KR20150081013A - Surface treating method for internal/external metal material, and internal/external metal material treated by the same - Google Patents

Abstract

The present invention relates to a method to process a surface of an internal/external metal material and a surface-processed internal/external metal material and, more specifically, relates to a method to process a surface of an internal/external metal material capable of forming a wall layer with valve metal on a surface of an internal/external metal material and forming a surface layer with an aluminum metal on the wall layer; and then performing anodic oxidation on the surface, and coloring and sealing the surface. According to the present invention, anodic oxidation, and coloring and sealing techniques are applied to a surface of various internal/external metal materials such as zinc, stainless steel, and magnesium; thereby making various, beautiful, and equal surface colors for the internal/external metal materials.

Description

TECHNICAL FIELD [0001] The present invention relates to a surface treatment method for a metal interior / exterior material, and a surface treated metal interior / exterior material. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

The present invention relates to a surface treatment method of a metal inner and outer material and a surface treated metal inner and outer material, and more particularly to a surface treatment method for forming a barrier layer made of a valve metal and a surface layer made of an aluminum- And an object of the present invention is to provide a surface treatment technology of a metal interior and exterior material which can achieve a beautiful but uniform surface color by applying anodizing treatment technique.

Anodizing is an electrochemical film forming method, in which an anodic oxidation film is formed on the surface of a metal such as aluminum by using a solution of sulfuric acid, anhydrous acid, chromic acid, or the like as an electrolytic solution to form a film having mechanical, electrical, Means a technique for forming an excellent coating film. The film formed by such anodizing treatment is extremely hard, has high corrosion resistance and can be dyed in various colors. Accordingly, it is used in various industrial fields. Especially, in the field of product related industries such as a mobile phone case, Technology.

However, in the case of aluminum materials, only an aluminum alloy sheet is machined and then subjected to anodic oxidation. In the case of pure aluminum, the strength is insufficient. On the other hand, aluminum alloy, So that a uniform anodic oxide film can not be formed.

On the other hand, the machining method can be applied only in the case of simple form considering the productivity, and it is difficult to apply it to the complicated form due to the economical efficiency according to the manufacturing cost. Accordingly, a method of vacuum-depositing aluminum on an aluminum die-casting product which is easy to mass-produce complicated shapes and anodizing the deposited aluminum has recently been developed, but there is a problem such as adhesion to a thin film of a vacuum evaporation method.

In order to solve this problem, the adhesion problem of the vacuum evaporation method is solved by a combination of a vacuum evaporation method and an arc method in Korean Patent Laid-Open Publication No. 10-2012-0116558 (High-speed Film Deposition Device and Film Deposition Method Using It, Oct. 23, 2012) And disclosed in Korean Patent Laid-Open Publication No. 10-2012-0116557 (a method of surface treatment of a die casting alloy and a die casting alloy material having a surface structure produced thereby, disclosed in Oct. 23, 2012) A method using nitride or oxynitride has also been proposed.

Also, in Korean Patent Laid-Open Publication No. 10-2013-0115475 (a surface treatment method of a metal inner and outer material, and a metal inner and outer material having a surface structure produced thereby, published on October 22, 2013), contact with a thin jig A method of reinforcing the thickness by a cold spray method is applied to a magnesium alloy material instead of an aluminum material. However, there is a problem that a separate process is required instead of a continuous process.

In the case of aluminum-based interior and exterior materials, if the thickness of aluminum deposition on the visible region is sufficient, the invisible hidden region will not be used uniformly in the subsequent coloring and sealing process, Although there is no great difficulty, in the case of metal interior and exterior materials such as magnesium alloy, stainless steel, and zinc alloy, if aluminum is thin, there is a problem that the part is blown out in the anodic oxidation process.

If the aluminum layer is too thin during the aluminum forming process, or if the aluminum layer is too thin due to the polishing process or the hairline forming process by electrolytic polishing, chemical polishing or mechanical polishing, The same problem occurred in the anodizing process.

Accordingly, there is a demand for a technique for stably anodizing the surface of metal interior and exterior materials other than aluminum materials, and for realizing various exterior colors on the surfaces of these metal interior and exterior materials.

Korean Patent Laid-Open Publication No. 10-2012-0116558 (High Speed Film Deposition Device and Film Deposition Method Using Same, Published on October 23, 2012) Korean Patent Laid-Open Publication No. 10-2012-0116557 (Diecasting alloy surface treatment method of die casting alloy and die casting alloy material having the surface structure thus produced, published on October 23, 2012) Korean Patent Laid-Open Publication No. 10-2013-0115475 (Method of surface treatment of metal inner and outer materials and metal inner and outer materials having surface structure produced thereon, published on October 22, 2013)

SUMMARY OF THE INVENTION The present invention has been developed to overcome the above-described problems, and an object of the present invention is to provide a method of manufacturing a semiconductor device, in which a barrier layer made of a valve metal and a surface layer made of an aluminum- To provide a surface treatment technique of a metal inner and outer material which realizes a beautiful but uniform surface color by applying the technique.

According to an embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: i) forming a barrier layer (10) on a surface of a metal inner and outer material (1) by a valve metal; Ii) forming a surface layer (20) of aluminum (Al) based metal on the barrier layer (10); Iii) anodizing the surface on which the surface layer 20 is formed; And iv) coloring and sealing the dye on the anodized surface. The present invention also provides a method for surface treatment of metal interior and exterior materials.

At this time, the valve metal may be formed of at least one selected from the group consisting of Ti, Nb, Ta, Zr, V, W, Hf, The valve metal may be an alloy of titanium (Ti), aluminum (Al) and vanadium (V), titanium (Ti), aluminum (Al) And niobium (Nb), and more preferably the valve metal may be Ti6Al4V or Ti6Al7Nb.

The surface layer 20 may be a single layer formed of one selected from the group consisting of aluminum, an aluminum alloy, an aluminum oxide, a nitride, and an oxynitride less than the stoichiometric composition ratio, or a composite layer formed by stacking two or more layers.

The method according to any one of the above claims, further comprising a step of sanding or hair line processing the product surface between step (ii) and step (iii), or at least one step selected from the group consisting of chemical polishing, electrolytic polishing and mechanical polishing The polishing step may further include a polishing step.

It is preferable that the thickness of the barrier layer 10 is 0.03 to 5 탆 and the thickness of the surface layer 20 is 5 to 100 탆 and that the barrier layer 10 and the surface layer 20 are PVD ) Method, and more preferably at least one selected from the group consisting of vacuum evaporation, sputtering, and cathodic vacuum arc method.

The method may further include a step of pre-treating the surface of the metal inner and outer casing 1 by ultrasonic cleaning or ion impact before the step i), and in the step iv) At least one or more coloring surfaces selected from the group consisting of a hydration barb, a metallic barb, an organic barb, and a low-temperature barb are subjected to a sealing treatment .

In order to achieve the above object, according to another embodiment of the present invention, a barrier layer 10 made of a valve metal is formed on the surface of a metal inner and outer material 1, and is made of an aluminum (Al) And a surface layer 20 whose surface is anodized is provided on the barrier layer 10.

At this time, it is preferable that the surface of the surface layer 20 subjected to the anodizing treatment is treated with a dye after dyeing.

The valve metal may be at least one selected from the group consisting of titanium, niobium, tantalum, zirconium, vanadium, tungsten, hafnium, aluminum, The valve metal may be an alloy of titanium (Ti), aluminum (Al) and vanadium (V), or may be an alloy of titanium (Ti), aluminum (Al ) And niobium (Nb), and more preferably the valve metal may be Ti6Al4V or Ti6Al7Nb.

It is preferable that the surface layer 20 is a single layer formed of one selected from the group consisting of aluminum, an aluminum alloy, an aluminum oxide, a nitride, and an oxynitride having a stoichiometric composition ratio, or a composite layer in which two or more layers are laminated.

It is preferable that the thickness of the barrier layer 10 is 0.03 to 5 탆 and the thickness of the surface layer 20 is 5 to 100 탆 and that the barrier layer 10 and the surface layer 20 are PVD More preferably at least one selected from the group consisting of vacuum evaporation, sputtering, and a cathodic vacuum arc method.

The surface treatment method and the surface treated metal inner and outer material of the present invention as described above can be applied to the surfaces of various commonly used metal interior and exterior materials such as zinc, stainless steel, and magnesium by applying anodic oxidation, It is possible to realize the surface color of the metal interior and exterior materials which are various and beautiful but uniform.

1 is a flow chart illustrating a surface treatment method of a metal inner and outer casing according to an embodiment of the present invention.
2 is a schematic view illustrating a laminated structure of a surface-treated metal inner and outer casing according to another embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. Prior to the description, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical concept of the present invention.

First, the present invention provides a method for surface treatment of metal interior and exterior materials comprising a barrier layer forming step, a surface layer forming step, an anodizing step and a dyeing / sealing step according to a preferred embodiment. A flow chart therefor is shown in Fig. Hereinafter, each of the time-series thermal steps will be described in detail.

First, the metal interior / exterior material 1 to be processed is prepared in the barrier layer forming step. Metal interior and exterior materials (1) means metals that can be used as internal and external materials of products. They include zinc, stainless steel, magnesium, aluminum alloys, die casting alloys (silicon, iron, copper, manganese ), Zinc (Zn), nickel (Ni), titanium (Ti), lead (Pb), tin (Sn) or chromium (Cr) The invention can be applied.

In particular, in the present invention, the metal inner and outer casing 1 may be a metal that does not include an aluminum component, and an anodizing process can be stably performed by the process according to the present invention even if the inner casing 1 does not contain aluminum.

In the step of forming the barrier layer, the barrier layer 10 is formed of valve metal on the surface of the metal inner and outer casing 1 described above. Valve metal is a metal that exhibits a valve effect. A valve effect is a phenomenon in which a current in a solution flows in a direction from a solution to a metal, whereas a flow in a solution does not flow in a direction from a metal to a solution .

Among the valve metals, titanium and niobium are used to produce various colors through the anodizing process in the decorative industry that deals with jewelry. More specifically, when these valve metals are anodized, an interference color such as blue, yellow, pink or green is developed according to an applied voltage, and an anodizing depth is controlled according to the magnitude of the applied voltage, Various colors are displayed.

In the present invention, the barrier layer 10 may be formed of a single metal such as titanium, niobium, tantalum, vanadium, zirconium, tungsten, hafnium, yttrium, or an alloy of two or more of these metals. Further, it is also possible to form the single metal or an alloy in which aluminum is added to each other, and it is more preferable to form the barrier layer 10 with Ti6Al4V or Ti6Al7Nb, which is a titanium aluminum alloy currently supplied in various compositions.

As used herein, the term "Ti6Al4V" or "Ti6Al7Nb" does not denote the stoichiometric ratio of the compound but refers to the weight ratio in the alloy. More specifically, the term " Ti6Al4N "means a titanium-aluminum-vanadium alloy containing 6 wt% of aluminum (Al) and 4 wt% of vanadium (V) based on the total weight, Refers to a titanium-aluminum-niobium alloy containing 6 wt% of aluminum (Al) and 7 wt% of niobium (Nb) based on weight.

When the barrier layer 10 is first formed on the surface of the metal inner and outer casing 1 with such valve metal, it is possible to prevent the surface of the inner and outer casing 1 from being blown out as described above when the anodizing process and the coloring / can do.

More specifically, when the aluminum-based material on the barrier layer 10 is anodically oxidized, the thicker portion remains unoxidized, while the thinner portion is entirely anodized and the barrier layer 10 is free And comes into contact with the dissolution solution. At this time, if the barrier layer 10 is formed of a valve metal, the barrier layer 10 is oxidized only at a maximum of 1 μm or less, and acts as a barrier layer. If the barrier layer 10 is not present, a phenomenon in which the surface is blown out with excessive current flow occurs at the portion.

In the case of the CVD (Chemical Vapor Deposition) method, the barrier layer 10 is not suitable because the process temperature is usually higher than 500 ° C., which may cause problems such as deformation of the material. Therefore, It is desirable to adopt a "Deposition" method. More specifically, the barrier layer 10 may be formed on the surface by employing at least one method selected from the group consisting of vacuum evaporation, sputtering, and cathodic vacuum arc. However, It is most preferable to use a sputtering method or an anode vacuum arc method in consideration of the adhesion of the formed product.

An ultrasonic cleaning process may be performed to remove oil components or foreign substances remaining on the surface of the metal inner and outer casing 1 as a workpiece before the formation of the barrier layer 10 or an argon gas ion collision or a metal ion It is preferable to carry out a process of removing surface impurities or oxides by a method of collision.

The thickness of the barrier layer 10 may vary depending on the process conditions at the time of the anodic oxidation and the thickness of the surface layer 20 to be described later. However, when the thickness of the surface layer 20 is sufficiently thick, the thickness may be 0.03 μm or more. However, it is very time-consuming and expensive to form all the parts of the metal interior and exterior material 1 uniformly and thickly by PVD coating, and the process is not easy. Therefore, a certain portion may be formed thinner than other portions, or a portion which is in contact with a jig or the like, a rear portion, or a hidden portion may be formed thinly.

Since the barrier layer 10 and the surface layer 20 are formed to be thinner than the thickest portion, the anodic oxidation is carried out not only to the outermost surface layer 20 but also to the barrier layer 10 in the anodic oxidation step. If there is no barrier layer 10 made of a valve metal in the lower part of the surface layer 20 made of an aluminum-based metal, the metal inner and outer material 1 reacts directly with the anodizing solution at this part, ), The barrier layer 10 is anodically oxidized and acts as a barrier of a certain thickness. In other words, when the known titanium or niobium is developed, the surface is developed depending on the applied voltage. On the other hand, the oxidized pore depth of this part is insufficient and it can not show a uniform coloring effect, but such a part does not detract from the value of the product because it is a part without appearance problems.

The thickness of the barrier layer 10 may be 0.03 占 퐉 or more, preferably 0.1 占 퐉 or more, more preferably 0.3 占 퐉 or less, and more preferably 0.3 占 퐉 or less, because the anodic oxidation depth of titanium is about 30 to 300 nm, , The surface of the metal inner and outer casing 1 can be sufficiently protected.

On the other hand, tantalum is oxidized to about 1.6 nm per 1V, 100V is oxidized to 160 nm by anodic oxidation, and niobium is oxidized to 300 to 400 nm to anodically oxidize the surface layer 20 according to the conditions for anodizing the surface layer 20 The minimum thickness should be changed appropriately.

The upper limit value of the thickness of the barrier layer 10 is not particularly limited, but it is preferably 5 占 퐉 or less in consideration of the formation speed of the barrier layer 10 and the economical efficiency depending on the price.

Next, the step of forming the surface layer 20 in the step ii) is a step of forming the surface layer 20 of the aluminum-based metal on the barrier layer 10 formed on the surface of the metal inner and outer material 1 as described above. As for the formation method, it is most preferable to use a sputtering method or an anode vacuum arc method in the same manner as the barrier layer 10 described above. In the case of the CVD method, since the processing temperature is usually 500 ° C or higher, It is not appropriate.

The surface layer 20 may be formed of various materials including an aluminum component such as pure aluminum or an aluminum alloy, and may be formed of an aluminum oxide, a nitride, or an oxynitride layer preferably having a stoichiometric composition ratio. The aluminum compound layer having a stoichiometric composition ratio less than that of pure aluminum or aluminum alloy is superior in hardness and has excellent adhesion and strong bonding force so that the barrier layer 10 on the metal inner and outer casing 1, This is because strong adhesion and adhesion can be imparted between the formed anodized film layers.

Next, the anodizing step iii) is a step of oxidizing a part of the surface layer 20 described above by an anodizing treatment into an anodic oxide coating layer, and may be in the range of 5 to 100 탆, depending on the thickness of the required anodized coating layer The surface layer 20 must be formed.

The surface layer 20 having an appropriate thickness range may be formed in various thicknesses in order to obtain the required thickness of the coating layer according to the product demand. However, if the thickness of the surface layer 20 is less than 5 탆, If the surface layer 20 is formed to have a thickness of more than 100 탆, the process time will become excessively long and the productivity will be deteriorated. In addition, since the process temperature is high The object to be processed is deformed or becomes thick, resulting in problems in assembly with other assemblies.

The anodizing treatment, that is, the anodizing treatment, is a process of forming a film of aluminum oxide (Al ₂ O ₃ ) or the like by polarizing a metal product such as aluminum as an anode under a suitable electrolytic solution under appropriate conditions. This coating is very resistant to corrosion and has a porous layer and can be dyed with various colors. Therefore, it is possible to increase the commercial value by imparting a beautiful, heavy color to the surface as well as practicality such as corrosion resistance and abrasion resistance to be.

Here, the anodic oxidation can be performed using any one of ordinary sulfuric acid, hydrochloric acid, chromic acid, and mixed acid thereof. Since the thickness of the film is controlled according to the required hue, the surface layer 20 is preferably preliminarily To 100 mu m.

The method may further include sanding the surface or treating the hair line before the step iii) anodizing the surface to improve the properties of the desired product or the hall. Sanding is a work for polishing a surface of a lower surface with a prescribed sand paper in order to achieve a required surface treatment purpose, and for removing surface defects and improving smoothness and adhesion. A hair line is a work that is used for the purpose of improving the quality of a product by giving a hair-like line to the surface.

If the final product is matt, it may be anodically oxidized. However, when a glossy product is manufactured, if the thickness of the thin film is increased, the gloss of the thin film is decreased. Therefore, It is preferable to further perform the polishing step prior to the step, more particularly, the chemical polishing, the electrolytic polishing or the mechanical polishing. Chemical polishing refers to a process of chemically smoothing the surface of a metal by performing polish polishing without using an external current. Typically, the main raw material for chemical polishing is phosphoric acid, which forms a phosphate film. Electrolytic polishing refers to a polishing method that overcomes the limit of surface gloss formation caused by chemical polishing and electrolyzes under a predetermined condition to make a smooth surface when a higher gloss is required.

Next, in the step of dyeing and sealing the dye, which is the step iv), when a porous coating layer is formed through anodic oxidation, the dye is colored on the anodized surface through a dyeing method such as organic coloring, inorganic coloring or electrolytic coloring And finally performing a sealing process for closing the pores of the anodized film by a method such as hydration, metallic, organic, or low-temperature sealing. It is possible to improve the product value by adding esthetics to the surface of the product through dyeing process, and it is possible to improve the weatherability, durability and corrosion resistance of the coating through the sealing process.

Hereinafter, embodiments of the surface treatment method and the surface treated metal interior / exterior material of the present invention will be described. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents. shall.

The surface of the metal inner and outer material 1 such as magnesium alloy is polished by buffing, and then the surface of the workpiece is cleaned with an organic solvent and an ultrasonic cleaning device. After the material is mounted on the vacuum furnace, argon gas ion collision or metal ion collision is performed.

A negative DC voltage and a pulsed DC voltage of several to several hundreds of volts are applied to the material, and then the surface is cleaned by applying argon gas while maintaining a cathodic arc discharge to remove surface impurities and oxide film of the material, Thereby enhancing adhesion with the layer to be formed.

The barrier layer 10 is formed by sputtering using a Ti6Al4V alloy so as to have a minimum thickness of 1 mu m. Thereafter, the surface layer 20 was formed to have a thickness of 30 탆 in the form of an aluminum thin film. After that, anodic oxidation was carried out by the sulfuric acid method, followed by coloring and sealing treatment.

The material to be treated (1) of the surface treated by the above-mentioned method had good anodic oxidation states on the top and bottom, left and right, and front surface. The part with the step on the rear part seemed to be somewhat dark due to the thickness variation of the aluminum film, but this was not visible after assembling, so there was no problem in use. Various colors such as black, red, gold, green, blue, and pink are embodied beautifully.

As a comparative example of the above-described embodiment, the same operation was performed without forming the barrier layer 10, and as a result, a phenomenon that a thin portion of the thin film melted and fused in the anodizing process was found.

The present invention is not limited to the above-described specific embodiment and description, and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention as claimed in the claims. And such modifications are within the scope of protection of the present invention.

1: Metal interior and exterior material
10: barrier layer
20: Surface layer

Claims (23)

I) forming a barrier layer (10) on the surface of the metal inner and outer casing (1) with a valve metal;
Ii) forming a surface layer (20) of aluminum (Al) based metal on the barrier layer (10);
Iii) anodizing the surface on which the surface layer 20 is formed; And
Iv) coloring and sealing the dye on the anodized surface;
And a surface treatment method of the metal inner and outer material. The method according to claim 1,
The valve metal is made of titanium (Ti), niobium (Nb), tantalum (Ta), zirconium (Zr), vanadium (V), tungsten (W), hafnium (Hf) Wherein the one or more metals are selected from the group consisting of a single metal or a combination of two or more metals. 3. The method of claim 2,
Wherein the valve metal is an alloy of titanium (Ti), aluminum (Al) and vanadium (V), or an alloy of titanium (Ti), aluminum (Al) and niobium (Nb). The method of claim 3,
Wherein the valve metal is Ti6Al4V or Ti6Al7Nb. The method according to claim 1,
The surface layer (20)
Wherein the metal layer is a single layer formed of one selected from the group consisting of aluminum, aluminum alloy, aluminum oxide, nitride, and oxynitride less than the stoichiometric composition ratio, or a composite layer in which two or more layers are stacked. The method according to claim 1,
Further comprising the step of sanding or hair line processing the surface of the product between the step ii) and the step iii). The method according to claim 1,
Further comprising a polishing step between the step (ii) and the step (iii), wherein at least one selected from the group consisting of chemical polishing, electrolytic polishing and mechanical polishing is carried out. The method according to claim 1,
Wherein the barrier layer (10) has a thickness of 0.03 to 5 占 퐉. The method according to claim 1,
Wherein the surface layer (20) has a thickness of 5 to 100 占 퐉. The method according to claim 1,
Wherein the barrier layer (10) and the surface layer (20) are formed by PVD (Physical Vapor Deposition) method. 11. The method of claim 10,
Wherein the PVD method is at least one selected from the group consisting of vacuum evaporation, sputtering, and cathodic vacuum arc method. The method according to claim 1,
Further comprising the step of pretreating the surface of the metal inner and outerwear material (1) through ultrasonic cleaning or ion impact before the step i). The method according to claim 1,
In the step iv)
Coloring the dye on the anodized surface in at least one manner selected from the group consisting of organic matter coloring, inorganic coloring and electrolytic coloring,
Wherein at least one colored surface selected from the group consisting of a hydration pier, a metallic pier, an organic pier, and a low temperature pier is subjected to a piercing treatment. A barrier layer 10 made of a valve metal is formed on the surface of the metal inner and outer casing 1,
A surface and a surface layer (20) made of an aluminum (Al) -based metal and whose surface is anodized is formed on the barrier layer (10). 15. The method of claim 14,
Characterized in that the surface of the surface layer (20) subjected to the anodizing treatment is subjected to a sealing treatment after dyeing. 15. The method of claim 14,
The valve metal is made of titanium (Ti), niobium (Nb), tantalum (Ta), zirconium (Zr), vanadium (V), tungsten (W), hafnium (Hf) Wherein the metal is one single metal or two or more alloys selected from the group consisting of the metals. 17. The method of claim 16,
Wherein the valve metal is an alloy of titanium (Ti), aluminum (Al) and vanadium (V) or an alloy of titanium (Ti), aluminum (Al) and niobium (Nb). 18. The method of claim 17,
Wherein the valve metal is Ti6Al4V or Ti6Al7Nb. 15. The method of claim 14,
The surface layer (20)
A single layer formed of one selected from the group consisting of aluminum, aluminum alloy, aluminum oxide, nitride, and oxynitride of less than the stoichiometric composition ratio, or a composite layer formed by stacking two or more layers. 15. The method of claim 14,
Wherein the barrier layer (10) has a thickness of 0.03 to 5 占 퐉. 15. The method of claim 14,
Wherein the surface layer (20) has a thickness of 5 to 100 占 퐉. 15. The method of claim 14,
Wherein the barrier layer (10) and the surface layer (20) are formed by PVD (Physical Vapor Deposition) method. 23. The method of claim 22,
Wherein the PVD method is at least one selected from the group consisting of vacuum evaporation, sputtering, and cathodic vacuum arc method.

Images