CN112899738A - Steel matrix direct cyanide-free copper plating electroplating solution under strong acid condition and preparation method thereof - Google Patents
Steel matrix direct cyanide-free copper plating electroplating solution under strong acid condition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a direct cyanide-free copper plating electroplating solution for a steel matrix under a strong acid condition, which comprises the following components: 50-250g/L of main salt, 30-100g/L of compound adsorbent, 1-5 g/L of additive and 300g/L of strong acid composition 160-; the effect that 1+1 is more than 2 is generated through the synergistic effect of the compound adsorbent, the additive and the strong acid composition, the speed of the iron-copper displacement reaction under the strong acid condition is effectively inhibited, so that an elemental copper layer with firm binding force is formed instantly when a steel matrix contacts an acid plating solution, the content of sulfuric acid is 150-250g/L, the technical problem that the stronger the acid is, the looser the plating layer is solved, and the plating layer is still firm when reaching 300 mu m.
Description
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to a direct cyanide-free copper plating electroplating solution for a steel matrix under a strong acid condition and an electroplating method.
Background
Since the advent of electroplating technology for over one hundred years, direct acid copper plating on steel substrates has been considered by the same industry as a "forbidden zone" and is considered to be infeasible. According to the metal activity sequence table: K. na, Ca, Mg, Al, Zn, Fe, Sn, Pb, (H), Cu, Hg, Ag, Pt and Au, wherein the steel substrate workpiece is subjected to instantaneous replacement reaction after entering an acidic copper plating solution: fe + CuS04=Cu+FeS04 And generating a replacement copper layer with loose tissue and extremely poor binding force. In general, the higher the acid content in the copper plating solution, the faster the displacement reaction, the coarser and porous the copper plating layer, and the poorer the binding force. Direct copper plating of steel parts under strongly acidic conditions has been regarded as a restricted area of industry and is considered to be infeasible.
In order to obtain good coating bonding force, at present, the direct copper plating on steel and iron base materials at home and abroad adopts an alkaline and extremely toxic cyaniding copper plating process (because cyanide is the best complexing agent in the metal electrodeposition process). However, cyanide is extremely toxic, 0.2 g can be fatal instantly, and the cyanide is careless in production, storage, transportation and use links, and the subsequent fruit cannot be imagined. Seriously pollutes the environment and endangers the human health, and brings huge potential safety hazard to the society. The elimination of virulent cyaniding electroplating is not only a vision of the industry, but also a government responsibility. In the seventies of the twentieth century, China has already started to eliminate the climax of virulent cyaniding electroplating and has achieved some achievements, but basically adopts a galvanizing process. However, in the field of copper plating, acid copper has the problem of replacing a copper layer, and cyanide-free alkali copper is mostly gradually eliminated and faded out of the industry due to the fact that the process is not related. So that the virulent cyaniding electroplating is remoistened after eighty and ninety years in China. Not only the direct copper plating of steel base materials in China and the developed countries in the world at present, but also the traditional virulent cyaniding process is still used.
In order to solve the problem of realizing cyanide-free copper plating, two technical problems of replacement reaction and passivation need to be solved simultaneously, the speed of copper and iron replacement reaction is effectively inhibited, and the instant dissolution of a passivation film formed in the air after the pretreatment of a steel matrix after entering a plating solution is ensured, so that the firm bonding force of a plating layer can be ensured. CN104975311A discloses a cyanide-free acidic copper plating solution on a steel substrate and a process thereof, wherein the plating solution does not contain cyanide, copper is directly plated on the steel substrate under an acidic condition, the obtained copper plating layer has fine crystallization and bright mirror surface, and the binding force reaches the national standard GB/5270-. However, the method is single, the complexing agent is used for reducing the copper ion potential in the plating solution, the displacement reaction is inhibited to improve the binding force, the copper-iron displacement reaction under the acidic condition cannot be completely inhibited, part of cuprous oxide is mixed in the copper plating layer, the cuprous oxide has no binding force with the steel matrix and the subsequent plating layer, the binding force can reach the national standard due to the mixing of the cuprous oxide in the copper plating layer, but the binding force is not optimal, and the plating layer thickness is only 30 mu m. Therefore, the method is only suitable for high-quality steel substrates, but in large-scale production, steel parts have various inclusions, so that the bonding force of a copper plating layer is poor, and the method is suitable for copper plating products. CN111321436A discloses a cyanide-free copper plating solution assistant and a copper plating solution, which utilize a complexing agent combination and copper ions to form copper complex ions to reduce the potential of the copper ions and inhibit the speed of displacement reaction. Meanwhile, the steel matrix passive film enters the plating solution to be instantly dissolved by utilizing the strong activation capacities of perchloric acid, hydrofluoric acid and hydrochloric acid. Even a dense stainless steel passivation film layer can be rapidly dissolved. Not only inhibits the rate of displacement reaction, but also solves the passivation problem well, and greatly improves the binding force of the plating layer. The copper plating layer has strong binding force, the plating layer with the thickness of 150 mu m firmly reaches GB5270-2005, but the plating layer with the thickness of more than 200 mu m generates peeling, which limits the application range of copper plating products.
Disclosure of Invention
The invention provides a direct cyanide-free copper plating electroplating solution for a steel matrix under a strong acid condition and a preparation method thereof, wherein the electroplating solution consists of a copper salt, a compound adsorbent, an additive and a strong acid, the synergistic effect of the compound adsorbent, the additive and the strong acid is utilized to generate an effect that 1+1 is more than 2, the speed of an iron-copper replacement reaction under the strong acid condition is effectively inhibited, so that the steel matrix instantly forms a simple substance copper layer with firm binding force instead of unorganized loose copper tree-shaped cuprous oxide when contacting the acid electroplating solution, and the simple substance copper layer has firm binding force with the matrix. The displacement reaction with the binding force and the copper electroplating are carried out simultaneously, so that a compact copper layer is quickly formed on the surface of the substrate, the contact between the acid plating solution and the substrate is isolated, the displacement reaction is quickly stopped, and the copper plating layer is ensured to have firm binding force. The technical problem that the bonding force of the copper plating layer is poorer as the acid content is higher is completely overcome, the copper plating layer has super-strong bonding force, not only reaches the national standard GB/T5270-.
The invention is realized by the following technical scheme:
a steel matrix direct cyanide-free copper plating electroplating solution under a strong acid condition comprises the following components in parts by weight: 50-250g/L of main salt, 30-100g/L of compound adsorbent, 0.1-5 g/L of additive and 300g/L of strong acid composition.
The main salt is copper chloride, copper carbonate, copper sulfate and copper hydroxide;
the compound adsorbent is a mixture of halide and one or more of ammonia water, phenylthiourea, diphenylthiourea, ethylene thiourea, cucurbituril and ferric sulfate, wherein the halide is 20-50g/L, the ammonia water is 20-100g/L, and the urea compound is 0.3-2 g/L; the halide is an alkali metal halide or an ammonium halide.
The compound adsorbent is adsorbed on the surface of the cathode, so that the electric potential of double-layer copper ions on the interface of the cathode can be reduced, the speed of a displacement reaction is effectively inhibited, a hydrogen evolution side reaction is inhibited, a compact simple substance copper layer with good binding force is formed by the displacement reaction, copper is quickly electrodeposited on the compact simple substance copper layer instead of the loose simple substance copper layer, and displacement and electroplating are carried out simultaneously. Because the speed of electrochemical deposition of the copper layer is very high, when the rapidly deposited compact copper layer reaches a certain thickness, the contact of the acid plating solution and the steel matrix is isolated, and the replacement reaction is rapidly stopped. So that the obtained copper layer has strong bonding force. The addition of ammonia water enables the compound adsorbent to have adsorption reversibility, and excessive impurities of the adsorbent in a coating in the electrodeposition process are effectively avoided.
The additive is preferably one or a mixture of more of urotropine, ascorbic acid, fatty amine polyoxyethylene ether, alkylphenol polyoxyethylene ether and polyethylene glycol; the additive is an antioxidant substance, can better control the oxidation of nascent copper, because the nascent copper has high reaction activity, can quickly generate oxidation-reduction reaction with bivalent copper ions to generate cuprous oxide, and is oxidized into cuprous oxide before entering the surface lattice of steel, and the cuprous oxide has no binding force with a matrix and a subsequent plating layer. Therefore, the addition of the antioxidant is important for forming a simple substance copper layer instead of a cuprous oxide layer on the surface of the substrate and improving the binding force. Meanwhile, the antioxidant generates more complex substances through the bridging action of divalent copper ions, so that the adsorption effect of the adsorbent is improved, and the replacement reaction speed is better inhibited.
The strong acid composition is a mixture of sulfuric acid and formic acid, and the contents of the strong acid composition in the electroplating solution are 150-250g/L of sulfuric acid and 10-50g/L of formic acid; in general, the higher the acid content in the copper plating solution, the faster the displacement reaction, the coarser and porous the copper plating layer, and the poorer the binding force. In the plating solution containing the compound adsorbent, the synergistic effect of the sulfuric acid, the formic acid and the compound adsorbent is that the higher the sulfuric acid content is, the stronger the adsorption effect is, the better the binding force is, and the best sulfuric acid content is 150-250g/L, thereby generating unexpected effect. The strong acid can form a complex with a certain stability constant with copper ions and iron ions. When the replacement reaction starts, strong acid and iron ions dissolved by corrosion form a viscous multi-ligand complex mucosa on the working surface of the cathode under the coordination of the adsorbent, and the mucosa can be used as a barrier layer to slow down the copper-iron replacement reaction speed and inhibit the corrosion of sulfuric acid to an iron substrate, so that the binding force of a plating layer is improved. The formic acid has certain reducibility, can form a mucosa with dissolved iron ions after being mixed with the sulfuric acid to slow down the replacement reaction speed, and can accelerate the deposition speed of copper ions on the surface of the cathode. The amount of sulfuric acid in the copper plating solution is 150-250g/L, which belongs to strong acid plating solution, is far higher than the contents of 20-80 g/L disclosed in CN104975311A and 50-120 g/L disclosed in CN111321436, overcomes the technical problem that the stronger the acid is, the looser the plating layer is, and in the two patents, the sulfuric acid mainly increases the conductivity of the plating solution in the plating solution, prevents copper salt from hydrolyzing, improves the crystallization of the plating layer, but does not have the adsorption effect.
The invention also discloses a preparation method of the cyanide-free copper plating solution, which comprises the following steps:
(1) adding a calculated amount 1/2 volume of pure water to the vessel;
(2) adding main salt, and stirring to dissolve; adding a strong acid composition under stirring; then adding the compound adsorbent, stirring and dissolving, and then adding the additive, stirring and dissolving.
(3) Adding the rest pure water to the working volume and stirring uniformly to implement electroplating.
The invention also discloses a method for directly plating copper on a steel matrix without cyanogen under the strong acid condition, which comprises the following steps:
and (3) sequentially carrying out oil removal, acid cleaning and activation treatment on the steel matrix, then placing the steel matrix in an electroplating bath for electroplating, and finishing the copper plating treatment of the steel matrix in the electroplating bath.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention abandons the traditional complexing theory, develops an effect that 1+1 is more than 2 by the synergistic action of compound adsorbent, additive and strong acid, effectively inhibits the iron-copper replacement reaction speed under the strong acid condition, and leads the steel matrix to form a simple substance copper layer with firm binding force instead of loose copper tree-shaped cuprous oxide at the moment of contacting with the acid plating solution, and the simple substance copper layer has firm binding force with the matrix. The compound adsorbent is adsorbed on the surface of the cathode, so that the electric potential of the double electric layers of the cathode interface copper ions can be reduced, the concentration of the copper ions in the double electric layers is changed, and the discharge and precipitation of the copper ions are inhibited, thereby effectively inhibiting the speed of the replacement reaction and inhibiting the side reaction of hydrogen evolution. Meanwhile, oxidation of the nascent copper can be well controlled by using the oxidation resistance of the additive, cuprous oxide with poor binding force is prevented from being formed, and meanwhile, the oxidation resistant substances generate more complex substances through the bridging action of divalent copper ions, so that the adsorption effect of the adsorbent is improved, and the replacement reaction speed is better inhibited. The strong acid composition can quickly dissolve the steel matrix passive film and can form a complex with a certain stability constant with copper ions and iron ions. When the replacement reaction starts, the multi-ligand complex mucosa which is viscous is formed on the working surface of the cathode with the dissolved iron ions under the coordination of the compound adsorbent to adsorb the surface of the cathode, so that the ionic heat movement is difficult, the thickness of the dispersion layer is reduced, the double electric layer structure is compact, the barrier layer is used as a barrier layer to effectively slow down the copper-iron replacement reaction speed, and meanwhile, the corrosion of sulfuric acid to an iron substrate can be inhibited, thereby improving the binding force of a plating layer. This CN104975311A is completely different from the action of sulfuric acid disclosed in CN111321436A in the plating solution, and the sulfuric acid has no adsorbability. The plating thickness can only reach 30 μm and 150 μm, while the plating solution of the invention can reach 300 μm.
The electroplating solution disclosed by the invention can replace virulent cyanide copper plating in the field of steel matrix copper plating, and can remove serious threats of virulent cyanide to operators and the environment. The defects that the binding force is not firm and the current is not large and the copper plating speed is low due to no activation capability of the existing cyanide-free alkaline copper plating are overcome. After the electroplating liquid is used by electroplating enterprises, the electroplating wastewater does not contain cyanide, so that the wastewater treatment cost can be reduced, and the sewage discharge can be reduced. Because the electroplating solution is a strong acid electroplating solution, the resistance is small, the electroplating voltage can be reduced, and a large amount of electric energy can be saved.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the following examples.
Example 1
A steel matrix direct cyanide-free copper plating electroplating solution under a strong acid condition, and the components and the contents are shown in table 1;
the preparation method of the electroplating solution comprises the following steps:
adding copper sulfate into 1/2 volume of pure water, stirring for dissolving, adding strong acid under continuous stirring, then respectively adding the compound adsorbent and the additive in turn, stirring uniformly, adding the rest pure water to the required volume to obtain the copper plating solution, and then implementing electroplating.
Table 1 shows the plating solutions of example 1:
| composition and operating conditions | Content g/L |
| Copper chloride | 100 |
| Sulfuric acid | 200 |
| Formic acid | 20 |
| Phenylthiourea | 0.3 |
| Ammonium chloride | 30 |
| Aqueous ammonia | 70 |
| Urotropine | 1 |
| Fatty amine polyoxyethylene ether | 0.2 |
| Electrode Current Density (A/dm)2) | 2 |
| Plating time (min) | 10 |
| Temperature/. degree.C | At room temperature |
| Anode | Phosphorus copper |
| Stirring method | Air agitation and cathode movement |
The electroplating method comprises the following steps: the steel test piece is sequentially subjected to oil removal, acid cleaning and activation treatment and then is placed in an electroplating bath for electroplating, and the current density is set to be 2A/dm2And electroplating for 10 min at room temperature to complete the copper plating treatment of the steel. The observation shows that the electroplated copper plating layer has fine and bright crystals.
And (3) detecting the binding force: detecting according to GB/T5270 and 2005 national standard:
(1) bending test: the copper-plated steel test piece is repeatedly bent until the test piece is broken, the copper-plated layer has no bubbling and peeling, and the copper layer at the broken position has no peeling and falling off.
(2) And (3) grid drawing test: and (4) scratching a square grid with the side length of 1 mm by using a hard steel scratch knife until the square grid reaches the test piece matrix, wherein the copper plating layer does not fall off.
(3) And (3) thermal vibration test: the copper-plated steel test piece is put into a heating furnace to be heated to 250 ℃, and is put into cold water to be quenched, and the copper-plated layer is not bubbled and stripped in a flaky shape.
The copper-plated layer has no bubbling, peeling and peeling through bending test, lattice test and thermal vibration test, and the binding force reaches the national standard GB/T5270-.
Example 2
The components and contents of the direct cyanide-free copper plating electroplating solution for the steel matrix under the strong acid condition are shown in the table 2;
the preparation method of the electroplating solution comprises the following steps: adding copper sulfate into 1/2 volume of pure water, stirring for dissolving, adding strong acid under continuous stirring, then respectively adding the compound adsorbent and the additive in turn, stirring uniformly, adding the rest pure water to the required volume to obtain the copper plating solution, and then implementing electroplating.
Table 2 copper plating solution of example 2:
| composition and operating conditions | Content g/L |
| Copper sulfate | 100 |
| Sulfuric acid | 150 |
| Formic acid | 30 |
| Cucurbiturils | 2 |
| Aqueous ammonia | 20 |
| Ammonium bromide | 30 |
| Ascorbic acid | 1 |
| Polyethylene glycol | 0.3 |
| Cathode current density (A/dm)2) | 3 |
| Plating time (min) | 10 |
| Temperature/. degree.C | At room temperature |
| Anode | Phosphorus copper |
| Stirring method | Air agitation and cathode movement |
The electroplating method comprises the following steps: the steel test piece is sequentially subjected to oil removal, acid cleaning and activation treatment and then is placed in an electroplating bath for electroplating, and the current density is set to be 3A/dm2And electroplating for 10 min at room temperature to complete the copper plating treatment of the steel. The observation shows that the electroplated copper coating is connectedThe crystal is fine and bright.
And (3) detecting the binding force: detecting according to GB/T5270 and 2005 national standard:
(1) bending test: the copper-plated steel test piece is repeatedly bent until the test piece is broken, the copper-plated layer has no bubbling and peeling, and the copper layer at the broken position has no peeling and falling off.
(2) And (3) grid drawing test: and (4) scratching a square grid with the side length of 1 mm by using a hard steel scratch knife until the square grid reaches the test piece matrix, wherein the copper plating layer does not fall off.
(3) And (3) thermal vibration test: the copper-plated steel test piece is put into a heating furnace to be heated to 250 ℃, and is put into cold water to be quenched, and the copper-plated layer is not bubbled and stripped in a flaky shape.
The copper-plated layer has no bubbling, peeling and peeling through bending test, lattice test and thermal vibration test, and the binding force reaches the national standard GB/T5270-.
Example 3
The components and contents of a steel matrix direct cyanide-free copper plating electroplating solution under the strong acid condition are shown in table 3;
the preparation method of the electroplating solution comprises the following steps:
adding copper sulfate into 1/2 volume of pure water, stirring for dissolving, adding strong acid under continuous stirring, then respectively adding the compound adsorbent and the additive in turn, stirring uniformly, adding the rest pure water to the required volume to obtain the copper plating solution, and then implementing electroplating.
Table 3 copper plating bath of example 3:
the electroplating method comprises the following steps: the steel test piece is sequentially subjected to oil removal, acid cleaning and activation treatment and then is placed in an electroplating bath for electroplating, and the current density is set to be 3A/dm2And electroplating for 10 min at room temperature to complete the copper plating treatment of the steel. The observation shows that the electroplated copper plating layer has fine and bright crystals.
And (3) detecting the binding force: detecting according to GB/T5270 and 2005 national standard:
(1) bending test: the copper-plated steel test piece is repeatedly bent until the test piece is broken, the copper-plated layer has no bubbling and peeling, and the copper layer at the broken position has no peeling and falling off.
(2) And (3) grid drawing test: and (4) scratching a square grid with the side length of 1 mm by using a hard steel scratch knife until the square grid reaches the test piece matrix, wherein the copper plating layer does not fall off.
(3) And (3) thermal vibration test: the copper-plated steel test piece is put into a heating furnace to be heated to 250 ℃, and is put into cold water to be quenched, and the copper-plated layer is not bubbled and stripped in a flaky shape.
The copper-plated layer has no bubbling, peeling and peeling through bending test, lattice test and thermal vibration test, and the binding force reaches the national standard GB/T5270-.
Example 4
A steel matrix direct cyanide-free copper plating electroplating solution under a strong acid condition, and the components and the contents are shown in table 1;
the preparation method of the electroplating solution comprises the following steps:
adding copper sulfate into 1/2 volume of pure water, stirring for dissolving, adding strong acid under continuous stirring, then respectively adding the compound adsorbent and the additive in turn, stirring uniformly, adding the rest pure water to the required volume to obtain the copper plating solution, and then implementing electroplating.
Table 4 shows the plating solution of example 4:
the electroplating method comprises the following steps: the steel test piece is sequentially subjected to oil removal, acid cleaning and activation treatment and then is placed in an electroplating bath for electroplating, and the current density is set to be 2A/dm2And electroplating for 10 min at room temperature to complete the copper plating treatment of the steel. The observation shows that the electroplated copper plating layer has fine and bright crystals.
And (3) detecting the binding force: detecting according to GB/T5270 and 2005 national standard:
(1) bending test: the copper-plated steel test piece is repeatedly bent until the test piece is broken, the copper-plated layer has no bubbling and peeling, and the copper layer at the broken position has no peeling and falling off.
(2) And (3) grid drawing test: and (4) scratching a square grid with the side length of 1 mm by using a hard steel scratch knife until the square grid reaches the test piece matrix, wherein the copper plating layer does not fall off.
(3) And (3) thermal vibration test: the copper-plated steel test piece is put into a heating furnace to be heated to 250 ℃, and is put into cold water to be quenched, and the copper-plated layer is not bubbled and stripped in a flaky shape.
The copper-plated layer has no bubbling, peeling and peeling through bending test, lattice test and thermal vibration test, and the binding force reaches the national standard GB/T5270-.
Comparative example
In the process of developing the electroplating technology, the judgment of the binding force is usually carried out by thickening and plating a high-hardness and high-stress coating to perform comparison test. The thicker the plating layer, the greater the shear stress generated in the bending test, and the more likely the plating layer is to peel, blister, or peel.
The plating was carried out in the plating solutions of examples 1 to 4 disclosed in CN104975311A, and the bending test adhesion was found to be good when the plating thickness was 30 μm, the bent plating layer was partially peeled when the plating thickness was 100 μm, and the bent plating layer was peeled off completely from the steel substrate when the plating thickness was 150 μm.
In the plating using the plating solutions of examples 1 to 8 disclosed in CN111321436A, the bend plating started to peel when the plating thickness was 200 μm, and the bend plating peeled off completely from the steel substrate when the plating thickness was 300 μm.
By electroplating with the electroplating solution disclosed by the application, the binding force detection of a bending test reaches the standard when the coating is 30 microns, the binding force of the bending coating is firm when the coating is 100 microns, and the binding force of the bending coating is firm when the coating is 150 microns. When the plating layer is 300 mu m, the bending test plating layer and the steel matrix have no cracking, peeling and stripping phenomena, and the bonding force is firm. The electroplating solution of the invention overcomes the technical problem of insufficient binding force caused by stronger cuprous oxide and acidity in the prior art. The results are shown in Table 6.
TABLE 6 comparison of the binding force of the coating bending test
| 30 μm | 100 μm | 150 μm | 200 μm | 300 μm | |
| CN104975311A | Firm and firm | Partially skinned | Peeling | Peeling off | Peeling off |
| CN111321436A | Firm and firm | Firm and firm | Firm and firm | Peeling | Peeling off |
| This application | Firm and firm | Firm and firm | Firm and firm | Firm and firm | Firm and firm |
Claims (10)
1. A steel matrix direct cyanide-free copper plating electroplating solution under a strong acid condition comprises the following components: 50-250g/L of main salt, 30-100g/L of compound adsorbent, 1-5 g/L of additive and 300g/L of strong acid composition 160-.
2. The electroplating bath as set forth in claim 1, wherein said built sorbent is a mixture of halides, ammonia, and urea compounds.
3. The electroplating solution as set forth in claim 2, wherein the urea compound is phenylthiourea, diphenylthiourea, ethylenethiourea or cucurbituril.
4. The electroplating solution as set forth in claim 1, wherein the additive is preferably a mixture of one or more of urotropin, ascorbic acid, fatty amine polyoxyethylene ether, alkylphenol polyoxyethylene ether, and polyethylene glycol.
5. The electroplating bath as set forth in claim 1, wherein the primary salt is copper chloride, copper carbonate, copper sulfate, copper hydroxide.
6. The electroplating solution as claimed in claim 1, wherein the content of the compound adsorbent in the electroplating solution is 20-50g/L of halide, 20-100g/L of ammonia water and 0.3-2g/L of urea compound; the halide is an alkali metal halide or an ammonium halide.
7. The electroplating bath as set forth in claim 1 wherein said strong acid composition is a mixture of sulfuric acid and formic acid.
8. The electroplating solution as set forth in claim 1, wherein the content of the strong acid composition in the electroplating solution is 150-250g/L sulfuric acid and 10-50g/L formic acid.
9. The method for preparing the steel matrix direct cyanide-free copper plating solution under the strong acid condition as claimed in claim 1, comprising the following steps:
(1) adding a calculated amount 1/2 volume of pure water to the vessel;
(2) adding main salt, and stirring to dissolve; adding a strong acid composition under stirring; then adding the compound adsorbent, stirring and dissolving, and then adding the additive, stirring and dissolving;
(3) adding the rest pure water to the working volume and stirring uniformly to implement electroplating.
10. A method for directly plating copper on a steel matrix without cyanogen under a strong acid condition comprises the following steps:
the steel matrix is sequentially degreased, pickled and activated and then placed in a plating bath for plating, and the plating solution is the plating solution of any one of claims 1 to 8.
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| CN202110181949.6A CN112899738B (en) | 2021-02-10 | 2021-02-10 | Steel matrix direct cyanide-free copper plating electroplating solution under strong acid condition and preparation method thereof |
| PCT/CN2021/131270 WO2022170803A1 (en) | 2021-02-10 | 2021-11-17 | Electroplating solution for steel substrate direct cyanide-free plating under strong acidic conditions, and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355707A (en) * | 2021-06-11 | 2021-09-07 | 刘玉亭 | Electroplating additive containing copper salt and application and preparation method thereof |
| WO2022170803A1 (en) * | 2021-02-10 | 2022-08-18 | 张志梁 | Electroplating solution for steel substrate direct cyanide-free plating under strong acidic conditions, and preparation method therefor |
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| CN111321436A (en) * | 2020-03-09 | 2020-06-23 | 张志梁 | Cyanide-free copper plating solution assistant and copper plating solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022170803A1 (en) * | 2021-02-10 | 2022-08-18 | 张志梁 | Electroplating solution for steel substrate direct cyanide-free plating under strong acidic conditions, and preparation method therefor |
| CN113355707A (en) * | 2021-06-11 | 2021-09-07 | 刘玉亭 | Electroplating additive containing copper salt and application and preparation method thereof |
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| WO2022170803A1 (en) | 2022-08-18 |
| CN112899738B (en) | 2022-04-29 |
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