WO2024053275A1 - Method for manufacturing aluminum substrate - Google Patents

Method for manufacturing aluminum substrate Download PDF

Info

Publication number
WO2024053275A1
WO2024053275A1 PCT/JP2023/027661 JP2023027661W WO2024053275A1 WO 2024053275 A1 WO2024053275 A1 WO 2024053275A1 JP 2023027661 W JP2023027661 W JP 2023027661W WO 2024053275 A1 WO2024053275 A1 WO 2024053275A1
Authority
WO
WIPO (PCT)
Prior art keywords
particles
foil
molten salt
aluminum base
base material
Prior art date
Application number
PCT/JP2023/027661
Other languages
French (fr)
Japanese (ja)
Inventor
盾 八百川
琢真 箕浦
加瑞馬 日比
航 高野
俊輔 高須
Original Assignee
株式会社豊田中央研究所
豊田通商株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社豊田中央研究所, 豊田通商株式会社 filed Critical 株式会社豊田中央研究所
Publication of WO2024053275A1 publication Critical patent/WO2024053275A1/en

Links

Images

Classifications

    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals

Definitions

  • the present invention relates to a method of manufacturing an aluminum base material.
  • Al-based particles (powders) made of pure Al or Al alloys can be used as composite material raw materials (fillers or base materials such as thermally conductive fillers and conductive fillers), sintering raw materials, and chemical reaction raw materials (thermite reactants, etc.). ), used in pigments, etc.
  • Al-based powder is produced by spraying of Al-based molten metal (atomization method), dispersion of Al-based molten metal (melt spin method), scattering of Al-based molten metal (melt extraction method), as described in Non-Patent Document 1 below. method), pulverization of Al-based pieces (ball mill method, attritor method), etc. Furthermore, in recent years, a method for producing Al-based particles using a molten salt has been proposed, and related descriptions are found in the following patent documents.
  • Patent Document 1 aluminum particles coated with sodium chloride are obtained by injecting a molten salt of aluminum chloride into molten sodium.
  • Metallic sodium which is a reducing agent, is difficult to use from the viewpoint of safety and cost.
  • Patent Document 2 metal A particles are subjected to a substitution reaction with ions of metal B, which is more noble than metal A, in a molten salt serving as a reaction medium to obtain alloy particles in which metal B is precipitated and diffused into metal A particles. ing.
  • metal B which is more noble than metal A
  • Patent Documents 3 to 5 contain descriptions of dissolution methods using molten salts, etc. There is no specific description regarding Al-based particles in any of the patent documents.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for obtaining aluminum-based particles by a new method different from conventional methods.
  • the present invention is a method for producing an aluminum base material in which aluminum base particles are obtained by bringing an aluminum base foil into contact with a molten salt.
  • the present invention may be a method for producing an aluminum base material, which includes, for example, a melting step of introducing an aluminum base foil into a molten salt layer and melting it, and a collection step of collecting aluminum base particles obtained after the melting step.
  • Al-based particles Al-based particles
  • Al base material Al base material
  • the standard free energy of formation when typical metal elements (e.g., Na, K, Mg, Ca, etc./specific metal elements) constituting molten salt becomes a halide (e.g., chloride, bromide, etc.) is It is much smaller than the standard free energy of formation when it becomes an oxide. Therefore, according to the manufacturing method of the present invention, Al-based particles can be obtained from which at least a portion of the oxide (oxide film on the surface, etc.) in the aluminum-based foil (Al-based foil) has been removed (reduced). Further, as long as the Al-based particles are surrounded by a molten salt or a coagulated salt thereof (including a film), oxidation is suppressed. Therefore, according to the production method of the present invention, purified Al-based particles containing no oxides or the like can be obtained.
  • a halide e.g., chloride, bromide, etc.
  • Al-based particles (liquid phase) obtained from Al-based foil are easily spheroidized in molten salt. Therefore, according to the manufacturing method of the present invention, it is also possible to obtain an Al base material consisting of Al base particles with a uniform particle shape (spherical shape).
  • Al-based particles/Al-based material may be in a liquid state, a solid state, or a solid-liquid coexistence state (semi-molten state).
  • An Al-based molten metal obtained from a particle group in which liquid-phase Al-based particles are aggregated (collected) or their bonds (connections) can be a form of an Al-based material.
  • the Al-based particles are liquid phase particles
  • the Al-based molten metal obtained from the liquid phase particles may be understood as the Al base material according to the present invention.
  • Al-based powder obtained from a particle group in which solid-phase Al-based particles are aggregated can also be a form of Al-based material.
  • the Al-based particles are solid-phase particles obtained by solidifying liquid-phase particles, and the Al-based powder obtained from these solid-phase particles may be understood as the Al base material according to the present invention.
  • Al-based particles do not need to be separated (separated, extracted, collected, recovered, etc.) from the molten salt or its coagulated salt. That is, a material in which Al-based particles and molten salt and/or coagulation salt coexist can also be a form of Al-based material.
  • the Al base particles are liquid phase particles, and a particle-dispersed molten salt obtained by dispersing the liquid phase particles in a molten salt may be understood as the Al base material.
  • Al-based particles are solid-phase particles that are solidified liquid-phase particles, and a particle-dispersed coagulated salt obtained by dispersing the solid-phase particles in a coagulated salt obtained by coagulating a molten salt is understood as an Al-based material. Good too.
  • a particle-dispersed molten salt in which solid phase particles of Al-based particles are dispersed in the molten salt can be understood as the Al base material.
  • particle-dispersed molten salt or particle-dispersed coagulated salt may be understood as an independent transaction object, or may be used as a temporary intermediate (intermediate raw material, etc.) for obtaining Al-based molten metal, Al-based powder, etc. ) may be understood as
  • Al-based ingots, Al-based castings (final products, intermediate products, etc.), Al-based sintered bodies (materials, products), Al-based ingots formed via Al-based particles obtained from Al-based foil Composites (materials, products), powders, etc. may also be understood as specific examples of the Al base material.
  • the powder which is an example of the Al base material, can be used as a filler that maintains the particle shape, and may also be used as a raw material for molten metal to be melted, a raw material for sintering to be molded or fired, and the like.
  • Collection refers to a state in which a plurality of particles (liquid phase particles or solid phase particles) are present. Moreover, “dispersion” is a state in which the plurality of particles are present in another medium (molten salt or coagulated salt). In either case, the degree or form of the damage does not matter.
  • concentration, composition, and particle size distribution referred to in this specification are expressed as a mass ratio (mass %) to the entire object (molten metal, particles, etc.). Where appropriate, mass % is simply indicated as "%".
  • x to y as used herein includes a lower limit x and an upper limit y.
  • a new range such as “a to b" can be established by setting any numerical value included in the various numerical values or numerical ranges described herein as a new lower limit or upper limit.
  • FIG. 2 is a schematic diagram illustrating a manufacturing process of Al-based particles (powder). It is a list showing the correspondence between the form (thickness and size) of the Al-based foil piece that is the raw material and the form (photograph) of the obtained Al-based particles. It is a SEM image of Al-based particles obtained from an Al-based foil piece (0.011 mm thick x 25 mm square).
  • One or more components arbitrarily selected from the present specification may be added to the components of the present invention described above.
  • the content described in this specification may be a method-related component or a component related to a product (eg, Al-based particles, Al-based material).
  • the Al base foil used as a raw material may be an Al base material (plate material, ingot, etc.) processed (rolled, etc.) to the desired thickness, or an Al base material that has already been made into a foil.
  • the material may be used as is.
  • the Al base material may be a waste material collected from the market, a factory, etc., or a recycled material thereof (in the form of a lump, a plate, a foil, etc.).
  • the recovered or recycled Al base foil may be used as is, or may be subjected to pretreatment such as ink removal and cleaning, thickness adjustment, etc.
  • the Al base foil laminated with a resin or the like may be added to the molten salt as it is, or may be added to the molten salt after removing the laminate layer.
  • the Al-based foil may or may not have wrinkles, folds, bends, etc.
  • the Al base foil may be pure aluminum (pure Al) or an aluminum alloy (Al alloy).
  • Al-based foils having different component compositions may be used in a mixed state.
  • the component composition of the Al-based foil used as a raw material is reflected in the component composition of the resulting Al-based particles. For this reason, Al-based particles having desired components may be obtained by adjusting the components, formulation, etc. of the Al-based foil serving as the raw material.
  • the thickness and size of the Al base foil are selected as appropriate. Depending on the desired particle size distribution of the Al-based particle group (powder), the thickness and size (size other than thickness) of the Al-based foil (foil piece) to be added to the molten salt may be adjusted. At this time, Al base foils (foil pieces) having different thicknesses and/or sizes may be mixed. Generally, the thinner and/or smaller the Al-based foil (foil piece) is, the higher the proportion of fine (small diameter) Al-based particles is. Conversely, the thicker and/or larger the Al-based foil (foil piece) is, the higher the proportion of coarse (large-diameter) Al-based particles becomes.
  • the thickness of the Al base foil has an upper limit value (threshold value below or below) of 0.5 mm, 0.3 mm, 0.2 mm, 0.1 mm, 0.07 mm, 0.03 mm, 0. It is .02mm.
  • the lower limit value is, for example, 0.001 mm, 0.005 mm, or even 0.008 mm.
  • the thickness of the Al-based foil is measured using a micrometer or the like.
  • the thickness of the Al base foil may vary by about ⁇ 10%.
  • the arithmetic mean value of the thicknesses measured at any number of locations (for example, 10 locations) may be appropriately determined as the thickness of the Al-based foil.
  • "foil” as used herein refers to a foil having a thickness of 0.5 mm or less (0.2 mm or less, further less than 0.1 mm).
  • the maximum length of the foil pieces is, for example, 200 mm, 150 mm, 100 mm, 50 mm, 30 mm, 20 mm, 10 mm, 5 mm, and 1 mm. Its minimum length is, for example, 10 mm, 5 mm, 1 mm or even 0.5 mm.
  • the size of the foil piece may be adjusted depending on the thickness of the foil piece. For example, when the foil is thin, a large foil piece may be used, and when the foil is thick, a small foil piece may be used. Note that the foil pieces are obtained, for example, by shredding Al-based foil (raw material) using a shredder or the like.
  • the molten salt may be made from, for example, a stable metal halide (especially chloride and/or bromide).
  • the metal element constituting the halide is, for example, one or more of Ca, Na, Li, Sr, K, Mg, Cs, Ba, and the like.
  • halides of Na and/or K are inexpensive and stable, and are suitable for molten salts.
  • the temperature may be adjusted by blending the raw materials (component adjustment) of the molten salt.
  • the temperature of the molten salt is preferably at least higher than (exceeds) the melting temperature of the Al-based foil.
  • the molten salt is not limited to a single layer, but may have multiple layers.
  • the molten salt is preferably a molten salt reservoir (tank) having at least enough depth or volume to immerse the Al base foil. Note that the Al-based particles (liquid phase) usually stay or settle below the molten salt due to the density difference.
  • the particle size of the Al-based particles (referred to as "particle size" regardless of particle shape) may be constant or distributed. The thinner and smaller a piece of Al-based foil is melted, the more likely a particle size distribution containing many fine Al-based particles will occur.
  • the Al-based particles may be liquid-phase particles or solid-phase particles obtained from an Al-based foil (piece), or may be liquid phase particles in which particles are connected (bonded) and integrated (larger in diameter) or alloyed. It may be a particle or a solid phase particle.
  • the Al particles may be used as they are, or may be used after particle size adjustment (classification). According to the production method of the present invention, it is possible to obtain an Al powder made of Al-based particles with a particle size of more than 1.7 mm, and it is also possible to obtain an Al powder made of Al-based particles with a particle size of less than 0.1 mm.
  • particle size (or particle size) of the powder referred to in this specification is specified by sieving, unless otherwise specified, and is expressed by the nominal opening (mesh size) of the sieve (according to JIS Z 8801).
  • Particle size ⁇ to ⁇ ( ⁇ ) means that particles (group) do not pass through a sieve with a nominal opening of ⁇ ⁇ m, but pass through a sieve with a nominal opening of ⁇ ⁇ m.
  • Particle size ⁇ means that it consists of particles (group) that did not pass through a sieve with a nominal opening of ⁇ m.
  • Particle size ⁇ means that it consists of particles that have passed through a sieve with a nominal opening of ⁇ ⁇ m.
  • the particle size of the liquid phase particles is considered to be approximately equal to the particle size of the solid phase particles, except for heat shrinkage.
  • Al-based particles and Al-based materials have various uses.
  • fillers thermalally conductive fillers, conductive fillers, etc.
  • a base material resin, dissimilar metal, ceramics, etc.
  • raw material powders for sintering materials main element powders, alloying element powders, etc.
  • raw materials reducing agents, etc.
  • Al-based foil was added to the molten salt to produce Al-based particles (liquid phase particles), and they were solidified.
  • the present invention will be explained in more detail based on such specific examples.
  • Example production (1) Raw materials As raw materials, various foil pieces with different dimensions (size (planar size) and thickness) were prepared. Each foil piece was made of pure Al (JIS 1000 series/purity 99% or more) and had a size of 100 mm x 100 mm or more (Al-based foil). The thickness of the foil was 0.011 mm, 0.018 mm, 0.025 mm, 0.05 mm, 0.1 mm, 0.3 mm or 0.8 mm.
  • the sizes of the foil pieces were 25 mm square (approximately square), 3 mm square, 5 mm wide (25 mm in length), and 1 mm wide (25 mm in length). Both the 5 mm width and the 1 mm width were adjusted by further cutting a 25 mm square foil piece into a predetermined width.
  • the cutting (shredding) of the foil or foil pieces was performed in the air using metal scissors. In this way, various foil pieces were obtained. The appearance of a part of it is shown in FIGS. 1A to 1C.
  • FIG. 5 shows the relationship between the thickness of the foil piece (25 mm square) used as the raw material and the particle size distribution of the obtained particle group.
  • FIG. 6 shows the relationship between the size of the foil piece and its particle size distribution.
  • observation Figure 4 shows an SEM image and an enlarged image of particles obtained using a 0.011 mm thick x 25 mm square foil piece (particle size: ⁇ 0.212 mm) observed with a scanning electron microscope (SEM).
  • the particle size distribution could be adjusted by adjusting the thickness of the Al base foil and the size of the foil piece.
  • using thin and small pieces of foil resulted in a powder with a particle size distribution rich in relatively fine particles. This is thought to be because the thin and small pieces of foil melted and became spherical within a short time, making them easier to disperse.
  • Such a tendency was remarkable when the thickness of the Al-based foil was 0.1 mm or less (or even less) or the width of the Al-based foil piece was 1 mm or less (or even less).
  • Al-based particles (liquid phase) with a particle size (diameter) of approximately 2 mm or less were difficult to integrate and were easy to maintain a dispersed state in the molten salt.
  • a particle-dispersed molten salt in which Al-based particles are dispersed in the molten salt can be obtained. Furthermore, a desired Al base material (powder, etc.) can be obtained efficiently or easily from the particle-dispersed molten salt.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Provided is a manufacturing method by which Al-based particles can be efficiently or easily obtained. According to the present invention, a particle-dispersed molten salt (an example of an Al substrate), in which Al-based particles (liquid phase) are dispersed in a molten salt, can be obtained by bringing an Al-based foil into contact with a molten salt. Through the particle-dispersed molten salt, for example, Al-based powder (an example of the Al substrate) comprising Al-based particles (solid phase) can be efficiently or easily obtained. By sorting the Al-based particle group, an Al-based powder with a desired particle size distribution may be obtained. The Al-based foil has a thickness of, for example, at most 0.5 mm, and even 0.1 mm. Preferably, the Al-based foil is supplied to a molten salt in the form of chopped foil pieces. Accordingly, it is possible to easily obtain Al-based powder having a particle size distribution including fine particles. For example, it is preferable that a mixed salt containing NaCl and KCl be used as the molten salt.

Description

アルミニウム基材の製造方法Manufacturing method of aluminum base material
　本発明は、アルミニウム基材の製造方法等に関する。 The present invention relates to a method of manufacturing an aluminum base material.
　純アルミニウム（Ａｌ）やＡｌ合金は、種々の製品や分野で用いられる。例えば、純ＡｌやＡｌ合金からなるＡｌ基粒子（粉末）は、複合材原料（熱伝導性フィラー、導電性フィラー等の充填材または母材）、焼結原料、化学反応原料（テルミット反応剤等）、顔料などに利用される。 Pure aluminum (Al) and Al alloys are used in various products and fields. For example, Al-based particles (powders) made of pure Al or Al alloys can be used as composite material raw materials (fillers or base materials such as thermally conductive fillers and conductive fillers), sintering raw materials, and chemical reaction raw materials (thermite reactants, etc.). ), used in pigments, etc.
　Ａｌ基粉末は、一般的に、下記の非特許文献１にもあるように、Ａｌ基溶湯の噴霧（アトマイズ法）、Ａｌ基溶湯の分散（メルトスピン法）、Ａｌ基溶湯の飛散（メルトエクストラクション法）、Ａｌ基片の粉砕（ボールミル法、アトライタ法）等により製造される。さらに近年では、溶融塩を用いたＡｌ基粒子の製造方法も提案されており、下記の特許文献に関連する記載がある。 Generally, Al-based powder is produced by spraying of Al-based molten metal (atomization method), dispersion of Al-based molten metal (melt spin method), scattering of Al-based molten metal (melt extraction method), as described in Non-Patent Document 1 below. method), pulverization of Al-based pieces (ball mill method, attritor method), etc. Furthermore, in recent years, a method for producing Al-based particles using a molten salt has been proposed, and related descriptions are found in the following patent documents.
特開２０１６－１９１１４８JP2016-191148 特開２００９－２１５５６９JP2009-215569 特開２０１７－２００６２JP2017-20062 特表２０１８－５１１７７６Special table 2018-511776 特表２０１９－５０２８９０Special table 2019-502890
　特許文献１では、塩化アルミニウムの溶融塩を溶融ナトリウムへ注入して、塩化ナトリウムで被覆されたアルミニウム粒子を得ている。還元剤である金属ナトリウムは、安全性やコスト等の観点から利用し難い。 In Patent Document 1, aluminum particles coated with sodium chloride are obtained by injecting a molten salt of aluminum chloride into molten sodium. Metallic sodium, which is a reducing agent, is difficult to use from the viewpoint of safety and cost.
　特許文献２では、反応媒体となる溶融塩中で、金属Ａ粒子と金属Ａよりも貴な金属Ｂのイオンとを置換反応させて、金属Ｂが金属Ａ粒子に析出および拡散した合金粒子を得ている。但し、Ａｌ基粒子に関する具体的な記載は特許文献２にない。 In Patent Document 2, metal A particles are subjected to a substitution reaction with ions of metal B, which is more noble than metal A, in a molten salt serving as a reaction medium to obtain alloy particles in which metal B is precipitated and diffused into metal A particles. ing. However, there is no specific description regarding Al-based particles in Patent Document 2.
　特許文献３～５には、溶融塩を用いた溶解方法等に関する記載がある。いずれの特許文献にも、Ａｌ基粒子に関する具体的な記載はない。 Patent Documents 3 to 5 contain descriptions of dissolution methods using molten salts, etc. There is no specific description regarding Al-based particles in any of the patent documents.
　本発明は、このような事情に鑑みてなされたものであり、従来とは異なる新たな方法により、アルミニウム基粒子を得る方法等を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for obtaining aluminum-based particles by a new method different from conventional methods.
　本発明者はこの課題を解決すべく鋭意研究した結果、溶融塩（溜）へＡｌ基箔を投入すると、凝集した溶湯（塊）とならず分散粒（液相）となることを新たに見出した。この発見を発展させることにより、以降に述べる本発明を完成するに至った。 As a result of intensive research to solve this problem, the present inventor has newly discovered that when Al base foil is introduced into a molten salt (reservoir), it becomes dispersed particles (liquid phase) instead of agglomerated molten metal (clumps). Ta. By developing this discovery, we have completed the present invention described below.
《アルミニウム基材の製造方法》
（１）本発明は、アルミニウム基箔を溶融塩に接触させてアルミニウム基粒子を得るアルミニウム基材の製造方法である。 《Method for manufacturing aluminum base material》
(1) The present invention is a method for producing an aluminum base material in which aluminum base particles are obtained by bringing an aluminum base foil into contact with a molten salt.
　本発明は、例えば、アルミニウム基箔を溶融塩層へ入れて溶解させる溶融工程と、該溶融工程後に得られたアルミニウム基粒子を収集する収集工程と、を備えるアルミニウム基材の製造方法でもよい。 The present invention may be a method for producing an aluminum base material, which includes, for example, a melting step of introducing an aluminum base foil into a molten salt layer and melting it, and a collection step of collecting aluminum base particles obtained after the melting step.
（２）本発明の製造方法によれば、アルミニウム基粒子（Ａｌ基粒子）またはＡｌ基粒子に基づくアルミニウム基材（Ａｌ基材）を簡易的、効率的または高歩留まりで得ることができる。 (2) According to the manufacturing method of the present invention, aluminum-based particles (Al-based particles) or an aluminum base material (Al base material) based on Al-based particles can be obtained simply, efficiently, or with a high yield.
　ちなみに、溶融塩を構成する代表的な金属元素（例えばＮａ、Ｋ、Ｍｇ、Ｃａ等／特定金属元素）がハロゲン化物（例えば塩化物や臭化物等）となるときの標準生成自由エネルギーは、Ａｌが酸化物となるときの標準生成自由エネルギーよりも遙かに小さい。このため本発明の製造方法によれば、アルミニウム基箔（Ａｌ基箔）にあった酸化物（表面にある酸化膜等）の少なくとも一部が除去（還元）されたＡｌ基粒子が得られる。またＡｌ基粒子は、溶融塩またはその凝固塩（膜状を含む）に包囲された状態である限り、酸化が抑制された状態となる。このため本発明の製造方法によれば、酸化物等を含まない精製されたＡｌ基粒子を得ることもできる。 By the way, the standard free energy of formation when typical metal elements (e.g., Na, K, Mg, Ca, etc./specific metal elements) constituting molten salt becomes a halide (e.g., chloride, bromide, etc.) is It is much smaller than the standard free energy of formation when it becomes an oxide. Therefore, according to the manufacturing method of the present invention, Al-based particles can be obtained from which at least a portion of the oxide (oxide film on the surface, etc.) in the aluminum-based foil (Al-based foil) has been removed (reduced). Further, as long as the Al-based particles are surrounded by a molten salt or a coagulated salt thereof (including a film), oxidation is suppressed. Therefore, according to the production method of the present invention, purified Al-based particles containing no oxides or the like can be obtained.
　さらにＡｌ基箔から得られるＡｌ基粒子（液相）は、溶融塩中で球状化し易い。このため本発明の製造方法によれば、粒形状が揃った（球形化した）Ａｌ基粒子からなるＡｌ基材を得ることもできる。 Furthermore, Al-based particles (liquid phase) obtained from Al-based foil are easily spheroidized in molten salt. Therefore, according to the manufacturing method of the present invention, it is also possible to obtain an Al base material consisting of Al base particles with a uniform particle shape (spherical shape).
《Ａｌ基粒子／Ａｌ基材》
（１）　Ａｌ基粒子は、液相状態でも、固相状態でも、固液共存状態（半溶融状態）でもよい。 《Al-based particles/Al-based material》
(1) The Al-based particles may be in a liquid state, a solid state, or a solid-liquid coexistence state (semi-molten state).
　液相のＡｌ基粒子が集合（収集）した粒子群またはその結合（連結）から得られるＡｌ基溶湯は、Ａｌ基材の一形態となり得る。具体的にいうと、Ａｌ基粒子が液相粒子であり、この液相粒子から得られたＡｌ基溶湯を、本発明に係るＡｌ基材として把握してもよい。 An Al-based molten metal obtained from a particle group in which liquid-phase Al-based particles are aggregated (collected) or their bonds (connections) can be a form of an Al-based material. Specifically, the Al-based particles are liquid phase particles, and the Al-based molten metal obtained from the liquid phase particles may be understood as the Al base material according to the present invention.
　固相のＡｌ基粒子が集合（収集）した粒子群から得られるＡｌ基粉末も、Ａｌ基材の一形態となり得る。具体的にいうと、Ａｌ基粒子は液相粒子が凝固した固相粒子であり、この固相粒子から得られたＡｌ基粉末を、本発明に係るＡｌ基材として把握してもよい。 Al-based powder obtained from a particle group in which solid-phase Al-based particles are aggregated (collected) can also be a form of Al-based material. Specifically, the Al-based particles are solid-phase particles obtained by solidifying liquid-phase particles, and the Al-based powder obtained from these solid-phase particles may be understood as the Al base material according to the present invention.
（２）Ａｌ基粒子は、溶融塩やその凝固塩と分別（分離、抽出、捕集、回収等）された状態でなくてもよい。つまり、Ａｌ基粒子と溶融塩および／または凝固塩とが共存した物も、Ａｌ基材の一形態となり得る。 (2) The Al-based particles do not need to be separated (separated, extracted, collected, recovered, etc.) from the molten salt or its coagulated salt. That is, a material in which Al-based particles and molten salt and/or coagulation salt coexist can also be a form of Al-based material.
　例えば、Ａｌ基粒子が液相粒子であり、この液相粒子が溶融塩中に分散してなる粒子分散溶融塩を、Ａｌ基材として把握してもよい。また、Ａｌ基粒子は、液相粒子が凝固した固相粒子であり、溶融塩が凝固した凝固塩中にその固相粒子が分散してなる粒子分散凝固塩を、Ａｌ基材として把握してもよい。さらに、溶融塩の種類（温度）を調整して、例えば、Ａｌ基粒子の固相粒子が溶融塩中に分散した粒子分散溶融塩を、Ａｌ基材として把握することもできる。 For example, the Al base particles are liquid phase particles, and a particle-dispersed molten salt obtained by dispersing the liquid phase particles in a molten salt may be understood as the Al base material. In addition, Al-based particles are solid-phase particles that are solidified liquid-phase particles, and a particle-dispersed coagulated salt obtained by dispersing the solid-phase particles in a coagulated salt obtained by coagulating a molten salt is understood as an Al-based material. Good too. Furthermore, by adjusting the type (temperature) of the molten salt, for example, a particle-dispersed molten salt in which solid phase particles of Al-based particles are dispersed in the molten salt can be understood as the Al base material.
　なお、粒子分散溶融塩または粒子分散凝固塩は、独立した取引対象として把握されてもよいし、Ａｌ基溶湯やＡｌ基粉末等を得るための一時的（暫定的）な中間物（中間原料等）として把握されてもよい。 Note that particle-dispersed molten salt or particle-dispersed coagulated salt may be understood as an independent transaction object, or may be used as a temporary intermediate (intermediate raw material, etc.) for obtaining Al-based molten metal, Al-based powder, etc. ) may be understood as
（３）Ａｌ基箔から得られたＡｌ基粒子を経由して形成されたＡｌ基鋳塊、Ａｌ基鋳物（最終品、中間品等）、Ａｌ基焼結体（素材、製品）、Ａｌ基複合体（素材、製品）、粉末等も、Ａｌ基材の具体例として把握されてもよい。なお、Ａｌ基材の一例である粉末は、粒子形態が維持される充填材等に用いられる他、溶解される溶湯原料、成形や焼成される焼結原料等に用いられてもよい。 (3) Al-based ingots, Al-based castings (final products, intermediate products, etc.), Al-based sintered bodies (materials, products), Al-based ingots formed via Al-based particles obtained from Al-based foil Composites (materials, products), powders, etc. may also be understood as specific examples of the Al base material. Note that the powder, which is an example of the Al base material, can be used as a filler that maintains the particle shape, and may also be used as a raw material for molten metal to be melted, a raw material for sintering to be molded or fired, and the like.
《その他》
（１）本明細書でいう「収集」は、複数の粒子（液相粒子または固相粒子）が存在している状態である。また「分散」は、その複数の粒子が他の媒体（溶融塩または凝固塩）中に存在している状態である。いずれの場合も、その程度や形態等を問わない。 "others"
(1) "Collection" as used herein refers to a state in which a plurality of particles (liquid phase particles or solid phase particles) are present. Moreover, "dispersion" is a state in which the plurality of particles are present in another medium (molten salt or coagulated salt). In either case, the degree or form of the damage does not matter.
（２）本明細書でいう濃度、組成、粒度分布は、特に断らない限り、対象物（溶湯、粒子等）の全体に対する質量割合（質量％）で示す。適宜、質量％を単に「％」で示す。 (2) Unless otherwise specified, the concentration, composition, and particle size distribution referred to in this specification are expressed as a mass ratio (mass %) to the entire object (molten metal, particles, etc.). Where appropriate, mass % is simply indicated as "%".
（３）特に断らない限り本明細書でいう「ｘ～ｙ」は、下限値ｘおよび上限値ｙを含む。本明細書に記載した種々の数値または数値範囲に含まれる任意の数値を新たな下限値または上限値として「ａ～ｂ」のような範囲を新設し得る。 (3) Unless otherwise specified, "x to y" as used herein includes a lower limit x and an upper limit y. A new range such as "a to b" can be established by setting any numerical value included in the various numerical values or numerical ranges described herein as a new lower limit or upper limit.
Ａｌ基箔片（０．０１８ｍｍ厚×２５ｍｍ角）の写真である。This is a photograph of an Al-based foil piece (0.018 mm thick x 25 mm square). Ａｌ基箔片（０．３ｍｍ厚×１ｍｍ幅）の写真である。This is a photograph of an Al-based foil piece (0.3 mm thick x 1 mm wide). Ａｌ基箔片（０．３ｍｍ厚×３ｍｍ角）の写真である。This is a photograph of an Al-based foil piece (0.3 mm thick x 3 mm square). Ａｌ基粒子（粉末）の製造過程を例示した模式図である。FIG. 2 is a schematic diagram illustrating a manufacturing process of Al-based particles (powder). 原料であるＡｌ基箔片の形態（厚さ・大きさ）と得られたＡｌ基粒子の形態（写真）との対応を示す一覧表である。It is a list showing the correspondence between the form (thickness and size) of the Al-based foil piece that is the raw material and the form (photograph) of the obtained Al-based particles. Ａｌ基箔片（０．０１１ｍｍ厚×２５ｍｍ角）から得られたＡｌ基粒子のＳＥＭ像である。It is a SEM image of Al-based particles obtained from an Al-based foil piece (0.011 mm thick x 25 mm square). 原料であるＡｌ基箔片（２５ｍｍ角）の厚さと得られたＡｌ基粒子の粒度分布との関係を示す棒グラフである。It is a bar graph showing the relationship between the thickness of a raw material Al-based foil piece (25 mm square) and the particle size distribution of the obtained Al-based particles. 原料であるＡｌ基箔片（０．３ｍｍ厚さ）の大きさと得られたＡｌ基粒子の粒度分布との関係を示す棒グラフである。It is a bar graph showing the relationship between the size of a raw material Al-based foil piece (0.3 mm thick) and the particle size distribution of the obtained Al-based particles. 原料であるＡｌ基箔片（０．１ｍｍ厚さ）の大きさと得られたＡｌ基粒子の粒度分布との関係を示す棒グラフである。It is a bar graph showing the relationship between the size of a raw material Al-based foil piece (0.1 mm thick) and the particle size distribution of the obtained Al-based particles. 原料であるＡｌ基箔片（０．０１８ｍｍ厚さ）の大きさと得られたＡｌ基粒子の粒度分布との関係を示す棒グラフである。It is a bar graph showing the relationship between the size of a raw material Al-based foil piece (0.018 mm thick) and the particle size distribution of the obtained Al-based particles.
　上述した本発明の構成要素に、本明細書中から任意に選択した一つまたは二つ以上の構成要素を付加し得る。本明細書で説明する内容は、方法的な構成要素であっても物（例えば、Ａｌ基粒子、Ａｌ基材）に関する構成要素ともなり得る。 One or more components arbitrarily selected from the present specification may be added to the components of the present invention described above. The content described in this specification may be a method-related component or a component related to a product (eg, Al-based particles, Al-based material).
《Ａｌ基箔》
（１）原料となるＡｌ基箔には、Ａｌ基材（板材、鋳塊等）を所望厚さに加工（圧延等）したものを用いてもよいし、既に箔状にされているＡｌ基材をそのまま用いてもよい。Ａｌ基材は、市場や工場等から回収した廃材やその再生材（塊状、板状、箔状等）でもよい。回収または再生したＡｌ基箔は、そのまま利用されてもよいし、インク除去や洗浄等の前処理、厚さ調整等がなされてもよい。樹脂等でラミネートされたＡｌ基箔は、そのまま溶融塩に加えられてもよいし、ラミネート層を除去して溶融塩に加えられてもよい。Ａｌ基箔には、皺、折れ、曲がり等があってもなくてもよい。 《Al base foil》
(1) The Al base foil used as a raw material may be an Al base material (plate material, ingot, etc.) processed (rolled, etc.) to the desired thickness, or an Al base material that has already been made into a foil. The material may be used as is. The Al base material may be a waste material collected from the market, a factory, etc., or a recycled material thereof (in the form of a lump, a plate, a foil, etc.). The recovered or recycled Al base foil may be used as is, or may be subjected to pretreatment such as ink removal and cleaning, thickness adjustment, etc. The Al base foil laminated with a resin or the like may be added to the molten salt as it is, or may be added to the molten salt after removing the laminate layer. The Al-based foil may or may not have wrinkles, folds, bends, etc.
（２）Ａｌ基箔は、純アルミニウム（純Ａｌ）でも、アルミニウム合金（Ａｌ合金）でもよい。成分組成の異なるＡｌ基箔が混在した状態で用いられてもよい。原料となるＡｌ基箔の成分組成が、得られるＡｌ基粒子の成分組成に反映される。このため、原料となるＡｌ基箔の成分や配合等を調整して、所望成分のＡｌ基粒子を得てもよい。 (2) The Al base foil may be pure aluminum (pure Al) or an aluminum alloy (Al alloy). Al-based foils having different component compositions may be used in a mixed state. The component composition of the Al-based foil used as a raw material is reflected in the component composition of the resulting Al-based particles. For this reason, Al-based particles having desired components may be obtained by adjusting the components, formulation, etc. of the Al-based foil serving as the raw material.
（３）Ａｌ基箔の厚さや大きさは適宜選択される。所望するＡｌ基粒子群（粉末）の粒度分布に応じて、溶融塩に加えるＡｌ基箔（箔片）の厚さや大きさ（厚さ以外のサイズ）を調整してもよい。この際、厚さおよび／または大きさが異なるＡｌ基箔（箔片）を混在させてもよい。通常、Ａｌ基箔（箔片）が薄い程および／または小さい程、細かい（小径な）Ａｌ基粒子の割合が多くなる。逆に、Ａｌ基箔（箔片）が厚い程および／または大きい程、粗い（大径な）Ａｌ基粒子の割合が多くなる。 (3) The thickness and size of the Al base foil are selected as appropriate. Depending on the desired particle size distribution of the Al-based particle group (powder), the thickness and size (size other than thickness) of the Al-based foil (foil piece) to be added to the molten salt may be adjusted. At this time, Al base foils (foil pieces) having different thicknesses and/or sizes may be mixed. Generally, the thinner and/or smaller the Al-based foil (foil piece) is, the higher the proportion of fine (small diameter) Al-based particles is. Conversely, the thicker and/or larger the Al-based foil (foil piece) is, the higher the proportion of coarse (large-diameter) Al-based particles becomes.
　Ａｌ基箔の厚さは、例えば、その上限値（～以下さらには～未満となる閾値）が０．５ｍｍ、０．３ｍｍ、０．２ｍｍ、０．１ｍｍ、０．０７ｍｍ、０．０３ｍｍ、０．０２ｍｍである。敢えていうと、その下限値（～以上さらには～超となる閾値）は、例えば、０．００１ｍｍ、０．００５ｍｍさらには０．００８ｍｍである。Ａｌ基箔の厚さは、マイクロメータ等により測定される。Ａｌ基箔の厚さには±１０％程度のバラツキがあってもよい。任意な数箇所（例えば１０箇所）で測定した厚さの算術平均値を、適宜、Ａｌ基箔の厚さとしてもよい。特に断らない限り、本明細書でいう「箔」は、厚さが０．５ｍｍ以下（０．２ｍｍ以下さらには０．１ｍｍ未満）である場合を意味する。 For example, the thickness of the Al base foil has an upper limit value (threshold value below or below) of 0.5 mm, 0.3 mm, 0.2 mm, 0.1 mm, 0.07 mm, 0.03 mm, 0. It is .02mm. To put it bluntly, the lower limit value (threshold value greater than or equal to or greater than or equal to) is, for example, 0.001 mm, 0.005 mm, or even 0.008 mm. The thickness of the Al-based foil is measured using a micrometer or the like. The thickness of the Al base foil may vary by about ±10%. The arithmetic mean value of the thicknesses measured at any number of locations (for example, 10 locations) may be appropriately determined as the thickness of the Al-based foil. Unless otherwise specified, "foil" as used herein refers to a foil having a thickness of 0.5 mm or less (0.2 mm or less, further less than 0.1 mm).
　箔片の大きさは、例えば、最大長が２００ｍｍ、１５０ｍｍ、１００ｍｍ、５０ｍｍ、３０ｍｍ、２０ｍｍ、１０ｍｍ、５ｍｍ、１ｍｍである。その最小長は、例えば、１０ｍｍ、５ｍｍ、１ｍｍさらには０．５ｍｍである。箔片の厚さに応じて、箔片の大きさを調整してもよい。例えば、薄いときは大きい箔片を用いてもよいし、厚いときは小さい箔片を用いてもよい。なお、箔片は、例えば、Ａｌ基箔（原料）をシュレッダー等により細断して得られる。 The maximum length of the foil pieces is, for example, 200 mm, 150 mm, 100 mm, 50 mm, 30 mm, 20 mm, 10 mm, 5 mm, and 1 mm. Its minimum length is, for example, 10 mm, 5 mm, 1 mm or even 0.5 mm. The size of the foil piece may be adjusted depending on the thickness of the foil piece. For example, when the foil is thin, a large foil piece may be used, and when the foil is thick, a small foil piece may be used. Note that the foil pieces are obtained, for example, by shredding Al-based foil (raw material) using a shredder or the like.
《溶融塩》
　溶融塩は、例えば、安定な金属ハロゲン化物（特に塩化物および／または臭化物）を原料とすればよい。ハロゲン化物を構成する金属元素は、例えば、Ｃａ、Ｎａ、Ｌｉ、Ｓｒ、Ｋ、Ｍｇ、Ｃｓ、Ｂａ等の一種以上である。特にＮａおよび／またはＫのハロゲン化物は、安価で安定しており、溶融塩に好適である。 《Molted salt》
The molten salt may be made from, for example, a stable metal halide (especially chloride and/or bromide). The metal element constituting the halide is, for example, one or more of Ca, Na, Li, Sr, K, Mg, Cs, Ba, and the like. In particular, halides of Na and/or K are inexpensive and stable, and are suitable for molten salts.
　溶融塩の原料配合（成分調整）により、その温度が調整されてもよい。溶融塩の温度は少なくとも、Ａｌ基箔の溶融温度以上（超）とされるとよい。溶融塩は、単層に限らず、複層でもよい。溶融塩は、少なくともＡｌ基箔の浸漬に十分な深さまたは量がある溶融塩溜（槽）であるとよい。なお、通常、Ａｌ基粒子（液相）は、密度差により、溶融塩の下方で滞留または沈降する。 The temperature may be adjusted by blending the raw materials (component adjustment) of the molten salt. The temperature of the molten salt is preferably at least higher than (exceeds) the melting temperature of the Al-based foil. The molten salt is not limited to a single layer, but may have multiple layers. The molten salt is preferably a molten salt reservoir (tank) having at least enough depth or volume to immerse the Al base foil. Note that the Al-based particles (liquid phase) usually stay or settle below the molten salt due to the density difference.
《Ａｌ基粒子》
（１）Ａｌ基粒子の粒サイズ（粒形状に依らず「粒径」という。）は、一定でも分布していてもよい。薄く小さいＡｌ基箔片を溶融させるほど、微細なＡｌ基粒子が多い粒度分布が生じ易い。 《Al-based particles》
(1) The particle size of the Al-based particles (referred to as "particle size" regardless of particle shape) may be constant or distributed. The thinner and smaller a piece of Al-based foil is melted, the more likely a particle size distribution containing many fine Al-based particles will occur.
　Ａｌ基粒子は、Ａｌ基箔（片）から得られたままの液相粒子または固相粒子でもよいし、粒子同士が連結（結合）して一体化（大径化）または合金化した液相粒子または固相粒子でもよい。Ａｌ粒子は、そのまま利用されてもよいし、粒度調整（分級）されても利用されてもよい。本発明の製造方法によれば、粒度１．７ｍｍ超のＡｌ基粒子からなるＡｌ粉末を得ることもできるし、粒度０．１ｍｍ未満のＡｌ基粒子からなるＡｌ粉末を得ることもできる。 The Al-based particles may be liquid-phase particles or solid-phase particles obtained from an Al-based foil (piece), or may be liquid phase particles in which particles are connected (bonded) and integrated (larger in diameter) or alloyed. It may be a particle or a solid phase particle. The Al particles may be used as they are, or may be used after particle size adjustment (classification). According to the production method of the present invention, it is possible to obtain an Al powder made of Al-based particles with a particle size of more than 1.7 mm, and it is also possible to obtain an Al powder made of Al-based particles with a particle size of less than 0.1 mm.
　なお、本明細書でいう粉末の粒度（または粒径）は、特に断らない限り、篩い分けにより特定され、その篩いの公称目開き（メッシュサイズ）により表現される（ＪＩＳ Ｚ ８８０１準拠）。粒度α～β（α＜β）は、公称目開きαμｍの篩いを通過せず、公称目開きβμｍの篩いを通過した粒子（群）からなることを意味する。粒度α～は、公称目開きαμｍの篩いを通過しなかった粒子（群）からなることを意味する。粒度～βは、公称目開きβμｍの篩いを通過した粒子（群）からなることを意味する。液相粒子の粒径は、熱収縮分を除けば、固相粒子の粒径とほぼ等しいと考えられる。 Note that the particle size (or particle size) of the powder referred to in this specification is specified by sieving, unless otherwise specified, and is expressed by the nominal opening (mesh size) of the sieve (according to JIS Z 8801). Particle size α to β (α<β) means that particles (group) do not pass through a sieve with a nominal opening of α μm, but pass through a sieve with a nominal opening of β μm. Particle size α~ means that it consists of particles (group) that did not pass through a sieve with a nominal opening of αμm. Particle size ˜β means that it consists of particles that have passed through a sieve with a nominal opening of β μm. The particle size of the liquid phase particles is considered to be approximately equal to the particle size of the solid phase particles, except for heat shrinkage.
（２）Ａｌ基粒子やＡｌ基材には、種々の用途がある。例えば、その一形態であるＡｌ基粉末（固相粒子）なら、母材（樹脂、異種金属、セラミックス等）中に分散させて複合材を構成する充填材（熱伝導性フィラー、導電性フィラー等）、焼結材の原料粉末（主元素粉末または合金元素粉末等）、化学反応（テルミット反応等）を生じさせる原料（還元剤等）、塗料に添加される顔料などに利用され得る。 (2) Al-based particles and Al-based materials have various uses. For example, in the case of Al-based powder (solid phase particles), which is one form, fillers (thermally conductive fillers, conductive fillers, etc.) are dispersed in a base material (resin, dissimilar metal, ceramics, etc.) to form a composite material. ), raw material powders for sintering materials (main element powders, alloying element powders, etc.), raw materials (reducing agents, etc.) that cause chemical reactions (thermite reactions, etc.), pigments added to paints, etc.
　Ａｌ基箔を溶融塩へ加えてＡｌ基粒子（液相粒子）を製造し、それらを凝固させた。このような具体例に基づいて本発明をより詳しく説明する。 Al-based foil was added to the molten salt to produce Al-based particles (liquid phase particles), and they were solidified. The present invention will be explained in more detail based on such specific examples.
《試料の製作》
（１）原料
　原料として、寸法（大きさ（平面的なサイズ）と厚さ）が異なる種々の箔片を用意した。いずれの箔片も純Ａｌ（JIS 1000系／純度９９％以上）からなる大きさ１００ｍｍ×１００ｍｍ以上の箔（Ａｌ基箔）を用いた。箔の厚さは、０．０１１ｍｍ、０．０１８ｍｍ、０．０２５ｍｍ、０．０５ｍｍ、０．１ｍｍ、０．３ｍｍまたは０．８ｍｍのいずれかとした。 《Sample production》
(1) Raw materials As raw materials, various foil pieces with different dimensions (size (planar size) and thickness) were prepared. Each foil piece was made of pure Al (JIS 1000 series/purity 99% or more) and had a size of 100 mm x 100 mm or more (Al-based foil). The thickness of the foil was 0.011 mm, 0.018 mm, 0.025 mm, 0.05 mm, 0.1 mm, 0.3 mm or 0.8 mm.
　箔片のサイズは、２５ｍｍ角（略正方形）、３ｍｍ角、５ｍｍ幅（長さ２５ｍｍ）、１ｍｍ幅（長さ２５ｍｍ）とした。５ｍｍ幅と１ｍｍ幅はいずれも、２５ｍｍ角の箔片を所定幅にさらに細断してサイズ調整した。 The sizes of the foil pieces were 25 mm square (approximately square), 3 mm square, 5 mm wide (25 mm in length), and 1 mm wide (25 mm in length). Both the 5 mm width and the 1 mm width were adjusted by further cutting a 25 mm square foil piece into a predetermined width.
　箔または箔片の切断（細断）は、いずれも大気雰囲気中で金属用ハサミを用いて行なった。こうして種々の箔片を得た。その一部の外観を図１Ａ～図１Ｃに示した。 The cutting (shredding) of the foil or foil pieces was performed in the air using metal scissors. In this way, various foil pieces were obtained. The appearance of a part of it is shown in FIGS. 1A to 1C.
（２）溶融塩
　カリウム塩化物とナトリウム塩化物の混合塩（ＫＣｌ－４４質量％ＮａＣｌ）：１００ｇをアルミナ製のるつぼ（株式会社ニッカトー製Ｂ３）に入れて、７００℃まで炉加熱した。こうして混合塩からなる溶融塩（層、溜）を得た。 (2) Molten Salt Mixed salt of potassium chloride and sodium chloride (KCl-44 mass% NaCl): 100 g was placed in an alumina crucible (B3 manufactured by Nikkato Co., Ltd.) and heated in a furnace to 700°C. In this way, a molten salt (layer, reservoir) consisting of a mixed salt was obtained.
（３）溶融工程
　図２に示すように、箔片（２．５ｇ）を溶融塩（１００ｇ）へ投入して溶融させる工程を、各箔片毎に行なった。この工程中に撹拌は行なわず、各箔片が溶融塩中に分散、溶融するまで静置（約１０分間程度）した。 (3) Melting process As shown in FIG. 2, a process of throwing a foil piece (2.5 g) into molten salt (100 g) and melting it was performed for each foil piece. During this step, stirring was not performed, and the foil pieces were allowed to stand (for about 10 minutes) until they were dispersed and melted in the molten salt.
（４）収集工程
　溶融工程後のるつぼを炉外で放冷し（冷却工程）、溶融塩（粒子分散溶融塩）を凝固させた（凝固工程）。るつぼから取り出した凝固物（粒子分散凝固塩）を水洗した（水洗工程／塩除去工程）。塩分の除去後に残存した粒子をろ過、乾燥した（濾別工程、乾燥工程）。こうして得られた各箔片に対応する粒子群を図３にまとめて示した。 (4) Collection process After the melting process, the crucible was allowed to cool outside the furnace (cooling process), and the molten salt (particle-dispersed molten salt) was solidified (solidification process). The coagulated material (particle-dispersed coagulated salt) taken out from the crucible was washed with water (water washing step/salt removal step). After removing the salt, the remaining particles were filtered and dried (filtration step, drying step). The particle groups corresponding to each foil piece thus obtained are collectively shown in FIG. 3.
（５）分級工程
　各粒子群を篩により分級した。篩には、開口寸法（メッシュサイズ）が１．７ｍｍ、０．８５ｍｍ、０．４２５ｍｍ、０．２１２ｍｍ、０．１０６ｍｍの５種類を用いた。各粒子群の粒度分布（質量割合）を、図５と図６Ａ～図６Ｃ（これらを併せて単に「図６」という。）に示した。図５は、原料に用いた箔片（２５ｍｍ角）の厚さと得られた粒子群の粒度分布との関係を示す。図６は、その箔片の大きさとその粒度分布との関係を示す。 (5) Classification process Each particle group was classified using a sieve. Five types of sieves were used, each having an opening size (mesh size) of 1.7 mm, 0.85 mm, 0.425 mm, 0.212 mm, and 0.106 mm. The particle size distribution (mass ratio) of each particle group is shown in FIG. 5 and FIGS. 6A to 6C (collectively referred to simply as "FIG. 6"). FIG. 5 shows the relationship between the thickness of the foil piece (25 mm square) used as the raw material and the particle size distribution of the obtained particle group. FIG. 6 shows the relationship between the size of the foil piece and its particle size distribution.
（６）比較試料
　上述した溶融塩（１００ｇ）を入れたるつぼへＡｌ塊（５０ｇ）を投入して、Ａｌ塊を溶融させた。溶融塩中にできたＡｌ溶湯（塊）をアルミナ製棒で撹拌し、溶融塩中にＡｌ溶湯を粒状に分散させた。上述した方法と同様にして、そのるつぼを放冷して得られた凝固物を水洗した後、得られた粒子をろ過、乾燥および分級した。 (6) Comparative Sample An Al block (50 g) was put into a crucible containing the above-mentioned molten salt (100 g), and the Al block was melted. The molten Al (lump) formed in the molten salt was stirred with an alumina rod to disperse the molten Al into particles in the molten salt. In the same manner as in the above-mentioned method, the crucible was left to cool and the resulting solidified product was washed with water, and the resulting particles were filtered, dried, and classified.
《観察》
　０．０１１ｍｍ厚×２５ｍｍ角の箔片を用いて得られた粒子（粒度：～０．２１２ｍｍ） を走査型電子顕微鏡（ＳＥＭ）で観察したＳＥＭ像とその拡大像を図４に示した。 "observation"
Figure 4 shows an SEM image and an enlarged image of particles obtained using a 0.011 mm thick x 25 mm square foil piece (particle size: ~0.212 mm) observed with a scanning electron microscope (SEM).
《評価》
（１）粒子形状
　図４から明らかなように、Ａｌ基箔片を溶融塩に接触させて得られるＡｌ基粒子は、溶融工程中に撹拌しなくても、ほぼ球状となることがわかった。なお、比較試料のＡｌ基粒子の形状は、やや扁平した球状であった。 "evaluation"
(1) Particle shape As is clear from FIG. 4, the Al-based particles obtained by bringing the Al-based foil piece into contact with the molten salt were found to be approximately spherical even without stirring during the melting process. Note that the shape of the Al-based particles of the comparative sample was a slightly flattened spherical shape.
（２）粒度分布
　図５から明らかなように、薄いＡｌ基箔を用いるほど、微細な粒子を多く含む粒度分布が得られた。逆に、厚いＡｌ基箔を用いるほど、粒径の大きな粒子を多く含む粒度分布が得られた。 (2) Particle size distribution As is clear from FIG. 5, the thinner the Al base foil was used, the more fine particles were obtained in the particle size distribution. On the contrary, the thicker the Al base foil was used, the more particles with large diameters were obtained.
　図６Ａから明らかなように、０．３ｍｍ厚以上（超）のＡｌ基箔を用いると、その大きさに依らず、粒径の大きい粒子が安定して得られた。厚いＡｌ基箔（片）は、各端面から徐々に溶け、球状化前に他のＡｌ基粒子（液相）と結合する機会が多くなったためと考えられる。なお、比較試料のＡｌ基粒子は、その殆どが粒度１．７mm超であった。 As is clear from FIG. 6A, when an Al base foil with a thickness of 0.3 mm or more (exceeding) was used, particles with a large particle size were stably obtained regardless of the size. This is thought to be because the thick Al-based foil (piece) gradually melted from each end face and had more opportunities to bond with other Al-based particles (liquid phase) before becoming spheroidal. Note that most of the Al-based particles in the comparative sample had a particle size of more than 1.7 mm.
　図６Ｂと図６Ｃから明らかなように、Ａｌ基箔の厚さや箔片の大きさにより、粒度分布を調整できることがわかった。例えば、薄く小さい箔片を用いると、比較的細かい粒子を多く含む粒度分布の粉末が得られた。薄く小さい箔片は、短時間内に溶融して球状化し、分散し易くなったためと考えられる。このような傾向は、Ａｌ基箔の厚さが０．１ｍｍ以下（さらには未満）またはＡｌ基箔片の幅が１ｍｍ以下（さらには未満）で顕著であった。 As is clear from FIGS. 6B and 6C, it was found that the particle size distribution could be adjusted by adjusting the thickness of the Al base foil and the size of the foil piece. For example, using thin and small pieces of foil resulted in a powder with a particle size distribution rich in relatively fine particles. This is thought to be because the thin and small pieces of foil melted and became spherical within a short time, making them easier to disperse. Such a tendency was remarkable when the thickness of the Al-based foil was 0.1 mm or less (or even less) or the width of the Al-based foil piece was 1 mm or less (or even less).
　ちなみに、粒径（直径）がおおよそ２ｍｍ以下のＡｌ基粒子（液相）は、一体化し難く、溶融塩中で分散状態を維持し易かった。 Incidentally, Al-based particles (liquid phase) with a particle size (diameter) of approximately 2 mm or less were difficult to integrate and were easy to maintain a dispersed state in the molten salt.
　このように、本発明によれば、Ａｌ基箔を用いることにより、Ａｌ基粒子が溶融塩に分散した粒子分散溶融塩が得られる。さらに、その粒子分散溶融塩から、所望のＡｌ基材（粉末等）を効率的または簡易的に得ることもできる。 As described above, according to the present invention, by using the Al-based foil, a particle-dispersed molten salt in which Al-based particles are dispersed in the molten salt can be obtained. Furthermore, a desired Al base material (powder, etc.) can be obtained efficiently or easily from the particle-dispersed molten salt.

Claims (10)

  1. 　アルミニウム基箔を溶融塩に接触させてアルミニウム基粒子を得るアルミニウム基材の製造方法。 A method for producing an aluminum base material in which aluminum base particles are obtained by bringing an aluminum base foil into contact with a molten salt.
  2. 　アルミニウム基箔を溶融塩層へ入れて溶融させる溶融工程と、
    　該溶融工程後に得られたアルミニウム基粒子を収集する収集工程と、
    　を備えるアルミニウム基材の製造方法。     a melting step of placing the aluminum base foil into a molten salt layer and melting it;
    a collecting step of collecting the aluminum-based particles obtained after the melting step;
    A method for producing an aluminum base material comprising:
  3. 　前記アルミニウム基箔は、細断された箔片からなる請求項１または２に記載のアルミニウム基材の製造方法。 The method for manufacturing an aluminum base material according to claim 1 or 2, wherein the aluminum base foil consists of shredded foil pieces.
  4. 　前記アルミニウム基箔は、厚さが０．１ｍｍ未満である請求項１または２に記載のアルミニウム基材の製造方法。 The method for manufacturing an aluminum base material according to claim 1 or 2, wherein the aluminum base foil has a thickness of less than 0.1 mm.
  5. 　前記溶融塩は、混合塩からなる請求項１または２に記載のアルミニウム基材の製造方法。 The method for producing an aluminum base material according to claim 1 or 2, wherein the molten salt is a mixed salt.
  6. 　前記混合塩は、ＮａＣｌとＫＣｌを含む請求項５に記載のアルミニウム基材の製造方法。 The method for producing an aluminum base material according to claim 5, wherein the mixed salt contains NaCl and KCl.
  7. 　前記アルミニウム基粒子は、液相粒子であり、
    　前記アルミニウム基材は、該液相粒子が前記溶融塩中に分散してなる粒子分散溶融塩である請求項１または２に記載のアルミニウム基材の製造方法。     The aluminum-based particles are liquid phase particles,
    3. The method for producing an aluminum base material according to claim 1, wherein the aluminum base material is a particle-dispersed molten salt in which the liquid phase particles are dispersed in the molten salt.
  8. 　前記アルミニウム基粒子は、液相粒子であり、
    　前記アルミニウム基材は、該液相粒子から得られたアルミニウム基溶湯である請求項１または２に記載のアルミニウム基材の製造方法。     The aluminum-based particles are liquid phase particles,
    The method for producing an aluminum base material according to claim 1 or 2, wherein the aluminum base material is an aluminum base molten metal obtained from the liquid phase particles.
  9. 　前記アルミニウム基粒子は、液相粒子が凝固した固相粒子であり、
    　前記アルミニウム基材は、前記溶融塩が凝固した凝固塩中に該固相粒子が分散してなる粒子分散凝固塩である請求項１または２に記載のアルミニウム基材の製造方法。     The aluminum-based particles are solid phase particles that are solidified liquid phase particles,
    3. The method for producing an aluminum base material according to claim 1, wherein the aluminum base material is a particle-dispersed coagulation salt in which the solid phase particles are dispersed in a coagulation salt obtained by coagulating the molten salt.
  10. 　前記アルミニウム基粒子は、液相粒子が凝固した固相粒子であり、
    　前記アルミニウム基材は、該固相粒子からなるアルミニウム基粉末である請求項１または２に記載のアルミニウム基材の製造方法。     The aluminum-based particles are solid phase particles that are solidified liquid phase particles,
    The method for producing an aluminum base material according to claim 1 or 2, wherein the aluminum base material is an aluminum base powder made of the solid phase particles.
PCT/JP2023/027661 2022-09-07 2023-07-27 Method for manufacturing aluminum substrate WO2024053275A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022141840A JP2024037205A (en) 2022-09-07 2022-09-07 Manufacturing method of aluminum base material
JP2022-141840 2022-09-07

Publications (1)

Publication Number Publication Date
WO2024053275A1 true WO2024053275A1 (en) 2024-03-14

Family

ID=90192363

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/027661 WO2024053275A1 (en) 2022-09-07 2023-07-27 Method for manufacturing aluminum substrate

Country Status (2)

Country Link
JP (1) JP2024037205A (en)
WO (1) WO2024053275A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61261491A (en) * 1985-05-14 1986-11-19 Sumitomo Light Metal Ind Ltd Manufacture of high purity aluminum-lithium alloy powder
JP2006299336A (en) * 2005-04-19 2006-11-02 Doshisha Method for recovering fine particle in molten salt
JP2009215569A (en) * 2008-03-07 2009-09-24 Doshisha Method for producing alloy powder using molten salt reaction bath
JP2021070851A (en) * 2019-10-31 2021-05-06 東邦チタニウム株式会社 Method for producing powdered metal

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61261491A (en) * 1985-05-14 1986-11-19 Sumitomo Light Metal Ind Ltd Manufacture of high purity aluminum-lithium alloy powder
JP2006299336A (en) * 2005-04-19 2006-11-02 Doshisha Method for recovering fine particle in molten salt
JP2009215569A (en) * 2008-03-07 2009-09-24 Doshisha Method for producing alloy powder using molten salt reaction bath
JP2021070851A (en) * 2019-10-31 2021-05-06 東邦チタニウム株式会社 Method for producing powdered metal

Also Published As

Publication number Publication date
JP2024037205A (en) 2024-03-19

Similar Documents

Publication Publication Date Title
US10130994B2 (en) Production of substantially spherical metal powders
US20200199716A1 (en) Additively manufactured high-temperature aluminum alloys, and feedstocks for making the same
TWI431140B (en) Method for manufacturing sputtering standard materials for aluminum - based alloys
US20210146439A1 (en) Functionalized aspherical powder feedstocks and methods of making the same
CN108772568A (en) A kind of preparation method of metal-base nanometer composite material powder for 3D printing
CN101168810A (en) High-strength high-modulus aluminum-base composite material and preparation method thereof
CN109014182A (en) Increasing material manufacturing 7000 line aluminium alloy powder and preparation method thereof
JP6955254B2 (en) Crystal grain refiner for casting containing heterogeneous particles in high concentration and its manufacturing method
AU2007268370B2 (en) Method for producing metal alloy and intermetallic products
WO2024053275A1 (en) Method for manufacturing aluminum substrate
US20220347746A1 (en) Method for refining large-particle-size pure copper or copper alloy particles by high-energy ball milling
CN113373355A (en) Multi-scale particle modified 7000 series alloy wire and preparation method thereof
CN112170861A (en) Preparation method of silver tungsten carbide contact material
WO2020196578A1 (en) Method of producing solid spherical powder, and method of producing shaped product
WO1992007676A1 (en) Hypereutectic aluminum/silicon alloy powder and production thereof
JP3283550B2 (en) Method for producing hypereutectic aluminum-silicon alloy powder having maximum crystal grain size of primary silicon of 10 μm or less
CN110355376A (en) A kind of method that ultrasonic excitation aluminium-salt blend melt prepares aluminum or aluminum alloy powder
WO2023181329A1 (en) Copper alloy powder for additive layer manufacturing, production method and evaluation method therefor, method for producing additive layer-manufactured copper alloy article, and additive layer-manufactured copper alloy article
Moazami Goudarzi et al. Fabrication of Al/SiC nanocomposite powders via in situ powder metallurgy method
CN1179061C (en) Method for mfg. aluminium alloy target material, and aluminium alloy target material obtained thereby
JP7424108B2 (en) Heat-treated unsintered copper alloy powder for additive manufacturing and its manufacturing method
Ab Kadir et al. Microstructural and physical characteristics of recycling aluminium chips AA6061/Al powder using powder metallurgy
Boppana et al. Synthesis of ceramic-based composite
JPS61502615A (en) Titanium, hafnium and zirconium group 4B transition metal group passivated metal powder for powder metallurgy and method for producing the same
Liang et al. Effect of powder characteristic on Al internal oxidation to prepare Al2O3-Cu composite

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23862818

Country of ref document: EP

Kind code of ref document: A1