EP4372115B1 - Carbure cémenté et outil de coupe utilisant celui-ci - Google Patents

Carbure cémenté et outil de coupe utilisant celui-ci

Info

Publication number
EP4372115B1
EP4372115B1 EP22943731.4A EP22943731A EP4372115B1 EP 4372115 B1 EP4372115 B1 EP 4372115B1 EP 22943731 A EP22943731 A EP 22943731A EP 4372115 B1 EP4372115 B1 EP 4372115B1
Authority
EP
European Patent Office
Prior art keywords
phase
cemented carbide
less
mass
vanadium
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.)
Active
Application number
EP22943731.4A
Other languages
German (de)
English (en)
Other versions
EP4372115A4 (fr
EP4372115A1 (fr
Inventor
Nobuo MIYASAKA
Takahiro Yamakawa
Kazuhiro Hirose
Katsuya Uchino
Tsuyoshi Yamamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Electric Hardmetal Corp
Original Assignee
Sumitomo Electric Hardmetal Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Electric Hardmetal Corp filed Critical Sumitomo Electric Hardmetal Corp
Publication of EP4372115A1 publication Critical patent/EP4372115A1/fr
Publication of EP4372115A4 publication Critical patent/EP4372115A4/fr
Application granted granted Critical
Publication of EP4372115B1 publication Critical patent/EP4372115B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C22C29/06—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 carbides, but not containing other metal compounds
    • C22C29/08—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 carbides, but not containing other metal compounds based on tungsten carbide
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/026—Spray drying of solutions or suspensions
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • 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
    • C22C29/06—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 carbides, but not containing other metal compounds
    • C22C29/067—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 carbides, but not containing other metal compounds comprising a particular metallic binder
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • 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
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/20—Use of vacuum
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/10—Carbide
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • C22C2200/00—Crystalline structure

Definitions

  • the present invention relates to a cemented carbide and a cutting tool using the same.
  • a so-called fine-grained cemented carbide in which a hard phase consists of a tungsten carbide particle having an average particle diameter of 1 ⁇ m or less, is used as the cemented carbide used in a tool such as a small diameter drill (for example, PTL 1 to PTL 3).
  • MASURU KAWAKAMI et a1 describes in "Effect of Sintering Cooling Rate on V Segregation Amount at WC/Co Interface in VC-doped WC-Co Fine-Grained Hardmetal", J. JPN. SOC.
  • POWDER POWDER METALLURGY vol. 51, no. 8, 15 August 2004 (2004-08-15), pages 576-585, XP093199791 and in " Segregation layers of grain growth inhibitors at WC/WC interfaces in VC-doped submicron-grained WC-Co cemented carbides", INTERNATIONAL JOURNAL OF REFRACTORY METALS AND HARD MATERIALS, vol. 52, 26 June 2015 (2015-06-26), pages 229-234, XP093199796 , a fine grained cemented carbide.
  • the cemented carbide according to the present invention is defined in claim 1.
  • the cutting tool according to the present invention is a cutting tool including a cutting edge formed from the above cemented carbide.
  • an object of the present invention is to provide a cemented carbide that can provide a cutting tool that has a long tool life, particularly even when used as a material for a cutting tool used for microfabrication of a printed circuit board, and a cutting tool including the same.
  • cemented carbide according to the present invention it is possible to provide a cutting tool that has a long tool life, particularly even when used for microfabrication of a printed circuit board.
  • the cemented carbide according to the present invention is defined in claim 1.
  • cemented carbide according to the present invention it is possible to provide a cutting tool that has a long tool life, particularly even when used for microfabrication of a printed circuit board.
  • the cemented carbide includes a third phase consisting of a third phase particle including 10 atomic % or more of vanadium,
  • the maximum value of the chromium content in the interface region is preferably 20 atomic % or less.
  • the WC particle is unlikely to fall off because of a decrease in interface strength, and a cutting tool using the cemented carbide can have excellent wear resistance and breakage resistance.
  • the cutting tool according to the present invention is a cutting tool including a cutting edge formed from the cemented carbide described above.
  • the cutting tool according to the present invention can have a long tool life, particularly even when used for microfabrication of a printed circuit board.
  • the expression of a range in the format "A to B" means the upper limit and the lower limit of the range (that is, A or more and B or less), and when no unit is written in A and a unit is only written in B, the unit for A and the unit for B are the same.
  • any one numerical value written as the lower limit and any one numerical value written as the upper limit shall also be disclosed.
  • a1 or more, b1 or more, and c1 or more are written as the lower limit, and a2 or less, b2 or less, and c2 or less are written as the upper limit, a1 or more and a2 or less, a1 or more and b2 or less, a1 or more and c2 or less, b1 or more and a2 or less, b1 or more and b2 or less, b1 or more and c2 or less, c1 or more and a2 or less, c1 or more and b2 or less, and c1 or more and c2 or less shall be disclosed.
  • the chemical formula shall include all conventionally known atomic ratios, and should not necessarily be limited only to those within the stoichiometric range.
  • crystallographic index that is negative is usually expressed by adding a "-" (bar) above the number, but in the present disclosure, a negative sign is added in front of the number.
  • the cemented carbide according to one embodiment of the present invention (hereinafter also referred to as “the present embodiment”) is according to claim 1.
  • cemented carbide According to the cemented carbide according to the present embodiment, it is possible to provide a cutting tool that has a long tool life, particularly even when used for microfabrication of a printed circuit board. Although the reason for this is not clear, it is presumed as described in (i) to (v) below.
  • the cemented carbide according to the present embodiment includes a first phase composed of a tungsten carbide particle and a second phase including cobalt as a main component.
  • the total content of the first phase and the second phase in the cemented carbide is 97% by volume or more and 100% by volume or less.
  • the cemented carbide has high hardness and strength, and a cutting tool using the cemented carbide can have excellent wear resistance and breakage resistance.
  • the lower limit of the total content of the first phase and the second phase in the cemented carbide is 97% by volume or more, preferably 98% by volume or more, and more preferably 99% by volume or more.
  • the upper limit of the total content of the first phase and the second phase in the cemented carbide is 100% by volume or less.
  • the total content of the first phase and the second phase in the cemented carbide is 97% by volume or more and 100% by volume or less, preferably 98% by volume or more and 100% by volume or less, and further preferably 99% by volume or more and 100% by volume or less.
  • the cemented carbide preferably consists of a first phase and a second phase.
  • the lower limit of the content of the first phase in the cemented carbide is preferably 82% by volume or more, more preferably 85% by volume or more, and further preferably 87% by volume or more.
  • the upper limit of the content of the first phase in the cemented carbide is less than 100% by volume, and from the viewpoint of improving the breakage resistance, the upper limit is preferably 95% by volume or less, more preferably 94% by volume or less, further preferably 93% by volume or less, and more further preferably 90% by volume or less.
  • the content of the first phase in the cemented carbide is preferably 82% by volume or more and 95% by volume or less, more preferably 85% by volume or more and 93% by volume or less, and further preferably 87% by volume or more and 90% by volume or less.
  • the lower limit of the content of the second phase in the cemented carbide is preferably 5% by volume or more, more preferably 7% by volume or more, and further preferably 9% by volume or more.
  • the upper limit of the content of the second phase in the cemented carbide is preferably 18% by volume or less, more preferably 16% by volume or less, and further preferably 14% by volume or less.
  • the content of the second phase in the cemented carbide is preferably 5% by volume or more and 18% by volume or less, more preferably 7% by volume or more and 16% by volume or less, and further preferably 9% by volume or more and 14% by volume or less.
  • the cemented carbide according to the present embodiment can include a third phase consisting of a third phase particle including 10 atomic % or more of vanadium.
  • the content of the third phase in the cemented carbide is preferably more than 0% by volume and 1% by volume or less. According to this, a decrease in the breakage resistance of the cemented carbide due to the presence of the third phase is suppressed.
  • the lower limit of the content of the third phase in the cemented carbide is preferably more than 0% by volume.
  • the upper limit of the content of the third phase in the cemented carbide is preferably 1% by volume or less, more preferably 0.8% by volume or less, and further preferably 0.7% by volume or less.
  • the content of the third phase in the cemented carbide is preferably more than 0% by volume and 1% by volume or less, more preferably more than 0% by volume and 0.8% by volume or less, and further preferably more than 0% by volume and 0.7% by volume or less.
  • the cemented carbide according to the present embodiment can include an unavoidable impurity in addition to the first phase, the second phase, and the third phase as long as the effect of the present disclosure is exhibited.
  • the unavoidable impurity include iron, molybdenum, and sulfur.
  • the content of the unavoidable impurity in the cemented carbide is preferably less than 0.1% by mass.
  • the content of the unavoidable impurity in the cemented carbide is measured by ICP emission spectroscopy (Inductively Coupled Plasma) Emission Spectroscopy (measuring apparatus: "ICPS-8100" (trademark) of Shimadzu Corporation).
  • the content of each of the first phase, the second phase, and the third phase in the cemented carbide is measured according to the following procedures (A1) to (D1).
  • a thin sample having a thickness of 50 nm or less is cut out from the cemented carbide by using an ion slicer or the like, and the surface of the thin sample is mirror-finished.
  • a mirror finishing method include a method involving polishing with a diamond paste, a method involving using a focused ion beam apparatus (FIB apparatus), a method involving using a cross section polisher apparatus (CP apparatus), and a method combining these.
  • Elemental mapping of tungsten (W), cobalt (Co), chromium (Cr), and vanadium (V) is carried out on the mirror-finished surface of the thin sample by EDX (Energy Dispersive X-ray Spectroscopy) accompanying Transmission Electron Microscopy (TEM) to obtain a mapping image of each element.
  • the measurement conditions are an observation magnification of 100,000 times and an acceleration voltage of 200 kV.
  • the number of pixels for element mapping is 125 ⁇ 125.
  • the elemental mapping images in five fields of view are prepared.
  • the photographing regions of the elemental mapping images in the five fields of view are different from each other. The photographing regions can be set arbitrarily.
  • a region including 70 atomic % or more of tungsten based on the sum of the numbers of atoms of tungsten (W), cobalt (Co), chromium (Cr), and vanadium (V) corresponds to a region in which a first phase is present.
  • a region including 70 atomic % or more of cobalt based on the sum of the numbers of atoms of tungsten, cobalt, chromium, and vanadium corresponds to a region in which a second phase is present.
  • a region including 10 atomic % or more of vanadium based on the sum of the numbers of atoms of tungsten, cobalt, chromium, and vanadium corresponds to a region in which a third phase is present.
  • the vanadium concentrated layer present in an interface region between a tungsten carbide particle and a second phase and the vanadium concentrated layer present in the interface region between second phases are each in the form of a layer having a constant thickness on the order of several atoms (for example, about 1 to 5 atoms), and thus are not detected at an observation magnification of 100,000 times.
  • C1 Image analysis software (ImageJ, version 1.51j8: https://imagej.nih.gov/ij/) is used on the elemental mapping images of each element in the five fields of view obtained in (B1) above to measure the area % of each of the first phase, the second phase, and the third phase with all the fields of view as the denominator.
  • the average value of the area % of the first phase obtained in the five fields of view is calculated.
  • the average value corresponds to the content (% by volume) of the first phase in the cemented carbide.
  • the average value of the area % of the second phase obtained in the five fields of view is calculated.
  • the average value corresponds to the content (% by volume) of the second phase in the cemented carbide.
  • the average value of the area % of the third phase obtained in the five fields of view is calculated.
  • the average value corresponds to the content (% by volume) of the third phase in the cemented carbide.
  • the first phase is composed of tungsten carbide particles.
  • the tungsten carbide particles include not only "pure WC particles (including WC containing no impurity element and also WC in which the content of an impurity element is below the detection limit)" but also "WC particles inside which an impurity element is intentionally or unavoidably contained as long as the effect of the present invention is not impaired.”
  • the content of an impurity in the first phase (when two or more elements constitute the impurity, the total concentration of the elements) is less than 0.1% by mass.
  • the content of the impurity element in the first phase is measured by ICP emission spectrometry.
  • the average value of the equivalent circle diameter of the tungsten carbide particles (hereinafter also referred to as the "average particle diameter of the WC particles") is 0.2 ⁇ m or more and 0.8 ⁇ m or less.
  • the cemented carbide has high hardness, and a cutting tool using the cemented carbide can have excellent wear resistance.
  • the cemented carbide has excellent strength, and the cutting tool using the cemented carbide can have excellent breakage resistance.
  • the average value of the equivalent circle diameter of the tungsten carbide particles means the number-based arithmetic mean of the equivalent circle diameter of the WC particles measured on a cross section of the cemented carbide.
  • the lower limit of the average particle diameter of the WC particles is 0.2 ⁇ m or more, more preferably 0.3 ⁇ m or more, and further preferably 0.4 ⁇ m or more.
  • the upper limit of the average particle diameter of the WC particles is 0.8 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.6 ⁇ m or less, and further preferably 0.4 ⁇ m or less.
  • the average particle diameter of the WC particles is 0.2 ⁇ m or more and 0.8 ⁇ m or less, more preferably 0.2 ⁇ m or more and 0.6 ⁇ m or less, and further preferably 0.2 ⁇ m or more and 0.5 ⁇ m or less.
  • the average value of the equivalent circle diameter of the tungsten carbide particles is measured by the following procedures (A2) to (D2).
  • A2 An arbitrary cross section of the cemented carbide is mirror-finished.
  • Examples of a mirror finishing method include a method involving polishing with a diamond paste, a method involving using a focused ion beam apparatus (FIB apparatus), a method involving using a cross section polisher apparatus (CP apparatus), and a method combining these.
  • FIB apparatus focused ion beam apparatus
  • CP apparatus cross section polisher apparatus
  • (B2) A worked surface of the cemented carbide is photographed by using a scanning electron microscope ("S-3400N” manufactured by Hitachi High-Technologies Corporation). Three photographed images are prepared. The photographing regions of the three photographed images are different from each other. The photographing regions can be set arbitrarily. The conditions are an observation magnification of 10,000 times, an acceleration voltage of 10 kV, and a backscattered electron image.
  • (C2) The three backscattered electron images obtained in (B2) above were imported into a computer and subjected to binarization processing by using image analysis software (ImageJ, version 1.51j8: https://imagej.nih.gov/ij/).
  • the binarization processing is executed under the conditions preset in the image analysis software by pressing the "Make Binary" display on the computer screen after the images are imported.
  • the first phase and the second phase can be distinguished by color shading. For example, in an image after binarization processing, the first phase is shown as a black region, and the second phase is shown as a white region.
  • the cemented carbide includes a third phase, the third phase is shown in the same color tone (white) as the second phase in an image after binarization processing.
  • the above image analysis software is used on the three obtained photographing images to measure the equivalent circle diameter (Heywood diameter: equal area equivalent circle diameter) of each of all tungsten carbide particles (black regions) in the three photographing images.
  • the number-based arithmetic mean value of the equivalent circle diameter of all tungsten carbide particles in three measurement fields of view is calculated.
  • the arithmetic mean value corresponds to the average value of the equivalent circle diameter of the WC particles.
  • the second phase includes cobalt as a main component.
  • the second phase is a binder phase that binds the tungsten carbide particles in the first phase to each other.
  • the "second phase including cobalt as a main component” means that in the second phase, the percentage of cobalt to all of tungsten, chromium, vanadium, and cobalt is 70% by mass or more.
  • the lower limit of the percentage of cobalt to all of tungsten, chromium, vanadium, and cobalt is 70% by mass or more, or can be 80% by mass or more, or 90% by mass or more.
  • the upper limit of the percentage can be less than 100% by mass.
  • the percentage is 70% by mass or more and can be less than 100% by mass, or can be 80% by mass or more and less than 100% by mass, or 90% by mass or more and less than 100% by mass.
  • the second phase in the cemented carbide according to the present disclosure as long as the percentage of cobalt to all of tungsten, chromium, vanadium, and cobalt is 70% by mass or more, the second phase functions as a binder phase, and the effect of the present disclosure is not impaired.
  • the percentage of cobalt to all of tungsten, chromium, vanadium, and cobalt in the second phase can be measured by ICP emission spectrometry (equipment used: "ICPS-8100" (trademark) manufactured by Shimadzu Corporation).
  • the second phase includes chromium (Cr), tungsten (W), vanadium (V), iron (Fe), nickel (Ni), carbon (C), and the like.
  • the second phase can consist of cobalt and at least one selected from the group consisting of chromium, tungsten, vanadium, iron, nickel, and carbon.
  • the second phase can consist of cobalt, at least one selected from the group consisting of chromium, tungsten, vanadium, iron, nickel, and carbon, and an impurity.
  • the impurity include manganese (Mn), magnesium (Mg), calcium (Ca), molybdenum (Mo), sulfur (S), titanium (Ti), and aluminum (Al).
  • the cemented carbide according to the present embodiment includes a third phase consisting of a third phase particle including 10 atomic % or more of vanadium, the content of the third phase in the cemented carbide is more than 0% by volume and 1% by volume or less, and the maximum value of the equivalent circle diameter of the third phase particle is 0.5 ⁇ m or less. According to this, there is no coarse third phase particle having an equivalent circle diameter of more than 0.5 ⁇ m, which can become a starting point for breakage, and thus the breakage resistance of a cutting tool using the cemented carbide is improved.
  • the third phase consists of a third phase particle including 10 atomic % or more of vanadium. It is presumed that the third phase is a fine precipitation phase of vanadium (V) derived from vanadium carbide (VC) added as a grain growth inhibitor in a step of manufacturing a cemented carbide.
  • V vanadium
  • VC vanadium carbide
  • a vanadium concentrated layer having a constant thickness on the order of several atoms does not correspond to the third phase.
  • the "third phase particle including 10 atomic % or more of vanadium” means that in the third phase particle, the percentage of vanadium to all of tungsten, chromium, vanadium, and cobalt is 10% by mass or more.
  • the third phase particle can include tungsten, cobalt, chromium, carbon, and the like.
  • the third phase particle can consist of vanadium and at least one selected from the group consisting of tungsten, cobalt, chromium, and carbon.
  • the third phase particle can consist of vanadium, at least one selected from the group consisting of tungsten, cobalt, chromium, and carbon, and an impurity.
  • the impurity include iron, nickel, manganese, niobium, magnesium, calcium, molybdenum, sulfur, titanium, and aluminum.
  • the lower limit of the percentage of vanadium to all of tungsten, chromium, vanadium, and cobalt is 10 atomic % or more, and can be 20 atomic % or more, or 30 atomic % or more.
  • the upper limit of the percentage can be 100 atomic % or less.
  • the percentage can be 10 atomic % or more and 100 atomic % or less, 20 atomic % or more and 100 atomic % or less, or 30 atomic % or more and 100 atomic % or less.
  • the method for measuring the percentage of vanadium to all of tungsten, chromium, vanadium, and cobalt in the third phase particle is as follows.
  • elemental mapping analysis is carried out according to the same procedures as (A1) to (B1) in the method for measuring the content of each of the first phase, the second phase, and the third phase in the cemented carbide, to obtain elemental mapping images in five fields of view.
  • a region including 10 atomic % or more of vanadium based on the sum of the numbers of atoms of tungsten, cobalt, chromium, and vanadium is identified. This region corresponds to a third phase particle.
  • the identified third phase particle is magnified to an observation magnification of 2,000,000 times, and the percentage of the number of atoms of vanadium to the sum of the numbers of atoms of tungsten, cobalt, chromium, and vanadium in the third phase particle (hereinafter also referred to as the "vanadium content of the third phase particle) is measured by EDX point analysis.
  • the measurement is carried out on five third phase particles.
  • the average value of the vanadium content of the five third phase particles is calculated.
  • the average value corresponds to the percentage of vanadium to all of tungsten, chromium, vanadium, and cobalt in the third phase particle in the present disclosure.
  • the maximum value of the equivalent circle diameter of the third phase particle (hereinafter also referred to as the "maximum value of the third phase particle") is 0.5 ⁇ m or less.
  • the upper limit of the maximum value of the equivalent circle diameter of the third phase particle is 0.5 ⁇ m or less, preferably 0.4 ⁇ m or less, preferably 0.3 ⁇ m or less, more preferably 0.2 ⁇ m or less, and further preferably 0.1 ⁇ m or less.
  • the lower limit of the maximum value of the equivalent circle diameter of the third phase particle is not particularly limited, and can be more than 0 ⁇ m.
  • the maximum value of the equivalent circle diameter of the third phase particle is preferably more than 0 ⁇ m and 0.5 ⁇ m or less, preferably more than 0 ⁇ m and 0.4 ⁇ m or less, preferably more than 0 ⁇ m and 0.3 ⁇ m or less, more preferably more than 0 ⁇ m and 0.2 ⁇ m or less, and further preferably more than 0 ⁇ m and 0.1 ⁇ m or less.
  • the maximum value of the equivalent circle diameter of the third phase particle is measured by the following procedures (A3) to (B3).
  • Elemental mapping images in five fields of view are analyzed by using the above image analysis software (ImageJ) according to the same procedures as (A1) to (C1) in the method for measuring the content of each of the first phase, the second phase, and the third phase in the cemented carbide described above, to identify the third phase.
  • ImageJ image analysis software
  • the equivalent circle diameter (Heywood diameter: equal area equivalent circle diameter) of each of all third phase particles in the five measurement regions is measured by using the above image analysis software.
  • the maximum value of the equivalent circle diameter of all the third phase particles in the five measurement fields of view corresponds to the maximum value of the equivalent circle diameter of the third phase particle in the present disclosure.
  • the cobalt content of the cemented carbide according to the present embodiment is 3% by mass or more and 10% by mass or less. According to this, the cemented carbide has high hardness and strength. A cutting tool using the cemented carbide can have excellent wear resistance and breakage resistance.
  • the lower limit of the cobalt content of the cemented carbide is 3% by mass or more, and preferably 4% by mass or more.
  • the upper limit of the cobalt content of the cemented carbide is 10% by mass or less, preferably 9% by mass or less, and more preferably 8% by mass or less.
  • the cobalt content of the cemented carbide is preferably 4% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 9% by mass or less, and further preferably 3% by mass or more and 8% by mass or less.
  • the cobalt content of the cemented carbide is measured by ICP emission spectrometry.
  • the vanadium content of the cemented carbide according to the present embodiment is 0.01% by mass or more and 0.30% by mass or less. According to this, the generation of a coarse WC particle is suppressed, and the structure of the cemented carbide is densified. Therefore, the cemented carbide has excellent hardness and strength, and a cutting tool using the cemented carbide can have excellent wear resistance and breakage resistance.
  • the lower limit of the vanadium content of the cemented carbide is 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.10% by mass or more.
  • the upper limit of the vanadium content of the cemented carbide is 0.30% by mass or less, and preferably 0.20% by mass or less.
  • the vanadium content of the cemented carbide is preferably 0.01% by mass or more and 0.20% by mass or less, and further preferably 0.10% by mass or more and 0.20% by mass or less.
  • the vanadium content of the cemented carbide is measured by ICP emission spectrometry.
  • the cemented carbide according to the present embodiment includes chromium (Cr).
  • the chromium content of the cemented carbide according to the present embodiment is 0.2% by mass or more and 0.8% by mass or less Chromium has the action of suppressing grain growth of a tungsten carbide particle.
  • Chromium has the action of suppressing grain growth of a tungsten carbide particle.
  • the lower limit of the chromium content of the cemented carbide is 0.2% by mass or more, and preferably 0.3% by mass or more.
  • the upper limit of the chromium content of the cemented carbide is 0.8% by mass or less, and preferably 0.5% by mass or less.
  • the chromium content of the cemented carbide is 0.2% by mass or more and 0.8% by mass or less, and preferably 0.3% by mass or more and 0.5% by mass or less.
  • the chromium content of the cemented carbide is measured by ICP emission spectrometry.
  • the maximum value of the vanadium content in an interface region between the (0001) crystal plane of a tungsten carbide particle and a second phase (hereinafter also referred to as a "WC/second phase interface region") is 1 atomic % or more and 15 atomic % or less. According to this, the formation of a vanadium concentrated layer in which vanadium is present in a concentrated manner is suppressed in the interface region. Because of this, a decrease in the interface strength between the WC particle and the second phase due to the vanadium concentrated layer is suppressed.
  • the WC particle is unlikely to fall off because of a decrease in interface strength, and a cutting tool using the cemented carbide can have excellent wear resistance and breakage resistance.
  • a conventional cemented carbide has a large amount of a vanadium concentrated layer at the interface, which tends to reduce the interface strength.
  • the maximum value of the vanadium content in the WC/second phase interface region is 15 atomic % or less
  • the maximum value of the vanadium content in the WC/WC interface region is also 15 atomic % or less, and the formation of a vanadium concentrated layer is suppressed in the WC/WC interface region. Because of this, a decrease in the interface strength between WC particles due to the vanadium concentrated layer is also suppressed.
  • the upper limit of the maximum value of the vanadium content in the WC/second phase interface region is 15 atomic % or less, preferably 14 atomic % or less, more preferably 13 atomic % or less, further preferably 12 atomic % or less, and more further preferably 11 atomic % or less.
  • the lower limit of the maximum value of the vanadium content in the WC/second phase interface region is 1 atomic % or more, or preferably 2 atomic % or more.
  • the maximum value of the vanadium content in the WC/second phase interface region is 1 atomic % or more and 15 atomic % or less, preferably 1 atomic % or more and 12 atomic % or less, further preferably 2 atomic % or more and 15 atomic % or less, and more further preferably 2 atomic % or more and 12 atomic % or less.
  • the maximum value of the vanadium content in the WC/second phase interface region is measured by the following procedures (A4) to (D4).
  • a thin sample having a thickness of 50 nm or less is cut out from the cemented carbide by using an ion slicer or the like.
  • the surface of the thin sample is mirror-finished.
  • Examples of a mirror finishing method include a method involving polishing with a diamond paste, a method involving using a focused ion beam apparatus (FIB apparatus), a method involving using a cross section polisher apparatus (CP apparatus), and a method combining these.
  • Fig. 1 schematically shows a transmission electron microscope (TEM) image of the thin sample.
  • TEM transmission electron microscope
  • a measurement region R for the line analysis is a rectangular region indicated by a sign R.
  • a portion of the interface between the (0001) crystal plane of a WC particle 1 and a second phase 2 adjacent to the (0001) crystal plane of WC particle 1 which is approximately straight and in which the length of the approximately straight portion is 25 nm or more is selected.
  • the line analysis is carried out in a direction perpendicular to the approximately straight portion (direction of an arrow B in Fig. 1 ).
  • the distance for the line analysis is 20 nm from the approximately straight portion as the center to each of the WC particle side and the second phase side.
  • the width for the line analysis is 25 nm, and the step interval is 0.4 nm.
  • measurement region R for the line analysis is set such that a third phase particle 3 is not included.
  • the maximum value of the percentage (atomic %) of vanadium is calculated when the sum of the numbers of atoms of W, Cr, V, and Co is 100 atomic %.
  • the maximum value is defined as the maximum value of the vanadium content in the interface region between the (0001) crystal plane of the WC particle and the second phase.
  • the measurement in (C4) above is carried out in an interface region between the (0001) crystal plane of each of five different WC particles and a second phase.
  • the average value of the vanadium content in the five interface regions is calculated.
  • the average value corresponds to the maximum value of the vanadium content in the interface region between the (0001) crystal plane of the tungsten carbide particle and the second phase in the cemented carbide according to the present invention. Therefore, when the average value of the vanadium content in the five interface regions is 15 atomic % or less in a cemented carbide, the maximum value of the vanadium content in the interface region between the (0001) crystal plane of the tungsten carbide particle and the second phase is 15 atomic % or less in the cemented carbide.
  • the maximum value of the chromium content in the interface region between the (0001) crystal place of the tungsten carbide particle and the second phase is preferably 20 atomic % or less. According to this, the formation of a chromium concentrated layer in which chromium is present in a concentrated manner is suppressed in the interface region. Because of this, a decrease in the interface strength between the WC particle and the second phase due to the chromium concentrated layer is suppressed. Therefore, in the cemented carbide, the WC particle is unlikely to fall off because of a decrease in interface strength, and a cutting tool using the cemented carbide can have excellent wear resistance and breakage resistance.
  • the maximum value of the chromium content in the WC/second phase interface region is 20 atomic % or less
  • the maximum value of the chromium content in the WC/WC interface region is also 20 atomic % or less, and the formation of a chromium concentrated layer in which chromium is present in a concentrated manner is suppressed in the WC/WC interface region. Because of this, a decrease in the interface strength between WC particles due to the chromium concentrated layer is also suppressed.
  • the upper limit of the maximum value of the chromium content in the WC/second phase interface region is preferably 20 atomic % or less, preferably 18 atomic % or less, more preferably 16 atomic % or less, further preferably 15 atomic % or less, and more further preferably 14 atomic % or less.
  • the lower limit of the maximum value of the chromium content in the WC/second phase interface region is not particularly limited, and can be, for example, 1 atomic % or more, or 2 atomic % or more.
  • the maximum value of the chromium content in the WC/second phase interface region is preferably 1 atomic % or more and 20 atomic % or less, more preferably 1 atomic % or more and 15 atomic % or less, further preferably 2 atomic % or more and 20 atomic % or less, and more further preferably 2 atomic % or more and 15 atomic % or less.
  • the maximum value of the chromium content in the WC/second phase interface region is obtained by calculating the percentage (atomic %) of chromium when the sum of the numbers of atoms of W, Cr, V, and Co is 100 atomic % instead of the percentage (atomic %) of vanadium when the sum of the numbers of atoms of W, Cr, V, and Co is 100 atomic % in (A4) to (D4) in the method for measuring the vanadium content in the WC/second phase interface region described above.
  • the amount of vanadium added as a grain growth inhibitor may be reduced.
  • the amount of vanadium added is reduced, the effect of suppressing grain growth is insufficient and the WC particle undergoes abnormal grain growth. This causes a decrease in the strength of the cemented carbide.
  • the present inventors have carried out extensive studies and as a result have newly found a method for manufacturing a cemented carbide that can reduce the vanadium content in the interface region while adding a sufficient amount of vanadium in order to suppress the generation of coarse WC particles. The details of the method for manufacturing a cemented carbide according to the present embodiment will be described below.
  • the cemented carbide according to the present embodiment can typically be manufactured by carrying out a raw material powder preparing step, a mixing step, a compacting step, a sintering step (including a preliminary sintering step and a main sintering step), a repeated heat treatment step, and a cooling step in presented order.
  • a raw material powder preparing step a mixing step
  • a compacting step a compacting step
  • a sintering step including a preliminary sintering step and a main sintering step
  • a repeated heat treatment step including a preliminary sintering step and a main sintering step
  • a cooling step in presented order.
  • the preparing step is a step for preparing all raw material powders of materials that constitute the cemented carbide.
  • the raw material powders include a tungsten carbide powder (hereinafter also referred to as a "WC powder”), which is a raw material for the first phase, a cobalt powder (hereinafter also referred to as a "Co powder”), which is a raw material for the second phase, and a vanadium carbide powder (hereinafter also referred to as a "VC powder”), which is a grain growth inhibitor.
  • a chromium carbide powder hereinafter also referred to as a "Cr 3 C 2 powder
  • the tungsten carbide powder, the cobalt powder, the vanadium carbide powder, and the chromium carbide powder commercially available ones can be used.
  • the average particle diameter of the tungsten carbide powder can be 0.2 ⁇ m or more and 1.0 ⁇ m or less.
  • the WC powder preferably has a ratio of the 20% cumulative volume particle diameter d20 thereof to the 80% cumulative volume particle diameter d80 thereof, d20/d80, of 0.2 or more and 1 or less.
  • Such a WC powder has a uniform particle diameter and has a low content of a fine-grained WC particle. Because of this, when a cemented carbide is produced by using the WC powder, the generation of a coarse WC particle due to dissolution and reprecipitation is suppressed in the sintering step.
  • the term "20% cumulative volume particle diameter d20" means the particle diameter at which the cumulative percentage from the smaller diameter side in the volume-based cumulative particle size distribution of crystal grains reaches 20%.
  • the term “80% cumulative volume particle diameter d80” means the particle diameter at which the cumulative percentage from the smaller diameter side in the volume-based cumulative particle size distribution of crystal grains reaches 80%.
  • the average particle diameter of the cobalt powder can be 0.5 ⁇ m or more and 1.5 ⁇ m or less.
  • the average particle diameter of the vanadium carbide powder can be 0.1 ⁇ m or more and 0.5 ⁇ m or less.
  • the VC powder can be sufficiently diffused into the mixed powder in the subsequent preliminary sintering step.
  • the average particle diameter of the chromium carbide powder can be 1.0 ⁇ m or more and 2.0 ⁇ m or less.
  • the average particle diameter of a raw material powder described above means the average particle diameter measured by an FSSS (Fisher Sub-Sieve Sizer) method.
  • the average particle diameter is measured by using "Sub-Sieve Sizer Model 95" (trademark) manufactured by Fisher Scientific.
  • the particle diameter distribution of the WC powder is measured by using a particle size distribution measuring apparatus (trade name: MT3300EX) manufactured by Microtrac.
  • the mixing step is a step of mixing the raw material powders prepared in the preparing step.
  • a mixed powder in which the raw material powders are mixed is obtained by the mixing step.
  • the content of each raw material powder in the mixed powder is appropriately adjusted in consideration of the content of each component such as the first phase, the second phase, and the third phase in the cemented carbide.
  • the content of the tungsten carbide powder in the mixed powder can be, for example, 88.85% by mass or more and 99.83% by mass or less.
  • the content of the cobalt powder in the mixed powder can be, for example, 3% by mass or more and 10% by mass or less.
  • the content of the vanadium carbide powder in the mixed powder can be, for example, 0.01% by mass or more and 0.37% by mass or less.
  • the content of the chromium carbide powder in the mixed powder can be, for example, 0.20% by mass or more and 0.92% by mass or less.
  • a ball mill is used for mixing.
  • the mixing time can be 15 hours or more and 36 hours or less. According to this, pulverization of the raw material powders can be suppressed, and the VC powder can be sufficiently dispersed into the mixed powder while maintaining the particle diameters of the raw material powders.
  • the mixed powder may be granulated as needed.
  • a known granulation method can be applied to the granulation, and for example, a commercially available granulator such as a spray dryer can be used.
  • the compacting step is a step of compacting the mixed powder obtained in the mixing step into a predetermined shape to obtain a compact.
  • a general method and general conditions may be adopted, and these are not particularly limited.
  • the predetermined shape include a cutting tool shape (for example, the shape of a small diameter drill).
  • the sintering step includes a preliminary sintering step and a main sintering step.
  • the compact is held at a sintering temperature of 800 to 1000°C for 2 hours.
  • the atmosphere is a vacuum.
  • a sintering temperature of 800 to 1000°C is a temperature range in which no grain growth of WC occurs.
  • VC in the mixed powder can be diffused throughout cobalt.
  • VC exhibits a uniform grain growth suppressing effect throughout the cemented carbide, and the generation of a coarse WC particle is suppressed.
  • the main sintering step is carried out.
  • the compact after the preliminary sintering step is held at a sintering temperature of 1350 to 1450°C for 1 to 2 hours in an argon (Ar) atmosphere to obtain a cemented carbide.
  • Ar argon
  • the generation of a coarse WC particle is suppressed.
  • the content of a fine-grained WC particle in the obtained cemented carbide can be reduced.
  • vanadium By carrying out the preliminary sintering step and the main sintering step, vanadium can be sufficiently solid-dissolved in cobalt.
  • the cemented carbide obtained in the sintering step is rapidly cooled.
  • the cemented carbide is rapidly cooled at a cooling rate of -60°C/min or more from the temperature in the main sintering step to 1100°C at which VC precipitates as a solid phase, and held at 1100°C for 30 minutes.
  • Such rapid cooling suppresses the movement of vanadium dissolved in cobalt, which is likely to occur during cooling.
  • a region having a high vanadium content in an interface region between a WC particle and a second phase (WC/second phase interface region) or an interface region between WC particles (WC/WC interface region) (corresponding to a "vanadium concentrated layer") and/or a fine precipitation phase of VC (hereinafter also referred to as a "VC fine precipitation phase”) are/is uniformly formed in the cemented carbide.
  • the step of rapidly cooling the cemented carbide to 1100°C at a cooling rate of -60°C/min or more and holding the cemented carbide at 1100°C for 30 minutes will also be referred to as a "rapid cooling step.”
  • the cemented carbide is heated to 1250°C and held at 1250°C for 10 to 20 minutes.
  • the holding time By setting the holding time at 1250°C to 20 minutes or less, vanadium in the vanadium concentrated layer having a large surface area can be preferentially solid-dissolved in cobalt.
  • solid dissolution of vanadium in the VC fine precipitation phase in cobalt is suppressed, and at least a part of the VC fine precipitation phase can remain in the alloy.
  • the step of heating the cemented carbide to 1250°C and holding the cemented carbide at 1250°C for 10 to 20 minutes will also be referred to as a "heat treatment step.”
  • the cemented carbide is rapidly cooled to 1100°C at a cooling rate of -60°C/min or more and held at 1100°C for 30 minutes (corresponding to the rapid cooling step). This suppresses the movement of vanadium solid-dissolved in cobalt in the heat treatment step. Therefore, a vanadium concentrated layer and/or a VC fine precipitation phase are/is uniformly formed in the cemented carbide.
  • the above rapid cooling step and heat treatment step are alternately repeated two or more times each. Thereby, the maximum value of the vanadium concentration in the vanadium concentrated layer present in each of the WC/second phase interface region and the WC/WC interface region is finally reduced. That is, the vanadium content in an interface region between the (0001) crystal plane of a tungsten carbide particle and a second phase in the cemented carbide, and the vanadium content in an interface region between the (0001) crystal plane of a WC particle and a WC particle adjacent to the (0001) crystal plane of the WC particle are reduced. Furthermore, even when the cemented carbide includes a VC particle, the VC particle is fine and uniformly dispersed in the cemented carbide.
  • the cemented carbide after the repeated heat treatment step is cooled.
  • the cooling conditions general conditions may be adopted, and these are not particularly limited.
  • a cemented carbide that does not include a coarse WC particle because abnormal grain growth of a WC particle is suppressed and that has a reduced vanadium content in an interface region can be obtained.
  • the cemented carbide has excellent wear resistance and breakage resistance.
  • the cutting tool of the present embodiment includes a cutting edge formed from the cemented carbide of Embodiment 1.
  • the cutting edge means a portion involved in cutting, and means a region surrounded by a cutting edge ridgeline thereof and a virtual plane at a distance of 2 mm along a line perpendicular to the tangent to the cutting edge ridgeline from the cutting edge ridgeline toward the cemented carbide side, in the cemented carbide.
  • Examples of the cutting tool include a cutting bit, a drill, an end mill, an indexable cutting insert for milling working, an indexable cutting insert for turning working, a metal saw, a gear cutting tool, a reamer, and a tap.
  • a cutting tool 10 of the present embodiment can exhibit an excellent effect in the case of a small diameter drill for working a printed circuit board.
  • a cutting edge 11 of cutting tool 10 shown in Fig. 2 is formed from the cemented carbide of Embodiment 1.
  • the cemented carbide according to the present embodiment may constitute the whole of each of these tools, or a part thereof.
  • the term "constituting a part” refers to, for example, a mode of forming a cutting edge portion by brazing the cemented carbide according to the present embodiment at a predetermined position of an arbitrary base material.
  • the cutting tool according to the present embodiment may further include a hard film that coats at least a part of the surface of a base material formed from the cemented carbide.
  • a hard film that coats at least a part of the surface of a base material formed from the cemented carbide.
  • diamond-like carbon or diamond can be used as the hard film.
  • cemented carbides of sample 1 to sample 12 and sample 1-1 to sample 1-10 were produced by changing the blending ratio of raw material powders and manufacturing conditions. A small diameter drill having a cutting edge formed from each of the cemented carbides was fabricated and evaluated.
  • Powders having the compositions shown in the "Mixed powder" column of Table 1 were prepared as the raw material powders.
  • the average particle diameter of the WC powder is 0.4 ⁇ m, and d20/d80 is 0.3 or more.
  • the average particle diameter of the Co powder is 1 ⁇ m
  • the average particle diameter of the VC powder is 0.3 ⁇ m
  • the average particle diameter of the Cr 3 C 2 powder is 1 ⁇ m.
  • the WC powder, the Co powder, the Cr 3 C 2 powder, and the VC powder are commercially available products.
  • Each raw material powder was mixed in the amount blended shown in “% by mass” in “Mixed powder” of Table 1 to produce a mixed powder.
  • “% by mass” in the “Mixed powder” column of Table 1 indicates the proportion of the mass of each raw material powder to the total mass of the raw material powders.
  • Mixing was carried out in a ball mill for 15 hours.
  • the obtained mixed powder was dried by using a spray dryer to obtain a granulated powder.
  • the obtained granulated powder was pressed to fabricate a round bar-shaped compact having ⁇ 3.4 mm.
  • the compact was subjected to a preliminary sintering step.
  • the compact was placed in a sintering furnace and held in vacuum for 2 hours at the temperature shown in the "Temperature” column in “Preliminary sintering” of Table 1.
  • the description of "No” in the "Preliminary Sintering" column of Table 1 indicates that the preliminary sintering step was not carried out.
  • the compact after the preliminary sintering step was held in an Ar atmosphere for 1 hour at the temperature shown in the "Temperature” column in "Main sintering" of Table 1 to obtain a cemented carbide.
  • the cemented carbide obtained in the sintering step was alternately subjected to a rapid cooling step and a heat treatment step twice each. That is, the rapid cooling step, the heat treatment step, the rapid cooling step, and the heat treatment step were carried out in presented order.
  • the cemented carbide was rapidly cooled to 1100°C at a cooling rate of -60°C/min or more and held at 1100°C for 30 minutes.
  • the cemented carbide was heated to 1250°C and held at 1250°C for 20 minutes.
  • cemented carbides after the repeated heat treatment step were slowly cooled in an argon (Ar) gas atmosphere to obtain a cemented carbide of each sample.
  • the cemented carbide of each sample was measured for the content of the first phase, the second phase, and the third phase in the cemented carbide (shown the "First phase (% by volume),” “Second phase (% by volume),” and “Third phase (% by volume)” columns, respectively, in Table 2), the cobalt content of the cemented carbide (shown in the “Co (% by mass)” column in Table 2), the vanadium content of the cemented carbide (shown in the "V (% by mass)” column in Table 2), the percentage of cobalt to all of tungsten, chromium, vanadium, and cobalt in the second phase (shown in the "Co/second phase (% by mass)” column in Table 2), the average value of the equivalent circle diameter of the WC particle (shown in the "WC particle Average particle diameter ( ⁇ m)” column in Table 2), the maximum value of the equivalent circle diameter of the third phase particle (shown in the "Third phase Maximum particle diameter ( ⁇ m)” column in Table
  • the round bar of each sample was worked to fabricate a small diameter drill (rotating tool for working a printed circuit board) having a cutting edge diameter ⁇ of 0.2 mm.
  • a drill rotating tool for working a printed circuit board
  • a drill was fabricated by subjecting the tip of a ⁇ 3.4 mm round bar to sharpening working.
  • a commercially available in-vehicle printed circuit board was subjected to drill working.
  • Fig. 3 is a diagram of a small diameter drill fabricated in the present Examples when viewed from the tip side thereof.
  • the width of the wear scar means a width L1 of a wear scar W at a location at a distance of 0.08 mm from a drill center C, as shown in Fig. 3 . Results thereof are shown in the "Wear resistance ( ⁇ m) in Cutting test" column of Table 2.
  • the width of the wear scar is 22 ⁇ m or less, it is determined that the wear resistance is good, and when the width of the wear scar is 20 ⁇ m or less, it is determined that the wear resistance is better.
  • cemented carbides and the cutting tools of sample 1 to sample 12 correspond to the Examples. It was confirmed that these samples had excellent wear resistance and breakage resistance.
  • cemented carbides and the cutting tools of sample 1-1 to sample 1-10 correspond to the Comparative Examples. It was confirmed that these samples had insufficient wear resistance and/or breakage resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Powder Metallurgy (AREA)
  • Drilling Tools (AREA)

Claims (7)

  1. Carbure cémenté comprenant une première phase composée d'une particule de carbure de tungstène, une deuxième phase comprenant du cobalt en tant que composant principal, éventuellement une troisième phase consistant en une particule de troisième phase comprenant du tungstène, du chrome, du cobalt, et 10 % atomique ou plus de vanadium, et toute impureté inévitable en une quantité inférieure à 0,1 % en masse, dans lequel
    une teneur totale en la première phase et la deuxième phase dans le carbure cémenté est de 97 % en volume ou plus et de 100 % en volume ou moins, telle que mesurée en utilisant la méthode décrite dans la description,
    une valeur moyenne d'un diamètre de cercle équivalent de la particule de carbure de tungstène est de 0,2 µm ou plus et de 0,8 µm ou moins, telle que mesurée en utilisant la méthode décrite dans la description,
    une teneur en cobalt du carbure cémenté est de 3 % en masse ou plus et de 10 % en masse ou moins, telle que mesurée en utilisant la méthode décrite dans la description,
    une teneur en vanadium du carbure cémenté est de 0,01 % en masse ou plus et de 0,30 % en masse ou moins, telle que mesurée en utilisant la méthode décrite dans la description,
    une teneur en chrome du carbure cémenté est de 0,2 % en masse ou plus et de 0,8 % en masse ou moins, telle que mesurée en utilisant la méthode décrite dans la description,
    la deuxième phase comprend du chrome, du tungstène, du vanadium, du fer, du nickel, ou du carbone en plus du cobalt,
    dans la deuxième phase, un pourcentage du cobalt sur la totalité du tungstène, du chrome, du vanadium, et du cobalt est de 70 % en masse ou plus, telle que mesurée en utilisant la méthode décrite dans la description,
    une teneur en la troisième phase dans le carbure cémenté, si elle est présente, est supérieure à 0 % en volume et de 1 % en volume ou moins, telle que mesurée en utilisant la méthode décrite dans la description, et
    une valeur maximale d'un diamètre de cercle équivalent de la particule de troisième phase est de 0,5 µm ou moins, telle que mesurée en utilisant la méthode décrite dans la description,
    le % atomique du vanadium dans la troisième phase dure étant mesuré en utilisant la méthode décrite dans la description,
    le % en masse d'impureté inévitable étant mesuré en utilisant la méthode décrite dans la description, et
    une valeur maximale de la teneur en vanadium dans une région d'interface entre un plan cristallin (0001) de la particule de carbure de tungstène et la deuxième phase est de 1 % atomique ou plus et de 15 % atomique ou moins, telle que mesurée en utilisant la méthode décrite dans la description.
  2. Carbure cémenté selon la revendication 1, dans lequel la teneur en cobalt du carbure cémenté est de 3 % en masse ou plus et 8 % en masse ou moins.
  3. Carbure cémenté selon la revendication 1 ou la revendication 2, dans lequel la teneur en vanadium du carbure cémenté est de 0,10 % en masse ou plus et 0,20 % en masse ou moins.
  4. Carbure cémenté selon l'une quelconque des revendications 1 à 3, dans lequel le carbure cémenté comprend la troisième phase.
  5. Carbure cémenté selon l'une quelconque des revendications 1 à 4, dans lequel une valeur maximale d'une teneur en chrome dans la région d'interface est de 20 % atomique ou moins, telle que mesurée en utilisant la méthode décrite dans la description.
  6. Carbure cémenté selon la revendication 5, dans lequel la valeur maximale de la teneur en chrome dans la région d'interface est de 1 % atomique ou plus, telle que mesurée en utilisant la méthode décrite dans la description.
  7. Outil de coupe comprenant un bord de coupe formé à partir du carbure cémenté selon l'une quelconque des revendications 1 à 6.
EP22943731.4A 2022-05-25 2022-05-25 Carbure cémenté et outil de coupe utilisant celui-ci Active EP4372115B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/021423 WO2023228328A1 (fr) 2022-05-25 2022-05-25 Carbure cémenté et outil de coupe utilisant celui-ci

Publications (3)

Publication Number Publication Date
EP4372115A1 EP4372115A1 (fr) 2024-05-22
EP4372115A4 EP4372115A4 (fr) 2024-10-23
EP4372115B1 true EP4372115B1 (fr) 2025-11-26

Family

ID=88918722

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22943731.4A Active EP4372115B1 (fr) 2022-05-25 2022-05-25 Carbure cémenté et outil de coupe utilisant celui-ci

Country Status (6)

Country Link
US (1) US20240352561A1 (fr)
EP (1) EP4372115B1 (fr)
JP (1) JP7401048B1 (fr)
CN (1) CN117916397A (fr)
TW (1) TW202346614A (fr)
WO (1) WO2023228328A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024166195A1 (fr) 2023-02-07 2024-08-15 住友電気工業株式会社 Alliage super-dur et outil de coupe utilisant ce dernier
JP7782777B1 (ja) * 2024-09-26 2025-12-09 住友電工ハードメタル株式会社 超硬合金および切削工具

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3811938B2 (ja) * 2000-02-28 2006-08-23 三菱マテリアル株式会社 高速穴あけ加工ですぐれた耐折損性および耐摩耗性を発揮する微粒組織加圧焼結体製ミニチュアドリル
JP2004162080A (ja) * 2002-11-08 2004-06-10 Hitachi Tool Engineering Ltd 強靱性微粒超硬合金
JP2006131974A (ja) * 2004-11-08 2006-05-25 Sumitomo Electric Ind Ltd 超硬合金
JP2006255825A (ja) * 2005-03-16 2006-09-28 Hitachi Tool Engineering Ltd Ｗｃ基超硬合金部材
JP3952209B2 (ja) 2005-09-27 2007-08-01 日立ツール株式会社 Ｗｃ基超硬合金部材
JP4924808B2 (ja) * 2006-08-08 2012-04-25 冨士ダイス株式会社 超微粒超硬合金
JP2011208268A (ja) * 2010-03-30 2011-10-20 Hitachi Tool Engineering Ltd 超微粒超硬合金
JP2012117100A (ja) 2010-11-30 2012-06-21 Sumitomo Electric Ind Ltd 超硬合金
JP5289532B2 (ja) 2011-10-07 2013-09-11 京セラ株式会社 超硬合金およびそれを用いた回転工具
CN110578067B (zh) * 2019-10-30 2021-08-10 株洲硬质合金集团有限公司 一种超细硬质合金的烧结方法

Also Published As

Publication number Publication date
CN117916397A (zh) 2024-04-19
EP4372115A4 (fr) 2024-10-23
US20240352561A1 (en) 2024-10-24
TW202346614A (zh) 2023-12-01
JPWO2023228328A1 (fr) 2023-11-30
EP4372115A1 (fr) 2024-05-22
JP7401048B1 (ja) 2023-12-19
WO2023228328A1 (fr) 2023-11-30

Similar Documents

Publication Publication Date Title
EP4350022B1 (fr) Carbure cémenté et outil le contenant
EP4357474B1 (fr) Carbure cémenté
EP4372115B1 (fr) Carbure cémenté et outil de coupe utilisant celui-ci
JP7173426B1 (ja) 超硬合金及び切削工具
TWI748676B (zh) 超硬合金及具備其之切削工具
EP4194576B1 (fr) Carbure cémenté et outil de coupe le comprenant
TWI896784B (zh) 超硬合金及具備其之切削工具
JP7574719B2 (ja) 超硬合金及び切削工具
CN119365618A (zh) 硬质合金以及包含硬质合金的工具
JP7810336B1 (ja) 超硬合金および切削工具
JP7782777B1 (ja) 超硬合金および切削工具
EP4471167A1 (fr) Alliage super-dur et outil de coupe utilisant ce dernier
EP4509623A1 (fr) Carbure cémenté et outil de coupe utilisant celui-ci
JP7593561B1 (ja) 超硬合金および切削工具
EP4397779A1 (fr) Carbure cémenté et outil le contenant
EP4692392A1 (fr) Carbure cémenté et outil de coupe

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240216

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

A4 Supplementary search report drawn up and despatched

Effective date: 20240925

RIC1 Information provided on ipc code assigned before grant

Ipc: B22F 5/00 20060101ALN20240919BHEP

Ipc: C22C 29/08 20060101AFI20240919BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: B22F 5/00 20060101ALN20250210BHEP

Ipc: C22C 29/08 20060101AFI20250210BHEP

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: B22F 5/00 20060101ALN20250304BHEP

Ipc: C22C 29/08 20060101AFI20250304BHEP

INTG Intention to grant announced

Effective date: 20250313

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

INTC Intention to grant announced (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 29/08 20060101AFI20250610BHEP

Ipc: B22F 5/00 20060101ALN20250610BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20250717

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

P01 Opt-out of the competence of the unified patent court (upc) registered

Free format text: CASE NUMBER: UPC_APP_0010135_4372115/2025

Effective date: 20251017

REG Reference to a national code

Ref country code: CH

Ref legal event code: F10

Free format text: ST27 STATUS EVENT CODE: U-0-0-F10-F00 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20251126

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602022025922

Country of ref document: DE