CN112251781A - Cyanide-free copper plating solution, preparation method thereof and cyanide-free copper plating method - Google Patents
Cyanide-free copper plating solution, preparation method thereof and cyanide-free copper plating method Download PDFInfo
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Abstract
The application discloses a cyanide-free copper plating solution, a preparation method thereof and a cyanide-free copper plating method, which belong to the technical field of electroplating processes, and the cyanide-free copper plating solution comprises the following components in parts by weight: polymeric potassium ammonium thiocyanate: 180-250 parts of polymeric cuprous thiocyanate: 30-40 parts of a pH regulator: 10-20 parts of tartaric acid: 30-50 parts of deionized water: 640-730 parts of sodium carboxylate: 5-10 parts of a refiner: 0.1 to 0.2 portion. The cyanide-free copper plating layer prepared by using the cyanide-free copper plating solution is not easy to peel and bubble, has good bonding force with other plating layers, and can be continuously and stably produced in batches.
Description
Technical Field
The application relates to the technical field of electroplating processes, in particular to cyanide-free copper plating solution, a preparation method thereof and a cyanide-free copper plating method.
Background
In the electroplating industry, cyanide is adopted as a complexing agent of a traditional alkaline copper plating solution, the cyanide copper plating performance is excellent, the porosity is low, the dispersing capacity is good, the deep plating capacity is good, and the plating solution is stable, however, the cyanide is a highly toxic substance, the death causing amount is only 5mg, the potential safety hazard exists in the use process, the post-treatment of waste water is extremely complex, and huge economic pressure is brought to enterprises, so the cyanide copper plating process is gradually replaced by a cyanide-free copper plating process.
However, the cyanide-free copper plating process on the market at present has the problem that the cyanide-free copper plating layer is easy to blister.
Disclosure of Invention
In view of the defects in the prior art, a first object of the present application is to provide a cyanide-free copper plating solution, in which a copper plating layer prepared by using the cyanide-free copper plating solution is not easy to foam, and the effect of improving the bonding strength of the cyanide-free copper plating layer is also provided.
The second purpose of the application is to provide a preparation method of the cyanide-free copper plating solution, which is used for preparing the cyanide-free copper plating solution.
The third purpose of the present application is to provide a cyanide-free copper plating method, and the method for preparing the cyanide-free copper plating layer has the advantages of simple process and easily controlled process conditions.
In order to achieve the first object, the invention provides the following technical scheme:
the cyanide-free copper plating solution comprises the following components in parts by weight: 250 parts of polymeric potassium ammonium thiocyanate, 30-40 parts of polymeric cuprous thiocyanate, 10-20 parts of pH regulator, 730 parts of deionized water 640-containing materials, 30-50 parts of tartaric acid, 5-10 parts of sodium carboxylate and 0.1-0.2 part of refiner.
By adopting the technical scheme, the polymerized ammonium potassium thiocyanate in the cyanide-free copper plating solution can be effectively complexed with copper ions of the cyanide-free copper plating solution to form stable metal complex ions, so that the concentration polarization and the electrochemical polarization of the cyanide-free copper plating solution are increased, the metal deposition speed is reduced, the cyanide-free copper plating layer is more uniform, and the ammonium potassium thiocyanate can also be used as a conductive salt in the cyanide-free copper plating solution to effectively improve the conductive capability of the cyanide-free copper plating solution, so that the consumption of electric energy is reduced; tartaric acid is added into the cyanide-free copper plating solution to improve the activation degree of the anode and promote the normal dissolution of the anode.
The sodium carboxylate is added into the cyanide-free copper plating solution, and oxygen atoms in carboxyl groups of the sodium carboxylate easily form stable hydrogen bonds with hydrogen atoms in water molecules, so that the probability of hydrogen precipitation side reaction of a cathode in the electroplating process is reduced, the current efficiency, the dispersing capacity and the covering capacity of the plating solution are greatly improved, and secondly, the reduction of hydrogen evolution amount can also reduce the porosity, reduce the probability of hydrogen embrittlement of a plating layer, inhibit the plating layer from forming a loose spongy plating layer, facilitate the improvement of the shape of the plating layer and reduce the generation of bubbles; meanwhile, sodium potassium tartrate is generated by the reaction of sodium carboxylate, tartaric acid and potassium ions in the solution, and the sodium potassium tartrate and polymeric potassium ammonium thiocyanate are matched to be used as an auxiliary complexing agent to form more stable copper complex ions, so that the cyanide-free copper plating layer is more uniform and fine, and the bonding strength of the cyanide-free copper plating layer is improved.
Preferably, the refiner is a n-butyraldehyde-aniline condensate.
The n-butyl aldehyde-aniline condensate has selective adsorbability, so that the potential of metal ions in cathode crystal reduction is changed to negative through adsorption on the surface of a cathode or complexation effect with metal ions, the reduction and precipitation of the metal ions or metal complex ions in a plating solution on the surface of the cathode are inhibited, the polarization of the cathode is increased, the formation speed of generated crystal nuclei is greater than the growth speed of crystal grains, and the crystal is thinned, so that a fine and compact electroplated layer is prepared.
Preferably, the refiner also comprises sulfaquinoline sodium, and the mass ratio of the n-butyl aldehyde-aniline condensate to the sulfaquinoline sodium is 5 (2-5).
After the cyanide-free copper plating solution is added with the n-butyl aldehyde-aniline condensation compound, an electroplated layer becomes fine and compact, pinholes and pits generated by the plated layer are reduced, microscopic wave peaks and wave troughs with small amplitude are formed on the surface of the plated layer, the microscopic peak positions of the surface of the plated layer are easier to adsorb sulfaquinoline sodium than the low trough positions, the sulfaquinoline sodium enables the deposition resistance at the peak positions to be increased, the deposition rate is slow, and after a certain period of time, the microscopic low trough positions are gradually filled with the plated layer, so that the plated layer is leveled.
Preferably, the mass ratio of the n-butyraldehyde-aniline condensate to the sulfaquinoline sodium is 5 (2-3).
By adopting the technical scheme, the proportion of each component of the refiner is further optimized, so that the proportion collocation of the components is more reasonable, and the refining and flattening effects of the refiner are further improved.
Preferably, the PH adjuster is one of potassium hydroxide, sodium hydroxide, or ammonium hydroxide.
By adopting the technical scheme, the cyanide-free copper plating solution is carried out under the alkaline condition, and the pH regulator has better effect in the cyanide-free copper plating solution by using potassium hydroxide, sodium hydroxide or ammonium hydroxide.
Preferably, the cyanide-free copper plating solution further comprises 0.5-0.7 parts of potassium nitrate.
By adopting the technical scheme, the introduction of K + and NO3 < - > enables the cyanide-free copper plating solution to have better conductivity, reduces the resistivity of the plating solution, and obviously reduces the cathode polarization and the current efficiency due to the interaction of NO3 < - > and H < + > in the electrolytic process.
In order to achieve the second object, the present application provides the following technical solutions:
a preparation method of cyanide-free copper plating solution comprises the following steps:
step 1: adding the corresponding parts by weight of polymeric potassium thiocyanate amine into an electroplating bath filled with deionized water, and stirring until the polymeric potassium thiocyanate amine is completely dissolved, wherein the temperature of the deionized water is 50-60 ℃;
step 2: adding the polymeric cuprous thiocyanate with the corresponding weight part into the electroplating bath, and stirring until the polymeric cuprous thiocyanate is completely dissolved;
and step 3: sequentially adding a pH regulator, tartaric acid, sodium carboxylate and a refiner in corresponding parts by weight into the electroplating bath, and stirring until the pH regulator, the tartaric acid, the sodium carboxylate and the refiner are completely dissolved;
and 4, step 4: electrolyzing for 5-8 hours by using an electrolytic net, wherein the current of the electrolytic net is 15-30A during electrolysis;
by adopting the technical scheme, firstly adding the polymeric potassium thiocyanate into an electroplating bath filled with deionized water at 50-60 ℃, improving the conductivity of the plating bath, then adding the polymeric cuprous thiocyanate, stirring until the polymeric potassium thiocyanate and the copper ions are completely dissolved, so that the polymeric potassium thiocyanate and the copper ions generate a metal complex, then adding a pH regulator, a refiner, tartaric acid and sodium carboxylate into the electroplating bath, wherein the pH regulator is used for regulating the pH of the cyanide-free copper plating solution to a specified range, the sodium carboxylate and the tartaric acid are used for improving the quality of a plating layer, the refiner is used for further improving the quality of the plating layer, and then electrolyzing for 5-8 hours by using an electrolytic network, so as to further improve the conductivity of the plating bath.
In order to achieve the third object, the present application provides the following technical solutions:
a cyanide-free copper plating method comprises the following steps:
8. a cyanide-free copper plating method is characterized in that: the method comprises the following steps:
1) pretreatment: hanging a zinc base material product, and carrying out wax removal, oil removal, acid-base neutralization and cleaning on the surface of the zinc base material product;
2) electroplating: electroplating the zinc-based product obtained in the step 1 in an electroplating bath using the cyanide-free copper plating solution as defined in claims 1-6, wherein the pH of the cyanide-free copper plating solution is 10-12, the temperature is 50-60 ℃, the current density is 10-30A/dm2, and the electroplating time is 5-10 minutes;
3) and (3) drying: washing and drying the electroplated product by using deionized water;
by adopting the technical scheme, the zinc base material product is pretreated firstly, which is beneficial to electroplating; relevant parameters are well controlled during electroplating, so that the prepared cyanide-free copper plating layer is high in hardness and moderate in thickness; the product is dried, which is beneficial to combining with other coatings.
Preferably, the surface of the product is plated with copper pyrophosphate or copper sulfate after being dried by blowing.
By adopting the technical scheme, the pyrophosphate copper or the copper sulfate is plated on the surface of the electroplated product, so that the stability of the surface of the product is improved, and the binding force of a cyanide-free copper plating layer and other plating layers can be improved.
In conclusion, the invention has the following beneficial effects:
firstly, a cyanide-free copper plating layer obtained by using the cyanide-free copper plating solution is uniform and compact, has good binding force with a substrate, is not easy to generate bubbles, and can be continuously and stably produced in batch;
secondly, adding n-butyl aldehyde-aniline condensation compound into the cyanide-free copper plating solution to increase the polarization of a cathode, wherein the formation speed of crystal nuclei generated by the cathode is greater than the growth speed of crystal grains, and the crystals are thinned, so that a fine and compact electroplated layer is prepared;
thirdly, potassium nitrate is added into the cyanide-free copper plating solution, the cyanide-free copper plating solution has better conductivity due to the introduction of K + and NO3-, the resistivity of the plating solution is reduced, and the interaction between NO 3-and H + in the electrolytic process obviously reduces the cathode polarization and the current efficiency.
Detailed Description
The present application will be described in further detail with reference to examples.
The following examples and comparative examples have the following raw material sources as shown in the table:
TABLE 1
Preparation example 1
The cyanide-free copper plating solution of the preparation example comprises the following components by weight: 180g of polymeric potassium ammonium thiocyanate, 30g of polymeric cuprous thiocyanate, 10g of potassium hydroxide, 744g of deionized water, 30g of tartaric acid, 6g of sodium carboxylate and 0.1g of n-butyl aldehyde-aniline condensate.
The preparation method of the cyanide-free copper plating solution comprises the following steps:
step 1: adding the corresponding parts by weight of polymeric potassium thiocyanate amine into an electroplating bath filled with deionized water, and stirring until the polymeric potassium thiocyanate amine is completely dissolved, wherein the temperature of the deionized water is 50 ℃;
step 2: adding the polymeric cuprous thiocyanate with the corresponding weight part into the electroplating bath, and stirring until the polymeric cuprous thiocyanate is completely dissolved;
and step 3: sequentially adding potassium hydroxide, sodium carboxylate, tartaric acid and n-butyl aldehyde-aniline condensation compound in corresponding parts by weight into the electroplating bath, and stirring until the potassium hydroxide, the sodium carboxylate, the tartaric acid and the n-butyl aldehyde-aniline condensation compound are completely dissolved;
and 4, step 4: electrolyzing for 5 hours by using an electrolytic net, wherein the current of the electrolytic net is 15A during electrolysis;
preparation example 2
The cyanide-free copper plating solution of the preparation example comprises the following components by weight: 210g of polymeric potassium ammonium thiocyanate, 35g of polymeric cuprous thiocyanate, 15g of potassium hydroxide, 693g of deionized water, 40g of tartaric acid, 7g of sodium carboxylate and 0.5g of n-butyl aldehyde-aniline condensate.
The preparation method of the cyanide-free copper plating solution comprises the following steps:
step 1: adding the corresponding parts by weight of polymeric potassium thiocyanate amine into an electroplating bath filled with deionized water, and stirring until the polymeric potassium thiocyanate amine is completely dissolved, wherein the temperature of the deionized water is 55 ℃;
step 2: adding the polymeric cuprous thiocyanate with the corresponding weight part into the electroplating bath, and stirring until the polymeric cuprous thiocyanate is completely dissolved;
and step 3: sequentially adding potassium hydroxide, sodium carboxylate, tartaric acid and n-butyl aldehyde-aniline condensation compound in corresponding parts by weight into the electroplating bath, and stirring until the potassium hydroxide, the sodium carboxylate, the tartaric acid and the n-butyl aldehyde-aniline condensation compound are completely dissolved;
and 4, step 4: electrolyzing for 6 hours by using an electrolytic net, wherein the current of the electrolytic net is 20A during electrolysis;
preparation example 3
The cyanide-free copper plating solution of the preparation example comprises the following components by weight: 250g of polymeric potassium ammonium thiocyanate, 40g of polymeric cuprous thiocyanate, 20g of potassium hydroxide, 630g of deionized water, 50g of tartaric acid, 10g of sodium carboxylate and 0.2g of n-butyl aldehyde-aniline condensate.
The preparation method of the cyanide-free copper plating solution comprises the following steps:
step 1: adding the corresponding parts by weight of polymeric potassium thiocyanate amine into an electroplating bath filled with deionized water, and stirring until the polymeric potassium thiocyanate amine is completely dissolved, wherein the temperature of the deionized water is 60 ℃;
step 2: adding the polymeric cuprous thiocyanate with the corresponding weight part into the electroplating bath, and stirring until the polymeric cuprous thiocyanate is completely dissolved;
and step 3: sequentially adding potassium hydroxide, sodium carboxylate, tartaric acid and n-butyl aldehyde-aniline condensation compound in corresponding parts by weight into the electroplating bath, and stirring until the potassium hydroxide, the sodium carboxylate, the tartaric acid and the n-butyl aldehyde-aniline condensation compound are completely dissolved;
and 4, step 4: electrolyzing for 8 hours by using an electrolytic net, wherein the current of the electrolytic net is 30A during electrolysis;
preparation example 4
The cyanide-free copper plating solution of the preparation example comprises the following components by weight: 190g of polymerized potassium ammonium thiocyanate, 34g of polymerized cuprous thiocyanate, 14g of potassium hydroxide, 719g of deionized water, 36g of tartaric acid, 7g of sodium carboxylate and 0.1g of n-butyl aldehyde-aniline condensate.
The preparation method of the cyanide-free copper plating solution comprises the following steps:
step 1: adding the corresponding parts by weight of polymeric potassium thiocyanate amine into an electroplating bath filled with deionized water, and stirring until the polymeric potassium thiocyanate amine is completely dissolved, wherein the temperature of the deionized water is 55 ℃;
step 2: adding the polymeric cuprous thiocyanate with the corresponding weight part into the electroplating bath, and stirring until the polymeric cuprous thiocyanate is completely dissolved;
and step 3: sequentially adding potassium hydroxide, sodium carboxylate, tartaric acid and n-butyl aldehyde-aniline condensation compound in corresponding parts by weight into the electroplating bath, and stirring until the potassium hydroxide, the sodium carboxylate, the tartaric acid and the n-butyl aldehyde-aniline condensation compound are completely dissolved;
and 4, step 4: electrolyzing for 6 hours by using an electrolytic net, wherein the current of the electrolytic net is 20A during electrolysis;
preparation example 5
The cyanide-free copper plating solution of the preparation example comprises the following components by weight: 192g of polymeric potassium ammonium thiocyanate, 35g of polymeric cuprous thiocyanate, 15g of potassium hydroxide, 712g of deionized water, 38g of tartaric acid, 8g of sodium carboxylate and 0.2g of n-butyl aldehyde-aniline condensate.
The preparation method of the cyanide-free copper plating solution comprises the following steps:
step 1: adding the corresponding parts by weight of polymeric potassium thiocyanate amine into an electroplating bath filled with deionized water, and stirring until the polymeric potassium thiocyanate amine is completely dissolved, wherein the temperature of the deionized water is 55 ℃;
step 2: adding the polymeric cuprous thiocyanate with the corresponding weight part into the electroplating bath, and stirring until the polymeric cuprous thiocyanate is completely dissolved;
and step 3: sequentially adding potassium hydroxide, sodium carboxylate, tartaric acid and n-butyl aldehyde-aniline condensation compound in corresponding parts by weight into the electroplating bath, and stirring until the potassium hydroxide, the sodium carboxylate, the tartaric acid and the n-butyl aldehyde-aniline condensation compound are completely dissolved;
and 4, step 4: electrolyzing for 6 hours by using an electrolytic net, wherein the current of the electrolytic net is 20A during electrolysis;
preparation example 6
The cyanide-free copper plating solution of the preparation example comprises the following components by weight: 194g of polymerized potassium ammonium thiocyanate, 35g of polymerized cuprous thiocyanate, 16g of potassium hydroxide, 707g of deionized water, 39g of tartaric acid, 9g of sodium carboxylate and 0.15g of n-butyl aldehyde-aniline condensate.
The preparation method of the cyanide-free copper plating solution comprises the following steps:
step 1: adding the corresponding parts by weight of polymeric potassium thiocyanate amine into an electroplating bath filled with deionized water, and stirring until the polymeric potassium thiocyanate amine is completely dissolved, wherein the temperature of the deionized water is 55 ℃;
step 2: adding the polymeric cuprous thiocyanate with the corresponding weight part into the electroplating bath, and stirring until the polymeric cuprous thiocyanate is completely dissolved;
and step 3: sequentially adding potassium hydroxide, sodium carboxylate, tartaric acid and n-butyl aldehyde-aniline condensation compound in corresponding parts by weight into the electroplating bath, and stirring until the potassium hydroxide, the sodium carboxylate, the tartaric acid and the n-butyl aldehyde-aniline condensation compound are completely dissolved;
and 4, step 4: electrolyzing for 6 hours by using an electrolytic net, wherein the current of the electrolytic net is 20A during electrolysis;
preparation example 7
The preparation method of the cyanide-free copper plating solution is different from the preparation method of the cyanide-free copper plating solution in the preparation example 6 in that: after the n-butyraldehyde-aniline condensate was added in step 3, 0.06g of sulfaquinoline sodium was also added and stirred until dissolved.
Preparation example 8
The preparation method of the cyanide-free copper plating solution is different from the preparation method of the cyanide-free copper plating solution in the preparation example 6 in that: after the n-butyraldehyde-aniline condensate was added in step 3, 0.09g of sulfaquinoline sodium was also added.
Preparation example 9
The preparation method of the cyanide-free copper plating solution is different from the preparation method of the cyanide-free copper plating solution in the preparation example 6 in that: after the n-butyraldehyde-aniline condensate was added in step 3, 0.12g of sulfaquinoline sodium was also added.
Preparation example 10
The preparation method of the cyanide-free copper plating solution is different from the preparation method of the cyanide-free copper plating solution in the preparation example 6 in that: after the n-butyraldehyde-aniline condensate was added in step 3, 0.15g of sulfaquinoline sodium was also added.
Preparation example 11
The preparation method of the cyanide-free copper plating solution is different from the preparation method of the cyanide-free copper plating solution in the preparation example 6 in that: in step 3, 0.6g of potassium nitrate was also added and stirred until dissolved.
Preparation example 12
The preparation method of the cyanide-free copper plating solution is different from the preparation method of the cyanide-free copper plating solution in the preparation example 6 in that: and replacing the potassium hydroxide in the step 3 with sodium hydroxide with equal parts by weight.
Preparation example 13
The preparation method of the cyanide-free copper plating solution is different from the preparation method of the cyanide-free copper plating solution in the preparation example 6 in that: and replacing the potassium hydroxide in the step 3 with ammonium hydroxide with equal parts by weight.
Preparation example 14
The preparation method of the cyanide-free copper plating solution is different from the preparation method of the cyanide-free copper plating solution in the preparation example 6 in that: after the pH adjuster and the refiner were added and dissolved in step 3, 0.15g of n-butyraldehyde-aniline condensate, 0.06g of sulfaquinoline sodium, and 0.6g of potassium nitrate were also added and stirred until completely dissolved.
Example 1
The cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 1.
The cyanide-free copper plating method comprises the following steps:
1) pretreatment: hanging a zinc base material product, and carrying out wax removal, oil removal, acid-base neutralization and cleaning on the surface of the zinc base material product;
2) electroplating: putting the zinc base material product in the step 1 into an electroplating bath using the cyanide-free copper plating solution for electroplating, wherein the pH of the cyanide-free copper plating solution is 10, the temperature is 50 ℃, the current density is 10A/dm2, and the electroplating time is 5 minutes;
3) and (3) drying: washing and drying the electroplated product by using deionized water;
4) surface treatment: and 4, plating copper pyrophosphate or copper sulfate on the surface of the product after the step 3.
Example 2
The cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 2.
The cyanide-free copper plating method comprises the following steps:
1) pretreatment: hanging a zinc base material product, and carrying out wax removal, oil removal, acid-base neutralization and cleaning on the surface of the zinc base material product;
2) electroplating: putting the zinc base material product in the step 1 into an electroplating bath using the cyanide-free copper plating solution for electroplating, wherein the pH of the cyanide-free copper plating solution is 11, the temperature is 50 ℃, the current density is 10A/dm2, and the electroplating time is 5 minutes;
3) and (3) drying: washing and drying the electroplated product by using deionized water;
4) surface treatment: and 4, plating copper pyrophosphate or copper sulfate on the surface of the product after the step 3.
Example 3
The cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 3.
The cyanide-free copper plating method comprises the following steps:
1) pretreatment: hanging a zinc base material product, and carrying out wax removal, oil removal, acid-base neutralization and cleaning on the surface of the zinc base material product;
2) electroplating: putting the zinc base material product in the step 1 into an electroplating bath using the cyanide-free copper plating solution for electroplating, wherein the PH of the cyanide-free copper plating solution is 12, the temperature is 60 ℃, the current density is 30A/dm2, and the electroplating time is 10 minutes;
3) and (3) drying: washing and drying the electroplated product by using deionized water;
4) surface treatment: and 4, plating copper pyrophosphate or copper sulfate on the surface of the product after the step 3.
Example 4
The cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 4.
The cyanide-free copper plating method comprises the following steps:
1) pretreatment: hanging a zinc base material product, and carrying out wax removal, oil removal, acid-base neutralization and cleaning on the surface of the zinc base material product;
2) electroplating: putting the zinc base material product in the step 1 into an electroplating bath using the cyanide-free copper plating solution for electroplating, wherein the pH of the cyanide-free copper plating solution is 10, the temperature is 50 ℃, the current density is 15A/dm2, and the electroplating time is 7 minutes;
3) and (3) drying: washing and drying the electroplated product by using deionized water;
4) surface treatment: and 4, plating copper pyrophosphate or copper sulfate on the surface of the product after the step 3.
Example 5
The cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 5.
The cyanide-free copper plating method comprises the following steps:
1) pretreatment: hanging a zinc base material product, and carrying out wax removal, oil removal, acid-base neutralization and cleaning on the surface of the zinc base material product;
2) electroplating: putting the zinc base material product in the step 1 into an electroplating bath using the cyanide-free copper plating solution for electroplating, wherein the pH of the cyanide-free copper plating solution is 10, the temperature is 50 ℃, the current density is 15A/dm2, and the electroplating time is 7 minutes;
3) and (3) drying: washing and drying the electroplated product by using deionized water;
4) surface treatment: and 4, plating copper pyrophosphate or copper sulfate on the surface of the product after the step 3.
Example 6
The cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 6.
The cyanide-free copper plating method comprises the following steps:
1) pretreatment: hanging a zinc base material product, and carrying out wax removal, oil removal, acid-base neutralization and cleaning on the surface of the zinc base material product;
2) electroplating: putting the zinc base material product in the step 1 into an electroplating bath using the cyanide-free copper plating solution for electroplating, wherein the pH of the cyanide-free copper plating solution is 10, the temperature is 50 ℃, the current density is 15A/dm2, and the electroplating time is 7 minutes;
3) and (3) drying: washing and drying the electroplated product by using deionized water;
4) surface treatment: and 4, plating copper pyrophosphate or copper sulfate on the surface of the product after the step 3.
Example 7
This example differs from example 6 in that: the cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 7.
Example 8
This example differs from example 6 in that: the cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 8.
Example 9
This example differs from example 6 in that: the cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 9.
Example 10
This example differs from example 6 in that: the cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 10.
Example 11
This example differs from example 6 in that: the cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 11.
Example 12
This example differs from example 6 in that: the cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 12.
Example 13
This example differs from example 6 in that: the cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 13.
Example 14
This example differs from example 6 in that: the cyanide-free copper plating solution used in the cyanide-free copper plating method of this example was the cyanide-free copper plating solution obtained in preparation example 14.
Comparative example 1
This comparative example differs from example 6 in that the sodium carboxylate is replaced by an equal part by weight of potassium carboxylate.
Comparative example 2
This comparative example differs from example 6 in that the cyanide-free copper plating bath does not contain sodium carboxylate.
Comparative example 3
This comparative example differs from example 6 in that the polymeric potassium ammonium thiocyanate was replaced with an equal part by weight of potassium thiocyanate.
Comparative example 4
This comparative example differs from example 6 in that: in step 3 of the method for producing a cyanide-free copper plating solution of the production example of example 6, 0.03g of sulfaquinoline sodium was added after the n-butyraldehyde-aniline condensate was added and stirred until dissolved.
Comparative example 5
This comparative example differs from example 6 in that: in step 3 of the method for producing a cyanide-free copper plating solution of the production example of example 6, 0.18g of sulfaquinoline sodium was added after the n-butyraldehyde-aniline condensate was added and stirred until dissolved.
Performance test
The cyanide-free copper plating layers obtained in examples 1 to 14 and comparative examples 1 to 5 were tested as samples.
Test one, hardness test: the test equipment uses HX-1000 microhardness tester produced by Shanghai second optical instrument factory, and the test part of the sample can be the surface or the section of the coating. When the surface of the coating is tested, the center of the main surface is preferably used, and the interference of the surface defects of the coating on the test is avoided. In the same test part of the test sample, the distance between the indentations should be more than 2.5 times of the diagonal length of the indentations. For the same sample, it should be measured three times or more under the same conditions, and the arithmetic mean value is taken as the measurement result of the hardness of the plating layer.
Test two, thickness test: the test equipment uses an OU 3500F type coating thickness gauge of the times company to test at the center of the main surface of the coating, so as to avoid testing at the surface defect of the coating. For the same sample, the measurement should be performed three or more times under the same conditions, and the arithmetic mean value is taken as the measurement result of the thickness of the plating layer.
Test three, porosity test: the porosity was determined according to GB/T17721-1999 porosity test iron reagent test for Metal coverings.
Test four, blistering test: and (3) heating the test sample in a heating furnace at 250 ℃ for 0.5h, quenching the test sample in water at room temperature, and checking whether a coating is foamed, wherein the heating equipment is a JDGP-25KW heating furnace produced by Zhang hong Kong Pond Qiaojinda electronic equipment factory.
Test four, bond strength test: and (3) carrying out a plating bonding strength test according to a bending test specified in GB/T5270-2005, namely test method comments on the adhesion strength of the metal coating and the chemical deposition layer on the metal substrate, repeatedly bending the sample by 180 degrees along an axis with the diameter equal to the thickness of the sample until the sample is broken, and judging whether the plating layer falls off or not.
TABLE 2 test results of cyanide-free copper plating layers of examples 1 to 13 and comparative examples 1 to 3
As can be seen from Table 2, the cyanide-free copper plating layers prepared from the cyanide-free copper plating baths of examples 1 to 14 and comparative examples 4 to 5 of the present application did not cause blistering and the plating layers did not peel off, the plating layers peeled off in comparative example 1, and the plating layers blistered and the plating layers peeled off in comparative examples 2 to 3.
By comparing examples 1 to 6, the cyanide-free copper plating layer prepared using the cyanide-free copper plating solution formulation of example 6 exhibited superior properties in terms of hardness and thickness when the components in the cyanide-free copper plating solution and the preparation process were changed.
A comparison of examples 6 and 7 shows that the addition of sulfaquinoxaline sodium to the cyanide-free copper plating bath increases the hardness and thickness of the cyanide-free copper plating layer and reduces the porosity of the cyanide-free copper plating layer.
Comparing examples 7-10 with comparative examples 4-5, the ratio of n-butyraldehyde-aniline condensate to sulfaquinoline sodium in examples 7-10 was 5: (2-5), the ratio of n-butyraldehyde-aniline condensate to sodium sulfaquinoline in comparative example 4 was 5:1, and the ratio of n-butyraldehyde-aniline condensate to sodium sulfaquinoline in comparative example 5 was 5:6, and it can be seen from the data in table 2 that the ratio of n-butyraldehyde-aniline condensate to sodium sulfaquinoline was 5: (2-5) to compare examples 7-8 with examples 9-10 for the preferred range of the formulation, the ratio of n-butyraldehyde-aniline condensate to sulfaquinoline sodium in examples 7-8 was 5: (2-3), showing that the ratio of n-butyraldehyde-aniline condensate to sulfaquinoline sodium is 5: (2-3) is a further preferable range of the formulation.
Comparing examples 6 and 11, the addition of potassium nitrate to the cyanide-free copper plating bath increases the hardness and thickness of the cyanide-free copper plating layer.
Examples 6, 12 and 13 were compared, and potassium hydroxide was preferably used as a pH adjusting agent in the cyanide-free copper plating bath.
Comparing example 6 with comparative examples 1-3, it is shown that the sodium carboxylate and the polymeric potassium ammonium thiocyanate in the cyanide-free copper plating solution cooperate with each other to have a better effect of solving the problems of blistering and shedding of the cyanide-free copper plating layer.
The above are preferred embodiments of the present application, and the scope of protection of the present application is not limited thereto, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (9)
1. A cyanide-free copper plating solution is characterized in that: the composition comprises the following components in parts by weight:
polymeric potassium ammonium thiocyanate: 180-250 parts;
polymeric cuprous thiocyanate: 30-40 parts;
pH regulators: 10-20 parts;
tartaric acid: 30-50 parts;
deionized water: 640-730 parts;
sodium carboxylate: 5-10 parts;
a refiner: 0.1 to 0.2 portion.
2. The cyanide-free copper plating solution according to claim 1, wherein: the refiner is a n-butyl aldehyde-aniline condensate.
3. The cyanide-free copper plating solution according to claim 2, wherein: the refiner also comprises sulfaquinoline sodium, and the mass ratio of the n-butyl aldehyde-aniline condensate to the sulfaquinoline sodium is 5 (2-5).
4. The cyanide-free copper plating solution according to claim 3, wherein: the mass ratio of the n-butyraldehyde-aniline condensate to the sulfaquinoline sodium is 5 (2-3).
5. The cyanide-free copper plating solution according to claim 1, wherein: the pH regulator is one of potassium hydroxide, sodium hydroxide or ammonium hydroxide.
6. The cyanide-free copper plating solution according to claim 1, wherein: also comprises 0.5 to 0.7 portion of potassium nitrate.
7. The method for preparing a cyanide-free copper plating bath according to any of claims 1 to 6, characterized in that: the method comprises the following steps:
step 1: adding the corresponding parts by weight of polymeric potassium thiocyanate amine into an electroplating bath filled with deionized water, and stirring until the polymeric potassium thiocyanate amine is completely dissolved, wherein the temperature of the deionized water is 50-60 ℃;
step 2: adding the polymeric cuprous thiocyanate with the corresponding weight part into the electroplating bath, and stirring until the polymeric cuprous thiocyanate is completely dissolved;
and step 3: sequentially adding a pH regulator, tartaric acid, sodium carboxylate and a refiner in corresponding parts by weight into the electroplating bath, and stirring until the pH regulator, the tartaric acid, the sodium carboxylate and the refiner are completely dissolved;
and 4, step 4: electrolyzing for 5-8 hr with electrolytic net with current of 15-30A.
8. A cyanide-free copper plating method is characterized in that: the method comprises the following steps:
1) pretreatment: hanging a zinc base material product, and carrying out wax removal, oil removal, acid-base neutralization and cleaning on the surface of the zinc base material product;
2) electroplating: electroplating the zinc-based product obtained in step 1 in an electroplating bath using the cyanide-free copper plating solution of claims 1-6, wherein the cyanide-free copper plating solution has a pH of 10-12, a temperature of 50-60 ℃, a current density of 10-30A/dm2 and an electroplating time of 5-10 minutes;
3) and (3) drying: and cleaning and drying the electroplated product by using deionized water.
9. The cyanide-free copper plating method according to claim 8, characterized in that: and after the product is dried, copper pyrophosphate or copper sulfate is plated on the surface of the product.
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