DE2249658A1 - PROCESS FOR MANUFACTURING PRECIOUS METAL GOODS FOR MECHANICAL, INDUSTRIAL, DECORATIVE PURPOSES AND JEWELERY USING GALVANOPLASTIC AND GOODS MANUFACTURED BY THIS PROCESS - Google Patents

Description

The present invention relates to a method of manufacture of parts, objects and goods made of precious metals or alloys for mechanical, industrial, decorative Purposes and for Sohmuok, the addition of the electrolytic coating of an electrically conductive or made conductive Layer carrier with at least one layer made of at least one noble metal or an alloy made of it

The invention also relates to the parts, objects and goods produced by this method.

There are several methods of manufacturing goods for decorative purposes and for jewelry are known, which in the application a noble metal layer on a layer substrate of any kind (metal, organic or mineral material)

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exist. However, these ancestors generally have dt Purpose, cheap decoration goods or costume jewelry (gallantry goods) to produce in which the precious metal precipitate is very thin and the substrate alone ensures the strength and rigidity of the entire workpiece.

The method according to the invention is characterized in that, after the noble metal layer on the substrate has been applied, the material of the support is completely removed, so that one can make an object solid precious metal or an alloy whose thickness is sufficient to maintain the stability and rigidity of the To ensure the object.

"Solid" is to be understood here as meaning that the object obtained as above is only made of noble metal or of an alloy is made.

The noble metal layer is preferably at least 75 μm thick; in practice, it can have any thickness, which is only due to weight and price considerations and due to the very thick Metal deposits occurring leveling effect of the original Reliefs of the substrate surface is limited. the The thickness of the deposit is generally between 75 μm and 0.1 cm, although these limits are in no way mandatory.

The precious metals forming the one or more layers of the coating can be selected from all precious metals or alloys used for jewelry and decorative purposes. As such, the following metals should be mentioned: Ag, Au, Pt, Pd, Rh, Ru and alloys of them. These precious metals can be used in their pure state or, in order to make them more durable, after being alloyed with an appropriate amount of common metals according to the usual standards. As a result, their fineness can be between 1 hour and 2 hours carat. The metals used to make precious metals less than 24 carats

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are the ones commonly used for jewelry for this purpose be used.

Those used as documents in the method according to the invention Supports can be made from many different types of materials. You can out of usual Metals for example Fe * Cu, Zn, Cd, Sn, Ni, Co, Al or from an alloy of at least two of these metals. »You can also be made from a non-metallic or be made of quasi-metallic materials, the electrical ones Conduct electricity or are semiconductors. From the quasi-metallic cn substances should be mentioned as an example graphite.

The substances forming the non-conductive substrates can be mineral, natural organic or synthetic substances j they can also be composed, for example be mineral-organic substances. The outer surface of this substrate can be chemically or physically be made conductive. You can, for example, with a conductive paint or varnish for this purpose coated or metallized in a vacuum or electrostatically. It can also be made conductive by applying one of the usual treatments to achieve non-electrolytic metal coatings * So the Layer supports are treated, for example, with a reducing solution and then with a metal salt solution, wherein in this way a thin layer of this metal is applied to the surface.

The electrochemical application of the precious metal to the conductive The layer carrier or the layer carrier made conductive can be used in the usual way, preferably over the entire surface of the ski clit carrier, which is then completely in this metal is embedded. Most known baths are electrochemical Application of precious metals, the malleable and

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crack-free precipitation results are for the aforementioned

Purpose usable, however, the baths that do not become one

lead early leveling of the decorative relief of the shoe carrier, preferably.

The noble metal layer preferably has a sufficient one Porosity, which allows the base material to become molten or converted into decomposition products, seeps through the walls.

In other cases it can be useful in the noble metal layer to provide one or more openings for the removal of the substrate material.

The removal of the layer carrier material, which takes place after the electrochemical application of the noble metal coating has ended, can be carried out chemically and / or physically. For example, the support can be melted or burned. One or more solvents or decomposition agents to which the noble metal is resistant can also be used separately or in combination.The following acids, among others, can be used: HCl, HNO-, HgSO., H-PO ₄ , HClO ₄ , HF , Cl-C-COOH and FC-COOH. In some cases bases such as NaOH, KOH, H.NOH or R.NOH, in which the R's are organic radicals, such as methyl and ethyl, can also be used. On a case-by-case basis, these compounds can be used either undiluted or after they have been diluted with at least one mineral or organic solvent. Mineral and organic salt solutions, for example the salts formed from the combination of the acids and rabbits described above, can also be used as solvents.

Organic or mineral-organic compounds can also be used as solvents, e.g. B. chlorinated solvents such as CIIOl.-, CHCl ₂ , trichlorethylene, tetrachloroethane; Esters,

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for example ethyl acetate, butyl acetate and isopropyl acetate; Esters such as monoglyme, dioxane and tetrahydrofuran} heterocycles such as pyridine, piperidine, morpholine and pyrrole | Amines like Triethylamine and ethylenediamine; Amides such as dimethylformamide and hexamethylphosphoramidj sulfur compounds such as dimethylsulfone and dimethyl sulfoxide j and ketones such as acetone and methyl ethyl acetone,

The method of the invention is also based on manufacturing of jewels or jewelry applicable if one is of natural ones or artificial herbal, animal or mineral Schiohtträger goes out.

For example, plant substances such as leaves, flowers, seeds, Bark etc. are used. As animal products can Insects and marine animals such as sponges, corals, starfish, mollusc shells, etc. can be used. As a mineral Supports can be natural or artificial crystals. They can also be relatively soft malleable materials such as waxes, plaster of paris and synthetic resins be used.

The present process is also useful for manufacture of jewels with at least one foreign body inserted in them, for example one made of a different metal than the metal the jewel self-made workpiece or a gem. In this case the procedure is as follows: In the original Layer support becomes a suitable recess for insertion of the foreign body is provided which, after electrochemical application of the noble metal, leads to the formation of a corresponding Opening in the precious metal layer leads. After that The method according to the invention has been carried out in its entirety and the material of the layer support has been removed, the Foreign bodies fitted into the opening of the precious metal of the jewelry. If necessary, the enclosure is covered with a protective

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Covering means covered, whereupon the item made of precious metal is digested in an electrolytic bath corresponding to the previously used electrolytic bath. «The additional amount of metal ensures a perfect fit of foreign inclusion as if it had been driven into it.

The method according to the invention is also very useful for the production of mechanical parts having unusual properties for special purposes. For example, can the process can be used to obtain 24-carat gold workpieces with high strength and high density, which are useful for producing gears, axles or flywheels with a high moment of inertia

The following examples explain the invention in detail; the temperatures are indicated in ⁰ C.

example 1 Manufacture of a piece of jewelry

A sheet of polystyrene foam 10 mm thick was cut into approximately square pieces of about 5 inches in size. A number of cavities and through openings of any shape and size were etched into the synthetic resin with the aid of a soldering iron heated to about 200 °. To During this process, the substrate has a rough and rough surface.

The polystyrene workpiece was immersed ^{in a degreasing solution (CC-I +} ) at room temperature for a period of 1 minute. It was then rinsed with distilled water and introduced into a solution of colloidal Pd and dilute HCl (METEX 90? 0 ⁺⁺ ) to activate its surface. After rinsing, the workpiece was immersed in a non-electrolytic copper bath to ensure at least one non-electrolytic bath

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Apply copper layer. The bathroom consisted of 2/3 METEX 9O72 ⁺⁺ and i / 3 HETEX 9073 **. The workpiece was left in the bath until a copper deposition of 2-3 / µm was achieved (5 to 10 minutes),

After the unwinding of the workpiece in a commercial Sulfidgoldbäd ⁺⁺⁺ at 50 ⁰ C and 4 A was / dm ² coated with a layer of gold. The electrolysis was continued until the gold was 200 µm thick.

After unwinding, the workpiece was immersed in a 1: 1 acetone CG1 _; -Mixture immersed until the support was completely dissolved (about 5 minutes at room temperature) ·. It should be noted that the material of the workpiece was sufficiently porous that the solvent could freely penetrate its body and easily dissolve the synthetic resin substrate.

⁺ Sold by Oxy Metal Finishing (Schweiz) AG, Avenches Switzerland

⁺⁺ Manufactured by MacDermid Inc., sold by Oxy Metal Finishing (Switzerland,) AG

Manufactured and sold by Oxy Metal Finishing International AG, Geneva

The workpiece was then immersed in 50% aqueous HNO at 6O-7O C until the copper and traces of palladium were completely dissolved. This state was indicated by the end of gas evolution. After its rinsing with distilled water, the workpiece was dried in air at IiO ⁰ C.

The finished item was made of solid 24-karat gold * It could be mounted as a brooch using the methods commonly used in jewelry making.

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Example 2 Making a piece of jewelry

The outer surface of an empty snail shell was coated with a kOfo e & ra fine copper powder and 60% one made of polystyrene in solution in an organic volatile solvent (for
Example acetone) coated conductive paint containing binder.

After the workpiece was made conductive, it became With the aid of the method described in Example 1, coated with a 600 .mu.m thick layer of gold.

The snail shell was then placed in dilute aqueous BCl
dissolved while the conductive paint was dissolved in warm dilute ENT as described in Example 1.

Example 3 Manufacture of a decorative item

A solid piece of paraffin wax was cut to size Obtaining a substrate suitable for making a table ornament.

The workpiece was subjected to the same treatment described in Example 1, which leads to the formation of a non-electrolytic copper layer. The workpiece was then immersed in an electrolytic copper bath (Cu-BATH ⁺ ) and coated with 60 μm copper. After it had been rinsed off, the workpiece was coated with a 250 μm gold layer according to the method of Example 1.

A hole large enough to allow enamel wax to pass through was drilled at a suitable point, whereupon the wax is removed from the workpiece by heating it to 150 ° C became.

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The workpiece was washed in benzene, followed by the copper as described in Example 1, was dissolved in UNO. as After treatment, the workpiece was welded to a base.

Example 4 . Making a brooch

A rose bud was coated with a conductive layer by dipping it in a conductive silver paint prepared by mixing hOfo silver powder, 5% polystyrene and 55% trichlorethylene.

The rose was then applied with a 50 / µm thick electrolytic Copper layer using the method described in Example 3 overdrawn. Then the copper-plated workpiece was as described in Example 1 with a 300 / um thick gold layer overdrawn.

+ The Maker Company; by Oxy Metal Finishing (Switzerland) A.G., Avenche, Switzerland, product sold,

The copper and silver were then dissolved by immersion for a period of about 1 l / 2 to 2 hours in warm diluted UNO “, which at the same time leads to the decomposition of the organic Materials of the Rose resulted in »Finally the workpiece usually presented as a brooch.

Example 5 Making an ornament

A decorative item made by an artist was found in Molded plaster. The resulting plaster of paris substrate was coated with a conductive paint containing copper as described in Example 2; the paint had as well the advantage that they are those present in the plaster surface Clogged pores. -.

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The article was as described in Example 1 by electrolytic means with a ^; 100 / µm thick gold layer. The plaster of paris was then removed by, if necessary, drilling a hole in the viand of the object and immersing the object in a solution of Nile. Cl and IIC1 or immersed in an aqueous solution of Na ₂ SoO-.

Example 6 Making a jewel

A jewel-like item was made by engraving a piece of soft iron. The workpiece was degreased as described in Example 1 and coated as described in Example 3 with a 3 / μm thick copper layer. The article was then plated with 300 µm gold by following the procedure of Example 1, whereupon the iron and copper were removed with 15 Io HCl at 50 ° C.

Example 7 Making a jewel

The shell of a marine mollusc was coated with a conductive silver paint as described in Example 4. The conductive workpiece was electrolytically coated with a 500 / Uta, thick silver layer ^{using a SEL-HEX AtOO + silver bath.} Then the CaCO ^ substrate was dissolved in dilute IiCl and the conductive paint layer in a 1: 1 mixture of acetone and CCl ^. The depressions in the silver surface of the resulting jewel were finally blackened in the usual way.

Example S , Manufacture of a balance wheel with high inertia

It has been found that the physical properties such as density and mechanical strength,

A product from Oxy Metal Finishing Interrmtional, Geneva

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of plated solid gold are not the same as those of Göldguss _c

This fact can be used for production of goods made of plated gold, if the special properties of plated gold. are expedient, as for example in Case of balance tires for watchmaking ^ -

In the present example, a smooth cylindrical brass rod was used with a diameter of 1.2 cm and a length of 22 cm by electrolytic route by using the in Example 1 mentioned commercial gold sulfite bath with a 0.3 cm thick Gold plated. The gold layer was made of malleable 24-carat gold of high strength and hardness with a Density- of about 18. After the gold-plated workpiece in halves was cut, the brass core was either marked with Η $ ΓΟ_ or more simply removed by machining, on what the remaining solid gold hollow cylinders are divided in the usual way into rings from 0.01 to 0.2 cm high with a high degree of inertia became. Finally, the rings were mechanically processed for installation as high-inertia balance strips in timekeeping equipment.

Patent claims :

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Claims (24)

Pat en tan sayings 1. Process for the manufacture of parts, objects and goods from precious metals or alloys for mechanical, industrial, decorative and jewelry, resulting from the electrolytic plating of an electrically conductive or layer support made conductive with at least one layer of at least one noble metal or an alloy consists of it, characterized in that after the noble metal layer is applied to the layer support has been, the material of the support is completely eliminated, so that you can have an object made of solid Precious metal or alloy is obtained whose thickness is sufficient to maintain the stability and rigidity of the To ensure the object. 2. The method according to claim 1, characterized in that the entire surface of the layer carrier coated with precious metal so that the substrate is completely encased in the noble metal. 3. The method according to claim 1 or 2, characterized in that that the noble metal layer is porous, so that the support material or its decomposition products through the Pores can pass through. 4. The method according to claim 1 or 2, characterized in that that at least one opening is provided in the noble metal layer so that the substrate material can be removed through this opening. - 13 3098 17/1037 5. Procedure according to. Claim 1, characterized in that the precious metal layer is at least 75 µm thick. 6. The method according to claim 1, characterized in that the noble metal is selected from Ag, Au, Pt, Pd, Bh, Ru and their alloys. 7. The method according to claim 1 and 2, characterized in that the Ieinheitsgrad of the noble metal or its alloy is between 14 and 24 carats, wherein the additional alloy metals are selected from the usual or base metals used in "jewelry production to precious metal with less than '2Pt carats., 8. The method according to claim 1, characterized in that the layer support is made of a conventional metal or such an alloy. 9. The method according to claim 1 and 8, characterized in that the layer support made of Fe, Gu, Zn, Cd, Sn, Ni, Go, Al, Mg, or an alloy of at least two of these metals is made. 10. The method according to claim 1, characterized in that the layer carrier is made of a metallic or quasi-metallic material that is electrically conductive or a semiconductor. 11. The method according to claim 1, characterized in that the substrate is made of a vegetable material. . - 14 - 309817/103 7 12. The method according to claim 1, characterized in that the layer support is made of an animal material is. 13. The method according to claim. 1, characterized in that . the substrate made of a natural or artificial mineral material is made. 14. The method according to claim. 1, characterized in that the substrate is made of a mineral or organic material, natural or synthetic or mixed mineral-organic non-conductive material is made, the surface of which has been made conductive by chemical or physical means. 15. Method according to claim 14, characterized in that the substrate surface with the help of a »conductive Paint or varnish made conductive has been. 16. The method according to claim 14, characterized in that the layer support surface by treatment with at least a solution for the non-electrolytic deposition of metals has been made conductive 17. The method according to claim. 1, characterized in that the layer carrier material is removed chemically and / or physically. 18. The method according to claim 17 », characterized in that the substrate material by its melting and the outflow of the melt from the interior of the workpiece Will get removed. - 15 309817/1037 19. The method according to claim. 17 »characterized in that the Schi ch carrier material with the help of at least one Solvent or decomposition agent is eliminated against that the precious metal is permanent. 20. Procedure according to. Claim 19, characterized in that the solvent or decomposition agent is an acid, a base or a mineral or an organic salt, which is used pure or as a solution in a mineral or organic solvent. 21. Procedure according to. Claim. 20, characterized in that the acid from HCl, HlTO ₅ , H ₂ SO ₄ , H ₅ PO ₄ , HOlO ₄ , HF, Cl ₃ O-GOOH, F ₃ C-GOOH and the base from KOH, NaOH, H ₄ NOH, or R ₄ NOH in which the R ¹ S are organic radicals. - 22. The method according to claim 19> characterized in that the solvent or decomposition agent is an organic or mineral-organic compound. 23.-Procedure according to. Claim 22, characterized in that the solvent is selected from chlorinated solvents, for example GHCl ₃ , CHpClp, trichlorethylene and tetrachloroethane; Esters such as ethyl acetate, butyl acetate and isopropyl acetate; Esters such as honoglyme, dioxane and tetrahydrofuran 5 heterocycles such as pyridine, piperidine, morpholine and pyrrole; Amines such as triethylamine and ethylenediamine j amides such as dimethylformamide and hexamethylphosphoramide} sulfur compounds such as dimethyl sulfoxide and dimethyl sulfone} and ketones such as acetone and methyl ethyl ketone / ' - 16 - 0 9 8 17/1037 24. Articles, parts and goods for industrial, decorative Purposes and for jewelry, characterized in that they are manufactured according to the method according to claim 1. 25 parts according to claim 24, characterized in that they Made from high density, high strength 24 carat gold. HB / Tue - 25 128 3 0 9 817/103