    Depth of cut: 2.0 mm
    Coolant: used
    Evaluation items: A time when a sample was fractured or had a maximum flank wear width of 0.2 mm was defined as the end of the tool life, and the machining time to reach the end of the tool life was measured.

    [Cutting test 2]



    [0060] Workpiece material: SCM415 round bar with two equidistant grooves extending in the length direction
    Cutting speed: 260 m/min
    Feed: 0.35 mm/rev
    Depth of cut: 1.5 mm
    Coolant: used
    Evaluation items: A time when a sample was fractured was defined as the end of the tool life, and the number of shocks the sample had received until the end of the tool life was measured. The number of times the sample and the workpiece material were brought into contact with each other was defined as the number of shocks, and the test was ended when the number of contacts reached 20,000 at a maximum. In other words, the number "20,000" for the tool life indicates that the end of the tool life was not reached even after the arrival of 20,000 shocks. It should be noted that, as to each sample, five inserts were prepared and the number of shocks was measured for each of such cutting inserts, and the arithmetic mean was obtained from the measurements of the number of shocks so as to serve as the tool life.

    [0061] As to the machining time to reach the end of the tool life in cutting test 1 (wear test), evaluations were made with grade "A" for 25 minutes or more, grade "B" for 20 minutes or more and less than 25 minutes, and grade "C" for less than 25 minutes. Further, as to the number of shocks until the end of the tool life in cutting test 2 (fracture test), evaluations were made with grade "A" for 15,000 or more, grade "B" for 12,000 or more and less than 15,000, and grade "C" for less than 12,000. In such evaluations, "A" refers to excellent, "B" refers to good and "C" refers to inferior, meaning that a sample involving a larger number of "A"s or "B"s has more excellent cutting performance. The resulting evaluation results are shown in Table 10.
    [Table 10]
    Sample No.Wear testFracture test
    Tool life (min)GradeDamage formTool life (shocks)Grade
    Invention sample 1 21 B Normal wear 20,000 A
    Invention sample 2 27 A Normal wear 18,300 A
    Invention sample 3 30 A Normal wear 20,000 A
    Invention sample 4 42 A Normal wear 16,000 A
    Invention sample 5 32 A Normal wear 18,900 A
    Invention sample 6 24 B Normal wear 15,700 A
    Invention sample 7 30 A Normal wear 15,500 A
    Invention sample 8 29 A Normal wear 15,000 A
    Invention sample 9 22 B Normal wear 16,500 A
    Invention sample 10 34 A Normal wear 17,600 A
    Invention sample 11 21 B Normal wear 18,200 A
    Invention sample 12 24 B Normal wear 17,900 A
    Invention sample 13 27 A Normal wear 19,200 A
    Invention sample 14 33 A Normal wear 20,000 A
    Invention sample 15 21 B Normal wear 18,500 A
    Invention sample 16 28 A Normal wear 15,400 A
    Invention sample 17 24 B Normal wear 19,600 A
    Comparative sample 1 14 C Normal wear 14,900 B
    Comparative sample 2 17 C Normal wear 14,400 B
    Comparative sample 3 19 C Normal wear 13,200 B
    Comparative sample 4 11 C Normal wear 13,900 B
    Comparative sample 5 17 C Normal wear 13,500 B
    Comparative sample 6 21 B Normal wear 10,500 C
    Comparative sample 7 19 C Normal wear 9,600 C
    Comparative sample 8 18 C Fracturing 5,200 C
    Comparative sample 9 18 C Normal wear 7,400 C
    Comparative sample 10 22 B Fracturing 7,900 C
    Comparative sample 11 15 C Normal wear 13,800 B
    Comparative sample 12 13 C Normal wear 13,200 B
    Comparative sample 13 12 C Fracturing 8,600 C
    Comparative sample 14 13 C Normal wear 14,100 B


    [0062] The results of Table 10 show that each invention sample had grade "B" or higher in the wear test and also show that each invention sample had grade "A" in the fracture test. Meanwhile, as to the evaluations on the comparative samples, each comparative sample had grade "C" in either the wear test or the fracture test. Further, in the fracture test, each of the samples of coated cutting tools was subjected to visual observations every 3,000 shocks, and as a result, it was confirmed that any of the samples which were fractured involved the occurrence of cracking before the fracturing. It was further confirmed that a sample for which the occurrence of cracking was observed in an earlier stage reached the end of its tool life earlier. Such occurrence of cracking can be considered to derive from the thermal shock caused by the use of coolant in high-speed cutting.

    [0063] It is apparent from the above results that each invention sample has excellent wear resistance and fracture resistance, resulting in a longer tool life.

    [0064] The present application is based on the Japanese patent application filed on November 2, 2016 (JP Appl. 2016-215100).

    Industrial Applicability



    [0065] As to a coated cutting tool according to the present invention, such coated cutting tool does not involve a reduction in wear resistance and has excellent thermal shock resistance, so that the tool life can be extended more than that involved in the prior art, and, from such perspective, the coated cutting tool has industrial applicability.


    Claims

    1. A coated cutting tool comprising a substrate and a coating layer formed on a surface of the substrate, the coating layer including at least one α-type aluminum oxide layer, wherein, in the α-type aluminum oxide layer, a texture coefficient TC (2,1,10) of a (2,1,10) plane represented by formula (1) below is 1.4 or more:

    (In formula (1), I (h,k,l) denotes a peak intensity for an (h,k,l) plane in X-ray diffraction of the α-type aluminum oxide layer, l0 (h,k,l) denotes a standard diffraction intensity for an (h,k,l) plane which is indicated on a JCPDS Card No. 10-0173 for α-type aluminum oxide, and (h,k,l) refers to eight crystal planes of (0,1,2), (1,0,4), (1,1,0), (1,1,3), (0,2,4), (1,1,6), (2,1,4) and (2,1,10)),

    wherein an average thickness of the α-type aluminum oxide layer is from 1.0 µm or more to 15.0 µm or less,

    wherein the coating layer comprises a TiCN layer between the substrate and the α-type aluminum oxide layer, and

    wherein the coating layer comprises, between the TiCN layer and the α-type aluminum oxide layer, an intermediate layer comprised of a compound of at least one kind selected from the group consisting of a Ti carbonate, a Ti oxynitride and a Ti carboxynitride.


     
    2. The coated cutting tool according to claim 1, wherein, in the α-type aluminum oxide layer, the texture coefficient TC (2,1,10) is from 2.0 or more to 6.9 or less.
     
    3. The coated cutting tool according to claim 1 or 2, wherein a residual stress value in a (1,1,6) plane of the α-type aluminum oxide layer is, in at least part thereof, from -300 MPa or higher to 300 MPa or lower.
     
    4. The coated cutting tool according to any one of claims 1 to 3, wherein an average particle size of the TiCN layer is from 0.3 µm or more to 1.5 µm or less
     
    5. The coated cutting tool according to any one of claims 1 to 4, wherein an average thickness of the TiCN layer is from 2.0 µm or more to 20.0 µm or less.
     
    6. The coated cutting tool according to any one of claims 1 to 5, wherein an average thickness of the coating layer is from 3.0 µm or more to 30.0 µm or less.
     
    7. The coated cutting tool according to any one of claims 1 to 6, wherein the coating layer comprises a TiN layer as an outermost layer on a side opposite to the substrate.
     
    8. The coated cutting tool according to any one of claims 1 to 7, wherein the substrate is comprised of any of a cemented carbide, cermet, ceramics and a sintered body containing cubic boron nitride.
     


    Ansprüche

    1. Beschichtetes Schneidwerkzeug mit einem Substrat und einer Beschichtung, die auf einer Oberfläche des Substrats gebildet ist, wobei die Beschichtung mindestens eine α-Aluminiumoxidschicht aufweist, wobei in der α-Aluminiumoxidschicht ein Texturkoeffizient TC (2,1,10) einer (2,1,10)-Ebene gemäß der nachstehenden Formel (1) mindestens 1,4 beträgt:

    (in der Formel (1) bezeichnet I(h,k,l) eine Peakintensität für eine (h,k,l)-Ebene in der Röntgenbeugung der α-Aluminiumoxidschicht, I0(h,k,l) bezeichnet eine Standard-Beugungsintensität für eine (h,k,l)-Ebene, die auf einer JCPDS-Karte Nr. 10-0173 für α-Aluminiumoxid angegeben ist, und (h,k,l) bezieht sich auf acht Kristallebenen (0,1,2), (1,0,4), (1,1,0), (1,1,3), (0,2,4), (1,1,6), (2,1,4) und (2,1,10)),

    wobei eine mittlere Dicke der α-Aluminiumoxidschicht mindestens 1,0 µm bis höchstens 15,0 µm beträgt,

    wobei die Beschichtung eine TiCN-Schicht zwischen dem Substrat und der α-Aluminiumoxidschicht aufweist und

    wobei die Beschichtung zwischen der TiCN-Schicht und der α-Aluminiumoxidschicht eine Zwischenschicht aufweist, die eine Verbindung mindestens einer Art aufweist, die aus der Gruppe ausgewählt ist, die aus einem Ti-Carbonat, einem Ti-Oxynitrid und einem Ti-Carboxynitrid besteht.


     
    2. Beschichtetes Schneidwerkzeug nach Anspruch 1, wobei in der α-Aluminiumoxidschicht der Texturkoeffizient TC (2,1,10) mindestens 2,0 bis höchstens 6,9 beträgt.
     
    3. Beschichtetes Schneidwerkzeug nach Anspruch 1 oder 2, wobei ein Eigenspannungswert in einer (1,1,6)-Ebene der α-Aluminiumoxidschicht in mindestens einem Teil davon mindestens -300 MPa bis höchstens 300 MPa beträgt.
     
    4. Beschichtetes Schneidwerkzeug nach einem der Ansprüche 1 bis 3, wobei eine mittlere Teilchengröße der TiCN-Schicht mindestens 0,3 µm bis höchstens 1,5 µm beträgt.
     
    5. Beschichtetes Schneidwerkzeug nach einem der Ansprüche 1 bis 4, wobei eine mittlere Dicke der TiCN-Schicht mindestens 2,0 µm bis höchstens 20,0 µm beträgt.
     
    6. Beschichtetes Schneidwerkzeug nach einem der Ansprüche 1 bis 5, wobei eine mittlere Dicke der Beschichtung mindestens 3,0 µm bis höchstens 30,0 µm beträgt.
     
    7. Beschichtetes Schneidwerkzeug nach einem der Ansprüche 1 bis 6, wobei die Beschichtung eine TiN-Schicht als äußerste Schicht auf einer zum Substrat entgegengesetzten Seite aufweist.
     
    8. Beschichtetes Schneidwerkzeug nach einem der Ansprüche 1 bis 7, wobei das Substrat ein Hartmetall, Cermet, Keramik und/oder einen kubisches Bornitrid enthaltenden Sinterkörper aufweist.
     


    Revendications

    1. Outil de coupe revêtu comprenant un substrat et une couche de revêtement formée sur une surface du substrat, la couche de revêtement incluant au moins une couche d'oxyde d'aluminium de type α, dans lequel, dans la couche d'oxyde d'aluminium de type α, un coefficient de texture TC (2, 10) d'un plan (2, 10) représenté par la formule (1) ci-dessous est de 1,4 ou supérieur :

    (dans la formule (1), I(h, k, l) indique une intensité de pic pour un plan (h, k, l) dans une diffraction de rayons X de la couche d'oxyde d'aluminium de type α, I0 (h, k, l) indique une intensité de diffraction standard pour un plan (h, k, l) qui est indiqué sur une carte JCPDS n° 10-0173 pour un oxyde d'aluminium de type α, et (h, k, l) fait référence à huit plans de cristaux de (0, 2), (1, 0, 4), (1, 0), (1, 3), (0, 2, 4), (1, 6), (2, 1, 4) et (2, 10)),

    dans lequel une épaisseur moyenne de la couche d'oxyde d'aluminium de type α est de 1,0 µm ou supérieure à 15,0 µm ou inférieure,

    dans lequel la couche de revêtement comprend une couche de TiCN entre le substrat et la couche d'oxyde d'aluminium de type α, et

    dans lequel la couche de revêtement comprend, entre la couche de TiCN et la couche d'oxyde d'aluminium de type α, une couche intermédiaire constituée d'un composé d'au moins un type choisi dans le groupe consistant en un carbonate de Ti, un oxynitrure de Ti et un carboxynitrure de Ti.


     
    2. Outil de coupe revêtu selon la revendication 1, dans lequel, dans la couche d'oxyde d'aluminium de type α, le coefficient de texture TC (2, 10) est de 2,0 ou supérieur à 6,9 ou inférieur.
     
    3. Outil de coupe revêtu selon la revendication 1 ou 2, dans lequel une valeur de contrainte résiduelle dans un plan (1, 1, 6) de la couche d'oxyde d'aluminium de type α est, dans au moins une partie de celui-ci, de -300 MPa ou supérieure à 300 MPa ou inférieure.
     
    4. Outil de coupe revêtu selon l'une quelconque des revendications 1 à 3, dans lequel une taille moyenne de particule de la couche de TiCN est de 0,3 µm ou supérieure à 1,5 µm ou inférieure.
     
    5. Outil de coupe revêtu selon l'une quelconque des revendications 1 à 4, dans lequel une épaisseur moyenne de la couche de TiCN est de 2,0 µm ou supérieure à 20,0 µm ou inférieure.
     
    6. Outil de coupe revêtu selon l'une quelconque des revendications 1 à 5, dans lequel une épaisseur moyenne de la couche de revêtement est de 3,0 µm ou supérieure à 30,0 µm ou inférieure.
     
    7. Outil de coupe revêtu selon l'une quelconque des revendications 1 à 6, dans lequel la couche de revêtement comprend une couche de TiN comme une couche extérieure sur un côté opposé au substrat.
     
    8. Outil de coupe revêtu selon l'une quelconque des revendications 1 à 7, dans lequel le substrat est constitué de l'un quelconque d'un carbure cémenté, d'un cermet, de céramiques et d'un corps fritté contenant du nitrure de bore cubique.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description