CN115821341B - Environment-friendly cyanide-free electroplating solution and electroplating process thereof - Google Patents
Environment-friendly cyanide-free electroplating solution and electroplating process thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly cyanide-free electroplating solution and an electroplating process thereof. The formula comprises the following components in mass concentration: 3-10g/L of gold salt, 30-60mg/L of composite brightening agent, 2-6g/L of complexing agent, 0.3-0.9g/L of composite crystal nucleus refiner, 30-60mg/L of accelerator, 25-75mg/L of composite leveling agent, 35-70mg/L of dispersing agent, 30-60mg/L of stabilizing agent and 15-60mg/L of surfactant. The gold plating layer obtained by the method has the advantages of no chromatic aberration, compactness, flatness, excellent gold cylinder stability, good binding force and the like, and simultaneously has the characteristics of high current resistance, wide application range and the like.
Description
Technical Field
The invention relates to the technical field of cyanide-free electroplating, in particular to an environment-friendly cyanide-free electroplating solution and an electroplating process thereof.
Background
Cyanide gold plating has excellent current density dispersion properties, but will gradually be replaced by cyanide-free gold plating due to its extremely toxic nature. The non-cyanide electroplating refers to a novel electroplating process using non-cyanide electrolyte instead of highly toxic cyanide electrolyte. In order to find new alternatives, gold salt compounds which are environment-friendly and meet the process requirements are obtained, and many researches are continuously carried out, but good results still cannot be obtained until now.
The patent CN103938232A discloses an electroless plating solution and application thereof, wherein gold sodium sulfite is used as gold salt, however, the salt has poor stability, gold is easily decomposed and reduced at high temperature so as to be separated out, and meanwhile, the brightness of a coating is poor because the formula components are too single. In addition, in patent CN101906649a, a plating solution for electroless gold plating and a plating method using the same are disclosed, wherein gold chloride is used as gold salt in the solution, and chloride ions promote corrosion of trivalent gold ions to a substrate due to the action of current.
Therefore, in order to meet the environmental protection requirement and meet the industrial production, the invention provides a formula and an electroplating method which are environment-friendly and stable and can obtain an excellent electroplated gold layer.
Disclosure of Invention
Aiming at the defects existing in the technology, the invention provides the environment-friendly cyanide-free electroplating solution and the electroplating process thereof, and the gold plating layer obtained by the invention has the advantages of no chromatic aberration, compactness, flatness, excellent gold cylinder stability, good binding force and the like, and simultaneously has the characteristics of high current resistance, wide application range and the like.
In order to achieve the above purpose, the invention provides an environment-friendly cyanide-free electroplating solution, which comprises the following components in mass concentration:
3-10g/L of gold salt, 30-60mg/L of composite brightening agent, 2-6g/L of complexing agent, 0.3-0.9g/L of composite crystal nucleus refiner, 30-60mg/L of accelerator, 25-75mg/L of composite leveling agent, 35-70mg/L of dispersing agent, 30-60mg/L of stabilizer and 15-60mg/L of surfactant;
pH is 5.0-6.0
The operation temperature is 25-35 DEG C
The current density is 0.2-6.5A/dm 2
The pH is regulated by sodium hydroxide with the mass concentration of 50% and concentrated sulfuric acid with the volume concentration of 50%;
the compound brightening agent is thiophene indolecarboxylic acid, is a composition formed by 8-methyl-8H-thieno [2,3-b ] -indole-2-carboxylic acid and 3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid, has the mass concentration ratio of 1:2, 8-methyl-8H-thieno [2,3-b ] -indole-2-carboxylic acid of 10-20mg/L and 3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid of 20-40mg/L when in use, can improve the gold uniformity of a plating layer and further promote the brightness of the plating layer, can protect the plating layer from being deposited with high current without generating chromatic aberration, and obviously improves the electroplating efficiency compared with the market electroplating gold liquid;
the gold salt is sodium gold thiosulfate.
The composite crystal nucleus refiner is a composition composed of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinoline carboxylic acid benzyl ester p-toluenesulfonate, 1H-pyrrolo [2,3-b ] pyridine-4-yl trifluoromethane sulfonate and 1-butyl-1-methylpyrrolidine trifluoromethane sulfonate, the mass concentration ratio of the three is 1:1:1 when in use, the composite crystal nucleus refiner can promote the continuous nucleation of a gold crystal nucleus, greatly promote the compactness of a plating layer, and has more uniformity compared with gold plating liquid on the market.
Wherein the compound leveling agent is an aromatic amino acid cyclohexanaminium salt compound, and is a composition composed of N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt and N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt, the mass concentration ratio of the compound leveling agent to the N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt is 1:4, the N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt is 5-15mg/L, and the N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt is 20-60mg/L. The composite leveling agent can inhibit a high-current area, promote the current area, improve the current utilization efficiency, enable plating crystal nuclei to be more uniform, and have excellent effects on plane electroplating, deep hole plating and irregular plating, and have a wide application range.
Wherein the stabilizer is 6-nitro quinolizine maleate; the accelerator is 6-nitropyrrolo [1,2-a ] quinoline, and the stabilizer can greatly improve the service cycle of the accelerator, and compared with the liquid medicine commonly used in the market, the service time can reach three months or even half a year.
Wherein the surfactant is allyloxy polyoxyethylene ether; the dispersing agent is polyethylene glycol 3000.
The mass concentration ratio of the stabilizer to the accelerator is 1:1, and the proportion of the stabilizer to the accelerator and the synergistic use can ensure that gold ions can reach the surface of a plated part in order and can not cause the precipitation of gold powder from the bath solution.
Wherein the complexing agent is a pyridine mercapto compound, and the complexing agent is 2-mercapto-5-nitropyridine.
An environment-friendly cyanide-free electroplating process comprises the following specific steps:
step 1, degreasing, cleaning with pure water, removing surface dirt, and then ultrasonic cleaning to remove chemical substances adsorbed on the surface of a substrate;
step 2, chemically plating atomic diffusion barrier layer palladium, cleaning a plating piece to remove surface dirt, then entering a chemical palladium plating tank to carry out chemical palladium plating, and washing after the palladium plating is completed;
and 3, electroplating, namely, after electroless palladium plating, the plating piece enters an electroplating tank to carry out gold plating, wherein the gold plating mode adopts a four-position electrode clamping mode to carry out the electroplating, and the electroplating liquid used for the electroplating is the environment-friendly cyanide-free electroplating liquid.
Wherein, the chemical palladium plating solution in the step 2 comprises the following components and process parameters: 200-500mg/L of palladium sulfate, 0.5-1.5g/L of nicotinic acid, 15-25mg/L of 1-butyl-1-methylpyrrolidine triflate, 10-30mg/L of 2-acetylpyrazine, 30-60mg/L of succinic acid, 10-15ml/L of formic acid, 15-25g/L of sodium hypophosphite, the temperature of 45-55 ℃ and the pH of 5.0-6.5 are regulated and controlled by adopting a sodium hydroxide solution with the mass concentration of 50% and a concentrated sulfuric acid solution with the volume concentration of 50%, the time is 10min, the thickness is 0.5-1 micron, the chemical palladium plating liquid provided by the invention can achieve the thickness of more than half micron, has obvious advantages compared with the domestic chemical palladium plating liquid, the service period of the chemical palladium plating liquid can reach 15MTO, the domestic common liquid medicine only has 10-12MTO, and the plating thickness is only 0.1-0.3 micron.
The specific conditions of the step 3 are as follows: the electroplating gold adopts a four-position electrode clamp mode, an anode divides an anode line into four ports through branching, and is connected with four electrode clamps, the four electrode clamps clamp plating pieces from the central positions of four sides of a base material at the same time when electroplating gold, then parameters such as current density, time and the like are set, the parameters such as current density, temperature and pH are set in the above range, the distance between the anode and the cathode is set to be 5-40cm, and the specific setting can be adjusted by production practice.
The invention adopts chemical palladium plating before electro-gold plating, and provides a special palladium plating solution, which not only can protect the base material from displacement erosion of gold ions, but also is stable, has low erosion effect on the base material, and has excellent and bright compactness, and has longer stability compared with the chemical palladium plating solution on the market.
The beneficial effects of the invention are as follows: compared with the prior art, the environment-friendly cyanide-free electroplating solution and the electroplating process thereof provided by the invention have the following advantages:
1) According to the invention, the composite brightening agent is a thiophene indole carboxylic acid compound, preferably a composition consisting of 8-methyl-8H-thieno [2,3-b ] -indole-2-carboxylic acid and 3- [ 1H-indole 3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid, and the mass concentration ratio of the composite brightening agent to the 3- [ 1H-indole 3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid is 1:2 when the composite brightening agent is used, so that the uniform compactness of a plating layer can be improved, the brightening property of the plating layer can be further promoted, the plating layer can be protected from high-current deposition without generating chromatic aberration, and the electroplating efficiency is obviously improved compared with a market gold electroplating solution.
2) The composite crystal nucleus refiner is a composition composed of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinoline carboxylic acid benzyl ester p-toluenesulfonate, 1H-pyrrolo [2,3-b ] pyridine-4-yl trifluoromethane sulfonate and 1-butyl-1-methylpyrrolidine trifluoromethane sulfonate, and the mass concentration ratio of the three is 1:1:1 when in use, the composite crystal nucleus refiner can promote the continuous nucleation of a gold crystal nucleus, greatly promote the compactness of a plating layer, and has more uniformity compared with gold plating liquid in the market.
3) The composite leveling agent is an aromatic amino acid cyclohexylammonium compound, preferably a composition consisting of N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt and N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt, the mass concentration ratio of the composite leveling agent to the N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt is 1:4, the N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt is 20-60mg/L, the composite leveling agent can inhibit a high current area, promote the current area, improve the current utilization efficiency, ensure that plating crystal nuclei are more uniform, have excellent effects on plane electroplating, deep hole plating parts and irregular plating parts, and have wide application range.
4) The invention adopts chemical palladium plating before electro-gold plating, and provides a special palladium plating solution, which not only can protect the base material from displacement erosion of gold ions, but also is stable, has low erosion effect on the base material, and has excellent and bright compactness, and compared with the chemical palladium plating solution on the market, the stability is longer, and the thickness is thicker than 0.5 micrometer.
Detailed Description
In order to more clearly describe the present invention, the present invention is further described below based on the text.
In order to achieve the above purpose, the invention provides an environment-friendly cyanide-free electroplating solution, which comprises the following components in mass concentration:
3-10g/L of gold salt, 30-60mg/L of composite brightening agent, 2-6g/L of complexing agent, 0.3-0.9g/L of composite crystal nucleus refiner, 30-60mg/L of accelerator, 25-75mg/L of composite leveling agent, 35-70mg/L of dispersing agent, 30-60mg/L of stabilizer and 15-60mg/L of surfactant;
pH is 5.0-6.0
The operation temperature is 25-35 DEG C
The current density is 0.2-6.5A/dm 2
The compound brightening agent is a thiophene indole carboxylic acid compound, and is a composition formed by 8-methyl-8H-thieno [2,3-b ] -indole-2-carboxylic acid and 3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid, wherein the mass concentration ratio of the compound brightening agent to the 3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid is 10-20mg/L, and the mass concentration ratio of the compound brightening agent to the 3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid is 20-40mg/L;
the gold salt is sodium gold thiosulfate.
In this embodiment, the compound nucleus refiner is a composition composed of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinoline carboxylic acid benzyl ester p-toluenesulfonate, 1H-pyrrolo [2,3-b ] pyridin-4-yl trifluoromethanesulfonate and 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, and the mass concentration ratio of the three is 1:1:1 when in use.
In the embodiment, the compound leveling agent is an aromatic amino acid cyclohexanaminium compound, and the compound leveling agent is a composition composed of N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt and N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt, wherein the mass concentration ratio of the compound leveling agent to the N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt is 1:4, the N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt is 5-15mg/L, and the N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt is 20-60mg/L.
In this embodiment, the stabilizer is a nitroquinolizine 6-maleate salt; the promoter is 6-nitropyrrolo [1,2-a ] quinoline.
In this embodiment, the surfactant is allyloxy polyoxyethylene ether; the dispersing agent is polyethylene glycol 3000.
In the embodiment, the mass concentration ratio of the stabilizer to the accelerator is 1:1, and the proportion and the synergistic use of the stabilizer and the accelerator can ensure that gold ions can reach the surface of a plated part in order and can not cause the precipitation of gold powder from the bath solution.
In this embodiment, the complexing agent is a pyridine thiol compound, and the complexing agent is 2-thiol-5-nitropyridine.
An environment-friendly cyanide-free electroplating process comprises the following specific steps:
step 1, degreasing, cleaning with pure water, removing surface dirt, and then ultrasonic cleaning to remove chemical substances adsorbed on the surface of a substrate;
step 2, chemically plating conductive barrier layer palladium, cleaning a plating piece to remove surface dirt, then entering a chemical palladium plating tank to carry out chemical palladium plating, and washing after the palladium plating is completed;
and 3, feeding the plated piece after electroless palladium plating into an electroplating groove for electroplating, wherein the electroplating is performed in a four-position electrode clamping mode, and the electroplating solution used for electroplating is the environment-friendly cyanide-free electroplating solution.
In this embodiment, the chemical palladium plating solution in step 2 includes the following components and process parameters: 200-500mg/L of palladium sulfate, 0.5-1.5g/L of nicotinic acid, 15-25mg/L of 1-butyl-1-methylpyrrolidine triflate, 10-30mg/L of 2-acetylpyrazine, 30-60mg/L of succinic acid, 10-15ml/L of formic acid, 15-25g/L of sodium hypophosphite, the temperature of 45-55 ℃ and the pH of 5.0-6.5 are controlled, and the pH can be controlled by adopting a sodium hydroxide solution with the mass concentration of 50% and a concentrated sulfuric acid solution with the volume concentration of 50% for 10min and the thickness of 0.5-1 micrometer.
In this embodiment, the specific conditions of the step 3 are: the electroplating gold adopts a four-position electrode clamp mode, an anode divides an anode line into four ports through branching, and is connected with four electrode clamps, the four electrode clamps clamp plating pieces from the central positions of four sides of a base material at the same time when electroplating gold, then parameters such as current density, time and the like are set, the parameters such as current density, temperature and pH are set in the above-mentioned right range, the distance between the anode and the cathode is set to be 5-40cm, and the specific setting can be practically adjusted by production.
The invention adopts chemical palladium plating before electro-gold plating, and provides a special palladium plating solution, which not only can protect the base material from displacement erosion of gold ions, but also is stable, has low erosion effect on the base material, and has excellent and bright compactness, and has longer stability compared with the chemical palladium plating solution on the market.
The beneficial effects of the invention are as follows: compared with the prior art, the environment-friendly cyanide-free electroplating solution and the electroplating process thereof provided by the invention have the following advantages:
1) According to the invention, the composite brightening agent is a thiophene indole carboxylic acid compound, preferably a composition consisting of 8-methyl-8H-thieno [2,3-b ] -indole-2-carboxylic acid and 3- [ 1H-indole 3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid, and the mass concentration ratio of the composite brightening agent to the 3- [ 1H-indole 3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid is 1:2 when the composite brightening agent is used, so that the uniform compactness of a plating layer can be improved, the brightening property of the plating layer can be further promoted, the plating layer can be protected from high-current deposition without generating chromatic aberration, and the electroplating efficiency is obviously improved compared with a market gold electroplating solution.
2) The composite crystal nucleus refiner is a composition composed of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinoline carboxylic acid benzyl ester p-toluenesulfonate, 1H-pyrrolo [2,3-b ] pyridine-4-yl trifluoromethane sulfonate and 1-butyl-1-methylpyrrolidine trifluoromethane sulfonate, and the mass concentration ratio of the three is 1:1:1 when in use, the composite crystal nucleus refiner can promote the continuous nucleation of a gold crystal nucleus, greatly promote the compactness of a plating layer, and has more uniformity compared with gold plating liquid in the market.
3) The composite leveling agent is an aromatic amino acid cyclohexylammonium compound, preferably a composition consisting of N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt and N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt, the mass concentration ratio of the composite leveling agent to the N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt is 1:4, the N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt is 20-60mg/L, the composite leveling agent can inhibit a high current area, promote the current area, improve the current utilization efficiency, ensure that plating crystal nuclei are more uniform, have excellent effects on plane electroplating, deep hole plating parts and irregular plating parts, and have wide application range.
4) The invention adopts chemical palladium plating before electro-gold plating, and provides a special palladium plating solution, which not only can protect the base material from displacement erosion of gold ions, but also is stable, has low erosion effect on the base material, and has excellent and bright compactness, and compared with the chemical palladium plating solution on the market, the stability is longer, and the thickness is thicker than 0.5 micrometer.
The following are several embodiments of the invention
The experimental test criteria are as follows:
1. uniform brightness test judgment standard: the brightness and no gold tumor are good; bright, even a few Jin Liu are good; slightly darkened, with obvious gold tumors producing worse; blackening, and chromatic aberration are poor.
2. Testing the binding force; baking at 280 deg.c for 5min to obtain gold layer with 1000 times enlarged size and no crack; baking at 280 deg.c for 5min to obtain gold layer with 1000 times enlarged cracks; baking at 280 ℃ for 5min, wherein the gold layer has 500 times of enlarged occasional cracks which are worse; the gold layer was 500 times amplified with obvious cracks being poor after baking at 280℃for 5 min.
3. The stability of the gold jar preferably means that the solution is clear and transparent within half a year and does not change color; the solution was clear within half a year, but slightly red solids precipitated on the walls of the tank; poor indicates that the solution reddened somewhat within half a year; the difference indicates that the solution became significantly red within half a year, and the cloudiness was very poor indicating that the cloudiness of the solution was severe within half a year.
4. Judging that the coating has no chromatic aberration: the color difference and blushing phenomena are avoided; slight blushing is sometimes good; the obvious blushing of the corner orifice is poor; blushing is significantly worse.
Example 1
An environment-friendly cyanide-free electroplating solution:
gold sodium thiosulfate 5g/L, 8-methyl-8H-thieno [2,3-b ] -indole-2-carboxylic acid 10mg/L,3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid 20mg/L, 2-mercapto-5-nitropyridine 2g/L, (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinolinecarboxylic acid benzyl ester p-toluenesulfonate 0.1g/L, 1H-pyrrolo [2,3-b ] pyridin-4-yl trifluoromethanesulfonate 0.1g/L, 1-butyl-1-methylpyrrolidine triflate 0.1g/L, 6-nitropyrrolo [1,2-a ] quinoline 30mg/L, N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt 5mg/L, N-2-nitrobenzenesulfinyl-L-isoleucine hexylammonium salt 20mg/L, polyethylene glycol 300035mg/L, 6-nitro-pyridin-4-yl triflate 0.1g/L, 1-nitro-1-methylpyrrolidine triflate 30mg/L, and the balance of polyoxyethylene ether 15mg/L
pH 5.5
Operating temperature of 30 DEG C
For 90min
The current density was 1.5A/dm 2
Example 1 the test results were: the uniformity and the brightness are excellent, the binding force test is excellent, the gold cylinder stability is excellent, and the color difference test is excellent.
Example 2
An environment-friendly cyanide-free electroplating solution:
gold sodium thiosulfate 6g/L, 8-methyl-8H-thieno [2,3-b ] -indole-2-carboxylic acid 20mg/L,3- [ 1H-indol 3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid 40mg/L, 2-mercapto-5-nitropyridine 6g/L, (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinolinecarboxylic acid benzyl ester p-toluenesulfonate 0.3g/L, 1H-pyrrolo [2,3-b ] pyridin-4-yl trifluoromethanesulfonate 0.3g/L, 1-butyl-1-methylpyrrolidine triflate 0.3g/L, 6-nitropyrrolo [1,2-a ] quinoline 60mg/L, N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt 15mg/L, N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt 60mg/L, polyethylene glycol 300070mg/L, 6-nitro-maleic acid 60mg/L, and the balance of quinolyl ether
pH 5.5
Operating temperature of 30 DEG C
For 50min
The current density was 3.5A/dm 2
Example 2 the test results were: the uniformity and the brightness are excellent, the binding force test is excellent, the gold cylinder stability is excellent, and the color difference test is excellent.
Example 3
An environment-friendly cyanide-free electroplating solution:
gold sodium thiosulfate 5g/L, 8-methyl-8H-thieno [2,3-b ] -indole-2-carboxylic acid 15mg/L,3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid 30mg/L, 2-mercapto-5-nitropyridine 4g/L, (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinolinecarboxylic acid benzyl ester p-toluenesulfonate 0.2g/L, 1H-pyrrolo [2,3-b ] pyridin-4-yl trifluoromethanesulfonate 0.2g/L, 1-butyl-1-methylpyrrolidine triflate 0.2g/L, 6-nitropyrrolo [1,2-a ] quinoline 40mg/L, N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt 10mg/L, N-2-nitrobenzenesulfinyl-L-isoleucine hexylammonium salt 40mg/L, polyethylene glycol 300050mg/L, 6-maleic acid benzyl sulfinyl-L, quinoline 40mg/L, and the balance of polyoxyl ether
pH 5.5
Operating temperature of 30 DEG C
For 30min
The current density was 5.5A/dm 2
Example 3 the test results were: the uniformity and the brightness are excellent, the binding force test is excellent, the gold cylinder stability is excellent, and the color difference test is excellent.
Comparative example
An environment-friendly cyanide-free electroplating solution:
6g/L of sodium gold thiosulfate, 2-mercapto-5-nitropyridine 2-6g/L, polyethylene glycol 300035-70mg/L, 6-nitropyrrolo [1,2-a ] quinoline 40mg/L, allyloxy polyoxyethylene ether 15-60mg/L and the balance of water
pH 5.5
Operating temperature of 30 DEG C
For 90min
The current density was 1.5A/dm 2
Comparative example and example comparison, comparative example lack compound flattening agent, compound brightening agent, compound crystal nucleus thinning agent, stabilizer, etc., the experimental result obtained is that the uniformity brightness is poor, the binding force test is poor, the gold cylinder stability is poor, and the color difference test is poor.
The above disclosure is merely an example of the present invention, but the present invention is not limited thereto, and any variations that can be considered by a person skilled in the art should fall within the protection scope of the present invention.
Claims (3)
1. The environment-friendly cyanide-free electroplating solution is characterized by comprising the following components in mass concentration:
3-10g/L of gold salt, 30-60mg/L of composite brightening agent, 2-6g/L of complexing agent, 0.3-0.9g/L of composite crystal nucleus refiner, 30-60mg/L of accelerator, 25-75mg/L of composite leveling agent, 35-70mg/L of dispersing agent, 30-60mg/L of stabilizer and 15-60mg/L of surfactant;
pH is 5.0-6.0
The operation temperature is 25-35 DEG C
The current density is 0.2-6.5A/dm2
The pH is regulated by sodium hydroxide with the mass concentration of 50% and concentrated sulfuric acid with the volume concentration of 50%;
the compound brightening agent is a thiophene indole carboxylic acid compound, and is a composition formed by 8-methyl-8H-thieno [2,3-b ] -indole-2-carboxylic acid and 3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid, wherein the mass concentration ratio of the compound brightening agent to the 3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid is 10-20mg/L, and the mass concentration ratio of the compound brightening agent to the 3- [ 1H-indol-3-yl ] -2- [ (thiophene-2-carbonyl) -amino ] -propionic acid is 20-40mg/L;
the gold salt is sodium gold thiosulfate;
the composite crystal nucleus refiner is a composition consisting of (S) - (-) -1,2,3, 4-tetrahydro-3-isoquinoline carboxylic acid benzyl ester p-toluenesulfonate, 1H-pyrrolo [2,3-b ] pyridin-4-yl trifluoromethanesulfonate and 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, and the mass concentration ratio of the three is 1:1:1 when in use;
the compound leveling agent is an aromatic amino acid cyclohexanaminium salt compound, and is a composition composed of N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt and N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt, wherein the mass concentration ratio of the compound leveling agent to the N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt is 1:4, the N-benzyloxycarbonyl-L-isoleucine dicyclohexylammonium salt is 5-15mg/L, and the N-2-nitrobenzenesulfinyl-L-isoleucine dicyclohexylammonium salt is 20-60mg/L;
the stabilizer is 6-maleic acid nitroquinolizine salt;
the accelerator is 6-nitropyrrolo [1,2-a ] quinoline;
the surfactant is allyloxy polyoxyethylene ether; the dispersing agent is polyethylene glycol 3000;
the mass concentration ratio of the stabilizer to the accelerator is 1:1 when the stabilizer and the accelerator are used;
the complexing agent is a pyridine mercapto compound, and the complexing agent is 2-mercapto-5-nitropyridine.
2. An environment-friendly cyanide-free electroplating process is characterized by comprising the following specific steps:
step 1, degreasing, cleaning with pure water, removing surface dirt, and then ultrasonic cleaning to remove chemical substances adsorbed on the surface of a substrate;
step 2, chemically plating atomic diffusion barrier layer palladium, cleaning a plating piece to remove surface dirt, then entering a chemical palladium plating tank to carry out chemical palladium plating, and washing after the palladium plating is completed;
step 3, after electro-plating and chemical palladium plating, the plating piece enters an electro-plating groove to perform gold plating, the gold plating mode adopts a four-position electrode clamping mode to perform electro-plating, and the electroplating solution used for electro-plating is the environment-friendly cyanide-free electroplating solution in claim 1;
the specific conditions of the step 3 are as follows: the gold plating adopts a four-position electrode clamp mode, an anode divides an anode line into four ports through branching, and is connected with four electrode clamps, the four electrode clamps respectively clamp plating pieces from the central positions of four sides of a base material during gold plating, and the distance between the anode and the cathode is set to be 5-40cm.
3. The environment-friendly cyanide-free electroplating process according to claim 2, wherein the chemical palladium plating solution in the step 2 comprises the following components in percentage by weight: 200-500mg/L of palladium sulfate, 0.5-1.5g/L of nicotinic acid, 15-25mg/L of 1-butyl-1-methylpyrrolidine triflate, 10-30mg/L of 2-acetylpyrazine, 30-60mg/L of succinic acid, 10-15ml/L of formic acid, 15-25g/L of sodium hypophosphite, the temperature of 45-55 ℃ and the pH of 5.0-6.5 are controlled, and the pH can be controlled by adopting a sodium hydroxide solution with the mass concentration of 50% and a concentrated sulfuric acid solution with the volume concentration of 50% for 10min and the thickness of 0.5-1 micrometer.
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| DE2445537A1 (en) * | 1974-09-20 | 1976-04-08 | Schering Ag | BATH FOR GALVANIC DEPOSITION OF GOLD |
| KR101079554B1 (en) * | 2008-06-11 | 2011-11-04 | 니혼 고쥰도가가쿠 가부시키가이샤 | Electrolytic gold plating solution and gold film obtained using same |
| CN105350035B (en) * | 2015-11-25 | 2018-11-09 | 广东致卓环保科技有限公司 | Organic amine system cyanide-free gold electroplating plating solution and method |
| CN105401181A (en) * | 2015-12-23 | 2016-03-16 | 苏州市金星工艺镀饰有限公司 | Electroplating method of environmentally-friendly cyanide-free gold-plating electroplating fluid |
| CN115522238B (en) * | 2022-11-23 | 2023-04-21 | 深圳创智芯联科技股份有限公司 | Cyanide-free gold electroplating solution of sodium gold sulfite and electroplating process thereof |
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