KR101117800B1 - Surface treatment process for magnesium parts and magnesium parts treated by using the same - Google Patents

Abstract

The present invention relates to a surface treatment method of a magnesium alloy member and a magnesium alloy member surface-treated using the same. The present invention is a sol-gel after the passivation process by dry depositing a film such as magnesium oxide film, magnesium fluoride film, magnesium oxide-magnesium fluoride on the surface of the natural oxide film and the magnesium alloy member from which all of these substances are removed by the surface treatment process By coating, the salt water resistance and scratch resistance of a magnesium alloy member can be improved and the metal texture inherent to a magnesium alloy can be expressed.

Magnesium Alloy Member, Surface Treated, Dry, Corrosion Resistant, Sol-gel Coating, Surface Hardness

Description

Surface treatment process for magnesium parts and magnesium parts treated by using the same}

The present invention relates to a method for surface treatment of a magnesium alloy member and a magnesium alloy member having a surface treated using the same. More specifically, the present invention relates to a surface treatment method having a metal texture of magnesium, excellent in salt water resistance and scratch resistance, and a magnesium alloy member having a surface treated using the same.

Magnesium is the 8th most abundant substance on earth, low in specific gravity and harmless to human body. Therefore, magnesium has the potential to be used as an interior and exterior material of various products. Magnesium is a relatively high-strength metal and is attracting attention as a new material that can replace existing materials and make up for the shortcomings of plastics according to the trend of light weight and energy saving. Magnesium alloys are used in automobiles, aerospace, electronic devices, and portable information devices, and are increasingly being used.

However, since the magnesium alloy member including magnesium has a disadvantage of relatively weak corrosion resistance, when applied to an exterior case expressing the intrinsic metal texture of magnesium, the appearance reliability of the product is not long. In order to manufacture the case-type products expressing the texture, the supplementation is essential.

Typical surface treatment methods for the magnesium alloy member include anodizing treatment, chemical conversion treatment, spark electrolytic oxidation treatment, zinc substitution method, electroless nickel plating method, and the like. However, most of these surface treatment methods are limited in their use because they contain waste materials from wet processes and contain substances regulated by the Restriction of Hazardous Substances Directive (RoHS). In addition, according to the method, there is a feature that the salt water resistance is implemented by a thick coating, there is a disadvantage that can not express the metal texture inherent in magnesium.

Therefore, the thin film passivation process by deposition and the sol-gel coating having saline and scratch resistance do not degrade the intrinsic metal surface texture of magnesium, and improve the saline and scratch resistance of the magnesium alloy member to exteriorize the magnesium alloy member. Research into new surface treatment methods that can be easily applied to the industrial field is currently active. However, a method having excellent desired physical properties has not been developed yet.

An object of the present invention is to suppress the rapid oxidation of the surface due to the weak acid resistance of magnesium when the sol-gel coating having a salt water resistance and scratch resistance on the surface of the magnesium alloy member, so that the sol-gel coating can proceed effectively It is to provide a method for surface treatment of a magnesium alloy member capable of expressing a surface texture unique to magnesium.

Another object of the present invention is to provide a magnesium alloy member having excellent brine resistance and scratch resistance having a surface treated by the surface treatment method.

In order to achieve the above object, the present invention

(a) dry depositing a metal-containing thin film on the surface of the magnesium alloy member,

(b) sol-gel coating the surface of the magnesium alloy member including the dry deposited metal-containing thin film, and

(c) drying and surface curing the magnesium alloy member

It provides a surface treatment method of a magnesium alloy member comprising a.

The metal-containing thin film deposited on the surface of the magnesium alloy member is a thin film formed using a magnesium oxide film, a magnesium fluoride film, a silicon fluoride film, hexamethyldisiloxane as a precursor, silicon dioxide, titanium dioxide, cerium oxide, and alumina. It may include a metal-containing film selected from the group or one or more composite films thereof.

The dry deposition may use electron beam vacuum deposition, sputtering deposition or chemical vapor deposition.

At this time, after the dry deposition step, further comprising the step of depositing a magnesium fluoride film on the magnesium oxide film may form a composite film of magnesium oxide film-magnesium fluoride film. The method may further include depositing a magnesium oxide film on the magnesium fluoride film after the dry deposition, thereby forming a composite film of a magnesium fluoride film and a magnesium oxide film. In the depositing step, an electron beam deposition method, a sputtering deposition method, or a chemical vapor deposition method (CVD, chemical vapor deposition) may be used. The sum of the thicknesses of the composite films is preferably 10 nm to 150 nm.

The present invention also provides a magnesium alloy member surface-treated in accordance with the above method.

Hereinafter, the present invention will be described in detail.

The present invention relates to a surface treatment method of magnesium, which is manufactured in a plate shape by rolling and exhibits a metallic texture unique to magnesium through mechanical surface processing such as polishing or buffing among magnesium alloy members processed into parts by molding. . In addition, the present invention relates to a magnesium alloy member that is surface-treated to have excellent salt water resistance and scratch resistance and exhibit magnesium intrinsic metal texture using the surface treatment method.

The surface treatment method of the present invention dry deposits a magnesium oxide film, a magnesium fluoride film or one or more composite films thereof on the surface of a magnesium alloy member from which both the natural oxide film and the surface contaminants are removed by an appropriate surface processing process such as surface polishing. It includes a step. After passing through the passivation process by the dry deposition, the step of performing a sol-gel coating process using an acid catalyst process. In the case of a magnesium alloy member which has been passivated by dry deposition, the suitability for Sol-gel process using an acid catalyst is excellent.

In other words, if the surface treatment using only the deposition method as in the conventional, the thickness is thick or there is a limit to the expression of the metal texture inherent in magnesium, and the saline and scratch resistance properties may also be reduced. In addition, the surface treatment through the existing sol-gel process may weaken the strength due to external impacts, and especially tends to be vulnerable to filiform corrosion, and the surface is rapidly oxidized during surface coating due to the weak acid resistance of magnesium. Can be.

Therefore, this invention deposits a specific metal containing film on the surface of a magnesium alloy member, and forms the thickness of a surface suitably. Through this process, a thin film is formed on the surface of the magnesium alloy to induce a passivation process that causes the magnesium to lose its reactivity with the acid solution. Thereafter, the present invention is characterized in that the surface of the metal film which has lost the reactivity is subjected to sol-gel coating having saline water resistance and scratch resistance, thereby preventing the surface from being rapidly oxidized due to the weak acid resistance of magnesium. Therefore, according to the present invention, it is possible to smoothly proceed with the magnesium alloy surface treatment according to the effective sol-gel coating progress, to express the surface texture inherent in magnesium and to obtain a magnesium alloy member having excellent physical properties.

In this case, the composite film may include a composite film of magnesium oxide film-magnesium fluoride film or a magnesium fluoride film-magnesium oxide composite film. In addition, the magnesium alloy member used in the composite film dry deposition may omit the plasma surface treatment in vacuum. In addition, the alloy ratio of the alloy member used before surface treatment in this invention is not specifically limited, A normal thing can be used.

Next, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In order to clearly describe the present invention, parts irrelevant to the description are omitted in the drawings, and like reference numerals designate like parts throughout the specification.

1 is a schematic view showing an example of an electron beam vacuum deposition apparatus used to perform the surface treatment method of a magnesium alloy member according to the present invention.

Referring to FIG. 1, the electron beam vacuum deposition apparatus includes a vacuum vessel 10, a holder 20 embedded in the vacuum vessel 10 to fix a magnesium alloy member, a gas inlet 30 through which gas is introduced, a gas after a process It is composed of the gas outlet 40, the evaporation source 50 for evaporating the target material, the vacuum pump 60 for vacuuming the vacuum vessel 10, and other elements necessary for vacuum deposition.

Therefore, according to the method for treating a surface of a magnesium alloy member of the present invention, a magnesium alloy member on which a natural oxide film is formed is prepared, the magnesium alloy member is mounted on the vacuum deposition apparatus of FIG. Thereafter, the surface of the magnesium alloy member is cleaned under vacuum conditions, a dry deposited metal-containing thin film is formed on the surface of the magnesium alloy member, and a sol-gel solution is applied to the surface of the magnesium alloy member including the dry deposited metal-containing thin film. Coating and drying and surface curing the magnesium alloy member.

In particular, the present invention forms a passivation film having excellent salt water resistance on the magnesium alloy surface by a vacuum deposition process to improve salt water resistance and prevent magnesium surface oxidation from occurring during the sol-gel coating process utilizing an acid catalyst. The beautiful metal texture can be realized as it is. In addition, the present invention induces hardening on the surface of the magnesium alloy member through the sol-gel coating, so that the coating film is hard and the appearance is beautiful, but a clean surface can be obtained.

2 is a flowchart illustrating a surface treatment method of the magnesium alloy member according to the first embodiment of the present invention.

Referring to FIG. 2, the surface treatment method of the magnesium alloy member according to the first embodiment of the present invention will be described.

As shown in Fig. 2, the method of the present invention arranges a magnesium alloy member in a vacuum container (S110), cleans the surface of the magnesium alloy member under vacuum conditions (S120), and magnesium oxide on the surface of the magnesium alloy member. Dry deposition of the film (S130), and a sol-gel coating on the surface of the magnesium alloy member including the dry-deposited magnesium oxide film, and drying and surface curing the magnesium alloy member (S150). This will be described in more detail below.

First, the present invention prepares a magnesium alloy member having a natural oxide film is disposed in a vacuum container (S210). The degree of vacuum of the vacuum vessel can maintain general conditions, and the conditions are not particularly limited. For example, the degree of vacuum is preferably maintained at a pressure of 10 ^-9 Torr to 10 ^-1 Torr.

At this time, since the magnesium alloy member reacts with oxygen in the air, a natural oxide film is inevitably formed on the surface thereof. The natural oxide film may include any one or more selected from the group consisting of magnesium oxide and magnesium hydroxide. The magnesium hydroxide may be produced by the reaction of magnesium oxide with water in the atmosphere or water used in the buffing process.

Subsequently, the surface of the magnesium alloy member is cleaned using a plasma under vacuum conditions (S220). However, in the present invention, the surface treatment of the magnesium alloy member can be omitted, if necessary, can be selectively carried out, it is not necessary to necessarily perform the magnesium alloy member obtained in a general process may be used as it is. Through the surface cleaning process, the natural oxide film on the surface of the magnesium alloy member may be removed, and other foreign matters may also be removed. Although the conditions are not specifically limited, The washing time is about 30 minutes specifically, preferable. Argon plasma may be used as the plasma, but is not limited thereto, and oxygen plasma may be used as necessary.

In addition, the present invention dry deposition of a magnesium oxide (MgO) film on the treated magnesium alloy surface (S130). Specifically, a target containing magnesium oxide is placed in the evaporation source 50. A gaseous magnesium oxide is formed by applying an electron beam to this target. The magnesium oxide in the gaseous state diffuses into the magnesium alloy member mounted on the holder 20 to form a magnesium oxide film on the surface of the magnesium alloy member. In this step, an electron beam deposition method or a sputtering deposition method may be used as the dry deposition method. In addition, when silicon dioxide is applied, in addition to the electron beam deposition method or the sputtering deposition method, it is also possible to use a chemical vapor deposition (CVD) method.

The thin film deposition process forms an acid-resistant passivation film on the magnesium alloy surface.

The magnesium oxide film may be formed to a thickness of 10nm to 150nm. If the thickness is thinner than 10 nm, there is a problem that the corrosion resistance is insufficient, and if the thickness is thicker than 150 nm, interference color is expressed, and thus the texture of magnesium inherent is not sufficiently expressed.

When the process is completed, the sol-gel coating is performed using a sol-gel solution on the surface of the magnesium alloy member (S140). That is, this invention processes the surface of a magnesium alloy member by a sol-gel method. The present invention forms an acid passivation film on the surface of the magnesium alloy by a thin film deposition process, and then performs a sol-gel coating using an acid catalyst to maintain a magnesium-specific metal texture.

The sol-gel method refers to making an inorganic network by hydrolysis and polycondensation of a precursor. The network structure obtained in the sol-gel reaction of the sol-gel method can be adjusted according to the polymerization reaction rate due to hydrolysis of the precursor and condensation of alcohol. Therefore, various types of network structures can be obtained by adjusting pH, temperature, and the nature and concentration of the catalyst and the concentration of the precursor during the sol-gel reaction, and the present invention does not specifically limit the conditions.

The sol-gel solution used to use the sol-gel method in the present invention may include an aqueous solution of silica sol undergoing hydrolysis and condensation polymerization.

Accordingly, the sol-gel solution of the present invention may include linear or branched alkylalkoxysilane having 1 to 20 carbon atoms and silicon oxide (alkoxysilane). In addition, the sol-gel solution may be prepared further comprising an alcohol.

The molar ratio of alkylalkoxysilane and water is preferably 1: 5.4 or more, but the condition is not limited to the above range, and may be a general molar ratio for preparing a sol-gel solution. In addition, the molar ratio of the alkylalkoxysilane and silicon oxide can also be appropriately adjusted depending on the reaction conditions. The molar ratio of the alkylalkoxysilane and alcohol may be appropriately changed depending on the filler volume of the coating.

The alkylalkoxysilane is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltribu Methoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane and the like can be used. Tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS) or a mixture thereof may be used as the silicon oxide. The silicon oxide is dissolved in alcohol and causes a sol-gel reaction by hydrolysis and polycondensation. The silicon oxide may be used as it is, but may be diluted with an alcohol such as anhydrous ethanol in order to control the measurement and the rate of hydrolysis reaction. The alcohol may be methanol, ethanol, isopropanol, butanol and the like, and it is preferable to use ethanol, which can be easily purchased and economical among them.

The hydrolysis catalyst may use a conventional acid catalyst series. For example, the acid catalyst may be maleic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, fluoric acid, oxalic acid, para-toluenesulphonic acid, trichloroacetic acid, and the like, but the type thereof is not limited thereto.

The temperature of the hydrolysis and polycondensation reaction can be carried out under the usual conditions, the conditions are not limited, for example, it can be carried out for 1 hour to 10 hours at room temperature. The present invention is to use a solution that has undergone hydrolysis and polymerization in order to accelerate the sol-gel reaction, it is more preferable to use when the solution is clear after shaking well to advance the reaction. In addition, since the gel molecule becomes more viscous as the solution becomes larger, the pH range may be maintained at 3.5 to 4.5 in order not to reduce the flexibility of the coating.

Using the sol-gel solution obtained by the above method, the surface of the magnesium alloy member is coated to form a film having a thickness of 1 to 60 µm. The coating method may use a spray method.

In the last step, the coated magnesium alloy member is dried and surface hardened (S150).

The present invention performs a drying process to remove alcohol and water, which are solvents of the sol-gel solution. In addition, a surface curing process may be performed to enhance the strength and appearance of the surface from which alcohol and water have been removed.

The drying may be performed as long as it is a condition capable of removing water and alcohol, for example, may be performed for 1 minute to 10 minutes at a temperature of room temperature to 80 degrees, preferably at 80 ℃, drying oven, etc. Can be proceeded using.

Surface hardening may be performed for 10 to 30 minutes at a temperature of 100 to 200 degrees. Preferably, the surface hardening proceeds at 200 ° C.

Thus, in the present invention, by coating the sol-gel solution at room temperature on the surface of the magnesium alloy member including the dry-deposited magnesium oxide film, the network structure in the solution can be chemically bonded to the surface of the magnesium alloy member to modify the surface with silica. have.

3 is a flowchart illustrating a surface treatment method of a magnesium alloy member according to a second embodiment of the present invention.

Referring to FIG. 3, the surface treatment method of the magnesium alloy member according to the second exemplary embodiment of the present invention will be described.

In the method of the present invention, the magnesium alloy member is placed in a vacuum container (S210), the surface of the magnesium alloy member is cleaned under vacuum conditions (S220), and a magnesium fluoride film is dry deposited on the surface of the magnesium alloy member (S230), Performing a sol-gel coating on the surface of the magnesium alloy member including the dry deposited magnesium fluoride film (S240), and drying and surface curing the magnesium alloy member (S250).

That is, the present invention includes, in the dry deposition step, depositing a magnesium fluoride film instead of depositing the magnesium oxide film in the first embodiment. To this end, the present invention dry deposition of a magnesium fluoride (MgF ₂ ) film on the treated magnesium alloy surface (S230). Specifically, a target containing magnesium fluoride is placed in the evaporation source 50. A gaseous magnesium fluoride is formed by applying an electron beam to this target. The magnesium fluoride in the gaseous state diffuses into the magnesium alloy member mounted on the holder 20 to form a magnesium fluoride film on the surface of the magnesium alloy member. In this step, an electron beam deposition method or a sputtering deposition method may be used as the dry deposition method.

The thin film deposition process forms an acid-resistant passivation film on the magnesium alloy surface.

The magnesium fluoride film may be formed with a thickness of 10 nm to 150 nm. If the thickness is thinner than 10 nm, there is a problem that the corrosion resistance is insufficient, and if the thickness is thicker than 150 nm, interference color is expressed, and thus the texture of magnesium inherent is not sufficiently expressed.

Before and after the dry deposition step of the magnesium fluoride film, the same method as in the first embodiment can be used, so a detailed description thereof will be omitted.

Meanwhile, according to the present invention, the method may further include depositing a magnesium fluoride film on the magnesium oxide film after the dry deposition of the first embodiment. Through this process, a composite film of magnesium oxide-magnesium fluoride can be formed.

Therefore, according to the third embodiment of the present invention, as shown in FIG. 4, before the sol-gel coating is applied, a magnesium fluoride (MgF ₂ ) film is further dry deposited on the magnesium oxide film (S340). In this step, electron beam vapor deposition or sputtering vapor deposition can be used. In this case, the sum total of the thickness of the magnesium oxide film and the magnesium fluoride film is 10 nm or more and 150 nm or less. If this value is thinner than 10 nm, there is a problem that the corrosion resistance is insufficient, and if it is thicker than 150 nm, interference color is expressed and the texture of magnesium inherent is not sufficiently expressed.

As a result, the thickness of the magnesium fluoride film to be further deposited is determined according to the thickness of the magnesium oxide film deposited first. In addition, this step can also be omitted as needed.

Here, except that the sol-gel solution is coated on the multilayer film (composite film) of the magnesium oxide-magnesium fluoride (S350), the same method as described in the first embodiment may be applied, and thus a detailed description thereof will be omitted. . In addition, the process after the sol-gel coating includes the step of drying and surface curing the magnesium alloy member completed until the sol-gel coating (S360).

In another aspect, the present invention may further comprise the step of depositing a magnesium oxide film on the magnesium fluoride film after the dry deposition step of the second embodiment. Through this process, a composite film of magnesium fluoride-magnesium oxide can be formed.

Therefore, according to the fourth embodiment of the present invention, as shown in FIG. 5, before the sol-gel coating is applied, a magnesium oxide film is further dry deposited on the magnesium fluoride film (S440). In this step, electron beam vapor deposition or sputtering vapor deposition can be used. In this case, the sum total of the thickness of a magnesium fluoride film and a magnesium oxide film is 10 nm or more and 150 nm or less. If this value is thinner than 10 nm, there is a problem that the corrosion resistance is insufficient, and if it is thicker than 150 nm, interference color is expressed and the texture of magnesium inherent is not sufficiently expressed.

As a result, the thickness of the magnesium oxide film to be further deposited is determined according to the thickness of the magnesium fluoride film deposited first. In addition, this step can also be omitted as needed.

The method is also applicable to the same method as described in the first embodiment, except that the sol-gel solution is coated on the multilayer film (composite film) of the magnesium fluoride-magnesium oxide (composite film), and thus a detailed description thereof is omitted. Let's do it. In addition, the process after the sol-gel coating includes a step of drying and surface curing the magnesium alloy member completed until the sol-gel coating (S460).

In the present invention, if necessary, instead of the magnesium oxide, magnesium fluoride, magnesium oxide-magnesium fluoride, magnesium fluoride-magnesium oxide, a thin film formed by using hexamethyldisiloxane as a precursor, silicon dioxide, titanium dioxide, alumina, fluoride Metal-containing thin films containing metal oxides such as silicon and cerium oxide may be deposited, and they may also be deposited in the form of one or more composite films. The thin film formed using the hexamethyldisiloxane as a precursor may be a coating thin film produced by plasma vapor deposition using HMDSO (hexamethyldisiloxane) as a precursor.

Therefore, the magnesium alloy member surface-treated by the above method includes a magnesium alloy member; A metal-containing thin film formed by dry deposition on a surface of the magnesium alloy member; And a surface cured film formed on the dry deposited metal-containing thin film.

That is, the dry deposited metal-containing thin film is a magnesium oxide film; Magnesium fluoride film; Silicon fluoride film; Metal containing films such as silicon dioxide, titanium dioxide, alumina and cerium oxide; Or one or more composite films thereof. The composite membrane may be a composite membrane of magnesium fluoride-magnesium oxide or a composite membrane of magnesium oxide-magnesium fluoride.

The present invention has the advantage of expressing the metal texture of magnesium by forming an acid passivation film on the magnesium alloy surface by a thin film deposition process and then performing a sol-gel coating using an acid catalyst. In addition, the passivation film using a thin film deposition process can significantly improve the corrosion resistance of the magnesium alloy member, it is possible to implement a surface treatment with excellent scratch resistance.

Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. However, these embodiments are merely presented as an example of the invention, whereby the scope of the invention is not determined.

Example  One

First, a magnesium alloy member having good surface contamination is removed from a sheet formed by molding, and then mounted on a deposition apparatus of FIG. 1, and then vacuum is applied at 10 ⁻⁵ torr and argon plasma is applied. The surface of the magnesium alloy member was cleaned for 30 minutes by using.

Then, in order to passivate the surface of the magnesium alloy member, magnesium oxide was dry deposited to form a magnesium oxide film.

Specifically, after placing magnesium oxide (MgO) in an evaporation source, an e-beam evaporator was provided to the target to form a gaseous magnesium oxide material through evaporation. The gaseous magnesium oxide material was deposited on the surface of the magnesium alloy member mounted on the holder to form a magnesium oxide film having a thickness of 10 nm to 150 nm in steps.

Then, the sol-gel solution was coated on the magnesium oxide film by a spray method to form a film having a thickness of 1 μm.

At this time, the solution used in the sol-gel coating process was prepared by the following method.

After weighing Ludox HS-40 (Sigma-Aldrich, 12 nm monodisperse particles, 40 wt.% In water), the molar ratio of methyltrimethoxysilane (MTMS, 95%, Sigma-Aldrich) and water is greater than 1: 5.4 Silica sol was prepared by adding water. Thereafter, maleic acid was added so that the pH became 3.5 to 4.5 while vigorously stirring the silica sol, followed by ethyl alcohol. MTMS and tetraethyl orthosilicate (TEOS, 98%, Sigma-Aldrich) were then added into the solution. The mixture was subjected to a hydration reaction for 1 to 2 hours to prepare a sol gel solution. Here, the molar ratio of MTMS: TEOS is 1: 0.02, and the molar ratio of MTMS: ethanol is 1: 1.5 when the filler volume of the coating is 0.21, 1:29 when the volume is 0.61, and 1:29 when the volume is 0.66. In the case of 1: 2.9 and 0.71, 1: 4.2 was used.

After drying the sol-gel coated magnesium alloy member in the drying oven at 80 ℃ for 5 minutes, the curing reaction was carried out at 200 ℃ 30 for 30 minutes to prepare a magnesium alloy member having a final surface treatment.

Example  2

Instead of forming the magnesium oxide film in Example 1, the magnesium alloy member was surface-treated in the same manner as in Example 1, except that the magnesium fluoride film was formed using magnesium fluoride (MgF ₂ ). At this time, magnesium fluoride was formed in the gas state using an electron beam evaporator in the same manner as in Example 1 and then dry-deposited on the surface of the magnesium alloy member.

Example  3

The magnesium alloy member was surface-treated in the same manner as in Example 1, except that dry magnesium fluoride (MgF ₂ ) was further deposited on the magnesium oxide film in Example 1. At this time, magnesium fluoride was formed in a gaseous state using an electron beam evaporator as in Example 1 and then dry-deposited on the magnesium oxide film.

Example  4

The magnesium alloy member was surface-treated in the same manner as in Example 2, except that dry oxide was further deposited on the magnesium fluoride film in Example 2. At this time, the magnesium oxide was made into a gas state using an electron beam evaporator in the same manner as in Example 1 and then dry deposition on the magnesium fluoride film.

Comparative example  One

The surface of the magnesium alloy member was treated in the same manner as in Example 1 except that the sol-gel coating process was not performed in Example 1.

Comparative example  2

In Example 1, the surface of the magnesium alloy member was treated by coating the sol-gel solution on the surface of the magnesium alloy member on which the natural oxide film was formed, without performing a dry deposition process.

Experimental Example  1: reliability test

Reliability tests were performed on Examples 1 to 4 and Comparative Examples 1 to 2 by the following methods, and the results are shown in Table 1.

(1) surface appearance observation

The surface state of the magnesium alloy member was visually observed after the sol-gel process. "Good" indicates that the magnesium texture is maintained after surface contamination is removed, and "poor" indicates that staining or discoloration is caused by oxidation during the process.

(2) salt spray test

According to ASTM B117 method, 5% saline spray was tested by spraying on magnesium alloy member specimens at 35 ° C. At this time, "good" as an evaluation standard indicates that the initial surface appearance quality is maintained for 24 hours or more, and "bad" indicates that the surface texture is damaged by discoloration or rust.

(3) corrosion resistance

It was measured according to ASTM D 2083 after coating with a thickness of 15 to 20 microns using a sol-gel coated sample. 2 and 3 of the ASTM D 2038 standards were carried out, and the humidity standing period was observed for 6 weeks. At this time, "good" as the evaluation criteria indicates that the corrosion of the foam does not occur, "bad" indicates that the corrosion proceeds in the film cutting portion.

(4) surface hardness

Pencil hardness was measured by a conventional method. Pencil hardness was measured by inserting a pencil hardness measuring pencil (Mitsubishi pencil) in the hardness measuring machine at a 45 degree angle and pushing it while applying a load of 1 kg.

(5) coating adhesion

A coating of 15 microns thick using a sol-gel coated sample, followed by heating in boiling water (distilled water) for 1 hour (standard mobile phone reliability test) was tested for adhesion tape test according to ASTM D 3359. It was.

At this time, "good" as a criterion indicates a 5B grade in the ASTM D 3359 standard, "bad" indicates 4B or less.

[Table 1]

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Surface appearance quality Good Good Good Good - Bad Salt Spray Test Good Good Good Good Bad Bad Filippo Corrosion Good Good Good Good Good Bad Pencil hardness 7H 7H 7H 7H - 4H Adhesion Good Good Good Good Good Bad

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

1 is a schematic view showing an example of an electron beam vacuum deposition apparatus used to perform the surface treatment method of a magnesium alloy member according to the present invention.

2 is a flowchart illustrating a surface treatment method of the magnesium alloy member according to the first embodiment of the present invention.

3 is a flowchart illustrating a surface treatment method of a magnesium alloy member according to a second embodiment of the present invention.

4 is a flowchart illustrating a surface treatment method of a magnesium alloy member according to a third embodiment of the present invention.

5 is a flowchart illustrating a surface treatment method of a magnesium alloy member according to a fourth embodiment of the present invention.

Claims (15)

(a) dry depositing a metal containing thin film having a thickness of 10 nm to 150 nm on the surface of the magnesium alloy member, (b) sol-gel coating the surface of the magnesium alloy member including the dry deposited metal-containing thin film to form a film having a thickness of 1 to 60 μm, and (c) drying and surface curing the magnesium alloy member, The sol-gel coating is a metal surface treatment method of a magnesium alloy member using a sol-gel solution containing a pH 3.5 to 4.5 of the hydrolysis and polycondensation reaction, alkyl alkoxysilane having 1 to 20 carbon atoms and silicon oxide. The thin film of claim 1, wherein the metal-containing thin film is selected from the group consisting of magnesium oxide film, magnesium fluoride film, silicon fluoride film, and hexamethyldisiloxane as precursors, silicon dioxide, titanium dioxide, cerium oxide, and alumina. A metal-textured surface treatment method of a magnesium alloy member comprising a metal containing film or at least one composite film thereof. The method of claim 1, wherein the dry deposition is A metal surface treatment method for a magnesium alloy member using an electron beam vacuum deposition method, a sputtering deposition method, or a chemical vapor deposition method. The method of claim 1, wherein the sol-gel solution is prepared further comprising an alcohol selected from the group consisting of methanol, ethanol, isopropanol and butanol. delete delete According to claim 1, wherein the hydrolysis and polycondensation reaction is carried out under an acid catalyst, the acid catalyst is maleic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, fluoric acid, oxalic acid, para-toluenesulphonic acid and trichloroacetic acid At least one selected from the group consisting of, the metal surface treatment method of the magnesium alloy member. 2. The method of claim 1, wherein the drying is performed at a temperature of from room temperature to 80 ° C., and the surface hardening is performed at a temperature of 80 ° C. to 200 ° C. 3. 3. The method of claim 2, wherein the magnesium oxide film is formed on the surface of the magnesium alloy member after the dry deposition step. And depositing a magnesium fluoride film on the magnesium oxide film to form a composite film of a magnesium oxide film-magnesium fluoride film. 3. The method of claim 2, wherein if a magnesium fluoride film is formed on the surface of the magnesium alloy member And depositing a magnesium oxide film on the magnesium fluoride film to form a composite film of a magnesium fluoride film and a magnesium oxide film. The method of claim 9 or 10, wherein in the depositing step A metal surface treatment method of a magnesium member using an electron beam deposition method or a sputtering deposition method. 10. The method of claim 9, The sum of the thickness of the magnesium oxide film and the magnesium fluoride film is 10nm to 150nm metal texture surface treatment method of a magnesium alloy member. The method of claim 10, The sum of the thickness of the magnesium fluoride film and the magnesium oxide film is 10nm to 150nm metal texture surface treatment method of a magnesium alloy member. The method of claim 1, wherein the method further comprises cleaning the surface of the magnesium alloy member with plasma under vacuum conditions prior to the dry deposition step. A magnesium alloy member exhibiting a metallic texture surface-treated according to the method of claim 1.

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