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WO2013031765A1 - Poudre pour composition similaire à de l'argile pour former un objet en alliage cuivre-argent fritté en utilisant un composé de cuivre, composition similaire à de l'argile et procédé de production de la composition similaire à de l'argile - Google Patents

Poudre pour composition similaire à de l'argile pour former un objet en alliage cuivre-argent fritté en utilisant un composé de cuivre, composition similaire à de l'argile et procédé de production de la composition similaire à de l'argile Download PDF

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Publication number
WO2013031765A1
WO2013031765A1 PCT/JP2012/071695 JP2012071695W WO2013031765A1 WO 2013031765 A1 WO2013031765 A1 WO 2013031765A1 JP 2012071695 W JP2012071695 W JP 2012071695W WO 2013031765 A1 WO2013031765 A1 WO 2013031765A1
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WIPO (PCT)
Prior art keywords
silver
powder
clay
copper
composition
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Ceased
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PCT/JP2012/071695
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English (en)
Japanese (ja)
Inventor
佳史 山本
貴司 山路
井戸　康夫
真二 大谷
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent

Definitions

  • the present invention relates to a powder for a clay-like composition for forming a silver-copper alloy sintered body, a clay-like composition, and a method for producing the clay-like composition.
  • silver jewelry and arts and crafts represented by rings and the like are generally manufactured by casting or forging a silver-containing material.
  • silver clay containing a silver powder (clay-like composition for forming a sintered body) is commercially available, and this silver clay is molded into an arbitrary shape and then fired to have an arbitrary shape.
  • a method for producing silver jewelry and arts and crafts has been proposed (see, for example, Patent Document 1). According to such a method, silver clay can be freely modeled in the same way as ordinary clay work, and after drying the molded body obtained by modeling, it is extremely fired by using a heating furnace. Silver jewelry, arts and crafts, etc. can be easily manufactured.
  • the silver clay as described in Patent Document 1 is generally obtained by adding and kneading a pure silver (pure Ag) powder with a binder, water, and a surfactant as required.
  • a silver sintered body is manufactured by molding silver clay using pure Ag silver powder, the strength of pure silver itself is weak, so the obtained silver sintered body has strength characteristics. There is a problem that it becomes inferior.
  • the Ag component ratio is set to 92.5%, and the silver-containing powder is constituted as a silver alloy containing copper (Cu). It has also been proposed to produce a silver alloy sintered body called so-called sterling silver by drying a molded body obtained by shaping a silver clay obtained by kneading by adding a binder and the like, followed by firing. (For example, refer to the column of the example of Patent Document 2).
  • a silver alloy sintered body called Sterling Silver made of an Ag—Cu alloy has improved strength characteristics compared to a silver sintered body using pure Ag silver powder.
  • the color tone of silver clay is likely to deteriorate because Cu contained in silver clay is easily altered.
  • discoloration has already been observed when several days have passed since the silver clay was produced, not only on the surface but also inside it. It has been pointed out that the color changes over time.
  • the present invention has been made in view of the above-described circumstances, and does not easily discolor even in the air atmosphere, and may be collectively referred to as tensile strength, bending strength, and surface hardness (hereinafter referred to as mechanical strength). ) And a clay-like composition for forming a sintered body capable of forming a silver-copper alloy sintered body excellent in elongation, etc., a powder for a clay-like composition for forming a silver-copper alloy sintered body, and a silver-copper alloy sintered body It aims at providing the manufacturing method of the clay-like composition for formation.
  • a powder for silver clay (for forming a silver-copper alloy sintered body) constituting silver clay (a clay-like composition for forming a silver-copper alloy sintered body) was obtained.
  • the powder for clay-like composition) is formed as a powder containing a silver-containing powder containing silver and a compound powder that changes to copper oxide by heating, such as copper hydroxide, for example. It has been found that discoloration of the silver-copper alloy sintered body-forming clay-like composition) can be suppressed.
  • This invention is made
  • the powder for clay-like composition for forming a silver-copper alloy sintered body of the present invention is a powder component containing a silver-containing powder and a copper compound powder, and the copper compound powder is converted to copper oxide at 550 ° C. or less. It is characterized by containing a changing compound.
  • the said copper compound powder is chemically stable compared with metal Cu, there is little possibility of quality change (the valence of a copper ion changes) easily in air
  • the copper compound powder contains a copper compound that changes to copper oxide at 550 ° C. or lower, such as copper hydroxide, thereby heating the clay-like composition to remove the binder. At this time, the heated copper compound changes to copper oxide. And by the main baking performed in a reducing atmosphere after temporary baking, copper oxide is reduced to metal Cu, and the produced metal Cu and silver-containing powder are alloyed and sintered.
  • a copper compound that changes to copper oxide at 550 ° C. or lower such as copper hydroxide
  • the compounds that change to copper oxide at 550 ° C. or lower include, besides copper hydroxide, basic copper carbonate (II), acetylacetone copper (II), stearate copper (II), benzoate copper (II), formic acid
  • Said copper compound powder shall contain the 1 or more types of compound selected from said substance.
  • Said copper compound powder shall contain the 1 or more types of compound selected from said substance.
  • basic copper carbonate (II) and copper formate (II) tetrahydrate it heated at 550 degreeC for 30 minutes in air
  • the copper compound powder may contain copper oxide in addition to the compound.
  • the copper oxide contained in a copper compound powder shall be 3 mass% or less with respect to the whole powder component.
  • the content is preferably 3% by mass or less based on the entire powder component.
  • the copper compounds that change to copper oxide at 550 ° C. or less contained in the copper compound powder as described above exhibit blue to green color derived from divalent copper ions. Therefore, when a clay-like composition is produced using silver-containing powder and copper oxide powder, since the copper oxide is black, the clay-like composition becomes a grayish dirty color, but the copper oxide is reduced. By adding the copper compound, the black color of copper oxide can be made inconspicuous.
  • a gas generated when the copper compound decomposes (for example, water in the case of copper hydroxide) forms fine communication holes when it escapes to the outside.
  • Gas for example, CO
  • the content rate of the copper compound powder with respect to the whole powder component is 4 mass% or more and 35 mass% or less with respect to the whole powder component of the said copper oxide, when a copper compound decomposes
  • the mechanical strength may not be sufficiently improved when the content of the copper oxide is less than 4% by mass when the copper compound is decomposed to become copper oxide. .
  • the content ratio of the copper oxide to the entire powder component when the copper compound is decomposed into copper oxide exceeds 35% by mass, the elongation decreases, and the silver-copper alloy sintered body is also polished after polishing. There is a possibility that beautiful silver color will not be exhibited. For this reason, it is preferable that the content rate with respect to the whole powder component of copper oxide when a copper compound decomposes
  • the said powder component may contain 2 mass% or less metal Cu with respect to the whole powder further.
  • the content rate of metal Cu in the said powder component 2 mass% or less, discoloration of the clay-like composition for silver-copper alloy sintered compact formation can be prevented reliably.
  • the metal Cu contained in the powder component include metal Cu powder, metal Cu contained in an alloy powder of Ag and Cu, and the like.
  • the average particle diameter of copper compound powder shall be 1 micrometer or more and 50 micrometers or less. In this case, it is possible to improve the mechanical strength and elongation of the silver-copper alloy sintered body obtained by firing the clay-like composition for forming the silver-copper alloy sintered body.
  • the average particle diameter shall be 20 micrometers or more and 50 micrometers or less.
  • the average particle diameter of the silver-containing powder may be, for example, 1 ⁇ m or more and 25 ⁇ m or less.
  • the clay-like composition for forming a silver-copper alloy sintered body of the present invention is characterized by containing the above-mentioned powder for clay-like composition for forming a silver-copper alloy sintered body, a binder, and water. Furthermore, the clay-like composition for forming a silver-copper alloy sintered body of the present invention may further contain at least one of fats and oils and a surfactant as necessary. Further, the clay-like composition for forming a silver-copper alloy sintered body according to the present invention includes the binder, a cellulose binder, a polyvinyl binder, an acrylic binder, a wax binder, a resin binder, starch, gelatin, and wheat flour.
  • a cellulose binder particularly water-soluble cellulose.
  • the type of the surfactant is not particularly limited, and a normal surfactant can be used.
  • the fats and oils include organic acids (oleic acid, stearic acid, phthalic acid, palmitic acid, sepacic acid, acetylcitric acid, hydroxybenzoic acid, lauric acid, myristic acid, caproic acid, enanthic acid, butyric acid, capric acid).
  • Organic acid esters organic acid esters having methyl, ethyl, propyl, butyl, octyl, hexyl, dimethyl, diethyl, isopropyl, and isobutyl groups
  • higher alcohols octanol, nonanol, decanol
  • polyhydric alcohols glycerin, arabit, sorbitan
  • ethers dioctyl ether, didecyl ether
  • the fats and oils may be one or two or more selected from these substances.
  • the clay-like composition may contain the above-mentioned powder for clay-like composition in a range of 70% by mass to 95% by mass.
  • the balance (5 to 30% by mass of the clay-like composition) contains a binder and water.
  • the balance (referred to as a binder) may contain 11 to 17% by mass of the above binder.
  • the other components may be water, but may contain the above fats and oils in a range of 5% by mass or less. Moreover, you may contain said surfactant in 2 mass% or less.
  • the method for producing a clay-like composition for forming a silver-copper alloy sintered body according to the present invention comprises the above-mentioned powder for clay-like composition for forming a silver-copper alloy sintered body, and a binder agent in which a binder and water are mixed. It is characterized by mixing and kneading. According to the method for producing a silver-copper alloy sintered body for forming a silver-copper alloy sintered body having this structure, a clay-like composition for forming a silver-copper alloy sintered body that has a copper compound powder and is difficult to discolor is produced. Is possible.
  • the binder agent may contain the above fats and oils and may contain a surfactant.
  • the clay-like composition for forming a silver-copper alloy sintered body of the present invention is fired to obtain a silver-copper alloy sintered body.
  • the silver-copper alloy sintered body of this configuration since the clay-like composition for forming a silver-copper alloy sintered body having the above-described configuration is fired, the silver clay made of pure Ag powder is fired. Compared to the above, the mechanical strength can be improved. That is, the silver-copper alloy sintered body obtained by heating and firing the above-mentioned clay-like composition for forming a silver-copper alloy sintered body has excellent mechanical strength, elongation, and the like.
  • the method for producing a silver-copper alloy sintered body using the clay-like composition for forming a silver-copper alloy sintered body according to the present invention has the above-mentioned clay-like composition for forming a silver-copper alloy sintered body in an arbitrary shape.
  • the molded body is dried at 350 to 550 ° C. after being dried. After pre-baking at a temperature of 5 minutes to 6 hours, silver is fired at a baking temperature in the range of 700 ° C. to 870 ° C. for 30 minutes to 6 hours in a reducing atmosphere. It is good also as a copper alloy sintered compact.
  • firing may be performed while the molded body is embedded in activated carbon. Good.
  • sintering of the formed body can be promoted by reduction with activated carbon.
  • the clay-like composition for forming a silver-copper alloy sintered body of the present invention using the powder for clay-like composition for forming a silver-copper alloy sintered body according to the above-described configuration and action.
  • discoloration of the clay-like composition for forming a silver-copper alloy sintered body can be suppressed.
  • discoloration of the clay-like composition for forming a silver-copper alloy sintered body can be suppressed and molded by the above-described configuration and action.
  • the mechanical strength, elongation, and the like of the sintered silver alloy obtained later by heating and firing It becomes possible to improve the mechanical strength, elongation, and the like of the sintered silver alloy obtained later by heating and firing.
  • the method for producing a clay-like composition for forming a silver-copper alloy sintered body of the present invention the above-mentioned clay-like composition for forming a silver-copper alloy sintered body can be reliably produced.
  • the mechanical strength is improved as compared with the case where silver clay made of pure Ag powder is fired. be able to.
  • the clay-like composition for forming a silver-copper alloy sintered body having the above-described structure is used.
  • a silver-copper alloy sintered body having excellent mechanical strength, elongation, etc. can be produced by drying treatment or firing under specified conditions.
  • FIG. 2A to 2D are schematic views showing one embodiment of a method for producing a silver-copper alloy sintered body using the clay-like composition for forming a silver-copper alloy sintered body of the present invention
  • FIG. 2B is a schematic diagram illustrating a process of drying the formed body of FIG. 2A.
  • FIG. 2C is a schematic diagram showing a step of firing the dried molded body.
  • FIG. 2D is a schematic diagram showing a silver-copper alloy sintered body obtained by firing the formed body.
  • clay-like composition for forming a silver-copper alloy sintered body according to the present invention, clay-like composition for forming a silver-copper alloy sintered body, clay-like composition for forming a silver-copper alloy sintered body
  • clay-like composition for forming a silver-copper alloy sintered body is referred to as silver clay
  • the clay-like composition powder for forming a silver-copper alloy sintered body is referred to as silver clay powder.
  • the powder for silver clay according to the present embodiment includes a silver-containing powder containing silver and a copper compound powder.
  • the copper compound powder contains the compound which changes to copper oxide at 550 degrees C or less.
  • copper hydroxide is used in the examples described later.
  • basic copper carbonate (II), copper formate (II) tetra It has been confirmed that hydrates have the same effect as copper hydroxide.
  • copper acetylacetone (II), copper stearate (II), copper benzoate (II), copper acetate (II) monohydrate, copper bromide (I), copper oleate (II), copper citrate ( II) and the like are also thermally decomposed by heating and converted to copper oxide.
  • a powder for silver clay kneading by adding the additives described later to constitute silver clay, in a silver-copper alloy sintered body obtained by heating and firing, mechanical strength, elongation, etc. As a result, the effect of suppressing discoloration of silver clay is obtained.
  • the copper compound powder may further contain copper oxide.
  • the silver-containing powder Ag powder, Ag—Cu alloy powder, or the like can be applied.
  • the content ratio of the copper oxide to the whole powder component is set to 4 mass% or more and 35 mass% or less, and the content ratio of the Ag element to the total metal component in the powder component is It is preferable to set it as 46 to 97 mass%.
  • Cu is an element having an effect of improving strength by diffusing into Ag of the silver-copper alloy sintered body during sintering.
  • the content ratio of the copper oxide powder obtained by decomposing the copper compound powder is 4% by mass or more and 35% by mass or less when converted to the content ratio of Cu in the silver-copper alloy sintered body, 3% by mass or more. 30% by mass or less. If the Cu content in the silver-copper alloy sintered body is less than 3% by mass, the effect of improving the mechanical strength of the silver-copper alloy sintered body obtained by firing silver clay may be difficult to obtain. . Moreover, when the content rate of Cu in a silver-copper alloy sintered compact exceeds 30 mass%, there exists a possibility that elongation may fall.
  • the copper oxide in the silver clay powder Is preferably set within a range of 4 mass% to 35 mass%.
  • the content ratio of copper oxide when the copper compound powder is all changed to copper oxide may be 35% by mass or less. preferable.
  • the silver clay is constituted by adjusting the mixing ratio.
  • copper hydroxide powder is used as the copper compound powder
  • Ag powder is used as the silver-containing powder.
  • the content rate with respect to the whole powder component of the said copper oxide may be 4 to 35 mass%.
  • a silver clay powder consisting of Ag and inevitable impurities was obtained.
  • the particle sizes of the Ag powder and the copper hydroxide powder contained in the silver clay powder according to the present embodiment will be described.
  • the particle sizes of Ag powder and copper hydroxide powder are not particularly limited, but formability when silver clay is made by adding and kneading a binder as an additive, etc. Considering these characteristics, it is preferable to set the particle size within the following range.
  • the average particle diameter of the Ag powder is preferably 25 ⁇ m or less. By making the average particle diameter of the Ag powder within this range, the color tone of the silver-copper alloy sintered body obtained by firing silver clay is improved, and the mechanical properties of the silver-copper alloy sintered body as described above are also obtained. The effect of improving strength and elongation can be obtained stably. If the average particle size of the Ag powder exceeds 25 ⁇ m, the color tone of the silver-copper alloy sintered body may be deteriorated, or the effect of improving the mechanical strength may be reduced.
  • the average particle size of the Ag powder is more than 25 ⁇ m, the sintering property of the powder is lowered, so that a long firing time is required and the workability of the silver-copper alloy sintered body is adversely affected. It is possible and not preferred.
  • the lower limit of the average particle diameter is not particularly defined. However, if the average particle diameter of the Ag powder is 1 ⁇ m or less, there is a risk of increasing the cost in terms of industrial production. Is preferably the lower limit.
  • the average particle size of Ag powder is more preferably in the range of 1 ⁇ m to 20 ⁇ m, and still more preferably in the range of 3 ⁇ m to 10 ⁇ m.
  • the average particle size of the copper hydroxide powder is preferably 50 ⁇ m or less. By making the average particle diameter of the copper hydroxide powder within this range, the effect of improving the mechanical strength and elongation of the silver-copper alloy sintered body as described above can be stably obtained. If the average particle size of the copper hydroxide powder exceeds 50 ⁇ m, the effect of improving the mechanical strength of the silver-copper alloy sintered body may be difficult to obtain. In addition, when the average particle size of the copper hydroxide powder exceeds 50 ⁇ m, the sinterability of the powder is reduced as in the case of the Ag powder. It may adversely affect the workability of the sintered body, which is not preferable.
  • the lower limit of the average particle diameter is not particularly defined, but the average particle diameter of the copper hydroxide powder is preferably 20 ⁇ m from the viewpoint of the limit of the apparatus and the cost of industrial production.
  • the average particle size of the copper hydroxide powder is more preferably in the range of 25 ⁇ m to 45 ⁇ m, and still more preferably in the range of 30 ⁇ m to 40 ⁇ m.
  • sufficient sinterability is obtained by restricting the average particle size of the Ag powder and the copper hydroxide powder constituting the silver clay powder to a predetermined particle size or less as described above.
  • d50 (median diameter) is the average particle diameter.
  • the silver clay according to the present embodiment includes the powder for silver clay having the above configuration, a binder (an organic binder in the present embodiment), and water.
  • the silver clay according to the present embodiment contains the powder for silver clay having the above-described structure in a range of 70% by mass to 95% by mass, and further includes 5% by mass to 30% of a binder agent containing an organic binder and water. It contains in the range below mass%.
  • a surfactant and fats and oils may be added to the binder as necessary.
  • this silver clay is a silver clay containing a powder component containing a chemically stable copper hydroxide powder and an Ag powder, discoloration is suppressed in an air atmosphere.
  • Copper hydroxide exhibits a blue color derived from divalent copper ions.
  • the clay-like composition is produced using a silver-containing powder and a copper oxide powder, the copper oxide is black, so the clay-like composition has a grayish and dirty color, but the copper oxide is reduced and hydroxylated. By adding copper, the black color of copper oxide can be made inconspicuous.
  • organic binder used for the silver clay which concerns on this embodiment,
  • the organic substance which can connect the powder for silver clay and can be used as a clay-like composition can be utilized.
  • cellulose-based binder particularly water-soluble cellulose.
  • the said surfactant is not specifically limited, A normal surfactant (for example, polyethyleneglycol etc.) can be used.
  • oil and fat is not particularly limited.
  • Enanthic acid, butyric acid, capric acid organic acid esters (organic acid esters having methyl, ethyl, propyl, butyl, octyl, hexyl, dimethyl, diethyl, isopropyl, and isobutyl groups), higher grades
  • Examples include alcohols (octanol, nonanol, decanol), polyhydric alcohols (glycerin, arabit, sorbitan), ethers (dioctyl ether, didecyl ether) and the like.
  • the manufacturing method of the silver clay 5 which concerns on this embodiment makes 70 mass% or more and 95 mass% or less of the said powder 1 for silver clay, and makes the binder agent 2 containing an organic binder and water 5 mass% or more and 30 mass% or less. This is a kneading method.
  • each of Ag powder 1A and copper hydroxide powder 1B is introduced into a mixing device 50 in a prescribed amount.
  • a mixing device 50 for example, 88.9% by mass of Ag powder 1A (average particle size 5 ⁇ m: Microtrack method; atomized powder), copper hydroxide powder 1B (Average particle size 30 ⁇ m: Microtrack method; reagent manufactured by Kishida Chemical Co., Ltd.) Is introduced as 11.1% by mass.
  • the powder 1 for silver clay is obtained by mixing each said material powder within the mixing apparatus 50.
  • the binder agent 2 is added to the silver clay powder 1 in the mixing device 50.
  • the binder agent 2 is an organic binder mixed in a blend of 11 mass% to 17 mass%, fats and oils 5 mass% or less, surfactant 2 mass% or less, and the balance water. .
  • the silver clay 5 is obtained by mixing and knead
  • the silver-copper alloy sintered body according to the present embodiment is obtained by shaping and molding the silver clay 5 having the above-described configuration into an arbitrary shape and then firing it under the conditions described below. Since this silver-copper alloy sintered body has excellent mechanical strength, for example, even when a large external force is applied, it is possible to suppress deformation and breakage. Become. Moreover, since the silver-copper alloy sintered body according to the present embodiment has high elongation along with excellent mechanical strength, for example, additional processing with bending is performed on the sintered silver-copper alloy sintered body. Even when applied, it is possible to suppress the occurrence of cracks, fractures, and the like.
  • the silver clay 5 having the above-described configuration is formed into an arbitrary shape to obtain a formed body 51.
  • the formed body 51 is, for example, room temperature to 150-150.
  • the molded body 51 is subjected to a drying treatment at a temperature of 30 ° C. for 30 minutes to 24 hours, and then the molded body 51 is pre-baked at a temperature of 350 to 550 ° C. for a time of 5 minutes to 6 hours.
  • the silver-copper alloy sintered body 10 is obtained by firing at a temperature of 870 ° C. for 30 minutes to 6 hours.
  • the silver clay 5 is shaped and molded into an arbitrary shape by, for example, machining by a stamper, press molding, extrusion molding, or manual processing by an operator, etc.
  • the molded body 51 is put into an electric furnace 80 and dried to remove moisture and the like.
  • the drying temperature at this time is preferably, for example, room temperature or a temperature in the range of about 80 ° C. to 150 ° C. from the viewpoint of effective drying treatment. From the same point of view, the drying time is, for example, 30 to 720 minutes, more preferably 30 to 90 minutes.
  • the drying temperature is about 100 ° C. and the drying time is 60 minutes.
  • the binder removal treatment is performed by pre-baking for 5 minutes to 6 hours at 350 to 550 ° C. in the air atmosphere using the electric furnace 80. At this time, the copper compound in the silver clay 5 is heated to change into copper oxide.
  • a method of manufacturing the silver-copper alloy sintered body 10 by firing the formed body 51 by using an apparatus such as the illustrated example can be employed.
  • the molded body 51 is embedded in the activated carbon 61 filled in the baking container 60 made of stainless steel.
  • the distance from the surface of the activated carbon 61 in the firing container 60 to the molded body 51 is set. It is preferable to secure 10 mm or more.
  • the firing container 60 in which the molded body 51 is embedded in the activated carbon 61 is put into the electric furnace 80, and as described above, at a temperature in the range of 700 to 870 ° C. for 30 minutes to 6 hours. Firing is performed by heating with time.
  • the silver-copper alloy sintered body 10 obtained by firing can be subjected to post-processing such as surface polishing and decoration treatment as necessary to obtain a product.
  • the silver clay 5 using the silver clay powder 1 is constituted by the above-described configuration and action, so that the drying treatment is performed after molding. Then, it becomes possible to improve the mechanical strength and elongation of the silver sintered body 10 obtained by heating and firing. Furthermore, since the silver clay 5 contains chemically stable copper hydroxide, the copper hydroxide is not easily denatured in the air atmosphere, and the discoloration of the silver clay 5 can be suppressed. Moreover, according to the silver clay 5 which is this embodiment, since it is obtained by kneading using the silver clay powder 1 having the above-described configuration, similarly to the above, a silver-copper alloy obtained by heating and firing after molding.
  • the mechanical strength and elongation of the sintered body 10 can be improved. Furthermore, since Cu is contained as copper hydroxide, discoloration of the silver clay 5 can be suppressed. Furthermore, according to the manufacturing method of the silver-copper alloy sintered body 10 according to the present embodiment, after forming using the silver clay 5 having the above-described configuration, mechanical strength or It becomes possible to manufacture the silver-copper alloy sintered body 10 excellent in elongation and the like.
  • this invention is not limited to this, It can change suitably in the range which does not deviate from the technical idea of the invention.
  • a silver clay powder composed of Ag powder and copper hydroxide powder it is not limited to this, and may be Ag—Cu alloy powder instead of Ag powder, In addition to copper hydroxide powder, copper oxide powder may be contained.
  • copper powder or Ag—Cu alloy powder may be added.
  • the content ratio of the metal Cu contained in the Cu powder and the Ag—Cu alloy powder is preferably 2% by mass or less with respect to the total silver clay powder. Thereby, discoloration of silver clay can be suppressed reliably.
  • the content ratio of copper oxide in the silver clay powder is set to the whole powder component in order not to deteriorate the color tone of the silver clay powder. It is preferable to set it as 3 mass% or less.
  • the silver clay powder became grayish due to the influence of black, which is the color of copper oxide.
  • the powder for clay-like composition for forming a silver-copper alloy sintered body of the present invention the clay-like composition for forming a silver-copper alloy sintered body, and for forming a silver-copper alloy sintered body
  • the method for producing the clay-like composition and the silver-copper alloy sintered body using the clay-like composition for forming the silver-copper alloy sintered body of the present invention and the method for producing the silver-copper alloy sintered body will be described in more detail.
  • the present invention is not limited to this embodiment.
  • a powder for clay-like composition for forming a silver-copper alloy sintered body (hereinafter referred to as silver clay powder) was prepared by the following procedure.
  • Ag powder (average particle diameter 5 ⁇ m: Microtrack method; atomized powder) and copper hydroxide powder (average particle diameter 30 ⁇ m: Microtrack method; reagent manufactured by Kishida Chemical Co., Ltd.) It mixed with the mixing apparatus as shown in FIG.
  • the powder for silver clay of the example of the present invention in which Ag-11. 1% by mass Cu (OH) 2 (CuO conversion: 9.2% by mass, Cu conversion: 7.5% by mass) was obtained.
  • CuO conversion means the content rate with respect to the whole powder component at the time of copper hydroxide thermally decomposing and changing all into CuO.
  • Cu conversion means the content rate of Cu with respect to all the metal components in a powder component.
  • a binder agent an organic binder, water, a surfactant, and fats and oils are mixed to obtain a binder agent.
  • a clay-like composition for silver copper alloy sintered compact formation (henceforth, silver clay) is added by kneading by adding a binder agent.
  • the binder agent is 15% by mass of methyl cellulose as an organic binder, 3% by mass of olive oil which is a kind of organic acid as fats and oils, 1% by mass of polyethylene glycol as a surfactant, and the balance
  • the formulation was water. And it knead
  • the binder agent is a water-soluble cellulose ester (Shin-Etsu Chemical Co., Ltd. Metroles SM8000) and potato starch (Nissho Chemical Co., Ltd. Delica M9) as an organic binder.
  • a mixture of potato starch at a ratio of 4: 3 was used as 13% by mass, with the balance being water. And it knead
  • the silver clay was washed with hot water at 90 ° C. or higher to remove the organic binder, the surfactant and the oil and fat, and then a predetermined amount (about 10 g) of a sample necessary for quantitative analysis was collected.
  • this analysis sample was subjected to quantitative analysis of Cu by ICP analysis. As a result, it was confirmed that the theoretical content of Cu mixed as copper hydroxide powder and the actual amount of Cu contained in the silver clay coincided.
  • the binder removal treatment was performed by performing a pre-baking step of raising the temperature from room temperature to a temperature of 540 ° C. for about 10 minutes in an air atmosphere and keeping it at a temperature of 540 ° C. for 30 minutes. .
  • a fired silver-copper alloy sintered body was produced by simultaneously firing each formed body 51 for each invention example.
  • a stainless firing container 60 filled with activated carbon 61 was prepared, and each molded body 51 was embedded in the activated carbon 61.
  • the distance from the surface of the activated carbon 61 to each compact 51 was about 10 mm.
  • the firing container 60 in which each molded body 51 is embedded in the activated carbon 61 is put into an electric furnace 80, and the temperature is raised from room temperature to 870 ° C. for about 30 minutes, and the temperature of 870 ° C. is common to all the invention examples.
  • wire-shaped and prismatic silver-copper alloy sintered bodies 10 were produced.
  • Comparative Example 1 an Ag-7.5 mass% Cu alloy powder (average particle size 33 ⁇ m: Microtrac method; atomized powder) was used as the silver clay powder, and silver clay was used in the same manner as in the above-described example of the present invention.
  • Comparative Example 2 Ag powder (average particle size 5 ⁇ m: microtrack method; atomized powder) and Cu powder (average particle size 20 ⁇ m: microtrack method; manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) were used as silver clay powder.
  • a silver clay was produced in the same manner as in the above-mentioned examples of the present invention using a powder for silver clay formulated with Ag-7.5 mass% Cu.
  • Comparative Example 3 silver clay was produced in the same manner as in the above-described Example of the present invention by using silver powder having a particle size of 1 ⁇ m to 15 ⁇ m and a purity of 99.9% as silver clay powder.
  • bending strength, tensile strength, density, surface hardness, and elongation were measured by the following test methods.
  • the tensile strength and elongation were measured using a wire-shaped sintered body, and the bending strength, density, and surface hardness were measured using a prismatic sintered body.
  • the bending strength was determined by measuring a stress curve using an autograph AG-X manufactured by Shimadzu Corporation at an indentation speed of 0.5 mm / min and measuring the maximum point stress in the elastic region.
  • the tensile strength was determined by measuring the stress curve at the moment when the test piece was broken using the autograph AG-X manufactured by Shimadzu Corporation, measuring the stress curve at a tensile speed of 5 mm / min.
  • the density was measured by an automatic specific gravity measuring device “Archimedes (driving unit SA301, data processing unit SA601)” manufactured by Chow Balance. Further, the surface hardness was determined by measuring the Vickers hardness after polishing the surface of the test piece and using a red microhardness meter under the conditions of a load of 100 g and a load holding time of 10 seconds. The elongation was determined by measuring the stress curve at the moment when the test piece broke by measuring the stress curve at a tensile rate of 5 mm / min using Shimadzu Autograph AG-X.
  • Tables 1 and 2 show a list of manufacturing conditions and evaluation results for the inventive examples and Comparative Examples 1 to 3.
  • the oxygen concentration of the silver copper alloy sintered compact was measured.
  • the oxygen concentration was measured by a high frequency furnace heating-infrared absorption method.
  • the oxygen concentration is 1000 ppm or less, and it is confirmed that the copper hydroxide contained in the silver clay is thermally decomposed into copper through copper oxide.
  • the silver-copper alloy sintered body obtained by firing the present invention example is composed of a high-purity silver-copper alloy, in which the copper hydroxide contained in the silver clay is completely pyrolyzed. I understand.
  • Table 2 the mechanical properties are superior to those of the sintered body obtained from pure Ag.
  • the silver clays of Comparative Examples 1 and 2 were confirmed to be discolored after storage for 3 days at room temperature in an air atmosphere. Moreover, the silver-copper alloy sintered compact formed using the silver clay of the comparative examples 1 and 2 had a small elongation compared with the silver-copper alloy sintered compact concerning the example of this invention. Further, for Comparative Example 3 using pure silver, although there is no discoloration, the bending strength, tensile strength, surface hardness, density and the like, which are indicators of mechanical strength, tend to be lower than those of the present invention example, It was confirmed that it was easily deformed.
  • the silver clay using the silver clay powder of the present invention can suppress discoloration, and a silver-copper alloy sintered body excellent in mechanical strength, elongation, and the like. It is clear that it is obtained.
  • the powder for clay-like composition of the present invention it is possible to form a clay-like composition that is not easily discolored even in the air atmosphere. If this clay-like composition is used, a silver-copper alloy sintered body excellent in properties such as mechanical strength and elongation can be formed.

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Abstract

La présente invention concerne une poudre pour une composition similaire à de l'argile pour former un objet en alliage cuivre-argent fritté, le poudre étant un composant de poudre contenant une poudre contenant de l'argent et une poudre d'un composé de cuivre, la poudre d'un composé de cuivre contenant un composé qui se transforme en oxyde de cuivre à une température inférieure ou égale à 550 °C.
PCT/JP2012/071695 2011-08-30 2012-08-28 Poudre pour composition similaire à de l'argile pour former un objet en alliage cuivre-argent fritté en utilisant un composé de cuivre, composition similaire à de l'argile et procédé de production de la composition similaire à de l'argile Ceased WO2013031765A1 (fr)

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JP2011186776A JP5861321B2 (ja) 2011-08-30 2011-08-30 銅化合物を用いた銀銅合金焼結体形成用の粘土状組成物用粉末、粘土状組成物および粘土状組成物の製造方法
JP2011-186776 2011-08-30

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JP6111999B2 (ja) * 2013-11-29 2017-04-12 トヨタ自動車株式会社 装飾被膜

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Publication number Priority date Publication date Assignee Title
JPH05263103A (ja) * 1992-03-19 1993-10-12 Mitsubishi Materials Corp 貴金属可塑性組成物
JP2002356702A (ja) * 2001-05-30 2002-12-13 Dowa Mining Co Ltd 低温焼成用銅粉または導電ペースト用銅粉
JP2006183076A (ja) * 2004-12-27 2006-07-13 Nippon Atomized Metal Powers Corp アトマイズ金粉末並びにそれを用いた導電性金ペーストおよび装飾用金粘土
WO2009009710A2 (fr) * 2007-07-11 2009-01-15 Battelle Memorial Institute Métaux d'apport pour brasure sous air à température élevée et leurs procédés de préparation et d'utilisation
WO2011125244A1 (fr) * 2010-04-09 2011-10-13 三菱マテリアル株式会社 Composition argileuse pour la formation d'un objet fritté, poudre pour une composition argileuse pour la formation d'un objet fritté, procédé pour la fabrication d'une composition argileuse pour la formation d'un objet fritté, objet en argent fritté et procédé pour la fabrication d'un objet en argent fritté

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011068958A (ja) * 2009-09-27 2011-04-07 Aida Kagaku Kogyo Kk 装飾金属物品の製造方法および装飾金属物品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05263103A (ja) * 1992-03-19 1993-10-12 Mitsubishi Materials Corp 貴金属可塑性組成物
JP2002356702A (ja) * 2001-05-30 2002-12-13 Dowa Mining Co Ltd 低温焼成用銅粉または導電ペースト用銅粉
JP2006183076A (ja) * 2004-12-27 2006-07-13 Nippon Atomized Metal Powers Corp アトマイズ金粉末並びにそれを用いた導電性金ペーストおよび装飾用金粘土
WO2009009710A2 (fr) * 2007-07-11 2009-01-15 Battelle Memorial Institute Métaux d'apport pour brasure sous air à température élevée et leurs procédés de préparation et d'utilisation
WO2011125244A1 (fr) * 2010-04-09 2011-10-13 三菱マテリアル株式会社 Composition argileuse pour la formation d'un objet fritté, poudre pour une composition argileuse pour la formation d'un objet fritté, procédé pour la fabrication d'une composition argileuse pour la formation d'un objet fritté, objet en argent fritté et procédé pour la fabrication d'un objet en argent fritté

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