WO2023181994A1 - 金属積層造形用アルミニウム粉末製品、およびアルミニウム粉末造形物の製造方法 - Google Patents

金属積層造形用アルミニウム粉末製品、およびアルミニウム粉末造形物の製造方法 Download PDF

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WO2023181994A1
WO2023181994A1 PCT/JP2023/009306 JP2023009306W WO2023181994A1 WO 2023181994 A1 WO2023181994 A1 WO 2023181994A1 JP 2023009306 W JP2023009306 W JP 2023009306W WO 2023181994 A1 WO2023181994 A1 WO 2023181994A1
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Prior art keywords
aluminum powder
mass
aluminum
less
powder
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PCT/JP2023/009306
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English (en)
French (fr)
Japanese (ja)
Inventor
純 加藤
信一 大森
佳吾 小林
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority to CN202380028319.2A priority Critical patent/CN118984748A/zh
Priority to US18/849,362 priority patent/US20250197975A1/en
Priority to JP2024509999A priority patent/JPWO2023181994A1/ja
Priority to EP23774593.0A priority patent/EP4501493A4/en
Publication of WO2023181994A1 publication Critical patent/WO2023181994A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B22F10/14—Formation of a green body by jetting of binder onto a bed of metal powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/64—Treatment of workpieces or articles after build-up by thermal means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
    • 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
    • B22F2301/05—Light metals
    • B22F2301/052—Aluminium
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • 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
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present invention relates to an aluminum powder product for metal additive manufacturing, and a method for manufacturing an aluminum powder shaped article.
  • This application claims priority based on Japanese Patent Application No. 2022-048834 filed in Japan on March 24, 2022, the contents of which are incorporated herein.
  • Aluminum is widely used as a material for heat sinks due to its light weight and high thermal conductivity, but in order to further improve its heat dissipation characteristics, it is necessary to use pins and fins with complex shapes that enable more efficient heat exchange. Design and manufacturing of grid shapes, etc. are required. Metal 3D printers are being used as a method for manufacturing products with complex shapes.
  • the binder jet method has been attracting attention as one of the additive manufacturing techniques using metal powder.
  • a binder containing a thermosetting resin, a thermoplastic resin, or a photocurable resin is selectively sprayed onto a metal powder layer from a print head, and the metal powder layer is repeatedly laminated.
  • This is a known method to obtain a three-dimensional metal molded object through repeated lamination to obtain a metal powder molded object fixed in a desired three-dimensional shape, and then undergo binder fixation, removal of unnecessary powder, degreasing, and sintering steps.
  • Patent Document 1 and Patent Document 2 disclose metal layered manufacturing using a binder jet method or a manufacturing apparatus thereof.
  • Patent Document 3 describes a method for improving the sinterability of aluminum using fine powder with a large specific surface area, but when applied to a binder jet method, it is difficult to form a powder layer with aluminum, which has a light specific gravity. In some cases, scattering may cause a reduction in uniformity or packing density, or there may be problems in terms of safety.
  • the present invention has been devised in view of the above-mentioned problems, and its purpose is to create a metal that can be applied to the binder jet method even with aluminum powder, which has an oxide film and is known as a difficult-to-sinter material.
  • An object of the present invention is to provide an aluminum powder product for additive manufacturing and a method for manufacturing an aluminum powder model using this aluminum powder product for metal additive manufacturing.
  • the present inventor adjusted the ratio of the amount of magnesium (mass %) to the amount of oxygen (mass %) contained in the raw material aluminum powder to 0.1 or more and 2.0 or less, and The application to the binder jet method was studied using a raw material in which the amount of oxygen contained in the aluminum powder was 0.3% by mass or less.
  • it has become necessary to perform the degreasing process after modeling using the binder jet method at 500°C or less in an oxidizing atmosphere, or to heat and sinter the obtained degreased body in a non-oxidizing gas flow under a reduced pressure of 1 Pa or more and 100 kPa or less.
  • We have developed a technology to sinter the aluminum powder and found that it is possible to obtain an aluminum sintered body with a relative density of 90% or more relative to the true density of the raw material aluminum powder.
  • the present inventors have provided an aluminum powder product for metal additive manufacturing and a method for manufacturing an aluminum powder model using this aluminum powder product for metal additive manufacturing.
  • the aluminum powder product for metal additive manufacturing according to Aspect 1 of the present invention has a purity of aluminum of 98% by mass or more based on the entire powder, and contains Mg of 0.01% by mass or more and 0.5% by mass or less. And, the ratio of Mg amount (mass %) to oxygen amount (mass %) contained is 0.1 or more and 2.0 or less.
  • the above-mentioned aluminum powder product for metal additive manufacturing contains an appropriate amount of Mg and has an appropriate amount of oxygen corresponding to the contained Mg.
  • Mg reduces and partially destroys the oxide film on the surface of the particles of the aluminum powder product for metal additive manufacturing, thereby improving sinterability.
  • the amount of Mg is required to be greater than a certain value relative to the amount of oxygen. If the amount of Mg is small, it becomes impossible to achieve partial destruction of the oxide film on the particle surface of the aluminum powder product for metal additive manufacturing.
  • the Mg amount may be more preferably 0.015% by mass or more and 0.4% by mass or less, and still more preferably 0.02% by mass or more and 0.3% by mass or less. The same may be applied to aspects 2 to 10 described later.
  • the value of Mg amount/oxygen amount is 0.1 or more.2. It needs to be 0 or less.
  • the value of Mg amount/oxygen amount may be more preferably 0.015 or more and 0.15 or less, and still more preferably 0.02 or more and 0.1 or less. The same may be applied to aspects 2 to 10 described later.
  • the aluminum powder product for metal additive manufacturing of Aspect 2 preferably contains 0.1% by mass or more and 1.0% by mass or less of Si in addition to the Mg in Aspect 1.
  • the Si content may be 0.15% by mass or more and 0.8% by mass or less, and more preferably 0.2% by mass or more and 0.7% by mass or less. The same may be applied to aspects 3 to 10 described later.
  • the aluminum powder product for metal additive manufacturing of Aspect 3 includes aluminum powder with a purity of 99% or more, Mg of 0.1% by mass or more and 1.0% by mass or less, and 3.0% by mass or more and 12.0% by mass. % or less of Si, and the ratio of Mg amount (mass %) to oxygen amount (mass %) contained is 0.1 or more and 2.0 or less. It is characterized by
  • the above-mentioned aluminum powder product for metal additive manufacturing can contain an appropriate amount of Mg in the entire mixture, and has an appropriate amount of oxygen corresponding to the contained Mg.
  • Mg reduces and partially destroys the oxide film on the surface of the aluminum powder particles having a purity of 99% or more, thereby improving sinterability.
  • the amount of Mg is required to be greater than a certain value relative to the amount of oxygen. If the amount of Mg is small, it becomes impossible to achieve partial destruction of the oxide film on the particle surface of the aluminum powder or the particle surface of the aluminum alloy powder. If the amount of Mg is too large, the effect of improving sinterability due to destruction of the oxide film will be reduced, and the increase in the amount of Mg will cause a decrease in electrical conductivity, a decrease in thermal conductivity, etc.
  • the amount of Mg/ It is necessary that the oxygen amount is 0.1 or more and 2.0 or less.
  • the oxygen amount is preferably 0.05% by mass or more and 0.3% by mass or less.
  • the range of the amount of Mg is defined, and the range of the amount of oxygen is set from the ratio of the amount of Mg/the amount of oxygen, which is the actual ratio, but the upper limit in particular is a value that can be taken in consideration of the manufacturing method of the powder for additive manufacturing. stipulated.
  • the amount of oxygen may be 0.05% by mass or more and 0.3% by mass or less. The same may be applied to aspects 5 to 10 described later.
  • the aluminum powder product for metal additive manufacturing of Aspect 5 preferably has a volume-based 50% cumulative particle size measured by laser diffraction/scattering method in Aspects 1 to 4 of 10 ⁇ m or more and 100 ⁇ m or less.
  • volume-based 50% cumulative particle size 10 ⁇ m or more and 100 ⁇ m or less, it is possible to provide aluminum powder with a particle size that is advantageous for laminating aluminum powder and suitable for a binder jet method.
  • the volume-based 50% cumulative particle diameter may be 10 ⁇ m or more and 50 ⁇ m or less. The same may be applied to aspects 6 to 10 described later.
  • Aspect 6 The method for manufacturing an aluminum powder shaped article according to Aspect 6 alternately repeats the step of laminating aluminum powder and the step of applying ink containing a binder for selectively fixing the laminated aluminum powder. After that, an aluminum powder molded body is formed by heating and hardening the resin in the binder, and then an aluminum powder degreased body, which is a sintering precursor, is created by heating and degreasing the aluminum powder molded body.
  • This is a method for forming an aluminum powder object, in which an aluminum object is obtained through a process of heating and sintering a powder degreased body.
  • the aluminum powder has a purity of 98% by mass or more of aluminum in the entire powder, contains Mg from 0.01% by mass to 0.5% by mass, and contains the amount of Mg (% by mass) and the amount of oxygen.
  • An aluminum powder product for metal additive manufacturing in which the ratio of Mg amount/oxygen amount (% by mass) is 0.1 or more and 2.0 or less is used.
  • the degreasing step is preferably carried out in an oxidizing atmosphere of 500° C. or lower, an inert atmosphere, or a reduced pressure atmosphere of 1 Pa or more and 100 kPa or less.
  • the aluminum powder shaped article may be a heat sink having fins.
  • Aspect 7 In the method for manufacturing an aluminum powder shaped article according to Aspect 7, in Aspect 6, an aluminum powder raw material containing 0.1% by mass or more and 1.0% by mass or less of Si in addition to the Mg can be used.
  • the melting point of the aluminum alloy can be lowered by adding Si, contributing to improved sinterability.
  • the method for manufacturing an aluminum powder shaped article according to Aspect 8 includes repeating the step of laminating aluminum powder and the step of applying ink containing a binder for selectively fixing the laminated aluminum powder. Later, an aluminum powder compact is formed by heating and curing the resin, and then an aluminum powder degreased body, which is a sintering precursor, is created by heating and degreasing the aluminum powder compact, and the aluminum powder degreased body is This is a method for forming an aluminum powder object through a process of heating and sintering to obtain an aluminum object.
  • the aluminum powder is an aluminum powder with a purity of 99% or more, and an aluminum alloy powder containing 0.1% by mass or more and 1.0% by mass of Mg and 3.0% by mass or more and 12.0% by mass or less of Si.
  • an aluminum powder product for metal additive manufacturing which is a mixture of Mg content (mass%) and oxygen content (mass%), where the Mg content/oxygen content is 0.1 or more and 2.0 or less.
  • the degreasing step is performed in an oxidizing atmosphere of 500° C. or lower, an inert atmosphere, or a reduced pressure atmosphere of 1 Pa or more and 100 kPa or less to prevent oxidation of Mg, and then heat sintering.
  • Mg without an oxide film can be maintained until the time of heating and sintering. Therefore, the effect of improving sinterability can be obtained by effectively utilizing the effect of Mg to destroy the aluminum film.
  • the heating and sintering step is performed in a reduced pressure atmosphere of 1 Pa or more and 100 kPa or less in an inert gas flow or a reducing gas flow. It can be carried out either in an inert gas flow at a pressure of 1 Pa to 100 kPa or in a reducing gas flow in a reduced pressure atmosphere of 1 Pa or more and 100 kPa or less.
  • the oxidizing atmosphere in the degreasing step may be in dry air with a dew point of 10° C. or less.
  • the oxidizing atmosphere in the degreasing step may more preferably be in dry air with a dew point of -80°C or higher and 0°C or lower.
  • the aluminum powder shaped article obtained by the method for producing an aluminum powder shaped article may have a relative density of 90% or more and a thermal conductivity of 180 W/K.
  • the aluminum powder product for metal additive manufacturing it is possible to manufacture an aluminum member with few internal defects and high relative density using a binder jet method. As a result, it becomes possible to obtain high density and high electrical conductivity and thermal conductivity of the obtained aluminum sintered body. This makes it possible to further improve the performance of heat exchange members, conductive members, and strength members that are created using the binder jet method, for example.
  • FIG. 1 shows an example of an aluminum powder product for metal additive manufacturing and its sintering process according to the first embodiment, in which (a) is a partially enlarged sectional view showing a laminate of aluminum powder, and (b) is a partially enlarged sectional view of the same laminate.
  • An explanatory diagram showing a state in which an object is sintered in a heating furnace (c) an explanatory diagram showing an outline of the obtained sintered body, and (d) an explanatory diagram showing a state in which the sintered body is subjected to final processing. It is a diagram.
  • Figure 2 shows an example of the process of sintering an aluminum powder product for metal additive manufacturing.
  • (c) is an explanatory diagram showing a state in which the liquid phase wets and spreads
  • (c) is an explanatory diagram showing a state in which each powder is integrated into a sintered body after sintering.
  • the present invention will be described in detail below, but the present invention is not limited to the embodiments described below.
  • the aluminum powder product for metal additive manufacturing according to the present embodiment is, for example, an aluminum-based powder with a purity of 98% or more, and this powder contains 0.01% by mass or more and 0.5% by mass or less of Mg, and , the ratio of Mg amount (mass %) to oxygen amount (mass %) contained is 0.1 or more and 2.0 or less.
  • the aluminum powder product for metal additive manufacturing includes aluminum powder with a purity of 99% or more, Mg of 0.1% by mass or more and 1.0% by mass or less, and 3.0% by mass or more and 12.0% by mass. It may be a powder mixture with an aluminum alloy powder containing Si of % or less.
  • the aluminum powder product for metal additive manufacturing is a powder mixture of aluminum powder with a purity of 99% or more and aluminum alloy powder containing Mg of 0.1% by mass or more and 1.0% by mass or less, based on the total mass of the powder It is preferable to adjust the amount of the aluminum alloy powder so that it contains Mg at a ratio of 0.01% by mass or more and 0.5% by mass or less, and then uniformly mix it with aluminum powder having a purity of 99% or more.
  • the aluminum powder product for metal additive manufacturing contains Mg as described above, and if necessary contains Si in the above range, but the remainder consists of inevitable impurities and aluminum.
  • Mg 0.01 to 0.5% by mass
  • the amount of Mg (mass%) and oxygen content (mass%) contained in the aluminum powder is determined. It is important that the ratio of Mg amount/oxygen amount is 0.1 or more and 2.0 or less.
  • an alloy component in which Mg is added to aluminum by adding the amount of Mg to the amount of oxygen at a ratio of 0.1 to 2.0, it reacts with the oxide film on the surface of the aluminum powder to form spinel (MgAl 2 O 4 ), the oxide film can be partially destroyed, and high sinterability can be obtained. If the value of the amount of Mg/the amount of oxygen is less than 0.1, there is not enough Mg in the aluminum oxide film, so that the effect of destroying the oxide film due to spinel formation cannot be sufficiently obtained.
  • Mg amount/Oxygen amount is larger than 2.0, there is excessive Mg for the effect of destroying the oxide film, and excessive Mg evaporates during heating and sintering under reduced pressure, causing damage inside the aluminum model. This may cause the formation of pores, which may reduce the achieved density of aluminum objects.
  • the oxygen content is preferably 0.3% by mass or less. If the oxygen content is greater than 0.3% by mass, the oxide film may become too thick and it may be difficult to partially destroy the oxide film by adding Mg. It is desirable that the oxygen content in aluminum powder products for metal additive manufacturing be as low as possible, but to reduce the oxygen content to less than 0.05% by mass, manufacturing conditions must be strictly controlled, so the oxygen content should be 0.05% by mass. % or more.
  • the aluminum powder product for metal additive manufacturing may contain 0.1% by mass or more and 1.0% by mass or less of Si as an alloy component.
  • Si content When the Si content is within the above range, it contributes to lowering the melting point of the aluminum alloy powder, improves sinterability, and maintains high thermal conductivity without significantly reducing electrical conductivity.
  • Al alloy powder 0.1 to 1.0 mass%, Si: 3.0 to 12.0 mass%
  • a powder mixture with aluminum alloy powder may also be used.
  • volume-based 50% cumulative particle diameter (D50) is 10 ⁇ m or more and 100 ⁇ m or less.
  • the above-mentioned aluminum powder, or the pure aluminum powder and aluminum alloy powder constituting the powder mixture preferably have a volume-based 50% cumulative particle diameter of 10 ⁇ m or more and 100 ⁇ m or less.
  • the volume-based 50% cumulative particle diameter is 10 ⁇ m or more and 100 ⁇ m or less, a powder mixture with stable fluidity and excellent sinterability can be obtained.
  • the powder particle diameter (D50) is less than 10 ⁇ m, there is a risk of a decrease in fluidity and a dust explosion due to scattering of the powder.
  • the powder particle diameter (D50) exceeds 100 ⁇ m, the specific surface area of the powder particles decreases, so the sinterability of the aluminum powder mixture decreases, and there is a possibility that a sufficient density as a sintered body cannot be obtained.
  • Method for manufacturing aluminum powder sintered body In order to manufacture an aluminum powder sintered body using the aluminum powder for additive manufacturing described above, first, the aluminum powder described above is used as a raw material powder (aluminum powder product for metal additive manufacturing), and the raw material powder is mixed with thermosetting resin, thermoplastic resin, etc.
  • a method can be used in which a binder containing a resin or a photocurable resin is selectively sprayed and laminated repeatedly to obtain a shape close to the desired shape, followed by degreasing treatment and then heating and sintering.
  • Aluminum powder with high purity for forming an aluminum powder product for metal additive manufacturing can be produced by a method such as a nitrogen gas atomization method, for example.
  • the aluminum alloy powder for constituting the aluminum powder mixture can be produced, for example, from a molten alloy having a desired composition by a nitrogen gas atomization method.
  • a required amount of aluminum master alloy is added to the required amount of pure aluminum according to the desired composition, and the mixture is charged into a melting furnace to produce a molten aluminum alloy.
  • the above-mentioned aluminum alloy powder is produced using an inert gas atomization method. can be created.
  • the obtained aluminum powder or aluminum alloy powder is divided into raw material powders after removing fine powders such as coarse powders and fumes by sieving and washing, and if necessary, sieving according to the target particle size. It can be used as
  • the raw material powder When laminating the above-mentioned aluminum powder to obtain the desired shape, the raw material powder is used to spray ink containing a selective binder, and by repeated lamination, a powder compact with a shape similar to the desired product shape is obtained. Obtainable. Through repeated lamination, the raw material powder is fixed in a shape that matches the desired three-dimensional shape. After fixation of the raw material powder in the binder ink application area by heating, removal of unnecessary powder, degreasing process, etc. are performed as necessary, and it is possible to obtain, for example, the cubic green body 1 shown in FIG. 1(a). This green body 1 is subjected to the following degreasing process.
  • the degreasing step is preferably performed at 500° C. or lower in an oxidizing atmosphere. Further, the degreasing step is more preferably carried out in an oxidizing atmosphere (such as in the atmosphere) with dry air having a temperature of 500° C. or lower and a dew point of 10° C. or lower.
  • an oxidizing atmosphere such as in the atmosphere
  • dry air having a temperature of 500° C. or lower and a dew point of 10° C. or lower.
  • Mg exists as an alloy component or a single substance in the degreased aluminum powder body in the state of a sintered precursor. It is not preferable for Mg to exist as an oxide at the stage of degreased aluminum powder. Therefore, in order to suppress oxidation of Mg, it is more desirable to perform the degreasing step at 400° C. or lower.
  • we promoted solid phase sintering by maintaining the temperature below the temperature at which the liquid phase forms, thereby stabilizing the gaps between the particles.
  • the heating process may be performed in two or more stages.
  • the added Mg can efficiently react with the oxide film on the surface of the aluminum powder and promote the spinel formation reaction. Further, by flowing in an inert gas or a reducing gas, it becomes possible to efficiently remove binder residue remaining on the degreased body.
  • FIG. 2 depicts an aluminum powder mixture in which aluminum powder particles 4 with a purity of 99% or more are mixed with aluminum alloy powder particles 5 whose melting point is lower than that of the aluminum powder particles 4. .
  • an aluminum powder mixture including four aluminum powder particles 4 and one aluminum alloy powder particle 5 is shown for modeling purposes, but the number of aluminum powder particles 4 and the number of aluminum alloy powder particles 5 The number may be any ratio as long as it is in the mass % ratio described above.
  • FIG. 2 is an explanatory diagram for modeling and showing the case where the aluminum powder mixture 3 is heated to a temperature of about 560 to 650°C.
  • the melting point of pure aluminum is about 660°C.
  • a eutectic alloying element such as Mg or Si
  • an aluminum alloy powder having a melting point lower than about 660° C., which is the melting point of pure aluminum can be obtained.
  • FIG. 2A shows a model configuration in which pure aluminum powder particles 4 and aluminum alloy powder particles 5 are mixed at a ratio of 4:1 to form an aluminum powder mixture 3.
  • the pure aluminum powder particles 4 shown in FIG. 2(a) may be omitted altogether, and the aluminum powder mixture 3 may be constructed from the aluminum alloy powder particles 5.
  • FIG. 1(c) shows a state in which the sintered body 7 is produced in the heating furnace 2.
  • the obtained sintered body 7 can be finished by processing with a cutting tool 8 or surface polishing as shown in FIG. 1(d) to obtain a product sintered body (aluminum powder shaped object) 9. can.
  • the sintered body 7 or the product sintered body 9 has an oxygen content of 0.3% by mass or less in the aluminum powder, contains Mg in the range of 0.01 to 0.5% by mass, and has a ratio of Mg amount/oxygen Since the amount is in the range of 0.1 to 2.0, the oxide film on the surface of the aluminum powder can be efficiently destroyed during sintering, so the liquid phase can effectively fill the gaps between the pure aluminum powder particles 4. It has a dense structure buried in the pores. Therefore, it is possible to obtain a well-shaped, high-density sintered body 7 or product sintered body 9 that is close to the desired shape. For example, it is possible to obtain an aluminum sintered body 7 or product sintered body 9 having a relative density of 80% or more and a thermal conductivity of 180 W/mK or more.
  • the above-described sintered body 7 or product sintered body 9 has a high density and can achieve high thermal conductivity. As a result, it is possible to further improve the performance of heat exchange members, conductive members, and strength members made using, for example, the above-described sintered body 7 or product sintered body 9. Further, the aluminum sintered body 7 or product sintered body 9 may be subjected to surface treatment such as polishing, anodizing, plating, etc. depending on the purpose.
  • the above-described sintered body 7 or product sintered body 9 has high density and high thermal conductivity, and is therefore desirable as a component of a heat exchanger. Since the sintered body 7 or the product sintered body 9 is dense and has high thermal conductivity, it contributes to improving the performance of a heat exchanger constructed using them.
  • a required amount of aluminum master alloy according to the target composition is added and charged into a melting furnace to produce molten aluminum alloy, and from this molten aluminum alloy powder of each composition shown in Table 1 (Example 1 to 6 and Comparative Examples 1 and 2) were prepared.
  • the necessary amount of pure aluminum or aluminum master alloy according to the target composition is prepared and put into multiple melting furnaces to produce pure aluminum molten metal or aluminum alloy molten metal, and then the molten metal in each melting furnace is subjected to inert gas atomization Pure aluminum powder (powder 1) and aluminum alloy powder (powder 2) having the respective compositions shown in Table 2 were prepared.
  • the obtained pure aluminum powder and aluminum alloy powder are subjected to sieving and washing to remove coarse powder and fine powder consisting of fume, etc., and then sieved according to the target particle size as necessary, and then subjected to the following methods.
  • An aluminum powder mixture was obtained by mixing pure aluminum powder (powder 1) and aluminum alloy powder (powder 2) at the mixing ratio shown in Table 2.
  • a metal binder jet type additive manufacturing device manufactured by Digital Metal, product name: DM-P2500 was used to create a size of 10 mm in length x 10 mm in width x 5 mm in thickness.
  • the resin was cured by heating at 250° C. in an air atmosphere or an inert gas atmosphere.
  • the obtained degreased body was heated and degreased at 400° C. in a dry air atmosphere with a dew point of 10° C. or less or in a humidified air atmosphere bubbled in a water tank. Furthermore, it was heated to 565 to 650°C to produce a sintered body.
  • the method for measuring each physical property value is shown below.
  • Measurement of particle size distribution The particle size distribution of pure aluminum powder and aluminum alloy powder was measured using a wet method using Microtrack Co., Ltd., trade name: MT3300EXII (laser diffraction/scattering method particle size distribution measuring device). A 50% volume-based frequency cumulative diameter D50 was calculated from the results.
  • [Aluminum purity, alloying element mass ratio] The mass ratio of Mg and Si contained in the aluminum powder, aluminum alloy powder, and aluminum powder mixture was measured using an inductively coupled plasma emission spectrometer. At the same time, we measured the mass ratio of 15 elements: Fe, Cu, Mn, Zn, Ti, Cr, Zr, B, Ni, Bi, Pb, Ga, V, Sn, and Be, and measured the mass ratio of 17 elements including Mg and Si. The value obtained by subtracting the total amount from 100% was measured as the aluminum purity. [Oxygen concentration] The oxygen concentration in the aluminum powder mixture was measured using an inert gas fusion-infrared absorption method.
  • the thermal conductivity of the sintered body was determined by processing the created sintered body into a size of 8 mm x 8 mm x 2 mm, and measuring the thermal conductivity by a laser flash method using LFA467 manufactured by NETZSCH. The above measurement results are summarized in Tables 1 to 3 below.
  • Examples 1 to 7 contain 0.02 to 0.45 mass% Mg and 0.03 to 0.25 mass% Si in aluminum, and the value of Mg amount/oxygen amount is This is a sample with a value of 0.1 or more and 2.0 or less. Examples 1-7 had excellent relative densities in the range of 0.88-0.95 and exhibited excellent thermal conductivities of 181-225 W/K. In contrast to these examples, in Comparative Example 1 containing 0.53% by mass of Mg, the thermal conductivity decreased because the Mg content was too high and the value of Mg amount/oxygen amount was too large. . In Comparative Example 2, the value of Mg amount/oxygen amount was too small, so the relative density of the sintered body was low and the thermal conductivity was also low.
  • Examples 8 to 14 shown in Table 2 aluminum powder (powder 1) with a purity of 99% or more and aluminum alloy powder (powder 2) were mixed at the powder mixing ratio (ratio of powder 1: powder 2 or powder 2) shown in Table 2.
  • Examples 8 to 14 contained 0.33 to 1.42 mass % of Si in addition to 0.019 to 0.15 mass % of Mg in the aluminum powder mixture, and the Mg amount/ This is a sample in which the value of oxygen amount is 0.13 or more and 1.10 or less. Examples 8-14 had excellent relative densities ranging from 0.915 to 0.966 and exhibited excellent thermal conductivity from 180 to 220 W/K.
  • the aluminum powder product for metal additive manufacturing it is possible to manufacture an aluminum member with few internal defects and high relative density using a binder jet method. As a result, it becomes possible to obtain high density and high electrical conductivity and thermal conductivity of the obtained aluminum sintered body. This makes it possible to further improve the performance of heat exchange members, conductive members, and strength members that are created using the binder jet method, for example. Therefore, the present invention can be used industrially.
  • SYMBOLS 1 Green body, 2... Heating furnace, 3... Aluminum powder mixture (aluminum powder product for metal additive manufacturing), 4... Pure aluminum powder, 5... Aluminum alloy powder, 6... Liquid phase, 7... Sintered compact, 9... Product sintered body (aluminum powder model).

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PCT/JP2023/009306 2022-03-24 2023-03-10 金属積層造形用アルミニウム粉末製品、およびアルミニウム粉末造形物の製造方法 Ceased WO2023181994A1 (ja)

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JP2020152001A (ja) 2019-03-20 2020-09-24 株式会社リコー 粉末積層造形方法
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