WO2014087707A1 - 酸化第二銅微粉末及びその製造方法 - Google Patents

酸化第二銅微粉末及びその製造方法 Download PDF

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Publication number
WO2014087707A1
WO2014087707A1 PCT/JP2013/072467 JP2013072467W WO2014087707A1 WO 2014087707 A1 WO2014087707 A1 WO 2014087707A1 JP 2013072467 W JP2013072467 W JP 2013072467W WO 2014087707 A1 WO2014087707 A1 WO 2014087707A1
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Prior art keywords
fine powder
electrolytic copper
copper
powder
cupric oxide
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PCT/JP2013/072467
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English (en)
French (fr)
Japanese (ja)
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岡田　浩
雄 山下
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住友金属鉱山株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/25—Oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the present invention relates to cupric oxide fine powder and a method for producing the same.
  • cupric oxide fine powder is used for pigments, paints, catalysts, ceramic colorants, copper sources for replenishing copper plating solutions, etc., and the production methods are roughly classified into wet methods and dry methods.
  • sodium hydroxide is added to an aqueous solution of cupric chloride or copper sulfate to form copper hydroxide, and then the copper hydroxide is heated (see Patent Document 1). More specifically, the etching waste solution of the printed circuit board containing cupric chloride is neutralized with caustic (NaOH), and the neutralized copper solution and caustic aqueous solution are placed in an aqueous solution maintained at a temperature of 40 to 50 ° C. At the same time, the mixture is added dropwise to produce a copper hydrate while maintaining the pH of the mixed aqueous solution in the range of weakly acidic to weakly alkaline. Next, the pH is adjusted to 12 to 13, and kept at a temperature of 70 to 80 ° C. for 30 minutes, and then washed with water and solid-liquid separation to produce cupric oxide.
  • CaOH caustic
  • cupric oxide powder produced by a wet method has an advantage of fast solubility in a copper plating solution.
  • cupric oxide powder is produced by a wet method, there is a problem that the residual concentration of S and the like derived from sulfate ions tends to be relatively high in addition to Na. If cupric oxide powder containing a large amount of impurities is added to the plating solution, plating defects may occur due to the impurities. For example, in the method described in Patent Document 1, impurities other than copper dissolved when etching a printed circuit board are included in the etching waste liquid used, and sodium chloride (NaCl) is used as an impurity during neutralization. As a by-product, etc., a water washing step is required to remove impurities.
  • NaCl sodium chloride
  • a method of drying the slurry-like cupric oxide fine powder a method of evaporating the solvent by heating the container, a method of drying by heating the container while stirring, or a method of heating with hot air
  • a medium fluidized drying method in which slurry is put into a medium such as alumina, powder dried on the surface of the medium is peeled off, exhausted with hot air, and recovered as a dry powder with a cyclone, bag filter or the like.
  • the dry method there is a method in which copper nitrate, copper sulfate, copper carbonate, copper hydroxide or the like is heated in air to a temperature of about 600 ° C. and thermally decomposed (see Non-Patent Document 1).
  • the dry method has a higher purity of cupric oxide obtained than the wet method, and is excellent in solubility in a plating solution.
  • the obtained copper oxide powder is required to be in a fine powder state, but the cupric oxide powder obtained by the dry method has a large particle size due to sintering. It is necessary to pulverize the cupric oxide powder.
  • metallic copper when used as a raw material, it is difficult to finely grind metal copper because it is soft and ductile when ground before heat treatment. For this reason, in order to heat-treat completely to copper oxide, it is necessary to heat to a higher temperature.
  • sintering of the copper particles occurs again by the heat treatment at a high temperature, so that it is necessary to grind again after the heat treatment, etc. In this respect, the dry method was not an efficient method.
  • Patent Documents 3 to 5 In order to increase the efficiency of the dry method, it has been proposed to pulverize electrolytic copper powder prepared in a copper sulfate solution by a jet mill pulverization method (see Patent Documents 3 to 5). According to Patent Documents 3 to 5, in order to finely pulverize the electrolytic copper powder, it can be said that the particle diameter of the electrolytic copper powder as a pulverized raw material is an important factor. For example, Patent Document 3 shows that in order to obtain a copper powder of 10 ⁇ m or less, the size of the electrolytic copper powder as a raw material must be 2000 cm 2 / g or more in terms of specific surface area.
  • the formation form of the electrolytic copper powder is a resin-grown structure
  • the electrolytic copper powder which is a pulverized raw material
  • the electrolytic copper powder after pulverization becomes agglomerated or flat due to properties such as ductility of metallic copper. It is difficult to refine the copper powder.
  • the present invention has been made by focusing on reducing the electrolytic copper powder and improving the solubility in the plating solution, and the subject is high purity, which is the conventional advantage of the dry method. It is to improve the solubility in the plating solution while taking advantage of this fact.
  • the inventors of the present invention pulverized electrolytic copper powder having an oxide film on the surface in a dry manner, and oxidized the electrolytic copper fine powder obtained by this pulverization, thereby The inventors have found that the object can be achieved and have completed the present invention.
  • the present invention provides the following.
  • the present invention comprises a dry pulverization step of pulverizing electrolytic copper powder having an oxide film on the surface by a dry method, and an oxidation step of oxidizing electrolytic copper fine powder obtained by this dry pulverization step. It is a manufacturing method of a fine powder.
  • the oxide film is formed by washing electrolytic copper powder obtained by electrolysis of a copper ion-containing solution with water and then drying at 70 ° C. to 150 ° C. in an oxygen-containing atmosphere.
  • the method for producing cupric oxide fine powder according to (1) is described in detail below.
  • this invention is a manufacturing method of the cupric oxide fine powder as described in (1) or (2) with which the said dry-type grinding
  • this invention uses the copper sulfate aqueous solution in which the cupric oxide fine powder obtained by the manufacturing method in any one of (1) to (4) was melt
  • the average particle size is 5 ⁇ m or less, the maximum particle size is 15 ⁇ m or less, and 10 g of cupric oxide fine powder is 228 g / L of CuSO 4 .5H 2 at 25 ° C.
  • the dissolution time is 1 minute or less. Copper fine powder.
  • cupric oxide fine powder having high copper oxide purity and high solubility in a plating solution.
  • This cupric oxide fine powder is suitably used as a copper source for replenishing a copper plating solution used industrially.
  • the scanning electron microscope image (SEM image) of the copper oxide powder which has an oxide film on the surface is shown.
  • the SEM image of the electrolytic copper fine powder which concerns on Example 1 is shown.
  • the SEM image of the electrolytic copper fine powder which concerns on the comparative example 1 is shown.
  • the SEM image of the electrolytic copper fine powder which concerns on the comparative example 2 is shown.
  • the X-ray-diffraction pattern of the cupric oxide fine powder concerning Example 1 is shown.
  • the production method of the present invention includes a dry pulverization step S1 in which electrolytic copper powder having an oxide film on the surface is pulverized in a dry manner, and an oxidation step S2 in which electrolytic copper fine powder obtained by the dry pulverization step S1 is oxidized.
  • electrolytic copper powder in order to clearly distinguish the state of electrolytic copper or copper oxide, the electrolytic copper before dry pulverization is referred to as “electrolytic copper powder”, and the electrolytic copper after dry pulverization but before oxidation is expressed as “ It is called “electrolytic copper fine powder”, and the oxidized copper oxide is called “cupric oxide fine powder”.
  • the electrolytic copper powder used in the dry pulverization step S1 may have any method for forming an oxide film as long as it has an oxide film on its surface.
  • the electrolytic copper powder is deposited on the surface of the electrode by electrolysis of copper and collected, and then subjected to an oxide film forming step S0 for forming an oxide film on the surface of the electrolytic copper powder.
  • the electrolytic copper powder has, for example, a bath composition of CuSO 4 ⁇ 5H 2 O: 5 to 50 g / L, free H 2 SO 4 : 50 to 250 g / L, a current density of 5 to 30 A / dm 2 , and a bath temperature of 20 to 60. It can be produced by electrolysis under the condition of ° C. and electrodepositing on the cathode.
  • the obtained electrolytic copper powder is preferably washed at a temperature of 70 to 150 ° C. in an oxygen-containing atmosphere in order to remove moisture after washing with water.
  • An oxygen-containing atmosphere means a state containing oxygen at least to the extent of the atmosphere, and may be an air atmosphere or a state in which oxygen is artificially supplied. In consideration, an air atmosphere is preferable.
  • the electrolytic copper powder reacts with oxygen in the gas, and an oxide film is formed on the surface of the electrolytic copper powder.
  • an oxide film is formed on the surface of the electrolytic copper powder.
  • it is preferably 20% or more of the theoretical weight when oxidized to copper, more preferably 30% or more, and further preferably 40% or more.
  • the present invention includes a dry pulverization step S1 in which electrolytic copper powder having an oxide film on the surface is pulverized in a dry manner to obtain electrolytic copper fine powder.
  • Electrolytic copper powder is soft and ductile, so it is difficult to grind finely. Therefore, the electrolytic copper powder is preferably pulverized in an oxygen-containing atmosphere. By pulverizing in an oxygen-containing atmosphere, the metal surface appearing by pulverization can be oxidized, and as a result, a new oxide film is formed. Therefore, the ductility of the electrolytic copper powder can be suppressed, and the electrolytic copper powder can be efficiently miniaturized.
  • the pulverization method is not particularly limited, but considering the manufacturing cost and efficiency, a method of colliding electrolytic copper powders in a fluid or colliding electrolytic copper powders with a collision plate in a fluid is preferable.
  • a method of colliding electrolytic copper powders in a fluid or colliding electrolytic copper powders with a collision plate in a fluid is preferable.
  • jet mills and cyclone mills are commercially available apparatuses such as jet mills and cyclone mills.
  • electrolytic copper fine powder can be obtained more efficiently.
  • the particle diameter of the electrolytic copper fine powder is not particularly limited, but the average particle diameter is preferably 5 ⁇ m or less, so that the oxidation step S2 described below can be performed efficiently, and preferably 4 ⁇ m or less. More preferably, it is more preferably 3 ⁇ m or less.
  • the maximum particle size is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the particle diameter is based on a volume sphere equivalent diameter when measured using a laser particle size distribution measuring instrument Macrotrac (manufactured by Nikkiso Co., Ltd.).
  • the present invention includes an oxidation step S2 for oxidizing the electrolytic copper fine powder obtained by the dry pulverization step S1.
  • the oxidation step S2 is preferably performed by heating the electrolytic copper fine powder at 300 ° C to 700 ° C. If it is this temperature range, the temperature which heat-processes will not be specifically limited, However, It is preferable to set with the particle diameter of electrolytic copper fine powder. For example, when the average particle diameter of the electrolytic copper fine powder is 5 ⁇ m or less, the electrolytic copper fine powder can be made into cupric oxide fine powder by heat treatment at a relatively low temperature. On the other hand, when the average particle diameter of the electrolytic copper fine powder exceeds 5 ⁇ m, heat treatment at a relatively high temperature is required to oxidize not only the surface of the electrolytic copper fine powder but also the center.
  • the electrolytic copper powder is pulverized to obtain the electrolytic copper fine powder, but the electrolytic copper fine powder is sintered and the particle size is increased. If it does so, the melt
  • the sintered cupric oxide powder is pulverized again even if the electrolytic copper fine powder is sintered.
  • the average particle diameter of the electrolytic copper fine powder is preferably 10 ⁇ m or less, and the maximum particle diameter is preferably 15 ⁇ m or less.
  • the heat treatment time depends on the heat treatment temperature.
  • the heat treatment time is preferably 5 hours or less, and when the heat treatment temperature is 500 ° C. to 700 ° C. Is preferably 3 hours or less.
  • the particle size of the second electrolytic copper fine powder is larger than that of the electrolytic copper fine powder, but in order to increase the solubility in the copper sulfate plating solution, It is preferable to suppress as much as possible. Therefore, the particle diameter of the cupric oxide fine copper powder is preferably about the same as that of the electrolytic copper fine powder. Specifically, the average particle diameter is preferably 5 ⁇ m or less, and preferably 4 ⁇ m or less. More preferably, it is more preferably 3 ⁇ m or less. The maximum particle size is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the cupric oxide fine powder obtained by the above production method is suitably used as a raw material for the electrolytic solution of the electrolytic copper plating apparatus.
  • the cupric oxide fine powder charged into the plating solution should not produce a dissolution residue.
  • cuprous oxide does not dissolve in the plating solution and becomes a residue, so it is necessary to avoid the production of fine cuprous oxide powder. Therefore, it is preferable that the purity of the cupric oxide fine powder in the cupric oxide fine powder is high, preferably 99% or more, and more preferably 99.5% or more. Since the cupric oxide fine powder obtained by the production method of the present invention is obtained by oxidizing the pulverized electrolytic copper fine powder by heat treatment, the electrolytic copper can be completely oxidized to cupric oxide. As a result, generation of cuprous oxide can be suppressed.
  • the solubility of the cupric oxide fine powder in the plating solution is high. 10 g of the cupric oxide fine powder obtained by the above production method was mixed with 228 g / L CuSO 4 .5H 2 O, 68 g / L free H 2 SO 4 and 60 mg / L chloride ion at 25 ° C. Is dissolved within 1 minute. In this respect, the cupric oxide fine powder obtained by the above production method is suitably used as a raw material for the electrolytic solution of the electrolytic copper plating apparatus.
  • cupric oxide fine powder obtained by the above production method is suitably used as a raw material for the electrolytic solution of the electrolytic copper plating apparatus.
  • a copper plating solution (copper sulfate aqueous solution) used for electrolytic plating of copper contains copper sulfate, sulfuric acid and chloride ions, and a pH lower than 1 is often used.
  • a known additive is added to the copper plating solution to improve the quality of the copper plating.
  • a problem is how to make a mechanism for supplying copper to the plating solution.
  • the copper source copper or a compound containing copper
  • the sulfate ion in the plating solution, etc. as the copper source dissolves.
  • C It is required that the additive contained in the plating solution does not decompose.
  • the cupric oxide fine powder obtained by the above production method can comply with any of the above (a) to (c).
  • a cupric oxide dissolution tank for dissolving the cupric oxide fine powder is provided separately from the plating tank for plating the electrolytic plating apparatus.
  • An aqueous solution (plating solution) may be circulated between the plating tank and the cupric oxide dissolution tank.
  • This cupric oxide dissolution tank returns an aqueous solution formed by dissolving cupric oxide fine powder in the aqueous solution supplied from the plating tank to the plating tank. It is preferable to attach a stirring mechanism such as a propeller to the cupric oxide dissolution tank to be used. Moreover, you may provide a well-known various filter between a plating tank and a cupric oxide dissolution tank for removal of a dust, a foreign material, etc.
  • Example 1 First, using a copper sulfate aqueous solution containing 32 g / L of CuSO 4 .5H 2 O and 55 g / L of free H 2 SO 4 , electrolysis was performed under conditions of an energization current density of 10 A / dm 2 and a bath temperature of 25 ° C. Copper powder was prepared. The electrolytic copper powder was thoroughly washed with water and then dried overnight at a temperature of 105 ° C. using a dryer.
  • this copper oxide powder was dry pulverized in an air atmosphere using a jet mill (device name: Nano Grinding Mill NJ-50, manufactured by Tokuju Kogakusha Co., Ltd.). Dry pulverization was carried out under the conditions of pulverization pressure: 1 MPa and supply rate: 300 g / h.
  • the pulverized electrolytic copper powder was heated in an electric furnace under an air atmosphere at a heating temperature of 500 ° C. for 3 hours to oxidize the electrolytic copper powder to obtain a cupric oxide fine powder according to Example 1. .
  • Example 2 Other than having made the supply rate at the time of dry pulverization 500 g / h, and oxidizing the pulverized electrolytic copper powder in an electric furnace in an air atmosphere at a heating temperature of 700 ° C. for 2 hours for 2 hours Obtained the cupric oxide fine powder based on Example 2 by the same method as described in Example 1.
  • Example 3 Example 1 except that the dry pulverization was repeated three times, and the pulverized electrolytic copper fine powder was kept in an electric furnace in an air atmosphere at a heating temperature of 300 ° C. for 5 hours to oxidize the electrolytic copper powder.
  • a cupric oxide fine powder according to Example 3 was obtained in the same manner as described.
  • FIG. 2 is an SEM image of the electrolytic copper powder after drying according to Example 1.
  • FIGS. 3 is an SEM image of the electrolytic copper fine powder according to Example 1
  • FIG. 4 is an SEM image of the electrolytic copper fine powder according to Comparative Example 1
  • FIG. 5 is an electrolytic copper fine powder according to Comparative Example 2. It is a SEM image of powder. Table 2 shows the result of observing the shape.
  • the electrolytic copper fine powders in Examples 1 to 3 were pulverized in a granular state.
  • the electrolytic copper fine powder in Comparative Examples 1 and 2 contained not only granular particles but also flat particles. This is presumed to be because the electrolytic copper powder could not be finely pulverized due to the ductility of metallic copper because the surface did not have an oxide film.
  • the average particle size and the maximum particle size of the electrolytic copper fine powder were measured. These particle diameters are based on the equivalent volume sphere diameters measured using a laser particle size distribution measuring instrument Macrotrac (manufactured by Nikkiso Co., Ltd.). The results are shown in Table 2.
  • the electrolytic copper fine powders in Examples 1 to 3 had an average particle size of 3.5 ⁇ m or less and a maximum particle size of 10 ⁇ m or less. From this, it was confirmed quantitatively that the electrolytic copper fine powders in Examples 1 to 3 were pulverized in a granular state.
  • the electrolytic copper fine powders in Comparative Examples 1 and 2 had an average particle size of 5.2 ⁇ m or more and a maximum particle size of 20 ⁇ m or more. From this, it has been quantitatively confirmed that the electrolytic copper fine powder in Comparative Examples 1 and 2 contains particles that are not properly pulverized.
  • FIG. 6 An example of the results is shown in FIG. 6 is an XRD pattern of a cupric oxide fine powder according to Example 1.
  • FIG. 6 From this XRD pattern, it was confirmed that the cupric oxide fine powder according to Example 1 was a CuO single phase.
  • illustration is abbreviate
  • the solubility with respect to a plating solution was added to 1 L of a plating solution while stirring with a stirrer at 25 ° C. with 10 g of cupric oxide fine powder according to Examples and Comparative Examples. Evaluation was made by measuring the time until the fine powder was completely dissolved.
  • the plating solution was a solution containing 228 g / L of CuSO 4 .5H 2 O, 68 g / L of free H 2 SO 4 and 60 mg / L of chloride ions. The results are shown in Table 3.
  • the cupric oxide fine powder according to the example could be dissolved in the plating solution within 35 seconds.
  • cupric oxide fine powder having high solubility in the plating solution can be provided even by the dry method.
  • the cupric oxide fine powder according to the comparative example could not be completely dissolved in the plating solution even after 20 minutes.
  • fine cupric oxide produced through a dry pulverization process in which electrolytic copper powder having an oxide film on the surface is pulverized in a dry process and an oxidation process in which electrolytic copper fine powder obtained by this dry pulverization process is oxidized. It was confirmed that the powder has both high purity, which is a conventional advantage of the dry method, and high solubility in a plating solution, which is a conventional advantage of the wet method. As a result, it was confirmed that it can be used very suitably as a copper source for replenishment of industrial copper plating solutions.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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PCT/JP2013/072467 2012-12-07 2013-08-22 酸化第二銅微粉末及びその製造方法 WO2014087707A1 (ja)

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JP3328378B2 (ja) 1993-07-09 2002-09-24 住友金属工業株式会社 高周波加熱装置
JP3320509B2 (ja) 1993-07-29 2002-09-03 住友金属工業株式会社 高周波加熱装置
JP3163037B2 (ja) 1997-05-22 2001-05-08 セア スチール コーポレーション 高周波電気抵抗溶接装置の自動入熱量制御システム及び制御方法
WO2016052373A1 (ja) * 2014-10-03 2016-04-07 三井金属鉱業株式会社 銅粉
KR20190047071A (ko) * 2016-09-29 2019-05-07 제이엑스금속주식회사 레이저 소결용 표면 처리 금속분

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS62199705A (ja) * 1986-02-25 1987-09-03 Fukuda Kinzoku Hakufun Kogyo Kk 微細粒状銅粉の製造方法
JP2008122030A (ja) * 2006-11-15 2008-05-29 Mitsui Mining & Smelting Co Ltd ヒートパイプ構成原料
JP2009047383A (ja) * 2007-08-22 2009-03-05 Mitsui Mining & Smelting Co Ltd ヒートパイプ構成原料
JP2012193068A (ja) * 2011-03-16 2012-10-11 Sumitomo Metal Mining Co Ltd 高純度酸化第二銅微粉末の製造方法、および硫酸銅水溶液の銅イオンの供給方法

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CN102441381A (zh) * 2011-10-28 2012-05-09 昆山德泰新材料科技有限公司 一种用氧化铜粉生产的催化剂及其制造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62199705A (ja) * 1986-02-25 1987-09-03 Fukuda Kinzoku Hakufun Kogyo Kk 微細粒状銅粉の製造方法
JP2008122030A (ja) * 2006-11-15 2008-05-29 Mitsui Mining & Smelting Co Ltd ヒートパイプ構成原料
JP2009047383A (ja) * 2007-08-22 2009-03-05 Mitsui Mining & Smelting Co Ltd ヒートパイプ構成原料
JP2012193068A (ja) * 2011-03-16 2012-10-11 Sumitomo Metal Mining Co Ltd 高純度酸化第二銅微粉末の製造方法、および硫酸銅水溶液の銅イオンの供給方法

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