WO2011021656A1 - Procédé de production d’un article métallique décoratif, et article métallique décoratif - Google Patents

Procédé de production d’un article métallique décoratif, et article métallique décoratif Download PDF

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Publication number
WO2011021656A1
WO2011021656A1 PCT/JP2010/063970 JP2010063970W WO2011021656A1 WO 2011021656 A1 WO2011021656 A1 WO 2011021656A1 JP 2010063970 W JP2010063970 W JP 2010063970W WO 2011021656 A1 WO2011021656 A1 WO 2011021656A1
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Prior art keywords
rod
copper
silver
shaped body
mixed
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PCT/JP2010/063970
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English (en)
Japanese (ja)
Inventor
雅司 平間
秀和 吉原
涼太 三ツ橋
知昭 粕川
昭孔 矢次
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相田化学工業株式会社
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Priority to JP2011527696A priority Critical patent/JPWO2011021656A1/ja
Publication of WO2011021656A1 publication Critical patent/WO2011021656A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B22F1/102—Metallic powder coated with 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
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention is a method for producing a decorative metal article having a complex marble pattern in which a silver or silver alloy sintering composition and a copper or copper alloy sintering composition used for jewelry, ornaments, jewelry, and the like are combined.
  • the present invention relates to methods and decorative metal articles.
  • Patent Documents 1 to 3 In a method using a plastic composition containing noble metal powder, methods disclosed in Patent Documents 1 to 3 have been proposed as methods for producing metal articles in which sintered bodies of different metals are combined.
  • copper is included in noble metals, but copper is significantly more resistant to corrosion (oxidation resistance) than general noble metals that are gold, silver, and white metal elements. Property) is inferior. That is, copper and copper alloys have the property of oxidizing when heated in an oxidizing atmosphere (in the air).
  • the technique described in Patent Document 1 is a second precious metal powder in which a plastic composition containing a first noble metal powder is formed into a plate shape, a plate portion in a desired region is removed, and the removed plate portion has a different color.
  • Patent Document 2 It is a method of packing and sintering a plastic composition containing.
  • a plastic composition containing the first noble metal powder is formed, a plurality of through holes are formed, and the through hole is filled with a plastic composition containing a noble metal powder exhibiting a different color
  • the technique described in Patent Document 3 is a method in which a plurality of noble metal plastic compositions each having a different color are pre-formed into blocks or plates by sintering, and these are combined and sintered so that the front and back patterns are different. .
  • Patent Documents 1 to 3 are methods for joining in a rough combination, and if the joining area (joining portion) is small (if it is small), separation occurs after firing. This method can be applied only to metal articles with a wide (many) design (joint part), and there is a great restriction on the design. In any of the methods described in Patent Documents 1 to 3, dissimilar metals having different colors are intertwined in an extremely complicated manner. The technique of forming a marble pattern could never be realized.
  • Patent Documents 1 to 3 do not provide a sufficiently clear description of the firing conditions. In particular, Patent Document 3 does not allow any description about the firing atmosphere.
  • the plastic composition containing pure gold powder is sintered in the air, that is, in an oxidizing atmosphere, and 75.0 wt% gold, 12.5 wt% silver, and 12.
  • a plastic composition containing a so-called alloy metal of K18 mixed at a ratio of 5% by weight it is described that sintering is performed in an argon gas atmosphere. That is, it is disclosed that even a plastic composition containing an alloy metal such as K18 containing only 12.5% by weight of copper must be sintered in an inert atmosphere.
  • Patent Documents 1 and 2 both propose an invention for firing in a state of physically combining metal powder plastic compositions having different colors, for example, an oxidation containing pure gold In a state where the plastic composition A that is fired in an atmosphere and the plastic composition B that is fired in an inert atmosphere containing copper such as K18 are combined, there is no disclosure as to under what conditions.
  • Patent Document 4 discloses that a plastic composition containing a precious metal mixed powder containing silver and copper is primarily sintered at 400 ° C. or higher in an oxidizing atmosphere, and then secondary at 800 ° C. or higher in a reducing atmosphere. A method of sintering is disclosed. However, since this patent document 4 does not describe the sintering time in each of the primary sintering and the secondary sintering, a verification experiment cannot be performed, but as an example, an alloy composition of K18 is used as a gold alloy. Only a few examples are included, and the copper content does not exceed the composition of K18. Further, only two kinds of alloy compositions have been verified as platinum alloys, and the copper content is even smaller.
  • Patent Document 4 describes performing primary sintering in an oxidizing atmosphere and secondary sintering in a reducing atmosphere
  • the technique described in Patent Document 4 contains copper or a copper alloy.
  • the firing technique is limited to firing of a noble metal plastic composition, and is not a firing technique for obtaining a metal article in which plastic compositions of different metals having different shades and appearances are combined.
  • Patent Documents 1 to 4 using a plastic composition containing a noble metal powder can produce a decorative metal product made of a different metal, but a method of joining in a rough combination, If the bonding area is small, it will be separated after firing, so that there is a great restriction on the design that the bonding area must be widened.
  • the technique of forming a marble pattern that is intricately intertwined is far from possible.
  • the firing condition of the copper plastic composition containing copper or copper alloy is basically performed in an inert atmosphere, that is, in a reducing atmosphere
  • copper plastic containing these copper or copper alloy is known.
  • a composite shaped article formed by combining a composition and a noble metal plastic composition containing a noble metal such as silver having an oxidation-resistant property that is not oxidized in the atmosphere during firing is fired without losing the shaping to obtain a decorative metal article. Therefore, it is not specifically known under what conditions and procedures the firing should be performed.
  • the present inventors contain copper or copper alloys that are known in many shades such as copper of bronze, bronze, and bronze.
  • a method for producing a decorative metal article and a decorative metal article for use in jewelry, ornaments, jewelry, etc. in which a copper plastic composition and a silver plastic composition containing silver or a silver alloy are combined.
  • the present invention has been achieved, and an object of the present invention is a decorative metal article having a marble-like pattern in which the color of copper or copper alloy and the color of silver or silver alloy are intertwined in a complicated manner, as if two kinds of It is an object of the present invention to provide a manufacturing method for obtaining a decorative metal article capable of forming a pattern as if it is formed by melting and tying together ultrafine metal wires of a book in a bundled state.
  • the method for producing a decorative metal article according to claim 1 of the present invention includes: Copper-containing plastic composition containing one or more powders selected from copper and copper alloys and an organic binder, and silver-containing plastic containing one or more powders selected from silver and silver alloys and an organic binder Forming the composition into a columnar shape to form a copper rod-shaped body and a silver rod-shaped body [bar-shaped body forming step]; [Mixed rod-shaped body forming step] in which a copper rod-shaped body and a silver rod-shaped body that have undergone the above [bar-shaped body forming step] are entangled and mixed to form a mixed rod-shaped body; [Adornment forming step] for flattening at least part of the mixed rod-like body that has undergone the [mixing rod-like body forming step] to form a decoration; Firing the resulting decorative object to obtain a decorative fired body [firing body manufacturing step]; It is characterized by including.
  • a copper rod-shaped body made of a copper-containing plastic composition and a silver rod-shaped body made of a silver-containing plastic composition are each stretched in the length direction in the mixed rod-shaped body ahead. It becomes a composite shaped body in which the color of copper or copper alloy and the color of silver or silver alloy are intricately intertwined, melting as if two types of copper fine wires and silver fine wires are entangled and bundled together
  • the decorative article in which the copper-containing plastic composition and the silver-containing plastic composition are mixed in a complicated manner may be fired in a reducing atmosphere or in the air (oxidizing atmosphere). Firing in a reducing atmosphere requires that an inert gas such as argon gas or nitrogen gas must continue to flow during firing, or a reducing agent such as carbon is placed in a sealed container together with a copper shaped body and heated from the outside. Since it takes time and effort, it is preferable to carry out by atmospheric firing. In order to carry out by air firing, it is particularly preferable to make the copper powder or copper alloy powder in the copper-containing plastic composition as fine as possible, as will be apparent from the examples described later.
  • the above-mentioned “silver alloy” of the present invention means an alloy having a silver content of 80% by weight or more.
  • silver grade 950, grade 925, grade 900 recognized by the Japanese grade certification system.
  • those of grade 800 include a silver-Pd alloy with improved sulfidation resistance.
  • the above-mentioned “copper alloy” of the present invention means an alloy having a copper content of 80% by weight or more, and examples thereof include bronze, gunmetal, and white bronze.
  • the copper alloy which does not contain copper oxide is preferable. By not containing copper oxide, it is possible to avoid becoming porous.
  • air firing means firing in the air and is synonymous with firing in an oxidizing atmosphere.
  • the reducing atmosphere includes an internal state in which a reducing agent such as carbon (a substance that is more easily oxidized than a copper shaped body during heating) is placed in a sealed container together with the copper shaped body and heated from the outside.
  • a reducing agent such as carbon (a substance that is more easily oxidized than a copper shaped body during heating) is placed in a sealed container together with the copper shaped body and heated from the outside.
  • the [mixed bar-shaped body forming step] mixes the copper bar-shaped body and the silver bar-shaped body by storing them in a syringe and injecting them. It is characterized by producing a rod-shaped body.
  • a mixed rod-like body having a predetermined uniform thickness is formed by injection molding with a syringe, and a flat surface for obtaining a decorative object thereafter. Can be easily performed.
  • the injection formation by the syringe may be a single syringe injection operation or a multistage syringe injection operation as described in claim 3 described later.
  • the [mixed bar-shaped body forming step] is performed by mixing and ejecting the copper bar-shaped body and the silver bar-shaped body in a syringe.
  • a rod-shaped body is formed, and the mixed rod-shaped body that has been ejected is stored in a syringe and injected to form a mixed rod-shaped body that has been ejected again is repeated at least once to form a mixed rod-shaped body.
  • the [mixed rod-shaped body forming step] forms the columnar shape by combining the copper rod-shaped body and the silver rod-shaped body,
  • the mixed rod-like body is formed by repeating the operation of dividing or folding the columnar bodies and rolling the columnar bodies together to form a columnar shape again at least once.
  • a decorative metal article according to claim 4 of the present invention it is tangled and mixed manually without using a syringe, as in claim 2 or claim 3.
  • a mixed rod can be formed, and a handy dexterous worker can create a decorative metal article with a marble-like pattern that is truly handmade and rich in originality.
  • the [decoration forming step] is to decorate the mixed rod-shaped body in a plane spiral shape, and flatten at least the upper surface thereof to form a plate shape. It is characterized by forming an object.
  • a plate-like ornament can be formed, for example, a decorative article fired body obtained by firing the plate-like ornament is placed on the upper end of the ring. It can be attached as a ring or a pendant.
  • the [decoration forming step] is to wind the mixing rod-like body into a plane spiral shape, flatten the upper surface and the lower surface to form a plate,
  • the plate is shaped like a ring to form a decoration.
  • a ring or the like can be formed.
  • the ends of the plates may be connected to each other by water, or the ends may be connected to each other, or the paste may be formed by adding water to the silver-containing plastic composition or the copper-containing plastic composition.
  • the method for manufacturing a decorative metal article according to claim 7 of the present invention is characterized in that the [fired body manufacturing step] is air-fired.
  • an inert gas such as argon gas or nitrogen gas is fired. It is possible to avoid the troublesome work that must be kept flowing inside and troublesome work such as heating from outside by putting a reducing agent such as carbon in a sealed container together with the copper shaped body, and it can be easily applied at culture schools etc. become able to.
  • the method for producing a decorative metal article according to claim 8 of the present invention is characterized in that the [fired body manufacturing step] is a firing temperature of 660 to 770 ° C. and a firing time of 3 to 40 minutes.
  • firing is performed at a lower temperature and in a shorter time than firing of a copper shaped body alone or firing of a silver shaped body alone.
  • the electric furnace may be preheated to the firing temperature, the decoration is put into the electric furnace maintained at that temperature, held at a predetermined temperature, taken out after the firing time, and rapidly cooled.
  • the powder selected from copper and a copper alloy of the copper-containing plastic composition is a first product having an average particle size of 0.1 to 4.0 ⁇ m.
  • a copper mixed powder comprising 25 to 75% by weight of a powder, and the balance being a second powder having an average particle size of more than 4.0 ⁇ m and an average particle size of 10 ⁇ m or less, from the silver and silver alloy of the silver-containing plastic composition
  • the selected powder contains 25 to 75% by weight of the first powder having an average particle size of 0.1 to 4.0 ⁇ m, and the remainder is from the second powder having an average particle size of more than 4.0 ⁇ m and an average particle size of 40 ⁇ m or less. It is characterized by being the silver mixed powder which becomes.
  • At least one powder selected from copper and a copper alloy in a copper-containing plastic composition is a powder having an average particle size of 10 ⁇ m or less.
  • the powder in the copper-containing plastic composition and the silver-containing plastic composition is a specific mixed powder having different average particle sizes, and the copper-containing plastic composition and the silver-containing plastic composition are combined to form Even if the decorated object is fired in the air at a predetermined firing temperature and firing time, the molding can be fired “without failure”, and both the copper shaped fired part and the silver shaped fired part can be used as a fired article for craft or decoration. Necessary constant strength can be obtained.
  • These copper-containing plastic composition and silver-containing plastic composition are obtained by using specific mixed powders having different average particle sizes, and the linear shrinkage rate after firing can be suppressed to the same level.
  • one of the shrinkages is too large and does not peel off or lose its shape after firing.
  • the oxide film on the surface of the copper molding fired part can be easily peeled off, and a product that can be sufficiently used as a fired article for crafts or decoration is obtained.
  • the “average particle diameter” of copper, copper alloy, silver, and silver alloy according to the present invention is also called a median diameter, a medium diameter, a median diameter, a median diameter, or a 50% particle diameter, and is usually expressed as D50. It means the particle size corresponding to 50% of the cumulative curve.
  • the measurement conditions are [particle permeability: reflection] and [true sphere / non-spherical: non-spherical]. ] (When the particle permeability setting is set to reflection and the true / non-spherical selection is set to non-spherical), the D50 value of the particle size distribution is measured.
  • the decorative composition is formed by combining 15 to 85% by weight of the copper-containing plastic composition and 85 to 15% by weight of the silver-containing plastic composition. It is characterized by forming an object.
  • the pattern to be formed is a marble pattern, and the silver is slightly silvery, or the silver is slightly coppery. There is nothing and a well-balanced marble pattern is obtained.
  • a decorative object is formed by combining 25 to 75% by weight of the copper-containing plastic composition and 75 to 25% by weight of the silver-containing plastic composition, a more attractive marble pattern can be obtained.
  • the decorative metal article according to claim 11 of the present invention is characterized by being manufactured by the manufacturing method according to any one of claims 1 to 6.
  • the pattern to be formed is a marble pattern, and the silver is slightly silvery, or the silver is slightly coppery And a well-balanced marble pattern is obtained.
  • a copper rod-shaped body made of a copper-containing plastic composition and a silver rod-shaped body made of a silver-containing plastic composition are each stretched in the length direction in the mixed rod-shaped body ahead. It becomes a composite shaped body in which the color of copper or copper alloy and the color of silver or silver alloy are intricately intertwined, melting as if two types of copper fine wires and silver fine wires are entangled and bundled together
  • a pattern as if it was formed, and it is possible to form a complicated marble pattern that cannot be obtained by any method other than the present invention.
  • a combination of a copper-containing plastic composition and a silver-containing plastic composition containing specific mixed powders each having a different average particle size it can be used for atmospheric firing. It can be used favorably, and both the copper shaped fired part and the silver shaped fired part can obtain a certain strength necessary for sintered articles for crafts and decorations.
  • the decorative metal article provided can be easily formed.
  • FIG. 1 It is a perspective view which shows the state which obtains a mixing rod-shaped body in the mixing rod-shaped body formation process in illustration Example A. It is a front view which shows the state which wound and mixed the mixing rod-shaped body in the plane spiral shape in the decoration formation process in illustration Example A. It is a front view which shows the state planarized in the ornament formation process in illustration Example A. It is a front view which shows the state made into plate shape in the ornament formation process in illustration Example A. It is a perspective view which shows the state shape
  • FIG. 1 It is a perspective view which shows the state cooled rapidly in the surface oxide film removal process in illustration Example A. It is a perspective view which shows the state of a pickling in the surface oxide film removal process in illustration Example A. It is a perspective view which shows the decoration metal goods (finger ring) obtained in illustration Example A. It is a front view which shows the copper rod-shaped body in the illustration Example B, and a silver rod-shaped body. It is a front view which shows the state which twists together in the mixing rod-shaped body formation process in illustration Example B, and forms in a column shape. It is a front view which shows the state extended in the length direction in the mixing rod-shaped body formation process in illustration Example B.
  • the copper-containing plastic composition preferably used is at least one powder selected from copper and a copper alloy, and 25 to 75% by weight of a first copper powder having an average particle size of 0.1 to 4.0 ⁇ m. And the balance contains a copper mixed powder composed of a second copper powder having an average particle size of more than 4.0 ⁇ m and an average particle size of 10 ⁇ m or less, and an organic binder.
  • the silver-containing plastic composition preferably used is one or more powders selected from silver and a silver alloy, and the first silver powder having an average particle size of 0.1 to 4.0 ⁇ m is 25 to 75.
  • the mixture contains a silver mixed powder composed of a second silver powder having an average particle size of more than 4.0 ⁇ m and an average particle size of 40 ⁇ m or less, and an organic binder.
  • copper has a bronze color
  • copper alloys include bronze, which is a copper alloy with tin
  • white copper which is a copper alloy with nickel.
  • silver has a white silver color
  • examples of silver alloys include silver grades 950, 925, 900 and 800, which are recognized by the above-mentioned Japanese grade certification system, Pd A silver-Pd alloy to which 1% is added can be used.
  • These copper powder, copper alloy powder, silver powder, and silver alloy powder are not particularly specified for production methods such as atomized powder and reduced powder, but it is preferable that the particles have a nearly spherical shape.
  • a decorative object formed by combining a copper-containing plastic composition and a silver-containing plastic composition containing specific mixed powders each having a different average particle diameter can be fired in the atmosphere, and both the copper shaped fired part and the silver shaped fired part A certain strength required for a craft or decorative sintered article can be obtained, and the shrinkage of each fired body (modeled fired part) after firing can be approximated. It is too large to peel off or lose its shape after firing. Moreover, even if the surface of a copper shaping
  • the average particle size is 0.5 to 4.0 ⁇ m.
  • a silver mixed powder comprising 25 to 75% by weight of the first silver powder of 0.0 ⁇ m and the balance of the second silver powder having an average particle diameter exceeding 4.0 ⁇ m and an average particle diameter of 30 ⁇ m or less is preferable.
  • a silver mixed powder comprising 30 to 70% by weight of the first silver powder having a diameter of 2.0 to 3.0 ⁇ m and the balance being the second silver powder having an average particle diameter of 5 to 20 ⁇ m is preferable.
  • groups such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carmellose (carboxymethylcellulose), carboxymethylcellulose sodium, carboxymethylcellulose potassium, carboxymethylcellulose calcium Alginate binder such as binder, sodium alginate, starch, starch starch, wheat flour, British gum, xanthan gum, dextrin, dextran, pullulan and other polysaccharide binders, gelatin and other animal binders, polyvinyl alcohol, polyvinylpyrrolidone and other vinyl binders , Polyacrylic acid, polyacrylic acid ester How an acrylic binder, polyethylene oxide, polypropylene oxide, and the like other resin-based binder such as polyethylene glycol for use in selecting one or more binders preferred.
  • the cellulose binder it is most preferable to use a water-soluble cellulose binder.
  • additives 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, citric acid.
  • 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, citric acid.
  • organic acid esters such as phthalic acid-n-dioctyl, phthalic acid-n-dipyl (methyl group, ethyl group, propyl group, butyl group, octyl group, hexyl group, dimethyl group, diethyl group, isopropyl group, isobutyl)
  • lignin which is a network polymer formed by condensing the structural unit to be rated, liquid paraffin, and oil It is done.
  • additives are added for the purpose of improving plasticity, or for the purpose of preventing the copper plastic composition and the silver plastic composition from adhering to the hand during molding.
  • the above additives, lignin and glycerin provide appropriate water retention.
  • examples of the additive include anionic, cationic, and nonionic surfactants.
  • the surfactant has an effect of improving the mixing property of silver powder or copper powder and an organic binder and an effect of improving water retention.
  • the water-soluble cellulose binder serves to impart plasticity.
  • polyethylene oxide has a function of improving the adhesion in a liquid state by giving a high viscosity at a low concentration.
  • sodium alginate gives moderate water retention like the said glycerol, it contributes also to the contact
  • the polyacrylic acid ester and the polyacrylic acid serve to strengthen the adhesiveness.
  • the water-soluble cellulose binder serves to impart plasticity as described above, but the water-soluble cellulose binder includes methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose sodium, carboxymethyl cellulose. Potassium, carboxymethyl cellulose calcium and the like are used and dissolved in water.
  • the total amount of the organic binder is a solid content display excluding water. It is desirable to be within the range of 0.1 to 4 wt%. In this case, when the amount of the organic binder is less than 0.1 wt%, it is difficult to obtain a homogeneous copper plastic composition and silver plastic composition. In addition, there is a disadvantage that the strength after coating and drying is weakened. When the amount of the organic binder exceeds 4 wt%, the shrinkage rate increases and cracks are likely to occur. Therefore, the amount of the organic binder is desirably 0.1 to 4 wt%.
  • polyethylene oxide When polyethylene oxide is used, it is desirable to use polyethylene oxide having a molecular weight of 100,000 to several million within the range of 0.1 to 3 wt%. Further, when a surfactant is used, it is preferably within a range of 0.03 to 3 wt%, and when an oil is used, it is preferably within a range of 0.1 to 3 wt%.
  • the copper plastic composition and silver plastic composition used in the present invention can be prepared in the form of clay, paste or slurry depending on the water content.
  • the metal powder is 75 to 99 wt% in any of the plastic compositions.
  • the amount is too small, the shrinkage becomes large and the sintering also becomes troublesome.
  • the ratio of water is reduced, which hinders modeling.
  • Bi, Se, Sb, In, Sn, Zn powder or alloy powder thereof may be added as a sintering accelerator.
  • a metal compound powder or glass powder selected from lead carbonate, lithium carbonate, zinc oxide, phosphoric acid, sodium carbonate, vanadium oxide, sodium silicate, phosphate and the like may be added as an adhesion improver.
  • a network polymer formed by condensation of structural units having a skeleton of phenylpropane such as lignin, glycerin, diglycerin, isoprene glycol, 1,3 butylene glycol, liquid paraffin, alcohols, Fats and oils, phthalic acid, phthalic acid-n-dioctyl, phthalic acid-n-dibutyl, and polyvinyl alcohol may be added, and surfactants and surfactants may be added as necessary.
  • a metal oxide such as zirconium oxide may be added for the purpose of preventing deformation during firing. This has the effect of forming a passage for the gas generated when the organic binder burns to diffuse outside by delaying the sintering with the metal oxide.
  • a rod-shaped body is formed in the method for producing a decorative metal article according to the present invention, wherein a decorative fired body is obtained by combining the copper-containing plastic composition and the silver-containing plastic composition.
  • a copper-containing plastic composition containing at least one powder selected from copper and a copper alloy and an organic binder, and at least one powder selected from silver and a silver alloy and an organic binder are contained.
  • a silver-containing plastic composition is formed into a columnar shape to produce a copper rod-shaped body and a silver rod-shaped body.
  • the copper rod-shaped body and the silver rod-shaped body to be formed do not necessarily have the same thickness (diameter), and the length does not necessarily have to be the same length. You may form in sheath length.
  • the mixed rod-shaped body is formed by entanglement and mixing of the copper rod-shaped body and the silver rod-shaped body that have been subjected to the [bar-shaped body forming step].
  • the specific method for forming the mixed rod-shaped body by entanglement and mixing the copper rod-shaped body and the silver rod-shaped body is not particularly limited, and may be formed in any way.
  • the mixed rod-shaped body should just be the state which the copper rod-shaped body and silver rod-shaped body which are comprised are each extended
  • a mixed rod-shaped body may be formed by accommodating a copper rod-shaped body and a silver rod-shaped body in a syringe and injecting the same.
  • Such injection molding with a syringe is a suitable technique for forming a mixed rod-like body having a predetermined uniform thickness, and it is possible to easily perform a flattening operation for obtaining a decorative object thereafter. it can.
  • the injection formation by this syringe may be a single syringe injection operation or a multistage syringe injection operation as will be described later.
  • a mixed rod-shaped body is formed by housing and ejecting a copper rod-shaped body and the silver rod-shaped body in a syringe, and further accommodating the ejected mixed rod-shaped body in a syringe.
  • the mixing rod-like body may be formed by repeating the operation of forming the mixing rod-like body that is injected and re-injected at least once. In such a method of repeatedly performing injection formation with a syringe, the copper-containing plastic composition and the silver-containing plastic composition are sufficiently entangled and mixed, and the resulting decorative marble pattern is formed in a complex manner. be able to.
  • the copper rod-shaped body and the silver rod-shaped body are wound together to form a columnar shape, then the columnar bodies are divided or folded, and the columnar bodies are twisted together to form a column again.
  • the mixing rod-like body may be formed by repeating the forming operation at least once. In this way, the method of forming a mixing rod-like body by entanglement by hand without using a syringe, if it is a dexterous worker at the hand, for decoration with a marble-like pattern rich in handmade originality Metal objects can be created.
  • the mixing rod-shaped body may be wound in a plane spiral shape, and at least the upper surface thereof may be flattened to form a plate shape to form an ornament.
  • a plate-like ornament can be formed, for example, a ornament fired body obtained by firing the plate-like ornament is brazed to the upper end of the ring to form a ring, It can be a pendant etc.
  • the mixing rod-shaped body may be wound in a plane spiral shape, and the upper and lower surfaces thereof may be flattened to form a plate, and the plate may be formed into a ring shape to form an ornament.
  • a ring-shaped ornament can be formed, it can be used for a ring or the like as shown in FIG.
  • the ends of the plates may be connected to each other by water, or the ends may be connected to each other, or the silver-containing plastic composition or the copper-containing plastic composition may be added with water to form a paste.
  • all of the mixing rod-like bodies are flattened to form the decoration, but only a part may be flattened.
  • the ornament obtained through the [decoration forming step] is baked to obtain a baked ornament.
  • the decorative article in which the copper-containing plastic composition and the silver-containing plastic composition of the present invention are intricately mixed may be fired in a reducing atmosphere or in the air (oxidizing atmosphere). In the case of atmospheric firing, it is particularly preferable to fire at 660 to 770 ° C. for 3 to 40 minutes, preferably 700 to 750 ° C. for 10 to 15 minutes.
  • a shaped body of a copper-containing plastic composition Compared to a lower temperature and a shorter time.
  • the firing temperature of the copper-containing plastic composition whose powder is pure copper is 990 ° C. ⁇ 3 to 6 minutes, 980 ° C. ⁇ 4 minutes to 15 970 ° C x 5 minutes to 30 minutes, 950 ° C x 5 minutes to 40 minutes, 850 ° C x 10 minutes to 50 minutes, 800 ° C x 30 minutes to 60 minutes, preferably 850 ° C to 980 ° C More preferably, it is 950 ° C. to 970 ° C.
  • the first half may be fired in the air, and the second half may be fired in a reducing atmosphere.
  • the decoration is immediately taken out from a heating source such as an electric furnace, and is put together with a reducing agent such as carbon and sealed.
  • the resulting stainless steel container is placed in an electric furnace, heated from room temperature to 700 ° C. to 800 ° C., and then maintained at that temperature for 30 minutes to 9 hours, whereby firing in a reducing atmosphere can be performed.
  • Firing in an argon gas atmosphere is performed by flowing argon gas through an electric furnace so as not to enter the atmosphere.
  • the decorative article fired body is rapidly cooled, pickled or polished to remove the oxide film formed on the surface.
  • the rapid cooling, pickling, and polishing are known techniques for firing this type of precious metal plastic composition, and pickling is performed using a solid acid agent for pickling (commercially available) such as sodium hydrogen sulfate. Put it in dilute sulfuric acid for about 5 minutes, polish it with a brush if necessary, and immediately wash it with water.
  • various polishing materials such as a polishing spatula, yarn buff, leuter, sponge polishing material, and stainless brush are commercially available.
  • the oxide film formed on the surface of the decorative fired body is removed.
  • the particle size of the powder selected from copper and copper alloy in the copper plastic composition is 10 ⁇ m or less, even if an oxide film is formed on the surface by baking in an oxidizing atmosphere, pickling or polishing Can be easily removed.
  • the clay-like silver-containing plastic composition comprises 92 wt% of silver mixed powder [mixed weight composition: 50% by weight of first silver powder (pure silver) having an average particle diameter of 2.5 ⁇ m, and second silver powder having an average particle diameter of 20 ⁇ m ( 50% by weight of pure silver), 0.7 wt% starch as an organic binder, 0.8 wt% cellulose, and a water-soluble binder with the balance being water.
  • a 2.0 ml syringe manufactured by Top Co., Ltd., medical device notification number 13B1 ⁇ 00085000023
  • a cylinder inner length of 8 cm an inner diameter of 6 mm
  • an extrusion port inner diameter of 1.4 mm was used as the syringe 21.
  • the obtained mixed rod-shaped body 3 is folded in half, and the two are crushed four times as shown in FIG. 4 and accommodated in the syringe again.
  • the rod-shaped body is formed by injection from the syringe, and this operation is repeated three times. As shown in FIG.
  • a single mixed rod 4 was obtained in which a large number of copper rods elongated in the lengthwise direction and a large number of silver rods were intricately entangled and mixed. .
  • the obtained mixed rod-shaped body was ejected onto a work table, the mixed rod-shaped body thus ejected was wound into a flat spiral shape, wound slightly long and collected, and pressed and integrated from the outside to obtain a shaped body 5 shown in FIG. .
  • the upper surface is flattened with a roller (1.5 mm thick) to form a shaped body 6 shown in FIG. 7, and the periphery is further cut to a width of about 1 cm with a cutter, and the plate-like shaped body 7 shown in FIG. did.
  • the plate-shaped shaped body 7 is wound around a wood core bar 22 of No. 16 to obtain a ring-shaped shaped body 8.
  • the shaped body 8 was put into a dryer set at a drying temperature of 100 ° C. and dried for a drying time of 30 minutes. After drying, the ring-shaped shaped body 8 was shaped with a file 23 as shown in FIG. ⁇ Firing body manufacturing process>
  • the resulting shaped body (decorated object) was air-fired at 750 ° C. for 10 minutes. The air firing was performed by preheating the electric furnace to the above temperature, putting it in the electric furnace maintained at that temperature, and maintaining a predetermined temperature and time.
  • ⁇ Surface oxide film removal process> After firing, the fired body 9 was placed in water 24 and rapidly cooled as shown in FIG. The oxide film was well removed in water. Next, as shown in FIG. 12, the fired body 9 is dipped in an aqueous solution 25 of a solid acid material for pickling (trade name: Pickling Compound, manufactured by GROBET FULE CO. OF AMERICA, INC.). The oxide film was removed. Gloss came out by polishing the surface with a stainless steel brush if necessary. As a result, a decorative metal article (ring) 10 having a complicated marble pattern made of two types (two colors) of silver and copper shown in FIG. 13 was completed. The obtained ring 10 was attached to FIG. 23 as a drawing substitute photograph. This marble pattern was a pattern as if it were formed by melting two types of ultrafine metal wires that were tangled and bundled together.
  • a solid acid material for pickling trade name: Pickling Compound, manufactured by GROBET FULE CO. OF AMERICA, INC.
  • the clay-like silver-containing plastic composition was 92 wt% [mixed weight composition: first silver powder (pure silver) with an average particle size of 2.5 ⁇ m, 50 wt%, 50% by weight of second silver powder (pure silver) having an average particle size of 20 ⁇ m], 0.7% by weight starch as an organic binder, 0.8% by weight cellulose, and a water-soluble binder with the balance being water.
  • ⁇ Bar-shaped body formation process> Using the silver-containing plastic composition and the copper-containing plastic composition, each is formed by extending it into a column having a width of about 3 mm with a finger to form a silver rod-like body 32 and a copper rod-like body 31 having a length of 70 mm shown in FIG.
  • ⁇ Mixed rod forming process> The obtained silver bar 32 and copper bar 31 are twisted together to form a column as shown in FIG. 15, stretched in the length direction as shown in FIG. 16, and then mixed bar 33 as shown in FIG. The mixed rod-like bodies 33, 33 were crushed together as shown in FIG. 18 and repeatedly formed into a columnar shape to form a mixed rod-like body.
  • ⁇ Decoration process> The obtained mixed rod-shaped body is wound in a plane spiral shape as shown in FIG. 19 to form a shaped body 34, and the upper surface thereof is flattened with a roller to form a shaped body 35 shown in FIG. 20, and the surroundings are further cut with a cutter.
  • a plate-like ornament 36 shown in FIG. 21 was obtained.
  • the decoration 36 was placed in a dryer set at a drying temperature of 100 ° C. and dried for a drying time of 30 minutes. After drying, it was calcined at 750 ° C. for 10 minutes.
  • ⁇ Surface oxide film removal process> After firing, the substrate was immersed in a dilute sulfuric acid aqueous solution or the like to remove the oxide film in the direction of the copper fired portion. Gloss came out by polishing the surface with a stainless steel brush if necessary.
  • a decorative metal article (brooch) 37 having a complicated marble pattern made of two kinds (two colors) of silver and copper was completed. Although the shapes are different, a ring obtained in substantially the same manner is attached as a drawing substitute photograph in FIG.
  • the clay-like silver-containing plastic composition comprises 92 wt% of silver mixed powder [mixed weight composition: 50% by weight of first silver powder (pure silver) having an average particle diameter of 2.5 ⁇ m, and second silver powder having an average particle diameter of 20 ⁇ m ( 50% by weight of pure silver), 0.7 wt% starch as an organic binder, 0.8 wt% cellulose, and a water-soluble binder with the balance being water.
  • ⁇ Create test piece> The silver-containing plastic composition and the copper-containing plastic composition are weighed so as to have a predetermined ratio, and are formed into a columnar shape having a width of about 3 mm with a finger to produce a silver bar and a copper bar, respectively. did.
  • the stretched silver bar and copper bar were put into an empty syringe without being twisted. When either one was long, the end was folded back and accommodated, and a columnar mixing rod-like body was ejected from the syringe.
  • a 2.0 ml syringe having a cylinder inner length of 8 cm, an inner diameter of 6 mm, and an extrusion port inner diameter of 1.4 mm (manufactured by Top Co., Ltd., medical device notification number 13B1 ⁇ 00085000023) was used.
  • the obtained mixing rod-shaped body was folded in half, and the two were twisted four times to form a columnar shape, which was then accommodated in the syringe, and the mixing rod-shaped body was ejected from the syringe. This operation was repeated three times to obtain a mixed rod-like body in which the linear shape of the copper-containing plastic composition and the linear shape of the silver-containing plastic composition were intertwined in an intricate manner.
  • the obtained mixed rod-like body was injected onto a work table and wound into a plane spiral shape, and the upper surface thereof was flattened to form a plate shape, and the plate was pressed from the outside to form a flat plate shape. Next, it was flattened with a roller (1.5 mm thickness), and a test piece (modeled body) of about 15 mm in length and 15 mm in width was created with a cutter. The obtained test pieces were dried and then fired in the air at 650 ° C. ⁇ 30 minutes to 850 ° C. ⁇ 5 minutes, and the firing time was shortened as the temperature increased.
  • the atmospheric firing was performed by preheating the electric furnace to the above temperature, putting it in the electric furnace maintained at the set temperature, and maintaining a predetermined temperature and time. After firing, it was quenched in water. The oxide film was removed well. Next, it was immersed in a solid acid material for pickling (trade name: Pickling Compound, manufactured by GROBET FULE CO. OF AMERICA, INC., Main component: sodium hydrogen sulfate) to remove the oxide film on the surface of the sintered body. Gloss came out by polishing the surface with a stainless steel brush if necessary. As a result, a test piece having a marbled surface layer pattern of two types (two colors) of silver and copper was obtained.
  • a solid acid material for pickling trade name: Pickling Compound, manufactured by GROBET FULE CO. OF AMERICA, INC., Main component: sodium hydrogen sulfate
  • Test 1 is a baking condition of 650 ° C. ⁇ 30 minutes, and Table 1 shows the result.
  • Test 2 was baking conditions at 700 ° C. for 15 minutes, and Table 2 shows the results.
  • Test 3 is a baking condition at 750 ° C. ⁇ 10 minutes, and Table 3 shows the result.
  • Test 4 is a baking condition of 780 ° C. ⁇ 5 minutes, and Table 4 shows the result.
  • Test 5 is a baking condition of 800 ° C. ⁇ 5 minutes, and Table 5 shows the result.
  • Test 6 is a baking condition of 850 ° C. ⁇ 5 minutes, and Table 6 shows the result.
  • Tables 1 to 6 “ ⁇ ” and “ ⁇ ” in the evaluation column are usable evaluations, and “ ⁇ ” is an unusable evaluation.
  • the “ ⁇ ” evaluation was an apparent problem that it was difficult to understand the marble pattern aesthetically, and it was not a problem for decorations with different designs, and had sufficient strength in use.
  • a decorative article when a decorative article is formed as a composite shaped body by appropriately combining a copper-containing plastic composition and a silver-containing plastic composition, it can be air-fired at 700 to 750 ° C. for 10 to 15 minutes. .
  • a combination of 15 to 85% by weight of a copper-containing plastic composition and 85 to 15% by weight of a silver-containing plastic composition It was confirmed that a combination of 25 to 75% by weight of the copper-containing plastic composition and 75 to 25% by weight of the silver-containing plastic composition is excellent in terms of balance.

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Adornments (AREA)

Abstract

Le but de la présente invention est de fournir un procédé de production d’un article métallique décoratif destiné à être utilisé dans des bijoux, des objets décoratifs, des accessoires vestimentaires etc., qui comprend un motif de marbre complexe comprenant une combinaison d’une composition pour le frittage qui comprend de l’argent ou un alliage d’argent avec une autre composition pour le frittage qui comprend du cuivre ou un alliage de cuivre, et un article métallique décoratif. A cette fin, l'invention concerne un article métallique décoratif produit grâce à un procédé comprenant : une étape de formation d'éléments en forme de tige qui comprend la formation d'une composition de plastique contenant du cuivre, qui contient une poudre d'au moins un élément sélectionné parmi du cuivre et un alliage de cuivre avec un liant organique, et une composition de plastique contenant de l'argent, qui contient une poudre d'au moins un élément sélectionné à partir d'argent et d'un alliage d'argent avec un liant organique, respectivement en tiges afin de produire ainsi un élément de cuivre en forme de tige et un élément d'argent en forme de tige ; une étape de formation d'un élément en forme de tige mélangé qui comprend l'entrelacement et l’alliance de l'élément de cuivre en forme de tige et de l'élément d'argent en forme de tige, obtenus chacun dans l'étape de formation d'éléments en forme de tige ci-dessus, pour ainsi produire un élément en forme de tige mélangé ; une étape de production d'un article décoratif qui comprend l'aplatissement d'au moins une partie dudit élément en forme de tige mélangé obtenu dans l'étape de formation d'un élément en forme de tige mélangé ci-dessus pour ainsi produire un article décoratif ; et une étape de production d'un élément chauffé qui comprend le chauffage de l'article décoratif ainsi obtenu afin de produire un article décoratif chauffé.
PCT/JP2010/063970 2009-08-19 2010-08-19 Procédé de production d’un article métallique décoratif, et article métallique décoratif WO2011021656A1 (fr)

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JP6241228B2 (ja) * 2013-11-28 2017-12-06 三菱マテリアル株式会社 貴金属焼結体形成用粘土状成形体
CN114807652B (zh) * 2021-12-24 2022-10-04 昆明冶金研究院有限公司北京分公司 一种艺术用粉末冶金复合材料的制备方法

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JPWO2011021649A1 (ja) 2013-01-24
JP5829914B2 (ja) 2015-12-09

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