WO2006046498A1 - 表面被覆切削工具 - Google Patents
表面被覆切削工具 Download PDFInfo
- Publication number
- WO2006046498A1 WO2006046498A1 PCT/JP2005/019476 JP2005019476W WO2006046498A1 WO 2006046498 A1 WO2006046498 A1 WO 2006046498A1 JP 2005019476 W JP2005019476 W JP 2005019476W WO 2006046498 A1 WO2006046498 A1 WO 2006046498A1
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- WIPO (PCT)
- Prior art keywords
- coating
- tensile stress
- stress
- cutting tool
- coated cutting
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
- B23B27/141—Specially shaped plate-like cutting inserts, i.e. length greater or equal to width, width greater than or equal to thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B51/00—Tools for drilling machines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23C—MILLING
- B23C5/00—Milling-cutters
- B23C5/16—Milling-cutters characterised by physical features other than shape
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2200/00—Details of cutting inserts
- B23B2200/24—Cross section of the cutting edge
- B23B2200/242—Cross section of the cutting edge bevelled or chamfered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2200/00—Details of cutting inserts
- B23B2200/24—Cross section of the cutting edge
- B23B2200/245—Cross section of the cutting edge rounded
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2200/00—Details of cutting inserts
- B23B2200/24—Cross section of the cutting edge
- B23B2200/247—Cross section of the cutting edge sharp
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2224/00—Materials of tools or workpieces composed of a compound including a metal
- B23B2224/04—Aluminium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2224/00—Materials of tools or workpieces composed of a compound including a metal
- B23B2224/32—Titanium carbide nitride (TiCN)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
- B23B2228/04—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner applied by chemical vapour deposition [CVD]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
- B23B2228/08—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
- B23B—TURNING; BORING
- B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
- B23B2228/10—Coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- the present invention relates to a drill, an end mill, a drill tip replacement tip, an end mill tip replacement tip, a milling tip replacement tip, a turning tip replacement tip, a metal saw, a gear cutting tool, a reamer,
- the present invention relates to a cutting tool such as a tap, and more particularly to a surface-coated cutting tool in which a coating that improves properties such as toughness and wear resistance is formed on the surface.
- cemented carbides (WC—Co alloys or alloys with carbonitrides such as Ti (titanium), Ta (tantalum), Nb (niobium), etc.) have been used as cutting tools. I came. However, along with the recent high-speed cutting, cemented carbide, cermet, cubic boron nitride sintered body or alumina-based silicon nitride-based ceramics is used as the base material, and CVD (Chemical Vapor) is formed on the surface.
- the Deposition method is a PVD (Physical Vapor Deposition) method, and the IVa group element, Va group element, Via group element, A1 (aluminum), S or B force in the Periodic Table of Elements is selected.
- One or more layers covered with a compound composed of one or more selected secondary elements (if the first element is B only, the second element is not B)
- the proportion of hard alloy tools that are coated and have a coating layer thickness of 3 to 20 m is increasing.
- Such a cutting tool has a rake face that comes into contact with chips of the work material during cutting and a flank face that comes into contact with the work material itself, and the rake face and the flank face intersect each other.
- the part corresponding to the edge to be cut (and its vicinity) is called the edge of the cutting edge.
- Patent Document 1 discloses that after a coating layer is formed on a substrate by a chemical vapor deposition method (CVD method) at a high temperature, So Attention is paid to the residual tensile stress of the coating layer that occurs when this is cooled to room temperature, and a solution to this is proposed as this tensile stress reduces the toughness of the cutting tool. That is, this tensile stress is generated due to the difference in thermal expansion coefficient between the substrate and the coating layer. First, a first coating layer having such a tensile stress is formed on the substrate.
- CVD method chemical vapor deposition method
- a second coating layer having a compressive stress is formed on the first coating layer, thereby maintaining toughness (anti-resistance) while maintaining high wear resistance.
- the technique is adopted.
- Patent Document 2 proposes a force that pays attention to the tensile stress of the coating layer, as described above.
- a structure in which an inner coating layer having a tensile stress is formed on the outer coating layer and an outer coating layer having a compressive stress is formed thereon has been proposed.
- Patent Document 3 proposes a cutting tool having the same configuration as Patent Document 2 using a cermet as a base material.
- Patent Document 4 discloses a cutting tool in which a hard coating layer is formed on a cemented carbide substrate by a chemical vapor deposition method! A cutting tool is proposed in which the tensile stress of the hard coating layer on the rake face portion is substantially removed while maintaining the tensile stress of the hard coating layer on the flank surface portion.
- Patent Document 1 Japanese Patent Laid-Open No. 05-177411
- Patent Document 2 Japanese Patent Laid-Open No. 05-177412
- Patent Document 3 Japanese Patent Laid-Open No. 05-177413
- Patent Document 4 Japanese Patent Laid-Open No. 06-055311
- Patent Document 5 Japanese Patent No. 3087465 (Japanese Patent Laid-Open No. 06-079502)
- the present invention has been made in view of the above-described situation, and an object of the present invention is to provide a surface-coated cutting tool in which both toughness and wear resistance are highly compatible. Means for solving the problem
- the present inventor has made extensive studies in order to solve the above-mentioned problems. As a result, the inventor selects a specific material as a film covering the base material and coats the base material with a plurality of layers. Focus on the specific part of the coating that is different from the adjustment of the stress in each layer unit, the rake face, the Z-flank face, and the adjustment of the stress in the unit of the connected plane, and the stress in that part is different from the stress in other parts As a result, the inventors have obtained the knowledge that adjusting to the most effective in achieving both toughness and wear resistance, and by further research based on this knowledge, the present invention has finally been completed.
- the present invention is a surface-coated cutting tool comprising a substrate and a coating formed on the substrate, the coating comprising a first coating having a TiCN force and a model AlO force.
- the second coating comprising a first coating having a TiCN force and a model AlO force.
- the first coating is located between the base material and the second coating, and the second coating is at least 0 in each of the direction of the rake face and the direction of the flank from the edge of the blade edge.
- the region A1 which has a distance of 5 mm has a compressive stress S1 and the region A2 other than this region A1 has a tensile stress S2, and the compressive stress SI and the tensile stress S2 are expressed by the following formula (I)
- a surface-coated cutting tool is provided.
- the first coating film may have a tensile stress, or may have a substantial stress when the tensile stress is released.
- the first coating has a tensile stress SS1 in the area A1 that extends at a distance of at least 0.5 mm from the edge of the cutting edge to the rake face and the flank face.
- the region A2 other than the region A1 has a tensile stress SS2, and the tensile stress SSI and the tensile stress SS2 can be defined by the following formula ( ⁇ ).
- the first coating has a columnar structure with an aspect ratio of 3 or more and a crystal yarn and weave with an average grain size of 0.05 ⁇ m or more and 1.5 ⁇ m or less. It can be.
- the first coating film may have a thickness of 2 to 20 m, and the second coating film may have a thickness of 0.5 to 20 ⁇ m.
- the first film may further contain oxygen, and a group force including IVa group element, Va group element, Via group element, Si, Y, ⁇ and S force in the periodic table is also selected. It can also contain at least one element.
- the second film further contains at least one element selected from the group force consisting of the I Va group element, Va group element, Via group element, Si, Y, ⁇ and S force of the periodic table. Can do.
- the surface-coated cutting tool of the present invention has both the toughness and the wear resistance by having the configuration as described above.
- FIG. 1 is a schematic view schematically showing a contact state between a surface-coated cutting tool and a work material during cutting.
- FIG. 2 is a schematic perspective view of a surface-coated cutting tool.
- FIG. 3 is a schematic enlarged cross-sectional view of a cutting edge ridge (sharp edge).
- FIG. 5 is a schematic enlarged cross-sectional view of a chamfered cutting edge ridge line portion.
- FIG. 6 is a schematic sectional view of a surface-coated cutting tool.
- the surface-coated cutting tool of the present invention has a configuration including a base material and a coating film formed on the base material.
- the edge edge line portion 4 of the present invention is a portion (sharp edge) corresponding to the edge where the rake face 2 and the flank face 3 intersect as shown in FIG.
- the sharp edge is subjected to cutting edge processing and processed to have R (R) (so-called cutting edge processing portion), or chamfering processing is performed as shown in Fig. 5.
- R cutting edge processing portion
- chamfering processing is performed as shown in Fig. 5.
- a portion processed by combining these blade edge processing and chamfering processing is also included.
- the region A1 extending at a distance of at least 0.5 mm from the edge 4 of the blade edge to the rake face 2 and the flank 3 is the edge of the blade as is apparent from FIGS.
- This is an area with a certain width in both the rake face 2 side and the flank face 3 side with the edge line 4 as the center, and the width of the spread is the edge of the edge edge line part 4 (as shown in Fig. 3).
- the force shall be at least 0.5 mm each.
- this area A1 needs to have a width of at least 0.5 mm from the edge line 4 of the cutting edge as described above, and this is related to the cutting of the work material as described above. This is because it is an area to be used. Therefore, considering that the maximum value of the width of the area A1 is an area that is substantially involved in cutting, the depth of cut at the time of cutting is determined. (The depth of cut depends on the chip breaker). In other words, the maximum width of the rake face may need to be about 10 mm because the width that comes into contact with the chips (the range in which the main component acts) increases when deeply cut. However, usually 5 mm or less, more preferably 4 mm or less, and even more preferably 3 mm or less are sufficient. On the other hand, since the width in the flank direction does not come into contact with the chips, the maximum value is usually 3 mm or less. Therefore, the width of the region A1 is particularly preferably 0.5 mm or more and 3 mm or less.
- the width of the region A1 is smaller than the portion involved in cutting, it becomes impossible to include all of the portions involved in cutting, and thus the toughness by adjusting the stress in the region A1. And the effect of achieving both wear resistance are not shown. Further, if the width of the area A1 exceeds the maximum value as described above, it is necessary to process a portion that is not substantially involved in cutting, which is costly and economically disadvantageous. Therefore, it is preferable that the width of the region A1 is appropriately selected from the relationship with the depth of cut, considering cutting conditions.
- Such surface-coated cutting tools include, for example, drills, end mills, drill tip changeable tips, end mill tip replacement tips, milling tip replacement tips, turning tip replacement tips, metal saws, etc. It can be used as a gear cutting tool, reamer, tap, etc.
- such a surface-coated cutting tool 1 can be provided with a through-hole 7 at the center thereof as shown in FIG. Can be attached.
- a through-hole 7 may be provided with another fixing means in addition to or instead of the through-hole, if necessary.
- a conventionally known base material known as a base material for such a cutting tool can be used without particular limitation.
- a base material cemented carbide (for example, WC-based cemented carbide, WC, Co, or further containing carbonitride such as Ti, Ta, Nb, etc.), cermet, etc. (Those mainly composed of TiC, TiN, TiCN, etc.), high speed Steel, ceramics (titanium carbide, silicon carbide, silicon nitride, aluminum nitride, aluminum oxide, etc.), cubic boron nitride sintered body, diamond sintered body, silicon nitride sintered body, or aluminum oxide And a mixture of titanium carbide and the like.
- a cemented carbide (WC-based cemented carbide) in the present invention.
- This is an extremely well balanced alloy as a base material for cutting tools that have both high hardness and high strength by containing iron group metals such as cobalt with a high hardness tungsten carbide as the main component. .
- the film 9 formed on the substrate 8 is formed mainly for the purpose of further improving the toughness and further improving the wear resistance. It includes a film 10 and a second film 11 having ⁇ -type Al repulsion.
- such a coating further improves the adhesion between the coating and the substrate, further improves the adhesion between the first coating and the second coating, or improves the state of the coating surface.
- a third coating other than the first coating and the second coating can be included.
- Examples of the third coating include TiN, TiC, TiCO, TiBN, ZrCN, TiZrCN, A1N, A10N, and TiAIN.
- such a third coating can be formed in one layer or two or more layers, and the mode of lamination is not particularly limited, for example, between the substrate and the first coating. It can be formed at any one or more locations such as between the first film and the second film, or on the surface of the second film.
- the second coating of the present invention is made of ⁇ -type Al. Composed of such materials
- the base material By forming the second coating on or near the outermost surface of the base material, the base material is effectively prevented from being oxidized and the constituent elements of the work material diffuse to the base material side during cutting. This can be prevented very effectively.
- Such a second coating can be composed of ⁇ -type Al ⁇ alone, Group IVa group elements (Ti, Zr, Hf, etc.), Va group elements (V, Nb, Ta, etc.), Via group elements (Cr, Mo, W, etc.), Si, Y, B, and S It may contain at least one element selected for its force.
- the content of such an element is not particularly limited. For example, such an element enters a normal position of the crystal lattice of the ⁇ -type Al ⁇ ⁇ ⁇ as a substitution type.
- it may be in any form such as entering as an interstitial type between the crystal lattices, forming an intermetallic compound, or existing as an amorphous material.
- the concentration distribution of such an element is such that when the element is homogeneously distributed in the film, when it is distributed at a crystal grain boundary at a high concentration or a low concentration, it is formed on the surface portion of the film. O! If it is distributed at a high or low concentration, it may be present with a concentration distribution of V deviation.
- the concentration of the element is 0.0 with respect to A1 of ⁇ -type AI O.
- the upper limit is 20 atomic%, more preferably 10 atomic%, and the lower limit is 0.05 atomic%, more preferably 0.1 atomic. %. If the content is less than 0.01 atomic%, the effects of such elements (for example, high temperature, high hardness, high strength, good lubricity, etc.) (Effect) may not be shown, and if it exceeds 30 atomic%, the crystal lattice of the second film may decrease in strain hardness and strength.
- the effects of such elements for example, high temperature, high hardness, high strength, good lubricity, etc.
- such a second coating has a compressive stress S1 in a region A1 that spreads at a distance of at least 0.5 mm in the direction of the edge edge line rake face and the flank face, respectively.
- the region A2 has a tensile stress S2, and the compressive stress S1 and the tensile stress S2 are defined by the following formula (I).
- the compressive stress is a kind of internal stress (intrinsic strain) existing in the film, and is a stress expressed by a numerical value (unit: MPa) of “one” (minus). Therefore, the concept that the compressive stress is large indicates that the absolute value of the numerical value is large, and the concept that the compressive stress is small indicates that the absolute value of the numerical value is small.
- the stress in the region A2 other than the region A1 is set to the tensile stress S2, thereby maintaining the adhesion of the film and thus maintaining the wear resistance.
- the tensile stress is also a kind of internal stress (inherent strain) existing in the coating, and means a stress represented by a “+” (plus) value (unit: MPa). For this reason, the concept that the tensile stress is large indicates that the above numerical value is large, and the concept that the tensile stress is small indicates that the numerical value is small.
- the second coating film of the present invention is characterized in that the compressive stress S1 and the tensile stress S2 are defined by the above formula (I). This makes it possible to achieve both toughness and wear resistance at a particularly high level.
- the absolute value of the difference between the compressive stress S1 and the tensile stress S2 (I S1 -S2 I) is less than 400 MPa, it will not be possible to sufficiently achieve the toughness-improving effect, but will exceed 3500 MPa. Then, there is a possibility that this second film may cause a state in which the ground strength peels off.
- the absolute value (I S1 -S2 I) of the difference between the compressive stress S1 and the tensile stress S2 is more preferably an upper limit of 3000 MPa, further preferably 1700 MPa, and a lower limit of 700 MPa, and more preferably lOOOMPa.
- the method for forming the stress distribution as described above is not particularly limited.
- a cemented carbide as described above is used as a base material, and a type Al
- An O-shaped film is formed by a known chemical vapor deposition method (CVD method), and this film is not
- the edge force at the edge of this coating is also brushed and blasted for area A1 with a distance of at least 0.5 mm each in the direction of the rake face and the relief face ( (For example, sand blasting or wet blasting), shot peening or PVD bombarding.
- a desired stress distribution can be formed by applying a force.
- PVD method physical vapor deposition method
- the edge edge line force of this film has a distance of at least 0.5 mm between the direction of the surface and the direction of the flank.
- the compressive stress S1 and the tensile stress S2 are 10 arbitrary points included in each region (each of these points represents the stress in each region). It is preferable to select a distance of 0.5 mm or more apart from each other so that it can be represented, and the stress can be measured by this method and the average value can be obtained.
- the tangent ratio and Poisson's ratio of the coating are required.
- the Young's modulus can be measured using a dynamic hardness meter or the like, and the Poisson's ratio does not vary greatly depending on the material, so a value around 0.2 should be used.
- a stress difference is not particularly important because an accurate stress value is not important. Therefore, when calculating the stress difference from the 2 ⁇ -sin 2 ⁇ diagram, it is possible to substitute the stress distribution by calculating the lattice constant and the lattice spacing without using the Young's modulus.
- the second film of the present invention has a group IVa element, a group Va element in the periodic table of elements as described above,
- the first coating of the present invention is located between the base material and the second coating, and is made of TiCN.
- the ⁇ -type Al repulsive second coating has the excellent effects as described above.
- the first coating of the present invention is formed for the purpose of correctly satisfying such a requirement, and has a very high hardness although it is easily oxidized by cutting at a high temperature. For this reason, by being positioned between the second coating and the base material, there is an effect of dramatically improving the wear resistance.
- Such a first coating can be composed of TiCN alone, but may further contain oxygen.
- oxygen-containing form is not particularly limited.
- Any form such as an amorphous state may be used.
- the first film has a group force including IVa group element, Va group element, Via group element, Si, Y, ⁇ and S force in the periodic table of elements. It can also contain at least one element selected. These elements can be contained alone with or without oxygen.
- the first coating film may be composed of TiCN alone, or may contain TiCN as a main component and the above-described elements including oxygen.
- the concentration distribution of such an element such as oxygen is such that when the element is uniformly distributed in the film, or when the element is distributed at a high concentration or a low concentration at the crystal grain boundary, the concentration is distributed on the surface portion of the film. In the case of distribution at a high concentration or a low concentration, it may be present so as to have a concentration distribution of V and deviation.
- the content concentration of such elements as oxygen is preferably 0.1 to 40 atomic% with respect to the total of C and N in TiCN, and more preferably the upper limit thereof. 30 atomic%, more preferably 20 atomic%, and the lower limit is 1 atomic%, more preferably 5 atomic%.
- the content is less than 1 atomic%, the effects brought about by the inclusion of elements such as oxygen (for example, refinement of crystal grains) may not be shown. If it exceeds 40 atomic%, the crystal lattice of the film may decrease in strain hardness and strength.
- such a first coating is formed with a thickness of 2 to 20 ⁇ m.
- the upper limit is preferably 15 ⁇ m, more preferably 10 ⁇ m, and the lower limit is 2.5 m, more preferably 3 ⁇ m. If the thickness is less than 2 ⁇ m, the wear progresses, and thus the substrate may be exposed to cause further wear. Further, if the thickness exceeds, the strength of the film is deteriorated and peeling of the film causes chipping. In the end, it may lead to defects.
- such a first film has a columnar structure with an aspect ratio of 3 or more and a crystal structure with an average grain size of 0.05 111 or more and 1.5 m or less. It is preferable.
- the aspect ratio is a numerical value obtained by measuring the average grain size of crystals contained in the first coating by the following method and dividing the thickness of the first coating by this average grain size. The average particle size is measured by mirror-processing the cross section of the first film and etching the crystal grain boundary, and then measuring the width (thickness of the film) at the 1Z2 point of the film thickness of the first film. The width of each crystal in the direction perpendicular to the direction) is measured, and the average value of the widths is taken as the average particle diameter.
- the abrasive wear resistance may not be improved.
- the higher the numerical value the more the abrasive wear resistance is improved.Therefore, it is not necessary to specify the upper limit, but those with an aspect ratio exceeding 300 have too much crystal strength. In some cases, the structure becomes brittle and the fracture resistance deteriorates.
- the aspect ratio is more preferably 7 to 200, still more preferably an upper limit of 100, particularly preferably 50, and a lower limit of 15, particularly preferably 20.
- the average particle size is less than 0.05 ⁇ m, the crystal becomes too fine, the structure becomes brittle, and the fracture resistance may deteriorate.
- the average grain size exceeds 1.5 / z m, the crystal structure becomes rough, the surface irregularities are also poor, and cutting resistance such as chip flow may be poor.
- the average particle size is more preferably 0.1 111 or more and 1. O / zm or less, and further preferably its upper limit force is 0.6 m, particularly preferably ⁇ or 0.4 m, its lower limit force is 0.15. m, particularly preferably ⁇ or 0.2 ⁇ m.
- Such a first coating has a tensile stress or is substantially It is preferable to have stress in the U. By setting the stress of the first film to such a stress, it is possible to obtain a high degree of adhesion with the base material and to realize particularly excellent wear resistance.
- such a first coating has a tensile stress SS1 in a region A1 that spreads from the edge of the cutting edge to the rake face direction and the flank face direction by a distance of at least 0.5 mm. It is preferable that the region A2 other than A1 has a tensile stress SS2 and that the tensile stress SS1 and the tensile stress SS2 are defined by the following formula ( ⁇ ).
- the region A1 and the region A2 indicate the same region as in the case of the second film.
- the tensile stress SS1 and the tensile stress SS2
- the predetermined stress is applied to the second coating.
- the effect of the treatment on the region A1 (or the treatment on the region A2) performed for the purpose of having a distribution is not substantially transmitted to the first coating. That is, the first coating does not have to have a stress distribution substantially like the second coating.
- the upper limit of the absolute value (I SS1 -SS2 I) of the difference between the tensile stress SS1 and the tensile stress SS2 is more preferably 200 MPa, and even more preferably lOOMPa.
- the stress of such a first coating by sin 2 phi method using X-ray stress measuring apparatus measurement
- the (422) plane of TiCN as the diffraction plane
- measurement can be performed in the same manner as in the case of the second coating.
- the first coating of the present invention further contains an element such as oxygen as described above, the stress is measured in the same manner because the (422) plane exists at a substantially equivalent position of 2 ⁇ . be able to.
- Each raw material powder was blended using a ball mill at a blending ratio of WC: 86% by mass, Co: 8.0% by mass, TiC: 2.0% by mass, NbC: 2.0% by mass, ZrC: 2.0% by mass. Wet mixed for hours. Subsequently, the mixture was dried and press-molded. After that, sintering was performed in a vacuum atmosphere at 1420 ° C. for 1 hour.
- a film having the following structure was formed on the surface of the base material by using a known thermal CVD method which is a chemical vapor deposition method. That is, a TiN film having a thickness of 0.5 m is first formed on the substrate, and a TiCN film having a thickness of 7. which is the first coating is formed on the TiN film. A 3.0 m thick AlO film as a second coating is formed on the
- the projection pressure is applied to the area A1 that is spread with a distance of 0.5 mm from the edge of the cutting edge to the rake face and the flank face. 0.01 to 0.5 MPa, projection distance 0.5 to 200 mm, fine powder concentration 5 to 40 vol%
- each second coating the IS 1-S2 I value and each Surface-coated cutting tools of Examples 1 to 5 and Comparative Examples 1 to 4 having (I SSI-SS2 I value) in one coating were prepared.
- Each of the surface-coated cutting tools of Examples 1 to 5 of the present invention has a compressive stress S1 in the region A1 of the second coating and a tensile stress S2 in the region A2 other than the region A1.
- the first coating had a tensile stress, or a bow I tension stress was released and was substantially stressed.
- the stress distribution in each example and comparative example is the above-described blasting condition.
- the stress distribution (I S1 -S2 I value in each second film and I SS1-SS2 I value in each first film) is measured by the above-mentioned sin 2 ⁇ method. did.
- the first film of the surface-coated cutting tools of Examples 1 to 5 had a columnar structure with an aspect ratio of 35 as a result of measurement by the method described above, and the average particle size was 0.3. It had a ⁇ m crystal structure.
- the absolute value of the difference between the compressive stress S1 and the tensile stress S2 (I S1-S2 I) in the above formula (I) for the second coating of the surface-coated cutting tool is 400 MPa or more 3500MPa
- the following (Examples 1 to 5) were highly compatible in toughness and wear resistance compared to those in which the absolute value of the difference was outside that range (Comparative Examples 1 to 4). .
- Example 1 to 5 all other operations were performed in the same manner except that the area A1 was an area extending from the edge of the cutting edge to the rake face direction and the flank face direction by a distance of 1.5 mm.
- the surface-coated cutting tools of Examples 6 to 10 were obtained (Examples 1 to 5 and Example 6 to: The correspondence relationship of LOs corresponds to each in numerical order, and the same stress distribution as shown in Table 1 was obtained. Adjusted as shown).
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Chemical Vapour Deposition (AREA)
- Drilling Tools (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/665,980 US8012611B2 (en) | 2004-10-29 | 2005-10-24 | Surface-coated cutting tool |
JP2006543119A JP4680932B2 (ja) | 2004-10-29 | 2005-10-24 | 表面被覆切削工具 |
EP05795685.6A EP1806193B1 (en) | 2004-10-29 | 2005-10-24 | Surface-coated cutting tool |
IL182724A IL182724A (en) | 2004-10-29 | 2007-04-22 | Surface-coated cutting tool |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2004-316338 | 2004-10-29 | ||
JP2004316338 | 2004-10-29 |
Publications (1)
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WO2006046498A1 true WO2006046498A1 (ja) | 2006-05-04 |
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ID=36227737
Family Applications (1)
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---|---|---|---|
PCT/JP2005/019476 WO2006046498A1 (ja) | 2004-10-29 | 2005-10-24 | 表面被覆切削工具 |
Country Status (7)
Country | Link |
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US (1) | US8012611B2 (ja) |
EP (1) | EP1806193B1 (ja) |
JP (1) | JP4680932B2 (ja) |
KR (1) | KR100817658B1 (ja) |
CN (1) | CN100496824C (ja) |
IL (1) | IL182724A (ja) |
WO (1) | WO2006046498A1 (ja) |
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JP2009034781A (ja) * | 2007-08-02 | 2009-02-19 | Sumitomo Electric Hardmetal Corp | 表面被覆切削工具 |
CN103958098A (zh) * | 2011-03-31 | 2014-07-30 | 住友电工硬质合金株式会社 | 表面被覆切削工具及其制造方法 |
WO2014132995A1 (ja) * | 2013-02-26 | 2014-09-04 | 三菱マテリアル株式会社 | 表面被覆切削工具 |
JP2017071045A (ja) * | 2016-02-24 | 2017-04-13 | 住友電工ハードメタル株式会社 | 表面被覆切削工具およびその製造方法 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05177411A (ja) * | 1991-12-26 | 1993-07-20 | Sumitomo Electric Ind Ltd | 被覆切削工具及びその製造方法 |
JPH0655311A (ja) * | 1992-08-11 | 1994-03-01 | Mitsubishi Materials Corp | 耐摩耗性および耐欠損性のすぐれた表面被覆炭化タングステン基超硬合金製切削工具 |
JPH06502352A (ja) * | 1990-09-17 | 1994-03-17 | ケンナメタル インコーポレイテッド | バインダーの豊富なcvd及びpvdによるコートされた切削工具 |
JPH0679502A (ja) * | 1992-08-27 | 1994-03-22 | Mitsubishi Materials Corp | 耐摩耗性および耐欠損性のすぐれた表面被覆炭窒化チタン基サーメット製切削工具 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE406090B (sv) * | 1977-06-09 | 1979-01-22 | Sandvik Ab | Belagd hardmetallkropp samt sett att framstalla en dylik kropp |
JP2854335B2 (ja) | 1989-08-31 | 1999-02-03 | 株式会社アイジー技術研究所 | 出隅構造 |
US5266388A (en) | 1990-09-17 | 1993-11-30 | Kennametal Inc. | Binder enriched coated cutting tool |
JP2825693B2 (ja) * | 1991-08-29 | 1998-11-18 | 京セラ株式会社 | コーティング工具およびその製造方法 |
JPH05177412A (ja) | 1991-12-26 | 1993-07-20 | Sumitomo Electric Ind Ltd | 被覆セラミックス切削工具及びその製造方法 |
JPH05177413A (ja) | 1991-12-26 | 1993-07-20 | Sumitomo Electric Ind Ltd | 被覆サーメット切削工具及びその製造方法 |
SE509201C2 (sv) * | 1994-07-20 | 1998-12-14 | Sandvik Ab | Aluminiumoxidbelagt verktyg |
BR9611781A (pt) | 1995-11-30 | 1999-02-23 | Sandvik Ab | Inserção revestida para torneamento e método de fabricação da mesma |
US6062776A (en) | 1995-11-30 | 2000-05-16 | Sandvik Ab | Coated cutting insert and method of making it |
JP3252711B2 (ja) | 1996-07-02 | 2002-02-04 | 住友電気工業株式会社 | 被覆窒化珪素系工具 |
SE509560C2 (sv) * | 1996-09-06 | 1999-02-08 | Sandvik Ab | Belagt hårdmetallskär för bearbetning av gjutjärn |
SE511211C2 (sv) * | 1996-12-20 | 1999-08-23 | Sandvik Ab | Ett multiskiktbelagt skärverktyg av polykristallin kubisk bornitrid |
US6293739B1 (en) * | 1998-04-14 | 2001-09-25 | Sumitomo Electric Industries, Ltd. | Coated cemented carbide cutting tool |
SE520795C2 (sv) | 1999-05-06 | 2003-08-26 | Sandvik Ab | Skärverktyg belagt med aluminiumoxid och process för dess tillverkning |
EP1306150B1 (en) * | 2000-07-12 | 2012-03-21 | Sumitomo Electric Industries, Ltd. | Coated cutting tool |
EP1311712A2 (de) * | 2001-03-27 | 2003-05-21 | Widia GmbH | Verfahren zur erhöhung der druckspannung oder zur erniedrigung der zugeigenspannung einer schicht |
JP3622846B2 (ja) | 2001-09-21 | 2005-02-23 | 住友電気工業株式会社 | 粘質材用ミーリング工具 |
SE526603C3 (sv) | 2003-01-24 | 2005-11-16 | Sandvik Intellectual Property | Belagt hårdmetallskär |
SE526526C3 (sv) * | 2003-04-01 | 2005-10-26 | Sandvik Intellectual Property | Sätt att belägga skär med A1203 samt ett med A1203 belagt skärverktyg |
EP1825943B1 (en) * | 2004-12-14 | 2017-01-25 | Sumitomo Electric Hardmetal Corp. | Coated cutting tool |
KR100576321B1 (ko) * | 2004-12-14 | 2006-05-03 | 한국야금 주식회사 | 고인성 절삭공구/내마모성 공구 |
US7803464B2 (en) * | 2004-12-27 | 2010-09-28 | Sumitomo Electric Hardmetal Corp. | Surface-coated cutting tool |
SE528696C2 (sv) * | 2005-02-25 | 2007-01-23 | Sandvik Intellectual Property | CVD-belagt skär av hårdmetall, cermet eller keramik och sätt att tillverka detsamma |
EP1864731B2 (en) * | 2005-03-30 | 2021-03-24 | Sumitomo Electric Hardmetal Corp. | Edge replacement cutter tip |
SE530735C2 (sv) * | 2006-10-18 | 2008-08-26 | Sandvik Intellectual Property | Ett belagt skär av hårdmetall, speciellt användbart för svarvning av stål |
-
2005
- 2005-10-24 WO PCT/JP2005/019476 patent/WO2006046498A1/ja active Application Filing
- 2005-10-24 EP EP05795685.6A patent/EP1806193B1/en active Active
- 2005-10-24 US US11/665,980 patent/US8012611B2/en active Active
- 2005-10-24 JP JP2006543119A patent/JP4680932B2/ja active Active
- 2005-10-24 CN CNB2005800370417A patent/CN100496824C/zh active Active
- 2005-10-24 KR KR1020077007027A patent/KR100817658B1/ko active IP Right Grant
-
2007
- 2007-04-22 IL IL182724A patent/IL182724A/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06502352A (ja) * | 1990-09-17 | 1994-03-17 | ケンナメタル インコーポレイテッド | バインダーの豊富なcvd及びpvdによるコートされた切削工具 |
JPH05177411A (ja) * | 1991-12-26 | 1993-07-20 | Sumitomo Electric Ind Ltd | 被覆切削工具及びその製造方法 |
JPH0655311A (ja) * | 1992-08-11 | 1994-03-01 | Mitsubishi Materials Corp | 耐摩耗性および耐欠損性のすぐれた表面被覆炭化タングステン基超硬合金製切削工具 |
JPH0679502A (ja) * | 1992-08-27 | 1994-03-22 | Mitsubishi Materials Corp | 耐摩耗性および耐欠損性のすぐれた表面被覆炭窒化チタン基サーメット製切削工具 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1806193A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007319964A (ja) * | 2006-05-31 | 2007-12-13 | Sumitomo Electric Hardmetal Corp | 刃先交換型切削チップ |
JP2009034781A (ja) * | 2007-08-02 | 2009-02-19 | Sumitomo Electric Hardmetal Corp | 表面被覆切削工具 |
CN103958098A (zh) * | 2011-03-31 | 2014-07-30 | 住友电工硬质合金株式会社 | 表面被覆切削工具及其制造方法 |
WO2014132995A1 (ja) * | 2013-02-26 | 2014-09-04 | 三菱マテリアル株式会社 | 表面被覆切削工具 |
JP2014193523A (ja) * | 2013-02-26 | 2014-10-09 | Mitsubishi Materials Corp | 表面被覆切削工具 |
US9782830B2 (en) | 2013-02-26 | 2017-10-10 | Mitsubishi Materials Corporation | Surface-coated cutting tool |
JP2017071045A (ja) * | 2016-02-24 | 2017-04-13 | 住友電工ハードメタル株式会社 | 表面被覆切削工具およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1806193A4 (en) | 2012-04-04 |
EP1806193B1 (en) | 2013-05-08 |
CN100496824C (zh) | 2009-06-10 |
US8012611B2 (en) | 2011-09-06 |
IL182724A0 (en) | 2007-07-24 |
KR20070041791A (ko) | 2007-04-19 |
CN101048250A (zh) | 2007-10-03 |
JPWO2006046498A1 (ja) | 2008-05-22 |
JP4680932B2 (ja) | 2011-05-11 |
KR100817658B1 (ko) | 2008-03-27 |
EP1806193A1 (en) | 2007-07-11 |
IL182724A (en) | 2013-01-31 |
US20070292670A1 (en) | 2007-12-20 |
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