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    • 专利摘要:
    COATED TOOL. The present invention relates to a coated tool including a substrate and the coating layer disposed on the surface of the substrate, the coating layer including the first stack structure (3) and the second stack structure (4). the first stack structure having a structure in which two or more types of layers with different compositions are periodically stacked in which the average layer thickness of each layer is 60 nm to 500 nm, the second stack structure having a structure in which two or more types of layers with different compositions are periodically stacked in which the average layer thickness of each layer is 2 nm less than 60 nm, the layers that make up the first stack structure and the layers that constitute the second stack structure including at least one selected from the group consisting of a metal including at least one metal element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, Si, Sr , Y, Sn and Bi: and compounds that include at least one of said metal elements and at least one non-metal element selected from carbon, nitrogen, (...).
    公开号:BR112015002527B1
    申请号:R112015002527-7
    申请日:2013-08-12
    公开日:2020-11-17
    发明作者:Shota Asari；Masakazu Kikuchi
    申请人:Tungaloy Corporation；
    IPC主号:
    专利说明:

    Technical Field
    [0001] The present invention relates to coated tools. Background Technique
    [0002] With a recent increase in demand for greater cutting efficiency, there is a need for a longer tool life than the one available so far. Consequently, the need for tool material properties that have become increasingly important is that the wear resistance and fracture resistance associated with the life of the cutting tools is increased. In order to obtain increases in said properties, coated tools are used in which a stack of alternating films of coating films is arranged on a substrate.
    [0003] Several techniques have been proposed to improve the properties of said stacks of alternating films. For example, Patent Literature 1 proposes a highly wear resistant cutting tool in which a specific metal element or component thereof and a specific alloy component are stacked with a stacking period of 0.4 nm to 50 nm on the surface of a base material.
    [0004] Patent Literature 2 proposes a cutting tool that exhibits excellent wear resistance even under heavy cutting conditions. Said tool is such that the surface of the base is coated with 4 or more layers having a total average Layer thickness of 2 to 10 pm which are in the form of an alternating stack of thin first layer of a composite nitride represented by the composition of formula (Tii-xAlx) N (x in atomic proportion: 0.30 to 0.70) and a second thin layer containing an aluminum oxide phase in a ratio of 35 to 65 mass% in relation to the total mass of the same and the mass of a titanium nitride phase, the average layer thickness of the individual layers being 0.2 to 1 pm.
    [0005] Patent Literature 3 proposes a cutting tool with excellent wear resistance and weld resistance that is such that stack layers of 100-5000 nm including a periodic stack of layers with thicknesses from 1 to 50 nm, and 100-5000 nm single layers are alternately stacked in 10 or more layers on top of each other in a rigid base material. BACKGROUND REFERENCES Patent Literature Patent Literature 1: Japanese Patent Application Publication No. H07-205361 Patent Literature 2: Japanese Patent Application Publication No. 2003-200306 Patent Literature 3: Kokai Application Publication Japanese Patent No. H11-12718 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
    [0006] Recent cutting tools are subjected to more marked increases in speed, feed and depth of cut. Consequently, it is more often the case that cracks that have occurred on the tool surface due to the load applied to the cutting edges during cutting reach the substrates, or cracks that have occurred on the substrates due to sudden changes in the temperature of the cutting edges. cuts penetrate the coating layers, resulting in tool fractures.
    [0007] Although the cutting tool of the Patent Literature 1 invention which includes a thin layer stack with a stacking period of 0.4 to 50 nm exhibits high wear resistance, the tool is problematically prone to fracture under the circumstances described above. The cutting tool of the Patent Literature 2 invention which includes an alternating stack of layers with a large thickness of the individual middle layer has a problem in which the hardness of the coating films is so insufficient that the tool exhibits poor wear resistance. In the cutting tool of the Patent Literature 3 invention which has a stacked structure formed of stack layers of thin films and single layers, fracture resistance is insufficient and the tool can no longer often satisfy the necessary performance described here above.
    [0008] The present invention was produced to solve said problems. It is, therefore, an object of the present invention to provide long-life coated tools that are increased in fracture resistance without any reduction in wear resistance. MEANS TO SOLVE PROBLEMS
    [0009] The present inventors have carried out studies on the life span of coated tools. The present inventors then observed that the fracture strength can be increased without causing a reduction in wear resistance by improving the layer configurations and the coating layer compositions. As a result, the life span of the coated tools was realized.
    [00010] Specifically, the present invention can be summarized as follows.
    [00011] (1) The coated tool comprising a substrate and the coating layer arranged on the surface of the substrate, the coating layer including a first pile structure and a second pile structure, the first pile structure having a structure in the which two or more types of layers with different compositions are periodically stacked where the average layer thickness of each layer is 60 nm to 500 nm, the second stack structure having a structure in which two or more types of layers with different compositions are periodically stacked in which the average layer thickness of each layer is 2 nm less than 60 nm, the layers making up the first stack structure and the layers making up the second stack structure including at least one selected from the group consisting of a metal including at least one metal element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, Si, Sr, Y, Sn and Bi; and compounds that include at least one of said metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron.
    [00012] (2) The coated tool of (1), wherein the first stack structure is an alternating stack structure that includes two types of layers with different compositions stacked alternately each in two or more layers.
    [00013] (3) The tool coated with (1) or (2), wherein the second stack structure is an alternating stack structure that includes two types of layers with different compositions stacked alternately each in two or more layers.
    [00014] (4) The coated tool of any of (1) to (3), wherein the coating layer includes a structure that includes the first stack structure and the second stack structure alternately and continuously stacked each in two or more layers.
    [00015] (5) The tool coated with any of (1) to (4), where (Ti - T2) is 20 nm to 996 nm where Ti is the average value of the stacking periods in the first pile structure and T2 is the average value of the stacking periods in the second stack structure.
    [00016] (6) The tool coated with any of (1) to (5), wherein the layers constituting the first stack structure and the layers constituting the second stack structure each include at least one selected from the group consisting of metals including at least two metal elements selected from Ti, Nb, Ta, Cr, W, Al, Si, Sr and Y; and compounds that include at least two of said metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron.
    [00017] (7) The tool coated with any of (1) to (6), wherein the metal elements present in the layers that constitute the first pile structure are identical between the layers that constitute the first pile structure and include one or more metal elements having a difference in absolute value of 5% or more between the ratio of the same in relation to the total of the metal elements present in a layer that constitutes the first pile structure and the relation of the identical metal element in relative to the total of the metal elements present in the layer that constitutes the first pile structure whose layer is adjacent to a layer.
    [00018] (8) The tool coated with any of (1) to (7), wherein the metal elements present in the layers that constitute the second pile structure are identical between the layers that constitute the second pile structure and include one or more metal elements having a difference in absolute value of 5% or more between the ratio of the same in relation to the total of the metal elements present in a layer that constitutes the second stack structure and the relationship of the identical metal element in relative to the total of the metal elements present in the layer that constitutes the second stack structure whose layer is adjacent to a layer.
    [00019] (9) The tool coated with any of (1) to (6), wherein a layer constituting the first stack structure contains one or more different metal elements from the metal element or elements present in the layer that constitutes the first stack structure whose layer is adjacent to a layer.
    [00020] (10) The tool coated with any of (1) to (6) and (9), wherein a layer constituting the second stack structure contains one or more different metal elements from the metal element or of the elements present in the layer that constitutes the second stack structure whose layer is adjacent to a layer.
    [00021] (11) The tool coated from any of (1) to (10), where the thickness of the total average Layer of the entire coating layer is 0.22 to 12 pm.
    [00022] (12) The tool coated with any of (1) to (11), where the average thickness of the first pile structure is 0.2 to 6 pm.
    [00023] (13) The tool coated with any of (1) to (12), wherein the average thickness of the second stack structure is 0.02 to 6 pm. EFFECTS OF THE INVENTION
    [00024] The coated tools of the present invention have excellent wear resistance and fracture resistance to achieve a longer tool life than hitherto possible. Brief Description of Drawings
    [00025] Figure 1 is an example of schematic views illustrating a sectional structure of the coated tool of the present invention. Description of Modalities
    [00026] The coated tool of the present invention includes a substrate and the coating layer disposed on the surface of the substrate. The substrates in the present invention are not particularly limited, and any coated tool substrates can be used. Examples of these include cemented carbides, cermets, ceramics, sintered cubic boron nitrides, sintered diamonds and high-speed steels. In particular, cemented carbide substrates are more preferred because of excellent wear resistance and fracture resistance.
    [00027] Wear resistance tends to be reduced if the total average Layer thickness of the entire coating layer on the coated tool of the present invention is less than 0.22 pm. A reduction in fracture resistance tends to be caused if the total average Layer thickness of the entire coating layer exceeds 12 pm. It is therefore preferred that the thickness of the total average Layer of the entire coating layer is 0.22 to 12 pm. In particular, the thickness of the total average Layer of the entire coating layer is more preferably 1.0 to 8.0 µm.
    [00028] As described above, the coating layer on the coated tool of the present invention includes a specific first stack structure and a second specific stack structure. Each of the layers that make up the first stack structure includes at least one selected from the group consisting of: a metal including at least one metal element selected from Ti, Zr, Hf, V, Nb, Ta, Cr , Mo, W, Al, Si, Sr, Y, Sn and Bi; and compounds that include at least one of said metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron. Said layers exhibit excellent wear resistance.
    [00029] In particular, it is more preferred that the layers constituting the first stack structure include at least one selected from the group consisting of: metals including at least two metal elements selected from Ti, Nb, Ta, Cr, W, Al, Si, Sr and Y; and compounds that include at least two of said metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron. Said configuration adds hardness. Specific examples of the metals or compounds to form the constituent layers in the first cell structure include (Alo, 5oTio.5o) N, (Alo.6oTio, 4o) N, (Alo.67Tio, 33) N, (Alo.67Tío, 33) CN, (AIO, 45TÍO, 45SÍO.1O) N, (AIO, 45TÍO, 45YO.1O) N, (Alo, 5oTio, 2oCro, 2o) N, (Alo.soTio / sNbo.osJN, (Alo.5oTio , 45Tao, o5) N, (Alo, 5oTio, 45Wo, o5) N, (TÍO.9OSÍO.IO) N and (Alo, 5oCro, 5o) N.
    [00030] In the coating layer on the coated tool of the present invention, the first stack structure has a structure in which two or more types of layers including any of said metals or compounds are periodically stacked on top of each other with each layer having an average layer of thickness from 60 nm to 500 nm. Said stack structure having a specific periodicity includes two or more types of layers with different compositions. To avoid crack penetration and to obtain greater resistance to fracture, it is preferred that said layers with different compositions are stacked alternately each in two or more layers.
    [00031] In the present invention, the thickness of the minimum unit whose repetition constitutes the stack is written as the "stacking period". The stacking period will be explained below with reference to figure 1 which is an example of schematic views illustrating a sectioned structure of a coated tool of the present invention. When, for example, the stack consists of the repetition of Layer A1 (5), Layer B1 (6), Layer C1 and Layer D1 having different compositions in the order of Layer A1 Layer B1 Layer C1 Layer D1 Layer A1 -> Layer B1 Layer C1 Layer D1 ■■■ from substrate 1 towards the surface of coating layer 2, the total layer thicknesses of Layer A1 through Layer D1 is defined as the "stacking period". In the case where the stack consists of the repetition of Layer A1 (5) and Layer B1 (6) having different compositions in the order of Layer A1 Layer B1 Layer A1 Layer B1 Layer A1 -> Layer B1 -> ■■■ from substrate 1 towards the surface of the coating layer 2, the "stacking period" indicates the total thickness of the layer of Layer A1 and the thickness of the layer of Layer B1.
    [00032] With the configuration in which the layers having different compositions and respective medium layer thicknesses from 60 nm to 500 nm are stacked with the periodicity above, the crack that occurred on the surface of the coating layer during the use of the coated tool is avoided from substrate penetration. Specifically, the said crack that reached the first pile structure is encouraged to advance in a direction parallel to the interface between the layers with different compositions. Advantageously, said effect is further enhanced when an alternating stack structure is adopted in which two types of layers having different compositions are stacked alternately in two or more layers. Specifically, the first stack structure is preferably an alternating stack structure in which Layers A1 and Layers B1 with different compositions are stacked alternately each in two or more layers in the order of Layer A1 Layer B1 Layer A1 Layer B1 ■■■ from the substrate towards the surface of the coating layer.
    [00033] With respect to each of the layers that constitute the first stack structure in the coating layer on the coated tool of the present invention, any average layer thickness of each layer that is less than 60 nm results in a reduction in the effect of prevent the penetration of cracks to the substrate. On the other hand, fracture strength is reduced if the average layer thickness exceeds 500 nm. Thus, the average layer thickness of each of the layers that make up the first stack structure is limited to 60 nm to 500 nm. More preferably, the average layer thickness of each of the layers that make up the first stack structure is 60 nm to 250 nm.
    [00034] If the average thickness of the first stack structure is less than 0.2 pm, the first stack structure has such a small number of repetitions of the periodic stacking of layers with different compositions that the first stack structure tends to reduce the effect of suppressing the penetration of cracks to the substrate. On the other hand, any average thickness that exceeds 6 pm results in an increase in the residual compressive stress in the entire coating layer, and consequently the coating layer is prone to be separated or fractured, that is, it tends to exhibit poor fracture resistance. . Thus, the average thickness of the first stack structure in the present invention is more preferably 0.2 to 6 pm.
    [00035] As described above, the coating layer on the coated tool of the present invention includes the second stack structure. The layers that make up the second stack structure include at least one selected from the group consisting of: a metal including at least one metal element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo , W, Al, Si, Sr, Y, Sn and Bi; and compounds that include at least one of said metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron. Said layers exhibit excellent wear resistance.
    [00036] In particular, it is more preferred that the layers constituting the second stack structure include at least one selected from the group consisting of: metals including at least two metal elements selected from Ti, Nb, Ta, Cr, W, Al, Si, Sr and Y; and compounds that include at least two of said metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron. Said configuration adds hardness. Specific examples of the metals or compounds to form the constituent layers in the second cell structure include (Alo, 5oTio, 5o) N, (Alo.6oTio, 4o) N, (Alo.6 - Unio, 33) N, (Alo. 67TÍo, 33) CN, (Alθ, 45Tiθ, 45Siθ.1θ) N, (Alθ, 45Tiθ, 45Yθ.1θ) N, (Alθ, 5θTiθ, 3θCro, 2θ) N, (Alθ, 5θTiθ, 45Nbθ, O5) N, (Alθ, 5θTiθ, 45T ao, os) N, (Alo, 5oTio, 45Wo, o5) N, (TÍO.9OSÍO.IO) N and (Alo, 5oCro, 5o) N.
    [00037] The second stack structure in the present invention has the structure in which two or more types of layers including any of said metals or compounds are periodically stacked on top of each other with each layer having an average layer thickness of 2 nm less than 60 nm. Said stack structure having a specific periodicity includes two or more types of layers with different compositions. To ensure high hardness and to obtain greater resistance to wear, it is preferred that the second stack structure is an alternate stack structure in which said layers of different compositions are stacked alternately in two or more layers.
    [00038] In the second stack structure, similarly as described above, the thickness of the minimum unit whose repetition constitutes the stack is written as the "stacking period". With reference to figure 1 as an example, when the stack consists of the repetition of Layer A2 (7), Layer B2 (8), Layer C2 and Layer D2 having different compositions in the order of Layer A2 Layer B2 Layer C2 -> Layer D2 Layer A2 -> Layer B2 -> Layer C2 -> Layer D2 ■ from the substrate 1 towards the surface of the coating layer 2, the total layer thicknesses of Layer A2 to Layer D2 is defined as the "stacking period" . In the case where the stack consists of the repetition of Layer A2 (7) and Layer B2 (8) having different compositions in the order of Layer A2 Layer B2 Layer A2 Layer B2 -> Layer A2 Layer B2 ••• from substrate 1 in the direction of the surface of the coating layer 2, the "stacking period" indicates the total layer thickness of Layer A2 and the layer thickness of Layer B2.
    [00039] With the configuration in which the layers having different compositions and respective average layer thicknesses of 2 nm less than 60 nm are stacked with the periodicity above, the second stack structure in the coated tool of the present invention achieves high hardness for achieve an increase in wear resistance. Advantageously, said effect is further enhanced when an alternating stack structure is adopted in which two types of layers having different compositions are stacked alternately in two or more layers. Specifically, the second stack structure is more preferably an alternating stack structure in which Layers A2 and Layers B2 with different compositions are stacked alternately each in two or more layers in the order of Layer A2 Layer B2 -> Layer A2 Layer B2 ■■■ from the substrate towards the surface of the coating layer.
    [00040] If the average layer thickness of each of the layers that make up the second stack structure is less than 2 nm, a difficulty is encountered in forming the layer with a uniform thickness. If the average layer thickness of each of the layers that make up the second stack structure is 60 nm or more, the hardness is reduced to cause a reduction in wear resistance. In addition, said second pile structure has little difference in layer thickness from the first pile structure with the result that it is difficult to fully achieve the effect of suppressing the penetration of cracks into the substrate by causing the crack to advance by a direction parallel to the interface between the first stack structure and the second stack structure. Thus, the average layer thickness of each of the layers that make up the second stack structure in the present invention is limited to 2 nm less than 60 nm. From the above views, the average layer thickness of each of the layers that make up the second stack structure is most preferably 5 nm to 30 nm.
    [00041] If the average thickness of the second stack structure is less than 0.02 pm, the second stack structure has such a small number of repetitions of the periodic stacking of the layers that the increase in hardness cannot be obtained. On the other hand, any average thickness of the second pile structure that exceeds 6 pm results in an increase in the residual compressive stress in the second pile structure, and consequently the coating layer is prone to be separated or fractured, that is, it tends to exhibit poor fracture resistance. Thus, the average thickness of the second stack structure is preferably 0.02 to 6 pm.
    [00042] The coated tool of the present invention preferably has the difference between Ti and T2 (Ti - T2) from 20 to 996 nm where Ti is the average value of the stacking periods in the first pile structure and T2 is the average value of the stacking periods in the second stack structure. If the difference (Ti - T2) is less than 20 nm, the coated tool tends to reduce its effect of suppressing the penetration of cracks in the substrate by causing the crack to advance in a direction parallel to the interface between the first stack and the second stack structure. If, on the other hand, the difference between Ti and T2 (Ti - T2) exceeds 996 nm, the average thickness of the first pile structure is so great that the fracture resistance tends to be reduced. In particular, the difference between TieT2 (Ti-T2) is more preferably 20 to 500 nm, and still more preferably 20 to 250 nm.
    [00043] Since the unit "Layer A2 -> Layer B2" is repeatedly stacked on top of each other 100 times, the average value of the stacking periods is calculated by obtaining the total of the stacking periods of the 100 repetition units " Layer A2 -> Layer B2 Layer A2 Layer B2 Layer A2 Layer B2 -> ••• "and divide the total of the stacking periods by the number of repetitions, that is, 100.
    [00044] In a preferred embodiment of the coated tool of the present invention, the metal elements present in the layers that make up the first stack structure are identical between the layers that make up the first stack structure and include one or more metal elements having the difference in absolute value of 5% or more between the ratio of the same in relation to the total of the metal elements present in a layer that constitutes the first stack structure and the relation of the identical metal element in relation to the total of the metal elements present on the other layer that constitutes the first stack structure that is adjacent to a layer.
    [00045] With said configuration, the misalignment of the crystal trusses can be obtained at the interface between adjacent layers that constitute the first pile structure without causing any reduction in adhesion between the layers. Consequently, the structure can easily cause a crack to advance in a direction parallel to the interface between the layers that constitute the first pile structure, and is therefore more advantageous in that the effect of suppressing the penetration of cracks into the substrate is increased.
    [00046] The phrase that the metal elements "include one or more metal elements that have an absolute value difference of 5% or more" will be described. When, for example, the first stack structure includes layers of (Alo, 55Tio, 45) N and layers of (Alo, 67Tio, 33) N, the two types of layers include identical metal elements, that is, element Al and element Ti. The ratio of the element Al present in the layer of (Alo, 55Tio, 45) N is 55% in relation to the total of the metal elements, and the ratio of the element Al present in the layer (Alo, 67Tio, 33) N is 67% of the total metal elements. Thus, the difference in the ratio of element Al between the two layers is 12%, which satisfies the need above. Additionally, the layers (Alo, 49Tio, 39Cro, i2) N and the layers (Alo.seTio.seCro.oeJN will be discussed. These two types of layers include identical metal elements, that is, element Al, element Ti and element Cr. Although the difference in the Ti element ratio between the two layers is 3% and the difference in the Cr element ratio between the two layers is 4%, that is, the differences for both elements are less than 5%, the structure satisfies the need for the fact that the difference in the Al ratio between the two layers is 7%.
    [00047] In the present invention, nitrides are sometimes written as (MaLb) N with the letter a indicating the atomic proportion of the element M and the letter b indicating the atomic proportion of the element L in relation to the total of the metal elements. For example, (Alo, 55Tio, 45) N means that the atomic ratio of the element Al to the total of the metal elements is 0.55 and the atomic ratio of the element Ti to the total of the metal elements is 0, 45, that is, the ratio of the element Al to the total of the metal elements is 55% and the ratio of the element Ti to the total of the metal elements is 45%.
    [00048] In a preferred embodiment of the coated tool of the present invention, the metal elements present in the layers making up the second stack structure are identical between the layers making up the second stack structure and include one or more metal elements having a difference in absolute value of 5% or more between its relation to the total of the metal elements present in a layer that constitutes the second pile structure and the relation of the identical metal element to the total of the metal elements present on the other layer that constitutes the second stack structure that is adjacent to a layer.
    [00049] With said configuration, the misalignment of crystal trusses can be obtained at the interface between the adjacent layers that constitute the second stack structure without causing any reduction in adhesion between the layers. Consequently, the structure can easily cause a crack to advance in a direction parallel to the interface between the layers that constitute the second stack structure, and is therefore more advantageous in that the effect of suppressing the penetration of cracks into the substrate is increased. The meaning of the phrase that the metal elements "include one or more metal elements that have an absolute value difference of 5% or more" is the same as described above with respect to the first stack structure.
    [00050] In another embodiment of the coated tool of the present invention, it is more preferred that one layer that constitutes the first pile structure and the other layer that constitutes the first pile structure that is adjacent to a layer includes one or more metal elements different between layers. With this configuration, the crystal trusses can be misaligned at the interface between the layers and consequently the structure can easily cause the crack to advance in a direction parallel to the interface between the layers, thus achieving an increase in the effect of suppressing the penetration of cracks in the substrate. When, for example, the first stack structure includes the layers (Alo, 5oTio, 5o) N and the layers (Alo, 5oTio.3oCro, 2o) N, the comparison of the metal elements present in said two types of layers shows that the element Al and the element Ti are contained in the two layers while the element Cr is present only in one of the layers. That is, the need above is met. Additionally, when the first stack structure includes the (Alo, 5oCro, 5o) N layers and the (Alo.67Tio, 33) N layers, the comparison of the metal elements present in said two types of layers shows that the element Al is contained in the two layers while the Cr element is present only in one layer and the Ti element is present only in the other layer. Thus, the above need is met.
    [00051] Similarly, in the coated tool of the present invention, it is more preferred that one layer constituting the second stack structure and the other layer constituting the second stack structure that is adjacent to a layer include one or more elements of different metal between the layers. With this configuration, the crystal trusses can be misaligned at the interface between the layers and consequently the structure can easily cause the crack to advance in a direction parallel to the interface between the layers, thus achieving an increase in the effect of suppressing the penetration of cracks in the substrate.
    [00052] In the coated tool of the present invention, the coating layer includes the first pile structure having excellent fracture resistance and the second pile structure having excellent wear resistance. As a result, the coated tool exhibits excellent fracture resistance and wear resistance. The coating layer may include an upper layer on the surface of the coating layer opposite the substrate through the first stack structure and the second stack structure. In addition, the coating layer may include a lower layer on the side closest to the substrate than the first and second stack structure. In addition, the coating layer can include an intermediate layer between the first stack structure and the second stack structure.
    [00053] The configurations of said upper layers, intermediate layers and lower layers are not particularly limited and any of the coating layers provided in coated tools can be used. In particular, increased wear resistance can advantageously be obtained by adopting a single layer configuration or a non-periodic multiple layer configuration including at least one selected from the group consisting of a metal including at least one metal element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, Si, Sr, Y, Sn and Bi; and compounds that include at least one of said metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron.
    [00054] In a more preferred embodiment, the first stack structure and the second stack structure are stacked alternately and continuously each in two or more layers. With said configuration, the structure can easily cause the crack to advance in a direction parallel to the interface between the first pile structure and the second pile structure, and thus effectively suppress the penetration of cracks into the substrate, that is, achieve greater fracture resistance. The position relationship between the first stack structure and the second stack structure is not limited and may be such that the first stack structure is closer to the substrate and the second stack structure is closer to the surface of the coating layer on the side opposite the substrate or it can be so that the second stack structure is closer to the substrate and the first stack structure is closer to the surface of the coating layer on the side opposite the substrate. Alternatively, the first stack structure or the second stack structure can be arranged closer not only to the substrate, but also to the surface of the coating layer on the side opposite the substrate. Based on the fact that the residual compressive stress on the first stack structure is lower than the residual compressive stress on the second stack structure, it is more preferred that the first stack structure is arranged closer to the substrate and the second stack is arranged closer to the surface. In this case, the coating layer tends to exhibit greater resistance to separation.
    [00055] The coating layer on the coated tool of the present invention can be produced by any methods without limitation. For example, a physical deposition method such as an ion lamination method, an arc ion lamination method, a scintillation method or an ion mixing method can be used to form the layers such as the first structure of stack and second stack structure mentioned above on the substrate. In particular, the arc ion lamination method is more preferred because of its excellent adhesion between the coating layer and the substrate.
    [00056] The coated tool of the present invention can be obtained by forming the layers on the substrate surface by a conventional coating method. An example of a production method is described below.
    [00057] A substrate processed in a tool format is disposed in a reaction vessel of a physical deposition apparatus, and a vacuum is produced by evacuating the inside of the reaction vessel at a pressure of 1 x 10'2 Pa or below. After the vacuum has been generated, the temperature of the substrate is raised to 200 to 800 ° C with a heater arranged in the reaction vessel. After heating, Ar gas is introduced into the reaction vessel to raise the pressure to 0.5 to 5.0 Pa. In the Ar gas atmosphere at a pressure of 0.5 to 5.0 Pa, an orientation voltage of -200 to -1000 V is applied to the substrate and a current of 5 to 20 A is passed through a tungsten filament disposed in the reaction vessel, thereby treating the surface of the substrate by ion bombardment of the Ar gas. After the surface of the substrate having been treated by ion bombardment, vacuum is implemented at a pressure of 1 x 10'2 Pa or below.
    [00058] Then, a reaction gas such as nitrogen gas is introduced into the reaction vessel to increase the pressure inside the reaction vessel to 0.5 to 5.0 Pa. The -10 to -150 V orientation voltage is applied to the substrate, and the sources of metal deposition according to the metal components of the respective layers are vaporized by arc discharge, thereby forming layers on the surface of the substrate. In the case where two or more types of metal deposition sources arranged separately are vaporized at the same time by arc discharge and the layers to constitute the first pile structure or the second pile structure are formed at the same time as rotating a turntable on which the substrate has been attached, the thickness of the layers of the respective layers to form the first stack structure or the second stack structure can be controlled by adjusting the rotational speed of the turntable that supports the substrate in the reaction vessel . When two or more types of metal deposition sources are alternately vaporized by arc discharge to form the layers to form the first pile structure or the second pile structure, the thickness of the layers of the respective layers to constitute the first pile structure or the second stack structure can be controlled by adjusting the arc discharge time for the respective metal deposition sources.
    [00059] The layer thickness of the respective layers that constitute the coating layer on the coated tool of the present invention can be measured by analyzing the sectioned structure of the coated tool with a device such as an optical microscope, an electron reading microscope (SEM ) or an electron transmission microscope (TEM). The average layer thickness of each layer in the coated tool of the present invention can be obtained by measuring the layer thickness of each layer with respect to the cross sections sampled from 3 or more regions approximately 50 pm from the edge of cut the surface opposite the metal deposition source towards the center of the surface, and calculate the average value of the thickness obtained from the layers.
    [00060] The composition of each of the layers in the coated tool of the present invention can be measured by analyzing the sectioned structure of the coated tool of the present invention with a device such as an energy dispersive X-ray spectrometer (EDS) or a spectrometer dispersive wavelength X-ray (WDS).
    [00061] Specific examples of the coated tools of the present invention include cutting inserts, drills and end drills. EXAMPLES Example 1
    [00062] A cemented carbide corresponding to P10 in the ISO SEEN 1203 inserter was provided as a substrate. Metal deposition sources were arranged in a reaction vessel of an arc ion laminating apparatus as to design layers that have the compositions described in any of Tables 1 to 3. The substrate was fixed to a table fixing hardware. swivel disposed in the reaction vessel.
    [00063] Subsequently, a vacuum was produced by evacuating the inside of the reaction vessel at a pressure of 5.0 x 10'3 Pa or below. After the vacuum was generated, the substrate was heated to a temperature of 500 ° C with a heater arranged in the reaction vessel. After heating, Ar gas was introduced into the reaction vessel to raise the pressure to 5.0 Pa.
    [00064] In the Ar gas atmosphere at a pressure of 5.0 Pa, the orientation voltage of -1000 V was applied to the substrate and a current of 10 A was passed through a tungsten filament disposed in the reaction vessel, thereby treating the surface of the substrate by ion bombardment of Ar gas for 30 minutes. After the completion of the ion bombardment treatment, the inside of the reaction vessel was evacuated to bring the vacuum to a pressure of 5.0 x 10'3 Pa or below.
    [00065] After the vacuum was produced, nitrogen gas was introduced into the reaction vessel to create an atmosphere of nitrogen gas having a pressure of 2.7 Pa. The -50 V orientation voltage was applied to the substrate, and a current 200 A arc was passed to produce arc discharge and thereby to vaporize the sources of metal deposition, thus forming the respective layers.
    [00066] In the formation of Layers A1 and Layers B1 in the products of the invention 1 to 11, the metal deposition source for Layers A1 and the metal deposition source for Layers B1 were alternately vaporized by arc discharge to form Layers A1 and Layers B1. During this process, the layer thickness of Layers A1 and Layers B1 was controlled by adjusting the respective arc discharge time. In the manufacture of Comparative Product 1, Layers X and Layers Y with great layer thickness were formed in a similar way by alternately vaporizing the metal deposition source for Layers X and the metal deposition source for Layers Y by discharge of bow. During said process, the layer thickness of Layers X and Layers Y was controlled by adjusting the respective arc discharge time.
    [00067] In the formation of Layers A2 and Layers B2 in the products of the invention 1 to 11, the metal deposition source for Layers A2 and the metal deposition source for Layers B2 were simultaneously vaporized by arc discharge to form Layers A2 and Layers B2. During this process, the layer thickness of Layers A2 and Layers B2 was controlled by adjusting the rotational speed of the turntable in the range of 0.2 to 10 min-1. In the manufacture of Comparative Product 2, Layers X and Y Layers with small layer thickness were formed in a similar way by simultaneously vaporizing the metal deposition source for Layers X and the metal deposition source for Layers Y by discharge of bow. During this process, the layer thickness of Layers X and Layers Y was controlled by adjusting the rotational speed of the turntable in the range of 0.2 to 10 min-1.
    [00068] After the layers have been formed on the substrate surface to the prescribed layer thickness, the heater has been turned off. After the sample temperature was reduced to 100 ° C or below, the sample was collected from the reaction vessel.






    [00069] The respective middle layer thicknesses of the layers in the samples obtained were determined by measuring the layer thickness of each layer by observing TEM with respect to the cross sections sampled from 3 regions approximately 50 pm from the cutting edge. of the coated tool surface opposite the metal deposition source towards the center of the surface, and calculate the average value of the thickness obtained from the layers. The respective layer compositions in the samples obtained were determined by analyzing the cross section sampled from a region of from the cutting edge of the coated tool's surface opposite the metal deposition source for the distance of 50 pm towards the center using an EDS. The results are described in Tables 1 to 3. The composition ratios of the metal elements in the layers described in Tables 1 to 3 indicate an atomic ratio of the metal elements to the total metal elements in the metal compounds that were the respective layers.
    [00070] The fracture strength of the samples obtained above was assessed by using the samples in the face crusher under the following test conditions. The results of the evaluation are described in Table 4. Test Conditions Workpieces: SCM440 Workpiece format: 105 mm x 200 mm x 60 mm cuboid (having 6 holes with a diameter of 30 mm on the face of 105 mm x 200 mm to be crushed from the cuboid) Cutting coefficient: 250 m / min Feeding: 0.4 mm / tooth Cutting depth: 2.0 mm Cutting width: 105 mm Refrigerant: none Effective cutter diameter: 125 mm Item evaluation: the extent of cut for the occurrence of sample fracture (the occurrence of fracture in the sample cutter blade) was measured. Table 4


    [00071] The results in Table 4 show that the Products of the invention achieved a longer cut length and had a longer tool life than Comparative Products that had an alternating pile structure composed of layers with various uniform layer thicknesses . Example 2
    [00072] A cemented carbide corresponding to P10 in the shape of the ISO SEEN 1203 inserter was provided as a substrate. Metal deposition sources were arranged in a reaction vessel of an arc ion lamination apparatus in order to design layers having the compositions described in Table 5. Samples having the layer configurations described in Tables 5 and 6 were manufactured by the same production method than in Example 1. Table 5






    [00073] The respective middle layer thicknesses and the respective layer compositions in the obtained samples were determined in the same way as in Example 1, the results being described in Tables 5 and 6. Additionally, the fracture resistance of the samples obtained was evaluated at if the samples are used for face grinding under the same test conditions as in Example 1. The results of the evaluation are described in Table 7. Table 7

    [00074] From Table 7, it was shown that the products of the invention achieved a longer cut length and had a longer tool life than the Comparative Products which had an alternating pile structure composed of layers with various uniform thicknesses of layers. Example 3
    [00075] A cemented carbide corresponding to the insertion device P10 in the format of ISO SEEN 1203 was provided as a substrate. In the manufacture of the Products of the invention 23 and 25 to 35 and Comparative Products 3 and 5 to 15, the sources of metal deposition were arranged in a reaction vessel of an arc ion lamination apparatus in order to design the layers having the compositions described in Tables 8 and 10, and samples having the layer configurations described in Tables 9 and 10 were manufactured by the same production method as that of Example 1.
    [00076] In the manufacture of the Product of the invention 24 and the Comparative Product 4, the sources of metal deposition were arranged in a reaction vessel of an arc ion lamination apparatus in order to design the layers having the compositions described in the Tables 8 and 10, and samples having the layer configurations described in Tables 9 and 10 were manufactured in the same manner as in Example 1 except that the atmosphere in the reaction vessel during layer formation was created by feeding a gas mixture that contains N2 gas and CH4 gas in a partial pressure ratio of N2: CH4 = 1: 1 at a pressure inside the reaction vessel of 2.7 Pa.









    [00077] The respective layer thicknesses and the respective layer compositions in the samples obtained were determined in the same way as in Example 1, the results being described in Tables 8 to 10. The composition ratios of the metal elements in the layers described in Tables 8 and 10 indicate an atomic proportion of the metal elements in relation to the total metal elements in the metal compounds forming the respective layers. The fracture strength of the samples obtained was evaluated by using the samples in face crushing under the same test conditions as in Example 1. The results of the evaluation are described in Tables 11 and 12.



    [00078] From Tables 11 and 12, it was shown that the Products of the invention achieved a longer cut length and had a longer tool life than the Comparative Products which had an alternating pile structure composed of layers with several uniform layer thicknesses. List of Reference Signs 1 Substrate 2 Coating layer 3 First cell structure 4 Second cell structure 5 Layer A1 6 Layer B1 7 Layer A2 8 Layer B2
    权利要求:
    Claims (14)
    [0001]
    1. Coated tool, characterized by the fact that it comprises a substrate and a coating layer arranged on the surface of the substrate, the coating layer including a first pile structure and a second pile structure, characterized by the fact that the first pile structure stack having a structure in which two or more types of layers with different compositions are periodically stacked in which the average layer thickness of each layer is 60 nm to 500 nm, the second stack structure having a structure in which two or more types of layers with different compositions are periodically stacked in which the average layer thickness of each layer is 2 nm less than 60 nm, the layers making up the first stack structure and the layers making up the second stack structure including at least one selected from the group consisting of compounds including at least two metal elements selected from Ti, Nb, Ta, Cr , W, Al, Si, Sr and Y and at least one non-metal element selected from carbon, nitrogen, oxygen and boron.
    [0002]
    2. Coated tool according to claim 1, characterized in that the first stack structure is an alternating stack structure that includes two types of layers with different compositions stacked alternately each in two or more layers.
    [0003]
    Coated tool according to claim 1 or 2, characterized in that the second stack structure is an alternating stack structure that includes two types of layers with different compositions stacked alternately each in two or more layers.
    [0004]
    Coated tool according to any one of claims 1 to 3, characterized in that the coating layer includes a structure including the first stack structures and the second stack structures alternately and continuously stacked every two or more structures.
    [0005]
    5. Coated tool according to any one of claims 1 to 4, characterized in that (Ti - T2) is 20 nm to 996 nm where Ti is 0 average value of the stacking periods in the first stack structure and T2 is the average value of the stacking periods in the second stack structure.
    [0006]
    Coated tool according to any one of claims 1 to 5, characterized in that the layers that make up the first stack structure and the layers that make up the second stack structure each include at least one selected from the group that consists of compounds including at least two metal elements selected from Ti, Cr, Al and Si and at least one non-metal element selected from carbon and nitrogen.
    [0007]
    Coated tool according to any one of claims 1 to 6, characterized in that the metal elements present in the layers that make up the first pile structure are identical between the layers that make up the first pile structure and include a or more metal elements having a difference in absolute value of 5% or more between the ratio of the same in relation to the total of the metal elements present in a layer that constitutes the first pile structure and the relation of the identical metal element in relation to the total of the metal elements present in the layer that constitutes the first stack structure whose layer is adjacent to a layer.
    [0008]
    Coated tool according to any one of claims 1 to 7, characterized in that the metal elements present in the layers making up the second stack structure are identical between the layers making up the second stack structure and include a or more metal elements having a difference in absolute value of 5% or more between the ratio of the same in relation to the total of the metal elements present in a layer that constitutes the second stack structure and the relation of the identical metal element in relation to the total of the metal elements present in the layer that constitutes the second stack structure whose layer is adjacent to a layer.
    [0009]
    Coated tool according to any one of claims 1 to 6, characterized in that a layer constituting the first stack structure contains one or more different metal elements from the metal element or elements present in the layer which constitutes the first stack structure whose layer is adjacent to a layer.
    [0010]
    Coated tool according to any one of claims 1 to 6 and 9, characterized in that a layer constituting the second stack structure contains one or more different metal elements from the metal element or elements present in the layer that constitutes the second stack structure whose layer is adjacent to a layer.
    [0011]
    Coated tool according to any one of claims 1 to 10, characterized in that the thickness of the total average layer of the entire coating layer is 0.22 to 12 pm.
    [0012]
    Coated tool according to any one of claims 1 to 11, characterized in that the average thickness of the first stack structure is 0.2 to 6 pm.
    [0013]
    Coated tool according to any one of claims 1 to 12, characterized in that the average thickness of the second stack structure is 0.02 to 6 pm.
    [0014]
    Coated tool according to any one of claims 1 to 13, characterized in that the layers constituting the first stack structure and the layers constituting the second stack structure each include at least one selected from the group consisting of in compounds including hair selected from the group consisting of compounds including Ti, Al and N.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2917348C2|1979-04-28|1984-07-12|Fried. Krupp Gmbh, 4300 Essen|Wear-resistant composite body|
    SU1132446A1|1983-12-12|1990-01-15|Всесоюзный Научно-Исследовательский Инструментальный Институт|Wear-resistant coating for cutting tools|
    SU1723840A1|1990-01-22|1997-01-20|Институт Физики Прочности И Материаловедения Со Ан Ссср|Method of increasing wear resistance of metal and alloy issues|
    CA2148251A1|1992-10-29|1994-05-11|Warren H. Hunt, Jr.|Metal matrix composite having enhanced toughness and method of making|
    JP3460287B2|1994-01-21|2003-10-27|住友電気工業株式会社|Surface coating member with excellent wear resistance|
    JP4185172B2|1997-06-19|2008-11-26|住友電工ハードメタル株式会社|Coated hard tool|
    US6689450B2|2001-03-27|2004-02-10|Seco Tools Ab|Enhanced Al2O3-Ti multi-coating deposited at low temperature|
    JP3849135B2|2001-12-27|2006-11-22|三菱マテリアル株式会社|Cutting tool made of surface-coated cemented carbide with a hard coating layer showing good biting properties against the work material under heavy cutting conditions|
    DE10332101B4|2003-07-15|2016-02-04|Kennametal Inc.|Cutting tool and method for its production|
    RU2266350C2|2003-10-31|2005-12-20|Ульяновский государственный технический университет|Method of forming wear-resistant coating for cutting tools|
    SE528108C2|2004-07-13|2006-09-05|Sandvik Intellectual Property|Coated cemented carbide inserts, especially for turning steel, and ways of manufacturing the same|
    RU2346078C2|2007-03-22|2009-02-10|Государственное образовательное учреждение высшего профессионального образования "Пермский государственный технический университет"|Method of antiwear multiple plating|
    KR101150145B1|2007-05-30|2012-06-08|스미또모 덴꼬오 하드메탈 가부시끼가이샤|Surface-coated cutting tool|
    US7947363B2|2007-12-14|2011-05-24|Kennametal Inc.|Coated article with nanolayered coating scheme|
    JP5257750B2|2008-04-04|2013-08-07|住友電工ハードメタル株式会社|Surface coated cutting tool|
    WO2010007958A1|2008-07-14|2010-01-21|株式会社タンガロイ|Coated member|
    JPWO2010010648A1|2008-07-22|2012-01-05|日本特殊陶業株式会社|Cutting insert and cutting tool|
    JP5235607B2|2008-10-23|2013-07-10|京セラ株式会社|Surface coating tool|
    JP2010207916A|2009-03-06|2010-09-24|Mitsubishi Materials Corp|Surface coated cutting tool|
    JP2011104722A|2009-11-18|2011-06-02|Mitsubishi Materials Corp|Diamond coating tool excellent in chipping resistance and fusion-bond resistance|
    BR112012016898A2|2010-01-11|2018-06-05|Iscar Ltd|"coated cutting tool, and method for coating a cutting tool substrate."|
    KR101190324B1|2010-02-11|2012-10-11|대구텍 유한회사|Cutting tool|
    JP5459507B2|2010-08-09|2014-04-02|三菱マテリアル株式会社|Surface coated cutting tool|WO2008018556A1|2006-08-09|2008-02-14|Mitsubishi Tanabe Pharma Corporation|Tablet|
    US10265775B2|2014-03-27|2019-04-23|Tungaloy Corporation|Coated tool|
    WO2015156383A1|2014-04-10|2015-10-15|株式会社タンガロイ|Coated tool|
    CN106573312B|2014-08-01|2019-08-06|株式会社泰珂洛|Coated cutting tool|
    DE102014018915A1|2014-12-22|2016-06-23|Oerlikon Surface Solutions Ag, Trübbach|AlCrN-based coating for improved resistance to crater wear|
    EP3290137B1|2015-04-27|2021-06-23|Tungaloy Corporation|Coated cutting tool|
    JP6004366B1|2015-04-27|2016-10-05|株式会社タンガロイ|Coated cutting tool|
    CN107835870B|2015-07-13|2020-04-03|山特维克知识产权股份有限公司|Coated cutting tool|
    US10676810B2|2015-09-04|2020-06-09|Osg Corporation|Hard coating and hard coating-covered member|
    JP6222675B2|2016-03-28|2017-11-01|住友電工ハードメタル株式会社|Surface-coated cutting tool and method for manufacturing the same|
    RU2637865C1|2016-10-11|2017-12-07|федеральное государственное бюджетное образовательное учреждение высшего образования "Ульяновский государственный технический университет"|Method of producing multi-layer coating for cutting tool|
    EP3549701A4|2016-11-29|2020-05-20|Sumitomo Electric Hardmetal Corp.|Surface-coated cutting tool|
    KR101887287B1|2016-12-14|2018-08-09|이종하|Medical tool having excellent corrosion and abrasion resistance, and manufacturing method of the same|
    JP2018111201A|2017-01-07|2018-07-19|株式会社タンガロイ|Coated cutting tool|
    RU2638874C1|2017-03-10|2017-12-18|федеральное государственное бюджетное образовательное учреждение высшего образования "Ульяновский государственный технический университет"|Method of producing multi-layer coating for cutting tool|
    JP6507399B2|2017-03-28|2019-05-08|株式会社タンガロイ|Coated cutting tool|
    JP6865277B2|2017-05-30|2021-04-28|京セラ株式会社|Covering tool and cutting tool equipped with it|
    CN107177825B|2017-07-03|2019-08-06|济宁学院|ZrNbC/ZrNbCN laminated coating cutter and its preparation process|
    CN107177829B|2017-07-03|2019-08-06|济宁学院|AlNbC/AlNbCN lamination composite coating layer cutter and its preparation process|
    DE112018004916T5|2017-08-29|2020-06-04|Kyocera Corporation|COATED TOOL AND CUTTING TOOL THAT HAS THIS|
    US20200222989A1|2017-08-29|2020-07-16|Kyocera Corporation|Coated tool and cutting tool including same|
    KR102317383B1|2018-02-27|2021-10-26|히다찌긴조꾸가부시끼가이사|Covering member and manufacturing method thereof|
    EP3808477A4|2018-06-15|2022-03-09|Sumitomo Electric Hardmetal Corp|Surface-coated cutting tool and process for producing same|
    US10994341B2|2018-06-15|2021-05-04|Sumitomo Electric Hardmetal Corp.|Surface-coated cutting tool and method for manufacturing same|
    RU2735478C1|2019-10-01|2020-11-03|федеральное государственное бюджетное образовательное учреждение высшего образования "Ульяновский государственный технический университет"|Method of producing multilayer coating for cutting tools|
    法律状态:
    2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-12-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-06-02| B09A| Decision: intention to grant|
    2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012-177843|2012-08-10|
    JP2012177843|2012-08-10|
    JP2012185370|2012-08-24|
    JP2012-185370|2012-08-24|
    PCT/JP2013/071753|WO2014025057A1|2012-08-10|2013-08-12|Coated tool|
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