CN109778299B - Electrolytic stripping agent for copper-plated layer on surface of iron base material, and preparation method and stripping process thereof - Google Patents
Electrolytic stripping agent for copper-plated layer on surface of iron base material, and preparation method and stripping process thereof Download PDFInfo
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Abstract
The invention discloses an electrolytic stripping agent for a copper-plated layer on the surface of an iron base material, and a preparation method and a stripping process thereof. The electrolytic stripping agent comprises the following components: 2-25 wt% of nitrate, 2-20 wt% of sulfate, 0.5-8 wt% of corrosion inhibitor, 3-12 wt% of complexing agent and the balance of water. The electrolytic stripping agent does not contain cyanide or high-concentration ammonia water, so that the electrolytic stripping agent is safer and more environment-friendly, has simple wastewater treatment and is beneficial to saving the cost. The electrolytic stripping agent disclosed by the invention cannot corrode a workpiece, the surface gloss of the stripped workpiece is good, the stripping line is neat, and the stripping efficiency is high.
Description
Technical Field
The invention relates to the field of metal protection, in particular to an electrolytic stripping agent for a copper-plated layer on the surface of an iron base material, and a preparation method and a stripping process thereof.
Background
In the actual electroplating process, various uncertain factors (such as machine equipment, materials, operation methods, environment, management and the like) are encountered in an electroplating factory, so that in large-scale industrial production, electroplating defective products often appear, a large amount of waste is caused, and the cost is increased. In order to reduce waste and save cost, various methods are generally used to strip off the copper plating layer on the surface of a defective workpiece, thereby realizing recycling of the workpiece.
In addition, some workpieces at special connection positions need to have a copper layer at partial positions and have no copper layer at partial positions, so that the electroplating process cannot be perfectly realized.
Common stripping methods are classified into chemical stripping and electrolytic stripping.
The chemical stripping agent sold in the market contains cyanide or high-concentration ammonia water, and has the following problems in the using process: (1) cyanide is extremely toxic, so that personal and property damage is easily caused, and personal safety of workers is seriously threatened; (2) the high-concentration ammonia water has very strong volatility, has very great harm to the bodies of workers and natural environment, and does not meet the requirements of safety and environmental protection; (3) the waste water treatment is difficult, and the waste water containing cyanide needs to be recycled by professional companies; wastewater containing high concentration ammonia water requires a large amount of a neutralizer and tap water, which leads to an increase in plant cost.
For the electrolytic stripping agent, CN104404611A discloses an electrolytic stripping agent for copper alloy surface coating, which is composed of 15-80 wt% of sulfuric acid, 0.1-8 wt% of sodium dodecyl sulfate, 0.5-35 wt% of citrate, 0.005-5 wt% of triazole and 15-65 wt% of water, but it cannot strip the copper coating on the surface of the iron substrate.
CN106167914A discloses a magnesium alloy electrolytic stripping liquid, which comprises the following raw materials by weight: 50-100 parts of an oxidant, 100-180 parts of a conductive agent, 30-60 parts of a corrosion inhibitor, 10-20 parts of a complexing agent, 1-5 parts of a fog inhibitor and 45-60 parts of a buffering agent, wherein the oxidant is dichromate, the conductive agent is nitrate, the corrosion inhibitor is hydrofluoric acid or hydrofluoride, the complexing agent is an alcohol compound, the fog inhibitor is sodium dodecyl benzene sulfonate, and the buffering agent is acetate; but corrodes the iron when applied to the surface of the iron substrate.
CN106119946A discloses an aluminum alloy electrolytic stripping agent, which comprises the following raw materials in parts by weight: 50-100 parts of an oxidant, 100-180 parts of a conductive salt, 30-60 parts of a corrosion inhibitor, 10-20 parts of a first complexing agent, 3-5 parts of a second complexing agent and 8-15 parts of a buffering agent, wherein the oxidant is dichromate, the conductive salt is nitrate, the first complexing agent is a polycyclic heterocyclic compound, the second complexing agent is an alkylamine compound, and the buffering agent is thiourea and a compound thereof, which can corrode an iron substrate.
Therefore, the development of an electrolytic stripping agent suitable for copper plating on the surface of an iron substrate still has certain challenges.
Disclosure of Invention
The invention aims to provide an electrolytic stripping agent for a copper-plated layer on the surface of an iron base material, a preparation method and a stripping process thereof.
The technical scheme adopted by the invention is as follows:
the invention aims to provide an electrolytic stripping agent for a copper-plated layer on the surface of an iron base material, which comprises the following components: 2-25 wt% of nitrate, 2-20 wt% of sulfate, 0.5-8 wt% of corrosion inhibitor, 3-12 wt% of complexing agent and the balance of water.
Preferably, the upper electrolytic stripper comprises the following components: 10-20 wt% of nitrate, 4-14 wt% of sulfate, 1-5 wt% of corrosion inhibitor, 5-10 wt% of complexing agent and the balance of water.
More preferably, the electrolytic stripping agent comprises the following components: 12-15 wt% of nitrate, 6-12 wt% of sulfate, 2.5-4 wt% of corrosion inhibitor, 6-10 wt% of complexing agent and the balance of water.
Preferably, the components also comprise 0.1-5 wt% of surfactant.
More preferably, the components also comprise 0.5-3 wt% of surfactant.
Preferably, the surfactant is at least one selected from the group consisting of AEO, alkylphosphates, APEO, polyoxyethylene fatty acid esters, ethylene glycol, and glycerol pentaerythritol.
Preferably, the surfactant is AEO, APEO, or a combination thereof.
Preferably, the corrosion inhibitor is selected from hexamethylenetetramine.
Preferably, the complexing agent is selected from at least one of R-COOH and potassium, sodium and ammonium salts thereof, R- (COOH)2 and potassium, sodium and ammonium salts thereof, R- (COOH)3 and potassium, sodium and ammonium salts thereof, HOOC-R1-R2-COOH and potassium, sodium and ammonium salts thereof, HO-R1 ═ R2-COOH and potassium, sodium and ammonium salts thereof, HO-R1-COOH and potassium, sodium and ammonium salts thereof, R1(OH) -COOH and potassium, sodium and ammonium salts thereof, wherein R, R1 and R2 are independently selected from alkyl groups of C1-C12.
The invention also aims to provide a preparation method of the electrolytic stripping agent, which comprises the steps of adding nitrate, sulfate, a corrosion inhibitor, a complexing agent and a surfactant into water, dissolving and forming.
The invention also provides a stripping process of the copper-plated layer on the surface of the iron base material, which takes the electrolytic stripping agent or the electrolytic stripping agent prepared by the method as electrolyte, stainless steel as a cathode and the iron base material with copper plated on the surface as an anode to carry out electrolytic stripping.
Preferably, the temperature of the electrolytic peeling is 25 to 40 ℃.
Preferably, the electrolytic stripping voltage is 2-8V; more preferably 2 to 5V.
Preferably, the pH of the electrolyte is 4.0 to 7.0.
The invention has the beneficial effects that:
1. the electrolytic stripping agent does not contain cyanide or high-concentration ammonia water, so that the electrolytic stripping agent is safer and more environment-friendly, has simple wastewater treatment and is beneficial to saving the cost.
2. The electrolytic stripping agent disclosed by the invention cannot corrode a workpiece, the surface gloss of the stripped workpiece is good, the stripping line is neat, and the stripping efficiency is high.
Detailed Description
The present invention will be described in further detail with reference to examples. It will also be understood that the following examples are included merely for purposes of further illustrating the invention and are not to be construed as limiting the scope of the invention, as the invention extends to insubstantial modifications and adaptations of the invention following in the light of the principles set forth herein. The specific process parameters and the like of the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific data of the following examples.
Example 1
| Electrolytic stripper composition | Tap water | Sodium nitrate | Potassium sulfate | Hexamethylenetetramine | Lactic acid | AEO |
| Mass percent (wt%) | 60 | 12 | 12 | 4 | 10 | 2 |
Example 2
| Electrolytic stripper composition | Tap water | Sodium nitrate | Potassium sulfate | Hexamethylenetetramine | Lactic acid | APEO |
| Mass percent (wt%) | 66.5 | 13 | 8 | 3 | 8 | 1.5 |
Example 3
| Electrolytic stripper composition | Tap water | Sodium nitrate | Potassium sulfate | Hexamethylenetetramine | Lactic acid | AEO |
| Mass percent (wt%) | 70 | 15 | 6 | 2.5 | 6 | 0.5 |
Comparative example 1
| Electrolytic stripper composition | Tap water | Sodium nitrate | Potassium sulfate | Hexamethylenetetramine | Citric acid | AEO |
| Mass percent (wt%) | 60 | 12 | 12 | 4 | 10 | 2 |
Comparative example 2
| Electrolytic stripper composition | Tap water | Sodium nitrate | Potassium sulfate | Hexamethylenetetramine | Citric acid | AEO |
| Mass percent (wt%) | 55 | 12 | 12 | 4 | 15 | 2 |
Comparative example 3
| Electrolytic stripper composition | Tap water | Sodium nitrate | Potassium sulfate | Hexamethylenetetramine | Citric acid | AEO |
| Mass percent (wt%) | 50 | 12 | 12 | 4 | 20 | 2 |
Comparative example 4
| Electrolytic stripper composition | Tap water | Sodium nitrate | Potassium sulfate | Ethylene diamine | Lactic acid | AEO |
| Mass percent (wt%) | 60 | 12 | 12 | 4 | 10 | 2 |
Comparative example 5
| Electrolytic stripper composition | Tap water | Sodium nitrate | Potassium sulfate | Ethylene diamine | Lactic acid | AEO |
| Mass percent (wt%) | 54 | 12 | 12 | 10 | 10 | 2 |
Comparative example 6
| Electrolytic stripper composition | Tap water | Sodium nitrate | Potassium sulfate | Ethylene diamine | Lactic acid | AEO |
| Mass percent (wt%) | 44 | 12 | 12 | 20 | 10 | 2 |
The methods for producing the electrolytic stripping agents of examples 1 to 3 and comparative examples 1 to 6 were as follows:
and (3) adding the electrolytic stripping agent component into water according to the proportion of the embodiment 1-3, fully dissolving, uniformly stirring, and forming to obtain the electrolytic stripping agent for the copper-plated layer on the surface of the iron base material.
The stripping process of the copper plating layer on the surface of the iron base material comprises the following steps:
1 part of the electrolytic stripping agent of the examples 1-3 and the comparative examples 1-6 is respectively mixed with 2-6 parts of water as electrolyte, the pH value of the electrolyte is 4.0-7.0, the anode is a workpiece with a copper-plated layer on the surface of an iron base material to be stripped, the cathode is a stainless steel plate, the stripping voltage is 2-8V, the stripping temperature is 25-40 ℃, stripping is carried out, and after the stripping is finished, the workpiece is taken out and washed clean by water.
The results show that: under the same conditions, stripping lines stripped by using the electrolytic strippers of examples 1-3 are regular, corrosion to a workpiece is avoided, and the surface gloss of the stripped workpiece is good, which indicates that the electrolytic strippers of examples 1-3 can effectively strip a copper plating layer on the surface of an iron base material, while comparative examples 1-6 can achieve a good stripping effect only by using a large amount of electrolytic strippers.
Meanwhile, the electrolytic stripping agent of example 3 (1 part of the electrolytic stripping agent of example 3, 4 parts of water as an electrolyte, pH 4-6) and a commercially available chemical stripping agent (aqueous sodium cyanide solution, sodium cyanide mass% 5%) were used as electrolytes to strip an iron-based workpiece having a copper plating layer thickness of 50 μm, and the effects thereof were compared: the bearing rate (the area of the work piece to be stripped per liter of stripping liquid) is 1dm2The time required for stripping the chemical stripping agent under the condition of/L is 120min, and under the condition of the same bearing rate and the voltage of 7V, the exampleThe electrolytic stripping agent 3 can completely strip in 50min, meanwhile, the stripping speed of the chemical stripping agent sold in the market can only be 0.1-0.4 mu m/min, and the stripping speed is slower and slower with the increase of the concentration of copper ions in the stripping agent, when the copper ions in the chemical stripping solution are saturated, the final stripping speed is reduced to below 0.05 mu m/min, and even fails, while the stripping speed of the electrolytic stripping agent in the embodiment 3 can be constantly 0.7-2.5 mu m/min, and simultaneously the stripped copper ions can be generated in a cathode stainless steel plate, so that the problem of copper ion saturation is avoided, and the electrolyte can be continuously operated until the stripping is complete.
Claims (8)
1. An electrolytic stripping agent for a copper-plated layer on the surface of an iron base material is characterized in that: comprises the following components: 2-25 wt% of nitrate, 2-20 wt% of sulfate, 0.5-8 wt% of corrosion inhibitor, 3-12 wt% of complexing agent and the balance of water;
the components also comprise 0.1-5 wt% of surfactant;
wherein the surfactant is selected from at least one of AEO, alkyl phosphate, APEO, polyoxyethylene fatty acid ester, glycol and glycerol pentaerythritol;
the pH = 4.0-7.0 of the electrolytic stripping agent.
2. The electrolytic stripping agent according to claim 1, characterized in that: the surfactant is AEO, APEO or a combination thereof.
3. The electrolytic stripping agent according to claim 1 or 2, characterized in that: the corrosion inhibitor is selected from hexamethylenetetramine.
4. The electrolytic stripping agent according to claim 1 or 2, characterized in that: the complexing agent is selected from R-COOH and potassium, sodium and ammonium salts thereof, R- (COOH)2And the potassium, sodium, ammonium salts thereof, R- (COOH)3And potassium, sodium, ammonium salts thereof, HOOC-R1-R2-COOH and potassium, sodium, ammonium salts thereof, HO-R1= R2-COOH and potassium, sodium, ammonium salts thereof, HO-R1-COOH and potassium, sodium, ammonium salts thereof, R1(OH) -COOH and potassium, sodium, ammonium salts thereofAt least one of R, R1 and R2 is selected from C1～C12Alkyl group of (1).
5. The method for producing the electrolytic stripping agent according to any one of claims 2 to 4, characterized in that: nitrate, sulfate, corrosion inhibitor, complexing agent and surfactant are added into water, dissolved and formed.
6. A stripping process of a copper plating layer on the surface of an iron base material is characterized in that: the electrolytic stripping agent according to any one of claims 1 to 4 or the electrolytic stripping agent produced according to claim 5 is used as an electrolyte, stainless steel is used as a cathode, and an iron substrate plated with copper on the surface is used as an anode to perform electrolytic stripping.
7. The lift-off process of claim 6, wherein: the temperature of the electrolytic stripping is 25-40 ℃.
8. The lift-off process of claim 6, wherein: the electrolytic stripping voltage is 2-8V.
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| CN111850670A (en) * | 2020-08-04 | 2020-10-30 | 郑州知淘信息科技有限责任公司 | Electrolytic stripping solution for steel electroplating hanger and stripping method |
| CN113564684B (en) * | 2021-07-07 | 2023-05-23 | 江门市瑞期精细化学工程有限公司 | Electrolytic stripping agent and application thereof |
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| JPH04371600A (en) * | 1991-06-21 | 1992-12-24 | Hitachi Cable Ltd | Production of partially silver plated product |
| JP4264338B2 (en) * | 2003-12-11 | 2009-05-13 | 新光電気工業株式会社 | Copper electrolytic stripping solution and electrolytic stripping method |
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