KR20110056706A - Method for conversion coating of surface to magnesium or magnesium alloy - Google Patents
Method for conversion coating of surface to magnesium or magnesium alloy Download PDFInfo
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- KR20110056706A KR20110056706A KR1020090113144A KR20090113144A KR20110056706A KR 20110056706 A KR20110056706 A KR 20110056706A KR 1020090113144 A KR1020090113144 A KR 1020090113144A KR 20090113144 A KR20090113144 A KR 20090113144A KR 20110056706 A KR20110056706 A KR 20110056706A
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- magnesium
- magnesium alloy
- chemical conversion
- aqueous solution
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 72
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000011777 magnesium Substances 0.000 title claims abstract description 55
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000007739 conversion coating Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 50
- 239000007864 aqueous solution Substances 0.000 claims description 39
- 238000011282 treatment Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000176 sodium gluconate Substances 0.000 claims description 3
- 235000012207 sodium gluconate Nutrition 0.000 claims description 3
- 229940005574 sodium gluconate Drugs 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 238000009499 grossing Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000007591 painting process Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 30
- 239000002184 metal Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 3
- 230000003796 beauty Effects 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare earth salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
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Classifications
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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
- C23C22/06—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 acidic solutions with pH less than 6
- C23C22/34—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 acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—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 acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
-
- 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
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/22—Acidic compositions for etching magnesium or alloys thereof
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
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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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
본 발명을 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법에 관한 것으로서, 보다 자세하게는 마그네슘 또는 마그네슘 합금 외면에 환경친화적이며, 높은 내식성을 부여할 수 있는 화성피막이 형성된 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법에 관한 것이다. The present invention relates to a method of forming a chemical conversion layer on the outer surface of magnesium or magnesium alloy, and more particularly, to the magnesium or magnesium alloy outer surface of the magnesium or magnesium alloy, the chemical conversion coating layer is formed on the outer surface of the magnesium or magnesium alloy It relates to a method of forming a.
일반적으로 마그네슘은 지구상에 풍부할 뿐 아니라 밀도가 약 1.74 g/cm³으로써, 구조용 금속재료 중 가장 경량이기 때문에 항공기, 자동차 및 휴대용 기기 등에 사용되고 있으며, 사용량 및 적용 범위가 급격히 증가하고 있다. In general, magnesium is not only abundant on the earth but also has a density of about 1.74 g / cm3, which is the lightest of the structural metal materials, and thus is used in aircraft, automobiles, and portable devices.
그러나 마그네슘 합금은 재질의 특성상 내식성이 떨어진다는 단점이 있기 때문에 표면에 화학처리를 필수적으로 해야 하며, 이러한 화학처리 중에서 가장 많이 사용되어온 방법 중 하나는 화성피막형성 후에 도장으로 마무리하는 공정이 있다.However, magnesium alloy has a disadvantage in that corrosion resistance is poor due to the characteristics of the material, so the surface of the chemical treatment is essential, and one of the most commonly used chemical treatments is the process of finishing the coating after the formation of chemical conversion film.
화성피막형성 방법은 마그네슘 표면에 다양한 화학 반응들에 의해서 피막이 형성되는 금속 표면처리의 하나로서 피막의 두께는 수백 nm 범위를 나타내며, 화성처리용액에 따라 다양한 종류가 있다. 또한, 화성피막형성 방법은 외부에서 전기를 가해주는 전기도금과는 달리 외부에서 전기를 가해주지 않고 금속 표면에서 일어나는 화학반응을 이용하여 피막을 얻는 특징이 있다. The chemical conversion film formation method is one of metal surface treatments in which a film is formed by various chemical reactions on the surface of magnesium. In addition, the method of forming a chemical film is characterized by obtaining a film by using a chemical reaction occurring on the metal surface without applying electricity from the outside, unlike the electroplating to apply electricity from the outside.
이러한 마그네슘 합금의 화성피막형성 방법은 일반적으로 크롬계 화성처리와 비크롬계 화성처리 방법이 있다. Chemical conversion coating method of the magnesium alloy is generally a chromium-based chemical conversion treatment and non-chromium-based chemical conversion treatment.
크롬계 화성처리는 70년대 Dow Chemical에서 개발되었으며, Dow1이나 Dow21과 같이 명명되어 사용되고 있다. 대표적인 Dow법은 중크롬산소다를 주성분으로 하여 산성용액에서 금속표면처리가 이뤄진다. Dow법에서 사용되는 산성용액은 관리가 용이하고, 표면 처리 이후 금속의 내식성 및 도장 밀착성이 좋은 장점이 있다. 하지만, 사용되는 산성용액 내의6가 크롬의 유해성이 발견되어 사용에 제한이 있다. The chromium-based chemical conversion treatment was developed by Dow Chemical in the 70's, and is named after Dow1 or Dow21. Representative Dow method is metal surface treatment in acidic solution based on sodium dichromate. The acid solution used in the Dow method is easy to manage and has the advantages of corrosion resistance and paint adhesion of metal after surface treatment. However, the use of hexavalent chromium in the acidic solution used is limited.
이에 따라 저크롬계 혹은 비크롬계 화성처리 방법이 개발되어 사용되고 있는데, 비크롬계 화성처리법은 주로 망간염계 및 지르코늄염계가 있으며, 기타 희토류염계와 유기계가 알려져 있으나, 처리액이 고가이거나 관리가 힘드는 단점이 있다. Accordingly, low chromium-based or non-chromium-based chemical treatment methods have been developed and used. Non-chromium-based chemical treatment methods mainly include manganese salts and zirconium salts. Other rare earth salts and organic salts are known, but treatment liquids are expensive or unmanageable. It has a hard disadvantage.
또한 화성피막의 색상이 크로메이트의 경우는 녹색이거나 붉은 회색을 띄고, 비크롬계의 경우는 회색이나 아이보리 색을 나타내기 때문에 마그네슘의 금속색상이 그대로 표현되지 못하기 때문에 마그네슘 합금 외관의 미려함이 저하된다. In addition, since the color of the chemical coating is green or reddish gray in the case of chromate, and gray or ivory in the case of non-chromium, the metallic color of magnesium cannot be expressed as it is, so the beauty of the appearance of magnesium alloy is deteriorated. .
본 발명의 하나의 목적은 내식성이 향상된 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법을 제공하는 것이다.One object of the present invention is to provide a method for forming a chemical conversion layer on the outer surface of magnesium or magnesium alloy with improved corrosion resistance.
본 발명의 다른 목적은, 친환경경적인 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for forming a chemical conversion layer on the outer surface of magnesium or magnesium alloy which is environmentally friendly.
본 발명의 다른 목적은 표면처리 후에도 외관의 손상을 최소화하는 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for forming a chemical conversion layer on the outer surface of magnesium or magnesium alloy to minimize damage to the appearance even after the surface treatment.
본 발명의 다른 목적은 외관의 미려함을 최대화할 수 있는 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for forming a chemical conversion layer on the outer surface of magnesium or magnesium alloy that can maximize the beauty of the appearance.
본 발명의 일 실시예에 따른 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법은, 마그네슘 또는 마그네슘 합금 외면에 탈지 처리 후 수세 처리하는 단계; 상기 마그네슘 또는 마그네슘 합금 외면의 산화 피막 제거를 위한 에칭처리 후 수세 처리하는 단계; 상기 마그네슘 또는 마그네슘 합금 외면에 발생한 스머트를 제거하기 위한 디스머트 처리 후 수세 처리하는 단계; 상기 마그네슘 또는 마그네슘 합금 외면에 화성피막형성처리 후 수세 처리하는 단계; 및 상기 화성피막 상에 도장처리를 하는 단계;를 포함한다.Method for forming a chemical conversion layer on the magnesium or magnesium alloy outer surface according to an embodiment of the present invention, the step of degreasing treatment on the magnesium or magnesium alloy outer surface after washing with water; Washing with water after etching to remove the oxide film from the outer surface of the magnesium or magnesium alloy; Washing with water after a smut treatment to remove smut generated on the magnesium or magnesium alloy outer surface; Washing with water after chemical conversion film formation on the outer surface of the magnesium or magnesium alloy; And coating on the chemical conversion film.
상기와 같은 방법에 의하여 내식성이 향상되고, 표면처리 후에도 외관의 손 상을 최소화하며, 미려함을 최대화할 수 있는 마그네슘 또는 마그네슘 합금이 제공될 수 있다. By the above method, magnesium or a magnesium alloy may be provided that may improve corrosion resistance, minimize appearance damage after surface treatment, and maximize beauty.
상기 마그네슘 또는 마그네슘 합금 외면에 탈지 처리 후 수세 처리하는 단계에서 상치 탈지 처리는 30~60g/L미만의 수산화칼륨(KOH), 150~200g/L의 수산화나트륨(NaOH), 20~30g/L의 아민옥사이드, 5~10g/L의 C6H11NaO7(글루코산나트륨) 및 침윤제(Wetting agent)로 조성된 제1 수용액에 의하여 처리될 수 있다. 상기와 같이 구성된 제1 수용액은 마그네슘 또는 마그네슘 합금 표면의 기름성분을 용이하게 제거할 수 있으며, 소재의 변색을 초소화할 수 있다. The degreasing treatment in the step of degreasing after washing with magnesium or magnesium alloy outer surface is less than 30 ~ 60g / L potassium hydroxide (KOH), 150 ~ 200g / L sodium hydroxide (NaOH), 20 ~ 30g / L It may be treated with a first aqueous solution composed of amine oxide, 5-10 g / L of C 6 H 11 NaO 7 (sodium gluconate) and a wetting agent. The first aqueous solution configured as described above can easily remove the oil component on the surface of magnesium or magnesium alloy, and can minimize the discoloration of the material.
상기 마그네슘 또는 마그네슘 합금 외면의 산화 피막 제거를 위한 에칭처리 후 수세 처리하는 단계에서 상기 엣칭처리는 600~800g/L의 질산(HNO₃), 200~400g/L의 인산(H₃PO₄) 및 침윤제(Wetting agent)를 혼합한 제2 수용액에 의해 처리될 수 있다. 한편, 제2 수용액은 증류수로 희석하여 pH 1.0~2.0 미만으로 조정될 수 있으며, 약 35~50°C의 온도 범위 내로 형성될 수 있다. 상기와 같이 구성된 제2 수용액에 의하여 마그네슘 또는 마그네슘 합금 표면의 산화막이 용이하게 제거될 수 있으며, 금속의 변색을 최소화할 수 있다. In the step of washing with water after etching to remove the oxide film of the magnesium or magnesium alloy, the etching treatment includes 600 to 800 g / L nitric acid (HNO₃), 200 to 400 g / L phosphoric acid (H₃PO₄) and a wetting agent (Wetting). agent) may be treated with a mixed second aqueous solution. On the other hand, the second aqueous solution may be adjusted to less than pH 1.0 ~ 2.0 by dilution with distilled water, it may be formed within a temperature range of about 35 ~ 50 ° C. By the second aqueous solution configured as described above, the oxide film on the surface of the magnesium or magnesium alloy may be easily removed, and discoloration of the metal may be minimized.
한편, 상기 마그네슘 또는 마그네슘 합금 외면에 발생한 스머트를 제거하기 위한 디스머트 처리 후 수세 처리하는 단계에서 상디 디스머트 처리는 50~200 g/L의 수산화칼륨(KOH) 및 5~10 g/L의 평활제를 혼합한 제3 수용액에 침치 처리될 수 있다. 상기와 같은 조성비율에 의하여 금속 표면에 수산화 피막이 발생되는 것을 방지할 수 있으며, 금속이 디스머트되는 것을 방지할 수 있다. Meanwhile, in the step of washing with water after the smut treatment for removing the smut generated on the outer surface of the magnesium or magnesium alloy, the simmering treatment is 50-200 g / L of potassium hydroxide (KOH) and 5-10 g / L. It can be immersed in the third aqueous solution mixed with the leveling agent. By the composition ratio as described above it is possible to prevent the generation of a hydroxide film on the surface of the metal, it is possible to prevent the metal from being dispersed.
또한, 상기 마그네슘 또는 마그네슘 합금 외면에 화성피막형성처리 후 수세 처리하는 단계에서 상기 화성피막형성처리는 600~800g/L의 질산(HNO), 200~400g/L의 인산(H₃PO) 및 0.5~10g/L의 불산(HF)을 혼합한 제4 수용액에 처리될 수 있다. 이때, 제4 수용액은 증류수로 희석하여 pH 2.0~4.0으로 조정하며, 20~ 60℃의 상기 제4 수용액 내에서 상기 화성피막이 형성될 수 있다. 이와 같이 제4 수용액의 온도를 한정함으로써, 피막형성 속도를 조절하여 금속 표면에 일정한 두께의 피막이 형성될 수 있게 하며, 금속 외관의 손상을 최소화할 수 있다.In addition, in the step of washing with water on the magnesium or magnesium alloy outer surface after forming the film, the film forming treatment is 600 to 800 g / L nitric acid (HNO), 200 to 400 g / L phosphoric acid (H₃PO) and 0.5 to 10 g. / L hydrofluoric acid (HF) can be treated with a fourth aqueous solution. In this case, the fourth aqueous solution may be diluted with distilled water to adjust the pH to 2.0 to 4.0, and the chemical conversion film may be formed in the fourth aqueous solution at 20 to 60 ° C. As such, by limiting the temperature of the fourth aqueous solution, the film formation rate may be controlled to form a film having a predetermined thickness on the metal surface, and damage to the metal appearance may be minimized.
본 발명의 일 실시예의 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법에 따르면, 산 알칼리와의 반응성이 뛰어나고 활성이 강하여 내식성이 향상될 수 있다. According to the method of forming the chemical conversion film layer on the outer surface of the magnesium or magnesium alloy of the embodiment of the present invention, it is excellent in reactivity with acid alkali and strong in activity, thereby improving corrosion resistance.
본 발명의 일 실시예의 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법에 따르면, 크롬산 등의 환경에 유해한 물질을 사용하지 않고 금속 표면에 피막을 형성하므로 친환경적으로 피막층을 형성할 수 있다.According to the method of forming the chemical conversion film layer on the outer surface of the magnesium or magnesium alloy of the embodiment of the present invention, since the film is formed on the metal surface without using a material harmful to the environment such as chromic acid, it is possible to form an environmentally friendly film layer.
본 발명의 일 실시예의 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법에 따르면, 마그네슘 또는 마그네슘 합금 외면에 표면처리를 한 후에도 마그네슘 그대로의 색상을 표현할 수 있게 된다.According to the method of forming the chemical conversion layer on the outer surface of the magnesium or magnesium alloy of the embodiment of the present invention, even after the surface treatment on the magnesium or magnesium alloy outer surface it is possible to express the color as it is magnesium.
이하에서, 본 발명에 따른 실시예들을 첨부된 도면을 참조하여 상세하게 설명한다. 그러나, 본 발명이 실시예들에 의해 제한되거나 한정되는 것은 아니다. 각 도면에 제시된 동일한 참조 부호는 동일한 부재를 나타낸다. Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited or limited by the embodiments. Like reference numerals in the drawings denote like elements.
도 1은 본 발명의 일 실시예에 따른 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법에 따라 표면처리된 마그네슘 합금판재의 표면조직의 확대도이고, 도 2는 도1의 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법을 도시한 순서도이다.1 is an enlarged view of a surface texture of a magnesium alloy plate material surface treated according to a method of forming a chemical conversion layer on the magnesium or magnesium alloy outer surface according to an embodiment of the present invention, Figure 2 is an outer surface of the magnesium or magnesium alloy of Figure 1 It is a flowchart which shows the method of forming a chemical conversion layer in the.
이하 도면을 설명하기 위하여 마그네슘 합금 표면에 화성피막층을 형성하는 예를 들어 설명하지만, 발명에서 요구되는 조건에 따라 마그네슘 금속판 표면위에 화성피막층이 형성될 수도 있다. In the following description, an example of forming a chemical conversion layer on the surface of a magnesium alloy is described.
도면 및 [표 1]을 참고하면, 성형한 마그네슘 합금 표면에 부착되어 있는 유지성분과 이물질을 제거하며, 금속의 변색을 방지하기 위하여 마그네슘 합금 표면을 탈지 처리 할 수 있는 제1 수용액을 형성할 수 있다(S210).Referring to the drawings and [Table 1], it is possible to form a first aqueous solution capable of degreasing the surface of the magnesium alloy in order to remove fats and oils adhered to the molded magnesium alloy surface and to prevent discoloration of the metal. There is (S210).
[표 1]TABLE 1
상기 제1 수용액에 제공된 첨가제는 침윤제(Wetting agent)로서, 금속 표면 에 제1 수용액이 잘 스며들도록 할 수 있는 계명활성제가 될 수 있다. 상기 계면활성제는 발명에서 요구되는 조건에 따라 다양한 침윤제가 사용될 수 있다. The additive provided in the first aqueous solution is a wetting agent, and may be a commanding agent capable of allowing the first aqueous solution to penetrate the metal surface well. The surfactant may be used a variety of wetting agents depending on the conditions required in the invention.
이때, 제1 수용액의 조성비율이 제시된 [표 1]의 범위에서 벗어나게 되면, 마그네슘 합금 표면의 기름 성분이 제거되는 속도나 늦거나 금속의 소재가 변색될 수 있기 때문에 제1 수용액의 조성비율은 도시된 범위 내에서 이루어지는 것이 바람직할 것이다.At this time, if the composition ratio of the first aqueous solution is out of the range shown in [Table 1], the composition ratio of the first aqueous solution is shown because the rate of removal of oil components on the surface of the magnesium alloy or the material of the metal may be discolored. It would be desirable to be within the range specified.
상기 제1 수용액을 이용하여 마그네슘 합금 표면의 유지성분과 이물질을 제거하게 되면 수세처리를 할 수 있다(S210). 상기 수세처리를 통해 마그네슘 합금 표면에 남아 있는 제1 수용액 성분을 완전히 제거할 수 있다.Using the first aqueous solution to remove the oil and foreign matter on the surface of the magnesium alloy may be washed with water (S210). The water treatment may completely remove the first aqueous solution component remaining on the magnesium alloy surface.
제1 수용액은 강 알카리 성분이기 때문에 만약 마그네슘 합금 표면에 제1 수용액 성분이 남아 있을 경우 후 공정에서 사용되는 강 산성 용액과 반응하여 금속 표면의 화학적인 반응을 저하시키며, 금속 표면이 불균형하게 형성될 수 있다. 따라서, 수세처리를 통하여 금속 표면에 남아 있는 제1 수용액을 완전히 제거하여 후 공정의 효율을 향상시킬 수 있다. Since the first aqueous solution is a strong alkali component, if the first aqueous solution component remains on the magnesium alloy surface, the first aqueous solution reacts with the strongly acidic solution used in the subsequent process to lower the chemical reaction of the metal surface, and the metal surface may be unbalanced. Can be. Therefore, the first aqueous solution remaining on the metal surface may be completely removed by washing with water to improve the efficiency of the post process.
탈지 처리가 종료되면, 금속 표면의 마그네슘 산화피막을 제거하기 위해 [표2]와 같은 제2수용액을 제조할 수 있다(S220).When the degreasing treatment is completed, a second aqueous solution as shown in Table 2 may be prepared to remove the magnesium oxide film on the metal surface (S220).
[표 2]TABLE 2
상기 제2 수용액에 제공된 침윤제는 앞서 설명한 바와 같이 금속에 용액이 잘 스며들도록 한 계명활성제로서 발명에서 요구되는 조건에 따라 다양하게 제공될 수 있다. The infiltrating agent provided in the second aqueous solution may be provided in various ways according to the conditions required in the invention as a commanding activator to allow the solution to penetrate the metal as described above.
상기 제2 수용액을 이용하여 마그네슘 합금 표면을 에칭처리하게 되면, 금속표면의 산화피막을 적절한 속도로 제거할 수 있으며, 금속의 변색을 방지할 수 있다. When the magnesium alloy surface is etched using the second aqueous solution, the oxide film on the metal surface can be removed at an appropriate speed, and discoloration of the metal can be prevented.
마그네슘 합급의 에칭처리가 종료되면 수세처리를 할 수 있다(S220). 앞서 설명한 바와 같이 수세처리는 금속 표면에 화성피막을 형성하는 과정에서 사용되는 용액이 공정 후에 표면에 남아 금속 외관이 손상되는 것을 방지할 수 있다. When the etching process of the magnesium alloy is finished, it can be washed with water (S220). As described above, the washing process may prevent the solution used in the process of forming the chemical conversion film on the metal surface remaining on the surface after the process to damage the metal appearance.
에칭 처리 및 수세처리가 종료되면 [표 3]과 같이 제3 수용액을 제조하여 마그네슘 합금 표면에 발생한 스머트를 제거할 수 있다(S230). After the etching treatment and the washing treatment are finished, the third aqueous solution may be prepared as shown in Table 3 to remove the smut generated on the surface of the magnesium alloy (S230).
[표 3][Table 3]
상기 [표 3]에 도시된 조성비율로 제조된 제3 수용액은 디스머트 용액으로써, 금속 표면의 얼룩 등을 제거할 수 있으며 첨가제인 평활제를 첨가하여 금속표면이 평평해질 수 있다.The third aqueous solution prepared at the composition ratio shown in [Table 3] is a dismert solution, and may remove stains on the metal surface, and the metal surface may be flattened by adding a leveling agent as an additive.
또한, 제3 수용액은 상기 [표 3]의 조성비율에 따라 조제되는 것이 바람직할 것이다. 만약 제3 수용액이 상기 조성비율보다 낮을 경우 금속 표면이 부분적으로 디스머트가 형성되고, 조성비율보다 높을 경우 금속 표면에 수산화 피막이 형성될 수 있다. 따라서 제3 수용액의 조성비율은 상기 범위에서 벗어나지 않는 것이 바람직할 것이다.In addition, it is preferable that the third aqueous solution is prepared according to the composition ratio of the above [Table 3]. If the third aqueous solution is lower than the composition ratio, the metal surface may be partially formed, and if it is higher than the composition ratio, the hydroxide film may be formed on the metal surface. Therefore, it is preferable that the composition ratio of the third aqueous solution does not depart from the above range.
한편, 마그네슘 합금 표면에 발생한 스머트가 제거되면 마그네슘 합금을 수세 처리 한 뒤(S230), 마그네슘 합금 외면에 화성피막을 형성할 수 있다(S240). 마그네슘 합금 외면에 화성피막을 형성하기 위하여 제4 수용액을 제조할 수 있으며, 제4 수용액의 조성비율은 다음과 같다.On the other hand, if the smut generated on the magnesium alloy surface is removed after washing the magnesium alloy (S230), it is possible to form a chemical film on the magnesium alloy outer surface (S240). A fourth aqueous solution may be prepared to form a chemical conversion film on the outer surface of the magnesium alloy, and the composition ratio of the fourth aqueous solution is as follows.
[표 4][Table 4]
상기와 같이 제조된 제4 수용액에 의하여 화성피막이 형성된 마그네슘 합금은 화성피막 상에 도장처리를 할 수 있다(S250). Magnesium alloy in which the chemical conversion film is formed by the fourth aqueous solution prepared as described above may be coated on the chemical conversion coating (S250).
상기 도장처리 이후 금속의 내식성 검사를 위한 염수부분 시험에서 36시간 이후 결과와 피막과 금속간의 밀착성 시험을 행한 결과 다음과 같이 나타났다.In the salt water test for the corrosion resistance test of the metal after the coating treatment result after 36 hours and the adhesion test between the film and the metal was shown as follows.
[표 5]TABLE 5
상기와 같은 화성피막을 형성하는 방법에 의하여 형성된 마그네슘 합금의 표면은 마그네슘 그대로의 금속색상을 유지할 수 있으며, 금속표면의 손상을 최소화할 수 있다. 또한, 마그네슘 합금의 내식성을 향상시켜 다양한 기기의 원료로써 사용될 수 있다. 더불어, 기존의 크로메이트, 크롬산 등과 같은 독성이 강한 화성피막을 사용하지 않기 때문에 친환경적인 피막층을 형성할 수도 있다. The surface of the magnesium alloy formed by the method of forming a chemical conversion film as described above can maintain the metal color of magnesium as it is, it is possible to minimize the damage to the metal surface. In addition, it improves the corrosion resistance of magnesium alloy can be used as a raw material of various devices. In addition, since an toxic chemical film such as chromate and chromic acid is not used, an environmentally friendly film layer may be formed.
이상에서는 본 발명의 바람직한 실시예를 예시적으로 설명하였으나, 본 발명의 범위는 이와 같은 특정 실시예에만 한정되는 것은 아니며, 특허청구범위에 기재된 범주 내에서 적절하게 변경 가능한 것이다.Although the preferred embodiments of the present invention have been described above by way of example, the scope of the present invention is not limited to these specific embodiments, and may be appropriately changed within the scope described in the claims.
도 1은 본 발명의 일 실시예에 따른 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법에 따라 표면처리된 마그네슘 합금판재의 표면조직의 확대도이다.1 is an enlarged view of the surface texture of a magnesium alloy plate material surface-treated in accordance with a method for forming a chemical conversion layer on the magnesium or magnesium alloy outer surface according to an embodiment of the present invention.
도 2는 도1의 마그네슘 또는 마그네슘 합금 외면에 화성피막층을 형성하는 방법을 도시한 순서도이다.FIG. 2 is a flowchart illustrating a method of forming a chemical conversion layer on the outer surface of the magnesium or magnesium alloy of FIG. 1.
Claims (7)
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| KR1020090113144A KR101067744B1 (en) | 2009-11-23 | 2009-11-23 | Method for conversion coating of surface to magnesium or magnesium alloy |
| JP2010112653A JP2011111678A (en) | 2009-11-23 | 2010-05-14 | Method for forming conversion coating on outer surface of magnesium or magnesium alloy |
| US12/785,235 US20110120595A1 (en) | 2009-11-23 | 2010-05-21 | Method for forming conversion coating on outer surface of magnesium or magnesium alloy |
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| CN110592570A (en) * | 2019-09-27 | 2019-12-20 | 山东华盛荣镁业科技有限公司 | Magnesium alloy surface black chemical conversion process |
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| JPH06220663A (en) * | 1993-01-13 | 1994-08-09 | Nippon Light Metal Co Ltd | Smut removal from mg alloy surface |
| JPH06330341A (en) * | 1993-05-25 | 1994-11-29 | Nippon Paint Co Ltd | Pretreatment of magnesium or magnesium alloy material before coating |
| JP2001288580A (en) * | 2000-03-31 | 2001-10-19 | Nippon Parkerizing Co Ltd | Surface treating method for magnesium alloy and magnesium alloy member |
| JP2005023422A (en) * | 2003-06-09 | 2005-01-27 | Nippon Paint Co Ltd | Metal surface treatment method and surface-treated metal |
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