WO2015131796A1 - 一种无氰电镀液及其应用 - Google Patents

一种无氰电镀液及其应用 Download PDF

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Publication number
WO2015131796A1
WO2015131796A1 PCT/CN2015/073547 CN2015073547W WO2015131796A1 WO 2015131796 A1 WO2015131796 A1 WO 2015131796A1 CN 2015073547 W CN2015073547 W CN 2015073547W WO 2015131796 A1 WO2015131796 A1 WO 2015131796A1
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Prior art keywords
gold
cyanide
plating solution
sulfite
free plating
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PCT/CN2015/073547
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English (en)
French (fr)
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庄龙三
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深圳市联合蓝海新技术有限公司
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins

Definitions

  • the present invention relates to a cyanide-free plating bath and its use.
  • the plating solution used in the electroplating process is mainly a solution containing gold potassium cyanide.
  • gold potassium cyanide is a highly toxic substance, which not only causes harm to the health of the manufacturer in the production process of gold products, but also costs a lot of money to deal with the production waste in order to reduce the environmental pollution of the production waste liquid. liquid.
  • the hardness of the gold product obtained by using gold potassium sulfite and/or gold sodium sulfite as the plating solution is low, which makes the gold product with higher purity, especially thousands of gold, easy to be deformed and sunken. It is extremely easy to damage during use. Therefore, how to improve the stability of the plating solution containing gold sulfite solution and obtain the electroplated gold with higher hardness is a technical problem that needs to be solved in the current gold industry.
  • the object of the present invention is to overcome the defects of the prior art plating solution containing gold sulfite solution and the low hardness of the obtained gold product, and to provide a cyanide-free plating solution having high stability and the cyanide-free solution.
  • the application of the plating solution in the preparation of gold products can obtain a gold product with higher hardness by using the cyanide-free plating solution.
  • the cyanide-free plating solution provided by the present invention contains a gold sulfite solution, a phosphate, a hydrogen phosphate, an alkali metal sulfite, a hardener, and a complexing agent.
  • the present invention also provides the use of the cyanide-free plating solution in the preparation of a gold product.
  • the inventors of the present invention have found through intensive research that the combination of the above-mentioned substances contained in the cyanide-free plating solution can not only significantly improve the stability of the gold sulfite solution in the cyanide-free plating solution, but also the electroplating process. It is smooth, and it can also improve the hardness of gold products, which has great industrial application prospects.
  • the obtained gold product can be further improved. hardness.
  • Figure 1 is a specific preparation method of the gold product provided by the present invention.
  • the cyanide-free plating solution provided by the invention contains gold sulfite solution, phosphate, hydrogen phosphate, alkali metal sulfite, hardener and complexing agent.
  • the content of each component in the above cyanide-free plating solution is not particularly limited, for example, the content of the phosphate may be 100-200 g with respect to 10 g of the gold sulfite solution in terms of gold element.
  • the content of the hydrogen phosphate may be 50-200 g
  • the content of the alkali metal sulfite may be 30-120 g
  • the content of the hardener may be 0.01-2 g
  • the content of the complexing agent may be It is 0.01-5 grams.
  • the phosphate is present in an amount of from 150 to 200 grams, and the hydrogen phosphate is in an amount of from 80 to 120 grams, based on 10 grams of the gold sulfite solution in terms of gold, the alkali metal sulfite.
  • the content is 40-100 g, the hardener is 0.5-1.5 g, and the complexing agent is 2-5 g.
  • the cyanide-free plating solution also contains water.
  • the amount of the water to be used may be a conventional choice in the art as long as the plating process can be ensured smoothly, for example, the amount of water can be made based on 1 L of the cyanide-free plating solution, based on the gold element.
  • the content of the gold sulfite solution may be 8-20 g, preferably 9-12 g.
  • the gold sulfite solution may be a variety of existing sulfite ion-containing and gold ion-containing substances capable of electroplating to obtain a gold product, and specific examples thereof include, but are not limited to, gold potassium sulfite, Gold sulfite One or more of sodium and gold ammonium sulfite.
  • the gold sulfite solution is particularly preferably gold potassium sulfite and/or gold sodium sulfite.
  • the type of the phosphate, hydrogen phosphate, and alkali metal sulfite is not particularly limited in the present invention.
  • the phosphate can be potassium phosphate and/or sodium phosphate.
  • the hydrogen phosphate may be monohydrogen phosphate and/or dihydrogen phosphate, and particularly preferably one or more selected from the group consisting of potassium monohydrogen phosphate, potassium dihydrogen phosphate, sodium monohydrogen phosphate, and sodium dihydrogen phosphate.
  • the alkali metal sulfite salt may be potassium sulfite and/or sodium sulfite.
  • the hardener may be any of various existing materials capable of improving the hardness of the electroplated gold product, preferably a barium salt and/or a selenium salt, more preferably a mixture of a barium salt and a selenium salt, which contains both a barium salt and a selenium salt.
  • the hardener of the salt not only further stabilizes the gold sulfite solution, but also further increases the hardness of the gold product.
  • the weight ratio of the phosphonium salt to the selenium salt is particularly preferably from 0.25 to 1:1.
  • examples of the onium salt include, but are not limited to, one or more of sodium bismuth tartrate, potassium bismuth tartrate, sodium citrate, and potassium citrate.
  • examples of the selenium salt include, but are not limited to, one or more of sodium selenosulfate, potassium selenosulfate, sodium selenite, and potassium selenite.
  • the complexing agent may be any of various existing compounds capable of forming complex ions with gold ions, for example, one or more selected from the group consisting of sodium ethylenediaminetetraacetate, thiourea, and sodium thiosulfate.
  • the present invention also provides the use of the above cyanide-free plating solution in the preparation of a gold product.
  • a major improvement of the present invention is the use of a new cyanide-free plating solution, and the specific method of forming the gold article can be the same as in the prior art.
  • the method for preparing the gold product may include:
  • Electroplating is carried out in a cyanide-free plating solution containing a gold sulfite solution, a phosphate, a hydrogen phosphate, an alkali metal sulfite, a hardener, and a complexing agent.
  • the anode material may be a conventional choice in the art, for example, may be at least one of a niobium titanium composite material, a niobium titanium composite material, a platinum titanium composite material, or the like, wherein The anode material is generally in a cladding structure, and the core layer is titanium metal.
  • the surface of the core layer is a thin layer formed of at least one of metal tantalum, metal tantalum, metal tantalum, platinum, or the like. The thickness is usually 2.5-5 microns.
  • the anode may exist in various existing shapes, and is particularly preferably a mesh shape, such as a rhombic mesh, a circular mesh, a square mesh, etc., which can improve the penetrability of the cyanide-free plating solution, and is more favorable for electroplating.
  • the gold layer went smoothly.
  • the mandrel mainly functions as a molding die, thereby not only obtaining gold products of various shapes, but Moreover, the gold product obtained after the removal of the mandrel is a hollow structure, thereby being capable of significantly reducing the amount of gold required for producing a gold product of the same size, and reducing the production cost.
  • the "low melting point" means that the melting point is not higher than 200 ° C, preferably 60 to 130 ° C.
  • the low melting core mandrel may be made of tin-bismuth alloy and/or wax. Wherein, in the tin antimony alloy, the tin to rhenium weight ratio may be 0.5-1.5:1.
  • the material of the low melting mandrel is wax
  • the wax include, but are not limited to, one or more of beeswax, mineral wax (such as montan wax, ozokerite, paraffin), and petroleum wax.
  • beeswax such as montan wax, ozokerite, paraffin
  • petroleum wax such as mineral wax, ozokerite, paraffin
  • the size and shape of the mandrel can be reasonably selected according to the size and shape of the gold product to be obtained, and will not be described herein.
  • the tin-bismuth alloy is usually etched at a high temperature, gold is usually corroded. Therefore, before the gold layer is electroplated on the mandrel, it is preferred to first plate the first copper layer on the mandrel, and then in the The gold layer is electroplated on the first copper layer, and the first copper layer is removed after the mandrel is melted and discharged. Further, as an alternative, the mandrel may also be removed after plating the first copper layer and before plating the gold layer. When the mandrel is removed, vibration can be used to assist in the discharge of the low melting point material.
  • the plating conditions may generally include: the temperature of the plating solution is 40-60 ° C, the pH of the plating solution is 6-8, and the cathode The current density is 0.1-1 A/dm 2 and the plating time is 8-20 hours. Further, the gold layer formed may have a thickness of 50 to 150 ⁇ m, preferably 100 to 130 ⁇ m.
  • a method of controlling the pH of the plating solution within the above range is well known to those skilled in the art, and for example, an acidic substance or an alkaline substance may be added to the plating solution.
  • the acidic substance may be, for example, one or more of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and the like.
  • the alkaline substance may be, for example, one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, aqueous ammonia, and the like. The amount of the acidic substance and the alkaline substance used is adjusted to adjust the pH of the plating solution to the above range, and will not be described herein.
  • the method of preparing the hard gold further includes sequentially plating a second copper layer and a nickel layer on the gold layer before forming the hole, and removing the core shaft after melting and discharging
  • the second copper layer and the nickel layer can prevent the gold layer from "dissolving" and thus provide protection.
  • the method of forming the first copper layer generally comprises using the low melting point material (such as tin antimony alloy and/or wax) as a cathode and the phosphor bronze composite material as an anode. Electroplating is carried out in a copper-containing plating bath.
  • the method of forming the second copper layer generally comprises electroplating a copper-plated electrolyte as a cathode and a phosphor bronze composite as an anode.
  • the copper-containing plating solution used in the above two steps of plating the copper layer may be a conventional choice in the art, and will not be described herein.
  • the phosphor bronze composite material is composed of 99.94% by weight of copper and 0.06% by weight of phosphorus, and when it is used as an anode material, it may exist in a shape of a sheet, a column, a sphere or the like.
  • the plating conditions for forming the first copper layer may be the same as or different from the plating conditions for forming the second copper layer, and each independently includes: the temperature of the plating solution may be 15-35 ° C, and the pH of the plating solution may be 0.1-0.5, the cathode current density may be 0.5-5 A/dm 2 , and the plating time may be 30-60 minutes. Further, the first copper layer formed may have a thickness of 40 to 60 ⁇ m, preferably 45 to 55 ⁇ m; and the second copper layer formed may have a thickness of 40 to 60 ⁇ m, preferably 45 to 55 ⁇ m.
  • the first copper layer is preferably bright and smooth so that the subsequently obtained gold layer is also bright and smooth.
  • the method of forming the nickel layer generally comprises electroplating a nickel-plated electrolyte in an article in which a second copper layer is plated as a cathode and metal nickel as an anode.
  • the nickel-containing electrolyte may be a conventional choice in the art and will not be described herein.
  • the plating conditions for forming the nickel layer may generally include: the temperature of the plating solution is 35-50 ° C, the pH of the plating solution is 3.5-5, the cathode current density is 2-4 A/dm 2 , and the plating time is 10-20 minutes. .
  • the nickel layer formed may have a thickness of 5-20 microns, preferably 5-10 microns.
  • the metallic nickel as the anode material may exist in a shape of a sheet, a column, a sphere or the like.
  • the residual low melting point material and the first copper layer, the second copper layer and the nickel layer may be removed by various existing methods.
  • the obtained gold preform may be immersed after removing the mandrel.
  • dilute nitric acid solution The concentration of the dilute nitric acid solution may be, for example, 5 to 10 mol/L.
  • the method for preparing the hard gold comprises: rotating a mandrel 10 formed of a low melting point alloy in a silicone rubber mold 11, and then the mandrel 10 is placed in the drum to remove the thorns or any parting lines, and then the mandrel 10 is attached to the hanger 20 of the plating rack and cleaned in the electrolysis and/or ultrasonic cleaning fluid 12. If the melting point of the mandrel 10 is lower than the temperature of the plating solution forming the gold layer, it is necessary to form the first copper layer on the mandrel 10, that is, transfer the cleaned mandrel 10 into the copper plating solution 13 and perform electroplating.
  • a first copper layer is formed on the surface of the mandrel 10.
  • the first copper layer should be bright and smooth so that the subsequently formed gold layer is also bright and smooth.
  • the mandrel 10 (plated with the first copper layer or not plated with the first copper layer) is placed in a plating solution 14 containing gold sulfite solution for electroplating to form a gold layer, and then the obtained article is placed in copper plating. Electroplating is performed in the liquid 13 to form a second copper layer on the gold layer. After the formation of the second copper layer, the resultant article is placed in a nickel plating bath 15 for electroplating to form a nickel layer on the second copper layer.
  • the resulting article is removed from the jig 20 and more than two holes through the respective plating layers to the center of the mandrel 10 are drilled in place.
  • the article was then placed in a furnace to heat it to about 200 ° C, and the low melting mandrel 10 melted and flowed out of the holes.
  • the article after removing the low melting core mandrel 10 is immersed in a dilute nitric acid solution to remove the residual low melting point material and the first copper layer, the second copper layer and the nickel layer, leaving only the gold layer, thereby obtaining a gold product. .
  • each of the above electroplating steps can be carried out in a conventional manner.
  • the article including the mandrel 10 and the associated metal layer formed thereafter can be electrically connected to the cathode of the direct current power source through the hanger 20 and inserted into the corresponding plating solution.
  • the anode is connected to the positive terminal of the DC power supply and inserted into the corresponding plating solution.
  • the method for preparing the hard gold further comprises treating the gold product after removing the residual low melting point material and the first copper layer, the second copper layer and the nickel layer by welding, sandblasting and polishing to become a jewelry. Pieces.
  • the anode material used in the gold plating process is a rhomboid-like yttrium-titanium composite material composed of a metal titanium core layer and a metal ruthenium layer attached on the surface of the metal titanium core layer, and the metal titanium core layer is horizontally
  • the cross section is a rectangle of 1 mm ⁇ 0.5 mm, the average thickness of the metal ruthenium layer is 5 ⁇ m, and the side length of the diamond shape in the diamond-shaped yttrium-titanium composite material is 10 mm, and the acute angle between the side lengths is 60°;
  • the anode material is a cylindrical phosphor bronze composite material (made of 99.94% by weight of copper and 0.06% by weight of phosphorus mixed uniformly), and has a size of 25 mm (radius of the bottom circle) ⁇ 30 mm (column height);
  • the anode material is a cylindrical metallic nickel having a size of 25 mm (radius of the bottom circle) x
  • a copper sulfate plating solution is prepared, which consists of copper sulfate, sulfuric acid, ethanol and water, wherein the copper sulfate content is 125 g/L.
  • the sulfuric acid content is 25 ml/L, and the ethanol content is 50 ml/L; then the above copper sulfate plating solution (1000 mL) and the cyanide-free plating solution (1000 mL) are respectively placed in the plating tank a (the size is 120 mm (length) ⁇ 120 mm (width) ⁇ 100mm (high)) and plating bath b (having a size of 120mm (length) ⁇ 120mm (width) ⁇ 100mm (height)), the phosphor bronze sheet (mixed by 99.94% by weight of copper and 0.06% by weight of phosphorus uniformly) It has a density of 8.89g/cm 3 and a size of 80mm (length) ⁇ 60mm (width) ⁇ 3mm (thickness).
  • anode a It is placed in the plating tank a as an anode (referred to as anode a), and a diamond-shaped mesh of titanium Composite material (composed of a metal titanium core layer and a metal ruthenium layer attached to the surface of the metal titanium core layer, the average thickness of the metal ruthenium layer is 3 micrometers, and the diamond-shaped yttrium-titanium composite material has a side length of 10 mm, side length The angle between the acute angles is 60°) is placed in the plating bath b as the anode (referred to as the anode b), and the cathode test piece a (the material is pure copper sheet, the size Rinse after 25mm (length) ⁇ 25mm (width) ⁇ 0.3mm (thickness) and cathode test piece b (material is pure copper, size 25mm (length) ⁇ 25mm (width) ⁇ 0.3mm (thickness)) Weighing, then placing the cathode test piece a
  • ⁇ 0.165 ⁇ ⁇ Ma / ⁇ Mb ⁇ 100% ( ⁇ : cathode current efficiency, ⁇ Ma: increased weight of cathode test piece a, ⁇ Mb: increased weight of cathode test piece b), and cathode current efficiency higher than 90% indicates that cyanide-free plating High liquid stability, but lower 85% indicates that the cyanide-free plating solution has low stability.
  • This preparation example is for explaining the cyanide-free plating solution provided by the present invention and a preparation method thereof.
  • This preparation example is for explaining the cyanide-free plating solution provided by the present invention and a preparation method thereof.
  • This preparation example is for explaining the cyanide-free plating solution provided by the present invention and a preparation method thereof.
  • This preparation example is for explaining the cyanide-free plating solution provided by the present invention and a preparation method thereof.
  • a cyanide-free plating solution was prepared in accordance with the method of Preparation Example 1, except that the sodium bismuth tartrate was replaced with the same parts by weight of sodium selenite to obtain a cyanide-free plating solution Z4.
  • the stability of the cyanide-free plating solution Z4 and the cathode current efficiency were tested in accordance with the method of Preparation Example 1. The results show that the stability of the cyanide-free plating solution Z4 is high, and the cathode current efficiency is maintained above 90%.
  • This comparative preparation example is for explaining a reference cyanide-free plating solution and a preparation method thereof.
  • a cyanide-free plating solution was prepared in accordance with the method of Preparation Example 4, except that the potassium phosphate was replaced with the same weight portion of potassium monohydrogen phosphate to obtain a reference cyanide-free plating solution DZ1.
  • the stability and cathode current efficiency of the reference cyanide-free plating solution DZ1 were tested in accordance with the method of Preparation 1. The results show that the reference cyanide-free plating solution DZ1 has low stability and the cathode current density can only reach 80%.
  • This comparative preparation example is for explaining a reference cyanide-free plating solution and a preparation method thereof.
  • a cyanide-free plating solution was prepared in accordance with the method of Preparation Example 4, except that the potassium monohydrogen phosphate was replaced with the same weight portion of potassium phosphate to obtain a reference cyanide-free plating solution DZ2.
  • the stability and cathode current efficiency of the reference cyanide-free plating solution DZ2 were tested in accordance with the method of Preparation 1. The results show that the reference cyanide-free plating solution DZ2 has low stability and the cathode current density can only reach 80%.
  • This comparative preparation example is for explaining a reference cyanide-free plating solution and a preparation method thereof.
  • a cyanide-free plating solution was prepared according to the method of Comparative Preparation Example 1, except that the potassium monohydrogen phosphate was replaced with the same weight portion of gold sodium sulfite to obtain a reference cyanide-free plating solution DZ3.
  • the stability and cathode current efficiency of the reference cyanide-free plating solution DZ3 were tested in accordance with the method of Preparation 1. The results show that the reference cyanide-free plating solution DZ3 has low stability and the cathode current density can only reach 75%.
  • This example is intended to illustrate the preparation of the gold product provided by the present invention.
  • a mandrel 10 formed of a low melting point tin-bismuth alloy (a weight ratio of tin to bismuth of 52:48, the same hereinafter) is spin-cast in a silicone rubber mold 11, and the mandrel 10 is placed thereon.
  • the roller is used to remove the thorn or any parting line, and then the mandrel 10 is attached to the hanger 20 of the plating rack and cleaned in the ultrasonic cleaning solution 12.
  • the washed mandrel 10 is transferred to a copper plating liquid 13 (a mixture of 200 g/L of copper sulfate and 70 g/L of sulfuric acid, the same hereinafter), and electroplating is performed, wherein the plating conditions include the temperature of the copper plating solution 13 being At 25 ° C, the copper plating solution 13 had a pH of 0.1, a cathode current density of 4 A/dm 2 , and a plating time of 1 hour to form a first copper layer having a thickness of 50 ⁇ m.
  • a copper plating liquid 13 a mixture of 200 g/L of copper sulfate and 70 g/L of sulfuric acid, the same hereinafter
  • the plating conditions include the temperature of the copper plating solution 13 being At 25 ° C, the copper plating solution 13 had a pH of 0.1, a cathode current density of 4 A/dm 2 , and a plating time of 1 hour to form a first copper layer having a thickness
  • the mandrel 10 plated with the first copper layer is plated in the cyanide-free plating solution Z1 containing the gold sulfite solution, wherein the plating conditions include the temperature of the cyanide-free plating solution Z1 is 60 ° C, and the cyanide-free plating solution Z1
  • the pH was 8, the cathode current density was 0.8 A/dm 2 , and the plating time was 8 hours to form a gold layer having a thickness of 130 ⁇ m.
  • the article plated with the gold layer is placed in the copper plating solution 13 for electroplating, wherein the plating conditions include the temperature of the copper plating solution 13 being 25 ° C, the pH of the copper plating solution 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a second copper layer having a thickness of 50 ⁇ m was formed.
  • the plating conditions include the temperature of the copper plating solution 13 being 25 ° C, the pH of the copper plating solution 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a second copper layer having a thickness of 50 ⁇ m was formed.
  • the article plated with the second copper layer is plated in a nickel plating solution 15 (a mixture of 20 g/L of boric acid, 100 g/L of sodium sulfate, and 100 g/L of nickel sulfate, the same below), wherein plating
  • the conditions include a nickel plating liquid 15 having a temperature of 45 ° C, a nickel plating liquid 15 having a pH of 4, a cathode current density of 2 A/dm 2 , and a plating time of 20 minutes to form a nickel layer having a thickness of 10 ⁇ m.
  • the article was then placed in a furnace to heat it to about 200 ° C, and the low melting point core 10 melted and flowed out of the holes. Then, the workpiece after removing the low melting point core 10 is immersed in a dilute nitric acid solution to remove the residual low melting point material and the first copper layer, the second copper layer and the nickel layer, thereby obtaining a gold product retaining only the gold layer. . It is verified by Vickers hardness tester (purchased from Suzhou Yunuo Quality Inspection Instrument Co., Ltd., YN21125HR-150, the same below). The hardness of the gold product is 130Hv, and the gold purity is 99.96% verified by the fire test method. The surface is smooth and conforms to the product. standard requirement.
  • This example is intended to illustrate the preparation of the gold product provided by the present invention.
  • a mandrel 10 formed of a low melting point tin-bismuth alloy is spin-cast in a silicone rubber mold 11, and the mandrel 10 is placed in a drum to remove a thorn or any parting line, and then the mandrel is 10 is attached to the hanger 20 of the plating rack and cleaned in the ultrasonic cleaning solution 12.
  • the washed mandrel 10 is transferred to the copper plating liquid 13 and subjected to electroplating, wherein the plating conditions include the temperature of the copper plating liquid 13 being 25 ° C, the pH of the copper plating liquid 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a first copper layer having a thickness of 50 ⁇ m was formed.
  • the plating conditions include the temperature of the copper plating liquid 13 being 25 ° C, the pH of the copper plating liquid 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a first copper layer having a thickness of 50 ⁇ m was formed.
  • the mandrel 10 plated with the first copper layer is plated in the cyanide-free plating solution Z2 containing the gold sulfite solution, wherein the plating conditions include the temperature of the cyanide-free plating solution Z2 is 40 ° C, and the cyanide-free plating solution Z2
  • the pH was 6, the cathode current density was 0.2 A/dm 2 , and the plating time was 16 hours to form a gold layer having a thickness of 100 ⁇ m.
  • the article plated with the gold layer is placed in the copper plating solution 13 for electroplating, wherein the plating conditions include the temperature of the copper plating solution 13 being 25 ° C, the pH of the copper plating solution 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a second copper layer having a thickness of 50 ⁇ m was formed.
  • the plating conditions include the temperature of the copper plating solution 13 being 25 ° C, the pH of the copper plating solution 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a second copper layer having a thickness of 50 ⁇ m was formed.
  • the part plated with the second copper layer is placed in the nickel plating liquid 15 for electroplating, wherein the plating conditions include the temperature of the nickel plating solution 15 being 45 ° C, the pH of the nickel plating liquid 15 being 4, and the cathode current density being 2A/dm 2 , plating time was 20 minutes, and a nickel layer having a thickness of 10 ⁇ m was formed.
  • the resulting article is removed from the hanger 20 and more than two holes through the respective plating layers to the center of the mandrel 10 are drilled in place. The article was then placed in a furnace to heat it to about 200 ° C, and the low melting point core 10 melted and flowed out of the holes.
  • the workpiece after removing the low melting point core 10 is immersed in a dilute nitric acid solution to remove the residual low melting point material and the first copper layer, the second copper layer and the nickel layer, thereby obtaining a gold product retaining only the gold layer.
  • the hardness of the gold product is 135Hv, and the gold purity is 99.92% verified by the fire test method.
  • the surface is smooth and meets the product standard requirements.
  • This example is intended to illustrate the preparation of the gold product provided by the present invention.
  • a mandrel 10 formed of a low melting point tin-bismuth alloy is spin-cast in a silicone rubber mold 11, and the mandrel 10 is placed in a drum to remove a thorn or any parting line, and then the mandrel is 10 is attached to the hanger 20 of the plating rack and cleaned in the ultrasonic cleaning solution 12.
  • the washed mandrel 10 is transferred to the copper plating liquid 13 and subjected to electroplating, wherein the plating conditions include the temperature of the copper plating liquid 13 being 25 ° C, the pH of the copper plating liquid 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a first copper layer having a thickness of 50 ⁇ m was formed.
  • the plating conditions include the temperature of the copper plating liquid 13 being 25 ° C, the pH of the copper plating liquid 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a first copper layer having a thickness of 50 ⁇ m was formed.
  • the mandrel 10 plated with the first copper layer is plated in a cyanide-free plating solution Z3 containing gold sulfite solution, wherein the plating conditions include the temperature of the cyanide-free plating solution Z3 is 45 ° C, and the cyanide-free plating solution Z3
  • the pH was 7, the cathode current density was 0.3 A/dm 2 , and the plating time was 12 hours to form a gold layer having a thickness of 120 ⁇ m.
  • the article plated with the gold layer is placed in the copper plating solution 13 for electroplating, wherein the plating conditions include the temperature of the copper plating solution 13 being 25 ° C, the pH of the copper plating solution 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a second copper layer having a thickness of 50 ⁇ m was formed.
  • the plating conditions include the temperature of the copper plating solution 13 being 25 ° C, the pH of the copper plating solution 13 being 0.1, and the cathode current density being 4 A/ Dm 2 , plating time was 1 hour, and a second copper layer having a thickness of 50 ⁇ m was formed.
  • the part plated with the second copper layer is placed in the nickel plating liquid 15 for electroplating, wherein the plating conditions include the temperature of the nickel plating solution 15 being 45 ° C, the pH of the nickel plating liquid 15 being 4, and the cathode current density being 2A/dm 2 , plating time was 20 minutes, and a nickel layer having a thickness of 10 ⁇ m was formed.
  • the resulting article is removed from the hanger 20 and more than two holes through the respective plating layers to the center of the mandrel 10 are drilled in place. The article was then placed in a furnace to heat it to about 200 ° C, and the low melting point core 10 melted and flowed out of the holes.
  • the workpiece after removing the low melting point core 10 is immersed in a dilute nitric acid solution to remove the residual low melting point material and the first copper layer, the second copper layer and the nickel layer, thereby obtaining a gold product retaining only the gold layer.
  • a dilute nitric acid solution to remove the residual low melting point material and the first copper layer, the second copper layer and the nickel layer, thereby obtaining a gold product retaining only the gold layer.
  • the hardness of the gold product is 145Hv
  • the gold purity is 99.95% by the fire test method.
  • the surface is smooth and meets the product standard requirements.
  • This example is intended to illustrate the preparation of the gold product provided by the present invention.
  • Gold was electroplated according to the method of Example 1 and preparation of hard gold was performed, except that the cyanide-free plating was performed.
  • the liquid Z1 was replaced with a cyanide-free plating solution Z4 to obtain a gold product which only retained the gold layer.
  • the hardness of the gold product was 102Hv by the Vickers hardness tester, and the gold purity was 99.94% verified by the fire test method.
  • the surface was smooth and met the product standard requirements.
  • This example is intended to illustrate the preparation of the gold product provided by the present invention.
  • Gold was electroplated according to the method of Example 4 and hard gold was prepared, except that in the preparation process, the steps of forming the second copper layer and the nickel layer were not included, but the first copper layer and the gold layer were directly formed.
  • the subsequent part is perforated to remove the low melting point axis 10, and the part after removing the low melting point axis 10 is immersed in the dilute nitric acid solution to remove the residual low melting point material and the first copper layer, thereby obtaining only the retained gold.
  • Layer of gold products According to the Vickers hardness tester, the hardness of the gold product is 90Hv, and the gold purity is 99.92% verified by the fire test method. The surface is smooth and meets the product standard requirements.
  • This example is intended to illustrate the preparation of the gold product provided by the present invention.
  • Gold was electroplated according to the method of Example 3 and hard gold was prepared, except that, in forming the mandrel 10, the low melting tin antimony alloy was replaced by the same volume of paraffin to obtain a gold product.
  • the hardness of the gold product was 142Hv by the Vickers hardness tester, and the gold purity was 99.93% verified by the fire test method. The surface was smooth and met the product standard requirements.
  • This comparative example is used to illustrate the preparation of the reference gold product.
  • Gold was electroplated according to the method of Example 1 and hard gold was prepared, except that the cyanide-free plating solution Z1 was replaced with a reference cyanide-free plating solution DZ1. According to the Vickers hardness tester, the hardness of the gold product obtained by this method is only 90Hv, and the gold purity is 98.97% verified by the fire test method. The surface is not smooth and fails to meet the product standard requirements.
  • This comparative example is used to illustrate the preparation of the reference gold product.
  • Gold was electroplated according to the method of Example 1 and hard gold was prepared, except that the cyanide-free plating solution Z1 was replaced with a reference cyanide-free plating solution DZ2. According to the Vickers hardness tester, the hardness of the gold product obtained by this method is only 70Hv, and the gold purity is 98.51% by the fire test method. The surface is not smooth and fails to meet the product standard requirements.
  • This comparative example is used to illustrate the preparation of the reference gold product.
  • Gold was electroplated according to the method of Example 1 and hard gold was prepared, except that the cyanide-free plating solution Z1 was replaced with a reference cyanide-free plating solution DZ3. According to the Vickers hardness tester, the hardness of the gold product obtained by this method is only 70Hv, and the gold purity is 98.45% by the fire test method. The surface is rough and fails to meet the product standard requirements.
  • the gold sulfite solution in the cyanide-free plating solution for forming a gold layer provided by the present invention has good stability, and the gold product obtained from the cyanide-free plating solution has high hardness and is highly industrially applicable. prospect.

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Abstract

本发明提供了一种无氰电镀液及其应用。所述无氰电镀液含有亚硫酸金液、磷酸盐、磷酸氢盐、亚硫酸碱金属盐、硬化剂和络合剂。采用本发明提供的形成金层的无氰电镀液中亚硫酸金液的稳定性很好，由该无氰电镀液得到的黄金制品具有很高的硬度，极具工业应用前景。

Description

一种无氰电镀液及其应用 技术领域
本发明涉及一种无氰电镀液及其应用。
背景技术
随着人们生活水平的日益提高，黄金制品越来越受到广大消费者的青睐。目前，用电镀的方式生产的黄金制品越来越多。其中，电镀过程中所用的电镀液主要为含有氰化金钾的溶液。然而，氰化金钾属于剧毒物质，不仅在黄金制品的生产过程中会对制造者的身体健康造成危害，而且为了降低生产废液对环境的污染，还需要花费大量的费用以处理生产废液。
为了克服含有氰化金钾电镀液的上述缺陷，近年来，也有部分企业采用含有亚硫酸金液(亚硫酸金钾和/或亚硫酸金钠)的溶液替代含有氰化金钾的溶液作为电镀液，以制备黄金制品。然而，由于亚硫酸金钾和亚硫酸金钠的稳定性较差，在电镀过程中极易析出，从而影响了电镀过程的稳定性以及黄金制品的性能。此外，以亚硫酸金钾和/或亚硫酸金钠作为电镀液得到的黄金制品的硬度较低，这样会使得制成纯度较高的黄金制品特别是千足金时，容易发生变形、凹陷，在使用过程中极易损坏，因而，如何提高含有亚硫酸金液的电镀液的稳定性并获得硬度较高的电镀黄金是目前黄金工工艺亟需解决的技术问题。
发明内容
本发明的目的是为了克服现有的含有亚硫酸金液的电镀液稳定性差并且获得的黄金制品硬度较低的缺陷，而提供一种具有较高稳定性的无氰电镀液以及所述无氰电镀液在制备黄金制品中的应用，采用该无氰电镀液能够得到硬度较高的黄金制品。
具体地，本发明提供的无氰电镀液含有亚硫酸金液、磷酸盐、磷酸氢盐、亚硫酸碱金属盐、硬化剂和络合剂。
此外，本发明还提供了所述无氰电镀液在制备黄金制品中的应用。
本发明的发明人通过深入研究发现，将所述无氰电镀液中所含的上述几种物质配合使用，不仅能够显著提高所述无氰电镀液中亚硫酸金液的稳定性，使得电镀过程平稳进行，而且还能够提高黄金制品的硬度，极具工业应用前景。
根据本发明的一种优选实施方式，当所述硬化剂为锑盐和硒盐的混合物，且所述锑盐与硒盐的重量比为0.25-1∶1时，能够进一步提高所得黄金制品的硬度。
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：
图1为本发明提供的黄金制品的一种具体制备方法。
附图标记说明
10-芯轴；11-硅橡胶模具；12-清洗液；13-镀铜液；14-电镀液；15-镀镍液；20-挂具。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
本发明提供的无氰电镀液含有亚硫酸金液、磷酸盐、磷酸氢盐、亚硫酸碱金属盐、硬化剂和络合剂。
本发明对上述无氰电镀液中各组分的含量没有特别地限定，例如，相对于10g以金元素计的所述亚硫酸金液，所述磷酸盐的含量可以为100-200克，所述磷酸氢盐的含量可以为50-200克，所述亚硫酸碱金属盐的含量可以为30-120克，所述硬化剂的含量可以为0.01-2克，所述络合剂的含量可以为0.01-5克。优选地，相对于10g以金元素计的所述亚硫酸金液，所述磷酸盐的含量为150-200克，所述磷酸氢盐的含量为80-120克，所述亚硫酸碱金属盐的含量为40-100克，所述硬化剂的含量为0.5-1.5克，所述络合剂的含量为2-5克。
通常来说，所述无氰电镀液还含有水。所述水的用量可以为本领域的常规选择，只要能够确保电镀过程顺利进行即可，例如，所述水的用量可以使得以1L的所述无氰电镀液为基准，以金元素计的所述亚硫酸金液的含量可以为8-20g，优选为9-12g。
根据本发明，所述亚硫酸金液可以为现有的各种无氰且能够电镀得到黄金制品的含有亚硫酸根离子和金离子的物质，其具体实例包括但不限于：亚硫酸金钾、亚硫酸金 钠和亚硫酸金铵中的一种或多种。然而，由于所述亚硫酸金铵在电镀过程中会产生有毒的氨气，因此，所述亚硫酸金液特别优选为亚硫酸金钾和/或亚硫酸金钠。
本发明对所述磷酸盐、磷酸氢盐和亚硫酸碱金属盐的种类没有特别地限定。例如，所述磷酸盐可以为磷酸钾和/或磷酸钠。所述磷酸氢盐可以为磷酸一氢盐和/或磷酸二氢盐，具体优选选自磷酸一氢钾、磷酸二氢钾、磷酸一氢钠和磷酸二氢钠中的一种或多种。所述亚硫酸碱金属盐可以为亚硫酸钾和/或亚硫酸钠。
所述硬化剂可以为现有的各种能够提高电镀黄金制品硬度的物质，优选为锑盐和/或硒盐，更优选为锑盐和硒盐的混合物，采用这种同时含有锑盐和硒盐的硬化剂不仅能够进一步稳定亚硫酸金液，而且还能够进一步提高黄金制品的硬度。当所述硬化剂为锑盐和硒盐的混合物时，所述锑盐与硒盐的重量比特别优选为0.25-1∶1。此外，所述锑盐的实例包括但不限于：酒石酸锑钠、酒石酸锑钾、锑酸钠和锑酸钾中的一种或多种。所述硒盐的实例包括但不限于：硒代硫酸钠、硒代硫酸钾、亚硒酸钠和亚硒酸钾中的一种或多种。
所述络合剂可以为现有的各种能够与金离子形成络合离子的化合物，例如，可以选自乙二胺四乙酸钠、硫脲和硫代硫酸钠中的一种或多种。
此外，本发明还提供了上述无氰电镀液在制备黄金制品中的应用。
本发明的主要改进之处在于采用了一种新的无氰电镀液，而形成所述黄金制品的具体方法可以与现有技术相同。
具体地，所述黄金制品的制备方法可以包括：
在由低熔点材料形成的芯轴上电镀金层；
形成穿过电镀层到达所述芯轴的孔，并将所述芯轴熔化以通过所述孔排出，其中，在所述芯轴上电镀金层的方法包括以所述芯轴为阴极，在含有亚硫酸金液、磷酸盐、磷酸氢盐、亚硫酸碱金属盐、硬化剂和络合剂的无氰电镀液中进行电镀。在所述芯轴上电镀金层的过程中，阳极材料可以为本领域的常规选择，例如，可以为铱钛复合材料、钌铱钛复合材料、铂金钛复合材料等中的至少一种，其中，上述阳极材料一般呈包覆结构，芯层为金属钛，附着在芯层表面的为由金属铱、金属钌和金属铱、铂金等中的至少一种形成的薄层，所述薄层的厚度通常为2.5-5微米。此外，阳极可以以现有的各种形状存在，特别优选为网状，例如菱形网状、圆形网状、方形网状等，这样可以提高无氰电镀液的穿透性，更有利于电镀金层的顺利进行。
所述芯轴主要起到成型模具的作用，从而不仅能够得到各种形状的黄金制品，而 且在将所述芯轴去除之后得到的黄金制品为中空结构，从而能够显著降低生产同一大小的黄金制品时所需的黄金用量，降低了生产成本。在本发明中，所述“低熔点”是指熔点不高于200℃，优选为60-130℃。所述低熔点的芯轴的材质可以为锡铋合金和/或蜡。其中，在所述锡铋合金中，所述锡与铋的重量比可以为0.5-1.5∶1。当所述低熔点的芯轴的材质为蜡时，通常需要在蜡的表面上涂布导电油。所述蜡的实例包括但不限于：蜂蜡、矿物蜡(如褐煤蜡、地蜡、石蜡)和石油蜡等中的一种或多种。所述芯轴的大小和形状可以根据需要获得的黄金制品的大小和形状进行合理选择，在此不作赘述。
此外，由于所述锡铋合金在高温熔出时，通常会腐蚀黄金，因此，在所述芯轴上电镀金层之前，优选先在所述芯轴上电镀第一铜层，然后再在所述第一铜层上电镀所述金层，并且在将所述芯轴熔化并排出之后去除所述第一铜层。此外，作为另一种可选的方式，所述芯轴也可以在电镀第一铜层之后、电镀金层之前去除。去除所述芯轴时，可以采用振动辅助所述低熔点材料的排出。
根据本发明，在所述芯轴或第一铜层上电镀金层时，所述电镀的条件通常可以包括：电镀液的温度为40-60℃，电镀液的pH值为6-8，阴极电流密度为0.1-1A/dm2，电镀时间为8-20小时。此外，形成的所述金层的厚度可以为50-150μm，优选为100-130μm。将所述电镀液的pH值控制在上述范围内的方法为本领域技术人员公知，例如，可以往所述电镀液中加入酸性物质或者碱性物质。所述酸性物质例如可以为硫酸、盐酸、磷酸、硝酸等中的一种或多种。所述碱性物质例如可以为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、氨水等中的一种或多种。上述酸性物质和碱性物质的用量以将所述电镀液的pH值调节至上述范围内为准，在此不作赘述。
根据本发明，所述硬质黄金的制备方法还包括在形成所述孔之前，先在所述金层上依次电镀第二铜层和镍层，并且在将所述芯轴熔化并排出之后去除所述第二铜层和镍层，这样能够防止金层“溶解”，从而起到保护作用。在所述硬质黄金的具体制备过程中，形成所述第一铜层的方法通常包括将所述低熔点材料(如锡铋合金和/或蜡)作为阴极，将磷铜复合材料作为阳极，在含铜电镀液中进行电镀。形成所述第二铜层的方法通常包括将电镀有金层的制品作为阴极，将磷铜复合材料作为阳极，在含铜电解液中进行电镀。上述两次电镀铜层的过程中所采用的含铜电镀液可以为本领域的常规选择，在此不作赘述。其中，所述磷铜复合材料由99.94重量％的铜和0.06重量％的磷组成，将其用作阳极材料使用时，其可以以片状、柱状、球状等形状存在。
形成所述第一铜层的电镀条件可以与形成所述第二铜层的电镀条件相同或不同， 并各自独立地包括：电镀液的温度可以为15-35℃，电镀液的pH值可以为0.1-0.5，阴极电流密度可以为0.5-5A/dm2，电镀时间可以为30-60分钟。此外，形成的所述第一铜层的厚度可以为40-60微米，优选为45-55微米；形成的所述第二铜层的厚度可以为40-60微米，优选为45-55微米。所述第一铜层优选是明亮且光滑的，这样能够使后续得到的金层也是明亮且光滑的。
根据本发明，形成所述镍层的方法通常包括将电镀有第二铜层的制品作为阴极，将金属镍作为阳极，在含镍电解液中进行电镀。所述含镍电解液可以为本领域的常规选择，在此不作赘述。形成所述镍层的电镀条件通常可以包括：电镀液的温度为35-50℃，电镀液的pH值为3.5-5，阴极电流密度为2-4A/dm2，电镀时间为10-20分钟。形成的所述镍层的厚度可以为5-20微米，优选为5-10微米。此外，作为阳极材料的金属镍可以以片状、柱状、球状等形状存在。
此外，可以采用现有的各种方法去除残留的低熔点材料以及第一铜层、第二铜层和镍层，例如，可以在将所述芯轴去除之后，将获得的黄金预制件浸泡在稀硝酸溶液中。所述稀硝酸溶液的浓度例如可以为5-10mol/L。
根据本发明的一种具体实施方式，如图1所示，所述硬质黄金的制备方法包括：在硅橡胶模具11中旋转铸造由低熔点合金形成的芯轴10，再将所述芯轴10放置在滚筒中以去除刺或任何分型线，然后将芯轴10连接到电镀架的挂具20上，并在电解和/或超声波清洗液12中清洗。如果芯轴10的熔点低于形成金层的电镀液的温度，则需要在芯轴10上形成第一铜层，即，将洗净的芯轴10转移到镀铜液13中并进行电镀，以在芯轴10的表面上形成第一铜层。所述第一铜层应当是明亮且光滑的，从而使后续形成的金层也是明亮且光滑的。将(电镀有第一铜层或未电镀有第一铜层的)芯轴10置于含有亚硫酸金液的电镀液14中进行电镀，形成金层，接着将得到的制件置于镀铜液13中进行电镀，以在金层上形成第二铜层。在形成第二铜层之后，将得到的制件置于镀镍液15中进行电镀，以在第二铜层上形成镍层。完成电镀之后，将得到的制件从夹具20中移去，并在合适的位置钻两个以上的穿过各个电镀层达到芯轴10中心的孔。然后将制件放入炉中以将其加热到约200℃，低熔点的芯轴10熔化并从孔流出。接着再将去除低熔点的芯轴10之后的制件浸泡在稀硝酸溶液中以去除残留的低熔点材料以及第一铜层、第二铜层和镍层，仅保留金层，从而得到黄金制品。
上述每个电镀步骤均可以通过传统方式实施，例如，可以将包括所述芯轴10和之后形成的关联金属层的制件通过挂具20电连接到直流电源的阴极并插入相应的电镀液 中，而阳极则连接到直流电源的正极端并插入相应的电镀液中。
此外，所述硬质黄金的制备方法还包括将去除残留的低熔点材料以及第一铜层、第二铜层和镍层之后的黄金制品采用焊接、喷砂和抛光等方式处理以变成珠宝件。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中：
在黄金制品的制备过程中，镀金过程所用的阳极材料为菱形网状的铱钛复合材料，其由金属钛芯层以及在金属钛芯层表面附着的金属铱层组成，金属钛芯层的横截面为1mm×0.5mm的长方形，金属铱层的平均厚度为5微米，菱形网状的铱钛复合材料中菱形的边长为10mm，边长间的锐角夹角为60°；镀铜过程所用的阳极材料为圆柱状的磷铜复合材料(由99.94重量％的铜和0.06重量％的磷混合均匀制成)，尺寸为25mm(底圆半径)×30mm(柱高)；镀镍过程所用的阳极材料为圆柱状的金属镍，尺寸为25mm(底圆半径)×30mm(柱高)。
无氰电镀液的稳定性和阴极电流效率采用阴极电流效率法进行测试，具体如下：配制硫酸铜电镀液，其由硫酸铜、硫酸、乙醇和水组成，其中，硫酸铜含量为125g/L，硫酸含量为25ml/L，乙醇含量为50ml/L；然后将上述硫酸铜电镀液(1000mL)和无氰电镀液(1000mL)分别置于电镀槽a(尺寸为120mm(长)×120mm(宽)×100mm(高))和电镀槽b(尺寸为120mm(长)×120mm(宽)×100mm(高))中，将磷铜片(由99.94重量％的铜和0.06重量％的磷混合均匀压制而成，密度为8.89g/cm3，尺寸为80mm(长)×60mm(宽)×3mm(厚))置于电镀槽a中作为阳极(记为阳极a)，将菱形网状的铱钛复合材料(由金属钛芯层以及在金属钛芯层表面附着的金属铱层组成，金属铱层的平均厚度为3微米，菱形网状的铱钛复合材料中菱形的边长为10mm，边长间的锐角夹角为60°)置于电镀槽b中作为阳极(记为阳极b)，将阴极试片a(材料为纯铜片，尺寸为25mm(长)×25mm(宽)×0.3mm(厚))和阴极试片b(材料为纯铜片，尺寸为25mm(长)×25mm(宽)×0.3mm(厚))冲洗干净后称重，随后将阴极试片a置于电镀槽a中，将阴极试片b置于电镀槽b中，接着将阳极a通过导线与电源正极连接在一起，将阴极试片a通过导线与阳极b连接在一起，将阴极试片b通过导线与电源负极连接在一起，然后通电，在恒流0.03A的电流下电镀10min，电镀完成后取出阴极试片a和阴极试片b，洗净烘干称重，按照以下公式计算阴极电流效率：
η＝0.165×ΔMa/ΔMb×100％(η：阴极电流效率，ΔMa：阴极试片a增加的重量，ΔMb：阴极试片b增加的重量)，阴极电流效率高于90％则表明无氰电镀液稳定性高，而低于 85％则表明无氰电镀液稳定性低。
制备例1
该制备例用于说明本发明提供的无氰电镀液及其制备方法。
在60℃下，将以金元素计用量为10克的亚硫酸金钠、200克磷酸钾、100克磷酸一氢钾、50克亚硫酸钠、0.5克酒石酸锑钠、0.5克亚硒酸钠和5克乙二胺四乙酸钠溶解在1L水中，得到无氰电镀液Z1。通过阴极电流效率法测定无氰电镀液Z1的稳定性和阴极电流效率。结果表明，无氰电镀液Z1的稳定性高，阴极电流效率维持在90％以上。
制备例2
该制备例用于说明本发明提供的无氰电镀液及其制备方法。
在40℃下，将以金元素计用量为10克的亚硫酸金钾、180克磷酸钠、80克磷酸一氢钠、40克亚硫酸钾、0.2克酒石酸锑钾、0.3克硒代硫酸钠和2克硫脲溶解在1L水中，得到无氰电镀液Z2。按照制备例1的方法对无氰电镀液Z2的稳定性和阴极电流效率进行测试。结果表明，无氰电镀液Z2的稳定性高，阴极电流效率维持在90％以上。
制备例3
该制备例用于说明本发明提供的无氰电镀液及其制备方法。
在45℃下，将以金元素计用量为10克的亚硫酸金钠、150克磷酸钾、120克磷酸二氢钾、100克亚硫酸钠、0.5克锑酸钠、1克亚硒酸钾和5克硫代硫酸钠溶解在1L水中，得到无氰电镀液Z3。按照制备例1的方法对无氰电镀液Z3的稳定性和阴极电流效率进行测试。结果表明，无氰电镀液Z3稳定性非常高，阴极电流效率维持在90％以上。
制备例4
该制备例用于说明本发明提供的无氰电镀液及其制备方法。
按照制备例1的方法制备无氰电镀液，不同的是，所述酒石酸锑钠用相同重量份的亚硒酸钠替代，得到无氰电镀液Z4。按照制备例1的方法对无氰电镀液Z4的稳定性和阴极电流效率进行测试。结果表明，无氰电镀液Z4的稳定性高，阴极电流效率维持在90％以上。
对比制备例1
该对比制备例用于说明参比的无氰电镀液及其制备方法。
按照制备例4的方法制备无氰电镀液，不同的是，所述磷酸钾用相同重量份的磷酸一氢钾替代，得到参比无氰电镀液DZ1。按照制备例1的方法对参比无氰电镀液DZ1的稳定性和阴极电流效率进行测试。结果表明，参比无氰电镀液DZ1的稳定性低，阴极电流密度仅能达到80％。
对比制备例2
该对比制备例用于说明参比的无氰电镀液及其制备方法。
按照制备例4的方法制备无氰电镀液，不同的是，所述磷酸一氢钾用相同重量份的磷酸钾替代，得到参比无氰电镀液DZ2。按照制备例1的方法对参比无氰电镀液DZ2的稳定性和阴极电流效率进行测试。结果表明，参比无氰电镀液DZ2的稳定性低，阴极电流密度仅能达到80％。
对比制备例3
该对比制备例用于说明参比的无氰电镀液及其制备方法。
按照对比制备例1的方法制备无氰电镀液，不同的是，所述磷酸一氢钾用相同重量份的亚硫酸金钠替代，得到参比无氰电镀液DZ3。按照制备例1的方法对参比无氰电镀液DZ3的稳定性和阴极电流效率进行测试。结果表明，参比无氰电镀液DZ3的稳定性低，阴极电流密度仅能达到75％。
实施例1
该实施例用于说明本发明提供的黄金制品的制备方法。
如图1所示，在硅橡胶模具11中旋转铸造由低熔点锡铋合金(锡与铋的重量比为52∶48，下同)形成的芯轴10，再将所述芯轴10放置在滚筒中以去除刺或任何分型线，然后将芯轴10连接到电镀架的挂具20上，并在超声波清洗液12中清洗。然后将洗净的芯轴10转移到镀铜液13(200g/L的硫酸铜和70g/L的硫酸的混合物，下同)中并进行电镀，其中，电镀条件包括镀铜液13的温度为25℃，镀铜液13的pH值为0.1，阴极电流密度为4A/dm2，电镀时间为1小时，形成厚度为50微米的第一铜层。然后将电镀有第一铜层的芯轴10置于含有亚硫酸金液的无氰电镀液Z1中进行电镀，其中，电镀 条件包括无氰电镀液Z1的温度为60℃，无氰电镀液Z1的pH值为8，阴极电流密度为0.8A/dm2，电镀时间为8小时，形成厚度为130微米的金层。接着将电镀有金层的制件置于镀铜液13中进行电镀，其中，电镀条件包括镀铜液13的温度为25℃，镀铜液13的pH值为0.1，阴极电流密度为4A/dm2，电镀时间为1小时，形成厚度为50微米的第二铜层。然后将电镀有第二铜层的制件置于镀镍液15(20g/L的硼酸、100g/L的硫酸钠和100g/L的硫酸镍的混合物，下同)中进行电镀，其中，电镀条件包括镀镍液15的温度为45℃，镀镍液15的pH值为4，阴极电流密度为2A/dm2，电镀时间为20分钟，形成厚度为10微米的镍层。完成电镀之后，将得到的制件从挂具20中移去，并在合适的位置钻两个以上的穿过各个电镀层达到芯轴10中心的孔。然后将制件放入炉中以将其加热到约200℃，低熔点的轴心10熔化并从孔流出。接着再将去除低熔点的轴心10之后的制件浸泡在稀硝酸溶液中以去除残留的低熔点材料以及第一铜层、第二铜层和镍层，从而得到仅保留金层的黄金制品。经维氏硬度计(购自苏州宇诺质检仪器有限公司，YN21125HR-150，下同)检定，该黄金制品的硬度为130Hv，金纯度经火试法检定为99.96％，表面光滑，符合产品标准要求。
实施例2
该实施例用于说明本发明提供的黄金制品的制备方法。
如图1所示，在硅橡胶模具11中旋转铸造由低熔点锡铋合金形成的芯轴10，再将所述芯轴10放置在滚筒中以去除刺或任何分型线，然后将芯轴10连接到电镀架的挂具20上，并在超声波清洗液12中清洗。然后将洗净的芯轴10转移到镀铜液13中并进行电镀，其中，电镀条件包括镀铜液13的温度为25℃，镀铜液13的pH值为0.1，阴极电流密度为4A/dm2，电镀时间为1小时，形成厚度为50微米的第一铜层。然后将电镀有第一铜层的芯轴10置于含有亚硫酸金液的无氰电镀液Z2中进行电镀，其中，电镀条件包括无氰电镀液Z2的温度为40℃，无氰电镀液Z2的pH值为6，阴极电流密度为0.2A/dm2，电镀时间为16小时，形成厚度为100微米的金层。接着将电镀有金层的制件置于镀铜液13中进行电镀，其中，电镀条件包括镀铜液13的温度为25℃，镀铜液13的pH值为0.1，阴极电流密度为4A/dm2，电镀时间为1小时，形成厚度为50微米的第二铜层。然后将电镀有第二铜层的制件置于镀镍液15中进行电镀，其中，电镀条件包括镀镍液15的温度为45℃，镀镍液15的pH值为4，阴极电流密度为2A/dm2，电镀时间为20分钟，形成厚度为10微米的镍层。完成电镀之后，将得到的制件从挂具20 中移去，并在合适的位置钻两个以上的穿过各个电镀层达到芯轴10中心的孔。然后将制件放入炉中以将其加热到约200℃，低熔点的轴心10熔化并从孔流出。接着再将去除低熔点的轴心10之后的制件浸泡在稀硝酸溶液中以去除残留的低熔点材料以及第一铜层、第二铜层和镍层，从而得到仅保留金层的黄金制品。经维氏硬度计验定，该黄金制品的硬度为135Hv，金纯度经火试法检定为99.92％，表面光滑，符合产品标准要求。
实施例3
该实施例用于说明本发明提供的黄金制品的制备方法。
如图1所示，在硅橡胶模具11中旋转铸造由低熔点锡铋合金形成的芯轴10，再将所述芯轴10放置在滚筒中以去除刺或任何分型线，然后将芯轴10连接到电镀架的挂具20上，并在超声波清洗液12中清洗。然后将洗净的芯轴10转移到镀铜液13中并进行电镀，其中，电镀条件包括镀铜液13的温度为25℃，镀铜液13的pH值为0.1，阴极电流密度为4A/dm2，电镀时间为1小时，形成厚度为50微米的第一铜层。然后将电镀有第一铜层的芯轴10置于含有亚硫酸金液的无氰电镀液Z3中进行电镀，其中，电镀条件包括无氰电镀液Z3的温度为45℃，无氰电镀液Z3的pH值为7，阴极电流密度为0.3A/dm2，电镀时间为12小时，形成厚度为120微米的金层。接着将电镀有金层的制件置于镀铜液13中进行电镀，其中，电镀条件包括镀铜液13的温度为25℃，镀铜液13的pH值为0.1，阴极电流密度为4A/dm2，电镀时间为1小时，形成厚度为50微米的第二铜层。然后将电镀有第二铜层的制件置于镀镍液15中进行电镀，其中，电镀条件包括镀镍液15的温度为45℃，镀镍液15的pH值为4，阴极电流密度为2A/dm2，电镀时间为20分钟，形成厚度为10微米的镍层。完成电镀之后，将得到的制件从挂具20中移去，并在合适的位置钻两个以上的穿过各个电镀层达到芯轴10中心的孔。然后将制件放入炉中以将其加热到约200℃，低熔点的轴心10熔化并从孔流出。接着再将去除低熔点的轴心10之后的制件浸泡在稀硝酸溶液中以去除残留的低熔点材料以及第一铜层、第二铜层和镍层，从而得到仅保留金层的黄金制品。经维氏硬度计验定，该黄金制品的硬度为145Hv，金纯度经火试法检定为99.95％，表面光滑，符合产品标准要求。
实施例4
该实施例用于说明本发明提供的黄金制品的制备方法。
按照实施例1的方法电镀黄金并进行硬质黄金的制备，不同的是，所述无氰电镀 液Z1用无氰电镀液Z4替代，得到仅保留金层的黄金制品。经维氏硬度计检定，该黄金制品的硬度为102Hv，金纯度经火试法检定为99.94％，表面光滑，符合产品标准要求。
实施例5
该实施例用于说明本发明提供的黄金制品的制备方法。
按照实施例4的方法电镀黄金并进行硬质黄金的制备，不同的是，在制备过程中，不包括形成第二铜层和镍层的步骤，而是直接将形成第一铜层和金层后的制件穿孔以去除低熔点轴心10，并将去除低熔点的轴心10之后的制件浸泡在稀硝酸溶液中以去除残留的低熔点材料以及第一铜层，从而得到仅保留金层的黄金制品。经维氏硬度计检定，该黄金制品的硬度为90Hv，金纯度经火试法检定为99.92％，表面光滑，符合产品标准要求。
实施例6
该实施例用于说明本发明提供的黄金制品的制备方法。
按照实施例3的方法电镀黄金并进行硬质黄金的制备，不同的是，在形成芯轴10时，低熔点锡铋合金由相同体积的石蜡替代，得到黄金制品。经维氏硬度计检定，该黄金制品的硬度为142Hv，金纯度经火试法检定为99.93％，表面光滑，符合产品标准要求。
对比例1
该对比例用于说明参比的黄金制品的制备方法。
按照实施例1的方法电镀黄金并进行硬质黄金的制备，不同的是，所述无氰电镀液Z1用参比无氰电镀液DZ1替代。经维氏硬度计验定，采用该方法得到的黄金制品的硬度仅为90Hv，金纯度经火试法检定为98.97％，表面不光滑，未能符合产品标准要求。
对比例2
该对比例用于说明参比的黄金制品的制备方法。
按照实施例1的方法电镀黄金并进行硬质黄金的制备，不同的是，所述无氰电镀液Z1用参比无氰电镀液DZ2替代。经维氏硬度计验定，采用该方法得到的黄金制品的硬度仅为70Hv，金纯度经火试法检定为98.51％，表面不光滑，未能符合产品标准要求。
对比例3
该对比例用于说明参比的黄金制品的制备方法。
按照实施例1的方法电镀黄金并进行硬质黄金的制备，不同的是，所述无氰电镀液Z1用参比无氰电镀液DZ3替代。经维氏硬度计验定，采用该方法得到的黄金制品的硬度仅为70Hv，金纯度经火试法检定为98.45％，表面粗糙，未能符合产品标准要求。
从以上结果可以看出，本发明提供的形成金层的无氰电镀液中亚硫酸金液的稳定性很好，由该无氰电镀液得到的黄金制品具有很高的硬度，极具工业应用前景。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (10)

  1. 一种无氰电镀液，其特征在于，所述无氰电镀液含有亚硫酸金液、磷酸盐、磷酸氢盐、亚硫酸碱金属盐、硬化剂和络合剂。
  2. 根据权利要求1所述的无氰电镀液，其中，在所述无氰电镀液中，相对于10g以金元素计的所述亚硫酸金液，所述磷酸盐的含量为100-200克，所述磷酸氢盐的含量为50-200克，所述亚硫酸碱金属盐的含量为30-120克，所述硬化剂的含量为0.01-2克，所述络合剂的含量为0.01-5克。
  3. 根据前述权利要求中任意一项所述的无氰电镀液，其中，所述无氰电镀液还含有水，且以1L的所述无氰电镀液为基准，以金元素计的所述亚硫酸金液的含量为8-20g。
  4. 根据前述权利要求中任意一项所述的无氰电镀液，其中，所述亚硫酸金液为亚硫酸金钾/亚硫酸金钠。
  5. 根据前述权利要求中任意一项所述的无氰电镀液，其中，所述磷酸盐为磷酸钾和/或磷酸钠；所述磷酸氢盐选自磷酸一氢钾、磷酸二氢钾、磷酸一氢钠和磷酸二氢钠中的一种或多种；所述亚硫酸碱金属盐为亚硫酸钾和/或亚硫酸钠。
  6. 根据前述权利要求中任意一项所述的无氰电镀液，其中，所述硬化剂为锑盐和/或硒盐。
  7. 根据权利要求6所述的无氰电镀液，其中，所述硬化剂为锑盐和硒盐的混合物，且所述锑盐与硒盐的重量比为0.25-1∶1。
  8. 根据权利要求6所述的无氰电镀液，其中，所述锑盐选自酒石酸锑钠、酒石酸锑钾、锑酸钠和锑酸钾中的一种或多种；所述硒盐选自硒代硫酸钠、硒代硫酸钾、亚硒酸钠和亚硒酸钾中的一种或多种。
  9. 根据前述权利要求中任意一项所述的无氰电镀液，其中，所述络合剂选自乙二 胺四乙酸钠、硫脲和硫代硫酸钠中的一种或多种。
  10. 权利要求1-9中任意一项所述的无氰电镀液在制备黄金制品中的应用。
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