WO2019098378A1 - Élément métallique en magnésium ou en aluminium doté d'un revêtement d'oxyde noir, et son procédé de fabrication - Google Patents

Élément métallique en magnésium ou en aluminium doté d'un revêtement d'oxyde noir, et son procédé de fabrication Download PDF

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WO2019098378A1
WO2019098378A1 PCT/JP2018/042730 JP2018042730W WO2019098378A1 WO 2019098378 A1 WO2019098378 A1 WO 2019098378A1 JP 2018042730 W JP2018042730 W JP 2018042730W WO 2019098378 A1 WO2019098378 A1 WO 2019098378A1
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Prior art keywords
magnesium
aluminum metal
metal member
black
aluminum
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PCT/JP2018/042730
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English (en)
Japanese (ja)
Inventor
紀明 佐々木
修平 三浦
孝 眞 金
星 衡 李
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株式会社東亜電化
ジオネーション株式会社
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Application filed by 株式会社東亜電化, ジオネーション株式会社 filed Critical 株式会社東亜電化
Priority to JP2019524301A priority Critical patent/JPWO2019098378A1/ja
Priority to KR1020207016990A priority patent/KR20200089698A/ko
Priority to CN201880073945.2A priority patent/CN111344439A/zh
Publication of WO2019098378A1 publication Critical patent/WO2019098378A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/14—Producing integrally coloured layers

Definitions

  • the present invention relates to a magnesium metal member or aluminum metal member (hereinafter referred to as magnesium or aluminum metal member) having a black oxide film, and more particularly to a magnesium or aluminum metal member having a black color without painting and a method of manufacturing the same.
  • magnesium or aluminum metal is a concept including magnesium metal, magnesium alloy, aluminum metal and aluminum alloy.
  • Magnesium, aluminum, magnesium alloys and aluminum alloys are widely used in communication devices and various parts because of their light weight and good processability.
  • magnesium and aluminum are active metals, they are corroded and can not be used as they are, so they are generally used by painting.
  • chemical conversion treatment is performed as the paint base treatment.
  • a magnesium or aluminum member is usually coated with a black color.
  • the black coating film has a problem in corrosion resistance and the like, and also has a problem in adhesion.
  • magnesium or a magnesium alloy is immersed as an anode in an electrolyte, and a cathode is provided in the electrolyte.
  • a method of anodic oxidation of magnesium or a magnesium alloy comprising or consisting of passing a current through an electrolyte, wherein the electrolyte has a pH greater than 7 and in water (1) ammonia or amines or these
  • a method of anodizing magnesium or magnesium alloys comprising or consisting of a mixture of two and (2) phosphoric acid or water soluble phosphate is disclosed.
  • JP 11-502567 A in a method for anodizing a material based on magnesium, preparing an electrolyte containing ammonia, a cathode in the solution, and Providing a magnesium based material as an anode in the solution, and passing a current between the cathode and the anode through the solution to form a coating on the material.
  • the method for anodizing magnesium based materials characterized in that the ammonia is supplied in the solution in the range of 1% to 33% w / v, and the solution is in the range of 0.01 to 0.2 mole.
  • a method of anodizing magnesium is described, which comprises the phosphate compound prepared in
  • JP-A-2004-538375 (Patent Document 3) describes a method for anodically oxidizing a magnesium material, wherein the magnesium material is added in the presence of phosphate in an aqueous electrolyte solution having a pH of more than 7.
  • a method is disclosed comprising the steps of anodizing while immersion in water, and wherein the electrolyte solution further comprises a sequestering agent.
  • the anodized film formed on the conventional magnesium or aluminum metal has a metallic color, and in order to make it black in order to suppress light reflection, it is black after forming the anodized film.
  • Dyeing, for example, painting needs to be performed, and thus the process becomes complicated, and the adhesion between the obtained black paint film and the anodized film becomes a problem,
  • the present invention has been made in view of the above-mentioned conventional problems, and a uniform black anodic oxide film is provided even on a complex shape magnesium or aluminum metal substrate, and it has excellent hardness and resistance. It is an object of the present invention to provide a magnesium or aluminum metal member provided with a black oxide film, which is also excellent in corrosiveness, and a method of manufacturing the same.
  • a thick and black anodized film is formed by the inclusion of a specific component in the anodized film of a magnesium alloy member or an aluminum alloy member.
  • the magnesium or aluminum metal member of the present invention is a magnesium or aluminum metal member in which an anodized film is formed on a magnesium or aluminum metal base composed of magnesium or aluminum metal, and the anodic oxide film is hydroxylated respectively.
  • the anodized film is made of R.
  • G. B is a magnesium or aluminum metal member with a black oxide film, characterized in that it has a black color such that 18 ⁇ R ⁇ 154, 20 ⁇ G ⁇ 135, 20 ⁇ B ⁇ 118.
  • the anodized film further contains phosphorus, and the magnesium or aluminum metal member provided with the black oxide film.
  • the film thickness of the anodized film is 1 to 100 ⁇ m, magnesium or aluminum metal provided with a black oxide film It is a member.
  • the total amount (% by mass) of vanadium and / or iron in the anodized films is 1 to 70%. It is a magnesium or aluminum metal member provided with a black oxide film.
  • a method of producing a magnesium or aluminum metal member provided with the black oxide film of the present invention is The electrolysis is carried out at a current density of 5 A / dm 2 to 60 A / dm 2 using a magnesium or aluminum metal substrate as the anode and an alkaline solution or neutral solution containing iron and / or vanadium at 20 to 70 ° C.
  • Anodic oxidation to form an anodic oxide film containing vanadium and / or iron in addition to magnesium hydroxide and magnesium oxide or aluminum hydroxide and aluminum oxide with a film thickness of 1 to 100 ⁇ m respectively on a magnesium or aluminum metal substrate Process A process for producing a magnesium or aluminum metal member having a black oxide film, comprising a water washing step of washing a magnesium or aluminum metal member having the anodized film formed thereon with water at a temperature of 5 ° C. or more and less than 60 ° C. It is a method.
  • the alkaline solution or the neutral solution further contains phosphorus, wherein the magnesium or aluminum metal member provided with a black oxide film is produced. It is a method.
  • the magnesium metal base is a base made of magnesium metal or magnesium alloy, and means a member / part in a state before the anodic oxidation film is formed
  • the magnesium metal member is a magnesium metal base It means a member / part in which an anodized film is formed on the material.
  • an aluminum metal base material is a base material which consists of aluminum metal and aluminum alloy, Comprising:
  • the member * components in the state before an anodic oxidation film is formed means an aluminum metal base material as an aluminum metal base material. It means a member / part on which an anodized film is formed.
  • the magnesium or aluminum metal member provided with the black oxide film of the present invention can uniformly form a black anodic oxide film on a complex shaped magnesium or aluminum metal substrate, so that no special coating is applied. It is possible to make a black or black magnesium or aluminum metal member. Therefore, as in the prior art, it is not necessary to further form a coated film to be black, so the problem of adhesion of the black coating is eliminated. Further, the magnesium or aluminum metal member provided with the black oxide film of the present invention does not have to be cleaned in advance of the surface of the magnesium or aluminum metal substrate forming the anodized film, and some impurities may be adhered or present. It is possible to provide a black anodic oxide film as it is. As described above, since the uniform black oxide film is formed on the complex shaped magnesium or aluminum metal substrate, the reflection of light is suppressed, and it becomes possible to use it effectively for optical applications.
  • the method of manufacturing a magnesium or aluminum metal member provided with the black oxide film according to the present invention can form a black uniform oxide film even if it has a complicated shape. Therefore, it is not necessary to provide a coating process for blackening again after providing the anodized film in order to obtain a black magnesium or aluminum metal member (part) as in the prior art, and the above-mentioned A magnesium or aluminum metal component with a black oxide coating can be produced. Furthermore, it is possible to form a thick black oxide film without using the surface of magnesium metal or aluminum metal base which forms the anodic oxide film, etc.
  • the magnesium metal member provided with the black oxide film of an example of this invention is a photograph figure of each magnesium metal member obtained by changing current density.
  • it is a photograph figure of each magnesium metal member obtained by changing the temperature of an anodic oxidation liquid.
  • it is a photograph figure of each aluminum metal member obtained by changing current density.
  • it is a photograph figure of each aluminum metal member obtained by changing the temperature of an anodic oxidation liquid.
  • it is a photograph figure of each aluminum metal member obtained by changing time of anodic oxidation.
  • the magnesium or aluminum metal member provided with the black oxide film of the present invention is a magnesium or aluminum metal member in which an anodized film is formed on a magnesium or aluminum metal substrate made of magnesium or aluminum metal, In addition to magnesium hydroxide and magnesium oxide or aluminum hydroxide and aluminum oxide, respectively, vanadium and / or iron are contained, and the anodized film is made of R.
  • G. B is a magnesium or aluminum metal member with a black oxide film, characterized in that it has a black color such that 18 ⁇ R ⁇ 154, 20 ⁇ G ⁇ 135, 20 ⁇ B ⁇ 118.
  • the magnesium or aluminum metal member of the present invention is obtained by forming a black anodized film formed by anodization on a magnesium or aluminum metal substrate.
  • the anodized film preferably has a thickness of 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and a thin black film or a thick black film is formed.
  • a black anodized film having better hardness and more excellent corrosion resistance, rather than a painted black paint film is formed on a magnesium or aluminum metal member. It can be equipped.
  • the film thickness is a magnesium or aluminum metal member on which a black oxide film is formed using FIB (Focused Ion Beam product number FB-2100; manufactured by Hitachi High-Technologies Corporation)
  • FIB Fluorine-Beam product number FB-2100; manufactured by Hitachi High-Technologies Corporation
  • TEM Transmission Electron Microscope: Transmission Electron Microscope Product No. JEM-2010FEF: manufactured by Nippon Denshi Co., Ltd.
  • the anodic oxide film on the magnesium or aluminum metal member can be made into a thick film thickness.
  • the film resistance is increased, so that the film is not formed further in the thickness direction, and when the voltage is increased to increase the film thickness, the film resistance is high.
  • the black anodic oxide film of the present invention can have a thickness of 1 to 100 ⁇ m without cracking or the like. Further, even if the shape of the magnesium or aluminum metal member is a complicated shape, it has a uniform film thickness without cracking or the like.
  • the anodized film formed on the magnesium or aluminum metal substrate provided with the anodic oxide film of the present invention contains vanadium and / or iron in addition to magnesium hydroxide and magnesium oxide or aluminum hydroxide and aluminum oxide Be
  • vanadium and / or iron in addition to magnesium hydroxide and magnesium oxide or aluminum hydroxide and aluminum oxide Be
  • the degree of blackness of the anodized film of the magnesium or aluminum metal member is measured by using R, G, B on the surface of the anodized film, for example, using a color difference meter (model number NF 555, manufactured by Nippon Denshoku Kogyo Co., Ltd.) It is in the range of 18 ⁇ R ⁇ 154, 20 ⁇ G ⁇ 135, 20 ⁇ B ⁇ 118, preferably 50 ⁇ R ⁇ 75, 50 ⁇ G ⁇ 70, 50 ⁇ B ⁇ 65.
  • a black film having such a range of R, G, and B for example, it becomes difficult to reflect light, and it becomes possible to effectively utilize it for optical applications.
  • vanadium and / or iron of the anodized film is obtained by measuring atomic components of the surface of the anodized film by EDS analysis (energy dispersive X-ray spectroscopy: model number JSM-5600, manufactured by JEOL Ltd.), for example
  • the total content of vanadium and / or iron in the anodized film is 1 to 70% by mass, and more preferably 15 to 40%, whereby the anodized film exhibits a black color.
  • magnesium hydroxide and magnesium oxide, or aluminum hydroxide and aluminum oxide are further contained in the anodic oxide film containing vanadium and / or iron. More preferably, phosphorus and the like are also included.
  • the inclusion of phosphorus in the anodized film desirably improves the corrosion resistance of the anodized film, and the content of phosphorus in the anodized film is desirably 10 to 30%, preferably 10 to 20% by mass. It is preferable at the point which improves the said corrosion resistance.
  • the shape of the surface of the anodized film is preferably a concavo-convex shape, more preferably a concavo-convex shape of 5 to 100 nm.
  • the surface unevenness being in the above range, it is a dense film, and the corrosion resistance becomes better.
  • the uneven shape in the size of the above range even if it becomes a thick film, it is possible to maintain stronger film performance without generating a crack in the film.
  • the magnesium or aluminum metal member provided with the black anodized film of the present invention has a Vickers hardness of 300 to 600 in the surface of the anodized film, and is excellent in wear resistance and corrosion resistance. It is excellent.
  • a method of producing a magnesium or aluminum metal member provided with a black anodic oxide film according to the present invention A method of producing a magnesium or aluminum metal member provided with a black anodic oxide film according to the present invention, The magnesium or aluminum metal substrate is used as an anode, and electrolysis is performed at a current density of 5 A / dm 2 to 60 A / dm 2 using an alkaline solution or neutral solution containing iron and / or vanadium at 20 to 70 ° C.
  • Anodizing step of forming an anodized film containing vanadium and / or iron in addition to the coating) The method further comprises a water washing step of washing the magnesium or aluminum metal member having the anodized film formed thereon with water at a temperature of 5 ° C. or more and less than 60 ° C.
  • an anodic oxidation method in which electrolysis is performed in an alkaline solution or neutral solution containing vanadium and / or iron in a solution, using a magnesium or aluminum metal substrate as an anode and an insoluble electrode as a cathode. It can apply.
  • the electrolytic method for example, the surface of the magnesium or aluminum metal substrate is anodized by electrolytic methods such as cyclic method, constant current method, constant potential method, pulse constant potential method and pulse constant current method, and vanadium and Alternatively, there is a method of forming an anodized film containing iron.
  • cathode can be used as long as it does not react with an alkaline solution or has extremely low conductivity.
  • insoluble conductor plates such as platinum, stainless steel, carbon and the like can be used.
  • the said alkaline solution or neutral solution is not specifically limited, For example, a sodium hydroxide, potassium hydroxide, an ammonium solution can be illustrated, These can be used 1 type or in mixture of 2 or more types.
  • potassium hydroxide is preferable from the viewpoint of the coating appearance.
  • the alkaline solution or neutral solution is used at a temperature of 20 to 70 ° C., preferably 30 to 60 ° C., and the anodic oxidation step is carried out at this temperature to form a dense anodic oxide film having extremely fine pores. can do.
  • the temperature is less than 20 ° C., the unevenness of the anodized film to be formed exceeds 100 nm, so the corrosion resistance of the film is poor, and if the temperature exceeds 70 ° C., the anodic oxide film dissolves violently. It is not desirable because a certain thickness of the coating can be secured.
  • vanadium and / or iron to be contained in the anodized film is blended.
  • the compounding amount thereof makes it possible to obtain the anodized film of the present invention by setting vanadium to 0.03 to 0.2 mol / L and iron to 0.0002 to 0.005 mol / L.
  • Vanadium contained in an alkaline solution or a neutral solution is not particularly limited as long as it dissolves in a solvent as an electrolyte salt, exhibits conductivity, and has stability.
  • vanadium pentoxide ammonium metavanadate, oxytrisodium Vanadium chloride, sodium metavanadate, potassium vanadate, sodium vanadate, vanadium tetrachloride, vanadium oxysulfate, vanadium oxydichloride, vanadium oxide, vanadium trichloride, vanadium oxide, hexasodium vanadium trioxide, etc.
  • electrolyte salts can be blended in an alkaline solution or a neutral solution to form an electrolyte.
  • iron contained in an alkaline solution or a neutral solution is not particularly limited as long as it dissolves in a solvent as an electrolyte salt, exhibits conductivity and has stability, for example, iron chloride, ammonium iron citrate, Examples include iron lactate, iron sulfate, iron gluconate, potassium hexacyanoferrate, monosodium ethylenediaminetetraacetate, iron ammonium oxalate, etc., and these electrolyte salts are mixed in an alkaline solution or neutral solution. Can be used as an electrolyte.
  • phosphorus is contained in the alkaline solution or neutral solution.
  • the phosphorus contained in the alkaline solution or neutral solution is, for example, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate And the like, and it is also possible to blend these electrolyte salts in an alkaline solution or a neutral solution.
  • the blending amount thereof is preferably 0.002 to 0.07 mol / L of phosphorus.
  • electrolytes can be contained in the alkaline solution or neutral solution, and the electrolyte salt is particularly limited as long as it can be dissolved in a solvent to exhibit conductivity and have stability.
  • the electrolyte salt is particularly limited as long as it can be dissolved in a solvent to exhibit conductivity and have stability.
  • NaOH, Na 2 CO 3 , Na 2 SO 4 , K 2 SO 3 , Na 2 SO 3 , K 2 SO 3 , NaNO 2 , KNO 2 , NaNO 3 , NaClO 4 , CH 3 COONa, Na 2 B 2 O 7 , NaH 2 PO 2 , (NaPO 3 ) 6 , Na 2 MoO 4 , Na 3 SiO 3 , Na 2 HPO 3 and the like can be suitably used.
  • the concentration of these is preferably in the range of 0.001 to 10 moles, more preferably 0.01 to 5 moles, in terms of effectively utilizing vanadium and iron.
  • the two solvents of the electrolytic solution are preferably those which dissolve the electrolyte, for example, water, methanol, ethanol, carbitol, cellosolve, dimethylformamide, methylpyrrolidone, acrylonitrile, ethylene carbonite, isopropyl alcohol, acetone, toluene, ethyl cellosolve, Dimethylformaldehyde, tetrahydrofuran, methyl ethyl ketone, benzene, ethyl acetate, etc. can be used.
  • water, methanol, ethanol, carbitol, cellosolve dimethylformamide, methylpyrrolidone, acrylonitrile, ethylene carbonite, isopropyl alcohol, acetone, toluene, ethyl cellosolve, Dimethylformaldehyde, tetrahydrofuran, methyl ethyl ketone, benzene, ethy
  • the temperature of the electrolyte can not be uniquely determined because it is related to the freezing point and the boiling point of the solvent, but for example, it is 20 to 70 ° C., preferably 30 to 60 ° C. for an aqueous solution. By setting the temperature of the electrolytic solution to such a range, it is possible to effectively form an anodic oxide film.
  • the current density of electrolysis is set to 5 A / dm 2 to 60 A / dm 2 , preferably 5 A / dm 2 to 20 A / dm 2 , and the film thickness is 1 to 100 ⁇ m.
  • Anodized film is formed.
  • the current density indicates a value obtained by dividing the current value set by the power supply (product number HKD-8200F; manufactured by Sansha Electric Mfg. Co., Ltd.) by the surface area of the magnesium metal member.
  • potassium hydroxide is added to the solution.
  • diammonium hydrogen phosphate 1-30 g / L
  • ammonium metavanadate 1-20 g / L
  • ammonium citrate 1 to 20 g / L
  • the current density is 5 A / dm.
  • a black anodic oxide film can be formed by performing anodic electrolysis for 60 seconds to 15 minutes at 2 to 60 A / dm 2 and at a temperature of 20 to 70 ° C.
  • the anodized film formed in this manner has R, G, and B in the above range, and has a concavo-convex shape having fine pores.
  • the magnesium or aluminum metal member having the black anodic oxide film formed thereon is washed with water at a temperature of 5 ° C. or more and less than 60 ° C., preferably 10 to 50 ° C.
  • the alkaline solution or neutral solution deposited on the anodized film is removed.
  • the temperature is less than 5 ° C., the alkaline solution and the like attached to the anodized film are not sufficiently removed, and if the temperature is 60 ° C. or more, sufficient strength can not be obtained and the temperature is lowered.
  • a film having a uniform thickness of 1 to 100 ⁇ m can be provided even if the shape of the magnesium or aluminum metal substrate is a complicated shape.
  • the film can be black in which R, G, B of the anodized film is in the above-mentioned range of R, G, B, it is difficult to reflect light, and it can be usefully used particularly for optical parts.
  • the hardness is high and the corrosion resistance is also excellent.
  • the invention is illustrated by the following examples, comparative examples and test examples. However, in the Example and the comparative example, it implemented using the following metal test boards, chemicals, etc.
  • Magnesium metal base material AZ91D
  • Aluminum metal base material ADC12 Carbon plate material: manufactured by Toyo Carbon Co., Ltd. Potassium hydroxide (KOH): manufactured by Wako Pure Chemical Industries, Ltd.
  • KOH Potassium hydroxide
  • Ammonium metavanadate (NH 4 VO 3 ) manufactured by Wako Pure Chemical Industries, Ltd.
  • Iron citrate ammonium manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 1 The magnesium metal substrate having the shape shown in FIG. 1 is immersed in an electrolytic solution having the component composition shown in Table 1 below, and constant current electrolysis is performed using the anodic oxidation conditions shown in Table 2 to carry out anodic oxidation Carried out.
  • the magnesium metal substrate having the component composition shown in Table 1 was heated in the electrolytic solution heated to a temperature of about 50 ° C. without particularly pretreating the magnesium metal substrate having the shape of FIG.
  • the current density is (1) 5 A / dm 2 , (2) 10 A / dm 2 , (3) 15 A / dm 2 , (4) 20 A / dm 2
  • Anodic electrolysis was performed for 600 seconds to form an anodized film on the magnesium metal substrate, followed by washing with water at 25 ° C. and drying.
  • the resulting magnesium metal members having an anodized film formed thereon are shown in FIGS. 1 (1) to 1 (4). All were visually black.
  • the white places in the figure are places where the surface was coated with white magic after anodic oxidation in order to attach sample numbers.
  • the average thickness of the film thickness of the obtained anodic oxide film is (1) 4 ⁇ m, (2) 8.8 ⁇ m, (3) 15.8 ⁇ m, and (4) 36.8 ⁇ m (measured by transmission electron microscope).
  • the current density indicates a value obtained by dividing the current value set by the power supply (product number HKD-8200F; manufactured by Sansha Electric Mfg. Co., Ltd.) by the surface area of the magnesium metal member.
  • FIB Flucused Ion Beam Product No. FB-2100; manufactured by Hitachi High-Technologies Corporation
  • TEM transmission electron microscope: Transmission Electron Microscope Product No. JEM-2010 FEF: The surface and the cross section of the magnesium metal member are observed using an electron oxide film upper end formed on the surface of the magnesium metal member and a magnesium metal base material. Indicates the measured value of the distance between boundaries
  • the total content (mass%) of vanadium and iron in the anodized film obtained is (1) 14.0%, (2) 22.8%, (3) 21.7% , (4) 23.8%.
  • R, G, B of the surface of each of the obtained magnesium metal members were measured, for example, in the case of Example 1 (2), R was 64, G was 63, and B was 62. In the other examples, the measured values were all in the ranges of 18 ⁇ R ⁇ 154, 20 ⁇ G ⁇ 135, 20 ⁇ B ⁇ 118. In addition, the measurement of R, G, B was measured using a color difference meter (model number NF 555, manufactured by Nippon Denshoku Kogyo Co., Ltd.). On the other hand, the magnesium metal base (AZ91D) itself exhibited a silver color with R being 460, G being 427, and B being 362.
  • Example 2 In the first embodiment, and 10A / dm 2, the temperature of the anodizing electrolyte (1) 20 °C, (2 ) 30 °C, (3) 40 °C, (4) 50 °C, during (5) 60 ° C.
  • the experiment was carried out in the same manner as in Example 1 except that the conditions were changed.
  • the resulting magnesium metal members are shown in FIGS. 2 (1) to 2 (5). All were visually black.
  • the thickness of the obtained anodic oxide film was measured in the same manner as in Example 1 above. The average of each film thickness is (1) 19.5 ⁇ m, (2) 18.2 ⁇ m, (3) 17.1 ⁇ m, (4) 14.2 ⁇ m, (5) 9.5 ⁇ m (measured by transmission electron microscope) Met.
  • the total content (mass%) of vanadium and iron in the anodized film obtained is (1) 26.1%, (2) 24.2%, (3) 23.0% (4) 24.8% and (5) 15.4%. Furthermore, when R, G, B of each magnesium metal member obtained were measured in the same manner as in Example 1, all were in the range of 18 ⁇ R ⁇ 154, 20 ⁇ G ⁇ 135, 20 ⁇ B ⁇ 118. The
  • Example 3 The shape of the magnesium metal substrate (AZ91D) is as shown in FIG. 3, the current density is 10 A / dm 2 , and the anodic electrolysis time is (1) 3 minutes, (2) 5 minutes, (3) 10 minutes ((3) 4) It carried out like the said Example 1 except having made it change into 15 minutes.
  • the resulting magnesium metal members are shown in FIGS. 3 (1) to 3 (4). All were visually black.
  • the thickness of the obtained anodic oxide film was measured in the same manner as in Example 1 above. The average thickness of each film was (1) 4 ⁇ m, (2) 5 ⁇ m, (3) 8.8 ⁇ m, and (4) 12 ⁇ m (measured by a transmission electron microscope).
  • the total content (mass%) of vanadium and iron in the anodized film obtained is (1) 13.7%, (2) 17.1%, (3) 24.9% , (4) was 27.4%. Furthermore, when R, G and B of each magnesium metal member obtained were measured in the same manner as in Example 1, all in the range of 18 ⁇ R ⁇ 154, 20 ⁇ G ⁇ 135, 20 ⁇ B ⁇ 118 were obtained. A black magnesium metal member was obtained.
  • Example 4 The aluminum metal base having the shape shown in FIG. 6 is immersed in an electrolytic solution having the component composition shown in Table 1 above, and constant current electrolysis is carried out using the anodic oxidation conditions shown in Table 2 above to conduct anodic oxidation. Carried out.
  • the aluminum metal substrate in the shape shown in FIG. 6 is not particularly pretreated in the electrolytic solution heated to a temperature of about 50 ° C. having the component composition shown in Table 1.
  • the current density is (1) 10 A / dm 2 , (2) 15 A / dm 2 , (3) 20 A / dm 2 , (4) 25 A / dm 2
  • Anodic electrolysis was performed for 600 seconds to form an anodized film on the aluminum metal base, followed by washing with water at 25 ° C. and drying.
  • the resulting aluminum metal members having an anodized film formed thereon are shown in FIGS. 6 (1) to 6 (4). All were visually black.
  • the average thickness of the obtained anodic oxide film is (1) 6.7 ⁇ m, (2) 15.6 ⁇ m, (3) 23.9 ⁇ m, (4) 31.5 ⁇ m (measured by transmission electron microscope). Met.
  • the current density indicates a value obtained by dividing the current value set by the power supply (product number HKD-8200F; manufactured by Sansha Electric Mfg. Co., Ltd.) by the surface area of the aluminum metal member. As described above, using FIB (Focused Ion Beam Product No.
  • the total content (mass%) of vanadium and iron in the anodized film obtained is (1) 26.3%, (2) 31.0%, (3) 33.5. %, (4) was 33.1%.
  • R, G, B of the surface of each obtained aluminum metal member were measured, for example, R was 67, G was 66, and B was 67 in Example 4 (2).
  • the measured values were all in the ranges of 18 ⁇ R ⁇ 154, 20 ⁇ G ⁇ 135, 20 ⁇ B ⁇ 118.
  • the measurement of R, G, B was measured using a color difference meter (model number NF 555, manufactured by Nippon Denshoku Kogyo Co., Ltd.).
  • the aluminum metal base (ADC 12) itself exhibited silver color with R: 161, G: 162, B: 163.
  • Example 5 In the above Example 4, the temperature of the anodic oxidation electrolyte is 15A / dm 2, and the temperature of the anodizing electrolyte is (1) 20 ° C, (2) 30 ° C, (3) 40 ° C, (4) 50 ° C, (5) 60 ° C
  • Example 4 was carried out in the same manner as in Example 4 except that the conditions were changed. The resulting aluminum metal members are shown in FIGS. 7 (1) to (5). All were visually black. The thickness of the obtained anodized film was measured in the same manner as in Example 4 above.
  • each film thickness is (1) 31.8 ⁇ m, (2) 23.4 ⁇ m, (3) 21.7 ⁇ m, (4) 17.5 ⁇ m, (5) 24.5 ⁇ m (measured by transmission electron microscope) Met.
  • the white places in the figure are places where the surface was coated with white magic after anodic oxidation in order to attach sample numbers.
  • the total content (mass%) of vanadium and iron in the anodized film obtained is (1) 31.3%, (2) 31.5%, and (3) 29.9%. (4) 31.9%, (5) 25.1%. Furthermore, when R, G, B of each aluminum metal member obtained were measured in the same manner as in Example 4, all were in the range of 18 ⁇ R ⁇ 154, 20 ⁇ G ⁇ 135, 20 ⁇ B ⁇ 118. The
  • Example 6 The shape of the aluminum base (ADC 12) is as shown in FIG. 8, the current density is 15 A / dm 2 , and the anodic electrolysis time is (1) 3 minutes, (2) 5 minutes, (3) 10 minutes, (4 2.) The procedure of Example 4 was repeated except that the time was changed to 15 minutes. The resulting aluminum metal members are shown in FIGS. 8 (1) to (4). All were visually black. The thickness of the obtained anodized film was measured in the same manner as in Example 4 above. The average thickness of each film was (1) 5.4 ⁇ m, (2) 11.8 ⁇ m, (3) 16.2 ⁇ m, and (4) 26.4 ⁇ m (measured with a transmission electron microscope).
  • EDS analysis energy dispersive X-ray spectrometry: model number JSM-5600 was performed in the same manner as in Example 4 for the atomic component of the anodic oxide film surface of the aluminum metal member of Example 6 (1) to (4). It measured by Nippon Denshi Co., Ltd. product). The results are shown in Table 8 below.
  • the total content (mass%) of vanadium and iron in the anodized film obtained is (1) 19.2%, (2) 29.6%, (3) 31.9% , (4) 33.9%. Furthermore, when R, G, B of each aluminum metal member obtained were measured in the same manner as in Example 4, all were in the range of 18 ⁇ R ⁇ 154, 20 ⁇ G ⁇ 135, 20 ⁇ B ⁇ 118.
  • Example 1 State of Surface of Anodized Film
  • the surfaces of the magnesium metal base material (AZ91D) itself are shown in (4) 500 times, (5) 1000 times, (6) 3000 times in FIG. . It can be seen from FIG. 4 that rough asperities are formed on the surface of the magnesium metal member of Example 1. The surface roughness of the magnesium metal member of the present invention is increased, so that the light absorbability is increased and black can be exhibited.
  • Example 4 Anodized film surface of an aluminum gold storage member of 15 A / dm 2 was subjected to (1) 500 times, (2) 1000 times using an electron microscope (model number JSM-5600, manufactured by JEOL Ltd.) (3) The electron micrograph was taken at 3000 ⁇ . Such photographs are shown in FIGS. 9 (1) to (3). For comparison, the surfaces of the aluminum metal base (ADC 12) itself are taken at (4) 500 times, (5) 1000 times, (6) 3000 times as shown in FIGS. 9 (4) to (6). . It can be seen from FIG. 9 that rough asperities are formed on the surface of the aluminum metal member of Example 4. Since the aluminum metal member of the present invention has a large surface roughness, it has high light absorption and can exhibit black.
  • Test Example 2 Hardness The Vickers hardness of each of the magnesium metal members and the magnesium metal base (AZ91D) in Examples 2 (1) to (5) was measured as follows. Specifically, the hardness was measured using an ultra-minute indentation hardness tester (Model: ENT-1100b, manufactured by Elionix). The results are shown in Table 9.
  • the Vickers hardness of the aluminum metal members and the aluminum metal base (ADC 12) of Examples 4 (1) to (4) was measured as follows. Specifically, the hardness was measured using an ultra-minute indentation hardness tester (Model: ENT-1100b, manufactured by Elionix). The results are shown in Table 10.
  • Example 3 Corrosion Resistance
  • a magnesium metal member having an anodized film was obtained in the same manner as (2) of Example 1 above using a magnesium metal base having the shape shown in FIG.
  • this magnesium metal member was subjected to a salt spray test (JIS Z 2371) to verify the state after the salt water was sprayed continuously for the following times (1) to (8).
  • the state after 168 hours and (8) 192 hours is shown in FIGS. 5 (1) to (8). It can be seen from FIGS. 5 (1) to 5 (8) that the obtained anodized film has excellent corrosion resistance.
  • An aluminum metal member having an anodized film was obtained in the same manner as (2) in Example 4 above using the aluminum metal base having the shape shown in FIG. Subsequently, the aluminum metal member was subjected to a salt spray test (JIS Z 2371) to verify the state after the salt water was sprayed continuously for the following time period (1) to (8). Specifically, (1) 24 hours later, (2) 48 hours later, (3) 72 hours later, (4) 96 hours later, (5) 12 hours later, (6) 144 hours later, (7) The states after 168 hours and (8) 192 hours are shown in FIGS. 10 (1) to (8). It can be seen from FIGS. 10 (1) to 10 (8) that the obtained anodic oxide film has excellent corrosion resistance.
  • the magnesium or aluminum metal member of the present invention can be effectively used for optical applications because the anodized film is black and light absorption is high, and particularly preferably used for external parts such as personal computers. Since it is possible, the hardness is also good, and the chemical resistance is excellent, it can be applied to various mechanical, electrical and electronic parts.

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Abstract

La présente invention concerne : un élément métallique en magnésium ou en aluminium dans lequel un revêtement d'oxyde noir ayant une bonne dureté et une excellente résistance à la corrosion obtenu par oxydation anodique est disposé, plutôt qu'un film de peinture noire appliqué, sur un substrat métallique en magnésium ou en aluminium ayant une forme complexe; et son procédé de fabrication. Dans l'élément métallique en magnésium ou en aluminium pourvu d'un revêtement d'oxyde noir, un revêtement d'oxyde anodique est formé sur un élément métallique de magnésium ou d'aluminium comprenant du magnésium ou de l'aluminium métallique, le revêtement d'oxyde anodique comprenant du vanadium et/ou du fer en plus de l'hydroxyde de magnésium et de l'oxyde de magnésium ou de l'hydroxyde d'aluminium et de l'oxyde d'aluminium, et le revêtement d'oxyde anodique ayant une couleur noire pour laquelle les valeurs RGB sont telles que 18 < R < 154, 20 < G < 135 et 20 < B < 118.
PCT/JP2018/042730 2017-11-17 2018-11-19 Élément métallique en magnésium ou en aluminium doté d'un revêtement d'oxyde noir, et son procédé de fabrication WO2019098378A1 (fr)

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JP2019524301A JPWO2019098378A1 (ja) 2017-11-17 2018-11-19 黒色酸化被膜を備えるマグネシウム又はアルミニウム金属部材及びその製造方法
KR1020207016990A KR20200089698A (ko) 2017-11-17 2018-11-19 흑색 산화 피막을 구비하는 마그네슘 또는 알루미늄 금속 부재 및 그의 제조 방법
CN201880073945.2A CN111344439A (zh) 2017-11-17 2018-11-19 具备黑色氧化覆膜的镁或铝金属部件及其制备方法

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CN111876811B (zh) * 2020-07-27 2022-02-25 上海交通大学 一种铝锂合金微弧氧化方法及其采用的电解液
CN111910238B (zh) * 2020-08-14 2022-05-31 常州大学 一种实现镁合金表面黑色化的电解液及黑色化的工艺方法
CN112663112B (zh) * 2020-12-02 2022-10-04 斯特凯新材料(上海)有限公司 一种电解液及镁合金复合氧化黑色陶瓷膜的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3832293A (en) * 1973-03-01 1974-08-27 D & M Technologies Process for forming a coating comprising a silicate on valve group metals
JPS5364630A (en) * 1976-11-22 1978-06-09 Kagaku Gijutsucho Mukizai Anode oxide film body of polychromic aluminium with fibered structure or aluminium alloy and its formation method
JPS53102843A (en) * 1977-02-11 1978-09-07 Pechiney Aluminium Electrolytic coloring method of aluminium that is not subject to anode oxidation and its alloy
JPS5524944A (en) * 1978-08-09 1980-02-22 Nippon Light Metal Co Ltd Surface treatment of aluminium alloy
JPS581094A (ja) * 1981-06-24 1983-01-06 Deitsupusoole Kk マグネシウム材表面に着色保護皮膜を形成する方法
JPS61194184A (ja) * 1985-02-22 1986-08-28 Kami Denshi Kogyo Kk アルミニウム又はアルミニウム合金に平滑な無電解メツキ皮膜を形成する方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5129328A (en) * 1974-08-29 1976-03-12 Sumitomo Chemical Co Aruminiumu mataha aruminiumugokin no hyomenniseiseisaseta yokyokusankahimaku no denkaichakushokuhoho
US4659440A (en) * 1985-10-24 1987-04-21 Rudolf Hradcovsky Method of coating articles of aluminum and an electrolytic bath therefor
US5066368A (en) * 1990-08-17 1991-11-19 Olin Corporation Process for producing black integrally colored anodized aluminum components
US5792335A (en) 1995-03-13 1998-08-11 Magnesium Technology Limited Anodization of magnesium and magnesium based alloys
EP1015661A4 (fr) 1997-03-24 2000-11-02 Magnesium Technology Ltd Anodisation du magnesium et d'alliages au magnesium
GB2395491B (en) 2001-08-14 2006-03-01 Magnesium Technology Ltd Magnesium anodisation system and methods
KR20100116901A (ko) * 2009-04-23 2010-11-02 안형진 알루미늄 양극산화피막의 흑색염색방법
DE102013110660A1 (de) * 2013-09-26 2015-03-26 AHC Oberflächentechnik GmbH Plasmachemisches Verfahren zur Herstellung schwarzer Oxidkeramikschichten und entsprechend beschichteter Gegenstand

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3832293A (en) * 1973-03-01 1974-08-27 D & M Technologies Process for forming a coating comprising a silicate on valve group metals
JPS5364630A (en) * 1976-11-22 1978-06-09 Kagaku Gijutsucho Mukizai Anode oxide film body of polychromic aluminium with fibered structure or aluminium alloy and its formation method
JPS53102843A (en) * 1977-02-11 1978-09-07 Pechiney Aluminium Electrolytic coloring method of aluminium that is not subject to anode oxidation and its alloy
JPS5524944A (en) * 1978-08-09 1980-02-22 Nippon Light Metal Co Ltd Surface treatment of aluminium alloy
JPS581094A (ja) * 1981-06-24 1983-01-06 Deitsupusoole Kk マグネシウム材表面に着色保護皮膜を形成する方法
JPS61194184A (ja) * 1985-02-22 1986-08-28 Kami Denshi Kogyo Kk アルミニウム又はアルミニウム合金に平滑な無電解メツキ皮膜を形成する方法

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