EP2177639A1 - Titanium-base cermet, coated cermet, and cutting tool - Google Patents
Titanium-base cermet, coated cermet, and cutting tool Download PDFInfo
- Publication number
- EP2177639A1 EP2177639A1 EP08791644A EP08791644A EP2177639A1 EP 2177639 A1 EP2177639 A1 EP 2177639A1 EP 08791644 A EP08791644 A EP 08791644A EP 08791644 A EP08791644 A EP 08791644A EP 2177639 A1 EP2177639 A1 EP 2177639A1
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- EP
- European Patent Office
- Prior art keywords
- hard phase
- cermet
- powder
- temperature
- surface region
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011195 cermet Substances 0.000 title claims abstract description 107
- 238000005520 cutting process Methods 0.000 title claims abstract description 55
- 239000011230 binding agent Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 150000004767 nitrides Chemical class 0.000 claims abstract description 9
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 59
- 239000011247 coating layer Substances 0.000 claims description 58
- 239000000758 substrate Substances 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 35
- 239000013078 crystal Substances 0.000 claims description 18
- 230000001965 increasing effect Effects 0.000 claims description 16
- 230000000630 rising effect Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 8
- 230000003247 decreasing effect Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 230000000717 retained effect Effects 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 43
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 37
- 239000007789 gas Substances 0.000 description 30
- 239000010936 titanium Substances 0.000 description 29
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 23
- 239000010410 layer Substances 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 230000035939 shock Effects 0.000 description 8
- 230000035882 stress Effects 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 230000002708 enhancing effect Effects 0.000 description 7
- 238000003466 welding Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000002542 deteriorative effect Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011656 manganese carbonate Substances 0.000 description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002173 cutting fluid Substances 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- UFZOPKFMKMAWLU-UHFFFAOYSA-N ethoxy(methyl)phosphinic acid Chemical compound CCOP(C)(O)=O UFZOPKFMKMAWLU-UHFFFAOYSA-N 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2204/00—End product comprising different layers, coatings or parts of cermet
Definitions
- the present invention relates to a titanium (Ti)-based cermet, a coated cermet, and a cutting tool, particularly to a cutting tool whose cutting edge has enhanced wear resistance.
- Sintered alloys such as cemented carbides composed mainly of WC, and Ti-based cermet composed mainly of Ti are currently widely used as members requiring wear resistance and sliding properties, as well as fracture resistance, such as cutting tools, wear-resistant members and sliding members. Developments of novel compositions for improving performance of these sintered alloys have been continued.
- patent document 1 discloses the technique of forming cemented carbide or a cermet by reaction sintering using microwaves, and describes that Mn or A1 is added in the proportion of 5% by mass or less into a metal binder phase such as Co.
- Patent document 2 discloses the gradient composition sintered alloy made by adding 0.1 to 10% by mass of a specific metal element such as Mn, in addition to a hard phase composed mainly of carbides or nitrides of metals selected from Group 4, Group 5 and Group 6 metals of the periodic table, and mutual solid solutions of these, and 1 to 40% by mass of an iron-group metal.
- a specific metal element such as Mn
- Ti-based cermets made by adding Mn are described in Samples No. 17 and No. 20 in Table 6.
- Table 8 indicates that the concentration of the Mn and the concentration of the binder phase in Sample No. 17 and No. 20 are increased in the interior of the cermet than the surface thereof.
- the cutting tool of the present invention has been made to solve the above problems, and aims to enhance the wear resistance and welding resistance of the Ti-based cermet.
- the Ti-based cermet of the invention is composed of at least one kind of element selected from Co and Ni; and one or more kinds of substances selected from carbides, nitrides, and carbonitrides of one or more kinds of metals selected from Group 4, Group 5 and Group 6 metals of the periodic table, each of which is composed mainly of Ti; and 0.1 to 0.5% by mass of Mn.
- SEM scanning electron microscope
- the method of manufacturing the Ti-based cermet of the invention includes forming a mixed powder as a mixture of TiCN powder; at least one kind of powder selected from carbonate powder, nitride powder and carbonitride powder each containing one or more kinds of elements selected from W, Mo, Ta, V, Zr and Nb; at least one kind of powder selected from Co and Ni; and a total amount of 0.2 to 3.0% by mass in terms of Mn of a metal Mn powder or an Mn compound powder, followed by sintering under the following conditions: (a) increasing temperature under vacuum from room temperature to 1200°C; (b) increasing the temperature under vacuum at a temperature rising rate of 0.1 to 2°C/min from 1200°C to a sintering temperature T 1 of 1330 to 1380°C; (c) increasing the temperature at a temperature rising rate of 4 to 15°C/min from the sintering temperature T 1 to a sintering temperature T 2 of 1450 to 1600°C in an inert gas atmosphere of 30 to 2000
- the coated cermet of the invention is produced by using the above Ti-based cermet as a substrate, and coating a surface of the substrate with a coating layer.
- the content ratio of the binder phase in the surface region of the substrate is not more than 3% by mass, and the coating layer is formed by chemical vapor deposition.
- the cutting tool of the invention is composed of the above Ti-based cermet or the above coated cermet, and a cutting edge is formed along a cross ridge part between a rake face and a flank face.
- the second hard phase is preferably subjected to compressive stress of not less than 150 MPa ( ⁇ 11 ⁇ -150 MPa).
- the Ti-based cermet of the invention 0.1 to 0.5% by mass of Mn is contained, and the surface region, in which the second hard phase whose content percentage is not less than 90% by area is observed, is formed in the surface of the cermet. This increases the toughness of the cermet as a whole, and enhances the hardness in the surface of the cermet, thereby improving wear resistance and also enhancing welding resistance.
- the Ti-based cermet (hereinafter referred to simply as "cermet") 1 in Fig. 1 is composed of at least one kind of element selected from Co and Ni; and one or more kinds of substances selected from carbides, nitrides, and carbonitrides of one or more kinds of metals selected from Group 4, Group 5, and Group 6 metals of the periodic table, each of which is composed mainly of Ti; and 0.1 to 0.5% by mass of Mn.
- a surface region 5 is formed in which a hard phase 2 whose interior comprises a black first hard phase 2a and a grayish white second hard phase 2b, and a binder phase 3 composed mainly of at least one kind of elements selected from Co and Ni are observed, and the second hard phase 2b whose content percentage is not less than 90% by area is observed in a surface part.
- the first hard phase 2a is observed as black particles
- the second hard phase 2b is observed as grayish white particles, or particles having a core-containing structure in which a grayish white peripheral part exists around a white core part. That is, the first hard phase 2a has a higher content ratio of a light element than the second hard phase 2b, and hence looks black.
- the first hard phase 2a corresponds to the black particles composed of TiCN, it may contain Co or Ni.
- other core-containing structure may be employed in which the grayish white second hard phase 2b exists as a peripheral part in the outer periphery of the first hard phase 2a.
- the binder phase 3 is observed as a white region, and Co and Ni constituting the binder phase 3 can be confirmed by energy dispersive spectroscopy (EMPA) annexed to the scanning electron microscope (SEM).
- EMPA energy dispersive spectroscopy
- the toughness of the cermet 1 is lowered. Conversely, if more than 0.5% by mass of Mn is contained in the cermet 1, the hardness of the cermet 1 is remarkably lowered.
- the suitable content of Mn is 0.2 to 0.5% by mass.
- the hardness in the surface of the cermet 1 cannot be enhanced, thus leading to insufficient wear resistance of the cermet 1. If the percentage of presence of the second hard phase 2b in the surface region 5 is less than 90% by area, the wear resistance and welding resistance in the surface of the cermet 1 become insufficient.
- the suitable thickness of the surface region 5 is 0.8 to 3 ⁇ m.
- the preferable percentage of area Bus of the second hard phase 2b in the surface region 5 is 93 to 97% by area, in the interest of adhesion with respect to a coating layer 13.
- the average particle diameter d 1s of the second hard phase 2b is preferably 0.5 to 3.0 ⁇ m, particularly 1.0 to 2.0 ⁇ m.
- the ratio (C s /C i ) of the content ratio C s of the binder phase 3 in the surface region 5 to the content ratio Ci of the binder phase 3 in the interior is preferably 0.01 to 0.1, with the view of enhancing the wear resistance in the surface of the cermet 1 and enhancing the welding resistance in the surface of the cermet 1.
- the average particle diameter of the second hard phase 2b is larger than the average particle diameter of the first hard phase 2a, preferably the ratio (b i /a i ) of a i and b i is 2 to 8, where a i is the average particle diameter of the first hard phase 2a in the interior, and b i is the average particle diameter of the second hard phase 2b in the interior, in the point that the second hard phase 2b effectively contributes to thermal propagation thereby to improve the thermal conductivity of the cermet 1 and improve the thermal shock resistance of the cermet 1.
- the suitable ratio (b i /a i ) of a i and b i is 3.5 to 7, with the view of maintaining the fracture resistance of the cermet 1.
- the particle diameter of the hard phase 2 is measured according to the method of measuring the average particle diameter of cemented carbide as prescribed in CIS-019D-2005. Specifically, when the hard phase 2 has the core-containing structure, the region extending up to the outer edge of the peripheral part including the core part and the peripheral part is regarded as a single hard phase, and the particle diameter thereof is measured. When observing the cross-sectional structure in the interior of the cermet 1 of the invention, the region extending in a depth of not less than 1000 ⁇ m from the surface of the cermet 1 is observed.
- the average area of the second hard phase 2b is larger than the average area of the first hard phase 2a, preferably the ratio (B i /A i ) of A 1 and B 1 is 1.5 to 5, where A i is the average area occupied by the first hard phase 2a, and B i is the average area occupied by the second hard phase 2b, with respect to the entirety of the hard phase 2 in the interior, in the point that the second hard phase 2b more effectively contributes to thermal propagation thereby to improve the thermal conductivity of the cermet 1 and improve the thermal shock resistance of the cermet 1.
- the total content ratio of nitrides or carbonitrides of Group 4, Group 5 and Group 6 metals of the periodic table, each of which constitutes the hard phase 2 and is composed mainly of Ti is preferably 70 to 96% by mass, particularly 85 to 96% by mass, with the view of improving wear resistance.
- the content ratio of the binder phase 3 is preferably 4 to 30% by mass, particularly 4 to 15% by mass. This achieves excellent balance between the hardness and toughness of the cermet 1.
- the binder phase 3 preferably contains not less than 65% by mass of Co with respect to the total amount of iron-family metals with the view of enhancing the thermal shock resistance of a cutting tool.
- the baked surface of the cermet 1 becomes a smooth surface
- a coating layer can be formed on the surface of the above cermet 1.
- An example thereof will now be described based on Fig. 2 , wherein (a) is a scanning electron microscope (SEM) photograph of important parts in a cross-section including a surface region of a coated cermet 10, and (b) is a scanning electron microscope (SEM) photograph of important parts of a ground surface before forming the coating layer of the coated cermet 10.
- SEM scanning electron microscope
- the coated cermet 10 of Fig. 2(a) has the structure that the surface of a substrate 12 composed of the above cermet 1 is coated with the coating layer 13.
- the coating layer 13 formed by chemical vapor deposition (CVD) method can also be formed. That is, conventional coated cermets generally employ physical vapor deposition (PVD) method carried out with the substrate heated to approximately 500°C. This is because if used CVD method that is carried out with a substrate heated to high temperatures of 700°C and above, the coating layer may cause partially abnormal particle growth and change into a needle shape due to Ni or Fe used as the binder phase of the Ti-based cermet, and the strength of the coating layer may be lowered, causing chipping or fracture.
- PVD physical vapor deposition
- the cermet 1 as the substrate 12 of the invention is adapted to reduce the existence of Ni in the surface of the substrate 12, and hence the coating layer 13 does not cause any abnormal particle growth. It is also capable of preventing the hardness deterioration of the coating layer 13 due to a large amount of diffusion of the binder phase 3 into the coating layer 13. Consequently, the coating layer 13 has high hardness and high strength characteristics. Additionally, when the surface region 5 and the coating layer 13 are similar to each other in structural components and crystal structure, there is a slight difference in thermal expansion coefficients between the two, and hence separation due to thermal stress does not occur in the interface between the substrate 12 and the coating layer 13.
- the coating layer 13 is formed by CVD method. This enhances the adhesion of the coating layer 13 with respect to the substrate 12 without deteriorating the hardness of the coating layer 13, thereby enhancing the fracture resistance in the surface of the coated cermet 10.
- Ni exists in the surface of the substrate 12, and the coating layer 13 to be formed in the surface causes abnormal particle growth, thus deteriorating both hardness and toughness.
- the thickness of the surface region 5 is preferably 0.8. to 3 ⁇ m, with the view of maintaining the shock resistance of the coated cermet 10.
- the percentage of area B s of the second hard phase 2b in the surface region 5 is preferably 70 to 100% by area to the entirety of the hard phase 2, with the view of enhancing the adhesion with respect to the coating layer 13.
- a binder phase-rich region 8 exists in a region extending 1 to 10 ⁇ m from immediately below the surface region 5, at 1.1 to 2.0 in terms of the ratio (A/B) of A to B, where A is the content ratio of the binder phase 3, and B is the content ratio of the binder phase 3 in the interior of the substrate 12.
- A/B the ratio of A to B
- the ingredients of the binder phase 3 diffuse into the coating layer 13, thus deteriorating the hardness of the coating layer 13.
- the binder phase 3 In order to maintain satisfactory sintering properties for achieving a smooth burned surface of the substrate 12, and also enhance the thermal shock resistance of the substrate 12, it is preferable for the binder phase 3 that the content ratio of Ni in the interior of the substrate is 0.1 to 0.5 in terms of Ni/(Ni+Co) ratio.
- the surface region 5 When the content ratio of N in the surface region 5 is larger than that in the interior of the sintered body, the surface region 5 has excellent toughness characteristic. Therefore, when the coating layer 13 having a higher hardness than the surface region 5 is formed immediately above the surface region 5, the high-hard and brittle coating layer 13 causes neither chipping nor separation even under shock exerted during cutting or the like, thereby achieving satisfactory wear resistance and fracture resistance.
- the distribution of the content ratio of N can be compared by X-ray photoelectron spectroscopic analysis in a depth direction from the surface of the cermet 1 toward the interior thereof.
- the coating layer 13 is composed of a columnar crystal extending vertically with respect to the surface of the substrate 12.
- the coating layer 13 preferably includes a columnar crystal coating layer in which the columnar crystal has an average crystal width of 0.1 to 1 ⁇ m, in the interest of high fracture resistance and excellent wear resistance of the coating layer 13.
- a TiCN layer is suitable in the interest of easy manufacture of the above-mentioned structure.
- the coating layer is capable of producing the above effect irrespective of whether the coating layer is a single columnar crystal coating layer, or a multilayer structure made up of one or more columnar crystal coating layers and other layer.
- the TiCN layer composed of the TiCN columnar crystal included in the coating layer 13 preferably has its strongest peak in (422) plane in an X-ray diffraction measurement, in the interest of high wear resistance of the coating layer 13 and excellent adhesion with respect to the substrate 12.
- FIGS. 3(a) and 3(b) are schematic perspective views thereof.
- the cutting tool 20 of the invention is constructed to have a rake face 21 on the main surface thereof, a flank face 22 on the side surface thereof, and cutting edges 23 (23a to 23d) along a cross ridge line between the rake face 21 and the flank face 22.
- a recessed part 25 including a breaker 24 is formed in the rake face 21.
- a screw hole 26 for mounting the cutting tool 20 onto a holder (not shown) is formed at the center of the rake face 21.
- the method of machining a work material includes the following three steps.
- the cutting tool 20 made of the cermet 1 or the coated cermet 10 and provided with the cutting edges 23 is prepared.
- the cutting edge 23 of the cutting tool 20 is brought into contact with the work material.
- the work material is subjected to cutting by using the cutting tool 20.
- the second hard phase 2b is preferably subjected to compressive stress of not less than 150 MPa ( ⁇ 11 ⁇ -150 MPa). This improves the fracture resistance in the cutting edges 23.
- a mixed powder is prepared by mixing TiCN powder having an average particle diameter of 0.1 to 2 ⁇ m, preferably 0.2 to 1.2 ⁇ m, one kind of powder selected from carbonate powder, nitride powder and carbonitride powder of the above-mentioned other metal having an average particle diameter of 0.1 to 2 ⁇ m, Co powder or Ni powder, metal Mn powder or Mn compound powder having an average particle diameter of 0.5 to 10 ⁇ m, wherein a total amount in terms of Mn is 0.2 to 3.0% by mass.
- a binder is added to the mixed powder and formed into a predetermined shape by any known forming method such as press forming, extrusion forming, injection forming, or the like.
- the cermet having the predetermined structure described above can be manufactured by performing sintering steps under the following conditions.
- the sintering conditions are as follows: (a) Temperature is increased under vacuum from room temperature to 1200°C; (b) The temperature is increased under vacuum at a temperature rising rate r 1 of 0.1 to 2°C/min from 1200°C to a sintering temperature T 1 of 1330 to 1380 °C; (c) The temperature is increased in an inert gas atmosphere of 30 to 2000 Pa at a temperature rising rate r 2 of 4 to 15°C/min from the sintering temperature T 1 to a sintering temperature T 2 of 1450 to 1600°C; (d) The sintering temperature T 2 is retained for 0.5 to 2 hours in an inert gas atmosphere of 30 to 2000 Pa; and (e) The temperature is decreased.
- the sintering atmosphere in the step (b) is an inert gas atmosphere instead of under vacuum, the volatilization of Mn is reduced, and the content of Mn in the cermet after sintering cannot be controlled, and the above surface region is not formed.
- the surface region is also not formed if the temperature rising rate in the step (b) is higher than 2°C/min. If the atmosphere in the step (c) is under vacuum or an inert gas atmosphere of less than 30 Pa, more than 0.5% by mass of Mn remains in the interior of the cermet 1, and the surface region is not formed. Conversely, if it is a high inert gas atmosphere exceeding 2000 Pa, the surface region is not formed.
- the sintering temperature T 2 in the step (d) is below 1450°C, the surface region is not formed. If the sintering temperature T 2 exceeds 1600°C, the surface region of not less than 5 ⁇ m is formed, resulting in poor toughness.
- the surface region 5 having high hardness and high welding resistance is achieved by performing the temperature decreasing step (e) in a vacuum atmosphere. If the temperature decreasing step (e) is performed in an inert gas atmosphere, the content ratio of N in the surface region 5 becomes larger than that in the interior of the cermet 1, thereby forming the surface region having high toughness.
- a coating layer is coated onto the surface of the substrate composed of the above cermet at 800 to 1100°C by CVD method.
- Specific film forming conditions are as follows. Firstly, a titanium nitride (TiN) layer is formed by preparing in a CVD furnace a mixed gas composed of, for example, 0.1 to 10% by volume of titanium chloride (TiCl 4 ), 10 to 60% by volume of nitrogen (N 2 ) gas, and the rest that is hydrogen (H 2 ) gas, and by admitting the mixed gas into a reaction chamber, followed by controlling the inside of the chamber in the range of 800 to 1100°C and 50 to 85 kPa.
- TiN titanium nitride
- TiCN titanium carbonitride
- TiN titanium nitride
- MT-CVD method a titanium carbonitride (TiCN) layer is formed on the titanium nitride (TiN) layer by admitting a mixed gas prepared so that titanium chloride (TiCl 4 ) is 0.5 to 5.0% by volume, acetonitrile (CH 3 CN) is 0.3 to 1.5% by volume, nitrogen (N 2 ) is 10 to 40% by volume, and the rest is hydrogen (H 2 ), at a reaction temperature of 800 to 900°C.
- the structure of the titanium carbonitride (TiCN) in the titanium carbonitride (TiCN) layer can be surely grown within the above-mentioned range.
- the titanium carbonitride (TiCN) layer composed of the columnar crystal having an average crystal width of 0.1 to 1 ⁇ m can be formed by setting the film forming temperature to 800°C to 850°C, and by controlling, in the titanium carbonitride (TiCN) crystal growth step in the early period of forming the titanium carbonitride (TiCN) layer, the proportion V A of the acetonitrile (CH 3 CN) gas in the range of 0.3 to 1.5% by volume, and also controlling the ratio (V A /V H ) of the proportion V H of the hydrogen gas (H 2 ) as carrier gas and the proportion V A of the acetonitrile (CH 3 CN) gas at a low concentration of not more than 0.03.
- the TiCN layer has a film thickness of not less than 2 ⁇ m, and (422) peak becomes the strongest in an XRD diffraction.
- TiCNO titanium oxycarbonitride
- a titanium oxycarbonitride (TiCNO) layer is formed by preparing and admitting a mixed gas composed of 0.1 to 3% by volume of titanium chloride (TiCl 4 ) gas, 0.1 to 10% by volume of methane (CH 4 ) gas, 0.01 to 5% by volume of carbon dioxide (CO 2 ) gas, 0.1 to 60% by volume of nitrogen (N 2 ) gas, and the rest that is hydrogen (H 2 ) gas, into the reaction chamber, and by controlling the conditions within the chamber in the range of 800 to 1100°C and 5 to 30 kPa.
- TiCl 4 titanium chloride
- CH 4 methane
- CO 2 carbon dioxide
- N 2 nitrogen
- H 2 hydrogen
- an aluminum oxide (Al 2 O 3 ) layer is formed by using a mixed gas composed of 3 to 20% by volume of aluminum chloride (AlCl 3 ) gas, 0.5 to 3.5% by volume of hydrogen chloride (HCl) gas, 0.01 to 5% by volume of carbon dioxide (CO 2 ) gas, 0 to 0.01% by volume of hydrogen sulfide (H 2 S) gas, and the rest that is hydrogen (H 2 ) gas, and by controlling in the range of 900 to 1100°C and 5 to 10 kPa.
- AlCl 3 aluminum chloride
- HHCl hydrogen chloride
- CO 2 carbon dioxide
- H 2 S hydrogen sulfide
- TiN titanium nitride
- TiCl 4 titanium chloride
- N 2 nitrogen
- H 2 hydrogen
- a predetermined portion of the surface of the formed coating layer 8 is subjected to mechanical grinding by means of brush, elastic grinding, or blast method. This grinding adjusts the residual stress generated during film formations and remaining in the coating layer.
- a mixed powder was prepared by blending, in the proportions shown in Table 1, TiCN powder having an average particle diameter of 0.6 ⁇ m, WC powder having an average particle diameter of 1.1 ⁇ m, TiN powder having an average particle diameter of 1.5 ⁇ m, TaC powder having an average particle diameter of 2 ⁇ m, MoC powder having an average particle diameter of 1.5 ⁇ m, NbC powder having an average particle diameter of 1.5 ⁇ m, ZrC powder having an average particle diameter of 1.8 ⁇ m, VC powder having an average particle diameter of 1.0 ⁇ m, Ni powder having an average particle diameter of 2.4 ⁇ m, Co powder having an average particle diameter of 1.9 ⁇ m, and MnCO 3 powder having an average particle diameter of 5.0 ⁇ m.
- d 50 values average particle diameters (d 50 values) were measured by microtrack method.
- the mixed powder was then wet mixed while adding isopropyl alcohol (IPA), and then 3% by mass of paraffin was added and mixed together by using a ball mill and carbide balls made of stainless steel. Subsequently, this mixed powder was press-formed into a throw-away tip tool shape of CNMG120408 at an applied pressure of 200 MPa. Thereafter, throw-away tips made of the cermets of Samples Nos.
- IPA isopropyl alcohol
- each of the obtained cermets was subjected to a scanning electron microscope (SEM) observation, and an image analysis was performed using commercially available image analysis software onto arbitrary five points in the surface and the interior thereof, respectively, at a region of 8 ⁇ m ⁇ 8 ⁇ m in a photograph taken at 10000 magnification. Then, it was confirmed whether or not the surface region existed by observing the existing states of the hard phase and the binder phase, and the structure states in the interior and the surface. In all the individual samples, it was confirmed that the binder phase was composed mainly of Co and Ni, based on the energy dispersive spectroscopic analysis (EMPA) annexed to the scanning electron microscope (SEM).
- EMPA energy dispersive spectroscopic analysis
- the residual stress in the rake face of each of Samples Nos. 4, 7 and 11 was measured by 2D method (an X-ray diffraction apparatus manufactured by Bruker AXS Inc., D8 DISCOVER with GADDS Super Speed, Ray source: CuK ⁇ , Collimater diameter: 0.3mm ⁇ , Measured diffraction line: TiN (422) plane).
- 2D method an X-ray diffraction apparatus manufactured by Bruker AXS Inc., D8 DISCOVER with GADDS Super Speed, Ray source: CuK ⁇ , Collimater diameter: 0.3mm ⁇ , Measured diffraction line: TiN (422) plane).
- d i Average particle diameter ( ⁇ m) of whole hard phase in interior 2) a i: Average particle diameter ( ⁇ m) of first hard phase in interior 3) b i : Average particle diameter ( ⁇ m) of second hard phase in interior 4)
- a i Percentage of area (% by area) of first hard phase in interior 5)
- B i Percentage of area (% by area) of second hard phase in interior 6)
- b s Average particle diameter ( ⁇ m) of second hard phase in surface region 7)
- B s Percentage of area (% by area) of second hard phase in surface region 8)
- c s /c i Content ratio c s of binder phase in surface region / content ratio c i of binder phase in interior
- the cermet substrates of Samples Nos. 19 to 31 were obtained under the same conditions as Example 1, except for the material compositions in Table 7 and the sintering conditions in Table 8.
- each of the obtained cermets was subjected to a scanning electron microscope (SEM) observation, and an image analysis was performed using commercially available image analysis software onto arbitrary five points in the surface and the interior thereof, respectively, at a region of 8 ⁇ m ⁇ 8 ⁇ m in a photograph taken at 10000 magnification. Then, it was confirmed whether or not the surface region existed and the binder phase-rich region existed by observing the existing states of the hard phase, and the structure states in the interior and the surface. Subsequently, the average particle diameter of each of these regions was measured, and the ratio thereof was calculated. Further, the content ratio of the Mn ingredient in the cermet substrate of each sample was determined by ICP analysis. The results were shown in Table 9.
- the coating layers having the structures shown in Table 11 were formed on the above cermet substrates by CVD method under the film forming conditions shown in Table 10, respectively.
- Table 11 in the scanning electron microscopic observations of Samples Nos. 19 to 22 and 24 in which a TiCN layer having a film thickness of not less than 2 ⁇ m was formed, it was confirmed that these samples were composed of the columnar crystal having an average crystal width of 0.1 to 1 ⁇ m extending vertically with respect to the surface of the cermet substrate, as shown in the photograph of Sample No. 24 in Figs. 2(a) and 2(b) . In each of their respective X-ray diffraction measurements, the peak of (422) plane was the strongest.
- Coating layer Mixed gas composition (% by volume) Mixed gas flow rate (l/min) Film forming temperature (°C) Pressure (kPa) TiN TiCl 4 :0.5, N 2 :33, H 2 :The rest 80 900 16 TiCN TiCl 4 :1.0, N 2 :30, CH 3 CN:0.4, H 2 :The rest 70 820 9 TiCNO TiCl 4 :0.7, CH 4 :4, N 2 :5.
- Nb diffusion indicates that the ratio of a content ratio of Nb in the region extending 0.5 ⁇ m from the surface of the cermet substrate to a content ratio of Nb in the surface of the cermet substrate, in the coating layer, is 10% or more.
- No. indicates that the ratio of a content ratio of Nb in the region extending 0.5 ⁇ m from the surface of the cermet substrate to a content ratio of Nb in the surface of the cermet substrate, in the coating layer, is less than 10%.
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Abstract
Description
- The present invention relates to a titanium (Ti)-based cermet, a coated cermet, and a cutting tool, particularly to a cutting tool whose cutting edge has enhanced wear resistance.
- Sintered alloys such as cemented carbides composed mainly of WC, and Ti-based cermet composed mainly of Ti are currently widely used as members requiring wear resistance and sliding properties, as well as fracture resistance, such as cutting tools, wear-resistant members and sliding members. Developments of novel compositions for improving performance of these sintered alloys have been continued.
- For example,
patent document 1 discloses the technique of forming cemented carbide or a cermet by reaction sintering using microwaves, and describes that Mn or A1 is added in the proportion of 5% by mass or less into a metal binder phase such as Co. -
Patent document 2 discloses the gradient composition sintered alloy made by adding 0.1 to 10% by mass of a specific metal element such as Mn, in addition to a hard phase composed mainly of carbides or nitrides of metals selected from Group 4,Group 5 and Group 6 metals of the periodic table, and mutual solid solutions of these, and 1 to 40% by mass of an iron-group metal. Ti-based cermets made by adding Mn are described in Samples No. 17 and No. 20 in Table 6. Table 8 indicates that the concentration of the Mn and the concentration of the binder phase in Sample No. 17 and No. 20 are increased in the interior of the cermet than the surface thereof. - Patent document 1: Japanese Unexamined Patent Publication No.
2000-503344 - Patent document 2: Japanese Unexamined Patent Publication No.
2004-292905 - However, there is a limit to the improvements in the hardness and toughness of the cermet with the method in which Mn is added and then microwave sintered, as described in the
patent document 1. Even in the gradient composition having the increased Mn concentration and the increased binder phase concentration in the interior of the sintered body, as described in thepatent document 2, there is the problem that the effect in improving the hardness of the cermet surface remains insufficient, and the finish-machined surface of a work material becomes rough due to the welding of the work material onto the cutting edge, thus causing abnormal wear or fracture. - Therefore, the cutting tool of the present invention has been made to solve the above problems, and aims to enhance the wear resistance and welding resistance of the Ti-based cermet.
- The Ti-based cermet of the invention is composed of at least one kind of element selected from Co and Ni; and one or more kinds of substances selected from carbides, nitrides, and carbonitrides of one or more kinds of metals selected from Group 4,
Group 5 and Group 6 metals of the periodic table, each of which is composed mainly of Ti; and 0.1 to 0.5% by mass of Mn. In a scanning electron microscope (SEM) photograph of an arbitrary cross-section of the Ti-based cermet, a surface region is formed in which a hard phase whose interior comprises a first hard phase and a second hard phase, and a binder phase composed mainly of at least one kind of element selected from Co and Ni are observed. The second hard phase looks whiter than the first hard phase, and the second hard phase whose content percentage is not less than 90% by area is observed in a surface part. - The method of manufacturing the Ti-based cermet of the invention includes forming a mixed powder as a mixture of TiCN powder; at least one kind of powder selected from carbonate powder, nitride powder and carbonitride powder each containing one or more kinds of elements selected from W, Mo, Ta, V, Zr and Nb; at least one kind of powder selected from Co and Ni; and a total amount of 0.2 to 3.0% by mass in terms of Mn of a metal Mn powder or an Mn compound powder, followed by sintering under the following conditions: (a) increasing temperature under vacuum from room temperature to 1200°C; (b) increasing the temperature under vacuum at a temperature rising rate of 0.1 to 2°C/min from 1200°C to a sintering temperature T1 of 1330 to 1380°C; (c) increasing the temperature at a temperature rising rate of 4 to 15°C/min from the sintering temperature T1 to a sintering temperature T2 of 1450 to 1600°C in an inert gas atmosphere of 30 to 2000 Pa; (d) retaining the sintering temperature T2 in the inert gas atmosphere of 30 to 2000 Pa for 0.5 to 2 hours; and (e) decreasing the temperature.
- The coated cermet of the invention is produced by using the above Ti-based cermet as a substrate, and coating a surface of the substrate with a coating layer. The content ratio of the binder phase in the surface region of the substrate is not more than 3% by mass, and the coating layer is formed by chemical vapor deposition.
- The cutting tool of the invention is composed of the above Ti-based cermet or the above coated cermet, and a cutting edge is formed along a cross ridge part between a rake face and a flank face. In the residual stress measured by 2D method in the rake face which is exerted in a σ11 direction (a direction to connect between the center of the rake face and the center of the cutting edge nearmost the measured point), the second hard phase is preferably subjected to compressive stress of not less than 150 MPa (σ11 ≤ -150 MPa).
- In accordance with the Ti-based cermet of the invention, 0.1 to 0.5% by mass of Mn is contained, and the surface region, in which the second hard phase whose content percentage is not less than 90% by area is observed, is formed in the surface of the cermet. This increases the toughness of the cermet as a whole, and enhances the hardness in the surface of the cermet, thereby improving wear resistance and also enhancing welding resistance.
- An example of the Ti-based cermet of the invention will now be described based on the scanning electron microscope (SEM) photograph of the cross-section of the important parts including the surface region of the Ti-based cermet as shown in
Fig. 1 . - The Ti-based cermet (hereinafter referred to simply as "cermet") 1 in
Fig. 1 is composed of at least one kind of element selected from Co and Ni; and one or more kinds of substances selected from carbides, nitrides, and carbonitrides of one or more kinds of metals selected from Group 4,Group 5, and Group 6 metals of the periodic table, each of which is composed mainly of Ti; and 0.1 to 0.5% by mass of Mn. - As shown in
Fig. 1 , in the scanning electron microscope (SEM) photograph of an arbitrary cross-section, asurface region 5 is formed in which ahard phase 2 whose interior comprises a black firsthard phase 2a and a grayish white secondhard phase 2b, and abinder phase 3 composed mainly of at least one kind of elements selected from Co and Ni are observed, and the secondhard phase 2b whose content percentage is not less than 90% by area is observed in a surface part. - This increases the toughness of the cermet as a whole, and enhances the hardness in the surface of the cermet, thereby improving wear resistance and also enhancing welding resistance.
- In the scanning electron microscope (SEM) photograph of the cross-sectional structure of the
cermet 1 as shown inFig. 1 , the firsthard phase 2a is observed as black particles, and the secondhard phase 2b is observed as grayish white particles, or particles having a core-containing structure in which a grayish white peripheral part exists around a white core part. That is, the firsthard phase 2a has a higher content ratio of a light element than the secondhard phase 2b, and hence looks black. Although the firsthard phase 2a corresponds to the black particles composed of TiCN, it may contain Co or Ni. Alternatively, other core-containing structure may be employed in which the grayish white secondhard phase 2b exists as a peripheral part in the outer periphery of the firsthard phase 2a. On the other hand, thebinder phase 3 is observed as a white region, and Co and Ni constituting thebinder phase 3 can be confirmed by energy dispersive spectroscopy (EMPA) annexed to the scanning electron microscope (SEM). - Unless not less than 0.1% by mass of Mn is contained in the
cermet 1, the toughness of thecermet 1 is lowered. Conversely, if more than 0.5% by mass of Mn is contained in thecermet 1, the hardness of thecermet 1 is remarkably lowered. The suitable content of Mn is 0.2 to 0.5% by mass. - In the absence of the
surface region 5 in the surface of thecermet 1, the hardness in the surface of thecermet 1 cannot be enhanced, thus leading to insufficient wear resistance of thecermet 1. If the percentage of presence of the secondhard phase 2b in thesurface region 5 is less than 90% by area, the wear resistance and welding resistance in the surface of thecermet 1 become insufficient. The suitable thickness of thesurface region 5 is 0.8 to 3 µm. The preferable percentage of area Bus of the secondhard phase 2b in thesurface region 5 is 93 to 97% by area, in the interest of adhesion with respect to acoating layer 13. - Like the scanning electron microscope (SEM) photograph of the cross-section in the vicinity of the surface of the
cermet 1 as shown inFig. 1 , the average particle diameter d1s of the secondhard phase 2b is preferably 0.5 to 3.0 µm, particularly 1.0 to 2.0 µm. The ratio (Cs/Ci) of the content ratio Cs of thebinder phase 3 in thesurface region 5 to the content ratio Ci of thebinder phase 3 in the interior is preferably 0.01 to 0.1, with the view of enhancing the wear resistance in the surface of thecermet 1 and enhancing the welding resistance in the surface of thecermet 1. - When the cross-sectional structure in the interior of the
cermet 1 is further observed, the average particle diameter of the secondhard phase 2b is larger than the average particle diameter of the firsthard phase 2a, preferably the ratio (bi/ai) of ai and bi is 2 to 8, where ai is the average particle diameter of the firsthard phase 2a in the interior, and bi is the average particle diameter of the secondhard phase 2b in the interior, in the point that the secondhard phase 2b effectively contributes to thermal propagation thereby to improve the thermal conductivity of thecermet 1 and improve the thermal shock resistance of thecermet 1. The suitable ratio (bi/ai) of ai and bi is 3.5 to 7, with the view of maintaining the fracture resistance of thecermet 1. - In the present invention, the particle diameter of the
hard phase 2 is measured according to the method of measuring the average particle diameter of cemented carbide as prescribed in CIS-019D-2005. Specifically, when thehard phase 2 has the core-containing structure, the region extending up to the outer edge of the peripheral part including the core part and the peripheral part is regarded as a single hard phase, and the particle diameter thereof is measured. When observing the cross-sectional structure in the interior of thecermet 1 of the invention, the region extending in a depth of not less than 1000 µm from the surface of thecermet 1 is observed. - Further in the cross-sectional structure of the interior of the
cermet 1, the average area of the secondhard phase 2b is larger than the average area of the firsthard phase 2a, preferably the ratio (Bi/Ai) of A1 and B1 is 1.5 to 5, where Ai is the average area occupied by the firsthard phase 2a, and Bi is the average area occupied by the secondhard phase 2b, with respect to the entirety of thehard phase 2 in the interior, in the point that the secondhard phase 2b more effectively contributes to thermal propagation thereby to improve the thermal conductivity of thecermet 1 and improve the thermal shock resistance of thecermet 1. - In the interior of the
cermet 1, the total content ratio of nitrides or carbonitrides of Group 4,Group 5 and Group 6 metals of the periodic table, each of which constitutes thehard phase 2 and is composed mainly of Ti, is preferably 70 to 96% by mass, particularly 85 to 96% by mass, with the view of improving wear resistance. On the other hand, the content ratio of thebinder phase 3 is preferably 4 to 30% by mass, particularly 4 to 15% by mass. This achieves excellent balance between the hardness and toughness of thecermet 1. Thebinder phase 3 preferably contains not less than 65% by mass of Co with respect to the total amount of iron-family metals with the view of enhancing the thermal shock resistance of a cutting tool. In order to maintain satisfactory sintering properties of thecermet 1 so that the baked surface of thecermet 1 becomes a smooth surface, it is preferable to contain 5 to 50% by mass of Ni, particularly 10 to 35% by mass of Ni with respect to the total amount of iron-family metals. - A coating layer can be formed on the surface of the
above cermet 1. An example thereof will now be described based onFig. 2 , wherein (a) is a scanning electron microscope (SEM) photograph of important parts in a cross-section including a surface region of a coated cermet 10, and (b) is a scanning electron microscope (SEM) photograph of important parts of a ground surface before forming the coating layer of the coated cermet 10. - The coated cermet 10 of
Fig. 2(a) has the structure that the surface of asubstrate 12 composed of theabove cermet 1 is coated with thecoating layer 13. - In the present invention, as shown in
Fig. 2 , thecoating layer 13 formed by chemical vapor deposition (CVD) method can also be formed. That is, conventional coated cermets generally employ physical vapor deposition (PVD) method carried out with the substrate heated to approximately 500°C. This is because if used CVD method that is carried out with a substrate heated to high temperatures of 700°C and above, the coating layer may cause partially abnormal particle growth and change into a needle shape due to Ni or Fe used as the binder phase of the Ti-based cermet, and the strength of the coating layer may be lowered, causing chipping or fracture. However, thecermet 1 as thesubstrate 12 of the invention is adapted to reduce the existence of Ni in the surface of thesubstrate 12, and hence thecoating layer 13 does not cause any abnormal particle growth. It is also capable of preventing the hardness deterioration of thecoating layer 13 due to a large amount of diffusion of thebinder phase 3 into thecoating layer 13. Consequently, thecoating layer 13 has high hardness and high strength characteristics. Additionally, when thesurface region 5 and thecoating layer 13 are similar to each other in structural components and crystal structure, there is a slight difference in thermal expansion coefficients between the two, and hence separation due to thermal stress does not occur in the interface between thesubstrate 12 and thecoating layer 13. - The
surface region 5, in which the content ratio of thebinder phase 3 is not more than 3% by mass, exists in the region extending 0.1 to 5 µm from the surface of thesubstrate 12, as shown inFig. 2(b) . Thecoating layer 13 is formed by CVD method. This enhances the adhesion of thecoating layer 13 with respect to thesubstrate 12 without deteriorating the hardness of thecoating layer 13, thereby enhancing the fracture resistance in the surface of the coated cermet 10. - That is, in the absence of the
surface region 5 in the surface of thesubstrate 12, Ni exists in the surface of thesubstrate 12, and thecoating layer 13 to be formed in the surface causes abnormal particle growth, thus deteriorating both hardness and toughness. - In the
substrate 12, the thickness of thesurface region 5 is preferably 0.8. to 3 µm, with the view of maintaining the shock resistance of the coated cermet 10. The percentage of area Bs of the secondhard phase 2b in thesurface region 5 is preferably 70 to 100% by area to the entirety of thehard phase 2, with the view of enhancing the adhesion with respect to thecoating layer 13. - Preferably, a binder phase-
rich region 8 exists in a region extending 1 to 10 µm from immediately below thesurface region 5, at 1.1 to 2.0 in terms of the ratio (A/B) of A to B, where A is the content ratio of thebinder phase 3, and B is the content ratio of thebinder phase 3 in the interior of thesubstrate 12. Thus, even if thecoating layer 13 is subjected to shock, the binder phase-rich region 8 relaxes the shock and reduces chipping or fracture in thecoating layer 13. - In the
coating layer 13, if the content of thebinder phase 3 in the region extending up to 0.1 to 5 µm from the surface of thesubstrate 12 is larger than 3% by mass, the ingredients of thebinder phase 3 diffuse into thecoating layer 13, thus deteriorating the hardness of thecoating layer 13. - In order to maintain satisfactory sintering properties for achieving a smooth burned surface of the
substrate 12, and also enhance the thermal shock resistance of thesubstrate 12, it is preferable for thebinder phase 3 that the content ratio of Ni in the interior of the substrate is 0.1 to 0.5 in terms of Ni/(Ni+Co) ratio. - When the content ratio of N in the
surface region 5 is larger than that in the interior of the sintered body, thesurface region 5 has excellent toughness characteristic. Therefore, when thecoating layer 13 having a higher hardness than thesurface region 5 is formed immediately above thesurface region 5, the high-hard andbrittle coating layer 13 causes neither chipping nor separation even under shock exerted during cutting or the like, thereby achieving satisfactory wear resistance and fracture resistance. The distribution of the content ratio of N can be compared by X-ray photoelectron spectroscopic analysis in a depth direction from the surface of thecermet 1 toward the interior thereof. - On the other hand, the
coating layer 13 is composed of a columnar crystal extending vertically with respect to the surface of thesubstrate 12. Thecoating layer 13 preferably includes a columnar crystal coating layer in which the columnar crystal has an average crystal width of 0.1 to 1 µm, in the interest of high fracture resistance and excellent wear resistance of thecoating layer 13. As the columnar crystal coating layer, a TiCN layer is suitable in the interest of easy manufacture of the above-mentioned structure. In this case, the coating layer is capable of producing the above effect irrespective of whether the coating layer is a single columnar crystal coating layer, or a multilayer structure made up of one or more columnar crystal coating layers and other layer. The TiCN layer composed of the TiCN columnar crystal included in thecoating layer 13 preferably has its strongest peak in (422) plane in an X-ray diffraction measurement, in the interest of high wear resistance of thecoating layer 13 and excellent adhesion with respect to thesubstrate 12. - An example of the cutting tool of the invention will now be described with reference to
Figs. 3(a) and 3(b) , which are schematic perspective views thereof. - Referring to
Fig. 3 , the cuttingtool 20 of the invention is constructed to have arake face 21 on the main surface thereof, aflank face 22 on the side surface thereof, and cutting edges 23 (23a to 23d) along a cross ridge line between therake face 21 and theflank face 22. As shown inFig. 3 , a recessedpart 25 including abreaker 24 is formed in therake face 21. Ascrew hole 26 for mounting thecutting tool 20 onto a holder (not shown) is formed at the center of therake face 21. - The method of machining a work material includes the following three steps. In the first step, the cutting
tool 20 made of thecermet 1 or the coated cermet 10 and provided with the cutting edges 23 is prepared. In the next step, the cutting edge 23 of thecutting tool 20 is brought into contact with the work material. In the last step, the work material is subjected to cutting by using thecutting tool 20. - According to the present invention, in the residual stress exerted in the σ11 direction (a direction to connect between the center of the
rake face 21 and thecutting edge 23a nearmost the measured point) measured by 2D method in a portion P other than the recessed part of therake face 21, the secondhard phase 2b is preferably subjected to compressive stress of not less than 150 MPa (σ11 ≤ -150 MPa). This improves the fracture resistance in the cutting edges 23. - An example of the method of manufacturing the above cermet will be described below.
- Firstly, a mixed powder is prepared by mixing TiCN powder having an average particle diameter of 0.1 to 2 µm, preferably 0.2 to 1.2 µm, one kind of powder selected from carbonate powder, nitride powder and carbonitride powder of the above-mentioned other metal having an average particle diameter of 0.1 to 2 µm, Co powder or Ni powder, metal Mn powder or Mn compound powder having an average particle diameter of 0.5 to 10 µm, wherein a total amount in terms of Mn is 0.2 to 3.0% by mass.
- Subsequently, a binder is added to the mixed powder and formed into a predetermined shape by any known forming method such as press forming, extrusion forming, injection forming, or the like.
- According to the present invention, the cermet having the predetermined structure described above can be manufactured by performing sintering steps under the following conditions. The sintering conditions are as follows: (a) Temperature is increased under vacuum from room temperature to 1200°C; (b) The temperature is increased under vacuum at a temperature rising rate r1 of 0.1 to 2°C/min from 1200°C to a sintering temperature T1 of 1330 to 1380 °C; (c) The temperature is increased in an inert gas atmosphere of 30 to 2000 Pa at a temperature rising rate r2 of 4 to 15°C/min from the sintering temperature T1 to a sintering temperature T2 of 1450 to 1600°C; (d) The sintering temperature T2 is retained for 0.5 to 2 hours in an inert gas atmosphere of 30 to 2000 Pa; and (e) The temperature is decreased.
- That is, among the above sintering conditions, if the sintering atmosphere in the step (b) is an inert gas atmosphere instead of under vacuum, the volatilization of Mn is reduced, and the content of Mn in the cermet after sintering cannot be controlled, and the above surface region is not formed. The surface region is also not formed if the temperature rising rate in the step (b) is higher than 2°C/min. If the atmosphere in the step (c) is under vacuum or an inert gas atmosphere of less than 30 Pa, more than 0.5% by mass of Mn remains in the interior of the
cermet 1, and the surface region is not formed. Conversely, if it is a high inert gas atmosphere exceeding 2000 Pa, the surface region is not formed. If the sintering temperature T2 in the step (d) is below 1450°C, the surface region is not formed. If the sintering temperature T2 exceeds 1600°C, the surface region of not less than 5 µm is formed, resulting in poor toughness. - The
surface region 5 having high hardness and high welding resistance is achieved by performing the temperature decreasing step (e) in a vacuum atmosphere. If the temperature decreasing step (e) is performed in an inert gas atmosphere, the content ratio of N in thesurface region 5 becomes larger than that in the interior of thecermet 1, thereby forming the surface region having high toughness. - Preferably, a coating layer is coated onto the surface of the substrate composed of the above cermet at 800 to 1100°C by CVD method. Specific film forming conditions are as follows. Firstly, a titanium nitride (TiN) layer is formed by preparing in a CVD furnace a mixed gas composed of, for example, 0.1 to 10% by volume of titanium chloride (TiCl4), 10 to 60% by volume of nitrogen (N2) gas, and the rest that is hydrogen (H2) gas, and by admitting the mixed gas into a reaction chamber, followed by controlling the inside of the chamber in the range of 800 to 1100°C and 50 to 85 kPa.
- Subsequently, with so-called MT-CVD method, a titanium carbonitride (TiCN) layer is formed on the titanium nitride (TiN) layer by admitting a mixed gas prepared so that titanium chloride (TiCl4) is 0.5 to 5.0% by volume, acetonitrile (CH3CN) is 0.3 to 1.5% by volume, nitrogen (N2) is 10 to 40% by volume, and the rest is hydrogen (H2), at a reaction temperature of 800 to 900°C.
- With regard to the above film forming conditions, by adjusting the proportion of acetonitrile gas in the gas to the above-mentioned range, the structure of the titanium carbonitride (TiCN) in the titanium carbonitride (TiCN) layer can be surely grown within the above-mentioned range. The titanium carbonitride (TiCN) layer composed of the columnar crystal having an average crystal width of 0.1 to 1 µm can be formed by setting the film forming temperature to 800°C to 850°C, and by controlling, in the titanium carbonitride (TiCN) crystal growth step in the early period of forming the titanium carbonitride (TiCN) layer, the proportion VA of the acetonitrile (CH3CN) gas in the range of 0.3 to 1.5% by volume, and also controlling the ratio (VA/VH) of the proportion VH of the hydrogen gas (H2) as carrier gas and the proportion VA of the acetonitrile (CH3CN) gas at a low concentration of not more than 0.03. The TiCN layer has a film thickness of not less than 2 µm, and (422) peak becomes the strongest in an XRD diffraction.
- Next, a titanium oxycarbonitride (TiCNO) layer is formed by preparing and admitting a mixed gas composed of 0.1 to 3% by volume of titanium chloride (TiCl4) gas, 0.1 to 10% by volume of methane (CH4) gas, 0.01 to 5% by volume of carbon dioxide (CO2) gas, 0.1 to 60% by volume of nitrogen (N2) gas, and the rest that is hydrogen (H2) gas, into the reaction chamber, and by controlling the conditions within the chamber in the range of 800 to 1100°C and 5 to 30 kPa.
- Subsequently, an aluminum oxide (Al2O3) layer is formed by using a mixed gas composed of 3 to 20% by volume of aluminum chloride (AlCl3) gas, 0.5 to 3.5% by volume of hydrogen chloride (HCl) gas, 0.01 to 5% by volume of carbon dioxide (CO2) gas, 0 to 0.01% by volume of hydrogen sulfide (H2S) gas, and the rest that is hydrogen (H2) gas, and by controlling in the range of 900 to 1100°C and 5 to 10 kPa.
- Further, a titanium nitride (TiN) layer is formed by preparing and admitting a mixed gas composed of 0.1 to 10% by volume of titanium chloride (TiCl4) gas, 10 to 60% by volume of nitrogen (N2) gas, and the rest that is hydrogen (H2) gas, into the reaction chamber, and by controlling the conditions within the chamber in the range of 800 to 1100°C and 50 to 85 kPa.
- Thereafter, as required, a predetermined portion of the surface of the formed
coating layer 8 is subjected to mechanical grinding by means of brush, elastic grinding, or blast method. This grinding adjusts the residual stress generated during film formations and remaining in the coating layer. - A mixed powder was prepared by blending, in the proportions shown in Table 1, TiCN powder having an average particle diameter of 0.6 µm, WC powder having an average particle diameter of 1.1 µm, TiN powder having an average particle diameter of 1.5 µm, TaC powder having an average particle diameter of 2 µm, MoC powder having an average particle diameter of 1.5 µm, NbC powder having an average particle diameter of 1.5 µm, ZrC powder having an average particle diameter of 1.8 µm, VC powder having an average particle diameter of 1.0 µm, Ni powder having an average particle diameter of 2.4 µm, Co powder having an average particle diameter of 1.9 µm, and MnCO3 powder having an average particle diameter of 5.0 µm. These average particle diameters (d50 values) were measured by microtrack method. The mixed powder was then wet mixed while adding isopropyl alcohol (IPA), and then 3% by mass of paraffin was added and mixed together by using a ball mill and carbide balls made of stainless steel. Subsequently, this mixed powder was press-formed into a throw-away tip tool shape of CNMG120408 at an applied pressure of 200 MPa. Thereafter, throw-away tips made of the cermets of Samples Nos. 1 to 11, respectively, were obtained through the following steps: (a) Temperature was increased under vacuum from room temperature to 1200°C at 10°C/min; (b) The temperature was increased in the sintering atmosphere and at the temperature rising rate r1 (°C/min) shown in Table 2, from 1200°C to the sintering temperature T1 shown in Table 2; (c) The temperature was increased in the sintering atmosphere shown in Table 2, at the temperature rising rate r2 (°C/min) shown in Table 2, from the sintering temperature T1 to the sintering temperature T2 shown in Table 2; (d) Sintering was carried out in the sintering atmosphere at the sintering temperature and the sintering time shown in Table 2; and (e) The temperature was decreased in the sintering atmosphere shown in Table 2.
-
[Table 1] Sample No. Material composition (% by mass) TiCN WC TiN TaC MoC NbC ZrC VC Ni Co MnCO 3 1 51.5 17 10 3 0 10 1 1 2 3 1.5 2 63.5 10 5 1 1 8 2 1 2 6 0.5 3 57 15 8 0 1 5 2 1 3 6 2 4 58 12 7 0 2 8 1 2 2 7 1 5 53.5 10 12 3 0 6 1 1 4 7 2.5 6 54.5 15 3 0 0 9 1 2 2 12 1.5 7 58 13 7 2 0 10 1 1 2 5 1 * 8 49 14. 12 3 0 8 2 2 4 6 - * 9 49 14 12 3 0 8 2 2 4 6 1 * 10 48 17 10 1 1 9 2 1 3 7 1 * 11 48 17 10 1 1 9 2 1 3 7 1 The samples marked "*" are out of the scope of the present invention. -
[Table 2] Sample No. Sintering condition Step (b) Step (c) Step (d) Step (e) Temperature rising rate r1 (°C/min) Sintering temperature T1 (°C) Sintering atmosphere Temperature rising rate r2 (°C/min) Sintering temperature T2 (°C) Sintering atmosphere Sintering time (hr) Sintering atmosphere Sintering atmosphere 1 1.5 1350 Vacuum 5 1550 N2 500Pa 1.5 N2 500Pa Vacuum 2 0.7 1350 Vacuum 10 1525 Ar 80Pa 1 Ar 80Pa Vacuum 3 0.5 1350 Vacuum 7 1600 N2 800Pa 0.5 N2 800Pa Vacuum 4 0.7 1360 Vacuum 8 1575 N2 1000Pa 1 N2 1000Pa Vacuum 5 1 1380 Vacuum 4 1450 N2 300Pa 2 N2 300Pa Vacuum 6 0.3 1330 Vacuum 15 1550 N2 700Pa 1 N2 700Pa Vacuum 7 0.7 1340 Vacuum 10 1575 He 1000Pa 1 He 1000Pa Vacuum * 8 1 1350 Vacuum 10 1550 He 1200Pa 1 He 1200Pa He 1200Pa * 9 5 1350 Vacuum 5 1550 He 1200Pa 1 He 1200Pa He 1200Pa * 10 1.0 1350 N2 800Pa 2 1650 N2 800Pa 1 N2 800Pa N2 800Pa * 11 1.0 1350 N2 800Pa 8 1550 Vacuum 1 Vacuum Vacuum The samples marked "*" are out of the scope of the present invention. - Each of the obtained cermets was subjected to a scanning electron microscope (SEM) observation, and an image analysis was performed using commercially available image analysis software onto arbitrary five points in the surface and the interior thereof, respectively, at a region of 8 µm × 8 µm in a photograph taken at 10000 magnification. Then, it was confirmed whether or not the surface region existed by observing the existing states of the hard phase and the binder phase, and the structure states in the interior and the surface. In all the individual samples, it was confirmed that the binder phase was composed mainly of Co and Ni, based on the energy dispersive spectroscopic analysis (EMPA) annexed to the scanning electron microscope (SEM). Subsequently, the average particle diameter of the hard phase in the above region of each sample was measured, and the ratio thereof was calculated. The results were shown in Table 3. Further, the content ratio of the metal Mn ingredient in the interior of the cermet substrate of each sample was determined by ICP analysis. The results were shown in Table 3.
- Next, these cutting tools made of the obtained cermets were subjected to a cutting test under the following cutting conditions. The results were also shown in Table 3.
- Work material: SCM435
- Cutting speed: 200m/min
- Feed rate: 0.20mm/rev
- Depth of cut: 1.0mm
- Cutting state: Wet (using water-soluble cutting fluid)
- Evaluation method: Time (min) elapsed until the amount of wear reached 0.2mm
-
[Table 3] Sample No. Interior Mn ratio (% by mass) Surface region Cutting performances9) di 1) ai 2) bi 3) bi/ai Ai 4) Bi 5) Bi/Ai b s 6) bs/bi Bs 7) Cs/c¡ 8) Thickness (µm) 1 0.44 0.40 1.26 3.15 26 74 2.85 0.25 1.85 1.47 93 0.05 2.1 53 2 0.50 0.26 0.90 3.46 38 62 1.63 0.12 1.20 1.33 92 0.08 0.8 46 3 0.45 0.37 1.38 3.73 25 75 3.00 0.30 2.13 1.54 91 0.10 3.9 55 4 0.50 0.21 1.05 5.00 37 63 1.70 0.20 1.58 1.50 94 0.07 2.8 57 5 0.49 0.18 0.95 5.28 40 60 1.50 0.40 1.27 1.34 96 0.02 2.5 50 6 0.45 0.35 1.26 3.60 27 73 2.70 0.15 1.95 1.55 91 0.08 4.5 52 7 0.40 0.49 1.75 3.57 18 82 4.56 0.12 2.11 1.21 93 0.03 1.5 48 * 8 0.41 0.28 1.21 4.32 27 73 2.70 <0.05 Absence 32 * 9 0.57 0.28 1.21 4.32 35 65 1.86 1.00 Absence 35 * 10 0.34 0.37 1.42 3.84 19 81 4.26 0.07 2.21 1.56 91 0.1 8 39 * 11 033 0.35 1.25 3.57 21 79 3.76 0.13 Absence 37 The samples marked "*" are out of the scope of the present invention.
1) di: Average particle diameter (µ m) of whole hard phase in interior
2) ai: Average particle diameter (µ m) of first hard phase in interior
3) bi: Average particle diameter (µ m) of second hard phase in interior
4) Ai: Percentage of area (% by area) of first hard phase in interior
5) Bi: Percentage of area (% by area) of second hard phase in interior
6) bs: Average particle diameter (µ m) of second hard phase in surface region
7) Bs: Percentage of area (% by area) of second hard phase in surface region
8) cs/ci: Content ratio cs of binder phase in surface region / content ratio ci of binder phase in interior
9) Cutting performance: Time (min) elapsed until amount of wear reached 0.2mm - The followings will be noted from Tables 1 to 3. That is, in Sample No. 8 without Mn addition, the surface region was not formed and wear occurred early. In Sample No. 10 in which the sintering temperature was higher than 1600°C and the content of Mn is less than 0.1% by mass, the wear resistance thereof was deteriorated due to the occurrence of chipping. Also in Sample No. 9 in which the content of Mn exceeded 0.5% by mass, the wear resistance thereof was poor. In Sample No. 11 in which the surface region was not formed due to the mismatched sintering conditions, the wear resistance thereof was lowered.
- On the contrary, all Samples Nos. 1 to 7, which were the cermets having the structures within the scope of the invention, exhibited excellent wear resistance and satisfactory wear resistance, thereby achieving a long tool life.
- The residual stress in the rake face of each of Samples Nos. 4, 7 and 11 was measured by 2D method (an X-ray diffraction apparatus manufactured by Bruker AXS Inc., D8 DISCOVER with GADDS Super Speed, Ray source: CuKα, Collimater diameter: 0.3mmΦ, Measured diffraction line: TiN (422) plane). In the residual stress exerted in the σ11 direction (the direction to connect between the center of the rake face and the center of the cutting edge nearmost the measured point), the individual second hard phases were subjected to compressive stress of 250 MPa (σ11 = -250 MPa), 150 MPa (σ11 = -150 MPa), 100 MPa (σ11 = -100 MPa), respectively.
- Cermets were manufactured under the same manufacturing conditions as in the throw-away tips made of the cermets of Samples Nos. 1 to 11 in Example 1, except for changing the atmosphere in the temperature decreasing step (e) into the atmospheres shown in Table 4. Similarly to Example 1, the structures of the obtained cermets were observed and the results thereof were shown in Table 5. In each of these cermets, the content of N in the interior of the cermet and that in the surface region thereof were compared by performing the X-ray photoelectron spectroscopic analysis in a depth direction from the surface of the sintered body to the interior thereof. Then, the ratio of the content of N in the surface region to the content of N in the interior was shown in Table 6. Thereafter, throw-away tips of Samples Nos. 12 to 18 were obtained by forming the coating layers of Table 6 on these cermets, respectively. The obtained throw-away tips made of the cermets were subjected to a cutting test under the same cutting conditions as Example 1. The results were also shown in Table 6.
-
[Table 4] Sample No. Material composition No. for substrates Sintering condition Step (b) Step (c) Step (d) Step (e) Temperature rising rate r1 (°C/min) Sintering temperature T1 (°C) Sintering atmosphere Temperature rising rate r2 (°C/min) Sintering temperature T2 (°C) Sintering atmosphere Sintering time (hr) Sintering atmosphere Sintering atmosphere 12 1 1.5 1350 Vacuum 5 1550 N2 500Pa 1 N2 500Pa N2 100Pa 13 2 0.7 1350 Vacuum 10 1525 Ar 80Pa 0.5 Ar 80Pa N2 500Pa 14 3 0.5 1350 Vacuum 7 1600 N2 800Pa 1.5 N2 800Pa N2 1000Pa 15 4 0.7 1360 Vacuum 8 1575 N2 1000Pa 1 N2 1000Pa N2 1500Pa 16 5 1 1380 Vacuum 4 1450 N2 600Pa 2 N2 600Pa N2 900Pa 17 6 0.3 1330 Vacuum 15 1550 N2 700Pa 1 N2 700Pa N2 1200Pa 18 7 0.7 1340 Vacuum 10 1575 He 1000Pa 1.5 He 1000Pa N2 1000Pa The samples marked "*" are out of the scope of the present invention. -
[Table 5] Sample No. Interior Mn ratio (% by mass) Surface region di 1) ai 2) bi 3) bi/ai Ai 4) Bi 5) Bi/Ai bs 6) bs/bi Bs 7) cs/ci 8) Thickness (µm) 12 0.45 0.35 1.25 3.57 27 73 2.70 0.24 1.75 1.40 94 0.05 2.1 13 0.52 0.26 0.85 3.27 40 60 1.50 0.15 1.30 1.53 92 0.03 1.2 14 0.43 0.41 1.45 3.54 23 77 3.35 0.25 2.10 1.45 93 0.07 4.2 15 0.50 0.21 1.05 5.00 37 63 1.70 0.20 1.78 1.70 95 0.06 3 16 0.43 0.20 0.95 4.75 35 65 1.86 0.38 1.57 1.65 94 0.04 2.8 17 0.45 0.35 1.26 3.60 27 73 2.70 0.17 1.95 1.55 91 0.08 4.5 18 0.39 0.51 1.80 3.53 17 83 4.88 0.14 2.35 1.31 92 0.02 2 The samples marked "*" are out of the scope of the present invention.
1) di: Average particle diameter (µm) of whole hard phase in interior
2) ai: Average particle diameter (µm) of first hard phase in interior
3) bi: Average particle diameter (µm) of second hard phase in interior
4) Ai: Percentage of area (% by area) of first hard phase in interior
5) Bi: Percentage of area (% by area) of second hard phase in interior
6) bs: Average particle diameter (µm) of second hard phase in surface region
7) Bs: Percentage of area (% by area) of second hard phase in surface region
8) cs/ci: Content ratio cs of binder phase in surface region / content ratio ci of binder phase in interior -
[Table 6] Sample No. Content percentage of N in surface region of cermets (Surface region / interior) Coating layer
Film thicknesses (µm) are shown in parentheses.Cutting performance 1)12 1.9 TiCN(3.5)+Al2O3(4)+TiN(0.5) 80 13 2 TiCN(4)Al2O3(2) 71 14 2.3 TiAIN(3) 65 15 1.8 TiCN(3.5)+Al2O3(4)+TiN(0.5) 85 16 1.7 TiCN(4)+Al2O3(2) 74 17 1.5 Al2O3(4) 68 18 1.2 TiCN(3) 63 The samples marked "*" are out of the scope of the present invention.
1) Cutting performance: Time (min) elapsed until amount of wear reached 0.2mm - It will be noted from Tables 4 to 6 that in each of Samples Nos. 12 to 18, the surface region having a higher content of N than that in the interior thereof was formed, and the throw-away tip with the coating layer formed thereon exhibited excellent wear resistance and had satisfactory wear resistance.
- The cermet substrates of Samples Nos. 19 to 31 were obtained under the same conditions as Example 1, except for the material compositions in Table 7 and the sintering conditions in Table 8.
-
[Table 7] Sample No. Material composition 1) TiCN WC TiN TaC MoC NbC ZrC VC Ni Co Ni/ (Co+Ni) MnCO3 19 55 18 5 0 0 10 1 1 2 8 0.20 3 20 50 15 10 2 0 12 1 1 2 7 0.22 3 21 63 18 3 1 1 3 1 1 4 5 0.44 2 22 50 18 11 0 0 9 0 2 2 8 0.20 4 23 48 18 10 4 1 8 1 2 1 7 0.13 2 24 48 15 13 0 4 10 1 1 3 5 0.38 3 25 60 20 10 1 0 1 1 1 4 2 0.67 4 * 26 51 10 18 5 0 0 2 2 4 8 0.33 3 * 27 50 5 17 3 1 12 3 0 4 5 0.44 3 * 28 52 12 9 1 5 10 1 0 7 3 0.70 0 * 29 49 10 14 0 5 10 1 1 3 7 0.30 3 * 30 44 18 12 0 5 10 1 0 6 4 0.60 3 * 31 52 10 10 1 5 10 1 1 0 10 0.00 0 The samples marked "*" are out of the scope of the present invention.
1) Material composition: The unit of materials other than MnCO3 is "% by mass." MnCO3 is represented in "parts by mass" to 100 parts by mass of the total amount of the other materials. -
[Table 8] Sample No. Step (b) Step (c)(d) Step (e) Temperature T1 (°C) Temperature rising rate a (°C/min) Step (c) gas pressure (Pa) Temperature T2 (°C) Step (d) gas pressure (Pa) Time (hr) Gas pressure (MPa) 19 1350 1 800 1525 800 1 0.2 20 1380 0.6 800 1575 500 1 0.1 21 1330 0.1 500 1525 1000 1 0.1 22 1350 0.1 2000 1575 1000 0.5 0.1 23 1330 2 500 1575 800 2 0.1 24 1300 0.6 500 1575 500 1.5 0.3 25 1400 1 9×105 1600 9 × 106, 1.5 0.6 * 26 1450 3 800 1550 800 1 0.1 * 27 1150 1 800 1550 500 1 0.1 * 28 1350 1 500 1550 500 1 0.1 * 29 1350 1 500 1575 Vacuum 1 0.1 * 30 1350 1 3000 1525 800 1 Vacuum * 31 1350 1 3000 1525 800 1 0.1 The samples marked "*" are out of the scope of the present invention. - Each of the obtained cermets was subjected to a scanning electron microscope (SEM) observation, and an image analysis was performed using commercially available image analysis software onto arbitrary five points in the surface and the interior thereof, respectively, at a region of 8 µm × 8 µm in a photograph taken at 10000 magnification. Then, it was confirmed whether or not the surface region existed and the binder phase-rich region existed by observing the existing states of the hard phase, and the structure states in the interior and the surface. Subsequently, the average particle diameter of each of these regions was measured, and the ratio thereof was calculated. Further, the content ratio of the Mn ingredient in the cermet substrate of each sample was determined by ICP analysis. The results were shown in Table 9.
-
[Table 9] Sample No. Interior structure Binder phase-rich region Surface region Average particle diameter of hard phase (µm) Mn ratio (% by mass) Content ratio B of binder phase (% by mass) Content ratio A of binder phase (% by mass) A/B Thickness (µm) Ratio of binder phase (% by mass) Thickness (µm) Nb ratio (% by mass) 19 0.7 0.2 10 18 1.5 2.5 1.5 2.1 15 20 0.8 0.1 9 9.9 1.3 4.7 1.2 1.5 21.6 21 0.6 0.2 9 9.9 1.2 3.9 1.7 2.3 7.2 22 1 0.3 10 13 1.7 2.3 0.9 1.7 16.2 23 0.9 0.4 8 12 1.8 1.8 2.5 5 17.6 24 1.5 0.4 8 16 2 2.1 2.8 2.7 21 25 2 0.5 6 6.6 2.1 3.5 3 1.5 2.8 * 26 0.8 0.1 12 35 2.9 7.9 - * 27 0.8 1.5 9 9.9 1.1 3.6 5.4 8.3 21.6 * 28 0.8 <0.05 10 - - * 29 0.8 0.1 10 - - * 30 0.8 2.2 10 2.3 0.2 1.2 - * 31 0.8 <0.05 10 - - The samples marked "*" are out of the scope of the present invention. - Next, the coating layers having the structures shown in Table 11 were formed on the above cermet substrates by CVD method under the film forming conditions shown in Table 10, respectively. As shown in Table 11, in the scanning electron microscopic observations of Samples Nos. 19 to 22 and 24 in which a TiCN layer having a film thickness of not less than 2 µm was formed, it was confirmed that these samples were composed of the columnar crystal having an average crystal width of 0.1 to 1 µm extending vertically with respect to the surface of the cermet substrate, as shown in the photograph of Sample No. 24 in
Figs. 2(a) and 2(b) . In each of their respective X-ray diffraction measurements, the peak of (422) plane was the strongest. -
[Table 10] Coating layer Mixed gas composition (% by volume) Mixed gas flow rate (ℓ/min) Film forming temperature (°C) Pressure (kPa) TiN TiCl4:0.5, N2:33, H2:The rest 80 900 16 TiCN TiCl4:1.0, N2:30, CH3CN:0.4, H2:The rest 70 820 9 TiCNO TiCl4:0.7, CH4:4, N2:5. CO2:1.0, H2:The rest 35 1010 10 TiNO TiCl4:0.7, CH4:4, N2:5, CO2:1.1, H2:The rest 35 1010 10 TiC TiCl4:1.0, CH4:6, H2:The rest 65 1000 10 Al2O3 AlCl3:15, HCl:2, CO2:4, H2S:0.01, H2:The rest 35 1005 6 ZrN ZrCl4:2.0, N2:20, H2:The rest 70 1010 16 - Next, the obtained cutting tools made of the cermets were subjected to cutting tests under the following cutting conditions. The results were shown in Table 11.
- Work material: SCM435
Cutting speed: 200m/min
Feed rate: 0.20mm/rev
Depth of cut: 1.0mm
Cutting state: Wet (using water-soluble cutting fluid)
Evaluation method: Time (min) elapsed until the amount of wear reached 0.2mm - Work material: SCM440
Cutting speed: 100m/min
Feed rate: 0.05mm/rev (increased by 0.05mm/rev at 10 seconds intervals, a maximum of 0.50mm/rev) - Depth of cut: 1.5mm
Cutting state: Dry
Evaluation method: Time measured until the cutting edge was fractured (a maximum of 100 seconds) -
[Table 11] Sample No. Structure of coating layers
Film thicknesses (µ m) are shown in parentheses.Wear resistance (Cutting time) (min) Fracture resistance (Cutting time) (sec) First layer Second layer Third layer Fourth layer Fifth layer Nb diffusion1) 19 TiCN
(4)TiCNO
(0.5)Al2O3
(2)TiN
(0.5)- Yes 88 100 20 TiCN
(4)TiCNO
(0.2)Al2O3 (2) - - Yes 82 94 21 TiCN
(5)TiCNO
(0.5)Al2O3
(2)ZrN
(1)- Yes 76 88 22 TiN
(0.5)TiCN
(4)TiCNO
(0.5)Al2O3
(3)TiN (0.5) Yes 69 85 23 TiC
(3)Al2O3
(2)TiN
(0.5)- - Yes 68 84 24 TiCN
(3.5)- - - - Yes 71 79 25 Al2O3
(4)- - - - No 73 73 * 26 TiCN
(4)- - - - No 38 66 * 27 TiCN
(4)TiCNO
(0.5)Al2O3
(3)TiN
(0.5)- Yes 46 43 * 28 TiCN
(4)TiCNO
(0.5)Al2O3
(3)TiN
(0.5)- No 36 48 * 29 TiCN
(4)TiCNO
(0.5)Al2O3
(2)TiN
(0.5)- No 43 36 * 30 TiN
(1)TiCN
(4)TiCNO
(0.5)Al2O3
(2)TiN (0.5) Yes 48 65 * 31 TiN
(0.5)TiCN
(5)TiCNO
(0.1)Al2O3
(2)TiN (0.5) No 44 25 The samples marked "*" are out of the scope of the present invention.
1) Nb diffusion: "yews" indicates that the ratio of a content ratio of Nb in the region extending 0.5 µm from the surface of the cermet substrate to a content ratio of Nb in the surface of the cermet substrate, in the coating layer, is 10% or more. "No." indicates that the ratio of a content ratio of Nb in the region extending 0.5 µm from the surface of the cermet substrate to a content ratio of Nb in the surface of the cermet substrate, in the coating layer, is less than 10%. - The followings will be noted from Tables 7 to 11. That is, in Sample No. 31 in which neither Ni nor Mn was added and the content of Mn was less than 0.1% by mass, a large amount of the binder phase was dispersed into the coating layer to thereby deteriorate the hardness of the coating layer, and the sintering properties of the cermet substrate was poor, thus being susceptible to chipping. In Sample No. 28 in which Mn was not added and the content of Mn was less than 0.1% by mass, the surface region was not formed and needle-shaped abnormal particles were grown in the coating layer, thus causing severe wear and fracture. In Sample No. 26 in which the sintering temperature T1 in the step (b) was higher than 1380°C and the temperature rising rate r1 was higher than 2°C/min in the temperature range from 1200°C to 1300-1380°C, and in Sample No. 29 in which the sintering atmosphere in the step (e) was under vacuum, and in Sample No. 30 in which the sintering atmosphere in the step (e) was under vacuum, the surface region was not formed, and needle-shaped abnormal particles were grown in the coating layer, thus deteriorating wear resistance and fracture resistance. In Sample No. 27 in which the sintering temperature T1 in the step (b) was below 1300°C, exceeding 3% by mass of Mn remained in the cermet substrate after sintering, thus deteriorating wear resistance.
- On the contrary, all Samples Nos. 19 to 25, which were the cermets having the structures within the scope of the invention, exhibited excellent wear resistance and satisfactory wear resistance, thereby achieving a long tool life.
-
-
Fig. 1 is a scanning electron microscope (SEM) photograph showing an example of the Ti-based cermet of the invention, specifically a cross-section of important parts including a surface region thereof; -
Figs. 2(a) and 2(b) are scanning electron microscope (SEM) photographs showing an example of the coated cermet of the invention, specifically cross-sections of important parts including a surface region thereof, respectively; and -
Figs. 3(a) and 3(b) are schematic diagrams of an example of the cutting tool of the invention. -
- 1
- Cermet(Ti-based cermet)
- 2
- Hard phase
2a First hard phase
2b Second hard phase - 3
- Binder phase
- 5
- Surface region
- 8
- Binder phase-rich region
- 10
- Coated cermet
- 12
- Substrate
- 13
- Coating layer
- 20
- Cutting tool
- 21
- Rake face
- 22
- Flank face
- 23
- Cutting edge
- 24
- Breaker
- 25
- Recessed part
- 26
- Screw hole
Claims (13)
- A Ti-based cermet comprising at least one kind of element selected from Co and Ni; one or more kinds of substances selected from carbides, nitrides, and carbonitrides of one or more kinds of metals selected from Group 4, Group 5, and Group 6 metals of the periodic table, each of which is composed mainly of Ti; and 0.1 to 0.5% by mass of Mn, wherein in a scanning electron microscope (SEM) photograph of an arbitrary cross-section of the Ti-based cermet, a surface region is formed in which a hard phase whose interior comprises a first hard phase and a second hard phase, and a binder phase composed mainly of at least one kind of element selected from Co and Ni are observed, and the second hard phase looks whiter than the first hard phase, and the second hard phase whose content percentage is not less than 90% by area is observed in a surface part.
- The Ti-based cermet according to claim 1 wherein the surface region has a thickness of 0.5 to 5 µm.
- The Ti-based cermet according to claim 1 or 2 wherein Nb is dissolved in the second hard phase to form a solid solution, and the proportion of Nb dissolved in the second hard phase to form solid solution in the surface region is larger than the proportion of Nb dissolved in the second hard phase to form solid solution in the interior.
- A method of manufacturing a Ti-based cermet comprising the steps of:forming a mixed powder as a mixture of TiCN powder; at least one kind of powder selected from carbonate powder, nitride powder and carbonitride powder each containing one or more kinds of elements selected from W, Mo, Ta, V, Zr and Nb; at least one kind of powder selected from Co and Ni; and a total amount of 0.2 to 3.0% by mass in terms of Mn of a metal Mn powder or an Mn compound powder; andsintering the mixed powder under the following conditions:(a) temperature is increased under vacuum from room temperature to 1200°C;(b) the temperature is increased under vacuum at a temperature rising rate of 0.1 to 2°C/min from 1200°C to a sintering temperature T1 of 1330°C to 1380°C;(c) the temperature is increased at a temperature rising rate of 4 to 15°C/min from the sintering temperature T1 to a sintering temperature T2 of 1450 to 1600°C in an inert gas atmosphere of 30 to 2000 Pa;(d) the sintering temperature T2 is retained in the inert gas atmosphere of 30 to 2000 Pa for 0.5 to 2 hours; and(e) the temperature is decreased.
- A coated cermet comprising a substrate comprising the Ti-based cermet according to any one of claims 1 to 3, and a coating layer coating a surface of the substrate, wherein the content ratio of the binder phase in the surface region of the substrate is not more than 3% by mass, and the coating layer is formed by chemical vapor deposition.
- The coated cermet according to claim 5 wherein a binder phase-rich region exists in a region extending 1 to 10 µm from immediately below the surface region, at 1.1 to 2.0 in terms of a ratio (A/B) of a content ratio A of the binder phase to a content ratio B of the binder phase in the interior of the substrate.
- The coated cermet according to claim 5 or 6 wherein the content ratio of Ni in the interior of the substrate is 0.1 to 0.5 in terms of Ni/(Ni+Co) ratio.
- The coated cermet according to any one of claims 5 to 7 wherein the content percentage of N in the surface region is larger than that of the interior of a sintered body.
- The coated cermet according to any one of claims 5 to 8 wherein the coating layer is composed of a columnar crystal extending vertically with respect to the surface of the substrate, and the columnar crystal has an average crystal width of 0.1 to 1 µm.
- The coated cermet according to claim 9 wherein the columnar crystal is TiCN.
- The coated cermet according to claim 10 wherein the coating layer has its strongest peak in (422) plane in an X-ray diffraction measurement.
- A cutting tool comprising the Ti-based cermet according to any one of claims 1 to 3, or the coated cermet according to any one of claims 5 to 11, wherein a cutting edge is formed along a cross ridge part between a rake face and a flank face.
- The cutting tool according to claim 12 wherein in the residual stress exerted in a σ11 direction (namely, a direction to connect between the center of the rake face and the center of the cutting edge nearmost a measured point) measured in the rake face by 2D method, the second hard phase is subjected to compressive stress of not less than 150 MPa (σ11 ≤ -150 MPa).
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JP2007195910 | 2007-07-27 | ||
JP2007195909 | 2007-07-27 | ||
JP2007306887 | 2007-11-28 | ||
PCT/JP2008/063400 WO2009017053A1 (en) | 2007-07-27 | 2008-07-25 | Titanium-base cermet, coated cermet, and cutting tool |
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EP2177639A1 true EP2177639A1 (en) | 2010-04-21 |
EP2177639A4 EP2177639A4 (en) | 2012-03-21 |
EP2177639B1 EP2177639B1 (en) | 2020-03-04 |
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EP (1) | EP2177639B1 (en) |
JP (1) | JP5328653B2 (en) |
CN (1) | CN101790594B (en) |
WO (1) | WO2009017053A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2687310A1 (en) * | 2011-03-15 | 2014-01-22 | Sumitomo Electric Hardmetal Corp. | Cutting edge-replaceable cutting tool |
EP2752263A1 (en) * | 2011-08-29 | 2014-07-09 | Kyocera Corporation | Cutting tool |
US8808871B2 (en) | 2009-11-26 | 2014-08-19 | Kyocera Corporation | Rotation tool |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
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JP5340028B2 (en) * | 2009-05-18 | 2013-11-13 | 京セラ株式会社 | Cutting tools |
JP5436083B2 (en) * | 2009-07-29 | 2014-03-05 | 京セラ株式会社 | Cermet sintered body and cutting tool |
JP5409199B2 (en) * | 2009-08-27 | 2014-02-05 | 京セラ株式会社 | Cutting tools |
JP5279099B1 (en) * | 2012-03-14 | 2013-09-04 | 住友電工ハードメタル株式会社 | Cutting tools |
WO2014208447A1 (en) * | 2013-06-28 | 2014-12-31 | 京セラ株式会社 | Cermet, and method for manufacturing same, as well as cutting tool |
CN103320667B (en) * | 2013-07-18 | 2015-06-17 | 成都成量工具集团有限公司 | Cemented carbide and its preparation method |
KR102178426B1 (en) * | 2016-04-13 | 2020-11-13 | 교세라 가부시키가이샤 | Cutting inserts and cutting tools |
CN107923006B (en) * | 2016-05-02 | 2019-08-30 | 住友电气工业株式会社 | Hard alloy and cutting element |
CN106346002A (en) * | 2016-11-16 | 2017-01-25 | 湖南文理学院 | Cemented carbide sintering process |
WO2018181036A1 (en) * | 2017-03-29 | 2018-10-04 | 京セラ株式会社 | Cutting insert and cutting tool provided with same |
KR101901725B1 (en) | 2017-07-11 | 2018-11-22 | 한국야금 주식회사 | Sintered alloy for cutting tools and cutting tools |
CN113564399B (en) * | 2021-07-28 | 2022-10-14 | 崇义章源钨业股份有限公司 | Gradient-structure TiCN-based metal ceramic and method for improving coating binding force thereof |
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US6190762B1 (en) * | 1996-01-15 | 2001-02-20 | Widia Gmbh | Composite body and method of producing the same |
EP1462534A1 (en) * | 2003-03-27 | 2004-09-29 | Toshiba Tungaloy Co., Ltd. | Compositionally graded sintered alloy and method of producing the same |
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JP4280048B2 (en) * | 2002-09-27 | 2009-06-17 | 京セラ株式会社 | Method for producing TiCN-based cermet |
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2008
- 2008-07-25 EP EP08791644.1A patent/EP2177639B1/en active Active
- 2008-07-25 JP JP2009525370A patent/JP5328653B2/en active Active
- 2008-07-25 WO PCT/JP2008/063400 patent/WO2009017053A1/en active Application Filing
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US6190762B1 (en) * | 1996-01-15 | 2001-02-20 | Widia Gmbh | Composite body and method of producing the same |
EP1462534A1 (en) * | 2003-03-27 | 2004-09-29 | Toshiba Tungaloy Co., Ltd. | Compositionally graded sintered alloy and method of producing the same |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8808871B2 (en) | 2009-11-26 | 2014-08-19 | Kyocera Corporation | Rotation tool |
EP2687310A1 (en) * | 2011-03-15 | 2014-01-22 | Sumitomo Electric Hardmetal Corp. | Cutting edge-replaceable cutting tool |
EP2687310A4 (en) * | 2011-03-15 | 2014-09-03 | Sumitomo Elec Hardmetal Corp | Cutting edge-replaceable cutting tool |
EP2752263A1 (en) * | 2011-08-29 | 2014-07-09 | Kyocera Corporation | Cutting tool |
EP2752263A4 (en) * | 2011-08-29 | 2015-02-25 | Kyocera Corp | Cutting tool |
Also Published As
Publication number | Publication date |
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EP2177639A4 (en) | 2012-03-21 |
JPWO2009017053A1 (en) | 2010-10-21 |
WO2009017053A1 (en) | 2009-02-05 |
JP5328653B2 (en) | 2013-10-30 |
CN101790594B (en) | 2013-06-19 |
CN101790594A (en) | 2010-07-28 |
EP2177639B1 (en) | 2020-03-04 |
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