KR102498078B1 - Surface treatment method of glasses frame made of magnesium alloy material using rhodium - Google Patents

Abstract

The present invention relates to a method for treating the surface of an eyeglass frame made of a magnesium alloy material using rhodium, and more specifically, a degreasing step, an etching step, a zinc gate step, a copper cyanide plating step, a copper sulfate plating step, a ternary alloy plating step, and a palladium plating step. It relates to a surface treatment method for a spectacle frame composed of a magnesium alloy material using rhodium, characterized in that it comprises step and electrodeposition step, and the surface treatment method according to an embodiment of the present invention is cyanide copper, cyanide in the ternary alloy plating step By using a ternary alloy plating solution containing zinc and sodium stannate, it is possible to obtain a highly reliable metal surface with excellent physical properties such as corrosion resistance, wear resistance and adhesion, so there is an advantage in that no defects are formed, and in the electrodeposition step, rhodium Silver color can be effectively expressed by electrodeposition using a white rhodium plating solution containing rhodium, which can effectively express silver color, and can prevent corrosion even when exposed to salt water due to its excellent corrosion resistance. It relates to a method for treating the surface of a spectacle frame made of a magnesium alloy material.

Description

Surface treatment method of eyeglass frame made of magnesium alloy material using rhodium {SURFACE TREATMENT METHOD OF GLASSES FRAME MADE OF MAGNESIUM ALLOY MATERIAL USING RHODIUM}

The present invention relates to a method for treating the surface of an eyeglass frame made of a magnesium alloy material using rhodium, and more specifically, a degreasing step, an etching step, a zinc gate step, a copper cyanide plating step, a copper sulfate plating step, a ternary alloy plating step, and a palladium plating step. It relates to a surface treatment method for a spectacle frame composed of a magnesium alloy material using rhodium, characterized in that it comprises step and electrodeposition step, and the surface treatment method according to an embodiment of the present invention is cyanide copper, cyanide in the ternary alloy plating step By using a ternary alloy plating solution containing zinc and sodium stannate, it is possible to obtain a highly reliable metal surface with excellent physical properties such as corrosion resistance, wear resistance and adhesion, so there is an advantage in that no defects are formed, and in the electrodeposition step, rhodium Silver color can be effectively expressed by electrodeposition using a white rhodium plating solution containing rhodium, which can effectively express silver color, and can prevent corrosion even when exposed to salt water due to its excellent corrosion resistance. It relates to a method for treating the surface of a spectacle frame made of a magnesium alloy material.

Magnesium or a magnesium alloy has the characteristics of having the smallest specific gravity and high specific strength among practical metals, and has advantages such as excellent castability, machinability, dimensional stability and durability. Due to this, magnesium-related products are used as materials for sports goods as well as automobile parts, communication parts, electronic parts, computers, and portable electronic devices. However, magnesium-related products are metals that are most easily corroded in the air, so surface treatment is essential for use as products.

Methods such as chromate treatment or anodic oxidation are used for surface treatment of magnesium-related products, but chromate treatment has a problem in that environmental problems arise due to chromium hexavalent ions in the solution. For this reason, the development of a surface treatment method such as a new plating technology for magnesium-related products is required.

Korean Patent Publication No. 10-2010-0104188 discloses an electroless or electrolytic plating method for improving the corrosion resistance of magnesium-related products such as magnesium sheets or molded products of magnesium alloys used in electrical and electronic devices, eyeglass frames, automobiles, and various mechanical parts. Technical content related to a plating method of magnesium or magnesium alloy products related to is disclosed. In addition, Korean Patent Publication No. 10-2012-0127840 discloses a magnesium alloy plating method and a pretreatment method for improving plating adhesion through a pretreatment of forming a substituted copper film on the surface of the magnesium alloy.

Although related researches are being actively conducted on surface treatment methods such as plating technology to improve the corrosion resistance of magnesium-related products as described above, it is especially optimized for eyeglass frames among magnesium-related products, and cyanide in the ternary alloy plating process By using a ternary alloy plating solution containing copper, zinc cyanide and sodium stannate, it is possible to obtain a highly reliable metal surface with excellent physical properties such as corrosion resistance, wear resistance and adhesion, so there is an advantage that no defects are formed, and electrodeposition In the process, by electrodeposition using a white rhodium plating solution containing rhodium, silver color can be effectively expressed, and corrosion resistance is excellent, so corrosion can be prevented even when exposed to salt water, which can improve the quality of the spectacle frame itself. Technology development related to the surface treatment method of the spectacle frame composed of magnesium alloy material using rhodium is insufficient.

Republic of Korea Patent Publication No. 10-2010-0104188 (published on September 29, 2010) Republic of Korea Patent Publication No. 10-2012-0127840 (published on November 26, 2012)

The present invention has been made to solve the problems described above and provide necessary technology,

The present invention is a spectacle frame composed of a magnesium alloy material using rhodium, characterized in that it includes a degreasing step, an etching step, a zinc gate step, a copper cyanide plating step, a copper sulfate plating step, a ternary alloy plating step, a palladium plating step, and an electrodeposition step. It is an object to provide a surface treatment method.

In addition, the present invention uses a ternary alloy plating solution containing copper cyanide, zinc cyanide and sodium stannate in the ternary alloy plating step to obtain a highly reliable metal surface with excellent physical properties such as corrosion resistance, wear resistance and adhesion. Another object is to provide a surface treatment method for a spectacle frame made of a magnesium alloy material using rhodium, which has the advantage of not forming defects according to the present invention.

In addition, in the present invention, by electrodeposition using a white rhodium plating solution containing rhodium in the electrodeposition step, silver color can be effectively expressed, and corrosion resistance is excellent, so corrosion can be prevented even when exposed to salt water, so that the spectacle frame itself Another object is to provide a method for treating the surface of a spectacle frame made of a magnesium alloy material using rhodium, which can improve the quality of.

As one embodiment of the present invention for achieving the above object,

One embodiment of the present invention is a surface treatment method for a spectacle frame composed of a magnesium alloy material, wherein the spectacle frame composed of a magnesium alloy material, which is an object to be plated, is immersed in a degreasing solution maintained at a temperature of 50 to 60 ° C. for 5 to 15 minutes Degreasing step of degreasing; an etching step of etching by immersing the plated body degreased in the degreasing step in an etchant maintained at a temperature of 18 to 25° C. for 1 to 2 minutes; a zinc gate step of immersing the plated body etched in the etching step in a zinc gate solution maintained at a temperature of 65 to 70° C. for 4 to 6 minutes to replace zinc; a copper cyanide plating step of electrolytically plating the plated body subjected to the zinc gate process at a current intensity of 1 to 2 A for 10 to 20 minutes at a temperature of 50 to 60° C. using a copper cyanide plating solution; a copper sulfate plating step of electrolytically plating the plated body plated with copper cyanide in the copper sulfate plating step at a temperature of 18 to 25° C. for 30 to 40 minutes at a current intensity of 1 to 2 A using a copper sulfate plating solution; A ternary alloy plating step of electrolytically plating the plated body plated with copper sulfate in the copper sulfate plating step using a ternary alloy plating solution at a temperature of 18 to 25° C. for 10 to 20 minutes at a current intensity of 1 to 2 A; A palladium plating step of electroplating the plated body plated with the ternary alloy in the ternary alloy plating step using a palladium plating solution at a temperature of 35 to 45° C. for 2 to 4 minutes at a current intensity of 0.25 to 0.5 A; And an electrodeposition step of depositing the palladium-plated plating body in the palladium plating step for 1 to 2 minutes in a white rhodium plating solution maintained at a temperature of 35 to 45 ° C. while stirring at a current intensity of 0.5 to 1A. It provides a method for treating the surface of a spectacle frame made of a magnesium alloy material using rhodium, characterized in that.

In the present invention, the degreasing solution in the degreasing step is an alkaline solution having a pH of 13 or higher, and contains 100 to 150 g/L of sodium hydroxide and 50 to 150 g/L of sodium carbonate based on 1 liter (L) of the total degreasing solution. It is characterized in that 100 g / L is included.

In the present invention, the etchant in the etching step is 5 to 10 g/L of ethylenediamine tetra acetic acid (EDTA) and 30 to 50 g/L of sodium hydroxide based on 1 liter (L) of the total etchant. It is characterized in that L is included.

In the present invention, the Zingate solution in the Zingate step is characterized in that it contains 30 to 80 g/L of zinc sulfate based on 1 liter (L) of the Zingate solution.

In the present invention, the copper cyanide plating solution in the copper cyanide plating step is 70 to 90 g/L of sodium cyanide, 60 to 80 g/L of copper cyanide, based on the total 1 liter (L) of the copper cyanide plating solution. It is characterized by including 20 to 40 g/L of potassium sodium tartrate and 40 to 60 g/L of sodium carbonate.

In the present invention, the copper sulfate plating solution in the copper sulfate plating step includes 150 to 250 g/L of copper sulfate and 45 to 60 g/L of sulfuric acid based on the total 1 liter (L) of the copper sulfate plating solution. characterized by that.

In the present invention, the ternary alloy plating solution in the ternary alloy plating step is 40 to 50 g / L of sodium cyanide and 16 copper cyanide based on the total 1 liter (L) of the ternary alloy plating solution to 20 g/L, 1.6 to 1.8 g/L of zinc cyanide, 80 to 90 g/L of sodium stannate, and 20 to 30 g/L of sodium hydroxide.

In the present invention, the palladium plating solution in the palladium plating step contains 3 to 8 g/L of palladium and 150 to 200 g/L of ammonium sulfate based on the total 1 liter (L) of the palladium plating solution. characterized by

In the present invention, the white rhodium plating solution in the electrodeposition step contains 1 to 2 g/L of rhodium and 10 to 15 g/L of sulfuric acid based on 1 liter (L) of the total white rhodium plating solution. characterized by

According to an embodiment of the present invention, the surface treatment method of a spectacle frame made of a magnesium alloy material using rhodium has corrosion resistance and wear resistance by using a ternary alloy plating solution containing copper cyanide, zinc cyanide, and sodium stannate in the ternary alloy plating step. There is an advantage in that defects are not formed as a highly reliable metal surface can be obtained due to excellent physical properties such as and adhesion.

In addition, in the surface treatment method of a spectacle frame made of magnesium alloy material using rhodium according to an embodiment of the present invention, silver color can be effectively expressed by electrodeposition using a white rhodium plating solution containing rhodium in the electrodeposition step. In addition, it has excellent corrosion resistance, so it can prevent corrosion even when exposed to salt water, which has the advantage of improving the quality of the spectacle frame itself.

1 is a flow chart showing a surface treatment method of a spectacle frame composed of a magnesium alloy material using rhodium according to an embodiment of the present invention step by step.
2 is a cross-sectional view showing a plating layer of a product surface-treated using the surface treatment method of a spectacle frame made of a magnesium alloy material using rhodium according to an embodiment of the present invention.
3 is a photograph taken in each process step of a magnesium alloy plated specimen subjected to surface treatment according to an embodiment of the present invention.
Figure 4 is a photograph and a graph showing the results of measuring the EDS plating layer of the magnesium alloy plated specimen surface-treated according to an embodiment of the present invention.
5 is a photograph showing the results of an experiment to confirm plating adhesion of a magnesium alloy plated specimen subjected to surface treatment according to an embodiment of the present invention.
6 is a photograph showing the results of a corrosion resistance confirmation experiment of a magnesium alloy plated specimen subjected to surface treatment according to an embodiment of the present invention.
7 is a photograph showing the results of a corrosion resistance test according to the increase of time in the copper cyanide plating step (S ₄₀₀ ) and the copper sulfate plating step (S ₅₀₀ ) of the magnesium alloy plated specimen subjected to surface treatment according to an embodiment of the present invention.
8 is a cyanide copper plating step (S ₄₀₀ ), a ternary alloy plating step (S ₆₀₀ ), a palladium plating step (S ₇₀₀ ) and an electrodeposition step (S ₈₀₀ ) of a magnesium alloy plated specimen subjected to surface treatment according to an embodiment of the present invention. It is a photograph showing the result of the corrosion resistance confirmation experiment according to the increase of time.
9 is a photograph showing the results of a corrosion resistance confirmation experiment of a spectacle frame composed of a magnesium alloy material surface-treated according to an embodiment of the present invention.
10 is a photograph showing the results of an experiment to confirm resistance to sweat of an eyeglass frame made of a magnesium alloy material surface-treated according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. Accordingly, the embodiments of the present invention may be modified in many different forms, and the scope of the present invention is not limited to the embodiments described below.

Throughout the specification of the present invention, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

Throughout the specification of the present invention, when a step is said to be located “on” or “before” another step, this is not only the case where a step is in a direct time-series relationship with another step, but also the mixing step after each step As such, the order of the two steps may include the same rights as in the case of an indirect time-series relationship in which the time-series order may change.

The terms "about," "substantially," and the like used throughout the specification of the present invention are used at or close to that value when manufacturing and material tolerances inherent in the stated meaning are given, and the present invention Accurate or absolute figures are used to prevent unfair use by unscrupulous infringers of the disclosed disclosures mentioned for the sake of understanding. The term “step of (doing)” or “step of” used throughout the present specification does not mean “step for”.

Terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In the present invention, terms such as “comprise” or “having” are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

The present invention relates to a method for treating the surface of a spectacle frame made of a magnesium alloy material using rhodium, and more specifically, a degreasing step (S ₁₀₀ ), an etching step (S ₂₀₀ ), a zinc gate step (S ₃₀₀ ), and cyan copper plating step (S ₄₀₀ ), copper sulfate plating step (S ₅₀₀ ), ternary alloy plating step (S ₆₀₀ ), palladium plating step (S ₇₀₀ ) and electrodeposition step (S ₈₀₀ ).

Hereinafter, a surface treatment method (hereinafter, also referred to as a 'surface treatment method') of a spectacle frame made of a magnesium alloy material using rhodium according to an embodiment of the present invention will be described in detail. A surface treatment method of a spectacle frame made of a magnesium alloy material using rhodium according to an embodiment of the present invention can be more clearly understood by the description below.

1 is a flow chart showing a surface treatment method of a spectacle frame composed of a magnesium alloy material using rhodium according to an embodiment of the present invention step by step.

First, a degreasing step (S ₁₀₀ ) may be performed.

A degreasing step (S ₁₀₀ ) of degreasing the spectacle frame made of a magnesium alloy material, which is a material to be plated, by immersing it in a degreasing solution maintained at a temperature of 50 to 60° C. for 5 to 15 minutes may be performed.

Degreasing is a process performed to remove oily contaminants, and in plating, it means alkali degreasing (cleaning), solvent degreasing (washing), and electrolytic degreasing (washing) in the meaning of degreasing and cleaning including washing.

The degreasing step (S ₁₀₀ ) of the present invention is a process performed to remove contaminants on the metal surface generated according to the material, shape, manufacturing process, and manufacturing environment of the object to be plated, and can be referred to as a general plating preparation work. It can be said that degreasing is an important process in the plating process, and insufficient degreasing can cause defects such as poor adhesion, poor gloss, rough plating and swelling.

In the degreasing step (S ₁₀₀ ), it is preferable to degrease the spectacle frame composed of a magnesium alloy material, which is the object to be plated, by immersing it in a degreasing solution maintained at a temperature of 50 to 60 ° C. This is because the degreasing time is prolonged and there is a possibility of non-degreasing phenomenon, and when degreasing is performed at a temperature exceeding 60° C., the lifetime of the degreasing liquid may be shortened.

In addition, in the degreasing step (S ₁₀₀ ), it is preferable to degrease the spectacle frame composed of magnesium alloy material, which is the object to be plated, by immersing it in a degreasing solution for 5 to 15 minutes. This is because there is a fear that non-degreasing may occur, and when degreasing is performed for a time exceeding 15 minutes, unnecessary time is consumed after complete degreasing, and productivity may be reduced.

According to one embodiment of the present invention, the degreasing solution of the degreasing step (S ₁₀₀ ) is an alkaline solution having a pH of 13 or more, and 100 to 150 g of sodium hydroxide (NaOH, Sodium hydroxide) based on 1 liter (L) of the total degreasing solution. / L and sodium carbonate (Na ₂ CO ₃ , Sodium carbonate) is characterized in that it includes 50 to 100g / L.

Next, an etching step (S ₂₀₀ ) may be performed.

An etching step (S ₂₀₀ ) of etching the object to be plated, which has been degreased in the degreasing step (S ₁₀₀ ), may be immersed in an etchant maintained at a temperature of 18 to 25° C. for 1 to 2 minutes to be etched.

Etching refers to a method of chemically or electrochemically corroding a metal or non-metal surface.

The etching step ( _S200 ) of the present invention is a process performed to improve plating adhesion by etching the object to be plated with a liquid containing an oxidizing agent to cause surface roughening and chemical change.

In the etching step (S ₂₀₀ ), it is preferable to immerse the object to be plated in an etchant maintained at a temperature of 18 to 25 ° C for 1 to 2 minutes to etch, which is etched at a temperature exceeding 25 ° C or exceeding 2 minutes. This is because, in the case of etching for a period of time during which the plating is performed, there is a concern that plating adhesion failure may occur on the surface of the object to be plated due to excessive etching.

According to one embodiment of the present invention, the etching solution in the etching step (S ₂₀₀ ) is ethylenediamine tetraacetic acid (EDTA, C ₁₀ H ₁₆ N ₂ O ₈ , Ethylene diamine tetra acetic acid) based on the total 1 liter (L) of the etching solution. ) 5 to 10 g/L and 30 to 50 g/L of sodium hydroxide (NaOH, Sodium hydroxide).

Next, a zinc gate step (S ₃₀₀ ) may be performed.

A zinc gate step (S ₃₀₀ ) of replacing zinc by immersing the plated body etched in the etching step (S ₂₀₀ ) in a zinc gate solution maintained at a temperature of 65 to 70 ° C. for 4 to 6 minutes may be performed. there is.

Zingate is a plating method that uses a potential difference between different metals, and belongs to electroless plating.

The zinc gate step ( _S300 ) of the present invention is performed as a pretreatment process to increase plating adhesion.

In the zinc gate step (S ₃₀₀ ), it is preferable to immerse the object to be plated in the zinc gate liquid for 4 to 6 minutes. This is because, when depositing for a time exceeding 6 minutes, unnecessary time is consumed after the coating layer is completely coated, and productivity may be reduced.

According to one embodiment of the present invention, the Zingate solution in the Zingate step (S ₃₀₀ ) contains 30 to 80 g/L of zinc sulfate (ZnSO ₄ , Zinc sulfate) based on the total 1 liter (L) of the Zingate solution. characterized by being

Next, a cyanide copper plating step (S ₄₀₀ ) may be performed.

_Cyanide copper plating step (S ₄₀₀ ) can be performed.

Copper cyan plating refers to a plating method that improves plating adhesion or improves plating coverage by covering the underlying surface with plating metal up to the low current density portion at the beginning of plating of the electroplating bath.

The copper cyanide plating step ( _S400 ) of the present invention is a step of undercoating. Since copper sulfate plating has poor adhesion to zinc and direct plating may be difficult, for plating adhesion before copper sulfate plating, plating with excellent direct adhesion to the metal As a process performed to perform cyanide copper plating first, it has the advantage of a fast plating speed because it is precipitation from monovalent copper.

Although not limited thereto, the copper cyanide plating step ( _S400 ) uses a pure copper plate at least twice the area of the object to be plated as an anode, covers the anode bag to prevent sludge from being generated at the anode, and then After depositing, it is preferable to proceed with air agitation while applying an electric current, and by evenly sending copper ions to the object to be plated, it becomes high current density and has the advantage of preventing the occurrence of pits.

In the cyanide copper plating step (S ₄₀₀ ), it is preferable to electrolytically plate the object to be plated by applying a current at a temperature of 50 to 60 ° C using a copper cyanide plating solution. This is because there is a risk of becoming vulnerable and poor adhesion, and when electroplating is performed at a temperature exceeding 60 ° C., there is a risk that the plating surface becomes rough.

In addition, in the cyanide copper plating step ( _S400 ), it is preferable to electrolytically plate the object to be plated by applying a current for 10 to 20 minutes using a cyanide copper plating solution. This is because the plating is not sufficiently progressed and the plating becomes thin, and there is a concern that a non-plating phenomenon may occur due to a reaction between the plated body and copper sulfate in the copper sulfate plating bath during the subsequent copper sulfate plating process.

In addition, in the cyanide copper plating step ( _S400 ), it is preferable to electrolytically plate the object to be plated at a current intensity of 1 to 2A using a copper cyanide plating solution. This is because there is a concern that the contact surface in contact with the jig may burn.

According to one embodiment of the present invention, the copper cyanide plating solution in the copper cyanide plating step (S ₄₀₀ ) is sodium cyanide (NaCN, Sodium cyanide) 70 to 90 g / L, copper cyanide based on the total 1 liter (L) of the copper cyanide plating solution (CuCN, Copper cyanide) 60 to 80 g/L, potassium sodium tartrate (Rossel salt, C ₄ H ₄ KNaO ₆ , Potassium sodium tartrate) 20 to 40 g/L and sodium carbonate (Na ₂ CO ₃ , Sodium carbonate) 40 to 60 g /L is characterized in that it is included.

Although not limited thereto, the Cu plating layer formed in the copper cyanide plating step (S ₄₀₀ ) is preferably formed to a thickness of 4 to 9 μm, which is too thin when the Cu plating layer is formed to a thickness of less than 4 μm. This is because there is a concern that the plated body and copper sulfate react in the copper sulfate plating bath during the copper sulfate plating process later to cause non-plating, and when the Cu plating layer is formed with a thickness exceeding 9㎛, the cause of poor plating adhesion because there is a risk of

Next, a copper sulfate plating step (S ₅₀₀ ) may be performed.

Copper sulfate plating step (S ₅₀₀ ) of electrolytically plating the cyanide plated body in the cyanide copper plating step (S 400 ₎ using a copper sulfate plating solution at a temperature of 18 to 25 ° C. for 30 to 40 minutes at a current intensity of 1 to 2 A ) can be performed.

Copper sulfate plating has the advantages of low pollution, low cost, and good smoothness. It is mainly used for undercoating, coloring, electroforming, and frit substrate plating. Direct plating is difficult due to poor adhesion on iron, zinc, lead, and zinc die-casting. It has a good leceling action, so it is easy to get rid of buff flaws and gloss, and it is possible to plate with a large current with a simple composition and has excellent current efficiency.

The copper sulfate plating step ( _S500 ) of the present invention is a process performed to perform intermediate layer plating among decorative plating undercoating.

Although not limited thereto, the copper sulfate plating step ( _S500 ) uses a pure copper plate at least twice the area of the plated body as the anode, covers the anode bag to prevent sludge from being generated at the anode, and then deposits in the copper sulfate plating solution After that, it is preferable to proceed with plating by performing air agitation while applying an electric current. Stirring is performed to obtain a uniform gloss. This is because there is a difference in gloss due to the difference in concentration between the top and bottom of the solution when no stirring is performed. Because it has advantages.

In the copper sulfate plating step ( _S500 ), it is preferable to electrolytically plate the plated body by applying a current at a temperature of 18 to 25 ° C using a copper sulfate plating solution. This is because there is a concern that plating adhesion failure may occur and copper sulfate crystals may occur, resulting in a problem of lowering the concentration. This is because there is a concern that a problem of increasing consumption may occur.

In addition, in the copper sulfate plating step ( _S500 ), it is preferable to electrolytically plate the plated body by applying a current for 30 to 40 minutes using a copper sulfate plating solution. This is because there is a concern that a proper plating layer may not be formed, resulting in a problem of low luster or deterioration of gloss.

According to one embodiment of the present invention, the copper sulfate plating solution in the copper sulfate plating step (S ₅₀₀ ) contains 150 to 250 g of copper sulfate (CuSO ₄ 5H ₂ O, copper sulfate) based on 1 liter (L) of the copper sulfate plating solution. It is characterized in that L and sulfuric acid (H ₂ SO ₄ , Sulfuric acid) 45 to 60g / L is included.

Although not limited thereto, the Cu plating layer formed in the copper sulfate plating step (S ₅₀₀ ) is preferably formed to a thickness of 15 to 20 μm, which is when the Cu plating layer exceeds or falls short of the thickness range of 15 to 20 μm. This is because it is not glossy, has poor corrosion resistance, and there is a concern that plating may not proceed properly in a later ternary alloy plating process.

Next, a ternary alloy plating step (S ₆₀₀ ) may be performed.

A ternary alloy plating step of electrolytically plating the copper sulfate plated body in the copper sulfate plating step ( _S500 ) using a ternary alloy plating solution at a temperature of 18 to 25 ° C. for 10 to 20 minutes at a current intensity of 1 to 2 A ( S ₆₀₀ ) may be performed.

Ternary alloy plating uses a cyan-type alkaline solution and means an alloy plating method by precipitation of three types of metals. Cu-Sn-Zn ternary alloy plating for decoration is used as a substitute gold plating (also called 'gold plating'). In particular, it is suitable for plating that requires no nickel, and it is suitable for plating accessories, connectors, and solder pins. It is a plating method that can respond to the Restriction of Use of Hazardous Substances Directive (RoHS) because it does not contain harmful substances. Excellent current efficiency and uniform color plating is possible.

The ternary alloy plating step (S ₆₀₀ ) of the present invention uses a ternary alloy plating solution containing copper cyanide, zinc cyanide, and sodium stannate to obtain a highly reliable metal surface with excellent physical properties such as corrosion resistance, wear resistance and adhesion. It is a process performed to prevent the formation of defects in the final product according to the presence of the coating, and it can be said to be a process performed to improve plating adhesion and corrosion resistance by undercoating, and to ensure that the plating film has good gloss and is deposited in a wide current density area. There are advantages to doing so.

Although not limited thereto, in the ternary alloy plating step (S ₆₀₀ ), carbon for an electrode at least twice the area of the plated body is used as an anode. After immersion in the ternary alloy plating solution, it is preferable to conduct cathode agitation (3 to 10 m/min) by applying an electric current. Stirring is carried out to obtain a uniform gloss, and this is because a difference in gloss occurs due to a difference in concentration between the upper and lower layers of the liquid without stirring, and it is effective in preventing the occurrence of mottled patterns in gloss.

In the ternary alloy plating step ( _S600 ), it is preferable to electrolytically plate the plated body by applying a current at a temperature of 18 to 25 ° C. using a ternary alloy plating solution. This is because there is a concern that a problem of not generating gloss may occur, and when electroplating is performed at a temperature exceeding 25 ° C., there is a concern that Cu of the plating layer is precipitated and a problem of deterioration in gloss may occur.

In addition, in the ternary alloy plating step ( _S600 ), it is preferable to electrolytically plate the plated body at a current intensity of 1 to 2A using a ternary alloy plating solution. This is because there is a concern that the coating film may be reduced and the plating without a white luster may occur, and when electrolytic plating is performed at a current intensity exceeding 2A, there is a concern that Cu precipitation in the plating layer may increase.

According to one embodiment of the present invention, the ternary alloy plating solution of the ternary alloy plating step (S ₆₀₀ ) is sodium cyanide (NaCN, Sodium cyanide) 40 to 50g based on the total 1 liter (L) of the ternary alloy plating solution /L, copper cyanide (CuCN) 16 to 20 g/L, zinc cyanide (ZN(CN) ₂ , zinc cyanide) 1.6 to 1.8 g/L, sodium stannate (Na ₂ SnO ₃ , Sodium Stannate) 80 to 90 g /L and sodium hydroxide (NaOH, Sodium hydroxide) is characterized in that it contains 20 to 30g / L.

Although not limited thereto, the Cu-Sn-Zn ternary alloy plating layer formed in the ternary alloy plating step (S ₆₀₀ ) is preferably formed to a thickness of 2 to 8 μm, which is a Cu-Sn-Zn ternary alloy plating layer. This is because when the thickness exceeds or falls below the range of 2 to 8 μm, there is a concern that gloss is not obtained and corrosion resistance is deteriorated.

Next, a palladium plating step (S ₇₀₀ ) may be performed.

In the ternary alloy plating step (S ₆₀₀ ), a palladium plating step of electrolytically plating the plated body plated with a ternary alloy at a temperature of 35 to 45 ° C. for 2 to 4 minutes at a current intensity of 0.25 to 0.5 A using a palladium plating solution. (S ₇₀₀ ) may be performed.

Palladium is cheaper than rhodium, but has low hardness and inferior corrosion resistance and wear resistance compared to rhodium plating. In addition, since the price of palladium is about 25% of that of gold and its specific gravity is about 33%, the price is lower than that of gold even with the same plating thickness. There are flaws that cause Palladium plating is used as an undercoat of rhodium or gold for decorative purposes.

The palladium plating step ( _S700 ) of the present invention is a process performed to form an underlying plating layer of rhodium for decoration.

Although not limited thereto, the palladium plating step ( _S700 ) uses a platinum/titanium network at least twice the area of the plated body as an anode, immerses it in a palladium plating solution, and then proceeds with plating by stirring while applying a current It is desirable to do

In the palladium plating step ( _S700 ), it is preferable to electrolytically plate the plated body at a current intensity of 0.25 to 0.5A for 2 to 4 minutes at a temperature of 35 to 45 ° C. using a palladium plating solution, which has a temperature range of 35 This is because plating adhesion failure may occur when the temperature exceeds or falls below 45 ° C, when the time range exceeds or falls short of 2 to 4 minutes, and when the current intensity range exceeds or falls short of 0.25 to 0.5 A. .

According to one embodiment of the present invention, the palladium plating solution in the palladium plating step (S ₇₀₀ ) includes 3 to 8 g/L of palladium (Pd, Palladium) and ammonium sulfate (( NH ₄ ) ₂ SO ₄ , Ammonium sulfate) is characterized in that it includes 150 to 200g / L.

Although not limited thereto, the palladium plating solution of the palladium plating step (S ₇₀₀ ) includes 3 to 8 g/L of palladium (Pd, Palladium) and ammonium sulfate ((NH ₄ ) based on the total 1 liter (L) of the palladium plating solution. ₂ SO ₄ , Ammonium sulfate) 150 to 200 g/L is included, and ammonia water (NH _{3 ·} H ₂ O, Ammonia water) having a pH of 8 to 9 is further included.

In addition, although not limited thereto, the Pd plating layer formed by the palladium plating step ( _S700 ) is preferably formed to a thickness of 0.2 to 1 μm, which is that the Pd plating layer exceeds or falls short of the thickness range of 0.2 to 1 μm. This is because there is a possibility that plating adhesion failure may occur in this case.

Next, an electrodeposition step (S ₈₀₀ ) may be performed.

In the palladium plating step (S ₇₀₀ ), the palladium-plated plated body is immersed in a white rhodium plating solution maintained at a temperature of 35 to 45 ° C. for 1 to 2 minutes, an electrodeposition step of electrodepositing while stirring at a current intensity of 0.5 to 1A. (S ₈₀₀ ) may be performed.

Electrodeposition is mainly used in the decorative field, that is, in the final plating of accessories, spectacle frames, fountain pens, etc.

The electrodeposition step (S ₈₀₀ ) of the present invention is used as a plating of electrical contacts during the palladium plating process, and organic matter in the air is deposited or the contact action is polymerized to generate a collimer. It is a process performed to effectively express silver color by electrodepositing using a white rhodium plating solution containing rhodium and to prevent corrosion even when exposed to salt water due to its excellent corrosion resistance.

Although not limited thereto, the electrodeposition step (S ₈₀₀ ) uses a platinum / titanium net at least twice the area of the plated body as an anode, deposits it in a white rhodium plating solution, and then proceeds with plating by stirring while applying a current It is desirable to do

In the electrodeposition step ( _S800 ), it is preferable to immerse the plated body in a white rhodium plating solution maintained at a temperature of 35 to 45 ° C. for 1 to 2 minutes, and electrodeposit while stirring at a current intensity of 0.5 to 1A. When the range exceeds or falls short of 35 to 45 ° C, when the time range exceeds or falls short of 1 to 2 minutes, and when the current intensity range exceeds or falls short of 0.5 to 1A, plating adhesion failure may occur. Because.

According to one embodiment of the present invention, the white rhodium plating solution of the electrodeposition step (S ₈₀₀ ) is 1 to 2 g / L of rhodium (Rh, Rhodium) and sulfuric acid (H ₂ SO ₄ , Sulfuric acid) is characterized in that it includes 10 to 15g / L.

Although not limited thereto, the white rhodium plating solution of the electrodeposition step (S ₈₀₀ ) is 1 to 2 g / L of rhodium (Rh, Rhodium) and sulfuric acid (H ₂ SO ₄ based on the total 1 liter (L) of the white rhodium plating solution) , Sulfuric acid) 10 to 15 g / L is included, characterized in that it is prepared by filling the rest with pure water and then stirring it sufficiently for about one day to stabilize the plating solution.

As described above, the surface treatment method of the spectacle frame composed of magnesium alloy material using rhodium according to an embodiment of the present invention includes a degreasing step (S ₁₀₀ ), an etching step (S ₂₀₀ ), a zincating step (S ₃₀₀ ), Cyanide copper plating step (S ₄₀₀ ), copper sulfate plating step (S ₅₀₀ ), ternary alloy plating step (S ₆₀₀ ), palladium plating step (S ₇₀₀ ) and electrodeposition step (S ₈₀₀ ), magnesium alloy A Zn substitution layer, a Cu plating layer, a Cu-Sn-Zn ternary alloy plating layer, a Pd plating layer, and a white rhodium electrodeposition layer may be formed on the surface of the material, as shown in the cross section of FIG. 2 below.

Hereinafter, a magnesium alloy plated specimen and a magnesium alloy material surface-treated by the surface treatment method of a spectacle frame composed of a magnesium alloy material using rhodium of the present invention so that those skilled in the art can easily carry out the present invention A spectacle frame composed of an example will be described in detail. A method for treating the surface of a spectacle frame made of a magnesium alloy material using rhodium according to an embodiment of the present invention can be more clearly understood by referring to the following examples. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein.

ready for plating

Specimen: Prepare a magnesium alloy plated specimen and an eyeglass frame made of magnesium alloy material.

Degreasing step (S ₁₀₀ ): Prepare a degreasing solution containing 125 g/L of sodium hydroxide and 75 g/L of sodium carbonate based on the total 1 liter (L) of the degreasing solution but having a pH of 13 or higher.

Etching step (S ₂₀₀ ): Prepare an etchant containing 7.5 g/L of ethylenediamine tetraacetic acid (EDTA) and 40 g/L of sodium hydroxide based on 1 liter (L) of the total etchant.

Zingate step (S ₃₀₀ ): Zingate solution containing 55 g/L of zinc sulfate is prepared based on the total 1 liter (L) of Zingate solution.

Copper cyanide plating step (S ₄₀₀ ): Copper cyanide plating solution containing 80 g/L of sodium cyanide, 70 g/L of copper cyanide, 30 g/L of potassium sodium tartrate and 50 g/L of sodium carbonate based on the total 1 liter (L) of copper cyanide plating solution and anode pure copper plate.

Copper sulfate plating step (S ₅₀₀ ): A copper sulfate plating solution containing 200 g/L of copper sulfate and 52 g/L of sulfuric acid based on 1 liter (L) of copper sulfate plating solution and a pure copper anode are prepared.

Ternary alloy plating step (S ₆₀₀ ): Sodium cyanide 45g/L, copper cyanide 18g/L, zinc cyanide 1.7g/L, sodium tartrate 85g/L and sodium hydroxide based on the total 1 liter (L) of the ternary alloy plating solution Prepare a ternary alloy plating solution containing 25 g/L and carbon for the anode electrode.

Palladium plating step (S ₇₀₀ ): Palladium plating solution containing 5 g/L of palladium and 175 g/L of ammonium sulfate based on the total 1 liter (L) of the palladium plating solution and an appropriate amount of ammonia water (pH 8-9) and anode platinum /Prepare the titanium net.

Electrodeposition step (S ₈₀₀ ): 1.5 g/L of rhodium and 12 g/L of sulfuric acid are included based on 1 liter (L) of the white rhodium plating solution, but the rest is filled with pure water and then stirred sufficiently for one day to stabilize the plating solution. Prepare a white rhodium plating solution and an anode platinum/titanium net.

Plating thickness measurement experiment for each stage of surface treatment process

An experiment was conducted to measure the plating thickness of the magnesium alloy plated specimens surface-treated by the following method.

[Surface treatment process]

1. Degreasing step (S ₁₀₀ ): The magnesium alloy plated specimen, which is the object to be plated, is immersed in a degreasing solution maintained at a temperature of 55 ° C. for 10 minutes to degrease.

2. Etching step (S ₂₀₀ ): The object to be plated is immersed in an etchant maintained at a temperature of 25° C. for 1.5 minutes to be etched.

3. Zingate step (S ₃₀₀ ): Zinc is substituted by immersing the object to be plated in a zincate solution maintained at a temperature of 70 ° C for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): The object to be plated is electrolytically plated with a copper cyanide plating solution at a temperature of 55° C. for 10 minutes at a current intensity of 2A.

5. Copper sulfate plating step (S ₅₀₀ ): The plated body is electrolytically plated with a copper sulfate plating solution at a temperature of 25° C. for 30 minutes at a current intensity of 2A.

6. Ternary alloy plating step (S ₆₀₀ ): The plated body is electroplated using a ternary alloy plating solution at a temperature of 25° C. for 10 to 30 minutes at a current intensity of 1 to 2A.

7. Palladium plating step ( _S700 ): The plated body is electroplated using a palladium plating solution at a temperature of 40° C. for 2 minutes at a current intensity of 0.5A.

8. Electrodeposition step (S ₈₀₀ ): The plating body is immersed in a white rhodium plating solution maintained at a temperature of 40° C. for 2.5 minutes, and electrodeposition is performed while stirring at a current intensity of 1A.

[Plating thickness measurement experiment]

The results of measuring the plating thickness of the magnesium alloy plated specimen surface-treated by the above surface treatment method are as follows.

For the surface-treated magnesium alloy plated specimen, the plating thickness of the front and back surfaces of the specimen was measured 5 times each using an X-ray fluorescence analyzer (XRF, X-Ray Fluorescence Analyzer) at each stage of the process, and the average value was indicated. As shown in Tables 1 to 9 below.

The Zn substitution layer formed by the zinc gate step (S ₃₀₀ ) is marked as “Zn”, and the Cu plating layer formed by the copper cyanide plating step (S ₄₀₀ ) or copper sulfate plating step (S ₅₀₀ ) is marked as “Cu”. The Cu-Sn-Zn ternary alloy plating layer formed by the original alloy plating step (S ₆₀₀ ) is marked as “d3”, the Pd plating layer formed by the palladium plating step (S ₇₀₀ ) is marked as “Pd”, and the electrodeposition step ( S ₈₀₀ ) is marked as “Rh W”.

Zingate step (S ₃₀₀ ): 70 ℃, 5min number Zn(μm) Cu(μm) number Zn(μm) Cu(μm) front-1 0.701 - back-1 0.658 - front-2 0.699 - back-2 0.657 - front-3 0.704 - back-3 0.653 - front-4 0.699 - back-4 0.659 - front-5 0.699 - back-5 0.655 - average 0.700 - average 0.656 - Precipitation amount (g) 0.013 - Precipitation amount (g) 0.012 -

Cyanide Copper Plating Step (S ₄₀₀ ): 55℃, 10min, 2A number Zn(μm) Cu(μm) number Zn(μm) Cu(μm) front-1 0.588 4.850 back-1 0.485 6.546 front-2 0.590 4.842 back-2 0.491 6.588 front-3 0.592 4.836 back-3 0.487 6.513 front-4 0.584 4.828 back-4 0.483 6.513 front-5 0.581 4.835 back-5 0.482 6.526 average 0.587 4.838 average 0.486 6.537 Precipitation amount (g) 0.010 0.108 Precipitation amount (g) 0.009 0.145

Copper sulfate plating step (S ₅₀₀ ): 25℃, 30min, 2A number Zn(μm) Cu(μm) number Zn(μm) Cu(μm) front-1 0.533 17.340 back-1 0.446 19.590 front-2 0.538 17.410 back-2 0.452 19.510 front-3 0.536 17.400 back-3 0.416 19.500 front-4 0.571 17.460 back-4 0.414 19.510 front-5 0.569 17.500 back-5 0.438 19.720 average 0.549 17.422 average 0.433 19.566 Precipitation amount (g) 0.010 0.388 Precipitation amount (g) 0.008 0.435

Tables 1 to 3 show the results of measuring the thickness of the Zn substitution layer and the Cu plating layer formed by the zinc gate step (S ₃₀₀ ), the copper cyanide plating step (S ₄₀₀ ) and the copper sulfate plating step (S ₅₀₀ ), and the plating thickness is found to be suitable.

ternary alloy plating step (S ₆₀₀ ): 25℃, 20min, 1A number Zn(μm) Cu(μm) d3(μm) number Zn(μm) Cu(μm) d3(μm) front-1 1.000 17.780 0.347 back-1 0.918 17.150 0.361 front-2 1.023 18.090 0.351 back-2 0.914 16.900 0.350 front-3 1.015 17.890 0.356 back-3 0.921 17.030 0.357 front-4 1.002 17.890 0.350 back-4 0.902 17.010 0.357 front-5 1.030 17.910 0.348 back-5 0.885 16.840 0.351 average 1.014 17.912 0.350 average 0.908 16.986 0.355

ternary alloy plating step (S ₆₀₀ ): 25℃, 20min, 2A number Zn(μm) Cu(μm) d3(μm) number Zn(μm) Cu(μm) d3(μm) front-1 1.246 14.960 0.836 back-1 1.181 14.720 0.838 front-2 1.262 15.150 0.858 back-2 1.180 14.820 0.851 front-3 1.218 14.950 0.530 back-3 1.206 14.870 0.860 front-4 1.290 15.250 0.585 back-4 1.382 15.730 0.914 front-5 1.205 14.760 0.830 back-5 1.249 15.170 0.876 average 1.244 15.014 0.728 average 1.240 15.062 0.868

Ternary alloy plating step (S ₆₀₀ ): 25℃, 30min, 2A number Zn(μm) Cu(μm) d3(μm) number Zn(μm) Cu(μm) d3(μm) front-1 1.103 15.860 0.669 back-1 1.046 15.880 0.695 front-2 1.152 16.210 0.693 back-2 1.010 15.580 0.682 front-3 1.166 16.300 0.696 back-3 0.096 15.720 0.694 front-4 1.059 15.800 0.659 back-4 1.076 15.880 0.699 front-5 1.114 15.910 0.678 back-5 1.040 15.730 0.684 average 1.119 16.016 0.679 average 0.854 15.758 0.691

ternary alloy plating step (S ₆₀₀ ): 25℃, 10min, 2A number Zn(μm) Cu(μm) d3(μm) number Zn(μm) Cu(μm) d3(μm) front-1 0.751 17.270 0.277 back-1 0.900 20.110 0.291 front-2 0.757 17.090 0.273 back-2 0.904 20.280 0.303 front-3 0.752 17.240 0.265 back-3 0.895 20.270 0.292 front-4 0.758 17.170 0.267 back-4 0.888 20.050 0.295 front-5 0.758 17.090 0.275 back-5 0.907 20.260 0.301 average 0.755 17.172 0.271 average 0.899 20.194 0.296

Tables 4 to 7 show the results of measuring the thickness of the Cu-Sn-Zn ternary alloy plating layer formed in the ternary alloy plating step (S ₆₀₀ ), in the case of the Zn substitution layer and the Cu plating layer among the ternary alloys, of the previous process. It is assumed that it affects the thickness and is not properly observed in the thickness of the ternary alloy.

Palladium plating step (S ₇₀₀ ): 25 ℃, 2min, 0.5A number Zn(μm) Cu(μm) d3(μm) Pd(μm) number Zn(μm) Cu(μm) d3(μm) Pd(μm) front-1 0.814 16.540 0.309 0.301 back-1 0.623 15.980 0.307 0.291 front-2 0.833 16.630 0.313 0.302 back-2 0.623 15.890 0.302 0.291 front-3 0.782 16.200 0.296 0.299 back-3 0.620 15.910 0.307 0.288 front-4 0.807 16.290 0.295 0.300 back-4 0.654 16.250 0.317 0.295 front-5 0.904 17.160 0.341 0.310 back-5 0.615 15.950 0.306 0.292 average 0.828 16.564 0.311 0.302 average 0.627 15.996 0.308 0.291

Table 8 shows the results of measuring the _thickness of the Pd plating layer formed by the palladium plating step (S _{700 ) after performing the ternary alloy plating step (S 600 )} for 10 minutes. minutes was found to be most desirable.

Electrodeposition step (S ₈₀₀ ): 25 ℃, 2.5min, 1A number Zn(μm) Cu(μm) d3(μm) Pd(μm) Rh W (μm) front-1 2.032 20.730 1.017 0.308 0.321 front-2 2.139 21.240 1.011 0.321 0.328 front-3 2.069 20.890 1.006 0.313 0.328 front-4 1.942 20.310 0.995 0.312 0.318 front-5 1.950 20.300 0.990 0.305 0.330 average 2.026 20.694 1.004 0.312 0.325 Precipitation amount (g) 0.036 0.460 - 0.009 0.010 front-1 2.820 25.580 1.051 0.322 0.279 front-2 2.545 24.780 1.033 0.322 0.277 front-3 2.655 25.140 1.056 0.318 0.278 front-4 2.582 24.940 1.031 0.322 0.283 front-5 2.791 25.790 1.071 0.316 0.272 average 2.679 25.246 1.048 0.320 0.278 Precipitation amount (g) 0.048 0.562 - 0.010 0.009

Table 9 shows the result of measuring the thickness of the electrodeposition layer (white rhodium electrodeposition layer) formed in the electrodeposition step (S ₈₀₀ ), and as the electrodeposition layer thickness was measured as 3 μm, the current or time of the electrodeposition step (S ₈₀₀ ) is presumed to be reduced.

Plating thickness and EDS plating layer measurement test and plating adhesion and corrosion resistance test

An experiment to measure the plating thickness and EDS plating layer of the magnesium alloy plated specimen surface-treated by the following method and an experiment to confirm plating adhesion and corrosion resistance were conducted. Photos taken of the surface-treated magnesium alloy plated specimen in each process step are shown in FIG. 3 below.

[Surface treatment process]

1. Degreasing step (S ₁₀₀ ): After ultrasonically degreasing a magnesium alloy plated specimen, which is a material to be plated, for 10 minutes, it is degreased by immersing it in a degreasing solution maintained at a temperature of 60 ° C. for 5 minutes.

2. Etching step (S ₂₀₀ ): The object to be plated is immersed in an etchant maintained at a temperature of 25° C. for 1 minute to be etched.

3. Zingate step (S ₃₀₀ ): Zinc is substituted by immersing the object to be plated in a zincate solution maintained at a temperature of 70 ° C for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): The object to be plated is electrolytically plated with a copper cyanide plating solution at a temperature of 55° C. for 10 minutes at a current intensity of 2A.

5. Copper sulfate plating step (S ₅₀₀ ): The plated body is electrolytically plated with a copper sulfate plating solution at a temperature of 25° C. for 30 minutes at a current intensity of 2A.

6. Ternary alloy plating step (S ₆₀₀ ): The plated body is electrolytically plated at a current of 2A for 10 minutes at a temperature of 25° C. using a ternary alloy plating solution.

7. Palladium plating step ( _S700 ): The plated body is electroplated using a palladium plating solution at a temperature of 40° C. for 2 minutes at a current intensity of 0.5A.

8. Electrodeposition step (S ₈₀₀ ): The plated body is immersed in a white rhodium plating solution maintained at a temperature of 40 ° C for 1 minute, and electrodeposited while stirring at a current intensity of 1A.

[Plating thickness measurement experiment]

The results of measuring the plating thickness of the magnesium alloy plated specimen surface-treated by the above surface treatment method are as follows.

For the surface-treated magnesium alloy plated specimen, the plating thickness of the front and back surfaces was measured 9 times each using an X-Ray Fluorescence Analyzer (XRF) at each stage of the process, and the average value was indicated. The results are shown in the table below. equal to 10

The Zn substitution layer formed by the zinc gate step (S ₃₀₀ ) is marked as “Zn”, and the Cu plating layer formed by the copper cyanide plating step (S ₄₀₀ ) or copper sulfate plating step (S ₅₀₀ ) is marked as “Cu”. The Cu-Sn-Zn ternary alloy plating layer formed by the original alloy plating step (S ₆₀₀ ) is marked as “d3”, the Pd plating layer formed by the palladium plating step (S ₇₀₀ ) is marked as “Pd”, and the electrodeposition step ( S ₈₀₀ ) is marked as “Rh W”.

number Zn(μm) Cu(μm) d3(μm) Pd(μm) Rh W (μm) front-1 7.039 45.810 0.439 0.480 0.267 front-2 3.471 37.160 0.409 0.445 0.226 front-3 1.099 22.350 0.251 0.364 0.162 front-4 3.441 37.890 0.387 0.437 0.235 front-5 1.270 26.360 0.308 0.392 0.190 front-6 0.918 20.010 0.227 0.315 0.124 front-7 4.529 38.880 0.418 0.480 0.238 front-8 2.560 32.590 0.347 0.408 0.154 front-9 7.510 45.630 0.408 0.457 0.243 average 3.537 34.076 0.355 0.420 0.204 Precipitation amount (g) 0.063 0.758 - 0.013 0.006 back-1 4.642 41.360 0.429 0.465 0.249 back-2 1.265 26.320 0.324 0.385 0.196 back-3 3.902 39.240 0.399 0.452 0.247 back-4 1.416 28.360 0.338 0.406 0.206 back-5 1.648 29.510 0.361 0.407 0.209 back-6 0.847 19.490 0.236 0.322 0.156 back-7 1.399 27.470 0.329 0.385 0.190 back-8 3.981 4.390 0.420 0.481 0.261 back - 9 2.848 34.630 0.383 0.431 0.210 average 2.439 27.863 0.358 0.415 0.214 Precipitation amount (g) 0.044 0.620 - 0.012 0.007

[EDS plating layer measurement experiment]

The results of measuring the EDS plating layer of the magnesium alloy plated specimen surface-treated by the above surface treatment method are shown in FIG. 4 below.

The Cu plating layer formed by the copper cyanide plating step (S ₄₀₀ ) and the copper sulfate plating step (S ₅₀₀ ) was measured to be 25 to 30 μm, and the Cu-Sn-Zn ternary alloy plating layer formed by the ternary alloy plating step (S ₆₀₀ ) was 2 μm. , and the Pd plating layer formed by the palladium plating step (S ₇₀₀ ) was measured to be 1 μm or less, and the white rhodium electrodeposition layer formed by the electrodeposition step (S ₈₀₀ ) was measured to be 1 μm.

In the case of the surface-treated magnesium alloy plating specimen, the boundary of the plating layer was not visible during SEM measurement, so it was measured by EDS, and it was confirmed that Mg, Zn, Cu, Sn, Pd, and Rh were all present, and the plating was well done layer by layer Confirmed.

[Plating Adhesion Confirmation Test]

The results of conducting an experiment to confirm the plating adhesion of the magnesium alloy plated specimen surface-treated by the above surface treatment method are shown in FIG. 5 below.

In order to check the plating adhesion, the surface-treated magnesium alloy plated specimen was sintered in a sintering furnace maintained at a temperature of 300 ° C. for 10 minutes, and then cut into a grid pattern and measured five times in a manner in which taping was attached. As a result, in the magnesium alloy plated specimens surface-treated by the surface treatment method according to an embodiment of the present invention, plating adhesion failure was not confirmed.

[Corrosion resistance test]

The results of the corrosion resistance confirmation test of the magnesium alloy plated specimen surface-treated by the above surface treatment method are shown in FIG. 6 below.

As a result of the salt spray test on the magnesium alloy plated specimen surface-treated by the surface treatment method according to an embodiment of the present invention, corrosion proceeded within 24 hours, but this indicates that plating adhesion failure did not occur even in the plating adhesion confirmation test. It is presumed that this phenomenon occurred because of the thin thickness and the gaps on the outside that were created when cutting the plate.

Cyan copper plating step (S ₄₀₀ ) and copper sulfate plating step (S ₅₀₀ ) Corrosion resistance test with increasing time

An experiment was conducted to confirm the corrosion resistance of the magnesium alloy plated specimen subjected to surface treatment by the following method.

[Surface treatment process]

1. Degreasing step (S ₁₀₀ ): After ultrasonically degreasing a magnesium alloy plated specimen, which is a material to be plated, for 10 minutes, it is degreased by immersing it in a degreasing solution maintained at a temperature of 60 ° C. for 5 minutes.

2. Etching step (S ₂₀₀ ): The object to be plated is immersed in an etchant maintained at a temperature of 25° C. for 1 minute to be etched.

3. Zingate step (S ₃₀₀ ): Zinc is substituted by immersing the object to be plated in a zincate solution maintained at a temperature of 70 ° C for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): The object to be plated is electrolytically plated with a copper cyanide plating solution at a temperature of 55° C. for 20 minutes at a current intensity of 2A.

5. Copper sulfate plating step (S ₅₀₀ ): The plated body is electrolytically plated with a copper sulfate plating solution at a temperature of 25° C. for 40 minutes at a current intensity of 2A.

6. Ternary alloy plating step (S ₆₀₀ ): The plated body is electrolytically plated at a current of 2A for 10 minutes at a temperature of 25° C. using a ternary alloy plating solution.

7. Palladium plating step ( _S700 ): The plated body is electroplated using a palladium plating solution at a temperature of 40° C. for 2 minutes at a current intensity of 0.5A.

8. Electrodeposition step (S ₈₀₀ ): The plated body is immersed in a white rhodium plating solution maintained at a temperature of 40 ° C for 1 minute, and electrodeposited while stirring at a current intensity of 1A.

[Corrosion resistance test]

The results of the corrosion resistance confirmation test of the magnesium alloy plated specimen surface-treated by the above surface treatment method are shown in FIG. 7 below.

In the case of the specimen in which the plating time of the copper cyanide plating step (S ₄₀₀ ) and the copper sulfate plating step (S ₅₀₀ ) was increased by 10 minutes compared to the surface-treated magnesium alloy plating specimen of Example 3, in the results of the 72-hour salt spray test, Example 3 It was confirmed that it was better than the corrosion resistance result, and white rust was seen on the round surface, but it was confirmed that the separation of the plating layer was hardly seen.

Cyan copper plating step (S ₄₀₀ ), ternary alloy plating step (S ₆₀₀ ), palladium plating step (S ₇₀₀ ) and electrodeposition step (S ₈₀₀ ) Corrosion resistance test with increasing time

An experiment was conducted to confirm the corrosion resistance of the magnesium alloy plated specimen subjected to surface treatment by the following method.

[Surface treatment process]

1. Degreasing step (S ₁₀₀ ): After ultrasonically degreasing a magnesium alloy plated specimen, which is a material to be plated, for 10 minutes, it is degreased by immersing it in a degreasing solution maintained at a temperature of 60 ° C. for 5 minutes.

2. Etching step (S ₂₀₀ ): The object to be plated is immersed in an etching solution maintained at a temperature of 25° C. for 1 minute to be etched.

3. Zingate step (S ₃₀₀ ): Zinc is substituted by immersing the object to be plated in a zincate solution maintained at a temperature of 70 ° C for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): The object to be plated is electrolytically plated with a copper cyanide plating solution at a temperature of 55° C. for 20 minutes at a current intensity of 2A.

5. Copper sulfate plating step (S ₅₀₀ ): The plated body is electrolytically plated with a copper sulfate plating solution at a temperature of 25° C. for 30 minutes at a current intensity of 2A.

6. Ternary alloy plating step (S ₆₀₀ ): The plated body is electrolytically plated at a current intensity of 2A for 20 minutes at a temperature of 25 ° C using a ternary alloy plating solution.

7. Palladium plating step ( _S700 ): The plated body is electroplated using a palladium plating solution at a temperature of 40° C. for 4 minutes at a current intensity of 0.5A.

8. Electrodeposition step (S ₈₀₀ ): The plating body is immersed in a white rhodium plating solution maintained at a temperature of 40 ° C for 2 minutes, and electrodeposition is performed while stirring at a current intensity of 1A.

[Corrosion resistance test]

The results of the corrosion resistance confirmation test of the magnesium alloy plated specimen surface-treated by the above surface treatment method are shown in FIG. 8 below.

In the case of specimens in which the plating time of the cyanide copper plating step (S ₄₀₀ ), the ternary alloy plating step (S ₆₀₀ ), the palladium plating step (S ₇₀₀ ) and the electrodeposition step (S ₈₀₀ ) were doubled, the above results were obtained from the 72-hour salt spray test. Among the corrosion resistance results of the examples, it was confirmed to be the best. It was confirmed that white rust was visible on the round surface, but it was small, and the separation of the plating layer was almost invisible.

Corrosion resistance and perspiration resistance test according to surface treatment of glasses frame made of magnesium alloy material

An experiment was conducted to confirm the corrosion resistance and sweat resistance of the spectacle frame composed of a magnesium alloy material surface-treated by the following method.

[Surface treatment process]

1. Degreasing step (S ₁₀₀ ): After ultrasonically degreasing the glasses frame composed of magnesium alloy material, which is a material to be plated, for 10 minutes, it is degreased by immersing it in a degreasing solution maintained at a temperature of 60 ° C. for 5 minutes.

2. Etching step (S ₂₀₀ ): The object to be plated is immersed in an etchant maintained at a temperature of 25° C. for 1 minute to be etched.

3. Zingate step (S ₃₀₀ ): Zinc is substituted by immersing the object to be plated in a zincate solution maintained at a temperature of 70 ° C for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): The object to be plated is electrolytically plated with a copper cyanide plating solution at a temperature of 55° C. for 20 minutes at a current intensity of 1A.

5. Copper sulfate plating step ( _S500 ): The plated body is electrolytically plated at a current intensity of 1A for 40 minutes at a temperature of 25°C using a copper sulfate plating solution.

6. Ternary alloy plating step (S ₆₀₀ ): The plated body is electrolytically plated with a ternary alloy plating solution at a temperature of 25° C. for 20 minutes at a current intensity of 1A.

7. Palladium plating step ( _S700 ): The plated body is electrolytically plated with a palladium plating solution at a temperature of 40°C for 4 minutes at a current intensity of 0.25A.

8. Electrodeposition step (S ₈₀₀ ): The plated body is immersed in a white rhodium plating solution maintained at a temperature of 40° C. for 2 minutes, and electrodeposition is performed while stirring at a current intensity of 0.5A.

[Corrosion resistance test]

The results of the corrosion resistance confirmation experiment of the spectacle frame composed of the magnesium alloy material surface-treated by the above surface treatment method are shown in FIG. 9, and as a result of the 72-hour salt spray test, it was confirmed that corrosion did not proceed.

[Experiment to confirm resistance to sweat]

The results of an experiment to confirm the sweat resistance of the eyeglass frame made of the magnesium alloy material surface-treated by the above surface treatment method are shown in FIG. 10, and it was confirmed that there was no abnormality as a result of the sweat resistance confirmation test.

In conclusion, through the above Examples 1 to 6, the surface treatment method of the spectacle frame composed of magnesium alloy material using rhodium according to an embodiment of the present invention is copper cyanide, zinc cyanide and sodium stannate in the ternary alloy plating step By using the ternary alloy plating solution containing this, it is possible to obtain a highly reliable metal surface with excellent physical properties such as corrosion resistance, wear resistance and adhesion, so there is an advantage in that no defects are formed, and in the electrodeposition step, white containing rhodium By electrodeposition using a rhodium plating solution, it was confirmed that not only can silver color be effectively expressed, but also excellent corrosion resistance can prevent corrosion even when exposed to salt water, so that the quality of the spectacle frame itself can be improved.

Above, the present invention has been described in detail with examples, but the present invention is not limited to the above embodiments, and can be modified in various forms, and conventional knowledge in the art within the technical spirit of the present invention It is clear that many variations are possible by those who have it. In addition, various forms of substitution, modification and change will be possible by those skilled in the art within the scope of the technical spirit of the present invention described in the claims, which also falls within the scope of the present invention. will do it

Claims (9)

As a surface treatment method of a spectacle frame made of magnesium alloy material,
A degreasing step of degreasing the spectacle frame made of a magnesium alloy material, which is a material to be plated, by immersing it in a degreasing solution maintained at a temperature of 50 to 60 ° C for 5 to 15 minutes;
an etching step of etching by immersing the plated body degreased in the degreasing step in an etchant maintained at a temperature of 18 to 25° C. for 1 to 2 minutes;
a zinc gate step of immersing the plated body etched in the etching step in a zinc gate solution maintained at a temperature of 65 to 70° C. for 4 to 6 minutes to replace zinc;
a copper cyanide plating step of electrolytically plating the plated body subjected to the zinc gate process at a current intensity of 1 to 2 A for 10 to 20 minutes at a temperature of 50 to 60° C. using a copper cyanide plating solution;
a copper sulfate plating step of electrolytically plating the plated body plated with copper cyanide in the copper sulfate plating step at a temperature of 18 to 25° C. for 30 to 40 minutes at a current intensity of 1 to 2 A using a copper sulfate plating solution;
In the copper sulfate plating step, the copper sulfate plated body is electrolyzed at a current intensity of 1 to 2A for 10 to 20 minutes at a temperature of 18 to 25 ° C using a ternary alloy plating solution containing copper cyanide, zinc cyanide and sodium stannate A ternary alloy plating step of plating;
A palladium plating step of electrolytically plating the plated body plated with the ternary alloy in the ternary alloy plating step using a palladium plating solution at a temperature of 35 to 45° C. for 2 to 4 minutes at a current intensity of 0.25 to 0.5 A; and
An electrodeposition step of depositing the palladium-plated plated body in the palladium plating step for 1 to 2 minutes in a white rhodium plating solution maintained at a temperature of 35 to 45 ° C. while stirring at a current intensity of 0.5 to 1A; In the surface treatment method of the spectacle frame composed of magnesium alloy material using rhodium, characterized in that,
The ternary alloy plating amount of the ternary alloy plating step,
40 to 50 g/L of sodium cyanide, 16 to 20 g/L of copper cyanide, and 1.6 to 1.8 g/L of zinc cyanide based on 1 liter (L) of the ternary alloy plating solution , Sodium stannate (Sodium Stannate) 80 to 90g / L and sodium hydroxide (Sodium hydroxide) 20 to 30g / L characterized in that it is included in the surface treatment method of the spectacle frame composed of magnesium alloy material using rhodium. The method of claim 1,
The degreasing liquid in the degreasing step,
It is an alkaline solution with a pH of 13 or higher,
Glasses frame made of magnesium alloy material using rhodium, characterized by containing 100 to 150 g/L of sodium hydroxide and 50 to 100 g/L of sodium carbonate based on 1 liter (L) of the total degreasing solution of the surface treatment method. The method of claim 1,
The etchant in the etching step,
Using rhodium, characterized in that 5 to 10 g/L of ethylenediamine tetra acetic acid (EDTA) and 30 to 50 g/L of sodium hydroxide are included based on 1 liter (L) of the total etchant. A surface treatment method for eyeglass frames made of magnesium alloy. The method of claim 1,
The Zingate solution in the Zingate step,
Surface treatment method of a spectacle frame composed of a magnesium alloy material using rhodium, characterized in that 30 to 80 g / L of zinc sulfate is included based on 1 liter (L) of the total Zingate solution. The method of claim 1,
The copper cyanide plating solution in the copper cyanide plating step,
70 to 90 g/L of sodium cyanide, 60 to 80 g/L of copper cyanide, and 20 to 40 g/L of potassium sodium tartrate based on 1 liter (L) of copper cyanide plating solution and 40 to 60 g/L of sodium carbonate. The method of claim 1,
The copper sulfate plating solution in the copper sulfate plating step,
Glasses frame made of magnesium alloy material using rhodium, characterized by containing 150 to 250 g/L of copper sulfate and 45 to 60 g/L of sulfuric acid based on 1 liter (L) of copper sulfate plating solution of the surface treatment method. delete The method of claim 1,
The palladium plating solution of the palladium plating step,
Glasses frame made of magnesium alloy material using rhodium, characterized in that it contains 3 to 8 g/L of palladium and 150 to 200 g/L of ammonium sulfate based on 1 liter (L) of palladium plating solution of the surface treatment method. The method of claim 1,
The white rhodium plating solution of the electrodeposition step,
Glasses frame made of magnesium alloy material using rhodium, characterized in that 1 to 2 g/L of rhodium and 10 to 15 g/L of sulfuric acid are included based on 1 liter (L) of the total white rhodium plating solution of the surface treatment method.

Images