Additive for bright copper plating, electroplating solution and anti-corrosion process

Abstract

The invention discloses an additive for bright copper plating, which comprises a brightener, a leveling agent and an inhibitor, the brightener is saccharin sodium, the leveling agent is Jannao green B, and the inhibitor is at least one of potassium aliphatate and sodium aliphatate. The method has the advantages of being simple in process, convenient to operate and environmentally friendly, and has wide application prospects. In addition, the invention further provides electroplating liquid for bright copper plating and an anti-corrosion process.

Description

Technical Field

[0001] The invention relates to the technical field of electroplating materials, and in particular to an additive, an electroplating solution and an anti-corrosion process for bright copper plating. Background Art

[0002] Metal materials such as carbon steel are common materials in industry. They are prone to electrochemical corrosion in oxygen-containing media, humid environments, and strong acidic and alkaline areas such as urban areas, which leads to red rust on the surface and increases the corrosion rate. Copper plating is an effective method for corrosion prevention. The copper film formed on the surface after copper plating can prevent corrosion and rust, and extend the service life. Additives are an important component of the electroplating solution and play an irreplaceable role in the electroplating process. Additives can effectively improve the current distribution during the electroplating process, improve the plating ability of the plating solution, and affect the transportation and electrocrystallization process of copper ions from the solution body to the reaction interface, thereby changing the electrochemical deposition rate of the micro-concave and micro-convex parts of the plate surface.

[0003] However, the acid bright copper plating additives used in the domestic electroplating industry currently have the following bottlenecks in formulation and process: (1) slow light emission speed; (2) unsatisfactory leveling effect; (3) poor positioning in the low current density area; (4) high pollution of brighteners. The above four problems plague most electroplating companies. Complex workpieces often have difficulty obtaining ideal coatings in the low current density area, which affects product quality and the economic benefits of the company. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an additive, an electroplating solution and an anti-corrosion process for bright copper plating.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: In a first aspect, the present invention provides an additive for bright copper plating, characterized in that it comprises a brightener, a leveler and an inhibitor, wherein the brightener is sodium saccharin, the leveler is Janus Green B, and the inhibitor is at least one of potassium fatty acid and sodium fatty acid.

[0006] Furthermore, the mass ratio of the brightener, the leveler and the inhibitor is (1-3):(4-6);(4-6); Preferably, the mass ratio of the brightener, the leveler and the inhibitor is 1:5:5.

[0007] In a second aspect, the present invention provides an electroplating solution for bright copper plating, the electroplating solution comprising sulfuric acid, copper sulfate, potassium chloride and any additive as described above.

[0008] Furthermore, the concentration of saccharin sodium is 0.01-0.1 g / L.

[0009] Furthermore, the concentration of the fatty acid potassium or the fatty acid sodium is 0.05 to 0.5 g / L.

[0010] Furthermore, the concentration of Janus Green B is 0.05-0.5 g / L.

[0011] Furthermore, the concentration of the sulfuric acid is 5 to 12 g / L.

[0012] Furthermore, the concentration of the copper sulfate is 150-200 g / L.

[0013] Furthermore, the concentration of potassium chloride is 0.1-0.5 g / L.

[0014] In a third aspect, the present invention provides an anti-corrosion process for bright copper plating using any of the above electroplating solutions, comprising the following steps: Step 1: Metal pretreatment: Cut the metal sheet, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh CuSO4·5H2O, KCl, sodium saccharin, sodium fatty acid, potassium fatty acid, Janus Green B, and concentrated sulfuric acid to prepare an aqueous solution; Step 3, (constant current or constant potential) electroplating zinc: use the metal sheet as the cathode and the copper sheet as the anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and perform (constant current or constant potential) electroplating; Furthermore, the electroplating method is a constant current of 0.1 to 10 A / dm 2 Electrodeposition or constant potential 1 ~ 20V electrodeposition copper plating.

[0015] In summary, the beneficial effects of the present invention are: The additive, electroplating solution and anti-corrosion process for bright copper plating of the present invention can avoid the problems of uneven traditional plating on the one hand, and can achieve no pollution to the environment on the other hand, produce a copper plating layer under electroplating conditions, improve the anti-corrosion performance of the metal, and have the characteristics of low cost and good repeatability. The present invention has the advantages of simple process, convenient operation, green and environmental protection, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The present invention is a process flow chart of the anti-corrosion process for bright copper plating. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] See also Figure 1 In a first aspect, the present invention provides an additive for bright copper plating, comprising a brightener, a leveler and an inhibitor, wherein the brightener is sodium saccharin, the leveler is Janus Green B, and the inhibitor is at least one of potassium fatty acid and sodium fatty acid.

[0019] In one embodiment, the mass ratio of the brightener, the leveler and the inhibitor is (1-3):(4-6);(4-6). Preferably, the mass ratio of the brightener, the leveler and the inhibitor is 1:5:5.

[0020] The brightener, the leveler and the inhibitor provided by the present invention are used in an electroplated copper plating solution and can be adsorbed on the copper surface, significantly reducing the internal stress between the molecules of the plated layer. The deposited copper plated layer is expected to have good corrosion resistance.

[0021] In a second aspect, the present invention provides an electroplating solution for bright copper plating, the electroplating solution comprising sulfuric acid, copper sulfate, potassium chloride and any additive as described above.

[0022] In one embodiment, the concentration of saccharin sodium is 0.01-0.1 g / L.

[0023] In one embodiment, the concentration of the fatty acid potassium or the fatty acid sodium is 0.05 to 0.5 g / L.

[0024] Furthermore, the concentration of Janus Green B is 0.05-0.5 g / L.

[0025] Furthermore, the concentration of the sulfuric acid is 5 to 12 g / L.

[0026] Furthermore, the concentration of the copper sulfate is 150-200 g / L.

[0027] Furthermore, the concentration of potassium chloride is 0.1-0.5 g / L.

[0028] In a third aspect, the present invention provides an anti-corrosion process for bright copper plating, comprising the following steps: Step 1: Metal pretreatment: Cut the metal sheet, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh CuSO4·5H2O, KCl, sodium saccharin, sodium fatty acid, potassium fatty acid, Janus Green B, and concentrated sulfuric acid to prepare an aqueous solution; Step 3, (constant current or constant potential) electroplating zinc: use the metal sheet as the cathode and the copper sheet as the anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and perform electroplating; Specifically, a metal sheet is used as a cathode and a copper sheet is used as an anode, and placed in the electroplating solution. A DC regulated power supply is used to connect the cathode and the anode to perform copper electroplating. Furthermore, the electroplating method is a constant current of 0.1 to 10 A / dm 2 Electrodeposition or constant potential 1 ~ 20V electrodeposition copper plating.

[0029] Example 1 Step 1: Pretreatment of carbon steel: Cut the carbon steel, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.001g saccharin sodium, 0.005g fatty acid potassium, 0.005g Jiana Green B, measure 2mL concentrated sulfuric acid, and prepare 50mL aqueous solution; Step 3: Constant current electroplating zinc: Use carbon steel as cathode and copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and conduct a constant current of 3A / dm 2 plating;

[0030] Example 2 Step 1: Pretreatment of carbon steel: Cut the carbon steel, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.001g saccharin sodium, 0.005g sodium fatty acid, 0.005g Janus Green B, and 2mL concentrated sulfuric acid to prepare 50mL aqueous solution; Step 3: Constant current electroplating zinc: Use carbon steel as cathode and copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and conduct a constant current of 3A / dm 2 plating;

[0031] Example 3 Step 1: Pretreatment of carbon steel: Cut the carbon steel, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.001g saccharin sodium, 0.005g sodium fatty acid, 0.005g Janus Green B, and 2mL concentrated sulfuric acid to prepare 50mL aqueous solution; Step 3: Constant potential electroplating zinc: Use carbon steel as cathode and copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and perform constant potential 15V electroplating;

[0032] Example 4 Step 1: Pretreatment of carbon steel: Cut the carbon steel, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.001g saccharin sodium, 0.0025g sodium fatty acid, 0.0025g potassium fatty acid, 0.005g Janus Green B, and 2mL concentrated sulfuric acid to prepare 50mL aqueous solution; Step 3: Constant current electroplating zinc: Use carbon steel as cathode and copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and conduct a constant current of 3A / dm 2 plating;

[0033] Example 5 Step 1: Pretreatment of carbon steel: Cut the carbon steel, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.002g saccharin sodium, 0.01g fatty acid potassium, 0.01g Janus Green B, and 2mL concentrated sulfuric acid to prepare 50mL aqueous solution; Step 3: Constant current electroplating zinc: Use carbon steel as cathode and copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and conduct a constant current of 3A / dm 2 plating;

[0034] Example 6 Step 1: pretreatment of cast iron: cut the cast iron, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.002g saccharin sodium, 0.01g fatty acid potassium, 0.01g Janus Green B, and 2mL concentrated sulfuric acid to prepare 50mL aqueous solution; Step 3: Constant current electroplating zinc: Use cast iron as cathode and copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and conduct a constant current of 3A / dm2 plating;

[0035] Example 7 Step 1: Pretreatment of carbon steel: Cut the carbon steel, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.002g saccharin sodium, 0.01g fatty acid potassium, 0.01g Janus Green B, and 2mL concentrated sulfuric acid to prepare 50mL aqueous solution; Step 3: Constant current electroplating zinc: Use carbon steel as cathode and copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and conduct a constant current of 5A / dm 2 plating;

[0036] Example 8 Step 1: Pretreatment of carbon steel: Cut the carbon steel, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.002g saccharin sodium, 0.01g fatty acid potassium, 0.01g Janus Green B, and 2mL concentrated sulfuric acid to prepare 50mL aqueous solution; Step 3: Constant current electroplating zinc: Use carbon steel as cathode and copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and conduct a constant current of 1A / dm 2 plating;

[0037] Example 9 Step 1: Pretreatment of carbon steel: Cut the carbon steel, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.002g saccharin sodium, 0.01g fatty acid potassium, 0.01g Janus Green B, and 2mL concentrated sulfuric acid to prepare 50mL aqueous solution; Step 3: Constant potential electroplating zinc: Use carbon steel as cathode and copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and perform constant potential 10V electroplating;

[0038] Example 10 Step 1: Pretreatment of carbon steel: Cut the carbon steel, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with 4% sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh 10g CuSO4·5H2O, 0.0052g KCl, 0.002g saccharin sodium, 0.01g fatty acid potassium, 0.01g Janus Green B, and 2mL concentrated sulfuric acid to prepare 50mL aqueous solution; Step 3, constant potential electroplating zinc plating; using carbon steel as the cathode and copper sheet as the anode, pour the electroplating solution obtained in step 2, connect a DC voltage-stabilized power supply, and perform constant potential 20V electroplating; the additive, electroplating solution, and anti-corrosion process for bright copper plating of the present invention innovatively use common industrial corrosive materials such as carbon steel and cast iron as electrode materials, adopt new green brighteners such as sodium saccharin, potassium fatty acid, and Jiana Green B as electroplating solutions, and use constant current method and constant potential method electroplating to improve the uniformity of the coating. The additive, electroplating solution, and anti-corrosion process for bright copper plating of the present invention have the advantages of cheap experimental raw materials, environmental protection, good scientificity, and strong operability. It is expected that carbon steel will have a good anti-corrosion effect after electroplating.

[0039] The additive, electroplating solution and anti-corrosion process for bright copper plating of the present invention can avoid the problems of uneven traditional plating on the one hand, and can achieve no pollution to the environment on the other hand, produce copper plating under electroplating conditions, improve the anti-corrosion performance of carbon steel, cast iron and the like, and have the characteristics of low cost and good repeatability. The additive, electroplating solution and anti-corrosion process for bright copper plating of the present invention have the advantages of simple process, convenient operation and green environmental protection, and have broad application prospects.

[0040] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. An additive for bright copper plating, characterized in that: The invention comprises a brightener, a leveler and an inhibitor, wherein the brightener is sodium saccharin, the leveler is Janus Green B, and the inhibitor is at least one of potassium fatty acid and sodium fatty acid.

2. The additive according to claim 1, characterized in that The mass ratio of the brightener, the leveler and the inhibitor is (1-3):(4-6);(4-6); Preferably, the mass ratio of the brightener, the leveler and the inhibitor is 1:5:

5.

3. A plating solution for bright copper plating, characterized in that: The electroplating solution comprises sulfuric acid, copper sulfate, potassium chloride and the additive according to any one of claims 1 to 2.

4. The electroplating solution according to claim 3, characterized in that The concentration of the saccharin sodium is 0.01-0.1 g / L.

5. The electroplating solution according to claim 3, characterized in that The concentration of the fatty acid potassium or the fatty acid sodium is 0.05-0.5 g / L.

6. The electroplating solution according to claim 3, characterized in that The concentration of the Janus Green B is 0.05-0.5 g / L.

7. The electroplating solution according to claim 3, characterized in that The concentration of the sulfuric acid is 5-12 g / L.

8. The electroplating solution according to claim 3, characterized in that: The concentration of the copper sulfate is 150-200 g / L.

9. The electroplating solution according to claim 3, characterized in that: The concentration of potassium chloride is 0.1-0.5 g / L.

10. An anti-corrosion process for bright copper plating using the electroplating solution according to any one of claims 3 to 9, characterized in that: The following steps are involved: Step 1: Metal pretreatment: Cut the metal sheet, polish it with metallographic sandpaper, degrease it with ethanol, pickle it with sulfuric acid solution, wash it with distilled water, and dry it for later use; Step 2, preparation of electroplating solution: weigh CuSO4·5H2O, KCl, sodium saccharin, sodium fatty acid, potassium fatty acid, Janus Green B, and concentrated sulfuric acid to prepare an aqueous solution; Step 3: Electroplating zinc: Use the metal sheet as cathode and the copper sheet as anode, pour the electroplating solution obtained in step 2, connect a DC regulated power supply, and perform electroplating. The electroplating method is a constant current of 0.1-10A / dm 2 Electrodeposition or constant potential 1 ~ 20V electrodeposition copper plating.

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