WO2017098848A1 - ハイエントロピー合金部材、該合金部材の製造方法、および該合金部材を用いた製造物 - Google Patents
ハイエントロピー合金部材、該合金部材の製造方法、および該合金部材を用いた製造物 Download PDFInfo
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- WO2017098848A1 WO2017098848A1 PCT/JP2016/083011 JP2016083011W WO2017098848A1 WO 2017098848 A1 WO2017098848 A1 WO 2017098848A1 JP 2016083011 W JP2016083011 W JP 2016083011W WO 2017098848 A1 WO2017098848 A1 WO 2017098848A1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C1/0433—Nickel- or cobalt-based alloys
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04D—NON-POSITIVE-DISPLACEMENT PUMPS
- F04D17/00—Radial-flow pumps, e.g. centrifugal pumps; Helico-centrifugal pumps
- F04D17/08—Centrifugal pumps
- F04D17/10—Centrifugal pumps for compressing or evacuating
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
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- F04D29/00—Details, component parts, or accessories
- F04D29/02—Selection of particular materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04D—NON-POSITIVE-DISPLACEMENT PUMPS
- F04D29/00—Details, component parts, or accessories
- F04D29/02—Selection of particular materials
- F04D29/023—Selection of particular materials especially adapted for elastic fluid pumps
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04D—NON-POSITIVE-DISPLACEMENT PUMPS
- F04D29/00—Details, component parts, or accessories
- F04D29/26—Rotors specially for elastic fluids
- F04D29/28—Rotors specially for elastic fluids for centrifugal or helico-centrifugal pumps for radial-flow or helico-centrifugal pumps
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04D—NON-POSITIVE-DISPLACEMENT PUMPS
- F04D29/00—Details, component parts, or accessories
- F04D29/26—Rotors specially for elastic fluids
- F04D29/28—Rotors specially for elastic fluids for centrifugal or helico-centrifugal pumps for radial-flow or helico-centrifugal pumps
- F04D29/284—Rotors specially for elastic fluids for centrifugal or helico-centrifugal pumps for radial-flow or helico-centrifugal pumps for compressors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/15—Nickel or cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/20—Refractory metals
- B22F2301/205—Titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/35—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
Definitions
- the present invention relates to a technology of a high entropy alloy, and more particularly to a high entropy alloy member produced by a powder additive manufacturing method, a method for producing the alloy member, and a product using the alloy member.
- High Entropy Alloy has been developed as an alloy with a new technical concept that is completely different from the technical concept of a conventional alloy (for example, an alloy obtained by adding a few minor component elements to one to three main component elements).
- Entropy Alloys has been proposed.
- HEA is defined as an alloy composed of five or more kinds of main metal elements (each 5 to 35 atomic%), and is known to exhibit the following characteristics.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2002-173732 discloses a high-entropy multicomponent alloy obtained by casting or synthesizing a plurality of types of metal elements, the alloy containing 5 to 11 types of main metal elements, A high-entropy multicomponent alloy is disclosed in which the number of moles of one main metal element is 5% to 30% of the total number of moles of the alloy. Further, it is described that the main metal element is selected from a metal element group including aluminum, titanium, vanadium, chromium, iron, cobalt, nickel, copper, zirconium, molybdenum, palladium, and silver.
- Patent Document 1 it is said that a high-entropy multicomponent alloy having higher hardness, higher heat resistance and higher corrosion resistance than conventional carbon steel and alloy carbon steel can be provided in a cast state.
- HEA is prone to element segregation and texture spots during casting due to the complexity of the alloy composition, and it is difficult to obtain a homogeneous ingot. It was. Element segregation and texture spots in alloy members are problems to be solved because they lead to variations in characteristics depending on the part.
- HEA has high hardness and resistance to tempering softening, so that it is difficult to process, and it is difficult to produce a desired shape member by machining. This is a major obstacle to commercialization and commercialization of HEA members, and a problem to be solved.
- HEA has attractive features that cannot be obtained with conventional alloys. Therefore, HEA members with excellent alloy composition / microstructure homogeneity and shape controllability, and their manufacture There is a strong need for method development.
- the object of the present invention is to use a high-entropy alloy (HEA) having high mechanical strength and high corrosion resistance to satisfy the above requirements, and is excellent in alloy composition / microstructure homogeneity and in shape controllability.
- An object of the present invention is to provide a HEA member, a manufacturing method thereof, and a product using the HEA member.
- One aspect of the present invention is an alloy member made of a high-entropy alloy, Co (cobalt), Cr (chromium), Fe (iron), Ni (nickel), Ti (titanium) elements each in the range of 5 atomic percent to 35 atomic percent, and Mo (molybdenum) 0 atoms In a range of more than 8% and less than 8 atomic%, with the remainder consisting of inevitable impurities,
- the alloy member provides a high entropy alloy member in which an intermetallic compound phase of needle-like crystals is dispersed and precipitated in a matrix crystal.
- the present invention can add the following improvements and changes to the high entropy alloy member (I).
- the acicular crystals are dispersed and precipitated in a three-dimensional lattice shape.
- the chemical composition of the high-entropy alloy is such that the Co is 20 atomic% to 35 atomic%, the Cr is 10 atomic% to 25 atomic%, and the Fe is 10 atomic% to 25 atomic%.
- the Ni is contained in an amount of 15 atomic% to 30 atomic% and the Ti is contained in an amount of 5 atomic% to 15 atomic%.
- the chemical composition of the high-entropy alloy is such that the Co is 25 atomic% to 33 atomic%, the Cr is 15 atomic% to 23 atomic%, and the Fe is 15 atomic% to 23 atomic%.
- the Ni is contained in an amount of 17 to 28 atomic%, the Ti is contained in an amount of 5 to 10 atomic%, and the Mo is contained in an amount of 1 to 7 atomic%.
- the high-entropy alloy has a chemical composition of 27 atomic% to 33 atomic% of Co, 18 atomic% to 23 atomic% of Cr, and 18 atomic% to 23 atomic% of Fe.
- the Ni is contained in an amount of 17 atom% to 24 atom%, the Ti is contained in an amount of 5 atom% to 8 atom%, and the Mo is contained in an amount of 1 atom% to 3 atom%.
- the intermetallic compound phase includes a Ni 3 Ti phase.
- Tensile strength is 1000 MPa or more and elongation at break is 3% or more.
- the parent phase crystal has a columnar crystal shape and includes a simple cubic crystal.
- “the crystal structure includes a simple cubic crystal” means “the main crystal structure is a simple cubic crystal”.
- Another aspect of the present invention is a method for producing the high entropy alloy member described above, A raw material mixing and melting step of mixing and melting the raw materials of the alloy to form a molten metal; An atomizing step of forming alloy powder from the molten metal; There is provided a manufacturing method of a high-entropy alloy member, comprising: a layered manufacturing step of forming an alloy layered body having a desired shape by a metal powder layered manufacturing method using the alloy powder.
- the present invention can add the following improvements and changes to the above-described high entropy alloy member production method (II).
- the additive manufacturing process includes a powder bed forming process for forming a powder bed of the alloy powder, A powder bed calcining step of heating the entire powder bed to form a pre-sintered powder bed; The temporary sintered body is locally heated to form a micro molten pool of the alloy, and the micro molten pool is moved and sequentially solidified while scanning the local heating in the plane of the temporary sintered body. And a local melting / solidifying layer forming step of forming a solidified layer of the alloy.
- Still another embodiment of the present invention is a product using the above-mentioned high entropy alloy member, Provided is a product using a high-entropy alloy member, wherein the product is an impeller of a fluid machine.
- the present invention can be improved or changed as follows.
- (Ix) The product is a centrifugal compressor incorporating the impeller.
- a high-entropy alloy having high mechanical strength and high corrosion resistance is used, an HEA member having excellent alloy composition / microstructure homogeneity and excellent shape controllability, and a manufacturing method thereof, and A product using the HEA member can be provided.
- HSA high-entropy alloys
- the present inventors have conducted extensive research on alloy compositions and shape control methods in order to develop HEA members having excellent shape controllability and ductility without sacrificing the characteristics of HEA.
- an HEA member that solves the problem can be obtained by forming an alloy additive manufacturing body by a metal powder additive manufacturing method using powder of a Co-Cr-Fe-Ni-Ti-Mo alloy. .
- the present invention has been completed based on this finding.
- FIG. 1 is a process diagram showing an example of a method for producing a high-entropy alloy member according to the present invention.
- the manufacturing method of this invention has a raw material mixing melt
- a raw material mixing and dissolving step is performed in which raw materials are mixed and dissolved to form a molten metal 10 so as to have a desired HEA composition (Co—Cr—Fe—Ni—Ti—Mo).
- HEA composition Co—Cr—Fe—Ni—Ti—Mo
- vacuum melting can be suitably used as a melting method.
- the HEA composition of the present invention includes 5 elements of Co, Cr, Fe, Ni, and Ti as main components in a range of 5 atomic% to 35 atomic%, respectively, and Mo as an auxiliary component is more than 0 atomic% and less than 8 atomic%. And the remainder consists of inevitable impurities.
- the Co component is preferably 20 atom% or more and 35 atom% or less, more preferably 25 atom% or more and 33 atom% or less, and further preferably 27 atom% or more and 33 atom% or less.
- the Cr component is preferably 10 atomic percent to 25 atomic percent, more preferably 15 atomic percent to 23 atomic percent, and still more preferably 18 atomic percent to 23 atomic percent.
- the Fe component is preferably 10 atomic percent to 25 atomic percent, more preferably 15 atomic percent to 23 atomic percent, and still more preferably 18 atomic percent to 23 atomic percent.
- the Ni component is preferably 15 atomic% to 30 atomic%, more preferably 17 atomic% to 28 atomic%, and still more preferably 17 atomic% to 24 atomic%.
- the Ti component is preferably 5 atom% or more and 15 atom% or less, more preferably 5 atom% or more and 10 atom% or less, and further preferably 5 atom% or more and 8 atom% or less.
- the Mo component is preferably more than 0 atom% and less than 8 atom%, more preferably 1 atom% to 7 atom%, and still more preferably 1 atom% to 3 atom%.
- an atomizing process for forming the alloy powder 20 from the molten metal 10 is performed.
- a conventional method can be used.
- a gas atomization method or a centrifugal atomization method that can obtain high-purity, homogeneous composition, and spherical particles can be preferably used.
- the average particle diameter of the alloy powder 20 is preferably 10 ⁇ m or more and 1 mm or less, and more preferably 20 ⁇ m or more and 500 ⁇ m or less, from the viewpoints of handling properties and filling properties.
- the average particle size is less than 10 ⁇ m, the alloy powder 20 is likely to rise in the subsequent layered manufacturing process, which causes a decrease in the shape accuracy of the alloy layered body.
- the average particle size exceeds 1 mm, it becomes a factor that the surface roughness of the alloy layered structure is increased or the melting of the alloy powder 20 becomes insufficient in the next layered manufacturing process.
- an additive manufacturing process for forming an alloy additive manufacturing body 230 having a desired shape is performed by a metal powder additive manufacturing method using the alloy powder 20 prepared above.
- a metal powder additive manufacturing method for forming a near net shape metal member by melting and solidification instead of sintering a three-dimensional member having a complex shape with a hardness equal to or higher than that of a cast material can be produced.
- the additive manufacturing method is not particularly limited, and a conventional method can be used.
- a metal powder additive manufacturing method using an electron beam melting (EBM) method or a selective laser melting (SLM) method can be suitably used.
- FIG. 2 is a schematic cross-sectional view showing an example of a structure of an EBM method powder additive manufacturing apparatus and an additive manufacturing method.
- the EBM powder additive manufacturing apparatus 100 is roughly divided into an electron beam control unit 110 and a powder control unit 120, and the whole is a vacuum chamber.
- the stage 121 is lowered by one layer thickness (for example, about 30 to 800 ⁇ m) of the alloy laminate model 230 to be modeled.
- the alloy powder 20 is supplied from the powder hopper 123 onto the base plate 122 on the upper surface of the stage 121, and the alloy powder 20 is flattened by the rake arm 124 to form a powder bed 210 (layered powder) (powder bed forming step).
- Thermoelectrons are emitted from the heated tungsten filament 111 (for example, 2500 ° C. or higher) and accelerated by the anode 112 (for example, about half the speed of light) to form an electron beam 113.
- the accelerated electron beam 113 is rounded by the astigmatism correction device 114 and focused on the powder bed 210 by the focus coil 115.
- a relatively weak (loose) focused beam is scanned by the deflection coil 116 to preheat the entire powder bed 210 to form a temporary sintered body of the powder bed.
- the calcining temperature of the powder bed 210 is preferably 900 ° C. or higher and 1000 ° C. or lower.
- the calcining temperature is less than 900 ° C., the sintering of the alloy powder hardly proceeds, and it becomes difficult to form a calcined body.
- the calcining temperature exceeds 1000 ° C., the sintering of the alloy powder proceeds so much that it is difficult to take out the alloy laminate model 230 (separation between the alloy laminate model 230 and the provisional sintered product).
- the presintered body of the powder bed is irradiated with a strong focused beam for local melting and alloyed
- a 2D slice-shaped solidified layer 220 is formed by scanning the focused beam and moving and sequentially solidifying the fine molten pool (local melting / solidified layer forming step).
- an extraction step of taking out the alloy layered model 230 is performed next.
- the method for taking out the alloy laminate model 230 the separation method between the alloy laminate model 230 and the temporary sintered body, the separation method between the alloy laminate model 230 and the base plate 122
- the conventional method can be used.
- sand blasting using the alloy powder 20 can be preferably used. Sandblasting using the alloy powder 20 has an advantage that it can be reused as the alloy powder 20 by crushing together with the alloy powder 20 sprayed with the removed pre-sintered body.
- the parent phase of the alloy laminate model 230 has a structure in which fine columnar crystals (average particle size of 100 ⁇ m or less) are forested along the lamination direction of the alloy laminate model 230 (so-called rapid solidification structure). It was. As a result of further observation, it was observed that in the alloy laminate model 230, acicular crystals of an intermetallic compound phase were dispersed and precipitated in a lattice pattern in the parent phase crystal.
- FIG. 3A is an electron microscope observation image showing an example of a microstructure of a cross section (a surface perpendicular to the stacking direction and a surface in which the stacking direction is a normal line) of an alloy laminate model formed of HEA according to the present invention.
- FIG. 3B is an electron microscope observation image showing an example of a microstructure of a longitudinal section (a surface along the stacking direction, a surface having a normal line perpendicular to the stacking direction) of the alloy laminate shaped body made of HEA according to the present invention.
- the acicular crystals are dispersed and precipitated in a lattice shape in both the cross section and the longitudinal section of the alloy laminate model 230, the acicular crystals are three-dimensional. It was thought that it was dispersed and precipitated in a lattice form.
- FIG. 4 is a photograph showing an impeller of a fluid machine as an example of a product using the HEA member according to the present invention. Since the HEA product of the present invention is manufactured by the metal powder additive manufacturing method, even a complicated shape as shown in FIG. 4 can be easily modeled. Further, since the impeller using the HEA member of the present invention has both high mechanical properties and high corrosion resistance, it can exhibit excellent durability even under severe stress / corrosion environments.
- FIG. 5 is a schematic cross-sectional view showing a centrifugal compressor in which the impeller of the present invention is incorporated, which is another example of a product using the HEA member according to the present invention.
- Example 1 (Preparation of HEA powder 1-6)
- the raw materials were mixed with the nominal composition shown in Table 1, and the raw material mixing and dissolving step was performed in which the molten metal was formed by melting by a vacuum melting method.
- the atomization process which forms alloy powder from a molten metal was performed by the gas atomization method.
- the obtained alloy powder was classified by sieving to select a particle size of 45 to 105 ⁇ m to prepare HEA powders 1 to 6.
- the average particle size of each was about 70 ⁇ m.
- Example 2 Preparation of HEA members 1e to 6e of an alloy laminate model
- the alloy additive manufacturing using the EBM method is performed according to the procedure of the additive manufacturing process.
- a body 14 mm diameter x 85 mm high columnar material, height direction is the stacking direction
- the calcining temperature of the powder bed was 950 ° C.
- an extraction process of removing the temporary sintered body around the alloy additive manufacturing body by sandblasting using HEA powder 1 was performed, and the HEA member 1e of the alloy additive manufacturing body was taken out.
- the HEA powders 2 to 6 were subjected to the additive manufacturing process and the extraction process in the same manner as described above, thereby producing HEA members 2e to 6e of alloy additive manufacturing objects.
- HEA members 2c to 4c of ordinary cast materials were produced in the same manner as the HEA member 1c.
- Example 4 (Microstructure observation of HEA materials) A specimen for microstructural observation was collected from each HEA member produced above, and microscopic observation was performed using an optical microscope, a scanning electron microscope (SEM), and an X-ray diffraction (XRD) apparatus. Table 2 shows the microstructure observation results together with the production specifications of each HEA member.
- the matrix structure of the HEA members 1e to 6e produced by the additive manufacturing method is a structure in which fine columnar crystals (average particle size of 100 ⁇ m or less) are forested along the stacking direction of the alloy additive manufacturing body. (So-called rapidly solidified structure).
- the crystal structure of the columnar crystals was basically simple cubic (SC).
- SC face-centered cubic
- the matrix structure of the HEA members 1c to 4c produced by the ordinary casting method had a structure composed of equiaxed crystals having an average particle diameter of more than 100 ⁇ m.
- the crystal structure of the columnar crystal clearly contained FCC.
- the main precipitation phase was a Ni 3 Ti phase in all HEA members. From the XRD measurement results, the precipitation of NiTi phase and NiTi 2 phase could not be denied (in other words, there was a possibility that NiTi phase and NiTi 2 phase were slightly precipitated).
- 3A and 3B shown above are electron microscope observation images showing examples of the microstructure of the HEA member 1e.
- FIG. 6 is an electron microscope observation image showing an example of the microstructure of the HEA member 1c.
- the acicular crystals of the main precipitation phase were dispersed and precipitated in a three-dimensional lattice shape.
- the acicular crystals were randomly assembled.
- Each specimen was subjected to a room temperature tensile test using a universal material testing machine (based on JIS Z 2241, strain rate: 5 ⁇ 10 ⁇ 5 s ⁇ 1 ), and the tensile strength and elongation at break were measured.
- the measurement result of the tensile test was obtained as an average value of 8 measurements excluding the maximum value and the minimum value of 10 measurements.
- 1000 MPa or more was judged as “pass”, and less than 1000 MPa was judged as “fail”.
- the evaluation of elongation at break was 3% or more as “pass” and less than 3% as “fail”. The results are shown in Table 3 below.
- a polarization test piece (15 mm long ⁇ 15 mm wide ⁇ 2 mm thick) for pitting corrosion test was collected from each HEA member produced above. The pitting corrosion test was performed on each polarization test piece in accordance with JIS G 0577.
- the HEA members 1e to 3e, 5e, and 6e produced by the additive manufacturing method as an example of the present invention exhibit a tensile strength of 1000 MPa or more and a breaking elongation of 3% or more, which are good. It has been demonstrated that it has excellent mechanical properties. Further, it was confirmed that the HEA members 5e and 6e having relatively low contents of the Ni component and the Ti component are particularly excellent in elongation at break.
- the HEA members 1c to 4c and the HEA member 4e whose alloy composition does not fall within the scope of the present invention, which are comparative casting examples, have a tensile strength of less than 1000 MPa and / or an elongation at break of less than 3%.
- the overall mechanical properties were unacceptable.
- the HEA member 4e was rejected in spite of being manufactured by the additive manufacturing method, so that it was confirmed that addition of Mo exceeding 8 atomic% was not preferable.
- the HEA member of the present invention is considered to have excellent corrosion resistance due to the combination of elements itself (Co—Cr—Fe—Ni—Ti—Mo).
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Abstract
Description
Co(コバルト)、Cr(クロム)、Fe(鉄)、Ni(ニッケル)、Ti(チタン)の各元素をそれぞれ5原子%以上35原子%以下の範囲で含み、かつMo(モリブデン)を0原子%超8原子%以下の範囲で含み、残部が不可避不純物からなる化学組成を有し、
前記合金部材は、母相結晶中に針状結晶の金属間化合物相が分散析出していることを特徴とするハイエントロピー合金部材を提供する。
(i)前記針状結晶は、三次元格子状に分散析出している。
(ii)前記ハイエントロピー合金の化学組成は、前記Coを20原子%以上35原子%以下で、前記Crを10原子%以上25原子%以下で、前記Feを10原子%以上25原子%以下で、前記Niを15原子%以上30原子%以下で、前記Tiを5原子%以上15原子%以下で含む。
(iii)前記ハイエントロピー合金の化学組成は、前記Coを25原子%以上33原子%以下で、前記Crを15原子%以上23原子%以下で、前記Feを15原子%以上23原子%以下で、前記Niを17原子%以上28原子%以下で、前記Tiを5原子%以上10原子%以下で、前記Moを1原子%以上7原子%以下で含む。
(iv)前記ハイエントロピー合金の化学組成は、前記Coを27原子%以上33原子%以下で、前記Crを18原子%以上23原子%以下で、前記Feを18原子%以上23原子%以下で、前記Niを17原子%以上24原子%以下で、前記Tiを5原子%以上8原子%以下で、前記Moを1原子%以上3原子%以下で含む。
(v)前記金属間化合物相は、Ni3Ti相を含む。
(vi)引張強さが1000 MPa以上であり、破断伸びが3%以上である。
(vii)前記母相結晶は、形状が柱状晶であり、その結晶構造が単純立方晶を含む。なお、ここでの「結晶構造が単純立方晶を含む」は、「主たる結晶構造が単純立方晶であること」を意味する。
前記合金の原料を混合・溶解して溶湯を形成する原料混合溶解工程と、
前記溶湯から合金粉末を形成するアトマイズ工程と、
前記合金粉末を用いた金属粉末積層造形法により所望形状を有する合金積層造形体を形成する積層造形工程とを有することを特徴とするハイエントロピー合金部材の製造方法を提供する。
(viii)前記積層造形工程は、前記合金粉末の粉末床を形成する粉末床形成工程と、
前記粉末床全体を加熱して粉末床の仮焼結体を形成する粉末床仮焼工程と、
前記仮焼結体を局所加熱して前記合金の微小溶融池を形成すると共に該局所加熱を該仮焼結体の面内で走査しながら前記微小溶融池を移動・逐次凝固させることにより、前記合金の凝固層を形成する局所溶融・凝固層形成工程とを有する。
前記製造物が、流体機械のインペラであることを特徴とするハイエントロピー合金部材を用いた製造物を提供する。
(ix)前記製造物は、前記インペラを組み込んだ遠心圧縮機である。
前述したように、ハイエントロピー合金(HEA)は、従来合金では得られない魅力的な特徴(例えば、高硬度、焼き戻し軟化抵抗性)を有しているが、難加工性であり、所望形状部材を作製することが難しいという問題があった。また、本発明者等がHEAについて種々研究したところ、従来の普通鋳造組織を有するHEA鋳塊は、変形抵抗が高い上に延性に乏しいことが判った。
図1は、本発明に係るハイエントロピー合金部材の製造方法の一例を示す工程図である。図1に示したように、本発明の製造方法は、原料混合溶解工程とアトマイズ工程と積層造形工程と取出工程とを有する。以下、本発明の実施形態をより具体的に説明する。
図1に示したように、まず、所望のHEA組成(Co-Cr-Fe-Ni-Ti-Mo)となるように原料を混合・溶解して溶湯10を形成する原料混合溶解工程を行う。原料の混合方法や溶解方法に特段の限定はなく、高強度・高耐食性合金の製造における従前の方法を利用できる。例えば、溶解方法として真空溶解を好適に利用できる。また、真空炭素脱酸法などを併用して、溶湯10を精錬することが好ましい。
次に、溶湯10から合金粉末20を形成するアトマイズ工程を行う。アトマイズ方法に特段の限定はなく、従前の方法を利用できる。例えば、高純度・均質組成・球形状粒子が得られるガスアトマイズ法や遠心力アトマイズ法を好ましく用いることができる。
次に、上記で用意した合金粉末20を用いた金属粉末積層造形法により、所望形状を有する合金積層造形体230を形成する積層造形工程を行う。焼結ではなく溶融・凝固によってニアネットシェイプの金属部材を造形する金属粉末積層造形法の適用により、鋳造材と同等以上の硬度とともに、複雑形状を有する三次元部材を作製することができる。積層造形方法に特段の限定はなく、従前の方法を利用できる。例えば、電子ビーム溶融(Electron Beam Melting:EBM)法や選択的レーザ溶融(Selective Laser Melting:SLM)法を用いた金属粉末積層造形法を好適に利用できる。
上記工程で造形した合金積層造形体230は仮焼結体中に埋没しているため、次に、合金積層造形体230を取り出す取出工程を行う。合金積層造形体230の取り出し方法(合金積層造形体230と仮焼結体との分離方法、合金積層造形体230とベースプレート122との分離方法)に特段の限定はなく、従前の方法を利用できる。例えば、合金粉末20を用いたサンドブラストを好ましく用いることができる。合金粉末20を用いたサンドブラストは、除去した仮焼結体を吹き付けた合金粉末20と共に解砕することで、合金粉末20として再利用することができる利点がある。
取出工程の後、合金積層造形体230から微細組織観察用の試料を採取し、光学顕微鏡および電子顕微鏡を用いて、該試料の微細組織を観察した。その結果、合金積層造形体230の母相は、微細な柱状晶(平均粒径100μm以下)が合金積層造形体230の積層方向に沿って林立した組織(いわゆる、急冷凝固組織)を有していた。さらに微細に観察したところ、合金積層造形体230は、その母相結晶中に金属間化合物相の針状結晶が格子状に分散析出している様子が観察された。
図4は、本発明に係るHEA部材を用いた製造物の一例であり、流体機械のインペラを示す写真である。本発明のHEA製造物は金属粉末積層造形法により製造されることから、図4に示したような複雑形状物でも容易に造形することができる。また、本発明のHEA部材を用いたインペラは、高い機械的特性と高い耐食性とを兼ね備えることから、厳しい応力・腐食環境下でも優れた耐久性を示すことができる。
(HEA粉末1~6の用意)
表1に示す名目組成で原料を混合し、真空溶解法により溶解して溶湯を形成する原料混合溶解工程を行った。次に、ガスアトマイズ法により、溶湯から合金粉末を形成するアトマイズ工程を行った。次に、得られた合金粉末に対して、ふるいによる分級を行って粒径45~105μmに選別してHEA粉末1~6を用意した。レーザ回折式粒度分布測定装置を用いて、HEA粉末1~6の粒度分布を測定したところ、それぞれの平均粒径は約70μmであった。
(合金積層造形体のHEA部材1e~6eの作製)
実験1で用意したHEA粉末1に対し、図2に示したような粉末積層造形装置(Arcam AB社製、型式:A2X)を用いて、積層造形工程の手順に沿ってEBM法による合金積層造形体(直径14 mm×高さ85 mmの円柱材、高さ方向が積層方向)を造形した。粉末床の仮焼温度は950℃とした。
(普通鋳造材のHEA部材1c~4cの作製)
実験1で用意したHEA粉末1に対し、銅製の水冷鋳型を用いたアーク溶解法により、普通鋳造材(幅14 mm×長さ80 mm×高さ15 mmの角柱材)を鋳造して、普通鋳造材のHEA部材1cを作製した。なお、鋳造時の元素偏析や組織斑をできるだけ抑制するため、5回以上繰り返し溶解を行った。
(HEA部材の微細組織観察)
上記で作製した各HEA部材から微細組織観察用の試験片を採取し、光学顕微鏡、走査型電子顕微鏡(SEM)、X線回折(XRD)装置を用いて、微細組織観察を行った。各HEA部材の作製仕様と共に、微細組織観察結果を表2に示す。
(HEA部材の機械的特性および耐食性の測定)
上記で作製した各HEA部材から引張試験用の試験片(平行部直径:4 mm、平行部長さ:20 mm)を採取した。なお、積層造形法で作製したHEA部材1e~6eは、試験片長手方向が積層造形方向と一致するように採取した。
(HEA部材を用いた製造物の作製・検査)
HEA部材1eの製造方法と同様にして(HEA粉末1を用いた積層造形によって)、図4に示したインペラを作製した。得られたインペラに対して、X線CTスキャンによる内部欠陥検査と、寸法測定とを行った。その結果、特段の内部欠陥は認められず、設計寸法に対する変形も認められなかった。本実験から、本発明の有効性が確認された。
Claims (12)
- ハイエントロピー合金からなる合金部材であって、
Co、Cr、Fe、Ni、Tiの各元素をそれぞれ5原子%以上35原子%以下の範囲で含み、かつMoを0原子%超8原子%以下の範囲で含み、残部が不可避不純物からなる化学組成を有し、
前記合金部材は、母相結晶中に針状結晶の金属間化合物相が分散析出していることを特徴とするハイエントロピー合金部材。 - 請求項1に記載のハイエントロピー合金部材において、
前記針状結晶は、三次元格子状に分散析出していることを特徴とするハイエントロピー合金部材。 - 請求項1又は請求項2に記載のハイエントロピー合金部材において、
前記ハイエントロピー合金の化学組成は、前記Coを20原子%以上35原子%以下で、前記Crを10原子%以上25原子%以下で、前記Feを10原子%以上25原子%以下で、前記Niを15原子%以上30原子%以下で、前記Tiを5原子%以上15原子%以下で含むことを特徴とするハイエントロピー合金部材。 - 請求項1又は請求項2に記載のハイエントロピー合金部材において、
前記ハイエントロピー合金の化学組成は、前記Coを25原子%以上33原子%以下で、前記Crを15原子%以上23原子%以下で、前記Feを15原子%以上23原子%以下で、前記Niを17原子%以上28原子%以下で、前記Tiを5原子%以上10原子%以下で、前記Moを1原子%以上7原子%以下で含むことを特徴とするハイエントロピー合金部材。 - 請求項1又は請求項2に記載のハイエントロピー合金部材において、
前記ハイエントロピー合金の化学組成は、前記Coを27原子%以上33原子%以下で、前記Crを18原子%以上23原子%以下で、前記Feを18原子%以上23原子%以下で、前記Niを17原子%以上24原子%以下で、前記Tiを5原子%以上8原子%以下で、前記Moを1原子%以上3原子%以下で含むことを特徴とするハイエントロピー合金部材。 - 請求項1乃至請求項5のいずれか一項に記載のハイエントロピー合金部材において、
前記金属間化合物相は、Ni3Ti相を含むことを特徴とするハイエントロピー合金部材。 - 請求項1乃至請求項6のいずれか一項に記載のハイエントロピー合金部材において、
引張強さが1000 MPa以上であり、破断伸びが3%以上であることを特徴とするハイエントロピー合金部材。 - 請求項1乃至請求項7のいずれか一項に記載のハイエントロピー合金部材において、
前記母相結晶は、形状が柱状晶であり、その結晶構造が単純立方晶を含むことを特徴とするハイエントロピー合金部材。 - 請求項1乃至請求項7のいずれか一項に記載のハイエントロピー合金部材の製造方法であって、
前記合金の原料を混合・溶解して溶湯を形成する原料混合溶解工程と、
前記溶湯から合金粉末を形成するアトマイズ工程と、
前記合金粉末を用いた金属粉末積層造形法により所望形状を有する合金積層造形体を形成する積層造形工程とを有することを特徴とするハイエントロピー合金部材の製造方法。 - 請求項9に記載のハイエントロピー合金部材の製造方法において、
前記積層造形工程は、前記合金粉末の粉末床を形成する粉末床形成工程と、
前記粉末床全体を加熱して粉末床の仮焼結体を形成する粉末床仮焼工程と、
前記仮焼結体を局所加熱して前記合金の微小溶融池を形成すると共に該局所加熱を該仮焼結体の面内で走査しながら前記微小溶融池を移動・逐次凝固させることにより、前記合金の凝固層を形成する局所溶融・凝固層形成工程とを有することを特徴とするハイエントロピー合金部材の製造方法。 - ハイエントロピー合金部材を用いた製造物であって、
前記ハイエントロピー合金部材が、請求項1乃至請求項8のいずれか一項に記載のハイエントロピー合金部材であり、
前記製造物が、流体機械のインペラであることを特徴とするハイエントロピー合金部材を用いた製造物。 - 請求項11に記載の前記インペラを組み込んでいることを特徴とする遠心圧縮機。
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Families Citing this family (27)
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US11434900B1 (en) | 2022-04-25 | 2022-09-06 | Vulcan Industrial Holdings, LLC | Spring controlling valve |
US11920684B1 (en) | 2022-05-17 | 2024-03-05 | Vulcan Industrial Holdings, LLC | Mechanically or hybrid mounted valve seat |
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CN115652173B (zh) * | 2022-10-25 | 2024-04-05 | 锑玛(苏州)精密工具股份有限公司 | 核电现场取样专用无钴无碳FeCrNiCuAl高熵合金刀具及制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080031769A1 (en) * | 2006-07-28 | 2008-02-07 | Jien-Wei Yeh | High-temperature resistant alloy with low contents of cobalt and nickel |
WO2016013498A1 (ja) * | 2014-07-23 | 2016-01-28 | 株式会社日立製作所 | 合金構造体及び合金構造体の製造方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020159914A1 (en) | 2000-11-07 | 2002-10-31 | Jien-Wei Yeh | High-entropy multielement alloys |
JP4190720B2 (ja) | 2000-11-29 | 2008-12-03 | 國立清華大學 | 多元合金 |
CN103252496B (zh) | 2013-05-03 | 2015-06-17 | 中国人民解放军装甲兵工程学院 | 一种含非晶纳米晶高熵合金粉末及其制备方法 |
WO2016013497A1 (ja) | 2014-07-23 | 2016-01-28 | 株式会社日立製作所 | 合金構造体及び合金構造体の製造方法 |
CN104308153B (zh) * | 2014-10-27 | 2016-08-03 | 西安交通大学 | 一种基于选区激光熔化的高熵合金涡轮发动机热端部件的制造方法 |
CN104841930B (zh) * | 2015-06-05 | 2017-03-01 | 哈尔滨工程大学 | 用于3d打印的高熵合金粉末及应用其制备高熵合金涂层的方法 |
-
2016
- 2016-11-08 JP JP2017554978A patent/JP6493561B2/ja active Active
- 2016-11-08 US US15/781,963 patent/US10787725B2/en active Active
- 2016-11-08 CN CN201680071488.4A patent/CN108431262B/zh active Active
- 2016-11-08 SG SG11201804917QA patent/SG11201804917QA/en unknown
- 2016-11-08 WO PCT/JP2016/083011 patent/WO2017098848A1/ja active Application Filing
- 2016-11-08 EP EP16872748.5A patent/EP3392359B1/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080031769A1 (en) * | 2006-07-28 | 2008-02-07 | Jien-Wei Yeh | High-temperature resistant alloy with low contents of cobalt and nickel |
WO2016013498A1 (ja) * | 2014-07-23 | 2016-01-28 | 株式会社日立製作所 | 合金構造体及び合金構造体の製造方法 |
Non-Patent Citations (2)
Title |
---|
CHOU Y. L. ET AL.: "Effect of Inhibitors on the Critical Pitting Temperature of the High- Entropy Alloy Co1.5CrFeNi1.5Ti0.5MO0.1", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 158, no. 8, 22 June 2011 (2011-06-22), pages C246 - C251, XP055390822 * |
See also references of EP3392359A4 * |
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US10787725B2 (en) | 2020-09-29 |
EP3392359A4 (en) | 2019-07-17 |
CN108431262A (zh) | 2018-08-21 |
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