KR101227059B1 - Plating solution and method for zirconium alloy plating and titanium alloy plating - Google Patents

Abstract

PURPOSE: A Zr alloy plating or Ti alloy plating method and a plating solution for the same are provided to uniformly coat fine parts of a product with minute electric current at 0.5A/dm^2 by using a link complexing agent as well as a reducing agent. CONSTITUTION: A method for preparing an electroplating solution for Ti alloy plating comprises the steps of: preparing a Ti compound, dissolving the Ti compound in water to liquefy, putting a citric acid compound as a complexing agent into the liquid, dissolving at least one of Ni to be alloyed with Ti, Co, Au, Pt, Cu, Pd, Pb, Ag, Zr, and metal compounds thereof in the liquefied solution, and regulating the pH of the solution to 1.0-12.0. [Reference numerals] (AA) Link complexing agent; (BB) Other metal ion susceptible to eutectoid

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plating solution and a plating solution for a zirconium alloy plating and a titanium alloy plating,

This technology relates to a zirconium alloy plating and a titanium alloy plating solution and a plating method.

The inventor of the present invention invented a titanium ion aqueous solution in February 2011 and discovered a patent of Korean Patent Application No. 10-2011-0074492 in recognition of the fact that alloy plating using the aqueous solution of titanium ion is possible. In addition, Korean Patent Application No. 10 -2011-0016960, Korean Patent Application No. 10-2011-0074496, and zirconium alloy plating and titanium alloy plating were carried out.

However, in the case of titanium, as described in Korean Patent Application No. 10-2011-0074492, when the electroplating is performed, the problem of not covering the low current portion occurs severely, and in order to eliminate such a problem, The vacancy ratio was lowered and the desired properties such as corrosion resistance could not be obtained.

Further, if the pH is further lowered to improve the vacancy ratio of Ti, the plating range is too narrow, the plating range is insufficient to be industrially applicable, and the surface is rough. In addition, the plating solution is easily decomposed into black due to strong electrical resistance of the titanium ion, which makes it difficult to manage the plating solution.

On the other hand, when a zirconium alloy plating is performed through a patent related to a zirconium alloy electroplating composition according to Korean Patent Application No. 10-2011-0074496, as shown in the photograph attached to the patent, the surface appearance is so rough , It was difficult to remove the cloudy phenomenon.

This problem is related to the intrinsic properties of metals with low electrical conductivity compared to other platable metals such as zirconium and titanium.

Electrical conductivity of major metals Metal name Circle symbol Electrical Conductivity (10 < ⁶ > / cm) silver Ag 0.6300 Copper Cu 0.5960 nickel Ni 0.1430 cobalt Co 0.1720 chrome Cr 0.0774 zirconium Zr 0.0236 titanium Ti 0.0234

As shown in Table 1, zirconium and titanium show significantly lower electrical conductivity than metals used as plating metals in ordinary cases. They are metals that have electric conductivity three times lower than that of chromium, which requires the most electricity reduction power in electrolytic plating. admit.

For this reason, a large amount of load and resistance were generated during plating to decompose the plating solution, requiring a high energy, and the surface of the plated product was so rough that the appearance did not have commercial merit.

In addition, in the case of titanium, the O ₂ coating is formed by taking oxygen from water (H ₂ O) as soon as it is reduced to metal, which makes plating in the aqueous solution more difficult. However, in the case of zirconium, an alloy plating layer by a conventional electroless plating method could be obtained, but the same problems were also caused by the electroconductivity as low as titanium by the electroplating method.

Although DL-Tartaric acid used as a complexing agent was a complexing agent for titanium and zirconium, it was not sufficient. However, it was not sufficient for other complex metals to be bonded together and could not serve as a conductive auxiliary agent. It did not help.

Therefore, it has been difficult to obtain a zirconium alloy plating layer or a titanium alloy plating layer having a high corrosion resistance and acid resistance at a low pH by a conventional electroplating method.

An object of the present invention is to provide a titanium or zirconium alloy plating method excellent in coating ability.

Another object of the present invention is to provide a plating solution for smoothly using the provided plating method.

Another object of the present invention is to provide a plated product having a zirconium alloy plating layer or a titanium alloy plating layer having a good appearance and high durability by using the plating solution provided.

The product plated with the titanium and zirconium alloy plating solution according to the present invention will rapidly replace the entire surface treatment with high durability and excellent decorative property in the future.

Especially, it has high durability and corrosion resistance as an alternative to hexavalent chromium, and it has excellent covering power, so it can be used without any trouble in the conventional plating process, and also has excellent economical efficiency with high bath stability.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Accordingly, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

1 is a model diagram of a coupling complex;
2 is a zirconium-nickel pure electroplating photograph.
3 is a zirconium-nickel composite reduction plating photograph.
Figure 4 is a pure titanium electroplating photo.
FIG. 5 is a photograph of a titanium-nickel composite reduction plating. FIG.

In order to achieve the above object, the present invention provides a composite reduction plating method for forming a titanium and zirconium alloy plating layer.

Also provided is a plating solution capable of selectively using a complex reduction plating method.

The present invention also provides a method for producing a plating solution capable of using a complex reduction plating method, comprising the steps of: a) providing at least one of a zirconium compound or a titanium compound; And b) liquefying the zirconium or titanium compound of step a); c) introducing the citric acid compound as a complexing agent into the liquid phase of step b); Dissolving the main metal compound to be alloyed with titanium or zirconium in the solution of step d); e) adding a reducing agent if necessary to the liquid phase of step d); f) additionally adding auxiliary metal ions to the liquid phase of step e) as required; and g) adjusting the pH of the alloy. The present invention also provides a method for producing a titanium and zirconium alloy composite reduction plating solution.

Hereinafter, the present invention will be described in detail with reference to the operation of the constituent means of the present invention and a preferred embodiment thereof.

Methods for adding zirconium ions and titanium ions to be used for plating are many and varied.

In the case of titanium, titanium dioxide identified by the inventor's invention may be dissolved in concentrated sulfuric acid, or titanium tetrachloride may be used as titanium chloride. In addition, various titanium compounds such as titanium trichloride, titanium dichloride and the like can be used.

In the case of zirconium, zirconium tetrachloride (ZrCl ₄ ), zirconium sulfate (Zr (SO ₄ ) ₂ .4H ₂ O), zirconium oxychloride (ZrOCl ₂ 8H ₂ O), zirconium dioxide (ZrO ₂ ), acetic acid, cas no. 7585-20-8).

Accordingly, the present invention will be described with reference to zirconium sulfate, zirconium oxychloride, and titanium sulfate which can easily obtain zirconium or titanium ions as a starting material, but the present invention is not limited thereto.

Since titanium and zirconium ions have poor electrical conductivity and can not secure a high covering power with a pure electricity reducing power, it is possible to use both a chemical reduction using a reducing agent and an electric reduction at the time of plating to secure a high covering power, Solves the problem of zirconium alloy plating.

In the case of zirconium, electroless alloy plating is possible as a chemical reducing agent. However, in the case of titanium, if electroless alloy plating is performed in an aqueous solution, reduction reaction occurs at first, then oxygen in water (H ₂ O) So that it is impossible to perform thickness plating afterwards. (The reaction is continued, but no plating layer is formed.)

Further, in electroplating, it has been difficult to obtain a wide covering ability due to the low electric conductivity as described above.

When the pH is increased to obtain a wide coverage, the corrosion resistance or acid resistance is lowered due to a low vacancy ratio, and the meaning of the alloy plating is reduced.

In order to solve the above problems, the present invention provides a method of reducing the amount of titanium and zirconium in a plating solution by using a chemical reducing agent, which is used in a reducing plating method other than displacement plating, Overcome the lack of electrical conductivity that you have.

In the present invention, as the reducing agent, a hypophosphite ion and a boron ion or formalin, glyoxylic acid, and hydrazine can be used. More specifically, there may be mentioned sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, dimethylamine borane (DMAB), diethylamine borane (DEAB), sodium borohydride, hydrazine, formalin and glyoxylic acid.

With the use of such a reducing agent, plating can be performed by applying electricity of 0.5 A / dm ² to 10 A / dm ² to secure wide coverage. When the current is less than 0.5 A / dm ^2, the amount of current to be applied is too weak and the effect is insignificant, and a high current exceeding 10 A / dm ² is not required.

DL-Tartaric acid, which is conventionally used as a complexing agent suitable for simultaneously using the reducing agent and the electric reduction, is not suitable because it does not serve as a conduction auxiliary agent and can not serve as a coupling agent for a metal to be plated together . That is, although DL-tartaric acid was a complexing agent for titanium ions and zirconium ions, it was harder to obtain a high coating power because it did not function as a complexing agent for nickel or cobalt which was co-deposited.

Herein, the term "coupling agent" refers to a complexing agent that can be commonly used with titanium and zirconium, and nickel and cobalt, which are major vacancy metals, between one complexing agent.

In addition, even when plated with gold, platinum, copper, palladium, lead, or silver as the main metal for alloy plating, wide coverage is ensured.

As the source of the main metal ions for such alloy plating, there are nickel sulfate, nickel sulfamide, nickel chloride, nickel acetate, cobalt sulfate, cobalt chloride, cobalt ammonium sulfate, ferric chloride (AuCl ₃ .2H 2 O) (HAuCl ₄ .4H ₂ O), cyanide gold (AuCN), cyanating agent 1 potassium potassium (KAu (CN) ₂ .2H ₂ O), gold sodium cyanide (NaAu (CN) ₂ ), chloroplatinic acid, It is also possible to use silver salts such as silver platinum, copper sulfate, copper chloride, copper cyanide, copper pyrophosphate, palladium sulfate, palladium chloride, ammonium palladium nitrate, lead acetate, lead pentafluoride, lead nitrate, basic lead carbonate, silver nitrate, Potassium, sodium cyanide, or the like may be dissolved and used.

In the present invention, the complexing agent may be selected from a group of citrate ions, that is, a group of citrate compounds. More specifically, citric acid, sodium citrate, and ammonium citrate may be used. This citrate ion is known to be a metal that is not plated with a single metal of titanium and zirconium, and thus serves as a common complexing agent for nickel and cobalt, the main metals used as the metal to be released, in any environment.

Ti-Zr-Co, and Ti-Zr-Ni-Co, for example, Ti-Ni, Ti-Co, Zr-Ni, Zr-Co, Ti-Zr- In addition, DL-Tartaric acid is used as a conductive auxiliary agent in accordance with its amount. However, in this case, it is possible to obtain a larger coverage than the case of using chemical reduction and electrical reduction at the same time It does not.

The citric acid ion, which is a linking complexing agent, fulfills its role as a reversing agent as a complexing agent at the same time in the reduction reaction and the electro-reduction through a chemical reducing agent.

In addition, a variety of alloy plating layers can be obtained through addition of various metal ions conventionally free from cobalt and nickel and vacancies. For example, vacancies with Au, Pt, Cu, Pd, Pb, and Ag can be easily induced.

In the plating of these metal ions, for example, Au, Pt, Cu, Pd, Pb, Ag and Ti or Zr alloy, citric acid ion can secure a wide plating range as compared with DL-Tartaric Acid, . In addition, it is also possible to apply a complex reduction method by applying a single agent.

Due to the use of this coupling type complexing agent, zirconium alloy plating or titanium alloy plating can cover a wide range evenly to a fine portion of the product even if only a minute current of 0.5 A / 1 dm ² is flowed. Under a strong acid environment of less than pH 2.0 Titanium and zirconium vacancies can be induced, so that many vacancies of titanium and zirconium are formed, and a wide range of thickness plating is possible by using a large amount of current less than 10 A / dm ² .

[Example 1]

Zirconium oxychloride octahydrate 100 g

Nickel chloride 20g

Citric acid 60g

Boric acid 30g

Current density: 2.5 A / dm ²

Anode: carbon anode

The above material was dissolved in 600 ml of pure water, and then water was filled to prepare a 1 liter plating solution. The plating was performed at a temperature of 85 ° C and a pH of 1.5 for 30 minutes. The specimens were cleaned of brass specimens. As a result of the experiment, the front part was covered evenly, but the rear part was hardly plated. The results are shown in Fig. Thereafter, the amount of current was increased to 10 A / dm ² , but the plating was scarcely raised on the backside.

[Example 2]

Plating solution: The solution of Example 1.

Reducing agent: Sodium hypophosphite 20g / L

Current density: 2.5 A / dm ²

Bipolar: Iridium-coated anode

Sodium hypophosphite was added to the solution of Example 1 and dissolved, followed by plating at 85 DEG C and pH 1.5 for 30 minutes. Plated products were plated so that both the front and back sides were not visible. The results are shown in Fig. After that, the current was reduced to 0.5 A / dm ^2, and even when the new specimen was plated, it was evenly plated to the backside.

Although it is a weak current for actual plating, it plays a role of continuously inducing a reduction reaction, and it is judged that such a result is obtained that the reducing agent plays a role of reducing at low pH.

[Example 3]

50 g of titanium sulfate (TiOSO ₄ 2H ₂ O)

Citric acid 60g

Element 15g

Nickel chloride 20g

Boric acid 30g

Current density: 2.5 A / dm ²

Bipolar: Iridium-coated anode

pH 3.5 (using hydrochloric acid and ammonia)

And the brass specimens were plated for 30 minutes at a temperature of 90 ° C. The plating was relatively uniformly plated, but the backside was hardly plated. The results are shown in FIG.

[Example 4]

Plating solution: solution of Example 3.

Additive: Sodium hypophosphite 20g / L

Current density: 2.5 A / dm ²

pH 1.5 (using hydrochloric acid and ammonia)

Bipolar: Iridium-coated anode

Sodium hypophosphite, a chemical reductant, was added to the solution of Example 3, and the solution was plated at 85 DEG C and pH 1.5 for 30 minutes. Plated products were plated so that both the front and back sides were not visible. The results are shown in FIG.

[Example 5]

50 g of titanium sulfate (TiOSO ₄ 2H ₂ O)

Zirconium sulfate (Zr (SO ₄ ) ₂ 4H ₂ O) 30 g

Citric acid 80g

Element 15g

Nickel chloride 20g

Boric acid 30g

Additive: Sodium hypophosphite 20g / L

Current density: 2.5 A / dm ²

pH 1.5 (using hydrochloric acid and ammonia)

Bipolar: Iridium-coated anode

One liter of the above composition was subjected to a bath of Ti-Zr-Ni plating at a temperature of 85 캜 for 1 hour, and a plating thickness of about 10.0 탆 was measured.

[Example 6]

50 g of titanium sulfate (TiOSO ₄ 2H ₂ O)

Zirconium sulfate (Zr (SO ₄ ) ₂ 4H ₂ O) 30 g

Citric acid 80g

Element 15g

Cobalt sulfate 20g

Ammonium chloride 50 g

Boric acid 30g

Additive: Sodium hypophosphite 20g / L

Current density: 2.5 A / dm ²

pH 1.5 (using hydrochloric acid and ammonia)

Bipolar: Iridium-coated anode

One liter of the above composition was subjected to a bath of Ti-Zr-Co plating at a temperature of 85 캜 for 1 hour, and a plating thickness of about 8.0 탆 was measured.

In the present invention, a conductive auxiliary agent can be used. The conductive auxiliary can be used regardless of whether or not a reducing agent is added, and sodium compounds, potassium compounds, and ammonium compounds can be used.

More specifically, ammonium compounds are more preferable than sodium or potassium, although sodium sulfate, potassium sulfate, ammonium sulfate, sodium chloride, potassium chloride, ammonium chloride, sodium nitrate, potassium nitrate, ammonium nitrate and the like can be used.

Therefore, it is preferable to use ammonium sulfate, ammonium chloride or ammonium nitrate, among which ammonium nitrate is a dangerous substance, so it is more preferable to refrain from using it.

[Example 7]

50 g of titanium sulfate (TiOSO ₄ 2H ₂ O)

Zirconium sulfate (Zr (SO ₄ ) ₂ 4H ₂ O) 30 g

Citric acid 100g

Element 15g

Cobalt sulfate 20g

Nickel chloride 20g

Ammonium chloride 50 g

Boric acid 30g

Additive: Sodium hypophosphite 20g / L

Current density: 2.5 A / dm ²

pH 1.5 (using hydrochloric acid and ammonia)

Bipolar: Iridium-coated anode

One liter of the above composition was subjected to a bath of Ti-Zr-Co-Ni plating at a temperature of 85 캜 for 1 hour, and a plating thickness of about 8.0 탆 was measured.

[Example 8]

Corrosion resistance and acid resistance test division Nitric acid 50% Hydrochloric acid 50% Sulfuric acid stock solution aqua regia Example 1 pH 1.5 OK OK OK OK Example 2 pH 1.5 OK OK OK OK Example 3 pH 3.5 NG (turned black) OK OK OK Example 4 pH 1.5 OK OK OK OK

Here, the pH in Table 2 is the pH of the plating solution used in the plating example.

Each of the plated products is very resistant to corrosion with a common salt spray that makes it difficult to test for corrosion resistance. Particularly, when the pH is less than 2.0, even when the thickness is plated, the surface is hardly eroded even in the nitric acid stock solution.

It is possible to use a chemical reducing agent and an electric reduction method at the same time to allow plating at such a low pH. In this process, citric acid ion as a coupling complexing agent plays a large role not only as a complexing agent but also as a conductive auxiliary agent.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, As will be appreciated by those of ordinary skill in the art.

Claims (29)

Electroplating solution for titanium alloy plating using citric acid compound as complexing agent.
The electroplating solution for plating a titanium alloy according to claim 1, wherein the titanium is used as a starting material of a citric acid compound, wherein titanium citrate is used as a starting material.
a) providing a titanium compound; And
b) liquefying the titanium compound of step a) in water;
c) introducing the citric acid compound as a complexing agent into the liquid phase of step b);
d) dissolving at least one of nickel, cobalt, gold, platinum, copper, palladium, lead, silver, zirconium metal and metal compounds of these metals to be alloyed with titanium in the liquefied solution of step c);
g) adjusting the pH in the liquid phase of step d) to 1.0 to 12.0, and using the citric acid compound as a complexing agent.
4. The method according to claim 3, wherein the nickel compound in step d) is formed by mixing any one of nickel sulfate, nickel sulfide nickel, nickel chloride and nickel acetate,
The cobalt compound is formed by mixing any one of cobalt sulfate, cobalt chloride, ammonium cobalt sulfate, or two or more groups,
Gold compound is ferric chloride gold _{(AuCl 3 · 2H 2 O)} , the second gold acid chloride _{(HAuC1 4 · 4H 2 0)} , cyanide, gold (AuCN), cyan agent 1 potassium gold _{(KAu (CN) 2 · 2H} 2 0) and gold sodium cyanide (NaAu (CN) ₂ ) or a mixture of two or more groups,
The platinum compound is characterized in that it is formed by mixing any one of the group consisting of chloroplatinic acid, platinous chloride and ammonium platinum nitrate, or a mixture of two or more groups.
The copper compound is characterized in that it is formed by mixing any one group or two or more of copper sulfate, copper chloride, copper cyanide and copper pyrophosphate, and the palladium compound is any one of palladium sulfate, palladium chloride and palladium ammonium nitrate Two or more groups are mixed and formed,
The lead compound is formed by mixing any one of the group consisting of acetic acid lead, lead borofluoride, lead nitrate, and basic lead carbonate,
The silver compound is formed by mixing any one of the group consisting of silver nitrate, silver chloride, silver oxide, silver sulfate, silver cyanide, potassium silver cadmium and silver silver cadmium or a mixture of two or more of the groups. The zirconium compound may be selected from zirconium sulfate, zirconium oxychloride, zirconium dichloride, The electroplating solution for electroplating of a titanium alloy using a citric acid compound as a complexing agent is formed by mixing at least one group selected from zirconium, zirconium nitrate, zirconium acetate, zirconium octanoate and potassium carbonate zirconium salt. Gt;
The method according to claim 3, wherein the citric acid compound used as a complexing agent in step c) is a citric acid compound which is used in combination with any one of citric acid, sodium citrate and ammonium citrate or two or more groups. A method for manufacturing an electroplating solution for titanium alloy plating.
delete The method according to claim 3, further comprising the step of adding e) a reducing agent between steps d) and g), wherein the citric acid compound is used as a complexing agent.
8. The method according to claim 7, wherein the reducing agent in step e) is selected from the group consisting of polyphosphoric acid, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, dimethylamine borane (DMAB), diethylamine borane (DEAB), sodium borohydride, hydrazine, Formalin, or a mixture of two or more of the above-mentioned citric acid compounds as a complexing agent. The method for producing an electroplating solution for plating a titanium alloy according to claim 1,
The electroplating solution for plating a titanium alloy according to claim 8, wherein the reducing agent is added when plating is performed by a complex reduction method which is a metal reduction using both electrical reduction and chemical reduction. Gt;
4. The method according to claim 3, further comprising the step of adding f) a metal ion to be alloyed between steps d) and g), wherein the step of f) further comprises the step of f) A method for producing an electroplating solution.
11. The method according to claim 10, wherein the metal ion to be further alloyed in step f) is one selected from the group consisting of Au, Pt, Cu, Pd, Pb, Ag and Zr, Wherein the plating solution is used as a complexing agent.
delete delete delete A plating product in which at least one layer of the plating layer plated with the plating solution of claim 1 is plated.
Electroplating solution for zirconium alloy plating using citric acid compound as complexing agent.
The electroplating solution for zirconium alloy plating according to claim 16, wherein the zirconium is used as a starting material, zirconium sulfate or zirconium oxychloride as a starting material.
a) providing a zirconium compound; And
b) liquefying the zirconium compound of step a) in water;
c) introducing the citric acid compound as a complexing agent into the liquid phase of step b);
d) dissolving at least one of nickel, cobalt, gold, platinum, copper, palladium, lead, silver metal and metal compounds of these metals to be alloyed with zirconium in the liquefied solution of step c);
g) adjusting the pH in the liquid phase of step d) to 1.0 to 12.0, wherein the citric acid compound is used as a complexing agent for the electroplating solution for zirconium alloy plating.
19. The method according to claim 18, wherein the nickel compound in step d) is formed by mixing any one of nickel sulfate, nickel sulfide nickel, nickel chloride and nickel acetate or two or more groups, and the cobalt compound is cobalt sulfate, cobalt chloride, Wherein the gold compound is at least one selected from the group consisting of gold chloride (AuCl ₃ .2H ₂ O), ferric chloride (HAuCl ₄ .4H ₂ O), cyanide gold (AuCN), cyanating agent 1 gold potassium (KAu (CN) ₂ .2H ₂ O), and gold sodium cyanide (NaAu (CN) ₂ ) Wherein the copper compound is formed by mixing any one of the group consisting of chloroplatinic acid, platinous chloride and ammonium nitrate, or a mixture of two or more groups. The copper compound may be any one group selected from among copper sulfate, copper chloride, copper cyanide and copper pyrophosphate Characterized in that it is formed by mixing two or more groups, Wherein the lead compound is formed by mixing any one of the group consisting of palladium sulfate, palladium chloride and ammonium palladium nitrate or a combination of two or more groups, and the lead compound is formed by mixing any one of the group consisting of acetic acid lead, boron fluoride, lead nitrate, Wherein the silver compound is formed by mixing any one of the group consisting of silver nitrate, silver chloride, silver oxide, silver sulfate, silver cyanide, potassium silver cyanide and silver cyanide, or a mixture of two or more groups. Gt; < RTI ID = 0.0 > 11. < / RTI >
19. The method according to claim 18, wherein the citric acid compound to be used as a complexing agent in step c) is a citric acid compound which is a mixture of any one of citric acid, sodium citrate and ammonium citrate, A method for manufacturing an electroplating solution for plating a zirconium alloy.
The electroplating solution as claimed in claim 18, further comprising e) adding a reducing agent between steps d) and g) as a complexing agent.
22. The method according to claim 21, wherein the reducing agent in step e) is selected from the group consisting of polyphosphoric acid, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, dimethylamine borane (DMAB), diethylamine borane (DEAB), sodium borohydride, hydrazine, Formalin, or a mixture of two or more of the above-mentioned citric acid compounds as a complexing agent. The method for producing an electroplating solution for plating a zirconium alloy according to claim 1,
The electric charge for zirconium alloy plating as a complexing agent according to claim 22, wherein the reducing agent is added when plating is performed by a complex reduction system (metal reduction system using both electrical reduction and chemical reduction) A method for producing a plating solution.
19. The method according to claim 18, further comprising the step of adding f) between the step d) and the step g), further comprising the step of f) adding the metal ion to be alloyed to the zirconium alloy plating A method for producing an electroplating solution.
The method according to claim 24, wherein the metal ion to be further alloyed in step f) is one selected from the group consisting of Au, Pt, Cu, Pd, Pb, Ag and Ti, As a complexing agent, for the plating of zirconium alloy.
delete delete delete A plating product obtained by plating at least one or more layers of a plating layer plated with the plating solution of claim 16.

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