WO2013172673A1

WO2013172673A1 - Plating method and plating solution for zirconium alloy plating and titanium alloy plating

Info

Publication number: WO2013172673A1
Application number: PCT/KR2013/004358
Authority: WO
Inventors: 윤종오
Original assignee: Yoon Jong-Oh
Priority date: 2012-05-18
Filing date: 2013-05-16
Publication date: 2013-11-21
Also published as: KR101227059B1

Abstract

The present invention relates to a complex reduced plating solution and to a plating method, in which a citric acid ion which is a link type reducing agent is used as substitute technology for hexavalent chrome to thus use a titanium ion and a zirconium ion which have been difficult to use in plating, thereby achieving high corrosion resistance and high acid resistance and wide covering power.

Description

Plating method and plating solution of zirconium alloy plating and titanium alloy plating

This technology relates to zirconium alloy plating and titanium alloy plating solutions and plating methods.

The inventor of this technology invented a titanium ion aqueous solution in February 2011, and invented the patent of Korean Patent Application No. 10-2011-0074492, knowing that alloy plating using this titanium ion aqueous solution is possible, and in addition, Korean Patent Application No. 10 Zirconium alloy plating and alloy plating of titanium were carried out through -2011-0016960, Korean Patent Application No. 10-2011-0074496.

However, in the case of titanium, as described in the Republic of Korea Patent Application No. 10-2011-0074492, there was a serious problem that the coating is not applied to the low current site during the electroplating, and to eliminate this problem, when the pH is raised, Vacancies ratio was lowered to obtain the desired properties such as corrosion resistance.

In addition, when trying to improve the vacancy ratio of Ti by further lowering the pH, the plating range was insufficient so that the plating range was too narrow to be industrially available, and the surface was rough. In addition, the plating solution was easily decomposed into black due to the strong electrical resistance of titanium ions, so that the plating solution was difficult to manage.

Meanwhile, even when the zirconium alloy plating is performed through a patent related to the zirconium alloy electroplating solution composition according to Korean Patent Application No. 10-2011-0074496, the surface appearance is severely rough so as not to have commercial properties, as shown in the photograph attached to the patent. It was difficult to remove the cloudy phenomenon.

This problem is related to the inherent properties of metals in which zirconium and titanium have lower electrical conductivity than other plateable metals.

Table 1

Electrical conductivity of the main metals

Metal name	Symbol	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 have a significantly lower electrical conductivity than metals used as plating metals in general, and have a metal conductivity three times lower than that of chromium, which requires the most electrical reducing power in electroplating. admit.

For this reason, the plating solution was decomposed by generating a lot of loads and resistances during plating, and high energy was required. The surface of this difficult-plated product was so rough that the appearance was difficult to have commerciality.

In addition, in the case of titanium, as soon as it is reduced to the metal deprives oxygen from water (H ₂ O) to make the O ₂ film to make the plating on the aqueous solution more difficult. However, in the case of zirconium, the alloy plating layer was obtained by the traditional electroless plating method, but the same problem occurred due to the electrical conductivity as low as titanium by the electroplating method.

In addition, DL-Tartaric acid, used as a complexing agent, acted as a complexing agent of titanium and zirconium, but was not sufficient. It was a sole complexing agent that did not connect other vacant metals together. It did not help.

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

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

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

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

Products coated with the titanium and zirconium alloy plating solution according to the present invention will replace the overall surface treatment at a high speed in the future with high durability and excellent decoration.

In particular, since hexavalent chromium has a high durability and corrosion resistance as well as excellent coating power, it can be used without any difficulty in the conventional plating process, and also excellent in economic efficiency due to high bath stability.

It is apparent that modifications and improvements of the present invention are possible by those skilled in the art within the technical spirit or protection scope of the present invention. Therefore, all the simple modifications and variations of this invention belong to the scope of the present invention, The specific protection scope of this invention will become clear by the attached claim and its equal range.

1 is a schematic view of a linked complexing agent.

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.

In addition, the present invention provides a plating solution capable of selectively using a composite reduction plating method.

In addition, the present invention provides a method for producing a plating solution that can use 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) adding a citric acid compound as a complexing agent to 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) injecting a reducing agent into the liquid phase of step d) as necessary; f) additionally adding auxiliary metal ions to the liquid phase of step e) as needed; g) adjusting the pH of the alloy plating solution; provides a method for producing a titanium and zirconium alloy composite reduction method plating solution comprising a.

Hereinafter, the present invention will be described in detail with reference to the action of the constituent means of the present invention and preferred embodiments.

There are many ways to add zirconium ions and titanium ions to be used for plating.

In the case of titanium, the titanium dioxide identified by the inventors' invention can be dissolved in concentrated sulfuric acid, titanium tetrachloride can be used as titanium chloride, and there are various titanium compounds such as titanium trichloride and titanium dichloride.

Also 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, zirconium salt ( cas no.7585-20-8) and about 40 species.

Therefore, the present invention is described as a starting material of zirconium sulfate, zirconium oxychloride and titanium sulfate, which can easily obtain zirconium or titanium ions as a means for achieving the above object, but is not limited thereto.

In the present invention, since titanium and zirconium ions are poor in electrical conductivity, high coating power cannot be secured by pure electric reducing power. Thus, both chemical reduction and electrical reduction using a reducing agent are used at the time of plating, thereby ensuring high coating power. It solves the problem of zirconium alloy plating.

In the case of zirconium, electroless alloy plating is possible with a chemical reducing agent, but in the case of titanium, when electroless alloy plating is performed in an aqueous solution, a reduction reaction occurs at first, but then receives oxygen from water (H ₂ O) in the plating solution. Since the oxide film is easily indented, there is a disadvantage in that thickness plating is impossible later. (Reaction continues but no plating layer is formed.)

In addition, in the electroplating, it is difficult to obtain a wide coating force because of the low electrical conductivity as described above.

When increasing the pH to obtain a wide coverage, due to the low vacancy ratio, there was a disadvantage that the meaning of the alloy plating is reduced due to the low corrosion resistance or acid resistance.

In order to solve this problem, titanium and zirconium are simultaneously used by using the reducing power of electricity in a manner of applying electricity while adding a chemical reducing agent used in a reducing plating method rather than a substitution plating method to the plating liquid to use the chemical reducing power. Overcome the lack of electrical conductivity you have.

In the present invention, the reducing agent may use hypophosphite ions and boron ions or formalin, glyoxylic acid, and hydrazine. More specifically, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, dimethylamine borane (DMAB), diethylamine borane (DEAB), sodium borohydride, hydrazine, formalin, glyoxylic acid, and the like.

Along with the use of such a reducing agent, it is possible to apply a plating of 0.5A / dm ² to 10A / dm ² by plating to secure a wide coating force. Less than 0.5 A / dm ^2, the amount of current to be applied is so small that the effect is insignificant, and does not require up to a high current of more than 10 A / dm ² .

In addition, DL-Tartaric acid, which is conventionally used as a complexing agent suitable for simultaneously using such a reducing agent and electrical reduction, does not play a role of a conducting aid and does not serve as a linking complexing agent with metals to be plated together. . In other words, DL-tartaric acid acted as a complexing agent for titanium ions or zirconium ions, but it was more difficult to obtain high coverage because it did not act as a complexing agent for nickel or cobalt.

Here, the linking complexing agent refers to a complexing agent in which titanium and zirconium and nickel and cobalt, which are main vacant metals, can be commonly used with one complexing agent interposed therebetween.

In addition, even when gold, platinum, copper, palladium, lead, and silver are used as the main metal for alloy plating, a wide coating power is secured.

As a source of the main metal ions for plating such an alloy, nickel sulfate, nickel sulfamate, nickel chloride, nickel acetate, cobalt sulfate, cobalt chloride, cobalt ammonium sulfate, ferric chloride (AuCl ₃ · 2H2O), dihydrogen chloride hydrochloride (HAuC1 ₄ · 4H20), gold cyanide (AuCN), potassium cyanide potassium (KAu (CN) ₂ · 2H20), sodium cyanide sodium (NaAu (CN) ₂ ), platinum chloride, platinum chloride, nitric acid Platinum ammonium, copper sulfate, copper chloride, copper cyanide, copper pyrophosphate, palladium sulfate, palladium chloride, palladium nitrate, lead acetate, lead borofluoride, lead nitrate, lead carbonate, silver nitrate, silver chloride, silver oxide, silver sulfate, silver cyanide, silver cyanide Metal compounds, such as potassium and silver cyanide, can be melt | dissolved and used.

In the present invention, the complexing agent may be selected from citric acid ions, that is, citric acid compound group, and more specifically, citric acid, sodium citrate, and ammonium citrate may be used. Since citrate ions are known to be metals in which titanium and zirconium are not plated with a single metal, they connect to each other as nickel and cobalt, the main metals used as vacant metals, as a common complexing agent in any environment.

For example, Ti-Ni, Ti-Co, Zr-Ni, Zr-Co, Ti-Zr-Ni, Ti-Zr-Co, Ti-Zr-Ni-Co, etc. Because it faithfully performs the role of conduction aid according to the amount, it can secure wider coverage than when using DL-Tartaric acid, but in this case, it has more coverage than chemical and electrical reduction. I don't have it.

Citrate ions, which are linked complexing agents, faithfully play the role of complexing agents and conduction aids in the reduction reaction and electroreduction through chemical reducing agents.

In addition, various alloy plating layers may be obtained through additional input of various metal ions, which were conventionally free of cobalt, nickel, and vacancies. For example, vacancy with Au, Pt, Cu, Pd, Pb, Ag can be easily induced.

Even in the plating of these metal ions, such as Au, Pt, Cu, Pd, Pb, Ag and Ti or Zr alloys, citric acid ions can secure a wider plating range than DL-Tartaric Acid and serve as conduction aids. In charge of. In addition, the plating of the composite reduction method is also possible by adding a Korean agent.

Due to the use of this complex type complexing agent, even in the case of zirconium alloy plating or titanium alloy plating, even a small current of 0.5A / 1dm ² can cover a wide range evenly to the minute parts of the product, and in a strong acid environment below pH 2.0 As it can induce vacancies of titanium and zirconium, many vacancies of titanium and zirconium are made, and a wide range of thickness can be applied by using a large amount of current of 10 A / dm ² or less.

Example 1

100 g of zirconium oxychloride octahydrate

Nickel Chloride 20g

60 g citric acid

30 g of boric acid

Current density: 2.5A / dm ²

Anode: Carbon Anode

After dissolving the material in 600 ml of pure water, water was filled to prepare a 1 liter plating solution, and the plating was performed at 85 ° C. and pH 1.5 for 30 minutes. The specimen was used to clean the brass specimen. The test results were evenly coated on the front part, but hardly plated on the back side. Since the amount of current was raised to 10A / dm ² but the plating almost did not rise on the back.

Example 2

Plating solution: solution of Example 1.

Reducing agent: Sodium hypophosphite 20g / L

Current density: 2.5A / dm ²

Anode: Iridium Coated Anode

After adding sodium hypophosphite to the solution of Example 1 and dissolving it, plating was performed at 85 ° C. and pH 1.5 over 30 minutes. Plated products were plated on the front and back so that no metal was visible. After the current was lowered to 0.5 A / dm ² , even when the new specimen was plated, it was evenly plated to the rear surface.

Although it is a weak current to be actually plated, it plays a role of continuously inducing a reduction reaction, and this result was judged to have the effect of reducing agent acting as a reducing role even at low pH.

Example 3

Titanium Sulfate (TiOSO ₄ 2H ₂ O) 50g

60 g citric acid

15 g of urea

Nickel Chloride 20g

30 g of boric acid

Current density: 2.5A / dm ²

Anode: Iridium Coated Anode

pH 3.5 (with hydrochloric acid and ammonia)

The plating was performed over 30 minutes on brass specimens under the temperature of 90 ° C. Plating was relatively evenly plated, but rarely plated on the back.

Example 4

Plating solution: solution of Example 3.

Additive: Sodium hypophosphite 20g / L

Current density: 2.5A / dm ²

pH 1.5 (with hydrochloric acid and ammonia)

Anode: Iridium Coated Anode

After adding and dissolving sodium hypophosphite, a chemical reducing agent, to the solution of Example 3, plating was performed at 85 ° C. and pH 1.5 over 30 minutes. Plated products were plated on the front and back so that no metal was visible.

Example 5

Titanium Sulfate (TiOSO ₄ 2H ₂ O) 50g

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

Citric acid 80g

15 g of urea

Nickel Chloride 20g

30 g of boric acid

Additive: Sodium hypophosphite 20g / L

Current density: 2.5A / dm ²

pH 1.5 (with hydrochloric acid and ammonia)

Anode: Iridium Coated Anode

1 liter of the bath was dried and Ti-Zr-Ni plating was carried out at a temperature of 85 ° C. for 1 hour, and the plating thickness of about 10.0 μm was measured.

Example 6

Titanium Sulfate (TiOSO ₄ 2H ₂ O) 50g

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

Citric acid 80g

15 g of urea

20 g of cobalt sulfate

50 g ammonium chloride

30 g of boric acid

Additive: Sodium hypophosphite 20g / L

Current density: 2.5A / dm ²

pH 1.5 (with hydrochloric acid and ammonia)

Anode: Iridium Coated Anode

Ti-Zr-Co plating was carried out for 1 hour at a temperature of 85 ° C. by drying 1 liter of the above composition, and a plating thickness of about 8.0 μm was measured.

In the present invention, a conductive aid can be used. Conductive aids can be used with or without reducing agent, and sodium, potassium and ammonium compounds can be used.

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

Therefore, it is preferable to use ammonium sulfate, ammonium chloride, ammonium nitrate, and ammonium nitrate is more preferable because it is a dangerous substance.

Example 7

Titanium Sulfate (TiOSO ₄ 2H ₂ O) 50g

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

100 g citric acid

15 g of urea

20 g of cobalt sulfate

Nickel Chloride 20g

50 g ammonium chloride

30 g of boric acid

Additive: Sodium hypophosphite 20g / L

Current density: 2.5A / dm ²

pH 1.5 (with hydrochloric acid and ammonia)

Anode: Iridium Coated Anode

1 liter of the bath was dried in the above composition, and Ti-Zr-Co-Ni plating was performed at a temperature of 85 ° C. for 1 hour, and a plating thickness of about 8.0 μm was measured.

Example 8

TABLE 2

Corrosion and Acid Resistance Test

division	Nitric Acid 50%	Hydrochloric acid 50%	Sulfuric acid	aqua regia
Example 1 pH1.5	OK	OK	OK	OK
Example 2 pH1.5	OK	OK	OK	OK
Example 3 pH 3.5	NG (turns black)	OK	OK	OK
Example 4 pH1.5	OK	OK	OK	OK

Here, the pH in the [Table 2] is the pH of the plating liquid used in the plating example.

Each plated product exhibits extremely high corrosion resistance, making it impractical to test corrosion resistance with normal salt spray. Particularly, when the thickness is less than 2.0, the surface is hardly eroded even in the nitrate stock solution.

It is possible to use the chemical reducing agent and the electrical reduction method at the same time to allow the plating at such a low pH, in this process, the citric acid ions, the linking complexing agent plays a big role not only as a complexing agent but also as a conductive aid.

Although the above-described embodiment has been described with respect to the preferred embodiment of the present invention, the present invention is not limited thereto and may be modified in various forms without departing from the technical spirit of the present invention. It is obvious to the ordinary technicians who are engaged in.

Claims

Electroplating solution for titanium alloy plating using citric acid compound as a complexing agent.
The electroplating solution for titanium alloy plating according to claim 1, wherein the titanium is made of titanium sulfate as a starting material.
a) providing a titanium compound; And

b) liquefying the titanium compound of step a) in water;

c) adding a citric acid compound as a complexing agent to the liquid phase of step b);

d) dissolving at least one material 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 to 1.0 to 12.0 in the liquid phase of step d); a method for producing an electroplating solution for titanium alloy plating using a citric acid compound as a complexing agent.
The method of claim 3, wherein the nickel compound in step d) is formed by mixing any one or two or more groups of nickel sulfate, nickel sulfamate, nickel chloride, and nickel acetate,

The cobalt compound is formed by mixing any one group or two or more groups of cobalt sulfate, cobalt chloride, and cobalt ammonium sulfate,

Gold compounds include dichlorochloride (AuCl 3 · 2H 2 O), dichlorohydrochloride (HAuC 1 4 · 4H 2 0), gold cyanide (AuCN), potassium cyanide (KAu (CN) 2 · 2H 2 0), sodium cyanide sodium (NaAu (CN) 2 ), or a mixture of two or more groups,

The platinum compound is characterized in that formed by mixing any one group or two or more groups of platinum chloride, platinum chloride, platinum ammonium nitrate,

The copper compound is formed by mixing any one or two or more groups of copper sulfate, copper chloride, copper cyanide, copper pyrophosphate, and the palladium compound is any one of palladium sulfate, palladium chloride, and palladium ammonium nitrate, or Formed by mixing two or more groups,

The lead compound is formed by mixing any one or two or more groups of lead acetate, lead boride fluoride, lead nitrate, and basic lead carbonate,

The silver compound is formed of silver nitrate, silver chloride, silver oxide, silver sulfate, silver cyanide, silver cyanide, silver cyanide, or a combination of two or more groups, and the zirconium compound is zirconium sulfate, zirconium oxychloride, dizirconia, fluorinated Zirconium, zirconium nitrate, zirconium acetate salt, zirconium octanate, potassium zirconium salt of any one group or a mixture of two or more groups formed by mixing a citric acid compound as a complexing agent of an electroplating solution for titanium alloy plating Manufacturing method.
4. The citric acid compound according to claim 3, wherein the citric acid compound used as the complexing agent in step c) is used as a complexing agent by using any one group of citric acid, sodium citrate, ammonium citrate or a mixture of two or more groups. Method for producing an electroplating solution for titanium alloy plating.
The method of claim 3, wherein the step d) and g) step of the step of introducing a reducing agent further comprises the step of e) using a citric acid compound as a complexing agent.
The method of claim 6, wherein the reducing agent in step e) is chaophosphate, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, dimethyl amineborane (DMAB), diethyl amineborane (DEAB), sodium borohydride, hydrazine, A method for producing an electroplating solution for plating titanium alloy using a citric acid compound as a complexing agent, characterized in that any one group of formalin or a mixture of two or more of them.
The method of claim 7, wherein the reducing agent is added when the plating is performed in a complex reduction method, which is a metal reduction using both electrical reduction and chemical reduction of the electroplating solution for titanium alloy plating using a citric acid compound as a complexing agent. Manufacturing method.
[4] The method of claim 3, wherein the step d) and g) further comprises a step f) of additionally injecting metal ions to be alloyed for the titanium alloy plating using the citric acid compound as a complexing agent. Method for producing an electroplating solution.
10. The citric acid compound according to claim 9, wherein the metal ion to be alloyed further in step f) is a mixture of any one of Au, Pt, Cu, Pd, Pb, Ag, Zr, or two or more groups. Method for producing an electroplating solution for the titanium alloy plating using a complexing agent.
A plated product in which at least one plating layer plated with the plating liquid of claim 1 is plated.
Electroplating solution for plating zirconium alloys using citric acid compounds as complexing agents.
The electroplating solution for plating a zirconium alloy according to claim 12, wherein the zirconium is characterized by using zirconium sulfate and zirconium oxychloride as starting materials.
a) providing a zirconium compound; And

b) liquefying the zirconium compound of step a) in water;

c) adding a citric acid compound as a complexing agent to the liquid phase of step b);

d) dissolving at least one material of nickel, cobalt, gold, platinum, copper, palladium, lead, silver metals and metal compounds of these metals to be alloyed with zirconium in the liquefied solution of step c);

g) adjusting the pH to 1.0 to 12.0 in the liquid phase of step d); a method for producing an electroplating solution for zirconium alloy plating using a citric acid compound as a complexing agent.
15. The method according to claim 14, wherein the nickel compound in step d) is formed by mixing any one or two or more groups of nickel sulfate, nickel sulfamate, nickel chloride, and nickel acetate, and the cobalt compound is cobalt sulfate, cobalt chloride, It is formed by mixing any one group or two or more groups of ammonium cobalt sulfate, and the gold compound is dichlorochloride (AuCl 3 · 2H 2 O), dichlorohydrochloride (HAuC1 4 · 4H 2 0), gold cyanide (AuCN), potassium cyanide potassium (KAu (CN) 2 .2H 2 0), sodium cyanide sodium (NaAu (CN) 2 ), or a mixture of two or more of the group formed by the platinum compound Silver is formed by mixing any one group or two or more groups of chloroplatinic acid, platinum chloride, platinum ammonium nitrate, and the copper compound is any one of copper sulfate, copper chloride, copper cyanide, copper pyrophosphate or Characterized in that formed by mixing two or more groups, The sodium compound is formed by mixing any one group or two or more groups of palladium sulfate, palladium chloride, and palladium ammonium nitrate, and the lead compound is any one or two or more groups of lead acetate, lead borofluoride, lead nitrate, and basic lead carbonate. The group is formed by mixing, and the silver compound is formed by mixing any one group of silver nitrate, silver chloride, silver oxide, silver sulfuric acid, silver cyanide, silver potassium cyanide, sodium cyanide, or two or more groups as a complexing agent. Method of producing an electrical plating solution for zirconium alloy plating.
The citric acid compound according to claim 14, wherein the citric acid compound used as the complexing agent in step c) is used as a complexing agent, wherein any one group of citric acid, sodium citrate, ammonium citrate or a mixture of two or more groups is used. Method for producing an electroplating solution for zirconium alloy plating.
15. The method of claim 14, wherein the step d) and g) step further comprises the step of e) injecting a reducing agent, the method of producing an electroplating solution for zirconium alloy plating using a citric acid compound as a complexing agent.
The method of claim 17, wherein the reducing agent in step e) is chaophosphate, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, dimethylamine borane (DMAB), diethylamine borane (DEAB), sodium borohydride, hydrazine, A method for producing an electroplating solution for plating a zirconium alloy using a citric acid compound as a complexing agent, characterized in that any one group of formalin or a mixture of two or more of them.
19. The method of claim 18, wherein the reducing agent is added when the plating is performed in the complex reduction method (metal reduction method using both electrical reduction and chemical reduction), the electric for zirconium alloy plating using the citric acid compound as a complexing agent Method of manufacturing plating solution.
15. The method of claim 14, wherein the step d) and g) step further comprises the step of adding a metal ion to be alloyed f) step for zirconium alloy plating using a citric acid compound as a complexing agent Method for producing an electroplating solution.
21. The citric acid compound according to claim 20, wherein the metal ion to be alloyed further in step f) is a mixture of any one of Au, Pt, Cu, Pd, Pb, Ag, Ti, or two or more groups. Method for producing an electroplating solution for zirconium alloy plating using a complexing agent.
A plated product in which at least one plating layer plated with the plating liquid of claim 12 is plated.