WO2011125266A1 - 銀合金焼結体形成用の粘土状組成物、銀合金焼結体形成用の粘土状組成物用粉末、銀合金焼結体形成用の粘土状組成物の製造方法、銀合金焼結体及び銀合金焼結体の製造方法 - Google Patents
銀合金焼結体形成用の粘土状組成物、銀合金焼結体形成用の粘土状組成物用粉末、銀合金焼結体形成用の粘土状組成物の製造方法、銀合金焼結体及び銀合金焼結体の製造方法 Download PDFInfo
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- WO2011125266A1 WO2011125266A1 PCT/JP2010/073698 JP2010073698W WO2011125266A1 WO 2011125266 A1 WO2011125266 A1 WO 2011125266A1 JP 2010073698 W JP2010073698 W JP 2010073698W WO 2011125266 A1 WO2011125266 A1 WO 2011125266A1
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- powder
- clay
- silver
- silver alloy
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- 0 CC(CCC1)C2C1C(*[C@](C)C(CC(*)CC1)CC(C)(C)*CC(CCC3)C4)C1CC4C3CC2 Chemical compound CC(CCC1)C2C1C(*[C@](C)C(CC(*)CC1)CC(C)(C)*CC(CCC3)C4)C1CC4C3CC2 0.000 description 3
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/002—Metallic materials
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/002—Metallic materials
- A44C27/003—Metallic alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
- B22F3/1025—Removal of binder or filler not by heating only
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0466—Alloys based on noble metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1026—Alloys containing non-metals starting from a solution or a suspension of (a) compound(s) of at least one of the alloy constituents
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the present invention relates to a clay-like composition for forming a silver alloy sintered body, a powder for the clay-like composition for forming a silver alloy sintered body, a method for producing a clay-like composition for forming a silver alloy sintered body, and
- the invention relates to a silver alloy sintered body obtained from a clay-like composition for forming a silver alloy sintered body, and a method for producing the silver alloy sintered body.
- silver jewelry and arts and crafts represented by a ring or 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 manner as ordinary clay work, and after drying a modeled body obtained by modeling, it is fired using a heating furnace. It becomes possible to manufacture silver jewelry and arts and crafts very easily.
- the silver clay as described in Patent Document 1 is generally obtained by kneading a pure silver (pure Ag) powder with a binder, water, and a surfactant as necessary.
- 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 powder is constituted as a silver alloy containing copper (Cu) and the like. It has also been proposed to produce a silver sintered body called so-called sterling silver by shaping a silver clay obtained by adding and kneading and then firing (for example, a column of an example of Patent Document 2). See).
- the silver clay made of sterling silver which is 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 tends to deteriorate because Cu contained in the 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 will change color over time.
- the present invention has been made in view of the above-described situation, and does not easily discolor even in an air atmosphere, and is also collectively referred to as tensile strength, bending strength, surface hardness (hereinafter referred to as mechanical strength).
- a clay-like composition for forming a silver alloy sintered body capable of forming a silver alloy sintered body excellent in elongation, etc., a powder for clay-like composition for forming a silver alloy sintered body, and a silver alloy sintered body It aims at providing the manufacturing method of the clay-like composition for formation, the silver alloy sintered compact, and the manufacturing method of a silver alloy sintered compact.
- the present inventors have intensively studied to solve the above problems, and found that a silver clay powder (a clay for forming a silver alloy sintered body) constituting silver clay (a clay composition for forming a silver alloy sintered body) was used. It was found that the discoloration of silver clay (a clay-like composition for forming a silver alloy sintered body) can be suppressed by constituting as a powder containing silver powder and copper oxide powder.
- This invention is made
- the clay-like composition for forming a silver alloy sintered body according to the present invention is characterized by containing a powder component containing silver powder and copper oxide powder, a binder, and water.
- the clay-like composition for forming a silver alloy sintered body having this configuration contains silver powder, copper oxide powder, a binder, and water.
- copper oxide is chemically more stable than metal Cu, there is little risk of alteration (the valence of copper ions changes) easily in an air atmosphere. For this reason, discoloration of this clay-like composition for forming a silver alloy sintered body can be suppressed.
- the binder in the clay-like composition for forming a silver alloy sintered body can be burned and removed, and sintering can be promoted.
- the clay-like composition for forming a silver alloy sintered body according to (1) contains at least a copper (II) oxide powder (CuO powder) as the copper oxide powder.
- CuO powder copper oxide powder
- the clay-like composition for forming a silver alloy sintered body with this structure contains a powder of copper (II) oxide, which is a stable compound, the clay-like composition for forming a silver alloy sintered body Discoloration can be reliably prevented.
- the binder in the clay-like composition for forming a silver alloy sintered body can be burned and removed by using oxygen of CuO.
- the binder can be burned by using the oxygen of CuO inside the molded body, and a high-quality silver alloy sintered body can be manufactured. It becomes possible to put out.
- the copper oxide powder made of CuO powder is 4% by mass or more to 35% by mass with respect to the entire powder component. It is preferable that the content of Ag element with respect to all the metal components excluding oxygen in the powder component is 46 mass% or more and 97 mass% or less. If the CuO powder content is less than 4% by mass, the mechanical strength may not be sufficiently improved. On the other hand, when the content of the CuO powder exceeds 35% by mass, the elongation decreases and the silver alloy sintered body using the silver clay powder may not exhibit a beautiful silver color even after polishing. For this reason, it is preferable to make content of CuO powder into the range of 4 to 35 mass%.
- the copper oxide powder made of CuO powder is added to the entire powder component.
- the content of Ag element is 46% by mass or more and 90% by mass or less with respect to all metal components except oxygen in the powder component in the range of 12% by mass to 35% by mass.
- the binder contained in the clay-like composition for forming a silver alloy sintered body can be burned and removed by using the oxygen of CuO. For this reason, it is not necessary to perform calcination for removing the binder in advance, and it is possible to perform a drying process after molding and then perform main baking.
- the powder component further contains metal Cu
- the content of the metal Cu is 2% by mass or less based on the entire powder component.
- 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 copper oxide powder may further contain copper oxide (I) (Cu 2 O It is preferable that the total of the content of copper oxide (II) and the content of copper oxide (I) in the powder component is 54% by mass or less with respect to the entire powder component.
- the total content of copper oxide (II) and the content of copper oxide (I) in the powder component is the whole powder component. It is preferable that it is 54 mass% or less with respect to this.
- the average particle diameter of the copper oxide powder is 1 ⁇ m or more and 25 ⁇ m or less. Preferably it is. In this case, it becomes possible to improve the mechanical strength and elongation of the silver alloy sintered body obtained by firing the clay-like composition for forming the silver alloy sintered body.
- the binder may be a cellulose binder, a polyvinyl binder, or an acrylic binder.
- Wax-based binder, resin-based binder, starch, gelatin, and wheat flour may be used in combination of at least one or two or more.
- 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 powder for clay-like composition for forming a silver alloy sintered body according to the present invention is a clay-like composition for forming a silver alloy sintered body according to any one of (1) to (9).
- a powder for a clay-like composition to be used comprising silver powder and copper oxide powder.
- the powder for clay-like compositions for forming a silver alloy sintered body according to (10) contains copper oxide (II) powder (CuO powder) as the copper oxide powder. Is preferred.
- the copper oxide powder made of CuO powder is added to the whole powder for clay-like composition.
- the content of the Ag element with respect to all metal components excluding oxygen in the powder for clay-like composition is 46 mass% or more and 97 mass% or less. Is preferred.
- the copper oxide powder made of CuO powder is used as the clay-like composition.
- the content of Ag element with respect to all metal components excluding oxygen in the powder for clay-like composition is 46 mass% or more and 90 mass% or less. It is preferable that (14) Further, in the powder for clay-like composition for forming a silver alloy sintered body according to any one of (10) to (13), the powder for clay-like composition further contains metal Cu.
- content of the said metal Cu in this powder for clay-like compositions shall be 2 mass% or less with respect to the whole powder for this clay-like composition.
- the powder for clay-like composition for forming a silver alloy sintered body according to any one of (10) to (14) the powder for clay-like composition further contains copper oxide (I ), And the total content of copper oxide (II) and copper oxide (I) in the clay-like composition powder is 54% by mass or less with respect to the entire clay-like composition powder. It is preferable that (16) Furthermore, in the powder for clay-like composition for forming a silver alloy sintered body according to any one of (10) to (15), the average particle diameter of the copper oxide powder is 1 ⁇ m or more and 25 ⁇ m or less.
- the powder for a clay-like composition for forming a silver alloy sintered body having the above structure it becomes possible to constitute the above-mentioned clay-like composition for forming a silver alloy sintered body, and for forming a silver alloy sintered body. It is possible to reliably prevent discoloration of the clay-like composition.
- a method for producing a clay-like composition for forming a silver alloy sintered body according to the present invention is the clay-like composition for forming a silver alloy sintered body according to any one of (10) to (16). It is characterized in that the powder for use and a binder agent in which a binder and water are mixed are mixed and kneaded. According to the method for producing a silver alloy sintered body for forming a silver alloy sintered body having this configuration, it is possible to produce a clay-like composition for forming a silver alloy sintered body having copper oxide powder and hardly discolored. It becomes.
- the silver alloy sintered body of the present invention is obtained by firing the clay-like composition for forming a silver alloy sintered body according to any one of (1) to (9). And according to the silver alloy sintered body having this configuration, since the clay-like composition for forming a silver alloy sintered body having the above-described configuration is fired, it is compared with that obtained by firing silver clay made of pure Ag powder. Thus, the mechanical strength can be improved. That is, the silver alloy sintered body obtained by heating and firing the above-mentioned clay-like composition for forming a silver alloy sintered body has excellent mechanical strength, elongation, and the like.
- a method for producing a silver alloy sintered body according to the present invention comprises forming the clay-like composition for forming a silver alloy sintered body according to any one of (1) to (9) into an arbitrary shape.
- firing is performed in a reducing atmosphere or a non-oxidizing atmosphere to form a silver alloy sintered body.
- the method for producing a silver alloy sintered body having the above-described configuration after forming the above-mentioned clay-like composition for forming a silver alloy sintered body, mechanical strength and elongation are obtained by performing a drying treatment or a heat firing treatment.
- a silver alloy sintered body excellent in the above can be produced.
- the binder contained in the clay-like composition for forming the silver alloy sintered body can be burned and removed, and thus the calcining step for removing the binder can be omitted.
- the molded body has a portion having a thickness of 5 mm or more, and the molded body is dried. Later, when firing in a reducing atmosphere or a non-oxidizing atmosphere, it is preferable that the rate of temperature rise from room temperature to the firing temperature is in the range of 15 ° C./min to 80 ° C./min.
- a molded body of a clay-like composition for forming a silver alloy sintered body having a thickness of 5 mm or more it is very difficult to burn and remove the binder inside the molded body. It is necessary to slow the rate of temperature rise to the firing temperature. This is because oxygen for burning the binder is supplied from the surface layer portion of the molded body, and therefore, the binder is insufficiently burned inside the molded body.
- the thickness of 5 mm or more means that the diameter of at least one inscribed sphere located inside the molded body is 5 mm or more.
- the clay-like composition for forming a silver alloy sintered body containing a copper oxide powder is used as described above, By using oxygen, it is possible to reliably burn the binder inside the molded body. Therefore, a molded body of a clay-like composition for forming a silver alloy sintered body having a relatively large thickness of 5 mm or more is heated at a rate of temperature increase from room temperature to the firing temperature of 15 ° C./min to 80 ° C./min. Even if it is set relatively fast within the following range, it is possible to produce a silver alloy sintered body that is sufficiently sintered to the inside. Therefore, the silver alloy sintered body can be efficiently manufactured.
- the clay-like composition for forming a silver alloy sintered body according to the present invention discoloration of the clay-like composition for forming a silver alloy sintered body can be suppressed by the above configuration and action, and heating is performed after molding. It becomes possible to improve the mechanical strength, elongation and the like of the sintered silver alloy obtained by firing.
- the powder for clay-like composition for forming a silver alloy sintered body according to the present invention the silver alloy sintered body using the powder for clay-like composition for forming a silver alloy sintered body has the above-described configuration and action. By constituting the clay-like composition for forming, discoloration of the clay-like composition for forming a silver alloy sintered body can be suppressed.
- the above-mentioned clay-like composition for forming a silver alloy sintered body can be reliably produced.
- the mechanical strength can be improved as compared with a sintered silver clay made of pure Ag powder.
- after forming using the clay-like composition for forming a silver alloy sintered body having the above-described configuration by performing drying treatment or firing under specified conditions. A silver alloy sintered body excellent in mechanical strength and elongation can be produced.
- a clay-like composition for forming a silver alloy sintered body according to the present invention a powder for a clay-like composition for forming a silver alloy sintered body, a method for producing a clay-like composition for forming a sintered body, silver
- An embodiment of a method for producing an alloy sintered body and a silver alloy sintered body will be described with reference to the drawings as appropriate.
- the clay-like composition for forming a silver alloy sintered body is referred to as silver clay
- the powder for the clay-like composition for forming a silver alloy sintered body is referred to as silver clay powder.
- the silver alloy sintered body will be described below as a sintered body or a silver sintered body.
- the powder for silver clay which concerns on this embodiment contains the silver containing metal powder (silver powder) containing silver, and the copper containing oxide powder (copper oxide powder) containing copper.
- the additive described below is added and kneaded to form silver clay, thereby improving the mechanical strength and elongation of the silver sintered body obtained by heating and firing.
- an effect of suppressing discoloration of silver clay can be obtained.
- CuO powder As the silver-containing metal powder, Ag powder, Ag-Cu alloy powder, or the like can be applied. And CuO powder is contained in the range of 4 mass% or more and 35 mass% or less with respect to the whole powder for silver clay, and content of Ag element with respect to all the metal components except the oxygen in the powder for silver clay is 46 mass% or more. It is preferable that it is 97 mass% or less. More preferably, CuO powder is contained in a range of 12% by mass to 35% by mass with respect to the entire silver clay powder, and the content of Ag element with respect to all metal components excluding oxygen in the silver clay powder is 46% by mass.
- Cu is an element having an effect of improving strength by diffusing into Ag of the silver sintered body during sintering.
- the content of the CuO powder is 4% by mass or more and 35% by mass or less, it is 3% by mass or more and 30% by mass or less when converted to the content of Cu in the silver sintered body. If the Cu content in the silver sintered body is less than 3% by mass, the effect of improving the mechanical strength of the silver sintered body obtained by firing silver clay may be difficult to obtain.
- content of Cu exceeds 30 mass%, there exists a possibility that elongation may fall.
- the content of CuO powder in the powder for silver clay is in the range of 4% by mass to 35% by mass so that the content of Cu in the silver sintered body is 3% by mass to 30% by mass. It is preferable to set to.
- content of CuO powder shall be 35 mass% or less. That is, considering the components of the silver-containing metal powder containing silver and the copper-containing oxide powder so that the amount of Cu contained in the silver sintered body is within the above range, these silver-containing metal powder and copper-containing It is preferable to configure the silver clay by adjusting the mixing ratio with the oxide powder.
- CuO powder is used as the copper-containing oxide powder
- Ag powder is used as the silver-containing metal powder.
- the powder for silver clay which contains CuO powder in the range of 4 mass% or more and 35 mass% or less with respect to the whole powder for silver clay, and the remainder consists of Ag and an unavoidable impurity.
- the particle diameters of Ag powder and CuO powder contained in the silver clay powder according to the present embodiment will be described.
- the particle diameters of Ag powder and CuO powder are not particularly limited, but the formability and the like in the case of silver clay by adding a binder as an additive and kneading are added. Considering various 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 sintered body obtained by firing the silver clay is improved, and the mechanical strength and elongation of the silver sintered body as described above, etc. The effect of improving is stably obtained. If the average particle diameter of the Ag powder exceeds 25 ⁇ m, the color tone of the silver sintered body may be deteriorated or the effect of improving the mechanical strength may be reduced. In addition, if the average particle size of the Ag powder is more than 25 ⁇ m, the sinterability of the powder is lowered, so that a long firing time is required and the workability of the silver sintered body may be adversely affected. Is not preferable.
- 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 the 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 CuO powder is preferably 25 ⁇ m or less. By setting the average particle diameter of the CuO powder within this range, the effect of improving the mechanical strength and elongation of the silver sintered body as described above can be stably obtained. If the average particle size of the CuO powder exceeds 25 ⁇ m, it may be difficult to obtain the effect of improving the mechanical strength of the silver sintered body. In addition, when the average particle size of the CuO powder exceeds 25 ⁇ m, the sinterability of the powder is reduced as in the case of the Ag powder. It may adversely affect workability and is not preferable.
- the lower limit of the average particle diameter is not particularly defined, but the average particle diameter of the CuO powder is preferably 1 ⁇ m from the viewpoint of the limit of the apparatus and the cost of industrial production.
- the average particle diameter of the CuO 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 Ag powder and CuO powder constituting the silver clay powder is limited to a predetermined particle size or less as described above, thereby firing the silver clay molded body. Since the cohesiveness is improved, it becomes possible to lower the processing temperature in the firing described below.
- 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 configuration in the range of 70% by mass to 95% by mass, and further contains 5% by mass to 30% of the 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. Since this silver clay is a silver clay containing a powder component containing a chemically stable CuO powder and an Ag powder, discoloration is suppressed in an air atmosphere.
- 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, but for example, 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 grades
- examples include alcohols (octanol, nonanol, decanol), polyhydric alcohols (glycerin, arabit, sorbitan), ethers (dioctyl ether, didecyl ether) and the like.
- the method for producing silver clay 5 according to the present embodiment is such that the powder 1 for silver clay is 70% by mass or more and 95% by mass or less, and the binder agent 2 containing an organic binder and water is 5% by mass or more and 30% by mass or less. This is a kneading method.
- each of Ag powder 1A and CuO powder 1B is introduce
- Ag powder 1A average particle size 5 ⁇ m: Microtrack method; atomized powder
- CuO powder 1B average particle size 5 ⁇ m: Microtrack method; reagent / purity 97 manufactured by Kishida Chemical Co., Ltd. % Or more
- the powder 1 for silver clay is obtained.
- 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 powder 1 and the binder agent 2 are mixed and kneaded to obtain the silver clay 5.
- the silver sintered body according to the present embodiment is obtained by shaping and molding the silver clay 5 having the above configuration into an arbitrary shape and then firing it under the conditions described later. Since this silver sintered body has excellent mechanical strength, for example, even when a large external force is applied, it is possible to suppress the occurrence of cracks and breaks. In addition, since the silver sintered body according to the present embodiment has high elongation with excellent mechanical strength, for example, even when additional processing with bending is performed on the sintered silver body after firing. It is possible to suppress the occurrence of cracks and breaks.
- the method for producing the silver sintered body 10 according to the present embodiment forms the molded body 51 by molding the silver clay 5 having the above-described configuration into an arbitrary shape, and then the molded body 51 is, for example, at room temperature to 150 ° C. Then, the molded body 51 is baked at a temperature of 650 to 830 ° C. for 15 to 120 minutes in a reducing atmosphere or a non-oxidizing atmosphere at a temperature of 30 minutes to 24 hours. This is a method of forming the bonded body 10.
- firing for example, after the dried molded body 51 is embedded in activated carbon, firing is performed in a reducing atmosphere at a temperature of 650 to 830 ° C. for 15 to 120 minutes.
- the method of performing can be adopted.
- 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.
- a drying process can be performed on the conditions made into the grade.
- the molded body 51 is fired to obtain a silver sintered body 10.
- the oxygen of CuO contained in the powder for silver clay the organic binder contained in the silver clay is burned, and it becomes possible to remove the organic binder.
- utilizing oxygen of CuO means that CuO is thermally decomposed during firing to release oxygen and contribute to the combustion of the organic binder.
- the method of manufacturing the silver sintered compact 10 can be employ
- the molded body 51 is embedded in activated carbon 61 filled in a ceramic firing container 60.
- 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 650 to 830 ° C., for 15 to 120 minutes. Firing is performed by heating.
- the silver 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 molded body 51 and the silver sintered body 10 obtained by molding the silver clay 5 are formed in a substantially block shape. Needless to say, various shapes can be obtained.
- stable heating condition management such as a gas heating apparatus If it is possible, it can be adopted without any limitation.
- the silver clay 5 using the silver clay powder 1 is constituted by the above-described configuration and action, and thus the drying treatment is performed after the 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 CuO, CuO does not easily change in the atmosphere, and the color change 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, silver sintering obtained by heating and firing after molding. The mechanical strength and elongation of the body 10 can be improved.
- 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 CuO powder the present invention is not limited to this, and a silver clay powder containing an Ag-Cu alloy powder and a copper-containing oxide powder may be used. Good.
- Cu powder or Ag—Cu alloy powder may be added in addition to Ag powder and copper-containing oxide powder.
- the content of metal Cu contained in the Cu powder and the Ag—Cu alloy powder is preferably 2% by mass or less with respect to the entire silver clay powder. Thereby, discoloration of silver clay can be suppressed reliably.
- the total content of copper oxide (II) (CuO) and copper oxide (I) (Cu 2 O) in the silver clay powder is 54% by mass or less based on the total silver clay powder. It is preferable that Thereby, sintering can be surely promoted using oxygen in the copper-containing oxide.
- the total content of copper oxide (II) (CuO) and copper oxide (I) (Cu 2 O) was 0.01% by mass or more and 54% by mass or less with respect to the entire powder for silver clay. May be.
- the clay-like composition for forming a sintered body according to the present invention examples will be shown, and the clay-like composition for forming a sintered body according to the present invention, the powder for clay-like composition for forming a sintered body, the method for producing a clay-like composition for forming a sintered body, silver
- the method for producing the sintered body and the silver sintered body will be described in more detail, but the present invention is not limited to this example.
- a powder for a clay-like composition for forming a sintered body (hereinafter referred to as a powder for silver clay) was prepared by the following procedure.
- Ag powder average particle size 5 ⁇ m: Microtrack method; atomized powder
- CuO powder Average particle size 5 ⁇ m: Microtrack method; reagent / purity 97% or more manufactured by Kishida Chemical Co., Ltd.
- a mixing apparatus as shown in FIG.
- the copper-containing oxide powder obtained by oxidizing the metal Cu powder had a black surface as a whole. From this, it was confirmed that CuO was formed on at least the surface portion of the copper-containing oxide powder obtained by oxidizing the metal Cu powder.
- an organic binder, water, surfactant and oil are mixed to obtain a binder agent.
- the clay-like composition for 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 an oil and fat, and polyethylene as a surfactant.
- the formulation was 1% by mass of glycol and the balance being water. And it knead
- a binder agent uses water-soluble cellulose ester (Shin-Etsu Chemical Co., Ltd. Metros SM8000) and potato starch (Nissho Chemical Co., Ltd. Delica M9) as an organic binder, water-soluble cellulose ester: 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 content of Cu contained in the obtained silver clay was analyzed.
- 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, as shown in Tables 1 and 2 to be described later, it was confirmed that the theoretical content of Cu mixed as CuO powder coincided with the actual amount of Cu contained in the silver clay.
- a prismatic shaped product having a thickness of about 3 mm (before firing) was produced.
- the wire-shaped molded body and the prismatic molded body 51 are put into an electric furnace (Orton: evenheat kiln inc.) 80 for each invention example at the same time, and the drying temperature is set to 100 ° C. And the moisture etc. which were contained in each above-mentioned fabrication object 51 were removed by performing drying processing on the conditions which made drying time 60 minutes.
- 2A to 2C only one prismatic shaped product is shown as the shaped product 51, and the wire shaped product is not shown.
- the binder removal treatment was performed by performing a calcination step for 30 minutes at a temperature of 500 ° C. in an air atmosphere using an electric furnace 80. It was.
- the above-described calcination step was omitted.
- a silver sintered body was produced by simultaneously firing each molded body 51 for each invention example.
- a ceramic 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 main firing is performed at a heating temperature of 760 ° C. and a heating time of 30 minutes common to all the invention examples.
- wire-shaped and prismatic silver sintered bodies 10 were produced.
- Comparative Example 4 silver powder having a particle diameter of 1 ⁇ m or more and 15 ⁇ m or less and a purity of 99.9% was used as a silver clay powder, and silver clay was produced in the same manner as in the above-described Examples 1 to 7 of the present invention. I put it out.
- a prismatic shaped product having a dimension of 3 mm (before firing) was produced.
- the wire-shaped molded body and the prism-shaped molded body 51 are put into an electric furnace (Orton: evenheat kiln inc.) 80 for each comparative example, and the drying temperature is 100 ° C. And the moisture etc. which were contained in each above-mentioned fabrication object 51 were removed by performing drying processing on the conditions which made drying time 60 minutes.
- the binder removal treatment was performed by performing a calcination step for 30 minutes at a temperature of 500 ° C. in an air atmosphere using an electric furnace 80.
- the above-mentioned calcination process was abbreviate
- a sintered silver body was produced by firing the respective compacts 51 simultaneously for each comparative example.
- a ceramic 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.
- the heating temperature is 800 ° C.
- the heating time is 60 minutes
- a wire-shaped and prismatic silver sintered body 10 was produced by performing main firing at a heating temperature of 700 ° C. and a heating time of 10 minutes.
- 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 obtained by measuring the stress curve at the moment when the test piece was broken using the autograph AG-X manufactured by Shimadzu Corporation and 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, 2 and 3 show a list of manufacturing conditions and evaluation results of Invention Examples 1 to 9, 17, 18 and Comparative Examples 1 to 4.
- the calcining step for removing the organic binder can be omitted. It was confirmed that a silver sintered body with sufficient strength could be obtained. This is presumed to be because the organic binder is burned and removed by the oxygen of the CuO powder in the main firing step.
- the carbon concentration and oxygen concentration of the silver sintered body were measured. The carbon concentration was measured by an impulse furnace heating-infrared absorption method. The oxygen concentration was measured by a high frequency furnace heating-infrared absorption method. The results are shown in Table 3. In Tables 2 and 3, by comparing Inventive Examples 3 and 7, it can be seen that even if the calcination step is omitted, the organic binder is burned and removed, and a sufficient silver sintered body strength can be obtained. .
- Example 5 of the present invention in which the content of CuO powder was 3% by mass, the effect of improving the strength (particularly bending strength) was not significant as compared with Examples 1 to 4 and 6 to 8 of the present invention.
- Invention Example 6 in which the content of CuO powder was 40% by mass, the sintered silver sintered body after polishing was not exhibited a beautiful silver color. Furthermore, no difference was observed in the characteristics etc. of Invention Example 8 using a mixture of water-soluble cellulose ester and potato starch as an organic binder as compared with Invention Examples 3 and 7.
- the silver clays of Comparative Examples 1 to 3 were all confirmed to be discolored after being stored for 3 days at room temperature in an air atmosphere.
- the comparative example 2 which did not implement a calcination process removal of the organic binder was inadequate and the tension test etc. could not be implemented.
- a phase in which the organic binder was carbonized was confirmed in the silver sintered body of Comparative Example 2.
- Comparative Example 4 using pure silver although there is no discoloration, the bending strength, tensile strength, surface hardness and density tend to be lower than those of Examples 1 to 8 of the present invention. It was confirmed that it was easily deformed.
- a silver clay was prepared by adding a binder agent to each of the above silver clay powders and kneading in the same manner as in Examples 1 to 7 of the present invention.
- molded bodies 51 of Invention Example 10 and Comparative Example 5 were produced as cubic molded bodies having a 10 mm square on each side.
- a molded body 51 made of silver clay containing silver clay powder made of Ag-12.2 mass% CuO is Example 10 of the present invention, and a molded body 51 made of silver clay containing silver powder having a purity of 99.9% is Comparative Example 5. is there.
- the silver sintered compact 10 was produced by giving baking. Specifically, as shown in FIG. 2C, a ceramic firing container 60 filled with activated carbon 61 was prepared, and the molded body 51 was embedded in the activated carbon 61. At this time, the distance from the surface of the activated carbon 61 to the molded body 51 was about 10 mm. Then, the firing container 60 in a state where the molded body 51 was embedded in the activated carbon 61 was put into an electric furnace 80 to perform main firing.
- the firing temperature was 760 ° C.
- the heating time was 30 minutes
- the rate of temperature increase from room temperature to the firing temperature (760 ° C.) was in the range of 15 ° C./min to 80 ° C./min.
- the main baking was performed at 30 ° C./min.
- the main calcination was performed at a calcination temperature of 900 ° C. and a heating time of 120 minutes at a rate of temperature increase from room temperature to the calcination temperature (900 ° C.) of 30 ° C./min.
- the cubic compact 51 having a high density of 9.3 g / cm 3 and a side of 10 mm square is dried and then subjected to a firing temperature from room temperature without performing a calcination step. Even when the main baking is carried out at a rate of temperature increase up to (760 ° C.) of 30 ° C./min, it is confirmed that the inside has been sufficiently fired. On the other hand, in the case of using the silver clay of Comparative Example 5, the density was about 8.6 g / cm 3 even though the firing temperature was set high and the heating time was set long, In comparison, the firing was insufficient.
- Ag powder (average particle size 5 ⁇ m: Microtrack method; atomized powder), CuO powder (Average particle size 5 ⁇ m: Microtrack method; reagent / purity 97% or more manufactured by Kishida Chemical Co., Ltd.), Cu powder (average Particle size 20 ⁇ m: Microtrac method; reduced powder manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) and Cu 2 O powder (average particle size 5 ⁇ m: Microtrac method; reagent manufactured by Kishida Chemical Co., purity 90% or more), Silver clay powders having the compositions shown in Invention Examples 11 to 16 in Table 5 were obtained.
- copper-containing oxide powder obtained by oxidizing metal Cu powder (average particle size 20 ⁇ m: Microtrac method; reduced powder manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) at 340 ° C. for 3 hours in an air atmosphere, and Ag powder ( An average particle diameter of 5 ⁇ m: Microtrac method; atomized powder) and Cu powder were mixed to obtain a powder for silver clay having the composition shown in Table 5 as Examples 19 and 20 of the present invention.
- a silver clay was prepared by adding a binder agent to each of the above silver clay powders and kneading in the same manner as in Examples 1 to 7 of the present invention.
- the contents of CuO and Cu 2 O in silver clay can be measured by performing X-ray analysis. Specifically, a silver sintered body obtained by firing silver clay was polished to remove surface stains, and this was performed using an X-ray diffractometer RINT Ultimate manufactured by Rigaku Corporation. As a result of this analysis, it was confirmed that the mixing ratio of the CuO powder and Cu 2 O powder in the silver clay powders of Invention Examples 11 to 16 and the content ratio of the CuO powder and Cu 2 O powder in the silver clay coincided.
- each shaped body 51 of the prismatic shaped shaped body is put into an electric furnace (Orton: evenheat kiln inc.) 80 for each invention example at the same time, the drying temperature is set to 100 ° C., and the drying time is set to 60 ° C. By performing a drying process under the condition of the minute, moisture and the like contained in each molded body 51 was removed.
- an electric furnace Orton: evenheat kiln inc.
- Example 16 of the present invention a binder removal treatment was performed by performing a calcination step for 30 minutes at a temperature of 500 ° C. in an air atmosphere using an electric furnace 80. Moreover, about the example 15 of this invention, the above-mentioned calcination process was abbreviate
- FIG. 2C a ceramic firing container 60 filled with activated carbon 61 was prepared, and each molded body 51 was embedded in the activated carbon 61. At this time, the distance from the surface of the activated carbon 61 to each compact 51 was about 10 mm. Then, 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 subjected to main firing at a heating temperature of 760 ° C. and a heating time of 30 minutes, whereby prismatic silver A sintered body 10 was produced.
- Example 15 the density of the silver sintered body was measured by an automatic specific gravity measuring device “Archimedes (drive unit SA301, data processing unit SA601)” manufactured by Chow Balance Co., Ltd. The evaluation results are shown in Table 6.
- the silver clay using the silver clay powder of the present invention can suppress discoloration and obtain a silver sintered body excellent in mechanical strength and elongation. It is clear.
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Abstract
Description
本願は、2010年4月9日に、日本に出願された特願2010-090530号、2010年7月27日に、日本に出願された特願2010-168119号、及び2010年10月22日に、日本に出願された特願2010-237797号に基づき優先権を主張し、その内容をここに援用する。
本発明は、上記知見に基づいてなされたものであり、以下に示す構成を有するものである。
この構成の銀合金焼結体形成用の粘土状組成物においては、銀粉末と酸化銅粉末と、バインダーと、水とを含むものとされている。ここで、酸化銅は、金属Cuに比べて化学的に安定していることから、大気雰囲気下において容易に変質(銅イオンの価数が変化)するおそれが少ない。このため、この銀合金焼結体形成用の粘土状組成物の変色を抑制することができるのである。
さらに、酸化銅中の酸素を利用することで、銀合金焼結体形成用の粘土状組成物中のバインダーを燃焼させて除去することが可能となり、焼結を促進することができる。
この構成の銀合金焼結体形成用の粘土状組成物においては、安定な化合物である酸化銅(II)の粉末を含有しているので、銀合金焼結体形成用の粘土状組成物の変色を確実に防止することができる。
また、CuOの酸素を利用することで、銀合金焼結体形成用の粘土状組成物中のバインダーを燃焼させて除去することができる。よって、厚さ5mm以上の比較的肉厚な成形体であっても、成形体の内部においてCuOの酸素を利用することでバインダーを燃焼させることができ、高品質な銀合金焼結体を製出することが可能となる。
CuO粉の含有量が4質量%未満であると、機械的強度を十分に向上させることができないおそれがある。一方、CuO粉の含有量が35質量%を超えると、伸びが低下するとともに、銀粘土用粉末を用いてなる銀合金焼結体が研磨後においても美麗な銀色を呈しなくなるおそれがある。このため、CuO粉の含有量を4質量%以上35質量%以下の範囲とすることが好ましい。
CuO粉の含有量を12質量%以上とした場合、CuOの酸素を利用することにより、銀合金焼結体形成用の粘土状組成物に含まれるバインダーを燃焼させて除去することができる。
このため、バインダーを予め除去するための仮焼を行う必要がなく、成形後に乾燥処理を行い、その後本焼成を実施することが可能となる。
前記粉末成分中の金属Cuを前記粉末成分全体に対して2質量%以下とすることにより、銀合金焼結体形成用の粘土状組成物の変色を確実に防止することができる。なお、前記粉末成分中に含まれる金属Cuとしては、例えば金属Cu粉末、AgとCuの合金粉末に含まれる金属Cu等が挙げられる。
CuOやCu2Oなどの酸化物が多量に前記粉末成分中に含まれると、バインダー焼失及びCOによる還元がなされ難くなり、銀合金焼結体形成用の粘土状組成物の焼成時に、焼結性に悪影響を及ぼす恐れがある。また、Cu2Oも徐々にCuOに変化していくが、金属Cu添加時ほどの急激な変色を伴うものではない。以上のことから、前記粉末成分中に酸化銅(I)が含まれる場合は、前記粉末成分中の酸化銅(II)の含有量と酸化銅(I)の含有量の合計が前記粉末成分全体に対して54質量%以下とされていることが好ましい。
この場合、銀合金焼結体形成用の粘土状組成物を焼成して得られる銀合金焼結体の機械的強度及び伸び等を向上させることが可能となる。
(9)また、(1)~(8)のいずれか一項に記載の銀合金焼結体形成用の粘土状組成物では、前記バインダーを、セルロース系バインダー、ポリビニール系バインダー、アクリル系バインダー、ワックス系バインダー、樹脂系バインダー、澱粉、ゼラチン、小麦粉の内の、少なくとも1種又は2種以上の組み合わせで構成しても良い。また、上記の中でも、セルロース系バインダー、特に水溶性セルロースから構成することが最も好ましい。
前記界面活性剤の種類は特に限定されるものではなく、通常の界面活性剤を使用することができる。
前記油脂としては、例えば、有機酸(オレイン酸、ステアリン酸、フタル酸、パルミチン酸、セパシン酸、アセチルクエン酸、ヒドロキシ安息香酸、ラウリン酸、ミリスチン酸、カプロン酸、エナント酸、酪酸、カプリン酸)、有機酸エステル(メチル基、エチル基、プロピル基、ブチル基、オクチル基、ヘキシル基、ジメチル基、ジエチル基、イソプロピル基、イソブチル基を有する有機酸エステル)、高級アルコール(オクタノール、ノナノール、デカノール)、多価アルコール(グリセリン、アラビット、ソルビタン)、エーテル(ジオクチルエーテル、ジデシルエーテル)等を挙げることができる。
(11)また、(10)に記載の銀合金焼結体形成用の粘土状組成物用粉末は、前記酸化銅粉末として、酸化銅(II)の粉末(CuO粉)を含有していることが好ましい。
(12)さらに、(10)又は(11)に記載の銀合金焼結体形成用の粘土状組成物用粉末では、CuO粉からなる前記酸化銅粉末を該粘土状組成物用粉末全体に対して4質量%以上35質量%以下の範囲で含有し、該粘土状組成物用粉末中の酸素を除く全金属成分に対するAg元素の含有量が46質量%以上97質量%以下とされていることが好ましい。
(13)また、(10)~(12)のいずれか一項に記載の銀合金焼結体形成用の粘土状組成物用粉末では、CuO粉からなる前記酸化銅粉末を該粘土状組成物用粉末全体に対して12質量%以上35質量%以下の範囲で含有し、該粘土状組成物用粉末中の酸素を除く全金属成分に対するAg元素の含有量が46質量%以上90質量%以下とされていることが好ましい。
(14)さらに、(10)~(13)のいずれか一項に記載の銀合金焼結体形成用の粘土状組成物用粉末では、該粘土状組成物用粉末は、さらに金属Cuを含有し、該粘土状組成物用粉末中の前記金属Cuの含有量が該粘土状組成物用粉末全体に対して2質量%以下とされていることが好ましい。
(15)また、(10)~(14)のいずれか一項に記載の銀合金焼結体形成用の粘土状組成物用粉末では、該粘土状組成物用粉末は、さらに酸化銅(I)を含有し、該粘土状組成物用粉末中の酸化銅(II)の含有量と酸化銅(I)の含有量の合計が該粘土状組成物用粉末全体に対して54質量%以下とされていることが好ましい。
(16)さらに、(10)~(15)のいずれか一項に記載の銀合金焼結体形成用の粘土状組成物用粉末では、前記酸化銅粉末の平均粒径が1μm以上25μm以下とされていることが好ましい。
上記構成の銀合金焼結体形成用の粘土状組成物用粉末によれば、上述の銀合金焼結体形成用の粘土状組成物を構成することが可能となり、銀合金焼結体形成用の粘土状組成物の変色を確実に防止することが可能となる。
この構成の銀合金焼結体形成用の粘土状組成物の製造方法によれば、酸化銅粉末を有し、変色し難い銀合金焼結体形成用の粘土状組成物を製造することが可能となる。
この構成の銀合金焼結体によれば、上述した構成の銀合金焼結体形成用の粘土状組成物を焼成したものであることから、純Ag粉末からなる銀粘土を焼成したものに比べて、機械的強度を向上させることができる。すなわち、上述の銀合金焼結体形成用の粘土状組成物を加熱焼成して得られた銀合金焼結体は、優れた機械的強度や伸び等を備えることになる。
上記構成の銀合金焼結体の製造方法によれば、上述の銀合金焼結体形成用の粘土状組成物を成形した後、乾燥処理や加熱焼成処理を行うことにより、機械的強度や伸び等に優れた銀合金焼結体を製造することができる。
なお、上述のように、銀合金焼結体形成用の粘土状組成物において、CuO粉末の含有量を前記粉末成分全体に対して12質量%以上とした場合には、CuOの酸素を利用することにより、銀合金焼結体形成用の粘土状組成物に含まれるバインダーを燃焼させて除去することが可能となるため、バインダーを除去するための仮焼工程を省略することができる。
この構成の銀合金焼結体の製造方法によれば、銀合金焼結体形成用の粘土状組成物の成形体の焼成条件を、上述のように限定していることから、バインダーを焼失させて焼結を確実に行うことができる。
なお、厚さが5mm以上とは、成形体の内部に位置する少なくとも1つの内接球の直径が5mm以上とされていることを意味する。
よって、銀合金焼結体の製造を効率的に行うことができるのである。
特に、酸化銅粉末として酸化銅(II)(CuO)を含む場合には、酸素の含有量が比較的多くなることから、焼結を促進することができ、厚さが5mm以上と比較的厚くされた銀合金焼結体形成用の粘土状組成物の成形体を確実に焼結することが可能となる。
この構成の銀合金焼結体の製造方法によれば、活性炭による還元により、成形体の焼結を促進することができる。
本発明の銀合金焼結体形成用の粘土状組成物用粉末によれば、上記構成及び作用により、この銀合金焼結体形成用の粘土状組成物用粉末を用いた銀合金焼結体形成用の粘土状組成物を構成することで、銀合金焼結体形成用の粘土状組成物の変色を抑制することができる。
本発明の銀合金焼結体形成用の粘土状組成物の製造方法によれば、上述の銀合金焼結体形成用の粘土状組成物を確実に製造することが可能となる。
本発明の銀合金焼結体によれば、純Ag粉末からなる銀粘土を焼成したものに比べて、機械的強度を向上させることができる。
また、本発明の銀合金焼結体の製造方法によれば、上記構成の銀合金焼結体形成用の粘土状組成物を用いて成形した後、規定条件で乾燥処理や焼成を行うことにより、機械的強度や伸び等に優れた銀合金焼結体を製造することができる。
なお、本実施形態では、銀合金焼結体形成用の粘土状組成物を銀粘土と、銀合金焼結体形成用の粘土状組成物用粉末を銀粘土用粉末と称して説明する。また、銀合金焼結体を以下焼結体又は銀焼結体と称して説明する。
本実施形態に係る銀粘土用粉末は、銀を含む銀含有金属粉末(銀粉末)と、銅を含む銅含有酸化物粉末(酸化銅粉末)を含むものである。
このような銀粘土用粉末を用いて、後述する添加物を加えて混練して銀粘土を構成することにより、加熱焼成して得られた銀焼結体において、機械的強度や伸び等が向上するとともに、銀粘土の変色を抑制できるといった効果が得られるものである。
そして、CuO粉を銀粘土用粉末全体に対して4質量%以上35質量%以下の範囲で含有し、銀粘土用粉末中の酸素を除く全金属成分に対するAg元素の含有量が46質量%以上97質量%以下とされていることが好ましい。
より好ましくは、CuO粉を銀粘土用粉末全体に対して12質量%以上35質量%以下の範囲で含有し、銀粘土用粉末中の酸素を除く全金属成分に対するAg元素の含有量が46質量%以上90質量%以下とされていることが好ましい。
ここで、Cuは、焼結中において銀焼結体のAgの中に拡散することにより強度向上効果を有する元素である。CuO粉の含有量が4質量%以上35質量%以下である場合、銀焼結体中のCuの含有量に換算すると3質量%以上30質量%以下となる。銀焼結体中のCuの含有量が3質量%未満だと、銀粘土を焼成して得られる銀焼結体の機械的強度を向上させる効果が得られ難くなるおそれがある。また、Cuの含有量が30質量%を超えると、伸びが低下するおそれがある。このため、銀焼結体中のCuの含有量が3質量%以上30質量%以下となるように、銀粘土用粉末中のCuO粉の含有量が4質量%以上35質量%以下の範囲内に設定することが好ましいのである。なお、銀粘土を焼成して得られる銀焼結体の色調を考慮した場合、CuO粉の含有量は35質量%以下とすることが好ましい。
すなわち、銀焼結体中に含有されるCu量が上記範囲となるように、銀を含む銀含有金属粉末の成分、銅含有酸化物粉末の成分を考慮し、これら銀含有金属粉末と銅含有酸化物粉末との混合比率を調整して、銀粘土を構成することが好ましい。
以下、本実施形態に係る銀粘土用粉末に含有される、Ag粉およびCuO粉の粒径について説明する。
本実施形態においては、Ag粉およびCuO粉の粒径については、特に限定されるものではないが、添加物としてのバインダー剤を加えて混練することで銀粘土とした場合の、成形性等の諸特性を考慮し、以下に示す範囲の粒径とすることが好適である。
Ag粉の平均粒径が25μmを超えると、銀焼結体の色調が劣化したり、機械的強度を向上させる効果が小さくなるおそれがある。また、Ag粉の平均粒径が25μm超だと、粉末の焼結性が低下することから、長時間にわたる焼成時間を要してしまうとともに、銀焼結体の加工性に悪影響を及ぼす可能性があり、好ましくない。
なお、平均粒径の下限については特に定めないが、Ag粉の平均粒径を1μm以下とすることは工業生産的にコスト高となるおそれがあり、また、装置の限界等も考慮し、これを下限とすることが好ましい。
また、Ag粉の平均粒径は、1μm以上20μm以下の範囲であることがより好ましく、3μm以上10μm以下の範囲であることがさらに好ましい。
CuO粉の平均粒径が25μmを超えると、銀焼結体の機械的強度を向上させる効果が得られ難くなるおそれがある。また、CuO粉の平均粒径が25μmを超えると、上記Ag粉の場合と同様、粉末の焼結性が低下することから、長時間にわたる焼成時間を要してしまうとともに、銀焼結体の加工性に悪影響を及ぼす可能性があり、好ましくない。
なお、上記Ag粉と同様、平均粒径の下限は特に定めないが、装置の限界や工業生産的なコストの観点から、CuO粉の平均粒径は1μmを下限とすることが好ましい。
また、CuO粉の平均粒径は、1μm以上20μm以下の範囲であることがより好ましく、3μm以上10μm以下の範囲であることがさらに好ましい。
次に、本実施形態の銀粘土について説明する。
本実施形態に係る銀粘土は、上記構成の銀粘土用粉末と、バインダー(本実施形態では有機バインダー)と、水とを含む。
例えば、本実施形態に係る銀粘土は、上記構成の銀粘土用粉末を70質量%以上95質量%以下の範囲で含有し、さらに、有機バインダーと水とを含むバインダー剤を5質量%以上30質量%以下の範囲で含有するものである。ここで、バインダー剤には、有機バインダーおよび水の他に、必要に応じて界面活性剤や油脂が添加されていてもよい。
この銀粘土は、化学的に安定なCuO粉と、Ag粉とを含有した粉末成分を含む銀粘土であることから、大気雰囲気下において変色が抑制されることになる。
前記界面活性剤は特に限定されるものではなく、通常の界面活性剤(例えばポリエチレングリコール等)を使用することができる。
本実施形態に係る銀粘土5の製造方法は、上記の銀粘土用粉末1を70質量%以上95質量%以下、有機バインダーと水とを含むバインダー剤2を5質量%以上30質量%以下として混練する方法である。
そして、混合装置50内で、上記各材料粉末を混合することにより、銀粘土用粉末1が得られる。
ここで、バインダー剤2は、有機バインダーを11質量%以上17質量%以下、油脂を5質量%以下、界面活性剤を2質量%以下、残部を水とした配合で混合したものとされている。
本実施形態に係る銀焼結体は、上記構成の銀粘土5を任意の形状に造形、成形した後、後述の条件で焼成することによって得られるものである。
この銀焼結体は、優れた機械的強度を有しているので、例えば、大きな外力が加えられた場合であっても、割れや破断が生じたりするのを抑制することが可能となる。また、本実施形態に係る銀焼結体は、優れた機械的強度とともに高い伸びを有しているので、例えば、焼成後の銀焼結体に対して曲げを伴う追加加工を施した場合でも、亀裂や破断等が生じるのを抑制することが可能となる。
本実施形態に係る銀焼結体10の製造方法は、上記構成の銀粘土5を任意の形状に成形することで成形体51とし、次いで、この成形体51を、例えば、室温~150℃の温度で、30分~24時間で乾燥処理し、次いで、成形体51を、還元雰囲気又は非酸化雰囲気において、650~830℃の温度で、15~120分の時間で焼成を行うことによって銀焼結体10とする方法である。ここで、上記焼成を行う方法としては、例えば、乾燥処理した成形体51を活性炭中に埋め込んだ状態とした後、650~830℃の温度で、15~120分の時間で、還元雰囲気で焼成を行う方法を採用することができる。
次いで、図2Bに示すように、電気炉80に成形体51を投入して乾燥処理を行うことにより、水分等を除去する。
この際の乾燥温度としては、効果的に乾燥処理を行う観点から、例えば、室温あるいは80℃程度の温度から150℃までの範囲の温度とすることが好ましい。また、同様の観点から、乾燥処理を行う時間は、例えば、30~720分、より好ましくは30~90分の範囲の時間とし、一例として、乾燥温度:100℃程度で、乾燥時間:60分程度とした条件で乾燥処理を行うことができる。
ここで、「CuOの酸素を利用する」とは、CuOが焼成中に熱分解することにより酸素を放出し、この酸素が有機バインダーの燃焼に寄与することを示す。
また、本実施形態においては、図示例のような装置を用いることにより、成形体51に対して焼成を施すことで銀焼結体10を製造する方法を採用することができる。
そして、内部において成形体51が活性炭61中に埋め込まれた状態の焼成容器60を電気炉80に投入し、上述したように、650~830℃の範囲の温度で、15~120分の時間で加熱することで、焼成を行う。
また、本実施形態においては、乾燥処理や焼成の各工程において、電気炉を用いる例を説明しているが、これに限定されるものではなく、例えば、ガス加熱装置等、安定した加熱条件管理が可能なものであれば、何ら制限無く採用することができる。
また、本実施形態である銀粘土5によれば、上記構成の銀粘土用粉末1を用いて混練して得られるものであることから、上記同様、成形後に加熱焼成して得られる銀焼結体10の機械的強度や伸び等を向上させることができる。さらに、CuをCuOとして含んでいるので、銀粘土5の変色を抑制することができる。
さらに、本実施形態である銀焼結体10の製造方法によれば、上記構成の銀粘土5を用いて成形した後、規定条件で乾燥処理や焼成を行うことにより、機械的強度や伸び等に優れた銀焼結体10を製造することが可能となる。
例えば、Ag粉とCuO粉とからなる銀粘土用粉末として説明したが、これに限定されることはなく、Ag-Cu合金粉末等と、銅含有酸化物粉末とを含む銀粘土用粉末としてもよい。あるいは、Ag粉末と銅含有酸化物粉末の他にCu粉末やAg-Cu合金粉末を加えたものであってもよい。この場合、Cu粉末、Ag-Cu合金粉末に含まれる金属Cuの含有量は、銀粘土用粉末全体に対して2質量%以下とすることが好ましい。これにより、銀粘土の変色を確実に抑制することができる。なお、金属Cuの含有量は0.01質量%以上2質量%以下であってもよい。
また、Ag粉、CuO粉以外に、Cu2O粉を加えても良い。この場合、銀粘土用粉末中の酸化銅(II)(CuO)の含有量と酸化銅(I)(Cu2O)の含有量の合計を銀粘土用粉末全体に対して54質量%以下とされていることが好ましい。これにより、銅含有酸化物中の酸素を利用して確実に焼結を促進することができる。なお、酸化銅(II)(CuO)の含有量と酸化銅(I)(Cu2O)の含有量の合計は銀粘土用粉末全体に対して0.01質量%以上54質量%以下であってもよい。
まず、以下の手順で焼結体形成用の粘土状組成物用粉末(以下、銀粘土用粉末と称す)を作製した。銀粘土用粉末の作製にあたっては、Ag粉末(平均粒径5μm:マイクロトラック法;アトマイズ粉)と、CuO粉末(平均粒径5μm:マイクロトラック法;キシダ化学株式会社製試薬・純度97%以上)と、を用いて、図1に示すような混合装置によって混合することによって、Ag-4質量%CuO(本発明例1)、Ag-9.2質量%CuO(本発明例2及び9)、Ag-12.2質量%CuO(本発明例3、7及び8)、Ag-35質量%CuO(本発明例4)、Ag-3質量%CuO(本発明例5)、Ag-40質量%CuO(本発明例6)、とされた銀粘土用粉末を得た。
ここで、金属Cu粉を酸化処理した銅含有酸化物粉末について、株式会社リガク製X線回折装置RINT Ultimaを用いてX線回折分析を実施した結果を図3に示す。X線回折分析の結果、CuO、Cu2Oのピークが明確に確認される。また、金属Cu粉を酸化処理した銅含有酸化物粉末は、目視において表面全体が黒色を呈していた。このことから、金属Cu粉を酸化処理した銅含有酸化物粉末の少なくとも表面部分には、CuOが形成されていることが確認された。
そして、銀粘土用粉末を85質量%、上述のバインダー剤を15質量%として混練し、銀粘土とした。
そして、銀粘土用粉末を85質量%、上述のバインダー剤を15質量%として混練し、銀粘土とした。
次いで、図2Bに示すように、前記ワイヤー状成形体および角柱状成形体の各成形体51を発明例毎に同時に電気炉(Orton:evenheat kiln inc.)80に投入し、乾燥温度を100℃とし、乾燥時間を60分とした条件で乾燥処理を行うことにより、前記各成形体51に含まれる水分等を除去した。
なお、図2A~図2Cにおいては、成形体51として1個の角柱状成形体のみを図示しており、ワイヤー状成形体の図示は省略している。
なお、本発明例3、4、6、8、9、17については、上述の仮焼工程を省略した。
具体的には、図2Cに示すように、内部に活性炭61が充填された陶器製の焼成容器60を用意し、各成形体51を活性炭61中に埋め込んだ。この際、活性炭61の表面から各成形体51までの距離を約10mmとした。
そして、各成形体51が活性炭61中に埋め込まれた状態の焼成容器60を電気炉80に投入し、全ての発明例共通で加熱温度:760℃、加熱時間:30分として本焼成を行うことにより、ワイヤー状および角柱状の銀焼結体10を作製した。
比較例1、2においては、銀粘土用粉末としてAg-7.5質量%Cuの合金粉末(平均粒径33μm:マイクロトラック法;アトマイズ粉)を使用して、上述の本発明例1~7と同様に銀粘土を製出した。
また、比較例3においては、銀粘土用粉末として、Ag粉末(平均粒径5μm:マイクロトラック法;アトマイズ粉)と、Cu粉末(平均粒径20μm:マイクロトラック法;福田金属箔粉工業社製還元粉)とを、用いて、Ag-7.5質量%Cuとなるように配合した銀粘土用粉末を使用して、上述の本発明例1~7と同様に銀粘土を製出した。
さらに、比較例4においては、銀粘土用粉末として粒径1μm以上15μm以下であって純度99.9%の銀粉末を使用して、上述の本発明例1~7と同様に銀粘土を製出した。
次いで、図2Bに示すように、前記ワイヤー状成形体および角柱状成形体の各成形体51を比較例毎に同時に電気炉(Orton:evenheat kiln inc.)80に投入し、乾燥温度を100℃とし、乾燥時間を60分とした条件で乾燥処理を行うことにより、前記各成形体51に含まれる水分等を除去した。
なお、比較例2、4については、上述の仮焼工程を省略した。
具体的には、図2Cに示すように、内部に活性炭61が充填された陶器製の焼成容器60を用意し、各成形体51を活性炭61中に埋め込んだ。この際、活性炭61の表面から各成形体51までの距離を約10mmとした。
そして、各成形体51が活性炭61中に埋め込まれた状態の焼成容器60を電気炉80に投入し、比較例1~3の場合には、加熱温度:800℃、加熱時間:60分とし、比較例4の場合には、加熱温度:700℃、加熱時間:10分として本焼成を行うことにより、ワイヤー状および角柱状の銀焼結体10を作製した。
作製した銀粘土及び銀焼結体について、以下のような評価試験を行った。
まず、銀粘土の変色については、所定量(10g)の銀粘土を採取し、この銀粘土を透明なポリエチレンフィルムで包んだ板材で挟み、厚さ3mmとなるように押し潰した。そして、室温、大気雰囲気下で保管して変色の有無を目視によって観察して評価した。
曲げ強度については、島津製作所製オートグラフ:AG-Xを用い、押し込み速度0.5mm/minで応力曲線を測定し、弾性領域の最大点応力を測定することで求めた。
また、引張強度については、上記同様、島津製作所製オートグラフAG-Xを用い、引張速度5mm/minで応力曲線を測定し、試験片が破断した瞬間の応力を測定することで求めた。
また、表面の硬さは、試験片の表面を研磨した後、アカシ微小硬度計を用い、荷重100g、荷重保持時間10秒という条件にてビッカース硬度を測定することによって求めた。
また、伸びは、島津製作所製オートグラフAG-Xを用い、引張速度5mm/minで応力曲線を測定し、試験片が破断した瞬間の試験片の伸びを測定することで求めた。
表1、2に示すように、本発明例1~9、17,18の銀粘土は、室温、大気雰囲気下で1ヶ月保管した後であっても、変色は認められなかった。
また、本発明例1~8、18の銀粘土を成形、焼成した銀焼結体においては、機械的強度の指標となる曲げ強度、引張強度、表面の硬さ、密度の何れも、純Agを用いた比較例4に比べて高い値を示し、また、伸びも同等以上であることが明らかとなった。
なお、Ag-9.2質量%CuOとされ、仮焼工程を実施しなかった本発明例9においては、焼成が不十分であり、引張試験等を実施できなかった。同様に、金属Cuを酸化処理した銅含有酸化物粉末を使用し、仮焼工程を実施しなかった本発明例17についても、焼成が不十分であり、引張試験等を実施できなかった。
ここで、本発明例3、7について、銀焼結体の炭素濃度、酸素濃度を測定した。なお、炭素濃度は、インパルス炉加熱-赤外線吸収法で測定した。また、酸素濃度は高周波炉加熱-赤外線吸収法で測定した。その結果を表3に示す。表2及び表3において、本発明例3と7とを比較することにより、仮焼工程を省略しても有機バインダーは燃焼して除去され、十分な銀焼結体強度が得られることがわかる。
さらに、水溶性セルロースエステルと馬鈴薯澱粉の混合物を有機バインダーとして使用した本発明例8についても、本発明例3、7と比較して、特性等に相違は認められなかった。
また、純銀を使用した比較例4については、変色はないものの、本発明例1~8に比べて、機械的強度の指標となる曲げ強度、引張強度、表面の硬さ、密度当が低い傾向であり、変形しやすいものであることが確認された。
また、銀粘土用粉末として粒径1μm以上15μm以下であって純度99.9%の銀粉末を準備した。
具体的には、図2Cに示すように、内部に活性炭61が充填された陶器製の焼成容器60を用意し、成形体51を活性炭61中に埋め込んだ。この際、活性炭61の表面から成形体51までの距離を約10mmとした。
そして、成形体51が活性炭61中に埋め込まれた状態の焼成容器60を電気炉80に投入して本焼成を実施した。
また、比較例5においては、焼成温度:900℃、加熱時間:120分とし室温から焼成温度(900℃)までの昇温速度を30℃/minとして、本焼成を実施した。
評価結果を表4に示す。
一方、比較例5の銀粘土を使用したものでは、焼成温度を高く、かつ、加熱時間を長く設定したにもかかわらず、密度が8.6g/cm3程度であって、本発明例10に比べて焼成が不十分であった。
また、金属Cu粉(平均粒径20μm:マイクロトラック法;福田金属箔粉工業社製還元粉)を大気雰囲気において340℃で3時間加熱して酸化処理した銅含有酸化物粉末と、Ag粉末(平均粒径5μm:マイクロトラック法;アトマイズ粉)と、Cu粉末を混合して、表5の本発明例19、20に示す組成の銀粘土用粉末を得た。
この分析の結果、本発明例11~16の銀粘土用粉末におけるCuO粉末、Cu2O粉末の混合比と、銀粘土におけるCuO粉末、Cu2O粉末の含有比が一致することを確認した。
具体的には、図2Cに示すように、内部に活性炭61が充填された陶器製の焼成容器60を用意し、各成形体51を活性炭61中に埋め込んだ。この際、活性炭61の表面から各成形体51までの距離を約10mmとした。
そして、各成形体51が活性炭61中に埋め込まれた状態の焼成容器60を電気炉80に投入し、加熱温度:760℃、加熱時間:30分として本焼成を行うことにより、角柱状の銀焼結体10を作製した。
作製した銀粘土及び銀焼結体について、以下のような評価試験を行った。
本発明例11~16、19、20においては、銀粘土の変色について次のように評価した。所定量(10g)の銀粘土を採取し、この銀粘土を透明なポリエチレンフィルムで包んだ板材で挟み、厚さ3mmとなるように押し潰した。そして、室温、大気雰囲気下で保管して変色の有無を目視によって観察して評価した。
評価結果を表5に示す。
評価結果を表6に示す。
表5に示すように、本発明例11~16、19、20の銀粘土は、室温、大気雰囲気下で5日間保管した後であっても、ほとんど変色は認められず、表1に示した比較例1~3に比べて変色が抑制されていることが確認された。
ただし、金属Cuの含有量が3質量%を超えた本発明例12、14、20においては、2週間経過後に変色が認められた。このことから、銀粘土の変色を確実に防止するためには、金属Cuの含有量を2質量%以下に設定することが好ましい。
1A Ag粉末
1B CuO粉末
5 銀粘土(銀合金焼結体形成用の粘土状組成物)
51 成形体
10 銀合金焼結体
Claims (15)
- 銀粉末と酸化銅粉末とを含有する粉末成分と、バインダーと、水とを含むことを特徴とする銀合金焼結体形成用の粘土状組成物。
- 前記酸化銅粉末として、少なくとも酸化銅(II)の粉末(CuO粉)を含有している請求項1に記載の銀合金焼結体形成用の粘土状組成物。
- CuO粉からなる前記酸化銅粉末を前記粉末成分全体に対して4質量%以上35質量%以下の範囲で含有し、前記粉末成分中の酸素を除く全金属成分に対するAg元素の含有量が46質量%以上97質量%以下とされている請求項1または請求項2に記載の銀合金焼結体形成用の粘土状組成物。
- CuO粉からなる前記酸化銅粉末を前記粉末成分全体に対して12質量%以上35質量%以下の範囲で含有し、前記粉末成分中の酸素を除く全金属成分に対するAg元素の含有量が46質量%以上90質量%以下とされている請求項1に記載の銀合金焼結体形成用の粘土状組成物。
- 前記粉末成分は、さらに金属Cuを含有し、
前記粉末成分中の前記金属Cuの含有量が前記粉末成分全体に対して2質量%以下とされている請求項1に記載の銀合金焼結体形成用の粘土状組成物。 - 前記酸化銅粉末は、さらに酸化銅(I)を含有し、
前記粉末成分中の酸化銅(II)の含有量と酸化銅(I)の含有量の合計が前記粉末成分全体に対して54質量%以下とされている請求項1に記載の銀合金焼結体形成用の粘土状組成物。 - 前記酸化銅粉末の平均粒径が1μm以上25μm以下とされている請求項1に記載の銀合金焼結体形成用の粘土状組成物。
- さらに、油脂および界面活性剤のうち少なくとも一方を含む請求項1に記載の銀合金焼結体形成用の粘土状組成物。
- 前記バインダーが、セルロース系バインダー、ポリビニール系バインダー、アクリル系バインダー、ワックス系バインダー、樹脂系バインダー、澱粉、ゼラチン、小麦粉の内の、少なくとも1種又は2種以上の組み合わせで構成されている請求項1に記載の銀合金焼結体形成用の粘土状組成物。
- 請求項1に記載の銀合金焼結体形成用の粘土状組成物に用いられる粘土状組成物用粉末であって、
銀粉末と酸化銅粉末とを含むことを特徴とする銀合金焼結体形成用の粘土状組成物用粉末。 - 請求項1に記載の銀合金焼結体形成用の粘土状組成物を焼成することで得られることを特徴とする銀合金焼結体。
- 請求項1に記載の銀合金焼結体形成用の粘土状組成物を任意の形状に成形することで成形体とし、
この成形体を乾燥させた後に、還元雰囲気又は非酸化雰囲気において、焼成を行うことにより、銀合金焼結体とすることを特徴とする銀合金焼結体の製造方法。 - 前記成形体を乾燥させた後に、還元雰囲気又は非酸化雰囲気において、650℃以上830℃以下の範囲の焼成温度で、15分以上120分以下の時間で焼成を行うことにより、銀合金焼結体とする請求項12に記載の銀合金焼結体の製造方法。
- 前記成形体は、厚さが5mm以上の部分を有しており、この成形体を乾燥させた後に、還元雰囲気又は非酸化雰囲気において焼成する際に、室温から前記焼成温度までの昇温速度を15℃/min以上80℃/min以下の範囲内とする請求項13に記載の銀合金焼結体の製造方法。
- 前記成形体を活性炭中に埋め込んだ状態で焼成を行う請求項12に記載の銀合金焼結体の製造方法。
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