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WO2011021571A1 - Procédé pour base de traitement de surface de magnésium ou d'un alliage de celui-ci et nanostructures - Google Patents

Procédé pour base de traitement de surface de magnésium ou d'un alliage de celui-ci et nanostructures Download PDF

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Publication number
WO2011021571A1
WO2011021571A1 PCT/JP2010/063717 JP2010063717W WO2011021571A1 WO 2011021571 A1 WO2011021571 A1 WO 2011021571A1 JP 2010063717 W JP2010063717 W JP 2010063717W WO 2011021571 A1 WO2011021571 A1 WO 2011021571A1
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Prior art keywords
magnesium
alloy
nanostructure
grown
base material
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Ceased
Application number
PCT/JP2010/063717
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English (en)
Japanese (ja)
Inventor
貴裕 石崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
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National Institute of Advanced Industrial Science and Technology AIST
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Priority to JP2011527655A priority Critical patent/JP5557839B2/ja
Publication of WO2011021571A1 publication Critical patent/WO2011021571A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8

Definitions

  • the present invention relates to a surface treatment method of magnesium or an alloy base material thereof, magnesium hydroxide obtained by this method, magnesium-aluminum hydroxide nanostructure, magnesium grown on the surface thereof, or magnesium or It relates to the alloy base material.
  • the present invention also relates to a method for imparting a color based on the structural color to the surface of magnesium and its alloy by using this nanostructure.
  • Mg (OH) 2 structures having nanoscales are attracting attention as biomaterials, adsorbents of toxic pollutants in solution, and structures for forming superhydrophobic surfaces.
  • magnesium and its alloys are being studied for various applications due to their light weight, but with improved corrosion resistance, the design of the electronic component housing requires a design, so it gives a metallic color. Technology is required.
  • Non-Patent Documents 1 and 2 various measures for forming nanostructures such as magnesium hydroxide have been conventionally studied (for example, see Non-Patent Documents 1 and 2).
  • Patent Document 1 it has been proposed to form a corrosion-resistant film such as magnesium sulfide by physically wet-blasting to improve corrosion resistance, followed by high-temperature steam treatment at a relative humidity of 80% or more.
  • the surface structure, the crystal structure, and the like are changed by blasting or heat treatment, which causes the target function to deteriorate.
  • the present invention eliminates the conventional problems from the background as described above, and does not impair the functionality of magnesium nanostructures such as hydroxides, and magnesium as a base material is integrated with the alloy. It is an object of the present invention to provide a new technical means that enables formation of nanostructures by simple operation and enables formation of nanostructures.
  • the present invention is characterized by the following as the means.
  • Magnesium or its alloy as a base material is immersed in pure water in an airtight container, and then heated to grow magnesium nanostructures on the base material surface. is there.
  • a magnesium hydroxide is grown as a magnesium nanostructure on the surface of the substrate.
  • the magnesium alloy as the base material is an aluminum-containing magnesium alloy, and a magnesium aluminum hydroxide is grown as a magnesium nanostructure on the surface of the base material.
  • the pressure in the sealed container is in the range of 0.1 to 0.4 MPa, and the heating temperature is in the range of 100 to 130 ° C.
  • the surface structure color is changed or imparted by controlling the growth of the magnesium structure.
  • ⁇ 6> A magnesium hydroxide nanostructure characterized by being grown on the surface of magnesium or an alloy thereof as a substrate.
  • ⁇ 7> Provided is magnesium or an alloy thereof, wherein a magnesium hydroxide nanostructure is grown on the surface of magnesium or an alloy thereof as a base material.
  • ⁇ 8> A magnesium / aluminum hydroxide nanostructure characterized by being grown on the surface of an aluminum-containing magnesium alloy as a substrate.
  • ⁇ 9> The nanostructure according to ⁇ 8>, which is grown together with the nanostructure of magnesium hydroxide.
  • a magnesium alloy characterized in that a magnesium / aluminum hydroxide nanostructure is grown on the surface of an aluminum-containing magnesium alloy as a base material; and A ⁇ 11> magnesium hydroxide nanostructure is also grown, and a magnesium alloy is provided.
  • ⁇ 12> Provided is a water-repellent magnesium or alloy base material, characterized in that any one of magnesium and alloys thereof is coated with an organic monomolecular film having a hydrophobic functional group on the surface.
  • magnesium hydroxide Mg (OH) 2 , [Mg 1-x Al x (OH) 2 ] (CO 3 ) x / 2 ⁇ nH 2 O, etc. on magnesium or its alloy Enables direct growth of nanostructures. It was an aqueous solution process that did not use any chemicals and so on, and by controlling the size and size of the nanostructure, it was realized to impart a color based on the structural color to the substrate surface.
  • nanostructures can be formed on magnesium and magnesium alloys in an aqueous solution process that does not use any chemicals, so high temperature heat treatment for crystallization and immobilization on a substrate is not required.
  • magnesium and magnesium alloy introduced into the aqueous solution are used as raw materials for the structure to be produced, it is a low environmental load type process that does not use any unnecessary metal salt, surfactant or other chemicals.
  • the nano / micro structure is formed on magnesium and a magnesium alloy, the adhesion to the substrate is extremely high.
  • a particle base material, a complex shape base material, or the like can also be used.
  • Reaction time 0 hours
  • Reaction time 1 hour
  • Reaction time 3 hours
  • Reaction time 6 hours
  • Reaction time 9 hours.
  • Reaction time 6 hours.
  • magnesium or an alloy thereof is used as a base material.
  • the alloy mainly contains magnesium and contains at least 50 atomic%, and exhibits various characteristics and functions of the magnesium alloy. Good.
  • additive elements that may coexist for example, aluminum (Al), zinc (Zn), manganese (Mn) and the like are preferably considered.
  • examples of the alloy include AZ31, AZ91D, AM60B and the like, which are alloys with aluminum, but are not limited thereto.
  • Such a base material may have various shapes formed by various means.
  • the surface treatment of the present invention is preferably performed with pure water in a sealed container, for example, by immersing the base material in ultrapure water having a resistivity of 18.2 M ⁇ , and then heating in a heating furnace.
  • Mg 1-x Al x (OH) 2 (CO 3 ) x / 2 ⁇ nH 2 O
  • nano means that in the present invention, the term “nano” usually means a nanoscale size of less than 1 ⁇ m.
  • the press-fitting in the sealed container in which the substrate is immersed is preferably 1 MPa or less, for example, 0.1 to 0.4 MPa.
  • the heating temperature is in the range of 100 to 130 ° C., and the heating time is 3 to 12 hours.
  • the structural color of the base material can be variously changed and imparted.
  • the product of the present invention can be used as an automobile part, a housing for electronic devices, an adsorbent of a toxic pollutant in a solution, a super water-repellent surface structure, a part of a corrosion-resistant film, and the like.
  • polycrystalline Mg (OH) 2 and [Mg 1-x Al x (OH) 2 ] (CO 3 ) x / 2 ⁇ nH 2 O nanostructures are fabricated and the reaction time is controlled. By doing so, various colors were imparted to the substrate surface.
  • the coefficient x in the chemical formula showing magnesium / aluminum hydroxide is determined by the type and composition of the alloy.
  • the surface of the substrate on which the polycrystalline Mg (OH) 2 and [Mg 1-x Al x (OH) 2 ] (CO 3 ) x / 2 ⁇ nH 2 O nanostructures are formed is hydrophobic. By coating an organic monomolecular film having a functional functional group, super-water repellency was imparted to the surface of the substrate.
  • the coloring is uniform over the entire surface of the magnesium alloy, indicating the uniformity of the structure.
  • FIG. 1 shows an XRD pattern of Mg (OH) 2 and [Mg 1-x Al x (OH) 2 ] (CO 3 ) x / 2 ⁇ nH 2 O nanostructures formed on a magnesium alloy (FIG. 1).
  • the intensity of the 101 diffraction line of Mg (OH) 2 is very strong, indicating high orientation.
  • the crystallite size in the direction perpendicular to the (101) plane was estimated to be about 15.17 nm using the Scherrer equation from the half-width of the diffraction line.
  • the film thickness formed with Mg (OH) 2 and [Mg 1 -xAl x (OH) 2 ] (CO 3 ) x / 2 ⁇ nH 2 O nanostructures increased depending on the treatment time.
  • the film thicknesses when the processing time was 3, 6, and 12 hours were 400, 600, and 1800 nm, respectively (shown by arrows in FIGS. 3 (a), (b), and (c)).
  • FIG. 4 An appearance photograph of the surface of a magnesium alloy (AZ31) on which a polycrystalline Mg (OH) 2 nanostructure is formed is shown (FIG. 4).
  • the reaction time of 1 hour there was no metallic luster and a black gray color was exhibited (b).
  • the reaction time was 3 hours, a reddish yellow color was observed (c).
  • the reaction time was 4 or 6 hours, and a bluish green color was exhibited (d) and (e).
  • a reaction time of 9 hours green and red were mixed (f).
  • the Mg (OH) 2 nanostructure was composed of a Brucite type polycrystalline Mg (OH) 2 phase.
  • the formed structure was not oxide (MgO) but hydroxide (Mg (OH) 2 (FIG. 6).
  • the color of the surface of the magnesium alloy (AZ31) on which the polycrystalline Mg (OH) 2 nano-microstructure was formed varied depending on the angle at which the surface was observed. This change is due to the structural color.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention se rapporte à des nanostructures qui sont formées sur la surface du magnésium ou d'un alliage de magnésium, ce qui permet de donner une couleur attribuable aux nanostructures. Le magnésium ou un alliage de celui-ci utilisé comme base est plongé dans de l'eau douce dans un récipient fermé et, par la suite, chauffé pour développer l'hydroxyde de magnésium sous la forme de nanostructures de magnésium sur la surface de base.
PCT/JP2010/063717 2009-08-20 2010-08-12 Procédé pour base de traitement de surface de magnésium ou d'un alliage de celui-ci et nanostructures Ceased WO2011021571A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2011527655A JP5557839B2 (ja) 2009-08-20 2010-08-12 アルミニウム含有マグネシウム合金基材の表面処理方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009191376 2009-08-20
JP2009-191376 2009-08-20

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WO2011021571A1 true WO2011021571A1 (fr) 2011-02-24

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014125639A (ja) * 2012-12-25 2014-07-07 Shibaura Institute Of Technology 高耐食性マグネシウム系材料及びその製造方法、並びに、マグネシウム系材料の表面処理方法
JP5978376B1 (ja) * 2015-11-04 2016-08-24 Ｔｏｄａ株式会社 音響用マグネシウム振動板の製造方法および音響用マグネシウム振動板
JP2017503077A (ja) * 2013-12-26 2017-01-26 ポスコＰｏｓｃｏ 発色処理された基材およびこのための基材の発色処理方法
WO2018062360A1 (fr) * 2016-09-28 2018-04-05 国立大学法人愛媛大学 Procédé de fabrication d'un matériau hybride et matériau hybride
JP2019026918A (ja) * 2017-08-03 2019-02-21 株式会社ユー・エム・アイ 金属とフッ素ゴムとの接合体およびその接合方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5230262A (en) * 1975-09-02 1977-03-07 Kyowa Chem Ind Co Ltd Method of reforming powder surface
JP2005054238A (ja) * 2003-08-05 2005-03-03 Araco Corp マグネシウム材またはマグネシウム合金材の表面処理方法
JP2008266709A (ja) * 2007-04-19 2008-11-06 National Institute Of Advanced Industrial & Technology 金属表面微細構造の作成方法
JP2009114504A (ja) * 2007-11-07 2009-05-28 Shingijutsu Kenkyusho:Kk マグネシウム合金物品、マグネシウム合金部材およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5230262A (en) * 1975-09-02 1977-03-07 Kyowa Chem Ind Co Ltd Method of reforming powder surface
JP2005054238A (ja) * 2003-08-05 2005-03-03 Araco Corp マグネシウム材またはマグネシウム合金材の表面処理方法
JP2008266709A (ja) * 2007-04-19 2008-11-06 National Institute Of Advanced Industrial & Technology 金属表面微細構造の作成方法
JP2009114504A (ja) * 2007-11-07 2009-05-28 Shingijutsu Kenkyusho:Kk マグネシウム合金物品、マグネシウム合金部材およびその製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014125639A (ja) * 2012-12-25 2014-07-07 Shibaura Institute Of Technology 高耐食性マグネシウム系材料及びその製造方法、並びに、マグネシウム系材料の表面処理方法
JP2017503077A (ja) * 2013-12-26 2017-01-26 ポスコＰｏｓｃｏ 発色処理された基材およびこのための基材の発色処理方法
JP5978376B1 (ja) * 2015-11-04 2016-08-24 Ｔｏｄａ株式会社 音響用マグネシウム振動板の製造方法および音響用マグネシウム振動板
WO2017078010A1 (fr) * 2015-11-04 2017-05-11 Ｔｏｄａ株式会社 Procédé pour fabriquer une membrane acoustique en magnésium et membrane acoustique en magnésium
WO2018062360A1 (fr) * 2016-09-28 2018-04-05 国立大学法人愛媛大学 Procédé de fabrication d'un matériau hybride et matériau hybride
JPWO2018062360A1 (ja) * 2016-09-28 2019-08-29 国立大学法人愛媛大学 ハイブリッド材料の製造方法及びハイブリッド材料
JP2019026918A (ja) * 2017-08-03 2019-02-21 株式会社ユー・エム・アイ 金属とフッ素ゴムとの接合体およびその接合方法

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