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WO2025182417A1 - Élément dur, insert de découpe, outil de découpe et procédé de fabrication de la pièce à découper - Google Patents

Élément dur, insert de découpe, outil de découpe et procédé de fabrication de la pièce à découper

Info

Publication number
WO2025182417A1
WO2025182417A1 PCT/JP2025/002855 JP2025002855W WO2025182417A1 WO 2025182417 A1 WO2025182417 A1 WO 2025182417A1 JP 2025002855 W JP2025002855 W JP 2025002855W WO 2025182417 A1 WO2025182417 A1 WO 2025182417A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorbent
atm
hard
tungsten
nitrogen
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.)
Pending
Application number
PCT/JP2025/002855
Other languages
English (en)
Japanese (ja)
Inventor
貴彦 牧野
直樹 岩井
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.)
Kyocera Corp
Original Assignee
Kyocera 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 Kyocera Corp filed Critical Kyocera Corp
Publication of WO2025182417A1 publication Critical patent/WO2025182417A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • 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
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys

Definitions

  • the disclosed embodiments relate to methods for manufacturing hard members, cutting inserts, cutting tools, and machined products.
  • Hard materials containing tungsten carbide in the hard phase have traditionally been widely used as the base material for components that require wear resistance, such as cutting tools.
  • a hard member has a substrate including a hard phase and a binder phase.
  • the hard phase contains tungsten carbide and nitrogen.
  • the binder phase contains nitrogen and at least one iron-group element selected from the group consisting of iron, cobalt, and nickel.
  • the substrate has an outer portion extending from the surface to 1 mm and an inner portion located deeper than the outer portion in the depth direction from the surface.
  • the nitrogen content of the hard phase in the outer portion is N OH [atm %]
  • the nitrogen content of the binder phase in the outer portion is N OB [atm %]
  • the nitrogen content of the hard phase in the inner portion is N IH [atm %]
  • the nitrogen content of the binder phase in the inner portion is N IB [atm %]
  • the difference between N OB and N OH is smaller than the difference between N IB and N IH .
  • FIG. 1 is a perspective view illustrating an example of a cutting insert according to an embodiment.
  • FIG. 2 is a side cross-sectional view showing an example of a cutting insert according to an embodiment.
  • FIG. 3 is a diagram schematically showing a scanning transmission electron microscope photograph of a cross section of a substrate according to an embodiment.
  • FIG. 4 is a graph showing the nitrogen content ratios in the hard phase and binder phase for the substrate according to the embodiment and the substrate of a conventional product.
  • FIG. 5 is a flowchart showing an example of a procedure for producing a tungsten carbide powder according to an embodiment.
  • FIG. 6 is a front view showing an example of a cutting tool according to an embodiment.
  • FIG. 1 is a perspective view illustrating an example of a cutting insert according to an embodiment.
  • FIG. 2 is a side cross-sectional view showing an example of a cutting insert according to an embodiment.
  • FIG. 3 is a diagram schematically showing a scanning transmission electron microscope photograph of a cross section of
  • FIG. 7 is an explanatory diagram for explaining an example of a method for manufacturing a machined product according to the embodiment.
  • FIG. 8 is an explanatory diagram for explaining an example of a method for manufacturing a machined product according to the embodiment.
  • FIG. 9 is an explanatory diagram for explaining an example of a method for manufacturing a machined product according to the embodiment.
  • FIG. 10 is a diagram showing an outer portion of the base body according to the embodiment.
  • Fig. 1 is a perspective view showing an example of a cutting insert 1 according to an embodiment.
  • Fig. 2 is a side cross-sectional view showing an example of the cutting insert 1 according to an embodiment.
  • the cutting insert 1 includes a base body 2 and a coating film 3.
  • the base 2 has, for example, a hexahedral shape in which the upper and lower surfaces (surfaces intersecting with the Z axis shown in FIG. 1) are parallelogram-shaped.
  • the cutting edge portion includes a first surface (e.g., an upper surface) and a second surface (e.g., a side surface) that is connected to the first surface.
  • the first surface functions as a "rake surface” that scoops up chips produced by cutting
  • the second surface functions as a "flank surface.”
  • a cutting edge is located on at least a portion of the ridge where the first and second surfaces intersect, and the cutting insert 1 cuts the workpiece by applying this cutting edge to the workpiece.
  • a through-hole 21 that passes through the base 2 from top to bottom may be located in the center of the base 2.
  • a screw 75 is inserted into the through-hole 21 to attach the cutting insert 1 to the holder 70 (described below) (see Figure 6).
  • the substrate 2 is composed of a hard member.
  • the hard member includes a hard phase and a binder phase.
  • the hard phase may contain W (tungsten).
  • the hard phase may contain WC (tungsten carbide).
  • the binder phase may be primarily composed of at least one iron group element selected from the group consisting of Fe (iron), Co (cobalt), and Ni (nickel).
  • the primary component may be one that accounts for 50% or more by mass of the constituent components. The specific configuration of the substrate 2 will be described later.
  • the coating film 3 coats the base 2 for the purpose of improving the abrasion resistance, heat resistance, etc. of the base 2. While Fig. 2 shows an example in which the coating film 3 covers the entire surface of the base 2, the coating film 3 does not necessarily have to cover the entire surface of the base 2. The coating film 3 only needs to be located on at least a portion of the surface of the base 2. When the coating film 3 is located on the first surface (here, the top surface) of the base 2, the abrasion resistance and heat resistance of the first surface are high. When the coating film 3 is located on the second surface (here, the side surface) of the base 2, the abrasion resistance and heat resistance of the second surface are high.
  • the coating film 3 is formed on the surface of the substrate 2 using, for example, chemical vapor deposition (CVD) or physical vapor deposition (PVD).
  • the coating film 3 may be, for example, a nitride film containing N (nitrogen).
  • the coating film 3 may contain, for example, Ti (titanium) and N.
  • the coating film 3 may be, for example, a TiN film containing TiN, a nitride of Ti.
  • the coating film 3 may also contain, for example, Ti, N, and C (carbon).
  • the coating film 3 may be, for example, a TiCN film containing TiCN, a carbonitride of Ti.
  • the coating film 3 may also contain, for example, Al (aluminum), Ti, and N.
  • the coating film 3 may be, for example, an AlTiN film containing AlTiN, a nitride of Al and Ti.
  • the coating film 3 may also be a single layer.
  • the cutting insert 1 may also have a layered coating film 3, i.e., two or more layers.
  • Fig. 3 is a schematic view showing a scanning transmission electron microscope photograph of a cross section of the base 2 according to the embodiment.
  • Fig. 3 shows a cross section perpendicular to the normal to the surface of the base 2.
  • the substrate 2 which is made of a hard material, includes a hard phase 5 and a binder phase 6. Specifically, the substrate 2 is made up of hard phases 5 bonded together by the binder phase 6.
  • the hard phase 5 contains WC and N.
  • the binder phase 6 contains at least one iron group element selected from the group consisting of Fe, Co, and Ni, and N.
  • the region up to 1 mm from the surface of the base 2 is defined as the "outer portion” of the base 2.
  • the region located inside the outer portion in the depth direction from the surface of the base 2 is defined as the “inner portion” of the base 2.
  • the inner portion of the base 2 may be a region that is more than 1.5 mm deep from the surface of the base 2.
  • Figure 4 is a graph showing the nitrogen content ratio in the hard phase and binder phase for substrate 2 according to the embodiment and a conventional substrate.
  • the vertical axis shows the N (nitrogen) content ratio in the hard phase 5 and binder phase 6 in each of the outer and inner parts of substrate 2, and the vertical axis shows the N content ratio in the hard phase and binder phase in the outer part of the conventional substrate.
  • Elemental analysis (line analysis) Analysis method Energy dispersive X-ray spectroscopy (EDX) Scanning transmission electron microscope: Hitachi High-Tech HD-2700 Acceleration voltage: 200 kV Beam diameter: approximately 0.2 nm ⁇ Elemental analyzer: Horiba EMAX Evolution X-ray detector: Si drift detector Energy resolution: approx. 130 eV X-ray extraction angle: 24.8° Solid angle: approx. 1.1sr
  • the nitrogen content ratio in the hard layer 5 can be calculated, for example, by performing line analysis over a certain length range on the hard layer 5 as shown in Figure 10, and averaging the total amount of N content measured at intervals of 10 times the beam diameter over that certain length range based on the number of measurement points.
  • the certain length is, for example, 100 nm.
  • the nitrogen content ratio in the bonding phase 6 can also be calculated using a similar method.
  • Figure 10 is a diagram showing the outer portion of the substrate 2 according to the embodiment.
  • the nitrogen content ratio of the outer portion is the nitrogen content ratio measured in a cross section 0.5 mm from the surface of the base 2
  • the nitrogen content ratio of the inner portion is the nitrogen content ratio measured in a cross section 2 mm from the surface of the base 2.
  • the nitrogen content in the hard phase 5 in the outer portion is N OH [atm %]
  • the nitrogen content in the binder phase 6 in the outer portion is N OB [atm %]
  • the nitrogen content in the hard phase 5 in the inner portion is N IH [atm %]
  • the nitrogen content in the binder phase 6 in the inner portion is N IB [atm %].
  • the substrate 2 according to the embodiment has a higher nitrogen content in the hard phase 5 in the outer portion compared to the substrate of the conventional product.
  • the difference ⁇ O between N OB and N OH is smaller than the difference ⁇ I between N IB and N IH .
  • N is appropriately distributed in the hard phase 5 and binder phase 6 in the outer portion, including the surface of the substrate 2, which makes it possible to uniformly improve the affinity of the N-containing coating film 3 with the hard phase 5 and binder phase 6. Therefore, according to this embodiment, the formation of the coating film 3 can be stabilized, which improves the film properties of the coating film 3, such as adhesion, strength, and crystallinity. Furthermore, the excellent strength and crystallinity of the coating film 3 make it possible to improve the durability of the coating film 3, thereby extending the tool life of the cutting insert 1.
  • the difference ⁇ I between N IB and N IH in the inner part of the substrate 2 is relatively large, which reduces the solubility of the hard phase 5 in the binder phase 6. Therefore, according to the embodiment, abnormal grain growth of the hard phase 5 in the inner part of the substrate 2 is inhibited, and the strength of the substrate 2 can be further improved.
  • N IB may be greater than N OB and N IH may be smaller than N OH .
  • the affinity between the hard phase 5 and the binder phase 6 can be improved in the inner portion of the substrate 2, so that the amount of binder phase 6 in the inner portion of the substrate 2 is greater than the amount of binder phase 6 in the outer portion.
  • the amount of binder phase 6 in the outer portion of the substrate 2 becomes relatively smaller, and compressive residual stress is generated in the outer portion of the substrate 2, thereby improving the strength, fracture resistance, and chipping resistance of the substrate 2.
  • the difference ⁇ O between N OB and N OH may be smaller than N OH .
  • the difference ⁇ I between N IB and N IH may be larger than N IH .
  • the solubility of the hard phase 5 in the binder phase 6 is further reduced. Therefore, according to the embodiment, abnormal grain growth of the hard phase 5 in the inner part of the base 2 is further inhibited, and the strength of the base 2 can be further improved.
  • the base 2 preferably has N OH of 0.04 to 0.06 [atm %], N OB of 0.065 to 0.085 [atm %], N IH of 0.02 to 0.04 [atm %], and N IB of 0.07 to 0.1 [atm %].
  • This configuration makes it possible to more uniformly improve the affinity of the hard phase 5 and the binder phase 6 with the coating film 3 in the outer portion, including the surface, of the base 2. Therefore, according to the embodiment, the film properties of the coating film 3 can be further improved.
  • Fig. 5 is a flowchart showing an example of the procedure for the process for producing tungsten carbide powder according to the embodiment.
  • the process for producing tungsten carbide powder includes the following steps (A) to (G).
  • a step of preparing a raw material containing tungsten includes the following steps (A) to (G).
  • D A step of adding a metal compound adsorbent (hereinafter sometimes referred to as an adsorbent) to the solution, reacting the adsorbent with the solution containing the eluted tungsten, and obtaining a compound containing the adsorbent and tungsten;
  • a raw material containing tungsten is prepared.
  • the raw material include ore and scrap containing tungsten.
  • ore containing tungsten include scheelite (CaWO 4 ), wolframite (MnWO 4 ), ferrite (FeWO 4 ), and wolframite ((Fe,Mn)WO 4 ).
  • Scrap containing tungsten is waste generated during the production process of products whose main components are metallic tungsten, tungsten carbide (WC), etc. Specific examples include scrap generated during the manufacturing process of cemented carbide tools, hard scrap such as used tools, and powdery soft scrap such as grinding sludge.
  • Cemented carbide a type of cemented carbide, is primarily composed of composite carbides such as metallic tungsten and tungsten carbide. Components primarily composed of these composite carbides contain iron, nickel, cobalt, or the like as a binder phase, and may optionally contain additives such as TiC, TaC, NbC, VC, and Cr3C2 .
  • Targeted materials containing cemented carbide include cutting tools ( cutting inserts, drills, end mills, etc.), molds (forming rolls, forming dies, etc.), and civil engineering and mining tools (oil drilling tools, rock crushing tools, etc.).
  • Methods for oxidizing tungsten include, for example, oxidizing roasting, which produces a mixture of tungsten oxide (WO 3 ) and cobalt tungstate (CoWO 4 ) by oxidizing roasting a cutting tool containing tungsten carbide and cobalt.
  • oxidizing roasting which produces a mixture of tungsten oxide (WO 3 ) and cobalt tungstate (CoWO 4 ) by oxidizing roasting a cutting tool containing tungsten carbide and cobalt.
  • steps A and B since the purpose of steps A and B is to obtain tungsten oxide from raw materials, these steps may be collectively referred to as the process of preparing raw materials containing tungsten oxide.
  • This process C is an alkali extraction/alkali fusion process in which metal components of the cemented carbide scrap are eluted into an alkali solution to obtain a tungsten compound solution in which tungsten compound ions are dissolved.
  • Methods for obtaining a tungsten compound solution include alkali extraction and alkali fusion.
  • the alkali extraction method is a method in which scrap that has been previously oxidized and roasted is subjected to alkali extraction using, for example, an NaOH aqueous solution.
  • the alkali dissolution method is a method in which molten salts of sodium salts such as NaNO3 , Na2SO4 , Na2CO3 , and NaOH are used to oxidize and dissolve the scrap simultaneously.
  • soft scrap is highly reactive and difficult to control, so it is more efficient to use the alkaline extraction method, while hard scrap can only be oxidized on the surface by oxidizing roasting, so it is more efficient to use the alkaline dissolution method.
  • adsorbent is added to the tungsten compound solution obtained in step C.
  • the adsorbent adsorbs tungsten compound ions in the tungsten compound solution.
  • the adsorbent may be, for example, a first adsorbent and/or a second adsorbent shown below.
  • the first adsorbent contains at least one first amino acid selected from the group consisting of alanine, cystine, methionine, tyrosine, lysine, valine, glutamic acid, histidine, proline, threonine, asparagine, glycine, isoleucine, ornithine, arginine, serine, citrulline, and cystathionine as a free amino acid.
  • the first adsorbent may contain 10 mol% or more of the first amino acid as a free amino acid (sometimes referred to as the first free amino acid) relative to the total amount of free amino acids.
  • the free amino acids in the adsorbent may exist as a solid, or may exist as free amino acids when dissolved in solution. In either case, the solution contains free amino acids, and by using these adsorbents, metal compounds can be recovered through a simple processing process.
  • the first adsorbent is a substrate with free amino acids supported on its surface.
  • the substrate can be, for example, peptides containing free amino acids, proteins, or substances that form living organisms such as microorganisms (hereinafter sometimes referred to as biological substances), organic materials such as resins, or inorganic materials.
  • Microorganisms include bacteria such as E. coli (Escherichia coli), Bacillus sp., Thiobacillus ferrooxidans, Streptomyces rimosus, Pseudomonas sp., Bacillus thuringiensis, Arthrobacternicotianae, Shewanella algae, and Shewanella oneidensis, yeasts such as Saccharomyces cerevisiae, Schizosaccharomyces pombe, Candida albicans, Yarrowia ipolytica, Pichiapastoris, Hansenula polymorpha, and Kluyveromyces lactis, and koji mold.
  • bacteria such as E. coli (Escherichia coli), Bacillus sp., Thiobacillus ferrooxidans, Streptomyces rimosus, Pseudomonas sp., Bacillus thuringiensis, Arthrobacternicotianae, Shewanella
  • Adsorbents made from biological substances come in a variety of forms, including powders, pellets formed from powder, gels, and aqueous solutions. Powders and pellets are easy to store and handle. If the adsorbent is a solid such as a powder or pellet, the solid can be dissolved in another liquid such as water and then added to a solution containing the metal compound, or the solid can be added directly to a solution containing the metal compound and stirred.
  • the first adsorbent preferably contains, as free amino acids, at least one amino acid selected from the group consisting of alanine, cystine, methionine, tyrosine, lysine, valine, glutamic acid, histidine, and proline (hereinafter sometimes referred to as the 1-1 amino acid), at least one amino acid selected from the group consisting of threonine, asparagine, glycine, isoleucine, ornithine, and arginine (hereinafter sometimes referred to as the 1-2 amino acid), and at least one amino acid selected from the group consisting of serine, citrulline, and cystathionine (hereinafter sometimes referred to as the 1-3 amino acid).
  • the 1-1 amino acid at least one amino acid selected from the group consisting of alanine, cystine, methionine, tyrosine, lysine, valine, glutamic acid, histidine, and proline
  • the 1-1 amino acid at least one amino acid selected
  • the first adsorbent may contain, as free amino acids, at least one second amino acid selected from the group consisting of phosphoserine, aspartic acid, leucine, and phenylalanine, in a ratio of 40 mol% or less of the total amount of free amino acids.
  • An adsorbent containing the 1-1 amino acid, the 1-2 amino acid, and the 1-3 amino acid as free amino acids can increase the recovery efficiency of metal compounds.
  • the 1-1 amino acid may be contained in a ratio of 5 mol% or more as free amino acids, assuming the total amount of free amino acids to be 100 mol%.
  • lysine may be contained in a ratio of 10 mol% or more as free amino acids.
  • the recovery efficiency of metal compounds is improved.
  • the total amount of the 1-1 amino acids is contained in a ratio of 10 mol% or more as free amino acids. This improves the recovery efficiency of metal compounds.
  • the total amount of free amino acids consisting of the first amino acid may be 0.5% by mass or more relative to the total amount of solids obtained by drying the adsorbent, i.e., the solid content of the adsorbent. In such cases, the recovery efficiency of metal compounds is improved.
  • the free amino acids contain aspartic acid and at least one of glutamic acid and valine as free amino acids
  • the content of at least one of glutamic acid and valine may be greater than that of aspartic acid.
  • Free amino acids consisting of glutamic acid and valine have a positive zeta potential when the pH of the solution is adjusted to the acidic side, and adsorb metal compound ions (anions) in the solution.
  • aspartic acid has a low ability to adsorb metal compounds (ions). Therefore, when the content of at least one of glutamic acid and valine in the free amino acids is greater than the content of aspartic acid, the adsorption efficiency of metal compounds can be improved.
  • the type and content of free amino acids contained in an adsorbent can be confirmed by free amino acid analysis (also known as biological amino acid analysis).
  • the ratio of the total free amino acid content to the solid content of the adsorbent can be calculated from the mass of the free amino acids in the adsorbent and the mass of the solid content of the adsorbent. If the adsorbent is a solid such as a powder, the adsorbent is added to pure water at a liquid temperature of 25°C, and the adsorbent is suspended by stirring for 10 minutes using a magnetic stirrer at 500 rpm. This suspension is used for free amino acid analysis.
  • the free amino acids in the solution are analyzed, and the mass can be calculated from the total amount of free amino acids and the mass of the solid content of the adsorbent obtained by centrifuging the adsorbent solution.
  • the mass of the solid content of the adsorbent is measured after it has been thoroughly dried under drying conditions, such as at 60°C for 24 hours.
  • the free amino acids contained in the biological material are supported on the surface of a substrate, which is a peptide or protein.
  • a substrate which is a peptide or protein. Supporting free amino acids on peptides or proteins with large molecular weights makes the adsorbent easier to handle, and when recovering the adsorbent with adsorbed metal compounds from a solution containing the metal compounds, it becomes possible to concentrate the adsorbent using a simple method such as filtration.
  • the substrate may be a biological material, a resin, or an inorganic material, but if it is a biological material, the free amino acids can be easily increased. In the first adsorbent, free amino acids are supported on the body surface of a microorganism.
  • the substrate of the adsorbent is a resin or inorganic material, and the substrate is in the form of a powder or porous body with a large specific surface area, a large number of free amino acids can be supported on the surface of the substrate. In the case of a porous body, amino acids can also be supported on the inner walls of the pores.
  • inactive amino acids When the adsorbent is made of a biological substance, in addition to free amino acids, there will be amino acids that do not contribute to the adsorption reaction (hereinafter sometimes referred to as inactive amino acids).
  • inactive amino acids include amino acids that are located in the middle position of amino acids linked by peptide bonds, and amino acids that are located in an internal position that is not exposed on the surface of the adsorbent.
  • the adsorbent When the adsorbent is made from biological substances, it is effective to increase the proportion of free amino acids in the adsorbent by treating it to cleave the peptide bonds of the inactive amino acids present in the adsorbent and converting them into free amino acids.
  • the organic matter is a microorganism
  • the peptide bonds present in the microorganism can be cleaved using existing processing methods.
  • the proteins that make up the microorganism are broken down using proteolytic enzymes such as trypsin, LYSYLENDOPEPTIDASE (registered trademark), and V8 Protease. This makes it possible to convert at least some of the inactive amino acids contained within the microorganism's body into free amino acids.
  • Another effective method for converting inactive amino acids into free amino acids is to subject the adsorbent to heating at 60°C or above, boiling, or heating and pressurizing using an autoclave or similar device to decompose the proteins. Furthermore, if the adsorbent is a living organism such as a microorganism, and does not need to be stored in a solution, but can be stored as a solid like a decomposed inanimate object, then large-scale facilities and maintenance for cultivation and storage are not required, and the facilities can be made smaller.
  • the second adsorbent contains at least one first amino acid selected from the group consisting of alanine, cystine, methionine, tyrosine, lysine, valine, glutamic acid, histidine, proline, threonine, asparagine, glycine, isoleucine, ornithine, arginine, serine, citrulline, and cystathionine, and at least a portion of the first amino acid is present as a free amino acid in the solution.
  • the second adsorbent may also contain 10 mol% or more of the first amino acid in total free amino acid content relative to the total amount of the free amino acids.
  • the second adsorbent exists as a solid and does not contain free amino acids in the solid state, but has free amino acids in solution.
  • An example of a second adsorbent is a salt of a first amino acid.
  • salts include hydrochloride, nitrate, sulfate, acetate, and carbonate.
  • An adsorbent made of an amino acid salt dissolves in a liquid to provide free amino acids.
  • the adsorbent is added to a solution containing a dissolved metal compound, and the pH is adjusted so that the zeta potential of the free amino acids in the adsorbent is positive.
  • the metal compound exists as an anion, and the anions of the metal compound adsorb to the positively charged free amino acids in the adsorbent.
  • the content of free amino acids in the adsorbent can be made higher compared to when free amino acids are supported on the surface of a substrate. This makes it possible to achieve high adsorption efficiency for metal compounds, allowing a large amount of metal compounds to be adsorbed with a small amount of adsorbent. Furthermore, when recovering metal compounds after adsorption, there is a small amount of waste material that needs to be disposed of, making it easy to handle and reducing manufacturing costs. Furthermore, because the adsorbent is not a living organism like bacteria or microorganisms, it is easy to store and manage.
  • the second adsorbent which is an adsorbent made of salt, may be in the form of a solution, but handling, storage, and management are easier when it is solid, and in particular, when it is in powder form, it can be easily dissolved in solution. Furthermore, to make handling of the adsorbent easier, the adsorbent may be in the form of pellets.
  • the adsorbent will have good adsorption efficiency.
  • a salt containing lysine may be used as the adsorbent.
  • examples of salts containing lysine include lysine hydrochloride, lysine sulfate, lysine nitrate, and lysine acetate.
  • lysine hydrochloride for example, L-lysine hydrochloride
  • lysine hydrochloride is stable and inexpensive. Furthermore, when lysine hydrochloride is used as an adsorbent, it is less likely that unwanted elements will be introduced during the acid treatment in the subsequent process.
  • "mainly composed of at least one salt of lysine or arginine” means that the total mass ratio of lysine salt or arginine salt in the adsorbent is 50% by mass or more relative to the total mass of the adsorbent.
  • the total amount of lysine salt and arginine salt present in the adsorbent is preferably 90% by mass or more. This allows a large amount of metal compound to be adsorbed with a small amount of adsorbent. A more desirable range for the total amount of lysine salt and arginine salt present in the adsorbent is 95% by mass or more.
  • Including a salt of glutamic acid as the salt of the first amino acid can reduce the cost of the adsorbent.
  • monosodium glutamate is stable and inexpensive.
  • the content of glutamic acid salts in the adsorbent should be 90% by mass or more. This allows for inexpensive recovery of metal compounds.
  • the desirable range for the total amount of glutamic acid salts in the adsorbent is 95% by mass or more.
  • the free amino acid is not limited to one type; for example, salts of other first amino acids such as lysine and arginine can be added along with the salt of glutamic acid.
  • the adsorbent when the adsorbent is made of microorganisms, 1 g to 10 kg of adsorbent is added per 1 m3 of tungsten compound solution adjusted to a tungsten concentration of 0.1 to 10 mmol/L (0.1 to 10 mmol of tungsten per 1 liter of alkaline solution).
  • the adsorbent is made of a salt of a first amino acid
  • the total amount of salt of the first amino acid added in the adsorbent is added at a content ratio of 0.2 to 1.1 mol per 1 mol of the metal component of the metal compound. This makes it possible to adsorb a large amount of metal compounds, such as tungsten compounds, with a small amount of adsorbent.
  • the total amount of the salt of the first amino acid added may be 10 to 300 g/L relative to the metal compound solution. In such cases, the viscosity of the solution does not increase, and the recovery efficiency of the metal compound is less likely to decrease. In particular, when the adsorbent is made of an amino acid salt, the viscosity of the solution does not increase easily, making it easier to work with.
  • the temperature can be adjusted depending on the activity of the free amino acid, and is usually room temperature.
  • the tungsten compound solution with added adsorbent is adjusted using hydrochloric acid or similar to make the zeta potential of the free amino acid positive. This causes the adsorbent to adsorb the anionic tungsten compound ions.
  • the pH of the solution is less than 7 (acidic).
  • the free amino acids are lysine and arginine
  • the preferred pH is 4 or less, preferably 1 to 3, and more preferably 1 to 2.3.
  • the free amino acid is glutamic acid
  • the preferred pH is 1.5 or less. This increases the recovery rate of tungsten compounds. Note that either the step of adjusting the pH of the solution or the step of adding an adsorbent to the solution containing the metal compound can be carried out first.
  • the adsorbent recovery efficiency is higher if the adsorption reaction lasts for less than one hour. In other words, if the adsorption reaction lasts for more than one hour, some of the adsorbed metal compound may be released from the free amino acid.
  • extracting includes a step of filtering the compound from the solution and a step of drying and powdering the compound recovered by filtering.
  • the adsorbent that has adsorbed tungsten compound ions is filtered through filter paper or the like to recover the compound in a slurry form on the filter paper.
  • the recovered compound is then dried and powdered to extract the powdered tungsten compound containing the adsorbent.
  • the tungsten compound containing the adsorbent refers to, for example, lysine- WO4 when the adsorbent is lysine.
  • Step F A predetermined amount of carbon powder (carbon black, graphite powder, activated carbon, etc.) or carbon slurry is added as a reducing agent to the extracted tungsten compound and mixed (Step F). This produces a mixture of tungsten compound and reducing agent. This mixture is then heated to 1100-2000°C under a predetermined atmosphere for a predetermined time, resulting in carbonization, and tungsten powder primarily composed of tungsten carbide can be obtained (Step G).
  • carbon powder carbon black, graphite powder, activated carbon, etc.
  • major component means that of the components contained in the powder, tungsten carbide accounts for the largest proportion by mass. Specifically, while the powder contains 99 mass% or more of tungsten carbide, it may contain less than 1 mass% of unavoidable impurities. Examples of unavoidable impurities include carbon, hydrogen, nitrogen, oxygen, chromium, vanadium, tantalum, niobium, and titanium.
  • the material may contain 99.2 mass% or more of tungsten carbide and be substantially free of at least one carbide, nitride, or carbonitride selected from the group consisting of elements from groups IVa, Va, and VIa, excluding W.
  • the above-mentioned specified atmosphere may be, for example, a reducing atmosphere containing carbon monoxide, nitrogen, hydrogen, methane, etc.
  • Process G carbonization is carried out in a mixed atmosphere primarily composed of nitrogen and hydrogen.
  • main components means that, of the components contained in the gas, nitrogen and hydrogen are present in greater amounts, in mole percent, than components other than nitrogen and hydrogen. More specifically, this refers to cases where the proportions of nitrogen and hydrogen are 40 mole percent or more and 10 mole percent or more, respectively.
  • the powder extracted in step E is incinerated to remove the adsorbent and extract WO3 .
  • Metallic tungsten is extracted by removing oxygen from this WO3 through a reduction treatment. This metallic tungsten is then carbonized to obtain tungsten carbide powder.
  • the process of removing the adsorbent and extracting WO3 requires incineration at a temperature of 300°C or higher, and the reduction process of WO3 requires heat treatment at a temperature of 800°C to 950°C in a reducing atmosphere (e.g., a hydrogen gas atmosphere). Therefore, a large burden is required to produce tungsten carbide powder.
  • a reducing atmosphere e.g., a hydrogen gas atmosphere
  • the tungsten compound extracted in the above-mentioned process E is directly carbonized to produce WC without undergoing the above-mentioned oxidation and reduction processes. This reduces the burden of producing tungsten carbide powder. Furthermore, when carbonizing the above-mentioned tungsten compound, carbon powder is mixed in to produce a mixture, and this mixture is then heated.
  • the carbon component contained in the adsorbent can be used to carbonize tungsten to obtain WC.
  • the carbon component contained in the adsorbent alone is likely to be insufficient in the G step of carbonizing tungsten, and therefore, not only WC but also W2C is likely to be produced in the G step.
  • step F of the production process of the embodiment carbon powder is mixed with the tungsten compound, which eliminates the above-mentioned carbon shortage, makes it difficult for W 2 C to be produced, and makes it possible to produce WC powder with high purity.
  • the amount of carbon powder added in step F may be adjusted so that the carbon content in the admixture is 5 mass % or more. In this case, tungsten is easily and stably carbonized in step G, so that W2C is not easily generated and WC is easily generated.
  • the amount of carbon powder added in step F may be adjusted so that the carbon content in the mixture is 6% by mass or less.
  • the greater the carbon content in the mixture the more stable the carbonization of tungsten becomes.
  • the carbon content in the mixture is too high, the process of removing the excess carbon that did not bond with tungsten after step G may become complicated.
  • the carbon content in the mixture is 6% by mass or less, the load required to remove the excess carbon is small.
  • the amount of carbon powder may be adjusted taking into account the amount of carbon components contained in the adsorbent.
  • the carbon components in tungsten carbide may not only be derived from the carbon powder, but may also be derived from the carbon components in the adsorbent. In other words, the carbon in the tungsten powder may contain carbon in the adsorbent. If the adsorbent is an organic substance as described above and contains carbon, and the carbon in the tungsten powder contains carbon in the adsorbent, the amount of carbon powder added in step F can be reduced.
  • the hydrogen content may be less than or equal to the nitrogen content. If there is less hydrogen than nitrogen, coarse particles are less likely to form. Note that the nitrogen and hydrogen content ratios being equal do not necessarily have to be exactly the same. If the ratio of (nitrogen content ratio)/(hydrogen content ratio) is between 0.9 and 1.1, it is considered to be "equal.”
  • the tungsten carbide powder production process of this embodiment reduces the number of steps and the amount of chemicals used and waste liquid used compared to conventional tungsten carbide powder production processes, allowing tungsten compounds to be recovered at low cost.
  • the total amount of CO2 emitted by the process of the present application may be approximately 40% of the total amount of CO2 (in terms of energy) emitted by a conventional ion exchange method for producing tungsten carbide via ammonium paratungstate and W metal powder.
  • a conventional ion exchange method for producing tungsten carbide via ammonium paratungstate and W metal powder it is possible to significantly reduce the amount of CO2 emitted.
  • the method for manufacturing the substrate 2 according to the embodiment includes the following steps (X) and (Y).
  • an appropriate amount of cobalt powder is added to the tungsten carbide powder obtained by the production process shown in Figure 5.
  • Metal powders other than cobalt powder and/or carbon powder may also be added at this time.
  • the mixture is then wet mixed in a ball mill for a predetermined period of time, dried, and then molded into a predetermined shape using a known molding method such as press molding, casting, extrusion molding, or cold isostatic pressing to obtain a compact.
  • the molded body is fired in a vacuum or a non-oxidizing atmosphere to produce the base body 2 of the cutting insert 1.
  • the surface of the produced base body 2 may be polished or honed.
  • a coating film 3 may be formed on the surface of the substrate 2 using a CVD or PVD method.
  • the coating film 3 include nitride films such as titanium nitride (TiN), titanium carbonitride (TiCN), and aluminum titanium nitride (AlTiN).
  • Fig. 6 is a front view showing an example of the cutting tool 100 according to the embodiment.
  • the cutting tool 100 includes a cutting insert 1 and a holder 70 for fixing the cutting insert 1.
  • the holder 70 is a rod-shaped member that extends from the front end (upper end in Figure 6) to the rear end (lower end in Figure 6).
  • the holder 70 is made of, for example, steel or cast iron. Of these materials, it is particularly preferable to use steel, which has high toughness.
  • the holder 70 has a pocket 73 at the tip end.
  • the pocket 73 is the portion where the cutting insert 1 is attached, and has a seating surface that intersects with the rotation direction of the workpiece, and a restraining side surface that is inclined relative to the seating surface.
  • the seating surface has a screw hole into which a screw 75 (described below) is threaded.
  • the cutting insert 1 is positioned in the pocket 73 of the holder 70 and attached to the holder 70 by a screw 75. That is, the screw 75 is inserted into the through hole 21 of the cutting insert 1, and the tip of this screw 75 is inserted into the threaded hole formed in the seating surface of the pocket 73 to thread the threaded portions together. In this way, the cutting insert 1 is attached to the holder 70 so that the cutting edge portion protrudes outward from the holder 70.
  • a cutting tool used for so-called turning is exemplified.
  • turning include internal diameter machining, external diameter machining, and grooving.
  • cutting tools are not limited to those used for turning.
  • the cutting insert 1 may be used in cutting tools used for milling.
  • cutting tools used for milling include milling cutters such as flat milling cutters, face milling cutters, side milling cutters, and groove milling cutters, as well as end mills such as single-blade end mills, multi-blade end mills, tapered-blade end mills, and ball end mills.
  • Figures 7 to 9 are explanatory diagrams for explaining an example of a method for manufacturing a machined product according to an embodiment.
  • the machined product is produced by cutting the workpiece 200.
  • the manufacturing method of the machined product in this embodiment includes the following steps: (1) rotating the workpiece 200; (2) bringing the cutting tool 100 into contact with the rotating workpiece 200; (3) a step of separating the cutting tool 100 from the workpiece 200; It is equipped with:
  • the workpiece 200 is rotated around axis O2, and the cutting tool 100 is brought relatively close to the workpiece 200.
  • Typical examples of materials for the workpiece 200 include carbon steel, alloy steel, stainless steel, cast iron, and non-ferrous metals.
  • the cutting edge of the cutting tool 100 is brought into contact with the workpiece 200 to cut the workpiece 200.
  • the cutting tool 100 is moved relatively away from the workpiece 200.
  • the axis O2 is fixed and the workpiece 200 is rotated around the axis O2 while the cutting tool 100 is moved in the Y1 direction to approach the workpiece 200.
  • the cutting edge of the cutting insert 1 is brought into contact with the rotating workpiece 200 to cut the workpiece 200.
  • the cutting tool 100 is moved away from the rotating workpiece 200 by moving it in the Y2 direction.
  • the cutting tool 100 is moved in each step to bring the cutting tool 100 into contact with the workpiece 200 or to move the cutting tool 100 away from the workpiece 200.
  • the cutting process is not limited to this form.
  • step (1) the workpiece 200 may be brought closer to the cutting tool 100.
  • step (3) the workpiece 200 may be moved away from the cutting tool 100.
  • the workpiece 200 can be kept rotating, and the process of bringing the cutting edge of the cutting insert 1 into contact with different locations on the workpiece 200 can be repeated.
  • the method for manufacturing a machined product may include the steps of rotating the cutting tool 100, bringing the cutting tool 100 into contact with the workpiece 200, and separating the cutting tool 100 from the workpiece 200.
  • the hard member according to the embodiment has a substrate (for example, substrate 2) including a hard phase (for example, hard phase 5) and a binder phase (for example, binder phase 6).
  • the hard phase contains tungsten carbide and nitrogen.
  • the binder phase contains nitrogen and at least one iron-group element selected from the group consisting of iron, cobalt, and nickel.
  • the substrate has an outer portion extending from the surface to a depth of 1 mm, and an inner portion located deeper than the outer portion in the depth direction from the surface.
  • the nitrogen content in the hard phase in the outer portion is N OH [atm %]
  • the nitrogen content in the binder phase in the outer portion is N OB [atm %]
  • the nitrogen content in the hard phase in the inner portion is N IH [atm %]
  • the nitrogen content in the binder phase in the inner portion is N IB [atm %]
  • the difference between N OB and N OH is smaller than the difference between N IB and N IH .
  • the hard member according to the embodiment can improve the film properties of the coating film that coats the substrate.
  • a cutting insert according to the present disclosure may, for example, have a rod-shaped body having a rotation axis and extending from the front end to the rear end, a cutting edge located at a first end of the body, and a groove extending spirally from the cutting edge toward the second end of the body.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

Cet élément dur comprend un corps de base comprenant une phase dure et une phase liante. La phase dure contient du carbure de tungstène et de l'azote. La phase liante contient : au moins un élément du groupe fer choisi dans le groupe constitué par le fer, le cobalt et le nickel ; et de l'azote. Le corps de base présente une partie extérieure comprise entre la surface et 1 mm à partir de celle-ci, et une partie intérieure positionnée davantage à l'intérieur que la partie extérieure dans le sens de la profondeur à partir de la surface. Lorsque NOH [atm%] représente le rapport de teneur en azote dans la phase dure dans la partie extérieure, NOB [atm%] représente le rapport de teneur en azote dans la phase liante dans la partie extérieure, NIH [atm%] représente le rapport de teneur en azote dans la phase dure dans la partie intérieure, et NIB [atm%] représente le rapport de teneur en azote dans la phase liante dans la partie intérieure, la différence entre NOB etNOH est inférieure à la différence entre NIB et NIH.
PCT/JP2025/002855 2024-02-28 2025-01-29 Élément dur, insert de découpe, outil de découpe et procédé de fabrication de la pièce à découper Pending WO2025182417A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013002270A1 (fr) * 2011-06-27 2013-01-03 京セラ株式会社 Alliage dur et outil de coupe
WO2014084389A1 (fr) * 2012-11-29 2014-06-05 京セラ株式会社 Fraise de forme et outil de forme pour bois
WO2019087844A1 (fr) * 2017-10-30 2019-05-09 京セラ株式会社 Plaquette de coupe, outil de coupe et procédé de fabrication de pièce découpée

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013002270A1 (fr) * 2011-06-27 2013-01-03 京セラ株式会社 Alliage dur et outil de coupe
WO2014084389A1 (fr) * 2012-11-29 2014-06-05 京セラ株式会社 Fraise de forme et outil de forme pour bois
WO2019087844A1 (fr) * 2017-10-30 2019-05-09 京セラ株式会社 Plaquette de coupe, outil de coupe et procédé de fabrication de pièce découpée

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