JPS6213065B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Fields> The present invention is applicable to magnesium (hereinafter referred to as "Mg") applications that require corrosion resistance, surface conductivity, abrasion resistance, and thermal shock resistance, such as aerospace equipment, precision electrical machinery equipment, and automobile parts. ) or a method for surface treatment of Mg alloys. <Conventional technology> Light alloys such as Al are often used for metal materials used in aerospace equipment, precision electrical equipment, and automobile parts in order to reduce energy consumption and improve performance. , recently, 30 than Al alloy
There is a tendency to use Mg alloys that can reduce the density by more than %. However, since Mg is the most chemically active of all practical alloys, corrosion protection technology has not yet been established. The reason for this is that even if a rust-preventive film is attached to the magnesium surface through normal chemical conversion treatment, anodizing treatment, wet plating, dry plating, or painting, there are microscopic pinholes in these films. As a result, it is impossible to prevent the underlying magnesium from diffusing to the surface, resulting in deterioration of corrosion resistance. Furthermore, the above devices usually have built-in electrical parts or circuits, and in order to obtain stable grounding and shield electromagnetic waves, the surface of the anti-rust film is coated with gold (hereinafter referred to as
It is written as “Au”. ), silver (hereinafter referred to as "Ag"), copper (hereinafter referred to as "Cu"), nickel (hereinafter referred to as "Ni")
It is written as It is necessary to apply a film made of a conductive material such as ). At present, attempts are being made to attach an oxide film to the Mg alloy surface and then attach a Ni film by electroless plating. <Problems to be solved by the invention> However, the above-mentioned Mg alloy surface treatment method
Not only was the corrosion resistance and surface conductivity of the Mg alloy insufficient, but also the thermal shock resistance and abrasion resistance were insufficient. The present invention was made to improve the drawbacks of such conventional surface treatment techniques for Mg or Mg alloys, and in particular improves the corrosion resistance of Mg or Mg alloy materials.
The present invention aims to provide a surface treatment method capable of improving surface conductivity and increasing thermal shock resistance and abrasion resistance. <Technical means for solving the problems> The surface treatment method of the present invention for solving the above problems includes a first step of forming an oxide film by anodizing the surface of Mg or Mg alloy, and a first step of forming an oxide film on the surface of Mg or Mg alloy. a second step of forming a thermosetting resin film on the oxide film formed in the first step; and a third step of forming a conductive film on the thermosetting resin film formed in the second step.
It is characterized by including the steps of. As the oxide film in the surface treatment method according to the present invention, Mg
Or Mg oxide, aluminum (hereinafter referred to as "Al") oxide, chromium (hereinafter referred to as "Cr") generated on the surface of Mg alloy material by anodizing method.
Examples include oxides. In addition, thermosetting resin materials to be formed on the oxide film include melamine resin, epoxy resin, phenolic resin, urea resin, xylene resin, silicone resin, polyimide resin, acrylic resin, polyurethane resin, methacrylic resin, polyvinyl formal resin, and nylon. It is formed by depositing a film made of one or more of resin and polyester resin. In addition, Au,
Ag, Cu, Al, Ni, Tin (hereinafter referred to as "Sn")
One or more other metals or alloys are used, and the film can be formed by ion plating,
It can be deposited by sputter deposition, vacuum deposition, electroless plating, or other methods. <Function> As described above, the method for surface treatment of Mg and Mg alloy according to the present invention applies
Since three layers of oxide film, thermosetting resin film, and conductive film are deposited in sequence, even if the conductive film and thermosetting resin film are damaged, the hard oxide film will protect the underlying layer. Extremely high wear resistance and corrosion resistance as it protects Mg or Mg alloy. In addition, the thermosetting resin film not only improves corrosion resistance, but also has elasticity unique to polymeric materials, so this thermosetting resin is bonded between the bottom layer of oxide film and the top layer of conductive film. Because it is interposed, it plays the role of buffering the difference in thermal expansion coefficient between the oxide film and the conductive film, improving thermal shock resistance. <Examples> Next, the content of the present invention will be specifically explained based on Examples and Comparative Examples. Example 1 After connecting an electrode lead wire to an alloy plate having a composition of Mg-3wt%Al-1wt%Zn, this alloy plate was
KOH165g, KF35g, _Na3PO435g , _Al
(OH) ₃ 35g, KMnO ₄ 10g, MnO ₄ 10g dissolved in 1 part water was immersed in a mixed aqueous solution and anodized for 15 minutes at a voltage of 50 V AC and a current density of 2.0 A/dm ² to give a thickness to the surface of the alloy plate. An oxide film of 20 μm was formed. Next, after applying melamine resin to a thickness of 40 μm on the oxide film, this alloy plate was heated in the atmosphere at a temperature of 30%.
The coated melamine resin was left to stand for 72 hours at a temperature of 35°C to completely dry. Furthermore, an Au film with a thickness of 5 μm was formed on the melamine resin film by ion plating. The alloy plate thus obtained was named Example Sample 1. Example 2 An oxide film of 20A was deposited on a Mg-6wt%Al-0.5%Zn alloy plate by the same anodic oxidation treatment as in Example 1. Spread 7 μm of epoxy resin on top of this oxide film.
Apply a thick coat under atmospheric humidity of 40% and temperature of 30°C.
The applied epoxy resin was left to stand for 48 hours to completely solidify. Furthermore, by sputtering on this coating film,
A gold film was deposited to a thickness of 0.5 μm. The alloy plate sample thus obtained was named Example Sample 2. Example 3 An oxide film of 30A was deposited on a Mg-9wt%Al-1wt%Zn alloy plate by the same anodic oxidation treatment as in Example 1. On top of this oxide film, apply 10μ of phenolic resin.
24°C under atmospheric humidity of 60% and temperature of 38°C.
The applied phenolic resin was left to stand for a period of time to completely solidify. Furthermore, an Au film with a thickness of 10 μm was deposited on this coating film by vacuum deposition. The alloy plate sample thus obtained was named Example Sample 3. Example 4 After connecting an electrode lead wire to a Mg-3wt%Al-1wt%Zn alloy plate, the alloy plate was heated to KOH, KF,
Immersed in a mixed positive solution of Na ₃ PO ₄ , Al(OH) ₃ , KMnO ₄ , MnO ₄ at a voltage of 50 V AC and a current density of 2.0 A/dm ^2.
Anodic oxidation was performed for 15 minutes to form an oxide film on the surface of the alloy plate. After applying melamine resin on this oxide film,
This alloy plate was tested under atmospheric humidity of 30% and temperature of 35°C.
The applied melamine resin was left to dry completely for 72 hours. Furthermore, an Au film was formed on this alloy plate by vacuum evaporation. The alloy plate sample thus obtained was named Example Sample 4. Example 5 After connecting an electrode lead wire to a Mg-3wt%Al-1wt%Zn alloy plate, the alloy plate was heated to KOH, KF,
Immersed in a mixed positive solution of Na ₃ PO ₄ , Al(OH) ₃ , KMnO ₄ , MnO ₄ at a voltage of 50 V AC and a current density of 2.0 A/dm ^2.
Anodic oxidation is performed for 15 minutes, and a thickness of 20 μm is formed on the surface of the alloy plate.
An oxide film was formed. After applying a melamine resin with a thickness of 40 μm on this oxide film, this alloy plate was placed in the atmosphere at a humidity of 30% and a temperature of 35%.
The coated melamine resin was left to stand for 72 hours at ℃ to completely dry. Furthermore, a 5 μm thick Au film was formed on this alloy plate by sputtering. The alloy plate sample thus obtained was named Example Sample 5. Comparative Example 1 After connecting an electrode lead wire to an alloy plate consisting of Mg-3wt%Al-1wt%Zn, this alloy plate was heated with KOH:
165g, KF: 35g _{, Na3PO4} : 35g, Al(OH) ₃ :
35 g, KMnO ₄ : 10 g, MnO ₄ : 10 g dissolved in 1 part water was immersed in a mixed aqueous solution and anodized for 15 minutes at a voltage of 50 V AC and a current density of 2.0 A/dm ² to form a 20 μm thick layer on the surface of the alloy plate. An oxide film was formed. Then, an Au film with a thickness of 5 μm was formed on the oxide film by ion plating. The alloy plate sample thus obtained was named Comparative Example Sample 1. Comparative Example 2 After coating a melamine resin with a thickness of 40 μm on an alloy plate consisting of Mg-3wt%Al-1wt%Zn, this alloy plate was left for 72 hours under an atmospheric humidity of 30% and a temperature of 35℃. Then, the applied melamine resin was dried. Next, an Au film with a thickness of 5 μm was formed on the melamine resin film by an ion plating method. The alloy plate sample thus obtained was named Comparative Example Sample 2. Next, the performance of Example Samples 1 to 5, Comparative Example Sample 1, and Comparative Example Sample 2 obtained in Examples 1 to 5 and Comparative Example 1 described above was measured, and the results are shown in Table 1 below. Obtained.

[Table] However, performance tests in Table 1, salt spray tests,
Contact load resistance and thermal shock tests were conducted according to the following criteria. Salt spray test: 5% of
Corrosion resistance was determined by spraying a NaCl solution and determining the time until corrosion occurred. Contact load resistance: Surface conductive performance was determined based on the electrical resistance value of the alloy sample when a 10 g load was applied to the electrode. Thermal shock test: The alloy plate sample was repeatedly thermally cycled by holding it at -190°C and +100°C for 30 minutes each, and the thermal shock resistance was judged by the number of times until the film peeled off, cracked, or changed in quality. Therefore, from the results in Table 1, it can be seen that in the salt spray test, none of the Example Samples 1 to 5 produced in accordance with the present invention showed any corrosion even after 1,000 hours had passed, and the surface treatment of the present invention did not cause any corrosion. It can be seen that excellent corrosion resistance can be obtained by this method. On the other hand, when an Au film is deposited on an anodic oxide film or an organic resin film on an alloy plate sample, when a salt spray test is performed under the same conditions as above, corrosion has already progressed after 2 hours. It is found that corrosion resistance is poor. In addition, the measured contact resistance of the Mg alloy plate to which the oxide film, organic paint film, and Au film were attached by the surface treatment method of the present invention showed a low contact resistance of 1.2 mΩ, whereas the comparative sample showed a low contact resistance of 1.2 mΩ. It showed a contact resistance of 1Ω, and it became clear that the surface treatment method of the present invention can be widely applied to parts related to electrical equipment because it enables low contact resistance, provides stable grounding, and can shield electromagnetic waves. Furthermore, in the surface treatment method of the present invention, the oxide film and
Because an organic paint film is inserted between the Au film,
The presence of this paint film serves to buffer the difference in thermal expansion coefficient between the oxide film and the Au film. In fact, the Mg alloy film treated with the surface treatment method of the present invention was heated to -190℃ and +
When subjected to a thermal shock test in which the film was held at 100°C for 30 minutes each, the film showed no peeling, cracking, or deterioration even after 10,000 cycles, demonstrating excellent thermal shock resistance. On the other hand, in the case of the comparative example, it was found that the film peeled off, cracked, and changed in quality after seven thermal cycles. This phenomenon also occurs in the case of Comparative Example 2, in which the Au film was provided directly through the melamine resin film without providing an anodized film on the alloy plate sample, due to poor adhesion between the melamine resin film and the alloy plate sample. It was found that the thermal shock resistance was low. In this example, a Mg and Al Zn alloy plate is used as the Mg alloy plate, a melamine resin film, an epoxy resin film, and a phenol resin film are used as the thermosetting resin film, and an Au film is used as the conductive film. However, the method of the present invention can also be applied to other Mg alloys or pure Mg. In anodic oxidation, the film thickness can be easily controlled by controlling the current density, current application time, etc., and NaOH (HO・CH ₂・CH ₂ ) ₂ O,
Mixed aqueous solutions of Na ₂ C ₂ O ₄ and others can also be used. In addition to those shown in the examples, the thermosetting resin may include urea resin, silicone resin, polyimide resin, polyurethane resin, nylon resin, and other resins. Furthermore, it goes without saying that the metal forming the conductive layer is not limited to Au, and other metals such as Ag, Cu, Al, Ni, and Su can be used. Electroless plating and other methods are also possible for forming the metal layer. <Effects of the Invention> As explained above, the Mg alloy surface treatment method of the present invention can not only significantly improve corrosion resistance, which is a drawback of Mg and Mg alloys, but also ensure surface conductivity, and further improve heat resistance. impact resistance,
Since wear resistance can be improved, Mg alloys can be widely used in aerospace equipment, precision electrical machinery equipment, and automobile parts.

Claims (1)

[Claims] 1. A first step of forming an oxide film by anodizing the surface of magnesium or magnesium alloy,
A second step of forming a thermosetting resin film on the oxide film formed in the first step, and a second step of forming a conductive film on the thermosetting resin film formed in the second step. A method for surface treatment of magnesium and magnesium alloys, comprising the steps of 3.