CN112342581A - Plating solution for electroplating gold-copper alloy by using cyanide-free sulfite - Google Patents
Plating solution for electroplating gold-copper alloy by using cyanide-free sulfite Download PDFInfo
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- CN112342581A CN112342581A CN202011121613.2A CN202011121613A CN112342581A CN 112342581 A CN112342581 A CN 112342581A CN 202011121613 A CN202011121613 A CN 202011121613A CN 112342581 A CN112342581 A CN 112342581A
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- parts
- plating solution
- gold
- sulfite
- cyanide
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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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Abstract
The invention discloses a cyanide-free sulfite electroplating gold-copper alloy plating solution, which comprises the following raw materials: 3-15 parts of sodium gold sulfite; 50-200 parts of sodium sulfite; 20-30 parts of DTPA; 0.5-10 parts of copper chloride; 30-80 parts of monopotassium phosphate; 30-100 parts of potassium citrate; 0.1-1 part of plating solution stabilizer; 0.5-2 parts of a brightening agent; and deionized water. Has the advantages that: the cyanide-free sulfite is adopted for gold plating, the plating solution is non-toxic, the dispersing capacity and the deep plating capacity are good, the crystallization of the plating layer is fine, and the alloy elements and the gold elements are coprecipitated, so that the hardness of the plating layer is improved; meanwhile, the use of gold elements can be reduced, and the cost is reduced; because the plating solution and the raw materials are nontoxic, the safety in the production process is good, and the discharge is more environment-friendly.
Description
Technical Field
The invention relates to the technical field of electroplating processing, in particular to a plating solution for electroplating gold-copper alloy by using cyanide-free sulfite.
Background
In the field of alloy plating, alkaline cyanide gold plating occupies an important place. However, although cyanide gold plating has many advantages, the gold plating solution is toxic and harmful to the health of workers, and the discharged sewage is also greatly harmful to the environment; in the prior art, the cyanide-free gold plating technology has higher cost. Based on this, the applicant proposes a gold plating solution which has good safety and is beneficial to environmental protection.
Disclosure of Invention
The present invention is directed to provide a plating solution for electroplating gold-copper alloy without cyanide sulfite, which solves the above problems, and a preferable embodiment among the various embodiments of the present invention comprises: the plating layer has stable quality, does not contain cyanide, has good safety, and can reduce the technical effects of cost and the like, and the details are described in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a cyanide-free sulfite electroplating gold-copper alloy plating solution, which comprises the following raw materials:
3-15 parts of sodium gold sulfite;
50-200 parts of sodium sulfite;
20-30 parts of DTPA;
0.5-10 parts of copper chloride;
30-80 parts of monopotassium phosphate;
30-100 parts of potassium citrate;
0.1-1 part of plating solution stabilizer;
0.5-2 parts of a brightening agent; and
deionized water.
Preferably, the plating solution further comprises a pH regulator, and the pH value of the plating solution is 8-11.
Preferably, the pH adjuster is phosphoric acid.
Preferably, the bath stabilizer includes a sulfite stabilizer and a gold ion stabilizer.
Preferably, the sulfite stabilizer is glycerol, and the gold ion stabilizer is a nitro compound.
Preferably, the brightener is a mixture of antimony salt and polyalcohol, wherein the content of antimony salt is not more than 1g/L, and the content of polyalcohol mixture is not more than 0.1 g/L.
Preferably, the raw materials comprise the following components:
7-15 parts of sodium gold sulfite;
90-200 parts of sodium sulfite;
22-30 parts of DTPA;
4-10 parts of copper chloride;
39-80 parts of monopotassium phosphate;
48-100 parts of potassium citrate;
0.5-1 part of plating solution stabilizer;
0.9-2 parts of a brightening agent; and
deionized water.
Preferably, the raw materials comprise the following components:
7.5-11 parts of sodium gold sulfite;
91-160 parts of sodium sulfite;
23-27 parts of DTPA;
5-8 parts of copper chloride;
40-65 parts of monopotassium phosphate;
50-72 parts of potassium citrate;
0.6-0.9 part of plating solution stabilizer;
1-1.8 parts of a brightening agent; and
deionized water.
Preferably, the raw materials comprise the following components:
8-10 parts of sodium gold sulfite;
115-135 parts of sodium sulfite;
25 parts of DTPA;
4-6 parts of copper chloride;
45-65 parts of monopotassium phosphate;
55-75 parts of potassium citrate;
0.4-0.6 part of plating solution stabilizer;
1.2-1.4 parts of brightener; and
deionized water.
In conclusion, the beneficial effects of the invention are as follows: 1. the cyanide-free sulfite is adopted for gold plating, the plating solution is non-toxic, the dispersing capacity and the deep plating capacity are good, the crystallization of the plating layer is fine, and the alloy elements and the gold elements are coprecipitated, so that the hardness of the plating layer is improved; meanwhile, the use of gold elements can be reduced, and the cost is reduced;
2. because the plating solution and the raw materials are nontoxic, the safety in the production process is good, and the discharge is more environment-friendly.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The invention provides a cyanide-free sulfite electroplating gold-copper alloy plating solution, which comprises the following raw materials: 3-15 parts of gold sodium sulfite, which exists in the form of gold sulfite complex ions [ Au (SOs) 23- ] and gold citrate complex ions [ Au (HC6H507) ] in the plating solution, has low gold content and allows the cathode current density to be low; the gold content is high, the allowable cathode current density is high, and the gold content in the plating layer is high; 50-200 parts of sodium sulfite, wherein the sodium sulfite is a main complexing agent of gold and cannot be low in content, otherwise, in an alkaline solution, Na3Au (S03)2 is easy to form Au (OH)3 precipitate, so that the plating solution is turbid, and the function of the sodium sulfite can improve the conductivity of the plating solution and the dispersing capacity of the plating solution; 20-30 parts of DTPA, wherein the DTPA is a main complexing agent of copper and mainly has the function of complexing copper, because the complexation of the citrate to the copper in the experiment can not reach the codeposition of gold and copper, and the DTPA is a brightening agent and has a certain brightening effect on a plating layer; 0.5-10 parts of copper chloride, wherein the copper chloride is main salt and exists in the plating solution in the form of copper citrate complex ions and DTPA copper complex ions, concentration change has great influence on the copper content in the plating layer, the concentration is increased, the copper content in the plating layer is increased, the required complexing agent is increased, and the plating solution is difficult to maintain; 30-80 parts of monopotassium phosphate, wherein the monopotassium phosphate is a pH value buffering agent, and hydrolysis of H2p 04-in the solution can not only keep the pH value stable within a certain range, but also increase the conductivity of the plating solution, so that the color is brighter, and the optimal range of the color is enlarged; 30-100 parts of potassium citrate, wherein the potassium citrate is an auxiliary complexing agent for gold and an auxiliary complexing agent for copper, and has the functions of promoting the codeposition of gold and copper, keeping the stability of the plating solution, improving the cathode polarization and improving the dispersing capacity of the plating solution; 0.1-1 part of plating solution stabilizer; 0.5-2 parts of a brightening agent; and 1L of deionized water.
Also comprises a pH regulator, and the pH value in the plating solution is 8-11; the pH regulator is phosphoric acid, and can increase the conductivity of the plating solution;
the plating solution stabilizer comprises a sulfite stabilizer and a gold ion stabilizer; the sulfite stabilizer is glycerol which is a stabilizer of the plating solution and can retard sulfite from being oxidized into sulfate at high temperature, so that the plating solution is stable, the service life of the plating solution is prolonged, and the concentration is controlled within 0.3 mL/L; the gold ion stabilizer is a nitro compound, can retard the precipitation of gold after being added, improves the stability of the plating solution, but has not high content, influences the performance of the plating solution before and after the stabilizer is added, improves the stability of the plating solution to a certain extent after the stabilizer is added, and has dark color, more yellow precipitates on the lower layer and brown attachments when the stabilizer is not added;
the brightener is a mixture of soluble antimony salt and polyalcohol, wherein the antimony salt is formed by depositing antimony element serving as a trace alloy element into a coating to change the structure of the coating, so that the brightness of the coating is increased, the hardness of the coating is increased, and the concentration is controlled within 1 g/L; the adsorption effect of the polyalcohol changes the interface property of the electrode and the solution, effectively increases and adjusts the cathode polarization, and the concentration is controlled within 0.1 g/L. Under the combined action of the two components, the coating can generate full-bright effect.
If the plating solution is turbid in the electroplating process, filtering in time to keep the plating solution clean; in the plating process, deionized water is added in time to ensure the stability of the concentration of electrolyte in the plating solution; the electroplating temperature is 40 ℃; the cathode was moved at a current density of 0.2A/dm 2.
The specific process flow is as follows: the method comprises the steps of sample preparation, chemical oil removal, hot water washing, ultrasonic wave removal, cathode activation, plating, water washing recovery, hot water washing, 5% acid leaching, hot water washing and drying.
The specific implementation mode of the plating solution is as follows:
example 1:
comprises the following raw materials: 7 parts of sodium gold sulfite; 90 parts of sodium sulfite; 22 parts of DTPA; 4 parts of copper chloride; 39 parts of monopotassium phosphate; 48 parts of potassium citrate; 0.5 part of plating solution stabilizer; 0.9 part of brightener; and 1L of deionized water;
example 2:
comprises the following raw materials: 15 parts of sodium gold sulfite; 200 parts of sodium sulfite; 30 parts of DTPA; 10 parts of copper chloride; 80 parts of monopotassium phosphate; 100 parts of potassium citrate; 1 part of plating solution stabilizer; 2 parts of a brightening agent; and 1L of deionized water;
example 3:
comprises the following raw materials: 11 parts of sodium gold sulfite; 145 parts of sodium sulfite; 26 parts of DTPA; 7 parts of copper chloride; 60 parts of monopotassium phosphate; 124 parts of potassium citrate; 0.75 part of plating solution stabilizer; 1.45 parts of a brightening agent; and 1L of deionized water;
example 4:
comprises the following raw materials: 7.5 parts of sodium gold sulfite; 91 parts of sodium sulfite; 23 parts of DTPA; 5 parts of copper chloride; 40 parts of monopotassium phosphate; 50 parts of potassium citrate; 0.6 part of plating solution stabilizer; 1 part of brightener; and 1L of deionized water;
example 5:
comprises the following raw materials: 11 parts of sodium gold sulfite; 160 parts of sodium sulfite; 27 parts of DTPA; 8 parts of copper chloride; 65 parts of monopotassium phosphate; 72 parts of potassium citrate; 0.9 part of plating solution stabilizer; 1.8 parts of a brightening agent; and 1L of deionized water;
example 6:
comprises the following raw materials: 9.25 parts of sodium gold sulfite; 125.5 parts of sodium sulfite; 25 parts of DTPA; 6.5 parts of copper chloride; 102.5 parts of monopotassium phosphate; 61 parts of potassium citrate; 0.75 part of plating solution stabilizer; 1.4 parts of a brightening agent; and 1L of deionized water;
example 7:
comprises the following raw materials: 8 parts of sodium gold sulfite; 115 parts of sodium sulfite; 25 parts of DTPA; 4 parts of copper chloride; 45 parts of monopotassium phosphate; 55 parts of potassium citrate; 0.4 part of plating solution stabilizer; 1.2 parts of a brightening agent; and 1L of deionized water;
example 8:
comprises the following raw materials: 10 parts of sodium gold sulfite; 135 parts of sodium sulfite; 25 parts of DTPA; 6 parts of copper chloride; 65 parts of monopotassium phosphate; 75 parts of potassium citrate; 0.6 part of plating solution stabilizer; 1.4 parts of a brightening agent; and 1L of deionized water;
example 9:
comprises the following raw materials: 9 parts of sodium gold sulfite; 125 parts of sodium sulfite; 25 parts of DTPA; 5 parts of copper chloride; 55 parts of monopotassium phosphate; 65 parts of potassium citrate; 0.5 part of plating solution stabilizer; 1.3 parts of a brightening agent; and 1L of deionized water.
The optimal process formula and the operation parameters of the electroplated K gold are obtained by taking the appearance of the plating layer and the gold content as main measurement standards and comprehensively considering the stability of the plating solution: 50-100g/L of sodium sulfite, 30g/L of diethyltriaminepentaacetic acid, 60g of potassium citrate, 0.8g/L of copper chloride, 8g/L (calculated by gold) of sodium gold sulfite, 40-50g/L of dipotassium hydrogen phosphate, 40 ℃ of plating temperature, 0.2A/dm2 of cathode current density, 8.80-9.20 of pH value and 4.6 of deep plating capacity under the process formula, thereby indicating that the plating solution has better dispersing capacity and deep plating capacity; the coating adopting the process formula is rose red or golden yellow, uniform and fine, is between two-level and three-level (bright), has the gold content reaching the K gold standard, and has better binding force and corrosion resistance, and the hardness is between 120 and 150 HV.
The cyanide-free sulfite is adopted for gold plating, the plating solution is non-toxic, the dispersing capacity and the deep plating capacity are good, the crystallization of the plating layer is fine, and the alloy elements and the gold elements are coprecipitated, so that the hardness of the plating layer is improved; meanwhile, the use of gold elements can be reduced, and the cost is reduced; because the plating solution and the raw materials are nontoxic, the safety in the production process is good, and the discharge is more environment-friendly.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. The cyanide-free sulfite electroplating gold-copper alloy plating solution is characterized by comprising the following raw materials:
3-15 parts of sodium gold sulfite;
50-200 parts of sodium sulfite;
20-30 parts of DTPA;
0.5-10 parts of copper chloride;
30-80 parts of monopotassium phosphate;
30-100 parts of potassium citrate;
0.1-1 part of plating solution stabilizer;
0.5-2 parts of a brightening agent; and
deionized water.
2. The plating solution for electroplating gold-copper alloy with cyanide-free sulfite according to claim 1, wherein the plating solution comprises: also comprises a pH regulator, and the pH value of the plating solution is 8-11.
3. The plating solution for electroplating gold-copper alloy with cyanide-free sulfite according to claim 2, wherein the plating solution comprises: the pH regulator is phosphoric acid.
4. The plating solution for electroplating gold-copper alloy with cyanide-free sulfite according to claim 1, wherein the plating solution comprises: the plating solution stabilizer comprises a sulfite stabilizer and a gold ion stabilizer.
5. The plating solution for electroplating gold-copper alloy with cyanide-free sulfite according to claim 4, wherein the plating solution comprises: the sulfite stabilizer is glycerin, and the gold ion stabilizer is a nitro compound.
6. The plating solution for electroplating gold-copper alloy with cyanide-free sulfite according to claim 1, wherein the plating solution comprises: the brightener is a mixture of antimony salt and polyalcohol, wherein the content of the antimony salt is not more than 1g/L, and the content of the polyalcohol mixture is not more than 0.1 g/L.
7. The plating solution for electroplating gold-copper alloy with cyanide-free sulfite according to claim 1, wherein the plating solution comprises: comprises the following raw materials:
7-15 parts of sodium gold sulfite;
90-200 parts of sodium sulfite;
22-30 parts of DTPA;
4-10 parts of copper chloride;
39-80 parts of monopotassium phosphate;
48-100 parts of potassium citrate;
0.5-1 part of plating solution stabilizer;
0.9-2 parts of a brightening agent; and
deionized water.
8. The plating solution for electroplating gold-copper alloy with cyanide-free sulfite according to claim 1, wherein the plating solution comprises: comprises the following raw materials:
7.5-11 parts of sodium gold sulfite;
91-160 parts of sodium sulfite;
23-27 parts of DTPA;
5-8 parts of copper chloride;
40-65 parts of monopotassium phosphate;
50-72 parts of potassium citrate;
0.6-0.9 part of plating solution stabilizer;
1-1.8 parts of a brightening agent; and
deionized water.
9. The plating solution for electroplating gold-copper alloy with cyanide-free sulfite according to claim 1, wherein the plating solution comprises: comprises the following raw materials:
8-10 parts of sodium gold sulfite;
115-135 parts of sodium sulfite;
25 parts of DTPA;
4-6 parts of copper chloride;
45-65 parts of monopotassium phosphate;
55-75 parts of potassium citrate;
0.4-0.6 part of plating solution stabilizer;
1.2-1.4 parts of brightener; and
deionized water.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011121613.2A CN112342581A (en) | 2020-10-20 | 2020-10-20 | Plating solution for electroplating gold-copper alloy by using cyanide-free sulfite |
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| CN202011121613.2A CN112342581A (en) | 2020-10-20 | 2020-10-20 | Plating solution for electroplating gold-copper alloy by using cyanide-free sulfite |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114016096A (en) * | 2021-10-22 | 2022-02-08 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free electroplated 18K rose gold liquid, preparation method and application thereof, and preparation method of 18K rose gold coating |
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| CN106283141A (en) * | 2016-08-11 | 2017-01-04 | 江捷新 | Bullion rose golden surface processes plating solution, preparation method and electro-plating method thereof |
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2020
- 2020-10-20 CN CN202011121613.2A patent/CN112342581A/en active Pending
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| CN114016096A (en) * | 2021-10-22 | 2022-02-08 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free electroplated 18K rose gold liquid, preparation method and application thereof, and preparation method of 18K rose gold coating |
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