TWI266814B - Magnesium product and magnesium alloy product having conductive anodic oxidation coatings thereon, and method for the production thereof - Google Patents

Magnesium product and magnesium alloy product having conductive anodic oxidation coatings thereon, and method for the production thereof Download PDF

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Publication number
TWI266814B
TWI266814B TW92106493A TW92106493A TWI266814B TW I266814 B TWI266814 B TW I266814B TW 92106493 A TW92106493 A TW 92106493A TW 92106493 A TW92106493 A TW 92106493A TW I266814 B TWI266814 B TW I266814B
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Taiwan
Prior art keywords
magnesium
magnesium alloy
surface
film
anodized film
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TW92106493A
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Chinese (zh)
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TW200413572A (en
Inventor
Yasuhiro Okuda
Koji Sakai
Makoto Hino
Minoru Hiramatsu
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Hori Metal Finishing Ind Ltd
Okayama Prefecture
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Application filed by Hori Metal Finishing Ind Ltd, Okayama Prefecture filed Critical Hori Metal Finishing Ind Ltd
Publication of TW200413572A publication Critical patent/TW200413572A/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/30Anodisation of magnesium or alloys based thereon

Abstract

The product is made of magnesium or magnesium alloy with conductive anodic oxidation coating, which possesses electrical resistance of below 100 Omega detected by 2 terminals distant from 10 mm each other on the surface. The product could be made by that magnesium or magnesium alloy is immersed into the electrolyte with 0.1 to 1 mol/L of phosphoric acid ion, 0.2 to 5 mol/L of ammonia or ammonium ion, and of pH of 8-14 to anodic oxidizing process the surface. By this method, the product made of magnesium or magnesium alloy with anodic oxidation cover of both conductivity and excellent ability of anti-erosion on the surface is provided.

Description

1266814 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 - - - - - - - - - - - - - A product made of magnesium or magnesium alloy of an anodized film excellent in properties. Further, it relates to a method of producing such products. (1) Prior art magnesium and magnesium alloys are the lightest in practical metals and therefore have high specific strength φ and good heat release properties. They are also excellent in recyclability compared with resins. In recent years, they have been widely used in electrical machines or Automotive parts use. In particular, it is suitable for use as a housing for electrical equipment that requires high performance, creativity, and recyclability as small size and light weight. However, since magnesium and magnesium alloys are easily corroded, it is necessary to have a corrosion-resistant surface treatment or coating. * Excellent corrosion resistance can be imparted by anodizing the magnesium or magnesium alloy. Typically, an anodizing treatment is carried out by a treatment method called D〇w 1 7 or HAE, whereby an anodized film having practically sufficient corrosion resistance of H can be formed. Further, a method of anodic oxidation of magnesium or a magnesium alloy by immersing in an electrolytic solution containing ammonia and a phosphate compound is described in JP-A-H01-150 2565 (W096 / 28 5 9 1) . Further, it is also possible to form a film having conductivity by forming a treatment magnesium or a magnesium alloy to provide a certain degree of corrosion resistance, and it is described in the following publication. Japanese Laid-Open Patent Publication No. 2000-96-625 discloses a formation film containing a fixed amount of potassium, manganese, and phosphorus and having a specific resistance of 〇·1 Ω·cm or less. Further, it is described in JP-A-2000-32 2826, that the surface of the magnesium alloy is etched with an acidic aqueous solution having a pH of 1 to 5, and an aqueous alkaline solution containing pH 7 to 丨4 containing an organic phosphorus compound is contacted, followed by contact formation treatment. The surface treatment method of the magnesium alloy of the liquid describes the purpose of obtaining a product having a small surface resistance. In various displays, mobile phones, and the like, such as a plasma display device, it is preferable to efficiently shield the generated electromagnetic waves. Since magnesium and magnesium alloys have good electrical conductivity, the frame of an electric machine using the same can have good electromagnetic wave shielding properties. In addition, in most electrical equipment, especially digital electronic equipment, it is important to remove electromagnetic interference by grounding (ground) in order to prevent erroneous operation. In this case, if the frame is made of magnesium or magnesium alloy, it can be grounded. On the magnesium and magnesium alloys as described above, surface treatment or coating having corrosion resistance is necessary. By performing anodizing treatment for imparting corrosion resistance to magnesium or a magnesium alloy, the insulating oxide film covers the magnesium or magnesium alloy and loses electromagnetic shielding, and it becomes impossible to ground. Therefore, for example, an anodic oxidation treatment is carried out after covering the portion for grounding, and a part of the anodic oxide film is removed by anodic oxidation after a full anodic oxidation treatment. However, these methods increase production costs due to cumbersome operations. Further, in the film formed by the forming process, the film of the film disclosed in Japanese Laid-Open Patent Publication No. 2000-96255 or JP-A No. 2000-32826 No. is disclosed. However, compared with the anodizing treatment which is formed by energizing a magnesium or magnesium alloy to form a strong oxide film, the film formed by the immersion treatment of the treatment liquid alone is resistant to corrosion 8 - 1266814 Insufficient. In recent years, in the frame of mobile machines, etc., this problem is particularly important because corrosion resistance in various environments becomes necessary. Therefore, in the case where a film is formed by the forming treatment, it is currently practiced to further apply a plurality of layers thereon to ensure any corrosion resistance. However, it is not always easy to carry out uniform coating on the frame of an electric machine having a complicated shape, and the cost increases greatly due to the multiple coating steps. Further, the Dow 17 method which is anodizing is widely used today, and the obtained anodized film contains chromium and contains HA in the HAE method. Further, a large number of products obtained by the treatment or the film contains a heavy metal element. Since the stomach contains such heavy metal elements, it is not preferable to mix heavy metals with magnesium or magnesium alloys during recycling. In particular, since magnesium and magnesium alloys are characterized by excellent recyclability compared to plastics, the amount of heavy metal elements accumulated due to the repeated number of times of recycling cannot be ignored. Further, since the treatment liquid contains heavy metal elements, it is not preferable from the viewpoint of the waste liquid treatment or environmental protection. The present invention has been made to solve the above problems, and is intended to provide a product made of a magnesium or magnesium φ alloy having an anodized film having both conductivity and excellent uranium resistance on the surface. Further, it is intended to provide a method of producing a product made of such magnesium or magnesium alloy. The anode oxide film obtained by the present invention can solve the above problems because it does not contain a heavy metal element, and is also excellent from the viewpoint of recycling property and environmental protection. Further, since the electrolytic solution to be used does not contain a heavy metal element, the anodic oxide film can be formed and the environmental protection around the factory can be provided, and the waste liquid processing cost can be reduced. (III) SUMMARY OF THE INVENTION # -9-1266814 Description of the Invention The above problem is to provide a conductive anode having a surface resistance 値 of 1 Ο Ω or less measured by a surface having a surface having a distance of 1 mm from each other. Achieved by a product made of magnesium or a magnesium alloy of an oxide film. Conventionally, a film obtained by anodizing magnesium or a magnesium alloy is a film mainly composed of an oxide, and is an insulator. It is not so much because it is an insulator, but it is considered that it does not circulate a corrosion current to magnesium or a magnesium alloy, and it can prevent oxidative degradation of itself. However, as a result of intensive research by the present inventors, it has been found that both an anodized film and a film having electrical conductivity are simultaneously provided. Moreover, it has an anodized film from the past, and it is also understood that the excellent corrosion-resistant uranium performance remains intact. Therefore, an article made of magnesium or a magnesium alloy having excellent corrosion resistance and good electrical conductivity is provided. In particular, it is possible to provide a housing for an electric machine which is excellent in electromagnetic shielding properties and grounding characteristics. Wherein, the film thickness of the anodized film is 0. 01 to 10/zm is preferable from the viewpoint of corrosion resistance and conductivity balance. In the present invention, the anodized film preferably contains 35 to 65 wt% of a magnesium element and 25 to 45 % of an oxygen element. Since the oxidized magnesium is contained as a main component, it is presumed that the anodized film having the surface of the magnesium or magnesium alloy is originally required to have corrosion resistance, but it is not necessarily the reason for having such corrosion resistance. Further, the anodized film preferably contains 4 to 15% by weight of a phosphorus element, and more preferably 5 to 20% by weight of an aluminum element. Since it contains an appropriate amount of elements other than magnesium and oxygen, it is presumed that the corrosion resistance is not impaired and the conductivity is good, but it is not necessarily the reason for having such conductivity. Further, the anodic oxide film of the present invention can exhibit excellent performance because it does not contain a heavy metal element such as a conventional anodic oxide film. A preferred embodiment of the present invention is a magnesium or magnesium alloy which is coated with an anodized film covering the entire surface of the magnesium or magnesium alloy, and which is only partially coated with a resin coating on the surface of the anodized film and exposes the remaining portion of the anodized film. The finished product. Since the exposed portion of the anodized film is provided in this portion, electromagnetic shielding properties or grounding characteristics are ensured, and a resin having excellent appearance and excellent abrasion resistance can be provided by resin coating. Specifically, a frame body of an electric machine in which the resin is coated on the inside of the frame and the resin is coated on the outside of the frame is particularly preferable. Further, the object of the present invention is to provide a nickel or magnesium alloy by impregnation. In an electrolytic solution having 1 to 1 mol/L of phosphate and having a pH of 8 to 14, the anode is oxidized to obtain a method for producing a product made of the above-mentioned magnesium or magnesium alloy. Wherein, the foregoing electrolyte solution contains 0. 2 to 5 mol/L of ammonia or ammonium ion is preferred. As described above, in the conventional anodizing treatment, the treatment liquid contains substantially heavy metal ions, and is also a fluorine ion which is difficult to handle the waste liquid. On the other hand, in the method for producing a product made of the magnesium or magnesium alloy of the present invention, an anodized film excellent in performance can be obtained without containing the components. In recent years, on the one hand, the discharge regulations for waste liquids containing heavy metal elements have become stricter, and it is also important from the viewpoint of environmental protection from the production method of the present invention. In the production method of the present invention, it is preferred that the magnesium or magnesium alloy is previously impregnated in an acidic aqueous solution during the anodizing treatment, and the anodizing treatment is preferably carried out by immersing in the electrolytic solution. The article which achieves the effects of the present invention is easily obtained by the oxidation treatment provided on the anode -11-1266814 after the proper pretreatment. Further, in the production method of the present invention, after the anodizing treatment, the resin coating film is applied only once to the surface of the anodized film, and the coating film is preferably dried by heating at a temperature of 40 to 120 °C. Since an anode oxide film having excellent corrosion resistance can be obtained, it is sufficient to simply apply the coating, and as a result, the manufacturing cost can be reduced. (4) Embodiments Hereinafter, the present invention will be described in detail. The present invention is a product made of a magnesium or magnesium alloy of a conductive anodized film having a surface resistance 値 of 1 〇〇 Ω or less measured between two terminals of a distance of 10 mm from each other. The magnesium or magnesium alloy as a raw material may be composed mainly of magnesium as a main component, a metal containing a magnesium monomer, or an alloy. Usually, a magnesium alloy for imparting formability, mechanical strength, ductility or the like is preferably used. In terms of magnesium alloys, there are listed-Ming-type alloys, watch-Ming-钵 alloys, watch-Ming-Clock alloys, magnesium-zinc··pin alloys, magnesium-rare earth element alloys, magnesium-zinc- Rare earth family alloys, etc. In the examples of the present invention, a magnesium-aluminum-zinc alloy is used, and the obtained anodized film contains an aluminum element. Therefore, in the case of the magnesium alloy of the raw material, it is presumed that it is preferable to contain aluminum. The form of the magnesium or magnesium alloy to be anodized is not particularly limited. A molded article formed by a die casting method, a thixoforming method, a press molding method, a forging method, or the like can be used. At the time of molding, there is a case where a release agent remains in the inside of the wrinkles or hollow portions formed near the surface of the molded article. In the case of the cation oxidation treatment, the residual -12-1266814 release agent tends to be less than that in the case of the formation treatment. The release agent remaining in the product volatilizes upon heating and expands upon resin coating. Among them, the release agent used in the forming is represented by a release agent made of an organic cerium compound. The molded article made of magnesium or a magnesium alloy is preferably a degreasing treatment because it has a contaminant on the surface of an organic substance such as a release agent adhered at the time of molding. For the liquid used for degreasing, it is preferred to use an aqueous solution containing a surfactant or a chelating agent. After the degreasing treatment is carried out as necessary, it is preferably immersed in an acidic aqueous solution and then immersed in an electrolytic solution to perform anodizing treatment. By immersing in an acidic aqueous solution to appropriately etch the surface of the magnesium or magnesium alloy, it is possible to remove the contamination of the organic oxide which has not formed an insufficient oxide film or remains. Although there is no particular limitation on the acidic aqueous solution, it is preferred that the aqueous phosphoric acid solution has a moderate acidity. In the case of using an aqueous phosphoric acid solution, magnesium phosphate is also formed on the surface at the same time as etching. Further, in the acidic aqueous solution of the surfactant or the chelating agent, the degreasing treatment may be simultaneously performed. Further, after treatment with such an acidic aqueous solution, it is preferably further washed with an aqueous solution and then subjected to anodizing treatment. In the acidic aqueous solution, since the insoluble component (dirt smut) adheres to the surface of the magnesium or magnesium alloy, it can be removed. As the alkaline aqueous solution, it is preferred to use an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. After the respective treatment steps of the above treatment, the acidic aqueous solution treatment, and the alkaline aqueous solution treatment, water washing or drying may be carried out if necessary. In this way, the magnesium or magnesium alloy which has been treated beforehand is immersed in the electrolyte. 0 - 13 - 1266814 The electrolyte of the present invention is preferably an alkaline aqueous solution containing a phosphate, more specifically containing 0. .  A solution of 1 to lino 1 / L phosphate and a pH of 8 to 14 is preferred. Since an appropriate amount of phosphate is contained, an appropriate amount of phosphorus is contained in the anodized film. Further, since it is alkaline, it is possible to prevent the magnesium or the magnesium alloy from being eluted unnecessarily. Among them, the phosphate is free of phosphoric acid, phosphate, hydrogen phosphate, and dihydrogen phosphate and is contained in the electrolyte. Further, in the case of polyphosphoric acid or a salt thereof obtained by phosphoric acid condensation, only the phosphate having the number of phosphates obtained by hydrolyzing the water is contained. In the case of a salt, it may be a metal salt or a non-metal salt such as an ammonium salt. The content of phosphate is 0. 1 to 1 mol/L is preferred. With 0. 15mol/L or more is preferred, and 0. More preferably 2 mol/L or more. It is preferably 0. 7mol/L or less.  5mol/L or less is more preferable. The pH of the electrolyte is preferably from 8 to 14. The pH is preferably 9 or more, more preferably 10 or more. Further, the pH is preferably 1 or less, more preferably 12 or less. Further, the total amount of the electrolyte solution is 0.  2 to 5 mol/L of ammonia or ammonium ion is preferred. Thus, the pH of the electrolyte is maintained to be properly alkaline. The content of ammonia or ammonium ions is 〇. 5 mc) l / L or more is preferred, and more preferably 1 mol / L or more. Further, it is preferably 3 mol/L or less, more preferably 2 mol/L or less. The electrolytic solution of the present invention may contain other components insofar as it does not impair the effects of the present invention, but is preferably substantially free of heavy metal elements. The heavy metal element may be a heavy metal element having a specific gravity of more than 4 as a monomer, and is a representative electrolyte contained in a conventional anodizing treatment, and examples thereof include chromium and manganese. It is particularly preferable to use a chromium-14-1266814 which does not contain strict and harmful discharge regulations. Further, it is generally not a problem that a heavy metal contained in magnesium, for example, zinc is eluted in a small amount and contained in an electrolytic solution. Further, it is preferable that the electrolytic solution of the present invention does not contain fluorine. Since the aqueous solution containing fluorine is more difficult to treat the waste liquid. In the above electrolyte, the magnesium or magnesium alloy which has been subjected to the treatment beforehand is immersed, and it is anodized and subjected to anodization by energization. There are no special restrictions on the power supply used. Although DC power and AC power can be used, it is better to use DC power. In addition, when a DC power supply is used, both a constant current power supply and a constant voltage power supply may be used, but it is preferable to use a constant current power source. The cathode material is not particularly limited, and for example, stainless steel or the like can be suitably used. The surface area of the cathode is preferably larger than the surface area of the magnesium or magnesium alloy subjected to the anodizing treatment, and is preferably 2 times or more, and usually 10 times or less. The current density of the anode surface when using a constant current source as the power source is usually 0. 1~ΙΟΑ/dm2. With 0. 2A/dm2 or more is better, with 0. More than 5A/dra2 is preferred. Further, it is preferably 5 A/dm 2 or less, and more preferably 2 A/dm 2 or less. The power-on time is usually 10 to 1 000 seconds. It is preferably 20 seconds or more, and more preferably 50 seconds or more. Further, it is preferably 500 seconds or less, and more preferably 200 seconds or less. When the constant current source is energized, the applied voltage at the start of energization is low, and the applied voltage is increased over time. The applied voltage at the end of energization is usually 50 to 400 volts. More preferably, it is 100 volts or more, and more preferably 150 volts or more. Further, it is preferably 300 volts or less, and more preferably 2 50 volts or less. In the Dow 17 method or the HAE method which is a conventional anodizing treatment method, the applied voltage is often set to less than 100 volts, and in the anodizing treatment of the 1266814 of the present invention, it is preferable to set it to a higher voltage. Therefore, it is easy to carry out an oxidation reaction of a portion containing an impurity such as an organic ruthenium release agent, and it is easy to form a good film on the entire surface of the magnesium or magnesium alloy. Further, since oxygen is strongly generated from the surface of the magnesium or magnesium alloy with the oxidation reaction, the above impurities are easily removed in the anodizing treatment. The electrolyte temperature during energization is usually 5 to 70 °C. It is preferably 10 ° C or more. Further, it is preferably 50 ° C or lower, and preferably 30 ° C or lower. After the completion of the energization, the electrolytic solution adhering to the surface of the anodized film was removed by a washing treatment. When washing, it is better to use not only water but also an acidic ® aqueous solution. Since the electrolytic solution is alkaline, it is washed with an acidic aqueous solution, and when the resin is applied, the adhesion of the coating film can be improved. As the acidic aqueous solution, an aqueous solution of nitric acid, an aqueous solution of hydrochloric acid, sulfur, an aqueous acid solution or the like can be used. After washing, it is dried to obtain an anodic oxygen from the surface.  A product made of a magnesium or magnesium alloy coated with a film. The product made of magnesium or a magnesium alloy of the present invention has a conductive anodized film having a surface resistance 値 of 100 φ Ω or less measured between two terminals at a distance of 10 mm from each other. The resistor 値 is the resistance 値 (Ω) measured by the terminal at any two points of the surface of the anodic oxide film at a distance of 10 mm. The article of the present invention may have at least one of the above surfaces. Resistance 値. Since the resistance of the magnesium or magnesium alloy itself is small, substantially, the resistance 値 associated with the thickness direction of the anodic oxide film existing between the terminal for measurement and the magnesium or magnesium alloy is measured. Thus, the resistance 对应 corresponds to the number of performances required for the article in terms of electromagnetic shielding or grounding characteristics. It is preferably 1 0 Ω or less, preferably 1 Ω or less, and 0.  5 ^ -16 - 1266814 Ω or less is the best. Further, the resistance 表面 of the surface of the molded article made of magnesium or a magnesium alloy which has not been subjected to surface treatment is usually 0 in the case of AZ91D. 02~0. About 1 Ω or so. According to the anodized film obtained by the present invention, as shown in Fig. 1, there are many cases in which a large number of holes are considered to be caused by an arc in the surface. This aspect is different from forming a treatment film. The film thickness of the anodized film is preferably 0 · 0 1 to 1 0 // m. It is better to use 0 · 1 / m or more, and 0.  5 // m or more is better. Further, it is preferably 5 / z m or more, and more preferably 3 # m or more. If the film thickness is too small, the corrosion resistance may be deteriorated. When the film thickness is too thick, the electrical conductivity may be lowered, and the electromagnetic wave shielding property or the grounding property may be lowered. The chemical composition of the anodized film obtained by the present invention is not particularly limited, and it is preferably 35 to 65 wt% of magnesium and 25 to 45 wt% of oxygen. That is, it is a product of the result of anodized magnesium or a magnesium alloy, and it is preferable to contain magnesium oxide as a main component. The content of magnesium strontium is preferably 40% by weight or more, and more preferably 45% by weight or more. Further, it is more preferably 60% by weight or less, more preferably 55% by weight or less. The oxygen content is preferably 30% by weight or more. Further, it is preferably 40% by weight or less. The anodized film preferably contains 4 to 15% by weight of a phosphorus element. The galaxies contained in the phosphonium are preferably 5% by weight or more, and more preferably 6% by weight or more. Further, it is preferably 12% by weight or less, and more preferably 1 〇 〇 / 〇 or less. Further, it is preferable to contain 5 to 20% by weight of an aluminum element. The content of the aluminum element is preferably 7% by weight or more, and more preferably 9% by weight or more. Further, it is preferably 17% by weight or less, more preferably 5% by weight or less. Since it contains the above elements other than magnesium and oxygen, it is presumed that a 17-1266814 is a non-destructive and corrosion-resistant one, and has good electrical conductivity. The anodic oxide film of the present invention may contain elements other than the above insofar as it does not impair the effects of the present invention. However, the magnesium alloy of the raw material is preferably one which does not contain heavy metals, particularly chromium, in order to remove the original one. Further, it is preferable that the fluorine element is not substantially contained. The use of the product made of the magnesium or magnesium alloy of the present invention having an anodized film on the surface is not particularly limited, and can be used for various electric machines, parts for automobiles, and the like. At the time of use, although the coating of the overcoat layer may be applied to the surface of the anodized film as necessary, in order to utilize the characteristics of the anodic oxide film of the present invention having good conductivity, it is not possible to cover with an insulating film. The whole product. The coating used is not particularly limited and can be used for various coatings used in the coating of metal surfaces. A resin coating film, an aqueous coating material, a powder coating material, or the like can be used to form a resin coating film. A heat-curable coating which requires high-temperature firing after coating, and a coating which can be used only in a lower temperature volatile solvent or water can be used. Further, in order to make the appearance beautiful, it is preferable to use a transparent resin coating, and it is also possible to use a suitable coloring. The coating method is also not particularly limited, and a known method such as spray coating, dip coating, electroplating coating, or powder coating can be employed. In the article made of the magnesium or magnesium alloy of the present invention which is preferably a part having no coating film, it is preferred to use a spray coating or a powder coating by a spray method. After the anodizing treatment, it is preferred to form the coating film by coating the surface of the anodized film only once. In the frame of an electric machine, etc., most of them have complicated shapes, and it is not necessarily easy to form a homogeneous coating film system. Although -1 8 - 1266814, most of the coatings can increase the corrosion resistance by a large number of coatings, but the cost increases as the number of coatings increases. On the other hand, in the products made of the magnesium or magnesium alloy of the present invention having good corrosion resistance, most of them are excellent in corrosion resistance only by one application. In the case of using a solvent-based paint or an aqueous paint, it is preferred to heat the film at a temperature of 40 to 120 ° C to dry the coating film. It is preferably 5 〇 ° C or more and 10 (TC or less. In the products made of the magnesium or magnesium alloy of the present invention having good corrosion resistance, most of the drying and hardening resin coating is performed only at a lower temperature heating step. That is, as a result, the manufacturing cost can be reduced. The heating and drying method is not particularly limited, and a general-purpose oven or the like can be used. A preferred example of the present invention covers all of the surface of the magnesium or magnesium alloy by an anodizing film, and Applying only one part of the surface of the anode anodic film - a product made of resin coated to expose the remaining portion of the anodic oxide film of magnesium or magnesium alloy. Since the magnesium or magnesium is covered with an anodized film The surface of the alloy can ensure the corrosion resistance of the entire product. However, all of the so-called all of the essences are only in the case where the φ point portion which is in communication with the power source during the anodizing treatment is not formed as an anodic oxide film portion. Since only a part of the surface of the anodized film is subjected to resin coating to expose a portion of the remaining anodic oxide film, electromagnetic wave shielding or grounding characteristics can be ensured, and at the same time, by the tree A product that is excellent in appearance and excellent in abrasion resistance is provided by lip coating. A particularly preferred example is a frame of an electric machine that is coated with resin on the outside of the frame and is coated with resin on the outside of the frame. Resin coating can not only make the appearance beautiful, but also prevent damage during use. Moreover, since the conductive anodized film ^ - 19 - 1266814 is exposed on the inner surface of the frame, it is easy to ensure electrical wiring. The grounding can effectively shield the electromagnetic waves from the electronic circuits inside the body. The articles made of the magnesium or magnesium alloy of the present invention thus obtained are used for various purposes, and can be used for mobile phones, personal computers, cameras, cameras, Optical disc drive, display (CRT, plasma, liquid crystal), frame of electric machine for projection, or parts for automobile, etc. Best example for carrying out the invention Hereinafter, the present invention will be described in more detail by way of examples, but The test method in this example is carried out according to the method. (1) Film thickness measurement of anodized film The test piece is cut into 5 m. Mx 1 Omm size, after being coated in an epoxy, honing the cut surface to obtain a mirror surface. From the cross-section of the sample, an X-ray microanalyzer "JXA-8900 photographic electron micrograph" manufactured by JEOL Ltd. The thickness of the film was measured. (2) The chemical composition of the anodized film was analyzed by using an X-ray microanalyzer "XA-" manufactured by JEOL Ltd., and the film composition was carried out from the surface of the film and the cross section. The measurement was performed in three directions in each direction, and the chemical was obtained from the average enthalpy. The measurement was carried out by applying an electric current of 15 kV and a 2 x 10_8 A sample. The data analysis was performed by ZAH correction. The resistance 値 of the surface of the anodized film was measured using Mitsubishi Chemical Corporation's low-resistivity meter "Ross pin MCP-T4 00", and the two-probe probe "MCP-TP01" was used to measure the frame. The machine and the like of the following resin, so that 8900 analysis of the composition of the -AP. The resistance 値 ( Ώ ) was measured by attaching the measurement terminal to the surface of the film at the center of the 1266814 i-type test piece. The probe is provided with a measurement terminal at intervals of 10 mm, and the terminal is plated on a tantalum alloy, and the front end shape is a cylindrical shape of a 2 mm diameter. The load on the surface of the coating is 240 g per one terminal. . (4) Warm water immersion test The test piece was immersed in warm water maintained at 70 ° C for 24 hours. After 24 hours, the test piece was taken out, and after wiping off the water, a checkerboard-like mesh was formed at intervals of about 1 mm through the resin coating film and the anodized film, and the tape peeling test was performed in accordance with i IS K5 400. , visually observe the peeling condition of the coating film or whether there are other defects. (5) Salt spray test On the surface of the test piece, after adding a cross-shaped score (cross-notch) through the resin coating film and the anodized film, a 5% salt spray test was carried out in accordance with ISZ - 2 3 7 1 1 20 hours. After the elapse of 10 hours, the test piece was taken out, and the state of expansion from the cross-notched portion or the occurrence of other defects was visually observed. [Example 1] ASTM No. made of 90% by weight of magnesium, 9% by weight of aluminum and 1% by weight of zinc.  The magnesium alloy of AZ91D was used as a raw material, and an alloy plate of a size of 170 mm X 50 m X 2 ιώ m cast by a hot cavity method was used as a test piece. The above test piece was immersed in containing 2 .  After 2% by weight of phosphoric acid and an acidic aqueous solution of a trace amount of a surfactant, it was washed with ion-exchanged water. Next, the surface of the test piece was pretreated by being immersed in an alkaline aqueous solution containing 18% by weight of sodium hydroxide and then washed with ion-exchanged water. -21- 1266814 Mixed aqueous phosphoric acid solution with ammonia water and prepared with 〇 · 2 5 m ο 1 / L phosphoric acid .  Root, electrolyte containing a total of 1 · / L ammonia or ammonium ions, and maintained at 20 ° C. The pH of the electrolyte was 1 1 . A magnesium alloy test piece which has been subjected to pretreatment has been used as an anode and anodized. At this time, a SUS 3 16 L plate having a surface area four times that of the foregoing anode was used for the cathode side. A constant current source was used to energize the anode surface at a current density of 1 A/dm2 for 120 seconds. The applied voltage at the beginning of energization rises to about 200 volts at the end of energization. After the completion of the energization, the cells were washed in the order of ion-exchanged water, aqueous nitric acid solution, and ion-exchanged water, and dried. ^ A photograph of the surface of the obtained anodized film observed by a scanning electron microscope is shown in Fig. 1. The presence of a plurality of holes thought to be caused by the arc in the energization was found on the surface of the anodized film. The film thickness of the anodized film is about 1 .  5 // m. The film thickness is the average distance from the thick partial surface to the magnesium alloy surface of the substrate on the film having a local film thickness unevenness due to a plurality of holes. The obtained anodized film system contains 48. 0% by weight of magnesium, 33. 5 wt% oxygen element, 7. 0% by weight of phosphorus and 11. 2 ^ weight % aluminum element. The resistance 値 of the surface of the anodized film is 0.  2 5 Ω. On the surface of the obtained anodized film, an air-sprayed acrylic organic enamel-based paint "Yascott 300" was applied by air. At this time, the non-base coating was applied at the time of coating, and the acrylic organic enamel coating was applied to the surface of the anodized film only once. After coating, it was heated at 60 ° C for 20 minutes to evaporate the solvent and harden the coating film. As a result, a coating film having a film thickness of about 20 // m was formed on the surface of the anodic oxide film. 'The test piece obtained was supplied to the warm water immersion test and the salt spray test ~ -22-1266814, and in any case, no change in appearance was observed on the surface. The surface of the test piece after the warm water test and the surface of the test piece after the spray test for water spray were not separately shown in Fig. 2 and Fig. 3. [Comparative Example 1] A mixed aqueous solution of phosphoric acid and aqueous ammonia were mixed to prepare cerium.  〇 8 m ο 1 / L phosphate, containing 0 in total.  8 mol / L ammonia or ammonium ion electrolyte, kept at 20 °C. The pH of the electrolyte was 1 1 . An anodizing treatment was carried out by impregnating a magnesium alloy test piece which had been subjected to the same treatment as in Example 1 as an anode. In the case of the cathode at this time, the same as in Example 1 was used. A constant current source was used and energized for 120 seconds with a current density of 1 A/dm2 on the anode surface. The applied voltage at the beginning of energization rises to approximately 200 volts at the end of energization. After completion of the energization, it was washed in the order of ion-exchanged water, aqueous nitric acid solution, and ion-exchanged water, and dried. The film thickness of the obtained anodized film was about 1.  5 // m, containing 5 4 .  8 weight% magnesium, 37. 7 wt% oxygen element, 3. 2% by weight of phosphorus and 4. 3 wt% aluminum. The resistance 表面 of the surface of the anodized film exceeds the limit of 1 Ο 7 Ω of the resistivity tester used for the measurement. A resin coating film was formed on the surface of the obtained anodized film in the same manner as in Example 1. When the obtained test piece was subjected to a warm water immersion test and a salt spray test, no change in appearance was observed on the surface under any circumstances. [Comparative Example 2] A test example of a method for forming a known anodized film called Dow 1 7 was carried out. An electrolyte containing 300 g/L of acidic ammonium fluoride, 100 g/L of sodium dichromate and 90 g/L of phosphoric acid was prepared and kept at 75 ° C. A magnesium alloy test piece which had been subjected to the same treatment as in Example 1 of 1266814 was impregnated therein as an anode, and anodizing treatment was carried out. The cathode side at this time was the same as in Example 1. A constant current source was used and the current was applied to the anode surface at a current density of 4 A/dm2 for 300 seconds. The applied voltage at the beginning of energization rises to approximately 70 volts at the end of energization. After the completion of the energization, it was washed with ion-exchanged water and dried. The film thickness of the obtained anodized film was about 1.  5 // m, containing 26 .  0 weight% magnesium element, 25. 7 wt% oxygen element, 11. 2% by weight of phosphorus, 1. 0% by weight of aluminum, 2 3 .  4% by weight of fluorine, 9 .  2% by weight of chromium and 3 .  6 wt% sodium. The resistance 表面 of the surface of the anodized film exceeds the limit of 1 Ο 7 Ω of the resistivity tester used for the measurement. [Comparative Example 3] Instead of the anodizing treatment, a commercially available forming treatment liquid was used to carry out the formation treatment. The treatment liquid "MC-1 000" prepared by Million Chemical Co., Ltd. containing 75 g/L was diluted with ion-exchanged water to prepare a treatment liquid, which was kept at 40 °C. Although the details of the chemical composition for forming the treatment liquid are not critical, it is estimated to be a treatment liquid containing a phosphate ion, a manganese (or manganese oxide) ion, and a potassium ion. In the treatment liquid, a magnesium alloy test piece which had been subjected to the same treatment as in Example 1 was immersed for 30 seconds. After the completion of the immersion, it was washed with ion-exchanged water and dried. The film thickness of the resulting formed film is 0. 1 Vm is a thin film thickness that is difficult to quantitatively measure. The compound film has an average content per unit area of 85 mg/m 2 potassium element, 95 mg/m 2 masculin element, and 220 mg/m 2 pity element. Further, the resistance 値 of the surface of the formed treatment film was 0.  5 Ω. On the surface of the obtained composite film, a tree-24-4026614 lipid coating film was formed in the same manner as in Example 1. The appearance of the obtained test piece after the warm water immersion test and the appearance after the spray test for the salt water are shown in Fig. 4 and Fig. 5, respectively. In any case, peeling of the resin coating film was apparently observed around the cut of the film. [Comparative Example 4] An example in which the formation treatment was carried out by using a commercially available treatment liquid different from that of Comparative Example 3 was used instead of the anodizing treatment. The treatment liquid "MB - C 10 M" prepared by the Japanese Paka Lai Co., Ltd. having a ratio of 75 g / L was diluted with ion-exchanged water to prepare a treatment liquid, which was kept at 50 °C. Although the details of the chemical composition of the treatment liquid are not significant, it is presumed to contain 14 weight%. Water-free chromic acid and 0.  7 wt% hydrofluoric acid as a main component forming treatment liquid. In the treatment liquid, the magnesium alloy test piece which had been subjected to the same treatment as in Example 1 was immersed for 60 seconds. After the completion of the immersion, it was washed with ion-exchanged water and dried. .  The film thickness of the resulting formed coating film was 0.  1 // πι is more or less, which is a thin film thickness that is difficult to quantitatively measure. The compounded film was obtained by containing 190 mg/m2 of chromium element in an average amount per unit area. Further, the resistance 値 of the surface φ of the formed treatment film was 0.  7 5 Ω. A resin coating film was formed on the surface of the obtained composite film in the same manner as in Example 1. After the obtained test piece was subjected to a warm water immersion test and a salt spray test, in any case, no peeling or swelling of the resin coating film added around the cut of the film was observed. However, after the warm water immersion test, it was observed that a large number of point-like expansion points (bubbles) were formed on the coating film near the edge portion of the test piece. As described above, the result obtained by anodizing in Example 1 is -25-1266814.  The product made of the invention of the magnesium alloy has both electrical conductivity and excellent corrosion resistance. The product obtained by the conventional anodizing treatment as shown in Comparative Example 1 or 2 was excellent in corrosion resistance, and no electrical conductivity was found. Further, a product made of a magnesium alloy obtained by the formation treatment of Comparative Example 3 was found to have conductivity but insufficient corrosion resistance. [Industrial Applicability] The product made of the magnesium or magnesium alloy of the present invention is an anodized film having both electrical conductivity and excellent corrosion resistance on the surface. Therefore, it is particularly useful as a casing for an electric machine by using a product made of magnesium or a magnesium alloy excellent in electromagnetic shielding properties or grounding properties. Moreover, the product does not contain heavy metals and is also suitable for recycling. Further, since the anodizing treatment is carried out without using an electrolyte solution of heavy metal ions or fluorine ions, it is possible to provide a production method which is excellent from the viewpoint of environmental protection. (5) Brief description of the drawings: Fig. 1 is a photograph of the surface of the anodic oxide film obtained in Example 1 observed by a scanning electron microscope. Figure 2 is a photograph of the surface of the test piece of Example 1 after the warm water immersion test. Figure 3 is a photograph of the surface of the test piece of Example 1 after the salt spray test. Fig. 4 is a photograph of the surface of the test piece of Comparative Example 3 after the warm water immersion test. Fig. 5 is a photograph of the surface of the test piece of Comparative Example 3 after the salt spray test. - 26 -

Claims (1)

1266814 No. 092 1 06493 "Magnesium or magnesium alloy products with conductive anodized film on the surface and its preparation method" (Amended on June 20, 2006) Pick up, apply for patent vanity 1 · A kind of magnesium or magnesium A product made of an alloy containing a conductive anodized film having a surface resistance 値 of 1 〇〇 Ω or less measured between two terminals each having a distance of 10 mm from each other. 2. An article made of magnesium or a magnesium alloy according to claim 1, wherein the anodized film contains 35 to 65 wt% of magnesium and 25 to 45 wt% of oxygen. 3. The article made of magnesium or a magnesium alloy according to claim 1, wherein the anodized film contains 4 to 15% by weight of a phosphorus element. 4. An article made of magnesium or a magnesium alloy according to claim 1, wherein the anodized film contains 5 to 20% by weight of an aluminum element. 5. A product made of magnesium or a magnesium alloy according to item 1 of the patent application, wherein the film thickness of the anodized film is 〇 丨〇 丨〇 μ m. 6. A product made of magnesium or a magnesium alloy according to item 1 of the patent application, wherein an anodized film covers all of the surface of the magnesium or magnesium alloy, and resin coating is applied only to a part of the surface of the anodized film. The anodized film is exposed to expose the remaining portion. 7. A product made of magnesium or a magnesium alloy according to item 6 of the patent application, which is a product of an electrical machine frame in which the resin is coated on the outside of the frame and is coated with a resin coated 1266814 on the outside of the frame. A method for producing a product according to claim 1, wherein the surface is formed by immersing the magnesium or magnesium alloy in an electrolyte containing 0.1 mol/L of phosphate and having a pH of 8 to 14. Anodized. 9. The manufacturing method of claim 8, wherein the electrolyte contains 0.2 to 5 mol/L of ammonia or ammonium ions. The manufacturing method of claim 8, wherein the magnesium or magnesium alloy is immersed in an acidic aqueous solution in advance, and then immersed in an electrolytic solution to perform anodizing treatment. The manufacturing method of claim 8, wherein after the anodizing treatment, only the resin coating film is applied once on the surface of the anodized film, and the coating film is dried by heating at a temperature of 40 to 120 °C. .
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JP5517024B2 (en) 2009-02-02 2014-06-11 独立行政法人物質・材料研究機構 Mg-based structural member
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