KR20220129709A - 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 magnesium alloy material using rhodium and, more specifically, to a method for treating the surface of an eyeglass frame made of magnesium an alloy material using rhodium, which 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. In accordance with one embodiment of the present invention, in the ternary alloy plating step, a ternary alloy plating solution containing copper cyanide, zinc cyanide, and sodium stannate is used to acquire a highly reliable metal surface with excellent matter properties such as corrosion resistance, wear resistance and adhesion, thereby bringing about an advantage of preventing the formation of a defect, and also, in the electrodeposition step, electrodeposition is performed with a white rhodium plating solution containing rhodium, thereby effectively manifesting a silver color as well as preventing corrosion even when exposed to salt water due to excellent corrosion resistance, which can lead to an improvement in the quality of the eyeglass frame.

Description

Surface treatment method of eyeglass frame composed of magnesium alloy material using rhodium

The present invention relates to a method for surface treatment of a spectacle frame made of a magnesium alloy material using rhodium, and more particularly, to a degreasing step, an etching step, a jingate 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 method for surface treatment of a spectacle frame made of a magnesium alloy material using rhodium, characterized in that it comprises a step and an electrodeposition step, wherein the surface treatment method according to an embodiment of the present invention comprises copper cyanide and cyanide in the ternary alloy plating step. By using a ternary alloy plating solution containing zinc and sodium stannate, it has excellent physical properties such as corrosion resistance, abrasion resistance and adhesion, so that a highly reliable metal surface can be obtained, which has the advantage that defects are not formed, and rhodium in the electrodeposition step By electrodeposition using the included white rhodium plating solution, not only can the silver color be effectively expressed, but also it has excellent corrosion resistance, so it can prevent corrosion even when exposed to salt water. It relates to a method for surface treatment of a spectacle frame made of a magnesium alloy material.

Magnesium or a magnesium alloy has the smallest specific gravity and high specific strength among practical metals, and has advantages in castability, machinability, dimensional stability and durability. For this reason, magnesium-related products are being used as materials for automobile parts, communication parts, electronic parts, computers, portable electronic devices, as well as sporting goods. However, magnesium-related products are the most corrosive metal in the air, so surface treatment is essential to be used as a product.

Although methods such as chromate treatment or anodization treatment are used for surface treatment of magnesium-related products, chromate treatment has a problem in that it causes environmental problems due to chromium hexavalent ions in the solution. For this reason, it is required to develop a surface treatment method such as a new plating technology for magnesium-related products.

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

As mentioned above, although related research is being actively conducted on surface treatment methods such as plating technology to improve the corrosion resistance of magnesium-related products, it is optimized for glasses 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 has excellent physical properties such as corrosion resistance, abrasion resistance and adhesion, so that a highly reliable metal surface can be obtained. By electrodeposition using a white rhodium plating solution containing rhodium in the process, silver color can be effectively expressed, and corrosion resistance is excellent, preventing corrosion even when exposed to salt water, thereby improving the quality of the glasses frame itself. The development of technology related to the surface treatment method of the spectacle frame composed of a 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 devised to solve the problems as described above and provide the necessary technology,

The present invention relates to a spectacle frame made of a magnesium alloy material using rhodium, characterized in that it includes a degreasing step, an etching step, a jingate step, a cyan copper plating step, a copper sulfate plating step, a ternary alloy plating step, a palladium plating step and an electrodeposition step. An object of the present invention is 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 excellent physical properties such as corrosion resistance, abrasion resistance and adhesion to obtain a highly reliable metal surface. Another object of the present invention is to provide a method for surface treatment of a spectacle frame made of a magnesium alloy material using rhodium, which has the advantage that defects are not formed.

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

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

One embodiment of the present invention is a method for surface treatment of a spectacle frame made of a magnesium alloy material, by immersing the spectacle frame made of a magnesium alloy material, which is a material to be plated, in a degreasing solution maintained at a temperature of 50 to 60° C. for 5 to 15 minutes. a degreasing step of degreasing; an etching step of etching by immersing the degreased object to be plated in the degreasing step for 1 to 2 minutes in an etchant maintained at a temperature of 18 to 25°C; a jingate step of substituting zinc by immersing the plated body etched in the etching step in a jingate solution maintained at a temperature of 65 to 70° C. for 4 to 6 minutes; a cyan copper plating step of electrolytically plating the body to be plated, which has been treated with the jingate in the jingate step, using a copper cyanide plating solution at a temperature of 50 to 60° C. for 10 to 20 minutes at a current strength of 1 to 2A; a copper sulfate plating step of electrolytically plating the cyan copper plated body in the cyan copper plating step using a copper sulfate plating solution at a temperature of 18 to 25° C. for 30 to 40 minutes at a current strength of 1 to 2 A; a ternary alloy plating step of electrolytically plating the copper sulfate plated body 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 strength of 1 to 2A; a palladium plating step of electrolytically plating the ternary alloy plated body at a temperature of 35 to 45° C. for 2 to 4 minutes at a current strength of 0.25 to 0.5 A using a palladium plating solution in the ternary alloy plating step; and an electrodeposition step of immersing 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 strength of 0.5 to 1 A; It provides a method for surface treatment of a spectacle frame made of a magnesium alloy material using rhodium, characterized in that it becomes.

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

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

In the present invention, the jingate solution in the jingate step is characterized in that it contains 30 to 80 g/L of zinc sulfate based on 1 liter (L) of the total jingate 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 1 liter (L) of the total copper cyanide plating solution. It is characterized in that it contains 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 contains 150 to 250 g/L of copper sulfate and 45 to 60 g/L of sulfuric acid based on 1 liter (L) of the total copper sulfate plating solution. is a characteristic feature.

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 to 50 g/L of sodium cyanide based on 1 liter (L) of the total ternary alloy plating solution. to 20 g/L, zinc cyanide 1.6 to 1.8 g/L, sodium stannate 80 to 90 g/L, and sodium hydroxide 20 to 30 g/L.

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 1 liter (L) of the total palladium plating solution. characterized in that

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 in that

The method for surface treatment of a spectacle frame made of a magnesium alloy material using rhodium according to an embodiment of the present invention uses a ternary alloy plating solution containing copper cyanide, zinc cyanide, and sodium stannate in the ternary alloy plating step to achieve corrosion resistance and wear resistance. And since it is excellent in physical properties such as adhesion, a highly reliable metal surface can be obtained, there is an advantage in that defects are not formed.

In addition, in the method for surface treatment of a spectacle frame made of a 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. It has excellent corrosion resistance, so it can prevent corrosion even when exposed to salt water, so it has the advantage of improving the quality of the glasses frame itself.

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

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily carry out the present invention. The embodiments of the present invention are provided in order to more completely explain the present invention to those of ordinary skill in the art. Accordingly, the embodiments of the present invention may be modified in various other 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 part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Throughout the specification of the present invention, when a step is located “on” or “before” another step, this means not only a case in which a step is in a direct time-series relationship with another step, but also a step of mixing after each step and Likewise, the order of two stages 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", etc. to the extent used throughout the specification of the present invention are used in or close to the numerical value when manufacturing and material tolerances inherent in the stated meaning are presented, and the present invention It is used to prevent an unconscionable infringer from using the disclosure in which exact or absolute figures are mentioned to help understand. As used throughout this specification, the term “step of (to)” or “step of” does not mean “step for”.

The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present invention, terms such as “comprise” or “have” are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

The present invention relates to a method for surface treatment 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 jingate step (S ₃₀₀ ), a 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 method for surface treatment of a spectacle frame made of a magnesium alloy material using rhodium according to an embodiment of the present invention may be more clearly understood by the following description.

1 is a flowchart illustrating a method for surface treatment of a spectacle frame made 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 by immersing the spectacle frame made of a magnesium alloy material, which is a body to be plated, 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 oleaginous contaminants. In plating, including cleaning, degreasing means alkaline degreasing (cleaning), solvent degreasing (cleaning), and electrolytic degreasing (cleaning).

The degreasing step (S ₁₀₀ ) of the present invention is a process performed to remove contaminants from the metal surface generated according to the material, shape, manufacturing process, and manufacturing environment of the object to be plated, and may be referred to as a general plating preparation operation. Degreasing is an important process in the plating process, and insufficient degreasing may 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 made of a magnesium alloy material, which is a material to be plated, by supporting it in a degreasing solution maintained at a temperature of 50 to 60 ° C. This is because the degreasing time becomes longer and there is a fear that a non-degreasing phenomenon may occur, and if the degreasing is performed at a temperature exceeding 60° C., the life of the degreasing solution may be shortened.

In addition, in the degreasing step ( S ₁₀₀ ), it is preferable to degrease the glasses frame made of a magnesium alloy material, which is a material to be plated, in a degreasing solution for 5 to 15 minutes, which is partially degreased for less than 5 minutes. This is because there is a possibility that non-degreasing may occur, and in the case of degreasing for a time exceeding 15 minutes, unnecessary time is consumed more after the degreasing is completely performed, and there is a fear that productivity may be reduced.

According to an 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 sodium hydroxide (NaOH, Sodium hydroxide) 100 to 150 g based on 1 liter (L) of the total degreasing solution /L and sodium carbonate (Na ₂ CO ₃ , Sodium carbonate) 50 to 100 g/L is included.

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

An etching step ( _S200 ) of etching the degreasing-treated object to be plated in the degreasing step ( _S100 ) may be performed by immersing it in an etchant maintained at a temperature of 18 to 25°C for 1 to 2 minutes.

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

The etching step (S ₂₀₀ ) 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, thereby causing surface roughness and chemical change.

In the etching step (S ₂₀₀ ), it is preferable to etch the object to be plated by immersing it in an etching solution maintained at a temperature of 18 to 25° C. for 1 to 2 minutes, 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, there is a risk of poor plating adhesion on the surface of the object to be plated due to excessive etching.

According to an embodiment of the present invention, the etching solution of 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 1 liter (L) of the total etching solution) ) 5 to 10 g/L and sodium hydroxide (NaOH, Sodium hydroxide) 30 to 50 g/L.

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

In the etching step (S ₂₀₀ ), the zincate step ( _S300 ) of substituting zinc by immersing the plated body etched in the zincate solution maintained at a temperature of 65 to 70°C for 4 to 6 minutes can be performed. have.

Jingate is a plating method using a potential difference between different metals, belongs to electroless plating, and refers to a method of depositing zinc by substituting zinc by immersion in a zincate solution.

The jingate step ( _S300 ) of the present invention is performed as a pretreatment process for increasing the plating adhesion.

In the jingate step (S ₃₀₀ ), it is preferable to immerse the object to be plated in the jingate solution for 4 to 6 minutes, which may cause a problem that the coating layer is not properly coated when immersed for less than 4 minutes. This is because, in the case of being immersed for a time exceeding 6 minutes, unnecessary time is consumed more after the coating layer is completely coated, thereby reducing productivity.

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

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

A cyan copper plating step (S 300) of electrolytically plating the zincate-treated body to be plated in the jingate step (S ₃₀₀ ) using a copper cyanide plating solution at a temperature of 50 to 60° C. for 10 to 20 minutes at a current strength of 1 to 2 A. ₄₀₀ ) can be performed.

Cyan copper plating refers to a plating method that improves the plating adhesion or improves the coating power of the plating by covering the underlying surface with the plating metal up to the low current density portion at the initial stage of plating of the electroplating bath.

The cyan copper plating step (S ₄₀₀ ) of the present invention is a base plating step, and since copper sulfate plating has poor adhesion to zinc, direct plating may be difficult. This is a process performed to perform cyan copper plating first, and since it is precipitation from monovalent copper, the plating speed is fast.

Although not limited thereto, the cyan copper plating step (S ₄₀₀ ) uses a pure copper plate that is at least twice the area to be plated as the anode and covers the anode bag to prevent sludge from being generated at the anode, and then to the cyan copper plating solution. After deposition, it is preferable to perform plating by stirring with air while applying an electric current, and as copper ions are evenly distributed to the body to be plated, high current density is achieved and pit generation is prevented.

In the copper cyanide plating step (S ₄₀₀ ), it is preferable to electrolytically plated the body 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 brittle and poor adhesion, and when electrolytic plating is performed at a temperature exceeding 60° C., there is a risk that the plating surface becomes rough.

In addition, in the copper cyanide plating step (S ₄₀₀ ), it is preferable to electrolytically plated the body to be plated by applying a current for 10 to 20 minutes using a copper cyanide plating solution, which is electrolytic plating for less than 10 minutes. This is because the plating does not proceed sufficiently, and the plating becomes thin, and there is a fear that the plating body and copper sulfate react in the copper sulfate plating tank during the subsequent copper sulfate plating process, resulting in non-plating.

In addition, in the copper cyanide plating step ( _S400 ), it is preferable to electrolytically plated the body to be plated with a current strength of 1 to 2A using a copper cyanide plating solution, which is electrolytically plated with a current strength exceeding 2A. This is because there is a risk that the contact surface in contact with the jig may burn.

According to an 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 1 liter (L) of the total 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 It is characterized in that /L is included.

Although not limited thereto, the Cu plating layer formed in the cyan copper plating step (S ₄₀₀ ) is preferably formed to a thickness of 4 to 9 μm, which is too thin plating when the Cu plating layer is formed to a thickness of less than 4 μm. This is because there is a risk that the plating body and copper sulfate react in the copper sulfate plating tank during the subsequent copper sulfate plating process to cause a non-plating phenomenon. because there is a risk of becoming

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

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

Copper sulfate plating has the advantages of low pollution, low cost, and good smoothness. It is mainly used for base plating, color base, electric pole, and frit substrate plating. Direct plating is difficult due to poor adhesion on iron, zinc, lead and zinc die-casting. It has good smoothing action, so it is easy to get rid of buff flaws and obtain gloss, and it can be plated at high current with a simple composition and has excellent current efficiency.

The copper sulfate plating step (S ₅₀₀ ) of the present invention is a process performed to perform intermediate layer plating among the base plating of decorative plating.

Although not limited thereto, in the copper sulfate plating step (S ₅₀₀ ), a pure copper plate of at least twice the area of the plating body is used as the anode, and the anode bag is covered to prevent sludge from being generated at the anode, and then immersed in the copper sulfate plating solution. It is preferable to proceed with plating by stirring with air while applying an electric current. Stirring is carried out to obtain uniform gloss, and this is because there is a difference in gloss due to a difference in concentration between the upper and lower liquids when there is no stirring. Because it has advantages.

In the copper sulfate plating step (S ₅₀₀ ), it is preferable to electrolytically plated 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 risk that there is a risk of poor plating adhesion and a problem of lowering the concentration due to the formation of copper sulfate crystals. This is because there is a risk that the problem of increased consumption may occur.

In addition, in the copper sulfate plating step ( S ₅₀₀ ), it is preferable to electrolytically plated the plating body by applying an electric current for 30 to 40 minutes using a copper sulfate plating solution. This is because there is a possibility that a problem of deterioration of gloss or glossiness may occur because a proper plating layer is not formed.

According to an embodiment of the present invention, the copper sulfate plating solution _in the copper _sulfate plating step (S ₅₀₀ ) is 150 to 250 g/ L and sulfuric acid (H ₂ SO ₄ , Sulfuric acid) 45 to 60 g/L is included.

Although not limited thereto, the Cu plating layer formed by the copper sulfate plating step (S ₅₀₀ ) is preferably formed to a thickness of 15 to 20 μm, which is more than or less than the thickness range of the Cu plating layer of 15 to 20 μm. This is because there is a fear that the plating does not proceed properly in the future ternary alloy plating process due to poor gloss, poor corrosion resistance.

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

A _ternary alloy plating step ( S ₆₀₀ ) can be performed.

The ternary alloy plating uses a cyan-type alkaline solution and refers to an alloy plating method by precipitating 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 is suitable for plating ornaments, connectors and solder pins. It is a plating method that can respond to the Restriction of Use of Hazardous Substances Directive (RoHS) as it does not contain harmful substances. Excellent current efficiency and uniform color plating is possible.

In the ternary alloy plating step ( _S600 ) of the present invention, by using a ternary alloy plating solution containing copper cyanide, zinc cyanide, and sodium stannate, it has excellent physical properties such as corrosion resistance, abrasion resistance and adhesion, so that a highly reliable metal surface can be obtained. This is a process performed to prevent defects from being formed in the final product as there are There are advantages to doing.

Although not limited thereto, the ternary alloy plating step (S ₆₀₀ ) uses carbon for an electrode at least twice the area of the plating body as an anode. After being immersed in the ternary alloy plating solution, it is preferable to apply an electric current to perform cathode stirring (3 to 10 m/min). Agitation is performed to obtain a uniform gloss, and this is because, when there is no stirring, there is a difference in concentration between the upper and lower liquids, resulting in a difference in gloss, and this is because there is an effect of preventing the occurrence of mottled patterns of gloss.

In the ternary alloy plating step (S ₆₀₀ ), it is preferable to electrolytically plated the plating body by applying a current at a temperature of 18 to 25° C. using a ternary alloy plating solution, which is electrolytically plated at a temperature less than 18° C. This is because there is a concern that a problem in which gloss is not generated may occur, and when electrolytic plating is performed at a temperature exceeding 25° C., Cu in the plating layer is precipitated and there is a possibility that a problem of lowering gloss may occur.

In addition, in the ternary alloy plating step ( _S600 ), it is preferable to electrolytically plated the plating body with a current strength of 1 to 2A using a ternary alloy plating solution, which is precipitated when electrolytically plated with a current strength of less than 1A. This is because there is a fear that the coating film is reduced and there is a risk of plating without white gloss.

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

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. If it exceeds or falls short of the thickness range of 2 to 8 μm, this is because there is a possibility that a problem of poor corrosion resistance may occur without glossiness.

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

In the ternary alloy plating step ( _S600 ), a palladium plating step of electrolytic plating the ternary alloy-plated body using a palladium plating solution at a temperature of 35 to 45° C. for 2 to 4 minutes at a current strength of 0.25 to 0.5A. (S ₇₀₀ ) may be performed.

Although palladium is cheaper than rhodium, it has low hardness and inferior corrosion resistance and wear resistance compared to rhodium plating. In addition, the price of palladium is about 25% of that of gold and the specific gravity is about 33%, so the price is lower than that of gold even with the same plating thickness. There are drawbacks that cause Palladium plating is used as a base plating of rhodium or gold for decoration.

The palladium plating step (S ₇₀₀ ) of the present invention is a process performed to form a base plating layer of rhodium for decoration.

Although not limited thereto, in the palladium plating step (S ₇₀₀ ), a platinum/titanium network of at least twice the area of the plating body is used as an anode, and after being immersed in a palladium plating solution, the plating is carried out by stirring while applying an electric current. It is preferable to do

In the palladium plating step (S ₇₀₀ ), it is preferable that the plating body be electrolytically plated using a palladium plating solution at a temperature of 35 to 45° C. for 2 to 4 minutes at a current strength of 0.25 to 0.5 A, which has a temperature range of 35 If it exceeds or falls short of to 45 ℃, if the time range exceeds or falls short of 2 to 4 minutes, and if the current intensity range exceeds or falls short of 0.25 to 0.5A, there is a fear that plating adhesion failure may occur. .

According to an embodiment of the present invention, the palladium plating solution of the palladium plating step (S ₇₀₀ ) is palladium (Pd, Palladium) 3 to 8 g/L and ammonium sulfate ((( NH ₄ ) ₂ SO ₄ , Ammonium sulfate) 150 to 200 g/L are included.

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 1 liter (L) of the total palladium plating solution. ₂ SO ₄ , Ammonium sulfate) 150 to 200 g/L is included, and ammonia water having a pH of 8 to 9 (NH _{3 ·} H ₂ O, Ammonia water) is further included.

In addition, although not limited thereto, the Pd plating layer formed in the palladium plating step (S ₇₀₀ ) is preferably formed to a thickness of 0.2 to 1 μm, which is a Pd plating layer exceeding or less than the thickness range of 0.2 to 1 μm. This is because there is a fear that plating adhesion failure may occur.

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

Electrodeposition step of immersing the palladium-plated plating body in the palladium plating step (S ₇₀₀ ) 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 strength of 0.5 to 1 A (S ₈₀₀ ) may be performed.

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

The electrodeposition step (S ₈₀₀ ) of the present invention is a process performed to compensate for a defect in which organic matter in the air is deposited or the contact action is polymerized to generate a collimer by using the palladium plating process as plating of the electrical contact. It is a process performed to effectively express silver color by electrodeposition 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, in the electrodeposition step (S ₈₀₀ ), a platinum/titanium network of at least twice the area of the plating body is used as the anode, immersed in a white rhodium plating solution, and then the plating is carried out by stirring while applying an electric current. It is preferable to do

In the electrodeposition step (S ₈₀₀ ), the plating body is immersed in a white rhodium plating solution maintained at a temperature of 35 to 45° C. for 1 to 2 minutes, but it is preferable to electrodeposit it while stirring at a current strength of 0.5 to 1 A, which 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, there is a risk of poor plating adhesion Because.

According to an embodiment of the present invention, the white rhodium plating solution in the electrodeposition step (S ₈₀₀ ) contains 1 to 2 g/L of rhodium (Rh, Rhodium) and sulfuric acid (H) based on 1 liter (L) of the total white rhodium plating solution. ₂ SO ₄ , Sulfuric acid) 10 to 15 g/L is included.

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

As described above, the surface treatment method of a spectacle frame made of a 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 jingate step (S ₃₀₀ ), Copper cyanide 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 ) Bar characterized in that it comprises a bar, 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 plating specimen and a magnesium alloy material surface-treated by the surface treatment method of a spectacle frame made of a magnesium alloy material using rhodium of the present invention so that those of ordinary skill in the art to which the present invention pertains can easily implement it A spectacle frame composed of will be described in detail with reference to an embodiment. The method for surface treatment of a spectacle frame made of a magnesium alloy material using rhodium according to an embodiment of the present invention may be more clearly understood by the examples to be described later. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Plating Preparation

Specimen: Prepare a magnesium alloy plated specimen and a spectacle frame made of a 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 1 liter (L) of the total degreasing solution, but having a pH of 13 or higher.

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

Jingate step (S ₃₀₀ ): Prepare a jingate solution containing 55 g/L of zinc sulfate based on 1 liter (L) of the total jingate solution.

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

Copper sulfate plating step (S ₅₀₀ ): Prepare a copper sulfate plating solution containing 200 g/L of copper sulfate and 52 g/L of sulfuric acid and a pure copper plate for an anode based on 1 liter (L) of the total copper sulfate plating solution.

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 1 liter (L) of the total ternary alloy plating solution Prepare a ternary alloy plating solution containing 25 g/L and carbon for anode electrode.

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

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 total white rhodium plating solution. Prepare a white rhodium plating solution and an anode platinum/titanium network.

Coating thickness measurement experiment for each step of the surface treatment process

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

[Surface treatment process]

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

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

3. Jingate step (S ₃₀₀ ): Substitute zinc by immersing the body to be plated in a zincate solution maintained at a temperature of 70° C. for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): Electrolytic plating of the body to be plated at a temperature of 55° C. with a current strength of 2A for 10 minutes using a copper cyanide plating solution.

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

6. Ternary alloy plating step (S ₆₀₀ ): Electrolytic plating of the plating body using a ternary alloy plating solution at a temperature of 25° C. for 10 to 30 minutes at a current strength of 1 to 2A.

7. Palladium plating step (S ₇₀₀ ): Electrolytic plating of the plating body using a palladium plating solution at a temperature of 40° C. for 2 minutes at a current strength of 0.5 A.

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 electrodeposited while stirring at a current strength of 1 A.

[Plating thickness measurement experiment]

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

For the surface-treated magnesium alloy plating 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) for each process step and expressed as the average value. It is shown in Tables 1 to 9 below.

The Zn substitution layer formed in the jingate step (S ₃₀₀ ) is marked with “Zn”, and the Cu plating layer formed by the copper cyanide plating step (S ₄₀₀ ) or the copper sulfate plating step (S ₅₀₀ ) is marked as “Cu”, 3 The Cu-Sn-Zn ternary alloy plating layer formed by the primary alloy plating step (S ₆₀₀ ) is marked with “d3”, and the Pd plating layer formed by the palladium plating step (S ₇₀₀ ) is marked with “Pd”, and the electrodeposition step ( The white rhodium electrodeposited layer formed of S ₈₀₀ ) is marked with “Rh W”.

Jingate step (S ₃₀₀ ): 70℃, 5min number Zn(㎛) Cu (μm) number Zn(㎛) 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 -

Cyan copper plating step (S ₄₀₀ ): 55℃, 10min, 2A number Zn(㎛) Cu (μm) number Zn(㎛) 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(㎛) Cu (μm) number Zn(㎛) 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 in the jingate step (S ₃₀₀ ), the copper cyanide plating step (S ₄₀₀ ) and the copper sulfate plating step (S ₅₀₀ ). was found to be suitable.

Triple alloy plating step (S ₆₀₀ ): 25℃, 20min, 1A number Zn(㎛) Cu (μm) d3 (μm) number Zn(㎛) 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

Triple alloy plating step (S ₆₀₀ ): 25℃, 20min, 2A number Zn(㎛) Cu (μm) d3 (μm) number Zn(㎛) 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

Triple alloy plating step (S ₆₀₀ ): 25℃, 30min, 2A number Zn(㎛) Cu (μm) d3 (μm) number Zn(㎛) 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

Triple alloy plating step (S ₆₀₀ ): 25℃, 10min, 2A number Zn(㎛) Cu (μm) d3 (μm) number Zn(㎛) 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 ), and in the case of the Zn substitution layer and Cu plating layer among the ternary alloys, It is presumed that it is not observed properly in the thickness of the ternary alloy because it affects the thickness.

Palladium plating step (S ₇₀₀ ): 25℃, 2min, 0.5A number Zn(㎛) Cu (μm) d3 (μm) Pd (μm) number Zn(㎛) 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 in the palladium plating step (S ₇₀₀ ) after performing the ternary alloy plating step (S ₆₀₀ ) for 10 minutes, and the palladium plating step (S ₇₀₀ ) is 2 Minutes were found to be the most desirable.

Electrodeposition step (S ₈₀₀ ): 25℃, 2.5min, 1A number Zn(㎛) Cu (μm) d3 (μm) Pd (μm) Rh W(㎛) 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 results of measuring the thickness of the electrodeposition layer (white rhodium electrodeposition layer) formed in the electrodeposition step (S ₈₀₀ ). As the thickness of the electrodeposition layer was measured to be 3 μm, the current or time of the electrodeposition step (S ₈₀₀ ) is expected 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 plating specimen surface-treated by the following method and an experiment to confirm the plating adhesion and corrosion resistance were conducted. The photos taken for each process step of the surface-treated magnesium alloy plating specimen are shown in FIG. 3 below.

[Surface treatment process]

1. Degreasing step (S ₁₀₀ ): After ultrasonically degreasing the magnesium alloy plating specimen 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 etched by immersion in an etching solution maintained at a temperature of 25° C. for 1 minute.

3. Jingate step (S ₃₀₀ ): Substitute zinc by immersing the body to be plated in a zincate solution maintained at a temperature of 70° C. for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): Electrolytic plating of the body to be plated at a temperature of 55° C. with a current strength of 2A for 10 minutes using a copper cyanide plating solution.

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

6. Ternary alloy plating step ( _S600 ): Electrolytic plating of the plating body using a ternary alloy plating solution at a temperature of 25°C for 10 minutes at a current strength of 2A.

7. Palladium plating step (S ₇₀₀ ): Electrolytic plating of the plating body using a palladium plating solution at a temperature of 40° C. for 2 minutes at a current strength of 0.5 A.

8. Electrodeposition step (S ₈₀₀ ): The plating 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 strength of 1 A.

[Plating thickness measurement experiment]

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

For the surface-treated magnesium alloy plating specimen, the plating thicknesses of the front and back sides were measured 9 times each using an X-ray fluorescence analyzer (XRF, X-Ray Fluorescence Analyzer) for each process step and expressed as the average value. The results are shown in the table below. equal to 10

The Zn substitution layer formed in the jingate step (S ₃₀₀ ) is marked with “Zn”, and the Cu plating layer formed by the copper cyanide plating step (S ₄₀₀ ) or the copper sulfate plating step (S ₅₀₀ ) is marked as “Cu”, 3 The Cu-Sn-Zn ternary alloy plating layer formed by the primary alloy plating step (S ₆₀₀ ) is marked with “d3”, and the Pd plating layer formed by the palladium plating step (S ₇₀₀ ) is marked with “Pd”, and the electrodeposition step ( The white rhodium electrodeposited layer formed of S ₈₀₀ ) is marked with “Rh W”.

number Zn(㎛) Cu (μm) d3 (μm) Pd (μm) Rh W(㎛) 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 plating specimen surface-treated by the surface treatment method are shown in FIG. 4 below.

The Cu plating layer formed by the cyan copper 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. was measured, 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. Confirmed.

[Experiment to confirm plating adhesion]

The results of the test for confirming the plating adhesion of the magnesium alloy plating specimen surface-treated by the surface treatment method are shown in FIG. 5 below.

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

[Corrosion resistance confirmation test]

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

As a result of the salt spray test on the magnesium alloy plating specimen surface-treated by the surface treatment method according to an embodiment of the present invention, corrosion progressed within 24 hours, but this did not cause plating adhesion failure even in the plating adhesion confirmation test. It is presumed that this phenomenon occurred because of the thin thickness and the outer gap that occurred during cutting of the plate.

Cyan copper plating step (S ₄₀₀ ) and copper sulfate plating step (S ₅₀₀ ), corrosion resistance confirmation test according to time increase

An experiment was conducted to confirm the corrosion resistance of the magnesium alloy plating specimen surface-treated by the following method.

[Surface treatment process]

1. Degreasing step (S ₁₀₀ ): After ultrasonically degreasing the magnesium alloy plating specimen 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 etched by immersion in an etching solution maintained at a temperature of 25° C. for 1 minute.

3. Jingate step (S ₃₀₀ ): Substitute zinc by immersing the body to be plated in a zincate solution maintained at a temperature of 70° C. for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): Electrolytic plating of the body to be plated using a copper cyanide plating solution at a temperature of 55°C for 20 minutes at a current strength of 2A.

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

6. Ternary alloy plating step ( _S600 ): Electrolytic plating of the plating body using a ternary alloy plating solution at a temperature of 25°C for 10 minutes at a current strength of 2A.

7. Palladium plating step (S ₇₀₀ ): Electrolytic plating of the plating body using a palladium plating solution at a temperature of 40° C. for 2 minutes at a current strength of 0.5 A.

8. Electrodeposition step (S ₈₀₀ ): The plating 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 strength of 1 A.

[Corrosion resistance confirmation test]

The results of the corrosion resistance confirmation test of the magnesium alloy plating specimen surface-treated by the 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 specimen of the surface-treated magnesium alloy plating of Example 3, the 72 hour salt spray test result of Example 3 It was confirmed that the corrosion resistance was better than the result, and although white rust was seen on the round surface of the surface, 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 the electrodeposition step (S ₈₀₀ ), corrosion resistance confirmation test according to time increase

An experiment was conducted to confirm the corrosion resistance of the magnesium alloy plating specimen surface-treated by the following method.

[Surface treatment process]

1. Degreasing step (S ₁₀₀ ): After ultrasonically degreasing the magnesium alloy plating specimen 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 etched by immersion in an etching solution maintained at a temperature of 25° C. for 1 minute.

3. Jingate step (S ₃₀₀ ): Substitute zinc by immersing the body to be plated in a zincate solution maintained at a temperature of 70° C. for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): Electrolytic plating of the body to be plated using a copper cyanide plating solution at a temperature of 55°C for 20 minutes at a current strength of 2A.

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

6. Ternary alloy plating step ( _S600 ): Electrolytic plating of the plating body using a ternary alloy plating solution at a temperature of 25°C for 20 minutes at a current strength of 2A.

7. Palladium Plating Step (S ₇₀₀ ): Electrolytic plating of the plating body using a palladium plating solution at a temperature of 40° C. for 4 minutes at a current strength of 0.5 A.

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 electrodeposited while stirring at a current strength of 1 A.

[Corrosion resistance confirmation test]

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

In the case of a specimen 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 ) is doubled, the 72-hour salt spray test results It was confirmed that it was the best among the corrosion resistance results of the examples. It was confirmed that white rust was seen on the round surface of the surface, but in a small amount, and the separation of the plating layer was hardly visible.

Corrosion resistance and sweat resistance confirmation test according to the surface treatment of the glasses frame made of magnesium alloy material

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

[Surface treatment process]

1. Degreasing step (S ₁₀₀ ): After ultrasonically degreasing a spectacle frame made of a magnesium alloy material, which is a body 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 etched by immersion in an etching solution maintained at a temperature of 25° C. for 1 minute.

3. Jingate step (S ₃₀₀ ): Substitute zinc by immersing the body to be plated in a zincate solution maintained at a temperature of 70° C. for 5 minutes.

4. Copper cyanide plating step (S ₄₀₀ ): Electrolytic plating of the body to be plated at a temperature of 55° C. with a current strength of 1A for 20 minutes using a copper cyanide plating solution.

5. Copper sulfate plating step (S ₅₀₀ ): The plating body is electrolytically plated with a copper sulfate plating solution at a temperature of 25° C. for 40 minutes at a current strength of 1 A.

6. Ternary alloy plating step ( _S600 ): Electrolytic plating of the plating body using a ternary alloy plating solution at a temperature of 25°C for 20 minutes at a current strength of 1A.

7. Palladium plating step (S ₇₀₀ ): Electrolytic plating of the plating body using a palladium plating solution at a temperature of 40° C. for 4 minutes at a current strength of 0.25 A.

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 electrodeposited while stirring at a current strength of 0.5 A.

[Corrosion resistance confirmation test]

The results of the test for confirming the corrosion resistance of the glasses frame made of the magnesium alloy material surface-treated by the surface treatment method are shown in FIG.

[Experiment to confirm resistance to sweat]

The results of an experiment to confirm the resistance to sweat of the glasses frame made of the magnesium alloy material surface-treated by the surface treatment method are shown in FIG.

In conclusion, through Examples 1 to 6, the surface treatment method of a spectacle frame made of a 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 By electrodeposition using a rhodium plating solution, not only can the silver color be effectively expressed, but also corrosion resistance can be prevented even when exposed to salt water, thereby improving the quality of the spectacle frame itself.

Above, the present invention has been described in detail by way of examples, but the present invention is not limited to the above embodiments, and may be modified in various forms, and common 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, within the scope that does not depart from the technical spirit of the present invention described in the claims, various forms of substitution, modification and change will be possible by those of ordinary skill in the art, and this also falls within the scope of the present invention will do it

Claims (9)

A method for surface treatment of a spectacle frame made of a magnesium alloy material, comprising:
A degreasing step of degreasing by immersing the spectacle frame made of a magnesium alloy material, which is a material to be plated, 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 degreased object to be plated in the degreasing step for 1 to 2 minutes in an etchant maintained at a temperature of 18 to 25°C;
a jingate step of substituting zinc by immersing the plated body etched in the etching step in a jingate solution maintained at a temperature of 65 to 70° C. for 4 to 6 minutes;
a cyan copper plating step of electrolytically plating the body to be plated, which has been treated with the jingate in the jingate step, using a copper cyanide plating solution at a temperature of 50 to 60° C. for 10 to 20 minutes at a current strength of 1 to 2A;
a copper sulfate plating step of electrolytically plating the cyan copper plated body in the cyan copper plating step using a copper sulfate plating solution at a temperature of 18 to 25° C. for 30 to 40 minutes at a current strength of 1 to 2 A;
a ternary alloy plating step of electrolytically plating the copper sulfate plated body 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 strength of 1 to 2A;
a palladium plating step of electrolytically plating the ternary alloy plated body at a temperature of 35 to 45° C. for 2 to 4 minutes at a current strength of 0.25 to 0.5 A using a palladium plating solution in the ternary alloy plating step; and
In the palladium plating step, an electrodeposition step of immersing the palladium-plated plating body in a white rhodium plating solution maintained at a temperature of 35 to 45° C. for 1 to 2 minutes, while stirring at a current strength of 0.5 to 1 A; A method for surface treatment of an eyeglass frame made of a magnesium alloy material using rhodium, characterized in that. The method according to claim 1,
The degreasing solution of 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 in that 100 to 150 g/L of sodium hydroxide and 50 to 100 g/L of sodium carbonate are included based on 1 liter (L) of total degreasing solution of surface treatment method. The method according to claim 1,
The etching solution of the etching step,
Ethylene diamine tetra acetic acid (EDTA) 5 to 10 g/L and sodium hydroxide 30 to 50 g/L based on 1 liter (L) of the total etching solution. A method for surface treatment of eyeglass frames made of magnesium alloy material. The method according to claim 1,
The jingate solution of the jingate step is,
A method for surface treatment of a spectacle frame made of a magnesium alloy material using rhodium, characterized in that 30 to 80 g/L of zinc sulfate is contained based on 1 liter (L) of the total zincate solution. The method according to claim 1,
The copper cyanide plating solution in the cyan copper plating step is,
Based on 1 liter (L) of total copper cyanide plating solution, sodium cyanide 70 to 90 g/L, copper cyanide 60 to 80 g/L, potassium sodium tartrate 20 to 40 g/L And Sodium carbonate (Sodium carbonate) 40 to 60 g / L surface treatment method of a spectacle frame composed of a magnesium alloy material using rhodium, characterized in that it contains. The method according to claim 1,
The copper sulfate plating solution in the copper sulfate plating step is,
Glasses frame made of magnesium alloy material using rhodium, characterized in that it contains 150 to 250 g/L of copper sulfate and 45 to 60 g/L of sulfuric acid based on 1 liter (L) of total copper sulfate plating solution of surface treatment method. The method according to claim 1,
The ternary alloy plating amount of the ternary alloy plating step is,
Sodium cyanide 40 to 50 g/L, Copper cyanide 16 to 20 g/L, Zinc cyanide 1.6 to 1.8 g/L based on total 1 liter (L) of ternary alloy plating solution , Sodium Stannate (Sodium Stannate) 80 to 90 g / L and Sodium hydroxide (Sodium hydroxide) 20 to 30 g / L A method of surface treatment of a spectacle frame composed of a magnesium alloy material using rhodium, characterized in that it contains. The method according to claim 1,
The palladium plating solution of the palladium plating step is,
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 the total palladium plating solution of surface treatment method. The method according to claim 1,
The white rhodium plating solution in the electrodeposition step is,
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 surface treatment method.

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