Organic coordination environment rose gold electrolyte system and electrodeposition method

Abstract

The invention discloses an organic coordination environment rose gold electrolyte system and an electro-deposition method, and the organic coordination environment rose gold electrolyte system comprises 20-150 g / L of an organic coordination agent, 5-40 g / L of gold potassium chloride, 5-40 g / L of copper chloride / zinc chloride, 30-120 g / L of potassium carbonate, 10-100 g / L of potassium hydroxide, 1-10 g / L of an organic interface additive and deionized water. According to the organic coordination environment rose gold electrolyte system, the organic coordination agent serves as a research object, the advantages of the organic coordination agent are exerted, the electrolyte and coating performance is improved, and an electro-deposition rose gold system which is wide in current density range, high in current efficiency, wide in temperature requirement, uniform and bright in coating appearance and flat and compact in crystal is obtained. In the preparation process of the electrolyte, the adding sequence, temperature, pH value and other conditions of all components in the electrolyte are required to be strictly controlled. And after the electrolyte is prepared, stirring is performed for a certain time under a certain temperature condition, so that full coordination of metal ions and the coordination agent is ensured, the obtained electrolyte can be stably used for a long time, and the same electrodeposition effect as that of a newly prepared electrolyte is obtained.

Description

Technical Field

[0001] The present application relates to the technical field of metal surface treatment, and in particular to an organic coordination environment rose gold electrolyte system and an electrodeposition method. Background Art

[0002] Rose gold is an alloy of gold and copper / zinc. It has a very beautiful and fashionable pink rose color and is widely used in jewelry design and processing. Rose gold has a higher hardness than pure gold. Compared with traditional gold and platinum, pink rose gold can make the color of colored gemstones more intense while reflecting the exquisiteness and delicacy of metal materials. Therefore, it is widely used in mobile phone cases, jewelry, handicrafts, medals, commemorative coins, high-end tableware, etc.

[0003] The technology of electrodeposition of single metals such as gold, copper, zinc and their alloys has a history of hundreds of years, but the traditional electrodeposition process uses cyanide electrolyte, which is highly toxic and poses great harm to workers and the environment. Green production processes require the use of environmentally friendly complexing agents and the development of electrolyte systems with performance comparable to that of cyanide systems.

[0004] After decades of development, cyanide-free electrodeposition technology has made great progress at home and abroad. However, the existing cyanide-free electrodeposition technology still has shortcomings in performance and cost, which limits its promotion and application. Summary of the invention

[0005] In order to solve the problems of the prior art, the present application provides an organic coordination environment rose gold electrolyte system and an electrodeposition method. The technical solution is as follows:

[0006] In a first aspect, an organic coordination environment rose gold electrolyte system is provided, comprising:

[0007] 20-150 g / L of organic complexing agent, 5-40 g / L of potassium gold chloride, 5-40 g / L of copper chloride and / or zinc chloride, 30-120 g / L of potassium carbonate, 10-100 g / L of potassium hydroxide, 1-10 g / L of organic interface additive and deionized water.

[0008] Further, it includes: 50-85g / L organic ligand, 5-10g / L potassium gold chloride, 5-10g / L copper chloride and / or zinc chloride, 30-45g / L potassium carbonate, 15-40g / L potassium hydroxide, 1-10g / L organic interface additive and deionized water.

[0009] Furthermore, the resistivity of the deionized water is 18 MΩ / cm.

[0010] Further, the organic ligand includes: potassium citrate, sodium citrate, ammonium citrate, hypoxanthine, adenine, thiourea, vinylthiourea, allylthiourea, semicarbazide, thiosemicarbazide, 1,3-dimethylthiourea, 4-pyridylthiourea, 2-aminopyridine, 3-aminopyridine, 4-dimethylaminopyridine, 2-methyl-4-aminopyridine, and one or more combinations of hydantoin derivatives, 5,5-dimethylhydantoin, 5,5-diphenylhydantoin, 3-hydroxymethyl-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, 1-aminohydantoin, 2-thiohydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dihydroxymethyl-5,5-dimethylhydantoin, and 2-thio-5,5-dimethylhydantoin.

[0011] Furthermore, the temperature of the electrolyte system during the preparation process is between 25°C and 65°C.

[0012] Furthermore, the temperature of the electrolyte system during the preparation process is 55°C.

[0013] Furthermore, the pH value of the electrolyte system is 8-13.

[0014] In the second aspect, a method for configuring the electrolyte system described in the first aspect is provided. According to the concentration of each component in the electrolyte system described in the first aspect, solutions of each component are configured respectively, and then potassium carbonate solution is added to the organic ligand solution, the pH value is adjusted to 8-13, and potassium gold chloride solution is continued to be added. After mixing evenly, copper chloride solution and / or zinc chloride solution are added. After mixing evenly, an organic interface additive is added. The temperature is controlled at 25-65°C and stirred for 0.1-24h.

[0015] Furthermore, the temperature is 55° C. and the stirring time is 10 h.

[0016] A third aspect provides an electrodeposition method of the electrolyte system according to the first aspect, comprising the following steps:

[0017] The substrate is pre-treated, then the pre-treated substrate is washed with water, and then nickel is electrodeposited;

[0018] The substrate after the nickel electrodeposition is cleaned with deionized water, and then placed in the electrolyte system described in any one of the first aspects above to electrodeposit rose gold;

[0019] The substrate after electrodeposition of rose gold was rinsed with deionized water and dried with cold air.

[0020] Furthermore, the electrodeposition of rose gold is carried out by constant current electrodeposition with a current density of 0.5-5A / dm 2The distance between the cathode and the anode is 3-30 cm, the temperature is 25-65° C., the electrodeposition time is 0.1-90 min, the cathode is the substrate, and the anode is an inert metal.

[0021] Furthermore, the current density is 1-2A / dm 2 , the distance between cathode and anode is 5-10cm, the temperature is 45-55℃, and the electrodeposition time is 5-10min.

[0022] Furthermore, the substrate is iron, copper or nickel.

[0023] Furthermore, the pretreatment method includes: taking the substrate and degreasing it by anodic electrolysis, then pickling it with a 1:1 HCl aqueous solution, and finally washing it with deionized water.

[0024] The technical solution provided in the embodiment of the present application has the following beneficial effects: the organic coordination environment rose gold electrolyte system of the present application comprises: 20-150g / L organic coordination agent, 5-40g / L potassium gold chloride, 5-40g / L copper chloride / zinc chloride, 30-120g / L potassium carbonate, 10-100g / L potassium hydroxide, 1-10g / L organic interface additive and deionized water. The organic coordination environment rose gold electrolyte system of the present application takes the organic coordination agent as the research object, gives full play to the advantages of the organic coordination agent, improves the performance of the electrolyte and the coating, and obtains an electrodeposited rose gold system with a wide current density range, high current efficiency, wide temperature requirements, uniform and bright coating appearance, and flat and dense crystals. During the preparation of the electrolyte, it is required to strictly control the order of addition of the components in the electrolyte as well as the conditions such as temperature and pH value. After the electrolyte is prepared, it is stirred for a certain period of time under certain temperature conditions to ensure that the metal ions and the complexing agent are fully coordinated, so that the obtained electrolyte can be used stably for a long time and obtain the same electrodeposition effect as the newly prepared electrolyte. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0026] Figure 1 This is a SEM image of the rose gold layer obtained in Example 1 of the present application. DETAILED DESCRIPTION

[0027] In order to make the objectives, technical solutions and advantages of the present application clearer, the implementation methods of the present application will be further described in detail below with reference to the accompanying drawings.

[0028] Example 1

[0029] (1) Configure rose gold electrolyte system

[0030] Take 75g of 5,5-dimethylhydantoin and add 750ml of deionized water to prepare a 5,5-dimethylhydantoin solution. Take 10g of potassium citrate and add 50ml of deionized water to prepare a potassium citrate solution. Add all the prepared potassium citrate solution to the 5,5-dimethylhydantoin solution and mix well. Take another 25g of potassium hydroxide and add 30ml of deionized water to prepare a potassium hydroxide solution. Add all the prepared potassium hydroxide solution to the mixed solution of 5,5-dimethylhydantoin and potassium citrate and mix well to obtain an organic complexing agent solution.

[0031] Take 45g potassium carbonate and add 50ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 11, then continue to add prepared potassium chloride solution (take 10g potassium chloride and add 50ml deionized water to prepare), mix well and then add copper chloride solution (take 5g copper chloride and add 40ml deionized water to prepare), mix well and add 30ml organic interface additive (take 0.2g polyacrylamide, 0.3g polyethylene glycol, 0.3g sodium dodecyl sulfate and 0.2g sodium polydisulfide propane sulfonate, add 30ml deionized water to prepare), control the temperature at 55℃ to ensure that all substances are completely dissolved, stir for 10h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0032] (2) Electrodeposition of rose gold

[0033] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0034] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0035] The substrate with the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 1.0 A / dm 2 , the distance between the cathode and the anode is 8 cm, the temperature is 50°C, and the electrodeposition time is 5 min. After the electrodeposition is completed, the substrate is removed from the electrolyte system, the surface is cleaned with deionized water, and the surface is dried with cold air. A rose gold layer with full brightness in the macroscopic view, uniform and smooth appearance, uniform and dense microscopic crystals under SEM observation, and no cracks is obtained (such as Figure 1 shown).

[0036] Example 2

[0037] (1) Configure rose gold electrolyte system

[0038] Take 45g of 5,5-dimethylhydantoin and add 500ml of deionized water to prepare a 5,5-dimethylhydantoin solution. Take 15g of adenine and add 250ml of deionized water to prepare an adenine solution. Add all the prepared adenine solution to the 5,5-dimethylhydantoin solution and mix well. Take another 30g of potassium hydroxide and add 50ml of deionized water to prepare a potassium hydroxide solution. Add all the prepared potassium hydroxide solution to the mixed solution of 5,5-dimethylhydantoin and adenine and mix well to obtain an organic complexing agent solution.

[0039] Take 35g potassium carbonate and add 50ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 12, then continue to add prepared potassium gold chloride solution (take 8g potassium gold chloride and add 50ml deionized water to prepare), mix well and then add copper chloride solution (take 7g copper chloride and add 50ml deionized water to prepare), mix well and add 50ml organic interface additive (take 0.5g polyacrylamide, 1.0g polyethylene glycol, 1.0g sodium dodecyl sulfate and 1.5g sodium polydisulfide propane sulfonate, add 50ml deionized water to prepare), control the temperature at 55℃ to ensure that all substances are completely dissolved, stir for 16h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0040] (2) Electrodeposition of rose gold

[0041] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0042] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0043] The substrate of the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 1.5A / dm 2, the distance between the cathode and the anode is 10 cm, the temperature is 45°C to ensure that all substances are completely dissolved, and the electrodeposition time is 5 minutes. After the electrodeposition is completed, the substrate is removed from the electrolyte system, the surface is cleaned with deionized water, and dried with cold air.

[0044] Example 3

[0045] (1) Configure rose gold electrolyte system

[0046] Take 25g of 3-hydroxymethyl-5,5-dimethylhydantoin and add 200ml of deionized water to prepare a 3-hydroxymethyl-5,5-dimethylhydantoin solution. Take 40g of 5,5-dimethylhydantoin and add 500ml of deionized water to prepare a 5,5-dimethylhydantoin solution. Add all the prepared 5,5-dimethylhydantoin solution to the 3-hydroxymethyl-5,5-dimethylhydantoin solution and mix well. Take another 40g of potassium hydroxide and add 50ml of deionized water to prepare a potassium hydroxide solution. Add all the prepared potassium hydroxide solution to the mixed solution of 3-hydroxymethyl-5,5-dimethylhydantoin and 5,5-dimethylhydantoin and mix well to obtain an organic complexing agent solution.

[0047] Take 30g potassium carbonate and add 50ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 9, then continue to add prepared potassium chloride solution (take 7.5g potassium chloride and add 60ml deionized water to prepare), mix well and then add copper chloride solution (take 6g copper chloride and add 60ml deionized water to prepare), mix well and add 80ml organic interface additive (take 2.0g polyacrylamide, 3.5g polyethylene glycol, 1.5g sodium dodecyl sulfate and 1.0g sodium polydisulfide propane sulfonate, add 80ml deionized water to prepare), control the temperature at 45℃ to ensure that all substances are completely dissolved, stir for 20h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0048] (2) Electrodeposition of rose gold

[0049] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0050] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0051] The substrate of the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 2.0 A / dm 2 , the distance between the cathode and the anode is 6 cm, the temperature is 50°C, and the electrodeposition time is 6 min. After the electrodeposition is completed, the substrate is taken out from the electrolyte system, the surface is cleaned with deionized water, and dried with cold air.

[0052] Example 4

[0053] (1) Configure rose gold electrolyte system

[0054] Take 55g of 1-aminohydantoin and add 500ml of deionized water to prepare 1-aminohydantoin solution. Take 5g of thiosemicarbazide and add 100ml of deionized water to prepare thiosemicarbazide solution. Add all the prepared thiosemicarbazide solution to the 1-aminohydantoin solution and mix well. Take another 5g of sodium citrate and add 50ml of deionized water to prepare sodium citrate solution. Add all the prepared sodium citrate solution to the mixed solution of 1-aminohydantoin and thiosemicarbazide and mix well. Finally, take 15g of potassium hydroxide and add 50ml of deionized water to prepare potassium hydroxide solution. Add all the prepared potassium hydroxide solution to the mixed solution of 1-aminohydantoin, thiosemicarbazide and sodium citrate and mix well to obtain an organic complexing agent solution.

[0055] Take 35g potassium carbonate and add 50ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 10, then continue to add prepared potassium gold chloride solution (take 10g potassium gold chloride and add 75ml deionized water to prepare), mix well and then add copper chloride solution (take 5g copper chloride and add 75ml deionized water to prepare), mix well and add 100ml organic interface additive (take 2.5g polyacrylamide, 4.0g polyethylene glycol, 0.5g sodium dodecyl sulfate and 3.0g sodium polydisulfide propane sulfonate, add 100ml deionized water to prepare), control the temperature at 65℃ to ensure that all substances are completely dissolved, stir for 10h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0056] (2) Electrodeposition of rose gold

[0057] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0058] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0059] The substrate of the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 1.5A / dm 2 , the distance between the cathode and the anode is 5 cm, the temperature is 50°C, and the electrodeposition time is 5 min. After the electrodeposition is completed, the substrate is removed from the electrolyte system, the surface is cleaned with deionized water, and dried with cold air.

[0060] Example 5

[0061] (1) Configure rose gold electrolyte system

[0062] Take 50g of 1,3-dihydroxymethyl-5,5-dimethylhydantoin and add 500ml of deionized water to prepare a 1,3-dihydroxymethyl-5,5-dimethylhydantoin solution. Take 15g of potassium citrate and add 75ml of deionized water to prepare a potassium citrate solution. Add all the prepared potassium citrate solution to the 1,3-dihydroxymethyl-5,5-dimethylhydantoin solution and mix well. Take another 5g of hypoxanthine and add 100ml of deionized water to prepare a hypoxanthine solution. Add all the prepared hypoxanthine solution to the mixed solution of 1,3-dihydroxymethyl-5,5-dimethylhydantoin and potassium citrate and mix well. Finally, take 20g of potassium hydroxide and add 80ml of deionized water to prepare a potassium hydroxide solution. Add all the prepared potassium hydroxide solution to the mixed solution of 1,3-dihydroxymethyl-5,5-dimethylhydantoin, potassium citrate and hypoxanthine, mix well, and obtain an organic complexing agent solution.

[0063] Take 50g potassium carbonate and add 80ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 11, then continue to add prepared potassium chloride gold solution (take 7.5g potassium chloride gold solution and add 80ml deionized water to prepare), mix well and then add copper chloride solution (take 5.5g copper chloride and add 60ml deionized water to prepare), mix well and add 25ml organic interface additive (take 0.5g polyacrylamide, 0.5g polyethylene glycol, 0.5g sodium dodecyl sulfate and 0.5g sodium polydisulfide propane sulfonate, add 25ml deionized water to prepare), control the temperature at 55℃ to ensure that all substances are completely dissolved, stir for 8h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0064] (2) Electrodeposition of rose gold

[0065] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0066] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0067] The substrate of the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 1.5A / dm 2 , the distance between the cathode and the anode is 7 cm, the temperature is 50°C, and the electrodeposition time is 10 min. After the electrodeposition is completed, the substrate is removed from the electrolyte system, the surface is cleaned with deionized water, and dried with cold air.

[0068] Example 6

[0069] (1) Configure rose gold electrolyte system

[0070] Take 25g of 1,3-dichloro-5,5-dimethylhydantoin and add 300ml of deionized water to prepare a 1,3-dichloro-5,5-dimethylhydantoin solution. Take 15g of 1-aminohydantoin and add 100ml of deionized water to prepare a 1-aminohydantoin solution. Add all the prepared 1-aminohydantoin solution to the 1,3-dichloro-5,5-dimethylhydantoin solution and mix well. Take another 5g of 5,5-diphenylhydantoin and add 100ml of deionized water to prepare a 5,5-diphenylhydantoin solution. Add all the prepared 5,5-diphenylhydantoin solution to the mixed solution of 1,3-dichloro-5,5-dimethylhydantoin and 1-aminohydantoin and mix well. Then, 5 g of thiourea was added to 100 ml of deionized water to prepare a thiourea solution, and the prepared thiourea solution was added to the mixed solution of 1,3-dichloro-5,5-dimethylhydantoin, 1-aminohydantoin and 5,5-diphenylhydantoin, and mixed evenly. Finally, 30 g of potassium hydroxide was added to 100 ml of deionized water to prepare a potassium hydroxide solution, and the prepared potassium hydroxide solution was added to the mixed solution of 1,3-dichloro-5,5-dimethylhydantoin, 1-aminohydantoin, 5,5-diphenylhydantoin and thiourea, and mixed evenly to obtain an organic complexing agent solution.

[0071] Take 37g potassium carbonate and add 50ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 11, then continue to add prepared potassium chloride gold solution (take 10g potassium chloride gold solution and add 100ml deionized water to prepare), mix well and then add copper chloride solution (take 14g copper chloride and add 75ml deionized water to prepare), mix well and add 75ml organic interface additive (take 2.0g polyacrylamide, 2.5g polyethylene glycol, 1.5g sodium dodecyl sulfate and 1.0g sodium polydisulfide propane sulfonate, add 75ml deionized water to prepare), control the temperature at 65℃ to ensure that all substances are completely dissolved, stir for 10h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0072] (2) Electrodeposition of rose gold

[0073] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0074] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0075] The substrate of the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 1.2A / dm 2 , the distance between the cathode and the anode is 8 cm, the temperature is 55°C, and the electrodeposition time is 10 min. After the electrodeposition is completed, the substrate is removed from the electrolyte system, the surface is cleaned with deionized water, and dried with cold air.

[0076] Example 7

[0077] (1) Configure rose gold electrolyte system

[0078] Take 45g of 5,5-dimethylhydantoin and add 500ml of deionized water to prepare a 5,5-dimethylhydantoin solution. Take 15g of 5,5-diphenylhydantoin and add 100ml of deionized water to prepare a 5,5-diphenylhydantoin solution. Add all the prepared 5,5-diphenylhydantoin solution to the 5,5-dimethylhydantoin solution and mix well. Take another 5g of thiosemicarbazide and add 100ml of deionized water to prepare a thiosemicarbazide solution. Add all the prepared thiosemicarbazide solution to the mixed solution of 5,5-dimethylhydantoin and 5,5-diphenylhydantoin and mix well. Finally, take 25g of potassium hydroxide and add 50ml of deionized water to prepare a potassium hydroxide solution. Add all the prepared potassium hydroxide solution to the mixed solution of 5,5-dimethylhydantoin, 5,5-diphenylhydantoin and thiosemicarbazide, mix well, and obtain an organic complexing agent solution.

[0079] Take 35g potassium carbonate and add 70ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 10, then continue to add prepared potassium gold chloride solution (take 8g potassium gold chloride and add 50ml deionized water to prepare), mix well and then add copper chloride solution (take 4.5g copper chloride and add 50ml deionized water to prepare), mix well and then add zinc chloride solution (take 1.5g zinc chloride and add 50ml deionized water to prepare), mix well and then add 30ml organic interface additive (take 0.5g polyacrylamide, 0.2g polyethylene glycol, 0.7g sodium dodecyl sulfate and 0.4g sodium polydisulfide propane sulfonate, add 55ml deionized water to prepare), control temperature at 55℃ to ensure that all substances are completely dissolved, stir for 10h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0080] (2) Electrodeposition of rose gold

[0081] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0082] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0083] The substrate of the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 1.5A / dm 2, the distance between the cathode and the anode is 10 cm, the temperature is 55°C, and the electrodeposition time is 5 min. After the electrodeposition is completed, the substrate is taken out from the electrolyte system, the surface is cleaned with deionized water, and dried with cold air.

[0084] Example 8

[0085] (1) Configure rose gold electrolyte system

[0086] Take 100g of 1,3-dibromo-5,5-dimethylhydantoin and add 300ml of deionized water to prepare a 1,3-dibromo-5,5-dimethylhydantoin solution. Take 20g of ammonium citrate and add 100ml of deionized water to prepare an ammonium citrate solution. Add all the prepared ammonium citrate solution to the 1,3-dibromo-5,5-dimethylhydantoin solution and mix well. Take another 100g of potassium hydroxide and add 150ml of deionized water to prepare a potassium hydroxide solution. Add all the prepared potassium hydroxide solution to the mixed solution of 1,3-dibromo-5,5-dimethylhydantoin and ammonium citrate and mix well to obtain an organic complexing agent solution.

[0087] Take 120g potassium carbonate and add 150ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 8, then continue to add prepared potassium gold chloride solution (take 40g potassium gold chloride and add 150ml deionized water to prepare), mix well and then add copper chloride solution (take 15g copper chloride and add 100ml deionized water to prepare), mix well and add 50ml organic interface additive (take 1g polyacrylamide, 1g polyethylene glycol, 1g sodium dodecyl sulfate and 1g sodium polydisulfide propane sulfonate, add 50ml deionized water to prepare), control the temperature at 65℃ to ensure that all substances are completely dissolved, stir for 24h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0088] (2) Electrodeposition of rose gold

[0089] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0090] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0091] The substrate with the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 3.5A / dm 2 , the distance between the cathode and the anode is 18 cm, the temperature is 30°C, and the electrodeposition time is 30 min. After the electrodeposition is completed, the substrate is removed from the electrolyte system, the surface is cleaned with deionized water, and dried with cold air.

[0092] Example 9

[0093] (1) Configure rose gold electrolyte system

[0094] 15 g of 2-thiohydantoin was added to 200 ml of deionized water to prepare a 2-thiohydantoin solution. 15 g of 2-aminopyridine was added to 200 ml of deionized water to prepare a 2-aminopyridine solution. The prepared 2-aminopyridine solution was added to the 2-thiohydantoin solution and mixed evenly. Finally, 60 g of potassium hydroxide was added to 100 ml of deionized water to prepare a potassium hydroxide solution. The prepared potassium hydroxide solution was added to the mixed solution of 2-thiohydantoin and 2-aminopyridine and mixed evenly to obtain an organic complexing agent solution.

[0095] Take 60g potassium carbonate and add 100ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 13, then continue to add prepared potassium gold chloride solution (take 15g potassium gold chloride and add 100ml deionized water to prepare), mix well and then add copper chloride solution (take 20g copper chloride and add 100ml deionized water to prepare), mix well and then add zinc chloride solution (take 20g zinc chloride and add 100ml deionized water to prepare), mix well and then add 100ml organic interface additive (take 2.5g polyacrylamide, 2g polyethylene glycol, 3g sodium dodecyl sulfate and 1.5g sodium polydisulfide propane sulfonate, add 55ml deionized water to prepare), control temperature at 55℃ to ensure that all substances are completely dissolved, stir for 0.5h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0096] (2) Electrodeposition of rose gold

[0097] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0098] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0099] The substrate of the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 5A / dm 2 , the distance between the cathode and the anode is 30 cm, the temperature is 65°C, and the electrodeposition time is 70 min. After the electrodeposition is completed, the substrate is removed from the electrolyte system, the surface is cleaned with deionized water, and dried with cold air.

[0100] Example 10

[0101] (1) Configure rose gold electrolyte system

[0102] Take 80g of allylthiourea and add 400ml of deionized water to prepare an allylthiourea solution. Take 15g of thiosemicarbazide and add 100ml of deionized water to prepare a thiosemicarbazide solution. Add all the prepared thiosemicarbazide solution to the allylthiourea solution and mix well. Finally, take 80g of potassium hydroxide and add 150ml of deionized water to prepare a potassium hydroxide solution. Add all the prepared potassium hydroxide solution to the mixed solution of allylthiourea and thiosemicarbazide and mix well to obtain an organic complexing agent solution.

[0103] Take 90g potassium carbonate and add 150ml deionized water to prepare potassium carbonate solution, then add potassium carbonate solution to organic ligand solution as conductive salt, take potassium hydroxide solution to adjust pH value to 13, then continue to add prepared potassium chloride solution (take 25g potassium chloride and add 75ml deionized water to prepare), mix well, then add copper chloride solution (take 15g copper chloride and add 75ml deionized water to prepare), mix well, add 50ml organic interface additive (take 1g polyacrylamide, 0.2g polyethylene glycol, 5g sodium dodecyl sulfate and 1g sodium polydisulfide propane sulfonate, add 55ml deionized water to prepare), control temperature at 55℃ to ensure that all substances are completely dissolved, stir for 6h to make metal ions fully coordinated, and obtain rose gold electrolyte system. Deionized water with resistivity of 18MΩ / cm is used in the preparation process.

[0104] (2) Electrodeposition of rose gold

[0105] The substrate iron, copper, nickel sheet or its metal film is sequentially degreased by anodic electrolysis, pickled with a 1:1 HCl aqueous solution and washed with deionized water, and dried for later use;

[0106] The dried substrate is placed in an electroplated nickel electrolyte for electroplating nickel treatment using a Watt nickel plating solution as a preparation process, and a nickel plating layer with a thickness of 2-10 μm is electroplated under direct current electroplating conditions;

[0107] The substrate of the electrodeposited nickel intermediate layer was rinsed with deionized water and then directly immersed in a plating tank containing a rose gold electrolyte system. The substrate was used as the cathode and the inert metal was used as the anode. Rose gold was electrodeposited by constant current electrodeposition at a current density of 5A / dm 2 , the distance between the cathode and the anode is 25 cm, the temperature is 35°C, and the electrodeposition time is 90 min. After the electrodeposition is completed, the substrate is removed from the electrolyte system, the surface is cleaned with deionized water, and dried with cold air.

[0108] The organic ligand includes but is not limited to the ones listed in the above embodiments. Specifically, one or more combinations can be selected from the following as the organic ligand: potassium citrate, sodium citrate, ammonium citrate, hypoxanthine, adenine, thiourea, vinyl thiourea, allyl thiourea, semicarbazide, thiosemicarbazide, 1,3-dimethylthiourea, 4-pyridylthiourea, 2-aminopyridine, 3-aminopyridine, 4-dimethylaminopyridine, 2-methyl-4-amino Pyridine and hydantoin derivatives hydantoin, 5,5-dimethylhydantoin, 5,5-diphenylhydantoin, 3-hydroxymethyl-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, 1-aminohydantoin, 2-thiohydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dihydroxymethyl-5,5-dimethylhydantoin, 2-thio-5,5-dimethylhydantoin, etc.

[0109] The organic coordination environment rose gold electrolyte system of the present application takes the organic coordination agent as the research object, gives full play to the advantages of the organic coordination agent, improves the performance of the electrolyte and the coating, and obtains an electrodeposited rose gold system with a wide current density range, high current efficiency, wide temperature requirements, uniform and bright coating appearance, and flat and dense crystals. In the preparation process of the electrolyte, it is required to strictly control the order of addition of each component in the electrolyte as well as the conditions such as temperature and pH value. First, the coordination agent organic matter is completely dissolved, and then the aqueous solution of the main salt is added. Full stirring is conducive to stable coordination, and after the coordination is stable, the pH of the plating solution is adjusted and the corresponding additives are added. After the electrolyte preparation is completed, it is stirred for a certain time under certain temperature conditions to ensure that the metal ions and the coordination agent are fully coordinated, so that the obtained electrolyte can be used stably for a long time and obtain the same electrodeposition effect as the newly prepared electrolyte.

[0110] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. An organic coordination environment rose gold electrolyte system, characterized in that: include: 20-150 g / L of organic complexing agent, 5-40 g / L of potassium gold chloride, 5-40 g / L of copper chloride and / or zinc chloride, 30-120 g / L of potassium carbonate, 10-100 g / L of potassium hydroxide, 1-10 g / L of organic interface additive and deionized water.

2. The electrolyte system according to claim 1, characterized in that The resistivity of the deionized water is 18 MΩ / cm.

3. The electrolyte system according to claim 1, characterized in that The organic ligand includes: potassium citrate, sodium citrate, ammonium citrate, hypoxanthine, adenine, thiourea, vinyl thiourea, allyl thiourea, semicarbazide, thiosemicarbazide, 1,3-dimethylthiourea, 4-pyridylthiourea, 2-aminopyridine, 3-aminopyridine, 4-dimethylaminopyridine, 2-methyl-4-aminopyridine, hydantoin derivative, 5,5-dimethylhydantoin, 5,5-diphenylhydantoin, 3-hydroxymethyl-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, 1-aminohydantoin, 2-thiohydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dihydroxymethyl-5,5-dimethylhydantoin, 2-thio-5,5-dimethylhydantoin.

4. The electrolyte system according to claim 1, characterized in that The temperature of the electrolyte system is 25-65° C. during the preparation process.

5. The electrolyte system according to claim 1, characterized in that The pH value of the electrolyte system is 8-13.

6. The method for configuring an electrolyte system according to any one of claims 1 to 5, characterized in that: According to the concentration of each component in the electrolyte system of claim 1, the solutions of each component are prepared respectively, and then potassium carbonate solution is added to the organic complexing agent solution, the pH value is adjusted to 8-13, and potassium gold chloride solution is continuously added. After mixing evenly, copper chloride solution and / or zinc chloride solution are added. After mixing evenly, an organic interface additive is added. The temperature is controlled at 25-65° C. and stirred for 0.1-24 hours.

7. The electrolytic deposition method of claim 1, wherein: The following steps are involved: The substrate is pre-treated, then the pre-treated substrate is washed with water, and then nickel is electrodeposited; The substrate after the nickel electrodeposition is cleaned with deionized water, and then placed in the electrolyte system according to any one of claims 1 to 5 to electrodeposit rose gold; The substrate after electrodeposition of rose gold was rinsed with deionized water and dried with cold air.

8. The electrodeposition method according to claim 7, characterized in that: The electrodeposition of rose gold is carried out by constant current electrodeposition, and the current density is 0.5-5A / dm 2 The distance between the cathode and the anode is 3-30 cm, the temperature is 25-65° C., the electrodeposition time is 0.1-90 min, the cathode is the substrate, and the anode is an inert metal.

9. The electrodeposition method according to claim 7, characterized in that: The substrate is iron, copper or nickel.

10. The electrodeposition method according to claim 7, characterized in that: The pretreatment method comprises: taking the substrate and degreasing it by anodic electrolysis, then pickling it with a 1:1 HCl aqueous solution, and finally washing it with deionized water.

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