WO2023157965A1 - Ｆｅ基合金、合金部材、製造物及び合金部材の製造方法 - Google Patents

Ｆｅ基合金、合金部材、製造物及び合金部材の製造方法 Download PDF

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WO2023157965A1
WO2023157965A1 PCT/JP2023/005937 JP2023005937W WO2023157965A1 WO 2023157965 A1 WO2023157965 A1 WO 2023157965A1 JP 2023005937 W JP2023005937 W JP 2023005937W WO 2023157965 A1 WO2023157965 A1 WO 2023157965A1
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alloy
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based alloy
bcc
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French (fr)
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晋哉 岡本
秀峰 小関
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Proterial Ltd
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Proterial Ltd
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Priority to JP2024501463A priority Critical patent/JP7708295B2/ja
Priority to EP23756489.3A priority patent/EP4382629A4/en
Priority to US18/689,609 priority patent/US20240392420A1/en
Publication of WO2023157965A1 publication Critical patent/WO2023157965A1/ja
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    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to Fe-based alloys, alloy members, products, methods of manufacturing alloy members, and the like.
  • Patent Document 1 in terms of mass ratio, C is 0.8 to 3.95%, the total amount of W and twice Mo is 30 to 50%, Cr is 3.0 to 5.0%, and V is A high speed tool steel made by powder metallurgy with 1.0-10.0% Co, 5-15% Co, balance Fe and impurities is disclosed.
  • Patent Document 1 when quenching, it contains a large amount of residual carbide, and by dispersing the residual carbide uniformly and finely in the matrix, it has high wear resistance and high toughness and excellent cutting durability.
  • a speed tool steel is disclosed.
  • an object of the present invention is to provide an Fe-based alloy, an alloy member, a product, and a method for manufacturing the alloy member, which are excellent in mechanical properties and wear resistance.
  • the first invention contains C, Cr, W, Mo, and V, the balance being Fe and unavoidable impurity elements, and contains an Fe--BCC phase and a W--Mo enriched phase.
  • the Fe-BCC phase contains 3% to 7% C, 2% to 6% Cr, 0.5% to 8% W, and 3% Mo. 8% or more
  • V is 2% or more and 20% or less
  • Fe is 60% or more and 90% or less
  • the W—Mo enriched phase has a C content of 5% or more and 13% or less and a Cr content of 2% or more and 12% or less.
  • W is 7% or more and 17% or less
  • Mo is 11% or more and 22% or less
  • V is 3% or more and 19% or less
  • Fe is 40% or more and 50% or less
  • the W—Mo enriched phase is composed of the Fe An Fe-based alloy characterized by being formed so as to surround a -BCC phase.
  • C is 0.3% or more and 2.8% or less
  • Cr is 3.0% or more and 10.0% or less
  • W is 1.5% or more and 10.5% or less.
  • Mo is 2.0% or more and 9.0% or less
  • V is 1.0% or more and 8.0% or less
  • the balance is Fe and unavoidable impurity elements.
  • the material further contains one or both of Si and Mn, and that Si is 1.0% or less and Mn is 0.1% or more and 1.0% or less in terms of mass %.
  • the Fe-based alloy as a whole further contains 10.5% or less of Co in terms of mass %
  • the Fe-BCC phase further contains 9% or more and 13% or less of Co
  • the W-Mo enriched phase further contains 6% of Co. More than 11% or less is desirable.
  • the W-Mo enriched phase preferably has a lamellar structure or substantially annular precipitates.
  • an alloy with excellent mechanical properties can be obtained.
  • it has an Fe—BCC phase and a W—Mo enriched phase, and the W—Mo enriched phase is formed so as to surround the Fe—BCC phase.
  • Fe--BCC phase which is relatively soft, is worn preferentially, and the worn portion is formed in the shape of a dimple. Oil such as lubricating oil is held in the dimple-shaped portion, and the occurrence of adhesive wear can be suppressed. Therefore, it has excellent wear resistance.
  • Such an alloy can be obtained by forming a metal powder of a desired composition by an additive manufacturing method (hereinafter referred to as metal additive manufacturing or simply additive manufacturing).
  • the W--Mo enriched phase forms a lamellar structure or substantially annular precipitates, high mechanical properties and wear resistance can be obtained more reliably.
  • a second invention is an alloy member comprising at least a part of the Fe-based alloy according to the first invention.
  • the Fe-based alloy is formed on the surface of the base material of the alloy member, the surface layer thickness from the interface of the base material to the surface of the Fe-based alloy is 0.1 to 2 mm, and the hardness of the surface layer is 700 HV or more.
  • An alloy member having an average grain size of Fe—BCC phase of 3.0 ⁇ m or more is desirable.
  • the alloy member may have one or more of a nitride layer, a compound layer and a ceramic coating layer on the surface of the Fe-based alloy.
  • an alloy layer made of the Fe-based alloy according to the first invention on the surface of the base material, it is possible to obtain a member having a wear-resistant surface.
  • it can be easily repaired by forming an alloy layer again by building up only the damaged part, and it has excellent mechanical properties and wear resistance. An excellent alloy member can be obtained.
  • a third invention is a product characterized by including the alloy member according to the second invention in at least a part thereof.
  • hot stamping dies, cold forging dies, or cold press dies are particularly suitable.
  • C is 0.3% or more and 2.8% or less
  • Cr is 3.0% or more and 10.0% or less
  • W is 1.5% or more and 10.5% or less
  • Mo is 2.0% or more and 9.0% or less
  • V is 1.0% or more and 8.0% or less
  • the balance is Fe and inevitable impurities.
  • the alloy powder further contains Co, and that the Co is 10.5% or less in terms of mass%.
  • the method may further include a surface treatment step of performing a surface treatment on the obtained alloy member, and the surface treatment step may be a nitriding treatment or film formation by a PVD method.
  • an Fe-based alloy an alloy member, a product, and a method for manufacturing an alloy member that are excellent in mechanical properties and wear resistance.
  • the figure which illustrates the schematic structure of the laser lamination-molding method A micrograph of the alloy member of the present invention after laser additive manufacturing.
  • the structure photograph after tempering of the alloy member of FIG. 2A. A micrograph of the alloy member of FIG. 2A after quenching.
  • the structure photograph after tempering of the alloy member of FIG. 2C. A photograph of the structure after quenching and tempering of the forged material F0.
  • the figure which shows HV0.5 of each alloy member. 4 is a micrograph of an alloy member according to another embodiment of the present invention after laser additive manufacturing.
  • the structure photograph after tempering of the alloy member of FIG. 5A. A photograph of the structure after quenching of the alloy member of FIG. 5A.
  • the structure photograph after tempering of the alloy member of FIG. 5C. A photograph of the structure after quenching and tempering of the forged material F01. Element mapping image after laser lamination manufacturing of the alloy member of the present invention
  • the Fe-based alloy of the present embodiment contains C, Cr, W, Mo, and V, the balance being Fe and unavoidable impurity elements, and has an alloy structure containing an Fe—BCC phase and a W—Mo concentrated phase.
  • the Fe-BCC phase contains 3% to 7% C, 2% to 6% Cr, 0.5% to 8% W, 3% to 8% Mo, and 2 to 8% V.
  • 20% Fe, 60% to 90% Fe, and the W—Mo enriched phase has 5% to 13% C, 2% to 12% Cr, 7% to 17% W, and 11% to Mo. 22%, V 3% to 19%, Fe 40% to 50%, and the W--Mo enriched phase is formed so as to surround the Fe--BCC phase.
  • the Fe-based alloy of the present embodiment further contains 10.5% or less Co by mass
  • the Fe-BCC phase contains 9% or more and 13% or less of Co
  • the W-Mo enriched phase contains Co is preferably 6% or more and 11% or less. Also, it is more preferably 3% to 11%, and even more preferably 6% to 10%.
  • the W—Mo concentrated phase is continuously formed in a substantially annular shape, or the W—Mo concentrated phase is divided and arranged in a substantially annular shape.
  • a texture can be obtained in which the enriched phase surrounds the Fe-BCC phase.
  • Such a microscopically inhomogeneous structure that is, a structure in which the W--Mo enriched phase and the Fe--BCC phase are not completely mixed and have a distribution, is formed into a sliding surface. Since the relatively soft Fe-BCC phase wears preferentially against the relatively hard W-Mo-enriched phase, the Fe-BCC phase surrounded by the W-Mo-enriched phase wears like a dimple. It will be done. However, lubricating oil is retained in this dimple-shaped portion, and wear resistance can be improved. Moreover, since such dimple-shaped portions are formed in a dispersed manner, it is possible to suppress the occurrence of adhesive wear.
  • the Fe-based alloy as a whole contains, in terms of % by mass, C of 0.3% or more and 2.8% or less, Cr of 3.0% or more and 10.0% or less, and W of 1.5% or more and 10.0%. 5% or less, Mo is 2.0% or more and 9.0% or less, V is 1.0% or more and 8.0% or less, Co is 10.5% or less, and the balance is Fe and unavoidable impurity elements become.
  • Si and Mn is further included, and that Si is 1.0% or less and Mn is 0.1% or more and 1.0% or less in terms of mass %.
  • Si can be expected to improve oxidation resistance. It is desirable to set it as the said range in consideration of workability.
  • Mn can be expected to have the effect of improving wear resistance and hardenability and reducing embrittlement. On the other hand, considering the influence of embrittlement due to quenching cracks and retained ⁇ , the above range is desirable.
  • the average grain size of the Fe-BCC phase is desirably 3.0 ⁇ m or more, more desirably 5.0 ⁇ m or more.
  • the Fe—BCC phase is a phase in which Fe, C, Cr, W, Mo, V, and Co in the BCC phase are in the ranges described above. A method for calculating the average grain size of the Fe—BCC phase will be described later.
  • the W--Mo enriched phase is a region in which W and Mo are enriched compared to the Fe--BCC phase.
  • the W—Mo enriched phase preferably forms a network lamellar structure or precipitates.
  • the network lamellar structure and precipitates contain particularly large amounts of W and Mo.
  • the lower limit of the total amount of W and Mo (W+Mo) is preferably 15% or more, more preferably 20% or more, still more preferably 26% or more.
  • the upper limit of the total amount of W and Mo (W+Mo) is preferably 60.0% or less, more preferably 52.0% or less, and even more preferably 45.0% or less.
  • the lower limit of the ratio of the total amount of W and Mo (W + Mo) to Fe ((W + Mo) / Fe) in the W-Mo enriched phase is preferably 0.25 or more, more preferably 0. .60 or higher.
  • the upper limit of the ratio of the total amount of W and Mo (W+Mo) to Fe ((W+Mo)/Fe) is preferably 2.50 or less, more preferably 2.40 or less.
  • the Fe-BCC phase is formed in the region surrounded by the network-like lamellar structure of the W-Mo enriched phase or the approximately ring-shaped precipitates. That is, the W--Mo enriched phase is continuously formed in a substantially annular shape so as to surround the Fe--BCC phase (and other phases).
  • the W—Mo-enriched phase continuously formed in a substantially annular shape is often formed in a substantially annular shape with an equivalent circle diameter of about 10 ⁇ m, preferably 5 ⁇ m to 20 ⁇ m in equivalent circle diameter.
  • the lower limit of the average grain size of the Fe-BCC phase formed in the region surrounded by the W-Mo enriched phase is 3.0 ⁇ m, preferably 4.8 ⁇ m, more preferably 5.0 ⁇ m.
  • the upper limit is not particularly limited, it is 8.0 ⁇ m or less, preferably 6.5 ⁇ m or less, and more preferably 5.5 ⁇ m or less.
  • the W--Mo concentrated phase may not be completely continuous and may be divided.
  • the alloy of the present embodiment when the alloy of the present embodiment is subjected to quenching treatment, quenching treatment and tempering treatment, precipitates having a grain size of about 1 ⁇ m are formed in a substantially ring-like arrangement having an equivalent circle diameter of 5 to 20 ⁇ m.
  • the precipitates with a grain size of about 1 ⁇ m are quenched, and the W—Mo enriched phase is once solid-dissolved in the base material, and the carbide-forming elements such as V, W, and Mo are dissolved in the cooling process and tempering process after quenching. is presumed to be a carbide phase precipitated as carbide.
  • the W--Mo concentrated phase should be arranged in a predetermined direction so as to form a generally circular shape as a whole instead of being uniformly dispersed. Such a form is defined as "formed so as to surround the Fe--BCC phase" or “formed in a substantially annular shape".
  • the region surrounded by the W—Mo enriched phase may have fine precipitates with a grain size of about 0.1 to 0.5 ⁇ m.
  • the carbide phase described above is a region in which V, Mo, and W are more concentrated than in the Fe-BCC phase, and C is abundant.
  • C is 10% to 16%
  • Cr is 1% to 5%
  • W is 8% to 25%
  • Mo is 13% to 23%
  • V is 25% to 35%
  • Co from 0% to 5%
  • Fe from 3% to 35%.
  • EDS Energy-Dispersive X-ray Spectroscopy
  • EBSD Backscattering Electron Diffraction
  • SEM Scanning Electron Microscope
  • the acceleration voltage in the SEM is 15 kV
  • the working distance from the objective lens to the observation surface is 10 mm
  • the observation magnification is 3000 times.
  • the evaluation method of the elemental distribution using EDS should just acquire an elemental mapping image by surface analysis in the same field of view of said SEM.
  • eight elements of C, Co, Cr, Fe, Mo, O, V, and W may be targeted.
  • the Fe-BCC phase can also be analyzed in the same manner as above.
  • a phase evaluation method using EBSD is to obtain a phase mapping image of a field of view of 200 ⁇ m ⁇ 200 ⁇ m at a magnification of 400 times.
  • the average grain size of the Fe—BCC phase described above can be calculated as follows. First, a phase map (for example, an RGB image, 200 ⁇ 200 ⁇ m) obtained by EBSD is divided into respective colors (red, green, and blue), and only the Fe-BCC portion is extracted. Noise in this image is filtered out, black-and-white binarization and black-and-white inversion of the image is performed (eg, the original red portion (Fe-BCC phase) is displayed as black).
  • a phase map for example, an RGB image, 200 ⁇ 200 ⁇ m
  • the Fe-BCC phase portion is segmented, and the crystal grain size that forms the Fe-BCC phase within the segmented field of view is calculated and averaged to obtain the Fe-
  • the average grain size forming the BCC phase (the average grain size of the Fe—BCC phase) can be calculated.
  • the phase map obtained by EBSD is red part (Fe-BCC phase), blue part (mainly Fe-FCC phase), green part (Fe-BCC phase, Fe-FCC phase) , hereinafter referred to as the zero solution portion).
  • the Fe—BCC phase is displayed in white by displaying the image of the divided red portion in black and white.
  • the blue portion and the green portion are displayed in white.
  • the value obtained by dividing the red portion (Fe—BCC phase) by the total area can be rephrased as the area ratio.
  • This zero solution portion is a portion that is neither Fe--BCC phase nor Fe--FCC phase, and corresponds to a precipitated carbide portion. After that, by calculating the average area of the precipitated carbide portion in the field of view and calculating the circle-equivalent diameter of that area, it is possible to calculate the circle-equivalent average grain size of the precipitated carbides in the Fe—BCC phase.
  • the unavoidable impurities mean trace impurities that are technically difficult to remove due to trace elements mixed in raw materials, reactions with various members that come into contact during the manufacturing process, and the like.
  • the inevitable impurities specifically refer to Al, Cu, N, Ni, O, P, S, and Ti, for example.
  • P, S, O, N and the like are impurities to be particularly limited. In % by mass, P is preferably 0.03% or less, S is preferably less than 0.003%, O is preferably 0.02% or less, and N is preferably 0.05% or less.
  • the content of these unavoidable impurities is preferably as small as possible, and even better if it is 0%.
  • the Fe-based alloy of the present embodiment uses alloy powder, irradiates the alloy powder with an electron beam or a laser beam to melt and solidify to form a solidified layer, forms a new solidified layer on the solidified layer, Thereafter, this operation can be repeated to obtain an alloy member having a laminated structure. That is, it is manufactured by a so-called additive manufacturing method.
  • the alloy powder is an Fe-based alloy powder containing C, Cr, W, Mo, V, and Co having the predetermined composition described above, with the balance being Fe and unavoidable impurity elements.
  • a predetermined amount of feed materials for each element is weighed so as to obtain an alloy having a predetermined composition range, and these materials are mixed to prepare a raw material powder.
  • Atomized powder is obtained using this raw material powder.
  • the raw material powder is loaded into a crucible, subjected to high-frequency melting, and the molten alloy is dropped from a nozzle below the crucible and sprayed with high-pressure argon to produce gas-atomized powder.
  • An alloy powder can be obtained by classifying the gas-atomized powder.
  • the additive manufacturing method is a manufacturing method in which individual powders are repeatedly melted and solidified to give shape, but if the particle size of the alloy powder is less than 5 ⁇ m, it is difficult to obtain the volume required for one melting and solidification. Therefore, it is difficult to obtain a sound laminate-molded product. On the other hand, if the particle size of the alloy powder exceeds 250 ⁇ m, the volume required for one melting and solidification is too large, making it difficult to obtain a sound laminate-molded product. Therefore, the particle size of the alloy powder is preferably 5 to 250 ⁇ m. More preferably, it is 10 ⁇ m to 150 ⁇ m. It should be noted that the powder obtained by the gas atomization method, which can obtain a spherical shape, is preferable. As for the particle size of the powder, the particle size distribution may be measured using, for example, a laser diffraction particle size distribution analyzer.
  • each layered manufacturing method it is more preferably 10 ⁇ m to 53 ⁇ m for Selective Laser Melting (SLM) and 45 ⁇ m to 105 ⁇ m for Electron Beam Melting (EBM). Also, in the laser beam powder deposition (LMD) method, the thickness is preferably 53 ⁇ m to 150 ⁇ m, more preferably 53 ⁇ m to 106 ⁇ m.
  • SLM Selective Laser Melting
  • EBM Electron Beam Melting
  • the thickness is preferably 53 ⁇ m to 150 ⁇ m, more preferably 53 ⁇ m to 106 ⁇ m.
  • D50 is 50 ⁇ m to 100 ⁇ m.
  • 70 ⁇ m to 80 ⁇ m is more preferable.
  • the Fe-based alloy powder contains, in mass ratio, 0.3% to 2.8% C, 3.0% to 10.0% Cr, 1.5% to 10.5% W, It preferably contains 2.0% to 9.0% Mo, 1.0% to 8.0% V, and the balance consists of Fe. Furthermore, it preferably contains either one or both of Si and Mn. In addition, when Co is included, it can be 10.5% or less.
  • C is 0.3% to 2.8%
  • Si is more than 0% and 1.0% or less
  • Mn is 0.1% to 1.0%
  • Cr is 3.0%.
  • W is 1.5% to 10.5%
  • Mo is 2.0% to 9.0%
  • V is 1.0% to 8.0%
  • the balance is Fe and An Fe-based alloy powder containing unavoidable impurity elements can be used.
  • the Fe-based alloy powder may contain Co.
  • C is 0.3% to 2.8%
  • Si is more than 0% and 1.0% or less
  • Mn is 0.1%
  • Cr is 3.0% to 10.0%
  • W is 1.5% to 10.5%
  • Mo is 2.0% to 9.0%
  • V is 1.0%.
  • An Fe-based alloy powder comprising 0% to 8.0%, more than 0% and 10.5% or less of Co, and the balance being Fe and unavoidable impurity elements can be used.
  • the composition of the alloy powder can be analyzed using, for example, high frequency inductively coupled plasma (ICP) emission spectrometry.
  • ICP inductively coupled plasma
  • a powder bed fusion method which is an additive manufacturing method (referred to as an additive manufacturing method in the present invention) targeting metal materials, is used.
  • PPF Powder Bed Fusion
  • DED Directed Energy Deposition
  • FIG. 1 is a diagram showing a schematic configuration of a layered manufacturing apparatus 1 that performs layered manufacturing using a laser as a heat source among the directional energy deposition methods.
  • the layered manufacturing apparatus 1 mainly includes a powder supply nozzle 3, a focusing lens 5, a protective lens 7, and the like.
  • An alloy powder 11 is supplied to the powder supply nozzle 3 and jetted to the tip of the powder supply nozzle 3 together with argon gas.
  • a laser beam 9 emitted from a laser oscillator (not shown) is condensed by a focusing lens 5 and irradiated near the tip of the powder supply nozzle 3 .
  • a protective lens 7 is provided below the focusing lens 5 .
  • the powder supply nozzle 3 is moved relative to the base plate 17 while supplying the alloy powder 11 onto the base plate 17 (direction A in FIG. 1).
  • the supplied alloy powder 11 is irradiated with a laser beam 9 focused by a focusing lens 5 to form a molten pool 13 in which the alloy powder 11 is melted and solidified to form a model 15 (Fe-based alloy). be able to. If necessary, this process is repeated to laminate the modeled object 15 on the base plate 17 to model a three-dimensional alloy member having at least a portion of the Fe-based alloy.
  • the alloy powder is ejected while moving onto the substrate, and the ejected alloy powder is irradiated with an electron beam or a laser beam to melt and solidify to form a solidified layer.
  • a new solidified layer is formed on top, and this operation is repeated thereafter to obtain an alloy member (molded body) having a laminated structure.
  • the base plate or the surface of the modeled body is melted at high speed by laser irradiation, the raw material powder is supplied into the molten pool created by melting, and then rapidly cooled and solidified. is repeated to produce a modeled body.
  • the shaped body formed on the base plate is the Fe-based alloy of this embodiment.
  • the additive manufacturing conditions are appropriately determined in consideration of the particle size and composition of the raw material powder, the size, shape, characteristics of the molded body, production efficiency, etc., but the alloy of the present embodiment can be selected from the following ranges. can.
  • the thickness of one layer during lamination molding is, for example, 0.1 to 1.0 mm, preferably 0.4 to 0.5 mm.
  • the thickness of the first layer of Fe-based alloy formed on the surface of the base material (base plate) (the thickness from the interface of the base material to the surface of the first layer of Fe-based alloy, including the diffusion layer near the interface) ) is 0.1 to 1 mm, and the total thickness from the interface of the base material to the surface of the Fe-based alloy (thickness including the diffusion layer near the interface) is 0.1 to 2 mm.
  • the beam diameter of the laser is preferably about 3 mm at the irradiation position.
  • the laser output is preferably 1500-2500W.
  • the laser scanning speed is preferably 500-1000 mm/min.
  • the powder supply rate is preferably 10 to 20 g/min.
  • the density of the energy (heat source energy density: J/mm) applied by laser irradiation to melt the raw material powder at a high speed is preferably 90 to 300 J/mm, more preferably 180 to 240 J/mm. If the energy density is too low, the defect rate will increase, and the supplied powder will not melt, making it difficult to maintain the shape of the shaped body. On the other hand, if the energy density is too high, the base plate or the modeled body will melt over a wide area centering on the laser irradiation position, making it difficult to maintain the shape of the modeled body.
  • Energy density E (J/mm) can be obtained from Equation 1 using laser output P (W) and laser scanning speed v (mm/min).
  • the alloys of this embodiment can be used as shaped without heat treatment. Although this is the basic method, heat treatment may be additionally performed as long as the cost is within the allowable range. As the heat treatment, for example, either one of quenching treatment and tempering treatment, or both of them may be applied. However, it is preferable that only the tempering treatment is performed without performing the high temperature quenching treatment.
  • the steel in the case of quenching, can be held at 1180-1220°C for 10-60 minutes and then cooled in oil or water. Cooling in oil is more preferable in order to prevent distortion and quenching cracks. Quenching and cooling using a salt bath may be performed.
  • the tempering treatment is a heat treatment process held at 400° C. or higher and 700° C. or lower. For example, it is preferable to air cool after holding at 560 to 580° C. for 2 to 6 hours.
  • a surface treatment process for surface-treating an alloy member includes, for example, nitriding treatment or film formation by a PVD method on the surface layer of an Fe-based alloy to form a nitride layer, a compound layer, or a ceramic coating layer.
  • any one or more of a nitride layer, a compound layer, and a ceramic coating layer may be selected.
  • the hardness of the surface layer of the alloy member can be evaluated by Vickers hardness HV (hereinafter referred to as hardness), which is preferably 350 HV or more, preferably 500 HV or more, more preferably 700 HV or more, and still more preferably 800 HV. , 900 HV or more is even more preferable. Without heat treatment, 350 HV or more is obtained, preferably 500 HV or more. Further, when heat treatment is performed, 700 HV or more is obtained, preferably 800 HV or more, and more preferably 900 HV or more is obtained.
  • HV Vickers hardness
  • Vickers hardness HV can be measured by, for example, setting the indentation load of the Vickers indenter to 0.5 kg and the residence time during indentation to 10 seconds, and measuring the hardness from the length of the diagonal line of the indentation formed on the measurement surface by indentation of the indenter. You can ask for
  • a product having at least a portion of the alloy member thus obtained is not particularly limited, but is particularly suitable for, for example, hot stamping dies, cold forging dies, and cold press dies.
  • hot stamping dies cold forging dies
  • cold press dies cold press dies.
  • the Fe-based alloy according to the present embodiment does not cause adhesion, etc., and has excellent mechanical properties and excellent wear resistance.
  • Example 1 As an example, a raw material obtained by weighing and mixing predetermined amounts of feed materials of each element so as to obtain a shaped body with the desired composition is charged into a crucible, high-frequency melted in a vacuum, and a nozzle with a diameter of 5 mm under the crucible. The melted alloy was dropped from the chamber and sprayed with high-pressure argon to prepare gas-atomized powder. This gas-atomized powder was classified to obtain an iron-based (Fe-based) alloy powder (raw material powder) having a diameter of 53 to 106 ⁇ m and a D50 of 71 ⁇ m. Tables 1 and 2 show the compositions of the obtained iron-based alloy powders.
  • the raw material powder is supplied to a molten pool formed by laser irradiation on the base plate, followed by high-speed melting and rapid solidification.
  • a shaped body having a width of 3 mm, a length of 80 mm, and a stacking height of about 10 mm was produced.
  • the additive manufacturing conditions were as follows. Maraging steel (YAG (YAG is a registered trademark of Proterial Co., Ltd.) 300 manufactured by Proterial Co., Ltd.) was used for the base plate.
  • the molded bodies those without heat treatment and those with heat treatment were evaluated.
  • As the heat treatment only tempering, only quenching, and quenching and tempering were evaluated.
  • a shaped body only shaped (without heat treatment) was F1
  • a shaped body only tempered was F2
  • a shaped body only quenched was F3
  • a shaped body F4 was quenched and tempered.
  • the quenching treatment was held at 1200° C. for 0.5 hours, and then cooled in oil.
  • the tempering process was held at 560°C for 4 hours, followed by air cooling. Through such heat treatment, a shaped body of the Fe-based alloy according to this example was obtained.
  • the obtained shaped bodies F1 to F4 of the Fe-based alloy of each example were observed and evaluated using SEM and EDS.
  • a test piece for observation was prepared by cutting a part of the shaped body into small pieces, embedding them in resin, and polishing the cut surface of the embedded shaped body to a mirror finish.
  • the observation magnification was 3000 times.
  • an elemental mapping image was obtained using EDS with the same field of view as the SEM image at a magnification of 3000 times. Eight elements of C, Co, Cr, Fe, Mo, O, V, and W were analyzed.
  • FIGS. 2A to 2E Examples of acquired SEM images are shown in FIGS. 2A to 2E.
  • FIG. 2A is a shaped body F1 that has not been heat treated (no heat treatment)
  • FIG. 2B is a shaped body F2 that has been tempered as a heat treatment
  • FIG. 2C is a shaped body F3 that has only been quenched as a heat treatment
  • FIG. 2D is a heat treatment
  • Fig. 2E shows an alloy with the same composition for comparison, but the powder is sintered and forged by a conventional powder metallurgy method, and after heat treatment (quenching + tempering 1 is a diagram showing the structure of a sample subjected to forging (this forged material is hereinafter referred to as F0).
  • FIG. 3 shows an example of an elemental mapping image (W, Mo, Fe, Cr) mapping obtained for the shaped body F1.
  • the elemental mapping image had a field area of 46 ⁇ m ⁇ 35 ⁇ m and a mag
  • FIGS. 2A to 2E it can be seen from the SEM images that a network-like lamellar structure 50 is present in a shaped body F1 that has not been heat-treated as shaped and a shaped body F2 that has only undergone tempering treatment after shaping. It was confirmed. From FIG. 3 showing the elemental mapping image, it was confirmed that the structure containing Mo and W formed a network lamellar structure. It should be noted that the mesh-like lamellar structure and the gray region 52 surrounded by the W—Mo thickened phase can be confirmed, but it is determined that the entire gray region 52 is the Fe—BCC phase. can't. Therefore, the crystal grain size forming the Fe-BCC phase is calculated by the method described above.
  • the mesh-like lamellar structure can be observed in a striped pattern.
  • the network-like lamellar structure 50 observed in this striped pattern contains Fe, Mo, and W.
  • the element concentration of Fe is relatively low, and the element concentration of Mo and W is relatively low.
  • the high portion and the portion having relatively high element concentrations of Fe and relatively low element concentrations of Mo and W were arranged so as to be adjacent to each other, so that the structure could be observed as a network.
  • the lamellar structure 50 is a W—Mo enriched phase in which W and Mo are concentrated compared to the portion other than the lamellar structure.
  • fine precipitates with a grain size of about 0.1 to 0.5 ⁇ m are contained inside the lamellar structure, that is, the Fe—BCC phase 52 (inside the black frame in the figure) surrounded by the W—Mo enriched phase. 56 was confirmed. Further, from the elemental mapping image of FIG. 3, it was confirmed that these precipitates also contained Mo and W.
  • a fine precipitate 56 with a grain size of about 0.1 to 0.5 ⁇ m exists inside the Fe-BCC phase 52 (inside the black frame in the figure) surrounded by precipitates 54 with a grain size of about 1 ⁇ m. From the elemental mapping image, it was confirmed that these precipitates also contained Mo and W.
  • Table 3 shows the composition of each phase of the shaped body F1 without heat treatment.
  • the Fe--BCC phase was analyzed in part A, the W--Mo enriched phase in part B, and the carbide in part C.
  • the W—Mo enriched phase (part B) of the shaped body F1 contains 15.6% W and 14.5% Mo, and the total amount of W and Mo (W+Mo) is It was 30.1%.
  • the ratio of the total amount of W and Mo to Fe ((W+Mo)/Fe) in the concentrated phase was 0.67.
  • the Fe-BCC phase was mainly composed of Fe, and contained Cr, W, Mo, V, Co, C, etc. within a predetermined range.
  • Table 4 shows the composition of each phase of the forged material F0.
  • the Fe—BCC phase was analyzed in part A and W, the Mo-enriched phase in part B, and the carbide in part C.
  • the W and Mo concentrated phase (B portion) of the forged material F0 contains 30.5% W and 22.6% Mo, and the total amount of W and Mo (W+Mo) was 53.1%. Since Fe is 22.1%, the ratio of the total amount of W and Mo to Fe ((W+Mo)/Fe) in the enriched phase was 2.40.
  • the Fe-BCC phase has substantially the same composition as the shaped bodies of the examples, but the forged material F0 has a significantly different composition of the W and Mo-enriched phase compared to the shaped bodies F1 to F4. That is, in the forged material F0, a phase in which W and Mo are concentrated exists, but the phase in which W and Mo are concentrated in the forged material F0 has less Fe than the shaped bodies F1 to F4, W and Mo became a considerably large phase. Also, focusing on V, which has a high carbide-forming ability, it is 5.2% in the W-Mo enriched phase of the shaped body F1, whereas it is 8.2% in the W and Mo enriched phase of the forged material F0.
  • the W and Mo enriched phase of the forged material F0 is harder than, for example, the W--Mo enriched phase of the shaped body F1 without heat treatment.
  • the hard W--Mo enriched phase is uniformly dispersed together with the Fe--BCC phase. As a result, the oil film on the sliding surface is depleted, and adhesive wear is likely to occur.
  • Table 5 is a table showing the results of calculating the average grain size of the Fe-BCC phase for each of F1 to F4 and forged material F0 by the method described above.
  • the average crystal grain size of the Fe-BCC phase is 5.28 ⁇ m for the shaped body F1 without heat treatment, 5.33 ⁇ m for the shaped body F2 subjected to the tempering treatment, and 5.33 ⁇ m for the shaped body F3 subjected to the quenching treatment. It was 4.65 ⁇ m, and the quenched and tempered shaped body F4 was 4.57 ⁇ m.
  • the forging pressure material F0 was 5.17 micrometers.
  • the forged material is obtained by forging after sintering powder and then heat-treating it in order to avoid weight segregation and obtain a uniform structure. According to this method, as described above, it is possible to obtain a structure in which the Fe--BCC phase is relatively small and the W--Mo enriched phase and the Fe--BCC phase are evenly dispersed microscopically.
  • the W—Mo enriched phase was formed continuously like a lamellar structure in a substantially annular shape, or the W—Mo enriched phase was divided but arranged in a substantially annular shape.
  • a structure in which the -Mo enriched phase surrounds the Fe-BCC phase can be obtained.
  • a microscopically inhomogeneous structure (a structure in which the W-Mo enriched phase and the Fe-BCC phase are not completely mixed and a distribution occurs), but when this becomes a sliding surface, , Since the relatively soft Fe-BCC phase wears preferentially against the relatively hard W-Mo-enriched phase, the Fe-BCC phase surrounded by the W-Mo-enriched phase has a thickness of 3.0 ⁇ m or more. It wears out like a dimple with an equivalent circle diameter. Therefore, lubricating oil is retained in the dimple-shaped portion, and wear resistance can be improved. In addition, since such dimple-like portions are dispersedly formed, it is possible to suppress the occurrence of adhesion.
  • the forged material F0 has a high hardness as a whole as described above, since the W--Mo enriched phase and the Fe--BCC phase are uniformly dispersed, the wear progresses substantially uniformly and simultaneously as a whole. . For this reason, dimples and the like do not occur, and the grease tends to run out, which may lead to adhesion. Thus, according to the present embodiment, it is possible to efficiently suppress adhesion and the like.
  • the modeled body F1 which was not heat-treated as it was shaped, exhibited high hardness like 916HV. This is considered to be the effect of the mesh-like lamellar structure.
  • the model F2 which was only tempered after modeling, had 944 HV
  • the forged material F0 which has undergone quenching and tempering, has the highest hardness, but the hardness of the forged material is less than half if it is not quenched and tempered, so it can be said that the molded body has higher hardness. As described above, in this example, a sufficient hardness of 900 HV or more could be obtained regardless of the presence or absence of heat treatment.
  • the shaped bodies F1 and F2 have a mesh-like lamellar structure and can be expected to have high toughness.
  • the Fe-BCC phase and the precipitates 54 are unevenly distributed due to the presence of annular precipitates 54 containing Mo and W in the shaped bodies F3 and F4. are doing.
  • it can be expected to exhibit high toughness like F1 and F2.
  • the shaped bodies containing Co were evaluated, but Co is not necessarily essential.
  • high mechanical properties can be obtained without heat treatment.
  • Sufficient mechanical properties can be obtained.
  • Example 2 Next, using the iron-based alloy powder having the alloy composition shown in Table 7, a shaped body was produced.
  • a crucible was charged with a raw material prepared by weighing and mixing predetermined amounts of feed materials for each element so as to obtain a shaped body with the desired composition, and high-frequency melting was performed in a vacuum.
  • the melted alloy was dropped from the chamber and sprayed with high-pressure argon to prepare gas-atomized powder.
  • This gas-atomized powder was classified to obtain an iron-based (Fe-based) alloy powder having a diameter of 53 to 106 ⁇ m and a D50 of 73 ⁇ m. Co is considered to be contained as an unavoidable impurity element.
  • the raw material powder is supplied to a molten pool formed by laser irradiation on the base plate, followed by high-speed melting and rapid solidification.
  • a shaped body having a width of 3 mm, a length of 80 mm, and a stacking height of about 10 mm was produced.
  • the conditions for layered manufacturing were the same as those in Experiment 1 described above.
  • maraging steel YAG manufactured by Proterial (YAG is a registered trademark of Proterial Co., Ltd.) 300 was used.
  • the molded bodies those without heat treatment and those with heat treatment were evaluated.
  • As the heat treatment only tempering, only quenching, and quenching and tempering were evaluated.
  • F11 is a shaped body only (without heat treatment)
  • F12 is a shaped body that is only tempered
  • F13 is a shaped body that is only quenched
  • F14 is a quenched and tempered shaped body.
  • the quenching treatment was carried out at 1200° C. for 0.5 hours, and then cooled in oil under the same conditions as in Experiment 1.
  • the tempering treatment was carried out by holding at 560°C for 4 hours and then air cooling.
  • the obtained shaped bodies F11 to F14 of the Fe-based alloy were observed and evaluated using SEM and EDS.
  • a test piece for observation was prepared by cutting a part of the shaped body into small pieces, embedding them in resin, and polishing the cut surface of the embedded shaped body to a mirror finish.
  • the observation magnification was 3000 times.
  • an elemental mapping image was obtained using EDS with the same field of view as the SEM image at a magnification of 3000 times. Eight elements of C, Co, Cr, Fe, Mo, O, V, and W were analyzed.
  • FIGS. 5A to 5E Examples of acquired SEM images are shown in FIGS. 5A to 5E.
  • FIG. 5A is a shaped body F11 that has not been heat treated (no heat treatment)
  • FIG. 5B is a shaped body F12 that has been tempered as a heat treatment
  • FIG. 5C is a shaped body F13 that has only been quenched as a heat treatment
  • FIG. Fig. 5E shows an alloy having the same composition for comparison, but the powder is sintered and forged by a conventional powder metallurgy method, and heat-treated (quenching + tempering).
  • 1 is a diagram showing the structure of a sample subjected to the forging (hereinafter referred to as F01).
  • FIG. 6 shows an example of an elemental mapping image (W, Mo, Fe, Cr) mapping obtained for the shaped body F11.
  • the elemental mapping image had a field area of 46 ⁇ m ⁇ 35 ⁇ m and a magnification of 3000 times.
  • the crystal grain size forming the Fe-BCC phase was calculated by the method described above. Further, as shown in FIGS. 5A and 5B , in the shaped body F11 which was not heat-treated as shaped and the shaped body F12 which was only subjected to tempering treatment after shaping, it was found from the SEM images that the network lamellar structure 50 was formed. Confirmed it exists.
  • this network lamellar structure 50 contains Fe, Mo and W, and the element concentration of Fe is relatively low and the element concentration of Mo and W is relatively high. It was confirmed that the structure that can be observed in a mesh shape is formed by arranging adjacent to a portion having a relatively high Mo and a relatively low element concentration of Mo and W. In addition, it was confirmed that the lamellar structure 50 is a W—Mo enriched phase in which W and Mo are concentrated compared to the portion other than the lamellar structure. From the elemental mapping image shown in FIG. 6, it was confirmed that the structure containing Mo and W was formed in a lamellar structure or network.
  • FIG. 5C which is an SEM image of the shaped body F13 subjected to quenching treatment after shaping
  • FIG. 5C which is an SEM image of the shaped body F13 subjected to quenching treatment after shaping
  • FIG. 5C which is an SEM image of the shaped body F13 subjected to quenching treatment after shaping
  • FIG. 5C which is an SEM image of the shaped body F13 subjected to quenching treatment after shaping
  • Table 8 shows the composition of each phase of the shaped body F11 as an example.
  • the Fe--BCC phase was analyzed in part A, the W--Mo enriched phase in part B, and the carbide in part C.
  • the W—Mo enriched phase (part B) of the shaped body F11 contains 7.9% W and 17.4% Mo, and the total amount of W and Mo (W+Mo) is It was 25.3%.
  • the ratio of the total amount of W and Mo to Fe ((W+Mo)/Fe) in the concentrated phase was 0.59.
  • the Fe-BCC phase was mainly composed of Fe, and Cr, W, Mo, V, Co, C, etc. were within a predetermined range.
  • Table 9 shows the composition of each phase of the forged material F01.
  • the Fe—BCC phase was analyzed in part A, the W—Mo enriched phase in part B, and the carbide in part C.
  • the W-Mo enriched phase (B part) of the forged material F01 contains 6.3% W and 10.6% Mo, and the total amount of W and Mo (W + Mo ) was 16.9%. Since Fe is 48.1%, the ratio of the total amount of W and Mo to Fe ((W+Mo)/Fe) in the enriched phase was 0.35.
  • the Fe--BCC phase has substantially the same composition as the compacts of Examples, but the forged material F01 has a different composition of the W--Mo enriched phase compared to the compact F11. More specifically, the W—Mo enriched phase in the forged material F01 has more Fe and less W and Mo than the compact F11.
  • the W--Mo enriched phase of the forged material F01 is harder than, for example, the W--Mo enriched phase of the shaped body F11 without heat treatment.
  • the hard W--Mo enriched phase and the Fe--BCC phase are uniformly dispersed. As a result, the oil film on the sliding surface is depleted, and adhesive wear is likely to occur.
  • Table 10 shows the results of calculating the average grain size of the Fe—BCC phase for each of F11 to F14 and forged material F01 by the method described above.
  • the average crystal grain size of the Fe-BCC phase of the shaped body F11 without heat treatment and the shaped body F12 only tempered is 5.34 ⁇ m for F11, 5.18 ⁇ m for F12, 5.05 ⁇ m for F13, F14 was 4.84 ⁇ m.
  • the average grain size of the Fe—BCC phase of the forged material F01 was 4.62 ⁇ m.
  • the proportion of precipitated carbides in F12 to F14 was 0.6% or more and 2.4% or less.
  • the proportion of Fe--BCC phase was 45.0% or more, and the proportion of precipitated carbides precipitated in the Fe--BCC phase was 0.5% or more.
  • the forged material is obtained by forging after sintering powder and then heat-treating it in order to avoid weight segregation and obtain a uniform structure. According to this method, as described above, it is possible to obtain a structure in which the Fe--BCC phase is relatively small and the W--Mo enriched phase and the Fe--BCC phase are evenly dispersed microscopically.
  • the W--Mo enriched phase is continuously formed in a substantially annular shape (lamellar structure), or the W--Mo enriched phase is divided and arranged in a substantially annular shape.
  • a structure in which the Fe--BCC phase is surrounded by the Mo-enriched phase can be obtained.
  • a microscopically inhomogeneous structure (a structure in which the W-Mo enriched phase and the Fe-BCC phase are not completely mixed and a distribution occurs), but when this becomes a sliding surface, , Since the relatively soft Fe-BCC phase wears preferentially against the relatively hard W-Mo-enriched phase, the Fe-BCC phase surrounded by the W-Mo-enriched phase has a thickness of 4.8 ⁇ m or more. It wears out like a dimple with an equivalent circle diameter. Therefore, oil is retained in the dimple-shaped portion, and wear resistance can be improved. In addition, since such dimple-like portions are dispersedly formed, it is possible to suppress the occurrence of adhesion.
  • the forged material F01 has a high hardness as a whole, since the W--Mo concentrated phase and the Fe--BCC phase are dispersed, the wear progresses almost uniformly and simultaneously. Therefore, dimples and the like do not occur, and the oil film is likely to run out, possibly resulting in adhesion. Thus, according to the present embodiment, it is possible to efficiently suppress adhesion and the like.
  • the modeled body F11 which was not subjected to heat treatment as it was shaped and the modeled body F12 which was only subjected to tempering treatment after shaping had a network-like lamellar structure.
  • ring-shaped precipitates 54 containing Mo and W are also present in the shaped body F13 subjected to quenching treatment after shaping and the shaped body F14 subjected to quenching treatment and tempering treatment. Therefore, the Fe-BCC phase and the precipitates 54 are unevenly distributed. As a result, since hard portions and relatively soft portions coexist in the structure, it can be expected to exhibit high toughness like F1 and F2.
  • the shaped bodies containing Co were evaluated, but Co is not necessarily essential.
  • Co is not necessarily essential.
  • high mechanical properties can be obtained without heat treatment, but even if Co is not contained, sufficient mechanical properties can be obtained by performing heat treatment such as quenching. can be done.

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JP7798238B2 (ja) 2023-09-22 2026-01-14 株式会社プロテリアル Ｆｅ基合金、合金部材及び合金部材の製造方法

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