WO2022091343A1 - Carbure métallique et outil de coupe comprenant du carbure métallique - Google Patents

Carbure métallique et outil de coupe comprenant du carbure métallique Download PDF

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Publication number
WO2022091343A1
WO2022091343A1 PCT/JP2020/040829 JP2020040829W WO2022091343A1 WO 2022091343 A1 WO2022091343 A1 WO 2022091343A1 JP 2020040829 W JP2020040829 W JP 2020040829W WO 2022091343 A1 WO2022091343 A1 WO 2022091343A1
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Prior art keywords
less
cemented carbide
mass
ratio
tungsten carbide
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PCT/JP2020/040829
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English (en)
Japanese (ja)
Inventor
隆洋 山川
和弘 広瀬
克哉 内野
剛志 山本
Original Assignee
住友電工ハードメタル株式会社
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Application filed by 住友電工ハードメタル株式会社 filed Critical 住友電工ハードメタル株式会社
Priority to PCT/JP2020/040829 priority Critical patent/WO2022091343A1/fr
Priority to JP2021521440A priority patent/JP6957828B1/ja
Priority to CN202080042790.3A priority patent/CN114698373A/zh
Priority to TW110137325A priority patent/TW202223114A/zh
Publication of WO2022091343A1 publication Critical patent/WO2022091343A1/fr

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    • 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
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B51/00—Tools for drilling machines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C5/00—Milling-cutters
    • B23C5/16—Milling-cutters characterised by physical features other than shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23D—PLANING; SLOTTING; SHEARING; BROACHING; SAWING; FILING; SCRAPING; LIKE OPERATIONS FOR WORKING METAL BY REMOVING MATERIAL, NOT OTHERWISE PROVIDED FOR
    • B23D77/00—Reaming tools
    • 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
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties

Definitions

  • This disclosure relates to cemented carbide and cutting tools equipped with it.
  • the cemented carbide of the present disclosure is a cemented carbide comprising a first phase composed of a plurality of tungsten carbide particles and a second phase containing cobalt.
  • the ratio of the first phase is 78 area% or more and less than 100 area%
  • the ratio of the second phase is more than 0 area% and 22 area% or less.
  • the average value of the circle-equivalent diameter is 0.5 ⁇ m or more and 1.2 ⁇ m or less.
  • the ratio of the number-based number of the tungsten carbide particles having the equivalent circle diameter of 0.3 ⁇ m or less is 10% or less.
  • the ratio of the number-based number of the tungsten carbide particles having the equivalent circle diameter of more than 1.8 ⁇ m is less than 2%.
  • the mass-based content of the cobalt in the cemented carbide is more than 0% by mass and 10% by mass or less.
  • the cutting tool disclosed in the present disclosure is a cutting tool equipped with a cutting edge made of the above-mentioned cemented carbide.
  • FIG. 1 is an example of an image taken by a scanning electron microscope of the cemented carbide of the present disclosure.
  • FIG. 2 is an image obtained by performing binarization processing on the captured image of FIG. 1.
  • cemented carbide capable of extending the life of a tool when used as a tool material, especially in microfabrication of a printed circuit board, and a cutting tool provided with the cemented carbide. ..
  • the cemented carbide of the present disclosure enables a long life of a tool, especially in microfabrication of a printed circuit board.
  • the cemented carbide of the present disclosure is a cemented carbide comprising a first phase composed of a plurality of tungsten carbide particles and a second phase containing cobalt.
  • the ratio of the first phase is 78 area% or more and less than 100 area%
  • the ratio of the second phase is more than 0 area% and 22 area% or less.
  • the average value of the circle-equivalent diameter is 0.5 ⁇ m or more and 1.2 ⁇ m or less.
  • the ratio of the number-based number of the tungsten carbide particles having the equivalent circle diameter of 0.3 ⁇ m or less is 10% or less.
  • the ratio of the number-based number of the tungsten carbide particles having the equivalent circle diameter of more than 1.8 ⁇ m is less than 2%.
  • the mass-based content of the cobalt in the cemented carbide is more than 0% by mass and 10% by mass or less.
  • the cemented carbide disclosed in the present disclosure makes it possible to extend the life of the tool, especially in the microfabrication of printed circuit boards.
  • the ratio of the second phase is preferably 5 area% or more and 12 area% or less. According to this, the tool life is further improved.
  • the content of the cemented carbide based on the mass of chromium is preferably 0.15% by mass or more and 1.0% by mass or less. According to this, the tool life is further improved.
  • the ratio of the chromium to the cobalt is preferably 5% or more and 10% or less on a mass basis. According to this, the tool life is further improved.
  • the mass-based content of vanadium in the cemented carbide is preferably 0 ppm or more and less than 2000 ppm. According to this, the tool life is further improved.
  • the mass-based content of vanadium in the cemented carbide is preferably 0 ppm or more and less than 100 ppm. According to this, the tool life is further improved.
  • the cutting tool of the present disclosure is a cutting tool provided with a cutting edge made of the above-mentioned cemented carbide.
  • the cutting tools of the present disclosure have a long tool life.
  • the cutting tool is preferably a rotary tool for processing a printed circuit board.
  • the cutting tool of the present disclosure is suitable for microfabrication of printed circuit boards.
  • the notation in the form of "A to B” means the upper and lower limits of the range (that is, A or more and B or less), and when there is no description of the unit in A and the unit is described only in B, A.
  • the unit of and the unit of B are the same.
  • a compound or the like when represented by a chemical formula, it shall include all conventionally known atomic ratios when the atomic ratio is not particularly limited, and should not necessarily be limited to those in the stoichiometric range.
  • the ratio of the number of atoms constituting the WC includes any conventionally known atomic ratio.
  • the present inventors describe the damage form of the tool when the printed circuit board is finely machined using a tool made of a conventional fine-grained cemented carbide. investigated. As a result, it was confirmed that in the conventional fine-grained cemented carbide, the tungsten carbide particles fall off and wear with the use of the tool. Further examination of the fall-off wear confirmed that tungsten carbide particles having a particle size of 0.3 ⁇ m or less were particularly easy to fall off.
  • the present inventors can reduce the content of tungsten carbide particles having a particle size of 0.3 ⁇ m or less, which easily falls off when the tool is used, in the fine cemented carbide. I guessed it was important.
  • fine tungsten carbide particles particle size of about 0.2 ⁇ m
  • grain growth of fine tungsten carbide particles is performed in the manufacturing process. It is possible to promote it.
  • fine tungsten carbide particles when sintering fine-grained tungsten carbide particles as a raw material, it is conceivable not to add vanadium or chromium having a grain growth inhibitory effect, or to perform sintering at a high temperature.
  • coarse tungsten carbide particles having a particle size of about 2 ⁇ m or more are generated due to abnormal grain growth.
  • the coarse tungsten carbide particles are a factor that lowers the strength of the fine cemented carbide.
  • the present inventors have a raw material and a composition capable of reducing the content of tungsten carbide particles having a particle size of 0.3 ⁇ m or less in the cemented carbide and suppressing the generation of coarse tungsten carbide particles.
  • the cemented carbide of the present disclosure was completed. The details of the cemented carbide of the present disclosure and the cutting tool provided with the same will be described below.
  • the cemented carbide of the present disclosure is A cemented carbide comprising a first phase composed of a plurality of tungsten carbide particles and a second phase containing cobalt.
  • the ratio of the first phase is 78 area% or more and less than 100 area%
  • the ratio of the second phase is more than 0 area% and 22 area% or less.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less is 10% or less.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of more than 1.8 ⁇ m is less than 2%.
  • the mass-based content of cobalt in cemented carbide is greater than 0% by mass and 10% by mass or less.
  • the cemented carbide disclosed in the present disclosure makes it possible to extend the life of the tool, especially in the microfabrication of printed circuit boards. The reason for this is not clear, but it is presumed to be as described in (i) to (v) below.
  • the ratio of the first phase composed of a plurality of tungsten carbide particles is 78 area% or more and less than 100 area%, and the ratio of the second phase containing cobalt is more than 0 area% and 22 areas. % Or less. According to this, the hardness and wear resistance required for processing the printed circuit board can be exhibited, and the occurrence of variation in the tool life can be suppressed.
  • the average value of the equivalent circle diameters of the tungsten carbide particles (hereinafter, also referred to as “WC particles”) is 0.5 ⁇ m or more and 1.2 ⁇ m or less.
  • the cemented carbide When the average value of the equivalent circle diameters of the tungsten carbide particles is 0.5 ⁇ m or more, the cemented carbide is less likely to cause falling wear due to use, and the cemented carbide can have excellent wear resistance. When the average value of the equivalent circle diameters of the tungsten carbide particles is 1.2 ⁇ m or less, the cemented carbide has high hardness, can have excellent wear resistance, and has high folding resistance, and is excellent. It can have breakage resistance.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less is 10% or less. According to this, the cemented carbide is less likely to cause falling-off wear due to use, and the cemented carbide can have excellent wear resistance.
  • the ratio based on the number of the tungsten carbide particles having a circle equivalent diameter of more than 1.8 ⁇ m is less than 2%. According to this, the cemented carbide has a high bending resistance and can have an excellent breaking resistance.
  • the mass-based content of cobalt in cemented carbide is more than 0% by mass and 10% by mass or less. According to this, the cemented carbide has a high hardness and can have excellent wear resistance.
  • the first phase consists of a plurality of tungsten carbide particles.
  • the tungsten carbide is not only "pure WC (including WC containing no impurity element and WC whose impurity element is below the detection limit)", but also "as long as the effect of the present disclosure is not impaired".
  • WC in which other impurity elements are intentionally or inevitably contained is also included.
  • the concentration of impurities contained in tungsten carbide (when two or more kinds of elements constituting the impurities are the total concentration thereof) is less than 0.1% by mass with respect to the total amount of the tungsten carbide and the impurities. ..
  • the content of the impurity element in the first phase is measured by ICP emission spectrometry (Inductively Coupled Plasma) Emission Spectroscopy (measuring device: Shimadzu Corporation "ICPS-8100" (trademark)).
  • the average value of the equivalent circle diameters of the tungsten carbide particles is 0.5 ⁇ m or more and 1.2 ⁇ m or less.
  • the cemented carbide is less likely to cause falling wear due to use, and the cemented carbide can have excellent wear resistance.
  • the cemented carbide has high hardness, can have excellent wear resistance, and has high folding resistance, and is excellent. It can have breakage resistance.
  • the lower limit of the average value of the equivalent circle diameters of the tungsten carbide particles is preferably 0.5 ⁇ m or more, 0.55 ⁇ m or more, and 0.60 ⁇ m or more.
  • the upper limit of the average value of the equivalent circle diameters of the tungsten carbide particles is preferably 1.2 ⁇ m or less, 1.1 ⁇ m or less, and 1.0 ⁇ m or less.
  • the average value of the equivalent circle diameters of the tungsten carbide particles is 0.5 ⁇ m or more and 1.2 ⁇ m or less, preferably 0.55 ⁇ m or more and 1.1 ⁇ m or less, and 0.60 ⁇ m or more and 1.0 ⁇ m or less.
  • the equivalent circle diameter of the tungsten carbide particles is measured by the following procedures (A1) to (C1).
  • A1 Any surface or any cross section of cemented carbide is mirror-finished. Examples of the mirror surface processing method include a method of polishing with diamond paste, a method of using a focused ion beam device (FIB device), a method of using a cross section polisher device (CP device), and a method of combining these.
  • FIB device focused ion beam device
  • CP device cross section polisher device
  • FIG. 1 shows an example of an image taken by a scanning electron microscope of the cemented carbide of the present disclosure.
  • (C1) The captured image obtained in (B1) above is taken into a computer by image analysis software (ImageJ, version 1.51j8: https://imagej.nih.gov/ij/) and binarized.
  • the binarization process is executed by pressing the display of "Make Binary" on the computer screen after capturing the image (the binarization process is performed under the conditions preset in the image analysis software). ).
  • a rectangular measurement field of view of 25.3 ⁇ m in length ⁇ 17.6 ⁇ m in width is set in the obtained image after binarization processing, and the equivalent circle diameter (Heywood diameter: equivalent area circle) of the tungsten carbide particles in the measurement field of view is set. Diameter) is calculated.
  • the first phase composed of tungsten carbide particles and the second phase containing cobalt can be distinguished from each other by the shade of color in the photographed image.
  • FIG. 2 shows an image obtained by performing binarization processing on the captured image of FIG. 1.
  • the black region is the first phase and the white region is the second phase.
  • White lines indicate grain boundaries.
  • the measurement results vary even if the diameter equivalent to the circle of the tungsten carbide particles in the cemented carbide is measured multiple times by changing the selection point of the measurement field. It was confirmed that even if the measurement field was set arbitrarily, it would not be arbitrary.
  • the cemented carbide of the present disclosure In the image of the cemented carbide of the present disclosure taken with a scanning electron microscope, the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less is 10% or less. According to this, the cemented carbide is less likely to cause falling-off wear due to use, and the cemented carbide can have excellent wear resistance.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less is 10% or less, preferably 9% or less, and 8% or less.
  • the lower limit of the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less is not particularly limited, but may be, for example, 0% or more, 2% or more, or 4% or more.
  • the percentage of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less is 0% or more and 10% or less, 0% or more and 9% or less, 0% or more and 8% or less, 2% or more and 10% or less, 2% or more. It can be 9% or less, 2% or more and 8% or less, 4% or more and 10% or less, 4% or more and 9% or less, 4% or more and 8% or less.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less in an image obtained by imaging a cemented carbide with a scanning electron microscope is calculated by the following procedures (D1) and (E1). Will be done.
  • (D1) Prepare three images (corresponding to three measurement fields) of cemented carbide captured by a scanning electron microscope according to the procedures (A1) and (B1) of the method for measuring the equivalent circle diameter of tungsten carbide particles. do.
  • the image processing (binarization processing) described in (C1) of the method for measuring the equivalent circle diameter of the tungsten carbide particles is performed in each of the three measurement fields of view.
  • the size of one measurement field of view is a rectangle having a length of 25.3 ⁇ m and a width of 17.6 ⁇ m.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less in the cemented carbide is changed at the selection point of the measurement field. It was confirmed that even if the measurement was performed multiple times, the variation in the measurement results was small, and even if the measurement field was set arbitrarily, it was not arbitrary.
  • the ratio of the number-based number of tungsten carbide particles having a circle equivalent diameter of more than 1.8 ⁇ m is less than 2%. According to this, the cemented carbide has a high bending resistance and can have an excellent breaking resistance.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of more than 1.8 ⁇ m is less than 2%, preferably 1% or less and 0.5% or less.
  • the lower limit of the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of more than 1.8 ⁇ m is not particularly limited, but may be, for example, 0% or more, 0.1% or more, and 0.2% or more.
  • the percentage of tungsten carbide particles having a circle equivalent diameter of more than 1.8 ⁇ m is 0% or more and less than 2%, 0% or more and 1% or less, 0% or more and 0.5% or less, 0.1% or more and less than 2%. , 0.1% or more and 1% or less, 0.1% or more and 0.5% or less, 0.2% or more and less than 2%, 0.2% or more and 1% or less, 0.2% or more and 0.5% or less can do.
  • the ratio based on the number of tungsten carbide particles having a diameter equivalent to a circle of more than 1.8 ⁇ m in an image obtained by imaging a cemented carbide with a scanning electron microscope is calculated by the following procedures (F1) and (G1). Will be done.
  • (F1) Prepare three images (corresponding to three measurement fields) of cemented carbide captured by a scanning electron microscope according to the procedures (A1) and (B1) of the method for measuring the equivalent circle diameter of tungsten carbide particles. do.
  • the image processing (binarization processing) described in (C1) of the method for measuring the equivalent circle diameter of the tungsten carbide particles is performed in each of the three measurement fields of view.
  • the size of one measurement field of view is a rectangle having a length of 25.3 ⁇ m and a width of 17.6 ⁇ m.
  • the ratio of the number-based ratio of the tungsten carbide particles having the equivalent circle diameter of more than 1.8 ⁇ m in the cemented carbide is changed, and the selection point of the measurement field is changed. It was confirmed that even if the measurement was performed multiple times, the variation in the measurement results was small, and even if the measurement field was set arbitrarily, it was not arbitrary.
  • the second phase contains cobalt.
  • the second phase is a bonded phase that binds the tungsten carbide particles constituting the first phase to each other.
  • the second phase contains cobalt (Co)
  • the main component of the second phase is Co.
  • the main component of the second phase is Co means that the mass ratio of cobalt in the second phase is 90% by mass or more and 100% by mass or less.
  • the mass ratio of cobalt in the second phase can be measured by ICP emission spectroscopic analysis (equipment used: "ICPS-8100” (trademark) manufactured by Shimadzu Corporation).
  • the second phase can contain iron elements such as nickel and dissolved substances in alloys (chromium (Cr), tungsten (W), vanadium (V), etc.).
  • the cemented carbide includes a first phase composed of a plurality of tungsten carbide particles and a second phase containing cobalt, and the ratio of the first phase is 78 in an image obtained by capturing the cemented carbide with a scanning electron microscope. % Or more and less than 100 area%, and the ratio of the second phase is more than 0 area% and 22 area% or less. According to this, the hardness and wear resistance required for processing the printed circuit board can be exhibited, and the occurrence of variation in the tool life can be suppressed.
  • the ratio of the first phase in the cemented carbide is 78 area% or more, the hardness of the cemented carbide is improved.
  • the lower limit of the ratio of the first phase in the cemented carbide can be 78 area% or more and 88 area% or more.
  • the upper limit of the ratio of the first phase in the cemented carbide can be less than 100 area% and 95 area% or less.
  • the ratio of the first phase in the cemented carbide can be 78 area% or more and less than 100 area%, 88 area% or more and 95 area% or less.
  • the ratio of the second phase in the cemented carbide is 22 area% or less, the hardness of the cemented carbide is improved.
  • the lower limit of the ratio of the second phase in the cemented carbide can be more than 0 area% and 5 area% or more.
  • the upper limit of the ratio of the second phase in the cemented carbide can be 22 area% or less and 12 area% or less.
  • the ratio of the second phase in the cemented carbide can be 0 area% or more and 22 area% or less, 5 area% or more and 12 area% or less.
  • the ratio of the first phase is preferably 88 area% or more and 95 area% or less, and the ratio of the second phase is 5 area% or more and 12 area% or less.
  • the area ratio of each of the first phase and the second phase in the cemented carbide is measured by the following procedures (A2) to (C2).
  • (A2) Prepare 5 images (corresponding to 5 measurement fields) of cemented carbide captured by a scanning electron microscope according to the procedures (A1) and (B1) of the method for measuring the equivalent circle diameter of tungsten carbide particles. do.
  • the image processing (binarization processing) described in (C1) of the method for measuring the equivalent circle diameter of the tungsten carbide particles is performed in each of the five measurement fields of view.
  • the size of one measurement field of view is a rectangle having a length of 25.3 ⁇ m and a width of 17.6 ⁇ m.
  • the mass-based content of vanadium in the cemented carbide of the present disclosure is preferably 0 ppm or more and less than 2000 ppm. That is, it is preferable that the cemented carbide of the present disclosure does not contain (a) vanadium, or (b) contains vanadium, the mass-based content of vanadium is less than 2000 ppm.
  • Vanadium has a grain growth inhibitory effect, so it was used in the production of conventional ultrafine cemented carbide. However, when vanadium was added to suppress grain growth, the fine-grained tungsten carbide particles used as a raw material tended to remain in the obtained fine-grained cemented carbide as they were.
  • the upper limit of the vanadium content of the cemented carbide is less than 2000 ppm, preferably less than 100 ppm. Since the smaller the vanadium content of the cemented carbide is, the more preferable it is, the lower limit thereof is 0 ppm.
  • the vanadium content of the cemented carbide can be 0 ppm or more and less than 2000 ppm, and 0 ppm or more and less than 100 ppm.
  • the vanadium content of cemented carbide is measured by ICP emission spectroscopy.
  • the mass-based content of cobalt in the cemented carbide of the present disclosure is more than 0% by mass and 10% by mass or less. According to this, the cemented carbide has a high hardness and can have excellent wear resistance.
  • the upper limit of the cobalt content of the cemented carbide is preferably 9% by mass or less and 8% by mass or less.
  • the lower limit of the cobalt content of the cemented carbide is preferably 1% by mass or more and 2% by mass or more.
  • the cobalt content of the cemented carbide is preferably 1% by mass or more and 9% by mass or less, and 2% by mass or more and 8% by mass or less.
  • the cobalt content in cemented carbide is measured by ICP emission spectroscopy.
  • the cemented carbide of the present disclosure contains chromium (Cr), and the content of the cemented carbide based on the mass of chromium is preferably 0.15% by mass or more and 1.0% by mass or less. Chromium has a grain growth inhibitory effect on tungsten carbide particles.
  • the chromium content in the cemented carbide is 0.15% by mass or more and 1.0% by mass or less, the obtained cemented carbide contains fine-grained tungsten carbide particles as a raw material. It was newly found that the residual particles can be effectively suppressed and the generation of coarse particles can be effectively suppressed.
  • the upper limit of the chromium content of the cemented carbide is preferably 0.95% by mass or less and 0.90% by mass or less.
  • the lower limit of the chromium content of the cemented carbide is preferably 0.20% by mass or more and 0.25% by mass or more.
  • the chromium content of the cemented carbide is preferably 0.20% by mass or more and 0.95% by mass or less, and preferably 0.25% by mass or more and 0.90% by mass or less.
  • the chromium content in cemented carbide is measured by ICP emission spectroscopy.
  • the ratio of chromium to cobalt is preferably 5% or more and 10% or less on a mass basis. Chromium has a grain growth inhibitory effect on tungsten carbide particles. Further, by solid-solving in cobalt, the generation of lattice strain of cobalt is promoted. Therefore, when the cemented carbide contains chromium in the above ratio, the breakage resistance is further improved.
  • chromium may precipitate as carbide and become the starting point of damage.
  • the ratio of chromium to cobalt is 5% or more and 10% or less, the precipitation of carbides of chromium is less likely to occur, and the effect of improving breakage resistance can be obtained.
  • the ratio of chromium to cobalt is 10% or less, the degree of the action of suppressing grain growth becomes appropriate, and the amount of tungsten carbide particles having a circle equivalent diameter of more than 1.2 ⁇ m in the cemented carbide becomes excessive. It can be suppressed.
  • the lower limit of the ratio of chromium to cobalt is preferably 5% or more, more preferably 7% or more.
  • the ratio of chromium to cobalt is preferably 10% or less, more preferably 9% or less.
  • the ratio of chromium to cobalt can be 5% or more and 10% or less, and 7% or more and 9% or less.
  • the cemented carbide of the present embodiment can be typically produced by performing a raw material powder preparation step, a mixing step, a molding step, a sintering step, and a cooling step in the above order. Hereinafter, each step will be described.
  • the preparation step is a step of preparing all the raw material powders of the materials constituting the cemented carbide.
  • the raw material powder include tungsten carbide powder, which is the raw material of the first phase, and cobalt (Co) powder, which is the raw material of the second phase, as essential raw material powders.
  • chromium carbide (Cr 3 C 2 ) powder can be prepared as a grain growth inhibitor.
  • tungsten carbide powder, cobalt powder, and chromium carbide powder commercially available ones can be used.
  • the average particle size of the raw material powder means the average particle size measured by the FSSS (Fisher Sub-Sieve Sizer) method.
  • the average particle size is measured using "Sub-Sive Sizer Model 95" (trademark) manufactured by Fisher Scientific.
  • the tungsten carbide powder preferably has a ratio d20 / d80 of its 20% volume particle diameter d20 and its 80% volume particle diameter d80 of 0.2 or more and 1 or less.
  • Such tungsten carbide powder has a uniform particle size and a small content of fine tungsten carbide particles having a particle size of 0.3 ⁇ m or less. Therefore, when a cemented carbide is produced using the tungsten carbide powder, the generation of coarse tungsten carbide particles due to dissolution and reprecipitation is suppressed in the sintering step. In addition, the content of fine tungsten carbide particles in the obtained cemented carbide can be reduced.
  • the distribution of the volume particle size of the tungsten carbide powder is measured using a particle size distribution measuring device (trade name: MT3300EX) manufactured by Microtrac.
  • the 20% volume particle diameter d20 means the particle size when the volumes of the particles constituting the tungsten carbide powder are integrated in ascending order and occupy 20% of the total volume.
  • the 80% volume particle diameter d80 means the particle size when the volume of each particle constituting the tungsten carbide powder is integrated in ascending order and occupies 80% of the total volume.
  • vanadium carbide (VC) powder having a high effect of suppressing grain growth which is generally used in the production of conventional fine-grained cemented carbide, is not used, or even if it is used, a trace amount is used.
  • the mass-based content in the raw material powder is less than 2000 ppm.
  • the content of fine tungsten carbide particles having a particle size of 0.3 ⁇ m or less in the raw material powder is reduced at the stage of preparing the raw material, so that the amount of vanadium (V) added is reduced. Regardless of this, the area ratio of the fine tungsten carbide particles in the cemented carbide can be kept low.
  • the average particle size of the cobalt powder can be 0.5 ⁇ m or more and 1.5 ⁇ m or less.
  • the average particle size of the chromium carbide powder can be 1.0 ⁇ m or more and 2.0 ⁇ m or less.
  • the average particle size is measured using "Sub-Sive Sizer Model 95" (trademark) manufactured by Fisher Scientific.
  • the mixing process is a step of mixing each raw material powder prepared in the preparation step. By the mixing step, a mixed powder in which each raw material powder is mixed is obtained.
  • the ratio 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 ratio of the cobalt powder in the mixed powder can be, for example, more than 0% by mass and 10% by mass or less.
  • the ratio of the chromium carbide powder in the mixed powder can be, for example, 0.17% by mass or more and 1.15% by mass or less.
  • the mixing time can be 15 hours or more and 36 hours or less. Under these conditions, crushing of the raw material powder can be suppressed, and the homogeneity of the particle size of the raw material powder can be maintained.
  • 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 molding step is a step of molding the mixed powder obtained in the mixing step into a predetermined shape to obtain a molded product.
  • a predetermined shape include a cutting tool shape (for example, the shape of a small-diameter drill).
  • the sintering step is a step of sintering a molded product obtained in the molding step to obtain a cemented carbide.
  • the sintering temperature can be 1350 to 1450 ° C. According to this, the generation of coarse tungsten carbide particles is suppressed. In addition, the content of fine tungsten carbide particles in the obtained cemented carbide can be reduced.
  • the cooling step is a step of cooling the cemented carbide after the sintering is completed.
  • the cooling conditions general conditions may be adopted, and there is no particular limitation.
  • vanadium carbide (VC) powder having a high effect of suppressing grain growth which is generally used in the production of conventional fine-grained cemented carbide, is not used or is used.
  • VC vanadium carbide
  • the cutting tool of the present disclosure includes a cutting edge made of the above cemented carbide.
  • the cutting edge means a portion involved in cutting, and in cemented carbide, the distance between the cutting edge ridge line and the cutting edge ridge line from the cutting edge ridge line to the cemented carbide side along the vertical line of the tangent line of the cutting edge ridge line is 2 mm. It means a virtual surface that is and an area surrounded by.
  • the cutting tool examples include a cutting tool, a drill, an end mill, a cutting tip with a replaceable cutting edge for milling, a cutting tip with a replaceable cutting edge for turning, a metal saw, a gear cutting tool, a reamer or a tap.
  • the cutting tool of the present disclosure can exert an excellent effect in the case of a small-diameter drill for processing a printed circuit board.
  • the cemented carbide of the present embodiment may constitute the whole of these tools, or may constitute a part of them.
  • “partially constituting” indicates an embodiment in which the cemented carbide of the present embodiment is brazed to a predetermined position of an arbitrary base material to form a cutting edge portion.
  • the cutting tool according to the present embodiment may further include a hard film that covers at least a part of the surface of a base material made of cemented carbide.
  • a hard film for example, diamond-like carbon or diamond can be used.
  • the average value of the equivalent circle diameters of the tungsten carbide particles is preferably 0.55 ⁇ m or more and 1.1 ⁇ m or less. In the cemented carbide of the present disclosure, the average value of the equivalent circle diameters of the tungsten carbide particles is preferably 0.60 ⁇ m or more and 1.0 ⁇ m or less.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less is preferably 0% or more and 10% or less.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less is preferably 0% or more and 9% or less.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of 0.3 ⁇ m or less is preferably 0% or more and 8% or less.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of more than 1.8 ⁇ m is preferably 0% or more and less than 2%.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of more than 1.8 ⁇ m is preferably 0% or more and 1% or less.
  • the ratio based on the number of tungsten carbide particles having a circle equivalent diameter of more than 1.8 ⁇ m is preferably 0% or more and 0.5% or less.
  • the ratio of the first phase is preferably 88 area% or more and 95 area% or less.
  • the ratio of the second phase is preferably 5 area% or more and 12 area% or less.
  • the ratio of the first phase is preferably 88 area% or more and 95 area% or less, and the ratio of the second phase is preferably 5 area% or more and 12 area% or less. ..
  • the mass-based content of vanadium in the cemented carbide of the present disclosure is preferably 0 ppm or more and less than 2000 ppm.
  • the mass-based content of vanadium in the cemented carbide of the present disclosure is preferably 0 ppm or more and less than 100 ppm.
  • the mass-based content of cobalt in the cemented carbide of the present disclosure is preferably 1% by mass or more and 9% by mass or less.
  • the mass-based content of cobalt in the cemented carbide of the present disclosure is preferably 2% by mass or more and 8% by mass or less.
  • the mass-based content of chromium in the cemented carbide of the present disclosure is preferably 0.20% by mass or more and 0.95% by mass or less.
  • the mass-based content of chromium in the cemented carbide of the present disclosure is preferably 0.25% by mass or more and 0.90% by mass or less.
  • the ratio of chromium to cobalt is preferably 7% or more and 9% or less on a mass basis.
  • Cemented carbides of Samples 1 to 17 were prepared by changing the type, compounding ratio and production conditions of the raw material powder. A small-diameter drill having a cutting edge made of the cemented carbide was produced and evaluated.
  • ⁇ Preparation of sample ⁇ As the raw material powder, a powder having the composition shown in the “raw material” column of Table 1 was prepared. A plurality of tungsten carbide (WC) powders having different average particle sizes were prepared. The average particle size of the WC powder is as shown in the "Average particle size ( ⁇ m)" column of "WC powder” in Table 1. The average particle size of the Co powder is 1.0 ⁇ m. The average particle size of the Cr 3 C 2 powder is 1.5 ⁇ m. The average particle size of the VC powder is 0.9 ⁇ m. The average particle size of the raw material powder is a value measured using "Sub-Sive Sizer Model 95" (trademark) manufactured by Fisher Scientific.
  • d20 / d80 of all the samples was 0.2 or more. It was in the following range.
  • d20 / d80 was measured for the WC powders of Samples 14 to 17, the d20 / d80 of all the samples was 0.1 or more and less than 0.2.
  • the d20 / d80 of the WC powder is a value measured using a particle size distribution measuring device (trade name: MT3300EX) manufactured by Microtrac.
  • Samples 1 to 13 correspond to Examples, and Samples 14 to 17 correspond to Comparative Examples. It was confirmed that the samples 1 to 13 had a smaller amount of wear and a longer tool life than the samples 14 to 17.
  • Samples 1 to 13 do not contain vanadium carbide powder, which is generally used as a grain growth inhibitor, or even when the raw material powder contains vanadium carbide powder, the amount is as small as 2000 ppm or less. It was confirmed that the proportion of WC particles having a circle equivalent diameter of 1.8 ⁇ m or more was less than 2% in the obtained cemented carbide, and the grain growth was suppressed.

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

Abstract

Ce carbure métallique comprend une première phase comprenant une pluralité de particules de carbure de tungstène, et une seconde phase contenant du cobalt. Dans une image obtenue par formation d'images du carbure métallique à l'aide d'un microscope électronique à balayage, la proportion de la première phase est supérieure ou égale à 78 % en surface mais inférieure à 100 % en surface, et la proportion de la seconde phase est supérieure à 0 % en surface et d'au plus 22 % en surface. Lorsque des diamètres de cercle équivalents sont calculés pour les particules de carbure de tungstène dans l'image, la valeur moyenne pour les diamètres de cercle équivalents est comprise entre 0,5 µm et 1,2 µm inclus, les particules de carbure de tungstène ayant des diamètres de cercle équivalents inférieurs ou égaux à 0,3 µm occupent une proportion basée sur le comptage inférieure ou égale à 10 %, et les particules de carbure de tungstène ayant des diamètres de cercle équivalents supérieurs à 1,8 µm occupent une proportion basée sur le comptage inférieure à 2 %. Le carbure métallique a une teneur en cobalt basée sur la masse supérieure à 0 % en masse et d'au plus 10 % en masse.
PCT/JP2020/040829 2020-10-30 2020-10-30 Carbure métallique et outil de coupe comprenant du carbure métallique WO2022091343A1 (fr)

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