EP2177639B1 - Titanium-base cermet, coated cermet, and cutting tool - Google Patents

Titanium-base cermet, coated cermet, and cutting tool Download PDF

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Publication number
EP2177639B1
EP2177639B1 EP08791644.1A EP08791644A EP2177639B1 EP 2177639 B1 EP2177639 B1 EP 2177639B1 EP 08791644 A EP08791644 A EP 08791644A EP 2177639 B1 EP2177639 B1 EP 2177639B1
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Prior art keywords
cermet
hard phase
powder
temperature
surface region
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German (de)
English (en)
French (fr)
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EP2177639A4 (en
EP2177639A1 (en
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Takashi Tokunaga
Hideyoshi Kinoshita
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Kyocera Corp
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Kyocera Corp
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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 Al 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 present invention provides a Ti-based cermet according to claim 1.
  • a further advantageous embodiment of the Ti-based cermet according to the present invention is disclosed in dependent claim 2.
  • the present invention further provides a method of manufacturing a Ti-based cermet according to claim 3.
  • the present invention further provides a coated cermet according to claim 4. Further advantageous embodiments of the coated cermet according to the present invention are disclosed in dependent claims 5-10.
  • the present invention further provides a cutting tool according to claim 11.
  • a further advantageous embodiment of the cutting tool according to the present invention is disclosed in dependent claim 12.
  • 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
  • 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, 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 B s 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 C i 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 carbide 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 2 ) 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).
  • 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.
  • Cutting performance 1 12 1.9 TiCN(3.5)+Al 2 O 3 (4)+TiN(0.5) 80 13 2 TiCN(4)+Al 2 O 3 (2) 71 14 2.3 TiAlN(3) 65 15 1.8 TiCN(3.5)+Al 2 O 3 (4)+TiN(0.5) 85 16 1.7 TiCN(4)+Al 2 O 3 (2) 74 17 1.5 Al 2 O 3 (4) 68 18 1.2 TiCN(3) 63
  • the samples marked "*" are out of the scope of the present invention.
  • Sample No. Material composition 1) TiCN WC TiN TaC MoC NbC ZrC VC Ni Co Ni/(Co+Ni) MnCO 3 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
  • Binder phase-rich region Surface region Average particle diameter of hard phase ( ⁇ m) Mn ratio (% by mass) Content ratio B of binder phase (% by mass) Content ratio A of binder phase (% by mass) A/B Thickness ( ⁇ m) Ratio of binder phase (% by mass) Thickness ( ⁇ m) 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 .
  • 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.
  • Nb diffusion “Yes” 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Powder Metallurgy (AREA)
  • Chemical Vapour Deposition (AREA)
  • Ceramic Products (AREA)
EP08791644.1A 2007-07-27 2008-07-25 Titanium-base cermet, coated cermet, and cutting tool Active EP2177639B1 (en)

Applications Claiming Priority (4)

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JP2007195909 2007-07-27
JP2007195910 2007-07-27
JP2007306887 2007-11-28
PCT/JP2008/063400 WO2009017053A1 (ja) 2007-07-27 2008-07-25 Ｔｉ基サーメットおよび被覆サーメット並びに切削工具

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JP5340028B2 (ja) * 2009-05-18 2013-11-13 京セラ株式会社 切削工具
JP5436083B2 (ja) * 2009-07-29 2014-03-05 京セラ株式会社 サーメット焼結体および切削工具
JP5409199B2 (ja) * 2009-08-27 2014-02-05 京セラ株式会社 切削工具
JP5355712B2 (ja) * 2009-11-26 2013-11-27 京セラ株式会社 回転工具
JP5062541B2 (ja) * 2011-03-15 2012-10-31 住友電工ハードメタル株式会社 刃先交換型切削工具
CN103813875B (zh) * 2011-08-29 2015-12-23 京瓷株式会社 切削工具
JP5279099B1 (ja) 2012-03-14 2013-09-04 住友電工ハードメタル株式会社 切削工具
WO2014208447A1 (ja) * 2013-06-28 2014-12-31 京セラ株式会社 サーメットおよびその製造方法並びに切削工具
CN103320667B (zh) * 2013-07-18 2015-06-17 成都成量工具集团有限公司 一种硬质合金及其制备方法
KR102178426B1 (ko) * 2016-04-13 2020-11-13 교세라 가부시키가이샤 절삭 인서트 및 절삭 공구
CN107923006B (zh) * 2016-05-02 2019-08-30 住友电气工业株式会社 硬质合金和切削工具
CN106346002A (zh) * 2016-11-16 2017-01-25 湖南文理学院 一种硬质合金烧结工艺
JP6955549B2 (ja) * 2017-03-29 2021-10-27 京セラ株式会社 切削インサート及びこれを備えた切削工具
KR101901725B1 (ko) 2017-07-11 2018-11-22 한국야금 주식회사 절삭공구용 소결합금과 절삭공구
CN113564399B (zh) * 2021-07-28 2022-10-14 崇义章源钨业股份有限公司 一种梯度结构TiCN基金属陶瓷及提高其涂层结合力的方法

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JP2004292905A (ja) * 2003-03-27 2004-10-21 Tungaloy Corp 傾斜組成燒結合金及びその製造方法

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CN101790594B (zh) 2013-06-19
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CN101790594A (zh) 2010-07-28
JPWO2009017053A1 (ja) 2010-10-21
WO2009017053A1 (ja) 2009-02-05

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