WO2015079590A1 - Film de revêtement lubrifiant dur et outil couvert d'un film de revêtement lubrifiant dur - Google Patents

Film de revêtement lubrifiant dur et outil couvert d'un film de revêtement lubrifiant dur Download PDF

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WO2015079590A1
WO2015079590A1 PCT/JP2013/082287 JP2013082287W WO2015079590A1 WO 2015079590 A1 WO2015079590 A1 WO 2015079590A1 JP 2013082287 W JP2013082287 W JP 2013082287W WO 2015079590 A1 WO2015079590 A1 WO 2015079590A1
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layer
hard
film
test
atomic ratio
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PCT/JP2013/082287
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English (en)
Japanese (ja)
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メイ ワン
博昭 杉田
正俊 櫻井
須藤　祐司
小池　淳一
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オーエスジー株式会社
国立大学法人東北大学
メイ ワン
博昭 杉田
正俊 櫻井
須藤　祐司
小池　淳一
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Application filed by オーエスジー株式会社, 国立大学法人東北大学, メイ ワン, 博昭 杉田, 正俊 櫻井, 須藤　祐司, 小池　淳一 filed Critical オーエスジー株式会社
Priority to JP2015550532A priority Critical patent/JP6168541B2/ja
Priority to PCT/JP2013/082287 priority patent/WO2015079590A1/fr
Publication of WO2015079590A1 publication Critical patent/WO2015079590A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C5/00—Milling-cutters
    • B23C5/28—Features relating to lubricating or cooling
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23C2228/08—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner applied by physical vapour deposition [PVD]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23C2228/10—Coating

Definitions

  • the present invention relates to a hard lubricating coating provided on the surface of a base material and a hard lubricating coating-coated tool coated with the hard lubricating coating, and more particularly to an improvement for improving both the hardness and the wear resistance.
  • Drilling and tapping holes such as carbon steel, stainless steel, and mild steel are used for drilling tools such as drills and taps. Properties are required. Therefore, a hard coating is provided on the surface of the base material of the cutting tool so as to improve the wear resistance.
  • this hard film for cutting tools coatings such as TiN, CrN, TiCN, and TiAlN are widely used, and improvements are made to further improve the performance.
  • the hard laminated film described in patent document 1 and patent document 2 is it.
  • Patent Document 1 first made of Ti a Cr b Al c Mo 1 -abc nitride or a first coating layer made of carbonitride, Ti d Cr e Al 1- de nitride or carbonitride A hard laminated film composed of a multilayer film in which two or more film layers are alternately laminated, and in Patent Document 2, from Ti a Cr b Al c Mo 1-abc nitride or carbonitride. A hard laminate coating composed of a single layer film is proposed.
  • the base material on which the hard multilayer coating is formed by the conventional technology as described above is still insufficient in lubricity and wear resistance. There was a problem that it might lead to. Accordingly, there has been a demand for the development of a hard laminate film that is hard and wear-resistant.
  • the present invention has been made against the background described above, and an object of the present invention is to provide a hard lubricant film and a hard lubricant film-coated tool that are hard and wear-resistant.
  • titanium (Ti) is easily oxidized, it is intended not to include Ti as an element constituting the coating, so that chromium (Cr), molybdenum ( Mo, tungsten (W), vanadium (V), and boron (B) are constituent elements of the A layer, and tungsten (W) is the constituent element of the B layer, and oxygen is introduced into the A layer, Cr, Mo, W, and V It has been found that a crystal microstructure composed of oxycarbide, oxynitride or oxycarbonitride is formed, so that higher lubricity can be obtained while having high hardness. The present invention has been made based on such findings.
  • the crystal of the A layer has a fine crystal structure in which crystal growth is suppressed by the thickness of the layer to increase the hardness of the coating, and the oxycarbide of Cr, Mo, W and V,
  • the crystal of oxynitride or oxycarbonitride has a solid lubricating structure similar to that of molybdenum sulfide or nitride, and thus it is estimated that the lubricity of the coating is improved.
  • the gist of the first invention is a hard lubricating coating coated on the surface of the base material, and (Cr a Mo b W c V d B e ) 1-xyz C x N y O z oxycarbide of the a layer made of oxynitride or oxycarbonitride thereof, W is a (1-f) consist of N f B layer, a laminated hard lubricant film two or more layers alternately,
  • the atomic ratio a relating to the A layer is 0.2 ⁇ a ⁇ 0.7, b is 0.05 ⁇ b ⁇ 0.6, c is 0 ⁇ c ⁇ 0.3, and d is 0 ⁇ d ⁇ 0.05.
  • E 1-abcd is 0 ⁇ e ⁇ 0.05, x is 0 ⁇ x ⁇ 0.6, y is 0 ⁇ y ⁇ 0.6, and z is 0 ⁇ z ⁇ 0.2. , X + y + z is 0.3 ⁇ x + y + z ⁇ 0.6, the atomic ratio f related to the B layer is 0.3 ⁇ f ⁇ 0.6, and the film thickness of the A layer is 2 nm or more and 500 nm or less, The thickness of the B layer is 1 nm or less 500nm or less, the total film thickness is in a hard lubricant film coated tool hard lubricant film and hard lubricating coating is coated, characterized in that it is in the range of 0.1 ⁇ m or more 10.0 ⁇ m or less.
  • the gist of the second invention is that the hard lubricant film of the first invention is characterized in that the layer A has a multiphase structure in which a crystal phase and an amorphous phase are mixed.
  • the hardness of the film is increased by forming a microstructure composed of oxides, oxycarbides, oxynitrides or oxycarbonitrides of Mo, W and V, and oxides, oxycarbides of Mo, W and V Since oxynitride or oxycarbonitride has solid lubricity, the lubricity of the film is enhanced, and therefore, a hard lubricant film and a hard lubricant film-coated tool having hard and wear resistance can be obtained. .
  • the A layer has a multiphase structure in which a crystalline phase and an amorphous phase are mixed.
  • a fine NaCl phase crystal phase ( ⁇ - (Cr, Mo, W, V) N, ⁇ -Mo 2 N, etc.) composed of Mo, W and V oxycarbides, oxynitrides or oxycarbonitrides. ) And an amorphous phase are formed, whereby a hard lubricating coating and a hard lubricating coating-coated tool having hard and wear resistance can be obtained.
  • FIG. 2 is a conceptual cross-sectional view for explaining a laminated structure of a surface portion of the end mill of FIG. 1. It is a process chart for forming the end mill of FIG. It is a schematic block diagram explaining the sputtering device used suitably when forming the end mill of FIG. It is a figure which shows the structure of the abrasion friction test machine used for the friction abrasion test for verifying the effect of the hard film of this invention.
  • FIG. 1 is a front view of an end mill 12 covered with a hard coating 10 according to an embodiment of the present invention, as viewed from a direction perpendicular to the axis C thereof.
  • the end mill 12 is a rotary cutting tool in which a shank and a blade portion 16 are integrally provided on a tool base material 14 made of, for example, a cemented carbide.
  • the blade portion 16 is provided with an outer peripheral blade 18 and a bottom blade 20 as cutting blades.
  • the outer peripheral blade 16 is attached to a cutting device (not shown) and rotated around the axis C by the cutting device. And the cutting work is performed on the work material by the bottom blade 18.
  • the hard coating 10 corresponds to the hard lubricating coating of the present invention
  • the tool base 14 corresponds to the base of the present invention
  • the end mill 12 corresponds to the hard lubricating coating coated tool of the present invention.
  • FIG. 2 is a conceptual cross-sectional view for explaining the laminated structure of the surface portion of the end mill 12 of FIG.
  • the surface of the end mill 12 is coated with a hard coating 10 covering the surface.
  • the hatched portion in FIG. 1 shows a portion of the end mill 12 where the hard coating 10 is provided.
  • the hard coating 10 is preferably a surface of the tool base material 14 corresponding to the blade portion 16 in the end mill 12. It is provided with a coating.
  • the hard coating 10 of this example is a multilayer film in which two or more A layers 22 containing oxygen elements and B layers 24 containing tungsten (W) are alternately laminated.
  • the A layer 22 and the B layer 24 are made of a material that satisfies the chemical composition shown below.
  • bc-d is 0 ⁇ e ⁇ 0.05, x is 0 ⁇ x ⁇ 0.6, y is 0 ⁇ y ⁇ 0.6, z is 0 ⁇ z ⁇ 0.2, x + y + z is 0.3 ⁇ x + y + z ⁇ 0.6.
  • a microstructure made of oxide, oxycarbide, oxynitride or oxycarbonitride of Mo, W and V having a solid lubricating structure similar to molybdenum sulfide or nitride is formed.
  • (Cr 0.4 Mo 0.6 ) 0.52 N 0.38 O 0.1 is preferably exemplified as the A layer 22 in the hard coating 10.
  • the B layer 24 is W (1-f) N f , and the atomic ratio f is 0.3 ⁇ f ⁇ 0.6.
  • W 0.70 N 0.30 and the like are preferably exemplified.
  • the thickness D1 of the A layer 22 is in the range of 2 nm to 500 nm
  • the thickness D2 of the B layer 24 is in the range of 1 nm to 500 nm
  • the total thickness D of the hard coating 10 is 0. It is set within a range of 1 ⁇ m or more and 10.0 ⁇ m or less. That is, the number of layers of the A layer 22 and the B layer 24 is appropriately determined as long as it does not deviate from the above numerical range related to the total film thickness D of the hard coating 10 and the film thicknesses D1 and D2 of the coating layers 22 and 24.
  • a multilayer film having one A layer 22 and one B layer 24 may be used.
  • the film thicknesses D1 of the plurality of A layers 22 in the hard coating 10 may be all equal or different from each other within the above numerical range.
  • the film thicknesses D2 of the plurality of B layers 24 in the hard coating 10 may all be equal, or may be different from each other within the above numerical range.
  • the stacking order of the A layer 22 and the B layer 24 is preferably A layer 22, B layer 24,..., A layer 22 from the tool base material 14 side as shown in FIG. , B layer 24 are laminated in this order. That is, the base layer (the lowermost layer in contact with the tool base material 14) of the hard coating 10 is the A layer, and the surface layer (the uppermost layer of the hard coating 10) is the B layer.
  • FIG. 3 is a process chart for forming the end mill 12 of FIG. 1
  • FIG. 4 is a schematic configuration diagram (schematic diagram) for explaining a sputtering apparatus 26 suitably used for forming the end mill 12 of FIG. .
  • the cemented carbide which is the base material of the tool base material 14 is ground to obtain the tool base material 14.
  • the cemented carbide is first subjected to cylindrical grinding to form a rough shape of the tool base material 14, that is, a cylindrical shape having an axis.
  • groove grinding is performed to form a spiral groove or the like on the outer peripheral side surface on one end side of the columnar shape.
  • a sharpening is applied to the tip so that the convex portion generated by forming the groove becomes an outer peripheral blade or a bottom blade for cutting the work material.
  • the cleaning process P ⁇ b> 2 the surface of the tool base material 14 is cleaned prior to the coating of the hard coating 10.
  • the surface of the tool base material 14 is roughened by the sputtering apparatus 26 as a pretreatment.
  • the end mill 12 is formed by coating the hard coating 10 on the blade portion of the tool base material 14 by the sputtering apparatus 26.
  • an inspection is performed to determine whether or not the end mill 12 coated with the hard coating 10 satisfies a use standard as a cutting tool.
  • the sputtering apparatus 26 includes a chamber 28, a rotating shaft that passes through a substantially central through hole in the bottom surface of the chamber 28, and a disk-shaped base 30 that is fixed to one end of the rotating shaft inside the chamber 28. .
  • the tool base material 14 is heated to about 500 ° C.
  • argon (Ar) gas is introduced into the chamber 28 while the inside of the chamber 28 is maintained at a vacuum level equal to or lower than a predetermined pressure.
  • a bias voltage of ⁇ 200 to ⁇ 500 V for example, is applied to the tool base material 14 by the bias power source 32, and the surface of the tool base material 14 is etched by Ar ions generated by glow discharge generated in Ar gas. Is called.
  • Ar gas is exhausted from the chamber 28.
  • a film forming process P4 is subsequently performed.
  • a constant cathode voltage (for example, about ⁇ 100 to ⁇ 500 V) is applied to the targets 34 and 35 such as Cr, Mo, and W constituting the hard coating 10 by the power source 36, and the tool base material 14 is applied by the bias power source 32.
  • a constant negative bias voltage (for example, about ⁇ 100 V) to the argon gas, argon ions Ar + collide with the targets 34 and 35 to strike and ionize constituent materials such as Cr, Mo, and W.
  • the voltage applied by the power source 36 and the bias power source 32 is controlled by a controller 38.
  • a reactive gas such as nitrogen gas (N 2 ), hydrocarbon gas (CH 4 , C 2 H 2 ) or oxygen gas (O 2 ) in addition to argon gas is selectively selected at a predetermined flow rate and pressure.
  • the introduced nitrogen atom (N), carbon atom (C) or oxygen atom (O) is combined with Cr, Mo, W, etc. knocked out from the targets 34 and 35 to form an A layer 22 such as (Cr 0.4 Mo 0.6 )
  • An oxynitride such as 0.52 N 0.38 O 0.1 or an oxycarbonitride such as (Cr 0.6 Mo 0.35 W 0.03 V 0.01 B 0.02 ) 0.45 C 0.4 N 0.1 O 0.05 is formed.
  • a nitride such as 0.45 N 0.55 is formed. And since the tool base material 14 is further rotated with respect to the base 30 on the base 30 rotated with respect to the chamber 28, they are coated on the surface of the tool base 14 as a uniform hard coating 10. It is done.
  • the A layer 22 and the B layer 24 are controlled only by controlling the composition ratios related to Cr, Mo, W, V, and B and various reaction gases during film formation, or only by controlling various reaction gases during film formation. A coating of is formed.
  • hydrocarbon gas as a reaction gas in the coating layer B 24 is (CH 4, C 2 H 2 ) and oxygen (O 2) for gas is not necessary, a hydrocarbon gas (CH 4, C 2 H 2 ) And oxygen (O 2 ) gas into the chamber 28 are turned off to form the B layer 24. Then, according to the switching of the reaction gas and the selection of the targets 34 and 35, the alternate coating on the tool base material 14 of the A layer 22 and the B layer 24 is repeated, and finally the end mill coated with the hard coating 10 12 is formed.
  • the hard coating 10 coated on the end mill 12 is composed of (Cr a Mo b W c V d B e ) 1-xyz C x N y O z oxycarbide, oxynitride or oxycarbonitride
  • a layer 22 which is a material and B layer 24 which is a nitride of W (1-f) N f are alternately laminated, that is, the B layer 24 is inserted at the thin film interface of the A layer 22 Therefore, the particle size of the coating particles constituting the A layer and the B layer is further reduced and a fine structure is formed, so that low wear and friction life are improved, and wear resistance is excellent. This results in improved tool life.
  • the hard coating 10 is formed by precisely controlling the thin film composition constituting the A layer 22 by the presence or absence of introduction of the reaction gas and the selection of the targets 34 and 35 in the sputtering apparatus 26. Excellent low friction characteristics and wear resistance under high temperature conditions.
  • Table 1 shows the thin film compositions of layer A and layer B of test products 1 to 40 and comparative products 1 to 6 subjected to this test, and Table 2 shows layer A of test products 1 to 40 and comparative products 1 to 6. Each film thickness and total film thickness of the B layer and the results of each test are shown.
  • the test products 1 to 40 satisfy the conditions of each film structure and film thickness of the hard coating 10, and the comparative products 1 to 6 do not satisfy the conditions required for the hard coating 10.
  • the hardness H (GPa) of the film in Table 2 was determined as follows. First, a hemispherical end face of a test piece made of a cemented carbide pin having a diameter of 6 mm ⁇ is coated with a hard film so as to satisfy the conditions of each film structure and film thickness shown in Table 1, and used for a film hardness test.
  • the test pieces 40 of the products 1 to 40 and the comparative products 1 to 6 were prepared in the same process as the processes indicated by P2, P3, and P4 in FIG. About the created said test piece 40, the hardness of each film
  • a triangular pyramid type indenter made of a diamond tip at the tip was pushed into the surface of the test piece 40 covered with the hard coating with the load P, and the projected area A under the indenter was calculated.
  • the film hardness H (GPa) is calculated by dividing the load P by the area A.
  • the friction coefficient ⁇ in Table 2 was obtained by conducting a frictional wear test as follows. First, a hard film was coated on the hemispherical end face of the test piece so as to satisfy the conditions of each film structure and film thickness shown in Table 1, and test pieces 40 corresponding to the test products 1 to 40 and the comparative products 1 to 6 were prepared. . Each of the prepared test pieces 40 was installed in a pin-on-disk wear friction tester 42.
  • FIG. 5 is a diagram showing the configuration of the abrasion friction tester 42.
  • the abrasion friction tester 42 includes a disk-shaped rotary stage 44 that is driven to rotate about the rotation center, a work material 46 that is fixed to the center of the rotary stage 44, and the rotation center of the work material 46.
  • a load weight 50 that obliquely presses the hemispherical end portion 48 coated with the hard coating of the above-mentioned test products 1 to 40 and comparative products 1 to 6 at a predetermined angle from the rotation center by a predetermined applied load W at a position shifted from the center.
  • a stress sensor 52 that detects a tensile force F received by the hemispherical end 48 pressed against the rotary stage 44 in the test piece 40 when the rotary stage 44 is rotated at a predetermined linear velocity.
  • Test piece 40 Carbide indenter (diameter 6mm ⁇ ) ⁇ Work material 46: S45C (diameter 25 mm ⁇ ) -Applied load W: 2 (N) -Linear velocity: 200 (mm / min) ⁇ Test time: 900 (s) ⁇ Temperature: 28 (°C) ⁇ Humidity: 57 (%)
  • the friction coefficients ⁇ of the test products 1 to 40 and the comparative products 1 to 6 were evaluated based on the average value of the friction coefficients measured from 200 seconds to 600 seconds after the start of the test.
  • FIG. 6 is a graph showing the hardness H (GPa) of the film obtained by the nanoindentation method and the friction coefficient ⁇ obtained by the frictional wear test for each of the test products 1 to 40 and the comparative products 1 to 6. That is, FIG. 6 is a graph showing the hardness H (GPa) and the friction coefficient ⁇ of the film in Table 2.
  • the horizontal axis represents the numbers of test products 1 to 40 and comparative products 1 to 6
  • the left horizontal axis represents the film hardness H (GPa) of test products 1 to 40 and comparative products 1 to 6, and the right
  • the horizontal axis indicates the friction coefficient ⁇ of each of the test products 1 to 40 and the comparative products 1 to 6. As shown in Table 2 and FIG.
  • the hardness H (GPa) of the film is 29.6 GPa or more, and the friction coefficient ⁇ was 0.34 or less.
  • the film hardness H (GPa) is 35.0 GPa or more and the friction coefficient ⁇ is 0.26 or less. Showed better values.
  • the hardness is evaluated as soft at 15 to 20 GPa, hard at 30 GPa or more, and brittle at 50 to 60 GPa.
  • the A layer 22 made of (Cr a Mo b W c V d B e ) 1-xyz C x N y O z oxycarbide, oxynitride or oxycarbonitride and , W (1-f) N f nitride B layers 24 are alternately stacked, and the atomic ratio a of the A layer 22 is 0.2 ⁇ a ⁇ 0.
  • b is 0.05 ⁇ b ⁇ 0.6
  • c is 0 ⁇ c ⁇ 0.3
  • d is 0 ⁇ d ⁇ 0.05
  • x is 0 ⁇ x ⁇ 0.6
  • y is 0 ⁇ y ⁇ 0.6
  • z is 0 ⁇ z ⁇ 0.2
  • x + y + z is 0.3 ⁇ x + y + z ⁇ 0.6
  • B layer 24 is 0.3 ⁇ f ⁇ 0.6
  • the film thickness D1 of the A layer 22 is 2 nm to 500 nm
  • the film thickness D2 of the B layer 24 is 1 nm to 500 nm
  • the total film thickness D is 0.1 ⁇ m or more
  • Test samples 1 to 40 coated with the hard coating 10 in the range of 10.0 ⁇ m or less have a hardness H of 29.6 GPa or more and a coefficient
  • the comparative product 1 is a single-layer film of A layer having a thickness of 90 nm made of (Ti 0.25 Mo 0.75 ) 0.46 N 0.24 O 0.3 , and the titanium (Ti) is contained in the A layer. ) Is not contained, the atomic ratio b of molybdenum (Mo) is 0.75, and the atomic ratio z of oxygen is 0.3, which is different from the thin film composition related to the A layer 22 of the hard coating 10.
  • Element titanium (Ti) is contained, and the atomic ratio a of chromium (Cr) is 0.2 ⁇ a ⁇ 0.7, the atomic ratio b of molybdenum (Mo) is 0.05 ⁇ b ⁇ 0.6, Since the atomic ratio z of oxygen (O) deviates from 0 ⁇ z ⁇ 0.2, and the B layer is not inserted into the thin film interface of the A layer, the A layer 22 and the B layer 24 of the hard coating 10 are Deviating from the requirement of being alternately laminated, the total film thickness is 0.1 ⁇ m of the total film thickness D of the hard coating 10. Is a departure from the scope of the following or 10.0 [mu] m.
  • the hardness H of the film of the comparative product 1 is 18.0 GPa, which is small compared to the test product, and the friction coefficient ⁇ is 0.65, which is a large value compared to the test product.
  • the atomic ratio a of chromium (Cr) in the A layer 22 is 0.2 or more
  • the atomic ratio b of molybdenum (Mo) is 0.6 or less
  • the atomic ratio z of oxygen (O) is 0.2.
  • the total film thickness D should be 0.1 ⁇ m or more
  • the B layer 24 should be inserted at the thin film interface of the A layer 22, and the A layer 22 and the B layer 24 should be alternately laminated. It was verified that the significance of the requirements for the hard coating 10 according to the present invention was confirmed.
  • Comparative product 2 is a single-layer film of A layer made of Mo 0.55 N 0.45 and having a thickness of 11000 nm.
  • the A layer does not contain chromium (Cr), and the atomic ratio b of molybdenum (Mo) is 1.
  • the hardness H of the film of the comparative product 2 is 25.0 GPa, which is small compared to the test product, and the friction coefficient ⁇ is 0.50, which is a large value compared to the test product.
  • the atomic ratio a of chromium (Cr) in the A layer 22 is 0.2 or more
  • the atomic ratio b of molybdenum (Mo) is 0.6 or less
  • the atomic ratio z of oxygen (O) is less than 0.
  • the thickness A1 of the A layer should be 500 nm or less and the total thickness D should be 10.0 ⁇ m or less
  • the B layer 24 is inserted at the thin film interface of the A layer 22. Were verified to be laminated alternately, and the significance of the requirements for the hard coating 10 according to the present invention was confirmed.
  • Comparative product 3 is a single layer film of A layer having a thickness of 2500 nm made of (Ti 0.25 Mo 0.75 ) 0.4 C 0.3 O 0.3 , and titanium (Ti) is contained in the A layer, and chromium (Cr) is contained. It is not contained, and since the atomic ratio b of molybdenum (Mo) is 0.75 and the atomic ratio z of oxygen (O) is 0.3, what is the thin film composition related to the A layer 22 of the hard coating 10?
  • the A layer 22 and the B layer 24 of the hard coating 10 are Deviating from the requirement that the layers are alternately laminated, the A layer is 2 of the film thickness D1 of the A layer 22 of the hard coating 10. It is intended to depart from the 500nm following range of m.
  • the hardness H of the film of the comparative product 3 is 19.0 GPa, which is small compared to the test product, and the friction coefficient ⁇ is 0.59, which is a large value compared to the test product.
  • the atomic ratio a of chromium (Cr) in the A layer 22 is 0.2 or more
  • the atomic ratio b of molybdenum (Mo) is 0.6 or less
  • the atomic ratio z of oxygen (O) is 0.2.
  • the thickness D1 of the A layer should be 500 nm or less
  • the B layer 24 should be inserted at the thin film interface of the A layer 22, and the A layer 22 and the B layer 24 should be alternately stacked. It was verified that the significance of the requirements for the hard coating 10 according to the present invention was confirmed.
  • Comparative product 4 was formed by alternately laminating two or more layers of a 20 nm thick A layer composed of Ti 0.75 C 0.1 N 0.1 O 0.05 and a 20 nm thick B layer composed of W 0.3 N 0.7 . It is a multilayer film with a total film thickness of 6.00 ⁇ m, and the layer A contains titanium (Ti), does not contain chromium (Cr) and molybdenum (Mo), and contains carbon (C) and nitrogen (N).
  • the hardness H of the film of the comparative product 4 is 22.0 GPa, which is a small value compared to the test product, and the friction coefficient ⁇ is 0.72, which is a large value compared to the test product.
  • the atomic ratio a of chromium (Cr) in the A layer 22 is 0.2 or more
  • the atomic ratio b of molybdenum (Mo) is 0.05 or more
  • the sum x + y + z of the atomic ratio of O) should be 0.3 or more
  • the atomic ratio f of nitrogen (N) related to the B layer 24 should be 0.6 or less, confirming the significance of the numerical range according to the present invention. It was.
  • Comparative product 5 is a stack of two or more alternating layers of 50 nm thick A layers composed of (Ti 0.15 Cr 0.1 Mo 0.75 ) 0.52 N 0.32 O 0.16 and 60 nm thick B layers composed of W 0.8 N 0.2.
  • the layer A contains titanium (Ti), the atomic ratio a of chromium (Cr) is 0.1, and molybdenum (Mo) Since the atomic ratio b is 0.75, an element titanium (Ti) different from the thin film composition related to the A layer 22 of the hard coating 10 is contained, and the atomic ratio a of chromium (Cr) is 0.2 ⁇ a Since ⁇ 0.7 and the atomic ratio b of molybdenum (Mo) 0.05 ⁇ b ⁇ 0.6 and the atomic ratio f of nitrogen (N) in the B layer is 0.2, the hard coating 10
  • the nitrogen (N) atomic ratio f of the B layer 24 de
  • the hardness H of the film of the comparative product 5 is 24.0, which is a small value compared to the test product, and the friction coefficient ⁇ is 0.55, which is a large value compared to the test product.
  • the atomic ratio a of chromium (Cr) in the A layer 22 is 0.2 or more
  • the atomic ratio b of molybdenum (Mo) is 0.6 or less
  • the atomic ratio of nitrogen (N) in the B layer 24 It was verified that f should be 0.3 or more and the total film thickness D should be 10.0 ⁇ m or less, and the significance of the numerical range according to the present invention was confirmed.
  • Comparative product 6 is composed of two alternating layers of a 100 nm thick A layer made of (Ti 0.15 Cr 0.1 Mo 0.7 W 0.05 ) 0.35 N 0.15 O 0.5 and a 150 nm thick B layer made of W 0.4 N 0.6. It is a multilayer film having a total film thickness of 8.00 ⁇ m formed by laminating as described above, the layer A contains titanium (Ti), the atomic ratio a of chromium (Cr) is 0.1, and molybdenum (Mo ) Is 0.7, the atomic ratio z of oxygen (O) is 0.5, and the total x + y + z of the atomic ratios of carbon (C), nitrogen (N), and oxygen (O) is 0.
  • Ti titanium
  • Cr chromium
  • Mo molybdenum
  • the hardness H of the film of the comparative product 6 is 10.0 GPa, which is a small value compared to the test product, and the friction coefficient ⁇ is 0.80, which is a large value compared to the test product.
  • the atomic ratio a of chromium (Cr) in the A layer 22 is 0.2 or more
  • the atomic ratio b of molybdenum (Mo) is 0.6 or less
  • the atomic ratio z of oxygen (O) is 0.2.
  • the sum x + y + z of atomic ratios of carbon (C), nitrogen (N), and oxygen (O) should be 0.6 or less, and the significance of the numerical range according to the present invention was confirmed.
  • FIG. 7 is a graph showing the transition of the moving average value of the friction coefficient ⁇ as the test time elapses in the frictional wear test of the hard coating 10.
  • the vertical axis represents the friction coefficient ⁇
  • the horizontal axis represents the elapsed time (s) from the start of the test.
  • a comparative product 1 and a comparative product 6 representing the product.
  • the friction coefficient ⁇ of each test product and the comparison product is a solid line for the test product 12
  • the test product 17 is a one-dot chain line
  • the test product 35 is a two-dot chain line
  • the comparison product 1 is a dotted line.
  • Articles 6 are each indicated by a broken line.
  • the friction coefficient of each of the test products 12, 17, 35 and the comparative products 1, 6 is stable from about 200 seconds after the start of the test, but the friction coefficient of the test products 12, 17, 35 falls within about 0.3 or less.
  • the friction coefficients of the comparative products 1 and 6 are about 0.35 or more.
  • the test products 12, 17, and 35 have a friction coefficient that is gradually increased from the start of the test to 200 seconds, while the comparative products 1 and 6 have a friction coefficient of 100 seconds from the start of the test. There was a phenomenon that it once rose to around 0.5 and then dropped slightly. This shows that the wear resistance of the comparative products 1 and 6 is not sufficient.
  • the test products 1 to 40 shown in Table 2 obtained a large value in the film hardness H and a small value in the friction coefficient ⁇ . It has been shown to have good wear resistance.
  • the comparative products 1 to 6 that deviate from the ranges of the thin film composition, the atomic ratio of each element, each film thickness, and the total film thickness required for the hard coating 10 are compared with the test products 1 to 40 in terms of film hardness. H was small and the coefficient of friction ⁇ was large, indicating that the hardness and wear resistance were not sufficient.
  • test products 31 to 40 in which boron (B) is contained in the thin film composition of the A layer 22 of the hard coating 10 metal boride and boron nitride (BN) are formed in the microstructure of the A layer 22.
  • boron (B) is contained in the thin film composition of the A layer 22 of the hard coating 10
  • metal boride and boron nitride (BN) are formed in the microstructure of the A layer 22.
  • the welding resistance in Table 2 was evaluated as follows. Scanning electron microscope shows wear marks on the hard coating caused by friction with the work material 46 formed on the hemispherical end 48 of each of the test pieces 40 of the test pieces 1 to 40 and the comparative products 1 to 6 subjected to the friction wear test. (SEM) was subjected to oxygen analysis using EDS component analysis and mapped to analyze oxide components and their amounts. In the EDS component analysis, a region where oxygen is present, that is, an oxide is generated, can be distinguished from other regions. The welding resistance was evaluated from the amount of oxide in the wear scar of the hard coating of each test piece 40 by the EDS component analysis.
  • the welding resistance when there is no welding on the hard coating wear scar, the welding resistance is excellent ( ⁇ ), and when the area of the welded portion is 20% or less of the hard coating wear scar area, the welding resistance is good ( ⁇ ), When the area of the welded portion was 50% or more of the area of the wear scar on the hard coating, the welding resistance was evaluated as poor (x).
  • the wear marks of the hard coatings related to the test product 12 representing the test products 1 to 40, the test product 35 and the comparative product 6 representing the comparison products 1 to 6 are observed with a microscope (MICROSCOPE) and a scanning electron microscope (SEM). And observed with magnification.
  • FIG. 9 and FIG. 10 are photographs of wear marks on the hard coating on the hemispherical ends of the test piece 35, the test piece 12 and the comparative product 6 used in the frictional wear test.
  • 8 (a), FIG. 9 (a) and FIG. 10 (a) are photographs taken with a microscope (MICROSCOPE),
  • FIG. 8 (b), FIG. 9 (b) and FIG. 10 (b) are scanning electron microscopes
  • FIGS. 8C, 9C, and 10C are photographs showing oxygen analysis results of EDS analysis by SEM.
  • Table 2 and FIG. 8 the hard coating 10 was coated, and the specimen 35 having a small friction coefficient ⁇ of 0.17 showed almost no wear marks on the hard coating 10, and the EDS analysis shown in FIG.
  • the welding resistance was evaluated as excellent. Further, in Table 2 and FIG. 9, the test article 12 coated with the hard coating 10 and having a small friction coefficient ⁇ of 0.24 is shown in FIG. 9C as the wear trace of the hard coating 10. Since welding was observed in a range corresponding to 20% or less of the area, the welding resistance was evaluated as good. On the other hand, in Table 2 and FIG. 10, a comparative product 6 that is coated with a film that does not satisfy the conditions required for the hard film 10 and that has a large friction coefficient ⁇ of 0.80 is surrounded by a circle in FIG. In this area, the wear resistance of the coating was observed over a range corresponding to 50% or more of the area of the wear scar, and the oxide considered to be an oxide of titanium (Ti) and superhard indenter. Rated bad.
  • Ti titanium
  • FIG. 11 is a photograph of a cross section of the A layer 22 in the hard coating 10 of the test product 1 taken with a transmission electron microscope (TEM).
  • crystal layers ( ⁇ - (Cr, Mo, W, V) N, ⁇ -Mo 2 N, etc.) 54 composed of fine crystal grains, which are regions where lattice fringes in FIG.
  • oxygen multiphase structure of the amorphous phase 56 containing (O 2) has been formed which is the other area.
  • the specimen 1 having such an A layer 22 has a high hardness of 31.2 GPa because the crystal layer 54 composed of fine crystal grains is present, and oxygen (O 2) in the A layer 22 is high.
  • Oxi 2 in the A layer 22 is high.
  • Containing amorphous phase 56 promotes the formation of molybdenum (Mo), tungsten (W) and vanadium (V) oxides due to wear, so that the friction coefficient ⁇ is 0.29 and good wear resistance. And has welding resistance.
  • the hard coating 10 of this embodiment is provided on the surface of the tool base material 14 and (Cr a Mo b W c V d B e ) 1-xy Two or more alternating layers of A layers 22 made of oxycarbide, oxynitride or oxycarbonitride of z C x N y O z and B layers 24 of nitride of W (1-f) N f
  • the atomic ratio a relating to the A layer 22 is 0.2 ⁇ a ⁇ 0.7
  • b is 0.05 ⁇ b ⁇ 0.6
  • c is 0 ⁇ c ⁇ 0.3.
  • D is 0 ⁇ d ⁇ 0.05
  • x is 0 ⁇ x ⁇ 0.6
  • y is 0 ⁇ y ⁇ 0.6.
  • Z is 0 ⁇ z ⁇ 0.2
  • x + y + z is 0.3 ⁇ x + y + z ⁇ 0.6
  • the atomic ratio f related to the B layer 24 is 0.3 ⁇ f ⁇ 0.6
  • the A layer The film thickness D1 of 22 is 2 nm or more and 500 m or less
  • the thickness D2 of the B layer 24 is 1 nm or more and 500 nm or less
  • the total thickness D is in the range of 0.1 ⁇ m or more and 10.0 ⁇ m or less.
  • the laminated A layer 22 includes Mo, W, and V
  • the hardness of the film is increased by forming a microstructure composed of oxide, oxycarbide, oxynitride or oxycarbonitride, and oxides, oxycarbides, oxynitrides or oxycarbons of Mo, W and V are increased. Since the nitride has solid lubricity, the lubricity of the coating is enhanced, so that the hard coating 10 and the end mill 12 having hardness and wear resistance can be obtained.
  • the A layer 22 has a multiphase structure in which the crystal phase 54 and the amorphous phase 56 are mixed.
  • a fine NaCl phase crystal phase ( ⁇ - (Cr, Mo, W, V) N, ⁇ -Mo 2 N, etc.) composed of Mo, W and V oxycarbides, oxynitrides or oxycarbonitrides. ) 54 and the amorphous phase 56 are formed, whereby the hard coating 10 and the end mill 12 having hardness and wear resistance can be obtained.
  • the stacking order of the A layer 22 and the B layer 24 in the hard coating 10 is preferably A layer 22, B layer 24,... From the tool base material 14 side as shown in FIG. -A layer 22 and B layer 24 are laminated in this order. That is, the base layer (the lowermost layer in contact with the tool base material 14) of the hard coating 10 is the A layer 22, and the surface layer (the uppermost layer of the hard coating 10) is the B layer 24. Although the base layer is the B layer 24 and the surface layer is the A layer 22 or the B layer 24, both the base layer and the surface layer are the A layer 22. There is a temporary effect of the invention.
  • the hard coating 10 is coated on the end mill 12, but is not limited to this.
  • a cutting tool such as a drill, a tap, or a die, or a metal such as punching or bending.
  • the hard coating 10 is coated with the sputtering device 26 when the end mill 12 is formed.
  • the present invention is not limited to this.
  • the physical coating method (PVD method) or chemical vapor deposition method (CVD method) such as plasma CVD method or thermal CVD method may be used to coat the hard coating 10.
  • Hard coating hard lubricating coating
  • End mill hard lubricant coated tool
  • a layer 24 B layer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Drilling Tools (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Abstract

L'invention concerne : un film de revêtement lubrifiant dur qui est dur et possède une résistance à l'usure ; et un outil couvert d'un film de revêtement lubrifiant dur. Un film de revêtement dur (10), qui est dur et présente une résistance à l'usure, et une fraise en bout (12) peuvent être obtenus en formant et en stratifiant en alternance deux couches A (22) ou plus composées d'un carboxyde, oxynitrure ou oxycarbonitrure de (CraMobWcVdBe)1-x-y-zCxNyOz et deux couches B (24) ou plus composées de W(1-f)Nf. À cet égard, les rapports atomiques a-e, x, y, z et (x + y + z) des couches A (22) sont dans des plages prédéfinies ; le rapport atomique f des couches B (24) satisfait 0,3 ≤ f ≤ 0,6 ; l'épaisseur de film (D1) des couches A (22) est dans la plage de 2 nm à 500 nm (inclus) ; l'épaisseur de film (D2) des couches B (24) est dans la plage de 1 nm à 500 nm (inclus) ; et l'épaisseur totale de film (D) est dans la plage de 0,1 μm à 10,0 μm (inclus).
PCT/JP2013/082287 2013-11-29 2013-11-29 Film de revêtement lubrifiant dur et outil couvert d'un film de revêtement lubrifiant dur WO2015079590A1 (fr)

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PCT/JP2013/082287 WO2015079590A1 (fr) 2013-11-29 2013-11-29 Film de revêtement lubrifiant dur et outil couvert d'un film de revêtement lubrifiant dur

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003231962A (ja) * 2002-02-13 2003-08-19 National Institute Of Advanced Industrial & Technology 高硬質表面をもつ金属、合金又はセラミックス成形体の製造方法
JP2005256081A (ja) * 2004-03-11 2005-09-22 Kobe Steel Ltd 硬質積層皮膜および硬質積層皮膜の形成方法
JP2008240157A (ja) * 2008-04-21 2008-10-09 Kobe Steel Ltd 成形用冶工具用硬質皮膜被覆部材および成形用冶工具
US20090074522A1 (en) * 2007-09-17 2009-03-19 Northwestern University Reduced-friction coatings
WO2010150411A1 (fr) * 2009-06-26 2010-12-29 オーエスジー株式会社 Film de revêtement dur et outil revêtu d'un film de revêtement dur
WO2013140989A1 (fr) * 2012-03-19 2013-09-26 シチズンホールディングス株式会社 Élément décoratif rigide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003231962A (ja) * 2002-02-13 2003-08-19 National Institute Of Advanced Industrial & Technology 高硬質表面をもつ金属、合金又はセラミックス成形体の製造方法
JP2005256081A (ja) * 2004-03-11 2005-09-22 Kobe Steel Ltd 硬質積層皮膜および硬質積層皮膜の形成方法
US20090074522A1 (en) * 2007-09-17 2009-03-19 Northwestern University Reduced-friction coatings
JP2008240157A (ja) * 2008-04-21 2008-10-09 Kobe Steel Ltd 成形用冶工具用硬質皮膜被覆部材および成形用冶工具
WO2010150411A1 (fr) * 2009-06-26 2010-12-29 オーエスジー株式会社 Film de revêtement dur et outil revêtu d'un film de revêtement dur
WO2013140989A1 (fr) * 2012-03-19 2013-09-26 シチズンホールディングス株式会社 Élément décoratif rigide

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